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Sample records for aba triblock copolymers

  1. Self-assembly of ABA triblock copolymers under soft confinement

    NASA Astrophysics Data System (ADS)

    Sheng, Yuping; An, Jian; Zhu, Yutian

    2015-05-01

    Using Monte Carlo method, the self-assembly of ABA triblock copolymers under soft confinement is investigated in this study. The soft confinement is achieved by a poor solvent environment for the polymer, which makes the polymer aggregate into a droplet. Various effects, including the block length ratio, the solvent quality for the blocks B, and the incompatibility between blocks A and B, on the micellar structures induced by soft confinement are examined. By increasing the solvent quality of B blocks, the micellar structure transforms from stacked lamella to bud-like structure, and then to onion-like structure for A5B8A5 triblock copolymers, while the inner micellar structure changes from spherical phase to various cylindrical phase, such as inner single helix, double helixes, stacked rings and cage-like structures, for A7B4A7 triblock copolymers. Moreover, the formation pathways of some typical aggregates are examined to illustrate their growth mechanisms.

  2. Imidazolium-Containing ABA Triblock Copolymers as Electroactive Devices.

    PubMed

    Margaretta, Evan; Fahs, Gregory B; Inglefield, David L; Jangu, Chainika; Wang, Dong; Heflin, James R; Moore, Robert B; Long, Timothy E

    2016-01-20

    Two-step reversible addition-fragmentation chain transfer (RAFT) polymerization and two subsequent postpolymerization modification steps afforded well-defined ABA triblock copolymers featuring mechanically reinforcing polystyrene outer blocks and 1-methylimidazole-neutralized poly(acrylic acid)-based central blocks. Size exclusion chromatography and (1)H NMR spectroscopy confirmed predictable molecular weights and narrow distributions. The ionic liquid (IL) 1-ethyl-3-methylimidazolium trifluoromethanesulfonate ([EMIm][OTf]) was incorporated at 30 wt % into polymeric films. Thermogravimetric analysis, differential scanning calorimetry, and dynamic mechanical analysis determined the thermomechanical properties of the polymers and polymer-IL composites. Atomic force microscopy, small-angle X-ray scattering (SAXS), and transmission electron microscopy (TEM) determined surface and bulk morphologies, and poly(Sty-b-AA(MeIm)-b-Sty) exhibited a change from packed cylindrical to lamellar morphology in SAXS upon IL incorporation. Electrochemical impedance spectroscopy determined the in-plane ionic conductivities of the polymer-IL membranes (σ ∼ 10(-4) S/cm). A device fabricated from poly(Sty-b-AA(MeIm)-b-Sty) with 30 wt % incorporated IL demonstrated mechanical actuation under a low applied voltage of 4 V. PMID:26699795

  3. Self-assembly of rod-coil-rod ABA-type triblock copolymers.

    PubMed

    Chen, Ji-Zhong; Sun, Zhao-Yan; Zhang, Cheng-Xiang; An, Li-Jia; Tong, Zhen

    2008-02-21

    Self-assembled behavior of symmetric ABA rod-coil-rod triblock copolymer melts is studied by applying self-consistent-field lattice techniques in three-dimensional space. The phase diagram is constructed to understand the effects of the chain architecture on the self-assembled behavior. Four stable structures are observed for the ABA rod-coil-rod triblock, i.e., spherelike, lamellar, gyroidlike, and cylindrical structures. Different from AB rod-coil diblock and BAB coil-rod-coil triblock copolymers, the lamellar structure observed in ABA rod-coil-rod triblock copolymer melts is not stable for high volume fraction of the rod component (f(rod)=0.8), which is attributed to the intramolecular interactions between the two rod blocks of the polymer chain. When 0.3

  4. 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.

  5. Unexpected consequences of block polydispersity on the self-assembly of ABA triblock copolymers.

    PubMed

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

    2012-02-29

    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(w)/M(n) = 1.73-2.00) flanked by relatively narrow dispersity S blocks (M(w)/M(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 ≤ f(B) ≤ 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. PMID:22280467

  6. Magnetic Hydrogels from Alkyne/Cobalt Carbonyl-Functionalized ABA Triblock Copolymers.

    PubMed

    Jiang, Bingyin; Hom, Wendy L; Chen, Xianyin; Yu, Pengqing; Pavelka, Laura C; Kisslinger, Kim; Parise, John B; Bhatia, Surita R; Grubbs, Robert B

    2016-04-01

    A series of alkyne-functionalized poly(4-(phenylethynyl)styrene)-block-poly(ethylene oxide)-block-poly(4-(phenylethynyl)styrene) (PPES-b-PEO-b-PPES) ABA triblock copolymers was synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization. PESn[Co2(CO)6]x-EO800-PESn[Co2(CO)6]x ABA triblock copolymer/cobalt adducts (10-67 wt % PEO) were subsequently prepared by reaction of the alkyne-functionalized PPES block with Co2(CO)8 and their phase behavior was studied by TEM. Heating triblock copolymer/cobalt carbonyl adducts at 120 °C led to cross-linking of the PPES/Co domains and the formation of magnetic cobalt nanoparticles within the PPES/Co domains. Magnetic hydrogels could be prepared by swelling the PEO domains of the cross-linked materials with water. Swelling tests, rheological studies and actuation tests demonstrated that the water capacity and modulus of the hydrogels were dependent upon the composition of the block copolymer precursors. PMID:26958699

  7. Segmental chain dynamics of ABA triblock copolymer micelles in aqueous solution

    NASA Astrophysics Data System (ADS)

    Prabhu, Vivek; Wei, Guangmin; Nagao, Michihiro; Venkataraman, Shrinivas; Yang, Yi Yan; Hedrick, James

    The polymer physics of hierarchical, aqueous self-assembled ABA block copolymers is an active area of research for both advanced materials and biomaterial applications. Scattering-based techniques provide a direct measure of the correlations and structure across multiple length and time scales. Hierarchical clusters of micelles are formed by well-defined poly(ethylene glycol) triblock copolymers with oligo-fluorene hydrophobic end-groups in aqueous solutions. The structure and dynamics of this system was studied by small-angle neutron scattering (SANS), and static and dynamic light scattering. We will present new neutron spin-echo spectroscopy (NSE) results that provides direct insight into the segmental chain dynamics constrained by the pi-pi stacking of the oligo-fluorene end groups. The dilute cluster regime within the temperature-composition phase diagram is of current interest. Nist Materials Genome Program.

  8. Rigidity effect on phase behavior of symmetric ABA triblock copolymers: A Monte Carlo simulation

    NASA Astrophysics Data System (ADS)

    Song, Jianhui; Shi, Tongfei; Li, Yunqi; Chen, Jizhong; An, Lijia

    2008-08-01

    The phase behavior of symmetric ABA triblock copolymers containing a semiflexible midblock is studied by lattice Monte Carlo simulation. As the midblock evolves from a fully flexible state to a semiflexible state in terms of increase in its persistence length, different phase behaviors are observed while cooling the system from an infinite high temperature to a temperature below TODT (order-disorder transition temperature). Within the midblock flexibility range we studied (lp/Nc<=0.105), a lamellar structure is formed at equilibrium state as the situation for fully flexible chains. The fraction of bridge chain is evaluated for the lamellar structures. We find that the increase in midblock rigidity indeed results in the increase in bridge chain fraction within the range from 44.9% to 51.8%. In order to elucidate phase behavior evolution observed in our simulation, a detailed conformation distribution analysis is also given. Our results bridge a gap of different phase behaviors between rod-coil block copolymer and coil-coil block copolymer and show a necessity to investigate rigidity influence on phase diagram.

  9. Diverse 2D structures obtained by adsorption of charged ABA triblock copolymer on different surfaces

    NASA Astrophysics Data System (ADS)

    Kontturi, Katri S.; Vesterinen, Arja-Helena; Seppälä, Jukka; Laine, Janne

    2012-11-01

    In the larger context of 2D polymeric structures, the morphologies obtained by adsorption and subsequent drying of charged, ABA type amphiphilic triblock copolymer of poly[2-(dimethylamino)ethyl metacrylate] (PDMAEMA) and poly(propylene oxide) (PPO) were investigated with atomic force microscopy and X-ray photoelectron spectroscopy as well as in situ adsorption analysis with quartz crystal microbalance with dissipation monitoring. Hydrophilic silica and hydrophobic polystyrene (PS) were used as substrates for adsorption. The structures emerging from the self-assembly of adsorbing polymer were profoundly influenced by composition of the aqueous solution and the choice of substrate. When adsorbed from dilute polymer solution where the concentration is so low that the polymer does not yet show surface-active behavior, the triblock copolymer unimers associated on hydrophilic silica surface forming large, irregular clustered aggregates, with sizes increasing with electrolyte concentration of the solution. On a hydrophobic PS substrate, on the other hand, unimers spread much more evenly, forming clear surface patterns. The roughness of these patterned structures was tuned with the electrolyte concentration of the solution. Adsorption from a more concentrated polymer solution, where the surface-activity of the polymer is perceptible, resulted in the formation of a smooth film with complete coverage over the hydrophilic silica substrate when the electrolyte concentration was high. On PS, on the other hand, nucleation of evenly scattered globular, disk-like micelles was induced. Besides the dry film morphology, the even distribution of the irreversibly adsorbed polymer over the PS surface was likely to serve as an optimal platform for the build-up of reversible hydrophobically bound multilayers at high electrolyte concentration. The multilayer formation was reversible because a decrease in the electrolyte concentration of the solution re-introduces strong electrostatic

  10. Characterization of a Poly(styrene-block-methylacrylate-random-octadecylacrylate-block-styrene) Shape Memory ABA Triblock Copolymer

    NASA Astrophysics Data System (ADS)

    Fei, Pengzhan; Cavicchi, Kevin

    2011-03-01

    A new ABA triblock copolymer of poly(styrene-block- methylacrylate-random-octadecylacrylate-block-styrene) (PS-b- PMA-r-PODA-b-PS) was synthesized by reversible addition fragmentation chain transfer polymerization. The triblock copolymer can generate a three-dimensional, physically crosslinked network by self-assembly, where the glassy PS domains physically crosslink the midblock chains. The side chain crystallization of the polyoctadecylacrylare (PODA) side chain generates a second reversible network enabling shape memory properties. Shape memory tests by uniaxial deformation and recovery of molded dog-bone shape samples demonstrate that shape fixities above 96% and shape recoveries above 98% were obtained for extensional strains up to 300%. An outstanding advantage of this shape memory material is that it can be very easily shaped and remolded by elevating the temperature to 140circ; C, and after remolding the initial shape memory properties are totally recovered by eliminating the defects introduced by the previous deformation cycling.

  11. Sequentially Different AB Diblock and ABA Triblock Copolymers as P3HT:PCBM Interfacial Compatibilizers for Bulk-Heterojunction Photovoltaics.

    PubMed

    Fujita, Hiroyuki; Michinobu, Tsuyoshi; Fukuta, Seijiro; Koganezawa, Tomoyuki; Higashihara, Tomoya

    2016-03-01

    The P3HT:PCBM (P3HT = poly(3-hexylthiophene, PCBM = phenyl-C61-butyric acid methyl ester) bulk-heterojunction (BHJ) organic photovoltaic (OPV) cells using the AB diblock and ABA triblock copolymers (A = polystyrene derivative with donor-acceptor units (PTCNE) and B = P3HT) as compatibilizers were fabricated. Under the optimized blend ratio of the block copolymer, the power conversion efficiency (PCE) was enhanced. This PCE enhancement was clearly related to the increased short-circuit current (J(sc)) and fill factor (FF). The incident photon to current efficiency (IPCE) measurement suggested that the P3HT crystallinity was improved upon addition of the block copolymers. The increased P3HT crystallinity was consistent with the increased photovoltaic parameters, such as J(sc), FF, and consequently the PCE. The surface energies of these block copolymers suggested their thermodynamically stable location at the interface of P3HT:PCBM, showing the efficient compatibilizing performance, resulting in enlarging and fixing the interfacial area and suppressing the recombination of the generated carriers. Grazing incidence X-ray scattering (GIXS) results confirmed the superior compatibilizing performance of the ABA triblock copolymer when compared to the AB diblock copolymer by the fact that, after blending the ABA triblock copolymer in the P3HT:PCBM system, the enhanced crystallinity of matrix P3HT was observed in the excluded areas of the less-aggregated PCBM domains, changing the P3HT crystalline domain orientation from "edge-on" to "isotropic". This is, to the best of our knowledge, the first sequential effect (AB vs ABA) of the block copolymers on the compatibilizing performances based on BHJ OPV device systems. PMID:26864393

  12. Spatial and orientation control of cylindrical nanostructures in ABA triblock copolymer thin films by raster solvent vapor annealing.

    PubMed

    Seppala, Jonathan E; Lewis, Ronald L; Epps, Thomas H

    2012-11-27

    We present a spatially resolved approach for the solvent vapor annealing (SVA) of block copolymer thin films that permits the facile and relatively rapid manipulation of nanoscale ordering and nanostructure orientation. In our method, a localized (point) SVA zone is created through the use of a vapor delivery nozzle. This point annealing zone can be rastered across the thin film using a motorized stage to control the local nanoscale structure and orientation in a cylinder-forming ABA triblock copolymer thin film. At moderate rastering speeds (∼100 μm/s) (i.e., relatively modest annealing time at a given point), the film displayed ordered cylindrical nanostructures with the cylinders oriented parallel to the substrate surface. As the rastering speed was decreased (∼10 μm/s), the morphology transformed into a surface nanostructure indicative of cylinders oriented perpendicular to the substrate surface. These perpendicular cylinder orientations also were created by rastering multiple times over the same region, and this effect was found when rastering in either retrace (overlapping) or crossed-path (orthogonal) geometries. Similar trends in nanostructure orientation and ordering were obtained from various nozzle diameters by accounting for differences in solvent flux and annealing time, illustrating the universality of this approach. Finally, we note that our "stylus-based" raster solvent vapor annealing technique allows a given point to be solvent annealed approximately 2 orders of magnitude faster than conventional "bell jar" solvent vapor annealing. PMID:23035916

  13. Microstructural study of mechanical properties of the ABA triblock copolymer using self-consistent field and molecular dynamics

    NASA Astrophysics Data System (ADS)

    Aoyagi, Takeshi; Honda, Takashi; Doi, Masao

    2002-11-01

    The molecular mechanism of the strain-stress behavior of the ABA triblock copolymer is studied by combining self-consistent field (SCF) calculation and molecular dynamics (MD) simulation. First, the equilibrium structure was obtained by the SCF calculation. The bridge fraction phibridge was found to be about 0.4, 0.6, and 0.8 for lamellar, cylindrical, and spherical phases, respectively. From the segment distribution calculated by the SCF, the equilibrium chain configuration was generated by the method reported previously [Aoyagi [et al.], Comput. Phys. Comm. 145, 267 (2002)]. The loading and unloading behavior was then studied by the MD simulation. The loading curve shows a strain-softening, and then a yielding at a strain of about 350%, where the breakup of microdomains takes place. The strain-stress curve in the second elongation-compression cycle is different from that of the first cycle. Such hysteresis effect is seen also for small elongation where the domain breakup does not take place.

  14. Combining Ring-Opening Metathesis Polymerization and Cyclic Ester Ring-Opening Polymerization To Form ABA Triblock Copolymers from 1,5-Cyclooctadiene and D,L-Lactide

    SciTech Connect

    Pitet, Louis M.; Hillmyer, Marc A.

    2009-07-31

    ABA triblock copolymers were synthesized by combining ring-opening metathesis polymerization (ROMP) of 1,5-cyclooctadiene (COD) with ring-opening polymerization of D,L-lactide. Hydroxyl-functionalized telechelic polyCOD was prepared by taking advantage of chain transfer during ROMP of COD using the acyclic chain transfer agent cis-1,4-diacetoxy-2-butene. These hydroxy-terminated macroinitiators were used as initiators for the polymerization of lactide to form a series of triblock copolymers with compositions in the range 0.24 {le} f{sub PLA} {le} 0.89 and molecular weights ranging from 22 to 196 kg mol{sup -1}. The ordered-state morphologies of the triblocks were determined using small-angle X-ray scattering; well-ordered microstructures were observed for several samples, in accordance with the predicted dependence of morphology on composition. The mechanical properties of these materials were also investigated by performing tensile measurements; the triblocks were considerably tougher than poly(D,L-lactide), most markedly in samples with low polyCOD midblock content.

  15. Self-Assembly and Critical Aggregation Concentration Measurements of ABA Triblock Copolymers with Varying B Block Types: Model Development, Prediction, and Validation.

    PubMed

    Aydin, Fikret; Chu, Xiaolei; Uppaladadium, Geetartha; Devore, David; Goyal, Ritu; Murthy, N Sanjeeva; Zhang, Zheng; Kohn, Joachim; Dutt, Meenakshi

    2016-04-21

    The dissipative particle dynamics (DPD) simulation technique is a coarse-grained (CG) molecular dynamics-based approach that can effectively capture the hydrodynamics of complex systems while retaining essential information about the structural properties of the molecular species. An advantageous feature of DPD is that it utilizes soft repulsive interactions between the beads, which are CG representation of groups of atoms or molecules. In this study, we used the DPD simulation technique to study the aggregation characteristics of ABA triblock copolymers in aqueous medium. Pluronic polymers (PEG-PPO-PEG) were modeled as two segments of hydrophilic beads and one segment of hydrophobic beads. Tyrosine-derived PEG5K-b-oligo(desaminotyrosyl tyrosine octyl ester-suberate)-b-PEG5K (PEG5K-oligo(DTO-SA)-PEG5K) block copolymers possess alternate rigid and flexible components along the hydrophobic oligo(DTO-SA) chain, and were modeled as two segments of hydrophilic beads and one segment of hydrophobic, alternate soft and hard beads. The formation, structure, and morphology of the initial aggregation of the polymer molecules in aqueous medium were investigated by following the aggregation dynamics. The dimensions of the aggregates predicted by the computational approach were in good agreement with corresponding results from experiments, for the Pluronic and PEG5K-oligo(DTO-SA)-PEG5K block copolymers. In addition, DPD simulations were utilized to determine the critical aggregation concentration (CAC), which was compared with corresponding results from an experimental approach. For Pluronic polymers F68, F88, F108, and F127, the computational results agreed well with experimental measurements of the CAC measurements. For PEG5K-b-oligo(DTO-SA)-b-PEG5K block polymers, the complexity in polymer structure made it difficult to directly determine their CAC values via the CG scheme. Therefore, we determined CAC values of a series of triblock copolymers with 3-8 DTO-SA units using DPD

  16. Hybrid micellar hydrogels of a thermosensitive ABA triblock copolymer and hairy nanoparticles: effect of spatial location of hairy nanoparticles on gel properties.

    PubMed

    Hu, Bin; Henn, Daniel M; Wright, Roger A E; Zhao, Bin

    2014-09-23

    This article reports a method for control of spatial location of nanoparticles (NPs) in hybrid micellar hydrogels of a thermosensitive ABA triblock copolymer and polymer brush-grafted NPs (hairy NPs), either inside or outside the core of micelles, and the study of the effect of different locations of NPs on gel properties. Two batches of thermosensitive polymer brush-grafted, 17 nm silica NPs with different lower critical solution temperatures (LCSTs) and a thermosensitive ABA triblock copolymer composed of a poly(ethylene oxide) central block and thermosensitive outer blocks (ABA-D) were synthesized. The different locations of NPs were achieved by controlling the LCST of hairy NPs (LCST(NP)) relative to that of the thermosensitive outer blocks of ABA-D (LCST(ABA)). When the LCST(NP) and LCST(ABA) were similar, the NPs resided in the core of micelles upon heating from below the LCST(NP) and LCST(ABA). When the LCST(NP) was significantly higher, the NPs were located outside the core of micelles as confirmed by fluorescent resonance energy transfer. The effects of different locations of hairy NPs and NP-to-polymer mass ratio on properties of hybrid micellar hydrogels formed from aqueous solutions of ABA-D with a concentration of 10 wt % and various amounts of hairy NPs were studied by rheological measurements. The sol-gel transition temperature (T(sol-gel)) and dynamic storage modulus G' of the gels with NPs inside the core of micelles did not change much with increasing the NP-to-polymer mass ratio. In contrast, the T(sol-gel) of gels with NPs in the interstitial space among micelles increased slightly and the G' decreased significantly with the increase of the NP-to-polymer ratio. The hairy NPs in the interstitial space appeared to affect the formation of polymer networks and increase the fraction of polymer loops, resulting in a lower density of bridging chains and thus a lower G'. In addition, for gels with NPs in the interstitial space, a noticeable increase in

  17. Thermosensitive aqueous gels with tunable sol-gel transition temperatures from thermo- and pH-responsive hydrophilic ABA triblock copolymer.

    PubMed

    O'Lenick, Thomas G; Jiang, Xueguang; Zhao, Bin

    2010-06-01

    This article reports on the synthesis of a well-defined hydrophilic ABA triblock copolymer composed of a poly(ethylene oxide) (PEO) middle block and thermo- and pH-sensitive outer blocks and the study of sol-gel transitions of its aqueous solutions at various pH values. The doubly responsive linear triblock copolymer, poly(methoxydi(ethylene glycol) methacrylate-co-methacrylic acid)-b-PEO-b-poly(methoxydi(ethylene glycol) methacrylate-co-methacrylic acid) (P(DEGMMA-co-MAA)-b-PEO-b-P(DEGMMA-co-MAA)), was prepared by atom transfer radical polymerization of a mixture of DEGMMA and tert-butyl methacrylate with a molar ratio of 100: 5 from a difunctional PEO macroinitiator and subsequent removal of tert-butyl groups using trifluoroacetic acid. Dynamic light scattering studies showed that the critical micellization temperature (CMT) of this ABA triblock copolymer in a 0.2 wt % aqueous solution was dependent on the solution pH and can be varied in a large temperature range (>20 degrees C). To study the sol-gel transitions, a 12.0 wt % aqueous solution of the triblock copolymer with a pH of 4.89 was made; its pH value can be readily changed and well controlled by the injection of either a 1.0 M HCl or a 1.0 M KOH solution. From rheological measurements, the sol-gel transition temperature (T(sol-gel)) versus pH curve was found to closely trace the CMT versus pH curve, though there was a shift. By cycling the solution pH between 3.2 and 5.4, we showed that the T(sol-gel) at a specific pH was reproducible. Moreover, multiple sol-gel-sol transitions were realized by judiciously controlling the temperature and pH simultaneously, demonstrating the possibility of achieving on-demand sol-gel transitions by using two external stimuli. In addition, the effect of polymer concentration on T(sol-gel) at pH = 4.0 was investigated. The sol-gel transition temperature increased with the decrease of polymer concentration and the critical gelation concentration was found to be between 4 and

  18. An asymmetric A-B-A' metallo-supramolecular triblock copolymer linked by Ni(2+)-bis-terpyridine complexes at one junction.

    PubMed

    Li, Haixia; Wei, Wei; Xiong, Huiming

    2016-02-01

    A metallo-supramolecular triblock copolymer polystyrene-b-polyisoprene-[Ni(2+)]-polystyrene (SI-[Ni(2+)]-S') has been efficiently prepared using a one-pot, two-step procedure, where the blocks are held by bis-terpyridine complexes at the junction of SI-S'. This specific metallo-supramolecular chemistry is demonstrated to be a robust approach to potentially broaden the diversity of block copolymers. The location of the metal-ligand complexes has a profound influence on the phase separation of the triblock copolymer in the bulk, which results in a distinctive phase segregation between the end blocks and leads to an unexpected asymmetry of the triblock copolymer. The metal-ligand complexes are found to be preferentially located on the adjacent spherical domain and form a core-shell structure. The resulting multiphase material exhibits distinct elastomeric properties with significant toughness and creep recovery behavior. This type of triblock copolymer is anticipated to be a novel class of hybrid thermo-plastic elastomeric material with wide tunability and functionality. PMID:26660271

  19. Influence of magnetic nanoparticle size on the particle dispersion and phase separation in an ABA triblock copolymer.

    PubMed

    Wu, Jinrong; Li, Hui; Wu, Siduo; Huang, Guangsu; Xing, Wang; Tang, Maozhu; Fu, Qiang

    2014-02-27

    Oleic acid modified iron oxide nanoparticles (IONs) with different sizes were synthesized and mixed with styrene-butadiene-styrene block copolymer (SBS) with a lamellar structure. The octadecene segments on the oleic acid molecules have chemical affinity with the polybutadiene (PB) blocks, which makes IONs tend to be selectively confined in the microphase-separated PB domains. However, the dispersion state strongly depends on the ratio of the particle diameter (d) to the lamellar thickness (l) of the PB domains, which further changes the phase separation of SBS. When d/l ∼0.5, most of IONs are concentrated in the middle of the PB layers at low particle loading. Upon increasing the particle loading, part of IONs contact each other to form long strings due to their strong magnetic interactions. Away from the strings, IONs are either selectively dispersed in the middle and at the interfaces of the PB domains, or randomly distributed at some regions in which the phase separation of SBS is suppressed. The phase separation of SBS transforms from the lamellar structure to a cylinder structure when the IONs loading is higher than 16.7 wt %. As d is comparable to l, IONs aggregate to form clusters of 100 to 300 nm in size, but within the clusters IONs are still selectively dispersed in the PB domains instead of forming macroscopic phase separation. It is interpreted in terms of the relatively small conformational entropy of the middle blocks of SBS; thus, incorporation of nanoparticles does not lead to much loss of conformational entropy. Although incorporation of IONs with d/l ∼1 significantly increases the interfacial curvature and roughness, it has less influence on the phase separation structure of SBS due to the inhomogeneous dispersion. When d is larger than l, IONs are macroscopically separated from the SBS matrix to form clusters of hundreds of nanometers to several micrometers. More interestingly, the phase separation of SBS transforms from the lamellar

  20. Photoreversible gelation of a triblock copolymer in an ionic liquid.

    PubMed

    Ueki, Takeshi; Nakamura, Yutaro; Usui, Ryoji; Kitazawa, Yuzo; So, Soonyong; Lodge, Timothy P; Watanabe, Masayoshi

    2015-03-01

    The reversible micellization and sol-gel transition of block copolymer solutions in an ionic liquid (IL) triggered by a photostimulus is described. The ABA triblock copolymer employed, denoted P(AzoMA-r-NIPAm)-b-PEO-b-P(AzoMA-r-NIPAm)), has a B block composed of an IL-soluble poly(ethylene oxide) (PEO). The A block consists of a random copolymer including thermosensitive N-isopropylacrylamide (NIPAm) units and a methacrylate with an azobenzene chromophore in the side chain (AzoMA). A phototriggered reversible unimer-to-micelle transition of a dilute ABA triblock copolymer (1 wt%) was observed in an IL, 1-butyl-3-methylimidazolium hexafluorophosphate ([C4mim]PF6), at an intermediate "bistable" temperature (50 °C). The system underwent a reversible sol-gel transition cycle at the bistable temperature (53 °C), with reversible association/fragmentation of the polymer network resulting from the phototriggered self-assembly of the ABA triblock copolymer (20 wt%) in [C4 mim]PF6. PMID:25613353

  1. Stimuli-Responsive Peptide-based Triblock and Star Copolymers

    NASA Astrophysics Data System (ADS)

    Ray, Jacob; Naik, Sandeep; Johnson, Ashley; Ly, Jack; Savin, Daniel

    2011-03-01

    Stimuli-responsive copolymers demonstrate diverse aggregation behavior in aqueous solution. In general, the molecular architecture and the balance of hydrophilic and hydrophobic volumes influence morphology. This study involves polypeptide-based ABA linear triblock and AB2 star copolymer (which structurally resemble phospholipids) amphiphiles. Model systems for this study are poly(L-lysine)-b-poly(propylene oxide)-b-poly(L-lysine) (KPK) triblocks and poly(L-glutamate) (PE) based star copolymers. Extensive studies with KPK systems have resulted in morphological transitions by modifying pH, and we hypothesize that a change in individual chain conformation is the driving force for these transitions. Preliminary results for PE-based star copolymers with various hydrophobic moieties suggest polymersome (vesicle) formation. Light scattering (dynamic and static) and TEM were used to determine aggregate size and morphology as a function of pH; furthermore, circular dichroism (CD) spectroscopy was used to measure helix-to-coil transitions of the polypeptide blocks.

  2. Rheology and Relaxation Timescales of ABA Triblock Polymer Gels

    NASA Astrophysics Data System (ADS)

    Peters, Andrew; Lodge, Timothy

    When dissolved in a midblock selective solvent, ABA polymers form gels composed of aggregated end block micelles bridged by the midblocks. While much effort has been devoted to the study of the structure of these systems, the dynamics of these systems has received less attention. We examine the underlying mechanism of shear relaxation of ABA triblock polymer gels, especially as a function of chain length, composition, and concentration. Recent work using time-resolved small-angle neutron scattering of polystyrene (PS)-block-poly(ethylene-alt-propylene) (PEP) in squalane has elucidated many aspects of the dynamics of diblock chain exchange. By using rheology to study bulk relaxation phenomena of the triblock equivalent, PS-PEP-PS, we apply the knowledge gained from the chain exchange studies to bridge the gap between the molecular and macroscopic relaxation phenomena in PS-PEP-PS triblock gels.

  3. Controlling Domain Orientations in Thin Films of AB and ABA Block Copolymers

    SciTech Connect

    Vu, Thai; Mahadevapuram, Nikhila; Perera, Ginusha M.; Stein, Gila E.

    2012-03-15

    Domain orientations in thin films of lamellar copolymers are evaluated as a function of copolymer architecture, film thickness, and processing conditions. Two copolymer architectures are considered: An AB diblock of poly(styrene-b-methyl methacrylate) and an ABA triblock of poly(methyl methacrylate-b-styrene-b-methyl methacrylate). All films are cast on substrates that are energetically neutral with respect to the copolymer constituents. Film structures are evaluated with optical microscopy, atomic force microscopy, and grazing-incidence small-angle X-ray scattering. For AB diblock copolymers, the domain orientations are very sensitive to film thickness, annealing temperature, and imperfections in the 'neutral' substrate coating: Diblock domains are oriented perpendicular to the substrate when annealing temperature is elevated ({>=} 220 C) and defects in the substrate coating are minimized; otherwise, parallel or mixed parallel/perpendicular domain orientations are detected for most film thicknesses. For ABA triblock copolymers, the perpendicular domain orientation is stable for all the film thicknesses and processing conditions that were studied. The orientations of diblock and triblock copolymers are consistent with recent works that consider architectural effects when calculating the copolymer surface tension (Macromolecules 2006, 39, 9346 and Macromolecules 2010, 43, 1671). Significantly, the data demonstrate that triblocks are easier to process for applications in nanopatterning - in particular, when high-aspect-ratio nanostructures are required. However, both diblock and triblock films contain a high density of 'tilted' or bent domains, and these kinetically trapped defects should be minimized for most patterning applications.

  4. Phase behavior of model ABC triblock copolymers

    NASA Astrophysics Data System (ADS)

    Chatterjee, Joon

    The phase behavior of poly(isoprene-b-styrene- b-ethylene oxide) (ISO), a model ABC triblock copolymer has been studied. This class of materials exhibit self-assembly, forming a large array of ordered morphologies at length scales of 5-100 nm. The formation of stable three-dimensionally continuous network morphologies is of special interest in this study. Since these nanostructures considerably impact the material properties, fundamental knowledge for designing ABC systems have high technological importance for realizing applications in the areas of nanofabrication, nanoporous media, separation membranes, drug delivery and high surface area catalysts. A comprehensive framework was developed to describe the phase behavior of the ISO triblock copolymers at weak to intermediate segregation strengths spanning a wide range of composition. Phases were characterized through a combination of characterization techniques, including small angle x-ray scattering, dynamic mechanical spectroscopy, transmission electron microscopy, and birefringence measurements. Combined with previous investigations on ISO, six different stable ordered state symmetries have been identified: lamellae (LAM), Fddd orthorhombic network (O70), double gyroid (Q230), alternating gyroid (Q214), hexagonal (HEX), and body-centered cubic (BCC). The phase map was found to be somewhat asymmetric around the fI = fO isopleth. This work provides a guide for theoretical studies and gives insight into the intricate effects of various parameters on the self-assembly of ABC triblock copolymers. Experimental SAXS data evaluated with a simple scattering intensity model show that local mixing varies continuously across the phase map between states of two- and three-domain segregation. Strategies of blending homopolymers with ISO triblock copolymer were employed for studying the swelling properties of a lamellar state. Results demonstrate that lamellar domains swell or shrink depending upon the type of homopolymer that

  5. Chain exchange in triblock copolymer micelles

    NASA Astrophysics Data System (ADS)

    Lu, Jie; Lodge, Timothy; Bates, Frank

    2015-03-01

    Block polymer micelles offer a host of technological applications including drug delivery, viscosity modification, toughening of plastics, and colloidal stabilization. Molecular exchange between micelles directly influences the stability, structure and access to an equilibrium state in such systems and this property recently has been shown to be extraordinarily sensitive to the core block molecular weight in diblock copolymers. The dependence of micelle chain exchange dynamics on molecular architecture has not been reported. The present work conclusively addresses this issue using time-resolved small-angle neutron scattering (TR-SANS) applied to complimentary S-EP-S and EP-S-EP triblock copolymers dissolved in squalane, a selective solvent for the EP blocks, where S and EP refer to poly(styrene) and poly(ethylenepropylene), respectively. Following the overall SANS intensity as a function of time from judiciously deuterium labelled polymer and solvent mixtures directly probes the rate of molecular exchange. Remarkably, the two triblocks display exchange rates that differ by approximately ten orders of magnitude, even though the solvophobic S blocks are of comparable size. This discovery is considered in the context of a model that successfully explains S-EP diblock exchange dynamics.

  6. Structural development and mechanical response of thermoreversible triblock copolymer gels and gel/nanotube composites

    NASA Astrophysics Data System (ADS)

    Schoch, Andrew B.

    Intensive research on block copolymers for their unique phase behavior and natural application as surfactants has gone on for a number of years now. The introduction of these materials into selective solvents has expanded the range of their application to diverse areas, from biological scaffolds and drug delivery to ceramics processing and nanocomposites. This dissertation focuses on a system of AB diblock copolymers and ABA triblock copolymers in the same B selective solvent. In fact, the solvent is only selective for the B blocks at low temperatures. At high temperatures both blocks are readily soluble and the polymers are quite mobile in solution, though upon cooling the copolymers form spherical micelles with the A blocks in the micelle core and B blocks in the micelle corona. The main difference between the diblock and triblock copolymer solutions is that in the triblock copolymer solutions the B midblocks have the ability to form bridges between micelles, ultimately forming a connected network of micelles. The formation of this connected network or gel occurs very quickly over a narrow temperature range and is reversible. It transforms the solution at elevated temperatures from a concentrated polymer solution that exhibits very little elasticity to a soft gel which is mostly elastic in its mechanical response. The fast transition, low elasticity at elevated temperatures, and surfactant nature of the block copolymers all make this a model system for the study of carbon nanotubes as fillers in polymers. Carbon nanotubes have been shown to exhibit unique mechanical, electrical, thermal, and optical properties which make them a potentially interesting filler material in polymer composites. The mechanical properties of both these nanocomposites and the nascent copolymer solutions have been studied extensively in this text. This research was motivated by a desire to understand structural development on a fundamental level for both the networks of block copolymers

  7. Alignment of Fatty Acid-Derived Triblock Copolymers under Large Amplitude Oscillatory Shear

    NASA Astrophysics Data System (ADS)

    Ding, Wenyue; Wang, Shu; Kesava, Sameer; Gomez, Enrique; Robertson, Megan

    Linear ABA triblock copolymers find widespread utilization as thermoplastic elastomers (TPEs): materials which exhibit elastomeric behavior at room temperature and can be readily processed at elevated temperatures. Traditional TPEs are derived from fossil fuels; however, the finite availability of petroleum and the environmental impact of petroleum processing has led to an increased interest in developing alternative sources for polymers. Vegetable oils and their fatty acids are promising replacements for petroleum sources due to their abundance, low cost, lack of toxicity, biodegradability and ease of functionalization that provides convenient routes to polymerization. In this study, triblock copolymer TPEs were synthesized containing lauryl and stearyl acrylate, derived from fatty acids found in vegetable oils. Small-angle X-ray scattering experiments revealed highly aligned triblock copolymer morphologies after the application of large amplitude oscillatory shear. The temperature and frequency dependence of the degree of alignment was investigated. In contrast to prior studies on shear-aligned morphologies in bulk and thin film block copolymers, hexagonal close packed and face centered cubic spherical structures were observed.

  8. Research Update: Triblock copolymers as templates to synthesize inorganic nanoporous materials

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

    This review focuses on the application of triblock copolymers as designed templates to synthesize nanoporous materials with various compositions. Asymmetric triblock copolymers have several advantages compared with symmetric triblock copolymers and diblock copolymers, because the presence of three distinct domains can provide more functional features to direct the resultant nanoporous materials. Here we clearly describe significant contributions of asymmetric triblock copolymers, especially polystyrene-block-poly(2-vinylpyridine)-block-poly(ethylene oxide) (abbreviated as PS-b-P2VP-b-PEO).

  9. Deformation studies of near single-crystal triblock copolymers

    SciTech Connect

    Honeker, C.; Villar, M.A.; Thomas, E.L.

    1993-12-31

    The mechanical behavior of block copolymers is being studied in order to determine the evolution of the microphase-separation morphologies with deformation. To facilitate analysis a novel processing technique termed {open_quotes}roll-casting{close_quotes} is used to orient the copolymers. Large, near single-crystal macroscopically oriented films are produced by applying a shear field on a homogeneous solution and allowing the solvent to evaporate until the copolymer has microphase separated. Deformation behavior is studied with in situ small angle x-ray diffraction and TEM studies of films deformed up to 700% extension. Initial studies on poly(styrene-butadiene-styrene) triblock copolymers with a cylindrical morphology indicate a break-up of the morphology at low deformations and a development of a characteristic 4 point pattern at high deformations. Hysteresis is observed in deformation directions of 0 and 90 degrees.

  10. Stimuli-responsive polypeptide-based triblock copolymers

    NASA Astrophysics Data System (ADS)

    Ray, Jacob; Naik, Sandeep; Savin, Daniel

    2010-03-01

    Stimuli-responsive copolymers demonstrate diverse aggregation behavior in aqueous solution, where the molecular architecture and hydrophilic/hydrophobic content influences morphology. The solution morphology of poly(lysine)-b-poly(propylene oxide)-b-poly(lysine) (KPK) triblock copolymers with high lysine content (> 75 wt.%) will be compared with complementary KP diblock copolymers in the same phase range. Light scattering and TEM were used to determine aggregate size and morphology as a function of pH and temperature; furthermore, circular dichroism was used to measure helix-to-coil transitions of the K blocks. PK diblocks in this composition range yield spherical micelles over the entire pH range whereas KPK systems appear to exhibit morphological transitions with changing pH.

  11. Nucleobase-functionalized ABC triblock copolymers: self-assembly of supramolecular architectures.

    PubMed

    Zhang, Keren; Fahs, Gregory B; Aiba, Motohiro; Moore, Robert B; Long, Timothy E

    2014-08-21

    RAFT polymerization afforded acrylic ABC triblock copolymers with self-complementary nucleobase-functionalized external blocks and a low-Tg soft central block. ABC triblock copolymers self-assembled into well-defined lamellar microphase-separated morphologies for potential applications as thermoplastic elastomers. Complementary hydrogen bonding within the hard phase facilitated self-assembly and enhanced mechanical performance. PMID:24984613

  12. Impact of morphological orientation in determining mechanical properties in triblock copolymer systems

    SciTech Connect

    Honeker, C.C.; Thomas, E.L.

    1996-08-01

    In contrast to other types of segmented multiblock thermoplastic elastomers, simple ABA block copolymers represent a class of well-defined nanostructured materials. Due to the inherent block lengths built in during the polymerization, the microdomain structure of block copolymers exhibits a size scale of typically 10-100 nm. The ability to control the individual chemistry of each block as well as the size and the shape of the domains in a block copolymer affords enormous advantages to tailor physical properties. By globally orienting the microdomains, a well-defined initial morphological state aids greatly in the interpretation and modeling of mechanical deformation and allows for exploitation of the inherent anisotropy of the cylindrical and lamellar structures. Several types of orientation techniques are reviewed. Experiments investigating structure-mechanical properties in styrene-diene triblock copolymers with spherical, cylindrical, and lamellar morphologies are discussed, with emphasis on the clarifying role of global morphological orientation in data interpretation. Composite theory which treats each microphase as a continuum describes small strain behavior of cylinders and lamellae quite well. Molecular variables such as the number of effective bridge vs loop conformations in the rubber midblock become more important at large strains. With controlled chemistry and morphology structure in influencing the deformation process is expected. 145 refs., 11 figs., 2 tabs.

  13. Ion gels by self-assembly of a triblock copolymer in an ionic liquid.

    PubMed

    He, Yiyong; Boswell, Paul G; Bühlmann, Philippe; Lodge, Timothy P

    2007-05-10

    We report a new way of developing ion gels through the self-assembly of a triblock copolymer in a room-temperature ionic liquid. Transparent ion gels were achieved by gelation of a poly(styrene-block-ethylene oxide-block-styrene) (SOS) triblock copolymer in 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF6]) with as low as 5 wt % SOS triblock copolymer. The gelation behavior, ionic conductivity, rheological properties, and microstructure of the ion gels were investigated. The ionic conductivity of the ion gels is only modestly affected by the triblock copolymer network. Its temperature dependence nearly tracks that of the bulk ionic liquid viscosity. The ion gels are thermally stable up to at least 100 degrees C and possess significant mechanical strength. The results presented here suggest that triblock copolymer gelation is a promising way to develop highly conductive ion gels and provides many advantages in terms of variety and processing. PMID:17474692

  14. Multifunctional triblock copolymers for intracellular messenger RNA delivery

    PubMed Central

    Cheng, C.; Convertine, A.J.; Stayton, P.S.; Bryers, J.D.

    2012-01-01

    Messenger RNA (mRNA) is a promising alternative to plasmid DNA (pDNA) for gene vaccination applications, but safe and effective delivery systems are rare. Reversible addition-fragmentation chain transfer (RAFT) polymerization was employed to synthesize a series of triblock copolymers designed to enhance the intracellular delivery of mRNA. These materials are composed of a cationic dimethylaminoethyl methacrylate (DMAEMA) segment to mediate mRNA condensation, a hydrophilic poly(ethylene glycol) methyl ether methacrylate (PEGMA) segment to enhance stability and biocompatibility, and a pH-responsive endosomolytic copolymer of diethylaminoethyl methacrylate (DEAEMA) and butyl methacrylate (BMA) designed to facilitate cytosolic entry. The blocking order and PEGMA segment length were systematically varied to investigate the effect of different polymer architectures on mRNA delivery efficacy. These polymers were monodisperse, exhibited pH-dependent hemolytic activity, and condensed mRNA into 86–216 nm particles. mRNA polyplexes formed from polymers with the PEGMA segment in the center of the polymer chain displayed the greatest stability to heparin displacement and were associated with the highest transfection efficiencies in two immune cell lines, RAW 264.7 macrophages (77%) and DC2.4 dendritic cells (50%). Transfected DC2.4 cells were shown to be capable of subsequently activating antigen-specific T cells, demonstrating the potential of these multifunctional triblock copolymers for mRNA-based vaccination strategies. PMID:22784603

  15. Enzyme cleavable nanoparticles from peptide based triblock copolymers

    NASA Astrophysics Data System (ADS)

    Fuchs, Adrian V.; Kotman, Niklas; Andrieu, Julien; Mailänder, Volker; Weiss, Clemens K.; Landfester, Katharina

    2013-05-01

    A solid-phase synthesis based approach towards protease cleavable polystyrene-peptide-polystyrene triblock copolymers and their formulation to nanoparticulate systems is presented. These nanoparticles are suitable for the optical detection of an enzyme and have the potential for application as a drug delivery system. Two different peptide sequences, one cleaved by trypsin (GFF), the other by hepsin (RQLRVVGG), a protease overexpressed in early stages of prostate cancer, are used as the central part of the triblock. For optical detection a fluorophore-quencher pair is introduced around the cleavage sequence. The solid phase synthesis is conduced such that two identical sequences are synthesized from one branching point. Eventually, carboxy-terminated polystyrene is introduced into the peptide synthesizer and coupled to the amino-termini of the branched sequence. Upon cleavage, a fragment is released from the triblock copolymer, which has the potential for use in drug delivery applications. Conducting the whole synthesis on a solid phase in the peptide synthesizer avoids solubility issues and post-synthetic purification steps. Due to the hydrophobic PS-chains, the copolymer can easily be formulated to form nanoparticles using a nanoprecipitation process. Incubation of the nanoparticles with the respective enzymes leads to a significant increase of the fluorescence from the incorporated fluorophore, thereby indicating cleavage of the peptide sequence and decomposition of the particles.A solid-phase synthesis based approach towards protease cleavable polystyrene-peptide-polystyrene triblock copolymers and their formulation to nanoparticulate systems is presented. These nanoparticles are suitable for the optical detection of an enzyme and have the potential for application as a drug delivery system. Two different peptide sequences, one cleaved by trypsin (GFF), the other by hepsin (RQLRVVGG), a protease overexpressed in early stages of prostate cancer, are used as the

  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. Structure-Property Relationships of Poly(lactide)-based Triblock and Multiblock Copolymers

    NASA Astrophysics Data System (ADS)

    Panthani, Tessie Rose

    Replacing petroleum-based plastics with alternatives that are degradable and synthesized from annually renewable feedstocks is a critical goal for the polymer industry. Achieving this goal requires the development of sustainable analogs to commodity plastics which have equivalent or superior properties (e.g. mechanical, thermal, optical etc.) compared to their petroleum-based counterparts. This work focuses on improving and modulating the properties of a specific sustainable polymer, poly(lactide) (PLA), by incorporating it into triblock and multiblock copolymer architectures. The multiblock copolymers in this work are synthesized directly from dihydroxy-terminated triblock copolymers by a simple step-growth approach: the triblock copolymer serves as a macromonomer and addition of stoichiometric quantities of either an acid chloride or diisocyanate results in a multiblock copolymer. This work shows that over wide range of compositions, PLA-based multiblock copolymers have superior mechanical properties compared to triblock copolymers with equivalent chemical compositions and morphologies. The connectivity of the blocks within the multiblock copolymers has other interesting consequences on properties. For example, when crystallizable poly(L-lactide)-based triblock and multiblock copolymers are investigated, it is found that the multiblock copolymers have much slower crystallization kinetics. Additionally, the total number of blocks connected together is found to effect the linear viscoelastic properties as well as the alignment of lamellar domains under uniaxial extension. Finally, the synthesis and characterization of pressure-sensitive adhesives based upon renewable PLA-containing triblock copolymers and a renewable tackifier is detailed. Together, the results give insight into the effect of chain architecture, composition, and morphology on the mechanical behavior, thermal properties, and rheological properties of PLA-based materials.

  18. Additives Induced Structural Transformation of ABC Triblock Copolymer Particles.

    PubMed

    Xu, Jiangping; Yang, Yi; Wang, Ke; Li, Jingyi; Zhou, Huamin; Xie, Xiaolin; Zhu, Jintao

    2015-10-13

    Here we report the structural control of polystyrene-b-polyisoprene-b-poly(2-vinylpyridine) (PS-b-PI-b-P2VP) asymmetric ABC triblock copolymer particles under 3D confinement by tuning the interactions among blocks. The additives, including 3-n-pentadecylphenol, homopolystyrene, and solvents, which can modulate the interactions among polymer blocks, play significant roles in the particle morphology. Moreover, the structured particles can be disassembled into isolated micellar aggregates with novel morphologies or mesoporous particles with tunable pore shape. Interestingly, the formed pupa-like PS-b-PI-b-P2VP particles display interesting dynamic stretch-retraction behavior when the solvent property is changed after partial cross-linking of the P2VP block. We further prove that such dynamic behavior is closely related to the density of cross-linking. The strategies presented here are believed to be promising routes to rationally design and fabricate block copolymer particles with desirable shape and internal structure. PMID:26388457

  19. Phase behavior and local dynamics of concentrated triblock copolymer micelles

    NASA Astrophysics Data System (ADS)

    Yardimci, H.; Chung, B.; Harden, J. L.; Leheny, R. L.

    2005-12-01

    We report a neutron-scattering study to characterize the ordering and local dynamics of spherical micelles formed by the triblock copolymer polyethylene oxide (PEO) - polypropylene oxide (PPO) - polyethylene oxide (Pluronic) in aqueous solution. The study focuses on two Pluronic species, F68 and F108, that have the same weight fraction of PEO but that differ in chain length by approximately a factor of 2. At sufficiently high concentration, both species undergo a sequence of phase changes with increasing temperature from dissolved chains to micelles with liquidlike order to a cubic crystal phase and finally back to a micelle liquid phase. A comparison of the phase diagrams constructed from small-angle neutron scattering indicates that crystallization is suppressed for shorter chain micelles due to fluctuation effects. The intermediate scattering function I(Q,t)/I(Q,0) determined by neutron spin echo displays a line shape with two distinct relaxations. Comparisons between I(Q,t)/I(Q,0) for fully hydrogenated F68 chains in D2O and for F68 with deuterated PEO blocks reveal that the slower relaxation corresponds to Rouse modes of the PPO segments in the concentrated micelle cores. The faster relaxation is identified with longitudinal diffusive modes in the PEO corona characteristic of a polymer brush.

  20. Polymer-Drug Interactions in Tyrosine-Derived Triblock Copolymer Nanospheres: a Computational Modeling Approach

    PubMed Central

    Costache, Aurora D.; Sheihet, Larisa; Zaveri, Krishna; Knight, Doyle D.; Kohn, Joachim

    2009-01-01

    A combination of Molecular Dynamics (MD) simulations and docking calculations was employed to model and predict polymer-drug interactions in self-assembled nanoparticles consisting of ABA-type triblock copolymers, where A-blocks are poly(ethylene glycol) units and B-blocks are low molecular weight tyrosine-derived polyarylates. This new computational approach was tested on three representative model compounds: nutraceutical curcumin, anti-cancer drug paclitaxel and pre-hormone vitamin D3. Based on this methodology, the calculated binding energies of polymer-drug complexes can be correlated with maximum drug loading determined experimentally. Furthermore, the modeling results provide an enhanced understanding of polymer-drug interactions, revealing subtle structural features that can significantly affect the effectiveness of drug loading (as demonstrated for a fourth tested compound, anticancer drug camptothecin). The present study suggests that computational calculations of polymer-drug pairs hold the potential of becoming a powerful prescreening tool in the process of discovery, development and optimization of new drug delivery systems, reducing both the time and the cost of the process. PMID:19650665

  1. Dissipative particle dynamics of triblock copolymer melts: A midblock conformational study at moderate segregation

    NASA Astrophysics Data System (ADS)

    Tallury, Syamal S.; Spontak, Richard J.; Pasquinelli, Melissa A.

    2014-12-01

    As thermoplastic elastomers, triblock copolymers constitute an immensely important class of shape-memory soft materials due to their unique ability to form molecular networks stabilized by physical, rather than chemical, cross-links. The extent to which such networks develop in triblock and higher-order multiblock copolymers is sensitive to the formation of midblock bridges, which serve to connect neighboring microdomains. In addition to bridges, copolymer molecules can likewise form loops and dangling ends upon microphase separation or they can remain unsegregated. While prior theoretical and simulation studies have elucidated the midblock bridging fraction in triblock copolymer melts, most have only considered strongly segregated systems wherein dangling ends and unsegregated chains become relatively insignificant. In this study, simulations based on dissipative particle dynamics are performed to examine the self-assembly and networkability of moderately segregated triblock copolymers. Utilizing a density-based cluster-recognition algorithm, we demonstrate how the simulations can be analyzed to extract information about microdomain formation and permit explicit quantitation of the midblock bridging, looping, dangling, and unsegregated fractions for linear triblock copolymers varying in chain length, molecular composition, and segregation level. We show that midblock conformations can be sensitive to variations in chain length, molecular composition, and bead repulsion, and that a systematic investigation can be used to identify the onset of strong segregation where the presence of dangling and unsegregated fractions are minimal. In addition, because this clustering approach is robust, it can be used with any particle-based simulation method to quantify network formation of different morphologies for a wide range of triblock and higher-order multiblock copolymer systems.

  2. Dissipative particle dynamics of triblock copolymer melts: a midblock conformational study at moderate segregation.

    PubMed

    Tallury, Syamal S; Spontak, Richard J; Pasquinelli, Melissa A

    2014-12-28

    As thermoplastic elastomers, triblock copolymers constitute an immensely important class of shape-memory soft materials due to their unique ability to form molecular networks stabilized by physical, rather than chemical, cross-links. The extent to which such networks develop in triblock and higher-order multiblock copolymers is sensitive to the formation of midblock bridges, which serve to connect neighboring microdomains. In addition to bridges, copolymer molecules can likewise form loops and dangling ends upon microphase separation or they can remain unsegregated. While prior theoretical and simulation studies have elucidated the midblock bridging fraction in triblock copolymer melts, most have only considered strongly segregated systems wherein dangling ends and unsegregated chains become relatively insignificant. In this study, simulations based on dissipative particle dynamics are performed to examine the self-assembly and networkability of moderately segregated triblock copolymers. Utilizing a density-based cluster-recognition algorithm, we demonstrate how the simulations can be analyzed to extract information about microdomain formation and permit explicit quantitation of the midblock bridging, looping, dangling, and unsegregated fractions for linear triblock copolymers varying in chain length, molecular composition, and segregation level. We show that midblock conformations can be sensitive to variations in chain length, molecular composition, and bead repulsion, and that a systematic investigation can be used to identify the onset of strong segregation where the presence of dangling and unsegregated fractions are minimal. In addition, because this clustering approach is robust, it can be used with any particle-based simulation method to quantify network formation of different morphologies for a wide range of triblock and higher-order multiblock copolymer systems. PMID:25554184

  3. Simulation study on the structure of rod-coil-rod triblock copolymer and nanoparticle mixture within slit.

    PubMed

    Huang, Jian-Hua; Fan, Zhong-Xiang; Luo, Meng-Bo

    2013-11-28

    Self-assembly structures of rod-coil-rod ABA triblock copolymer and nanoparticle mixture within a slit are simulated by dissipative particle dynamics method. Results show that the structures are dependent on the rigidity of the rod block kθ, the interaction between the rod block and slit a(wA), the fraction of rod block f(A), and the slit height H. With an increase in kθ, we observe a transition from parallel lamellae to hexagonal cylinders. While with the increase in a(wA), the parallel lamellae at small kθ and hexagonal cylinders at large kθ change to perpendicular lamellae at large a(wA) close to a(As). At last, we present a phase diagram of structure with respect to f(A) and H at large kθ. PMID:24289376

  4. Use of amphiphilic triblock copolymers for enhancing removal efficiency of organic pollutant from contaminated media

    NASA Astrophysics Data System (ADS)

    Lee, Jun Hyup; Lee, Byungsun; Son, Intae; Kim, Jae Hong; Kim, Chunho; Yoo, Ji Yong; Wu, Jong-Pyo; Kim, Younguk

    2015-11-01

    We have studied amphiphilic triblock copolymers poly(ethylene glycol)- b-poly(propylene glycol)- b-poly(ethylene glycol) (PEG- b-PPG- b-PEG) and poly(propylene glycol)- b-poly(ethylene glycol)- b-poly(propylene glycol) (PPG- b-PEG- b-PPG) as possible substitutes for sodium dodecyl sulfate as anionic surfactants for the removal of hydrophobic contaminants. The triblock copolymers were compared with sodium dodecyl sulfate in terms of their abilities to remove toluene as hydrophobic contaminant in fuel, and the effects of polymer structure, PEG content, and concentration were studied. The PEG- b-PPG- b-PEG copolymer containing two hydrophilic PEG blocks was more effective for the removal of hydrophobic contaminant at extremely high concentration. We also measured the removal capabilities of the triblock copolymers having various PEG contents and confirmed that removal capability was greatest at 10% PEG content regardless of polymer structure. As with sodium dodecyl sulfate, the removal efficiency of a copolymer has a positive correlation with its concentration. Finally, we proposed the amphiphilic triblock copolymer of PPG- b-PEG- b-PPG bearing 10% PEG content that proved to be the most effective substitute for sodium dodecyl sulfate.

  5. Development of a new tri-block copolymer with a functional end and its feasibility for treatment of metastatic breast cancer.

    PubMed

    Song, Ho-Taek; Hoang, Ngoc Ha; Yun, Jeong Min; Park, Young Jin; Song, Eun Hye; Lee, Eun Seong; Youn, Yu Seok; Oh, Kyung Taek

    2016-08-01

    We have developed nanomedicine vehicle based on a biocompatible tri-block copolymer, poly(ethylene glycol)-block-poly(lactic acid)-block-poly(ethylene glycol) (PEG-PLA-PEG) by simple approach without toxic linker to escalate therapeutic efficacy of anticancer agent by enhanced targeting to metastasized breast cancers. The synthesized ABA type copolymer had a low polydispersity index and formed small, highly stable spherical micelles. Furthermore, a functional group at the end site of the copolymer can be decorated with imaging agents and targeting moieties. The doxorubicin loaded micelles (DLM) showed higher drug-loading capacity, faster drug release, and better cell toxicity compared to those using di-block copolymers. DLM efficiently delivered to the metastatic breast cancers in brain and bone and suppressed growing of metastasis. In demonstration of treating metastasized animal model, we present a tri-block copolymer as a potential nanomedicine vehicle to efficiently deliver anticancer drug and to effectively treat metastatic breast cancer. PMID:27070054

  6. A numerical study of the phase behaviors of drug particle/star triblock copolymer mixtures in dilute solutions for drug carrier application

    SciTech Connect

    Wang, Shanhui; Tong, Chaohui; Zhu, Yuejin

    2014-04-14

    The complex microstructures of drug particle/ABA star triblock copolymer in dilute solutions have been investigated by a theoretical approach which combines the self-consistent field theory and the hybrid particle-field theory. Simulation results reveal that, when the volume fraction of drug particles is smaller than the saturation concentration, the drug particle encapsulation efficiency is 100%, and micelle loading capacity increases with increasing particle volume fraction. When the volume fraction of drug particles is equal to the saturation concentration, the micelles attain the biggest size, and micelle loading capacity reaches a maximum value which is independent of the copolymer volume fraction. When the volume fraction of drug particles is more than the saturation concentration, drug particle encapsulation efficiency decreases with increasing volume fraction of drug particles. Furthermore, it is found that the saturation concentration scales linearly with the copolymer volume fraction. The above simulation results are in good agreement with experimental results.

  7. 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.

  8. A new polymer-based hydrogen getter. [Styrene-butadiene triblock copolymer

    SciTech Connect

    Gilliom, L.R.

    1987-01-01

    Styrene-butadiene triblock copolymer PS-PB-PS was hydrogenated in the bulk using the Crabtree catalyst (Ir(COD)(py)(tcyp))PF/sub 6/ (COD = 1,5-cyclooctadiene, py = pyridene, tcyp = tricyclohexylphosphine). Since this polymer/catalyst mixture reacts rapidly with hydrogen at ambient temperature and low hydrogen pressures, it should act as an effective hydrogen getter. 7 refs., 2 figs.

  9. 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.

  10. Study of Low Molecular Weight Impurities in Pluronic Triblock Copolymers using MALDI, Interaction Chromatography, and NMR

    NASA Astrophysics Data System (ADS)

    Helming, Z.; Zagorevski, D.; Ryu, C. Y.

    2014-03-01

    Poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) triblock copolymers are a group of commercial macromolecular amphiphilic surfactants that have been widely studied for their applications in polymer-based nanotechnology and drug-delivery. It has been well-established that the synthesis of commercial Pluronic triblocks results in low molecular weight ``impurities,'' which are generally disregarded in the applications and study of these polymers. These species have been shown to have significant effects on the rheological properties of the material, as well as altering the supramolecular ``micellar'' structures for which the polymers are most often used. We have isolated the impurities from the bulk Pluronic triblock using Interaction Chromatography (IC) techniques, and subjected them to analysis by H1 NMR and MALDI (Matrix-Assisted Laser Desorption Ionization) Mass Spectrometry to identify relative block composition and molecular weight information. We report significant evidence of at least two polymeric components: a low-molecular-weight homopolymer of poly(ethylene oxide) and a ``blocky'' copolymer of both poly(ethylene oxide) and poly(propylene oxide). This has significant implications, not only for the applied usage of Pluronic triblock copolymers, but for the general scientific acceptance of the impurities and their effects on Pluronic micelle and hydrogel formation.

  11. Therapeutic nanoreactors: combining chemistry and biology in a novel triblock copolymer drug delivery system.

    PubMed

    Ranquin, An; Versées, Wim; Meier, Wolfgang; Steyaert, Jan; Van Gelder, Patrick

    2005-11-01

    Triblock copolymeric nanoreactors are introduced as an alternative for liposomes as encapsulating carrier for prodrug activating enzymes. Inosine-adenosine-guanosine preferring nucleoside hydrolase of Trypanosoma vivax, a potential prodrug activating enzyme, was encapsulated in nanometer-sized vesicles constructed of poly(2-methyloxazoline)-block-poly(dimethylsiloxane)-block-(2-methyloxazoline) triblock copolymers. The nanoreactor is functionalized by incorporation of bacterial porins, OmpF or Tsx, in the reactor wall. Efficient cleavage of three natural substrates and one prodrug, 2-fluoroadenosine, by the nanoreactors was demonstrated. PMID:16277457

  12. Amphiphilic Surface Active Triblock Copolymers with Mixed Hydrophobic and Hydrophilic Side Chains for Tuned Marine Fouling-Release Properties

    SciTech Connect

    Park, D.; Weinman, C; Finlay, J; Fletcher, B; Paik, M; Sundaram, H; Dimitriou, M; Sohn, K; Callow, M; et al.

    2010-01-01

    Two series of amphiphilic triblock surface active block copolymers (SABCs) were prepared through chemical modification of two polystyrene-block-poly(ethylene-ran-butylene)-block-polyisoprene ABC triblock copolymer precursors. The methyl ether of poly(ethylene glycol) [M{sub n} {approx} 550 g/mol (PEG550)] and a semifluorinated alcohol (CF{sub 3}(CF{sub 2}){sub 9}(CH{sub 2}){sub 10}OH) [F10H10] were attached at different molar ratios to impart both hydrophobic and hydrophilic groups to the isoprene segment. Coatings on glass slides consisting of a thin layer of the amphiphilic SABC deposited on a thicker layer of an ABA polystyrene-block-poly(ethylene-ran-butylene)-block-polystyrene thermoplastic elastomer were prepared for biofouling assays with algae. Dynamic water contact angle analysis, X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure (NEXAFS) measurements were utilized to characterize the surfaces. Clear differences in surface structure were realized as the composition of attached side chains was varied. In biofouling assays, the settlement (attachment) of zoospores of the green alga Ulva was higher for surfaces incorporating a large proportion of the hydrophobic F10H10 side chains, while surfaces with a large proportion of the PEG550 side chains inhibited settlement. The trend in attachment strength of sporelings (young plants) of Ulva did not show such an obvious pattern. However, amphiphilic SABCs incorporating a mixture of PEG550 and F10H10 side chains performed the best. The number of cells of the diatom Navicula attached after exposure to flow decreased as the content of PEG550 to F10H10 side chains increased.

  13. Low-Friction Adsorbed Layers of a Triblock Copolymer Additive in Oil-Based Lubrication.

    PubMed

    Yamada, Shinji; Fujihara, Ami; Yusa, Shin-ichi; Tanabe, Tadao; Kurihara, Kazue

    2015-11-10

    The tribological properties of the dilute solution of an ABA triblock copolymer, poly(11-acrylamidoundecanoic acid)-block-poly(stearyl methacrylate)-block-poly(11-acrylamidoundecanoic acid (A5S992A5), in poly(α-olefin) (PAO) confined between mica surfaces were investigated using the surface forces apparatus (SFA). Friction force was measured as a function of applied load and sliding velocity, and the film thickness and contact geometry during sliding were analyzed using the fringes of equal chromatic order (FECO) in the SFA. The results were contrasted with those of confined PAO films; the effects of the addition of A5S992A5 on the tribological properties were discussed. The thickness of the A5S992A5/PAO system varied with time after surface preparation and with repetitive sliding motions. The thickness was within the range from 40 to 70 nm 1 day after preparation (the Day1 film), and was about 20 nm on the following day (the Day2 film). The thickness of the confined PAO film was thinner than 1.4 nm, indicating that the A5S992A5/PAO system formed thick adsorbed layers on mica surfaces. The friction coefficient was about 0.03 to 0.04 for the Day1 film and well below 0.01 for the Day2 film, which were 1 or 2 orders of magnitude lower than the values for the confined PAO films. The time dependent changes of the adsorbed layer thickness and friction properties should be caused by the relatively low solubility of A5S992A5 in PAO. The detailed analysis of the contact geometry and friction behaviors implies that the particularly low friction of the Day2 film originates from the following factors: (i) shrinkage of the A5S992A5 molecules (mainly the poly(stearyl methacrylate) blocks) that leads to a viscoelastic properties of the adsorbed layers; and (ii) the intervening PAO layer between the adsorbed polymer layers that constitutes a high-fluidity sliding interface. Our results suggest that the block copolymer having relatively low solubility in a lubricant base oil is

  14. Photophysics and charge transfer in donor-acceptor triblock copolymer photovoltaic materials

    NASA Astrophysics Data System (ADS)

    Schwarz, Kyra N.; Jones, David J.; Smith, Trevor A.; Ghiggino, Kenneth P.

    2014-10-01

    Efficient conversion of solar energy to electricity in low-cost organic photovoltaic (OPV) devices requires the complex interplay between multiple processes and components over various length and time scales. Optimizing device morphology to ensure efficient exciton diffusion and charge transport as well as ensuring efficient charge photogeneration is necessary to achieve optimum performance in new materials. The conjugated polymer electron donor PFM (poly(9,9-diocetyluorene-co-bis-N,N-(4-methylphenyl)-bis-N,N-phenyl-1,4-phenylenediamine)) and electron acceptor F8BT (poly[(9,9-di-n-octyluorenyl-2,7-diyl)-alt-(benzo[2,1,3]thiadiazol-4,8-diyl)), comprise the novel triblock copolymer PFM-F8BT-PFM. This copolymer is designed to phase separate on the 20-30 nm scale, a domain size ideal for maximizing exciton collection at the donor-acceptor interface. Using steady-state and ultrafast spectroscopic characterization including high repetition rate transient absorption spectroscopy, the dynamics of charge and energy transfer of the component polymers and the triblock co-polymer have been investigated. The results demonstrate that for the homopolymers solvent dependent exciton transport processes dominate, while in the triblock copolymer solutions transient spectroscopy provides evidence for interfacial charge separation.

  15. Self-assembly of ABC triblock copolymers under 3D soft confinement: a Monte Carlo study.

    PubMed

    Yan, Nan; Zhu, Yutian; Jiang, Wei

    2016-01-21

    Under three-dimensional (3D) soft confinement, block copolymers can self-assemble into unique nanostructures that cannot be fabricated in an un-confined space. Linear ABC triblock copolymers containing three chemically distinct polymer blocks possess relatively complex chain architecture, which can be a promising candidate for the 3D confined self-assembly. In the current study, the Monte Carlo technique was applied in a lattice model to study the self-assembly of ABC triblock copolymers under 3D soft confinement, which corresponds to the self-assembly of block copolymers confined in emulsion droplets. We demonstrated how to create various nanostructures by tuning the symmetry of ABC triblock copolymers, the incompatibilities between different block types, and solvent properties. Besides common pupa-like and bud-like nanostructures, our simulations predicted various unique self-assembled nanostructures, including a striped-pattern nanoparticle with intertwined A-cages and C-cages, a pyramid-like nanoparticle with four Janus B-C lamellae adhered onto its four surfaces, an ellipsoidal nanoparticle with a dumbbell-like A-core and two Janus B-C lamellae and a Janus B-C ring surrounding the A-core, a spherical nanoparticle with a A-core and a helical Janus B-C stripe around the A-core, a cubic nanoparticle with a cube-shape A-core and six Janus B-C lamellae adhered onto the surfaces of the A-cube, and a spherical nanoparticle with helical A, B and C structures, from the 3D confined self-assembly of ABC triblock copolymers. Moreover, the formation mechanisms of some typical nanostructures were also examined by the variations of the contact numbers with time and a series of snapshots at different Monte Carlo times. It is found that ABC triblock copolymers usually aggregate into a loose aggregate at first, and then the microphase separation between A, B and C blocks occurs, resulting in the formation of various nanostructures. PMID:26571300

  16. Diamino Telechelic Polybutadienes for Solventless Styrene-butadiene-styrene (SBS) Triblock Copolymer Formation.

    PubMed

    Ji, Shengxiang; Hoye, Thomas R; Macosko, Christopher W

    2008-11-10

    High molecular weight, high functionality diamino telechelic polybutadienes (TPBs) were synthesized by ring-opening metathesis polymerization (ROMP) of 1,5-cyclooctadiene (COD) in the presence of a chain transfer agent, 1,8-dicyano-4-octene, followed by lithium aluminum hydride reduction. Melt coupling of diamino TPB with anhydride-terminated polystyrene (PS-anh) resulted in the formation of styrene-butadiene-styrene (SBS) triblock copolymers; ca. 80% maximum conversion of PS-anh was achieved within 30 seconds. The results from SAXS, TEM, and rheological measurements of the coupling products confirmed the formation of SBS triblock copolymers having lamellar morphology. A fluororesent-labeled PS-anh was used to study the coupling kinetics by diluting the reactants by the addition of non-functional PS. PMID:19907636

  17. Antimicrobial Behavior of Semifluorinated-Quaternized Triblock Copolymers against Airborne and Marine Microorganisms

    SciTech Connect

    Park, D.; Finlay, J; Ward, R; Weinman, C; Krishnan, S; Park, M; Sohn, K; Callow, M; Callow, J; et. al.

    2010-01-01

    Semifluorinated-quaternized triblock copolymers (SQTCs) were synthesized by chemical modification of polystyrene-block-poly(ethylene-ran-butylene)-block-polyisoprene ABC triblock copolymers. Surface characterization of the polymers was performed by X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure (NEXAFS) analysis. The surface of the SQTC showed very high antibacterial activity against the airborne bacterium Staphylococcus aureus with >99 % inhibition of growth. In contrast in marine fouling assays, zoospores of the green alga Ulva settled on the SQTC, which can be attributed to the positively charged surface. The adhesion strength of sporelings (young plants) of Ulva and Navicula diatoms (a unicellular alga) was high. The SQTC did not show marked algicidal activity.

  18. Diamino Telechelic Polybutadienes for Solventless Styrene-butadiene-styrene (SBS) Triblock Copolymer Formation

    PubMed Central

    Ji, Shengxiang; Hoye, Thomas R.; Macosko, Christopher W.

    2008-01-01

    High molecular weight, high functionality diamino telechelic polybutadienes (TPBs) were synthesized by ring-opening metathesis polymerization (ROMP) of 1,5-cyclooctadiene (COD) in the presence of a chain transfer agent, 1,8-dicyano-4-octene, followed by lithium aluminum hydride reduction. Melt coupling of diamino TPB with anhydride-terminated polystyrene (PS-anh) resulted in the formation of styrene-butadiene-styrene (SBS) triblock copolymers; ca. 80% maximum conversion of PS-anh was achieved within 30 seconds. The results from SAXS, TEM, and rheological measurements of the coupling products confirmed the formation of SBS triblock copolymers having lamellar morphology. A fluororesent-labeled PS-anh was used to study the coupling kinetics by diluting the reactants by the addition of non-functional PS. PMID:19907636

  19. Local and segmental dynamics in homopolymer and triblock copolymers with one semicrystalline block.

    PubMed

    Laredo, E; Hernandez, M C; Bello, A; Grimau, M; Müller, A J; Balsamo, V

    2002-02-01

    Thermally stimulated depolarization currents, TSDC, experiments have been performed on a series of poly(styrene)-b-poly(butadiene)-b-poly(epsilon-caprolactone) triblock copolymers SBC with different proportions of the poly(epsilon-caprolactone) crystallizable block, PCL. The morphology of the segregated microphases varies with the PCL content and has been observed by transmission electron microscopy. The crystallinity of the PCL block is estimated by wide angle x-ray scattering, WAXS. The relaxation times distribution is extracted by a numerical decomposition of the TSDC spectra and it is shown that this distribution is not significantly changed on going from the homopolymer to the triblock copolymer with 16 wt % to 77 wt % of PCL in the original samples. Better segregation of the mesophase structure is reached when the samples are annealed at 413 K and important variations in the TSDC and WAXS spectra are observed as a result of the thermal treatment. For the S09B14C77 triblock copolymer the results obtained can be explained by postulating the existence of a rigid amorphous phase in the PCL block. Such rigid amorphous phase is located between the core-shell cylinders formed by the other blocks [with poly(styrene)(PS) as core and poly(butadiene)(PB) as shell] and is constrained by undulated lamellae of crystalline PCL material. In the case of S35B15C50 triblock copolymer, an important amount of diffuse PS-PCL interphase where the homopolymers are mixed must be present before annealing. The results for the material with the less abundant PCL block are explained as a result of the confinement in nanotubes of PCL surrounded by PB embedded in a vitreous PS matrix. Broadband dielectric experiments on these same materials confirm the results obtained by TSDC spectroscopy. PMID:11863555

  20. Spatial distribution of a midblock-associating homopolymer blended into a triblock copolymer

    SciTech Connect

    Lee, S.H.; Koberstein, J.T. . Dept. of Chemical Engineering); Quan, X. ); Gancarz, I. ); Wignall, G.D. ); Wilson, F.C. )

    1994-06-06

    The spatial distribution of midblock associating homopolymer confined within the lamellar microdomain structure of a triblock copolymer is probed with small angle neutron scattering experiments. The materials examined are poly(styrene-b-[saturated 1,2-butadiene]-b-styrene) triblock copolymers to which a low molecular weight poly(saturated 1,2-butadiene) homopolymer has been added. The butadienes are saturated with either hydrogen, deuterium, or mixtures of the two gases in order to vary their neutron scattering contrast with respect to polystyrene. The results of contrast matching experiments demonstrate that there is a strong tendency for the homopolymer to localize at the center of the midblock microdomain. Experimental scattering profiles are modeled using one-dimensional scattering density profiles in order to obtain a quantitative description of the blend morphologies. This modeling indicates that two distinct scenarios exist for homopolymer localization in a triblock copolymer: one wherein the microdomain structure contracts and a second wherein there is an expansion of the microdomain. Possible origins of this behavior are proposed on the basis of the consideration of the configuration available to the midblock sequence, that is, tie chains that traverse the midblock domain, or loops that enter and exit the midblock microdomain through the same interface.

  1. Positively charged micelles based on a triblock copolymer demonstrate enhanced corneal penetration

    PubMed Central

    Li, Jingguo; Li, Zhanrong; Zhou, Tianyang; Zhang, Junjie; Xia, Huiyun; Li, Heng; He, Jijun; He, Siyu; Wang, Liya

    2015-01-01

    Purpose The cornea is a main barrier to drug penetration after topical application. The aim of this study was to evaluate the abilities of micelles generated from a positively charged triblock copolymer to penetrate the cornea after topical application. Methods The triblock copolymer poly(ethylene glycol)-poly(ε-caprolactone)-g-polyethyleneimine was synthesized, and the physicochemical properties of the self-assembled polymeric micelles were investigated, including hydrodynamic size, zeta potential, morphology, drug-loading content, drug-loading efficiency, and in vitro drug release. Using fluorescein diacetate as a model drug, the penetration capabilities of the polymeric micelles were monitored in vivo using a two-photon scanning fluorescence microscopy on murine corneas after topical application. Results The polymer was successfully synthesized and confirmed using nuclear magnetic resonance and Fourier transform infrared. The polymeric micelles had an average particle size of 28 nm, a zeta potential of approximately +12 mV, and a spherical morphology. The drug-loading efficiency and drug-loading content were 75.37% and 3.47%, respectively, which indicates that the polymeric micelles possess a high drug-loading capacity. The polymeric micelles also exhibited controlled-release behavior in vitro. Compared to the control, the positively charged polymeric micelles significantly penetrated through the cornea. Conclusion Positively charged micelles generated from a triblock copolymer are a promising vehicle for the topical delivery of hydrophobic agents in ocular applications. PMID:26451109

  2. Dual modes of self-assembly in superstrongly segregated bicomponent triblock copolymer melts

    NASA Astrophysics Data System (ADS)

    Woloszczuk, Sebastian; Mineart, Kenneth P.; Spontak, Richard J.; Banaszak, Michal

    2015-01-01

    While A B C triblock copolymers are known to form a plethora of dual-mode (i.e., order-on-order) nanostructures, bicomponent A B A triblock copolymers normally self-assemble into single morphologies at thermodynamic incompatibility levels up to the strong-segregation regime. In this study, we employ on-lattice Monte Carlo simulations to examine the phase behavior of molecularly asymmetric A1B A2 copolymers possessing chemically identical endblocks differing significantly in length. In the limit of superstrong segregation, interstitial micelles composed of the minority A2 endblock are observed to arrange into two-dimensional hexagonal arrays along the midplane of B -rich lamellae in compositionally symmetric (50 :50 A :B ) copolymers. Simulations performed here establish the coupled molecular-asymmetry and incompatibility conditions under which such micelles form, as well as the temperature dependence of their aggregation number. Beyond an optimal length of the A2 endblock, the propensity for interstitial micelles to develop decreases, and the likelihood for colocation of both endblocks in the A1-rich lamellae increases. Interestingly, the strong-segregation theory of Semenov developed to explain the formation of free micelles by diblock copolymers accurately predicts the onset of interstitial micelles confined at nanoscale dimensions between parallel lamellae.

  3. Effects of Solvent Composition on the Assembly and Relaxation of Triblock Copolymer-Based Polyelectrolyte Gels

    SciTech Connect

    Henderson, Kevin J.; Shull, Kenneth R.

    2012-03-26

    The role of solvent selectivity has been explored extensively with regard to its role in the phase behavior of block copolymer assemblies. Traditionally, thermally induced phase separation is employed for generating micelles upon cooling a block copolymer dissolved in a selective solvent. However few amphiphilic, polyelectrolyte-containing block copolymers demonstrate a thermally accessible route of micellization, and solvent exchange routes are frequently employed instead. Here, we describe the use of mixed solvents for obtaining thermoreversible gelation behavior of poly(methyl methacrylate)-poly(methacrylic acid)-poly(methyl methacrylate) (PMMA-PMAA-PMMA) triblock copolymers. One solvent component (dimethyl sulfoxide) is a good solvent for both blocks, and the second solvent component (water) is a selective solvent for the polymer midblock. Rheological frequency sweeps at variable solvent compositions and temperatures demonstrate an adherence to time-temperature-composition superposition, so that changes in the solvent composition are analogous to changes in the Flory-Huggins interaction parameter between end block and solvent. Shift factors used for this superposition are related to the effective activation energy describing the viscosity and stress relaxation response of the triblock copolymer gels. The effectiveness of solvent exchange processes for producing hydrogels with this system is shown to originate from the ability of a small amount of added water to greatly increase the relaxation times of the self-assembled polymer gels that are formed by this process.

  4. Adsorption and functionality of fibrinogen on triblock copolymer-coated surfaces

    NASA Astrophysics Data System (ADS)

    O'Connor, Stephen Moss

    To assess the influence of the surface microenvironment on the adsorption and biologic activity of fibrinogen, a series of poly(ethylene oxide)/poly(propylene oxide) triblock copolymers were adsorbed to solid, hydrophobic polystyrene-divinylbenzene beads. The copolymers, which were of the form PEOsb{b}PPOsb{a}PEOsb{b}, varied in their hydrophile/lipophile balances (HLB) due only to differences in their PEO chain length (5 to 129 EO units) as the hydrophobic PPO core segment was of fixed length (56 or 69 PO units). The surface coverage of copolymers was determined first and after exposing the beads to fibrinogen or to human plasma, the total amount of protein adsorbed to their surface was measured. The functionality of fibrinogen bound to copolymer-modified beads was assessed in terms of fibrin clot formation and by the adherence of macrophages (THP-1 tumor cells). Enzymatic processing was used to probe the surface orientation of fibrinogen. The copolymers appear to adsorb in an expanded fashion, a conclusion supported by surface pressure-area isotherms of the copolymers spread at the air-water interface. As compared to copolymer-free surfaces, protein adsorption decreases by up to 90% as the PEO chain length of the copolymers increases. The copolymer coatings appear to lower fibrinogen adsorption by limiting the available surface area. On surfaces coated with the hydrophobic versions of the copolymers, the biologic assays demonstrate that fibrinogen is as reactive/coagulable as for surfaces with saturated coverages of fibrin despite that these copolymer-coated surfaces have 60% less fibrinogen adsorbed to them. When adsorbed at the same low surface concentration in the absence of copolymer, fibrinogen is not active. Enzymatic processing of bound fibrinogen suggests that the presence of the copolymers promote the adsorption of the protein in end-on fashion. It is proposed here, that when adsorbed end-on, fibrinogen is functional because its reactive sites are

  5. Comprehensive triblock copolymer analysis by coupled thermal field-flow fractionation-NMR.

    PubMed

    van Aswegen, Werner; Hiller, Wolf; Hehn, Mathias; Pasch, Harald

    2013-07-12

    Thermal field-flow fractionation (ThFFF) is used as a novel fractionation technique to investigate the molecular heterogeneity of PB-b-PVP-b-PtBMA triblock copolymers. Such copolymers cause major problems in liquid chromatography due to very strong polar interactions with the stationary phase. ThFFF separates the copolymers with regard to size and/or chemical composition based on the normal and thermal diffusion coefficients. The separation mechanism in ThFFF and the chemical composition of the separated species is elucidated by online (1) H NMR. Based on the compositional analysis and a calibration of the system with the respective homopolymers, the samples are quantified regarding their molar masses, chemical compositions, and microstructures providing comprehensive information on the complex structure of these block copolymers. PMID:23722993

  6. 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.

  7. Modeling and self-assembly behavior of PEG-PLA-PEG triblock copolymers in aqueous solution

    NASA Astrophysics Data System (ADS)

    Wu, Xiaohan; Li, Suming; Coumes, Fanny; Darcos, Vincent; Lai Kee Him, Joséphine; Bron, Patrick

    2013-09-01

    A series of poly(ethylene glycol)-polylactide-poly(ethylene glycol) (PEG-PLA-PEG) triblock copolymers with symmetric or asymmetric chain structures were synthesized by combination of ring-opening polymerization and copper-catalyzed click chemistry. The resulting copolymers were used to prepare self-assembled aggregates by dialysis. Various architectures such as nanotubes, polymersomes and spherical micelles were observed from transmission electron microscopy (TEM), cryo-TEM and atomic force microscopy (AFM) measurements. The formation of diverse aggregates is explained by modeling from the angle of both geometry and thermodynamics. From the angle of geometry, a ``blob'' model based on the Daoud-Cotton model for star polymers is proposed to describe the aggregate structures and structural changes with copolymer composition and molar mass. In fact, the copolymer chains extend in aqueous medium to form single layer polymersomes to minimize the system's free energy if one of the two PEG blocks is short enough. The curvature of polymersomes is dependent on the chain structure of copolymers, especially on the length of PLA blocks. A constant branch number of aggregates (f) is thus required to preserve the morphology of polymersomes. Meanwhile, the aggregation number (Nagg) determined from the thermodynamics of self-assembly is roughly proportional to the total length of polymer chains. Comparing f to Nagg, the aggregates take the form of polymersomes if Nagg ~ f, and change to nanotubes if Nagg > f to conform to the limits from both curvature and aggregation number. The length of nanotubes is mainly determined by the difference between Nagg and f. However, the hollow structure becomes unstable when both PEG segments are too long, and the aggregates eventually collapse to yield spherical micelles. Therefore, this work gives new insights into the self-assembly behavior of PEG-PLA-PEG triblock copolymers in aqueous solution which present great interest for biomedical and

  8. Substrate Surface Energy Dependent Morphology and Dewetting in an ABC Triblock Copolymer Film

    SciTech Connect

    Epps,T.; DeLongchamp, D.; Fasolka, M.; Fischer, D.; Jablonski, E.

    2007-01-01

    A gradient combinatorial approach was used to examine the effect of substrate surface energy on the morphology and stability of films of a poly(isoprene-b-styrene-b-ethylene oxide) triblock copolymer that exhibits an alternating gyroid morphology in the bulk. Atomic force microscopy data across our surface energy (water contact angle) library suggest a transformation to predominantly surface parallel lamellae with an antisymmetric ordering. For substrate water contact angles below 70{sup o} the film exhibited autophobic dewetting from an adsorbed half-period triblock copolymer monolayer at longer annealing times. X-ray photoelectron spectroscopy and near edge X-ray absorption fine structure analysis along gradient specimens indicated that the substrate surface energy governed the composition profile of the monolayer, and this variation in chemical expression was key to whether the film was stable or autophobically dewet. These observations demonstrate that enthalpic interactions, in addition to entropic considerations, can play a major role in autophobic dewetting of block copolymer films.

  9. Electrodeposition of mesoporous manganese dioxide supercapacitor electrodes through self-assembled triblock copolymer templates

    NASA Astrophysics Data System (ADS)

    Xue, Tong; Xu, Cai-Ling; Zhao, Dan-Dan; Li, Xiao-Hong; Li, Hu-Lin

    Mesoporous manganese dioxide supercapcitor electrode materials were electrochemically deposited onto silicon substrates coated with Pt using triblock copolymer species (Pluronic P123 and F127) as the structure-directing agents. Deposited electrodes of manganese dioxide film were physically characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM), and were electrochemically characterized by cyclic voltammetry (CV) in 0.5 M Na 2SO 4 electrolyte. Maximum specific capacitance (SC) values of 449 F g -1 was obtained at a scan rate of 10 mV s -1 from F127 templated mesoporous MnO 2.

  10. Continuous poly(2-oxazoline) triblock copolymer synthesis in a microfluidic reactor cascade.

    PubMed

    Baeten, Evelien; Verbraeken, Bart; Hoogenboom, Richard; Junkers, Thomas

    2015-07-25

    Cationic ring-opening polymerizations of 2-oxazolines were investigated in continuous microflow reactors. Fast homopolymerizations of 2-ethyl-2-oxazoline (EtOx) and 2-n-propyl-2-oxazoline (nPropOx) were carried out up to 180 °C, yielding well-controlled polymers. Also well-defined diblock and triblock copolymers were produced in a microfluidic reactor cascade, demonstrating the high value of microflow synthesis for the built-up of advanced poly(2-oxazoline)-based polymers. PMID:26104687

  11. Architectural effect on the self-assembly of supramolecular triblock copolymer melts

    NASA Astrophysics Data System (ADS)

    Lee, Won Bo; Elliott, Richard; Katsov, Kirill; Fredrickson, Glenn H.

    2007-03-01

    Thermoreversible, supramolecular self-assembly in multi-block copolymer melts is studied within the framework of self-consistent field theory. This approach is adapted to study a system composed of two chemically distinct, but reactive homopolymer species: a linear A-homopolymer with a single reactive group at one of the ends, and a linear B-homopolymer with reactive groups at both ends. Reversible bonding occurs between the functional groups from different polymer species so that the reacting system can contain A, B, AB and ABA (co)polymer species whose overall volume fractions are controlled by the segmental incompatibility, bonding strength and homopolymer chain lengths. Architectural variations of these copolymers, arising from the differing lengths of A and B homopolymers, have a dramatic effect on not only the micro-phase separation but also on the extent of reversible bonding. Two characteristic phase diagrams are constructed to illustrate this behavior and possible technological applications are discussed.

  12. Responsive Hydrogels and Ion Gels by Self-Assembly of ABA and ABC Triblock Polymers

    NASA Astrophysics Data System (ADS)

    Lodge, Timothy

    2014-03-01

    Gels - polymeric networks swollen with a substantial amount of solvent - represent a fascinating class of soft materials, with wide-ranging applications in fields as diverse as biomedicine, pharmaceutics, personal care products, foods, sensors, actuators, flexible electronics, oil recovery, and adhesives. Physical gels are held together by non-covalent interactions, which may be as specific as hydrogen bonds, or as general as solvophobic association of insoluble blocks. Among the attractive features of physical gels are reversibility, stimuli-responsiveness, and tunability of macroscopic properties. In this talk two classes of physical gels will be highlighted. In one, the ability of ABC block terpolymers to form novel structures will be demonstrated, where blocks A and C are mutually immiscible and solvophobic, while B is solvophilic. In particular, the formation of gels by sequential association (first A, then C) leads to a remarkably sharp gelation transition, at a relatively low polymer concentration, compared to analogous gels formed from ABA systems. In the second class, gels formed by self-assembly of a variety of ABA systems in ionic liquids will be described, and in particular how gelation can be controlled through factors such as block chemistry, temperature, choice of ionic liquid, and application of light.

  13. Comprehensive Phase Behavior of Poly(isoprene-b-styrene-b-ethylene oxide) Triblock Copolymers

    SciTech Connect

    Chatterjee, Joon; Jain, Sumeet; Bates, Frank S.

    2010-03-05

    The phase behavior of 44 poly(isoprene-b-styrene-b-ethylene oxide) (ISO) linear triblock copolymer melts was investigated at weak to intermediate segregation strengths and spanning a comprehensive range of compositions. Phases were characterized by a combination of experimental techniques, including small-angle X-ray scattering, dynamic mechanical spectroscopy, transmission electron microscopy, and birefringence measurements. Combined with our previous results, six different stable ordered state symmetries have been identified: lamellae (LAM), Fddd orthorhombic network (O{sup 70}), double gyroid (Q{sup 230}), alternating gyroid (Q{sup 214}), hexagonal (HEX), and body-centered cubic (BCC). The phase map of ISO specimens was found to be somewhat asymmetric around the f{sub I} = f{sub O} isopleth. This work provides a guide for theoretical studies and gives insight into the intricate effects of various parameters on the self-assembly of ABC triblock copolymers. Experimental SAXS data evaluated with a simple scattering intensity model show that local mixing varies continuously across the phase map between states of two- and three-domain segregation.

  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. Cationic triblock copolymer micelles enhance antioxidant activity, intracellular uptake and cytotoxicity of curcumin.

    PubMed

    Yoncheva, Krassimira; Kamenova, Katya; Perperieva, Teodora; Hadjimitova, Vera; Donchev, Petar; Kaloyanov, Kaloyan; Konstantinov, Spiro; Kondeva-Burdina, Magdalena; Tzankova, Virginia; Petrov, Petar

    2015-07-25

    The aim of the present study was to develop curcumin loaded cationic polymeric micelles and to evaluate their loading, preservation of curcumin antioxidant activity and intracellular uptake ability. The micelles were prepared from a triblock copolymer consisting of poly(ϵ-caprolactone) and very short poly(2-(dimethylamino) ethyl methacrylate) segments (PDMAEMA9-PCL70-PDMAEMA9). The micelles showed monomodal size distribution, mean diameter of 145 nm, positive charge (+72 mV), critical micellar concentration around 0.05 g/l and encapsulation efficiency of 87%. The ability of the micellar curcumin to scavenge the ABTS radical and hypochlorite ions was higher than that of the free curcumin. Confocal microscopy revealed that the uptake of curcumin by chronic myeloid leukemia derived K-562 cells and human multiple myeloma cells U-266 was more intensive when curcumin was loaded into the micelles. These results correlated with the higher cytotoxicity of the micellar curcumin compared to free curcumin. Intraperitoneal treatment of Wistar rats indicated that PDMAEMA-PCL-PDMAEMA copolymer, comprising very short cationic chains, did not change the levels of malondialdehyde and glutathione in livers indicating an absence of oxidative stress. Thus, PDMAEMA-PCL-PDMAEMA triblock micelles could be considered efficient and safe platform for curcumin delivery. PMID:26026253

  16. Polydiacetylene/triblock copolymer nanoblend applied as a sensor for micellar casein: A thermodynamic approach.

    PubMed

    de Souza, Luana Cypriano; de Paula Rezende, Jaqueline; Pires, Ana Clarissa dos Santos; da Silva, Luis Henrique Mendes; da Silva, Maria do Carmo Hespanhol; Castrillon, Elkin Dario Castellon; de Andrade, Nélio José

    2016-04-15

    Polydiacetylene (PDA) and triblock copolymer nanoblends were synthesized to detect micellar casein (MC), the main milk protein and an indicator of milk quality. UV-Vis spectrum showed that MC induced blue-to-red transition in nanoblends. When nanoblends and MC were separated by dialysis membrane colorimetric response (CR) was similar, whereas a remarkable CR reduction was noticed after addition of dialyzed-MC, suggesting that small molecules present in MC (salts) caused PDA color change. Interaction enthalpy variation between nanoblends and MC showed an abrupt increase that coincided with MC concentration when colorimetric transition occurred. Copolymer hydrophobic/hydrophilic balance and presence of other molecules in the system affected nanoblends CR. MC salts were found to interact with nanoblends leading to color changes. MC concentration, MC salt release, copolymer hydrophobic/hydrophilic balance, and presence of other molecules in the system affected responses of the sensors. These results contribute to future applications of PDA/copolymer nanosensors to dairy models. PMID:26617025

  17. Morphology and rheology of SIS and SEPS triblock copolymers in the presence of a midblock-selective solvent

    SciTech Connect

    Laurer, J.H.; Khan, S.A.; Spontak, R.J.; Satkowski, M.M.; Grothaus, J.T.; Smith, S.D.; Lin, J.S.

    1999-11-09

    While numerous fundamental studies have sought to elucidate the effect of a parent homopolymer on the morphological characteristics and mechanical properties of microphase-ordered block copolymer blends, few comparable efforts have extended such studies to concentrated copolymer solutions in the presence of a low-molar-mass block-selective solvent. In this work, the authors investigate the microstructures that form in blends of a poly(styrene-block-isoprene-block-styrene)(SIS)triblock copolymer with a midblock-selective aliphatic mineral oil. To discern the influence of midblock/oil compatibility on blend morphology and properties, identical blends with a poly[styrene-block-(ethylene-alt-propylene)-block-styrene] (SEPS) copolymer, the hydrogenated variant of the SIS copolymer, have likewise been examined. The saturated midblock of the SEPS copolymer is responsible for the observed shifts in morphology stability limits and higher dynamic elastic shear moduli relative to the SIS analogue. These results reveal that the morphologies and properties of such triblock copolymer/oil blends are sensitive to the chemical/statistical nature of the copolymer midblock and may be judiciously tailored to satisfy application-specific requirements.

  18. Complex microstructures of ABC triblock copolymer thin films directed by polymer brushes based on self-consistent field theory.

    PubMed

    Jiang, Zhibin; Xu, Chang; Qiu, Yu Dong; Wang, Xiaoliang; Zhou, Dongshan; Xue, Gi

    2014-01-01

    The morphology and the phase diagram of ABC triblock copolymer thin film directed by polymer brushes are investigated by the self-consistent field theory in three dimensions. The polymer brushes coated on the substrate can be used as a good soft template to tailor the morphology of the block copolymer thin films compared with those on the hard substrates. The polymer brush is identical with the middle block B. By continuously changing the composition of the block copolymer, the phase diagrams are constructed for three cases with the fixed film thickness and the brush density: identical interaction parameters, frustrated and non-frustrated cases. Some ordered complex morphologies are observed: parallel lamellar phase with hexagonally packed pores at surfaces (LAM3 (ll) -HFs), perpendicular lamellar phase with cylinders at the interface (LAM(⊥)-CI), and perpendicular hexagonally packed cylinders phase with rings at the interface (C2 (⊥)-RI). A desired direction (perpendicular or parallel to the coated surfaces) of lamellar phases or cylindrical phases can be obtained by varying the composition and the interactions between different blocks. The phase diagram of ABC triblock copolymer thin film wetted between the polymer brush-coated surfaces is very useful in designing the directed pattern of ABC triblock copolymer thin film. PMID:25114650

  19. Multicomponent Solvated Triblock Copolymer Network Systems: Fundamental Insights and Emerging Applications

    NASA Astrophysics Data System (ADS)

    Krishnan, Arjun Sitaraman

    Block copolymers have received significant research attention in recent times due to their ability to spontaneously self-assemble into a variety of nanostructures. Thermoplastic elastomers composed of styrenic triblock copolymers are of great importance in applications such as adhesives and vibration dampening due to their shape memory, resilience and facile processing. The swelling of these polymers by adding midblock selective solvents or oligomers provides an easy route by which to modify the morphology and mechanical behavior of these systems. We first consider a ternary blend of a poly[styrene- b-(ethylene-co-butylene)-b-styrene] triblock copolymer (SEBS) and mixtures of two midblock selective co-solvents, with significantly different physical states. We use dynamic rheology to study the viscoelastic response of a wide variety of systems under oscillatory shear. Frequency spectra acquired at ambient temperature display viscoelastic behavior that shifts in the frequency domain depending on the co-solvent composition. For each copolymer concentration, all the frequency data can be shifted by time-composition superpositioning (tCS) to yield a single master-curve. tCS fails at low frequencies due to presence of endblock pullout, which is a fundamentally different relaxation process from segmental relaxation of the midblock. As an emerging technology, we examine SEBS-oil gels as dielectric elastomers. Dielectric elastomers constitute one class of electroactive polymers (EAPs), polymeric materials that respond to an electric stimulus by changing their macroscopic dimensions, thereby converting electrical energy into mechanical work. We use standard configuration of EAP devices involving stretching, or "prestraining," the elastomer film biaxially. The effect of experimental parameters such as film thickness and amount of prestrain on the (electro)mechanical properties of the material become apparent by recasting as-obtained electroactuation data into compressive

  20. Triblock siloxane copolymer surfactant: template for spherical mesoporous silica with a hexagonal pore ordering.

    PubMed

    Stébé, M J; Emo, M; Forny-Le Follotec, A; Metlas-Komunjer, L; Pezron, I; Blin, J L

    2013-02-01

    Ordered mesoporous silica materials with a spherical morphology have been prepared for the first time through the cooperative templating mechanism (CTM) by using a silicone triblock copolymer as template. The behavior of the pure siloxane copolymer amphiphile in water was first investigated. A direct micellar phase (L(1)) and a hexagonal (H(1)) liquid crystal were found. The determination of the structural parameters by SAXS measurements leads us to conclude that in the hexagonal liquid crystal phase a part of the ethylene oxide group is not hydrated as observed for the micelles. Mesoporous materials were then synthesized from the cooperative templating mechanism. The recovered materials were characterized by SAXS measurements, nitrogen adsorption-desorption analysis, and transmission and scanning electron microscopy. The results clearly evidence that one can control the morphology and the nanostructuring of the resulting material by modifying the synthesis parameters. Actually, highly ordered mesoporous materials with a spherical morphology have been obtained with a siloxane copolymer/tetramethoxysilane molar ratio of 0.10 after hydrothermal treatment at 100 °C. Our study also supports the fact that the interactions between micelles and the hydrolyzed precursor are one of the key parameters governing the formation of ordered mesostructures through the cooperative templating mechanism. Indeed, we have demonstrated that when the interactions between micelles are important, only wormhole-like structures are recovered. PMID:23305163

  1. End Group Effects on the Hydrogel Formation of PEO-PPO-PEO Triblock Copolymers

    NASA Astrophysics Data System (ADS)

    Cohen, Aaron; Ryu, Chang Y.; Jung, Gyoo Y.; Hwang, Hee Sung

    2012-02-01

    Pluronic F108, a triblock copolymer consisting of outer polyethylene oxide (PEO) chains and an inner polypropylene oxide (PPO) chains, has been shown to be an effective hydrogel matrix for DNA separation by capillary electrophoresis using single-stranded conformation polymorphism. This presentation will discuss a new pathway to potentially enhance the separation abilities of F108 by altering the chain end groups of the block copolymers. F108 is believed to form a micelle in aqueous solutions with the hydrophobic group in the interior, thus we expect considerable interaction between the DNA sample and the end groups found at the hydrophilic brush layers of the micelle. The rheological properties of end group derivatives of F108, in combination of small angle x-ray scattering, can reveal structural differences in the micelles. In particular, gelation temperature of the end group derivatives can be linked to differences in the micelle structure. Dynamic light scattering can also be used to determine the effects of chain end groups on the hydrodynamic size of the block copolymer micelles in dilute solution.

  2. Protective effects of nonionic tri-block copolymers on bile acid-mediated epithelial barrier disruption.

    SciTech Connect

    Edelstein, A.; Fink, D.; Musch, M.; Valuckaite, V.; Zabornia, O.; Grubjesic, S.; Firestone, M. A.; Matthews, J. B.; Alverdy, J. C.

    2011-11-01

    Translocation of bacteria and other luminal factors from the intestine following surgical injury can be a major driver of critical illness. Bile acids have been shown to play a key role in the loss of intestinal epithelial barrier function during states of host stress. Experiments to study the ability of nonionic block copolymers to abrogate barrier failure in response to bile acid exposure are described. In vitro experiments were performed with the bile salt sodium deoxycholate on Caco-2 enterocyte monolayers using transepithelial electrical resistance to assay barrier function. A bisphenol A coupled triblock polyethylene glycol (PEG), PEG 15-20, was shown to prevent sodium deoxycholate-induced barrier failure. Enzyme-linked immunosorbent assay, lactate dehydrogenase, and caspase 3-based cell death detection assays demonstrated that bile acid-induced apoptosis and necrosis were prevented with PEG 15-20. Immunofluorescence microscopic visualization of the tight junctional protein zonula occludens 1 (ZO-1) demonstrated that PEG 15-20 prevented significant changes in tight junction organization induced by bile acid exposure. Preliminary transepithelial electrical resistance-based studies examining structure-function correlates of polymer protection against bile acid damage were performed with a small library of PEG-based copolymers. Polymer properties associated with optimal protection against bile acid-induced barrier disruption were PEG-based compounds with a molecular weight greater than 10 kd and amphiphilicity. The data demonstrate that PEG-based copolymer architecture is an important determinant that confers protection against bile acid injury of intestinal epithelia.

  3. Multiblock copolymers exhibiting spatio-temporal structure with autonomous viscosity oscillation

    PubMed Central

    Onoda, Michika; Ueki, Takeshi; Shibayama, Mitsuhiro; Yoshida, Ryo

    2015-01-01

    Here we report an ABA triblock copolymer that can express microscopic autonomous formation and break-up of aggregates under constant condition to generate macroscopic viscoelastic self-oscillation of the solution. The ABA triblock copolymer is designed to have hydrophilic B segment and self-oscillating A segment at the both sides by RAFT copolymerization. In the A segment, a metal catalyst of chemical oscillatory reaction, i.e., the Belousov-Zhabotinsky (BZ) reaction, is introduced as a chemomechanical transducer to change the aggregation state of the polymer depending on the redox states. Time-resolved DLS measurements of the ABA triblock copolymer confirm the presence of a transitional network structure of micelle aggregations in the reduced state and a unimer structure in the oxidized state. This autonomous oscillation of a well-designed triblock copolymer enables dynamic biomimetic softmaterials with spatio-temporal structure. PMID:26511660

  4. Triblock copolymer P104 detailed behavior through a density, sound velocity and DLS study

    NASA Astrophysics Data System (ADS)

    Bravo-Anaya, L. M.; Fierro-Castro, C.; Rharbi, Y.; Martínez, J. F. A. Soltero

    2014-05-01

    Pluronic triblock copolymers usually present complex phase behavior depending on the number of PEO and PPO blocks contained in the polymer. They have a great dependence to temperature and concentration, both considered as key factors in the pluronic phase behavior. The evaluation of physicochemical properties such as densimetry and sound velocity, as well as the determination of the size distribution profile of particles of P-104/water in solution allow obtaining a detailed temperature-concentration behavior of the system. In this work we present a study of P104/water behavior through density, ultrasound velocity and dynamic slight scattering (DLS) measurements in a wide range of temperatures. The critical micellar temperature (CMT) and the sphere-to-rod micelle transition temperature (GMT) were determinate as a function of concentration.

  5. Measurement of the Longitudinal Dynamic Modulus in Macroscopically Ordered Triblock Copolymers using Brillouin Light Scattering

    NASA Astrophysics Data System (ADS)

    Lehman, S. Y.; McNeil, L. E.; Albalak, Ramon; Grimsditch, M.

    1996-11-01

    Triblock copolymers, under certain preparation conditions, organize themselves into macroscopically-ordered, though microscopically-disordered films. We studied films of styrene-butadiene-styrene of varying molecular weight ratios, organized either in lamellae or in cylinders of styrene hexagonally packed in a matrix of butadiene. The polymer chains are tethered at the styrene-butadiene interface, constraining their motion. These films have possible applications including optical waveguides and quantum wire arrays. We have studied the longitudinal acoustic modes in the temperature range 20-475 K in the hypersonic frequency regime using Brillouin light scattering. In addition to measuring the storage modulus M' from the Brillouin frequency shift, we also obtain the loss modulus M" by measuring the FWHM of the Brillouin peaks. Using M" to determine the relaxation times of the polymer strands, we then study the effects of chain tethering on the polymer chain dynamics.

  6. Triblock copolymer gels - structure, fracture behavior and application in ceramic processing

    NASA Astrophysics Data System (ADS)

    Seitz, Michelle E.

    Acrylic triblock copolymer gels transition rapidly from free-flowing liquids to elastic solids and their nanoscale self-assembly leads to reproducible structure and properties. They are an ideal model system for understanding the link between gel structure and the deformation and fracture behavior of soft, self-assembled materials. While a basic understanding of gel structure and linear viscoelastic response exists, this research aims to extend this understanding to include the nonlinear mechanical response and fracture behavior as well as the effect of gel concentration, block length, endblock fraction, and homopolymer solubilization. This expanded understanding will be applied to optimize triblock design for the thermoreversible gelcasting of ceramics. Gel structure was characterized using small angle scattering and self-consistent field theory simulations while mechanical properties were studied using a combination of rheology, swelling, indentation, uniaxial compression, and fracture experiments. Birefringence and shear alignment were used to differentiate between spherical and cylindrical micelle morphologies. An effective energy barrier of 550 kJ/mol describes gels relaxation behavior over a 40°C temperature range where the relaxation times vary by a factor of 1010. At high endblock contents, gels exhibit greater permanent deformation and moduli over an order of magnitude larger than would be expected from rubber elasticity alone due to a transition from spherical to cylindrical micelles. The rate dependence of a gels energy release rate, G , is independent of the gel concentration when G is normalized by the small strain Young's modulus, E. The gels exhibit a transition from rough, slow crack propagation to smooth, fast crack propagation for a well-defined value of the characteristic length, G /E. Crack tip stresses become highly anisotropic at stress values below the failure strength of the gels and are poorly described using linear elastic fracture

  7. Phase Behavior of Binary Blends of High Molecular Weight Diblock Copolymers with a Low Molecular Weight Triblock

    SciTech Connect

    Mickiewicz, Rafal A.; Ntoukas, Eleftherios; Avgeropoulos, Apostolos; Thomas, Edwin L.

    2009-08-26

    Binary blends of four different high molecular weight poly(styrene-b-isoprene) (SI) diblock copolymers with a lower molecular weight poly(styrene-b-isoprene-b-styrene) (SIS) triblock copolymer were prepared, and their morphology was characterized by transmission electron microscopy and ultra-small-angle X-ray scattering. All the neat block copolymers have nearly symmetric composition and exhibit the lamellar morphology. The SI diblock copolymers had number-average molecular weights, Mn, in the range 4.4 x 10{sup 5}--1.3 x 10{sup 6} g/mol and volume fractions of poly(styrene), {Phi}{sub PS}, in the range 0.43--0.49, and the SIS triblock had a molecular weight of Mn 6.2 x 10{sup 4} g/mol with {Phi}{sub PS} = 0.41. The high molecular weight diblock copolymers are very strongly segregating, with interaction parameter values, {chi}N, in the range 470--1410. A morphological phase diagram in the parameter space of molecular weight ratio (R = M{sub n}{sup diblock}/1/2M{sub n}{sup triblock}) and blend composition was constructed, with R values in the range between 14 and 43, which are higher than previously reported. The phase diagram revealed a large miscibility gap for the blends, with macrophase separation into two distinct types of microphase-separated domains for weight fractions of SI, w{sub SI} < 0.9, implying virtually no solubility of the much higher molecular weight diblocks in the lower molecular weight triblock. For certain blend compositions, above R 30, morphological transitions from the lamellar to cylindrical and bicontinuous structures were also observed.

  8. Heat capacity anomaly in a self-aggregating system: Triblock copolymer 17R4 in water

    NASA Astrophysics Data System (ADS)

    Dumancas, Lorenzo V.; Simpson, David E.; Jacobs, D. T.

    2015-05-01

    The reverse Pluronic, triblock copolymer 17R4 is formed from poly(propylene oxide) (PPO) and poly(ethylene oxide) (PEO): PPO14 - PEO24 - PPO14, where the number of monomers in each block is denoted by the subscripts. In water, 17R4 has a micellization line marking the transition from a unimer network to self-aggregated spherical micelles which is quite near a cloud point curve above which the system separates into copolymer-rich and copolymer-poor liquid phases. The phase separation has an Ising-like, lower consolute critical point with a well-determined critical temperature and composition. We have measured the heat capacity as a function of temperature using an adiabatic calorimeter for three compositions: (1) the critical composition where the anomaly at the critical point is analyzed, (2) a composition much less than the critical composition with a much smaller spike when the cloud point curve is crossed, and (3) a composition near where the micellization line intersects the cloud point curve that only shows micellization. For the critical composition, the heat capacity anomaly very near the critical point is observed for the first time in a Pluronic/water system and is described well as a second-order phase transition resulting from the copolymer-water interaction. For all compositions, the onset of micellization is clear, but the formation of micelles occurs over a broad range of temperatures and never becomes complete because micelles form differently in each phase above the cloud point curve. The integrated heat capacity gives an enthalpy that is smaller than the standard state enthalpy of micellization given by a van't Hoff plot, a typical result for Pluronic systems.

  9. Equilibrium Structure of a Triblock Copolymer System Revealed by Mesoscale Simulation and Neutron Scattering

    SciTech Connect

    Do, Changwoo; Chen, Wei-Ren; Hong, Kunlun; Smith, Gregory Scott

    2013-01-01

    We have performed both mesoscale simulations and neutron scattering experiments on Pluronic L62, a poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) triblock copolymer system in aqueous solution. The influence of simulation variables such PEO/PPO block ratio, interaction parameters, and coarse-graining methods is extensively investigated by covering all permutations of parameters found in the literatures. Upon increasing the polymer weight fraction from 50 wt% to 90 wt%, the equilibrium structure of the isotropic, reverse micellar, bicontinuous, worm-like micelle network, and lamellar phases are respectively predicted from the simulation depending on the choices of simulation parameters. Small angle neutron scattering (SANS) measurements show that the same polymer systems exhibit the spherical micellar, lamellar, and reverse micellar phases with the increase of the copolymer concentration at room temperature. Detailed structural analysis and comparison with simulations suggest that one of the simulation parameter sets can provide reasonable agreement with the experimentally observed structures.

  10. Equilibrium structure of a triblock copolymer system revealed by mesoscale simulation and neutron scattering

    NASA Astrophysics Data System (ADS)

    Do, Changwoo; Chen, Wei-Ren; Hong, Kunlun; Smith, Gregory S.

    2013-12-01

    We have performed both mesoscale simulations and neutron scattering experiments on Pluronic L62, a poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) triblock copolymer system in aqueous solution. The influence of simulation variables such PEO/PPO block ratio, interaction parameters, and coarse-graining methods is extensively investigated by covering all permutations of parameters found in the literatures. Upon increasing the polymer weight fraction from 50 wt% to 90 wt%, the equilibrium structure of the isotropic, reverse micellar, bicontinuous, worm-like micelle network, and lamellar phases are respectively predicted from the simulation depending on the choices of simulation parameters. Small angle neutron scattering (SANS) measurements show that the same polymer systems exhibit the spherical micellar, lamellar, and reverse micellar phases with the increase of the copolymer concentration at room temperature. Detailed structural analysis and comparison with simulations suggest that one of the simulation parameter sets can provide reasonable agreement with the experimentally observed structures.

  11. Dependence of aggregation behavior on concentration in triblock copolymer solutions: The effect of chain architecture.

    PubMed

    Han, Xiang-Gang; Zhang, Xue-Feng

    2015-12-01

    Using the self-consistent field lattice technique, the effects of concentration and hydrophobic middle block length (where the chain length remains constant) on aggregation behavior are studied in amphiphilic symmetric triblock copolymer solutions. The heat capacity peak for the unimer-micelle transition and the distribution peaks for the different degrees of aggregation for micelles and small aggregates (submicelles) are calculated. Analysis of the conducted computer simulations shows that the transition broadness dependence on concentration is determined by the hydrophobic middle block length, and this dependence is distinctly different when the length of the hydrophobic middle block changes. Different size for small aggregates simultaneously appear in the transition region. As temperature decreases, the number of different size small aggregates for the large hydrophobic middle block length first ascends and then descends in aggregation degree order. These results indicate that any transition broadness change with concentration is related to the mechanism of fragmentation and fusion. These results are helpful for interpreting the aggregation process of amphiphilic copolymers at equilibrium. PMID:26646888

  12. Expanding mesoporosity of triblock-copolymer-templated silica under weak synthesis acidity.

    PubMed

    Li, Jinjun; Hu, Qin; Tian, Hua; Ma, Chunyan; Li, Landong; Cheng, Jie; Hao, Zhengping; Qiao, Shizhang

    2009-11-01

    With initial aging at low temperature for enough time, silicas with large mesoporosity were synthesized using triblock copolymer as template agent under weak acidities. SBA-15 with periodic mesostructure and short mesochannels could be synthesized at pH 2.5-3.0 within weak acidity range, and the surface areas, pore diameters and pore volumes reached up to ca. 1000m(2)/g, 8.8nm and 2.0cm(3)/g, respectively, which were significantly higher than those of the conventional SBA-15 synthesized under strong acidities. Mesoporous silica with wormhole structure and abundant textural porosity was formed at pH approximately 3.5. The increased hydrophobic volume of the copolymer micelles at elevated pH values was responsible for the enlargement of mesoporosity in the products. The materials synthesized under weak acidities showed lower hexagonal ordering in comparison to the general SBA-15 synthesized under strong acidities because the decreased hydronium ion concentration induced relatively weaker assembly forces during the synthesis. Nonetheless, the short mesochannels and large pore diameter in the products might be beneficial to some applications in which fast diffusion of molecules is required. PMID:19683247

  13. Dependence of aggregation behavior on concentration in triblock copolymer solutions: The effect of chain architecture

    SciTech Connect

    Han, Xiang-Gang Zhang, Xue-Feng

    2015-12-07

    Using the self-consistent field lattice technique, the effects of concentration and hydrophobic middle block length (where the chain length remains constant) on aggregation behavior are studied in amphiphilic symmetric triblock copolymer solutions. The heat capacity peak for the unimer-micelle transition and the distribution peaks for the different degrees of aggregation for micelles and small aggregates (submicelles) are calculated. Analysis of the conducted computer simulations shows that the transition broadness dependence on concentration is determined by the hydrophobic middle block length, and this dependence is distinctly different when the length of the hydrophobic middle block changes. Different size for small aggregates simultaneously appear in the transition region. As temperature decreases, the number of different size small aggregates for the large hydrophobic middle block length first ascends and then descends in aggregation degree order. These results indicate that any transition broadness change with concentration is related to the mechanism of fragmentation and fusion. These results are helpful for interpreting the aggregation process of amphiphilic copolymers at equilibrium.

  14. Structure of PEO-b-PPO-b-PEO Triblock Copolymer Inclusion Complexes with Beta-Cyclodextrin

    NASA Astrophysics Data System (ADS)

    Tsai, Chi-Chun; Cheng, Stephen Z. D.; Lotz, Bernard; Huang, Jin; Chen, Yongming

    2009-03-01

    Inclusion complexes, formed by non-covalent host-guest interactions, have been extensively investigated because they can be useful as building blocks for constructing supramolecular structures. Cyclodextrins (CDs), due to their good water-solubility and ability to include a wide range of guest molecules, have been the most intensively studied host molecules. CDs are shaped like a shallow truncated cone, with a hydrophilic outer surface as well as primary (narrower end) and secondary (wider end) hydroxyl groups on the rim of the molecule. The cavity, which is constructed with alkyl groups and glycosidic oxygen atoms, is hydrophobic and can act as a host for a great variety of hydrophobic molecular guests. A series of host-guest inclusion complexes were prepared with beta-cyclodextrin (beta-CD) and PEO-PPO-PEO triblock copolymers of varying molecular weights and compositions. The middle PPO block of the copolymers can be selectively included by beta-CD to form an inclusion complex while the PEO blocks cannot. These inclusion complexes can further self-assembled into supramolecular structures in aqueous solution. The inclusion complexes and self-assembled supramolecular structures were characterized by Nuclear Magnetic Resonance, X-ray diffraction, and Differential Scanning Calorimetry experimental methods.

  15. Gas-tight triblock-copolymer membranes are converted to CO2 permeable by insertion of plant aquaporins

    PubMed Central

    Uehlein, Norbert; Otto, Beate; Eilingsfeld, Adrian; Itel, Fabian; Meier, Wolfgang; Kaldenhoff, Ralf

    2012-01-01

    We demonstrate that membranes consisting of certain triblock-copolymers were tight for CO2. Using a novel approach, we provide evidence for aquaporin facilitated CO2 diffusion. Plant aquaporins obtained from heterologous expression were inserted into triblock copolymer membranes. These were employed to separate a chamber with a solution maintaining high CO2 concentrations from one with depleted CO2 concentrations. CO2 diffusion was detected by measuring the pH change resulting from membrane CO2 diffusion from one chamber to the other. An up to 21 fold increase in diffusion rate was determined. Besides the supply of this proof of principle, we could provide additional arguments in favour of protein facilitated CO2 diffusion to the vivid on-going debate about the principles of membrane gas diffusion in living cells. PMID:22844579

  16. Nanoparticle-Induced Ellipse-to-Vesicle Morphology Transition of Rod-Coil-Rod Triblock Copolymer Aggregates.

    PubMed

    Yang, Chaoying; Li, Qing; Cai, Chunhua; Lin, Jiaping

    2016-07-12

    Cooperative self-assembly behavior of rod-coil-rod poly(γ-benzyl-l-glutamate)-block-poly(ethylene glycol)-block-poly(γ-benzyl-l-glutamate) (PBLG-b-PEG-b-PBLG) amphiphilic triblock copolymers and hydrophobic gold nanoparticles (AuNPs) was investigated by both experiments and dissipative particle dynamics (DPD) simulations. It was discovered that pure PBLG-b-PEG-b-PBLG copolymers self-assemble into ellipse-like aggregates, and the morphology transforms into vesicles as AuNPs are introduced. When the hydrophobicity of AuNPs is close to that of the copolymers, AuNPs are homogeneously distributed in the vesicle wall. While for the AuNPs with higher hydrophobicity, they are embedded in the vesicle wall as clusters. In addition to the experimental observations, DPD simulations were performed on the self-assembly behavior of triblock copolymer/nanoparticle mixtures. Simulations well reproduced the morphology transition observed in the experiments and provided additional information such as chain packing mode in aggregates. It is deduced that the main reason for the ellipse-to-vesicle transition of the aggregates is attributed to the breakage of ordered and dense packing of PBLG rods in the aggregate core by encapsulating AuNPs. This study deepens our understanding of the self-assembly behavior of rod-coil copolymer/nanoparticle mixtures and provides strategy for designing hybrid polypeptide nanostructures. PMID:27314970

  17. Adsorption and desorption phenomena of PEO-PPO-PEO triblock copolymer systems on model surfaces

    NASA Astrophysics Data System (ADS)

    Brandani, Pietro

    This thesis reports on the kinetic and equilibrium behavior for the adsorption from solution of a family of copoly(ethyleneoxide-propyleneoxide-ethyleneoxide), PEO-PPO-PEO, triblock copolymers on gold surfaces modified by a methyl terminated self-assembled monolayer of a long chain alkanethiol (CH3(CH 2)10SH) and by a long chain mercaptoalkanoic acid (HOOC(CH 2)10SH). Events at the surface were monitored with a surface plasmon resonance technique with a high time resolution (0.1 s). Atomic force microscopy (AFM) in the liquid environment was conducted on a selected number of cases to discern the morphology of the copolymer coated surfaces. The data were analyzed in the context a mass transfer corrected Langmuir kinetics model. The model is only able to reproduce the observations for very dilute solutions, or for the initial stages of the process, but it allows to better discriminate the onset of the different mechanisms of adsorption. For the hydrophobic surface, the adsorbed amounts go through a maximum near the critical micelle concentration (CMC) and thus the process is not consistent with a Langmuir isotherm; in addition we the process is partially irreversible. The kinetics show that, for a series of compounds with the same length of the PPO block, the character of the adsorption process is affected by the relative balance of the hydrophilic and hydrophobic content within the copolymer: higher hydrophobic content leads to enhanced adsorption rates past the CMC. AFM observations confirm that globular micelle-like aggregates are present at the surface for the more hydrophobic species. In contrast, a uniform monolayer-like morphology is observed for the more hydrophilic species. For the hydrophilic surface, it is again found that the adsorbed amounts go through a maximum near the critical micelle concentration (CMC), however, in this case, the process is reversible. Enhanced adsorption rates past the CMC are observed irrespective of the relative balance of the

  18. Wall slip, shear banding, and instability in the flow of a triblock copolymer micellar solution

    NASA Astrophysics Data System (ADS)

    Manneville, Sébastien; Colin, Annie; Waton, Gilles; Schosseler, François

    2007-06-01

    The shear flow of a triblock copolymer micellar solution (PEO-PPO-PEO Pluronic P84 in brine) is investigated using simultaneous rheological and velocity profile measurements in the concentric cylinder geometry. We focus on two different temperatures below and above the transition temperature Tc which was previously associated with the apparition of a stress plateau in the flow curve. (i) At T=37.0°CTc , the stress plateau is shown to correspond to stationary shear-banded states characterized by two high shear rate bands close to the walls and a very weakly sheared central band, together with large slip velocities at the rotor. In both cases, the high shear branch of the flow curve is characterized by flow instability. Interpretations of wall slip, three-band structure, and instability are proposed in light of recent theoretical models and experiments.

  19. Self-Assembly and Relaxation Behavior of Graphene Containing Acrylic Triblock Copolymer Gels

    NASA Astrophysics Data System (ADS)

    Zabet, Mahla; Hashemnejad, Seyedmeysam; Kundu, Santanu

    2015-03-01

    Investigation of gel mechanical properties as a function of their structure is a significant research interest. This study presents the effect of graphene (or few-layer graphene) on the self-assembly and the relaxation behavior of a thermoreversible gel consists of a physically cross-linked poly (methyl methacrylate)-poly (n-butyl acrylate)-poly (methyl methacrylate) [PMMA-PnBA-PMMA] triblock copolymer in 2-ethyl-1-hexanol, a midblock selective solvent. Graphene was obtained by sonicating exfoliated graphite in 2-ethyl-1-hexanol at various concentrations. Filtration technique and spectrophotometry were utilized to measure the graphene concentration in the dispersions. The dispersed graphene was then incorporated in a series of gels and the effect of graphene on mechanical properties, including the relaxation behavior were studied. Small angle X-ray scattering (SAXS) was used to investigate the microstructure of these gels at room temperature. SAXS data were analyzed to estimate the number of end blocks per junction zone, the average spacing between the junctions, and the change of these properties as a function of graphene concentration. The results indicate that the presence of graphene affects the self-assembly process.

  20. DNA electrophoresis in tri-block copolymer gels--experiments and Brownian dynamics simulation

    NASA Astrophysics Data System (ADS)

    Wei, Ling; van Winkle, David H.

    2015-03-01

    The mobility of double-stranded DNA ladders in Pluronics®P105, P123 and F127, was measured by two-dimensional gel electrophoresis. Pluronics®are triblock copolymers which form gel-like phases of micelles arranged with cubic order at room temperature. A 10 base pair and a 25 base pair DNA ladder were used as samples in gel electrophoresis. The monotonically decreasing mobility with increasing length observed in the agarose separations is not observed in separations in Pluronics®. Rather, a complicated dependence of mobility on DNA length is observed, where mobility vs. length increases for short DNA molecules then decreases for longer molecules. There is also a variation of mobility with length correlated to the micelle diameter. Brownian dynamics simulations of a discrete wormlike chain model were performed to simulate short DNA molecules migrating in free solution and in a face-centered cubic matrix. By incorporating hydrodynamic interactions, the trend of simulated length-dependent mobility qualitatively agrees with experimental measurements.

  1. Mechanistic Investigation of Seeded Growth in Triblock Copolymer Stabilized Gold Nanoparticles

    PubMed Central

    Sabir, Theodore S.; Rowland, Leah; Milligan, Jamie R.; Yan, Dong; Aruni, A. Wilson; Chen, Qiao; Boskovic, Danilo S.; Kurti, R. Steven; Perry, Christopher C.

    2015-01-01

    We report the seeded synthesis of gold nanoparticles (GNPs) via the reduction of HAuCl4 by (L31 and F68) triblock copolymer (TBP) mixtures. In the present study, we focused on [TBP]/[Au(III)] ratios of 1–5 (≈ 1 mM HAuCl4) and seed sizes ~ 20 nm. Under these conditions, the GNP growth rate is dominated by both the TBP and seed concentrations. With seeding, the final GNP size distributions are bimodal. Increasing the seed concentration (up to ~ 0.1 nM) decreases the mean particle sizes 10-fold, from ~1000 to 100 nm. The particles in the bimodal distribution are formed by the competitive direct growth in solution and the aggregative growth on the seeds. By monitoring kinetics of GNP growth, we propose that (1) the surface of the GNP seeds embedded in the TBP cavities form catalytic centers for GNP growth and; (2) large GNPs are formed by the aggregation of GNP seeds in an autocatalytic growth process. PMID:23473268

  2. Mesoporous aluminosilicates assembled from dissolved LTA zeolite and triblock copolymer in the presence of tetramethylammonium hydroxide.

    PubMed

    Tanaka, Shunsuke; Okada, Hiroaki; Nakatani, Norihito; Maruo, Takanori; Nishiyama, Norikazu; Miyake, Yoshikazu

    2009-05-15

    Zeolite Na-A crystals dissolved in a HCl solution were used as a single-source of silicon and aluminum for the synthesis of mesoporous aluminosilicates via a template-assisted method with an organic base tetramethylammonium hydroxide (TMAOH). Amphiphilic triblock copolymer Pluronic F127 (EO(106)PO(70)EO(106)) was used as template. Increasing the amount of TMAOH in the synthetic solution resulted in an increase in the aluminum content of the products. On the other hand, mesostructural periodicity was deteriorated with higher content of aluminum incorporated into the mesoporous framework. The samples with low Si/Al ratios less than 5 have wormhole-like pore structure, while the samples with Si/Al ratios more than 7 possess highly ordered mesoporous structure, a body-centered Im3m symmetry, with single crystal like morphology. The samples with Si/Al ratio of 7, which prepared at TMAOH molar concentration of 25 mM in the templating solution, possess BET surface area of 470 m(2)/g, pore size of 6.4 nm, and pore volume of 0.56 cm(3)/g. Aluminum atoms have successfully been incorporated in a tetra-coordinated position and remained stable even after calcination at 600 degrees C. PMID:19223041

  3. Nanocomposites of polystyrene-b-poly(isoprene)-b-polystyrene triblock copolymer with clay-carbon nanotube hybrid nanoadditives.

    PubMed

    Enotiadis, Apostolos; Litina, Kiriaki; Gournis, Dimitrios; Rangou, Sofia; Avgeropoulos, Apostolos; Xidas, Panagiotis; Triantafyllidis, Kostas

    2013-01-24

    Polystyrene-b-polyisoprene-b-polystyrene (PS-b-PI-b-PS), a widely used linear triblock copolymer of the glassy-rubbery-glassy type, was prepared in this study by anionic polymerization and was further used for the development of novel polymer nanocomposite materials. Hybrid nanoadditives were prepared by the catalytic chemical vapor deposition (CCVD) method through which carbon nanotubes were grown on the surface of smectite clay nanolayers. Side-wall chemical organo-functionalization of the nanotubes was performed in order to enhance the chemical compatibilization of the clay-CNT hybrid nanoadditives with the hydrophobic triblock copolymer. The hybrid clay-CNT nanoadditives were incorporated in the copolymer matrix by a simple solution-precipitation method at two nanoadditive to polymer loadings (one low, i.e., 1 wt %, and one high, i.e., 5 wt %). The resulting nanocomposites were characterized by a combination of techniques and compared with more classical nanocomposites prepared using organo-modified clays as nanoadditives. FT-IR and Raman spectroscopies verified the presence of the hybrid nanoadditives in the final nanocomposites, while X-ray diffraction and transmission electron microscopy proved the formation of fully exfoliated structures. Viscometry measurements were further used to show the successful incorporation and homogeneous dispersion of the hybrid nanoadditives in the polymer mass. The so prepared nanocomposites exhibited enhanced mechanical properties compared to the pristine polymer and the nanocomposites prepared by conventional organo-clays. Both tensile stress and strain at break were improved probably due to better interfacial adhesion of the clay-CNT hybrid of the flexible rubbery PI middle blocks of the triblock copolymer matrix. PMID:23256576

  4. Morphology and Dynamic Mechanical Properties of Styrene Containing Tri-Block Copolymers for Electromagnetic Wave Interaction Applications

    NASA Astrophysics Data System (ADS)

    Peddini, S.; Mauritz, K.; Nikles, D.; Weston, J.

    2008-03-01

    Styrene containing triblock copolymers, namely poly(styrene-ethylene/butylene-styrene) (SEBS) and poly(styrene-butadiene-styrene)] (SBS), were selectively modified by attaching polar groups to facilitate the in-growth of an inorganic component. In case of SEBS, the styrene block was sulfonated, and in SBS, the butadiene block was hydroxylated. The extent of modification was determined by analytical and spectroscopic methods. This presentation shows the morphology and dynamical mechanical properties of both block copolymers before and after modification. Nanocomposites of these block copolymers were prepared by inclusion of magnetic metal oxides via an in-situ precipitation and self assembly processes and their morphology and dynamical mechanical properties were studied. Magnetic properties of these polymers filled with iron oxide nanoparticles were measured using an alternating gradient magnetometer (AGM) at room temperature to observe the magnetic hysteresis.

  5. Effects of cationic ammonium gemini surfactant on micellization of PEO-PPO-PEO triblock copolymers in aqueous solution.

    PubMed

    Wang, Ruijuan; Tang, Yongqiang; Wang, Yilin

    2014-03-01

    Effects of cationic ammonium gemini surfactant hexamethylene-1,6-bis(dodecyldimethylammonium bromide) (12-6-12) on the micellization of two triblock copolymers of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide), F127 (EO97PO69EO97) and P123 (EO20PO70EO20), have been studied in aqueous solution by differential scanning calorimetry (DSC), dynamic light scattering (DLS), isothermal titration calorimetry (ITC), and NMR techniques. Compared with traditional single-chain ionic surfactants, 12-6-12 has a stronger ability of lowering the CMT of the copolymers, which should be attributed to the stronger aggregation ability and lower critical micelle concentration of 12-6-12. The critical micelle temperature (CMT) of the two copolymers decreases as the 12-6-12 concentration increases and the ability of 12-6-12 in lowering the CMT of F127 is slightly stronger than that of P123. Moreover, a combination of ITC and DLS has shown that 12-6-12 binds to the copolymers at the temperatures from 16 to 40 °C. At the temperatures below the CMT of the copolymers, 12-6-12 micelles bind on single copolymer chains and induce the copolymers to initiate aggregation at very low 12-6-12 concentration. At the temperatures above the CMT of the copolymers, the interaction of 12-6-12 with both monomeric and micellar copolymers leads to the formation of the mixed copolymer/12-6-12 micelles, then the mixed micelles break into smaller mixed micelles, and finally free 12-6-12 micelles form with the increase of the 12-6-12 concentration. PMID:24528103

  6. Amphiphilic PEO-b-PBLG diblock and PBLG-b-PEO-b-PBLG triblock copolymer based nanoparticles: doxorubicin loading and in vitro evaluation.

    PubMed

    Kakkar, Dipti; Mazzaferro, Silvia; Thevenot, Julie; Schatz, Christophe; Bhatt, Anant; Dwarakanath, Bilikere S; Singh, Harpal; Mishra, Anil K; Lecommandoux, Sebastien

    2015-01-01

    Huisgen's 1,3-dipolar cycloaddition ("Click Chemestry") has been used to prepare amphiphilic PEO-b-PBLG diblock and PBLG-b-PEO-b-PBLG triblock copolymers as potential carriers of anticancer drugs. Spherical and flower shaped micelles (D ≈ 100 nm) were obtained from diblock and triblock copolymers respectively. DOX was effectively encapsulated up to 18 wt.% and 50-60% of it was steadily released from the micelles over a period of 7 d. Flow cytometry and fluorescence microscopy confirmed the effective intracellular uptake as well as the sustained release of DOX from micelles. These results suggest that the diblock as well as triblock copolymers are promising carriers for intra-cellular drug delivery. PMID:25557884

  7. Chirality Effect on Flory-Huggins Interaction Parameters in Polylactide-b-Poly(ethylene-co-1-butene)-b-Polylactide Triblock Copolymers

    NASA Astrophysics Data System (ADS)

    Cao, Weiqiang; Zhu, Lei; Rong, Lixia; Hsiao, Benjamin S.

    2009-03-01

    In this work, a set of well-defined polylactide-b-poly(ethylene-co-1-butene)-b-polylactide (PLA-PEB-PLA) triblock copolymers were synthesized by controlled ring-opening polymerization of corresponding lactide monomers (L-lactide and racemic mixture of D- and L-lactides) using Sn(Oct)2 as the catalyst. The volume fractions of PLA in the triblock copolymers were adjusted by tuning its molecular weight. The mesophase morphology and phase transitions in these triblock copolymers were studied by temperature-dependent small-angle X-ray scattering (SAXS). The Flory-Huggins interaction parameter χ between EB and lactide as a function of temperature were estimated from the order-disorder transition temperature (TODT) using the mean-field critical (χN)c values. The effects of PLA chirality on both Flory-Huggins interaction parameter and segmental lengths were investigated.

  8. Biodegradable nanoparticles of amphiphilic triblock copolymers based on poly(3-hydroxybutyrate) and poly(ethylene glycol) as drug carriers.

    PubMed

    Chen, Cheng; Yu, Chung Him; Cheng, Yin Chung; Yu, Peter H F; Cheung, Man Ken

    2006-09-01

    New amorphous amphiphilic triblock copolymers of poly(3-hydroxybutyrate)-poly(ethylene glycol)-poly(3-hydroxybutyrate) (PHB-PEG-PHB) were synthesized using the ring-opening copolymerization of beta-butyrolactone monomer. They were characterized by fluorescence, SEM and (1)H NMR. These triblock copolymers can form biodegradable nanoparticles with core-shell structure in aqueous solution. Comparing to the poly(ethylene oxide)-PHB-poly(ethylene oxide) (PEO-PHB-PEO) copolymers, these nanoparticles exhibited much smaller critical micelle concentrations and better drug loading properties, which indicated that the nanoparticles were very suitable for delivery carriers of hydrophobic drugs. The drug release profile monitored by fluorescence showed that the release of pyrene from the PHB-PEG-PHB nanoparticles exhibited the second-order exponential decay behavior. The initial biodegradation rate of the PHB-PEG-PHB nanoparticles was related to the enzyme amount, the initial concentrations of nanoparticle dispersions and the PHB block length. The biodegraded products detected by (1)H NMR contained 3HB monomer, dimer and minor trimer, which were safe to the body. PMID:16740306

  9. Reversible, voltage-activated formation of biomimetic membranes between triblock copolymer-coated aqueous droplets in good solvents.

    PubMed

    Tamaddoni, Nima; Taylor, Graham; Hepburn, Trevor; Michael Kilbey, S; Sarles, Stephen A

    2016-06-21

    Biomimetic membranes assembled from block copolymers attract considerable interest because they exhibit greater stability and longetivity compared to lipid bilayers, and some enable the reconstitution of functional transmembrane biomolecules. Yet to-date, block copolymer membranes have not been achieved using the droplet interface bilayer (DIB) method, which uniquely allows assembling single- and multi-membrane networks between water droplets in oil. Herein, we investigate the formation of poly(ethylene oxide)-b-poly(dimethyl siloxane)-b-poly(ethylene oxide) triblock copolymer-stabilized interfaces (CSIs) between polymer-coated aqueous droplets in solutions comprising combinations of decane, hexadecane and AR20 silicone oil. We demonstrate that triblock-coated droplets do not spontaneously adhere in these oils because all are thermodynamically good solvents for the hydrophobic PDMS middle block. However, thinned planar membranes are reversibly formed at the interface between droplets upon the application of a sufficient transmembrane voltage, which removes excess solvent from between droplets through electrocompression. At applied voltages above the threshold required to initiate membrane thinning, electrowetting causes the area of the CSI between droplets to increase while thickness remains constant; the CSI electrowetting response is similar to that encountered with lipid-based DIBs. In combination, these results reveal that stable membranes can be assembled in a manner that is completely reversible when an external pressure is used to overcome a barrier to adhesion caused by solvent-chain interactions, and they demonstrate new capability for connecting and disconnecting aqueous droplets via polymer-stabilized membranes. PMID:27174295

  10. Synthesis of zwitterionic polymer-based amphiphilic triblock copolymers by atom transfer radical polymerization for production of extremely stable nanoemlusions

    NASA Astrophysics Data System (ADS)

    Lee, Jin Yong; Kim, Ji Eun; Kim, Jin Woong

    2015-03-01

    In fields of soft matter, there have been growing interests in utilizing amphiphilic block copolymers due to their intriguing properties, such as surface activity as well as self-assembly. In this work, we synthesize a series of poly (2-(methacryloyloxy) ethyl phosphorylcholine)- b-poly (ɛ-caprolactone)- b-poly (2-(methacryloyloxy) ethyl phosphorylcholine) (PMPC- b-PCL- b-PMPC) triblock copolymers by using atom transfer radical polymerization (ATRP). We have a particular interest in using poly (2-(methacryloyloxy) ethyl phosphorylcholine) (PMPC) as a hydrophilic block, since it can have both electrostatic repulsion and steric repulsion in complex fluid systems. Assembling them at the oil-water interface by using the phase inversion method enables production of highly stable nanoemulsions. From the analyses of the crystallography and self-assembly behavior, we have found that the triblock copolymers assemble to form a flexible but tough molecular thin film at the interface, which is essential for the remarkable improvement in the emulsion stability.

  11. Hydrogels composed of cyclodextrin inclusion complexes with PLGA-PEG-PLGA triblock copolymers as drug delivery systems.

    PubMed

    Khodaverdi, Elham; Mirzazadeh Tekie, Farnaz Sadat; Hadizadeh, Farzin; Esmaeel, Haydar; Mohajeri, Seyed Ahmad; Sajadi Tabassi, Sayyed A; Zohuri, Gholamhossein

    2014-02-01

    Although conventional pharmaceuticals have many drug dosage forms on the market, the development of new therapeutic molecules and the low efficacy of instant release formulations for the treatment of some chronic diseases and specific conditions encourage scientists to invent different delivery systems. To this purpose, a supramolecular hydrogel consisting of the tri-block copolymer PLGA-PEGPLGA and α-cyclodextrin was fabricated for the first time and characterised in terms of rheological, morphological, and structural properties. Naltrexone hydrochloride and vitamin B12 were loaded, and their release profiles were determined. PMID:24234803

  12. Effect of nanoscale morphology on selective ethanol transport through block copolymer membranes

    Technology Transfer Automated Retrieval System (TEKTRAN)

    We report on the effect of block copolymer domain size on transport of liquid mixtures through the membranes by presenting pervaporation data of an 8 wt% ethanol/water mixture through A-B-A and B-A-B triblock copolymer membranes. The A-block was chosen to facilitate ethanol transport while the B-blo...

  13. Structural insights into the effect of cholinium-based ionic liquids on the critical micellization temperature of aqueous triblock copolymers.

    PubMed

    Khan, Imran; Umapathi, Reddicherla; Neves, Márcia C; Coutinho, João A P; Venkatesu, Pannuru

    2016-03-16

    Symmetrical poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) (PEG-PPG-PEG) triblock copolymer with 82.5% PEG as the hydrophilic end blocks, and PPG as the hydrophobic middle block, was chosen to study the effect of ionic liquids (ILs) on the critical micellization temperature (CMT) of block copolymers in aqueous solution. In the present work, cholinium-based ILs were chosen to explore the effect of the anions on the copolymer CMT using fluorescence spectroscopy, dynamic light scattering (DLS), viscosity (η), FT-IR spectroscopy, nuclear magnetic resonance (NMR), and direct visualization of the various self-assembled nanostructures by scanning electron microscopy (SEM). The result suggests that ILs have the ability to decrease the CMT of the aqueous copolymer solution which is dependent on the nature of the anions of the ILs. The present study reveals that the hydrophobic part PPG of the copolymer has more influence on this behavior than the PEG hydrophilic part. PMID:26700649

  14. Biodegradable poly(ether ester urethane)urea elastomers based on poly(ether ester) triblock copolymers and putrescine: synthesis, characterization and cytocompatibility.

    PubMed

    Guan, Jianjun; Sacks, Michael S; Beckman, Eric J; Wagner, William R

    2004-01-01

    Polymers with elastomeric mechanical properties, tunable biodegradation properties and cytocompatibility would be desirable for numerous biomedical applications. Toward this end a series of biodegradable poly(ether ester urethane)urea elastomers (PEEUUs) based on poly(ether ester) triblock copolymers were synthesized and characterized. Poly(ether ester) triblock copolymers were synthesized by ring-opening polymerization of epsilon-caprolactone with polyethylene glycol (PEG). PEEUUs were synthesized from these triblock copolymers and butyl diisocyanate, with putrescine as a chain extender. PEEUUs exhibited low glass transition temperatures and possessed tensile strengths ranging from 8 to 20MPa and breaking strains from 325% to 560%. Increasing PEG length or decreasing poly(caprolactone) length in the triblock segment increased PEEUU water absorption and biodegradation rate. Human umbilical vein endothelial cells cultured in a medium supplemented with PEEUU biodegradation solution suggested a lack of degradation product cytotoxicity. Endothelial cell adhesion to PEEUUs was less than 60% of tissue culture polystyrene and was inversely related to PEEUU hydrophilicity. Surface modification of PEEUUs with ammonia gas radio-frequency glow discharge and subsequent immobilization of the cell adhesion peptide Arg-Gly-Asp-Ser increased endothelial adhesion to a level equivalent to tissue culture polystyrene. These biodegradable PEEUUs thus possessed properties that would be amenable to applications where high strength and flexibility would be desirable and exhibited the potential for tuning with appropriate triblock segment selection and surface modification. PMID:14580912

  15. Challenges in Fabrication of Mesoporous Carbon Films with Ordered Cylindrical Pores via Phenolic Oligomer Self-Assembly with Triblock Copolymers

    SciTech Connect

    Song, Lingyan; Feng, Dan; Fredin, Nathaniel J.; Yager, Kevin G.; Jones, Ronald L.; Wu, Quanyan; Zhao, Dongyuan; Vogt, Bryan D.

    2010-06-22

    Mesoporous phenol formaldehyde (PF) polymer resin and carbon films are prepared by a solution self-assembly of PF oligomers with amphiphilic triblock copolymers. After thermopolymerization of the PF to cross-link the network, the films show an ordered morphology as determined by X-ray diffraction and grazing incidence small-angle X-ray scattering (GISAXS). Our results show that the amphiphilic triblock copolymer template greatly influences the stability of the final porous mesostructures. The pyrolysis of the two-dimensional (2-D) hexagonal films with p6mm symmetry templated by Pluronic F127 yields a disordered porous structure following the template removal. Conversely, films templated by Pluronic P123 can exhibit well-ordered cylindrical pores after the template removal, but the solution composition range to yield ordered cylindrical mesopores is significantly reduced (nearly 70%) for thin films in comparison to bulk powders. We propose two dominant difficulties in fabricating well-ordered cylindrical mesopores in films: first, the stress from contraction during the pyrolysis can lead to a collapse of the mesostructure if the wall thickness is insufficient, and second, the surface wetting behavior in thin films leads to a small compositional range.

  16. ABC triblock surface active block copolymer with grafted ethoxylated fluoroalkyl amphiphilic side chains for marine antifouling/fouling-release applications.

    PubMed

    Weinman, Craig J; Finlay, John A; Park, Daewon; Paik, Marvin Y; Krishnan, Sitaraman; Sundaram, Harihara S; Dimitriou, Michael; Sohn, Karen E; Callow, Maureen E; Callow, James A; Handlin, Dale L; Willis, Carl L; Kramer, Edward J; Ober, Christopher K

    2009-10-20

    An amphiphilic triblock surface-active block copolymer (SABC) possessing ethoxylated fluoroalkyl side chains was synthesized through the chemical modification of a polystyrene-block-poly(ethylene-ran-butylene)-block-polyisoprene polymer precursor. Bilayer coatings on glass slides consisting of a thin layer of the amphiphilic SABC spray coated on a thick layer of a polystyrene-block-poly(ethylene-ran-butylene)-block-polystyrene (SEBS) thermoplastic elastomer were prepared for biofouling assays with the green alga Ulva and the diatom Navicula. Dynamic water contact angle analysis and X-ray photoelectron spectroscopy (XPS) were used to characterize the surfaces. Additionally, the effect of the Young's modulus of the coating on the release properties of sporelings (young plants) of the green alga Ulva was examined through the use of two different SEBS thermoplastic elastomers possessing modulus values of an order of magnitude in difference. The amphiphilic SABC was found to reduce the settlement density of zoospores of Ulva as well as the strength of attachment of sporelings. The attachment strength of the sporelings was further reduced for the amphiphilic SABC on the "low"-modulus SEBS base layer. The weaker adhesion of diatoms, relative to a PDMS standard, further highlights the antifouling potential of this amphiphilic triblock hybrid copolymer. PMID:19821626

  17. From multi-responsive tri- and diblock copolymers to diblock-copolymer-decorated gold nanoparticles: the effect of architecture on micellization behaviors in aqueous solutions.

    PubMed

    Song, Lichun; Sun, Hui; Chen, Xiaolu; Han, Xia; Liu, Honglai

    2015-06-28

    This work reports on the aqueous stimuli-responsive behaviors of an ABA triblock copolymer, a BAB triblock copolymer, an AB diblock copolymer and citrate-based gold nanoparticles decorated with AB diblock copolymers (where A is the pH- and thermo-responsive poly[N,N-(dimethylamino)ethyl methacrylate] (PDMAEMA) and B is the thermo-responsive poly[2-(2-methoxyethoxy)ethyl methacrylate] (PMEO2MA)). The symmetric triblock polymers were synthesized via sequential atom transfer radical polymerization (ATRP) using a disulfide-functionalized initiator. Subsequently, the thiol-ended diblock copolymers were facilely obtained by reducing these triblock copolymers and were grafted onto gold nanoparticle (AuNP) surfaces via ligand exchange to yield stimuli-sensitive gold nanoparticles (Au@AB and Au@BA). The ABA and BAB triblock copolymers exhibited two-step thermo-induced aggregation behavior in water at a pH near the isoelectric point (IEP), which resulted in the formation of micelles after the first lower critical solution temperature (LCST) and large aggregates consisting of clustered micelles above the second LCST transition. The significant difference between the micelle sizes of the ABA and BAB copolymers, such that the micelle size of the BAB copolymer was smaller than that of the ABA copolymer although both had a similar unit composition, suggests a distinction between the micelle structures. The "branch" and "flower-like" micelles that are formed in the ABA and BAB aqueous solutions, respectively, ultimately governed the phase transition behaviors. The AB diblock copolymer exhibited similar micellization behavior and a micelle size roughly similar to that of the ABA triblock copolymer, although the chain length of the AB copolymer is only half that of the ABA copolymer. Both Au@PDMAEMA-PMEO2MA and Au@PMEO2MA-PDMAEMA showed similar dual LCST behaviors and pH-responsive behaviors in aqueous solutions without the addition of salt. A significant difference was observed

  18. Organic additive, 5-methylsalicylic acid induces spontaneous structural transformation of aqueous pluronic triblock copolymer solution: a spectroscopic investigation of interaction of curcumin with pluronic micellar and vesicular aggregates.

    PubMed

    Ghosh, Surajit; Kuchlyan, Jagannath; Banik, Debasis; Kundu, Niloy; Roy, Arpita; Banerjee, Chiranjib; Sarkar, Nilmoni

    2014-10-01

    This article presents the interaction of curcumin in the microenvironments provided by aggregation of pluronic triblock copolymer P123 into micellar and vesicular assemblies. The formation of vesicles using triblock copolymer P123 and 5-methylsalicylic acid (5 mS) has been successfully characterized by optical spectroscopy, light scattering measurement, and eventually microscopic techniques. Besides, to make a comparative study between the polymeric micelles, we have also investigated the photophysical changes of curcumin in F127 triblock copolymer micelles having variation in poly(ethylene oxide) (PPO) and poly(propylene oxide) (PEO) unit of polymer chain to that of P123. Time-dependent UV-vis measurement suggests that these polymer micelles are able to stabilize poorly water-soluble curcumin by suppressing the degradation rate in micellar nanocavity. However, experimental observations suggest that P123 micelles are more efficient than F127 to perturb excited state intramolecular proton transfer (ESIPT)-related nonradiative decay of curcumin. We also observed that rigid and confined microenvironment of P123/5 mS vesicles enhances emission intensity and lifetime of curcumin more compared to P123 micelles. All the observations suggest that modulation of photophysics of curcumin is responsible due to its interaction with poly(ethylene oxide) or poly(propylene oxide) unit of triblock copolymer. PMID:25192258

  19. Self-assembled supramolecular hydrogel based on PCL-PEG-PCL triblock copolymer and γ-cyclodextrin inclusion complex for sustained delivery of dexamethasone.

    PubMed

    Khodaverdi, Elham; Gharechahi, Marzieh; Alibolandi, Mona; Tekie, Farnaz Sadat Mirzazadeh; Khashyarmanesh, Bibi Zahra; Hadizadeh, Farzin

    2016-01-01

    In this study, thermosensitive, water-soluble, and biodegradable triblock copolymer PCL600-PEG6000-PCL600 was used to form supramolecular hydrogel (SMGel) by inclusion complexation with γ-cyclodextrin (γ-CD). The prepared SMGel was investigated as a carrier for sustained release of dexamethasone. The triblock copolymer PCL-PEG-PCL [where PCL = polycaprolactone, PEG = poly(ethylene glycol)] was synthesized by the ring-opening polymerization method using microwave irradiation. The polymerization reaction and the copolymer structures were evaluated by nuclear magnetic resonance (NMR) and gel permeation chromatography (GPC). SMGel was prepared in aqueous solution by blending an aqueous γ-CD solution with aqueous solution of PCL-PEG-PCL triblock copolymer at room temperature. The sol-to-gel transition time was measured at various concentrations of copolymer and γ-CD. As-prepared SMGel was used to prepare a sustained, controllable drug delivery system of dexamethasone sodium phosphate. The SMGel was also characterized in terms of rheological, morphological, and structural properties. Results obtained from proton nuclear magnetic resonance ( (1)H-NMR) and GPC demonstrated that microwave irradiation is a simple and reliable method for synthesis of PEG-PCL copolymer. The SMGel with excellent syringability was prepared by mixing of 20% wt γ-CD and 10% wt of copolymer within 4 s. The SMGel containing 10% wt copolymer, 20% wt γ-CD, and 0.5% or 0.1% wt dexamethasone released approximately 100% and 45% of drug over up to 23 days, respectively. It could be concluded that SMGel based on self-assembly of inclusion complexes between PCL-PEG-PCL copolymer and γ-CD could be used as a basis for injectable drug delivery systems that provide sustained and controlled release of macromolecular drugs such as dexamethasone. PMID:27051627

  20. Self-assembled supramolecular hydrogel based on PCL-PEG-PCL triblock copolymer and γ-cyclodextrin inclusion complex for sustained delivery of dexamethasone

    PubMed Central

    Khodaverdi, Elham; Gharechahi, Marzieh; Alibolandi, Mona; Tekie, Farnaz Sadat Mirzazadeh; Khashyarmanesh, Bibi Zahra; Hadizadeh, Farzin

    2016-01-01

    In this study, thermosensitive, water-soluble, and biodegradable triblock copolymer PCL600-PEG6000-PCL600 was used to form supramolecular hydrogel (SMGel) by inclusion complexation with γ-cyclodextrin (γ-CD). The prepared SMGel was investigated as a carrier for sustained release of dexamethasone. The triblock copolymer PCL-PEG-PCL [where PCL = polycaprolactone, PEG = poly(ethylene glycol)] was synthesized by the ring-opening polymerization method using microwave irradiation. The polymerization reaction and the copolymer structures were evaluated by nuclear magnetic resonance (NMR) and gel permeation chromatography (GPC). SMGel was prepared in aqueous solution by blending an aqueous γ-CD solution with aqueous solution of PCL-PEG-PCL triblock copolymer at room temperature. The sol-to-gel transition time was measured at various concentrations of copolymer and γ-CD. As-prepared SMGel was used to prepare a sustained, controllable drug delivery system of dexamethasone sodium phosphate. The SMGel was also characterized in terms of rheological, morphological, and structural properties. Results obtained from proton nuclear magnetic resonance ( 1H-NMR) and GPC demonstrated that microwave irradiation is a simple and reliable method for synthesis of PEG-PCL copolymer. The SMGel with excellent syringability was prepared by mixing of 20% wt γ-CD and 10% wt of copolymer within 4 s. The SMGel containing 10% wt copolymer, 20% wt γ-CD, and 0.5% or 0.1% wt dexamethasone released approximately 100% and 45% of drug over up to 23 days, respectively. It could be concluded that SMGel based on self-assembly of inclusion complexes between PCL-PEG-PCL copolymer and γ-CD could be used as a basis for injectable drug delivery systems that provide sustained and controlled release of macromolecular drugs such as dexamethasone. PMID:27051627

  1. Effect of interfaces on the melting of PEO confined in triblock PS-b-PEO-b-PS copolymers.

    PubMed

    Beaudoin, E; Phan, T N T; Robinet, M; Denoyel, R; Davidson, P; Bertin, D; Bouchet, R

    2013-08-27

    Block copolymers form nanostructures that have interesting physical properties because they combine, for a single compound, the complementary features brought by each block. However, in order to fully exploit these properties, the physical state of each kind of domain must be precisely controlled. In this work, triblock PS-b-PEO-b-PS copolymers consisting of a central poly(ethylene oxide) (PEO) block covalently bonded to polystyrene (PS) blocks were synthesized by Atom Transfer Radical Polymerization. Their morphology was investigated by X-ray scattering and TEM experiments whereas their thermodynamic behavior was characterized by DSC. A strong decrease of both the melting temperature and the degree of crystallinity of PEO, due to its confinement between the PS domains, was observed and analyzed with a modified Gibbs-Thomson equation, following the approaches used for fluids confined in porous media. The existence of an amorphous bound layer, a few nanometers thick, at the PEO/PS interface, that does not undergo any phase transition in the temperature range investigated, accounts for both the melting temperature depression and the decrease of crystallinity upon confinement. This interfacial layer may significantly affect the mechanical and transport properties of these block copolymers that find applications as solid polymer electrolytes in batteries for example. Moreover, the value obtained for the solid PEO/liquid PEO surface tension is lower than those previously published but is thermodynamically consistent with the surface tensions of polymers at the solid/vapor and liquid/vapor interfaces. PMID:23865710

  2. Effects of temperature and salt concentration on the structural and dynamical features in aqueous solutions of charged triblock copolymers.

    PubMed

    Kjøniksen, Anna-Lena; Zhu, Kaizheng; Behrens, Manja A; Pedersen, Jan Skov; Nyström, Bo

    2011-03-17

    Effects of temperature and salt addition on the association behavior in aqueous solutions of a series of charged thermosensitive methoxypoly(ethylene glycol)-block-poly(N-isopropylacrylamide)-block-poly(4-styrenesulfonic acid sodium) triblock copolymers (MPEG(45)-b-P(NIPAAM)(n)-b-P(SSS)(22)) with different lengths of the PNIPAAM block (n=17, 48, and 66) have been studied with the aid of turbidity, small-angle X-ray scattering (SAXS), and dynamic light scattering (DLS). Increasing temperature and salinity as well as longer PNIPAAM blocks are all factors that promote the formation of association structures. The SAXS data show that, for the copolymers with n=48 and n=66, increasing temperature and salt concentration induce interchain associations and higher values of the aggregation number, whereas no aggregation was observed for the copolymer with the shortest PNIPAAM chain. However, DLS measurements reveal the presence of larger association clusters. The cloud point is found to decrease with raising salinity and longer PNIPAAM block. The general picture that emerges is the delicate interplay between repulsive electrostatic forces and hydrophobic interactions and that this balance can be tuned by changing the temperature, salinity, and the length of the PNIPAAM block. PMID:21338148

  3. Model photo-responsive elastomers based on the self-assembly of side group liquid crystal triblock copolymers (Presentation Recording)

    NASA Astrophysics Data System (ADS)

    Kurji, Zuleikha; Kornfield, Julia A.; Kuzyk, Mark G.

    2015-10-01

    We report the synthesis of azobenzene-containing coil-liquid crystal-coil triblock copolymers that form uniform and highly reproducible elastomers by self-assembly. To serve as actuators to (non-invasively) steer a fiber optic, for example in deep brain stimulation, the polymers are designed to become monodomain "single liquid crystal" elastomers during the fiber-draw process and to have a large stress/strain response to stimulation with either light or heat. A fundamental scientific question that we seek to answer is how the interplay between the concentration of photoresponsive mesogens and the proximity to the nematic-isotropic transition governs the sensitivity of the material to stimuli. Specifically, a matched pair of polymers, one with ~5% azobenzene-containing side groups (~95% cyanobiphenyl side groups) and the other with 100% cyanobiphenyl side groups were synthesized from identical triblock pre-polymers (with polystyerene end blocks and 1,2-polybutadiene midblocks). These can be blended in various ratios to prepare a series of elastomers that are precisely matched in terms of the backbone length between physical crosslinks (because each polymer is derived from the same pre-polymer), while differing in % azobenzene side groups, allowing the effect of concentration of photoresponsive groups to be unambiguously determined.

  4. Kinetics of Transition between HEX and Lamellar Phases in a triblock copolymer solution in a selective solvent.

    NASA Astrophysics Data System (ADS)

    Liu, Yongsheng; Bansil, Rama; Steinhart, Milos

    2006-03-01

    Synchrotron based time-resolved small angle x-ray scattering (SAXS), was used to study the kinetics of ordering transition (OOT) between cylindrical micelles in HEX phase and lamellar (LAM) phase in a 0.4 (w/v) solution of a triblock of polystyrene (PS) and poly(ethylene-co-butylene) (PEB), SEBS (PS-PEB-PS) copolymer in Dibutyl Phthalate (DBP), a selective solvent for the PS block. From a temperature ramp experiment the OOT was identified at about 137C and an ODT above 160 C. Several temperature jump experiments from HEX to LAM and the reverse were performed over the temperature range of 110-155C. Detailed analysis of the time evolution of the intensities of the Bragg peaks to follow the kinetics of the transition between HEX and LAM phases will be presented. A model to explain the transition mechanism will be discussed. This research was supported by NSF-DMR.

  5. Mechanical behaviour׳s evolution of a PLA-b-PEG-b-PLA triblock copolymer during hydrolytic degradation.

    PubMed

    Breche, Q; Chagnon, G; Machado, G; Girard, E; Nottelet, B; Garric, X; Favier, D

    2016-07-01

    PLA-b-PEG-b-PLA is a biodegradable triblock copolymer that presents both the mechanical properties of PLA and the hydrophilicity of PEG. In this paper, physical and mechanical properties of PLA-b-PEG-b-PLA are studied during in vitro degradation. The degradation process leads to a mass loss, a decrease of number average molecular weight and an increase of dispersity index. Mechanical experiments are made in a specific experimental set-up designed to create an environment close to in vivo conditions. The viscoelastic behaviour of the material is studied during the degradation. Finally, the mechanical behaviour is modelled with a linear viscoelastic model. A degradation variable is defined and included in the model to describe the hydrolytic degradation. This variable is linked to physical parameters of the macromolecular polymer network. The model allows us to describe weak deformations but become less accurate for larger deformations. The abilities and limits of the model are discussed. PMID:26919565

  6. Enhanced Dispersion and Stability of Petroleum Coke Water Slurries via Triblock Copolymer and Xanthan Gum: Rheological and Adsorption Studies.

    PubMed

    Williams, Brian P; Pinge, Shubham; Kim, Young-Kwang; Kim, Juhoe; Joo, Yong Lak

    2015-08-25

    The rheology of petroleum coke (petcoke) water slurries was investigated with a variety of nonionic and anionic dispersants including poly(ethylene oxide) (PEO)-b-poly(propylene oxide) (PPO)-b-PEO triblock copolymers (trade name: Pluronic, BASF), poly(vinyl alcohol) (PVA), polyvinylpyrrolidone (PVP), poly(ethylene oxide) (PEO), poly(carboxylate acid) (PCA), sodium lignosulfonate (SLS), and poly(acrylic acid) (PAA). Each effective dispersant system shared very similar rheological behavior to the others when examined at the same volume fraction from its maximum petcoke loading. Triblock copolymer, Pluronic F127 (F127), was found to be the best dispersant by comparing the maximum petcoke loading for each dispersant. The yield stress was measured as a function of petcoke loading and dispersant concentration for F127, and a minimum dispersant concentration was observed. An adsorption isotherm and atomic force microscopy (AFM) images reveal that this effective dispersion of petcoke particles by F127 is due to the formation of a uniform monolayer of brushes where hydrophobic PPO domains of F127 adhere to the petcoke surface, while hydrophilic PEO tails fill the gap between petcoke particles. F127 was then compared to other Pluronics with various PEO and PPO chain lengths, and the effects of surface and dispersant hydrophilicity were examined. Finally, xanthan gum (XG) was tested as a stabilizer in combination with F127 for potential industrial application, and F127 appears to break the XG aggregates into smaller aggregates through competitive adsorption, leading to an excellent degree of dispersion but the reduced stability of petcoke slurries. PMID:26245829

  7. Growth of ordered silver nanoparticles in silica film mesostructured with a triblock copolymer PEO-PPO-PEO

    SciTech Connect

    Bois, L.; Chassagneux, F.; Parola, S.; Bessueille, F.; Battie, Y.; Destouches, N.; Boukenter, A.; Moncoffre, N.

    2009-07-15

    Elaboration of mesostructured silica films with a triblock copolymer polyethylene oxide-polypropylene oxide-polyethylene oxide, (PEO-PPO-PEO) and controlled growth of silver nanoparticles in the mesostructure are described. The films are characterized using UV-visible optical absorption spectroscopy, TEM, AFM, SEM, X-ray diffraction (XRD) and Rutherford backscattering spectrometry (RBS). Organized arrays of spherical silver nanoparticles with diameter between 5 and 8 nm have been obtained by NaBH{sub 4} reduction. The size and the repartition of silver nanoparticles are controlled by the film mesostructure. The localization of silver nanoparticles exclusively in the upper-side part of the silica-block copolymer film is evidenced by RBS experiment. On the other hand, by using a thermal method, 40 nm long silver sticks can be obtained, by diffusion and coalescence of spherical particles in the silica-block copolymer layer. In this case, migration of silver particles toward the glass substrate-film interface is shown by the RBS experiment. - Graphical abstract: Growth of silver nanoparticles in a mesostructured block copolymer F127-silica film is performed either by a chemical route involving NaBH{sub 4} reduction or by a thermal method. An array of spherical silver nanoparticles with 10 nm diameter on the upper-side of the mesostructured film or silver sticks long of 40 nm with a preferential orientation are obtained according to the method used. a: TEM image of the Fag5SiNB sample illustrating the silver nanoparticles array obtained by the chemical process; b: HR-TEM image of the Fag20Sid2 sample illustrating the silver nanosticks obtained by the thermal process.

  8. siRNA delivery from triblock copolymer micelles with spatially-ordered compartments of PEG shell, siRNA-loaded intermediate layer, and hydrophobic core.

    PubMed

    Kim, Hyun Jin; Miyata, Kanjiro; Nomoto, Takahiro; Zheng, Meng; Kim, Ahram; Liu, Xueying; Cabral, Horacio; Christie, R James; Nishiyama, Nobuhiro; Kataoka, Kazunori

    2014-05-01

    Hydrophobized block copolymers have widely been developed for construction of polymeric micelles for stable delivery of nucleic acids as well as anticancer drugs. Herein, we elaborated an A-B-C type of triblock copolymer featuring shell-forming A-segment, nucleic acid-loading B-segment, and stable core-forming C-segment, directed toward construction of a three-layered polymeric micelle as a small interfering RNA (siRNA) vehicle. The triblock copolymer was prepared with nonionic and hydrophilic poly(ethylene glycol) (PEG), cationic poly(l-lysine) (PLys), and poly{N-[N-(2-aminoethyl)-2-aminoethyl]aspartamide} [PAsp(DET)] bearing a hydrophobic dimethoxy nitrobenzyl ester (DN) moiety in the side chain [PEG-PLys-PAsp(DET-DN)]. The resulting triblock copolymers spontaneously formed sub-100 nm-sized polymeric micelles with a hydrophobic PAsp(DET-DN) core as well as PEG shell in an aqueous solution. This micelle was able to incorporate siRNA into the intermediate PLys layer, associated with slightly reduced size and a narrow size distribution. The triblock copolymer micelles (TCMs) stably encapsulated siRNA in serum-containing medium, whereas randomly hydrophobized triblock copolymer [PEG-PLys(DN)-PAsp(DET-DN)] control micelles (RCMs) gradually released siRNA with time and non-PEGylated diblock copolymer [PLys-PAsp(DET-DN)] control micelles (DCMs) immediately formed large aggregates. The TCMs thus induced appreciably stronger sequence-specific gene silencing in cultured cancer cells, compared to those control micelles. The siRNA delivery with TCMs was further examined in terms of cellular uptake and intracellular trafficking. The flow cytometric analysis revealed that the cellular uptake of TCMs was more efficient than that of RCMs, but less efficient than that of DCMs. The intracellular trafficking study using confocal laser scanning microscopy combined with fluorescence resonance energy transfer (FRET) revealed that the TCMs could readily release the siRNA payload

  9. Synthesis, self-assembly, and pH-responsive behavior of (photo-crosslinked) star amphiphilic triblock copolymer.

    PubMed

    Bian, Qingqing; Xiao, Yan; Zhou, Chen; Lang, Meidong

    2013-02-15

    Conventional polymeric micelles employed as drug carriers suffer from the drawback of disaggregation when diluted into body fluids, giving rise to premature release of drugs. In this work, cinnamate was chosen as a crosslinker to overcome this issue and regulate pH response. A series of photo-crosslinkable star amphiphilic triblock copolymers, star poly(ε-caprolactone)-b-poly(2-cinnamoyloxyethyl methacrylate)-b-poly(2-(dimethylamino)ethyl methacrylate) (SPCL-b-PCEMA-b-PDMAEMA), were prepared by combination of stepwise reversible addition-fragment chain transfer (RAFT) polymerization and carbodiimide-mediated coupling reaction. These star amphiphilic copolymers could self-assemble into core-shell-corona micelles. Facile photo crosslinking of the micelles was carried out via UV irradiation. The crosslinked micelles showed an improved stability determined by critical micelle concentration (CMC). The degree of photo crosslinking was easily regulated by tuning UV irradiation time, and the hydrodynamic diameters (D(h)) decreased with increasing degree of photo crosslinking. The pH responses of micelles were investigated by dynamic light scattering (DLS), indicating pH-induced swelling-shrinking behavior. For photo-crosslinked micelle, its capability of swelling-shrinking weakened with increasing crosslinking degree, suggesting that pH response was controlled by crosslinking density. This novel photo-crosslinked micelle system with adjustable pH response was expected to have potential as drug carriers for controlled release. PMID:23127872

  10. Triblock Copolymers with Grafted Fluorine-Free Amphiphilic Non-Ionic Side Chains for Antifouling and Fouling-Release Applications

    SciTech Connect

    Y Cho; H Sundaram; C Weinman; M Paik; M Dimitriou; J Finlay; M Callow; J Callow; E Kramer; C Ober

    2011-12-31

    Fluorine-free, amphiphilic, nonionic surface active block copolymers (SABCs) were synthesized through chemical modification of a polystyrene-block-poly(ethylene-ran-butylene)-block-polyisoprene triblock copolymer precursor with selected amphiphilic nonionic Brij and other surfactants. Amphiphilicity was imparted by a hydrophobic aliphatic group combined with a hydrophilic poly(ethylene glycol) (PEG) group-containing moiety. The surfaces were characterized by dynamic water contact angle, atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), and near edge X-ray absorption fine structure (NEXAFS) analysis. In biofouling assays, settlement (attachment) of both spores of the green alga Ulva and cells of the diatom Navicula on SABCs modified with Brij nonionic side chains was significantly reduced relative to a PDMS standard, with a nonionic surfactant combining a PEG group and an aliphatic moiety demonstrating the best performance. Additionally, a fouling-release assay using sporelings (young plants) of Ulva and Navicula suggested that the SABC derived from nonionic Brij side chains also out-performed PDMS as a fouling-release material. Good antifouling and fouling-release properties were not demonstrated for the other two amphiphilic surfaces derived from silicone and aromatic group containing nonionic surfactants included in this study. The results suggest that small differences in chemical surface functionality impart more significant changes with respect to the antifouling settlement and fouling-release performance of materials than overall wettability behavior.

  11. Synthesis, morphology, and sensory applications of multifunctional rod-coil-coil triblock copolymers and their electrospun nanofibers.

    PubMed

    Chiu, Yu-Cheng; Chen, Yougen; Kuo, Chi-Ching; Tung, Shih-Huang; Kakuchi, Toyoji; Chen, Wen-Chang

    2012-07-25

    We report the synthesis, morphology, and applications of conjugated rod-coil-coil triblock copolymers, polyfluorene-block-poly(N-isopropylacrylamide)-block-poly(N-methylolacrylamide) (PF-b-PNIPAAm-b-PNMA), prepared by atom transfer radical polymerization first and followed by click coupling reaction. The blocks of PF, PNIPAAm, and PNMA were designed for fluorescent probing, hydrophilic thermo-responsive and chemically cross-linking, respectively. In the following, the electrospun (ES) nanofibers of PF-b-PNIPAAm-b-PNMA were prepared in pure water using a single-capillary spinneret. The SAXS and TEM results suggested the lamellar structure of the PF-b-PNIPAAm-b-PNMA along the fiber axis. These obtained nanofibers showed outstanding wettability and dimension stability in the aqueous solution, and resulted in a reversible on/off transition on photoluminescence as the temperatures varied. Furthermore, the high surface/volume ratio of the ES nanofibers efficiently enhanced the temperature-sensitivity and responsive speed compared to those of the drop-cast film. The results indicated that the ES nanofibers of the conjugated rod-coil block copolymers would have potential applications for multifunctional sensory devices. PMID:22712723

  12. Thermally Switchable Thin Films of an ABC Triblock Copolymer of Poly(n-butyl methacrylate)-poly(methyl methacrylate)-poly(2-fluoroethyl methacrylate)

    SciTech Connect

    Zhang, Shanju; Liu, Zhan; Bucknall, David G.; He, Lihong; Hong, Kunlun; Mays, Jimmy; Allen, Mark

    2011-01-01

    The thermo-responsive behavior of polymer films consisting of novel linear triblock copolymers of poly(n-butyl methacrylate)-poly(methyl methacrylate)-poly(2-fluoroethyl methacrylate) (PnBuMA-PMMA-P2FEMA) are reported using differential scanning calorimetry (DSC), atomic forcing microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and contacting angle (CA) measurements. The surface morphology, wettability and chemical structure of thin films of these triblock copolymers on silicon wafers as a function of temperature have been investigated. It has been shown that the wettability of the films is thermally switchable. Detailed structural analysis shows that thermo-responsive surface composition changes are produced. The underlying mechanism of the thermoresponsive behavior is discussed.

  13. Triblock Copolymer Nanovesicles for pH-Responsive Targeted Delivery and Controlled Release of siRNA to Cancer Cells.

    PubMed

    Gallon, Elena; Matini, Teresa; Sasso, Luana; Mantovani, Giuseppe; Armiñan de Benito, Ana; Sanchis, Joaquin; Caliceti, Paolo; Alexander, Cameron; Vicent, Maria J; Salmaso, Stefano

    2015-07-13

    New pH-responsive polymersomes for active anticancer oligonucleotide delivery were prepared from triblock copolymers. The delivery systems were formed by two terminal hydrophilic blocks, PEG and polyglycerolmethacrylate (poly-GMA), and a central weakly basic block, polyimidazole-hexyl methacrylate (poly-ImHeMA), which can complex with oligonucleotides and control vesicle formation/disassembly via pH variations. Targeted polymersomes were prepared by mixing folate-derivatized and underivatized copolymers. At pH 5, ds-DNA was found to complex with the pH-responsive copolymers at a N/P molar ratio above ∼2:1, which assisted the encapsulation of ds-DNA in the polymersomes, while low association was observed at pH 7.4. Cytotoxicity studies performed on folate receptor overexpressing KB and B16-F10 cells and low folate receptor expressing MCF-7 cells showed high tolerance of the polymersomes at up to 3 mg/mL concentration. Studies performed with red blood cells showed that at pH 5.0 the polymersomes have endosomolytic properties. Cytofluorimetric studies showed a 5.5-fold higher uptake of ds-DNA loaded folate-functional polymersomes in KB cells compared to nontargeted polymersomes. In addition, ds-DNA was found to be localized both in the nucleus and in the cytosol. The incubation of luciferase transfected B16-F10 cells with targeted polymersomes loaded with luciferase and Hsp90 expression silencing siRNAs yielded 31 and 23% knockdown in target protein expression, respectively. PMID:25988940

  14. Directed Self-Assembly of Triblock Copolymer on Chemical Patterns for Sub-10-nm Nanofabrication via Solvent Annealing.

    PubMed

    Xiong, Shisheng; Wan, Lei; Ishida, Yoshihito; Chapuis, Yves-Andre; Craig, Gordon S W; Ruiz, Ricardo; Nealey, Paul F

    2016-08-23

    Directed self-assembly (DSA) of block copolymers (BCPs) is a leading strategy to pattern at sublithographic resolution in the technology roadmap for semiconductors and is the only known solution to fabricate nanoimprint templates for the production of bit pattern media. While great progress has been made to implement block copolymer lithography with features in the range of 10-20 nm, patterning solutions below 10 nm are still not mature. Many BCP systems self-assemble at this length scale, but challenges remain in simultaneously tuning the interfacial energy atop the film to control the orientation of BCP domains, designing materials, templates, and processes for ultra-high-density DSA, and establishing a robust pattern transfer strategy. Among the various solutions to achieve domains that are perpendicular to the substrate, solvent annealing is advantageous because it is a versatile method that can be applied to a diversity of materials. Here we report a DSA process based on chemical contrast templates and solvent annealing to fabricate 8 nm features on a 16 nm pitch. To make this possible, a number of innovations were brought in concert with a common platform: (1) assembling the BCP in the phase-separated, solvated state, (2) identifying a larger process window for solvated triblock vs diblock BCPs as a function of solvent volume fraction, (3) employing templates for sub-10-nm BCP systems accessible by lithography, and (4) integrating a robust pattern transfer strategy by vapor infiltration of organometallic precursors for selective metal oxide synthesis to prepare an inorganic hard mask. PMID:27482932

  15. Ultrafast photoinduced electron transfer in the micelle and the gel phase of a PEO-PPO-PEO triblock copolymer

    SciTech Connect

    Mandal, Ujjwal; Ghosh, Subhadip; Dey, Shantanu; Adhikari, Aniruddha; Bhattacharyya, Kankan

    2008-04-28

    Ultrafast photoinduced electron transfer (PET) from N,N-dimethylaniline (DMA) to coumarin dyes is studied in the micelle and the gel phase of a triblock copolymer, (PEO){sub 20}-(PPO){sub 70}-(PEO){sub 20} (Pluronic P123) by picosecond and femtosecond emission spectroscopies. The rate of PET in a P123 micelle and gel is found to be nonexponential and faster than the slow components of solvation dynamics. In a P123 micelle and gel, PET occurs on multiple time scales ranging from a subpicosecond time scale to a few nanoseconds. In the gel phase, the highest rate constant (9.3x10{sup 9} M{sup -1} s{sup -1}) of ET for C152 is about two times higher than that (3.8x10{sup 9} M{sup -1} s{sup -1}) observed in micelle phase. The ultrafast components of electron transfer (ET) exhibits a bell shaped dependence with the free energy change which is similar to the Marcus inversion. Possible reasons for slower PET in P123 micelle compared to other micelles and relative to P123 gel are discussed.

  16. Habit modification of 5,6-dimethyl-1H-benzotriazole in the presence of nonionic triblock copolymers

    NASA Astrophysics Data System (ADS)

    Molloy, Meghan R.; Partch, Richard

    2013-06-01

    The effects of different nonionic surfactants on the habit modification of 5,6-dimethyl-1H-benzotriazole (5,6-DMBTA) were evaluated. Three different triblock copolymers, Pluronic® F-127, Pluronic® L44NF, and Pluronic® P-123 were selected as nonionic surfactants. Crystallization was achieved by pH adjustment in an aqueous solution with or without the presence of surfactants. Pluronic® P-123 was found to have the most dramatic effect in changing the crystal habit of 5,6-DMBTA from needles to platelets. The surfactant with a smaller hydrophobic block, Pluronic® L44NF, or the one with a larger hydrophilic block, Pluronic® F-127, yield only shorter needles for the crystal habit. This indicates that both blocks of a surfactant backbone have an impact on habit modification. Analytical data confirmed that none of the three surfactants were incorporated into the crystal lattice of 5,6-DMBTA after crystallization. All the habit modified crystals have the same crystal form as the original 5,6-DMBTA crystal sample, indicating that solely a habit modifying process took place.

  17. Amphiphilic triblock copolymer-assisted synthesis of hierarchical NiCo nanoflowers by homogeneous nucleation in liquid polyols

    NASA Astrophysics Data System (ADS)

    Arief, Injamamul; Mukhopadhyay, P. K.

    2014-12-01

    Rose-like NiCo nanoflowers were synthesized by homogeneous, one-pot polyol reduction of Ni and Co-acetates in presence of an amphiphilic triblock copolymer and KOH. 1,2-propanediol was used as solvent-cum-reducing agent as no external reducing agent was found to be necessary in this process. Detailed x-ray diffraction and morphological characterizations confirmed formation of fcc hierarchical NiCo nanoflowers containing 2D nanosheet-like subunits (thickness of about 30 nm) with an average diameter of ~700 nm. Amphiphilic polymer played a pivotal role in the growth of nanorose as it favored a preferential growth of nanocrystals along a particular crystal plane as was observed in transmission electron microscopy. Effects of other parameters like use of hydrophilic polymer, surfactants, ratio of initial metal concentrations, choice of polyol media and concentration of KOH on the morphology of nanoflowers were also investigated. Room temperature magnetic studies revealed higher saturation magnetization and low coercivity (108.6 emu/g and 78.4 Oe) of nanorose. Based on LaMer model, a kinetically-controlled growth mechanism for the formation of NiCo nanorose is also proposed.

  18. Experimental and theoretical studies on inhibition of mild steel corrosion by some synthesized polyurethane tri-block co-polymers

    PubMed Central

    Kumar, Sudershan; Vashisht, Hemlata; Olasunkanmi, Lukman O.; Bahadur, Indra; Verma, Hemant; Singh, Gurmeet; Obot, Ime B.; Ebenso, Eno E.

    2016-01-01

    Polyurethane based tri-block copolymers namely poly(N-vinylpyrrolidone)-b-polyurethane-b-poly(N-vinylpyrrolidone) (PNVP-PU) and poly(dimethylaminoethylmethacrylate)-b-polyurethane-b-poly(dimethylaminoethylmethacrylate) (PDMAEMA-PU) were synthesized through atom transfer radical polymerization (ATRP) mechanism. The synthesized polymers were characterized using nuclear magnetic resonance (NMR) spectroscopy and gel permeation chromatography (GPC) methods. The corrosion inhibition performances of the compounds were investigated on mild steel (MS) in 0.5 M H2SO4 medium using electrochemical measurements, surface analysis, quantum chemical calculations and molecular dynamic simulations (MDS). Potentiodynamic polarization (PDP) measurements revealed that the polymers are mixed-type corrosion inhibitors. Electrochemical impedance spectroscopy (EIS) measurements showed that the polymers inhibit MS corrosion by adsorbing on MS surface to form pseudo-capacitive interface. The inhibitive effects of the polymers increase with increasing concentration and decrease with increasing temperature. The adsorption of both the polymers on MS surface obey the Langmuir adsorption isotherm and involves both physisorption and chemisorption mechanisms. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) analyses showed that the polymers formed protective film on MS surface and shield it from direct acid attack. Quantum chemical calculations and molecular dynamic simulations studies corroborate experimental results. PMID:27515383

  19. Morphology and Phase Transitions in Styrene-Butadiene-Styrene Triblock Copolymer Grafted with Isobutyl-Substituted Polyhedral Oligomeric Silsesquioxanes

    SciTech Connect

    Drazkowski, Daniel B.; Lee, Andre; Haddad, Timothy S.

    2008-10-03

    Two symmetric triblock polystyrene-butadiene-polystyrene (SBS) copolymers with different initial morphologies were grafted with varying amounts of isobutyl-substituted polyhedral oligomeric silsesquioxane (POSS) molecules. The POSS octamers, R{prime}R{sub 7}Si{sub 8}O{sub 12}, were designed to contain a single silane functional group, R{prime}, which was used to graft onto the dangling 1,2-butadienes in the polybutadiene block and seven identical organic groups, R = isobutyl (iBu). Morphology and phase transitions of these iBu-POSS-modified SBS were investigated using small-angle X-ray scattering and rheological methods. It was observed that when iBu-POSS was grafted to the butadiene segment, the long-range and local order of the morphology were preserved, and the d-spacing showed a small, systematic increase with increasing POSS content. These observations suggest that grafted iBu-POSS were well-distributed within the butadiene domains and did not interact with the styrene domains; effectively, grafting of iBu-POSS to butadiene did not affect the segregation between butadiene and styrene domains. However, addition of iBu-POSS reduces the overall polystyrene volume. Consequently, from a morphology standpoint, this modification effectively shifts the phase diagram to lower styrene content. This was supported with SAXS and transition temperatures measurements made from the different host morphologies.

  20. Experimental and theoretical studies on inhibition of mild steel corrosion by some synthesized polyurethane tri-block co-polymers.

    PubMed

    Kumar, Sudershan; Vashisht, Hemlata; Olasunkanmi, Lukman O; Bahadur, Indra; Verma, Hemant; Singh, Gurmeet; Obot, Ime B; Ebenso, Eno E

    2016-01-01

    Polyurethane based tri-block copolymers namely poly(N-vinylpyrrolidone)-b-polyurethane-b-poly(N-vinylpyrrolidone) (PNVP-PU) and poly(dimethylaminoethylmethacrylate)-b-polyurethane-b-poly(dimethylaminoethylmethacrylate) (PDMAEMA-PU) were synthesized through atom transfer radical polymerization (ATRP) mechanism. The synthesized polymers were characterized using nuclear magnetic resonance (NMR) spectroscopy and gel permeation chromatography (GPC) methods. The corrosion inhibition performances of the compounds were investigated on mild steel (MS) in 0.5 M H2SO4 medium using electrochemical measurements, surface analysis, quantum chemical calculations and molecular dynamic simulations (MDS). Potentiodynamic polarization (PDP) measurements revealed that the polymers are mixed-type corrosion inhibitors. Electrochemical impedance spectroscopy (EIS) measurements showed that the polymers inhibit MS corrosion by adsorbing on MS surface to form pseudo-capacitive interface. The inhibitive effects of the polymers increase with increasing concentration and decrease with increasing temperature. The adsorption of both the polymers on MS surface obey the Langmuir adsorption isotherm and involves both physisorption and chemisorption mechanisms. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) analyses showed that the polymers formed protective film on MS surface and shield it from direct acid attack. Quantum chemical calculations and molecular dynamic simulations studies corroborate experimental results. PMID:27515383

  1. Solvent-Driven Formation of Worm-Like Micelles Assembled from a CO₂-Responsive Triblock Copolymer.

    PubMed

    Liu, Hanbin; Wang, Wei; Yin, Hongyao; Feng, Yujun

    2015-08-18

    Polymer worm-like micelles (WLMs) are difficult to target due to the narrow composition window. In this work, we report polymer WLMs self-assembled from a linear ABC triblock copolymer consisting of an intermediate fluorinated block of poly(2,2,3,4,4,4-hexafluorobutyl methacrylate) (F), a hydrophilic segment of poly(ethylene oxide) (O) and a CO2-responsive flank of poly(2-(diethylamino)ethyl methacrylate) (E). In the mixed solvent of water and ethanol, the polymer aggregates evolve from spheres to short rods, then long cylinders and finally WLMs when the volume ratio of water increases from 0 to 50%. Upon the stimulus of CO2, the E block is protonated, thus transforms from hydrophobic to hydrophilic. However, the WLMs just partially return back to spheres even the protonation degree of E block is up to 95%. The closely packed arrangement of fluorinated block caused by the increasing interfacial tension of the fluorinated blocks and solvent could account for the formation of WLMs and its shape alternation under CO2 stimulus. PMID:26192273

  2. Fluorinated amphiphilic polymers and their blends for fouling-release applications: the benefits of a triblock copolymer surface.

    PubMed

    Sundaram, Harihara S; Cho, Youngjin; Dimitriou, Michael D; Finlay, John A; Cone, Gemma; Williams, Sam; Handlin, Dale; Gatto, Joseph; Callow, Maureen E; Callow, James A; Kramer, Edward J; Ober, Christopher K

    2011-09-01

    Surface active triblock copolymers (SABC) with mixed polyethylene glycol (PEG) and two different semifluorinated alcohol side chains, one longer than the other, were blended with a soft thermoplastic elastomer (TPE), polystyrene-block-poly(ethylene-ran-butylene)-block-polystyrene (SEBS). The surface composition of these blends was probed by X-ray photoelectron spectroscopy (XPS) and near edge X-ray absorption fine structure (NEXAFS) spectroscopy. The surface reconstruction of the coatings in water was monitored qualitatively by dynamic water contact angles in air as well as air bubble contact angle measurements in water. By blending the SABC with SEBS, we minimize the amount of the SABC used while achieving a surface that is not greatly different in composition from the pure SABC. The 15 wt % blends of the SABC with long fluoroalkyl side chains showed a composition close to that of the pure SABC while the SABC with shorter perfluoroakyl side chains did not. These differences in surface composition were reflected in the fouling-release performance of the blends for the algae, Ulva and Navicula. PMID:21830813

  3. Thermodynamic and kinetic control of charged, amphiphilic triblock copolymer assembly via interaction with organic counterions in solvent mixtures

    NASA Astrophysics Data System (ADS)

    Cui, Honggang

    2007-12-01

    Amphiphilic block copolymers, consisting of at least two types of monomers with different affinity to the dissolving solvent(s), have been recognized as a molecular building unit for their chemical tunability and design flexibility. Amphiphilic block copolymers with a chargeable block have structural features of polyelectrolytes, block copolymers and surfactants. The combination of these different features offers great flexibility for developing novel assembled morphologies at the nanoscale and outstanding ability to control and manipulate those morphologies. The nanostructures, formed from the spontaneous association of amphiphilic block copolymer in selective solvents, show promise for applications in nanotechnology and pharmaceuticals, including drug delivery, tissue engineering and bio-imaging. A basic knowledge of their modes of self-assembly and their correspondence to application-related properties is just now being developed and poses a considerable scientific challenge. The goal of this dissertation is to investigate the associative behavior of charged, amphiphilic block copolymers in solvent mixtures while in the presence of organic counterions. Self-assembly of poly (acrylic acid)- block-poly (methyl acrylate)-block-polystyrene (PAA- b-PMA-b-PS) triblock copolymers produces nanodomains in THF/water solution specifically through the interaction with organic counterions (polyamines). These assembled structures can include classic micelles (spheres, cylinders and vesicles), but, more importantly, include non-classic micelles (disks, toroids, branched micelles and segmented micelles). Each micelle structure is stable and reproducible at different assembly conditions. The assembled micellar structures depend on not only solution components (thermodynamics) but also mixing procedure and consequent self-assembly pathway (kinetics). The key factors that determine the thermodynamic interactions that partially define the assembled structures and the kinetic

  4. ROP and ATRP Fabricated Dual Targeted Redox Sensitive Polymersomes Based on pPEGMA-PCL-ss-PCL-pPEGMA Triblock Copolymers for Breast Cancer Therapeutics.

    PubMed

    Kumar, Arun; Lale, Shantanu V; Mahajan, Shveta; Choudhary, Veena; Koul, Veena

    2015-05-01

    To minimize cardiotoxicity and to increase the bioavailability of doxorubicin, polymersomes based on redox sensitive amphiphilic triblock copolymer poly(polyethylene glycol methacrylate)-poly(caprolactone)-s-s-poly(caprolactone)-poly(polyethylene glycol methacrylate) (pPEGMA-PCL-ss-PCL-pPEGMA) with disulfide linkage were designed and developed. The polymers were synthesized by ring opening polymerization (ROP) of ε-caprolactone followed by atom transfer radical polymerization (ATRP) of PEGMA. The triblock copolymers demonstrated various types of nanoparticle morphologies by varying hydrophobic/hydrophilic content of polymer blocks, with PEGMA content of ∼18% in the triblock copolymer leading to the formation of polymersomes in the size range ∼150 nm. High doxorubicin loading content of ∼21% was achieved in the polymersomes. Disulfide linkages were incorporated in the polymeric backbone to facilitate degradation of the nanoparticles by the intracellular tripeptide glutathione (GSH), leading to intracellular drug release. Release studies showed ∼59% drug release in pH 5.5 in the presence of 10 mM GSH, whereas only ∼19% was released in pH 7.4. In cellular uptake studies, dual targeted polymersomes showed ∼22-fold increase in cellular uptake efficiency in breast cancer cell lines (BT474 and MCF-7) as compared to nontargeted polymersomes with higher apoptosis rates. In vivo studies on Ehrlich's ascites tumor (EAT) bearing Swiss albino mouse model showed ∼85% tumor regression as compared to free doxorubicin (∼42%) without any significant cardiotoxicity associated with doxorubicin. The results indicate enhanced antitumor efficacy of the redox sensitive biocompatible nanosystem and shows promise as a potential drug nanocarrier in cancer therapeutics. PMID:25838044

  5. Ultrafast proton transfer of pyranine in a supramolecular assembly: PEO-PPO-PEO triblock copolymer and CTAC.

    PubMed

    Ghosh, Subhadip; Dey, Shantanu; Mandal, Ujjwal; Adhikari, Aniruddha; Mondal, Sudip Kumar; Bhattacharyya, Kankan

    2007-12-01

    Excited-state proton transfer (ESPT) of pyranine (8-hydroxypyrene-1,3,6-trisulfonate, HPTS) is studied in a polymer-surfactant aggregate using femtosecond emission spectroscopy. The polymer-surfactant aggregate is a supramolecular assembly consisting of a triblock copolymer (PEO)(20)-(PPO)(70)-(PEO)(20) (P123) and a cationic surfactant, cetyltrimethylammonium chloride (CTAC). ESPT of the protonated species (HA) in HPTS leads to the formation of A(-). The dynamics of ESPT may be followed from the decay of the HA emission (at approximately 440 nm) and rise of the A(-) emission (at approximately 550 nm). Both steady-state and time-resolved studies suggest that ESPT of HPTS in P123-CTAC aggregate is much slower than that in bulk water, in P123 micelle, or in CTAC micelle. The ratio of the steady-state emission intensities (HA/A(-)) in P123-CTAC aggregate is 2.2. This ratio is approximately 50, 12, and 2 times higher than that respectively in water, in P123 micelle, and in CTAC micelle. Retardation of ESPT causes an increase in the rise time of the A(-) emission of HPTS. In P123-CTAC aggregate, A(-) displays three rise times: 30, 250, and 2400 ps. These rise times are longer than those in CTAC micelle (23, 250, and 1800 ps), in bulk water (0.3, 3, and 90 ps), and in P123 micelle (15 and 750 ps). The rate constants for initial proton transfer, recombination, and dissociation of the ion pair are estimated using a simple kinetic scheme. The slow fluorescence anisotropy decay of HPTS in P123-CTAC aggregate is analyzed in terms of the wobbling-in-cone model. PMID:17988110

  6. Amphiphilic triblock copolymers with PEGylated hydrocarbon structures as environmentally friendly marine antifouling and fouling-release coatings.

    PubMed

    Zhou, Zhaoli; Calabrese, David R; Taylor, Warren; Finlay, John A; Callow, Maureen E; Callow, James A; Fischer, Daniel; Kramer, Edward J; Ober, Christopher K

    2014-01-01

    The ideal marine antifouling (AF)/fouling-release (FR) coating should be non-toxic, while effectively either resisting the attachment of marine organisms (AF) or significantly reducing their strength of attachment (FR). Many recent studies have shown that amphiphilic polymeric materials provide a promising solution to producing such coatings due to their surface dual functionality. In this work, poly(ethylene glycol) (PEG) of different molecular weights (Mw = 350, 550) was coupled to a saturated difunctional alkyl alcohol to generate amphiphilic surfactants (PEG-hydrocarbon-OH). The resulting macromolecules were then used as side chains to covalently modify a pre-synthesized PS8 K-b-P(E/B)25 K-b-PI10 K (SEBI or K3) triblock copolymer, and the final polymers were applied to glass substrata through an established multilayer surface coating technique to prepare fouling resistant coatings. The coated surfaces were characterized with AFM, XPS and NEXAFS, and evaluated in laboratory assays with two important fouling algae, Ulva linza (a green macroalga) and Navicula incerta, a biofilm-forming diatom. The results suggest that these polymer-coated surfaces undergo surface reconstruction upon changing the contact medium (polymer/air vs polymer/water), due to the preferential interfacial aggregation of the PEG segment on the surface in water. The amphiphilic polymer-coated surfaces showed promising results as both AF and FR coatings. The sample with longer PEG chain lengths (Mw = 550 g mol(-1)) exhibited excellent properties against both algae, highlighting the importance of the chemical structures on ultimate biological performance. Besides reporting synthesis and characterization of this new type of amphiphilic surface material, this work also provides insight into the nature of PEG/hydrocarbon amphiphilic coatings, and this understanding may help in the design of future generations of fluorine-free, environmentally friendly AF/FR polymeric coatings. PMID:24730510

  7. pH-Sensitive Micelles Based on Double-Hydrophilic Poly(methylacrylic acid)-Poly(ethylene glycol)-Poly(methylacrylic acid) Triblock Copolymer

    NASA Astrophysics Data System (ADS)

    Tao, Youhua; Liu, Ren; Liu, Xiaoya; Chen, Mingqing; Yang, Cheng; Ni, Zhongbin

    2009-04-01

    pH-sensitive micelles with hydrophilic core and hydrophilic corona were fabricated by self-assembling of triblock copolymer of poly(methylacrylic acid)-poly(ethylene glycol)-poly(methylacrylic acid) at lower solution pH. Transmission electron microscopy and laser light scattering studies showed micelles were in nano-scale with narrow size distribution. Solution pH value and the micelles concentration strongly influenced the hydrodynamic radius of the spherical micelles (48-310 nm). A possible mechanism for the formation of micelles was proposed. The obtained polymeric micelle should be useful for biomedical materials such as carrier of hydrophilic drug.

  8. Encapsulation and Release of Amphotericin B from an ABC Triblock Fluorous Copolymer

    PubMed Central

    Jee, Jun-Pil; McCoy, Aaron; Mecozzi, Sandro

    2011-01-01

    Purpose PEG-phospholipid-based micelles have been successfully used for the solubilization of several hydrophobic drugs but generally lack sustained stability in blood. Our novel PEG-Fluorocarbon-DSPE polymers were designed to increase stability and improve time-release properties of drug-loaded micelles. Methods Novel ABC fluorous copolymers were synthesized, characterized, and used for encapsulation release of amphotericin B. FRET studies were used to study micelle stability. Results The micelles formed by the new polymers showed lower critical micelle concentrations and higher viscosity cores compared with those formed by the polymers lacking the fluorous block. FRET studies indicated that fluorocarbon-containing micelles had increased stability in the presence of human serum. Physicochemical properties and in vitro release profile of the micelles loaded with Amphotericin B (AmB) were studied. Conclusions The effect of PEG length and fluorocarbon incorporation were investigated. The shorter hydrophilic PEG-2K induced greater stability than PEG-5K by decreasing the proportion of hydrophilic block of the polymer. The fluorocarbon placed between hydrophilic and hydrophobic block formed a fluorous shell contributing to the enhanced thermodynamic stability of micelles and to the drug sustained release. Polymer mPEG2K-F10-DSPE, bearing both a fluorocarbon block and a shorter mPEG, showed the greatest stability and the longest half-life for AmB release. PMID:21739321

  9. Biomimetic Nanocomposites of Calcium Phosphate and Self-Assembling Triblock and Pentablock Copolymers

    SciTech Connect

    Drew Lenzen Enlow

    2006-08-09

    In an effort to mimic the growth of natural bone, self-assembling, micelle and gel-forming copolymers were used as a template for calcium phosphate precipitation. Because of the cationic characteristics imparted by PDEAEM end group additions to commercially available Pluronic{reg_sign} Fl27, a direct ionic attraction mechanism was utilized and a polymer-brushite nanocomposite spheres were produced. Brushite coated spherical micelles with diameters of {approx}40 nm, and agglomerates of these particles (on the order of 0.5 {mu}m) were obtained. Thickness and durability of the calcium phosphate coating, and the extent of agglomeration were studied. The coating has been shown to be robust enough to retain its integrity even below polymer critical micelle concentration and/or temperature. Calcium phosphate-polymer gel nanocomposites were also prepared. Gel samples appeared as a single phase network of agglomerated spherical micelles, and had a final calcium phosphate concentration of up to 15 wt%. Analysis with x-ray diffraction and NMR indicated a disordered brushite phase with the phosphate groups linking inorganic phase to the polymer.

  10. Single-ion BAB triblock copolymers as highly efficient electrolytes for lithium-metal batteries

    NASA Astrophysics Data System (ADS)

    Bouchet, Renaud; Maria, Sébastien; Meziane, Rachid; Aboulaich, Abdelmaula; Lienafa, Livie; Bonnet, Jean-Pierre; Phan, Trang N. T.; Bertin, Denis; Gigmes, Didier; Devaux, Didier; Denoyel, Renaud; Armand, Michel

    2013-05-01

    Electrochemical energy storage is one of the main societal challenges of this century. The performances of classical lithium-ion technology based on liquid electrolytes have made great advances in the past two decades, but the intrinsic instability of liquid electrolytes results in safety issues. Solid polymer electrolytes would be a perfect solution to those safety issues, miniaturization and enhancement of energy density. However, as in liquids, the fraction of charge carried by lithium ions is small (<20%), limiting the power performances. Solid polymer electrolytes operate at 80 °C, resulting in poor mechanical properties and a limited electrochemical stability window. Here we describe a multifunctional single-ion polymer electrolyte based on polyanionic block copolymers comprising polystyrene segments. It overcomes most of the above limitations, with a lithium-ion transport number close to unity, excellent mechanical properties and an electrochemical stability window spanning 5 V versus Li+/Li. A prototype battery using this polyelectrolyte outperforms a conventional battery based on a polymer electrolyte.

  11. Rich Phase Behavior of Sphere-Forming Asymmetric ABA'C Block Copolymer Melts

    NASA Astrophysics Data System (ADS)

    Chanpuriya, Sid; Arora, Akash; Kim, Kyungtae; Dorfman, Kevin; Bates, Frank

    Motivated by self-consistent field theory simulations, the effect of ABA' corona block length asymmetry on the phase behavior of ABA'C-type tetrablock terpolymers has been examined. The chosen model system, poly(styrene)- b-poly(isoprene)- b-poly(styrene)- b-poly(ethylene oxide) (SIS'O), has been characterized using a combination of small-angle X-ray scattering, transmission electron microscopy, and dynamic mechanical spectroscopy. Asymmetric SIS'O tetrablocks reveal a rich variety of sphere-forming phases over compositions and molecular weights where symmetric SISO polymers formed only hexagonally oriented cylinders. These include FCC, HCP, and complex symmetries such as the Frank-Kasper σ and A15 phases. NSF Award 1333669.

  12. Biodegradable Nanoparticles of mPEG-PLGA-PLL Triblock Copolymers as Novel Non-Viral Vectors for Improving siRNA Delivery and Gene Silencing

    PubMed Central

    Du, Jing; Sun, Ying; Shi, Qiu-Sheng; Liu, Pei-Feng; Zhu, Ming-Jie; Wang, Chun-Hui; Du, Lian-Fang; Duan, You-Rong

    2012-01-01

    Degradation of mRNA by RNA interference is one of the most powerful and specific mechanisms for gene silencing. However, insufficient cellular uptake and poor stability have limited its usefulness. Here, we report efficient delivery of siRNA via the use of biodegradable nanoparticles (NPs) made from monomethoxypoly(ethylene glycol)-poly(lactic-co-glycolic acid)-poly-l-lysine (mPEG-PLGA-PLL) triblock copolymers. Various physicochemical properties of mPEG-PLGA-PLL NPs, including morphology, size, surface charge, siRNA encapsulation efficiency, and in vitro release profile of siRNA from NPs, were characterized by scanning electron microscope, particle size and zeta potential analyzer, and high performance liquid chromatography. The levels of siRNA uptake and targeted gene inhibition were detected in human lung cancer SPC-A1-GFP cells stably expressing green fluorescent protein. Examination of the cultured SPC-A1-GFP cells with fluorescent microscope and flow cytometry showed NPs loading Cy3-labeled siRNA had much higher intracellular siRNA delivery efficiencies than siRNA alone and Lipofectamine-siRNA complexes. The gene silencing efficiency of mPEG-PLGA-PLL NPs was higher than that of commercially available transfecting agent Lipofectamine while showing no cytotoxicity. Thus, the current study demonstrates that biodegradable NPs of mPEG-PLGA-PLL triblock copolymers can be potentially applied as novel non-viral vectors for improving siRNA delivery and gene silencing. PMID:22312268

  13. Volume shrinkage and rheological studies of epoxidised and unepoxidised poly(styrene-block-butadiene-block-styrene) triblock copolymer modified epoxy resin-diamino diphenyl methane nanostructured blend systems.

    PubMed

    George, Sajeev Martin; Puglia, Debora; Kenny, Josè M; Parameswaranpillai, Jyotishkumar; Vijayan P, Poornima; Pionteck, Jűrgen; Thomas, Sabu

    2015-05-21

    Styrene-block-butadiene-block-styrene (SBS) copolymers epoxidised at different epoxidation degrees were used as modifiers for diglycidyl ether of the bisphenol A-diamino diphenyl methane (DGEBA-DDM) system. Epoxy systems containing modified epoxidised styrene-block-butadiene-block-styrene (eSBS) triblock copolymer with compositions ranging from 0 to 30 wt% were prepared and the curing reaction was monitored in situ using rheometry and pressure-volume-temperature (PVT) analysis. By controlling the mole percent of epoxidation, we could generate vesicles, worm-like micelles and core-shell nanodomains. At the highest mole percent of epoxidation, the fraction of the epoxy miscible component in the triblock copolymer (epoxidised polybutadiene (PB)) was maximum. This gave rise to core-shell nanodomains having a size of 10-15 nm, in which the incompatible polystyrene (PS) becomes the core, the unepoxidised PB becomes the shell and the epoxidised PB interpenetrates with the epoxy phase. On the other hand, the low level of epoxidation gave rise to bigger domains having a size of ∼1 μm and the intermediate epoxidation level resulted in a worm-like structure. This investigation specifically focused on the importance of cure rheology on nanostructure formation, using rheometry. The reaction induced phase separation of the PS phase in the epoxy matrix was carefully explored through rheological measurements. PVT measurements during curing were carried out to understand the volume shrinkage of the blend, confirming that shrinkage behaviour is related to the block copolymer phase separation process during curing. The volume shrinkage was found to be maximum in the case of blends with unmodified SBS, where a heterogeneous morphology was observed, while a decrease in the shrinkage was evidenced in the case of SBS epoxidation. It could be explained by two effects: (1) solubility of the epoxidised block copolymer in the DGEBA leads to the formation of nanoscopic domains upon

  14. Co-delivery of siRNA and paclitaxel into cancer cells by biodegradable cationic micelles based on PDMAEMA-PCL-PDMAEMA triblock copolymers.

    PubMed

    Zhu, Caihong; Jung, Sooyeon; Luo, Sibin; Meng, Fenghua; Zhu, Xiulin; Park, Tae Gwan; Zhong, Zhiyuan

    2010-03-01

    Biodegradable cationic micelles were prepared from PDMAEMA-PCL-PDMAEMA triblock copolymers and applied for the delivery of siRNA and paclitaxel into cancer cells. PDMAEMA-PCL-PDMAEMA copolymers were readily obtained by reversible addition-fragmentation chain transfer (RAFT) polymerization of dimethylaminoethyl methacrylate (DMAEMA) using CPADN-PCL-CPADN (CPADN: 4-cyanopentanoic acid dithionaphthalenoate; PCL: 3600 Da) as a macro-RAFT agent. The molecular weights of PDMAEMA blocks, controlled by monomer/CPADN-PCL-CPADN mole ratios, varied from 2700, 4800 to 9100 (denoted as polymer 1, 2 and 3, respectively). These triblock copolymers formed nano-sized micelles in water with positive surface charges ranging from +29.3 to +35.5 mV. Both micelles 1 and 2 revealed a low cytotoxicity. Gel retardation assay showed that micelles 1 and 2 could effectively complex with siRNA at and above N/P ratios of 4/1 and 2/1, respectively. Notably, GFP siRNA complexed with micelle 1 exhibited significantly enhanced gene silencing efficiency as compared to that formulated with 20 kDa PDMAEMA or 25kDa branched PEI in GFP-expressed MDA-MB-435-GFP cells. Moreover, micelle 1 loaded with paclitaxel displayed higher drug efficacy than free paclitaxel in PC3 cells, due to most likely improved cellular uptake. The combinatorial delivery of VEGF siRNA and paclitaxel showed an efficient knockdown of VEGF expression. Confocal laser scanning microscope studies on GFP siRNA complexed with nile red-loaded micelle revealed that nile red was delivered into GFP-expressed MDA-MB-435-GFP cells and that GFP expression was significantly inhibited. These results demonstrated that cationic biodegradable micelles are highly promising for the combinatorial delivery of siRNA and lipophilic anti-cancer drugs. PMID:19963269

  15. Surface structures of an amphiphilic tri-block copolymer in air and in water probed using sum frequency generation vibrational spectroscopy.

    PubMed

    Kristalyn, Cornelius B; Lu, Xiaolin; Weinman, Craig J; Ober, Christopher K; Kramer, Edward J; Chen, Zhan

    2010-07-01

    Sum frequency generation (SFG) vibrational spectroscopy has been applied to investigate surface structures of an amphiphilic surface-active block copolymer (SABC) film deposited on a CaF(2) substrate, in air and in water in situ. Developed as a surface-active component of an antifouling coating for marine applications, this amphiphilic triblock copolymer contains both hydrophobic fluorinated alkyl groups as well as hydrophilic ethoxy groups. It was found that surface structures of the copolymer film in air and in water cannot be probed directly using the SFG experimental geometry we adopted because SFG signals can be contributed from the polymer/air (or polymer/water) interface as well as the buried polymer/CaF(2) substrate interface. Using polymer films with varied thicknesses, structural information about the polymer surfaces in air and in water can be deduced from the detected SFG signals. With SFG, surface restructuring of this polymer has been observed in water, especially the methyl and methylene groups change orientations upon contact with water. However, the hydrophobic fluoroalkyl group was present on the surface in both air and water, and we believe that it was held near the surface in water by its neighboring ethoxy groups. PMID:20465236

  16. Stereocomplex Film Using Triblock Copolymers of Polylactide and Poly(ethylene glycol) Retain Paxlitaxel on Substrates by an Aqueous Inkjet System.

    PubMed

    Ajiro, Hiroharu; Kuroda, Ayaka; Kan, Kai; Akashi, Mitsuru

    2015-09-29

    The stereocomplex formation of poly(L,L-lactide) (PLLA) and poly(D,D-lactide) (PDLA) using an inkjet system was expanded to the amphiphilic copolymers, using poly(ethylene glycol) (PEG) as a hydrophilic polymer. The diblock copolymers, which are composed of PEG and PLLA (MPEG-co-PLLA) and PEG and PDLA (MPEG-co-PDLA), were employed for thin-film preparation using an aqueous inkjet system. The solvent and temperature conditions were optimized for the stereocomplex formation between MPEG-co-PLLA and MPEG-co- PDLA. As a result, the stereocomplex was adequately formed in acetonitrile/water (1:1, v/v) at 40 °C. The aqueous conditions improved the stereocomplex film preparation, which have suffered from clogging when using the organic solvents in previous work. The triblock copolymers, PLLA-co-PEG-co-PLLA and PDLA-co-PEG-co-PDLA, were employed for square patterning with the inkjet system, which produced thin films. The amphiphilic polymer film was able to retain hydrophobic compounds inside. The present result contributed to the rapid film preparation by inkjet, retaining drugs with difficult solubility in water, such as paclitaxel within the films. PMID:26343286

  17. Polyisobutylene based thermoplastic elastomers. IV. Synthesis of poly(styrene-b-isobutylene-b-styrene) triblock copolymers usig n-butyl chloride as solvent

    SciTech Connect

    Fordor, Zs.; Faust, R.

    1995-12-31

    The polymerization of isobutylene and styrene was studied using the 2-chloro-2,4,4-trimethylpentane/TiCl{sub 4} initiating system in the presence of proton trap in halogenated hydrocarbons as solvents at {approximately}80{degrees}C. The polymerization of isobutylene was found to be living and both homopolymers were soluble in n-butyl chloride. However, side reactions, namely polymerization by direct initiation and intermolecular alkylation are operational in the polymerization of styrene in n-butyl chloride. Polymerization by direct initiation can be minimized by increasing the initiator concentration and intermolecular alkylation can be reduced by quenching the polymerization system when the conversion reaches {approximately}100%. Polystyrene-polyisobutylene-polystyrene triblock copolymers prepared by sequential monomer addition in n-butyl chloride exhibited {approximately}24 MPa tensile strength indicating the virtual absence of diblock contamination.

  18. Folate Receptor Targeted Delivery of siRNA and Paclitaxel to Ovarian Cancer Cells via Folate Conjugated Triblock Copolymer to Overcome TLR4 Driven Chemotherapy Resistance.

    PubMed

    Jones, Steven K; Lizzio, Vincent; Merkel, Olivia M

    2016-01-11

    This paper focuses on the ability of a folate-decorated triblock copolymer to deliver a targeted dose of siRNA in order to overcome chemotherapy resistance which can commonly cause complications in ovarian cancer patients. The micelleplexes that are formed upon electrostatic interaction with siRNA are used to deliver siRNA in a targeted manner to SKOV-3 ovarian cancer cells that overexpress folate receptor-α (FRα). The triblock copolymer consists of polyethylenimine-graft-polycaprolactone-block-poly(ethylene glycol) (PEI-g-PCL-b-PEG-Fol). In this work, polymers of different molecular weights of PEG, as well as different grafting degrees of the (g-PCL-b-PEG-Fol) chains to PEI, were analyzed to optimize targeted siRNA delivery. The polymers, their micelleplexes, and the in vitro performance of the latter were characterized by nuclear magnetic resonance, dynamic light scattering, transmission electron microscopy, flow cytrometry, western blot, confocal microscopy, and in luciferase assays. The different PEI-g-PCL-b-PEG-Fol conjugates showed suitable sizes below 260 nm, especially at N/P 5, which also allowed for full siRNA condensation. Furthermore, flow cytometry and Western blot analysis demonstrated that our best polymer was able to effectively deliver siRNA and that siRNA delivery resulted in efficient protein knockdown of toll-like receptor 4 (TLR4). Consequently, TLR4 knock down within SKOV-3 cells resensitized them toward paclitaxel (PTX) treatment, and apoptotic events increased. This study demonstrates that PEI-g-PCL-b-PEG-Fol conjugates are a reliable delivery system for siRNA and are able to mediate therapeutic protein knockdown within ovarian cancer cells. Additionally, this study provides further evidence to link TLR4 levels to chemotherapy resistance. PMID:26636884

  19. PNIPAm(x)-PPO(36)-PNIPAm(x) thermo-sensitive triblock copolymers: chain conformation and adsorption behavior on a hydrophobic gold surface.

    PubMed

    Li, Jianyuan; Zhang, Zhijun; Zhou, Xianjing; Chen, Tongquan; Nie, Jingjing; Du, Binyang

    2016-01-01

    The chain conformations and adsorption behaviors of four thermo-sensitive poly(N-isopropylacrylamide)x-poly(propylene oxide)36-poly(N-isopropylacrylamide)x (PNIPAmx-PPO36-PNIPAmx) triblock copolymers with x values of 15, 33, 75, and 117 in dilute aqueous solutions were investigated by combined techniques of micro-differential scanning calorimetry (micro-DSC), static and dynamic light scattering (SLS & DLS), and the quartz crystal microbalance (QCM). PNIPAm15-PPO36-PNIPAm15 only exhibited the lower critical solution temperature (LCST) of the PPO block, i.e. 25 °C, because the PNIPAm block with x = 15 was too short to maintain its own LCST. With middle lengths x of 33 and 75, the LCSTs of PPO and PNIPAm blocks were observed, respectively. For the longest PNIPAm block with x = 117, only LCST of PNIPAm block dominated, i.e. 32.3 °C. DLS results revealed that the four PNIPAmx-PPO36-PNIPAmx triblock copolymers formed "associate" structures in their dilute aqueous solutions at 20 °C, which was well below the LCSTs of the PPO and PNIPAm blocks. QCM results indicated that the adsorption time constant decreased with increasing adsorption temperature but tended to increase with increasing length x of the PNIPAm block. A complex adsorption behavior with large adsorption amounts was only observed at the corresponding LCST of the PNIPAm block for PNIPAmx-PPO36-PNIPAmx with longer PNIPAm blocks with x = 33, 75, and 117. Furthermore, the adsorbed PNIPAmx-PPO36-PNIPAmx layers obtained at 20 °C were rigid with less energy dissipation. PMID:26616793

  20. Self-organization of hydrophobic-capped triblock copolymers with a polyelectrolyte midblock: a coarse-grained molecular dynamics simulation study.

    PubMed

    Ghelichi, Mahdi; Qazvini, Nader Taheri

    2016-05-18

    We present the results of a Langevin dynamics simulation study of micellar organization and hydrogel formation in the solutions of coarse-grained ABA copolymer chains. Polymer chains are modeled as bead-spring chains of Lennard-Jones particles by explicit treatment of ionic species in implicit solvent. The studied copolymer is composed of a polyelectrolyte midblock flanked by two hydrophobic endblocks. We explore the self-assembly of copolymer solutions at a fixed polymer concentration and temperature upon systematic variation of the midblock charge fraction, valency of neutralizing counterions, and the stiffness and length of hydrophobic endblocks. Minimization of the surface energy, conformational entropy of the midblock chains, electrostatic repulsion of midblock charges, and the translational entropy of counterions are found to play central roles in controlling the self-organization features of copolymer solutions. Flower-like micelles with A-blocks forming the core of spherical aggregates and B-blocks constituting the micelle corona are established for the neutral midblocks. Increasing the charge content of B chains lowers the fraction of loop conformations and yields a spanning hydrogel network with midblocks bridging the hydrophobic clusters. Counterion valence is shown to exert a strong effect on the micelle size and network structure. The increase in the rigidity of terminal A-blocks increases the fraction of bridging chains and results in the formation of a hydrogel network with bundle-like hydrophobic domains. Longer endblocks are shown to increase the hydrophobic cluster size and enhance the bridged midblock fraction. The qualitative agreement between the experimental and theoretical studies is also discussed. The comprehensive molecular picture provides a framework for the future studies of stimuli-responsive copolymer systems. PMID:27116478

  1. Reversibly shielded DNA polyplexes based on bioreducible PDMAEMA-SS-PEG-SS-PDMAEMA triblock copolymers mediate markedly enhanced nonviral gene transfection.

    PubMed

    Zhu, Caihong; Zheng, Meng; Meng, Fenghua; Mickler, Frauke Martina; Ruthardt, Nadia; Zhu, Xiulin; Zhong, Zhiyuan

    2012-03-12

    Reversibly shielded DNA polyplexes based on bioreducible poly(dimethylaminoethyl methacrylate)-SS-poly(ethylene glycol)-SS-poly(dimethylaminoethyl methacrylate) (PDMAEMA-SS-PEG-SS-PDMAEMA) triblock copolymers were designed, prepared and investigated for in vitro gene transfection. Two PDMAEMA-SS-PEG-SS-PDMAEMA copolymers with controlled compositions, 6.6-6-6.6 and 13-6-13 kDa, were obtained by reversible addition-fragmentation chain transfer (RAFT) polymerization of dimethylaminoethyl methacrylate (DMAEMA) using CPADN-SS-PEG-SS-CPADN (CPADN: 4-cyanopentanoic acid dithionaphthalenoate; PEG: 6 kDa) as a macro-RAFT agent. Like their nonreducible PDMAEMA-PEG-PDMAEMA analogues, PDMAEMA-SS-PEG-SS-PDMAEMA triblock copolymers could effectively condense DNA into small particles with average diameters less than 120 nm and close to neutral zeta potentials (0 ∼ +6 mV) at and above an N/P ratio of 3/1. The resulting polyplexes showed excellent colloidal stability against 150 mM NaCl, which contrasts with polyplexes of 20 kDa PDMAEMA homopolymer. In the presence of 10 mM dithiothreitol (DTT), however, polyplexes of PDMAEMA-SS-PEG-SS-PDMAEMA were rapidly deshielded and unpacked, as revealed by significant increase of positive surface charges as well as increase of particle sizes to over 1000 nm. Release of DNA in response to 10 mM DTT was further confirmed by gel retardation assays. These polyplexes, either stably or reversibly shielded, revealed a low cytotoxicity (over 80% cell viability) at and below an N/P ratio of 12/1. Notably, in vitro transfection studies showed that reversibly shielded polyplexes afforded up to 28 times higher transfection efficacy as compared to stably shielded control under otherwise the same conditions. Confocal laser scanning microscope (CLSM) studies revealed that reversibly shielded polyplexes efficiently delivered and released pDNA into the perinuclei region as well as nuclei of COS-7 cells. Hence, reduction-sensitive reversibly shielded DNA

  2. Bioreducible poly(2-ethyl-2-oxazoline)-PLA-PEI-SS triblock copolymer micelles for co-delivery of DNA minicircles and Doxorubicin.

    PubMed

    Gaspar, Vítor M; Baril, Patrick; Costa, Elisabete C; de Melo-Diogo, Duarte; Foucher, Frédéric; Queiroz, João A; Sousa, Fani; Pichon, Chantal; Correia, Ilídio J

    2015-09-10

    The co-delivery of minicircle DNA (mcDNA) and small anti-cancer drugs via stimuli-sensitive nanocarriers is a promising approach for combinatorial cancer therapy. However, the simultaneous loading of drugs and DNA in nanosized delivery systems is remarkably challenging. In this study we describe the synthesis of triblock copolymer micelles based on poly(2-ethyl-2-oxazoline)-poly(L-lactide) grafted with bioreducible polyethylenimine (PEOz-PLA-g-PEI-SS) for co-delivery of supercoiled (sc) mcDNA vectors and Doxorubicin (Dox). These amphiphilic carriers take advantage of non-fouling oxazolines to confer biological stability, of PLA to provide a hydrophobic core for drug encapsulation and of bioreducible PEI-SS to provide mcDNA complexation and an on-demand stimuli-responsive release. The obtained results show that mcDNA-loaded micelleplexes penetrate into in vitro tumor spheroid models with specific kinetics and exhibit a higher gene expression when compared to non-bioreducible nanocarriers. Moreover, in vivo bioluminescence imaging showed that gene expression is detected up to 8days following mcDNA-micelles intratumoral administration. Furthermore, drug-gene co-delivery in PEOz-PLA-g-PEI-SS carriers was verified by successful encapsulation of both Dox and mcDNA with high efficacy. Moreover, dual-loaded micelleplexes presented significant uptake and a cytotoxic effect in 2D cultures of cancer cells. The co-delivery of mcDNA-Dox to B16F10-Luciferase tumor bearing mice resulted in a reduction in tumor volume and cancer cells viability. Overall, such findings indicate that bioreducible triblock micelles are efficient for focal delivery in vivo and have potential for future application in combinatorial DNA-drug therapy. PMID:26184050

  3. Novel cationic triblock copolymer of poly[2-(dimethylamino)ethyl methacrylate]-block-poly(β-amino ester)-block-poly[2-(dimethylamino)ethyl methacrylate]: a promising non-viral gene delivery system.

    PubMed

    Cordeiro, Rosemeyre A; Farinha, Dina; Rocha, Nuno; Serra, Arménio C; Faneca, Henrique; Coelho, Jorge F J

    2015-02-01

    This manuscript reports the synthesis of a new cationic block copolymer based on poly[2-(dimethylamino)ethyl methacrylate] and poly(β-amino ester) from different polymerization strategies. For the first time, it is proposed a triblock copolymer based only on cationic segments, aiming a high biocompatibility, enhanced buffering capacity and stimuli-responsive character in a single structure. The new block copolymer successfully condensed the plasmid DNA into nanosized polyplexes. The polyplexes were tested in two different cell lines revealing ∼4-fold and ∼6-fold (in HeLa cells), and ∼11-fold (in COS-7 cells) higher transgene expression than branched PEI and TurboFect™, respectively. These results show that this new block copolymer is a promising candidate to be used as a polymeric non-viral vector. PMID:25399846

  4. Photoluminescence and solid state properties of rigid pi- conjugated polymers with applications to LED: Alkyl- substituted p-phenyleneethynylene polymers and triblock copolymers

    NASA Astrophysics Data System (ADS)

    Huang, Wen-Yao

    A series of substituted poly(p-phenyleneethynylene)s, PPE, were synthesized by alkyne metathesis. The substituents dibutyl (a), dioctyl (b), ditetradecyl (c), di-2-ethylhexyl (d) and di-2-cyclohexylethyl; (e)were placed on the 2,5 positions of the phenyl rings. X-ray diffraction studies indicated that the main chains of each polymer were arranged in regular, layered arrays. Liquid crystalline structures were observed by polarized optical microscopy in PPE 4b, 4c and 4d. The temperatures of isotropization of the liquid crystalline structures coincided with the disordering temperatures determined by differential scanning calorimetry. The UV absorption spectra showed a gradual blue shift of the λmax for all these polymers, suggesting a decrease in the electronic delocalization along the chain as the size and geometry of the side group changed. The photoluminescence spectra in dilute toluene solutions are consistent with vibronic coupling and emission from localized excited states. The emission spectra of thin films show characteristics typical of excimer or aggregate formation in the solid state. Lastly, an improved method of molecular weight determination by end group analysis was devised. Molecular organization and orientation in thin films (~100 nm) of a triblock copolymer, PPEPEG, was studied. The morphology of the thin film can be visualized as consisting of PMMA as the major phase in which domains of vertically oriented triblock copolymers are dispersed with PEG groups facing the air-film interface. The molecular and supramolecular structure of a series of well-defined fully conjugated poly(2,5- diakyl-p-phenyleneethynylene)s, PPE, in toluene has been studied in the sol state and in the gel state by surface tension and photoluminescence measurements. Poly (2,6[4- phenyl quinoline]), I, and poly (2,6[p-phenylene] 4- phenyl quinoline), II, were synthesized by the self- condensation of 5-acetyl-2-aminobezophenone and 4-amino- 4 '-acetyl-3-benzoyl biphenyl

  5. Micelle Morphology and Mechanical Response of Triblock Gels

    SciTech Connect

    Seitz, Michelle E.; Burghardt, Wesley R.; Shull, Kenneth R.

    2010-01-12

    The effect of polymer concentration on mechanical response and micelle morphology of ABA and AB copolymers in B-selective solvents has been systematically studied. Micelle morphology was determined using a combination of small-angle X-ray scattering, shear, and birefringence while mechanical response at low and high strains was determined using indentation techniques. Self-consistent field theory calculations were used to determine micelle volume fraction profiles and to construct an equilibrium phase map. The transition from spherical to cylindrical micelles increases the triblock gel modulus and energy dissipation. Combining knowledge of gel relaxation time, which determines the rate at which the gel can equilibrate its micelle structure, with the equilibrium phase map allows estimation of the experimental temperatures and time scales over which kinetic trapping will arrest micelle structure evolution. Kinetic trapping enables cylindrical morphologies to be obtained at significantly lower polymer fractions than is possible in equilibrated systems.

  6. Preparation of micron-sized spherical particles of mesoporous silica from a triblock copolymer surfactant, usable as a stationary phase for liquid chromatography

    NASA Astrophysics Data System (ADS)

    Mesa, Monica; Sierra, Ligia; López, Betty; Ramirez, Alejandro; Guth, Jean-Louis

    2003-09-01

    Spherical particles (∅>3 μm, with 5-10 nm pore size) of SBA15-type mesoporous silica, usable as stationary phase for HPLC, were prepared with tetraethoxysilane (TEOS) as silica source, triblock copolymer Pluronic P123 (EO 20PO 70EO 20) as surfactant S 0 and cetyltrimethylammonium bromide (CTMABr) as co-surfactant S +. The synthesis mechanism involves a surfactant-silica species self-assembly process in acidic medium under quiescent conditions, where S 0H 3O +X -I + and S +X -I + interactions occur. The syntheses were carried out using two procedures: (a) with one heating step and (b) with two heating steps. Synthesis conditions, such as the dilution, temperature and acidity of the reaction mixture and the temperature and duration of the reaction, influence the porous characteristics as well as the morphology and size of the particles. Spherical particles were obtained with one heating step under conditions that weaken the surfactants-silicate interactions such as high dilution, high temperature and low acidity. The modification of the micelle volume with the temperature and acidity allowed the adjustment of the pore size.

  7. Immobilization of poly(ɛ-caprolactone)-poly(ethylene oxide)-poly(ɛ-caprolactone) triblock copolymer on poly(lactide- co-glycolide) surface and dual biofunctional effects

    NASA Astrophysics Data System (ADS)

    Zhu, Aiping; Lu, Ping; Wu, Hao

    2007-01-01

    Poly(ɛ-caprolactone)-poly(ethylene oxide)-poly(ɛ-caprolactone) (PCL-PEG-PCL) triblock copolymer was covalently immobilized onto poly(lactide- co-glycolide) (PLGA) surface with the precursor of photopolymerizable and biodegradable PCL-PEG-PCL diacrylates. Argon plasma technique was exploited to obtain hydrophilic PLGA surface (HPLGA). The surface properties were characterized by Water contact angle and X-ray photoelectron spectroscopy (XPS) techniques. PCL-PEG-PCL surface modified hydrophobic PLGA and hydrophilic PLGA results in different surface physicochemical properties. PCL-PEG-PCL modified hydrophobic PLGA surface (PLGA-PCL-PEG-PCL) demonstrates excellent inhibition of platelet adhesion and activation; while PCL-PEG-PCL modified hydrophilic PLGA surface (HPLGA-PCL-PEG-PCL) results in good cytocompatibility. The possible mechanism was discussed and the driven force was ascribed to the different assembly behavior of PCL-PEG-PCL on PLGA surface dependant on the hydrophilic/hydrophobic property of PLGA. This simple and effective surface engineering method is also suitable for the other biomaterials such as polyurethane (PU), silicon rubber and poly(ethylene terephthalate) (PET) to obtain the enhanced biocompatibility.

  8. Fabrication of Hollow Porous Silica Using a Combined Emulsion Sol-Gel Process and Amphiphilic Triblock Copolymer for Loading of Quercetin.

    PubMed

    Lee, Sang Gil; Kim, Young Ho; Bae, Jun Tae; Lee, Chung Hee; Pyo, Hyeong Bae; Kang, Kuk Hyoun; Lee, Dong Kyu

    2015-10-01

    Flavonoids have recently attracted significant interest as potential reducing agents, hydrogen-donating antioxidants, and singlet oxygen-quenchers. Quercetin, in particular, induces the expression of a gene, known to be associated with cell protection, in dose- and time-dependent manners. Therefore, quercetin may be used as an effective cosmeceutical material useful in the protection of dermal skin. In this study, hollow porous silica spheres used to load quercetin were prepared by using a combined emulsion sol-gel process and triblock copolymer as a template. Fabrication of hollow porous silica spheres was performed under various conditions such as the molar ratios of H2O/TEOS (Rw) and weight ratios of poloxamer 184/poloxamer 407. Loading of quercetin in hollow porous silica spheres was devised to improve the stability of quercetin and to consider the possibility as a raw cosmetic material. The surface of inclusion complexes of quercetin in hollow porous silicas was modified to enhance the stability of quercetin. The physicochemical properties of the samples were investigated using scanning electron microscopy (SEM), Fourier-transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA)-differential thermal analysis (DTA) and Brunauer-Emmett-Teller (BET) surface area and porosity analysis. Determination of quercetin concentration was carried out by high-performance liquid chromatography (HPLC) analysis. PMID:26726443

  9. Reduction-responsive core-shell-corona micelles based on triblock copolymers: novel synthetic strategy, characterization, and application as a tumor microenvironment-responsive drug delivery system.

    PubMed

    Zhao, Xubo; Liu, Peng

    2015-01-14

    A facile and effective approach was established for fabricating core-shell-corona micelles by self-assembly of poly(ethylene glycol)-b-poly(acrylic acid-co-tert-butyl acrylate)-poly(ε-caprolactone) (PEG43-b-P(AA30-co-tBA18)-b-PCL53) triblock copolymer, synthesized via a combination of ring-opening polymerization (ROP), atom transfer radical polymerization (ATRP), click chemistry, and hydrolyzation. The prenanovehicles with three different hydrolysis degrees from PEG43-b-PtBA48-b-PCL53 were developed to evaluate the drug loading capacity (DLC) and drug encapsulation efficiency (DEE). After cross-linking with a disulfide bond to regulate the drug release kinetics, the spherical core-shell-corona micelles with average diameter of 52 ± 4 nm were obtained in aqueous solution. The reduction-responsive cross-linked micelles showed a slow sustained release in normal physiological conditions and a rapid release upon exposure to simulated tumor intracellular conditions. In addition, the cytotoxic analysis and HepG2 cell growth inhibition assays demonstrated their remarkable biocompatibility and similar excellent anticancer activity as the free doxorubicin (DOX), which has also been revealed by the confocal laser scanning microscope (CLSM) analysis. So the reduction-sensitive core-shell-corona micelles are expected to be promising tumor microenvironment-responsive nanovehicles for hydrophobic drugs by glutathione (GSH) triggering. PMID:25394962

  10. Micellization of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) triblock copolymers in aqueous solutions: Thermodynamics of copolymer association

    SciTech Connect

    Alexandridis, P.; Hatton, T.A. . Dept. of Chemical Engineering); Holzwarth, J.F. )

    1994-04-25

    The critical micellization temperature (cmt) and critical micellization concentration (cmc) values of 12 Pluronic poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) block copolymers, covering a wide range of molecular weights (2,900--14,600) and PPO/PEO ratios (0.19--1.79), were determined employing a dye solubilization method. A closed association model was found to describe adequately the copolymer micellization process for the majority of the Pluronics and used to obtain the standard free energies ([Delta]G[degree]), enthalpies ([Delta]H[degree]), and entropies ([Delta]S[degree]) of micellization. It was determined that the micellization process is entropy-driven and has an endothermic micellization enthalpy. The hydrophobic part of the Pluronics, PPO, was responsible for the micellization, apparently due to diminishing hydrogen bonding between water and PPO with increasing temperature. The cmc dependence on temperature and size of headgroup (PEO) of Pluronics follows a similar trend with lower molecular weight C[sub i]E[sub j] nonionic surfactants, the effect of temperature being more pronounced with the Pluronics. The PEO-PPO-PEO block copolymers were compared to PPO-PEO-PPO block and PEO-PPO random copolymers, in an attempt to probe the effect of molecular architecture in the formation of micelles. No micelles were observed in aqueous PPO-PEO-PPO block copolymer solutions with increasing temperature, up to the cloud point.

  11. Time and Temperature Dependent Rheological Behavior of Single-Walled Carbon Nanotubes Dispersed in Thermoreversible Acrylic Copolymer & Alcohol Solutions

    NASA Astrophysics Data System (ADS)

    Schoch, Andrew B.; Shull, Kenneth R.; Brinson, L. Catherine

    2008-03-01

    SWCNT stabilized by A-B diblock and A-B-A triblock copolymers are excellent model systems for studying the relationship between nanotube dispersion and mechanical response. We have investigated the mechanical properties of these materials with low-amplitude oscillatory shear rheological measurements. The solvent used here, 2-ethyl-1-hexanol, is a poor solvent for PMMA (A) at low temperatures but a good solvent for PnBA (B) over the entire temperature range studied. The solubility of the PMMA blocks in 2-ethyl-1-hexanol drives the formation of an elastic gel in the ABA triblock copolymer at low temperatures. In these SWCNT/copolymer materials the storage and loss moduli have been observed to increase with time at fixed temperature. When triblock copolymer gels are used as the matrix, we find that the aging effect is erased by cycling the temperature through the gel transition. An increase in storage modulus is observed upon cooling before the gel formation. However, the moduli revert back to lower values when the gel dissolves on heating. We believe this is a result of semi-permanent nanotube junctions being pulled apart when the gel forms. This reversibility is not observed when the nanotubes are dispersed in solutions of diblock copolymer, which do not form gels.

  12. Self-assembled polymersomes formed by symmetric, asymmetric and side-chain-tethered coil-rod-coil triblock copolymers.

    PubMed

    Lin, Yung-Lung; Chang, Hung-Yu; Sheng, Yu-Jane; Tsao, Heng-Kwong

    2014-03-21

    Self-assembly behaviors of coil-rod-coil copolymers in selective solvents are explored by dissipative particle dynamics. The morphological phase diagram as a function of rod length and coil length shows five distinct types of aggregates, including spherical micelles, worm-like micelles, disk-like aggregates, honeycomb structures, and polymersomes. Small polymersomes are formed at rather poor alignment associated with monolayered rod domains. Some of the rods are even lying perpendicular to the radial direction. For symmetric copolymers (CmRxCm), the condition of vesicle formation is restricted to short coil and rod lengths. To favor the formation of CRC-polymersomes, two architecture modifications are adopted. One is to increase the coil length asymmetrically to be CmRxCn, where n > m. The other one is to tether a T-block onto the middle of the rod-block as Cm(RxTy)Cm copolymers. For those CRC-polymersomes, structural, transport, and mechanical properties of the vesicular membrane are determined, including membrane thickness, area density of coil blocks, order parameter, solvent permeability, frequency of flip-flop, membrane tension, and stretching and bending moduli. The influences of the coil length (n) and tethered block length (y) on membrane properties are examined. Finally, the mechanism of membrane fusion between CRC-polymersomes is investigated. The fusion process involves four stages and in the contact region the rods lying perpendicular to the radial direction of the polymersome play the key role. The encounter of two vesicles may result in a fused, hemifused, or non-fused polymersome. The final fate is determined by the competition between membrane tension and the steric barrier of the coil corona. The fusion outcome may change if the tension is altered by manipulating the lumen pressure. PMID:24651905

  13. Increasing the Mechanical Strength of Block Polymer Ion Gels Through the Stepwise Self-Assembly of a Thermoresponsive ABC Triblock Terpolymer

    NASA Astrophysics Data System (ADS)

    Hall, Cecilia; Zhou, Can; Danielsen, Scott; Lodge, Timothy

    Blends of network-forming block polymers and ionic liquids have remarkable potential for solid electrolytes, as they allow the combination of desirable mechanical and electrical properties. While ABA triblock copolymers have successfully been implemented as the network component of ion gels, these networks contain looped defects, where the endblocks of the polymer loop back into the same spherical core instead of forming a bridge between two cores. We demonstrate that the ABC triblock terpolymer poly(ethylene-alt-propylene)-block-poly(ethylene oxide)-block-poly(N-isopropylacrylamide) (PEP-b-PEO-b-PNIPAm) in the ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide forms a thermoreversible gel network with negligible looping defects. PEP-core micelles exist at all temperatures, while cooling causes association of the PNIPAm micelle corona to form a bridging network. Small-angle x-ray scattering and dynamic light scattering were used to characterize the high-temperature micelles. These gels show enhanced mechanical properties and the ability to form gels at lower concentrations than the corresponding thermoresponsive ABA triblock copolymers.

  14. Folic acid conjugated δ-valerolactone-poly(ethylene glycol) based triblock copolymer as a promising carrier for targeted doxorubicin delivery.

    PubMed

    Nair K, Lekha; Jagadeeshan, Sankar; Nair S, Asha; Kumar, G S Vinod

    2013-01-01

    The aim of this study is to test the hypothesis that the newly synthesized poly(δ-valerolactone)/poly(ethylene glycol)/poly(δ-valerolactone) (VEV) copolymer grafted with folic acid would impart targetability and further enhance the anti-tumor efficacy of doxorubicin (DOX). Here, folic acid conjugated VEV (VEV-FOL) was synthesized by a modified esterification method and characterized using IR and NMR. DOX loaded VEV-FOL micelles were synthesized using a novel solvent evaporation method and were obtained with a mean diameter of 97 nm with high encapsulation efficiency and sustained in vitro release profile. Comparative studies of polymer micelles with and without folate for cellular uptake and cytotoxicity were done on folate receptor-positive breast cancer cell line, MDAMB231. The intracellular uptake tests showed significant increase in folate micellar uptake when compared to non-folate-mediated micelles. MTT assay followed by apoptosis assays clearly indicated that folate decorated micelles showed significantly better cytotoxicity (IC50 = 0.014 µM) and efficiency to induce apoptosis than other treated groups. Moreover, a significant G2/M arrest was induced by DOX loaded VEV-FOL micelles at a concentration where free drug failed to show any activity. Thus, our results show that the folic acid-labeled VEV copolymer is a promising biomaterial with controlled and sustainable tumor targeting ability for anticancer drugs which can open new frontiers in the area of targeted chemotherapy. PMID:23990912

  15. Folic Acid Conjugated δ-Valerolactone-Poly(ethylene glycol) Based Triblock Copolymer as a Promising Carrier for Targeted Doxorubicin Delivery

    PubMed Central

    Nair K, Lekha; Jagadeeshan, Sankar; Nair S, Asha; Kumar, G. S. Vinod

    2013-01-01

    The aim of this study is to test the hypothesis that the newly synthesized poly(δ-valerolactone)/poly(ethylene glycol)/poly(δ-valerolactone) (VEV) copolymer grafted with folic acid would impart targetability and further enhance the anti-tumor efficacy of doxorubicin (DOX). Here, folic acid conjugated VEV (VEV-FOL) was synthesized by a modified esterification method and characterized using IR and NMR. DOX loaded VEV-FOL micelles were synthesized using a novel solvent evaporation method and were obtained with a mean diameter of 97 nm with high encapsulation efficiency and sustained in vitro release profile. Comparative studies of polymer micelles with and without folate for cellular uptake and cytotoxicity were done on folate receptor-positive breast cancer cell line, MDAMB231. The intracellular uptake tests showed significant increase in folate micellar uptake when compared to non-folate-mediated micelles. MTT assay followed by apoptosis assays clearly indicated that folate decorated micelles showed significantly better cytotoxicity (IC50 = 0.014 µM) and efficiency to induce apoptosis than other treated groups. Moreover, a significant G2/M arrest was induced by DOX loaded VEV-FOL micelles at a concentration where free drug failed to show any activity. Thus, our results show that the folic acid-labeled VEV copolymer is a promising biomaterial with controlled and sustainable tumor targeting ability for anticancer drugs which can open new frontiers in the area of targeted chemotherapy. PMID:23990912

  16. Influence of triblock copolymer (pluronic F127) on enhancing the physico-chemical properties and photocatalytic response of mesoporous TiO2

    NASA Astrophysics Data System (ADS)

    Samsudin, Emy Marlina; Hamid, Sharifah Bee Abd; Juan, Joon Ching; Basirun, Wan Jefrey

    2015-11-01

    The utilization of triblock copolymer, pluronic F127 as a structure directing agent for the preparation of TiO2 played an important role in enhancing the photocatalytic degradation rate of atrazine by a factor of 1.7. The mesoporous F127-TiO2 showed significant modification of morphology, particle and crystallite size, and presence of defect energy belt within the catalyst forbidden band as proven via photoluminescence spectra and x-ray photon spectroscopy. Hence the photogenerated carriers have longer lifespan to migrate to the catalyst surface for redox activities. Furtherance, surface reactive {0 0 1} facets proven by the formation of new geometrical single crystal of square and rhombus surfaces in F127-TiO2 facilitates atrazine degradation as well. The increased surface area of F127-TiO2 promotes greater atrazine absorption, thus governs improved interaction between absorbed atrazine molecules and surface generated active radicals as a pre-requisite for good photocatalytic activity. Interestingly, using the same synthesis procedure, it was observed that the addition of pluronic F127 significantly affects anatase crystal structure as opposed to the more thermodynamically stable rutile, generating 61% and 25% of total crystallite size modification for anatase and rutile, respectively. However, there were no changes on the final composition of anatase and rutile crystal structure. In overall, enhancement of the photocatalytic degradation of atrazine is ruled out to the following factors (1) modification of geometrical structures and size, (2) narrowing of band gap due to defect energy belt, (3) longer lifespan of photoexcited charges to the catalyst surface, (4) enhanced surface textural properties and (5) increased exposure of reactive {0 0 1} facets, which were all observed in F127-TiO2.

  17. Creep-resistant porous structures based on stereo-complex forming triblock copolymers of 1,3-trimethylene carbonate and lactides.

    PubMed

    Zhang, Zheng; Grijpma, Dirk W; Feijen, Jan

    2004-04-01

    Stereo-complexes (poly(ST-TMC-ST)) of enantiomeric triblock copolymers based on 1,3-trimethylene carbonate (TMC) and L- or D-lactide (poly(LLA-TMC-LLA) and poly(DLA-TMC-DLA)) were prepared. Films of poly(ST-TMC-ST) could be prepared by solvent casting mixtures of equal amounts of poly(LLA-TMC-LLA) and poly(DLA-TMC-DLA) solutions and by compression moulding co-precipitates. Although compression moulding was performed at 191 degrees C, thermal degradation was not apparent and materials with good tensile properties could be obtained. For compression-moulded poly(ST-TMC-ST) specimens containing approximately 16 mol % lactide, the values for E-modulus, yield stress and elongation at break were respectively 17, 1.7 MPa and 90%. Also a very low long-term creep rate of 2.2 x 10(-7)s(-1) was determined when specimens were loaded to 20% of the yield stress. When compared with compression-moulded poly(TMC), poly(ST-TMC-ST) specimens deform at a rate that is one to two orders of magnitude lower. Furthermore, poly(ST-TMC-ST) specimens showed complete dimensional recovery within 24 h after loading to 20% and 40% of the yield stress for 40 and 5.5 h, respectively. Highly porous poly(TMC) and poly(ST-TMC-ST) structures with interconnected pores were prepared by a method combining co-precipitation, compression moulding and salt leaching. After prolonged compressive deformation, solid and porous poly(ST-TMC-ST) discs showed significantly better recovery behaviour than poly(TMC) discs. PMID:15332603

  18. Robust conductive mesoporous carbon-silica composite films with highly ordered and oriented orthorhombic structures from triblock-copolymer template co-assembly

    SciTech Connect

    Song, Lingyan; Feng, Dan; Campbell, Casey G; Gu, Dong; Forster, Aaron M; Yager, Kevin G; Fredin, Nathaniel; Lee, Hae-Jeong; Jones, Ronald L; Zhao, Dongyuan; Vogt, Bryan D

    2012-07-11

    In this work, we describe a facile approach to improve the robustness of conductive mesoporous carbon-based thin films by the addition of silica to the matrix through the triconstituent organic-inorganic-organic co-assembly of resol (carbon precursor) and tetraethylorthosilicate (silica precursor) with triblock-copolymer Pluronic F127. The pyrolysis of the resol-silica-pluronic F127 film yields a porous composite thin film with well-defined mesostructure. X-Ray diffraction (XRD), grazing incidence small angle X-ray scattering (GISAXS), and electron microscopy measurements indicate that the obtained carbon-based thin films have a highly ordered orthorhombic mesostructure (Fmmm) with uniform large pore size (~3 nm). The orthorhombic mesostructure is oriented and the (010) plane is parallel to the silicon wafer substrate. The addition of silica to the matrix impacts the pore size, surface area, porosity, modulus and conductivity. For composite films with approximately 40 wt% silica, the conductivity is decreased by approximately an order of magnitude in comparison to a pure carbon mesoporous film, but the conductivity is comparable to typical printed carbon inks used in electrochemical sensing, {approx}10 S cm-1. The mechanical properties of these mesoporous silica-carbon hybrid films are similar to the pure carbon analogs with a Young's modulus between 10 GPa and 15 GPa, but the material is significantly more porous. Moreover, the addition of silica to the matrix appears to improve the adhesion of the mesoporous film to a silicon wafer. These mesoporous silica-carbon composite films have appropriate characteristics for use in sensing applications.

  19. RAFT polymerization of temperature- and salt-responsive block copolymers as reversible hydrogels

    PubMed Central

    Hemp, Sean T.; Smith, Adam E.; Bunyard, W. Clayton; Rubinstein, Michael H.; Long, Timothy E.

    2016-01-01

    Reversible-addition fragmentation chain transfer (RAFT) polymerization enabled the synthesis of novel, stimuli-responsive, AB and ABA block copolymers. The B block contained oligo(ethylene glycol) methyl ether methacrylate (OEG) and was permanently hydrophilic in the conditions examined. The A block consisted of diethylene glycol methyl ether methacrylate (DEG) and [2-(methacryloyloxy)ethyl]trimethylammonium chloride (TMA). The A block displayed both salt- and temperature-response with lower critical solution temperatures (LCSTs) dependent on the molar content of TMA and the presence of salt. Higher TMA content in the AB diblock copolymers increased the critical micelle temperatures (CMT) in HPLC-grade water due to an increased hydrophilicity of the A block. Upon addition of 0.9 wt% NaCl, the CMTs of poly(OEG-b-DEG95TMA5) decreased from 50 °C to 36 °C due to screening of electrostatic repulsion between the TMA units. ABA triblock copolymers displayed excellent hydrogel properties with salt- and temperature-dependent gel points. TMA incorporation in the A block increased the gel points for all triblock copolymers, and salt-response increased with higher TMA composition in the A block. For example, poly(DEG98TMA2-b-OEG-b-DEG98TMA2) formed a hydrogel at 40 °C in HPLC-grade water and 26 °C in 0.9 wt% NaCl aqueous solution. These salt- and temperature-responsive AB diblock and ABA triblock copolymers find applications as drug delivery vehicles, adhesives, and hydrogels. PMID:27041771

  20. Plastic deformation of triblock elastomers by molecular simulation

    NASA Astrophysics Data System (ADS)

    Parker, Amanda; Rottler, Jörg

    2015-03-01

    The mechanical properties of thermoplastic elastomers (TPE) can be greatly enhanced by exploiting the complex morphology of triblock copolymers. A common strategy consists of confining chain ends into hard glassy regions that effectively crosslink a soft rubbery phase. We present molecular dynamics simulations that provide insight into key microscopic behaviour of the copolymer chains during deformation. First, a coarse-grained polymer model with an ABA type configuration and soft interactions is employed to achieve equilibrated spherical morphologies. Our model TPEs contain at least 30 spheres in order to ensure configurational averaging. Elastoplastic deformation with uniaxial extension or volume conserving shear is then studied after hard excluded volume interactions have been reintroduced. We consider trends of stress-strain curves for different chain lengths, and compare to equivalent homopolymeric systems. During deformation we simultaneously track the evolution of the number and shape of the minority spheres, the proportion of chains bridging from one sphere to another, as well as local plastic deformation. The simulations reveal strong differences between deformation modes, the evolution of sphere morphology and chain anisotropy.

  1. Thermo-responsive release of curcumin from micelles prepared by self-assembly of amphiphilic P(NIPAAm-co-DMAAm)-b-PLLA-b-P(NIPAAm-co-DMAAm) triblock copolymers.

    PubMed

    Hu, Yanfei; Darcos, Vincent; Monge, Sophie; Li, Suming; Zhou, Yang; Su, Feng

    2014-12-10

    Thermo-responsive micelles are prepared by self-assembly of amphiphilic triblock copolymers composed of a poly(l-lactide) (PLLA) central block and two poly(N-isopropylacrylamide-co-N,N-dimethylacrylamide) (P(NIPAAm-co-DMAAm)) lateral blocks, using solvent evaporation/film hydration method. The resulting micelles exhibit very low critical micelle concentration (CMC) which slightly increases from 0.0113 to 0.0144 mg mL(-1) while the DMAAm content increases from 31.8 to 39.4% in the hydrophilic P(NIPAAm-co-DMAAm) blocks. The lower critical solution temperatures (LCST) of copolymers varies from 44.7 °C to 49.4 °C in water as determined by UV spectroscopy, and decreases by ca. 3.5 °C in phosphate buffered saline (PBS). Curcumin was encapsulated in the core of micelles. High drug loading up to 20% is obtained with high loading efficiency (>94%). The LCST of drug loaded micelles ranges from 37.5 to 38.0 °C with drug loading increasing from 6.0 to 20%. The micelles with diameters ranging from 47.5 to 88.2 nm remain stable over one month due to the negative surface charge as determined by zeta potential (-12.4 to -18.7 mV). Drug release studies were performed under in vitro conditions at 37 °C and 40 °C, i.e. below and above the LCST, respectively. Initial burst release is observed in all cases, followed by a slower release. The release rate is higher at 40 °C than that at 37 °C due to thermo-responsive release across the LCST. On the other hand, micelles with lower drug loading exhibit higher release rate than those with higher drug loading, which is assigned to the solubility effect. Peppas' theory was applied to describe the release behaviors. Moreover, the in vitro cytotoxicity of copolymers was evaluated using MTT assay. The results show that the copolymers present good cytocompatibility. Therefore, the nano-scale size, low CMC, high drug loading and stability, as well as good biocompatibility indicate that these thermo-responsive triblock copolymer micelles

  2. Order-order transitions in ABC triblock nanostructures

    SciTech Connect

    Zhong-Ren Chen; Kornfield, J.A.; Smith, S.; Satkowski, M.

    1996-12-31

    This report discusses a triblock copolymer of isoprene I, styrene S, and a random copolymer of styrene and isoprene. Optical methods are used to examine flow-induced alignment kinetics and final alignment state; nanostructures and global order are also studied.

  3. Block copolymer ion gels for gas separation

    NASA Astrophysics Data System (ADS)

    Gu, Yuanyan; Lodge, Timothy

    2012-02-01

    Carbon dioxide removal from light gases (eg. N2, CH4, and H2) is a very important technology for industrial applications such as natural gas sweetening, CO2 capture from coal-fire power plant exhausts and hydrogen production. Current CO2 separation method uses amine-absorption, which is energy-intensive and requires frequent maintenance. Membrane separation is a cost-effective solution to this problem, especially in small-scale applications. Ionic liquids have recently received increasing interest in this area because of their selective solubility for CO2 and non-volatility. However, ionic liquid itself lacks the persistent structure and mechanical integrity to withstand the high pressure for gas separation. Here, we report the development and gas separation performances of physically crosslinked ion gels based on self-assembly of ABA-triblock copolymers in ionic liquids. Three different types of polymers was used to achieve gelation in ionic liquids. Specifically, a triblock copolymer ion gel with a polymerized ionic liquid mid-block shows performances higher than the upper bound of well-known ``Robeson Plot'' for CO2/N2.

  4. Comparative Fluorescence Resonance Energy-Transfer Study in Pluronic Triblock Copolymer Micelle and Niosome Composed of Biological Component Cholesterol: An Investigation of Effect of Cholesterol and Sucrose on the FRET Parameters.

    PubMed

    Roy, Arpita; Kundu, Niloy; Banik, Debasis; Sarkar, Nilmoni

    2016-01-14

    The formation of pluronic triblock copolymer (F127)-cholesterol-based niosome and its interaction with sugar (sucrose) molecules have been investigated. The morphology of F127-cholesterol -based niosome in the presence of sucrose has been successfully demonstrated using dynamic light scattering (DLS) and transmission electron microscopic (TEM) techniques. The DLS profiles and TEM images clearly suggest that the size of the niosome aggregates increases significantly in the presence of sucrose. In addition to structural characterization, a detailed comparative fluorescence resonance energy transfer (FRET) study has been carried out in these F127-containing aggregates, involving coumarin 153 (C153) as donor (D) and rhodamine 6G (R6G) as an acceptor (A) to monitor the dynamic heterogeneity of the systems. Besides, time-resolved anisotropy and fluorescence correlation spectroscopy measurements have been carried out to monitor the rotational and lateral diffusion motion in these F127-cholesterol-based aggregates using C153 and R6G, respectively. During the course of FRET study, we have observed multiple time constants of FRET inside the F127-cholesterol-based niosomes in contrast with the F127 micelle. This corresponds to the presence of more than one preferential donor-acceptor (D-A) distance in niosomes than in F127 micelle. FRET has also been successfully used to probe the effect of sucrose on the morphology of F127-cholesterol-based niosome. In the presence of sucrose, the time constant of FRET further increases as the D-A distances increase in sucrose-decorated niosome. Finally, the excitation-wavelength-dependent FRET studies have indicated that as the excitation of donor molecules varies from 408 to 440 nm the contribution of the faster rise component of the acceptor enhances considerably, which clearly establishes the dynamics heterogeneity of both systems. Our findings also indicate that FRET is completely intravesicular in nature in these block copolymer

  5. Internal Nanoparticle Structure of Temperature-Responsive Self-Assembled PNIPAM-b-PEG-b-PNIPAM Triblock Copolymers in Aqueous Solutions: NMR, SANS, and Light Scattering Studies.

    PubMed

    Filippov, Sergey K; Bogomolova, Anna; Kaberov, Leonid; Velychkivska, Nadiia; Starovoytova, Larisa; Cernochova, Zulfiya; Rogers, Sarah E; Lau, Wing Man; Khutoryanskiy, Vitaliy V; Cook, Michael T

    2016-05-31

    In this study, we report detailed information on the internal structure of PNIPAM-b-PEG-b-PNIPAM nanoparticles formed from self-assembly in aqueous solutions upon increase in temperature. NMR spectroscopy, light scattering, and small-angle neutron scattering (SANS) were used to monitor different stages of nanoparticle formation as a function of temperature, providing insight into the fundamental processes involved. The presence of PEG in a copolymer structure significantly affects the formation of nanoparticles, making their transition to occur over a broader temperature range. The crucial parameter that controls the transition is the ratio of PEG/PNIPAM. For pure PNIPAM, the transition is sharp; the higher the PEG/PNIPAM ratio results in a broader transition. This behavior is explained by different mechanisms of PNIPAM block incorporation during nanoparticle formation at different PEG/PNIPAM ratios. Contrast variation experiments using SANS show that the structure of nanoparticles above cloud point temperatures for PNIPAM-b-PEG-b-PNIPAM copolymers is drastically different from the structure of PNIPAM mesoglobules. In contrast with pure PNIPAM mesoglobules, where solidlike particles and chain network with a mesh size of 1-3 nm are present, nanoparticles formed from PNIPAM-b-PEG-b-PNIPAM copolymers have nonuniform structure with "frozen" areas interconnected by single chains in Gaussian conformation. SANS data with deuterated "invisible" PEG blocks imply that PEG is uniformly distributed inside of a nanoparticle. It is kinetically flexible PEG blocks which affect the nanoparticle formation by prevention of PNIPAM microphase separation. PMID:27159129

  6. Impact of hydrogenation on physicochemical and biomedical properties of pH-sensitive PMAA-b-HTPB-b-PMAA triblock copolymer drug carriers.

    PubMed

    Xu, Feng; Xu, Jing-Wen; Luo, Yan-Ling

    2016-05-01

    pH-Sensitive poly(methacrylic acid)-block-hydroxyl-terminated polybutadiene-block-poly(methacrylic acid) (PMAA-b-HTPB-b-PMAA) was synthesized and then hydrogenated in this work. The chain structure, phase behavior and thermal properties were characterized by(1)H NMR, FTIR, XRD, DSC, TGA, etc., and the physicochemical and biomedical properties were investigated via fluorescence spectroscopy, TEM, DLS, loading and release of drug and MTT, and so on. The experimental results indicated that the hydrogenation led to the change in the chain aggregate structure of hydrophobic HTPB blocks and the formation of more stable spherical core-shell micelle aggregates, and the critical micelle concentration decreased from 41.8 mg L(-1)before hydrogenation to 4.4 mg L(-1)after hydrogenation. The hydrogenated block copolymer micelle aggregates exhibited pH-triggered response, and could entrap twice as much hydrophobic drug as the unhydrided counterparts and the encapsulation efficiency was significantly improved, which makes them fine to meet the requirements for drug carriers. Therefore, the hydrogenated PMAA-b-HTPB-b-PMAA copolymer micelles as drug target release carriers can be well used in the field of prevention and treatment of cancers. PMID:26939939

  7. Nano-ordered surface morphologies by stereocomplexation of the enantiomeric polylactide chains: specific interactions of surface-immobilized poly(D-lactide) and poly(ethylene glycol)-poly(L-lactide) block copolymers.

    PubMed

    Nakajima, Maho; Nakajima, Hajime; Fujiwara, Tomoko; Kimura, Yoshiharu; Sasaki, Sono

    2014-11-25

    Both AB diblock and ABA triblock copolymers consisting of poly(L-lactide) (PLLA: A) and poly(ethylene glycol) (PEG: B) were deposited on a silicon surface on which poly(D-lactide) (PDLA) had been preimmobilized. The deposit of the diblock copolymer (PLLA-PEG) formed band structures similar to those observed when the same copolymer was directly deposited on the silicon surface. In contrast, the deposit of the triblock copolymer (PLLA-PEG-PLLA) formed many particulates scattering over the surface. When the PLLA-PEG deposit was subjected to water-soaking, the original band morphology was completely replaced by the particulate morphology that was identical to that of the PLLA-PEG-PLLA deposit. Their FT-IR analyses revealed that both copolymers had been bound through the stereocomplex (sc) formation between the preimmobilized PDLA chains and the PLLA blocks of the copolymers. Grazing-incidence small-angle X-ray scattering (GISAXS) also supported these surface morphologies. It was therefore evident that hydrophilic PEG chains can be immobilized on the PDLA-preimmobilized surface by the sc formation. PMID:25365934

  8. Order-Disorder Transition (ODT) in Micelle-Forming A-B/A and A-B/B Diblock Copolymer/Homopolymer Blends

    NASA Astrophysics Data System (ADS)

    Dormidontova, Elena E.; Lodge, Timothy P.

    2002-03-01

    In the framework of strong segregation (Semenov-like) theory we consider the phase behavior and properties of solvent-free diblock copolymer/homopolymer blends. We consider the case in which the homopolymer is similar to either the A or B block of diblock copolymer. Addition of a homopolymer that is similar to the corona-forming block of the diblock copolymer decreases the ODT temperature and increases the temperature window corresponding to the stable disordered micelle state. Above some critical homopolymer concentration no ordered micelle state can be found. In the case that the added homopolymer is similar to the core-forming block macrophase separation plays an important role. In the framework of standard Flory-Huggins theory macrophase separation into ordered or disordered diblock copolymer micelle phase and pure homopolymer phase seems to be preferable to co-micellization of the homopolymers and diblock copolymers. In reality kinetic factors as well as surface interactions between co-existing phases can produce a metastable phase of ordered or disordered micelles formed by both diblock and homopolymers. We discuss the order-disorder and co-micellisation transitions for this case, the latter often having an anomalous character (very large initial miceller size) when the fraction of homopolymers is not too small.

  9. Fabrication of biomolecule copolymer hybrid nanovesicles as energy conversion systems

    NASA Astrophysics Data System (ADS)

    Ho, Dean; Chu, Benjamin; Lee, Hyeseung; Brooks, Evan K.; Kuo, Karen; Montemagno, Carlo D.

    2005-12-01

    This work demonstrates the integration of the energy-transducing proteins bacteriorhodopsin (BR) from Halobacterium halobium and cytochrome c oxidase (COX) from Rhodobacter sphaeroides into block copolymeric vesicles towards the demonstration of coupled protein functionality. An ABA triblock copolymer-based biomimetic membrane possessing UV-curable acrylate endgroups was synthesized to serve as a robust matrix for protein reconstitution. BR-functionalized polymers were shown to generate light-driven transmembrane pH gradients while pH gradient-induced electron release was observed from COX-functionalized polymers. Cooperative behaviour observed from composite membrane functionalized by both proteins revealed the generation of microamp-range currents with no applied voltage. As such, it has been shown that the fruition of technologies based upon bio-functionalizing abiotic materials may contribute to the realization of high power density devices inspired by nature.

  10. Block copolymers useful for enhanced oil recovery processes

    SciTech Connect

    Shu, P.

    1989-10-03

    This patent describes a method for permeability control of a subterranean formation and for enhancing oil recovery from the subterranean formation. The method comprising injecting into the subterranean formation an aqueous solution comprised of a block copolymer having the structural form of ABA triblock or (AB){sub n} multiblock wherein A is a crosslinkable polymer, B is a non-crosslinkable polymer or a polymer having low reactivity to crosslinking agents, n is a number of at least 2 and a crosslinking agent. Wherein A is selected from the group consisting of polyacrylic acid, partially hydrolyzed polyacrylamide, highly hydrolyzed polyacrylamide, partially hydrolyzed polyacrylic ester, highly hydrolyzed polyacrylic ester, polyvinyl alcohol and mixtures thereof and B is selected from the group consisting of polyacrylamide, partially hydrolyzed polyacrylamide, polyalkylene ethers, polyvinyl alcohol and polyvinylpyridine.

  11. Self-assembly of block copolymers grafted onto a flat substrate: Recent progress in theory and simulations

    NASA Astrophysics Data System (ADS)

    Zheng, Wang; Bao-Hui, Li

    2016-01-01

    Block copolymers are a class of soft matter that self-assemble to form ordered morphologies on the scale of nanometers, making them ideal materials for various applications. These applications directly depend on the shape and size of the self-assembled morphologies, and hence, a high degree of control over the self-assembly is desired. Grafting block copolymer chains onto a substrate to form copolymer brushes is a versatile method to fabricate functional surfaces. Such surfaces demonstrate a response to their environment, i.e., they change their surface topography in response to different external conditions. Furthermore, such surfaces may possess nanoscale patterns, which are important for some applications; however, such patterns may not form with spun-cast films under the same condition. In this review, we summarize the recent progress of the self-assembly of block copolymers grafted onto a flat substrate. We mainly concentrate on the self-assembled morphologies of end-grafted AB diblock copolymers, junction point-grafted AB diblock copolymers (i.e., Y-shaped brushes), and end-grafted ABA triblock copolymers. Special emphasis is placed on theoretical and simulation progress. Project supported by the National Natural Science Foundation of China (Grant Nos. 20990234, 20925414, and 91227121), the Program for Changjiang Scholars and Innovative Research Team in University, China (Grant No. IRT1257), the Programme of Introducing Talents of Discipline to Universities, China, and by the Tianhe No. 1, China.

  12. Enhanced Binding of Phenosafranin to Triblock Copolymer F127 Induced by Sodium Dodecyl Sulfate: A Mixed Micellar System as an Efficient Drug Delivery Vehicle.

    PubMed

    Mondal, Ramakanta; Ghosh, Narayani; Mukherjee, Saptarshi

    2016-03-24

    In this study, we explored the interaction of a cationic phenazinium dye, phenosafranin (PSF, here used as a model drug), with pluronic block copolymer F127, both in the presence and in the absence of the anionic surfactant sodium dodecyl sulfate (SDS), which forms mixed micelles with F127. We applied both steady-state and time-resolved spectroscopic techniques, along with isothermal titration calorimetry (ITC), to demonstrate the binding of the probe PSF to both the pluronic and F127/SDS mixed micelles. Dynamic light scattering (DLS) study revealed that, upon interaction with SDS, the hydrodynamic diameter (dH) of F127 micelles decreased due to the formation of the mixed micelles. The PSF penetrated to the more hydrophobic interior of the mixed micellar system as compared to F127 micelles alone. Micropolarity and fluorescence-quenching experiments revealed that PSF is more deeply seated in the case of F127/SDS mixed micelles. Through a partition coefficient, lifetime measurements, and time-resolved anisotropy experiments, we also established that the partitioning of the probe within the F127 micelles in the presence of SDS is almost double than that in its absence. ITC data corroborates the fact that the binding of PSF is the strongest and most thermodynamically favorable when mixed micelles are formed, which enables our system to serve as an excellent drug delivery vehicle when compared to F127 alone. PMID:26936205

  13. Integrated method of thermosensitive triblock copolymer-salt aqueous two phase extraction and dialysis membrane separation for purification of lycium barbarum polysaccharide.

    PubMed

    Wang, Yun; Hu, Xiaowei; Han, Juan; Ni, Liang; Tang, Xu; Hu, Yutao; Chen, Tong

    2016-03-01

    A polymer-salt aqueous two-phase system (ATPS) consisting of thermosensitive copolymer ethylene-oxide-b-propylene-oxide-b-ethylene-oxide (EOPOEO) and NaH2PO4 was employed in deproteinization for lycium barbarum polysaccharide (LBP). The effects of salt type and concentration, EOPOEO concentration, amount of crude LBP solution and temperature were studied. In the primary extraction process, LBP was preferentially partitioned to the bottom (salt-rich) phase with high recovery ratio of 96.3%, while 94.4% of impurity protein was removed to the top (EOPOEO-rich) phase. Moreover, the majority of pigments could be discarded to top phase. After phase-separation, the LBP in the bottom phase was further purified by dialysis membrane to remove salt and other small molecular impurities. The purity of LBP was enhanced to 64%. Additionally, the FT-IR spectrum was used to identify LBP. EOPOEO was recovered by a temperature-induced separation, and reused in a new ATPS. An ideal extraction and recycle result were achieved. PMID:26471552

  14. Effect of chain topology of block copolymer on micellization: ring vs linear block copolymer

    NASA Astrophysics Data System (ADS)

    Kim, Kwang Hee; Huh, June; Jo, Won Ho

    2003-03-01

    The aggregation of amphiphilic block copolymers in solution to form micelles has attracted great interest in recent years because of its importance in industrial applications. Many studies on these systems have mainly focused on a di- or triblock copolymer and much less attention was given to other architectures such as ring block copolymer. Recent experimental work has extended those works to include ring block copolymer, made by end-linking the triblock copolymer. Although the micellization of the ring block copolymer seemed to be favored over that of the linear triblock copolymer, two block copolymers showed similar values of cmc in experiments. In the present work, micellization of ring block copolymer (ring-B9A8) was simulated by Brownian dyanmics and micellar behavior is compared with triblock copolymer (A4B9A4) to investigate more systematically the effect of molecular architecture. Critical micelle concentration (cmc), average aggregation number and micellar distribution are compared with corresponding quantities measured for linear triblock copolymers having the same chain length and composition. Simulation results show that the cmc of ring-B9A8 is smaller than that of A4B9A4. The difference is explained by simple mean-field type theory.

  15. Sustained intra-articular release of celecoxib from in situ forming gels made of acetyl-capped PCLA-PEG-PCLA triblock copolymers in horses.

    PubMed

    Petit, Audrey; Redout, Everaldo M; van de Lest, Chris H; de Grauw, Janny C; Müller, Benno; Meyboom, Ronald; van Midwoud, Paul; Vermonden, Tina; Hennink, Wim E; René van Weeren, P

    2015-01-01

    In this study, the intra-articular tolerability and suitability for local and sustained release of an in situ forming gel composed of an acetyl-capped poly(ε-caprolactone-co-lactide)-b-poly(ethylene glycol)-b-poly(ε-caprolactone-co-lactide) (PCLA-PEG-PCLA) copolymer loaded with celecoxib was investigated in horse joints. The systems were loaded with two dosages of celecoxib, 50 mg/g ('low CLB gel') and 260 mg/g ('high CLB gel'). Subsequently, they were injected into the joints of five healthy horses. For 72 h after intra-articular injection, they induced a transient inflammatory response, which was also observed after application of Hyonate(®), a commercial formulation containing hyaluronic acid for the intra-articular treatment of synovitis in horses. However, only after administration of the 'high CLB gel' the horses showed signs of discomfort (lameness score: 1.6 ± 1.3 on a 5-point scale) 1 day after injection, which completely disappeared 3 days after injection. Importantly, there was no indication of cartilage damage. Celecoxib Cmax in the joints was reached at 8 h and 24 h after administration of the 'low CLB gel' and 'high CLB gel', respectively. In the joints, concentrations of celecoxib were detected 4 weeks post administration. Celecoxib was also detected in plasma at concentrations of 150 ng/ml at day 3 post administration and thereafter its concentration dropped below the detection limit. These results show that the systems were well tolerated after intra-articular administration and showed local and sustained release of celecoxib for 4 weeks with low and short systemic exposure to the drug, demonstrating that these injectable in situ forming hydrogels are promising vehicles for intra-articular drug delivery. PMID:25890740

  16. Directed self-assembly of high-chi block copolymer for nano fabrication of bit patterned media via solvent annealing.

    PubMed

    Xiong, Shisheng; Chapuis, Yves-Andre; Wan, Lei; Gao, He; Li, Xiao; Ruiz, Ricardo; Nealey, Paul F

    2016-10-14

    We report the formation of nanoimprint master templates that can be used for the fabrication of bit patterned media (BPM). The template was formed by directed self-assembly, with solvent annealing, of a symmetric ABA triblock copolymer to form perpendicularly oriented lamellae on chemical patterns. We used a high-χ block copolymer, poly(2-vinyl pyridine)-block-polystyrene-block-poly(2-vinyl pyridine) to achieve smaller feature sizes than are possible with polystyrene-block-poly(methyl methacrylate). The work shows that triblock copolymers can provide a large processing window in terms of pitch commensurability. Using block-selective infiltration (atomic layer deposition with sequential long soaking/purge cycles), an alumina composite with high etch resistance was specifically incorporated into the polar and hydrophilic P2VP domains. Subsequently, the surface pattern was successfully transferred into underlying Si substrates by etching with a fluorine-containing plasma to create a nanoimprint master. The line/space pattern of the nanoimprint master met the BPM fabrication requirement of defectivity <10(-3). For demonstration purposes, the nanoimprint master was used to imprint a replica pattern of photoresist on a quartz wafer. PMID:27606926

  17. Mixing a sol and a precipitate of block copolymers with different block ratios leads to an injectable hydrogel.

    PubMed

    Yu, Lin; Zhang, Zheng; Zhang, Huan; Ding, Jiandong

    2009-06-01

    A facile method to obtain a thermoreversible physical hydrogel was found by simply mixing an aqueous sol of a block copolymer with a precipitate of a similar copolymer but with a different block ratio. Two ABA-type triblock copolymers poly(D,L-lactic acid-co-glycolic acid)-B-poly(ethylene glycol)-B-poly(D,L-lactic acid-co-glycolic acid) (PLGA-PEG-PLGA) were synthesized. One sample in water was a sol in a broad temperature region, while the other in water was just a precipitate. The mixture of these two samples with a certain mix ratio underwent, however, a sol-to-gel-to-precipitate transition upon an increase of temperature. A dramatic tuning of the sol-gel transition temperature was conveniently achieved by merely varying mix ratio, even in the case of a similar molecular weight. Our study indicates that the balance of hydrophobicity and hydrophilicity within this sort of amphiphilic copolymers is critical to the inverse thermal gelation in water resulting from aggregation of micelles. The availability of encapsulation and sustained release of lysozyme, a model protein by the thermogelling systems was confirmed. This "mix" method provides a very convenient approach to design injectable thermogelling biomaterials with a broad adjustable window, and the novel copolymer mixture platform is potentially used in drug delivery and other biomedical applications. PMID:19385649

  18. Controlled/Living Radical Polymerization in the Undergraduate Laboratories. 1. Using ATRP to Prepare Block and Statistical Copolymers of n-Butyl Acrylate and Styrene

    NASA Astrophysics Data System (ADS)

    Beers, Kathryn L.; Woodworth, Brian; Matyjaszewski, Krzysztof

    2001-04-01

    A simple method of preparing well-defined (co)polymers has been developed for application in an advanced undergraduate laboratory. The method utilizes atom transfer radical polymerization (ATRP), a controlled/living radical polymerization, to prepare difunctional poly(n-butyl acrylate) with bromine end groups, which is chain-extended with styrene to yield an ABA triblock copolymer. Simultaneously, a statistical copolymer of the two monomers is prepared for comparison. The two copolymers are isolated and compositions and molecular weights are determined using 1H NMR and SEC, respectively. Optional additions to the experiment include performing a kinetic analysis of the homopolymerization using GC and SEC, and possibly comparing the results to those expected for conventional radical polymerization. Material differences in the copolymers can be observed qualitatively or measured using thermal or mechanical analysis. The lab is designed in such a way that several parts of the whole can be used to emphasize different areas of polymer science. A more synthetic course such as the organic synthesis lab can opt to investigate only the kinetic and composition analyses, whereas an engineering or materials science course may pursue more rigorous analysis of the materials' properties. Results included here are intended for application in an organic synthesis laboratory course.

  19. Calorimetric Study of Gradient Block-copolymers of Poly(butylacrylate) and Poly(methylmethacrylate)

    NASA Astrophysics Data System (ADS)

    Buzin, A. I.; Pyda, M.; Matyjaszewski, K.; Wunderlich, B.

    2002-03-01

    The miscibility and phase separation in the diblock (AB) and triblock (ABA) copolymers consisting of poly(butyl acrylate) (block B) and gradient copolymers of butyl acrylate and methyl methacrylate (block A) were investigated by means of conventional DSC as a function of the composition of the blocks A. In all copolymers studied, both blocks are presented by two separate glass transition temperatures. The low-temperature transition corresponds to devitrification of block B and is independent of composition and temperature is close to that of pure poly(butyl acrylate), while the higher transition corresponds to glass transition of the copolymeric block A, which decreases and broadens with increasing methylmethacrylate content in block A. The immiscible polymers are connected by chemical bonds, so that the mobilities of the phases influence each other. Shifts in the glass transition temperature and the broadening of the transitions as well as their asymmetry are discussed. --- Supported by NSF, Polymers Program, DMR-9703692, and the Div. of Mat. Sci., BES, DOE at ORNL, managed by UT-Batelle, LLC, for the U.S. Department of Energy, under contract number DOE-AC05-00OR22725.

  20. Structure and Dynamics of Cylinder Forming Block Copolymers in Thin Films

    NASA Astrophysics Data System (ADS)

    Tsarkova, Larisa A.

    In this chapter, we present fundamental aspects of the phase behavior and ordering dynamics in thin films of compositionally asymmetric block copoly- mers. Cylinder-forming AB diblock and ABA triblock copolymers are used as model systems. In the introduction we briefly describe the physics which commonly governs block copolymer phase behavior both in bulk and in thin films; then we define characteristic features of thin film behavior with spe- cial emphasis on the parameters that are readily controlled in experiments. Along with the discussion of surface fields and confinement effects in Sect. 2, we focus on the issues that are seldom discussed in the literature such as molecular weight and molecular architecture effects on the phase behavior and on microdomain dynamics (Sect. 2), and the analysis of the characteristic microdomain dimensions (Sect. 3).We present measurements of the character- istic spacings and film thickness with sub-micron resolution and demonstrate confinement induced distortions of microdomain dimensions in thin films rela- tive to the respective parameters in bulk. In Sect. 4 we describe time-resolved details of structural ordering of cylinder microdomains which indicate that the dynamics of defect annihilation in block copolymer thin films is considerably more complex than anticipated so far.

  1. Self-assembly of the triblock copolymer 17R4 poly(propylene oxide)₁₄-poly(ethylene oxide)₂₄-poly(propylene oxide)₁₄ in D₂O.

    PubMed

    Kumi, Bryna C; Hammouda, Boualem; Greer, Sandra C

    2014-11-15

    Our recent investigation of the three regions of the phase diagram of 17R4 in D2O (Huff et al., 2011) has led us to study the copolymer structure in this system by small-angle neutron scattering, rheometry, and dynamic light scattering. In region I at low temperatures and copolymer concentrations (0-30°C, 0.1-0.2 mass fraction ω), the cloudy solution contains the copolymer in large clusters made of hydrophobic PPO-rich "knots" bridged by dissolved hydrophilic PEO chains. These clusters vanish in region I at the lower temperatures and concentrations (below 39°C and ω=0.01). In region I over long times (weeks) at 25°C, a white liquid/gel film forms at the air-D2O interface. In region II at temperatures above the micellization line (above about 35°C, at ω=0.22) the large clusters dissipate and unimers coexist with "flower micelles," where the PPO blocks are the centers of the micelles and the PEO blocks loop into the solvent. In region III at still higher temperatures (above about 40°C at ω=0.2), the solution separates into coexisting liquid phases, where the upper phase of higher copolymer concentration is in region II, and the lower phase is in region I. The concentrated upper phase may contain micelles so crowded as to form a network. PMID:25203912

  2. Structure property relations in glassy-semicrystalline block copolymers

    NASA Astrophysics Data System (ADS)

    Khanna, Vikram

    The ability of block copolymers to segregate into nanoscale morphologies makes them a versatile class of engineering materials. This work investigates the relation between the block copolymer structure and its mechanical properties, film dynamics and diffusion kinetics. The first part investigates the influence of structure on the mechanical properties of poly(cyclohexylethylene)-poly(ethylene) (PCHE-PE) block copolymer films. For lamellar block copolymers the mechanical properties depend significantly on the chain architecture (diblock, triblock and pentablock). Diblock copolymer films show complete failure at small strains and pentablock copolymer films show the toughest, response. Moreover, the orientation of the cylinders in a cylinder forming pentablock copolymer affects the toughness of the block copolymer films. In the second part, the effect of surface energy and chain architecture on the orientation of microdomains in the same block copolymer films is investigated. Cylindrical and lamellar triblock copolymers with a PE midblock orient their microdomains normal to the surface. However, a lamellar diblock copolymer prefers a parallel orientation of the sheets with an E surface. Moreover, a cylindrical triblock copolymer with a reduced surface energy poly(ethylene-butylene) midblock orders with the cylinder domains oriented parallel to the surface. Self-consistent field theory calculations suggest that the entropic cost of forming a wetting layer comprised entirely of looping blocks for the triblock architecture, a constraint absent in diblock copolymers, stabilizes the perpendicular orientation. Thus in triblock copolymers, parallel orientations are only stabilized when the surface energy of the midblock is small enough to compensate for this conformational penalty. Finally, a study of the diffusion kinetics of cylinder forming poly(styrene)-poly(ethylene) triblock (SES) and pentablock (SESES) copolymers suggests that for similar molecular weights SESES

  3. Membranes with artificial free-volume enabled by block copolymer self-assembly

    NASA Astrophysics Data System (ADS)

    Petzetakis, Nikos; Balsara, Nitash

    2015-03-01

    There has been considerable success towards the development of polymeric porous materials with pore sizes in the meso- or macro-scale regime. However, manipulation of polymer porosity in the micro-scale (pore diameter < 2nm) remains challenging. Previous studies relied on changes on the chemical composition and structure of the polymeric material in order to achieve the formation of larger fractional free volume. In the present report we demonstrate a methodology with which we can force a polymeric material away from structural equilibrium and then kinetically arrest it at this -out of equilibrium- state, ultimately, enabling the creation of a polymeric material with artificial free volume. Our methodology is based on block copolymer/homopolymer binary blend self-assembly where the membranes are made by first creating a heterogeneous film of a ABA type triblock copolymer containing a soluble homopolymer, B. Then in a second washing step the soluble homopolymer chains are dissolved away. The volume fraction of the composite membrane occupied initially by chains of homopolymer B is now converted to extra free volume in the microphase of block B. Key role of block A is to kinetically arrest the structure of the polymer during and after the washing step.

  4. Amphiphilic block copolymer nanocontainers as bioreactors

    NASA Astrophysics Data System (ADS)

    Nardin, C.; Widmer, J.; Winterhalter, M.; Meier, W.

    2001-04-01

    Self-assembly of an amphiphilic triblock copolymer carrying polymerizable end-groups is used to prepare nanometer-sized vesicular structures in aqueous solution. The triblock copolymer shells of the vesicles can be regarded as a mimetic of biological membranes although they are 2 to 3 times thicker than a conventional lipid bilayer. Nevertheless, they can serve as a matrix for membrane-spanning proteins. Surprisingly, the proteins remain functional despite the extreme thickness of the membranes and that even after polymerization of the reactive triblock copolymers. This opens a new field to create mechanically stable protein/polymer hybrid membranes. As a representative example we functionalize (polymerized) triblock copolymer vesicles by reconstituting a channel-forming protein from the outer cell wall of Gram-negative bacteria. The protein used (OmpF) acts as a size-selective filter, which allows only for passage of molecules with a molecular weight below 400 g mol^{-1}. Therefore substrates may still have access to enzymes encapsulated in such protein/polymer hybrid nanocontainers. We demonstrate this using the enzyme β -lactamase which is able to hydrolyze the antibiotic ampicillin. In addition, a transmembrane voltage above a given threshold causes a reversible gating transition of OmpF. This can be used to reversibly activate or deactivate the resulting nanoreactors.

  5. Controlled/Living Radical Polymerization in the Undergraduate Laboratories. 2. Using ATRP in Limited Amounts of Air to Prepare Block and Statistical Copolymers of n-Butyl Acrylate and Styrene

    NASA Astrophysics Data System (ADS)

    Matyjaszewski, Krzysztof; Beers, Kathryn L.; Woodworth, Brian; Metzner, Zachary

    2001-04-01

    Developments in controlled radical polymerization have facilitated the use of living polymer chemistry in the undergraduate laboratories. In the first paper of this series, a procedure for the use of atom transfer radical polymerization (ATRP) to prepare block and statistical copolymers was described and the use of kinetic analysis to differentiate between living and conventional processes was demonstrated. In this paper, the experiment is extended to polymerizations run in limited amounts of air so that the use of inert gases is unnecessary. The Cu(I) catalyst can be lost owing to oxidation or termination reactions; however, a scavenger, Cu(0), is added to react with oxidized catalyst to regenerate the Cu(I) complex. A difunctional macroinitiator of poly(n-butyl acrylate) is prepared and chain-extended with polystyrene. A statistical copolymer using the same monomer pair is also prepared. These copolymers are isolated and characterized along with the homopolymeric macroinitiator using 1H NMR and SEC. Kinetic analysis is also carried out using GC and SEC. The significant difference in these two approaches, in addition to slight variations in the reaction conditions, is apparent in the chain extension to yield the ABA triblock copolymer.

  6. Mechanistic analysis of Zein nanoparticles/PLGA triblock in situ forming implants for glimepiride

    PubMed Central

    Ahmed, Osama Abdelhakim Aly; Zidan, Ahmed Samir; Khayat, Maan

    2016-01-01

    Objectives The study aims at applying pharmaceutical nanotechnology and D-optimal fractional factorial design to screen and optimize the high-risk variables affecting the performance of a complex drug delivery system consisting of glimepiride–Zein nanoparticles and inclusion of the optimized formula with thermoresponsive triblock copolymers in in situ gel. Methods Sixteen nanoparticle formulations were prepared by liquid–liquid phase separation method according to the D-optimal fractional factorial design encompassing five variables at two levels. The responses investigated were glimepiride entrapment capacity (EC), particle size and size distribution, zeta potential, and in vitro drug release from the prepared nanoparticles. Furthermore, the feasibility of embedding the optimized Zein-based glimepiride nanoparticles within thermoresponsive triblock copolymers poly(lactide-co-glycolide)-block-poly(ethylene glycol)-block-poly(lactide-co-glycolide) in in situ gel was evaluated for controlling glimepiride release rate. Results Through the systematic optimization phase, improvement of glimepiride EC of 33.6%, nanoparticle size of 120.9 nm with a skewness value of 0.2, zeta potential of 11.1 mV, and sustained release features of 3.3% and 17.3% drug released after 2 and 24 hours, respectively, were obtained. These desirability functions were obtained at Zein and glimepiride loadings of 50 and 75 mg, respectively, utilizing didodecyldimethylammonium bromide as a stabilizer at 0.1% and 90% ethanol as a common solvent. Moreover, incorporating this optimized formulation in triblock copolymers-based in situ gel demonstrated pseudoplastic behavior with reduction of drug release rate as the concentration of polymer increased. Conclusion This approach to control the release of glimepiride using Zein nanoparticles/triblock copolymers-based in situ gel forming intramuscular implants could be useful for improving diabetes treatment effectiveness. PMID:26893561

  7. Effect of poly(ethylene oxide) homopolymer and two different poly(ethylene oxide-b-poly(propylene oxide)-b-poly(ethylene oxide) triblock copolymers on morphological, optical, and mechanical properties of nanostructured unsaturated polyester.

    PubMed

    Builes, Daniel H; Hernández-Ortiz, Juan P; Corcuera, Ma Angeles; Mondragon, Iñaki; Tercjak, Agnieszka

    2014-01-22

    Novel nanostructured unsaturated polyester resin-based thermosets, modified with poly(ethylene oxide) (PEO), poly(propylene oxide) (PPO), and two poly(ethylene oxide-b-propylene oxide-b-ethylene oxide) block copolymers (BCP), were developed and analyzed. The effects of molecular weights, blocks ratio, and curing temperatures on the final morphological, optical, and mechanical properties were reported. The block influence on the BCP miscibility was studied through uncured and cured mixtures of unsaturated polyester (UP) resins with PEO and PPO homopolymers having molecular weights similar to molecular weights of the blocks of BCP. The final morphology of the nanostructured thermosetting systems, containing BCP or homopolymers, was investigated, and multiple mechanisms of nanostructuration were listed and explained. By considering the miscibility of each block before and after curing, it was determined that the formation of the nanostructured matrices followed a self-assembly mechanism or a polymerization-induced phase separation mechanism. The miscibility between PEO or PPO blocks with one of two phases of UP matrix was highlighted due to its importance in the final thermoset properties. Relationships between the final morphology and thermoset optical and mechanical properties were examined. The mechanisms and physics behind the morphologies lead toward the design of highly transparent, nanostructured, and toughened thermosetting UP systems. PMID:24354274

  8. Computer simulations of block copolymer tethered nanoparticle self-assembly

    NASA Astrophysics Data System (ADS)

    Chan, Elaine R.; Ho, Lin C.; Glotzer, Sharon C.

    2006-08-01

    We perform molecular simulations to study the self-assembly of block copolymer tethered cubic nanoparticles. Minimal models of the tethered nanoscale building blocks (NBBs) are utilized to explore the structures arising from self-assembly. We demonstrate that attaching a rigid nanocube to a diblock copolymer affects the typical equilibrium morphologies exhibited by the pure copolymer. Lamellar and cylindrical phases are observed in both systems but not at the corresponding relative copolymer tether block fractions. The effect of nanoparticle geometry on phase behavior is investigated by comparing the self-assembled structures formed by the tethered NBBs with those of their linear ABC triblock copolymer counterparts. The tethered nanocubes exhibit the conventional triblock copolymer lamellar and cylindrical phases when the repulsive interactions between different blocks are symmetric. The rigid and bulky nature of the cube induces interfacial curvature in the tethered NBB phases compared to their linear ABC triblock copolymer counterparts. We compare our results with those structures obtained from ABC diblock copolymer tethered nanospheres to further elucidate the role of cubic nanoparticle geometry on self-assembly.

  9. Microphase Separation within Disk Shaped Aggregates of Triblock Bottlebrushes.

    PubMed

    Long, Meiling; Shi, Yi; Zhang, Ke; Chen, Yongming

    2016-04-01

    Well-defined AbBA triblock bottlebrush with poly(N,N-dimethyl acrylamide) (PAm) as A block and polyacrylate, densely grafted with poly(tert-butyl acrylate)-block-polystyrene (PBA-b-PS), as brush bB block is prepared by controlled radical polymerization and click chemistry. The triblock copolymer with a composition of PAm200 -b-b(PBA14 -b-PS47 )167 -b-PAm200 is obtained and is further transformed into PAm200 -b-b(PAA14 -b-PS47 )167 -b-PAm200 by hydrolysis of the PBA segment into poly(acrylic acid) (PAA). In a mixture of N,N-dimethylformamide (DMF) and methanol, a poor solvent of bB block, PAm200 -b-b(PAA14 -b-PS47 )167 -b-PAm200 self-assembled into disk-like platelets, which have an internal lamellar structure by further microphase-separation of PAA-b-PS branches in 2D. Moreover, Ag nanoparticles are aligned by PAA segments along the disk to form a pattern. PMID:26866716

  10. Pluronic triblock copolymer systems and their interactions with Ibuprofen.

    PubMed

    Foster, Beth; Cosgrove, Terence; Hammouda, Boualem

    2009-06-16

    Small-angle neutron scattering and pulsed-field gradient stimulated-echo nuclear magnetic resonance (NMR) have been used to study the structural characteristics of aqueous Pluronic solutions. In particular, changes in the micellar structure upon addition of ibuprofen to the solutions and altering the temperature have been investigated. Increases in temperature and ibuprofen concentration both appear to favor micellization, with increases observed in the aggregation number, fraction of polymer micellized, and core radius of the micelle, along with a decrease in the volume fraction of the solvent in the core. At high drug concentrations and/or temperatures, micelles of the more hydrophobic Pluronics scatter neutrons strongly at low Q, indicating attractive interactions between micelles or a change in the shape of the aggregates. The addition of ibuprofen to Pluronic P104 has also been found to reduce the critical micellization temperature from approximately 20 degrees C to below 13 degrees C. The hydrophobicity of the Pluronic, quantity of ibuprofen present, and temperature of the solution all seem to have a strong influence on the extent and nature of aggregation observed. PMID:19374338

  11. Nonlinear Elasticity and Cavitation of a Triblock Copolymer Gel

    NASA Astrophysics Data System (ADS)

    Kundu, Santanu; Hashemnejad, Seyed Meysam; Zabet, Mahla; Mishra, Satish

    2015-03-01

    Polymer gels are subjected to large-strain deformation during their applications. The gel deformation at large-strain is non-linear and can often lead to failure of the material. Here, we report the large-strain deformation behavior of a physically cross-linked, swollen polymer gel, which displays unique strain-stiffening response at large-strain. Investigations were performed using large amplitude oscillatory shear (LAOS) and custom developed cavitation rheology techniques. Gent constitutive model, which considers finite extensibility of midblock, was fitted with the LAOS data, therefore, linking the estimated parameters from LAOS analysis to the structure of the gel. Cavitation experiments were conducted as a function of temperature. Both analytical method and finite-element based modeling have been implemented to capture the pressure response in cavitation experiments. Our results provide a critical understanding of gel failure mechanism at large-strain.

  12. A strategy to explore stable and metastable ordered phases of block copolymers.

    PubMed

    Xu, Weiquan; Jiang, Kai; Zhang, Pingwen; Shi, An-Chang

    2013-05-01

    Block copolymers with their rich phase behavior and ordering transitions have become a paradigm for the study of structured soft materials. A major challenge in the study of the phase behavior of block copolymers is to obtain different stable and metastable phases of the system. A strategy to discover complex ordered phases of block copolymers within the self-consistent field theory framework is developed by a combination of fast algorithms and novel initialization procedures. This strategy allows the generation of a large number of candidate structures, which can then be used to construct phase diagrams. Application of the strategy is illustrated using ABC star triblock copolymers as an example. A large number of candidate structures, including many three-dimensionally ordered phases, of the system are obtained and categorized. A phase diagram is constructed for symmetrically interacting ABC star triblock copolymers. PMID:23551204

  13. Biochemical characterization of the aba2 and aba3 mutants in Arabidopsis thaliana.

    PubMed Central

    Schwartz, S H; Léon-Kloosterziel, K M; Koornneef, M; Zeevaart, J A

    1997-01-01

    Abscisic acid (ABA)-deficient mutants in a variety of species have been identified by screening for precocious germination and a wilty phenotype. Mutants at two new loci, aba2 and aba3, have recently been isolated in Arabidopsis thaliana (L.) Hynh. (K.M. Léon-Kloosterziel, M. Alvarez-Gil, G.J. Ruijs, S.E. Jacobsen, N.E. Olszewski, S.H. Schwartz, J.A.D. Zeevaart, M. Koornneef [1996] Plant J 10: 655-661), and the biochemical characterization of these mutants is presented here. Protein extracts from aba2 and aba3 plants displayed a greatly reduced ability to convert xanthoxin to ABA relative to the wild type. The next putative intermediate in ABA synthesis, ABA-aldehyde, was efficiently converted to ABA by extracts from aba2 but not by extracts from aba3 plants. This indicates that the aba2 mutant is blocked in the conversion of xanthoxin to ABA-aldehyde and that aba3 is impaired in the conversion of ABA-aldehyde to ABA. Extracts from the aba3 mutant also lacked additional activities that require a molybdenum cofactor (Moco). Nitrate reductase utilizes a Moco but its activity was unaffected in extracts from aba3 plants. Moco hydroxylases in animals require a desulfo moiety of the cofactor. A sulfido ligand can be added to the Moco by treatment with Na2S and dithionite. Treatment of aba3 extracts with Na2S restored ABA-aldehyde oxidase activity. Therefore, the genetic lesion in aba3 appears to be in the introduction of S into the Moco. PMID:9159947

  14. Biochemical characterization of the aba2 and aba3 mutants in Arabidopsis thaliana.

    PubMed

    Schwartz, S H; Léon-Kloosterziel, K M; Koornneef, M; Zeevaart, J A

    1997-05-01

    Abscisic acid (ABA)-deficient mutants in a variety of species have been identified by screening for precocious germination and a wilty phenotype. Mutants at two new loci, aba2 and aba3, have recently been isolated in Arabidopsis thaliana (L.) Hynh. (K.M. Léon-Kloosterziel, M. Alvarez-Gil, G.J. Ruijs, S.E. Jacobsen, N.E. Olszewski, S.H. Schwartz, J.A.D. Zeevaart, M. Koornneef [1996] Plant J 10: 655-661), and the biochemical characterization of these mutants is presented here. Protein extracts from aba2 and aba3 plants displayed a greatly reduced ability to convert xanthoxin to ABA relative to the wild type. The next putative intermediate in ABA synthesis, ABA-aldehyde, was efficiently converted to ABA by extracts from aba2 but not by extracts from aba3 plants. This indicates that the aba2 mutant is blocked in the conversion of xanthoxin to ABA-aldehyde and that aba3 is impaired in the conversion of ABA-aldehyde to ABA. Extracts from the aba3 mutant also lacked additional activities that require a molybdenum cofactor (Moco). Nitrate reductase utilizes a Moco but its activity was unaffected in extracts from aba3 plants. Moco hydroxylases in animals require a desulfo moiety of the cofactor. A sulfido ligand can be added to the Moco by treatment with Na2S and dithionite. Treatment of aba3 extracts with Na2S restored ABA-aldehyde oxidase activity. Therefore, the genetic lesion in aba3 appears to be in the introduction of S into the Moco. PMID:9159947

  15. Macroscopic phase decomposition in block copolymers driven by thermooxidative reactions

    NASA Astrophysics Data System (ADS)

    Fan, Shaobin

    Macroscopic phase separations have been observed in a commercial styrene- block-butadiene-block-styrene (SBS) triblock copolymer (Kraton 1102), an as-synthesized SBS triblock copolymer, an as-synthesized styrene-block-butadiene (SB) diblock copolymer and a commercial styrene-block-isoprene-block-styrene (SIS) triblock copolymer (Kraton 1107) at elevated temperatures. To the best of our knowledge, this is the first report on macroscopic phase separations in neat copolymers, including block copolymers. The temporal evolution of the structure, growth dynamics, origin and mechanism of the macroscopic phase separations have been investigated. A theoretical model has been established to describe such phase separation in SB diblock copolymer and numerical simulations have been undertaken to predict the structure evolution and growth dynamics. For styrene-butadiene block copolymers, the phase transition process consists of the first and second phase separations. The origin of such phase separations is attributed to chain scission and crosslinking reactions due to thermooxidative degradation. The formation of phase separated domains is the result of separation of polystyrene-rich domains from polybutadiene-rich domains. A mechanism, termed secondary spinodal decomposition, has been proposed to explain second phase separation. It has also demonstrated that the theoretical model and numerical simulations capture the essential features of the experimental observations. Growth rate was seen to depend on phase separation as well as reaction kinetics. The universal scaling laws have been shown to be invalid in macroscopic phase separations of styrene-butadiene block copolymers. The macroscopic phase separation process is more complex in the SIS triblock copolymer. It consists of a first phase separation, phase dissolution and a second phase separation. The origin of such phase decompositions has been shown to be a progressive chain scission reaction during thermal oxidative

  16. Fluorine-Containing ABC Linear Triblock Terpolymers: Synthesis and Self-assembly in Solution

    SciTech Connect

    He, Lihong; Hinestrosa Salazar, Juan P; Pickel, Joseph M; Kilbey, II, S Michael; Mays, Jimmy; Zhang, Shanju; Bucknall, David G.; Hong, Kunlun

    2011-01-01

    In this paper a fluorine-containing monomer, 2-fluroroethyl methacrylate (2FEMA) was used to synthesize the linear triblock terpolymer poly(n-butyl methacrylate)-poly(methyl methacrylate)-poly(2-fluoroethyl methacrylate) (PnBMA-PMMA-P2FEMA). A kinetic study of the homopolymerization of 2FEMA by reversible addition-fragmentation chain transfer (RAFT) polymerization showed that it demonstrates living character and produces well defined polymers with reasonably narrow polydispersities (~1.30). Triblock terpolymers were prepared sequentially using a purified Macro-CTA at 70 oC, resulting in final terpolymers with high Dp for each block (>150) and with polydispersities between 1.6 and 2.1. The structure and molecular weights of the resultant PnBMA-PMMA-P2FEMA triblock terpolymers were characterized via 1H NMR, 19F NMR, and gel permeation chromatography (GPC). Self-assembly of these polymers was carried out in a selective solvent and the micellar aggregates (MAs) thereby formed were analyzed using scanning electron microscopy (SEM) and dynamic light scattering (DLS). It was confirmed from SEM that these copolymers could directly self-organize into large compound micelles in tetrahydrofuran/methanol with different diameters, depending on polymer composition.

  17. Morphologies of ABC Triblock Terpolymer Melts Containing Poly(Cyclohexadiene): Effects of Conformational Asymmetry

    SciTech Connect

    Kumar, Rajeev; Sides, Scott W.; Goswami, Monojoy; Sumpter, Bobby G.; Hong, Kunlun; Wu, Xiaodong; Russell, Thomas P.; Gido, Samuel P.; Misichronis, Konstantinos; Rangou, Sofia; Avgeropoulos, Apostolos; Tsoukatos, Thodoris; Hadjichristidis, Nikos; Beyer, Frederick L.; Mays, Jimmy W.

    2013-02-12

    We have synthesized linear ABC triblock terpolymers containing poly(1,3-cyclohexadiene), PCHD, as an end block and characterized their morphologies in the melt. Specifically, we have studied terpolymers containing polystyrene (PS), polybutadiene (PB), and polyisoprene (PI) as the other blocks. Systematically varying the ratio of 1,2- /1,4-microstructures of poly(1,3-cyclohexadiene), we have studied the effects of conformational asymmetry among the three blocks on the morphologies using transmission electron microscopy (TEM), small-angle X-ray scattering (SAXS), and self-consistent field theory (SCFT) performed with PolySwift++. Our work reveals that the triblock terpolymer melts containing a high percentage of 1,2-microstructures in the PCHD block are disordered at 110 °C for all the samples, independent of sequence and volume fraction of the blocks. In contrast, the triblock terpolymer melts containing a high percentage of 1,4-microstructure form regular morphologies known from the literature. The accuracy of the SCFT calculations depends on calculating the χ parameters that quantify the repulsive interactions between different monomers. Simulations using χ values obtained from solubility parameters and group contribution methods are unable to reproduce the morphologies as seen in the experiments. However, SCFT calculations accounting for the enhancement of the χ parameter with an increase in the conformational asymmetry lead to an excellent agreement between theory and experiments. These results highlight the importance of conformational asymmetry in tuning the χ parameter and, in turn, morphologies in block copolymers.

  18. Hierarchical templating of a BiFeO3-CoFe2O4 multiferroic nanocomposite by a triblock terpolymer film.

    PubMed

    Choi, Hong Kyoon; Aimon, Nicolas M; Kim, Dong Hun; Sun, Xue Yin; Gwyther, Jessica; Manners, Ian; Ross, Caroline A

    2014-09-23

    A process route to fabricate templated BiFeO3/CoFe2O4 (BFO/CFO) vertical nanocomposites is presented in which the self-assembly of the BFO/CFO is guided using a self-assembled triblock terpolymer. A linear triblock terpolymer was selected instead of a diblock copolymer in order to produce a square-symmetry template, which had a period of 44 nm. The triblock terpolymer pattern was transferred to a (001) Nb:SrTiO3 substrate to produce pits that formed preferential sites for the nucleation of CFO crystals, in contrast to the BFO, which wetted the flat regions of the substrate. The crystallographic orientation and magnetic properties of the templated BFO/CFO were characterized. PMID:25184546

  19. ABA-alcohol is an intermediate in abscisic acid biosynthesis

    SciTech Connect

    Rock, C.D.; Zeevaart, J.A.D. )

    1990-05-01

    It has been established that ABA-aldehyde is a precursor to ABA. The ABA-deficient flacca and sitiens mutants of tomato are blocked in the conversion of ABA-aldehyde to ABA, and accumulate trans-ABA-alcohol. {sup 18}O-Labeling studies of ABA in flacca and sitiens show that these mutants synthesize a large percentage of ({sup 18}O)ABA which contains two {sup 18}O atoms in the carboxyl group. Furthermore, the mutants synthesize much greater amounts of trans-ABA-glucose ester (t-ABA-GE) compared with the wild type, and this ({sup 18}O)t-ABA-GE is also double labeled in the carboxyl group. Our interpretation of these data is that the {sup 18}O in ABA-aldehyde is trapped in the side chain by reduction to ({sup 18}O)ABA-alcohol, followed by isomerization to ({sup 18}O)t-ABA-alcohol and oxidation with {sup 18}O{sub 2} to ({sup 18}O)t-ABA. The ({sup 18}O)t-ABA is then rapidly converted to ({sup 18}O)t-ABA-GE. Because ({sup 18}O)ABA doubly labeled in the carboxyl group has been observed in small amounts in labeling experiments with several species, and various species have been shown to convert ABA-aldehyde to ABA-alcohol and t-ABA-alcohol, we propose that ABA-alcohol is an ABA intermediate in a shunt pathway.

  20. 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.

  1. ABA Receptors: Past, Present and Future

    SciTech Connect

    Guo, Jianjun; Yang, Xiaohan; Weston, David; Chen, Jay

    2011-01-01

    Abscisic acid (ABA) is the key plant stress hormone. Consistent with the earlier studies in support of the presence of both membrane- and cytoplasm-localized ABA receptors, recent studies have identified multiple ABA receptors located in various subcellular locations. These include a chloroplast envelope-localized receptor (the H subunit of Chloroplast Mg2+-chelatase/ABA Receptor), two plasma membrane-localized receptors (G-protein Coupled Receptor 2 and GPCR-type G proteins), and one cytosol/nucleus-localized Pyrabactin Resistant (PYR)/PYR-Like (PYL)/Regulatory Component of ABA Receptor 1 (RCAR). Although the downstream molecular events for most of the identified ABA receptors are currently unknown, one of them, PYR/PYL/RACR was found to directly bind and regulate the activity of a long-known central regulator of ABA signaling, the A-group protein phosphatase 2C (PP2C). Together with the Sucrose Non-fermentation Kinase Subfamily 2 (SnRK2s) protein kinases, a central signaling complex (ABA-PYR-PP2Cs-SnRK2s) that is responsible for ABA signal perception and transduction is supported by abundant genetic, physiological, biochemical and structural evidence. The identification of multiple ABA receptors has advanced our understanding of ABA signal perception and transduction while adding an extra layer of complexity.

  2. Rational design of ABC triblock terpolymer solution nanostructures with controlled patch morphology

    PubMed Central

    Löbling, Tina I.; Borisov, Oleg; Haataja, Johannes S.; Ikkala, Olli; Gröschel, André H.; Müller, Axel H. E.

    2016-01-01

    Block copolymers self-assemble into a variety of nanostructures that are relevant for science and technology. While the assembly of diblock copolymers is largely understood, predicting the solution assembly of triblock terpolymers remains challenging due to complex interplay of block/block and block/solvent interactions. Here we provide guidelines for the self-assembly of linear ABC triblock terpolymers into a large variety of multicompartment nanostructures with C corona and A/B cores. The ratio of block lengths NC/NA thereby controls micelle geometry to spheres, cylinders, bilayer sheets and vesicles. The insoluble blocks then microphase separate to core A and surface patch B, where NB controls the patch morphology to spherical, cylindrical, bicontinuous and lamellar. The independent control over both parameters allows constructing combinatorial libraries of unprecedented solution nanostructures, including spheres-on-cylinders/sheets/vesicles, cylinders-on-sheets/vesicles, and sheets/vesicles with bicontinuous or lamellar membrane morphology (patchy polymersomes). The derived parameters provide a logical toolbox towards complex self-assemblies for soft matter nanotechnologies. PMID:27352897

  3. Rational design of ABC triblock terpolymer solution nanostructures with controlled patch morphology

    NASA Astrophysics Data System (ADS)

    Löbling, Tina I.; Borisov, Oleg; Haataja, Johannes S.; Ikkala, Olli; Gröschel, André H.; Müller, Axel H. E.

    2016-06-01

    Block copolymers self-assemble into a variety of nanostructures that are relevant for science and technology. While the assembly of diblock copolymers is largely understood, predicting the solution assembly of triblock terpolymers remains challenging due to complex interplay of block/block and block/solvent interactions. Here we provide guidelines for the self-assembly of linear ABC triblock terpolymers into a large variety of multicompartment nanostructures with C corona and A/B cores. The ratio of block lengths NC/NA thereby controls micelle geometry to spheres, cylinders, bilayer sheets and vesicles. The insoluble blocks then microphase separate to core A and surface patch B, where NB controls the patch morphology to spherical, cylindrical, bicontinuous and lamellar. The independent control over both parameters allows constructing combinatorial libraries of unprecedented solution nanostructures, including spheres-on-cylinders/sheets/vesicles, cylinders-on-sheets/vesicles, and sheets/vesicles with bicontinuous or lamellar membrane morphology (patchy polymersomes). The derived parameters provide a logical toolbox towards complex self-assemblies for soft matter nanotechnologies.

  4. 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.

  5. Synthesis, Characterization (Molecular-Morphological) and Theoretical Morphology Predictions of Poly(cyclohexadiene) Containing Linear Triblock Terpolymers

    SciTech Connect

    Kumar, Rajeev; Dadmun, Mark D; Sumpter, Bobby G; Mays, Jimmy; Avgeropoulos, Apostolos; Zafeiropoulos, N.E.; Misichoronis, K.; Rangou, S.; Ashcraft, E.

    2013-01-01

    The synthesis via anionic polymerization of six linear triblock terpolymers with various sequences of blocks such as PS (polystyrene), PB (polybutadiene), PI (polyisoprene) and PCHD (poly(1,3-cyclohexadiene)) is reported. The synthesis of the terpolymers was accomplished by the use of anionic polymerization with high vacuum techniques and sequential monomer addition. Molecular characterization of the samples was performed via size exclusion chromatography and membrane osmometry to measure polydispersity indices and the number-average molecular weights, respectively. Proton nuclear magnetic resonance spectroscopy was adopted to verify the type of microstructure for the polydienes as well as to calculate the molar composition. Structural characterization was performed via transmission electron microscopy and small angle X-ray scattering and several morphologies were observed including one which has not been reported previously. Real-space self-consistent field theory (SCFT) without a priori knowledge about the symmetry of the periodic structures was used to elucidate the thermodynamics of the synthesized triblock copolymers.

  6. New Linear and Star-Shaped Thermogelling Poly([R]-3-hydroxybutyrate) Copolymers.

    PubMed

    Barouti, Ghislaine; Liow, Sing Shy; Dou, Qingqing; Ye, Hongye; Orione, Clément; Guillaume, Sophie M; Loh, Xian Jun

    2016-07-18

    The synthesis of multi-arm poly([R]-3-hydroxybutyrate) (PHB)-based triblock copolymers (poly([R]-3-hydroxybutyrate)-b-poly(N-isopropylacrylamide)-b-[[poly(methyl ether methacrylate)-g-poly(ethylene glycol)]-co-[poly(methacrylate)-g-poly(propylene glycol)

  7. Mixing thermodynamics of block-random copolymers

    NASA Astrophysics Data System (ADS)

    Beckingham, Bryan Scott

    regular mixing prediction, XA-ArB = fB2 XA-B, thereby confirming the utility of this simple relationship in designing block copolymers with targeted interaction strengths using only these two common monomers. Thus, this fB 2 scaling is a useful "design rule" for tuning the interblock segregation strength in A-ArB (and B-ArB) block-random copolymers using styrene and isoprene as constituents. The reduction in XA-ArB over X A-B permits the synthesis of polymers having much larger M and domain spacing d while maintaining a thermally-accessible ODT; measured domain spacings are found to closely follow the expected scaling, d ~ X1/6M2/3. The decoupling of the order-disorder transition temperature from polymer molecular weight---and thereby interdomain spacing---provides an additional means to alter the polymer structure-property dynamic through synthesis, in addition to more common molecular variations, such as changes in block sequence, length of the blocks, and number of blocks. A similar examination of the interaction energy densities between E (hydrogenated Bd) and both hydrogenated derivatives of random copolymers of styrene and isoprene (SrhI and VCHrhI) found large positive deviations from regular mixing in the E-SrhI system and smaller but significant negative deviations in the E-VCHrhI system. Nevertheless, a ternary mixing model ("copolymer equation"), using independently-determined values of the three component interaction energy densities, is found to provide a good representation of the experimental interaction energies. Random copolymer blocks are also incorporated into linear A-B-C triblock copolymers, and the extent of block microphase separation in nonfrustrated E-hI-ArhI, where A is either S or VCH, triblock copolymers forming a "three-domain, four-layer" lamellar morphology is examined. Specifically, the extent of separation between the B and C blocks is probed, for the case where the B and C blocks are sufficiently compatible that they would not be

  8. Junction-Controlled Elasticity of Single-Walled Carbon Nanotube Dispersions in Acrylic Copolymer Gels and Solutions

    SciTech Connect

    Schoch, Andrew B.; Shull, Kenneth R.; Brinson, L. Catherine

    2008-08-26

    Oscillatory shear rheometry is used to study the mechanical response of single-walled carbon nanotubes dispersed in solutions of acrylic diblock or triblock copolymers in 2-ethyl-1-hexanol. Thermal transitions in the copolymer solutions provide a route for the easy processing of these composite materials, with excellent dispersion of the nanotubes as verified by near-infrared photoluminescence spectroscopy. The nanotube dispersions form elastic networks with properties that are controlled by the junction points between nanotubes, featuring a temperature-dependent elastic response that is controlled by the dynamic properties of the matrix copolymer solution. The data are consistent with the formation of micelle-like aggregates around the nanotubes. At low temperatures the core-forming poly(methyl methacrylate) blocks are glassy, and the overall mechanical response of the composite does not evolve with time. At higher temperatures the enhanced mobility of the core-forming blocks enables the junctions to achieve more intimate nanotube-nanotube contact, and the composite modulus increases with time. These aging effects are observed in both diblock and triblock copolymer solutions but are partially reversed in the triblock solutions by cooling through the gel transition of the triblock copolymer. This result is attributed to the generation of internal stresses during gelation and the ability of these stresses to break or weaken the nanotube junctions.

  9. Chemical inhibition of potato ABA 8'-hydroxylase activity alters in vitro and in vivo ABA metabolism and endogenous ABA levels but does not affect potato microtuber dormancy duration

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The effects of azole-type P450 inhibitors and two metabolism-resistant ABA analogs on in vitro ABA 8'-hydroxylase activity, in planta ABA metabolism, endogenous ABA content, and tuber meristem dormancy duration were examined in potato (Solanum tuberosum L. cv. Russet Burbank). When functionally expr...

  10. Fluctuation Dynamics of Block Copolymer Vesicles

    SciTech Connect

    Falus, P.; Borthwick, M.A.; Mochrie, S.G.J.

    2010-07-13

    X-ray photon correlation spectroscopy was used to characterize the wave-vector- and temperature-dependent dynamics of spontaneous thermal fluctuations in a vesicle (L4) phase that occurs in a blend of a symmetric poly(styrene-ethylene/butylene-styrene) triblock copolymer with a polystyrene homopolymer. Measurements of the intermediate scattering function reveal stretched-exponential behavior versus time, with a stretching exponent slightly larger than 2/3. The corresponding relaxation rates show an approximate q{sup 3} dependence versus wave vector. Overall, the experimental measurements are well described by theories that treat the dynamics of independent membrane plaquettes.

  11. Identification and mechanism of ABA receptor antagonism

    SciTech Connect

    Melcher, Karsten; Xu, Yong; Ng, Ley-Moy; Zhou, X. Edward; Soon, Fen-Fen; Chinnusamy, Viswanathan; Suino-Powell, Kelly M; Kovach, Amanda; Tham, Fook S.; Cutler, Sean R.; Li, Jun; Yong, Eu-Leong; Zhu, Jian-Kang; Xu, H. Eric

    2010-11-11

    The phytohormone abscisic acid (ABA) functions through a family of fourteen PYR/PYL receptors, which were identified by resistance to pyrabactin, a synthetic inhibitor of seed germination. ABA activates these receptors to inhibit type 2C protein phosphatases, such as ABI1, yet it remains unclear whether these receptors can be antagonized. Here we demonstrate that pyrabactin is an agonist of PYR1 and PYL1 but is unexpectedly an antagonist of PYL2. Crystal structures of the PYL2-pyrabactin and PYL1-pyrabactin-ABI1 complexes reveal the mechanism responsible for receptor-selective activation and inhibition, which enables us to design mutations that convert PYL1 to a pyrabactin-inhibited receptor and PYL2 to a pyrabactin-activated receptor and to identify new pyrabactin-based ABA receptor agonists. Together, our results establish a new concept of ABA receptor antagonism, illustrate its underlying mechanisms and provide a rational framework for discovering novel ABA receptor ligands.

  12. Arylenesiloxane copolymers

    NASA Technical Reports Server (NTRS)

    Breed, L. W.; Elliott, R. L.

    1967-01-01

    Arylenesiloxane copolymers with regularly ordered structures were discovered during efforts to develop organosilicon polymers. Arylenesilane and siloxane monomers were both synthesized in these experiments.

  13. Toward Anisotropic Hybrid Materials: Directional Crystallization of Amphiphilic Polyoxazoline-Based Triblock Terpolymers.

    PubMed

    Rudolph, Tobias; von der Lühe, Moritz; Hartlieb, Matthias; Norsic, Sebastien; Schubert, Ulrich S; Boisson, Christophe; D'Agosto, Franck; Schacher, Felix H

    2015-10-27

    We present the design and synthesis of a linear ABC triblock terpolymer for the bottom-up synthesis of anisotropic organic/inorganic hybrid materials: polyethylene-block-poly(2-(4-(tert-butoxycarbonyl)amino)butyl-2-oxazoline)-block-poly(2-iso-propyl-2-oxazoline) (PE-b-PBocAmOx-b-PiPrOx). The synthesis was realized via the covalent linkage of azide-functionalized polyethylene and alkyne functionalized poly(2-alkyl-2-oxazoline) (POx)-based diblock copolymers exploiting copper-catalyzed azide-alkyne cycloaddition (CuAAC) chemistry. After purification of the resulting triblock terpolymer, the middle block was deprotected, resulting in a primary amine in the side chain. In the next step, solution self-assembly into core-shell-corona micelles in aqueous solution was investigated by dynamic light scattering (DLS) and transmission electron microscopy (TEM). Subsequent directional crystallization of the corona-forming block, poly(2-iso-propyl-2-oxazoline), led to the formation of anisotropic superstructures as demonstrated by electron microscopy (SEM and TEM). We present hypotheses concerning the aggregation mechanism as well as first promising results regarding the selective loading of individual domains within such anisotropic nanostructures with metal nanoparticles (Au, Fe3O4). PMID:26372093

  14. On the Use of Self-Assembling Block Copolymers to Toughen A Model Epoxy

    NASA Astrophysics Data System (ADS)

    Chen, Yilin

    Block copolymers have been receiving considerable attention in toughening epoxy due to their ability to form a wide variety of nanostructures. This study focuses on using both triblock and diblock copolymers to improve the fracture toughness of an aromatic-amine cured epoxy system. The curing system consisted of 1,3- phenylenediamine (mPDA) as curing agent and aniline as a chain extender. Three triblock copolymers and three diblock copolymers were incorporated in the same lightly crosslinked model epoxy system, which was chosen to mimic an underfill material in flip-chip packaging for the microelectronics industry. In this research, rubber particles were formed in situ using self-assembling block copolymers. Mechanical, thermal and microscopic studies were conducted with the main goal to study the relationship between the block parameters and the final morphologies and their effects on static and dynamic mechanical properties of the toughened resin, especially fracture toughness. In these block-copolymer-modified epoxies, spherical micelles and wormlike micelles were obtained by varying block lengths, molecular weight, polarities and compositions. It was found that miscibility of the epoxy-miscible block played a crucial role in the formation of different types of morphologies. At a low loading level, diblock copolymers were able to toughen the model epoxy as effectively as triblock copolymers. The fracture toughness was improved to almost three times with respect to that of the neat resin with addition of 10 phr AM*-27. At the same time, other mechanical properties, such as yield strength and modulus, were well retained. Incorporation of block copolymers did not have a significant effect on glass transition temperature but caused an increase in coefficient of thermal expansion (CTE) of the modified epoxy. Particle cavitation and matrix void growth were proved to be the toughening mechanisms for SBM-Modified epoxies. However, these typical toughening mechanisms for

  15. Equilibrium crystal phases of triblock Janus colloids.

    PubMed

    Reinhart, Wesley F; Panagiotopoulos, Athanassios Z

    2016-09-01

    Triblock Janus colloids, which are colloidal spheres decorated with attractive patches at each pole, have recently generated significant interest as potential building blocks for functional materials. Their inherent anisotropy is known to induce self-assembly into open structures at moderate temperatures and pressures, where they are stabilized over close-packed crystals by entropic effects. We present a numerical investigation of the equilibrium phases of triblock Janus particles with many different patch geometries in three dimensions, using Monte Carlo simulations combined with free energy calculations. In all cases, we find that the free energy difference between crystal polymorphs is less than 0.2 kBT per particle. By varying the patch fraction and interaction range, we show that large patches stabilize the formation of structures with four bonds per patch over those with three. This transition occurs abruptly above a patch fraction of 0.30 and has a strong dependence on the interaction range. Furthermore, we find that a short interaction range favors four bonds per patch, with longer range increasingly stabilizing structures with only three bonds per patch. By quantifying the effect of patch geometry on the stability of the equilibrium crystal structures, we provide insights into the fundamental design rules for constructing complex colloidal crystals. PMID:27609002

  16. Application of ABA Principles to General Communication Instruction.

    ERIC Educational Resources Information Center

    Ogletree, Billy T.; Oren, Thomas

    2001-01-01

    This article examines applied behavior analysis (ABA) based communication instruction for students with autism. It offers an historical context for ABA in speech-language pathology and reviews the literature on the use of ABA as a treatment method for communication impairment in autism, comparing contemporary ABA with the developmental…

  17. In vitro drug release behavior, mechanism and antimicrobial activity of rifampicin loaded low molecular weight PLGA-PEG-PLGA triblock copolymeric nanospheres.

    PubMed

    Gajendiran, M; Divakar, S; Raaman, N; Balasubramanian, S

    2013-12-01

    Poly (lactic-co-glycolic acid) (PLGA (92:8)) and a series of PLGA-PEG-PLGA tri block copolymers were synthesized by direct melt polycondensation. The copolymers were characterized by FTIR, and 1HNMR spectroscopic techniques, viscosity, gel permeation chromatography (GPC) and powder x-ray diffraction (XRD). The rifampicin (RIF) loaded polymeric nanospheres (NPs) were prepared by ultrasonication-W/O emulsification technique. The NPs have been characterized by field emission scanning electron microscopy (FESEM), TEM, powder X-ray diffraction (XRD), UVvisible spectroscopy and DLS measurements. The drug loaded triblock copolymeric NPs have five folds higher drug content and drug loading efficiency than that of PLGA microspheres (MPs). The in vitro drug release study shows that the drug loaded NPs showed an initial burst release after that sustained release up to 72 h. All the triblock copolymeric NPs follow anomalous drug diffusion mechanism while the PLGA MPs follow non-Fickian super case-II mechanism up to 12 h. The overall in-vitro release follows second order polynomial kinetics up to 72 h. The antimicrobial activity of the RIF loaded polymer NPs was compared with that of pure RIF and tetracycline (TA). The RIF loaded triblock copolymeric NPs inhibited the bacterial growth more effectively than the pure RIF and TA. PMID:23701139

  18. Wounding of potato tubers induces increases in ABA biosynthesis and catabolism and alters expression of ABA metabolic genes

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The effects of physical wounding on ABA biosynthesis and catabolism and expression of genes encoding key ABA metabolic enzymes were determined in potato (Solanum tuberosum L.) tubers. An increase in ABA and ABA metabolite content was observed 48 h after wounding and remained elevated through 96 h. ...

  19. Preparation and in vitro evaluation of doxorubicin-loaded Fe3O4 magnetic nanoparticles modified with biocompatible copolymers

    PubMed Central

    Akbarzadeh, Abolfazl; Mikaeili, Haleh; Zarghami, Nosratollah; Mohammad, Rahmati; Barkhordari, Amin; Davaran, Soodabeh

    2012-01-01

    Background Superparamagnetic iron oxide nanoparticles are attractive materials that have been widely used in medicine for drug delivery, diagnostic imaging, and therapeutic applications. In our study, superparamagnetic iron oxide nanoparticles and the anticancer drug, doxorubicin hydrochloride, were encapsulated into poly (D, L-lactic-co-glycolic acid) poly (ethylene glycol) (PLGA-PEG) nanoparticles for local treatment. The magnetic properties conferred by superparamagnetic iron oxide nanoparticles could help to maintain the nanoparticles in the joint with an external magnet. Methods A series of PLGA:PEG triblock copolymers were synthesized by ring-opening polymerization of D, L-lactide and glycolide with different molecular weights of polyethylene glycol (PEG2000, PEG3000, and PEG4000) as an initiator. The bulk properties of these copolymers were characterized using 1H nuclear magnetic resonance spectroscopy, gel permeation chromatography, Fourier transform infrared spectroscopy, and differential scanning calorimetry. In addition, the resulting particles were characterized by x-ray powder diffraction, scanning electron microscopy, and vibrating sample magnetometry. Results The doxorubicin encapsulation amount was reduced for PLGA:PEG2000 and PLGA:PEG3000 triblock copolymers, but increased to a great extent for PLGA:PEG4000 triblock copolymer. This is due to the increased water uptake capacity of the blended triblock copolymer, which encapsulated more doxorubicin molecules into a swollen copolymer matrix. The drug encapsulation efficiency achieved for Fe3O4 magnetic nanoparticles modified with PLGA:PEG2000, PLGA:PEG3000, and PLGA:PEG4000 copolymers was 69.5%, 73%, and 78%, respectively, and the release kinetics were controlled. The in vitro cytotoxicity test showed that the Fe3O4-PLGA:PEG4000 magnetic nanoparticles had no cytotoxicity and were biocompatible. Conclusion There is potential for use of these nanoparticles for biomedical application. Future work

  20. Thermoresponsive physical hydrogels of poly(lactic acid)/poly(ethylene glycol) stereoblock copolymers tuned by stereostructure and hydrophobic block sequence.

    PubMed

    Mao, Hailiang; Shan, Guorong; Bao, Yongzhong; Wu, Zi Liang; Pan, Pengju

    2016-05-18

    CBABC-type poly(lactic acid) (PLA)/poly(ethylene glycol) (PEG) pentablock copolymers composed of a central PEG block (A) and enantiomeric poly(l-lactic acid) (PLLA, B), poly(d-lactic acid) (PDLA, C) blocks were synthesized. Such pentablock copolymers form physical hydrogels at high concentrations in an aqueous solution, which stem from the aggregation and physical bridging of copolymer micelles. These gels are thermoresponsive and turn into sols upon heating. Physical gelation, gel-to-sol transition, crystalline state, microstructure, rheological behavior, biodegradation, and drug release behavior of PLA/PEG pentablock copolymers and their gels were investigated; they were also compared with PLA-PEG-PLA triblock copolymers containing the isotactic PLLA or atactic poly(d,l-lactide) (PDLLA) endblocks and PLLA-PEG-PLLA/PDLA-PEG-PDLA enantiomeric mixtures. PLA hydrophobic domains in pentablock copolymer gels changed from a homocrystalline to stereocomplexed structure as the PLLA/PDLA block length ratio approached 1/1. The gel of symmetric pentablock copolymer exhibited a wider gelation region, higher gel-to-sol transition temperature, higher hydrophobic domain crystallinity, larger intermicellar distance, higher storage modulus, and slower degradation and drug release rate compared to those of the asymmetric PLA/PEG pentablock copolymers or triblock copolymers. SAXS results indicated that the PLLA/PDLA blocks stereocomplexation in pentablock copolymers facilitated the intermicellar aggregation and bridging. Cylindrical ordered structures were observed in all the gels formed from the PLA/PEG pentablock and triblock copolymers. The stereocomplexation degree and intermicellar distance of the pentablock copolymer gels increased with heating. PMID:27121732

  1. Chemical inhibition of potato ABA-8'-hydroxylase activity alters in vitro and in vivo ABA metabolism and endogenous ABA levels but does not affect potato microtuber dormancy duration.

    PubMed

    Suttle, Jeffrey C; Abrams, Suzanne R; De Stefano-Beltrán, Luis; Huckle, Linda L

    2012-09-01

    The effects of azole-type P450 inhibitors and two metabolism-resistant abscisic acid (ABA) analogues on in vitro ABA-8'-hydroxylase activity, in planta ABA metabolism, endogenous ABA content, and tuber meristem dormancy duration were examined in potato (Solanum tuberosum L. cv. Russet Burbank). When functionally expressed in yeast, three potato CYP707A genes were demonstrated to encode enzymatically active ABA-8'-hydroxylases with micromolar affinities for (+)-ABA. The in vitro activity of the three enzymes was inhibited by the P450 azole-type inhibitors ancymidol, paclobutrazol, diniconazole, and tetcyclasis, and by the 8'-acetylene- and 8'-methylene-ABA analogues, with diniconazole and tetcyclasis being the most potent inhibitors. The in planta metabolism of [(3)H](±)-ABA to phaseic acid and dihydrophaseic acid in tuber meristems was inhibited by diniconazole, tetcyclasis, and to a lesser extent by 8'-acetylene- and 8'-methylene-ABA. Continuous exposure of in vitro generated microtubers to diniconazole resulted in a 2-fold increase in endogenous ABA content and a decline in dihydrophaseic acid content after 9 weeks of development. Similar treatment with 8'-acetylene-ABA had no effects on the endogenous contents of ABA or phaseic acid but reduced the content of dihydrophaseic acid. Tuber meristem dormancy progression was determined ex vitro in control, diniconazole-, and 8'-acetylene-ABA-treated microtubers following harvest. Continuous exposure to diniconazole during microtuber development had no effects on subsequent sprouting at any time point. Continuous exposure to 8'-acetylene-ABA significantly increased the rate of microtuber sprouting. The results indicate that, although a decrease in ABA content is a hallmark of tuber dormancy progression, the decline in ABA levels is not a prerequisite for dormancy exit and the onset of tuber sprouting. PMID:22664582

  2. Tribological Behavior of Aqueous Copolymer Lubricant in Mixed Lubrication Regime.

    PubMed

    Ta, Thi D; Tieu, A Kiet; Zhu, Hongtao; Zhu, Qiang; Kosasih, Prabouno B; Zhang, Jie; Deng, Guanyu

    2016-03-01

    Although a number of experiments have been attempted to investigate the lubrication of aqueous copolymer lubricant, which is applied widely in metalworking operations, a comprehensive theoretical investigation at atomistic level is still lacking. This study addresses the influence of loading pressure and copolymer concentration on the structural properties and tribological performance of aqueous copolymer solution of poly(propylene oxide)-poly(ethylene oxide)-poly(propylene oxide) (PPO-PEO-PPO) at mixed lubrication using a molecular dynamic (MD) simulation. An effective interfacial potential, which has been derived from density functional theory (DFT) calculations, was employed for the interactions between the fluid's molecules and iron surface. The simulation results have indicated that the triblock copolymer is physisorption on iron surface. Under confinement by iron surfaces, the copolymer molecules form lamellar structure in aqueous solution and behave differently from its bulk state. The lubrication performance of aqueous copolymer lubricant increases with concentration, but the friction reduction is insignificant at high loading pressure. Additionally, the plastic deformation of asperity is dependent on both copolymer concentration and loading pressure, and the wear behavior shows a linear dependence of friction force on the number of transferred atoms between contacting asperities. PMID:26828119

  3. Super-resurgence: ABA renewal increases resurgence.

    PubMed

    Kincaid, Stephanie L; Lattal, Kennon A; Spence, Jake

    2015-06-01

    Previously extinguished operant responding recurs under both resurgence and renewal procedures, but the effects of combining these procedures on recurrence has not been studied. Because renewal and resurgence are known to independently produce response recurrence, we examined whether greater resurgence would occur if the resurgence procedure was combined with an ABA renewal procedure, relative to a resurgence procedure without contextual changes. Three pigeons were exposed to a concurrent resurgence procedure in which key colors served as contextual stimuli. In the Training phase, reinforcement for pecking two keys was scheduled on concurrent variable-interval (VI) 120-s VI 120-s schedules, each correlated with different key colors. In the Alternative Reinforcement phase, reinforcement occurred when neither key was pecked for 20-s (a differential-reinforcement-of-other-behavior [DRO] 20-s schedule). During this phase, one of the key colors was changed (ABA key), while the other key color remained as in the Training phase (AAA key). In the third phase, reinforcement was not provided and the color of the ABA key was changed back to the color in effect during the Training phase while the same color remained in effect on the other key. Greater resurgence occurred on the ABA renewal key with each pigeon, demonstrating that a superimposed ABA renewal procedure increases resurgence. PMID:25712040

  4. An ABA-increased interaction of the PYL6 ABA receptor with MYC2 Transcription Factor: A putative link of ABA and JA signaling.

    PubMed

    Aleman, Fernando; Yazaki, Junshi; Lee, Melissa; Takahashi, Yohei; Kim, Alice Y; Li, Zixing; Kinoshita, Toshinori; Ecker, Joseph R; Schroeder, Julian I

    2016-01-01

    Abscisic acid (ABA) is a plant hormone that mediates abiotic stress tolerance and regulates growth and development. ABA binds to members of the PYL/RCAR ABA receptor family that initiate signal transduction inhibiting type 2C protein phosphatases. Although crosstalk between ABA and the hormone Jasmonic Acid (JA) has been shown, the molecular entities that mediate this interaction have yet to be fully elucidated. We report a link between ABA and JA signaling through a direct interaction of the ABA receptor PYL6 (RCAR9) with the basic helix-loop-helix transcription factor MYC2. PYL6 and MYC2 interact in yeast two hybrid assays and the interaction is enhanced in the presence of ABA. PYL6 and MYC2 interact in planta based on bimolecular fluorescence complementation and co-immunoprecipitation of the proteins. Furthermore, PYL6 was able to modify transcription driven by MYC2 using JAZ6 and JAZ8 DNA promoter elements in yeast one hybrid assays. Finally, pyl6 T-DNA mutant plants show an increased sensitivity to the addition of JA along with ABA in cotyledon expansion experiments. Overall, the present study identifies a direct mechanism for transcriptional modulation mediated by an ABA receptor different from the core ABA signaling pathway, and a putative mechanistic link connecting ABA and JA signaling pathways. PMID:27357749

  5. An ABA-increased interaction of the PYL6 ABA receptor with MYC2 Transcription Factor: A putative link of ABA and JA signaling

    PubMed Central

    Aleman, Fernando; Yazaki, Junshi; Lee, Melissa; Takahashi, Yohei; Kim, Alice Y.; Li, Zixing; Kinoshita, Toshinori; Ecker, Joseph R.; Schroeder, Julian I.

    2016-01-01

    Abscisic acid (ABA) is a plant hormone that mediates abiotic stress tolerance and regulates growth and development. ABA binds to members of the PYL/RCAR ABA receptor family that initiate signal transduction inhibiting type 2C protein phosphatases. Although crosstalk between ABA and the hormone Jasmonic Acid (JA) has been shown, the molecular entities that mediate this interaction have yet to be fully elucidated. We report a link between ABA and JA signaling through a direct interaction of the ABA receptor PYL6 (RCAR9) with the basic helix-loop-helix transcription factor MYC2. PYL6 and MYC2 interact in yeast two hybrid assays and the interaction is enhanced in the presence of ABA. PYL6 and MYC2 interact in planta based on bimolecular fluorescence complementation and co-immunoprecipitation of the proteins. Furthermore, PYL6 was able to modify transcription driven by MYC2 using JAZ6 and JAZ8 DNA promoter elements in yeast one hybrid assays. Finally, pyl6 T-DNA mutant plants show an increased sensitivity to the addition of JA along with ABA in cotyledon expansion experiments. Overall, the present study identifies a direct mechanism for transcriptional modulation mediated by an ABA receptor different from the core ABA signaling pathway, and a putative mechanistic link connecting ABA and JA signaling pathways. PMID:27357749

  6. Thermosensitive PNIPAM-b-HTPB block copolymer micelles: molecular architectures and camptothecin drug release.

    PubMed

    Luo, Yan-Ling; Yang, Xiao-Li; Xu, Feng; Chen, Ya-Shao; Zhang, Bin

    2014-02-01

    Two kinds of thermo-sensitive poly(N-isoproplacrylamide) (PNIPAM) block copolymers, AB4 four-armed star multiblock and linear triblock copolymers, were synthesized by ATRP with hydroxyl-terminated polybutadiene (HTPB) as central blocks, and characterization was performed by (1)H NMR, FT-IR and SEC. The multiblock copolymers could spontaneously assemble into more regular spherical core-shell nanoscale micelles than the linear triblock copolymer. The physicochemical properties were detected by a surface tension technique, nano particle analyzer, TEM, DLS and UV-vis measurements. The multiblock copolymer micelles had lower critical micelle concentration than the linear counterpart, TEM size from 100 to 120 nm and the hydrodynamic diameters below 150 nm. The micelles exhibited thermo-dependent size change, with low critical solution temperature about 33-35 °C. The characteristic parameters were affected by the composition ratios, length of PNIPAM blocks and molecular architectures. The camptothecin release demonstrated that the drug release was thermo-responsive, accompanied by the temperature-induced structural changes of the micelles. MTT assays were performed to evaluate the biocompatibility or cytotoxicity of the prepared copolymer micelles. PMID:24184534

  7. Elevated CO2-Induced Responses in Stomata Require ABA and ABA Signaling.

    PubMed

    Chater, Caspar; Peng, Kai; Movahedi, Mahsa; Dunn, Jessica A; Walker, Heather J; Liang, Yun-Kuan; McLachlan, Deirdre H; Casson, Stuart; Isner, Jean Charles; Wilson, Ian; Neill, Steven J; Hedrich, Rainer; Gray, Julie E; Hetherington, Alistair M

    2015-10-19

    An integral part of global environment change is an increase in the atmospheric concentration of CO2 ([CO2]) [1]. Increased [CO2] reduces leaf stomatal apertures and density of stomata that plays out as reductions in evapotranspiration [2-4]. Surprisingly, given the importance of transpiration to the control of terrestrial water fluxes [5] and plant nutrient acquisition [6], we know comparatively little about the molecular components involved in the intracellular signaling pathways by which [CO2] controls stomatal development and function [7]. Here, we report that elevated [CO2]-induced closure and reductions in stomatal density require the generation of reactive oxygen species (ROS), thereby adding a new common element to these signaling pathways. We also show that the PYR/RCAR family of ABA receptors [8, 9] and ABA itself are required in both responses. Using genetic approaches, we show that ABA in guard cells or their precursors is sufficient to mediate the [CO2]-induced stomatal density response. Taken together, our results suggest that stomatal responses to increased [CO2] operate through the intermediacy of ABA. In the case of [CO2]-induced reductions in stomatal aperture, this occurs by accessing the guard cell ABA signaling pathway. In both [CO2]-mediated responses, our data are consistent with a mechanism in which ABA increases the sensitivity of the system to [CO2] but could also be explained by requirement for a CO2-induced increase in ABA biosynthesis specifically in the guard cell lineage. Furthermore, the dependency of stomatal [CO2] signaling on ABA suggests that the ABA pathway is, in evolutionary terms, likely to be ancestral. PMID:26455301

  8. Block copolymer mediated stabilization of sub-5 nm superparamagnetic nickel nanoparticles in an aqueous medium

    NASA Astrophysics Data System (ADS)

    Bala, Tanushree; Gunning, Robert Denis; Venkatesan, Munuswamy; Godsell, Jeffrey F.; Roy, Saibal; Ryan, Kevin M.

    2009-10-01

    This paper presents a facile method for decreasing the size of water dispersible Ni nanoparticles from 30 to 3 nm by the incorporation of a passivating surfactant combination of pluronic triblock copolymer and oleic acid into a wet chemical reduction synthesis. A detailed study revealed that the size of the Ni nanoparticles is not only critically governed by the concentration of the triblock copolymers but also dependent on the hydrophobic nature of the micelle core formed. The synthesized Ni nanoparticles were thoroughly characterized by means of transmission electron microscopy, x-ray diffraction, x-ray photoelectron spectroscopy and temperature and field dependent magnetic measurements, along with a comprehensive Fourier transform infrared spectroscopy analysis, in order to predict a possible mechanism of formation.

  9. Synthetic Strategy for Preparing Chiral Double-semicrystalline Polyether Block Copolymers

    PubMed Central

    McGrath, Alaina J.; Shi, Weichao; Rodriguez, Christina G.; Kramer, Edward J.

    2014-01-01

    We report an effective strategy for the synthesis of semi-crystalline block copolyethers with well-defined architecture and stereochemistry. As an exemplary system, triblock copolymers containing either atactic (racemic) or isotactic (R or S) poly(propylene oxide) end blocks with a central poly(ethylene oxide) mid-block were prepared by anionic ring-opening procedures. Stereochemical control was achieved by an initial hydrolytic kinetic resolution of racemic terminal epoxides followed by anionic ring-opening polymerization of the enantiopure monomer feedstock. The resultant triblock copolymers were highly isotactic (meso triads [mm]% ~ 90%) with optical microscopy, differential scanning calorimetry, wide angle x-ray scattering and small angle x-ray scattering being used to probe the impact of the isotacticity on the resultant polymer and hydrogel properties. PMID:25914726

  10. Non-Classical Order in Sphere Forming ABAC Tetrablock Copolymers

    NASA Astrophysics Data System (ADS)

    Zhang, Jingwen; Sides, Scott; Bates, Frank

    2013-03-01

    AB diblock and ABC triblock copolymers have been studied thoroughly. ABAC tetrablock copolymers, representing the simplest variation from ABC triblock by breaking the molecular symmetry via inserting some of the A block in between B and C blocks, have been studied systematically in this research. The model system is poly(styrene-b-isoprene-b-styrene-b-ethylene oxide) (SISO) tetrablock terpolymers and the resulting morphologies were characterized by nuclear magnetic resonance, gel permeation chromatography, small-angle X-ray scattering, transmission electron microscopy, differential scanning calorimetry and dynamic mechanical spectroscopy. Two novel phases are first discovered in a single component block copolymers: hexagonally ordered spherical phase and tentatively identified dodecagonal quasicrystalline (QC) phase. In particular, the discovery of QC phase bridges the world of soft matters to that of metals. These unusual sets of morphologies will be discussed in the context of segregation under the constraints associated with the tetrablock molecular architecture. Theoretical calculations based on the assumption of Gaussian chain statistics provide valuable insights into the molecular configurations associated with these morphologies. the U.S. Department of Energy, Basic Energy Sciences, Division of Materials Science and Engineering, under contract number DEAC05-00OR22725 with UT-Battelle LLC at Oak Ridge National Lab.

  11. Azidated Ether-Butadiene-Ether Block Copolymers as Binders for Solid Propellants

    NASA Astrophysics Data System (ADS)

    Cappello, Miriam; Lamia, Pietro; Mura, Claudio; Polacco, Giovanni; Filippi, Sara

    2016-07-01

    Polymeric binders for solid propellants are usually based on hydroxyl-terminated polybutadiene (HTPB), which does not contribute to the overall energy output. Azidic polyethers represent an interesting alternative but may have poorer mechanical properties. Polybutadiene-polyether copolymers may combine the advantages of both. Four different ether-butadiene-ether triblock copolymers were prepared and azidated starting from halogenated and/or tosylated monomers using HTPB as initiator. The presence of the butadiene block complicates the azidation step and reduces the storage stability of the azidic polymer. Nevertheless, the procedure allows modifying the binder properties by varying the type and lengths of the energetic blocks.

  12. Controlling sub-microdomain structure in microphase-ordered block copolymers and their nanocomposites

    NASA Astrophysics Data System (ADS)

    Bowman, Michelle Kathleen

    Block copolymers exhibit a wealth of morphologies that continue to find ubiquitous use in a diverse variety of mature and emergent (nano)technologies, such as photonic crystals, integrated circuits, pharmaceutical encapsulents, fuel cells and separation membranes. While numerous studies have explored the effects of molecular confinement on such copolymers, relatively few have examined the sub-microdomain structure that develops upon modification of copolymer molecular architecture or physical incorporation of nanoscale objects. This work will address two relevant topics in this vein: (i) bidisperse brushes formed by single block copolymer molecules and (ii) copolymer nanocomposites formed by addition of molecular or nanoscale additives. In the first case, an isomorphic series of asymmetric poly(styrene-b -isoprene-b-styrene) (S1IS2) triblock copolymers of systematically varied chain length has been synthesized from a parent SI diblock copolymer. Small-angle x-ray scattering, coupled with dynamic rheology and self-consistent field theory (SCFT), reveals that the progressively grown S2 block initially resides in the I-rich matrix and effectively reduces the copolymer incompatibility until a critical length is reached. At this length, the S2 block co-locates with the S1 block so that the two blocks generate a bidisperse brush (insofar as the S1 and S2 lengths differ). This single-molecule analog to binary block copolymer blends affords unique opportunities for materials design at sub-microdomain length scales and provides insight into the transition from diblock to triblock copolymer (and thermoplastic elastomeric nature). In the second case, I explore the distribution of molecular and nanoscale additives in microphase-ordered block copolymers and demonstrate via SCFT that an interfacial excess, which depends strongly on additive concentration, selectivity and relative size, develops. These predictions are in agreement with experimental findings. Moreover, using a

  13. Activation of dimeric ABA receptors elicits guard cell closure, ABA-regulated gene expression, and drought tolerance

    PubMed Central

    Okamoto, Masanori; Peterson, Francis C.; Defries, Andrew; Park, Sang-Youl; Endo, Akira; Nambara, Eiji; Volkman, Brian F.; Cutler, Sean R.

    2013-01-01

    Abscisic acid (ABA) is an essential molecule in plant abiotic stress responses. It binds to soluble pyrabactin resistance1/PYR1-like/regulatory component of ABA receptor receptors and stabilizes them in a conformation that inhibits clade A type II C protein phosphatases; this leads to downstream SnRK2 kinase activation and numerous cellular outputs. We previously described the synthetic naphthalene sulfonamide ABA agonist pyrabactin, which activates seed ABA responses but fails to trigger substantial responses in vegetative tissues in Arabidopsis thaliana. Here we describe quinabactin, a sulfonamide ABA agonist that preferentially activates dimeric ABA receptors and possesses ABA-like potency in vivo. In Arabidopsis, the transcriptional responses induced by quinabactin are highly correlated with those induced by ABA treatments. Quinabactin treatments elicit guard cell closure, suppress water loss, and promote drought tolerance in adult Arabidopsis and soybean plants. The effects of quinabactin are sufficiently similar to those of ABA that it is able to rescue multiple phenotypes observed in the ABA-deficient mutant aba2. Genetic analyses show that quinabactin’s effects in vegetative tissues are primarily mediated by dimeric ABA receptors. A PYL2-quinabactin-HAB1 X-ray crystal structure solved at 1.98-Å resolution shows that quinabactin forms a hydrogen bond with the receptor/PP2C “lock” hydrogen bond network, a structural feature absent in pyrabactin-receptor/PP2C complexes. Our results demonstrate that ABA receptors can be chemically controlled to enable plant protection against water stress and define the dimeric receptors as key targets for chemical modulation of vegetative ABA responses. PMID:23818638

  14. Rapid Phosphoproteomic Effects of Abscisic Acid (ABA) on Wild-Type and ABA Receptor-Deficient A. thaliana Mutants*

    PubMed Central

    Minkoff, Benjamin B.; Stecker, Kelly E.; Sussman, Michael R.

    2015-01-01

    Abscisic acid (ABA)1 is a plant hormone that controls many aspects of plant growth, including seed germination, stomatal aperture size, and cellular drought response. ABA interacts with a unique family of 14 receptor proteins. This interaction leads to the activation of a family of protein kinases, SnRK2s, which in turn phosphorylate substrates involved in many cellular processes. The family of receptors appears functionally redundant. To observe a measurable phenotype, four of the fourteen receptors have to be mutated to create a multilocus loss-of-function quadruple receptor (QR) mutant, which is much less sensitive to ABA than wild-type (WT) plants. Given these phenotypes, we asked whether or not a difference in ABA response between the WT and QR backgrounds would manifest on a phosphorylation level as well. We tested WT and QR mutant ABA response using isotope-assisted quantitative phosphoproteomics to determine what ABA-induced phosphorylation changes occur in WT plants within 5 min of ABA treatment and how that phosphorylation pattern is altered in the QR mutant. We found multiple ABA-induced phosphorylation changes that occur within 5 min of treatment, including three SnRK2 autophosphorylation events and phosphorylation on SnRK2 substrates. The majority of robust ABA-dependent phosphorylation changes observed were partially diminished in the QR mutant, whereas many smaller ABA-dependent phosphorylation changes observed in the WT were not responsive to ABA in the mutant. A single phosphorylation event was increased in response to ABA treatment in both the WT and QR mutant. A portion of the discovery data was validated using selected reaction monitoring-based targeted measurements on a triple quadrupole mass spectrometer. These data suggest that different subsets of phosphorylation events depend upon different subsets of the ABA receptor family to occur. Altogether, these data expand our understanding of the model by which the family of ABA receptors directs

  15. ABA Inducible Rice Protein Phosphatase 2C Confers ABA Insensitivity and Abiotic Stress Tolerance in Arabidopsis

    PubMed Central

    Singh, Amarjeet; Jha, Saroj K.; Bagri, Jayram; Pandey, Girdhar K.

    2015-01-01

    Arabidopsis PP2C belonging to group A have been extensively worked out and known to negatively regulate ABA signaling. However, rice (Oryza sativa) orthologs of Arabidopsis group A PP2C are scarcely characterized functionally. We have identified a group A PP2C from rice (OsPP108), which is highly inducible under ABA, salt and drought stresses and localized predominantly in the nucleus. Genetic analysis revealed that Arabidopsis plants overexpressing OsPP108 are highly insensitive to ABA and tolerant to high salt and mannitol stresses during seed germination, root growth and overall seedling growth. At adult stage, OsPP108 overexpression leads to high tolerance to salt, mannitol and drought stresses with far better physiological parameters such as water loss, fresh weight, chlorophyll content and photosynthetic potential (Fv/Fm) in transgenic Arabidopsis plants. Expression profile of various stress marker genes in OsPP108 overexpressing plants revealed interplay of ABA dependent and independent pathway for abiotic stress tolerance. Overall, this study has identified a potential rice group A PP2C, which regulates ABA signaling negatively and abiotic stress signaling positively. Transgenic rice plants overexpressing this gene might provide an answer to the problem of low crop yield and productivity during adverse environmental conditions. PMID:25886365

  16. ABA inducible rice protein phosphatase 2C confers ABA insensitivity and abiotic stress tolerance in Arabidopsis.

    PubMed

    Singh, Amarjeet; Jha, Saroj K; Bagri, Jayram; Pandey, Girdhar K

    2015-01-01

    Arabidopsis PP2C belonging to group A have been extensively worked out and known to negatively regulate ABA signaling. However, rice (Oryza sativa) orthologs of Arabidopsis group A PP2C are scarcely characterized functionally. We have identified a group A PP2C from rice (OsPP108), which is highly inducible under ABA, salt and drought stresses and localized predominantly in the nucleus. Genetic analysis revealed that Arabidopsis plants overexpressing OsPP108 are highly insensitive to ABA and tolerant to high salt and mannitol stresses during seed germination, root growth and overall seedling growth. At adult stage, OsPP108 overexpression leads to high tolerance to salt, mannitol and drought stresses with far better physiological parameters such as water loss, fresh weight, chlorophyll content and photosynthetic potential (Fv/Fm) in transgenic Arabidopsis plants. Expression profile of various stress marker genes in OsPP108 overexpressing plants revealed interplay of ABA dependent and independent pathway for abiotic stress tolerance. Overall, this study has identified a potential rice group A PP2C, which regulates ABA signaling negatively and abiotic stress signaling positively. Transgenic rice plants overexpressing this gene might provide an answer to the problem of low crop yield and productivity during adverse environmental conditions. PMID:25886365

  17. 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.

  18. Formation and structural properties of multi-block copolymer vesicles

    NASA Astrophysics Data System (ADS)

    Wang, Rong; Ma, Shiying

    2014-03-01

    Due to the unique structure, vesicles have attracted considerable attention for their potential applications, such as gene and drug delivery, microcapsules, nanoreactors, cell membrane mimetic, synthetic organelles, etc. By using dissipative particle dynamics, we studied the self-assembly of amphiphilic multi-block copolymer. The phase diagram was constructed by varying the interaction parameters and the composition of the block copolymers. The results show that the vesicles are stable in a large region which is different from the diblock copolymer or triblock copolymer. The structural properties of vesicles can be controlled by varying the interaction parameters and the length of the hydrophobic block. The relationship between the hydrophilic and hydrophobic block length vs the aqueous cavity size and vesicle size are revealed. The copolymers with shorter hydrophobic blocks length or the higher hydrophilicity are more likely to form vesicles with larger aqueous cavity size and vesicle size as well as thinner wall thickness. However, the increase in hydrophobic-block length results to form vesicles with smaller aqueous cavity size and larger vesicle size. Acknowledgments. This work has been supported by NNSFC (No. 21074053) and NBRPC (No. 2010CB923303).

  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. Photocontrol over the Disorder-to-Order Transition (DOT) in Thin Film of Polystyrene-block-Poly(methyl methacrylate) Block Copolymers Containing Photodimerizable anthracene functionality

    NASA Astrophysics Data System (ADS)

    Chen, Wei; Li, Le; Wei, Xinyu; Balazs, Anna; Matyjaszewski, Krzysztof; Russell, Thomas

    2010-03-01

    Reversible photocontrol over the disorder-to-order transition (DOT) of block copolymers can be used to fabricate defect-free, long-range ordered nanomaterials over macroscopic distances by ``photo-combing'' the microdomains. Here, we randomly copolymerized anthracene functionalities in a ``dilute'' way with 2-hydroxyethyl methacrylate as the middle block, forming deuterated polystyrene-block-poly(2-(methacryloyloxy)ethyl anthracene-9-carboxylate-random-2-hydroxyethyl methacrylate)-block-poly(methyl methacrylate) (d8-PS-b-P(9AnEMA-r-HEMA)-b-PMMA) triblock copolymers. Upon UV irradiation of a thin film of the phase-mixed triblock copolymer, photodimerization of anthracene links the junction of d8-PS and PMMA blocks and produces an artificial interface to force a phase-separation, i.e. a UV-induced DOT, as evidenced by small angle neutron scattering (SANS). Reversible photocontrol over the DOT can be achieved by taking advantage of photodimerization and photodissociation of anthracene.

  1. Thermosensitive AB4 four-armed star PNIPAM-b-HTPB multiblock copolymer micelles for camptothecin drug release.

    PubMed

    Luo, Yan-Ling; Fu, Jing-Yu; Xu, Feng; Chen, Ya-Shao; Zhang, Bin

    2014-01-01

    Thermo-sensitive poly(N-isoproplacrylamide)m-block-hydroxyl-terminated polybutadiene-block-poly(N-isoproplacrylamide)m (PNIPAMm-b-HTPB-b-PNIPAMm, m = 1 or 2) block copolymers, AB4 four-armed star multiblock and linear triblock copolymers, were synthesized by ATRP with HTPB as central blocks, and characterization was performed by (1)H NMR, Fourier transform infrared, and size exclusion chromatography. The multiblock copolymers could spontaneously assemble into more regular spherical core-shell nanoscale micelles than the linear triblock copolymer. The physicochemical properties were detected by a surface tension, nanoparticle analyzer, transmission electron microscope (TEM), dynamic light scattering, and UV-vis measurements. The multiblock copolymer micelles had lower critical micelle concentration than the linear counterpart, TEM size from 100 to 120 nm, and the hydrodynamic diameters below 150 nm. The micelles exhibited thermo-dependent size change, with low critical solution temperature of about 33-35 °C. The characteristic parameters were affected by the composition ratios, length of PNIPAM blocks, and molecular architectures. The camptothecin release demonstrated that the drug release was thermo-responsive, accompanied by the temperature-induced structural changes of the micelles. MTT assays were performed to evaluate the biocompatibility or cytotoxicity of the prepared copolymer micelles. PMID:24236748

  2. Synthesis and self-assembly of terpyridine end-capped poly(N-isopropylacrylamide)-block-poly(2-(dimethylamino)ethyl methacrylate) diblock copolymers.

    PubMed

    Brassinne, Jérémy; Poggi, Elio; Fustin, Charles-André; Gohy, Jean-François

    2015-04-01

    At the basis of smart self-assembled materials are lying small building blocks that can hierarchically assemble in response to stimuli, e.g., temperature or chemical species. In this context, the synthesis of terpyridine end-capped poly(2-(dimethylamino)ethyl methacrylate)-block-poly(N-isopropylacrylamide) diblock copolymers via controlled radical copolymerization is reported here. The self-assembly of those copolymers is investigated in dilute aqueous solutions while varying temperature or adding transition metal ions, respectively, leading to the formation of micellar nanostructures or metallosupramolecular triblock copolymers. PMID:25491079

  3. Effect of monomer sequencing on the phase behavior of novel block copolymer/homopolymer blends

    SciTech Connect

    Laurer, J.H.; Fung, J.C.; Agard, D.A.

    1996-12-31

    Blends consisting of a block copolymer and a parent or block-specific homopolymer exhibit macrophase or microphase separation, depending on (i) the homopolymer chain length relative to that of the host block, (ii) the bulk composition of the blend, and (iii) the state of the copolymer. Recent studies of copolymer/homopolymer blends composed of block, random or alternating copolymers have shown that monomer sequencing plays a crucial role in phase behavior and morphological development. In this work, we examine this effect more closely by probing local segment interactions in both the ordered and disordered block copolymer regimes. In the disordered regime, the effects of blend concentration and molecular weight disparity were analyzed using a poly[(styrene-r-isoprene){prime}-b-(styrene-r-isoprene){double_prime}] (S/I) {prime}-b-(S/I){double_prime} copolymer and three homopolystyrenes of varying molecular weight. To probe segmental interactions in the ordered regime, a series of poly[styrene-b-(styrene-r-isoprene)-b-isoprene] S(S/I)I triblock copolymers has been blended with a single low-molecular-weight homopolystyrene. The phase behavior of all these blends has been examined with transmission electron microscopy (TEM). Electron microtomography was also used to produce the first relatively high-resolution 3-D reconstruction of the L{sub 3} morphology in a copolymer-dilute blend.

  4. Defect Structures in Block Copolymer/Nanoparticle Blends

    NASA Astrophysics Data System (ADS)

    Ryu, Hyung Ju; Bockstaller, Michael

    2009-03-01

    We present a systematic study of the implications of nanoparticle additives on the defect formation in block copolymer/nanoparticle blends (BCP). The morphology of lamellar styrene/isoprene-based di- and triblock copolymers blended with polystyrene-coated gold nanocrystals at various filling fractions was analyzed using electron microscopy using stereology and image reconstruction. Three structural characteristics, i.e. the grain size distribution, grain orientation distribution and grain boundary structure, were analyzed as a function of polymer chain architecture, particle filling fraction and film processing conditions. With increasing particle filling fraction the average anisotropy as well as average grain size is observed to decrease as is the rate of grain growth during thermal annealing. The results are interpreted in terms of the stabilization of grain boundary structures through segregation of particle fillers to the grain boundary regions.

  5. Morphology, Modulus, and Ionic Conductivity of a Triblock Terpolymer/Ionic Liquid Electrolyte Membrane

    NASA Astrophysics Data System (ADS)

    McIntosh, Lucas D.; Lodge, Timothy P.

    2013-03-01

    A key challenge in designing solid polymer electrolytes is increasing bulk mechanical properties such as stiffness, without sacrificing ionic conductivity. Previous work has focused on diblock copolymers, where one block is a stiff, glassy insulator and the other is a flexible ion conductor. Disadvantages of these systems include difficulty in achieving network morphologies, which minimize dead-ends for ion transport, and the necessity to operate below both the Tg of the glassy block and the order-disorder temperature. We have investigated the triblock terpolymer poly[isoprene-b-(styrene-co-norbornenylethyl styrene)-b-ethylene oxide] because it self-assembles into a triply-continuous network structure. SAXS and TEM revealed the bulk morphology of INSO to be disordered but strongly correlated after solvent casting from dichloromethane. This apparent disordered network structure was retained after chemical crosslinking and addition of the ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide. Impedance spectroscopy confirmed the expected conductivity for ions confined to continuous PEO channels. The mechanical response before and after crosslinking showed an increase in the material modulus.

  6. Abscisic acid (ABA) regulates grape bud dormancy, and dormancy release stimuli may act through modification of ABA metabolism

    PubMed Central

    Zheng, Chuanlin; Halaly, Tamar; Acheampong, Atiako Kwame; Takebayashi, Yumiko; Jikumaru, Yusuke; Kamiya, Yuji; Or, Etti

    2015-01-01

    In warm-winter regions, induction of dormancy release by hydrogen cyanamide (HC) is mandatory for commercial table grape production. Induction of respiratory stress by HC leads to dormancy release via an uncharacterized biochemical cascade that could reveal the mechanism underlying this phenomenon. Previous studies proposed a central role for abscisic acid (ABA) in the repression of bud meristem activity, and suggested its removal as a critical step in the HC-induced cascade. In the current study, support for these assumptions was sought. The data show that ABA indeed inhibits dormancy release in grape (Vitis vinifera) buds and attenuates the advancing effect of HC. However, HC-dependent recovery was detected, and was affected by dormancy status. HC reduced VvXERICO and VvNCED transcript levels and induced levels of VvABA8’OH homologues. Regulation of these central players in ABA metabolism correlated with decreased ABA and increased ABA catabolite levels in HC-treated buds. Interestingly, an inhibitor of ethylene signalling attenuated these effects of HC on ABA metabolism. HC also modulated the expression of ABA signalling regulators, in a manner that supports a decreased ABA level and response. Taken together, the data support HC-induced removal of ABA-mediated repression via regulation of ABA metabolism and signalling. Expression profiling during the natural dormancy cycle revealed that at maximal dormancy, the HC-regulated VvNCED1 transcript level starts to drop. In parallel, levels of VvA8H-CYP707A4 transcript and ABA catabolites increase sharply. This may provide initial support for the involvement of ABA metabolism also in the execution of natural dormancy. PMID:25560179

  7. A key ABA catabolic gene, OsABA8ox3, is involved in drought stress resistance in rice.

    PubMed

    Cai, Shanlan; Jiang, Guobin; Ye, Nenghui; Chu, Zhizhan; Xu, Xuezhong; Zhang, Jianhua; Zhu, Guohui

    2015-01-01

    Expressions of ABA biosynthesis genes and catabolism genes are generally co-regulated in plant development and responses to environmental stress. Up-regulation of OsNCED3 gene, a key gene in ABA biosynthesis, has been suggested as a way to enhance plant drought resistance but little is known for the role of ABA catabolic genes during drought stress. In this study, we found that OsABA8ox3 was the most highly expressed gene of the OsABA8ox family in rice leaves. Expression of OsABA8ox3 was promptly induced by rehydration after PEG-mimic dehydration, a tendency opposite to the changes of ABA level. We therefore constructed rice OsABA8ox3 silencing (RNA interference, RNAi) and overexpression plants. There were no obvious phenotype differences between the transgenic seedlings and wild type under normal condition. However, OsABA8ox3 RNAi lines showed significant improvement in drought stress tolerance while the overexpression seedlings were hypersensitive to drought stress when compared with wild type in terms of plant survival rates after 10 days of unwatering. Enzyme activity analysis indicated that OsABA8ox3 RNAi plants had higher superoxide dismutase (SOD) and catalase (CAT) activities and less malondialdehyde (MDA) content than those of wild type when the plants were exposed to dehydration treatment, indicating a better anti-oxidative stress capability and less membrane damage. DNA microarray and real-time PCR analysis under dehydration treatment revealed that expressions of a group of stress/drought-related genes, i.e. LEA genes, were enhanced with higher transcript levels in OsABA8ox3 RNAi transgenic seedlings. We therefore conclude that that OsABA8ox3 gene plays an important role in controlling ABA level and drought stress resistance in rice. PMID:25647508

  8. Thermosensitive block copolymer hydrogels based on poly(ɛ-caprolactone) and polyethylene glycol for biomedical applications: state of the art and future perspectives.

    PubMed

    Boffito, Monica; Sirianni, Paolo; Di Rienzo, Anna Maria; Chiono, Valeria

    2015-03-01

    This review focuses on the challenges associated with the design and development of injectable hydrogels of synthetic origin based on FDA approved blocks, such as polyethylene glycol (PEG) and poly(ɛ-caprolactone) (PCL). An overview of recent studies on inverse thermosensitive PEG/PCL hydrogels is provided. These systems have been proposed to overcome the limitations of previously introduced degradable thermosensitive hydrogels [e.g., PEG/poly(lactide-co-glycolic acid) hydrogels]. PEG/PCL hydrogels are advantageous due to their higher gel strength, slower degradation rate and availability in powder form. Particularly, triblock PEG/PCL copolymers have been widely investigated, with PCL-PEG-PCL (PCEC) hydrogels showing superior gel strength and slower degradation kinetics than PEG-PCL-PEG (PECE) hydrogels. Compared to triblock PEG/PCL copolymers, concentrated solutions of multiblock PEG/PCL copolymers were stable due to their slower crystallization rate. However, the resulting hydrogel gel strength was low. Inverse thermosensitive triblock PEG/PCL hydrogels have been mainly applied in tissue engineering, to decrease tissue adherence or, in combination with bioactive molecules, to promote tissue regeneration. They have also found application as in situ drug delivery carriers. On the other hand, the wide potentialities of multiblock PEG/PCL hydrogels, associated with the stability of their water-based solutions under storage, their higher degradation time compared to triblock copolymer hydrogels and the possibility to insert bioactive building blocks along the copolymer chains, have not been fully exploited yet. A critical discussion is provided to highlight advantages and limitations of currently developed themosensitive PEG/PCL hydrogels, suggesting future strategies for the realization of PEG/PCL-based copolymers with improved performance in the different application fields. PMID:24912941

  9. Identification and Characterization of ABA Receptors in Oryza sativa

    PubMed Central

    He, Yuan; Hao, Qi; Li, Wenqi; Yan, Chuangye

    2014-01-01

    Abscisic acid (ABA) is an essential phytohormone that regulates plant stress responses. ABA receptors in Arabidopsis thaliana (AtPYLs) have been extensively investigated by structural, biochemical, and in vivo studies. In contrast, relatively little is known about the ABA signal transduction cascade in rice. Besides, the diversities of AtPYLs manifest that the information accumulated in Arabidopsis cannot be simply adapted to rice. Thus, studies on rice ABA receptors are compulsory. By taking a bioinformatic approach, we identified twelve ABA receptor orthologs in Oryza sativa (japonica cultivar-group) (OsPYLs), named OsPYL1–12. We have successfully expressed and purified OsPYL1–3, 6 and 10–12 to homogeneity, tested the inhibitory effects on PP2C in Oryza sativa (OsPP2C), and measured their oligomerization states. OsPYL1–3 mainly exhibit as dimers and require ABA to inhibit PP2C’s activity. On the contrary, OsPYL6 retains in the monomer-dimer equilibrium state and OsPYL10–11 largely exist as monomers, and they all display an ABA-independent phosphatase inhibition manner. Interestingly, although OsPYL12 seems to be a dimer, it abrogates the phosphatase activity of PP2Cs in the absence of ABA. Toward a further understanding of OsPYLs on the ABA binding and PP2C inhibition, we determined the crystal structure of ABA-OsPYL2-OsPP2C06 complex. The bioinformatic, biochemical and structural analysis of ABA receptors in rice provide important foundations for designing rational ABA-analogues and breeding the stress-resistant rice for commercial agriculture. PMID:24743650

  10. ABA and cytokinins: challenge and opportunity for plant stress research.

    PubMed

    Verslues, Paul E

    2016-08-01

    Accumulation of the stress hormone abscisic acid (ABA) induces many cellular mechanisms associated with drought resistance. Recent years have seen a rapid advance in our knowledge of how increased ABA levels are perceived by ABA receptors, particularly the PYL/RCAR receptors, but there has been relatively less new information about how ABA accumulation is controlled and matched to stress severity. ABA synthesis and catabolism, conjugation and deconjugation to glucose, and ABA transport all are involved in controlling ABA levels. This highly buffered system of ABA metabolism represents both a challenge and opportunity in developing a mechanistic understanding of how plants detect and respond to drought. Recent data have also shown that direct manipulation of cytokinin levels in transgenic plants has dramatic effect on drought phenotypes and prompted new interest in the role of cytokinins and cytokinin signaling in drought. Both ABA and cytokinins will continue to be major foci of drought research but likely with different trajectories both in terms of basic research and in translational research aimed at increasing plant performance during drought. PMID:26910054

  11. Fracture of Semicrystalline-Glassy Block Copolymers: Chain Architecture Effects

    NASA Astrophysics Data System (ADS)

    Ryu, C. Y.; Fredrickson, G. H.; Kramer, E. J.; Hahn, S. F.

    2000-03-01

    We investigate the influence of chain architecture on the deformation and fracture of poly(vinylcyclohexane)-poly(ethylene) (PCHE-PE) block copolymers. Ordered thin films of PCHE-PE-PCHE (CEC) triblock and CECEC pentablock copolymers are bonded to ductile copper grids and deformed in tension and then examined by optical and transmission electron microscopy. Both PCHE homopolymer (M = 283,000 g/mol) and CEC triblock (M = 107,000 g/mol; fE =3D 0.29) undergo fracture via crazing followed by breakdown of crazes to form cracks producing catastrophic failure at a strain ɛ < 6%. The mechanism of deformation and the strain for catastrophic failure changes dramatically for CECEC. Deformation of the CECEC pentablock (M = 110,000 g/mol; fE = 0.29) takes place mainly by (shear) deformation zone formation. Shear deformation and crazing compete and the shear blunting of craze tips is frequently observed. The strain for the catastrophic failure increases in CECEC to ɛ > 30%, and breakdown of the deformed film occurs only locally. We attribute this change in deformation and failure mechanisms to the bridging chains within the C domains of CECEC.

  12. Synthesis and antibacterial activity of nisin-containing block copolymers.

    PubMed

    Joshi, Pranav R; McGuire, Joseph; Neff, Jennifer A

    2009-10-01

    Nisin, an antibacterial peptide proven to be an effective inhibitor of Gram-positive bacteria, was incorporated into novel block copolymer constructs and tested for retained antibacterial activity. Covalent coupling was achieved by chemical modification of the N-terminal isoleucine to introduce a thiol group. Thiolated-nisin derivatives were then linked to poly[ethylene oxide]-poly[propylene oxide]-poly[ethylene oxide] (PEO-PPO-PEO) triblocks that had been end-activated such that terminal hydroxyl groups of the PEO chains were replaced with pyridyl disulfide moieties. The nisin-containing block copolymers were separated from free nisin by dialysis and showed antimicrobial activity against the Gram-positive indicator strain Pediococcus pentosaceus. The contribution to antimicrobial activity from nisin that was covalently linked was not distinguished from the contribution of nisin that had associated with the PEO-PPO-PEO triblocks through noncovalent interactions. However, nisin that was covalently linked showed activity upon reduction of the disulfide bond and release from the end-activated PEO. PMID:19358262

  13. Micelles, Lamellaes and Connected Bilayer Membranes in Block Copolymer Melts, Blends and Solutions

    NASA Astrophysics Data System (ADS)

    Mortensen, Kell

    1997-03-01

    Block copolymers of poly(ethylene oxide), PEO, and poly(propylene oxide), PPO, provide a unique model system for studies of aqueous systems of amphilic macromolecules, as the amphiphilic character can be changed continuously by changing temperature(K Mortensen, W Brown, B. Nordén , Phys. Rev. Letters 13 2340 (1992)) or pressure(K Mortensen, D Schwahn S Janssen Phys. Rev. Letters 71 1728 (1993)). The structural characteristics of aqueous solutions of the PEO-PPO-PEO copolymers and their self-associated assemblies are reviewed(K Mortensen, J. Phys. Cond. Matter 8 A103 (1996)). It is shown by small-angle neutron scattering that at low temperatures and/or concentration the individual copolymers exist in solution as individual unimers. Depending on molecular design, i.e. size of the individual blocks, various aggregates are formed, including spherical, worm-like and disc-shaped micelles. The spherical micelles provide the basis for liquid-crystalline mesophases of cubic structure. The crystallization can be understood as a simple hard-sphere condensation. Worm- or rod-like micelles may form nematic or hexagonally ordered structures, whereas the discs may condense into lamellar phases. While bi-continuous microemulsions frequently appear in ternary phase diagrams of oil, water and low-molecular surfactants, there has only recently been observations of such phases in binary systems of block copolymers and solvent. The first observation was made in an aqueous solution of a low PEO-content PEO-PPO-PEO triblock copolymer(E Hecht, K Mortensen, H Hoffmann, Macromolecules 28 5465, 1995). More recently, the microemulsion sponge phase has been observed in a system of tri-block copolymers dissolved in homopolymers( JH Laurer, JC Fung, JW Sedat, DA Agard, SD Schmit, J Samseth, K Mortensen, RJ Spontak, Langmuir, submitted) and in a ternary systems of diblock copolymer and homopolymers(FS Bates, WW Maurer, PM Lipic MA Hillmyer, KA Almdal, K Mortensen, TP Lodge Science, submitted).

  14. Acid-Labile Amphiphilic PEO-b-PPO-b-PEO Copolymers: Degradable Poloxamer Analogs.

    PubMed

    Worm, Matthias; Kang, Biao; Dingels, Carsten; Wurm, Frederik R; Frey, Holger

    2016-05-01

    Poly ((ethylene oxide)-b-(propylene oxide)-b-(ethylene oxide)) triblock copolymers commonly known as poloxamers or Pluronics constitute an important class of nonionic, biocompatible surfactants. Here, a method is reported to incorporate two acid-labile acetal moieties in the backbone of poloxamers to generate acid-cleavable nonionic surfactants. Poly(propylene oxide) is functionalized by means of an acetate-protected vinyl ether to introduce acetal units. Three cleavable PEO-PPO-PEO triblock copolymers (Mn,total = 6600, 8000, 9150 g·mol(-1) ; Mn,PEO = 2200, 3600, 4750 g·mol(-1) ) have been synthesized using anionic ring-opening polymerization. The amphiphilic copolymers exhibit narrow molecular weight distributions (Ð = 1.06-1.08). Surface tension measurements reveal surface-active behavior in aqueous solution comparable to established noncleavable poloxamers. Complete hydrolysis of the labile junctions after acidic treatment is verified by size exclusion chromatography. The block copolymers have been employed as surfactants in a miniemulsion polymerization to generate polystyrene (PS) nanoparticles with mean diameters of ≈200 nm and narrow size distribution, as determined by dynamic light scattering and scanning electron microscopy. Acid-triggered precipitation facilitates removal of surfactant fragments from the nanoparticles, which simplifies purification and enables nanoparticle precipitation "on demand." PMID:27000789

  15. Field-Theoretic Studies of Nanostructured Triblock Polyelectrolyte Gels

    NASA Astrophysics Data System (ADS)

    Audus, Debra; Fredrickson, Glenn

    2012-02-01

    Recently, experimentalists have developed nanostructured, reversible gels formed from triblock polyelectrolytes (Hunt et al. 2011, Lemmers et al. 2010, 2011). These gels have fascinating and tunable properties that reflect a heterogeneous morphology with domains on the order of tens of nanometers. The complex coacervate domains, aggregated oppositely charged end-blocks, are embedded in a continuous aqueous matrix and are bridged by uncharged, hydrophilic polymer mid-blocks. We report on simulation studies that employ statistical field theory models of triblock polyelectrolytes, and we explore the equilibrium self-assembly of these remarkable systems. As the charge complexation responsible for the formation of coacervate domains is driven by electrostatic correlations, we have found it necessary to pursue full ``field-theoretic simulations'' of the models, as opposed to the familiar self-consistent field theory approach. Our investigations have focused on morphological trends with mid- and end-block lengths, polymer concentration, salt concentration and charge density.

  16. Network of nano-droplets by a tri-block polymer

    NASA Astrophysics Data System (ADS)

    Sharifi, Soheil; Doodman, Esmaeil

    2014-11-01

    Mixtures of oil in water nano-droplets with two molecular weights of a tri-block polymer was studied by quasi elastic light scattering and small angle X-ray scattering. The results showed that the size and interaction of droplets didn't change with increase of the tri-block polymer length but the order parameters increased. The increase of length of the tri-block biopolymer changed the dynamics of the droplets. A network formation is resulted with increase of the amount of tri-block polymer in the microemulsions.

  17. Aggregation of poly(acrylic acid)-containing elastin-mimetic copolymers

    PubMed Central

    Paik, Bradford A.; Blanco, Marco A.; Jia, Xinqiao; Roberts, Christopher J.; Kiick, Kristi L.

    2015-01-01

    Polymer-peptide conjugates were produced via the copper-catalyzed alkyne-azide cycloaddition of poly(tert butyl acrylate) (PtBA) and elastin-like peptides. An azide-functionalized polymer was produced via atom-transfer radical polymerization (ATRP) followed by conversion of bromine end groups to azide groups. Subsequent reaction of the polymer with a bis-alkyne-functionalized, elastin-like peptide proceeded with high efficiency, yielding di- and tri-block conjugates, which after deprotection, yielded poly(acrylic acid) (PAA)-based diblock and triblock copolymers. These conjugates were solubilized in dimethyl formamide, and titration of phosphate buffered saline (PBS) induced aggregation. The presence of polydisperse spherical aggregates was confirmed by dynamic light scattering and transmission electron microscopy. Additionally, a coarse-grained molecular model was designed to reasonably capture inter- and intramolecular interactions for the conjugates and its precursors. This model was used to assess the effect of the different interacting molecular forces on the conformational thermodynamic stability of the copolymers. Our results indicated that the PAA’s ability to hydrogen-bond with both itself and the peptide is the main interaction for stabilizing the diblocks and triblocks and driving their self-assembly, while interactions between peptides are suggested to play only a minor role on the conformational and thermodynamic stability of the conjugates. PMID:25611563

  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. Preparation and characterization of heparin-containing SBS-g-DMAEMA copolymer membrane.

    PubMed

    Yang, J M; Jong, Y J; Hsu, K Y; Chang, C H

    1998-01-01

    The grafting of dimethyl amino ethyl methacrylate (DMAEMA) onto styrene-butadiene-styrene triblock copolymer (SBS) membrane was subsequently conducted by UV-radiation induced graft copolymerization without degassing to obtain the SBS-g-DMAEMA copolymer membrane. The substituted amino groups on the SBS-g-DMAEMA graft copolymer membrane were quaternized with iodomethane, and then the membrane was treated with heparin to prepare the heparin-containing SBS-g-DMAEMA copolymer membrane (SBS-g-DMAEMA-HEP). The graft copolymer membrane (SBS-g-DMAEMA) and the heparin-containing SBS-g-DMAEMA copolymer membrane (SBS-g-DMAEMA-HEP) were characterized by FTIR spectroscopy. The heparin content was determined by toluidine blue heparin assay. Contact angle, water content, and protein adsorption of fibrinogen and albumin experiments were also performed to evaluate the effect of graft amount and heparin content on the biocompatibility of SBS-g-DMAEMA and SBS-g-DMAEMA-HEP graft copolymer membranes. By using Kaelble's equation, the surface tension of SBS-g-DMAEMA and SBS-g-DMAEMA-HEP were determined. It was found that with increasing grafting amount and the heparin content, the surface tension and water content of SBS-g-DMAEMA membrane increased, whereas the contact angle decreased. The amount of the adsorption of albumin and fibrinogen decreased with increasing graft amount and heparin content. However, there was a minimum for adsorption of proteins in the SBS-g-DMAEMA and SBS-g-DMAEMA-HEP membranes. PMID:9429100

  20. Surface and Aggregation Behavior of Pentablock Copolymer PNIPAM7-F127-PNIPAM7 in Aqueous Solutions.

    PubMed

    Parekh, P; Ohno, S; Yusa, S; Lage, Emílio V; Casas, Matilde; Sández-Macho, I; Aswal, V K; Bahadur, P

    2016-08-01

    The triblock Pluronic F127 was modified by introducing poly(N-isopropylacrylamide) (PNIPAM) at both the poly(ethylene oxide) ends, and the pentablock copolymer so-prepared was characterized by gel permeation chromatography and (1)H NMR. The degree of polymerization of NIPAM blocks at the two ends was 7. The solution behavior and microstructure of copolymer aggregates in water and aqueous salt solution were examined and compared with F127 by UV-visible absorption spectroscopy, microdifferential scanning calorimetry, dynamic light scattering (DLS), and small-angle neutron scattering (SANS). The behavior of the pentablock copolymer at the air/water interface was determined by Langmuir film balance. Two lower critical solution temperatures were observed for pentablock copolymer, corresponding to poly(propylene oxide) and PNIPAM blocks, respectively. DLS studies show that micelle size increased with increase in temperature and in the presence of salt. SANS measurements provided temperature-dependent structural evolution of copolymer micelles in water and salt solution. The copolymer displays an isotherm with four classical regions (pancake, mushroom, brush, and condensed state). The study has potential applications in controlled drug delivery due to the tunable phase behavior and biocompatibility of the copolymer. PMID:27385006

  1. Isolation of ABA hypersensitive mutants in allhexaploid breadwheat

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The plant hormone abscisic acid (ABA) stimulates seed dormancy during embryo maturation, inhibits germination of mature seed, and stimulates stress responses such as stomatal closure in response to drought stress. Arabidopsis mutants isolated for ABA hypersensitive (ABH) seed germination showed incr...

  2. Wheat ABA-insensitive mutants result in reduced grain dormancy

    Technology Transfer Automated Retrieval System (TEKTRAN)

    This paper describes the isolation of wheat mutants in the hard red spring Scarlet resulting in reduced sensitivity to the plant hormone abscisic acid (ABA) during seed germination. ABA induces seed dormancy during embryo maturation and inhibits the germination of mature seeds. Wheat sensitivity t...

  3. Synthesis of Electroneutralized Amphiphilic Copolymers with Peptide Dendrons for Intramuscular Gene Delivery.

    PubMed

    Pu, Linyu; Wang, Jiali; Li, Na; Chai, Qiuxia; Irache, Juan M; Wang, Gang; Tang, James Zhenggui; Gu, Zhongwei

    2016-06-01

    Intramuscular gene delivery materials are of great importance in plasmid-based gene therapy system, but there is limited information so far on how to design and synthesize them. A previous study showed that the peptide dendron-based triblock copolymer with its components arranged in a reversed biomembrane architecture could significantly increase intramuscular gene delivery and expression. Herein, we wonder whether copolymers with biomembrane-mimicking arrangement may have similar function on intramuscular gene delivery. Meanwhile, it is of great significance to uncover the influence of electric charge and molecular structure on the function of the copolymers. To address the issues, amphiphilic triblock copolymers arranged in hydrophilic-hydrophobic-hydrophilic structure were constructed despite the paradoxical characteristics and difficulties in synthesizing such hydrophilic but electroneutral molecules. The as-prepared two copolymers, dendronG2(l-lysine-OH)-poly propylene glycol2k(PPG2k)-dendronG2(l-lysine-OH) (rL2PL2) and dendronG3(l-lysine-OH)-PPG2k-dendronG3(l-lysine-OH) (rL3PL3), were in similar structure but had different hydrophilic components and surface charges, thus leading to different capabilities in gene delivery and expression in skeletal muscle. rL2PL2 was more efficient than Pluronic L64 and rL3PL3 when mediating luciferase, β-galactosidase, and fluorescent protein expressions. Furthermore, rL2PL2-mediated growth-hormone-releasing hormone expression could significantly induce mouse body weight increase in the first 21 days after injection. In addition, both rL2PL2 and rL3PL3 showed good in vivo biosafety in local and systemic administration. Altogether, rL2PL2-mediated gene expression in skeletal muscle exhibited applicable potential for gene therapy. The study revealed that the molecular structure and electric charge were critical factors governing the function of the copolymers for intramuscular gene delivery. It can be concluded that, combined

  4. ABA Levels and Sensitivity in Developing Wheat Embryos of Sprouting Resistant and Susceptible Cultivars 1

    PubMed Central

    Walker-Simmons, Mary

    1987-01-01

    A sprouting-resistant and a sprouting-susceptible wheat cultivar were utilized to examine the role of ABA levels and sensitivity responses in wheat embryonic germination. Endogenous embryonic ABA levels were measured in both cultivars throughout grain maturation utilizing a new and sensitive ABA immunoassay. Embryonic ABA levels of each cultivar were similar with the sprouting-susceptible cultivar having about a 25% lower ABA level than that of the sprouting-resistant cultivar. Larger differences between the cultivars were noted in sensitivity to ABA, as measured by capability of ABA to block embryonic germination. ABA inhibited embryonic germination much more effectively in the sprouting-resistant cultivar. PMID:16665406

  5. Fabrication of PbS microstructures with different shapes in aqueous solutions of amphiphilic triblock copolymer

    NASA Astrophysics Data System (ADS)

    Ding, Yuanhua; Liu, Xiaoxia; Guo, Rong

    2007-09-01

    Hollow PbS nanospheres and branch-like PbS microstructures have been successfully synthesized by the reaction of Pb(Ac) 2 with the S 2- ions released slowly from thioacetamide (TAA) in Pluronic F127 aqueous solutions at room temperature. The obtained hollow PbS nanospheres have a wall thickness of about 40 nm, and the branch-like PbS microstructures have an average size of 0.7-2.2 μm. Both the wall of the hollow PbS nanospheres and the branch-like structures consist of cubic PbS nanocrystallites. It has been found that a minimum F127 concentration is required for the formation of hollow and branch-like PbS structures. With increasing F127 concentration, the diameter of the obtained hollow spheres increases gradually, whereas the size of the branch-like structures decreases. The addition of cyclohexane makes the diameter of hollow spheres decrease, but has little effect on the branch-like structures. Increasing the temperature of the solutions can significantly decrease the sizes of the hollow and branch-like structures. The complex micelles formed by Pb(Ac) 2 and F127 micelles act as soft templates for the formation of hollow PbS nanospheres, and the complex monomeric F127 aggregates formed by Pb(Ac) 2 and monomeric F127 chains play a structure-directing role in the formation of branch-like PbS microstructures.

  6. Crystallization of bifonazole and acetaminophen within the matrix of semicrystalline, PEO-PPO-PEO triblock copolymers.

    PubMed

    Chen, Zhen; Liu, Zhengsheng; Qian, Feng

    2015-02-01

    The morphology and microstructure of crystalline drug/polymer solid dispersions could influence their physical stability and dissolution performance. In this study, the drug crystallization mechanism within PEG, PPG, and poloxamer matrix was investigated, and the resultant microstructure of various solid dispersions of acetaminophen (ACM) and bifonazole (BFZ) in the aforementioned polymers was characterized by differential scanning calorimetry (DSC), polarized optical microscopy (POM), and wide/small-angle X-ray diffraction (WAXD/SAXS). With a stronger molecular interaction with the PEG segments, ACM decreased the crystallization onset temperature and crystallinity of PEG and poloxamers much more than BFZ. The stronger molecular interaction and better miscibility between ACM and PEG also induced a more defective lamellar structure in the ACM solid dispersions compared with that in the BFZ systems, as revealed by DSC and SAXS investigation. Observed under polarized optical microscopy, PEG, PPG, and poloxamer could all significantly improve the crystallization rate of ACM and BFZ, because of the largely reduced Tg of the solid dispersions by these low Tg polymers. Moreover, when the drug loading was below 60%, crystallization of BFZ in PEG or poloxamer occurred preferably along the radial direction of PEG spherulite, rather than the perpendicular direction, which was attributed to the geometric restriction of well-ordered polymer lamellar structure in the BFZ solid dispersions. Similar phenomena were not observed in the ACM solid dispersions regardless of the drug loading, presumably because ACM could diffuse freely across the perpendicular direction of the PEG spherulite, through the well-connected interlamellar or interfibrillar spaces produced by the defective PEG lamellar structure. The different drug-polymer interaction also caused a difference in the microstructure of polymer crystal, as well as a difference in drug distribution within the polymer matrix, which then synergistically facilitated a "confined crystallization" process to reduce the drug crystallite size below 100 nm. PMID:25569586

  7. Surface hydroxylation of styrene-butadiene-styrene block copolymers for biomaterials.

    PubMed

    Sefton, M V; Merrill, E W

    1976-01-01

    This work pertains to the development of high strength elastomers potentially useful as nonthrombogenic cardiovascular prostheses. Triblock copolymers of the styrene-butadiene-styrene type have been subjected to surface hydroxylation which provide reactive sites at the surface for the subsequent coupling of heparin while retaining the unique mechanical properties of the SBS copolymers. Curves of hydroxyl content versus the copolymer film thickness demonstrate the effect of swelling in the surface region on the product distribution and on the time dependence of the hydroxylation process. In addition, the effect of time, temperature, and the composition of the reaction bath on the diffusion/reaction process is shown. Finally, the general applicability of this surface modification scheme to the development of biomaterials is discussed. PMID:1249089

  8. Selective Semiconductor Nanocluster Deposition on Eptaxially Patterned Semicrystalline Block Copolymer Film

    NASA Astrophysics Data System (ADS)

    Park, Cheolmin; Lee, Jinwook; Jensen, Klavs F.; Bawendi, Moungi G.; Thomas, Edwin L.

    2001-03-01

    Monodisperse ZnS encapsulated CdSe semiconductor nanoclusters are sequestered in between the crystalline polyethylene (PE) lamellae of poly (ethylene-b-ethylene-alt-propylene-b ethylene) semicrystalline triblock copolymer epitaxially crystallized on single crystal of anthracene (AN). Epitaxy between PE block and An created a cross oriented texture of the edge-on crystalline PE lamellae in the thin film. At the same time, the nanoclusters, initially dissolved in the mixture of block copolymer and AN, were rejected out of the crystalline lamellae during epitaxial crystallization and selectively deposited in the amorphous region of the block copolymer. Selective distribution of nanoclusters on the cross oriented pattern structure is clearly evidenced by selected area diffraction (SAD) and bright field transmission electron microscope (TEM).

  9. Hemocompatibility of styrenic block copolymers for use in prosthetic heart valves.

    PubMed

    Brubert, Jacob; Krajewski, Stefanie; Wendel, Hans Peter; Nair, Sukumaran; Stasiak, Joanna; Moggridge, Geoff D

    2016-02-01

    Certain styrenic thermoplastic block copolymer elastomers can be processed to exhibit anisotropic mechanical properties which may be desirable for imitating biological tissues. The ex-vivo hemocompatibility of four triblock (hard-soft-hard) copolymers with polystyrene hard blocks and polyethylene, polypropylene, polyisoprene, polybutadiene or polyisobutylene soft blocks are tested using the modified Chandler loop method using fresh human blood and direct contact cell proliferation of fibroblasts upon the materials. The hemocompatibility and durability performance of a heparin coating is also evaluated. Measures of platelet and coagulation cascade activation indicate that the test materials are superior to polyester but inferior to expanded polytetrafluoroethylene and bovine pericardium reference materials. Against inflammatory measures the test materials are superior to polyester and bovine pericardium. The addition of a heparin coating results in reduced protein adsorption and ex-vivo hemocompatibility performance superior to all reference materials, in all measures. The tested styrenic thermoplastic block copolymers demonstrate adequate performance for blood contacting applications. PMID:26704549

  10. Biocompatible fluorinated polyglycerols for droplet microfluidics as an alternative to PEG-based copolymer surfactants.

    PubMed

    Wagner, Olaf; Thiele, Julian; Weinhart, Marie; Mazutis, Linas; Weitz, David A; Huck, Wilhelm T S; Haag, Rainer

    2016-01-01

    In droplet-based microfluidics, non-ionic, high-molecular weight surfactants are required to stabilize droplet interfaces. One of the most common structures that imparts stability as well as biocompatibility to water-in-oil droplets is a triblock copolymer surfactant composed of perfluoropolyether (PFPE) and polyethylene glycol (PEG) blocks. However, the fast growing applications of microdroplets in biology would benefit from a larger choice of specialized surfactants. PEG as a hydrophilic moiety, however, is a very limited tool in surfactant modification as one can only vary the molecular weight and chain-end functionalization. In contrast, linear polyglycerol offers further side-chain functionalization to create custom-tailored, biocompatible droplet interfaces. Herein, we describe the synthesis and characterization of polyglycerol-based triblock surfactants with tailored side-chain composition, and exemplify their application in cell encapsulation and in vitro gene expression studies in droplet-based microfluidics. PMID:26626826

  11. The De-Etiolated 1 Homolog of Arabidopsis Modulates the ABA Signaling Pathway and ABA Biosynthesis in Rice.

    PubMed

    Zang, Guangchao; Zou, Hanyan; Zhang, Yuchan; Xiang, Zheng; Huang, Junli; Luo, Li; Wang, Chunping; Lei, Kairong; Li, Xianyong; Song, Deming; Din, Ahmad Ud; Wang, Guixue

    2016-06-01

    DEETIOLATED1 (DET1) plays a critical role in developmental and environmental responses in many plants. To date, the functions of OsDET1 in rice (Oryza sativa) have been largely unknown. OsDET1 is an ortholog of Arabidopsis (Arabidopsis thaliana) DET1 Here, we found that OsDET1 is essential for maintaining normal rice development. The repression of OsDET1 had detrimental effects on plant development, and leaded to contradictory phenotypes related to abscisic acid (ABA) in OsDET1 interference (RNAi) plants. We found that OsDET1 is involved in modulating ABA signaling in rice. OsDET1 RNAi plants exhibited an ABA hypersensitivity phenotype. Using yeast two-hybrid (Y2H) and bimolecular fluorescence complementation assays, we determined that OsDET1 interacts physically with DAMAGED-SPECIFIC DNA-BINDING PROTEIN1 (OsDDB1) and CONSTITUTIVE PHOTOMORPHOGENIC10 (COP10); DET1- and DDB1-ASSOCIATED1 binds to the ABA receptors OsPYL5 and OsDDB1. We found that the degradation of OsPYL5 was delayed in OsDET1 RNAi plants. These findings suggest that OsDET1 deficiency disturbs the COP10-DET1-DDB1 complex, which is responsible for ABA receptor (OsPYL) degradation, eventually leading to ABA sensitivity in rice. Additionally, OsDET1 also modulated ABA biosynthesis, as ABA biosynthesis was inhibited in OsDET1 RNAi plants and promoted in OsDET1-overexpressing transgenic plants. In conclusion, our data suggest that OsDET1 plays an important role in maintaining normal development in rice and mediates the cross talk between ABA biosynthesis and ABA signaling pathways in rice. PMID:27208292

  12. Seed dormancy and ABA signaling: the breakthrough goes on.

    PubMed

    Rodríguez-Gacio, María del Carmen; Matilla-Vázquez, Miguel A; Matilla, Angel J

    2009-11-01

    The seed is an important organ of higher plants regarding plant survival and species dispersion. The transition between seed dormancy and germination represents a critical stage in the plant life cycle and it is an important ecological and commercial trait. A dynamic balance of synthesis and catabolism of two antagonistic hormones, abscisic acid (ABA) and giberellins (GAs), controls the equilibrium between seed dormancy and germination. Embryonic ABA plays a central role in induction and maintenance of seed dormancy, and also inhibits the transition from embryonic to germination growth. Therefore, the ABA metabolism must be highly regulated at both temporal and spatial levels during phase of dessication tolerance. On the other hand, the ABA levels do not depend exclusively on the seeds because sometimes it becomes a strong sink and imports it from the roots and rhizosphere through the xylem and/or phloem. All theses events are discussed in depth here. Likewise, the role of some recently characterized genes belonging to seeds of woody species and related to ABA signaling, are also included. Finally, although four possible ABA receptors have been reported, not much is known about how they mediate ABA signalling transduction. However, new publications seem to shown that almost all these receptors lack several properties to consider them as such. PMID:19875942

  13. 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.

  14. ABA receptor PYL9 promotes drought resistance and leaf senescence

    PubMed Central

    Zhao, Yang; Chan, Zhulong; Gao, Jinghui; Xing, Lu; Cao, Minjie; Yu, Chunmei; Hu, Yuanlei; You, Jun; Shi, Haitao; Zhu, Yingfang; Gong, Yuehua; Mu, Zixin; Wang, Haiqing; Deng, Xin; Wang, Pengcheng; Bressan, Ray A.; Zhu, Jian-Kang

    2016-01-01

    Drought stress is an important environmental factor limiting plant productivity. In this study, we screened drought-resistant transgenic plants from 65 promoter-pyrabactin resistance 1-like (PYL) abscisic acid (ABA) receptor gene combinations and discovered that pRD29A::PYL9 transgenic lines showed dramatically increased drought resistance and drought-induced leaf senescence in both Arabidopsis and rice. Previous studies suggested that ABA promotes senescence by causing ethylene production. However, we found that ABA promotes leaf senescence in an ethylene-independent manner by activating sucrose nonfermenting 1-related protein kinase 2s (SnRK2s), which subsequently phosphorylate ABA-responsive element-binding factors (ABFs) and Related to ABA-Insensitive 3/VP1 (RAV1) transcription factors. The phosphorylated ABFs and RAV1 up-regulate the expression of senescence-associated genes, partly by up-regulating the expression of Oresara 1. The pyl9 and ABA-insensitive 1-1 single mutants, pyl8-1pyl9 double mutant, and snrk2.2/3/6 triple mutant showed reduced ABA-induced leaf senescence relative to the WT, whereas pRD29A::PYL9 transgenic plants showed enhanced ABA-induced leaf senescence. We found that leaf senescence may benefit drought resistance by helping to generate an osmotic potential gradient, which is increased in pRD29A::PYL9 transgenic plants and causes water to preferentially flow to developing tissues. Our results uncover the molecular mechanism of ABA-induced leaf senescence and suggest an important role of PYL9 and leaf senescence in promoting resistance to extreme drought stress. PMID:26831097

  15. Directed Assembly of Supramolecular Copolymers in Thin Films: Thermodynamic and Kinetic Advantages

    NASA Astrophysics Data System (ADS)

    Daoulas, Kostas Ch.; Cavallo, Anna; Shenhar, Roy; Müller, Marcus

    2010-09-01

    Using computer simulation of a coarse-grained model for supramolecular polymers, we investigate the potential of quasiblock copolymers (QBCPs) assembled on chemically patterned substrates for creating device-oriented nanostructures. QBCPs are comprised of AB diblock copolymers and supramolecular B segments that can reversibly bond to any available B terminus, on either the copolymers or the B oligomers, creating a polydisperse blend of B homopolymers, and AB and ABA copolymers. We demonstrate the defect-free replication of patterns with perpendicularly crossing, A-preferential lines, where the same QBCP can simultaneously replicate patterns differing by up to 50% in their length scales. We demonstrate how the pattern affects the distribution of molecular architectures and the key role of supramolecular associations for replicating patterns with different length scales.

  16. Synthesis and Characterization of Stimuli Responsive Block Copolymers, Self-Assembly Behavior and Applications

    SciTech Connect

    Michael Duane Determan

    2005-12-17

    The central theme of this thesis work is to develop new block copolymer materials for biomedical applications. While there are many reports of stimuli-responsive amphiphilic [19-21] and crosslinked hydrogel materials [22], the development of an in situ gel forming, pH responsive pentablock copolymer is a novel contribution to the field, Figure 1.1 is a sketch of an ABCBA pentablock copolymer. The A blocks are cationic tertiary amine methacrylates blocked to a central Pluronic F127 triblock copolymer. In addition to the prerequisite synthetic and macromolecular characterization of these new materials, the self-assembled supramolecular structures formed by the pentablock were experimentally evaluated. This synthesis and characterization process serves to elucidate the important structure property relationships of these novel materials, The pH and temperature responsive behavior of the pentablock copolymer were explored especially with consideration towards injectable drug delivery applications. Future synthesis work will focus on enhancing and tuning the cell specific targeting of DNA/pentablock copolymer polyplexes. The specific goals of this research are: (1) Develop a synthetic route for gel forming pentablock block copolymers with pH and temperature sensitive properties. Synthesis of these novel copolymers is accomplished with ATRP, yielding low polydispersity and control of the block copolymer architecture. Well defined macromolecular characteristics are required to tailor the phase behavior of these materials. (2) Characterize relationship between the size and shape of pentablock copolymer micelles and gel structure and the pH and temperature of the copolymer solutions with SAXS, SANS and CryoTEM. (3) Evaluate the temperature and pH induced phase separation and macroscopic self-assembly phenomenon of the pentablock copolymer. (4) Utilize the knowledge gained from first three goals to design and formulate drug delivery formulations based on the multi

  17. The induction of free proline accumulation by endogenous ABA in Arabidopsis thaliana during drought

    SciTech Connect

    Gottlieb, M.L.; Bray, E.A. )

    1991-05-01

    Endogenous levels of abscisic acid (ABA) and free proline increase in response to drought stress. Exogenous ABA has been shown to induce proline accumulation, suggesting that ABA triggers the amino acid response. To determine if endogenous ABA induces free proline accumulation, increases in ABA and proline during drought stress were compared between wild type (WT), ABA-insensitive (abi) and ABA-deficient (aba) mutants of Arabidopsis thaliana. If elevated levels of endogenous ABA signal the proline response, then the mutants would not be expected to accumulate proline during stress. abi should be unable to respond to increased levels of endogenous ABA, while aba should be unable to accumulate sufficient ABA to elicit a proline response. Drought-stressed three week old shoots of WT, abi, and aba exhibited different patterns of endogenous ABA accumulation, but similar patterns of proline accumulation over 24 hours. Although the patterns of endogenous ABA accumulation differed, maximum levels were similar in WT and abi, but aba produced approximately 25% less. However, free proline accumulated in all three plant lines. abi exhibited a greater, more rapid increase in free proline over that in either WT or aba. aba, however, showed the same pattern and levels of accumulation as that in WT. Since free proline accumulated to at least similar levels in both WT and mutants, regardless of the levels of ABA accumulation, it may be that only a small endogenous ABA accumulation is required for proline accumulation. Alternatively, endogenous ABA may not be the direct signal for the proline response during drought stress.

  18. Phase Behavior and Micellar Packing of Impurity-Free Pluronic Block Copolymers in Water

    NASA Astrophysics Data System (ADS)

    Ryu, Chang Yeol; Park, Hanjin

    We have investigated the impacts of the non-micellizable polymeric impurities on the micellar packing and solution phase behavior of Pluronic block copolymers in water. In particular, small angle x-ray scattering, rheology and dynamic light scattering techniques have been employed to elucidate how the low MW impurities affect the micellar packing and solution phase diagram in water, when ordered cubic structures of spherical micelles are formed. A silica slurry method has been developed using the competitive adsorption of the PEO-PPO-PEO triblock copolymers over the low MW polymeric impurities for a large scale purification of Pluronics and it purity of Pluronics has been assessed by interaction chromatography. Based on the comparative studies on micellar packing between As-Received (AR) and Purified (Pure) Pluronic F108 solutions, we found experimental evidence to support the hypothesis that the inter-micellar distance of Pluronic cubic structures in aqueous solution is governed by the effective polymer concentration in terms of PEO-PPO-PEO triblock copolymers. Removal of the impurities in AR F108 offers an important clue on window into the onset of BCC ordering via hydrodynamic contact between micelles in solution. NSF DMR Polymers.

  19. 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.

  20. Structure, Mechanics, and Transport in Block Copolymer-Nanoparticle Composites at the Macroscopic and Nanometer Lengthscales

    NASA Astrophysics Data System (ADS)

    Cheng, Vicki Alice

    2013-08-01

    Pluronic triblock copolymers self-assemble in water to form thermoreversible soft solids that comprise of periodically spaced micelles. The interstitial spacings of these micellar crystals are on the order of tens of nanometers, and have been used to template comparably sized nanoparticles with hydrodynamic diameters (Dh) ranging from 4-7 nm. Here, nanoparticle diffusivity is studied and modeled in these self-assembling block copolymers across a range of polymer concentrations. Transport in the disordered micellar solution is described as diffusion through a polymer solution, while diffusive behavior in the structured micellar phase is modeled as an activated hopping process. The effects of protein loading, shear alignment, particle type, and block copolymer composition on particle transport are also examined, and they affect particle diffusivity to varying degrees. Block copolymer architecture influences the micellar structure and dimensions, which in turn affects protein templating and protein aggregation behavior. The overall micellar dimensions are smaller in block copolymers with shorter block lengths, and efforts to template particles which are larger than the interstitial spacings result in changes to the block copolymer structure and mechanics. It is possible, however, for block copolymers to accommodate a limited amount of particles which are larger than the estimated micellar interstitial site. When examining protein aggregation behavior in block copolymers with varying PEO chain lengths, striking differences in aggregation behavior are observed as well. Ultimately, this work underscores the interplay between the structure, mechanics, and transport behavior in nanoparticle-block copolymer composites, and this knowledge can be applied towards the design of self-assembling nanoscale materials.

  1. Nanoporous polysulfone membranes via a degradable block copolymer precursor for redox flow batteries

    SciTech Connect

    Gindt, Brandon P.; Abebe, Daniel G.; Tang, Zhijiang J.; Lindsey, Melanie B.; Chen, Jihua; Elgammal, Ramez A.; Zawodzinski, Thomas A.; Fujiwara, Tomoko

    2016-01-01

    In this study, nanoporous polysulfone (PSU) membranes were fabricated via post-hydrolysis of polylactide (PLA) from PLA–PSU–PLA triblock copolymer membranes. The PSU scaffold was thermally crosslinked before sacrificing PLA blocks. The resulting nanopore surface was chemically modified with sulfonic acid moieties. The membranes were analyzed and evaluated as separators for vanadium redox flow batteries. Nanoporous PSU membranes prepared by this new method and further chemically modified to a slight degree exhibited unique behavior with respect to their ionic conductivity when exposed to solutions of increasing acid concentration.

  2. Nanoporous polysulfone membranes via a degradable block copolymer precursor for redox flow batteries

    DOE PAGESBeta

    Gindt, Brandon P.; Abebe, Daniel G.; Tang, Zhijiang J.; Lindsey, Melanie B.; Chen, Jihua; Elgammal, Ramez A.; Zawodzinski, Thomas A.; Fujiwara, Tomoko

    2016-01-01

    In this study, nanoporous polysulfone (PSU) membranes were fabricated via post-hydrolysis of polylactide (PLA) from PLA–PSU–PLA triblock copolymer membranes. The PSU scaffold was thermally crosslinked before sacrificing PLA blocks. The resulting nanopore surface was chemically modified with sulfonic acid moieties. The membranes were analyzed and evaluated as separators for vanadium redox flow batteries. Nanoporous PSU membranes prepared by this new method and further chemically modified to a slight degree exhibited unique behavior with respect to their ionic conductivity when exposed to solutions of increasing acid concentration.

  3. ABI1 regulates carbon/nitrogen-nutrient signal transduction independent of ABA biosynthesis and canonical ABA signalling pathways in Arabidopsis.

    PubMed

    Lu, Yu; Sasaki, Yuki; Li, Xingwen; Mori, Izumi C; Matsuura, Takakazu; Hirayama, Takashi; Sato, Takeo; Yamaguchi, Junji

    2015-05-01

    Plants are able to sense and mediate the balance between carbon (C) and nitrogen (N) nutrient availability to optimize metabolism and growth, described as the C/N response. To clarify the C/N signalling mechanism, C/N-insensitive plants were obtained from an Arabidopsis FOX hunting population, which over-expresses full-length cDNAs for individuals. The resulting cni2-D (carbon/nitrogen insensitive 2-dominant) plant was found to overcome the post-germination growth checkpoint and to expand green cotyledons in disrupted high C/low N stress conditions. The CNI2 gene encodes ABI1, a phosphatase type 2C protein, which negatively regulates abscisic acid (ABA) signal transduction. Over-expressors of ABI1 were found to be insensitive to disrupted C/N stress, whereas the loss-of function mutant abi1-2 was hypersensitive, suggesting that ABI1 plays an essential role in the plant C/N response. By contrast, the C/N-dependent growth phenotype observed in wild-type plants was not associated with endogenous ABA content. Accordingly, the ABA-insensitive mutant abi1-1, which could not bind to the ABA-ABA receptor complex, was not insensitive and restored normal sensitivity to high C/low N stress. The canonical ABA signalling mutants abi4 and abi5 were also sensitive to disrupted C/N stress. Further gene expression analysis demonstrated that several genes in the SnRK2s and SnRK1s pathways are transcriptionally affected by high C/low N stress in wild-type plants regardless of the lack of increased endogenous ABA contents, whereas the expression of these genes were significantly suppressed in ABI1 over-expressors. Taken together, these results suggest direct cross-talk between C/N and non-canonical ABA signalling pathways, regulated by ABI1, in plants. PMID:25795738

  4. Isolation of a wheat (Triticum aestivum L.) mutant in ABA 8'-hydroxylase gene: effect of reduced ABA catabolism on germination inhibition under field condition.

    PubMed

    Chono, Makiko; Matsunaka, Hitoshi; Seki, Masako; Fujita, Masaya; Kiribuchi-Otobe, Chikako; Oda, Shunsuke; Kojima, Hisayo; Kobayashi, Daisuke; Kawakami, Naoto

    2013-03-01

    Pre-harvest sprouting, the germination of mature seeds on the mother plant under moist condition, is a serious problem in cereals. To investigate the effect of reduced abscisic acid (ABA) catabolism on germination in hexaploid wheat (Triticum aestivum L.), we cloned the wheat ABA 8'-hydroxyase gene which was highly expressed during seed development (TaABA8'OH1) and screened for mutations that lead to reduced ABA catabolism. In a screen for natural variation, one insertion mutation in exon 5 of TaABA8'OH1 on the D genome (TaABA8'OH1-D) was identified in Japanese cultivars including 'Tamaizumi'. However, a single mutation in TaABA8'OH1-D had no clear effect on germination inhibition in double haploid lines. In a screen for a mutation, one deletion mutant lacking the entire TaABA8'OH1 on the A genome (TaABA8'OH1-A), TM1833, was identified from gamma-ray irradiation lines of 'Tamaizumi'. TM1833 (a double mutant in TaABA8'OH1-A and TaABA8'OH1-D) showed lower TaABA8'OH1 expression, higher ABA content in embryos during seed development under field condition and lower germination than those in 'Tamaizumi' (a single mutant in TaABA8'OH1-D). These results indicate that reduced ABA catabolism through mutations in TaABA8'OH1 may be effective in germination inhibition in field-grown wheat. PMID:23641187

  5. Block copolymer blends with improved oil absorption resistance

    SciTech Connect

    Himes, G.R.; Sanders, A.

    1989-11-14

    This patent describes a thermoplastic blend. It comprises: about 80 to about 20 parts by weight of an elastometric block copolymer having the general configuration A-B-A, wherein: each A block is a polymerized monoalkenyl aromatic hydrocarbon block having an average molecular weight of about 4000 to about 115,000; the A blocks, in combination, comprise about 5 to about 35w% of the elastomeric block copolymer; and each B block is a non-hydrogenated butadiene hydrocarbon block consisting of 8 to 55 mole percent condensed butadiene units in the 1,2 configuration, or a hydrogenated butadiene hydrocarbon block consisting of 35 to 55 mole percent condensed butadiene units in the 1,2 configuration, and the B block has an average molecular weight of between about 20,000 and about 450,000; and about 20 to about 80 parts by weight of a block copolymer having the general configuration A-B-A wherein: each A block is a polymerized monoalkenyl aromatic hydrocarbon block having an average molecular weight of about 4000 to about 115,000; the A blocks, in combination, comprise about 5 to about 35 w % of the block copolymer; each B block is a polymerized butadiene hydrocarbon block consisting of about 18 to 34 mole percent condensed butadiene units in the 1,2 configuration, and the B block has an average molecular weight of between about 20,000 and about 450,000; and the B blocks are hydrogenated to an unsaturation that is less than about 5% of the original unsaturation.

  6. Development of new generation of copolymers via reactive extrusion in a twin screw extruder and application in various PVC blends

    NASA Astrophysics Data System (ADS)

    Kim, In

    Polymerization in twin screw extruders has largely involved homopolymers. Here we generalize this and polymerize a range of copolymers and terpolymers including epsilon-caprolactam(CA), o-lauryl lactam(LA), epsilon-caprolactone(CL), and gamma-butyrolactone(GBL) in a modular intermeshing co-rotating twin screw extruder. We considered different types of copolymer structures (di-block, tri-block, and random-block) and different backbones of copolymer(lactams-lactones) as well as the variables of temperature profile, screw speed, monomer feed rate, the ratio of monomer to initiator, and feeding order of co-monomers on reactive extrusion of polyamides-polylactones based (co)polymers. Specially designed block copolymers have played a role as compatibilizing agents in the system of immiscible polymer blends. We apply the di-block copolymer(P(LA-b-CL)) and random block copolymer (P(LA/CA-b-CL)) produced by reactive extrusion as a compatibilizing agent in immiscible polymer blend systems: (i) poly(vinyl chloride) (PVC)/polyamide 12 (PA12), (ii) PVC/polypropylene(PP), and (iii) PVC/Ethylene-propylene-non-conjugated diene elastomer(EPDM).

  7. Impact of transcriptional, ABA-dependent, and ABA-independent pathways on wounding regulation of RNS1 expression.

    PubMed

    Hillwig, Melissa S; Lebrasseur, Nicole D; Green, Pamela J; Macintosh, Gustavo C

    2008-09-01

    Injured plants induce a wide range of genes whose products are thought to help to repair the plant or to defend against opportunistic pathogens that might infect the wounded plant. In Arabidopsis thaliana L., oligogalacturonides (OGAs) and jasmonic acid (JA) are the main regulators of the signaling pathways that control the local and systemic wound response, respectively. RNS1, a secreted ribonuclease, is induced by wounding in Arabidopsis independent of these two signals, thus indicating that another wound-response signal exists. Here we show that abscisic acid (ABA), which induces wound-responsive genes in other systems, also induces RNS1. In the absence of ABA signaling, wounding induces only approximately 45% of the endogenous levels of RNS1 mRNA. However, significant levels of RNS1 still accumulate in the absence of ABA signaling. Our results suggest that wound-responsive increases in ABA production may amplify induction of RNS1 by a novel ABA-independent pathway. To elucidate this novel pathway, we show here that the wound induction of RNS1 is due in part to transcriptional regulation by wounding and ABA. We also show evidence of post-transcriptional regulation which may contribute to the high levels of RNS1 transcript accumulation in response to wounding. PMID:18607631

  8. Self-assembling triblock proteins for biofunctional surface modification

    NASA Astrophysics Data System (ADS)

    Fischer, Stephen E.

    Despite the tremendous promise of cell/tissue engineering, significant challenges remain in engineering functional scaffolds to precisely regulate the complex processes of tissue growth and development. As the point of contact between the cells and the scaffold, the scaffold surface plays a major role in mediating cellular behaviors. In this dissertation, the development and utility of self-assembling, artificial protein hydrogels as biofunctional surface modifiers is described. The design of these recombinant proteins is based on a telechelic triblock motif, in which a disordered polyelectrolyte central domain containing embedded bioactive ligands is flanked by two leucine zipper domains. Under moderate conditions of temperature and pH, the leucine zipper end domains form amphiphilic alpha-helices that reversibly associate into homo-trimeric aggregates, driving hydrogel formation. Moreover, the amphiphilic nature of these helical domains enables surface adsorption to a variety of scaffold materials to form biofunctional protein coatings. The nature and stability of these coatings in various solution conditions, and their interaction with mammalian cells is the primary focus of this dissertation. In particular, triblock protein coatings functionalized with cell recognition sequences are shown to produce well-defined surfaces with precise control over ligand density. The impact of this is demonstrated in multiple cell types through ligand density-dependent cell-substrate interactions. To improve the stability of these physically self-assembled coatings, two covalent crosslinking strategies are described---one in which a zero-length chemical crosslinker (EDC) is utilized and a second in which disulfide bonds are engineered into the recombinant proteins. These targeted crosslinking approaches are shown to increase the stability of surface adsorbed protein layers with minimal effect on the presentation of many bioactive ligands. Finally, to demonstrate the versatility

  9. 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

  10. Directed assembly of supramolecular copolymers in thin films

    NASA Astrophysics Data System (ADS)

    Muller, Marcus; Daoulas, Kostas Ch.; Cavallo, Anna; Shenhar, Roy

    2011-03-01

    Using computer simulation of a coarse-grained model for supramolecular polymers we investigate the potential of quasi-block copolymers (QBCP) assembled on chemically patterned substrates for creating device-oriented nanostructures. QBCP are comprised of AB diblock copolymers and supramolecular B segments that can reversibly bond to any available B terminus, either on the copolymers or the B oligomers, creating a polydisperse blend of B homopolymers, AB and ABA copolymers. We focus on an AB incompatibility, χ , and strength of supramolecular bonds where a lamellar morphology, a bicontinous structure and a macrophase-separated state have comparable free energy in the bulk. We consider substrate patterns with perpendicularly crossing, A-preferential lines and demonstrate their defect-free replication by QBCP. The same QBCP replicates simultaneously patterns differing by up to 50 % in their length scales, illustrating the high versatility of QBCP materials. We discuss the interplay between pattern geometry and distribution of molecular architectures and verify the key role of supramolecular associations for replicating patterns with different length scales.

  11. Double network physical gels from elastin-like polypeptide block copolymers: nanoscale control of thermoresponsive reinforcement

    NASA Astrophysics Data System (ADS)

    Glassman, Matthew; Olsen, Bradley

    2014-03-01

    Triblock copolymers with associative protein midblocks and thermoresponsive endblocks form shear thinning hydrogels with a low yield stress at low temperatures, but can be reinforced by a self-assembled network of the endblock aggregates. Here, we compare the use of bioengineered elastin-like polypeptides (ELPs) to synthetic poly(N-isopropylacrylamide) (PNIPAM) as endblocks to control the self-assembly of the reinforcing network. The temperature dependence of the mechanics of these hydrogels is a strong function of the domain size and morphology in the endblock network. Despite the architectural similarities, triblock ELP fusions and PNIPAM bioconjugates exhibit distinct reinforcement maxima at fixed block composition and polymer concentration, and these differences can be attributed to the nanostructural features of the two systems. Furthermore, in ELP fusions, the amino acid sequence can be readily modified to manipulate the solvation kinetics of the endblock domains. Finally, various endblocks have been combined to form triblock terpolymer hydrogels, demonstrating how the choice of thermoresponsive blocks can be used to tune the reinforcement of shear thinning hydrogels.

  12. 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

  13. Structure and rheology of associative triblocks in microemulsion solutions

    NASA Astrophysics Data System (ADS)

    Bhatia, Surita Rani

    This thesis describes our theoretical and experimental work on the rheology, static structure, and phase behavior of associative solutions. Our theoretical efforts have centered on solving the diffusion equation model of Dolan and Edwards for ideal associative triblocks between surfaces to yield the segment density profile and free energy. We have shown that polymers between two spheres cause an O(kT) attraction, similar to that calculated by Milner and Witten for associative polymer brushes between flat plates. The attraction we calculate is weaker than that given by the Derjaguin approximation, and excluded volume moderates the attraction and softens the repulsion between spheres. The free energy was used to estimate an interparticle potential, which in turn was used to compute structure factors for solutions of associative polymers via Monte Carlo simulations. As a model system for our experiments, we have chosen PEO-PI-PEO triblocks in an AOT/water/decane microemulsion. Upon dilution with decane, the solutions phase separate into a dense, high viscosity phase and a dilute, low viscosity phase. We have performed both small-angle neutron scattering (SANS) and rheology on these solutions. Structure factors derived from our SANS data agree fairly well with those predicted by our theory and indicate that the droplets reside in an attractive minimum. The rheology of these solutions shows several interesting features that are not predicted by classical reversible network theory. Data from oscillatory experiments indicate a single relaxation time at low polymer concentrations but show evidence of a slower relaxation for higher concentrations. In addition, some solutions exhibit a maximum in the high shear viscosity. Some of our observations are predicted by the flowerlike micelle theory developed by Semenov and co-workers; however, our data is not completely consistent with the theoretical predictions. The high frequency modulus scales roughly quadratically with

  14. Arabidopsis plants deficient in plastidial glyceraldehyde-3-phosphate dehydrogenase show alterations in abscisic acid (ABA) signal transduction: interaction between ABA and primary metabolism

    PubMed Central

    Muñoz-Bertomeu, Jesús; Bermúdez, María Angeles; Segura, Juan; Ros, Roc

    2011-01-01

    Abscisic acid (ABA) controls plant development and regulates plant responses to environmental stresses. A role for ABA in sugar regulation of plant development has also been well documented although the molecular mechanisms connecting the hormone with sugar signal transduction pathways are not well understood. In this work it is shown that Arabidopsis thaliana mutants deficient in plastidial glycolytic glyceraldehyde-3-phosphate dehydrogenase (gapcp1gapcp2) are ABA insensitive in growth, stomatal closure, and germination assays. The ABA levels of gapcp1gapcp2 were normal, suggesting that the ABA signal transduction pathway is impaired in the mutants. ABA modified gapcp1gapcp2 gene expression, but the mutant response to the hormone differed from that observed in wild-type plants. The gene expression of the transcription factor ABI4, involved in both sugar and ABA signalling, was altered in gapcp1gapcp2, suggesting that their ABA insensitivity is mediated, at least partially, through this transcriptional regulator. Serine supplementation was able partly to restore the ABA sensitivity of gapcp1gapcp2, indicating that amino acid homeostasis and/or serine metabolism may also be important determinants in the connections of ABA with primary metabolism. Overall, these studies provide new insights into the links between plant primary metabolism and ABA signalling, and demonstrate the importance of plastidial glycolytic glyceraldehyde-3-phosphate dehydrogenase in these interactions. PMID:21068209

  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. Confinement of block copolymers

    SciTech Connect

    1995-12-31

    The following were studied: confinement of block copolymers, free surface confinement, effects of substrate interactions, random copolymers at homopolymer interfaces, phase separation in thin film polymer mixtures, buffing of polymer surfaces, and near edge x-ray absorption fine structure spectroscopy.

  17. The Tricontinuous 3ths(5) Phase: A New Morphology in Copolymer Melts

    NASA Astrophysics Data System (ADS)

    Fischer, Michael; de Campo, Liliana; Kirkensgaard, Jacob; Hyde, Stephen; Schroeder-Turk, Gerd

    2015-03-01

    Self-assembly remains one of the most efficient routes to the formation of ordered nanostructures, including the double gyroid network phase in diblock copolymers based on two intergrown network domains. This talk demonstrates the use of self-consistent field theory to show that a tricontinuous structure with monoclinic symmetry, called 3ths(5), based on the intergrowth of three distorted ths nets, is an equilibrium phase of triblock star-copolymer melts when an extended molecular core is introduced. The introduction of the core enhances the role of chain stretching by enforcing larger structural length scales, thus destabilizing the hexagonal columnar phase in favor of morphologies with less packing frustration. This study further demonstrates that the introduction of molecular cores is a general concept for tuning the relative importance of entropic and enthalpic free energy contributions, hence providing a tool to stabilize an extended repertoire of self-assembled nanostructured materials.

  18. Local root abscisic acid (ABA) accumulation depends on the spatial distribution of soil moisture in potato: implications for ABA signalling under heterogeneous soil drying

    PubMed Central

    Puértolas, Jaime; Conesa, María R.; Ballester, Carlos; Dodd, Ian C.

    2015-01-01

    Patterns of root abscisic acid (ABA) accumulation ([ABA]root), root water potential (Ψroot), and root water uptake (RWU), and their impact on xylem sap ABA concentration ([X-ABA]) were measured under vertical partial root-zone drying (VPRD, upper compartment dry, lower compartment wet) and horizontal partial root-zone drying (HPRD, two lateral compartments: one dry, the other wet) of potato (Solanum tuberosum L.). When water was withheld from the dry compartment for 0–10 d, RWU and Ψroot were similarly lower in the dry compartment when soil volumetric water content dropped below 0.22cm3 cm–3 for both spatial distributions of soil moisture. However, [ABA]root increased in response to decreasing Ψroot in the dry compartment only for HPRD, resulting in much higher ABA accumulation than in VPRD. The position of the sampled roots (~4cm closer to the surface in the dry compartment of VPRD than in HPRD) might account for this difference, since older (upper) roots may accumulate less ABA in response to decreased Ψroot than younger (deeper) roots. This would explain differences in root ABA accumulation patterns under vertical and horizontal soil moisture gradients reported in the literature. In our experiment, these differences in root ABA accumulation did not influence [X-ABA], since the RWU fraction (and thus ABA export to shoots) from the dry compartment dramatically decreased simultaneously with any increase in [ABA]root. Thus, HPRD might better trigger a long-distance ABA signal than VPRD under conditions allowing simultaneous high [ABA]root and relatively high RWU fraction. PMID:25547916

  19. Local root abscisic acid (ABA) accumulation depends on the spatial distribution of soil moisture in potato: implications for ABA signalling under heterogeneous soil drying.

    PubMed

    Puértolas, Jaime; Conesa, María R; Ballester, Carlos; Dodd, Ian C

    2015-04-01

    Patterns of root abscisic acid (ABA) accumulation ([ABA]root), root water potential (Ψroot), and root water uptake (RWU), and their impact on xylem sap ABA concentration ([X-ABA]) were measured under vertical partial root-zone drying (VPRD, upper compartment dry, lower compartment wet) and horizontal partial root-zone drying (HPRD, two lateral compartments: one dry, the other wet) of potato (Solanum tuberosum L.). When water was withheld from the dry compartment for 0-10 d, RWU and Ψroot were similarly lower in the dry compartment when soil volumetric water content dropped below 0.22cm(3) cm(-3) for both spatial distributions of soil moisture. However, [ABA]root increased in response to decreasing Ψroot in the dry compartment only for HPRD, resulting in much higher ABA accumulation than in VPRD. The position of the sampled roots (~4cm closer to the surface in the dry compartment of VPRD than in HPRD) might account for this difference, since older (upper) roots may accumulate less ABA in response to decreased Ψroot than younger (deeper) roots. This would explain differences in root ABA accumulation patterns under vertical and horizontal soil moisture gradients reported in the literature. In our experiment, these differences in root ABA accumulation did not influence [X-ABA], since the RWU fraction (and thus ABA export to shoots) from the dry compartment dramatically decreased simultaneously with any increase in [ABA]root. Thus, HPRD might better trigger a long-distance ABA signal than VPRD under conditions allowing simultaneous high [ABA]root and relatively high RWU fraction. PMID:25547916

  20. Structural basis for selective activation of ABA receptors

    SciTech Connect

    Peterson, Francis C.; Burgie, E. Sethe; Park, Sang-Youl; Jensen, Davin R.; Weiner, Joshua J.; Bingman, Craig A.; Chang, Chia-En A.; Cutler, Sean R.; Phillips, Jr., George N.; Volkman, Brian F.

    2010-11-01

    Changing environmental conditions and lessening fresh water supplies have sparked intense interest in understanding and manipulating abscisic acid (ABA) signaling, which controls adaptive responses to drought and other abiotic stressors. We recently discovered a selective ABA agonist, pyrabactin, and used it to discover its primary target PYR1, the founding member of the PYR/PYL family of soluble ABA receptors. To understand pyrabactin's selectivity, we have taken a combined structural, chemical and genetic approach. We show that subtle differences between receptor binding pockets control ligand orientation between productive and nonproductive modes. Nonproductive binding occurs without gate closure and prevents receptor activation. Observations in solution show that these orientations are in rapid equilibrium that can be shifted by mutations to control maximal agonist activity. Our results provide a robust framework for the design of new agonists and reveal a new mechanism for agonist selectivity.

  1. The Top 10 Reasons Children With Autism Deserve ABA

    PubMed Central

    Walsh, Mary Beth

    2011-01-01

    We who advocate for applied behavior analysis (ABA) for children with autism spectrum disorders often construct our arguments based on the scientific evidence. However, the audience that most needs to hear this argument, that is, the parents of children, especially very young children, diagnosed with autism, may not be convinced by the science alone. This essay attempts to make the case for the multiple benefits of ABA intervention through the use of humor and anecdotes couched in a “Top Ten List,” and illustrating most points with stories of an engaging child with autism (my son, Ben). PMID:22532906

  2. Intriguing transmission electron microscopy images observed for perpendicularly oriented cylindrical microdomains of block copolymers

    NASA Astrophysics Data System (ADS)

    Ohnogi, Hiroshi; Isshiki, Toshiyuki; Sasaki, Sono; Sakurai, Shinichi

    2014-08-01

    Intriguing images of dislocation structures were observed by the transmission electron microscopy (TEM) technique for hexagonally packed cylindrical microdomains in a block copolymer (polystyrene-block-polyethylenebutylene-block-polystyrene triblock copolymer) film. The polystyrene (PS) cylinders were embedded in the polyethylenebutylene (PEB) matrix and oriented perpendicular to the surface of the thin section for the TEM observations. In order to understand such strange dislocation structures, we applied an image processing technique using two-dimensional Fourier transform (FT) and inverse Fourier transform (IFT) methods. It was found that these intriguing images were not ascribed to real dislocation structures but were fake ones due to the moiré effect caused by the overlapping of hexagons with a slightly mismatched orientation. Furthermore, grain boundaries in the ultrathin section can be identified by image processing using FT and IFT methods.Intriguing images of dislocation structures were observed by the transmission electron microscopy (TEM) technique for hexagonally packed cylindrical microdomains in a block copolymer (polystyrene-block-polyethylenebutylene-block-polystyrene triblock copolymer) film. The polystyrene (PS) cylinders were embedded in the polyethylenebutylene (PEB) matrix and oriented perpendicular to the surface of the thin section for the TEM observations. In order to understand such strange dislocation structures, we applied an image processing technique using two-dimensional Fourier transform (FT) and inverse Fourier transform (IFT) methods. It was found that these intriguing images were not ascribed to real dislocation structures but were fake ones due to the moiré effect caused by the overlapping of hexagons with a slightly mismatched orientation. Furthermore, grain boundaries in the ultrathin section can be identified by image processing using FT and IFT methods. Electronic supplementary information (ESI) available. See DOI: 10.1039/c

  3. Effects of hydrophobic drug polyesteric core interactions on drug loading and release properties of poly(ethylene glycol) polyester poly(ethylene glycol) triblock core shell nanoparticles

    NASA Astrophysics Data System (ADS)

    Khoee, Sepideh; Hassanzadeh, Salman; Goliaie, Bahram

    2007-05-01

    BAB amphiphilic triblock copolymers consisting of poly(ethylene glycol) (B) (PEG) as the hydrophilic segment and different polyesters (A) as the hydrophobic block were prepared by a polycondensation reaction as efficient model core-shell nanoparticles to assay the effect of interactions between the hydrophobic drug and the polyesteric core in terms of drug loading content and release profile. PEG-poly(hexylene adipate)-PEG (PEG-PHA-PEG) and PEG-poly(butylene adipate)-PEG (PEG-PBA-PEG) to PEG-poly(ethylene adipate)-PEG (PEG-PEA-PEG) core-shell type nanoparticles entrapping quercetin (an anticarcinogenic, allergy inhibitor and antibacterial agent), were prepared by a nanoprecipitation method and characterized by dynamic light scattering (DLS), transmission electron microscopy (TEM) and x-ray diffraction (XRD) techniques. It was found that the obtained nanoparticles showed a smooth surface and spherical shape with controllable sizes in the range of 64-74 nm, while drug loading varied from 7.24% to 19% depending on the copolymer composition and the preparation conditions. The in vitro release behaviour exhibited a sustained release and was affected by the polymer-drug interactions. UV studies revealed the presence of hydrogen bonding as the main existing interaction between quercetin and polyesters in the nanosphere cores.

  4. Preparation and characterization of tri-block poly(lactide)-poly(ethylene glycol)-poly(lactide) nanogels for controlled release of naltrexone.

    PubMed

    Asadi, H; Rostamizadeh, K; Salari, D; Hamidi, M

    2011-09-15

    Tri-block poly(lactide)-poly(ethylene glycol)-poly(lactide) (PLA-PEG-PLA) copolymers and related acrylated derivative were synthesized and used to prepare micelles and nanogels for controlled release of naltrexone. The resulting copolymers, micelles and nanogels were characterized by various techniques such as proton nuclear magnetic resonance spectroscopy, Fourier transform infrared spectroscopy, gel permeation chromatography, fluorescence spectrometry, differential scanning calorimetry, photon correlation spectroscopy and scanning electron microscopy. The nanogels exhibited high encapsulation efficiency around 60% and excellent stability for long periods of time. The drug release profiles of micelles and nanogels were compared and it was found that the naltrexone loaded nanogels offered a steady and long-term release pattern for different periods of time up to 35 days, depending on the crosslinker concentration, compared to the micelles. The size of nanogels could be manipulated easily in the range of 128-200nm by variations in polymer concentration used in the nanogels preparation step. From the results obtained it can be concluded that PLA-PEG-PLA nanogels can be considered as a promising carrier for drug delivery purpose. PMID:21729744

  5. Highly protein-resistant coatings and suspension cell culture thereon from amphiphilic block copolymers prepared by RAFT polymerization.

    PubMed

    Haraguchi, Kazutoshi; Kubota, Kazuomi; Takada, Tetsuo; Mahara, Saori

    2014-06-01

    Novel amphiphilic block copolymers composed of hydrophobic (poly(2-methoxyethyl acrylate): M) and hydrophilic (poly(N,N-dimethylacrylamide): D) segments were synthesized by living radical polymerization: a reversible addition-fragmentation chain-transfer polymerization. Two types of amphiphilic block copolymers, triblock (MDM) and 4-arm block ((MD)4) copolymers with specific compositions (D/M = (750-1500)/250), were prepared by a versatile one-pot synthesis. These copolymers show good adhesion to various types of substrates (e.g., polystyrene, polycarbonate, polypropylene, Ti, and glass), and the surface coating showed high protein repellency and a low contact angle for water, regardless of the substrate. The two opposing characteristics of high protein repellency and good substrate adhesion were achieved by the combined effects of the molecular architecture of the block copolymers, the high molecular weight, and the characteristics of each segment, that is, low protein adsorption capability of both segments and low glass transition temperature of the hydrophobic segment. Further, a polystyrene dish coated with the MDM block copolymer could be sterilized by γ-ray irradiation and used as a good substrate for a suspension cell culture that exhibits low cell adhesion and good cell growth. PMID:24773089

  6. Nanostructure in block copolymer solutions: Rheology and small-angle neutron scattering

    SciTech Connect

    Habas, Jean-Pierre; Pavie, Emmanuel; Perreur, Christelle; Lapp, Alain; Peyrelasse, Jean

    2004-12-01

    Triblock copolymers composed of poly(ethylene oxide) (PEO) and poly(propylene oxide) (PPO) present an amphiphilic character in aqueous solutions. Since PPO is less hydrophilic than PEO and since their solubilities decrease when the temperature increases, the copolymers self-assemble spontaneously, forming micelles at moderate temperatures. For higher temperatures or concentrations, the copolymers or the micelles are ordered because of repulsive interactions and form lyotropic liquid crystalline phases. These are phases of very great viscosity with the aspect of gels, and transitions between different crystalline phases can occur at fixed concentration during an increase of temperature. We studied solutions of three different copolymers. The first two have a star structure. They are both composed of four branches (EO){sub x}(PO){sub y} fixed on an ethylene diamine, but differ by the values of x and y. Their commercial name is Tetronic 908 (x=114, y=21) and Tetronic 704 (x=16, y=18). The third copolymer (EO){sub 37}(PO){sub 56}(EO){sub 37} is linear and is known under the name of Pluronic P105. The measurements of the shear complex elastic modulus according to the temperature is used to determine the temperatures of the different transitions. Then, small-angle neutron scattering on samples under flow and true crystallographic arguments make it possible to identify the nature of the crystalline phases. For the systems studied, we show that the branched copolymers form only one type of liquid crystalline phase, which is bcc for the T908 and lamellar for the T704. For the linear copolymer, it is possible to identify three transitions: micellar solution to hexagonal phase, hexagonal phase to body-centered cubic phase, and finally body-centered cubic phase to lamellar phase.

  7. PCL-PDMS-PCL copolymer-based microspheres mediate cardiovascular differentiation from embryonic stem cells

    NASA Astrophysics Data System (ADS)

    Song, Liqing

    Poly-epsilon-caprolactone (PCL) based copolymers have received much attention as drug or growth factor delivery carriers and tissue engineering scaffolds due to their biocompatibility, biodegradability, and tunable biophysical properties. Copolymers of PCL and polydimethylsiloxane (PDMS) also have shape memory behaviors and can be made into thermoresponsive shape memory polymers for various biomedical applications such as smart sutures and vascular stents. However, the influence of biophysical properties of PCL-PDMS-PCL copolymers on stem cell lineage commitment is not well understood. In this study, PDMS was used as soft segments of varying length to tailor the biophysical properties of PCL-based co-polymers. While low elastic modulus (<10 kPa) of the tri-block copolymer PCL-PDMS-PCL affected cardiovascular differentiation of embryonic stem cells, the range of 60-100 MPa PCL-PDMS-PCL showed little influence on the differentiation. Then different size (30-140 mum) of microspheres were fabricated from PCL-PDMS-PCL copolymers and incorporated within embryoid bodies (EBs). Mesoderm differentiation was induced using bone morphogenetic protein (BMP)-4 for cardiovascular differentiation. Differential expressions of mesoderm progenitor marker KDR and vascular markers CD31 and VE-cadherin were observed for the cells differentiated from EBs incorporated with microspheres of different size, while little difference was observed for cardiac marker alpha-actinin expression. Small size of microspheres (30 mum) resulted in higher expression of KDR while medium size of microspheres (94 mum) resulted in higher CD31 and VE-cadherin expression. This study indicated that the biophysical properties of PCL-based copolymers impacted stem cell lineage commitment, which should be considered for drug delivery and tissue engineering applications.

  8. Effects of high night temperature and abscisic acid (ABA) on rice (Oryza sativa L.) physiology

    Technology Transfer Automated Retrieval System (TEKTRAN)

    High night temperature (HNT) is known to decrease rice yields. The impact of abscisic acid (ABA) on plants has been the subject of many studies. However, little or no work has been carried out on rice response to ABA under HNT-stress conditions. This study determined the effects of ABA on rice leaf ...

  9. Coping as a Predictor of Burnout and General Health in Therapists Working in ABA Schools

    ERIC Educational Resources Information Center

    Griffith, G. M.; Barbakou, A.; Hastings, R. P.

    2014-01-01

    Background: Little is known about the work-related well-being of applied behaviour analysis (ABA) therapists who work in school-based contexts and deliver ABA interventions to children with autism. Methods: A questionnaire on work-related stress (burnout), general distress, perceived supervisor support and coping was completed by 45 ABA therapists…

  10. Role of metabolism in ABA homeostasis during potato tuber dormancy

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Endogenous hormones play a essential role in the regulation of potato tuber dormancy. Abscisic acid has been shown to be critically involved in tuber dormancy induction and maintenance. Genes encoding enzymes catalyzing the terminal steps of ABA synthesis and metabolism have been cloned from tuber...

  11. Adaptive Behaviour Assessment System: Indigenous Australian Adaptation Model (ABAS: IAAM)

    ERIC Educational Resources Information Center

    du Plessis, Santie

    2015-01-01

    The study objectives were to develop, trial and evaluate a cross-cultural adaptation of the Adaptive Behavior Assessment System-Second Edition Teacher Form (ABAS-II TF) ages 5-21 for use with Indigenous Australian students ages 5-14. This study introduced a multiphase mixed-method design with semi-structured and informal interviews, school…

  12. ABA and Diverse Cultural and Linguistic Environments: A Welsh Perspective

    ERIC Educational Resources Information Center

    Jones, E. W.; Hoerger, M.; Hughes, J. C.; Williams, B. M.; Jones, B.; Moseley, Y.; Hughes, D. R.; Prys, D.

    2011-01-01

    Gwynedd Local Education Authority (LEA) in North West Wales, UK, is funding a small-scale autism-specific specialist education service using ABA methodology. The program is available through the medium of Welsh, English or bilingually, depending on the individual needs of the child (Jones and Hoerger in Eur J Behav Anal 10:249-253, "2009").…

  13. Personality Traits Associated with Occupational "Burnout" in ABA Therapists

    ERIC Educational Resources Information Center

    Hurt, Amy A.; Grist, Cathy Lann; Malesky, Lann A., Jr.; McCord, David M.

    2013-01-01

    Background: Applied behaviour analysis (ABA) therapists typically work one-to-one with children with autism for extended periods of time, which often leads to high levels of job-related stress, lower levels of job satisfaction, increased frequency of occupational "burnout" and higher than average job turnover (Journal of Autism…

  14. Dissociations among ABA, ABC, and AAB Recovery Effects

    ERIC Educational Resources Information Center

    Ungor, Metin; Lachnit, Harald

    2008-01-01

    In a human predictive learning experiment, the strengths of ABA, ABC, and AAB recovery effects after discrimination reversal learning were compared. Initially, a discrimination between two stimuli (X+, Y-) was trained in Context A. During Phase 2, participants received discrimination reversal training (X-, Y+) either in Context A (Group AAB) or in…

  15. ABA, AAB and ABC Renewal in Taste Aversion Learning

    ERIC Educational Resources Information Center

    Bernal-Gamboa, Rodolfo; Juarez, Yectivani; Gonzalez-Martin, Gabriela; Carranza, Rodrigo; Sanchez-Carrasco, Livia; Nieto, Javier

    2012-01-01

    Context renewal is identified when the conditioned response (CR) elicited by an extinguished conditioned stimulus (CS) reappears as a result of changing the contextual cues during the test. Two experiments were designed for testing contextual renewal in a conditioned taste aversion preparation. Experiment 1 assessed ABA and AAB context renewal,…

  16. Synthesis of Block Copolymers of Varying Architecture Through Suppression of Transesterification during Coordinated Anionic Ring Opening Polymerization

    PubMed Central

    Lipik, Vitali T.; Abadie, Marc J. M.

    2012-01-01

    Well-defined di- and triblock copolymers consisting of ε-caprolactone (CL), L-lactide (LA), and trimethylene carbonate (TMC) were synthesized via “PLA first route” in coordinated anionic ring opening polymerization/copolymerization (CAROP) with tin (II) octoate as catalyst. The desired block structure was preserved by use of protective additive α-methylstyrene by preventing the transesterification side-reactions. MALDI-TOF analysis revealed that the protection mechanism is associated with α-methylstyrene and tin (II) octoate complexation. Additionally, it was shown that use of α-methylstyrene in ring opening polymerization allowed the formation of polyesters with high molar mass. PMID:22844286

  17. Multicompartment Core Micelles of Triblock Terpolymers in Organic Media

    SciTech Connect

    Schacher, Felix; Walther, Andreas; Ruppel, Markus A; Drechsler, Markus; Muller, Axel

    2009-01-01

    The formation of multicompartment micelles featuring a spheres on sphere core morphology in acetone as a selective solvent is presented. The polymers investigated are ABC triblock terpolymers, polybutadieneb-poly(2-vinyl pyridine)-b-poly(tert-butyl methacrylate) (BVT), which were synthesized via living sequential anionic polymerization in THF. Two polymers with different block lengths of the methacrylate moiety were studied with respect to the formation of multicompartmental aggregates. The micelles were analyzed by static and dynamic light scattering as well as by transmission electron microscopy. Cross-linking of the polybutadiene compartment could be accomplished via two different methods, cold vulcanization and with photopolymerization after the addition of a multifunctional acrylate. In both cases, the multicompartmental character of the micellar core is fully preserved, and the micelles could be transformed into core-stabilized nanoparticles. The successful cross-linking of the polybutadiene core is indicated by 1H NMR and by the transfer of the aggregates into nonselective solvents such as THF or dioxane.

  18. Antimicrobial Graft Copolymer Gels.

    PubMed

    Harvey, Amanda C; Madsen, Jeppe; Douglas, C W Ian; MacNeil, Sheila; Armes, Steven P

    2016-08-01

    In view of the growing worldwide rise in microbial resistance, there is considerable interest in designing new antimicrobial copolymers. The aim of the current study was to investigate the relationship between antimicrobial activity and copolymer composition/architecture to gain a better understanding of their mechanism of action. Specifically, the antibacterial activity of several copolymers based on 2-(methacryloyloxy)ethyl phosphorylcholine [MPC] and 2-hydroxypropyl methacrylate (HPMA) toward Staphylococcus aureus was examined. Both block and graft copolymers were synthesized using either atom transfer radical polymerization or reversible addition-fragmentation chain transfer polymerization and characterized via (1)H NMR, gel permeation chromatography, rheology, and surface tensiometry. Antimicrobial activity was assessed using a range of well-known assays, including direct contact, live/dead staining, and the release of lactate dehydrogenase (LDH), while transmission electron microscopy was used to study the morphology of the bacteria before and after the addition of various copolymers. As expected, PMPC homopolymer was biocompatible but possessed no discernible antimicrobial activity. PMPC-based graft copolymers comprising PHPMA side chains (i.e. PMPC-g-PHPMA) significantly reduced both bacterial growth and viability. In contrast, a PMPC-PHPMA diblock copolymer comprising a PMPC stabilizer block and a hydrophobic core-forming PHPMA block did not exhibit any antimicrobial activity, although it did form a biocompatible worm gel. Surface tensiometry studies and LDH release assays suggest that the PMPC-g-PHPMA graft copolymer exhibits surfactant-like activity. Thus, the observed antimicrobial activity is likely to be the result of the weakly hydrophobic PHPMA chains penetrating (and hence rupturing) the bacterial membrane. PMID:27409712

  19. Bismaleimide Copolymer Matrix Resins

    NASA Technical Reports Server (NTRS)

    Parker, John A.; Heimbuch, Alvin H.; Hsu, Ming-Ta S.; Chen, Timothy S.

    1987-01-01

    Graphite composites, prepared from 1:1 copolymer of two new bismaleimides based on N,N'-m-phenylene-bis(m-amino-benzamide) structure have mechanical properties superior to those prepared from other bismaleimide-type resins. New heat-resistant composites replace metal in some structural applications. Monomers used to form copolymers with superior mechanical properties prepared by reaction of MMAB with maleic or citraconic anhydride.

  20. Radiation-induced graft copolymer SBS-g-VP for biomaterial usage.

    PubMed

    Yang, J M; Hsiue, G H

    1996-06-01

    The grafting of 4-vinyl pyridine (VP) to styrene-butadienestyrene triblock copolymer (SBS) by radiation-induced graft copolymerization was studied. The cohesive properties such as cohesive energy (Ecoh), molar volume (V), solubility parameter (delta), molar molecular weight (WM), specific volume (Vg), and density (1/Vg) of SBS-g-VP graft copolymer were calculated according to the group contribution of Fedors. The morphology of SBS-g-VP was studied by optical polarizing microscopy. We also measured the glass transition temperature and the mechanical properties of SBS-g-VP graft copolymer. Contact angle and blood-clotting time experiments were also performed to evaluate the biocompatibility of SBS-g-VP. A second domain was found in the SBS-g-VP graft copolymer, which resulted in different properties between SBS-g-VP and SBS. The blood compatibility of SBS-g-VP as measured by the Lee-White clotting test was better than that of SBS and polystyrene. PMID:8731218

  1. Continuous spin fractionation and characterization by size-exclusion chromatography for styrene-butadiene block copolymers.

    PubMed

    Xiong, Xiaopeng; Eckelt, John; Wolf, Bernhard A; Zhang, Zhengjun; Zhang, Lina

    2006-03-31

    Linear and star-shaped styrene-butadiene block copolymers synthesized by anionic polymerization of butadiene and styrene were fractionated by applying a newly developed large-scale fractionation technique, named continuous spin fractionation (CSF). Their molecular weight and polydispersity index (d=M(w)/M(n)) were measured with size-exclusion chromatography and static light scattering. For the linear triblock copolymer a fractionation via temperature variation turned out to be better suited than the usual isothermal procedure. The star-shaped polymer with the d value of 1.33 was fractionated in two CSF steps to get the targeted sample, which has a considerably more uniform structure and a narrower molecular weight distribution (d=1.11). The corresponding starting linear diblock copolymer was fractionated in one step reducing d from 1.68 to 1.17. With one set of simple laboratory equipment, 1kg polymer can be fractionated per day. Utilizing CSF, for the first time, we fractionated successfully the block copolymers. PMID:16466731

  2. Preparation and properties of SBS-g-DMAEMA copolymer membrane by ultraviolet radiation.

    PubMed

    Yang, J M; Jong, Y J; Hsu, K Y

    1997-05-01

    A styrene-butadiene-styrene triblock copolymer (SBS) membrane was prepared by solvent casting. Grafting of dimethyl amino ethyl methacrylate (DMAEMA) to this SBS membrane was subsequently conducted by ultraviolet radiation-induced graft copolymerization without degassing to obtain a SBS-g-DMAEMA copolymer membrane. The graft copolymer was characterized by infrared spectroscopy and scanning electron microscopy. The degree of grafting and the mechanical properties of SBS and SBS-g-DMAEMA were measured. Contact angle, water content, and protein absorption of fibrinogen and albumin experiments were also performed to evaluate the biocompatibility of SBS-g-DMAEMA graft copolymer membranes. It was found that the degree of grafting was related to the irradiation time, DMAEMA concentration, and temperature. The tensile strength of the SBS-g-DMAEMA membrane increased with an increase in the degree of grafting. By using Kaelble's equation and the contact angle data, the surface tension of SBS-g-DMAEMA was determined. It was found that with an increase in the degree of grafting, the surface tension and water content of SBS-g-DMAEMA membrane increased, whereas the contact angle decreased. The amount of absorption of albumin and fibrinogen decreased with an increase in amount of grafting. However, there was a minimum for the adsorption of proteins in the SBS-g-DMAEMA membrane. PMID:9135166

  3. Function of ABA in Stomatal Defense against Biotic and Drought Stresses

    PubMed Central

    Lim, Chae Woo; Baek, Woonhee; Jung, Jangho; Kim, Jung-Hyun; Lee, Sung Chul

    2015-01-01

    The plant hormone abscisic acid (ABA) regulates many key processes involved in plant development and adaptation to biotic and abiotic stresses. Under stress conditions, plants synthesize ABA in various organs and initiate defense mechanisms, such as the regulation of stomatal aperture and expression of defense-related genes conferring resistance to environmental stresses. The regulation of stomatal opening and closure is important to pathogen defense and control of transpirational water loss. Recent studies using a combination of approaches, including genetics, physiology, and molecular biology, have contributed considerably to our understanding of ABA signal transduction. A number of proteins associated with ABA signaling and responses—especially ABA receptors—have been identified. ABA signal transduction initiates signal perception by ABA receptors and transfer via downstream proteins, including protein kinases and phosphatases. In the present review, we focus on the function of ABA in stomatal defense against biotic and abiotic stresses, through analysis of each ABA signal component and the relationships of these components in the complex network of interactions. In particular, two ABA signal pathway models in response to biotic and abiotic stress were proposed, from stress signaling to stomatal closure, involving the pyrabactin resistance (PYR)/PYR-like (PYL) or regulatory component of ABA receptor (RCAR) family proteins, 2C-type protein phosphatases, and SnRK2-type protein kinases. PMID:26154766

  4. Function of ABA in Stomatal Defense against Biotic and Drought Stresses.

    PubMed

    Lim, Chae Woo; Baek, Woonhee; Jung, Jangho; Kim, Jung-Hyun; Lee, Sung Chul

    2015-01-01

    The plant hormone abscisic acid (ABA) regulates many key processes involved in plant development and adaptation to biotic and abiotic stresses. Under stress conditions, plants synthesize ABA in various organs and initiate defense mechanisms, such as the regulation of stomatal aperture and expression of defense-related genes conferring resistance to environmental stresses. The regulation of stomatal opening and closure is important to pathogen defense and control of transpirational water loss. Recent studies using a combination of approaches, including genetics, physiology, and molecular biology, have contributed considerably to our understanding of ABA signal transduction. A number of proteins associated with ABA signaling and responses--especially ABA receptors--have been identified. ABA signal transduction initiates signal perception by ABA receptors and transfer via downstream proteins, including protein kinases and phosphatases. In the present review, we focus on the function of ABA in stomatal defense against biotic and abiotic stresses, through analysis of each ABA signal component and the relationships of these components in the complex network of interactions. In particular, two ABA signal pathway models in response to biotic and abiotic stress were proposed, from stress signaling to stomatal closure, involving the pyrabactin resistance (PYR)/PYR-like (PYL) or regulatory component of ABA receptor (RCAR) family proteins, 2C-type protein phosphatases, and SnRK2-type protein kinases. PMID:26154766

  5. Molecular cloning and characterization of the ABA-specific glucosyltransferase gene from bean (Phaseolus vulgaris L.).

    PubMed

    Palaniyandi, Sasikumar Arunachalam; Chung, Gyuhwa; Kim, Sang Hyon; Yang, Seung Hwan

    2015-04-15

    Levels of the plant hormone abscisic acid (ABA) are maintained in homeostasis by a balance of its biosynthesis, catabolism and conjugation. The detailed molecular and signaling events leading to strict homeostasis are not completely understood in crop plants. In this study, we obtained cDNA of an ABA-inducible, ABA-specific UDP-glucosyltransferase (ABAGT) from the bean plant (Phaseolus vulgaris L.) involved in conjugation of a glucose residue to ABA to form inactive ABA-glucose ester (ABA-GE) to examine its role during development and abiotic stress in bean. The bacterially expressed PvABAGTase enzyme showed ABA-specific glucosylation activity in vitro. A higher level of the PvABAGT transcript was observed in mature leaves, mature flowers, roots, seed coats and embryos as well as upon rehydration following a period of dehydration. Overexpression of 35S::PvABAGT in Arabidopsis showed reduced sensitivity to ABA compared with WT. The transgenic plants showed a high level of ABA-GE without significant decrease in the level of ABA compared with the wild type (WT) during dehydration stress. Upon rehydration, the levels of ABA and phaseic acid (PA) decreased in the WT and the PvABAGT-overexpressing lines with high levels of ABA-GE only in the transgenic plants. Our findings suggest that the PvABAGT gene could play a role in ABA homeostasis during development and stress responses in bean and its overexpression in Arabidopsis did not alter ABA homeostasis during dehydration stress. PMID:25747288

  6. Diversity and Evolution of AbaR Genomic Resistance Islands in Acinetobacter baumannii Strains of European Clone I▿†

    PubMed Central

    Krizova, Lenka; Dijkshoorn, Lenie; Nemec, Alexandr

    2011-01-01

    To assess the diversity of AbaR genomic resistance islands in Acinetobacter baumannii European clone I (MLST clonal complex 1), we investigated 26 multidrug-resistant strains of this major clone isolated from hospitals in 21 cities of 10 European countries between 1984 and 2005. Each strain harbored an AbaR structure integrated at the same position in the chromosomal ATPase gene. AbaR3, including four subtypes based on variations in class 1 integron cassettes, and AbaR10 were found in 15 and 2 strains, respectively, whereas a new, unique AbaR variant was discovered in each of the other 9 strains. These new variants, designated AbaR11 to AbaR19 (19.8 kb to 57.5 kb), seem to be truncated derivatives of AbaR3, likely resulting from the deletions of its internal parts mediated by either IS26 elements (AbaR12 to AbaR19) or homologous recombination (AbaR11). AbaR3 was detected in all 10 strains isolated in 1984 to 1991, while AbaR11 to AbaR19 were carried only by strains isolated since 1997. Our results and those from previous publications suggest that AbaR3 is the original form of AbaR in European clone I, which may have provided strains of the lineage with a selective advantage facilitating their spread in European hospitals in the 1980s or before. PMID:21537009

  7. A multiscale modeling study of loss processes in block-copolymer-based solar cell nanodevices

    NASA Astrophysics Data System (ADS)

    Donets, Sergii; Pershin, Anton; Christlmaier, Martin J. A.; Baeurle, Stephan A.

    2013-03-01

    Flexible photovoltaic devices possess promising perspectives in opto-electronic technologies, where high mobility and/or large-scale applicability are important. However, their usefulness in such applications is currently still limited due to the low level of optimization of their performance and durability. For the improvement of these properties, a better understanding and control of small-scale annihilation phenomena involved in the photovoltaic process, such as exciton loss and charge carrier loss, is necessary, which typically implicates multiple length- and time-scales. Here, we study the causes for their occurrence on the example of nanostructured diblock- and triblock-copolymer systems by making use of a novel solar-cell simulation algorithm and explore new routes to optimize their photovoltaic properties. A particular focus is set on the investigation of exciton and charge carrier loss phenomena and their dependence on the inter-monomeric interaction strength, chain architecture, and external mechanical loading. Our simulation results reveal that in the regime from low up to intermediate χ-parameters an increasing number of continuous percolation paths is created. In this parameter range, the internal quantum efficiency (IQE) increases up to a maximum, characterized by a minimum in the number of charge losses due to charge recombination. In the regime of high χ-parameters both block-copolymer systems form nanostructures with a large number of bottlenecks and dead ends. These lead to a large number of charge losses due to charge recombination, charge trapping, and a deteriorated exciton dissociation, resulting in a significant drop in the IQE. Moreover, we find that the photovoltaic performance of the triblock-copolymer material decreases with increasing mechanical loading, caused by a growing number of charge losses due to charge recombination and charge accumulation. Finally, we demonstrate that the process of charge trapping in defects can be reversed

  8. Fabrication of Ordered Mesoporous Silica with Encapsulated Iron Oxide Particles using Ferritin-Doped Block Copolymer Templates

    NASA Astrophysics Data System (ADS)

    Hess, D.; Watkins, J.; Naik, R.

    2006-03-01

    Recently, two-dimensional arrays of iron oxide clusters were fabricated by dip-coating a silica substrate into an aqueous solution. Here we report the encapsulation of ferritin in 3D mesoporous silica structures by the replication of block copolymer templates in supercritical CO2. In our approach, preparation of the highly ordered, doped template via spincasting and microphase separation and silica network formation occur in discreet steps. A solution of an amphiphilic PEO-PPO-PEO triblock copolymer (Pluronic) template, horse spleen ferritin and a low concentration of PTSA acid was prepared and spin-coated onto a Si wafer. Upon drying the block copolymer microphase separates resulting in partitioning of the acid catalyst and ferritin to the hydrophilic domain. The polymer template was then exposed to a solution of supercritical carbon dioxide and tetraethyl orthosilicate (TEOS) at 125 bar and 40^oC. Equilibrium limited CO2 sorption in the block copolymer template resulted in modest dialation of the microphase segregated structure. Under these conditions, the precursor was readily infused into the copolymer and reacted within the hydrophilic domain containing the acid catalyst. The resultant film was calcined in air at 400^oC for 6 hours producing a well-ordered iron oxide-doped mesoporous silica film. TEM and XRD revealed crystalline iron oxide structures within the mesoporous silica supports. Magnetic properties were analyzed using a superconducting quantum intereference device (SQUID).

  9. Directed Self-assembly of Block Copolymer with Sub-15 nm Domain Spacing Using Nanoimprinted Photoresist Templates

    NASA Astrophysics Data System (ADS)

    Sun, Zhiwei; Chen, Zhenbin; Zhang, Wenxu; Coughlin, E. Bryan; Xiao, Shuaigang; Russell, Thomas

    There has been increasing interest in preparing block copolymer thin films with ultra-small domain spacings for use as etching masks for ultra-high resolution nanolithography. One method to prepare block copolymer materials with small feature sizes is salt doping, increasing the Flory-Huggins interaction and allowing microphase separation to be maintained at lower molecular weights. Lamellae-forming P2VP- b-PS- b-P2VP block copolymer with various molecular weight was synthesized using RAFT polymerization with a dual functional chain transfer agent. Copper (II) Chloride or Gold (III) chloride was found to be selectively associated with P2VP block and increase the unfavorable interactions between PS and P2VP blocks, driving the disordered block copolymer into the ordered state. A 14 nm lamellar spacing of P2VP- b-PS- b-P2VP thin film was prepared using copper (II) Chloride doping after acetone vapor annealing on neutral brushes. Metallic nano-wire arrays were prepared after selective infiltration of platinum salt into the P2VP domain and oxygen plasma treatment. The directed self-assembly of salt doped P2VP- b-PS- b-P2VP triblock copolymer having long-rang lateral order on nanoimprinted photoresist templates with shallow trenches was also studied.

  10. ABA-Cloud: support for collaborative breath research.

    PubMed

    Elsayed, Ibrahim; Ludescher, Thomas; King, Julian; Ager, Clemens; Trosin, Michael; Senocak, Uygar; Brezany, Peter; Feilhauer, Thomas; Amann, Anton

    2013-06-01

    This paper introduces the advanced breath analysis (ABA) platform, an innovative scientific research platform for the entire breath research domain. Within the ABA project, we are investigating novel data management concepts and semantic web technologies to document breath analysis studies for the long run as well as to enable their full automatic reproducibility. We propose several concept taxonomies (a hierarchical order of terms from a glossary of terms), which can be seen as a first step toward the definition of conceptualized terms commonly used by the international community of breath researchers. They build the basis for the development of an ontology (a concept from computer science used for communication between machines and/or humans and representation and reuse of knowledge) dedicated to breath research. PMID:23619467

  11. ABA-Cloud: support for collaborative breath research

    PubMed Central

    Elsayed, Ibrahim; Ludescher, Thomas; King, Julian; Ager, Clemens; Trosin, Michael; Senocak, Uygar; Brezany, Peter; Feilhauer, Thomas; Amann, Anton

    2016-01-01

    This paper introduces the advanced breath analysis (ABA) platform, an innovative scientific research platform for the entire breath research domain. Within the ABA project, we are investigating novel data management concepts and semantic web technologies to document breath analysis studies for the long run as well as to enable their full automatic reproducibility. We propose several concept taxonomies (a hierarchical order of terms from a glossary of terms), which can be seen as a first step toward the definition of conceptualized terms commonly used by the international community of breath researchers. They build the basis for the development of an ontology (a concept from computer science used for communication between machines and/or humans and representation and reuse of knowledge) dedicated to breath research. PMID:23619467

  12. Separation of parent homopolymers from polystyrene and poly(ethylene oxide) based block copolymers by liquid chromatography under limiting conditions of desorption-3. Study of barrier efficiency according to block copolymers' chemical composition.

    PubMed

    Rollet, Marion; Pelletier, Bérengère; Berek, Dušan; Maria, Sébastien; Phan, Trang N T; Gigmes, Didier

    2016-09-01

    Liquid Chromatography under Limiting Conditions of Desorption (LC LCD) is a powerful separation tool for multicomponent polymer systems. This technique is based on a barrier effect of an appropriate solvent, which is injected in front of the sample, and which decelerates the elution of selected macromolecules. In this study, the barrier effects have been evaluated for triblock copolymers polystyrene-b-poly(ethylene oxide)-b-polystyrene (PS-b-PEO-b-PS) according to the content of polystyrene (wt% PS) and PEO-block molar mass. PS-b-PEO-b-PS samples were prepared by Atom Transfer Radical Polymerization (ATRP). The presence of respective parent homopolymers was investigated by applying optimized LC LCD conditions. It was found that the barrier composition largely affects the efficiency of separation and it ought to be adjusted for particular composition range of block copolymers. PMID:27495367

  13. Common and unique elements of the ABA-regulated transcriptome of Arabidopsis guard cells

    PubMed Central

    2011-01-01

    Background In the presence of drought and other desiccating stresses, plants synthesize and redistribute the phytohormone abscisic acid (ABA). ABA promotes plant water conservation by acting on specialized cells in the leaf epidermis, guard cells, which border and regulate the apertures of stomatal pores through which transpirational water loss occurs. Following ABA exposure, solute uptake into guard cells is rapidly inhibited and solute loss is promoted, resulting in inhibition of stomatal opening and promotion of stomatal closure, with consequent plant water conservation. There is a wealth of information on the guard cell signaling mechanisms underlying these rapid ABA responses. To investigate ABA regulation of gene expression in guard cells in a systematic genome-wide manner, we analyzed data from global transcriptomes of guard cells generated with Affymetrix ATH1 microarrays, and compared these results to ABA regulation of gene expression in leaves and other tissues. Results The 1173 ABA-regulated genes of guard cells identified by our study share significant overlap with ABA-regulated genes of other tissues, and are associated with well-defined ABA-related promoter motifs such as ABREs and DREs. However, we also computationally identified a unique cis-acting motif, GTCGG, associated with ABA-induction of gene expression specifically in guard cells. In addition, approximately 300 genes showing ABA-regulation unique to this cell type were newly uncovered by our study. Within the ABA-regulated gene set of guard cells, we found that many of the genes known to encode ion transporters associated with stomatal opening are down-regulated by ABA, providing one mechanism for long-term maintenance of stomatal closure during drought. We also found examples of both negative and positive feedback in the transcriptional regulation by ABA of known ABA-signaling genes, particularly with regard to the PYR/PYL/RCAR class of soluble ABA receptors and their downstream targets

  14. Mussel-inspired antifouling coatings bearing polymer loops.

    PubMed

    Li, Lin; Yan, Bin; Zhang, Ling; Tian, Yu; Zeng, Hongbo

    2015-11-11

    This work reports the preparation of antifouling coatings bearing polymer loops using a mussel-inspired ABA triblock copolymer using a simple drop coating method. With similar end graft density, the loop-bearing surfaces show a more enhanced protein-reduction performance than the brush-bearing surfaces. PMID:26364998

  15. Type One Protein Phosphatase 1 and Its Regulatory Protein Inhibitor 2 Negatively Regulate ABA Signaling

    PubMed Central

    Zhao, Yang; Xie, Shaojun; Batelli, Giorgia; Wang, Bangshing; Duan, Cheng-Guo; Wang, Xingang; Xing, Lu; Lei, Mingguang; Yan, Jun; Zhu, Xiaohong; Zhu, Jian-Kang

    2016-01-01

    The phytohormone abscisic acid (ABA) regulates plant growth, development and responses to biotic and abiotic stresses. The core ABA signaling pathway consists of three major components: ABA receptor (PYR1/PYLs), type 2C Protein Phosphatase (PP2C) and SNF1-related protein kinase 2 (SnRK2). Nevertheless, the complexity of ABA signaling remains to be explored. To uncover new components of ABA signal transduction pathways, we performed a yeast two-hybrid screen for SnRK2-interacting proteins. We found that Type One Protein Phosphatase 1 (TOPP1) and its regulatory protein, At Inhibitor-2 (AtI-2), physically interact with SnRK2s and also with PYLs. TOPP1 inhibited the kinase activity of SnRK2.6, and this inhibition could be enhanced by AtI-2. Transactivation assays showed that TOPP1 and AtI-2 negatively regulated the SnRK2.2/3/6-mediated activation of the ABA responsive reporter gene RD29B, supporting a negative role of TOPP1 and AtI-2 in ABA signaling. Consistent with these findings, topp1 and ati-2 mutant plants displayed hypersensitivities to ABA and salt treatments, and transcriptome analysis of TOPP1 and AtI-2 knockout plants revealed an increased expression of multiple ABA-responsive genes in the mutants. Taken together, our results uncover TOPP1 and AtI-2 as negative regulators of ABA signaling. PMID:26943172

  16. Membrane-associated transcription factor peptidase, site-2 protease, antagonizes ABA signaling in Arabidopsis.

    PubMed

    Zhou, Shun-Fan; Sun, Le; Valdés, Ana Elisa; Engström, Peter; Song, Ze-Ting; Lu, Sun-Jie; Liu, Jian-Xiang

    2015-10-01

    Abscisic acid plays important roles in maintaining seed dormancy while gibberellins (GA) and other phytohormones antagonize ABA to promote germination. However, how ABA signaling is desensitized during the transition from dormancy to germination is still poorly understood. We functionally characterized the role of membrane-associated transcription factor peptidase, site-2 protease (S2P), in ABA signaling during seed germination in Arabidopsis. Genetic analysis showed that loss-of-function of S2P conferred high ABA sensitivity during seed germination, and expression of the activated form of membrane-associated transcription factor bZIP17, in which the transmembrane domain and endoplasmic reticulum (ER) lumen-facing C-terminus were deleted, in the S2P mutant rescued its ABA-sensitive phenotype. MYC and green fluorescent protein (GFP)-tagged bZIP17 were processed and translocated from the ER to the nucleus in response to ABA treatment. Furthermore, genes encoding negative regulators of ABA signaling, such as the transcription factor ATHB7 and its target genes HAB1, HAB2, HAI1 and AHG3, were up-regulated in seeds of the wild-type upon ABA treatment; this up-regulation was impaired in seeds of S2P mutants. Our results suggest that S2P desensitizes ABA signaling during seed germination through regulating the activation of the membrane-associated transcription factor bZIP17 and therefore controlling the expression level of genes encoding negative regulators of ABA signaling. PMID:25919792

  17. Comprehensive Analysis of ABA Effects on Ethylene Biosynthesis and Signaling during Tomato Fruit Ripening

    PubMed Central

    Bu, Jianwen; Jiang, Yuanyuan; Khan, Zia Ullah; Luo, Zisheng; Mao, Linchun; Ying, Tiejin

    2016-01-01

    ABA has been widely acknowledged to regulate ethylene biosynthesis and signaling during fruit ripening, but the molecular mechanism underlying the interaction between these two hormones are largely unexplored. In the present study, exogenous ABA treatment obviously promoted fruit ripening as well as ethylene emission, whereas NDGA (Nordihydroguaiaretic acid, an inhibitor of ABA biosynthesis) application showed the opposite biological effects. Combined RNA-seq with time-course RT-PCR analysis, our study not only helped to illustrate how ABA regulated itself at the transcription level, but also revealed that ABA can facilitate ethylene production and response probably by regulating some crucial genes such as LeACS4, LeACO1, GR and LeETR6. In addition, investigation on the fruits treated with 1-MCP immediately after ABA exposure revealed that ethylene might be essential for the induction of ABA biosynthesis and signaling at the onset of fruit ripening. Furthermore, some specific transcription factors (TFs) known as regulators of ethylene synthesis and sensibility (e.g. MADS-RIN, TAGL1, CNR and NOR) were also observed to be ABA responsive, which implied that ABA influenced ethylene action possibly through the regulation of these TFs expression. Our comprehensive physiological and molecular-level analysis shed light on the mechanism of cross-talk between ABA and ethylene during the process of tomato fruit ripening. PMID:27100326

  18. The short-chain alcohol dehydrogenase ABA2 catalyzes the conversion of xanthoxin to abscisic aldehyde.

    PubMed

    González-Guzmán, Miguel; Apostolova, Nadezda; Bellés, José M; Barrero, José M; Piqueras, Pedro; Ponce, María R; Micol, José L; Serrano, Ramón; Rodríguez, Pedro L

    2002-08-01

    Mutants able to germinate and perform early growth in medium containing a high NaCl concentration were identified during the course of two independent screenings and named salt resistant (sre) and salobreño (sañ). The sre and sañ mutants also were able to germinate in high-osmoticum medium, indicating that they are osmotolerant in a germination assay. Complementation analyses revealed that sre1-1, sre1-2, sañ3-1, and sañ3-2 were alleles of the abscisic acid (ABA) biosynthesis ABA2 gene. A map-based cloning strategy allowed the identification of the ABA2 gene and molecular characterization of four new aba2 alleles. The ABA2 gene product belongs to the family of short-chain dehydrogenases/reductases, which are known to be NAD- or NADP-dependent oxidoreductases. Recombinant ABA2 protein produced in Escherichia coli exhibits a K(m) value for xanthoxin of 19 micro M and catalyzes in a NAD-dependent manner the conversion of xanthoxin to abscisic aldehyde, as determined by HPLC-mass spectrometry. The ABA2 mRNA is expressed constitutively in all plant organs examined and is not upregulated in response to osmotic stress. The results of this work are discussed in the context of previous genetic and biochemical evidence regarding ABA biosynthesis, confirming the xanthoxin-->abscisic aldehyde-->ABA transition as the last steps of the major ABA biosynthetic pathway. PMID:12172025

  19. Comprehensive Analysis of ABA Effects on Ethylene Biosynthesis and Signaling during Tomato Fruit Ripening.

    PubMed

    Mou, Wangshu; Li, Dongdong; Bu, Jianwen; Jiang, Yuanyuan; Khan, Zia Ullah; Luo, Zisheng; Mao, Linchun; Ying, Tiejin

    2016-01-01

    ABA has been widely acknowledged to regulate ethylene biosynthesis and signaling during fruit ripening, but the molecular mechanism underlying the interaction between these two hormones are largely unexplored. In the present study, exogenous ABA treatment obviously promoted fruit ripening as well as ethylene emission, whereas NDGA (Nordihydroguaiaretic acid, an inhibitor of ABA biosynthesis) application showed the opposite biological effects. Combined RNA-seq with time-course RT-PCR analysis, our study not only helped to illustrate how ABA regulated itself at the transcription level, but also revealed that ABA can facilitate ethylene production and response probably by regulating some crucial genes such as LeACS4, LeACO1, GR and LeETR6. In addition, investigation on the fruits treated with 1-MCP immediately after ABA exposure revealed that ethylene might be essential for the induction of ABA biosynthesis and signaling at the onset of fruit ripening. Furthermore, some specific transcription factors (TFs) known as regulators of ethylene synthesis and sensibility (e.g. MADS-RIN, TAGL1, CNR and NOR) were also observed to be ABA responsive, which implied that ABA influenced ethylene action possibly through the regulation of these TFs expression. Our comprehensive physiological and molecular-level analysis shed light on the mechanism of cross-talk between ABA and ethylene during the process of tomato fruit ripening. PMID:27100326

  20. Rheology, Morphology and Phase Behavior in Amphiphilic Block Copolymer/microemulsion Systems

    NASA Astrophysics Data System (ADS)

    Gottlieb, Moshe; Braun, Liora; Zhang, Zeng-Rong

    2000-03-01

    Joining together by means of covalent bonds hydrophobic and hydrophilic entities on the same molecule gives rise to materials with interesting properties in aqueous systems or in the presence of mixed solvents such as water/oil microemulsions. In this paper we describe the rheological properties of a synthetic amphiphilic block copolymer dissolved in a water-in-oil microemulsion. The block copolymer is an ABA type copolymer composed of poly(oxyethylene) (PEO) as the hydrophilic A block and poly(dimethyl siloxane) (PDMS) as the hydrophobic center B block. Different polymers have been prepared with a B block of D_p=160 and three different sizes of the A blocks with D_p= 10, 45, and 120 respectively. The resulting copolymer is insoluble in water and hardly soluble in decane (good solvent for the PDMS). In the presence of water in oil microemulsion stabilized by the small molecular weight surfactant AOT a one-phase region is maintained when the copolymer is added. Yet, peculiar rheological behavior is observed. For constant water-microemulsion concentration (φ) addition of polymer increases the system viscosity as expected. Yet, the lower φ the higher the viscosity and at high φ the effect of polymer addition is quite low.

  1. Bactericidal block copolymer micelles.

    PubMed

    Vyhnalkova, Renata; Eisenberg, Adi; van de Ven, Theo

    2011-05-12

    Block copolymer micelles with bactericidal properties were designed to deactivate pathogens such as E. coli bacteria. The micelles of PS-b-PAA and PS-b-P4VP block copolymers were loaded with biocides TCMTB or TCN up to 20 or 30 wt.-%, depending on the type of antibacterial agent. Bacteria were exposed to loaded micelles and bacterial deactivation was evaluated. The micelles loaded with TCN are bactericidal; bacteria are killed in less than two minutes of exposure. The most likely interpretation of the data is that the biocide is transferred to the bacteria by repeated micelle/bacteria contacts, and not via the solution. PMID:21275041

  2. ABA-HYPERSENSITIVE BTB/POZ PROTEIN 1 functions as a negative regulator in ABA-mediated inhibition of germination in Arabidopsis.

    PubMed

    Kim, Hani; Kim, Soon-Hee; Seo, Dong Hye; Chung, Sunglan; Kim, Sang-Woo; Lee, Jeong-Soo; Kim, Woo Taek; Lee, Jae-Hoon

    2016-02-01

    To elucidate the contribution of CRL3-ABA-mediated responses, we attempted to find CRL3 substrate receptors involved in ABA signaling. One gene named ABA-HYPERSENSITIVE BTB/POZ PROTEIN 1 (AHT1) was upregulated more than 2.5 times by ABA, and its coding region possessed a BTB/POZ domain, which is the common feature of CRL3 substrate receptors. Loss of AHT1 led to retardation of the germination process, not inhibition of root growth. AHT1 transcripts also increased in response to mannitol, NaCl and drought treatments at the seedling stage and in dry seeds. High expression of AHT1 in dry seeds was inhibited by the defect of ABA signaling components such as ABI1, ABI3 and SRKs indicating that the expression of AHT1 is dependent on ABA signaling. Among bZIP transcription factors participating in ABA signaling, the losses of ABI5/DPBF1, AREB1/ABF2, EEL/DPBF4 and DPBF2/bZIP67 resulted in reduced AHT1 expression, showing that these transcription factors play a positive role in ABA-induced AHT1 expression. While loss of AHT1 did not affect the expression pattern of NCED3, ABI2, SRKs and AREB/ABF genes, it led to hyperinduction of ABI5/DPBF genes such as ABI5/DPBF1, EEL/DPBF4 and AREB3/DPBF3, which are mainly involved in seed development and germination, as well as ABA-inducible genes transactivated by ABI5. Overall, these findings indicate that AHT1 negatively regulates ABA-mediated inhibition of germination, possibly by repressing the expression of a subset of ABI5/DPBF subfamily genes, and that AHT1 may be regulated by a negative feedback process through its linkage with a part of ABI5/DPBF proteins. PMID:26667153

  3. Syntheses and luminescent properties of a copolymer of terbium-p-aminobenzoic acid-methacrylic acid and styrene.

    PubMed

    Zhang, A Q; Yang, Y M; Li, L P; Zhai, G M; Jia, H S; Liu, X G; Xu, B S

    2015-11-01

    A reactive Tb(III) complex with p-aminobenzoic acid (p-ABA) and methacrylic acid (MAA) as ligands was synthesized. A novel copolymer was synthesized by free radical copolymerization of styrene and the reactive Tb(III) complex in dimethyl sulfoxide (DMSO) with 2,2'-azobis(2-methylpropionitrile) (AIBN) as the initiator. IR and UV/Vis spectra indicate that the copolymer exhibited absorption from polystyrene and the complex. Thermogravimetric analysis indicates that the copolymer remained stable up to 357°C and the thermal stability was significantly improved in comparison with polymer matrix and the Tb(III) complex. The luminescent intensity of the synthetic terbium macromolecular complexes increased with increasing complex monomer content. Moreover, concentration quenching was not observed. PMID:25712787

  4. A recombinant triblock protein polymer with dispersant and binding properties for digital printing.

    PubMed

    Qi, Min; O'Brien, John P; Yang, Jianjun

    2008-01-01

    A structured triblock protein was designed to explore the potential of engineered peptides to function as high-performance ink dispersants and binders. The protein consists of three functional elements, including a pigment binding domain, a hydrophilic linker, and a printing surface binding domain. To construct such a chimeric protein, a carbon black binding peptide, FHENWPS, and a cellulose binding peptide, THKTSTQRLLAA, were identified from phage display libraries through biopanning, based on their strong and specific binding affinities to carbon black and cellulose. They were used as carbon black and cellulose binding domains, respectively, in a recombinant triblock protein. A linker sequence, PTPTPTPTPTPTPTPTPTPTPTP, was adapted from endoglucanase A of the bacterium Cellulomonas fimi, as a small, rigid, and hydrophilic interdomain linker. When incorporated into the triblock structure between the carbon black and cellulose binding sequences, the linker sufficiently isolates these two elements and allows dual binding activity. The structured triblock protein was shown to disperse carbon black particles and attach it to paper surfaces. Thus, the utility of structured proteins having useful dispersant and binding properties for digital printing inks was demonstrated. PMID:17972282

  5. Molecular Mimicry Regulates ABA Signaling by SnRK2 Kinases and PP2C Phosphatases

    SciTech Connect

    Soon, Fen-Fen; Ng, Ley-Moy; Zhou, X. Edward; West, Graham M.; Kovach, Amanda; Tan, M.H. Eileen; Suino-Powell, Kelly M.; He, Yuanzheng; Xu, Yong; Chalmers, Michael J.; Brunzelle, Joseph S.; Zhang, Huiming; Yang, Huaiyu; Jiang, Hualiang; Li, Jun; Yong, Eu-Leong; Cutler, Sean; Zhu, Jian-Kang; Griffin, Patrick R.; Melcher, Karsten; Xu, H. Eric

    2014-10-02

    Abscisic acid (ABA) is an essential hormone for plants to survive environmental stresses. At the center of the ABA signaling network is a subfamily of type 2C protein phosphatases (PP2Cs), which form exclusive interactions with ABA receptors and subfamily 2 Snfl-related kinase (SnRK2s). Here, we report a SnRK2-PP2C complex structure, which reveals marked similarity in PP2C recognition by SnRK2 and ABA receptors. In the complex, the kinase activation loop docks into the active site of PP2C, while the conserved ABA-sensing tryptophan of PP2C inserts into the kinase catalytic cleft, thus mimicking receptor-PP2C interactions. These structural results provide a simple mechanism that directly couples ABA binding to SnRK2 kinase activation and highlight a new paradigm of kinase-phosphatase regulation through mutual packing of their catalytic sites.

  6. A Putative PP2C-Encoding Gene Negatively Regulates ABA Signaling in Populus euphratica

    PubMed Central

    Chen, Jinhuan; Zhang, Dongzhi; Zhang, Chong; Xia, Xinli; Yin, Weilun; Tian, Qianqian

    2015-01-01

    A PP2C homolog gene was cloned from the drought-treated cDNA library of Populus euphratica. Multiple sequence alignment analysis suggested that the gene is a potential ortholog of HAB1. The expression of this HAB1 ortholog (PeHAB1) was markedly induced by drought and moderately induced by ABA. To characterize its function in ABA signaling, we generated transgenic Arabidopsis thaliana plants overexpressing this gene. Transgenic lines exhibited reduced responses to exogenous ABA and reduced tolerance to drought compared to wide-type lines. Yeast two-hybrid analyses indicated that PeHAB1 could interact with the ABA receptor PYL4 in an ABA-independent manner. Taken together; these results indicated that PeHAB1 is a new negative regulator of ABA responses in poplar. PMID:26431530

  7. A Putative PP2C-Encoding Gene Negatively Regulates ABA Signaling in Populus euphratica.

    PubMed

    Chen, Jinhuan; Zhang, Dongzhi; Zhang, Chong; Xia, Xinli; Yin, Weilun; Tian, Qianqian

    2015-01-01

    A PP2C homolog gene was cloned from the drought-treated cDNA library of Populus euphratica. Multiple sequence alignment analysis suggested that the gene is a potential ortholog of HAB1. The expression of this HAB1 ortholog (PeHAB1) was markedly induced by drought and moderately induced by ABA. To characterize its function in ABA signaling, we generated transgenic Arabidopsis thaliana plants overexpressing this gene. Transgenic lines exhibited reduced responses to exogenous ABA and reduced tolerance to drought compared to wide-type lines. Yeast two-hybrid analyses indicated that PeHAB1 could interact with the ABA receptor PYL4 in an ABA-independent manner. Taken together; these results indicated that PeHAB1 is a new negative regulator of ABA responses in poplar. PMID:26431530

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. Unique drought resistance functions of the highly ABA-induced clade A protein phosphatase 2Cs.

    PubMed

    Bhaskara, Govinal Badiger; Nguyen, Thao Thi; Verslues, Paul E

    2012-09-01

    Six Arabidopsis (Arabidopsis thaliana) clade A protein phosphatase 2Cs (PP2Cs) have established abscisic acid (ABA) signaling roles; however, phenotypic roles of the remaining three "HAI" PP2Cs, Highly ABA-Induced1 (HAI1), AKT1-Interacting PP2C1/HAI2, and HAI3, have remained unclear. HAI PP2C mutants had enhanced proline and osmoregulatory solute accumulation at low water potential, while mutants of other clade A PP2Cs had no or lesser effect on these drought resistance traits. hai1-2 also had increased expression of abiotic stress-associated genes, including dehydrins and late embryogenesis abundant proteins, but decreased expression of several defense-related genes. Conversely, the HAI PP2Cs had relatively less impact on several ABA sensitivity phenotypes. HAI PP2C single mutants were unaffected in ABA sensitivity, while double and triple mutants were moderately hypersensitive in postgermination ABA response but ABA insensitive in germination. The HAI PP2Cs interacted most strongly with PYL5 and PYL7 to -10 of the PYL/RCAR ABA receptor family, with PYL7 to -10 interactions being relatively little affected by ABA in yeast two-hybrid assays. HAI1 had especially limited PYL interaction. Reduced expression of the main HAI1-interacting PYLs at low water potential when HAI1 expression was strongly induced also suggests limited PYL regulation and a role of HAI1 activity in negatively regulating specific drought resistance phenotypes. Overall, the HAI PP2Cs had greatest effect on ABA-independent low water potential phenotypes and lesser effect on classical ABA sensitivity phenotypes. Both this and their distinct PYL interaction demonstrate a new level of functional differentiation among the clade A PP2Cs and a point of cross talk between ABA-dependent and ABA-independent drought-associated signaling. PMID:22829320

  13. Root ABA Accumulation in Long-Term Water-Stressed Plants is Sustained by Hormone Transport from Aerial Organs.

    PubMed

    Manzi, Matías; Lado, Joanna; Rodrigo, María Jesús; Zacarías, Lorenzo; Arbona, Vicent; Gómez-Cadenas, Aurelio

    2015-12-01

    The reduced pool of the ABA precursors, β,β-carotenoids, in roots does not account for the substantial increase in ABA content in response to water stress (WS) conditions, suggesting that ABA could be transported from other organs. Basipetal transport was interrupted by stem-girdling, and ABA levels were determined in roots after two cycles of WS induced by transplanting plants to dry perlite. Leaf applications of isotope-labeled ABA and reciprocal grafting of ABA-deficient tomato mutants were used to confirm the involvement of aerial organs on root ABA accumulation. Disruption of basipetal transport reduced ABA accumulation in roots, and this decrease was more severe after two consecutive WS periods. This effect was linked to a sharp decrease in the β,β-carotenoid pool in roots in response to water deficit. Significant levels of isotope-labeled ABA were transported from leaves to roots, mainly in plants subjected to water dehydration. Furthermore, the use of different ABA-deficient tomato mutants in reciprocal grafting combinations with wild-type genotypes confirmed the involvement of aerial organs in the ABA accumulation in roots. In conclusion, accumulation of ABA in roots after long-term WS periods largely relies on the aerial organs, suggesting a reduced ability of the roots to synthesize ABA from carotenoids. Furthermore, plants are able to transport ABA basipetally to sustain high hormone levels in roots. PMID:26542111

  14. Dual Function of NAC072 in ABF3-Mediated ABA-Responsive Gene Regulation in Arabidopsis

    PubMed Central

    Li, Xiaoyun; Li, Xiaoling; Li, Meijuan; Yan, Youcheng; Liu, Xu; Li, Ling

    2016-01-01

    The NAM, ATAF1/2, and CUC2 (NAC) domain proteins play various roles in plant growth and stress responses. Arabidopsis NAC transcription factor NAC072 has been reported as a transcriptional activator in Abscisic acid (ABA)-responsive gene expression. However, the exact function of NAC072 in ABA signaling is still elusive. In this study, we present evidence for the interrelation between NAC072 and ABA-responsive element binding factor 3 (ABF3) that act as a positive regulator of ABA-responsive gene expression in Arabidopsis. The transcript of NAC072 is up-regulated by ABF3 in ABA response, and NAC072 protein interacts with ABF3. Enhanced ABA sensitivity occurs in nac072 mutant plants that overexpressed ABF3. However, overexpression of NAC072 weakened the ABA sensitivity in the abf3 mutant plants, but instead of recovering the ABA sensitivity of abf3. NAC072 and ABF3 cooperate to regulate RD29A expression, but are antagonistic when regulating RD29B expression. Therefore, NAC072 displays a dual function in ABF3-mediated ABA-responsive gene regulation. PMID:27486475

  15. Bimodal mesoporous carbon synthesized from large organic precursor and amphiphilic tri-block copolymer by self assembly

    SciTech Connect

    Saha, Dipendu; Contescu, Cristian I; Gallego, Nidia C

    2012-01-01

    Owing to several disadvantages of traditional hard template based synthesis, soft-template or self-assembly was adopted to synthesize mesoporous carbon. In this work, we have introduced hexaphenol as a new and large organic precursor for the synthesis of mesoporous carbon by self-assembly with pluronic P123 as structure dictating agent. The resultant mesoporous carbon is bimodal in nature with median pore widths of 29 and 45 and BET surface area of 312 m2/g. Unlike previously synthesized mesoporous carbon, this carbon possesses negligible micropore volume. This mesoporous carbon is very suitable candidate for several applications including membrane separation, chemical sensor or selective sorption of larger molecules.

  16. An ABA down-regulated bHLH transcription repressor gene, bHLH129 regulates root elongation and ABA response when overexpressed in Arabidopsis

    PubMed Central

    Tian, Hainan; Guo, Hongyan; Dai, Xuemei; Cheng, Yuxin; Zheng, Kaijie; Wang, Xiaoping; Wang, Shucai

    2015-01-01

    Plant hormone abscisic acid (ABA) plays a crucial role in modulating plant responses to environmental stresses. Basic helix-loop-helix (bHLH) transcription factors are one of the largest transcription factor families that regulate multiple aspects of plant growth and development, as well as of plant metabolism in Arabidopsis. Several bHLH transcription factors have been shown to be involved in the regulation of ABA signaling. We report here the characterization of bHLH129, a bHLH transcription factor in Arabidopsis. We found that the expression level of bHLH129 was reduced in response to exogenously applied ABA, and elevated in the ABA biosynthesis mutant aba1-5. Florescence observation of transgenic plants expressing bHLH129-GFP showed that bHLH129 was localized in the nucleus, and transient expression of bHLH129 in protoplasts inhibited reporter gene expression. When expressed in Arabidopsis under the control of the 35S promoter, bHLH129 promoted root elongation, and the transgenic plants were less sensitivity to ABA in root elongation assays. Quantitative RT-PCR results showed that ABA response of several genes involved in ABA signaling, including ABI1, SnRK2.2, SnRK2.3 and SnRK2.6 were altered in the transgenic plants overexpressing bHLH129. Taken together, our study suggests that bHLH129 is a transcription repressor that negatively regulates ABA response in Arabidopsis. PMID:26625868

  17. Jasmonic acid accumulation and systemic photosynthetic and electrical changes in locally burned wild type tomato, ABA-deficient sitiens mutants and sitiens pre-treated by ABA.

    PubMed

    Hlavinka, Jan; Nožková-Hlaváčková, Vladimíra; Floková, Kristýna; Novák, Ondřej; Nauš, Jan

    2012-05-01

    Burning the terminal leaflet of younger tomato (Lycopersicon esculentum Mill.) leaf caused local and systemic changes in the surface electrical potential (SEP) and gas exchange (GE) parameters. The local and systemic accumulation of endogenous abscisic acid (ABA) and jasmonic acid (JA) was measured 85 min after burning. The experiments were conducted with wild type (WT) plants, ABA-deficient mutant sitiens (SIT) and ABA pre-treated SIT plants (SITA). First changes in SEP were detected within 1.5 min after burning and were followed by a decrease in GE parameters within 3-6 min in WT, SIT and SITA plants. GE and SEP time courses of SIT were different and wave amplitudes of SEP of SIT were lower compared to WT and SITA. ABA content in WT and SITA control plants was similar and substantially higher compared to SIT, JA content was similar among WT, SIT and SITA. While changes in the ABA content in systemic leaves have not been recorded after burning, the systemic JA content was substantially increased in WT and more in SIT and SITA. The results suggest that ABA content governs the systemic reaction of GE and the SEP shape upon local burning. ABA, JA and SEP participate in triggering the GE reaction. The ABA shortage in the SIT in the reaction to burning is partly compensated by an enhanced JA accumulation. This JA compensation is maintained even in SIT endogenously supplied with ABA. A correlation between the systemic JA content and changes in GE parameters or SEP was not found. PMID:22391126

  18. Block Copolymer Modified Epoxy Amine System for Reactive Rotational Molding: Structures, Properties and Processability

    NASA Astrophysics Data System (ADS)

    Lecocq, Eva; Nony, Fabien; Tcharkhtchi, Abbas; Gérard, Jean-François

    2011-05-01

    Poly(styrene-butadiene-methylmethacrylate) (SBM) and poly(methylmethacrylate-butyle-acrylate-methylmethacrylate) (MAM) triblock copolymers have been dissolved in liquid DGEBA epoxy resin which is subsequently polymerized by meta-xylene diamine (MXDA) or Jeffamine EDR-148. A chemorheology study of these formulations by plate-plate rheology and by thermal analysis has allowed to conclude that the addition of these copolymer blocks improve the reactive rotational moulding processability without affecting the processing time. Indeed, it prevents the pooling of the formulation at the bottom of the mould and a too rapid build up of resin viscosity of these thermosetting systems. The morphology of the cured blends examined by scanning electron microscopy (SEM) shows an increase of fracture surface area and thereby a potential increase of the toughness with the modification of epoxy system. Dynamic mechanical spectroscopy (DMA) and opalescence of final material show that the block PMMA, initially miscible, is likely to induce phase separation from the epoxy-amine matrix. Thereby, the poor compatibilisation between the toughener and the matrix has a detrimental effect on the tensile mechanical properties. The compatibilisation has to be increased to improve in synergy the processability and the final properties of these block copolymer modified formulations. First attempts could be by adapting the length and ratio of each block.

  19. DNA/Amphiphilic Block Copolymer Nanospheres Promote Low-dose DNA Vaccination

    PubMed Central

    McIlroy, Dorian; Barteau, Benoît; Cany, Jeannette; Richard, Peggy; Gourden, Clothilde; Conchon, Sophie; Pitard, Bruno

    2009-01-01

    Intramuscular (i.m.) DNA vaccination induces strong cellular immune responses in the mouse, but only at DNA doses that cannot be achieved in humans. Because antigen expression is weak after naked DNA injection, we screened five nonionic block copolymers of poly(ethyleneoxide)-poly(propyleneoxide) (PEO-PPO) for their ability to enhance DNA vaccination using a β-galactosidase (βGal) encoding plasmid, pCMV-βGal, as immunogen. At a high DNA dose, formulation with the tetrafunctional block copolymers 304 (molecular weight [MW] 1,650) and 704 (MW 5,500) and the triblock copolymer Lutrol (MW 8,600) increased βGal-specific interferon-γ enzyme-linked immunosorbent spot (ELISPOT) responses 2–2.5-fold. More importantly, 704 allowed significant reductions in the dose of antigen-encoding plasmid. A single injection of 2 µg pCMV-βGal with 704 gave humoral and ELISPOT responses equivalent to those obtained with 100 µg naked DNA and conferred protection in tumor vaccination models. However, 704 had no adjuvant properties for βGal protein, and immune responses were only elicited by low doses of pCMV-βGal formulated with 704 if noncoding carrier DNA was added to maintain total DNA dose at 20 µg. Overall, these results show that formulation with 704 and carrier DNA can reduce the dose of antigen-encoding plasmid by at least 50-fold. PMID:19417740

  20. The Citrus ABA signalosome: identification and transcriptional regulation during sweet orange fruit ripening and leaf dehydration.

    PubMed

    Romero, Paco; Lafuente, María T; Rodrigo, María J

    2012-08-01

    The abscisic acid (ABA) signalling core in plants include the cytosolic ABA receptors (PYR/PYL/RCARs), the clade-A type 2C protein phosphatases (PP2CAs), and the subclass III SNF1-related protein kinases 2 (SnRK2s). The aim of this work was to identify these ABA perception system components in sweet orange and to determine the influence of endogenous ABA on their transcriptional regulation during fruit development and ripening, taking advantage of the comparative analysis between a wild-type and a fruit-specific ABA-deficient mutant. Transcriptional changes in the ABA signalosome during leaf dehydration were also studied. Six PYR/PYL/RCAR, five PP2CA, and two subclass III SnRK2 genes, homologous to those of Arabidopsis, were identified in the Citrus genome. The high degree of homology and conserved motifs for protein folding and for functional activity suggested that these Citrus proteins are bona fide core elements of ABA perception in orange. Opposite expression patterns of CsPYL4 and CsPYL5 and ABA accumulation were found during ripening, although there were few differences between varieties. In contrast, changes in expression of CsPP2CA genes during ripening paralleled those of ABA content and agreeed with the relevant differences between wild-type and mutant fruit transcript accumulation. CsSnRK2 gene expression continuously decreased with ripening and no remarkable differences were found between cultivars. Overall, dehydration had a minor effect on CsPYR/PYL/RCAR and CsSnRK2 expression in vegetative tissue, whereas CsABI1, CsAHG1, and CsAHG3 were highly induced by water stress. The global results suggest that responsiveness to ABA changes during citrus fruit ripening, and leaf dehydration was higher in the CsPP2CA gene negative regulators than in the other ABA signalosome components. PMID:22888124

  1. 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.

  2. Block copolymer self-assembly–directed synthesis of mesoporous gyroidal superconductors

    PubMed Central

    Robbins, Spencer W.; Beaucage, Peter A.; Sai, Hiroaki; Tan, Kwan Wee; Werner, Jörg G.; Sethna, James P.; DiSalvo, Francis J.; Gruner, Sol M.; Van Dover, Robert B.; Wiesner, Ulrich

    2016-01-01

    Superconductors with periodically ordered mesoporous structures are expected to have properties very different from those of their bulk counterparts. Systematic studies of such phenomena to date are sparse, however, because of a lack of versatile synthetic approaches to such materials. We demonstrate the formation of three-dimensionally continuous gyroidal mesoporous niobium nitride (NbN) superconductors from chiral ABC triblock terpolymer self-assembly–directed sol-gel–derived niobium oxide with subsequent thermal processing in air and ammonia gas. Superconducting materials exhibit a critical temperature (Tc) of about 7 to 8 K, a flux exclusion of about 5% compared to a dense NbN solid, and an estimated critical current density (Jc) of 440 A cm−2 at 100 Oe and 2.5 K. We expect block copolymer self-assembly–directed mesoporous superconductors to provide interesting subjects for mesostructure-superconductivity correlation studies. PMID:27152327

  3. Self-Assembly of Pluronic Block Copolymers in Solutions: Simulation and Neutron Scattering

    NASA Astrophysics Data System (ADS)

    Zhang, Zhe; Hong, Kunlun; Do, Changwoo; Biology and Soft-Matter Division, Oak Ridge National Laboratory Team; Chemical Science Division, Oak Ridge National Laboratory Team

    2014-03-01

    Poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) triblock copolymers in water solution display various phase behaviors such as micellar, lamellar, and hexagonal phases and have been of great interest to researchers for their wide range of applications including templates of various nanostructures in solar cell and transportation of nanoparticles in drug delivery. In this study, we combined density functional theory-based mesoscale simulation and small-angle neutron scattering (SANS) experiments to investigate equilibrium structures of L62/water systems at different concentrations. Various simulation parameters found in the literature have been revisited with the experimental findings. Scattering experiments were found to be an excellent. This research is supported by the U.S. Department of Energy, Basic Energy Sciences, Materials Sciences and Energy Division.

  4. Block copolymer self-assembly-directed synthesis of mesoporous gyroidal superconductors.

    PubMed

    Robbins, Spencer W; Beaucage, Peter A; Sai, Hiroaki; Tan, Kwan Wee; Werner, Jörg G; Sethna, James P; DiSalvo, Francis J; Gruner, Sol M; Van Dover, Robert B; Wiesner, Ulrich

    2016-01-01

    Superconductors with periodically ordered mesoporous structures are expected to have properties very different from those of their bulk counterparts. Systematic studies of such phenomena to date are sparse, however, because of a lack of versatile synthetic approaches to such materials. We demonstrate the formation of three-dimensionally continuous gyroidal mesoporous niobium nitride (NbN) superconductors from chiral ABC triblock terpolymer self-assembly-directed sol-gel-derived niobium oxide with subsequent thermal processing in air and ammonia gas. Superconducting materials exhibit a critical temperature (T c) of about 7 to 8 K, a flux exclusion of about 5% compared to a dense NbN solid, and an estimated critical current density (J c) of 440 A cm(-2) at 100 Oe and 2.5 K. We expect block copolymer self-assembly-directed mesoporous superconductors to provide interesting subjects for mesostructure-superconductivity correlation studies. PMID:27152327

  5. Effects of solvent casting copolymer materials as related to mechanical properties.

    PubMed

    Bagrodia, S; Wilkes, G L

    1976-01-01

    Using a well characterized series of styrene butadiene triblock copolymers a systematic study was carried out to determine the influence of casting solvent, used for film preparation, on the final mechanical properties. The results clearly indicate that in the range of styrene contents of 30-40 mol %, the modulus behavior is greatly affected as the solubility parameter of the casting solvent, delta, is varied. Specifically, the modulus increases as delta increases to the value of polystyrene. At lower or higher styrene content, the properties are influenced but to a much lesser degree. Other mechanical properties measured were yield stress and breaking stress. The ramifications of these data are discussed in light of preparing prosthetic material via solvent casting. PMID:1249085

  6. X-ray Intensity Fluctuation Spectroscopy Studies of Dynamics of Block Copolymers in Selective Solvents

    NASA Astrophysics Data System (ADS)

    Liu, Yongsheng; Spring, Julian; Ludwig, Karl; Bansil, Rama

    2010-03-01

    We investigated the dynamics of a block copolymer SEBS (triblock of styrene (S) and ethylene-butylene, EB) in selective solvents using X-ray Intensity Fluctuation Spectroscopy (XIFS). We examined the temperature dependence of dynamics in cylindrical, spherical and lamellar phases as well as in coexisting phases through the transitions. We were able to observe dynamics in hexagonally-packed-cylinders (HEX) and body-centered-cubic (BCC) phases in 45% SEBS in mineral oil as well as HEX and lamellar (LAM) phases in 40% SEBS in dibutyl phthalate (selective to S). We observed two exponentially decaying dynamic modes in coexisting HEX and BCC phases, and in coexisting LAM and HEX phases. While the slower mode has a q-independent decay rate, the faster mode's decay rate decreases with increasing q, consistent with the well-known deGennes narrowing as q varies through a structural peak

  7. Block copolymer battery separator

    DOEpatents

    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. ABA-induced CCCH tandem zinc finger protein OsC3H47 decreases ABA sensitivity and promotes drought tolerance in Oryza sativa.

    PubMed

    Wang, Wenyi; Liu, Bohan; Xu, Mengyun; Jamil, Muhammad; Wang, Guoping

    2015-08-14

    Water deficit causes multiple negative impacts on plants, such as reactive oxygen species (ROS) accumulation, abscisic acid (ABA) induction, stomatal closure, and decreased photosynthesis. Here, we characterized OsC3H47, which belongs to CCCH zinc-finger families, as a drought-stress response gene. It can be strongly induced by NaCl, PEG, ABA, and drought conditions. Overexpression of OsC3H47 significantly enhanced tolerance to drought and salt stresses in rice seedlings, which indicates that OsC3H47 plays important roles in post-stress recovery. However, overexpression of OsC3H47 reduced the ABA sensitivity of rice seedlings. This suggests that OsC3H47 is a newly discovered gene that can control rice drought-stress response, and it may play an important role in ABA feedback and post-transcription processes. PMID:26047696

  9. Partial Miscibility in Copolymer Blends

    NASA Astrophysics Data System (ADS)

    Clark, Elizabeth; Lipson, Jane

    2011-03-01

    Copolymers can be used to affect the miscibility of otherwise immiscible polymer blends by acting as compatibilizers. To better understand the energetics of these types of systems, we use a simple lattice model to study phase separation in binary copolymer/homopolymer blends. We focus on a copolymer that contains both A and B type monomers and a homopolymer that contains purely A type monomer. An example of a system that we are investigating is polyethylene mixed with either random or alternating poly(ethylene-co-propylene). The sequence effect on miscibility as the copolymer microstructure is varied from random to alternating is investigated as well. The support of GAANN is gratefully acknowledged.

  10. 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.

  11. Peptide-directed self-assembly of functionalized polymeric nanoparticles part I: design and self-assembly of peptide-copolymer conjugates into nanoparticle fibers and 3D scaffolds.

    PubMed

    Ding, Xiaochu; Janjanam, Jagadeesh; Tiwari, Ashutosh; Thompson, Martin; Heiden, Patricia A

    2014-06-01

    A robust self-assembly of nanoparticles into fibers and 3D scaffolds is designed and fabricated by functionalizing a RAFT-polymerized amphiphilic triblock copolymer with designer ionic complementary peptides so that the assembled core-shell polymeric nanoparticles are directed by peptide assembly into continuous "nanoparticle fibers," ultimately leading to 3D fiber scaffolds. The assembled nanostructure is confirmed by FESEM and optical microscopy. The assembly is not hindered when a protein (insulin) is incorporated within the nanoparticles as an active ingredient. MTS cytotoxicity tests on SW-620 cell lines show that the peptides, copolymers, and peptide-copolymer conjugates are biocompatible. The methodology of self-assembled nanoparticle fibers and 3D scaffolds is intended to combine the advantages of a flexible hydrogel scaffold with the versatility of controlled release nanoparticles to offer unprecedented ability to incorporate desired drug(s) within a self-assembled scaffold system with individual control over the release of each drug. PMID:24610743

  12. The HAB1 PP2C is inhibited by ABA-dependent PYL10 interaction

    PubMed Central

    Li, Juan; Shi, Chaowei; Sun, Demeng; He, Yao; Lai, Chaohua; Lv, Pei; Xiong, Ying; Zhang, Longhua; Wu, Fangming; Tian, Changlin

    2015-01-01

    PYL10 is a monomeric abscisic acid (ABA) receptor that inhibits protein phosphatase 2C (PP2C) activity in Arabidopsis thaliana. Previous studies reported that the PP2C phosphatase inhibition by PYL10 was ABA-independent. Here, systematic PYL10 biochemical studies demonstrated that PYL10 activity was ABA-dependent, and the previously reported studies was interfered by the presence of BSA in the commercial kit. To investigate dynamic mechanism of how ABA binding to PYL10 induces PP2C phosphatase inhibiting activity, solution NMR relaxation analysis of apo-PYL10 and PYL10/ABA were conducted following backbone resonance assignments. Reduced spectrum density mapping of the backbone relaxation data revealed that PYL10 was more flexible in ABA bound form than apo-PYL10, indicating an increased conformational entropy upon ligand binding. Moreover, to illustrate conformation exchanges of PYL10 upon ABA binding, NMR line shape analysis was performed with increasing concentrations of ABA, and the results indicated that PYL10 backbone conformational changes occur at different time scales. PMID:26044871

  13. Overexpression of an ABA biosynthesis gene using a stress inducible promoter enhances drought resistance in petunia

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Plants respond to drought stress by closing their stomata and reducing transpirational water loss. The plant hormone abscisic acid (ABA) regulates growth and stomatal closure particularly when the plant is under environmental stresses. One of the key enzymes in the ABA biosynthesis of higher plants ...

  14. ABA, ROS and NO are key players during switchgrass seed germination

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Seed dormancy and germination are complex physiological processes usually under hormonal control. Germination of seeds from many plants including switchgrass, are inhibited by ABA and promoted by NO and by ROS. However, ABA apparently requires both ROS and NO as intermediates in its action, with R...

  15. Aba Women's Rebellion [And] Hoda Sha'arawi: Nationalist and Feminist.

    ERIC Educational Resources Information Center

    African-American Inst., New York, NY. School Services Div.

    Two modules comprise this document--one on the Aba women's rebellion in Nigeria and one on the Egyptian feminist movement. The paper on the Aba women's rebellion in Nigeria presents a background discussion of the women's movement and colonialism in Nigeria. The larger part of the paper is a lesson plan which investigates the women's rebellion…

  16. None of the As in ABA Stand for Autism: Dispelling the Myths

    ERIC Educational Resources Information Center

    Dillenburger, Karola; Keenan, Mickey

    2009-01-01

    Interventions that are based on scientific principles of applied behaviour analysis (ABA) are recognised as effective treatments for children with autism spectrum disorder (ASD) by many governments and professionals (Office of the Surgeon General, 2000; Ontario IBI Initiative, 2002). However, many still view ABA as one of many treatments for…

  17. Belowground ABA boosts aboveground production of DIMBOA and primes induction of chlorogenic acid in maize.

    PubMed

    Erb, Matthias; Gordon-Weeks, Ruth; Flors, Victor; Camañes, Gemma; Turlings, Ted C J; Ton, Jurriaan

    2009-07-01

    Plants are important mediators between above- and belowground herbivores. Consequently, interactions between root and shoot defenses can have far-reaching impacts on entire food webs. We recently reported that infestation of maize roots by larvae of the beetle Diabrotica virgifera virgifera induced shoot resistance against herbivores and pathogens. Root herbivory also enhanced aboveground DIMBOA and primed for enhanced induction of chlorogenic acid, two secondary metabolites that have been associated with plant stress resistance. Interestingly, the plant hormone abscisic acid (ABA) emerged as a putative long-distance signal in the regulation of these systemic defenses. In this addendum, we have investigated the role of root-derived ABA in aboveground regulation of DIMBOA and the phenolic compounds chlorogenic acid, caffeic and ferulic acid. Furthermore, we discuss the relevance of ABA in relation to defense against the leaf herbivore Spodoptera littoralis. Soil-drench treatment with ABA mimicked root herbivore-induced accumulation of DIMBOA in the leaves. Similarly, ABA mimicked aboveground priming of chlorogenic acid production, causing augmented induction of this compound after subsequent shoot attack by S. littoralis caterpillars. These findings confirm our notion that ABA acts as an important signal in the regulation of aboveground defenses during belowground herbivory. However, based on our previous finding that ABA alone is not sufficient to trigger aboveground resistance against S. littoralis caterpillars, our results also suggest that the ABA-inducible effects on DIMBOA and chlorogenic acid are not solely responsible for root herbivore-induced resistance against S. littoralis. PMID:19820311

  18. The effects of abscisic acid (ABA) addition on cadmium accumulation of two ecotypes of Solanum photeinocarpum.

    PubMed

    Wang, Jin; Lin, Lijin; Luo, Li; Liao, Ming'an; Lv, Xiulan; Wang, Zhihui; Liang, Dong; Xia, Hui; Wang, Xun; Lai, Yunsong; Tang, Yi

    2016-03-01

    The study of the effects of exogenous abscisic acid (ABA) addition on cadmium (Cd) accumulation of two ecotypes (mining and farmland) of Solanum photeinocarpum was operated through a pot experiment. The results showed that the biomass and chlorophyll content of the two ecotypes of S. photeinocarpum increased with increasing ABA concentration. Applying exogenous ABA increased Cd content in the two ecotypes of S. photeinocarpum. The maximum Cd contents in shoots of the two ecotypes of S. photeinocarpum were obtained at 20 μmol/L ABA; shoot Cd contents respectively for the mining and farmland ecotypes were 33.92 and 24.71% higher than those for the control. Applying exogenous ABA also increased Cd extraction by the two ecotypes of S. photeinocarpum, and the highest Cd extraction was obtained at 20 μmol/L ABA with 569.42 μg/plant in shoots of the mining ecotype and 520.51 μg/plant in shoots of the farmland ecotype respectively. Therefore, exogenous ABA can be used for enhancing the Cd extraction ability of S. photeinocarpum, and 20 μmol/L ABA was the optimal dose. PMID:26899030

  19. From the Classroom to the Family Room: Using ABA for Best Behavior

    ERIC Educational Resources Information Center

    Smith, Dawn

    2010-01-01

    When it comes to supporting individuals with disabilities including Autism Spectrum Disorder (ASD), Applied Behavior Analysis (ABA) can be an invaluable tool in understanding and changing behavior. More than a technique or method, ABA is a disciplined approach rooted in science to teach specific skills and then reinforce them so individuals can…

  20. Block copolymer investigations

    NASA Astrophysics Data System (ADS)

    Yufa, Nataliya A.

    The research presented in this thesis deals with various aspects of block copolymers on the nanoscale: their behavior at a range of temperatures, their use as scaffolds, or for creation of chemically striped surfaces, as well as the behavior of metals on block copolymers under the influence of UV light, and the healing behavior of copolymers. Invented around the time of World War II, copolymers have been used for decades due to their macroscopic properties, such as their ability to be molded without vulcanization, and the fact that, unlike rubber, they can be recycled. In recent years, block copolymers (BCPs) have been used for lithography, as scaffolds for nano-objects, to create a magnetic hard drive, as well as in photonic and other applications. In this work we used primarily atomic force microscopy (AFM) and transmission electron microscopy (TEM), described in Chapter II, to conduct our studies. In Chapter III we demonstrate a new and general method for positioning nanoparticles within nanoscale grooves. This technique is suitable for nanodots, nanocrystals, as well as DNA. We use AFM and TEM to demonstrate selective decoration. In Chapters IV and V we use AFM and TEM to study the structure of polymer surfaces coated with metals and self-assembled monolayers. We describe how the surfaces were created, exhibit their structure on the nanoscale, and prove that their macroscopic wetting properties have been altered compared to the original polymer structures. Finally, Chapters VI and VII report out in-situ AFM studies of BCP at high temperatures, made possible only recently with the invention of air-tight high-temperature AFM imaging cells. We locate the transition between disordered films and cylinders during initial ordering. Fluctuations of existing domains leading to domain coarsening are also described, and are shown to be consistent with reptation and curvature minimization. Chapter VII deals with the healing of PS-b-PMMA following AFM-tip lithography or

  1. Physiological impacts of ABA-JA interactions under water-limitation.

    PubMed

    de Ollas, Carlos; Dodd, Ian C

    2016-08-01

    Plant responses to drought stress depend on highly regulated signal transduction pathways with multiple interactions. This complex crosstalk can lead to a physiological outcome of drought avoidance or tolerance/resistance. ABA is the principal mediator of these responses due to the regulation of stomatal closure that determines plant growth and survival, but also other strategies of drought resistance such as osmotic adjustment. However, other hormones such as JA seem responsible for regulating a subset of plant responses to drought by regulating ABA biosynthesis and accumulation and ABA-dependent signalling, but also by ABA independent pathways. Here, we review recent reports of ABA-JA hormonal and molecular interactions within a physiological framework of drought tolerance. Understanding the physiological significance of this complex regulation offers opportunities to find strategies of drought tolerance that avoid unwanted side effects that limit growth and yield, and may allow biotechnological crop improvement. PMID:27299601

  2. Reactive triblock polymers from tandem ring-opening polymerization for nanostructured vinyl thermosets

    SciTech Connect

    Amendt, Mark A.; Pitet, Louis M.; Moench, Sarah; Hillmyer, Marc A.

    2013-03-07

    Multiply functional hydroxyl telechelic poly(cyclooctene-s-5-norbornene-2-methylene methacrylate) was synthesized by ring opening metathesis (co)polymerization of cis-cyclooctene and 5-norbornene-2-methylene methacrylate using the second generation Grubbs catalyst in combination with a symmetric chain transfer agent bearing hydroxyl functionality. The resulting hydroxyl-telechelic polymer was used as a macroinitiator for the ring opening transesterification polymerization of d,l-lactide to form reactive poly(lactide)-b-poly(cyclooctene-s-5-norbornene-2-methylene methacrylate)-b-poly(lactide) triblock polymers. Subsequently, the triblocks were crosslinked by free radical copolymerization with several vinyl monomers including styrene, divinylbenzene, methyl methacrylate, and ethyleneglycol dimethacrylate. Certain conditions led to optically transparent thermosets with mesoscale phase separation as evidenced by small angle X-ray scattering, differential scanning calorimetry and transmission electron microscopy. Disordered, bicontinuous structures with nanoscopic domains were generated in several cases, rendering the samples attractive for size-selective membrane applications.

  3. Controlled Thermoresponsive Hydrogels by Stereocomplexed PLA-PEG-PLA Prepared via Hybrid Micelles of Pre-Mixed Copolymers with Different PEG Lengths

    SciTech Connect

    Abebe, Daniel G.; Fujiwara, Tomoko

    2012-09-05

    The stereocomplexed hydrogels derived from the micelle mixture of two enantiomeric triblock copolymers, PLLA-PEG-PLLA and PDLA-PEG-PDLA, reported in 2001 exhibited sol-to-gel transition at approximately body temperature upon heating. However, the showed poor storage modulus (ca. 1000 Pa) determined their insufficiency as injectable implant biomaterials for many applications. In this study, the mechanical property of these hydrogels was significantly improved by the modifications of molecular weights and micelle structure. Co-micelles composed of block copolymers with two sizes of PEG block length were shown to possess unique and dissimilar properties from the micelles composed of single-sized block copolymers. The stereomixture of PLA-PEG-PLA comicelles showed a controllable sol-to-gel transition at a wide temperature range of 4 and 80 C. The sol-gel phase diagram displays a linear relationship of temperature versus copolymer composition; hence, a transition at body temperature can be readily achieved by adjusting the mixed copolymer ratio. The resulting thermoresponsive hydrogels exhibit a storage modulus notably higher (ca. 6000 Pa) than that of previously reported hydrogels. As a physical network solely governed by self-reorganization of micelles, followed by stereocomplexation, this unique system offers practical, safe, and simple implantable biomaterials.

  4. Controlled thermoresponsive hydrogels by stereocomplexed PLA-PEG-PLA prepared via hybrid micelles of pre-mixed copolymers with different PEG lengths.

    PubMed

    Abebe, Daniel G; Fujiwara, Tomoko

    2012-06-11

    The stereocomplexed hydrogels derived from the micelle mixture of two enantiomeric triblock copolymers, PLLA-PEG-PLLA and PDLA-PEG-PDLA, reported in 2001 exhibited sol-to-gel transition at approximately body temperature upon heating. However, the showed poor storage modulus (ca. 1000 Pa) determined their insufficiency as injectable implant biomaterials for many applications. In this study, the mechanical property of these hydrogels was significantly improved by the modifications of molecular weights and micelle structure. Co-micelles composed of block copolymers with two sizes of PEG block length were shown to possess unique and dissimilar properties from the micelles composed of single-sized block copolymers. The stereomixture of PLA-PEG-PLA comicelles showed a controllable sol-to-gel transition at a wide temperature range of 4 and 80 °C. The sol-gel phase diagram displays a linear relationship of temperature versus copolymer composition; hence, a transition at body temperature can be readily achieved by adjusting the mixed copolymer ratio. The resulting thermoresponsive hydrogels exhibit a storage modulus notably higher (ca. 6000 Pa) than that of previously reported hydrogels. As a physical network solely governed by self-reorganization of micelles, followed by stereocomplexation, this unique system offers practical, safe, and simple implantable biomaterials. PMID:22537225

  5. The role of ABA in triggering ethylene biosynthesis and ripening of tomato fruit

    PubMed Central

    Zhang, Mei; Yuan, Bing; Leng, Ping

    2009-01-01

    In order to understand more details about the role of abscisic acid (ABA) in fruit ripening and senescence of tomato, two cDNAs (LeNCED1 and LeNCED2) which encode 9-cis-epoxycarotenoid dioxygenase (NCED) as a key enzyme in ABA biosynthesis, two cDNAs (LeACS2 and LeACS4) which encode 1-aminocyclopropane-1-carboxylic acid (ACC) synthase, and one cDNA (LeACO1) which encodes ACC oxidase involved in ethylene biosynthesis were cloned from tomato fruit using a reverse transcription-PCR (RT-PCR) approach. The relationship between ABA and ethylene during ripening was also investigated. Among six sampling times in tomato fruits, the LeNCED1 gene was highly expressed only at the breaker stage when the ABA content becomes high. After this, the LeACS2, LeACS4, and LeACO1 genes were expressed with some delay. The change in pattern of ACO activity was in accordance with ethylene production reaching its peak at the pink stage. The maximum ABA content preceded ethylene production in both the seeds and the flesh. The peak value of ABA, ACC, and ACC oxidase activity, and ethylene production all started to increase earlier in seeds than in flesh tissues, although they occurred at different ripening stages. Exogenous ABA treatment increased the ABA content in both flesh and seed, inducing the expression of both ACS and ACO genes, and promoting ethylene synthesis and fruit ripening, while treatment with fluridone or nordihydroguaiaretic acid (NDGA) inhibited them, delaying fruit ripening and softening. Based on the results obtained in this study, it was concluded that LeNCED1 initiates ABA biosynthesis at the onset of fruit ripening, and might act as an original inducer, and ABA accumulation might play a key role in the regulation of ripeness and senescence of tomato fruit. PMID:19246595

  6. AbaA Regulates Conidiogenesis in the Ascomycete Fungus Fusarium graminearum

    PubMed Central

    Son, Hokyoung; Kim, Myung-Gu; Min, Kyunghun; Seo, Young-Su; Lim, Jae Yun; Choi, Gyung Ja; Kim, Jin-Cheol; Chae, Suhn-Kee; Lee, Yin-Won

    2013-01-01

    Fusarium graminearum (teleomorph Gibberella zeae) is a prominent pathogen that infects major cereal crops such as wheat, barley, and maize. Both sexual (ascospores) and asexual (conidia) spores are produced in F. graminearum. Since conidia are responsible for secondary infection in disease development, our objective of the present study was to reveal the molecular mechanisms underlying conidiogenesis in F. graminearum based on the framework previously described in Aspergillus nidulans. In this study, we firstly identified and functionally characterized the ortholog of AbaA, which is involved in differentiation from vegetative hyphae to conidia and known to be absent in F. graminearum. Deletion of abaA did not affect vegetative growth, sexual development, or virulence, but conidium production was completely abolished and thin hyphae grew from abnormally shaped phialides in abaA deletion mutants. Overexpression of abaA resulted in pleiotropic defects such as impaired sexual and asexual development, retarded conidium germination, and reduced trichothecene production. AbaA localized to the nuclei of phialides and terminal cells of mature conidia. Successful interspecies complementation using A. nidulans AbaA and the conserved AbaA-WetA pathway demonstrated that the molecular mechanisms responsible for AbaA activity are conserved in F. graminearum as they are in A. nidulans. Results from RNA-sequencing analysis suggest that AbaA plays a pivotal role in conidiation by regulating cell cycle pathways and other conidiation-related genes. Thus, the conserved roles of the AbaA ortholog in both A. nidulans and F. graminearum give new insight into the genetics of conidiation in filamentous fungi. PMID:24039821

  7. "Cross" Supermicelles via the Hierarchical Assembly of Amphiphilic Cylindrical Triblock Comicelles.

    PubMed

    Li, Xiaoyu; Gao, Yang; Boott, Charlotte E; Hayward, Dominic W; Harniman, Robert; Whittell, George R; Richardson, Robert M; Winnik, Mitchell A; Manners, Ian

    2016-03-30

    Self-assembled "cross" architectures are well-known in biological systems (as illustrated by chromosomes, for example); however, comparable synthetic structures are extremely rare. Herein we report an in depth study of the hierarchical assembly of the amphiphilic cylindrical P-H-P triblock comicelles with polar (P) coronal ends and a hydrophobic (H) central periphery in a selective solvent for the terminal segments which allows access to "cross" supermicelles under certain conditions. Well-defined P-H-P triblock comicelles M(PFS-b-PtBA)-b-M(PFS-b-PDMS)-b-M(PFS-b-PtBA) (M = micelle segment, PFS = polyferrocenyldimethylsilane, PtBA = poly(tert-butyl acrylate), and PDMS = polydimethylsiloxane) were created by the living crystallization-driven self-assembly (CDSA) method. By manipulating two factors in the supermicelles, namely the H segment-solvent interfacial energy (through the central H segment length, L1) and coronal steric effects (via the PtBA corona chain length in the P segment, L2 related to the degree of polymerization DP2) the aggregation of the triblock comicelles could be finely tuned. This allowed a phase-diagram to be constructed that can be extended to other triblock comicelles with different coronas on the central or end segment where "cross" supermicelles were exclusively formed under predicted conditions. Laser scanning confocal microscopy (LSCM) analysis of dye-labeled "cross" supermicelles, and block "cross" supermicelles formed by addition of a different unimer to the arm termini, provided complementary characterization to transmission electron microscopy (TEM) and dynamic light scattering (DLS) and confirmed the existence of these "cross" supermicelles as kinetically stable, micron-size colloidally stable structures in solution. PMID:26878261

  8. 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.

  9. Terminal groups control self-assembly of amphiphilic block copolymers in solution

    NASA Astrophysics Data System (ADS)

    Grzelakowski, M.; Kita-Tokarczyk, K.

    2016-03-01

    The terminal groups of amphiphilic block copolymers are shown to control macromolecular self-assembly in aqueous solutions, in the micellar/lamellar region of the phase diagram. At the same concentration and using the same self-assembly conditions, dramatic differences are observed in polymer hydration and the resulting nano-/microstructure for two series of polymers with identical block chemistry and hydrophilic-lipophilic balance (HLB). This suggests a strong contribution from end groups to the hydration as the initial step of the self-assembly process, and could be conveniently used to guide the particle morphology and size. Additionally, for polymers with those head groups which drive vesicular structures, differences in membrane organization affect their physical properties, such as permeability.The terminal groups of amphiphilic block copolymers are shown to control macromolecular self-assembly in aqueous solutions, in the micellar/lamellar region of the phase diagram. At the same concentration and using the same self-assembly conditions, dramatic differences are observed in polymer hydration and the resulting nano-/microstructure for two series of polymers with identical block chemistry and hydrophilic-lipophilic balance (HLB). This suggests a strong contribution from end groups to the hydration as the initial step of the self-assembly process, and could be conveniently used to guide the particle morphology and size. Additionally, for polymers with those head groups which drive vesicular structures, differences in membrane organization affect their physical properties, such as permeability. Electronic supplementary information (ESI) available: Fig. S1: Particle diameters for hydrated NH2-ABA-NH2 polymers with different degrees of functionalization; Fig. S2: TEM characterization of compound micelles from BA-OH polymer after extrusion; Fig. S3: Cryo-TEM and stopped flow characterization of lipid vesicles; Fig. S4 and S5: NMR spectra for ABA and BA polymers

  10. Phase behavior of ABC-type triple-hydrophilic block copolymers in aqueous solutions.

    PubMed

    Zheng, Lingfei; Wu, Jianqi; Wang, Zheng; Yin, Yuhua; Jiang, Run; Li, Baohui

    2016-07-01

    The phase behavior of symmetric ABC triple-hydrophilic triblock copolymers in concentrated aqueous solutions is investigated using a simulated annealing technique. Two typical cases, in which the hydrophilicity of the middle B-block is either stronger or weaker than that of the end A- and C-blocks, are studied. In these two cases, a variety of phase diagrams are constructed as a function of the volume fraction of the B-block and the copolymer concentration ([Formula: see text] for both non-frustrated and frustrated copolymers. Structures, such as two-color alternatingly packed cylinders or gyroid, and lamellae-in-lamellae etc. that do not occur in the melt system, are obtained in solutions. Rich phase transition sequences, especially re-entrant phase transitions involving complex continuous networks of alternating gyroid and alternating diamond are observed for a given copolymer with decreasing [Formula: see text] . The difference in hydrophilicity among different blocks can result in inhomogeneous distribution of solvent molecules in the morphology, and with the decrease of [Formula: see text] , the distribution of solvent molecules presents a non-monotonic variation. This results in a non-monotonic variation of the effective volume fraction of each domain with the decrease of [Formula: see text] , which induces the re-entrant phase transitions. The presence of a good solvent for all the blocks can cause changes in the effective segregation strengths between different blocks and also in chain conformations, hence can alter the bulk phases and results in the occurrence of new structures and phase transitions. Especially, structures having A-C interfaces or A-C mixed domains can be obtained even in the non-frustrated copolymer systems, and structures obtained in the frustrated systems may be similar to those obtained in the non-frustrated systems. The window of the alternating gyroid structures may occupy a large part of the phase diagram for non

  11. Lateral structuring and stability phenomena induced by block copolymers and core-shell nanogel particles at immiscible polymer/polymer interfaces

    NASA Astrophysics Data System (ADS)

    Gozen, Arif Omer

    We have investigated the parameters such as copolymer/nanoparticle concentration, architecture and molecular weight combined with film thickness, time and temperature in order to develop a molecular-level insight on how lateral interfacial structuring occurs at immiscible polymer/polymer interfaces. I order to develop a molecular-level understanding of how these 'smart' self-assembling materials and core-shell nanogel particles interact both intra- and inter-molecularly and form ordered structures in bulk, as well as at immiscible interfaces, we first focused on the response of core-shell polymer nanoparticles, designated CSNGs, composed of a cross-linked divinylbenzene core and poly(methyl methacrylate) (PMMA) arms as they segregate from PMMA homopolymer. We have demonstrated that these nanogel particles exhibit autophobic character when dispersed in high molecular weight homopolymer matrices and segregate to the interface with another fluid. We have further explored the migration of these new-generation nanogel particles (CSNG-Rs) segregating from PS homopolymer to PS/PMMA interfaces. Unlike the instability patterns observed with the CSNGs, which exhibit classical nucleation and growth mechanism with circular hole formation, we have observed an intriguing dewetting pattern and CSNG-Rs forming lateral aggregates and tentacle-like structures at the interface. In parallel with our core-shell particle studies, we have also explored the structuring of copolymer molecules that are far from equilibrium in bulk and complex laminate of polymer thin films. Our early triblock copolymer studies have proven that molecular asymmetry has a profound effect on order-disorder transition temperature. We focused primarily on the effect of the copolymer chemical composition (i.e., block sizes) on the dewetting behavior of PS/SM thin films on PMMA. We elucidate the interfacial segregation and concurrent micellization of diblock copolymers in a dynamically evolving environment with

  12. Dwarf apple MbDREB1 enhances plant tolerance to low temperature, drought, and salt stress via both ABA-dependent and ABA-independent pathways.

    PubMed

    Yang, Wei; Liu, Xiao-Dan; Chi, Xiao-Juan; Wu, Chang-Ai; Li, Yan-Ze; Song, Li-Li; Liu, Xiu-Ming; Wang, Yan-Fang; Wang, Fa-Wei; Zhang, Chuang; Liu, Yang; Zong, Jun-Mei; Li, Hai-Yan

    2011-02-01

    In higher plants, DREB1/CBF-type transcription factors play an important role in tolerance to low temperatures, drought, and high-salt stress. These transcription factors bind to CRT/DRE elements in promoter regions of target genes, regulating their expression. In this study, we cloned and characterized a novel gene encoding a DREB1 transcription factor from dwarf apple, Malus baccata (GenBank accession number: EF582842). Expression of MbDREB1 was induced by cold, drought, and salt stress, and also in response to exogenous ABA. Subcellular localization analyses revealed that MbDREB1 localizes in the nucleus. A yeast activity assay demonstrated that the MbDREB1 gene encodes a transcription activator, which specifically binds to DRE/CRT elements. Compared with wild-type plants, transgenic Arabidopsis overexpressing MbDREB1 showed increased tolerance to low temperature, drought, and salt stresses. Analysis of the MbDREB1 promoter revealed an ABA-responsive element (ABRE), an inducer of CBF expression 1 (ICE1)-like binding site, two MYB recognition sites, and three stress-inducible GT-1 boxes. GUS activities driven by the MbDREB1 promoter in transgenic Arabidopsis increased in response to ABA, cold temperature, drought, and salt treatments. Interestingly, the expression of both ABA-independent and ABA-dependent stress-induced genes (COR15a and rd29B, respectively) was activated under normal growth conditions in Arabidopsis overexpressing MbDREB1. These results suggest that MbDREB1 functions as a transcription factor and increases plant tolerance to low temperature, drought, and salt stress via both ABA-dependent and ABA-independent pathways. PMID:20967459

  13. Modular nature of abscisic acid (ABA) response complexes: composite promoter units that are necessary and sufficient for ABA induction of gene expression in barley.

    PubMed Central

    Shen, Q; Zhang, P; Ho, T H

    1996-01-01

    The modular nature of the abscisic acid response complex (ABRC), the promoter unit necessary and sufficient for abscisic acid (ABA) induction of gene expression in barley, is defined in this study. We investigated ABA induction of a barley late embrogenesis abundant (Lea) gene, HVA1, and found that the ABRC of this gene consists of a 10-bp box with an ACGT core (ACGT-box) and the 11 bp directly upstream, named coupling element 3 (CE3). Only one copy of this ABRC is sufficient to confer ABA induction when linked to a minimal promoter. Because we previously reported another ABRC in the barley HVA22 gene, which consists of an ACGT-box with a distal coupling element (CE1), exchange experiments were conducted to study the interaction among modular elements in these ABRCs. We show that ACGT-boxes in these ABRCs are interchangeable, indicating that an ACGT-box can interact with either a distal or a proximal coupling element to confer ABA response. However, the two coupling elements are not fully exchangeable. Although CE3 can function either proximal or distal to the ACGT-box, CE1 is only functional at the distal position. The presence of both the distal and the proximal coupling elements has a synergistic effect on the absolute level of expression as well as on ABA induction. These ABRCs function in both seed and vegetative tissues. In seeds, ABA induction of the ABRC containing the proximal CE3, but not the ABRC with the distal CE1, is enhanced in the presence of the transcription regulator Viviparous1, indicating that these two ABRCs are mediated by different ABA signal transduction pathways. PMID:8768371

  14. Chemical Promotion of Endogenous Amounts of ABA in Arabidopsis thaliana by a Natural Product, Theobroxide.

    PubMed

    Yamashita, Yudai; Ota, Maremichi; Inoue, Yutaka; Hasebe, Youko; Okamoto, Masanori; Inukai, Tsuyoshi; Masuta, Chikra; Sakihama, Yasuko; Hashidoko, Yasuyuki; Kojima, Mikiko; Sakakibara, Hitoshi; Inage, Yasuyuki; Takahashi, Kosaku; Yoshihara, Teruhiko; Matsuura, Hideyuki

    2016-05-01

    Plant hormones are a group of structurally diverse small compounds that orchestrate the cellular processes governing proper plant growth and environmental adaptation. To understand the details of hormonal activity, we must study not only their inherent activities but also the cross-talk among plant hormones. In addition to their use in agriculture, plant chemical activators, such as probenazole and uniconazole, have made great contributions to understand hormonal cross-talk. However, the use of plant chemical activators is limited due to the lack of activators for certain hormones. For example, to the best of our knowledge, there are only a few chemical activators previously known to stimulate the accumulation of ABA in plants, such as absinazoles and proanthocyanidins. In many cases, antagonistic effects have been examined in experiments using exogenously applied ABA, although these studies did not account for biologically relevant concentrations. In this report, it was found that a natural product, theobroxide, had potential as a plant chemical activator for stimulating the accumulation of ABA. Using theobroxide, the antagonistic effect of ABA against GAs was proved without exogenously applying ABA or using mutant plants. Our results suggest that ABA levels could be chemically controlled to elicit ABA-dependent biological phenomena. PMID:26917631

  15. [Role of NO signal in ABA-induced phenolic acids accumulation in Salvia miltiorrhiza hairy roots].

    PubMed

    Shen, Lihong; Ren, Jiahui; Jin, Wenfang; Wang, Ruijie; Ni, Chunhong; Tong, Mengjiao; Liang, Zongsuo; Yang, Dongfeng

    2016-02-01

    To investigate roles of nitric oxide (NO) signal in accumulations of phenolic acids in abscisic.acid (ABA)-induced Salvia miltiorrhiza hairy roots, S. miltiorrhiza hairy roots were treated with different concentrations of sodium nitroprusside (SNP)-an exogenous NO donor, for 6 days, and contents of phenolic acids in the hairy roots are determined. Then with treatment of ABA and NO scavenger (2-(4-carboxy-2-phenyl)-4,4,5,5-tetramethylimidazoline-1- oxyl-3-oxide, c-PTIO) or NO synthase inhibitor (NG-nitro-L-arginine methyl ester, L-NAME), contents of phenolic acids and expression levels of three key genes involved in phenolic acids biosynthesis were detected. Phenolic acids production in S. miltiorrhiza hairy roots was most significantly improved by 100 µmoL/L SNP. Contents of RA and salvianolic acid B increased by 3 and 4 folds. ABA significantly improved transcript levels of PAL (phenylalanine ammonia lyase), TAT (tyrosine aminotransferase) and RAS (rosmarinic acid synthase), and increased phenolic acids accumulations. However, with treatments of ABA+c-PTIO or ABA+L-NAME, accumulations of phenolic acids and expression levels of the three key genes were significantly inhibited. Both NO and ABA can increase accumulations of phenolic acids in S. miltiorrhiza hairy roots. NO signal probably mediates the ABA-induced phenolic acids production. PMID:27382772

  16. Endodermal ABA Signaling Promotes Lateral Root Quiescence during Salt Stress in Arabidopsis Seedlings[C][W

    PubMed Central

    Duan, Lina; Dietrich, Daniela; Ng, Chong Han; Chan, Penny Mei Yeen; Bhalerao, Rishikesh; Bennett, Malcolm J.; Dinneny, José R.

    2013-01-01

    The endodermal tissue layer is found in the roots of vascular plants and functions as a semipermeable barrier, regulating the transport of solutes from the soil into the vascular stream. As a gateway for solutes, the endodermis may also serve as an important site for sensing and responding to useful or toxic substances in the environment. Here, we show that high salinity, an environmental stress widely impacting agricultural land, regulates growth of the seedling root system through a signaling network operating primarily in the endodermis. We report that salt stress induces an extended quiescent phase in postemergence lateral roots (LRs) whereby the rate of growth is suppressed for several days before recovery begins. Quiescence is correlated with sustained abscisic acid (ABA) response in LRs and is dependent upon genes necessary for ABA biosynthesis, signaling, and transcriptional regulation. We use a tissue-specific strategy to identify the key cell layers where ABA signaling acts to regulate growth. In the endodermis, misexpression of the ABA insensitive1-1 mutant protein, which dominantly inhibits ABA signaling, leads to a substantial recovery in LR growth under salt stress conditions. Gibberellic acid signaling, which antagonizes the ABA pathway, also acts primarily in the endodermis, and we define the crosstalk between these two hormones. Our results identify the endodermis as a gateway with an ABA-dependent guard, which prevents root growth into saline environments. PMID:23341337

  17. ABA-Mediated ROS in Mitochondria Regulate Root Meristem Activity by Controlling PLETHORA Expression in Arabidopsis

    PubMed Central

    Yang, Li; Zhang, Jing; He, Junna; Qin, Yingying; Hua, Deping; Duan, Ying; Chen, Zhizhong; Gong, Zhizhong

    2014-01-01

    Although research has determined that reactive oxygen species (ROS) function as signaling molecules in plant development, the molecular mechanism by which ROS regulate plant growth is not well known. An aba overly sensitive mutant, abo8-1, which is defective in a pentatricopeptide repeat (PPR) protein responsible for the splicing of NAD4 intron 3 in mitochondrial complex I, accumulates more ROS in root tips than the wild type, and the ROS accumulation is further enhanced by ABA treatment. The ABO8 mutation reduces root meristem activity, which can be enhanced by ABA treatment and reversibly recovered by addition of certain concentrations of the reducing agent GSH. As indicated by low ProDR5:GUS expression, auxin accumulation/signaling was reduced in abo8-1. We also found that ABA inhibits the expression of PLETHORA1 (PLT1) and PLT2, and that root growth is more sensitive to ABA in the plt1 and plt2 mutants than in the wild type. The expression of PLT1 and PLT2 is significantly reduced in the abo8-1 mutant. Overexpression of PLT2 in an inducible system can largely rescue root apical meristem (RAM)-defective phenotype of abo8-1 with and without ABA treatment. These results suggest that ABA-promoted ROS in the mitochondria of root tips are important retrograde signals that regulate root meristem activity by controlling auxin accumulation/signaling and PLT expression in Arabidopsis. PMID:25522358

  18. Linking Turgor with ABA Biosynthesis: Implications for Stomatal Responses to Vapor Pressure Deficit across Land Plants.

    PubMed

    McAdam, Scott A M; Brodribb, Timothy J

    2016-07-01

    Stomatal responses to changes in vapor pressure deficit (VPD) constitute the predominant form of daytime gas-exchange regulation in plants. Stomatal closure in response to increased VPD is driven by the rapid up-regulation of foliar abscisic acid (ABA) biosynthesis and ABA levels in angiosperms; however, very little is known about the physiological trigger for this increase in ABA biosynthesis at increased VPD Using a novel method of modifying leaf cell turgor by the application of external pressures, we test whether changes in turgor pressure can trigger increases in foliar ABA levels over 20 min, a period of time most relevant to the stomatal response to VPD We found in angiosperm species that the biosynthesis of ABA was triggered by reductions in leaf turgor, and in two species tested, that a higher sensitivity of ABA synthesis to leaf turgor corresponded with a higher stomatal sensitivity to VPD In contrast, representative species from nonflowering plant lineages did not show a rapid turgor-triggered increase in foliar ABA levels, which is consistent with previous studies demonstrating passive stomatal responses to changes in VPD in these lineages. Our method provides a new tool for characterizing the response of stomata to water availability. PMID:27208264

  19. POLYAMINE OXIDASE2 of Arabidopsis contributes to ABA mediated plant developmental processes.

    PubMed

    Wimalasekera, Rinukshi; Schaarschmidt, Frank; Angelini, Riccardo; Cona, Alessandra; Tavladoraki, Parasklevi; Scherer, Günther F E

    2015-11-01

    Polyamines (PA) are catabolised by two groups of amine oxidases, the copper-binding amine oxidases (CuAOs) and the FAD-binding polyamine oxidases (PAOs). Previously, we have shown that CuAO1 is involved in ABA associated growth responses and ABA- and PA-mediated rapid nitric oxide (NO) production. Here we report the differential regulation of expression of POLYAMINE OXIDASE2 of Arabidopsis (AtPAO2) in interaction with ABA, nitrate and ammonium. Without ABA treatment germination, cotyledon growth and fresh weight of pao2 knockdown mutants as well as PAO2OX over-expressor plants were comparable to those of the wild type (WT) plants irrespective of the N source. In the presence of ABA, in pao2 mutants cotyledon growth and fresh weights were more sensitive to inhibition by ABA while PAO2OX over-expressor plants showed a rather similar response to WT. When NO3(-) was the only N source primary root lengths and lateral root numbers were lower in pao2 mutants both without and with exogenous ABA. PAO2OX showed enhanced primary and lateral root growth in media with NO3(-) or NH4(+). Vigorous root growth of PAO2OX and the hypersensitivity of pao2 mutants to ABA suggest a positive function of AtPAO2 in root growth. ABA-induced NO production in pao2 mutants was lower indicating a potential contributory function of AtPAO2 in NO-mediated effects on root growth. PMID:26310141

  20. Polyplex Micelles with Double-Protective Compartments of Hydrophilic Shell and Thermoswitchable Palisade of Poly(oxazoline)-Based Block Copolymers for Promoted Gene Transfection.

    PubMed

    Osawa, Shigehito; Osada, Kensuke; Hiki, Shigehiro; Dirisala, Anjaneyulu; Ishii, Takehiko; Kataoka, Kazunori

    2016-01-11

    Improving the stability of polyplex micelles under physiological conditions is a critical issue for promoting gene transfection efficiencies. To this end, hydrophobic palisade was installed between the inner core of packaged plasmid DNA (pDNA) and the hydrophilic shell of polyplex micelles using a triblock copolymer consisting of hydrophilic poly(2-ethyl-2-oxazoline), thermoswitchable amphiphilic poly(2-n-propyl-2-oxazoline) (PnPrOx) and cationic poly(L-lysine). The two-step preparation procedure, mixing the triblock copolymer with pDNA below the lower critical solution temperature (LCST) of PnPrOx, followed by incubation above the LCST to form a hydrophobic palisade of the collapsed PnPrOx segment, induced the formation of spatially aligned hydrophilic-hydrophobic double-protected polyplex micelles. The prepared polyplex micelles exhibited significant tolerance against attacks from nuclease and polyanions compared to those without hydrophobic palisades, thereby promoting gene transfection. These results corroborated the utility of amphiphilic poly(oxazoline) as a molecular thermal switch to improve the stability of polyplex gene carriers relevant for physiological applications. PMID:26682466

  1. Networks of ABA and ABC stacked graphene on mica observed by scanning tunneling microscopy

    NASA Astrophysics Data System (ADS)

    Hattendorf, S.; Georgi, A.; Liebmann, M.; Morgenstern, M.

    2013-04-01

    Graphene flakes are prepared on freshly cleaved mica by exfoliation and studied by scanning tunneling microscopy in ultra high vacuum. On few-layer graphene, a triangular network of partial dislocations separating ABC stacked and ABA stacked graphene was found similar to the networks occasionally visible on freshly cleaved HOPG. We found differences in the electronic structure of ABC and ABA stacked areas by scanning tunneling spectroscopy, i.e., a pronounced peak at 0.25 eV above the Fermi level exclusively in the ABA areas, which is shown to be responsible for the different apparent heights observed in STM images.

  2. Loss of heterophylly in aquatic plants: not ABA-mediated stress but exogenous ABA treatment induces stomatal leaves in Potamogeton perfoliatus.

    PubMed

    Iida, Satoko; Ikeda, Miyuki; Amano, Momoe; Sakayama, Hidetoshi; Kadono, Yasuro; Kosuge, Keiko

    2016-09-01

    Heterophyllous aquatic plants produce aerial (i.e., floating and terrestrial) and submerged leaves-the latter lack stomata-while homophyllous plants contain only submerged leaves, and cannot survive on land. To identify whether differences in morphogenetic potential and/or physiological stress responses are responsible for variation in phenotypic plasticity between two plants types, responses to abscisic acid (ABA) and salinity stress were compared between the closely related, but ecologically diverse pondweeds, Potamogeton wrightii (heterophyllous) and P. perfoliatus (homophyllous). The ABA-treated (1 or 10 μM) P. wrightii plants exhibited heterophylly and produced leaves with stomata. The obligate submerged P. perfoliatus plants were able to produce stomata on their leaves, but there were no changes to leaf shape, and stomatal production occurred only at a high ABA concentration (10 μM). Under salinity stress conditions, only P. wrightii leaves formed stomata. Additionally, the expression of stress-responsive NCED genes, which encode a key enzyme in ABA biosynthesis, was consistently up-regulated in P. wrightii, but only temporarily in P. perfoliatus. The observed species-specific gene expression patterns may be responsible for the induction or suppression of stomatal production during exposure to salinity stress. These results suggest that the two Potamogeton species have an innate morphogenetic ability to form stomata, but the actual production of stomata depends on ABA-mediated stress responses specific to each species and habitat. PMID:27324202

  3. Towards entropy-driven interstitial micelles at elevated temperatures from selective A1BA2 triblock solutions.

    PubMed

    Wołoszczuk, S; Jurga, S; Banaszak, M

    2016-08-01

    We simulate selective A1BA2-A and A1BA2-B triblock solutions (that is, mixtures of the A1BA2 triblock with a solvent of either type A or type B) using a lattice Monte Carlo method. Although the simulated triblock chains are compositionally symmetric in terms of the A to B volume ratio, the A1 block is significantly shorter than the A2 block. For the pure A1BA2 melt the phase behavior is relatively well known, including the existence and stability of the recently discovered interstitial micelles which were found at the very strong segregation limit. In this paper, we investigate the stability of the interstitial micelles as a function of triblock volume fraction in a selective solvent of either type A or type B. The main finding of this paper is that adding a selective solvent of type A shifts the stability of the interstitial micelles into significantly higher temperatures which may provide a pathway towards experimental studies of interstitial micelles in real triblock solutions. We also find that adding selective solvents to the A1BA2 melt gives rise to a variety of nonlamellar nanostructures for temperatures and compositions at which the interstitial micelles are stable. PMID:27627353

  4. In-situ crosslinkable and self-assembling elastin-like polypeptide block copolymers for cartilage tissue repair

    NASA Astrophysics Data System (ADS)

    Lim, Dong Woo

    This work describes the development of genetically engineered elastin-like polypeptide (ELP) block copolymers as in-situ gelling scaffolds for cartilage tissue repair. The central hypothesis underlying this work is that ELP based biopolymers can be exploited as injectable biomaterials by rapid chemical crosslinking. To prove this, gene libraries encoding ELP having different molecular weights and amino acid sequences, and ELP block copolymers composed of various ELP blocks having diverse amino acid composition, length, and phase transition behavior were synthesized by recursive directional ligation, expressed in E. Coli and purified by inverse transition cycling. Mannich-type condensation of hydroxymethylphosphines (HMPs) with primary- and secondary-amines of amino acids was developed as a new crosslinking method of polypeptides. Chemically crosslinked ELP hydrogels were formed rapidly in an aqueous solution by reaction of ELPs containing periodic lysine residues with HMPs. The crosslinking density and mechanical property of the ELP hydrogels were controlled at the sequence level by varying the Lys density in ELPs composed of mono-block as well as by segregation of the Lys residues within specific blocks of tri-block architectures. Fibroblasts embedded in ELP hydrogels survived the crosslinking process and were viable after in vitro culture for at least 3 days. The DNA content of fibroblasts within the tri-block gels was significantly higher than that in the mono-block gels at day 3. These results suggest that the HMP crosslinked ELP block copolymer hydrogels show finely tuned mechanical properties and different microenvironments for cell viability as well as potential as in-situ crosslinkable biopolymers for tissue repair applications with load-bearing environments. As an alternative, rheological behavior of the ELP block copolymers and ELP-grafted hyaluronic acids (HAs) as artificial extracellular matrices (ECMs) showed that they were thermally aggregated into

  5. Plastid casein kinase 2 knockout reduces abscisic acid (ABA) sensitivity, thermotolerance, and expression of ABA- and heat-stress-responsive nuclear genes.

    PubMed

    Wang, Yu; Chang, Hongping; Hu, Shuai; Lu, Xiutao; Yuan, Congying; Zhang, Chen; Wang, Ping; Xiao, Wenjun; Xiao, Langtao; Xue, Gang-Ping; Guo, Xinhong

    2014-08-01

    Plastid casein kinase 2 (CK2) is a major Ser/Thr-specific enzyme for protein phosphorylation in the chloroplast stroma and its kinase activity is regulated by redox signals. To understand the role of CK2 phosphorylation of chloroplast proteins in abiotic stress signalling, an Arabidopsis plastid CK2 (CKA4) knockout mutant was investigated in terms of the plant response to abscisic acid (ABA) and heat stress. CKA4 expression was upregulated by ABA and heat treatment. The cka4 mutant showed reduced sensitivity to ABA during seed germination and seedling growth, and increased stomatal aperture and leaf water loss with a slightly reduced leaf ABA level. The cka4 mutant was more sensitive to heat stress than the wild-type Columbia-0. The expression levels of a number of genes in the ABA regulatory network were reduced in the cka4 mutant. Many heat-upregulated genes (heat-shock factors and heat-shock proteins) were also reduced in the cka4 mutant. The cka4 mutant showed reduced expression levels of plastid-encoded RNA polymerase target genes (atpB and psbA). CKA4 knockout mutation also resulted in a reduction in expression of some critical genes (PTM, ABI4, and PRS1) involved in retrograde signalling from the chloroplast to the nucleus. Similar results were observed in mutant plants with the knockout mutation in both CKA4 and CKA3, which encodes a nuclear CK2 α3 subunit. CKA3 expression was not responsive to ABA and heat stress. These results suggest that CKA4 is an enhancing factor in abiotic stress signalling through modulating the expression of some molecular players in retrograde signalling. PMID:24803505

  6. Plastid casein kinase 2 knockout reduces abscisic acid (ABA) sensitivity, thermotolerance, and expression of ABA- and heat-stress-responsive nuclear genes

    PubMed Central

    Wang, Yu; Chang, Hongping; Hu, Shuai; Lu, Xiutao; Yuan, Congying; Zhang, Chen; Wang, Ping; Xiao, Wenjun; Xiao, Langtao; Xue, Gang-Ping; Guo, Xinhong

    2014-01-01

    Plastid casein kinase 2 (CK2) is a major Ser/Thr-specific enzyme for protein phosphorylation in the chloroplast stroma and its kinase activity is regulated by redox signals. To understand the role of CK2 phosphorylation of chloroplast proteins in abiotic stress signalling, an Arabidopsis plastid CK2 (CKA4) knockout mutant was investigated in terms of the plant response to abscisic acid (ABA) and heat stress. CKA4 expression was upregulated by ABA and heat treatment. The cka4 mutant showed reduced sensitivity to ABA during seed germination and seedling growth, and increased stomatal aperture and leaf water loss with a slightly reduced leaf ABA level. The cka4 mutant was more sensitive to heat stress than the wild-type Columbia-0. The expression levels of a number of genes in the ABA regulatory network were reduced in the cka4 mutant. Many heat-upregulated genes (heat-shock factors and heat-shock proteins) were also reduced in the cka4 mutant. The cka4 mutant showed reduced expression levels of plastid-encoded RNA polymerase target genes (atpB and psbA). CKA4 knockout mutation also resulted in a reduction in expression of some critical genes (PTM, ABI4, and PRS1) involved in retrograde signalling from the chloroplast to the nucleus. Similar results were observed in mutant plants with the knockout mutation in both CKA4 and CKA3, which encodes a nuclear CK2 α3 subunit. CKA3 expression was not responsive to ABA and heat stress. These results suggest that CKA4 is an enhancing factor in abiotic stress signalling through modulating the expression of some molecular players in retrograde signalling. PMID:24803505

  7. Thermodynamics of the multi-stage self-assembly of pH-sensitive gradient copolymers in aqueous solutions.

    PubMed

    Černochová, Zulfiya; Bogomolova, Anna; Borisova, Olga V; Filippov, Sergey K; Černoch, Peter; Billon, Laurent; Borisov, Oleg V; Štěpánek, Petr

    2016-08-10

    The self-assembly thermodynamics of pH-sensitive di-block and tri-block gradient copolymers of acrylic acid and styrene was studied for the first time using isothermal titration calorimetry (ITC) and dynamic light scattering (DLS) performed at varying pH. We were able to monitor each step of micellization as a function of decreasing pH. The growth of micelles is a multi-stage process that is pH dependent with several exothermic and endothermic components. The first step of protonation of the acrylic acid monomer units was accompanied mainly by conformational changes and the beginning of self-assembly. In the second stage of self-assembly, the micelles become larger and the number of micelles becomes smaller. While solution acidity increases, the isothermal calorimetry data show a broad deep minimum corresponding to an exothermic process attributed to an increase in the size of hydrophobic domains and an increase in the structure's hydrophobicity. The minor change in heat capacity (ΔCp) confirms the structural changes during this exothermic process. The exothermic process terminates deionization of acrylic acid. The pH-dependence of the ζ-potential of the block gradient copolymer micelles exhibits a plateau in the regime corresponding to the pH-controlled variation of the micellar dimensions. The onset of micelle formation and the solubility of the gradient copolymers were found to be dependent on the length of the gradient block. PMID:27451979

  8. Polydispersity-Driven Block Copolymer Amphiphile Self-Assembly into Prolate-Spheroid Micelles

    SciTech Connect

    Schmitt, Andrew L.; Repollet-Pedrosa, Milton H.; Mahanthappa, Mahesh K.

    2013-09-26

    The aqueous self-assembly behavior of polydisperse poly(ethylene oxide-b-1,4-butadiene-b-ethylene oxide) (OBO) macromolecular triblock amphiphiles is examined to discern the implications of continuous polydispersity in the hydrophobic block on the resulting aqueous micellar morphologies of otherwise monodisperse polymer surfactants. The chain length polydispersity and implicit composition polydispersity of these samples furnishes a distribution of preferred interfacial curvatures, resulting in dilute aqueous block copolymer dispersions exhibiting coexisting spherical and rod-like micelles with vesicles in a single sample with a O weight fraction, w{sub O}, of 0.18. At higher w{sub O} = 0.51-0.68, the peak in the interfacial curvature distribution shifts and we observe the formation of only American football-shaped micelles. We rationalize the formation of these anisotropically shaped aggregates based on the intrinsic distribution of preferred curvatures adopted by the polydisperse copolymer amphiphiles and on the relief of core block chain stretching by chain-length-dependent intramicellar segregation.

  9. LTP3 contributes to disease susceptibility in Arabidopsis by enhancing abscisic acid (ABA) biosynthesis.

    PubMed

    Gao, Shan; Guo, Wenya; Feng, Wen; Liu, Liang; Song, Xiaorui; Chen, Jian; Hou, Wei; Zhu, Hongxia; Tang, Saijun; Hu, Jian

    2016-04-01

    Several plant lipid transfer proteins (LTPs) act positively in plant disease resistance. Here, we show that LTP3 (At5g59320), a pathogen and abscisic acid (ABA)-induced gene, negatively regulates plant immunity in Arabidopsis. The overexpression of LTP3 (LTP3-OX) led to an enhanced susceptibility to virulent bacteria and compromised resistance to avirulent bacteria. On infection of LTP3-OX plants with Pseudomonas syringae pv. tomato, genes involved in ABA biosynthesis, NCED3 and AAO3, were highly induced, whereas salicylic acid (SA)-related genes, ICS1 and PR1, were down-regulated. Accordingly, in LTP3-OX plants, we observed increased ABA levels and decreased SA levels relative to the wild-type. We also showed that the LTP3 overexpression-mediated enhanced susceptibility was partially dependent on AAO3. Interestingly, loss of function of LTP3 (ltp3-1) did not affect ABA pathways, but resulted in PR1 gene induction and elevated SA levels, suggesting that LTP3 can negatively regulate SA in an ABA-independent manner. However, a double mutant consisting of ltp3-1 and silent LTP4 (ltp3/ltp4) showed reduced susceptibility to Pseudomonas and down-regulation of ABA biosynthesis genes, suggesting that LTP3 acts in a redundant manner with its closest homologue LTP4 by modulating the ABA pathway. Taken together, our data show that LTP3 is a novel negative regulator of plant immunity which acts through the manipulation of the ABA-SA balance. PMID:26123657

  10. Crosstalk between ABA and auxin signaling pathways in roots of Arabidopsis thaliana (L.) Heynh.

    PubMed

    Rock, Christopher D; Sun, Xin

    2005-09-01

    Studies of abscisic acid (ABA) and auxin have revealed that these pathways impinge on each other. The Daucus carota (L.) Dc3 promoter: uidA (beta-glucuronidase: GUS) chimaeric reporter (ProDc3:GUS) is induced by ABA, osmoticum, and the auxin indole-3-acetic acid (IAA) in vegetative tissues of transgenic Arabidopsis thaliana (L.) Heynh. Here, we describe the root tissue-specific expression of ProDc3:GUS in the ABA-insensitive-2 (abi2-1), auxin-insensitive-1 (aux1), auxin-resistant-4 (axr4), and rooty (rty1) mutants of Arabidopsis in response to ABA, IAA and synthetic auxins naphthalene acetic acid (NAA), and 2, 4-(dichlorophenoxy) acetic acid. Quantitative analysis of ProDc3:GUS expression showed that the abi2-1 mutant had reduced GUS activity in response to ABA, IAA, or 2, 4-D: , but not to NAA. Similarly, chromogenic staining of ProDc3:GUS activity showed that the aux1 and axr4 mutants gave predictable hypomorphic ProDc3:GUS expression phenotypes in roots treated with IAA or 2, 4-D: , but not the diffusible auxin NAA. Likewise the rty mutant, which accumulates auxin, showed elevated ProDc3:GUS expression in the absence or presence of hormones relative to wild type. Interestingly, the aux1 and axr4 mutants showed a hypomorphic effect on ABA-inducible ProDc3:GUS expression, demonstrating that ABA and IAA signaling pathways interact in roots. Possible mechanisms of crosstalk between ABA and auxin signaling are discussed. PMID:15889272

  11. Change Detection of Lake Aba Samuel in Ethiopia

    NASA Astrophysics Data System (ADS)

    Kaczynski, R.; Rylko, A.

    2016-06-01

    Old topographic map published in 1975 elaborated from aerial photographs taken in 1972, Landsat TM data acquired in May 1986 and Landsat ETM+ from June 2002 have been used to assess the changes of the lake Aba Samuel in Ethiopia. First map of the lake has been done in the framework of UNDP project running in 1988-90 in the Ethiopian Mapping Authority. The second classification map has been done as M.Sc. thesis in the MUT in 2015. Supervised classification methods with the use of ground truth data have been used for elaboration of the Landsat TM data. From the year 1972 up to 1986 the area of the lake has decreased by 23%. From 1986 up to 2002 the area of the lake has decreased by 20%. Therefore, after 30 years the lake was smaller by 43%. This have had very bad influence on the lives of the local population. From other recent data in the period from 2002-2015 the lake has practically disappeared and now it is only a small part of the river Akaki. ENVI 5.2 and ERDAS IMAGINE 9.2 have been used for Radiometric Calibration, Quick Atmospheric Correction (QUAC) and supervised classification of Landsat ETM+ data. The Optimum Index Factor shows the best combination of Landsat TM and ETM+ bands for color composite as 1,4,5 in the color filters: B, G, R for the signature development. Methodology and final maps are enclosed in the paper.

  12. Molecular characterization of an ABA insensitive 5 orthologue in Brassica oleracea.

    PubMed

    Zhou, Xiaona; Yuan, Feifei; Wang, Mengyao; Guo, Aiguang; Zhang, Yanfeng; Xie, Chang Gen

    2013-01-18

    ABI5 (ABA insensitive 5), a bZIP (Basic leucine zipper) transcription factor, has been shown to be a major mediator of plant ABA responses during seed germination. Although the molecular basis of ABI5-modulated processes has been well demonstrated in Arabidopsis thaliana, its identity and function in cabbage (Brassica oleracea var. capitata L.) remain elusive. Here, we describe our identification of BolABI5 (an ABI5 orthologue in B.oleracea) as a functional bZIP transcription factor in the modulation of plant ABA responses. Expression of BolABI5 was dramatically induced by drought stress and exogenous ABA. Heterogeneous expression of BolABI5 rescued the insensitive phenotype of Arabidopsis abi5-1 to ABA during seed germination. Subcellular localization and trans-activation assays revealed that BolABI5 was localized in the nucleus and possessed DNA binding and trans-activation activities. Deletion of the bZIP domain generated BolABI5ΔbZIP, which no longer localized exclusively in the nucleus and had almost no detectable DNA-binding or trans-activation activities. Overall, these results suggest that BolABI5 may function as ABI5 in the positive regulation of plant ABA responses. PMID:23246838

  13. New biodegradable amphiphilic block copolymers of epsilon-caprolactone and delta-valerolactone catalyzed by novel aluminum metal complexes. II. Micellization and solution to gel transition.

    PubMed

    Yang, Jing; Jia, Lin; Hao, Qinghui; Li, Yang; Li, Qiaobo; Fang, Qiang; Cao, Amin

    2005-09-16

    In our previous study [J. Yang, L. Jia, L. Yin, J. Yu, Z. Shi, Q. Fang, A. Cao, Macromol. Biosci. 2004, 4, 1092.], new biodegradable copolymers of diblock methoxy poly(ethylene glycol)-block-poly(epsilon-caprolactone) and methoxy poly(ethylene glycol)-block-poly(delta-valerolactone), and triblock poly(epsilon-caprolactone)-block-poly(ethylene glycol)-block-poly(epsilon-caprolactone) and poly(delta-valerolactone)-block-poly(ethylene glycol)-block-poly(delta-valero-lactone) bearing narrow molecular weight distributions and well-defined block architectures were reported to be prepared with our original aluminum metal complex templates. This work will continue to report new investigations on their water solubility, and reversible thermal responsive micellization and solution to gel transition in distilled water. Among the new synthesized copolymers (P1-P23), seven diblock or triblock samples (P3, P6, P7, P11, P12, P19, and P21) with higher hydrophilic building block populations were revealed to be water soluble under ambient temperature. By means of UV spectrophotometer attached with a thermostat, important parameters as critical micellization mass concentrations (CMCs) and critical micellization temperatures (CMTs) were characterized for these new amphiphile dilute aqueous solution with the aid of an lipophilic organic dye probe of 1,6-diphenyl-1,3,5-hexatriene (DPH). Furthermore, the critical gelation temperatures (CGTs) were simultaneously investigated for these water-soluble block copolymers via a tube tilting method. It was found that the CMC, CMT, and CGT were strongly affected by the population and nature of the hydrophobic building blocks, and a higher hydrophobicity of the new amphiphilic block copolymer finally led to lower CMC and CMT, and higher CGT. In addition, the salts of KBr and NaCl were found to play as a salt-out effect on the solution to gel transition for the diblock P6 and triblock P11, exhibiting an interesting tunable gelation temperature close

  14. Development of flexible LEO-resistant PI films for space applications using a self-healing mechanism by surface-directed phase separation of block copolymers.

    PubMed

    Fischer, Hartmut R; Tempelaars, Karin; Kerpershoek, Aat; Dingemans, Theo; Iqbal, M; Lonkhuyzen, Henk van; Iwanowsky, Boris; Semprimoschnig, Christopher

    2010-08-01

    Polimide-block-polydimethylsiloxane (PI-b-PDMS) block copolymers have been synthesized from commercially available amino-terminated polysiloxanes with different molecular weights, for use as polymeric materials resistant to the low earth orbit (LEO) space environment. A structural optimization with respect to maximum environmental protection has been performed by varying the PDMS block length as well as the architecture of the block copolymers spanning from multiblock to triblock and star-shaped morphologies. The synthesized polymers and casted films show good mechanical and thermal performance. For block copolymers with a load of 2% PDMS (in the case of the multiblock copolymers), a complete surface coverage of the PDMS has been found. It has been shown that the transfer of the surface enriched PDMS layer into a thin silica layer after atomic oxygen (AO) exposure results in a drastic decrease in AO erosion rate. The silica layer protects the underlying material from oxygen initiated erosion resulting in a drastic decrease of surface roughness. This phenomena is observable for loads as small as 6 wt % PDMS. PMID:20690681

  15. Skin delivery by block copolymer nanoparticles (block copolymer micelles).

    PubMed

    Laredj-Bourezg, Faiza; Bolzinger, Marie-Alexandrine; Pelletier, Jocelyne; Valour, Jean-Pierre; Rovère, Marie-Rose; Smatti, Batoule; Chevalier, Yves

    2015-12-30

    Block copolymer nanoparticles often referred to as "block copolymer micelles" have been assessed as carriers for skin delivery of hydrophobic drugs. Such carriers are based on organic biocompatible and biodegradable materials loaded with hydrophobic drugs: poly(lactide)-block-poly(ethylene glycol) copolymer (PLA-b-PEG) nanoparticles that have a solid hydrophobic core made of glassy poly(d,l-lactide), and poly(caprolactone)-block-poly(ethylene glycol) copolymer (PCL-b-PEG) nanoparticles having a liquid core of polycaprolactone. In vitro skin absorption of all-trans retinol showed a large accumulation of retinol in stratum corneum from both block copolymer nanoparticles, higher by a factor 20 than Polysorbate 80 surfactant micelles and by a factor 80 than oil solution. Additionally, skin absorption from PLA-b-PEG nanoparticles was higher by one order of magnitude than PCL-b-PEG, although their sizes (65nm) and external surface (water-swollen PEG layer) were identical as revealed by detailed structural characterizations. Fluorescence microscopy of histological skin sections provided a non-destructive picture of the storage of Nile Red inside stratum corneum, epidermis and dermis. Though particle cores had a different physical states (solid or liquid as measured by (1)H NMR), the ability of nanoparticles for solubilization of the drug assessed from their Hildebrand solubility parameters appeared the parameter of best relevance regarding skin absorption. PMID:26602293

  16. Precise sequence control in linear and cyclic copolymers of 2,5-bis(2-thienyl)pyrrole and aniline by DNA-programmed assembly.

    PubMed

    Chen, Wen; Schuster, Gary B

    2013-03-20

    A series of linear and cyclic, sequence controlled, DNA-conjoined copolymers of aniline (ANi) and 2,5-bis(2-thienyl)pyrrole (SNS) were synthesized. In one approach, linear copolymers were prepared from complementary DNA oligomers containing covalently attached SNS and ANi monomers. Hybridization of the oligomers aligns the monomers in the major groove of the DNA. Treatment of the SNS- and ANi-containing duplexes with horseradish peroxidase (HRP) and H2O2 causes rapid and efficient polymerization. In this way, linear copolymers (SNS)4(ANi)6 and (ANi)2(SNS)2(ANi)2(SNS)2(ANi)2 were prepared and analyzed. A second approach to the preparation of linear and cyclic copolymers of ANi and SNS employed a DNA encoded module strategy. In this approach, single-stranded DNA oligomers composed of a central region containing (SNS)6 or (ANi)5 covalently attached monomer blocks and flanking 5'- and 3'-single-strand DNA recognition sequences were combined in buffer solution. Self-assembly of these oligomers by Watson-Crick base pairing of the recognition sequences creates linear or cyclic arrays of SNS and ANi monomer blocks. Treatment of these arrays with HRP/H2O2 causes rapid and efficient polymerization to form copolymers having patterns such as cyclic BBA and linear ABA, where B stands for an (SNS)6 block and A stands for an (ANi)5 block. These DNA-conjoined copolymers were characterized by melting temperature analysis, circular dichroism spectroscopy, native and denaturing polyacrylamide gel electrophoresis, and UV-visible-near-IR optical spectroscopy. The optical spectra of these copolymers are typical of those of conducting polymers and are uniquely dependent on the specific order of monomers in the copolymer. PMID:23448549

  17. Water deficit effect on ABA accumulation in leaves of two Phaseolus species that differ in drought tolerance

    SciTech Connect

    Janssen, M.G.; Markhart, A.H. )

    1991-05-01

    Phaseolus acutifolius Gray (Pa) is regarded as a dehydration postponer and has stomata that are more sensitive to low leaf water potential than P. vulgaris L. (Pv). This study was designed to determine if the greater sensitivity of Pa stomata is related to greater ABA concentration in Pa or to a greater sensitivity of Pa stomata to ABA. To test these hypotheses bulk leaf ABA accumulation was measured and the sensitivity to ABA was monitored using epidermal strips. To determine if part of the ABA accumulated in the leaves is produced in the roots a novel detached leaf system was used. Stomatal behavior and ABA accumulation at low leaf water potential was monitored and compared to intact leaves. The results of these experiments and the usefulness of the detached leaf system are discussed.

  18. Root water potential integrates discrete soil physical properties to influence ABA signalling during partial rootzone drying.

    PubMed

    Dodd, Ian C; Egea, Gregorio; Watts, Chris W; Whalley, W Richard

    2010-08-01

    To investigate the influence of different growing substrates (two mineral, two organic) on root xylem ABA concentration ([ABA](root)) and the contribution of the drying root system to total sap flow during partial rootzone drying (PRD), sunflower (Helianthus annuus L.) shoots were grafted onto the root systems of two plants grown in separate pots. Sap flow through each hypocotyl was measured below the graft union when one pot ('wet') was watered and other ('dry') was not. Each substrate gave unique relationships between dry pot matric potential (Psi(soil)), volumetric water content ((v)) or penetrometer resistance (Q) and either the fraction of photoperiod sap flow from roots in drying soil or [ABA](root). However, decreased relative sap flow, and increased [ABA](root), from roots in drying soil varied with root water potential (Psi(root)) more similarly across a range of substrates. The gradient between Psi(soil) and Psi(root) was greater in substrates with high sand or peat proportions, which may have contributed to a more sensitive response of [ABA](root) to Psi(soil) in these substrates. Whole plant transpiration was most closely correlated with the mean Psi(soil) of both pots, and then with detached leaf xylem ABA concentration. Although Psi(root) best predicted decreased relative sap flow, and increased [ABA](root), from roots in drying soil across a range of substrates, the inaccessibility of this variable in field studies requires a better understanding of how measurable soil variables (Psi(soil), (v), Q) affect Psi(root). PMID:20591896

  19. Amplification of ABA biosynthesis and signaling through a positive feedback mechanism in seeds.

    PubMed

    Nonogaki, Mariko; Sall, Khadidiatou; Nambara, Eiji; Nonogaki, Hiroyuki

    2014-05-01

    Abscisic acid is an essential hormone for seed dormancy. Our previous study using the plant gene switch system, a chemically induced gene expression system, demonstrated that induction of 9-cis-epoxycarotenoid dioxygenase (NCED), a rate-limiting ABA biosynthesis gene, was sufficient to suppress germination in imbibed Arabidopsis seeds. Here, we report development of an efficient experimental system that causes amplification of NCED expression during seed maturation. The system was created with a Triticum aestivum promoter containing ABA responsive elements (ABREs) and a Sorghum bicolor NCED to cause ABA-stimulated ABA biosynthesis and signaling, through a positive feedback mechanism. The chimeric gene pABRE:NCED enhanced NCED and ABF (ABRE-binding factor) expression in Arabidopsis Columbia-0 seeds, which caused 9- to 73-fold increases in ABA levels. The pABRE:NCED seeds exhibited unusually deep dormancy which lasted for more than 3 months. Interestingly, the amplified ABA pathways also caused enhanced expression of Arabidopsis NCED5, revealing the presence of positive feedback in the native system. These results demonstrated the robustness of positive feedback mechanisms and the significance of NCED expression, or single metabolic change, during seed maturation. The pABRE:NCED system provides an excellent experimental system producing dormant and non-dormant seeds of the same maternal origin, which differ only in zygotic ABA. The pABRE:NCED seeds contain a GFP marker which enables seed sorting between transgenic and null segregants and are ideal for comparative analysis. In addition to its utility in basic research, the system can also be applied to prevention of pre-harvest sprouting during crop production, and therefore contributes to translational biology. PMID:24520869

  20. Unique Drought Resistance Functions of the Highly ABA-Induced Clade A Protein Phosphatase 2Cs1[W][OA

    PubMed Central

    Bhaskara, Govinal Badiger; Nguyen, Thao Thi; Verslues, Paul E.

    2012-01-01

    Six Arabidopsis (Arabidopsis thaliana) clade A protein phosphatase 2Cs (PP2Cs) have established abscisic acid (ABA) signaling roles; however, phenotypic roles of the remaining three “HAI” PP2Cs, Highly ABA-Induced1 (HAI1), AKT1-Interacting PP2C1/HAI2, and HAI3, have remained unclear. HAI PP2C mutants had enhanced proline and osmoregulatory solute accumulation at low water potential, while mutants of other clade A PP2Cs had no or lesser effect on these drought resistance traits. hai1-2 also had increased expression of abiotic stress-associated genes, including dehydrins and late embryogenesis abundant proteins, but decreased expression of several defense-related genes. Conversely, the HAI PP2Cs had relatively less impact on several ABA sensitivity phenotypes. HAI PP2C single mutants were unaffected in ABA sensitivity, while double and triple mutants were moderately hypersensitive in postgermination ABA response but ABA insensitive in germination. The HAI PP2Cs interacted most strongly with PYL5 and PYL7 to -10 of the PYL/RCAR ABA receptor family, with PYL7 to -10 interactions being relatively little affected by ABA in yeast two-hybrid assays. HAI1 had especially limited PYL interaction. Reduced expression of the main HAI1-interacting PYLs at low water potential when HAI1 expression was strongly induced also suggests limited PYL regulation and a role of HAI1 activity in negatively regulating specific drought resistance phenotypes. Overall, the HAI PP2Cs had greatest effect on ABA-independent low water potential phenotypes and lesser effect on classical ABA sensitivity phenotypes. Both this and their distinct PYL interaction demonstrate a new level of functional differentiation among the clade A PP2Cs and a point of cross talk between ABA-dependent and ABA-independent drought-associated signaling. PMID:22829320

  1. ZmABA2, an interacting protein of ZmMPK5, is involved in abscisic acid biosynthesis and functions.

    PubMed

    Ma, Fangfang; Ni, Lan; Liu, Libo; Li, Xi; Zhang, Huan; Zhang, Aying; Tan, Mingpu; Jiang, Mingyi

    2016-02-01

    In maize (Zea mays), the mitogen-activated protein kinase ZmMPK5 has been shown to be involved in abscisic acid (ABA)-induced antioxidant defence and to enhance the tolerance of plants to drought, salt stress and oxidative stress. However, the underlying molecular mechanisms are poorly understood. Here, using ZmMPK5 as bait in yeast two-hybrid screening, a protein interacting with ZmMPK5 named ZmABA2, which belongs to a member of the short-chain dehydrogenase/reductase family, was identified. Pull-down assay and bimolecular fluorescence complementation analysis and co-immunoprecipitation test confirmed that ZmMPK5 interacts with ZmABA2 in vitro and in vivo. Phosphorylation of Ser173 in ZmABA2 by ZmMPK5 was shown to increase the activity of ZmABA2 and the protein stability. Various abiotic stimuli induced the expression of ZmABA2 in leaves of maize plants. Pharmacological, biochemical and molecular biology and genetic analyses showed that both ZmMPK5 and ZmABA2 coordinately regulate the content of ABA. Overexpression of ZmABA2 in tobacco plants was found to elevate the content of ABA, regulate seed germination and root growth under drought and salt stress and enhance the tolerance of tobacco plants to drought and salt stress. These results suggest that ZmABA2 is a direct target of ZmMPK5 and is involved in ABA biosynthesis and functions. PMID:26096642

  2. Novel Variants of AbaR Resistance Islands with a Common Backbone in Acinetobacter baumannii Isolates of European Clone II

    PubMed Central

    Povilonis, Justas; Sužiedėlienė, Edita

    2012-01-01

    In this study, the genetic organization of three novel genomic antibiotic resistance islands (AbaRs) in Acinetobacter baumannii isolates belonging to group of European clone II (EC II) comM integrated sequences of 18-, 21-, and 23-kb resistance islands were determined. These resistance islands carry the backbone of AbaR-type transposon structures, which are composed of the transposition module coding for potential transposition proteins and other genes coding for the intact universal stress protein (uspA), sulfate permease (sul), and proteins of unknown function. The antibiotic resistance genes strA, strB, tetB, and tetR and insertion sequence CR2 element were found to be inserted into the AbaR transposons. GenBank homology searches indicated that they are closely related to the AbaR sequences found integrated in comM in strains of EC II (A. baumannii strains 1656-2 and TCDC-AB0715) and AbaR4 integrated in another location of A. baumannii AB0057 (EC I). All of the AbaRs showed structural similarity to the previously described AbaR4 island and share a 12,008-bp backbone. AbaRs contain Tn1213, Tn2006, and the multiple fragments which could be derived from transposons Tn3, Tn10, Tn21, Tn1000, Tn5393, and Tn6020, the insertion sequences IS26, ISAba1, ISAba14, and ISCR2, and the class 1 integron. Moreover, chromosomal DNA was inserted into distinct regions of the AbaR backbone. Sequence analysis suggested that the AbaR-type transposons have evolved through insertions, deletions, and homologous recombination. AbaR islands, sharing the core structure similar to AbaR4, appeared to be distributed in isolates of EC I and EC II via integration into distinct genomic sites, i.e., pho and comM, respectively. PMID:22290980

  3. Imide/arylene ether copolymers. I

    NASA Technical Reports Server (NTRS)

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

    1991-01-01

    The preparation of a series of novel imide/arylene ether copolymers is described together with the results of viscosity and DSC Tg(Tm) measurements. The copolymers were synthesized from an arylene ether block and either an amorphous or semicrystalline imide block. One block copolymer was end-capped, and the molecular weight was controlled to improve compression moldability. The paper also presents results of mechanical properties tests on copolymer samples.

  4. Quantitative iTRAQ-based proteomic analysis of phosphoproteins and ABA-regulated phosphoproteins in maize leaves under osmotic stress

    PubMed Central

    Hu, Xiuli; Li, Nana; Wu, Liuji; Li, Chunqi; Li, Chaohai; Zhang, Li; Liu, Tianxue; Wang, Wei

    2015-01-01

    Abscisic acid (ABA) regulates various developmental processes and stress responses in plants. Protein phosphorylation/dephosphorylation is a central post-translational modification (PTM) in ABA signaling. However, the phosphoproteins regulated by ABA under osmotic stress remain unknown in maize. In this study, maize mutant vp5 (deficient in ABA biosynthesis) and wild-type Vp5 were used to identify leaf phosphoproteins regulated by ABA under osmotic stress. Up to 4052 phosphopeptides, corresponding to 3017 phosphoproteins, were identified by Multiplex run iTRAQ-based quantitative proteomic and LC-MS/MS methods. The 4052 phosphopeptides contained 5723 non-redundant phosphosites; 512 phosphopeptides (379 in Vp5, 133 in vp5) displayed at least a 1.5-fold change of phosphorylation level under osmotic stress, of which 40 shared common in both genotypes and were differentially regulated by ABA. Comparing the signaling pathways involved in vp5 response to osmotic stress and those that in Vp5, indicated that ABA played a vital role in regulating these pathways related to mRNA synthesis, protein synthesis and photosynthesis. Our results provide a comprehensive dataset of phosphopeptides and phosphorylation sites regulated by ABA in maize adaptation to osmotic stress. This will be helpful to elucidate the ABA-mediate mechanism of maize endurance to drought by triggering phosphorylation or dephosphorylation cascades. PMID:26503333

  5. Identification of ICE1 as a negative regulator of ABA-dependent pathways in seeds and seedlings of Arabidopsis.

    PubMed

    Liang, Ching-Hsing; Yang, Chien-Chih

    2015-07-01

    Inducer of CBF expression 1 (ICE1) mediates the cold stress signal via an abscisic acid (ABA)-independent pathway. A possible role of ICE1 in ABA-dependent pathways was examined in this study. Seedling growth was severely reduced in a T-DNA insertion mutant of ICE1, ice1-2, when grown on 1/2 MS medium lacking sugars, but was restored to wild-type (WT) levels by supplementation with 56 mM glucose. In addition to this sugar-dependent phenotype, germination and establishment of ice1-2 were more sensitive to high glucose concentrations than in the WT. Hypersensitivity to ABA was also observed in ice1-2, suggesting its sensitivity to glucose might be mediated through the ABA signaling pathway. Glucose and ABA induced much higher expression of two genes related to ABA signal transduction, ABA-INSENSITIVE 3 (ABI3) and ABA-INSENSITIVE 4 (ABI4), in ice1-2 than in the WT during establishment. In summary, in addition to its known roles in regulating cold responses, stomatal development, and endosperm breakdown, ICE1 is a negative regulator of ABA-dependent responses. PMID:26048037

  6. Degradation of the ABA co-receptor ABI1 by PUB12/13 U-box E3 ligases

    PubMed Central

    Kong, Lingyao; Cheng, Jinkui; Zhu, Yujuan; Ding, Yanglin; Meng, Jingjing; Chen, Zhizhong; Xie, Qi; Guo, Yan; Li, Jigang; Yang, Shuhua; Gong, Zhizhong

    2015-01-01

    Clade A protein phosphatase 2Cs (PP2Cs) are abscisic acid (ABA) co-receptors that block ABA signalling by inhibiting the downstream protein kinases. ABA signalling is activated after PP2Cs are inhibited by ABA-bound PYR/PYL/RCAR ABA receptors (PYLs) in Arabidopsis. However, whether these PP2Cs are regulated by other factors remains unknown. Here, we report that ABI1 (ABA-INSENSITIVE 1) can interact with the U-box E3 ligases PUB12 and PUB13, but is ubiquitinated only when it interacts with ABA receptors in an in vitro assay. A mutant form of ABI1-1 that is unable to interact with PYLs is more stable than the wild-type protein. Both ABI1 degradation and all tested ABA responses are reduced in pub12 pub13 mutants compared with the wild type. Introducing the abi1-3 loss-of-function mutation into pub12 pub13 mutant recovers the ABA-insensitive phenotypes of the pub12 pub13 mutant. We thus uncover an important regulatory mechanism for regulating ABI1 levels by PUB12 and PUB13. PMID:26482222

  7. GEM, a member of the GRAM domain family of proteins, is part of the ABA signaling pathway

    PubMed Central

    Mauri, Nuria; Fernández-Marcos, María; Costas, Celina; Desvoyes, Bénédicte; Pichel, Antonio; Caro, Elena; Gutierrez, Crisanto

    2016-01-01

    Abscisic acid (ABA) is fundamental for plant development. Multiple factors have been identified that participate in the ABA signaling network, although a role of many proteins still await to be demonstrated. Here we have investigated the role of GEM (GL2 EXPRESSION MODULATOR), originally annotated as an ABA-responsive protein. GEM contains a GRAM domain, a feature shared with other eight Arabidopsis proteins for which we propose the name of GRE (GEM-RELATED) proteins. We found that (i) GEM expression responds to ABA, (ii) its promoter contains ABRE sites required for ABA response, and (iii) GEM expression depends on members of the ABA signaling pathway. This is consistent with the expression pattern of GEM during development in plant locations were ABA is known to play a direct role. We also found that GEM binds various phospholipids, e.g. mono and diphosphates and phosphatidic acid, suggesting a potential link of GEM with membrane-associated processes. Consistent with this, we found that the phosphoinositol-4-phosphate kinase PIP5K9 binds GEM in vivo. Finally, we demonstrated a role of GEM in seed dormancy. Together, our data led us to propose that GEM is an ABA-responsive protein that may function downstream of ABI5 as part of the ABA signaling pathway. PMID:26939893

  8. GEM, a member of the GRAM domain family of proteins, is part of the ABA signaling pathway.

    PubMed

    Mauri, Nuria; Fernández-Marcos, María; Costas, Celina; Desvoyes, Bénédicte; Pichel, Antonio; Caro, Elena; Gutierrez, Crisanto

    2016-01-01

    Abscisic acid (ABA) is fundamental for plant development. Multiple factors have been identified that participate in the ABA signaling network, although a role of many proteins still await to be demonstrated. Here we have investigated the role of GEM (GL2 EXPRESSION MODULATOR), originally annotated as an ABA-responsive protein. GEM contains a GRAM domain, a feature shared with other eight Arabidopsis proteins for which we propose the name of GRE (GEM-RELATED) proteins. We found that (i) GEM expression responds to ABA, (ii) its promoter contains ABRE sites required for ABA response, and (iii) GEM expression depends on members of the ABA signaling pathway. This is consistent with the expression pattern of GEM during development in plant locations were ABA is known to play a direct role. We also found that GEM binds various phospholipids, e.g. mono and diphosphates and phosphatidic acid, suggesting a potential link of GEM with membrane-associated processes. Consistent with this, we found that the phosphoinositol-4-phosphate kinase PIP5K9 binds GEM in vivo. Finally, we demonstrated a role of GEM in seed dormancy. Together, our data led us to propose that GEM is an ABA-responsive protein that may function downstream of ABI5 as part of the ABA signaling pathway. PMID:26939893

  9. Interactions between soybean ABA receptors and type 2C protein phosphatases

    PubMed Central

    Ha, Si; Yang, Fen; Ma, Jun; Gao, Xiao-Su; Wang, Zhi-Min; Zhu, Jian-Kang

    2013-01-01

    The plant hormone abscisic acid (ABA) plays important roles in regulating plant growth, development, and responses to environmental stresses. Proteins in the PYR/PYL/RCAR family (hereafter referred to as PYLs) are known as ABA receptors. Since most studies thus far have focused on Arabidopsis PYLs, little is known about PYL homologs in crop plants. We report here the characterization of 21 PYL homologs (GmPYLs) in soybean. Twenty three putative GmPYLs can be found from soybean genome sequence and categorized into three subgroups. GmPYLs interact with AtABI1 and two GmPP2Cs in diverse manners. A lot of the subgroup I GmPYLs interact with PP2Cs in an ABA-dependent manner, whereas most of the subgroup II and III GmPYLs bind to PP2Cs in an ABA-independent manner. The subgroup III GmPYL23, which cannot interact with any of the tested PP2Cs, differs from other GmPYLs. The CL2/gate domain is crucial for GmPYLs-PP2Cs interaction, and a mutation in the conserved proline (P109S) abolishes the interaction between GmPYL1 and AtABI1. Furthermore, the ABA dependence of GmPYLs-PP2Cs interactions are partially correlated with two amino acid residues preceding the CL2/gate domain of GmPYLs. We also show that GmPYL1 interacts with AtABI1 in an ABA-dependent manner in plant cells. Three GmPYLs differentially inhibit AtABI1 and GmPP2C1 in an ABA-dependent or -enhanced manner in vitro. In addition, ectopically expressing GmPYL1 partially restores ABA sensitivity of the Arabidopsis triple mutant pyr1/pyl1/pyl4. Taken together, our results suggest that soybean GmPYLs are ABA receptors that function by interacting and inhibiting PP2Cs. PMID:23934343

  10. Copolymers For Capillary Gel Electrophoresis

    DOEpatents

    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.

  11. Grafting cucumber onto luffa improves drought tolerance by increasing ABA biosynthesis and sensitivity

    PubMed Central

    Liu, Shanshan; Li, Hao; Lv, Xiangzhang; Ahammed, Golam Jalal; Xia, Xiaojian; Zhou, Jie; Shi, Kai; Asami, Tadao; Yu, Jingquan; Zhou, Yanhong

    2016-01-01

    Balancing stomata-dependent CO2 assimilation and transpiration is a key challenge for increasing crop productivity and water use efficiency under drought stress for sustainable crop production worldwide. Here, we show that cucumber and luffa plants with luffa as rootstock have intrinsically increased water use efficiency, decreased transpiration rate and less affected CO2 assimilation capacity following drought stress over those with cucumber as rootstock. Drought accelerated abscisic acid (ABA) accumulation in roots, xylem sap and leaves, and induced the transcript of ABA signaling genes, leading to a decreased stomatal aperture and transpiration in the plants grafted onto luffa roots as compared to plants grafted onto cucumber roots. Furthermore, stomatal movement in the plants grafted onto luffa roots had an increased sensitivity to ABA. Inhibition of ABA biosynthesis in luffa roots decreased the drought tolerance in cucumber and luffa plants. Our study demonstrates that the roots of luffa have developed an enhanced ability to sense the changes in root-zone moisture and could eventually deliver modest level of ABA from roots to shoots that enhances water use efficiency under drought stress. Such a mechanism could be greatly exploited to benefit the agricultural production especially in arid and semi-arid areas. PMID:26832070

  12. Arabidopsis COP1-interacting protein 1 is a positive regulator of ABA response.

    PubMed

    Ren, Chenxia; Zhu, Xili; Zhang, Pingping; Gong, Qingqiu

    2016-09-01

    COP1-interacting protein 1 (CIP1, At5g41790) was the first reported interacting protein for CONSTITUTIVE PHOTOMORPHOGENIC 1 (COP1) of Arabidopsis; however its physiological function has remained unknown for two decades. Here we show that CIP1 is a positive regulator of abscisic acid (ABA) response. CIP1 is mainly expressed in the photosynthetic cells and the vascular tissue, and its promoter activity can be induced by osmotic stress and ABA. The CIP1 protein is localized to the plasma membrane. A T-DNA insertion mutant cip1-1 was then characterized. The mutant is sensitive to osmotic stress and has ABA insensitive phenotypes. RNA sequencing showed that cip1-1 has lower levels of gene expression in abiotic stress response compared with the wild-type. Meanwhile, transcript levels of ABA biosynthesis genes are higher in cip1-1 than in the wild-type. These results suggested that CIP1 is positively involved in ABA response. PMID:27372427

  13. New fava bean guard cell signaling mutant impaired in ABA-induced stomatal closure.

    PubMed

    Iwai, Sumio; Shimomura, Naoki; Nakashima, Atsushi; Etoh, Takeomi

    2003-09-01

    We isolated a mutant from Vicia faba L. cv. House Ryousai. It wilts easily under strong light and high temperature conditions, suggesting that its stomatal movement may be disturbed. We determined responses of mutant guard cells to some environmental stimuli. Mutant guard cells demonstrated an impaired ability to respond to ABA in 0.1 mM CaCl(2) and stomata did not close in the presence of up to 1 mM ABA, whereas wild-type stomata closed when exposed to 10 micro M ABA. Elevating external Ca(2+) caused a similar degree of stomatal closure in the wild type and the mutant. A high concentration of CO(2) (700 micro l liter(-1)) induced stomatal closure in the wild type, but not in the mutant. On the basis of these results, we propose the working hypothesis that the mutation occurs in the region downstream of CO(2) and ABA sensing and in the region upstream of Ca(2+) elevation. The mutant is named fia (fava bean impaired in ABA-induced stomatal closure). PMID:14519772

  14. Engineering the ABA Plant Stress Pathway for Regulation of Induced Proximity

    PubMed Central

    Liang, Fu-Sen; Ho, Wen Qi; Crabtree, Gerald R.

    2011-01-01

    Chemically induced proximity (CIP) systems use small molecules and engineered proteins to control and study biological processes. However, small molecule–based systems for controlling protein abundance or activities have been limited by toxicity, instability, cost, and slow clearance of the small molecules in vivo. To address these problems, we modified proteins of the plant abscisic acid (ABA) stress response pathway to control the proximity of cellular proteins and showed that the system could be used to regulate transcription, signal transduction, and subcellular localization of proteins in response to exogenously applied ABA. We also showed that the ABA CIP system can be combined with other CIP systems to simultaneously control multiple processes. We found that, when given to mice, ABA was orally available and had a 4-hour half-life. These properties, along with its lack of toxicity and low cost, suggest that ABA may be well suited for therapeutic applications and as an experimental tool to control diverse cellular activities in vivo. PMID:21406691

  15. Azospirillum brasilense ameliorates the response of Arabidopsis thaliana to drought mainly via enhancement of ABA levels.

    PubMed

    Cohen, Ana C; Bottini, Rubén; Pontin, Mariela; Berli, Federico J; Moreno, Daniela; Boccanlandro, Hernán; Travaglia, Claudia N; Piccoli, Patricia N

    2015-01-01

    Production of phytohormones is one of the main mechanisms to explain the beneficial effects of plant growth-promoting rhizobacteria (PGPR) such as Azospirillum sp. The PGPRs induce plant growth and development, and reduce stress susceptibility. However, little is known regarding the stress-related phytohormone abscisic acid (ABA) produced by bacteria. We investigated the effects of Azospirillum brasilense Sp 245 strain on Arabidopsis thaliana Col-0 and aba2-1 mutant plants, evaluating the morphophysiological and biochemical responses when watered and in drought. We used an in vitro-grown system to study changes in the root volume and architecture after inoculation with Azospirillum in Arabidopsis wild-type Col-0 and on the mutant aba2-1, during early growth. To examine Arabidopsis development and reproductive success as affected by the bacteria, ABA and drought, a pot experiment using Arabidopsis Col-0 plants was also carried out. Azospirillum brasilense augmented plant biomass, altered root architecture by increasing lateral roots number, stimulated photosynthetic and photoprotective pigments and retarded water loss in correlation with incremented ABA levels. As well, inoculation improved plants seed yield, plants survival, proline levels and relative leaf water content; it also decreased stomatal conductance, malondialdehyde and relative soil water content in plants submitted to drought. Arabidopsis inoculation with A. brasilense improved plants performance, especially in drought. PMID:24796562

  16. Isolation and characterization of an osmotic stress and ABA induced histone deacetylase in Arachis hygogaea

    PubMed Central

    Su, Liang-Chen; Deng, Bin; Liu, Shuai; Li, Li-Mei; Hu, Bo; Zhong, Yu-Ting; Li, Ling

    2015-01-01

    Histone acetylation, which together with histone methylation regulates gene activity in response to stress, is an important epigenetic modification. There is an increasing research focus on histone acetylation in crops, but there is no information to date in peanut (Arachis hypogaea). We showed that osmotic stress and ABA affect the acetylation of histone H3 loci in peanut seedlings by immunoblotting experiments. Using RNA-seq data for peanut, we found a RPD3/HDA1-like superfamily histone deacetylase (HDAC), termed AhHDA1, whose gene is up-regulated by PEG-induced water limitation and ABA signaling. We isolated and characterized AhHDA1 from A. hypogaea, showing that AhHDA1 is very similar to an Arabidopsis HDAC (AtHDA6) and, in recombinant form, possesses HDAC activity. To understand whether and how osmotic stress and ABA mediate the peanut stress response by epigenetics, the expression of AhHDA1 and stress-responsive genes following treatment with PEG, ABA, and the specific HDAC inhibitor trichostatin A (TSA) were analyzed. AhHDA1 transcript levels were enhanced by all three treatments, as was expression of peanut transcription factor genes, indicating that AhHDA1 might be involved in the epigenetic regulation of stress resistance genes that comprise the responses to osmotic stress and ABA. PMID:26217363

  17. Integration of C/N-nutrient and multiple environmental signals into the ABA signaling cascade

    PubMed Central

    Lu, Yu; Yamaguchi, Junji; Sato, Takeo

    2015-01-01

    Due to their immobility, plants have developed sophisticated mechanisms to robustly monitor and appropriately respond to dynamic changes in nutrient availability. Carbon (C) and nitrogen (N) are especially important in regulating plant metabolism and development, thereby affecting crop productivity. In addition to their independent utilization, the ratio of C to N metabolites in the cell, referred to as the “C/N balance”, is important for the regulation of plant growth, although molecular mechanisms mediating C/N signaling remain unclear. Recently ABI1, a protein phosphatase type 2C (PP2C), was shown to be a regulator of C/N response in Arabidopsis plants. ABI1 functions as a negative regulator of abscisic acid (ABA) signal transduction. ABA is versatile phytohormone that regulates multiple aspects of plant growth and adaptation to environmental stress. This review highlights the regulation of the C/N response mediated by a non-canonical ABA signaling pathway that is independent of ABA biosynthesis, as well as recent findings on the direct crosstalk between multiple cellular signals and the ABA signaling cascade. PMID:26786013

  18. Grafting cucumber onto luffa improves drought tolerance by increasing ABA biosynthesis and sensitivity.

    PubMed

    Liu, Shanshan; Li, Hao; Lv, Xiangzhang; Ahammed, Golam Jalal; Xia, Xiaojian; Zhou, Jie; Shi, Kai; Asami, Tadao; Yu, Jingquan; Zhou, Yanhong

    2016-01-01

    Balancing stomata-dependent CO2 assimilation and transpiration is a key challenge for increasing crop productivity and water use efficiency under drought stress for sustainable crop production worldwide. Here, we show that cucumber and luffa plants with luffa as rootstock have intrinsically increased water use efficiency, decreased transpiration rate and less affected CO2 assimilation capacity following drought stress over those with cucumber as rootstock. Drought accelerated abscisic acid (ABA) accumulation in roots, xylem sap and leaves, and induced the transcript of ABA signaling genes, leading to a decreased stomatal aperture and transpiration in the plants grafted onto luffa roots as compared to plants grafted onto cucumber roots. Furthermore, stomatal movement in the plants grafted onto luffa roots had an increased sensitivity to ABA. Inhibition of ABA biosynthesis in luffa roots decreased the drought tolerance in cucumber and luffa plants. Our study demonstrates that the roots of luffa have developed an enhanced ability to sense the changes in root-zone moisture and could eventually deliver modest level of ABA from roots to shoots that enhances water use efficiency under drought stress. Such a mechanism could be greatly exploited to benefit the agricultural production especially in arid and semi-arid areas. PMID:26832070

  19. Stomatal closure is induced by hydraulic signals and maintained by ABA in drought-stressed grapevine

    PubMed Central

    Tombesi, Sergio; Nardini, Andrea; Frioni, Tommaso; Soccolini, Marta; Zadra, Claudia; Farinelli, Daniela; Poni, Stefano; Palliotti, Alberto

    2015-01-01

    Water saving under drought stress is assured by stomatal closure driven by active (ABA-mediated) and/or passive (hydraulic-mediated) mechanisms. There is currently no comprehensive model nor any general consensus about the actual contribution and relative importance of each of the above factors in modulating stomatal closure in planta. In the present study, we assessed the contribution of passive (hydraulic) vs active (ABA mediated) mechanisms of stomatal closure in V. vinifera plants facing drought stress. Leaf gas exchange decreased progressively to zero during drought, and embolism-induced loss of hydraulic conductance in petioles peaked to ~50% in correspondence with strong daily limitation of stomatal conductance. Foliar ABA significantly increased only after complete stomatal closure had already occurred. Rewatering plants after complete stomatal closure and after foliar ABA reached maximum values did not induced stomatal re-opening, despite embolism recovery and water potential rise. Our data suggest that in grapevine stomatal conductance is primarily regulated by passive hydraulic mechanisms. Foliar ABA apparently limits leaf gas exchange over long-term, also preventing recovery of stomatal aperture upon rewatering, suggesting the occurrence of a mechanism of long-term down-regulation of transpiration to favor embolism repair and preserve water under conditions of fluctuating water availability and repeated drought events. PMID:26207993

  20. Stomatal closure is induced by hydraulic signals and maintained by ABA in drought-stressed grapevine.

    PubMed

    Tombesi, Sergio; Nardini, Andrea; Frioni, Tommaso; Soccolini, Marta; Zadra, Claudia; Farinelli, Daniela; Poni, Stefano; Palliotti, Alberto

    2015-01-01

    Water saving under drought stress is assured by stomatal closure driven by active (ABA-mediated) and/or passive (hydraulic-mediated) mechanisms. There is currently no comprehensive model nor any general consensus about the actual contribution and relative importance of each of the above factors in modulating stomatal closure in planta. In the present study, we assessed the contribution of passive (hydraulic) vs active (ABA mediated) mechanisms of stomatal closure in V. vinifera plants facing drought stress. Leaf gas exchange decreased progressively to zero during drought, and embolism-induced loss of hydraulic conductance in petioles peaked to ~50% in correspondence with strong daily limitation of stomatal conductance. Foliar ABA significantly increased only after complete stomatal closure had already occurred. Rewatering plants after complete stomatal closure and after foliar ABA reached maximum values did not induced stomatal re-opening, despite embolism recovery and water potential rise. Our data suggest that in grapevine stomatal conductance is primarily regulated by passive hydraulic mechanisms. Foliar ABA apparently limits leaf gas exchange over long-term, also preventing recovery of stomatal aperture upon rewatering, suggesting the occurrence of a mechanism of long-term down-regulation of transpiration to favor embolism repair and preserve water under conditions of fluctuating water availability and repeated drought events. PMID:26207993

  1. 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.

  2. Nanostructured Membranes from Triblock Polymer Precursors as High Capacity Copper Adsorbents.

    PubMed

    Weidman, Jacob L; Mulvenna, Ryan A; Boudouris, Bryan W; Phillip, William A

    2015-10-13

    Membrane adsorbers are a proposed alternative to packed beds for chromatographic separations. To date, membrane adsorbers have suffered from low binding capacities and/or complex processing methodologies. In this work, a polyisoprene-b-polystyrene-b-poly(N,N-dimethylacrylamide) (PI-PS-PDMA) triblock polymer is cast into an asymmetric membrane that possesses a high density of nanopores (d ∼ 38 nm) at the upper surface of the membrane. Exposing the membrane to a 6 M aqueous hydrochloric acid solution converts the PDMA brushes that line the pore walls to poly(acrylic acid) (PAA) brushes, which are capable of binding metal ions (e.g., copper ions). Using mass transport tests and static binding experiments, the saturation capacity of the PI-PS-PAA membrane was determined to be 4.1 ± 0.3 mmol Cu(2+) g(-1). This experimental value is consistent with the theoretical binding capacity of the membranes, which is based on the initial PDMA content of the triblock polymer precursor and assumes a 1:1 stoichiometry for the binding interaction. The uniformly sized nanoscale pores provide a short diffusion length to the binding sites, resulting in a sharp breakthrough curve. Furthermore, the membrane is selective for copper ions over nickel ions, which permeate through the membrane over 10 times more rapidly than copper during the loading stage. This selectivity is present despite the fact that the sizes of these two ions are nearly identical and speaks to the chemical selectivity of the triblock polymer-based membrane. Furthermore, addition of a pH 1 solution releases the bound copper rapidly, allowing the membrane to be regenerated and reused with a negligible loss in binding capacity. Because of the high binding capacities, facile processing method implemented, and ability to tailor further the polymer brushes lining the pore walls using straightforward coupling reactions, these membrane adsorbers based on block polymer precursors have potential as a separation media that can

  3. Xylem sap collection and extraction methodologies to determine in vivo concentrations of ABA and its bound forms by gas chromatography-mass spectrometry (GC-MS)

    PubMed Central

    2012-01-01

    Background Accurate quantification of xylem sap ABA concentrations is important to underpin models of root-to-shoot ABA signalling to predict the physiological effects of soil drying. Growing tomato plants in a whole plant pressure chamber allowed sequential xylem sap collection from a detached leaf, the petiole stub of an otherwise intact plant and finally the de-topped root system of the same plant, to determine the impact of xylem sap sampling methodology on xylem ABA concentration. Since xylem sap can contain bound forms of ABA, a novel gas chromatography-mass spectrometry (GC-MS) procedure was developed to chemically separate free ABA from two in planta bound ABA forms known as Adducts I and II and ABA-glucose-ester (ABA-GE). Results Xylem sap ABA concentrations were highly dependent on the sampling methodology used: the highest concentrations were detected in sap collected by applying an overpressure to detached leaves following the measurement of leaf water potential. Irrespective of xylem sap source, the wild-type cultivars Ailsa Craig and Rheinlands Ruhm had higher free ABA concentrations than a range of ABA-deficient mutants (notabilis, flacca and sitiens). However, in the mutants, concentrations of bound forms of ABA were similar to wild-type plants, and similar to free ABA concentrations. Conclusions Although xylem concentrations of these bound ABA forms and ABA-GE suggest they have a limited physiological impact on ABA homeostasis in tomato, the methods developed here will allow a more complete understanding of ABA biochemistry and root-to-shoot signalling in species known to have higher concentrations of these compounds. PMID:22439865

  4. Aquaporins Contribute to ABA-Triggered Stomatal Closure through OST1-Mediated Phosphorylation.

    PubMed

    Grondin, Alexandre; Rodrigues, Olivier; Verdoucq, Lionel; Merlot, Sylvain; Leonhardt, Nathalie; Maurel, Christophe

    2015-07-01

    Stomatal movements in response to environmental stimuli critically control the plant water status. Although these movements are governed by osmotically driven changes in guard cell volume, the role of membrane water channels (aquaporins) has remained hypothetical. Assays in epidermal peels showed that knockout Arabidopsis thaliana plants lacking the Plasma membrane Intrinsic Protein 2;1 (PIP2;1) aquaporin have a defect in stomatal closure, specifically in response to abscisic acid (ABA). ABA induced a 2-fold increase in osmotic water permeability (Pf) of guard cell protoplasts and an accumulation of reactive oxygen species in guard cells, which were both abrogated in pip2;1 plants. Open stomata 1 (OST1)/Snf1-related protein kinase 2.6 (SnRK2.6), a protein kinase involved in guard cell ABA signaling, was able to phosphorylate a cytosolic PIP2;1 peptide at Ser-121. OST1 enhanced PIP2;1 water transport activity when coexpressed in Xenopus laevis oocytes. Upon expression in pip2;1 plants, a phosphomimetic form (Ser121Asp) but not a phosphodeficient form (Ser121Ala) of PIP2;1 constitutively enhanced the Pf of guard cell protoplasts while suppressing its ABA-dependent activation and was able to restore ABA-dependent stomatal closure in pip2;1. This work supports a model whereby ABA-triggered stomatal closure requires an increase in guard cell permeability to water and possibly hydrogen peroxide, through OST1-dependent phosphorylation of PIP2;1 at Ser-121. PMID:26163575

  5. A Role for Arabidopsis miR399f in Salt, Drought, and ABA Signaling

    PubMed Central

    Baek, Dongwon; Chun, Hyun Jin; Kang, Songhwa; Shin, Gilok; Park, Su Jung; Hong, Hyewon; Kim, Chanmin; Kim, Doh Hoon; Lee, Sang Yeol; Kim, Min Chul; Yun, Dae-Jin

    2016-01-01

    MiR399f plays a crucial role in maintaining phosphate homeostasis in Arabidopsis thaliana. Under phosphate starvation conditions, AtMYB2, which plays a role in plant salt and drought stress responses, directly regulates the expression of miR399f. In this study, we found that miR399f also participates in plant responses to abscisic acid (ABA), and to abiotic stresses including salt and drought. Salt and ABA treatment induced the expression of miR399f, as confirmed by histochemical analysis of promoter-GUS fusions. Transgenic Arabidopsis plants overexpressing miR399f (miR399f-OE) exhibited enhanced tolerance to salt stress and exogenous ABA, but hypersensitivity to drought. Our in silico analysis identified ABF3 and CSP41b as putative target genes of miR399f, and expression analysis revealed that mRNA levels of ABF3 and CSP41b decreased remarkably in miR399f-OE plants under salt stress and in response to treatment with ABA. Moreover, we showed that activation of stress-responsive gene expression in response to salt stress and ABA treatment was impaired in miR399f-OE plants. Thus, these results suggested that in addition to phosphate starvation signaling, miR399f might also modulates plant responses to salt, ABA, and drought, by regulating the expression of newly discovered target genes such as ABF3 and CSP41b. PMID:26674968

  6. Nanoparticle-Reinforced Associative Network Hydrogels

    PubMed Central

    Agrawal, Sarvesh K.; Sanabria-DeLong, Naomi; Tew, Gregory N.; Bhatia, Surita R.

    2009-01-01

    ABA triblock copolymers in solvents selective for the midblock are known to form associative micellar gels. We have modified the structure and rheology of ABA triblock copolymer gels comprising poly(lactide)-poly(ethylene oxide)-poly(lactide) (PLA-PEO-PLA) through addition of a clay nanoparticle, laponite. Addition of laponite particles resulted in additional junction points in the gel via adsorption of the PEO corona chains onto the clay surfaces. Rheological measurements showed that this strategy led to a significant enhancement of the gel elastic modulus with small amounts of nanoparticles. Further characterization using SAXS and DLS confirmed that nanoparticles increase the intermicellar attraction and result in aggregation of PLA-PEO-PLA micelles. PMID:18947244

  7. Structure of 5-hydroxymethylcytosine-specific restriction enzyme, AbaSI, in complex with DNA

    SciTech Connect

    Horton, John R.; Borgaro, Janine G.; Griggs, Rose M.; Quimby, Aine; Guan, Shengxi; Zhang, Xing; Wilson, Geoffrey G.; Zheng, Yu; Zhu, Zhenyu; Cheng, Xiaodong

    2014-07-03

    AbaSI, a member of the PvuRts1I-family of modification-dependent restriction endonucleases, cleaves DNA containing 5-hydroxymethylctosine (5hmC) and glucosylated 5hmC (g5hmC), but not DNA containing unmodified cytosine. AbaSI has been used as a tool for mapping the genomic locations of 5hmC, an important epigenetic modification in the DNA of higher organisms. Here we report the crystal structures of AbaSI in the presence and absence of DNA. These structures provide considerable, although incomplete, insight into how this enzyme acts. AbaSI appears to be mainly a homodimer in solution, but interacts with DNA in our structures as a homotetramer. Each AbaSI subunit comprises an N-terminal, Vsr-like, cleavage domain containing a single catalytic site, and a C-terminal, SRA-like, 5hmC-binding domain. Two N-terminal helices mediate most of the homodimer interface. Dimerization brings together the two catalytic sites required for double-strand cleavage, and separates the 5hmC binding-domains by ~ 70 Å, consistent with the known activity of AbaSI which cleaves DNA optimally between symmetrically modified cytosines ~ 22 bp apart. The eukaryotic SET and RING-associated (SRA) domains bind to DNA containing 5-methylcytosine (5mC) in the hemi-methylated CpG sequence. They make contacts in both the major and minor DNA grooves, and flip the modified cytosine out of the helix into a conserved binding pocket. In contrast, the SRA-like domain of AbaSI, which has no sequence specificity, contacts only the minor DNA groove, and in our current structures the 5hmC remains intra-helical. A conserved, binding pocket is nevertheless present in this domain, suitable for accommodating 5hmC and g5hmC. We consider it likely, therefore, that base-flipping is part of the recognition and cleavage mechanism of AbaSI, but that our structures represent an earlier, pre-flipped stage, prior to actual recognition.

  8. 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.

  9. Nanostructured assemblies from amphiphilic ABC multiblock polymers

    NASA Astrophysics Data System (ADS)

    Hillmyer, Marc A.

    2012-02-01

    Amphiphilic AB diblock copolymers containing a water compatible segment can self-assemble in aqueous media to give supramolecular structures that include simple spherical micelles and macromolecular vesicles termed polymersomes. Amphiphilic ABA triblocks with hydrophobic end blocks can adopt analogous structures but can also form gels at high polymer concentrations. The structural and chemical diversity demonstrated in block copolymer micelles and gels makes them attractive for applications ranging from drug delivery to personal care products to nanoreactors. The inclusion of a third block in amphiphilic ABC triblock systems can lead to a much wider array of self-assembled structures that depend not only on composition but also on block sequence, architecture and incompatibility considerations. I will present our recent efforts on tuning micelle and gel structure and behavior using controlled architecture ABC triblocks. The combination of diverse polymer segments into a single macromolecule is a powerful method for development of self-assembled structures with both new form and new function.

  10. Phase behavior and kinetics of disorder-order and order-order transitions in multi-block copolymers in selective solvents

    NASA Astrophysics Data System (ADS)

    Nie, Huifen

    The primary aim of this thesis is to investigate the phase behavior and kinetics of the disorder-order transition (ODT) and the order-order transition (OOT) in block copolymer solutions in selective solvents, using small-angle x-ray scattering (SAXS) and small-angle neutron scattering (SANS) techniques. The kinetics of the ODT and OOT in a triblock of polystyrene (PS) and poly(ethylene-co-butylene) (PEB), in mineral oil, a selective solvent for the middle PEB block, was followed by time-resolved SAXS using temperature ramp and rapid temperature quench techniques. In semi-dilute solutions, spherical micelles exhibited liquid-like ordering at elevated temperatures and ordered onto body-centered-cubic (BCC) lattice at intermediate temperatures. In concentrated solutions, both BCC ordering of spherical micelles and hexagonal packing (HEX) of cylindrical micelles were detected. The disorder to order transformation kinetics exhibit two-stage growth: the first stage reflecting the temperature equilibration and supercooling of the micellar fluid, and the second stage corresponding to the nucleation and growth of the ordered state. The order-order transformation from HEX to BCC was characterized by a continuous shift in the primary peak position and simultaneous growth of all higher order Bragg diffraction peaks in the scattering profiles. The data were interpreted in terms of a model, according to which cylindrical micelles exhibit fluctuations with a characteristic wavelength along the cylindrical axis before breaking up into spherical micelles. Our results show that the wavelength of the fluctuation remains unchanged while the amplitude of the fluctuations grows with time. The association behavior of triblock, pentablock, and heptablock copolymers of polystyrene and polybutadiene in selective solvents was examined by SANS measurement. Comparison of the scattering profiles shows that: (i) multiblock copolymers with the outer block in a poor solvent environment have a

  11. The ABA receptor PYL9 together with PYL8 plays an important role in regulating lateral root growth.

    PubMed

    Xing, Lu; Zhao, Yang; Gao, Jinghui; Xiang, Chengbin; Zhu, Jian-Kang

    2016-01-01

    Abscisic acid is a phytohormone regulating plant growth, development and stress responses. PYR1/PYL/RCAR proteins are ABA receptors that function by inhibiting PP2Cs to activate SnRK2s, resulting in phosphorylation of ABFs and other effectors of ABA response pathways. Exogenous ABA induces growth quiescence of lateral roots, which is prolonged by knockout of the ABA receptor PYL8. Among the 14 members of PYR1/PYL/RCAR protein family, PYL9 is a close relative of PYL8. Here we show that knockout of both PYL9 and PYL8 resulted in a longer ABA-induced quiescence on lateral root growth and a reduced sensitivity to ABA on primary root growth and lateral root formation compared to knockout of PYL8 alone. Induced overexpression of PYL9 promoted the lateral root elongation in the presence of ABA. The prolonged quiescent phase of the pyl8-1pyl9 double mutant was reversed by exogenous IAA. PYL9 may regulate auxin-responsive genes in vivo through direct interaction with MYB77 and MYB44. Thus, PYL9 and PYL8 are both responsible for recovery of lateral root from ABA inhibition via MYB transcription factors. PMID:27256015

  12. The ABA receptor PYL9 together with PYL8 plays an important role in regulating lateral root growth

    PubMed Central

    Xing, Lu; Zhao, Yang; Gao, Jinghui; Xiang, Chengbin; Zhu, Jian-Kang

    2016-01-01

    Abscisic acid is a phytohormone regulating plant growth, development and stress responses. PYR1/PYL/RCAR proteins are ABA receptors that function by inhibiting PP2Cs to activate SnRK2s, resulting in phosphorylation of ABFs and other effectors of ABA response pathways. Exogenous ABA induces growth quiescence of lateral roots, which is prolonged by knockout of the ABA receptor PYL8. Among the 14 members of PYR1/PYL/RCAR protein family, PYL9 is a close relative of PYL8. Here we show that knockout of both PYL9 and PYL8 resulted in a longer ABA-induced quiescence on lateral root growth and a reduced sensitivity to ABA on primary root growth and lateral root formation compared to knockout of PYL8 alone. Induced overexpression of PYL9 promoted the lateral root elongation in the presence of ABA. The prolonged quiescent phase of the pyl8-1pyl9 double mutant was reversed by exogenous IAA. PYL9 may regulate auxin-responsive genes in vivo through direct interaction with MYB77 and MYB44. Thus, PYL9 and PYL8 are both responsible for recovery of lateral root from ABA inhibition via MYB transcription factors. PMID:27256015

  13. The Arabidopsis MIEL1 E3 ligase negatively regulates ABA signalling by promoting protein turnover of MYB96.

    PubMed

    Lee, Hong Gil; Seo, Pil Joon

    2016-01-01

    The phytohormone abscisic acid (ABA) regulates plant responses to various environmental challenges. Controlled protein turnover is an important component of ABA signalling. Here we show that the RING-type E3 ligase MYB30-INTERACTING E3 LIGASE 1 (MIEL1) regulates ABA sensitivity by promoting MYB96 turnover in Arabidopsis. Germination of MIEL1-deficient mutant seeds is hypersensitive to ABA, whereas MIEL1-overexpressing transgenic seeds are less sensitive. MIEL1 can interact with MYB96, a regulator of ABA signalling, and stimulate its ubiquitination and degradation. Genetic analysis shows that MYB96 is epistatic to MIEL1 in the control of ABA sensitivity in seeds. While MIEL1 acts primarily via MYB96 in seed germination, MIEL1 regulates protein turnover of both MYB96 and MYB30 in vegetative tissues. We find that ABA regulates the expression of MYB30-responsive genes during pathogen infection and this regulation is partly dependent on MIEL1. These results suggest that MIEL1 may facilitate crosstalk between ABA and biotic stress signalling. PMID:27615387

  14. Parents' Experiences of Applied Behaviour Analysis (ABA)-Based Interventions for Children Diagnosed with Autistic Spectrum Disorder

    ERIC Educational Resources Information Center

    McPhilemy, Catherine; Dillenburger, Karola

    2013-01-01

    Applied behaviour analysis (ABA)-based programmes are endorsed as the gold standard for treatment of children with autistic spectrum disorder (ASD) in most of North America. This is not the case in most of Europe, where instead a non-specified "eclectic" approach is adopted. We explored the social validity of ABA-based interventions with…

  15. BRI1-Associated Receptor Kinase 1 Regulates Guard Cell ABA Signaling Mediated by Open Stomata 1 in Arabidopsis.

    PubMed

    Shang, Yun; Dai, Changbo; Lee, Myeong Min; Kwak, June M; Nam, Kyoung Hee

    2016-03-01

    Stomatal movements are critical in regulating gas exchange for photosynthesis and water balance between plant tissues and the atmosphere. The plant hormone abscisic acid (ABA) plays key roles in regulating stomatal closure under various abiotic stresses. In this study, we revealed a novel role of BAK1 in guard cell ABA signaling. We found that the brassinosteroid (BR) signaling mutant bak1 lost more water than wild-type plants and showed ABA insensitivity in stomatal closure. ABA-induced OST1 expression and reactive oxygen species (ROS) production were also impaired in bak1. Unlike direct treatment with H2O2, overexpression of OST1 did not completely rescue the insensitivity of bak1 to ABA. We demonstrated that BAK1 forms a complex with OST1 near the plasma membrane and that the BAK1/OST1 complex is increased in response to ABA in planta. Brassinolide, the most active BR, exerted a negative effect on ABA-induced formation of the BAK1/OST1 complex and OST1 expression. Moreover, we found that BAK1 and ABI1 oppositely regulate OST1 phosphorylation in vitro, and that ABI1 interacts with BAK1 and inhibits the interaction of BAK1 and OST1. Taken together, our results suggest that BAK1 regulates ABA-induced stomatal closure in guard cells. PMID:26724418

  16. 40 CFR 63.1295 - Standards for slabstock flexible polyurethane foam production-HAP ABA storage vessels.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... polyurethane foam production-HAP ABA storage vessels. 63.1295 Section 63.1295 Protection of Environment... Pollutants for Flexible Polyurethane Foam Production § 63.1295 Standards for slabstock flexible polyurethane foam production—HAP ABA storage vessels. Each owner or operator of a new or existing slabstock...

  17. 40 CFR 63.1295 - Standards for slabstock flexible polyurethane foam production-HAP ABA storage vessels.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... polyurethane foam production-HAP ABA storage vessels. 63.1295 Section 63.1295 Protection of Environment... Pollutants for Flexible Polyurethane Foam Production § 63.1295 Standards for slabstock flexible polyurethane foam production—HAP ABA storage vessels. Each owner or operator of a new or existing slabstock...

  18. 40 CFR 63.1297 - Standards for slabstock flexible polyurethane foam production-HAP ABA emissions from the...

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... polyurethane foam production-HAP ABA emissions from the production line. 63.1297 Section 63.1297 Protection of... Pollutants for Flexible Polyurethane Foam Production § 63.1297 Standards for slabstock flexible polyurethane... § 63.1293(a)(1) shall control HAP ABA emissions from the slabstock polyurethane foam production line...

  19. 40 CFR 63.1297 - Standards for slabstock flexible polyurethane foam production-HAP ABA emissions from the...

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... polyurethane foam production-HAP ABA emissions from the production line. 63.1297 Section 63.1297 Protection of... Pollutants for Flexible Polyurethane Foam Production § 63.1297 Standards for slabstock flexible polyurethane... § 63.1293(a)(1) shall control HAP ABA emissions from the slabstock polyurethane foam production line...

  20. 40 CFR 63.1296 - Standards for slabstock flexible polyurethane foam production-HAP ABA equipment leaks.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... polyurethane foam production-HAP ABA equipment leaks. 63.1296 Section 63.1296 Protection of Environment... Pollutants for Flexible Polyurethane Foam Production § 63.1296 Standards for slabstock flexible polyurethane foam production—HAP ABA equipment leaks. Each owner or operator of a new or existing slabstock...

  1. 40 CFR 63.1297 - Standards for slabstock flexible polyurethane foam production-HAP ABA emissions from the...

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... polyurethane foam production-HAP ABA emissions from the production line. 63.1297 Section 63.1297 Protection of... Hazardous Air Pollutants for Flexible Polyurethane Foam Production § 63.1297 Standards for slabstock flexible polyurethane foam production—HAP ABA emissions from the production line. (a) Each owner...

  2. 40 CFR 63.1297 - Standards for slabstock flexible polyurethane foam production-HAP ABA emissions from the...

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... polyurethane foam production-HAP ABA emissions from the production line. 63.1297 Section 63.1297 Protection of... Hazardous Air Pollutants for Flexible Polyurethane Foam Production § 63.1297 Standards for slabstock flexible polyurethane foam production—HAP ABA emissions from the production line. (a) Each owner...

  3. 40 CFR 63.1296 - Standards for slabstock flexible polyurethane foam production-HAP ABA equipment leaks.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... polyurethane foam production-HAP ABA equipment leaks. 63.1296 Section 63.1296 Protection of Environment... Pollutants for Flexible Polyurethane Foam Production § 63.1296 Standards for slabstock flexible polyurethane foam production—HAP ABA equipment leaks. Each owner or operator of a new or existing slabstock...

  4. Interplay between ABA and GA Modulates the Timing of Asymmetric Cell Divisions in the Arabidopsis Root Ground Tissue.

    PubMed

    Lee, Shin Ae; Jang, Sejeong; Yoon, Eun Kyung; Heo, Jung-Ok; Chang, Kwang Suk; Choi, Ji Won; Dhar, Souvik; Kim, Gyuree; Choe, Jeong-Eun; Heo, Jae Bok; Kwon, Chian; Ko, Jae-Heung; Hwang, Yong-Sic; Lim, Jun

    2016-06-01

    In multicellular organisms, controlling the timing and extent of asymmetric cell divisions (ACDs) is crucial for correct patterning. During post-embryonic root development in Arabidopsis thaliana, ground tissue (GT) maturation involves an additional ACD of the endodermis, which generates two different tissues: the endodermis (inner) and the middle cortex (outer). It has been reported that the abscisic acid (ABA) and gibberellin (GA) pathways are involved in middle cortex (MC) formation. However, the molecular mechanisms underlying the interaction between ABA and GA during GT maturation remain largely unknown. Through transcriptome analyses, we identified a previously uncharacterized C2H2-type zinc finger gene, whose expression is regulated by GA and ABA, thus named GAZ (GA- AND ABA-RESPONSIVE ZINC FINGER). Seedlings ectopically overexpressing GAZ (GAZ-OX) were sensitive to ABA and GA during MC formation, whereas GAZ-SRDX and RNAi seedlings displayed opposite phenotypes. In addition, our results indicated that GAZ was involved in the transcriptional regulation of ABA and GA homeostasis. In agreement with previous studies that ABA and GA coordinate to control the timing of MC formation, we also confirmed the unique interplay between ABA and GA and identified factors and regulatory networks bridging the two hormone pathways during GT maturation of the Arabidopsis root. PMID:26970019

  5. Dynamic subnuclear relocalization of WRKY40, a potential new mechanism of ABA-dependent transcription factor regulation

    PubMed Central

    Geilen, Katja; Böhmer, Maik

    2015-01-01

    The phytohormone ABA plays a major role during plant development, e.g. seed maturation and seed germination, and during adaptation to abiotic stresses like stomatal aperture regulation. The three closely related WRKY transcription factors WRKY18, WRKY40 and WRKY60 function in ABA signal transduction. We recently demonstrated that WRKY18 and WRKY40 but not WRKY60 localize to nuclear bodies in A. thaliana mesophyll protoplasts. WRKY40, a negative regulator of ABA-dependent inhibition of seed germination, relocalizes from PNBs to the nucleoplasm in the presence of ABA in a dynamic and phosphorylation-dependent manner. We propose that subnuclear relocalization of WRKY40 might constitute a new regulatory mechanism of ABA-dependent modulation of transcription factor activity. PMID:26479147

  6. Dynamic subnuclear relocalization of WRKY40, a potential new mechanism of ABA-dependent transcription factor regulation.

    PubMed

    Geilen, Katja; Böhmer, Maik

    2015-01-01

    The phytohormone ABA plays a major role during plant development, e.g. seed maturation and seed germination, and during adaptation to abiotic stresses like stomatal aperture regulation. The three closely related WRKY transcription factors WRKY18, WRKY40 and WRKY60 function in ABA signal transduction. We recently demonstrated that WRKY18 and WRKY40 but not WRKY60 localize to nuclear bodies in A. thaliana mesophyll protoplasts. WRKY40, a negative regulator of ABA-dependent inhibition of seed germination, relocalizes from PNBs to the nucleoplasm in the presence of ABA in a dynamic and phosphorylation-dependent manner. We propose that subnuclear relocalization of WRKY40 might constitute a new regulatory mechanism of ABA-dependent modulation of transcription factor activity. PMID:26479147

  7. pH-responsive inorganic-organic hybrid supramolecular hydrogels with jellyfish-like switchable chromic luminescence.

    PubMed

    Wei, Haibing; Shi, Nan; Zhang, Jinlong; Guan, Yan; Zhang, Jie; Wan, Xinhua

    2014-08-25

    A unique type of novel supramolecular hybrid hydrogel based on the co-assembly of the anionic polyoxometalate and the cationic ABA triblock copolymer via electrostatic interaction was reported to show jellyfish-like switchable chromic luminescence. The hydrogel undergoes reversible sol-gel transition in response to pH changes, and simultaneously exhibits an unprecedented luminescent chromism from weak green to strong white. PMID:25001843

  8. Macromol. Rapid Commun. 8/2016.

    PubMed

    Hayashi, Mikihiro; Noro, Atsushi; Matsushita, Yushu

    2016-04-01

    Back Cover: Highly extensible supramolecular elastomers with large stress generation ability can be prepared from large ABA triblock copolymers bearing hydrogen-bonded B soft block. The large stress is induced by extension of both network strands and hydrogen bonds on the strands while stress concentration at glassy domains is avoided by hydrogen bond breaking, attaining high extensibility. Further details can be found in the article by M. Hayashi,* A. Noro,* and Y. Matsushita on page 678. PMID:27089229

  9. Interaction between abscisic acid receptor PYL3 and protein phosphatase type 2C in response to ABA signaling in maize.

    PubMed

    Wang, Ying-Ge; Yu, Hao-Qiang; Zhang, Yuan-Yuan; Lai, Cong-Xian; She, Yue-Hui; Li, Wan-Chen; Fu, Feng-Ling

    2014-10-01

    Abscisic acid (ABA) is a ubiquitous hormone that regulates plant growth, development and responses to environmental stresses. In recent researches, pyrabactin resistance 1-like protein (PYL) and protein phosphatase type 2C (PP2C) were identified as the direct receptor and the second component of ABA signaling pathway, respectively. However, a lot of PYL and PP2C members were found in Arabidopsis and several other plants. Some of them were found not to be involved in ABA signaling. Because of the complex diversity of the genome, few documents have been available on the molecular details of the ABA signal perception system in maize. In the present study, we conducted bioinformatics analysis to find out the candidates (ZmPYL3 and ZmPP2C16) of the PYL and PP2C members most probably involved in ABA signaling in maize, cloned their encoding genes (ZmPYL3 and ZmPP2C16), verified the interaction between these two proteins in response to exogenous ABA induction by yeast two-hybrid assay and bimolecular fluorescence complementation, and investigated the expression patterns of these two genes under the induction of exogenous ABA by real-time fluorescence quantitative PCR. The results indicated that the ZmPYL3 and ZmPP2C16 proteins interacted in vitro and in vivo in response to the induction of exogenous ABA. The downregulated expression of the ZmPYL3 gene and the upregulated expression of the ZmPP2C16 gene are responsive to the induction of exogenous ABA. The ZmPYL3 and ZmPP2C16 proteins are the most probable members of the receptors and the second components of ABA signaling pathway, respectively. PMID:25091169

  10. Organic solvent-free low temperature method of preparation for self assembled amphiphilic poly(ϵ-caprolactone)-poly(ethylene glycol) block copolymer based nanocarriers for protein delivery.

    PubMed

    Payyappilly, Sanal Sebastian; Panja, Sudipta; Mandal, Pijush; Dhara, Santanu; Chattopadhyay, Santanu

    2015-11-01

    Degradation and denaturation of labile biomolecules during preparation of micelles by organic solvent at high temperature are some of the limitations for fabrication of advanced polymer based protein delivery systems. In this paper, effectiveness of heat-chill method for preparation of micelles containing large labile biomolecules was investigated using insulin as a model protein molecule. Micelles (average size, <120 nm) were prepared using amphiphilic diblock and triblock copolymers of poly(ethylene glycol) (PEG) and poly(ϵ-caprolactone) (PCL). Micelles were prepared by heating PEG-PCL block copolymers with distilled water at 60 °C followed by sudden chilling in an ice-water bath. Effects of molecular architecture on morphology, stability and protein loading capacity of micelles were investigated. Micelles prepared using high molecular weight block copolymers exhibited good colloidal stability, encapsulation efficiency and insulin release characteristics. Insulin retained its secondary structure after micelles preparation as confirmed by CD spectroscopic study. Furthermore, in vitro cytotoxicity test suggested that the prepared micellar nanoparticles possessed biocompatibility. In a nut shell, heat-chill method of micellar nanoparticles preparation is well suited for encapsulating labile proteins and other allied biomolecules which degrade in presence of toxic organic solvents and at elevated temperatures. PMID:26291587

  11. Solubility of block copolymer surfactants in compressed CO{sub 2} using a lattice flui