WorldWideScience

Sample records for oxide triblock copolymers

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

    Directory of Open Access Journals (Sweden)

    Yunqi Li

    2016-04-01

    Full Text Available 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.

  2. Phase behavior of model ABC triblock copolymers

    Science.gov (United States)

    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

  3. The effects of ethylene oxide containing lipopolymers and tri-block copolymers on lipid bilayers of dipalmitoylphosphatidylcholine

    DEFF Research Database (Denmark)

    Baekmark, T. R.; Pedersen, S.; Jorgensen, K.

    1997-01-01

    oxide moity, anchored to the bilayer by a 1,2-dioctadecanoyl-s,n-glycero-3-phosphoethanolamine (DC18PE) lipid. The second type, which is a novel type of membrane-spanning object, is an amphiphilic tri-block copolymer composed of two hydrophilic stretches of polyethylene oxide separated by a hydrophobic...... stretch of polystyrene. Hence the tri-block copolymer may act as a membrane-spanning macromolecule mimicking an amphiphilic protein or polypeptide. Differential scanning calorimetry is used to determine a partial phase diagram for the lipopolymer systems and to assess the amount of lipopolymer that can...... be loaded into DC16PC lipid bilayers before micellization takes place. Unilamellar and micellar phase structures are investigated by fluorescence quenching using bilayer permeating dithionite. The chain length-dependent critical lipopolymer concentration, denoting the lamellar-to-micellar phase transition...

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

    OpenAIRE

    Yunqi Li; Bishnu Prasad Bastakoti; Yusuke Yamauchi

    2016-01-01

    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 p...

  5. Hollow carbon nanospheres using an asymmetric triblock copolymer structure directing agent.

    Science.gov (United States)

    Li, Yunqi; Tan, Haibo; Salunkhe, Rahul R; Tang, Jing; Shrestha, Lok Kumar; Bastakoti, Bishnu Prasad; Rong, Hongpan; Takei, Toshiaki; Henzie, Joel; Yamauchi, Yusuke; Ariga, Katsuhiko

    2016-12-20

    We introduce a simple method to prepare hollow carbon nanospheres (HCNs) by using triblock copolymer poly(styrene-b-2-vinylpyridine-b-ethylene oxide) (PS-b-P2VP-b-PEO) micelles as a new class of soft-templates. Simply by changing the solvent we can prepare ultra-small sized micelles of the triblock copolymer PS-b-P2VP-b-PEO soft template to obtain HCNs with ultra-small diameters (43 nm) and hollow cores (19 nm). Furthermore, we use these HCNs to make electric double-layer capacitors (EDLCs) that exhibit superior performance.

  6. Ordering phenomena in ABA triblock copolymer gels

    DEFF Research Database (Denmark)

    Reynders, K.; Mischenko, N.; Kleppinger, R.

    1997-01-01

    Temperature and concentration dependencies of the degree of order in ABA triblock copolymer gels are discussed. Two factors can influence the ordering phenomena: the conformation of the midblocks (links of the network) and the polydispersity of the endblock domains (nodes of the network). The lat......Temperature and concentration dependencies of the degree of order in ABA triblock copolymer gels are discussed. Two factors can influence the ordering phenomena: the conformation of the midblocks (links of the network) and the polydispersity of the endblock domains (nodes of the network...

  7. ABC triblock copolymer vesicles with mesh-like morphology.

    Science.gov (United States)

    Zhao, Wei; Chen, Dian; Hu, Yunxia; Grason, Gregory M; Russell, Thomas P

    2011-01-25

    Polymer vesicles made from poly(isoprene-b-styrene-b-2-vinyl pyridine) (PI-b-PS-b-P2VP) triblock copolymer confined within the nanopores of an anodic aluminum oxide (AAO) membrane are studied. It was found that these vesicles have well-defined, nanoscopic size, and complex microphase-separated hydrophobic membranes, comprised of the PS and PI blocks, while the coronas are formed by the P2VP block. Vesicle formation was tracked using both transmission and scanning electron microscopy. A mesh-like morphology formed in the membrane at a well-defined composition of the three blocks that can be tuned by changing the copolymer composition. The nanoscale confinement, copolymer composition, and subtle molecular interactions contribute to the generation of these vesicles with such unusual morphologies.

  8. Study of crystalline morphology and phase structure in poly(styrene-b-ethylene oxide-b-styrene) triblock copolymers bu solid state RMN spin diffusion

    International Nuclear Information System (INIS)

    Mantovani, Gerson L.; Phan, Trang; Bertin, Denis; Azevedo, Eduardo R. de; Bonagamba, Tito J.

    2009-01-01

    The phase structure and crystalline morphology of a series of polystyrene-b-polyethylene oxide-b-polystyrene (PS-b- PEO-b-PS) triblock copolymers, with different compositions and molecular weights, has been studied by solid-state NMR. WAXS and DSC measurements were used to detect the presence of crystalline domains of polyethylene oxide (PEO) blocks at room temperature as a function of the copolymer composition. 1 H NMR spin diffusion analyses provided an estimation of the size of the dispersed phases of the nano structured copolymers. (author)

  9. Blends of Styrene-Butadiene-Styrene Triblock Copolymer with Random Styrene-Maleic Anhydride Copolymers

    NARCIS (Netherlands)

    Piccini, Maria Teresa; Ruggeri, Giacomo; Passaglia, Elisa; Picchioni, Francesco; Aglietto, Mauro

    2002-01-01

    Blends of styrene-butadiene-styrene triblock copolymer (SBS) with random styrene-maleic anhydride copolymers (PS-co-MA), having different MA content, were prepared in a Brabender Plastigraph mixer. The presence of polystyrene (PS) blocks in the SBS copolymer and the high styrene content (93 and 86

  10. ABC Triblock Copolymer Vesicles with Mesh-like Morphology

    Science.gov (United States)

    Zhao, Wei; Russell, Thomas; Grason, Gregory

    2010-03-01

    Polymer vesicles can be made from poly(isoprene-b-styrene-b-2-vinylpyridene) (PI-b-PS-b-P2VP) triblock copolymer under the confinement of anodic aluminum oxide (AAO) membrane. It was found that these vesicles have well-defined, nanoscopic size and a microphase-separated hydrophobic core, comprised of PS and PI blocks. Vesicle formation was tracked using both transmission and scanning electron microscopy. A mesh-like morphology formed in the core at a well-defined composition of three blocks. Confinement played an important role in generating these vesicles with such an unusual morphology.

  11. Networks of gel-forming triblock copolymer solutions: In situ SANS and rheological measurements

    DEFF Research Database (Denmark)

    Mortensen, K.; Almdal, K.; Kleppinger, R.

    1998-01-01

    Triblock copolymers in a solvent, selective for their middle blocks provide the basis for the formation of novel physical networks where cross-links are formed by self-assembled domains of the end-blocks. Triblock copolymers of poly(styrene)-poly(ethylene,butylene)-poly(styrene) (SEBS) dissolved...

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

    Science.gov (United States)

    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.

  13. Adsorption of non-ionic ABC triblock copolymers: Surface modification of TiO2 suspensions in aqueous and non-aqueous medium

    Science.gov (United States)

    Lerch, Jean-Philippe; Atanase, Leonard Ionut; Riess, Gérard

    2017-10-01

    A series of non-ionic ABC triblock copolymers, such as poly(butadiene)-b-poly(2-vinylpyrridine)-b-poly(ethylene oxide) (PB-P2VP-PEO) were synthesized by sequential anionic polymerizations. For these copolymers comprising an organo-soluble PB and a water-soluble PEO block, their P2VP middle block has been selected for its anchoring capacity on solid surfaces. The adsorption isotherms on TiO2 were obtained in heptane and in aqueous medium, as selective solvents. In both of these cases, the P2VP middle block provides the surface anchoring, whereas PB and PEO sequences are acting as stabilizing moieties in heptane and water respectively. By extension to ABC triblock copolymers of the scaling theory developed for diblock copolymers, the density of adsorbed chains could be correlated with the molecular characteristics of the PB-P2VP-PEO triblock copolymers. From a practical point a view, it could be demonstrated that these copolymers are efficient dispersing agents for the TiO2 pigments in both aqueous and non-aqueous medium.

  14. Design and Synthesis of Network-Forming Triblock Copolymers Using Tapered Block Interfaces

    Science.gov (United States)

    Kuan, Wei-Fan; Roy, Raghunath; Rong, Lixia; Hsiao, Benjamin S.; Epps, Thomas H.

    2012-01-01

    We report a strategy for generating novel dual-tapered poly(isoprene-b-isoprene/styrene-b-styrene-b-styrene/methyl methacrylate-b-methyl methacrylate) [P(I-IS-S-SM-M)] triblock copolymers that combines anionic polymerization, atom transfer radical polymerization (ATRP), and Huisgen 1,3-dipolar cycloaddition click chemistry. The tapered interfaces between blocks were synthesized via a semi-batch feed using programmable syringe pumps. This strategy allows us to manipulate the transition region between copolymer blocks in triblock copolymers providing control over the interfacial interactions in our nanoscale phase-separated materials independent of molecular weight and block constituents. Additionally, we show the ability to retain a desirous and complex multiply-continuous network structure (alternating gyroid) in our dual-tapered triblock material. PMID:23066522

  15. Tri-block copolymers with mono-disperse crystallizable diamide segments: synthesis, analysis and rheological properties

    NARCIS (Netherlands)

    Araichimani, A.; Gaymans, R.J.

    2008-01-01

    Tri-block copolymers with polyether mid-segments and mono-disperse amide end segments were synthesized, analyzed and some properties studied. The end segment was an aromatic diamide (diaramide, TΦB). The polyether mid-segment was a difunctional poly(tetramethylene oxide) (PTMO, 1000 and 2900 g/mol).

  16. A neutron scattering study of triblock copolymer micelles

    Energy Technology Data Exchange (ETDEWEB)

    Gerstenberg, M.C.

    1997-11-01

    The thesis describes the neutron scattering experiments performed on poly(ethylene oxide)/poly(propylene oxide)/poly(ethylene oxide) triblock copolymer micelles in aqueous solution. The studies concern the non-ionic triblock copolymer P85 which consists of two outer segments of 25 monomers of ethylene oxide attached to a central part of 40 monomers of propylene oxide. The amphiphilic character of P85 leads to formation of various structures in aqueous solution such as spherical micelles, rod-like structures, and a BCC liquid-crystal mesophase of spherical micelles. The present investigations are centered around the micellar structures. In the first part of this thesis a model for the micelle is developed for which an analytical scattering form factor can be calculated. The micelle is modeled as a solid sphere with tethered Gaussian chains. Good agreement was found between small-angle neutron scattering experiments and the form factor of the spherical P85 micelles. Above 60 deg. C some discrepancies were found between the model and the data which is possibly due to an elongation of the micelles. The second part focuses on the surface-induced ordering of the various micellar aggregates in the P85 concentration-temperature phase diagram. In the spherical micellar phase, neutron reflection measurements indicated a micellar ordering at the hydrophilic surface of quartz. Extensive modeling was performed based on a hard sphere description of the micellar interaction. By convolution of the distribution of hard spheres at a hard wall, obtained from Monte Carlo simulations, and the projected scattering length density of the micelle, a numerical expression was obtained which made it possible to fit the data. The hard-sphere-hard-wall model gave an excellent agreement in the bulk micellar phase. However, for higher concentrations (25 wt % P85) close to the transition from the micellar liquid into a micellar cubic phase, a discrepancy was found between the model and the

  17. A neutron scattering study of triblock copolymer micelles

    International Nuclear Information System (INIS)

    Gerstenberg, M.C.

    1997-11-01

    The thesis describes the neutron scattering experiments performed on poly(ethylene oxide)/poly(propylene oxide)/poly(ethylene oxide) triblock copolymer micelles in aqueous solution. The studies concern the non-ionic triblock copolymer P85 which consists of two outer segments of 25 monomers of ethylene oxide attached to a central part of 40 monomers of propylene oxide. The amphiphilic character of P85 leads to formation of various structures in aqueous solution such as spherical micelles, rod-like structures, and a BCC liquid-crystal mesophase of spherical micelles. The present investigations are centered around the micellar structures. In the first part of this thesis a model for the micelle is developed for which an analytical scattering form factor can be calculated. The micelle is modeled as a solid sphere with tethered Gaussian chains. Good agreement was found between small-angle neutron scattering experiments and the form factor of the spherical P85 micelles. Above 60 deg. C some discrepancies were found between the model and the data which is possibly due to an elongation of the micelles. The second part focuses on the surface-induced ordering of the various micellar aggregates in the P85 concentration-temperature phase diagram. In the spherical micellar phase, neutron reflection measurements indicated a micellar ordering at the hydrophilic surface of quartz. Extensive modeling was performed based on a hard sphere description of the micellar interaction. By convolution of the distribution of hard spheres at a hard wall, obtained from Monte Carlo simulations, and the projected scattering length density of the micelle, a numerical expression was obtained which made it possible to fit the data. The hard-sphere-hard-wall model gave an excellent agreement in the bulk micellar phase. However, for higher concentrations (25 wt % P85) close to the transition from the micellar liquid into a micellar cubic phase, a discrepancy was found between the model and the

  18. Acrylic Triblock Copolymers Incorporating Isosorbide for Pressure Sensitive Adhesives

    Energy Technology Data Exchange (ETDEWEB)

    Gallagher, James J.; Hillmyer, Marc A.; Reineke, Theresa M. (UMM)

    2016-05-10

    A new monomer acetylated acrylic isosorbide (AAI) was prepared in two steps using common reagents without the need for column chromatography. Free radical polymerization of AAI afforded poly(acetylated acrylic isosorbide) (PAAI), which exhibited a glass transition temperature (Tg) = 95 °C and good thermal stability (Td, 5% weight loss; N2 = 331 °C, air = 291 °C). A series of ABA triblock copolymers with either poly(n-butyl acrylate) (PnBA) or poly(2-ethylhexyl acrylate) (PEHA) as the low Tg midblocks and PAAI as the high Tg end blocks were prepared using Reversible Addition–Fragmentation chain Transfer (RAFT) polymerization. The triblock copolymers ranging from 8–24 wt % PAAI were evaluated as pressure sensitive adhesives by 180° peel, loop tack, and static shear testing. While the PAAI-PEHA-PAAI series exhibited poor adhesive qualities, the PAAI-PnBA-PAAI series of triblock copolymers demonstrated peel forces up to 2.9 N cm–1, tack forces up to 3.2 N cm–1, and no shear failure up to 10000 min. Dynamic mechanical analysis indicated that PAAI-PEHA-PAAI lacked the dissipative qualities needed to form an adhesive bond with the substrate, while the PAAI-PnBA-PAAI series exhibited a dynamic mechanical response consistent with related high performing PSAs.

  19. Formation of integral asymmetric membranes of AB diblock and ABC triblock copolymers by phase inversion.

    Science.gov (United States)

    Jung, Adina; Filiz, Volkan; Rangou, Sofia; Buhr, Kristian; Merten, Petra; Hahn, Janina; Clodt, Juliana; Abetz, Clarissa; Abetz, Volker

    2013-04-12

    The formation of integral asymmetric membranes from ABC triblock terpolymers by non-solvent-induced phase separation is shown. They are compared with the AB diblock copolymer precursors. Triblock terpolymers of polystyrene-block-poly(2-vinylpyridine)-block-poly(ethylene oxide) (PS-b-P2VP-b-PEO) with two compositions are investigated. The third block supports the formation of a membrane in a case, where the corresponding diblock copolymer does not form a good membrane. In addition, the hydrophilicity is increased by the third block and due to the hydroxyl group the possibility of post-functionalization is given. The morphologies are imaged by scanning electron microscopy. The influence of the PEO on the membrane properties is analyzed by water flux, retention, and dynamic contact angle measurements. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Impact of triblock copolymers on the biophysical function of naturally-derived lung surfactant

    DEFF Research Database (Denmark)

    Beck-Broichsitter, Moritz; Ruge, Christian A.; Bohr, Adam

    2017-01-01

    The current study aimed at investigating the general applicability of triblock copolymers consisting of poly(ethylene glycol) and poly(propylene glycol) (Pluronic®) as excipients for lung delivery. After thorough physicochemical characterization of the diverse polymers, their cytotoxicity...... was evaluated using alveolar epithelial cells. Next, a naturally-derived lung surfactant was challenged with the distinct triblock copolymers with respect to changes in microstructure, adsorption to the air/liquid interface and dynamic surface tension behavior under bubble pulsation. Biocompatibility assessment...

  1. A new polymer electrolyte based on a discotic liquid crystal triblock copolymer

    International Nuclear Information System (INIS)

    Stoeva, Zlatka; Lu, Zhibao; Ingram, Malcolm D.; Imrie, Corrie T.

    2013-01-01

    A discotic liquid crystal triblock copolymer consisting of a central main chain triphenylene-based liquid crystal block capped at both ends by blocks of poly(ethylene oxide) (PEO) (M W = 2000 g mol −1 ) has been doped with lithium perchlorate in an EO:Li 6:1 ratio. The polymer electrolyte exhibits a phase separated morphology consisting of a columnar hexagonal liquid crystal phase and PEO-rich regions. The polymer electrolyte forms self-supporting, solid-like films. The ionic conductivity on initial heating of the sample is very low below ca. 60 °C but increases rapidly above this temperature. This is attributed to the melting of crystalline PEO-rich regions. Crystallisation is suppressed on cooling, and subsequent heating cycles exhibit higher conductivities but still less than those measured for the corresponding lithium perchlorate complex in poly(ethylene glycol) (M W = 2000 g mol −1 ). Instead the triblock copolymer mimics the behaviour of high molecular weight poly(ethylene oxide) (M W = 300,000 g mol −1 ). This is attributed, in part, to the anchoring of the short PEG chains to the liquid crystal block which prevents their diffusion through the sample. Temperature and pressure variations in ion mobility indicate that the ion transport mechanism in the new material is closely related to that in the conventional PEO-based electrolyte, opening up the possibility of engineering enhanced conductivities in future

  2. Nanoporous Network Channels from Self-Assembled Triblock Copolymer Supramolecules

    NARCIS (Netherlands)

    du Sart, Gerrit Gobius; Vukovic, Ivana; Vukovic, Zorica; Polushkin, Evgeny; Hiekkataipale, Panu; Ruokolainen, Janne; Loos, Katja; ten Brinke, Gerrit

    2011-01-01

    Supramolecular complexes of a poly(tert-butoxystyrene)-block-polystyrene-block-poly(4-vinylpyridine) triblock copolymers and less than stoichiometric amounts of pentadecylphenol (PDP) are shown to self-assemble into a core-shell gyroid morphology with the core channels formed by the hydrogen-bonded

  3. Synthesis of PMMA-b-PU-b-PMMA tri-block copolymers through ARGET ATRP in the presence of air

    Directory of Open Access Journals (Sweden)

    P. Krol

    2013-03-01

    Full Text Available ARGET (activators regenerated by electron transfer ATRP (atom transfer radical polymerization has been successfully performed (in flasks fitted with rubber septa without the need for use of Schlenk line in the presence of limited amount of air and with a very small (370 ppm amount of copper catalyst together with an appropriate reducing agent Cu(0. Novelty of this work is that the poly(methyl methacrylate-block-polyurethane-block-poly(methyl methacrylate triblock copolymers were synthesized for the first time through ARGET ATRP, by using tertiary bromine-terminated polyurethane as a macroinitiator (MBP-PU-MBP, CuBr2 or CuCl2 as a catalyst and N,N,N',N",N"-pentamethyldiethylenetriamine (PMDETA or 2,2'-bipyridine (Bpy as a complexing agent. As the polymerization time increases, both the monomer conversion and ln([M]0/[M] increased and the molecular weight of copolymer increases linearly with increasing conversion. Theoretical number-average molecular weight (Mn, th of the tri-block copolymers was found to be comparable with number-average molecular weight determined by GPC analyses (Mn, GPC. These results indicate that the formation of the tri-block copolymers was through atom transfer radical polymerization mechanism. 1H and 13C NMR spectral methods were employed to confirm chemical structures of synthesized macroinitiator and tri-block copolymers. Mole percentage of PMMA in the tri-block copolymers was calculated using 1H NMR spectroscopy and was found to be comparable with the GPC results. Additionally, the studies of surface properties (confocal microscopy and SFE of tri-block copolymer coatings confirmed the presence of MMA segments.

  4. Triblock copolymers based on epsilon-caprolactone and trimethylene carbonate for the 3D printing of tissue engineering scaffolds

    NARCIS (Netherlands)

    Guney, Aysun; Malda, Jos; Dhert, Wouter J. A.; Grijpma, Dirk W.

    Background: Biodegradable PCL-b-PTMC-b-PCL triblock copolymers based on trimethylene carbonate (TMC) and epsilon-caprolactone (CL) were prepared and used in the 3D printing of tissue engineering scaffolds. Triblock copolymers of various molecular weights containing equal amounts of TMC and CL were

  5. Triblock copolymers based on ε-caprolactone and trimethylene carbonate for the 3D printing of tissue engineering scaffolds

    NARCIS (Netherlands)

    Güney, Aysun; Malda, Jos; Dhert, Wouter J A; Grijpma, Dirk W

    BACKGROUND: Biodegradable PCL-b-PTMC-b-PCL triblock copolymers based on trimethylene carbonate (TMC) and ε-caprolactone (CL) were prepared and used in the 3D printing of tissue engineering scaffolds. Triblock copolymers of various molecular weights containing equal amounts of TMC and CL were

  6. Triblock copolymers based on ε-caprolactone and trimethylene carbonate for the 3D printing of tissue engineering scaffolds

    NARCIS (Netherlands)

    Güney, Aysun; Malda, Jos; Dhert, Wouter J.A.; Grijpma, Dirk W.

    2017-01-01

    Background: Biodegradable PCL-b-PTMC-b-PCL triblock copolymers based on trimethylene carbonate (TMC) and ε-caprolactone (CL) were prepared and used in the 3D printing of tissue engineering scaffolds. Triblock copolymers of various molecular weights containing equal amounts of TMC and CL were

  7. Biomimetic triblock copolymer membrane arrays: a stable template for functional membrane proteins

    DEFF Research Database (Denmark)

    Gonzalez-Perez, A.; Jensen, Karin Bagger Stibius; Vissing, Thomas

    2009-01-01

    It is demonstrated that biomimetic stable triblock copolymer membrane arrays can be prepared using a scaffold containing 64 apertures of 300 μm diameter each. The membranes were made from a stock solution of block copolymers with decane as a solvent using a new deposition method. By using decane...

  8. One-step routes from di- and triblock copolymer precursors to hydrophilic nanoporous poly(acrylic acid)-b-polystyrene

    DEFF Research Database (Denmark)

    Guo, Fengxiao; Jankova Atanasova, Katja; Schulte, Lars

    2008-01-01

    Nanoporous polystyrene with hydrophilic pores was prepared from di- and triblock copolymer precursors. The precursor material was either a poly(tert-butyl acryl ate)-b-polystyrene (PtBA-b-PS) diblock copolymer synthesized by atom transfer radical polymerization (ATRP) or a polydimethylsiloxane......-b-poly(tertbutyl acrylate)-b-polystyrene (PDMS-b-PtBA-b-PS) triblock copolymer synthesized by a combination of living anionic polymerization and ATRP. In the latter copolymer, PS was the matrix and mechanically stable component, PtBA was converted by acidic deprotection to hydrophilic poly(acrylic acid) (PAA) providing...

  9. Sustainable Triblock Copolymers for Application as Thermoplastic Elastomers

    Science.gov (United States)

    Ding, Wenyue; Wang, Shu; Ganewatta, Mitra; Tang, Chuanbing; Robertson, Megan

    Thermoplastic elastomers (TPEs), combining the processing advantages of thermoplastics with the flexibility and extensibility of elastomeric materials, have found versatile applications in industry, including electronics, clothing, adhesives, and automotive components. ABA triblock copolymers, in which A represents glassy endblocks and B the rubbery midblock, are commercially available as TPEs, such as poly(styrene-b-butadiene-b-styrene) (SBS) or poly(styrene-b-isoprene-b-styrene) (SIS). However, the commercial TPEs are derived from fossil fuels. The finite availability of fossil fuels and the environmental impact of the petroleum manufacturing have led to the increased interest in the development of alternative polymeric materials from sustainable sources. Rosin acids are promising replacement for the petroleum source due to their abundance in conifers, rigid molecular structures, and ease of functionalization. In this study, we explored the utilization of a rosin acid derivative, poly(dehydroabietic ethyl methacrylate) (PDAEMA), as a sustainable alternative for the glassy domain. The triblock copolymer poly(dehydroabietic ethyl methacrylate-b-n-butyl acylate-b-dehydroabietic ethyl methacrylate) (DnBD) was synthesized and characterized. DnBD exhibited tunable morphological and thermal properties. Tensile testing revealed elastomeric behavior.

  10. Fabrication of Ordered Nanopattern by using ABC Triblock Copolymer with Salt in Toluene

    OpenAIRE

    Huang, Hailiang; Zhong, Benbin; Zu, Xihong; Luo, Hongsheng; Lin, Wenjing; Zhang, Minghai; Zhong, Yazhou; Yi, Guobin

    2017-01-01

    Ordered nanopatterns of triblock copolymer polystyrene-block-poly(2-vinylpyridine)-block- poly (ethylene oxide)(PS-b-P2VP-b-PEO) have been achieved by the addition of lithium chloride (LiCl). The morphological and structural evolution of PS-b-P2VP-b-PEO/LiCl thin films were systematically investigated by varying different experimental parameters, including the treatment for polymer solution after the addition of LiCl, the time scale of ultrasonic treatment and the molar ratio of Li+ ions to t...

  11. Triblock copolymers based on ε-caprolactone and trimethylene carbonate for the 3D printing of tissue engineering scaffolds.

    Science.gov (United States)

    Güney, Aysun; Malda, Jos; Dhert, Wouter J A; Grijpma, Dirk W

    2017-05-09

    Biodegradable PCL-b-PTMC-b-PCL triblock copolymers based on trimethylene carbonate (TMC) and ε-caprolactone (CL) were prepared and used in the 3D printing of tissue engineering scaffolds. Triblock copolymers of various molecular weights containing equal amounts of TMC and CL were prepared. These block copolymers combine the low glass transition temperature of amorphous PTMC (approximately -20°C) and the semi-crystallinity of PCL (glass transition approximately -60°C and melting temperature approximately 60°C). PCL-b-PTMC-b-PCL triblock copolymers were synthesized by sequential ring opening polymerization (ROP) of TMC and ε-CL. From these materials, films were prepared by solvent casting and porous structures were prepared by extrusion-based 3D printing. Films prepared from a polymer with a relatively high molecular weight of 62 kg/mol had a melting temperature of 58°C and showed tough and resilient behavior, with values of the elastic modulus, tensile strength and elongation at break of approximately 120 MPa, 16 MPa and 620%, respectively. Porous structures were prepared by 3D printing. Ethylene carbonate was used as a crystalizable and water-extractable solvent to prepare structures with microporous strands. Solutions, containing 25 wt% of the triblock copolymer, were extruded at 50°C then cooled at different temperatures. Slow cooling at room temperature resulted in pores with widths of 18 ± 6 μm and lengths of 221 ± 77 μm, rapid cooling with dry ice resulted in pores with widths of 13 ± 3 μm and lengths of 58 ± 12 μm. These PCL-b-PTMC-b-PCL triblock copolymers processed into porous structures at relatively low temperatures may find wide application as designed degradable tissue engineering scaffolds. In this preliminary study we prepared biodegradable triblock copolymers based on 1,3-trimethylene carbonate and ε-caprolactone and assessed their physical characteristics. Furthermore, we evaluated their potential as melt-processable thermoplastic

  12. Well-defined triblock copolymers of polyethylene with polycaprolactone or polystyrene using a novel difunctional polyhomologation initiator

    KAUST Repository

    Hadjichristidis, Nikolaos

    2017-08-04

    α,ω-Dihydroxy polyethylene was synthesized by polyhomologation of dimethylsulfoxonium methylide with 9-thexyl-9-BBN (9-BNN: 9-Borabicyclo[3.3.1]nonane), a novel difunctional initiator produced from 9-BBN and 2,3-dimethylbut-2-ene, with two active and one blocked sites, followed by hydrolysis/oxidation. The terminal hydroxy groups were either used directly as initiators, in the presence of 1-tert-butyl-2,2,4,4,4-pentakis(dimethylamino)-2λ5,4λ5-catenadi(phosphazene) (t-BuP2), for the ring opening polymerization of ɛ-caprolactone to afford polycaprolactone-b-polyethylene-b-polycaprolactone (PCL-b-PE-b-PCL) or after transformation to atom transfer radical polymerization initiating sites, for the polymerization of styrene to produce polystyrene-b-polyethylene-b-polystyrene (PSt-b-PE-b-PSt) triblock copolymers. Molecular characterization by 11B, 13C and 1H NMR as well as FTIR, and high temperature GPC (HT-GPC) confirmed the well-defined nature of the synthesized new difunctional initiator and triblock copolymers. Differential scanning calorimetry was used to determine the melting points of PE and PCL.

  13. Synthesis by ATRP of triblock copolymers with densely grafted styrenic end blocks from a polyisobutylene macroinitiator

    DEFF Research Database (Denmark)

    Truelsen, Jens Høg; Kops, Jørgen; Pedersen, Walther Batsberg

    2000-01-01

    A macroinitiator was prepared from a triblock copolymer of polyisobutylene (PIB) with end blocks of poly(p-methylstyrene) (P(p-MeS)) by bromination to obtain initiating bromomethyl groups for atom transfer radical polymerization (ATRP). Controlled polymerization of styrene and p-acetoxystyrene yi......A macroinitiator was prepared from a triblock copolymer of polyisobutylene (PIB) with end blocks of poly(p-methylstyrene) (P(p-MeS)) by bromination to obtain initiating bromomethyl groups for atom transfer radical polymerization (ATRP). Controlled polymerization of styrene and p...

  14. Fabrication of Pt/Au concentric spheres from triblock copolymer.

    Science.gov (United States)

    Koh, Haeng-Deog; Park, Soojin; Russell, Thomas P

    2010-02-23

    Dispersion of an aqueous H(2)PtCl(6) solution into a trifluorotoluene (TFT) solution of a polystyrene-block-poly(2-vinylpyridine)-block-poly(ethylene oxide) (PS-b-P2VP-b-PEO) triblock copolymer produced an emulsion-induced hollow micelle (EIHM), comprising a water nanodroplet stabilized by PEO, H(2)PtCl(6)/P2VP, and PS, sequentially. The following addition of an aqueous LiAuCl(4) solution into the dispersion led to a coordination of LiAuCl(4) and PEO. The resulting spherical EIHM structure was transformed to a hollow cylindrical micelle by the fusion of spherical EIHM with the addition of methanol. This structural transition was reversible by the alternative addition of methanol and TFT. Oxygen plasma was used to generate Pt/Au concentric spheres and hollow cylindrical Pt/Au nano-objects.

  15. Consequences of block sequence on the orthogonal folding of triblock copolymers

    NARCIS (Netherlands)

    Hosono, N.; Stals, P.J.M.; Palmans, A.R.A.; Meijer, E.W.

    2014-01-01

    ABA- and BAB-type triblock copolymers possessing pendant, self-assembling motifs in the A and B blocks were synthesized, with 2-ureidopyrimidinone (UPy) and benzene-1,3,5-tricarboxamide (BTA) for the A and B block, respectively. They were investigated to assess if and how the polymer's

  16. Simultaneous determination of the styrene unit content and assessment of molecular weight of triblock copolymers in adhesives by a size exclusion chromatography method.

    Science.gov (United States)

    Wang, Mingfang; Wang, Yuerong; Luo, Pei; Zhang, Hongyang; Zhang, Min; Hu, Ping

    2017-10-01

    The content of styrene units in nonhydrogenated and hydrogenated styrene-butadiene-styrene and styrene-isoprene-styrene triblock copolymers significantly influences product performance. A size exclusion chromatography method was developed to determine the average styrene content of triblock copolymers blended with tackifier in adhesives. A complete separation of the triblock copolymer from the other additives was realized with size exclusion chromatography. The peak area ratio of the UV and refraction index signals of the copolymers at the same effective elution volume was correlated to the average styrene unit content using nuclear magnetic resonance spectroscopy with commercial copolymers as standards. The obtained calibration curves showed good linearity for both the hydrogenated and nonhydrogenated styrene-butadiene-styrene and styrene-isoprene-styrene triblock copolymers (r = 0.974 for styrene contents of 19.3-46.3% for nonhydrogenated ones and r = 0.970 for the styrene contents of 23-58.2% for hydrogenated ones). For copolymer blends, the developed method provided more accurate average styrene unit contents than nuclear magnetic resonance spectroscopy provided. These results were validated using two known copolymer blends consisting of either styrene-isoprene-styrene or hydrogenated styrene-butadiene-styrene and a hydrocarbon tackifying resin as well as an unknown adhesive with styrene-butadiene-styrene and an aromatic tackifying resin. The methodology can be readily applied to styrene-containing polymers in blends such as poly(acrylonitrile-butadiene styrene). © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Reduced graphene oxide/hydroxylated styrene-butadiene-styrene tri-block copolymer electroconductive nanocomposites: Preparation and properties

    Energy Technology Data Exchange (ETDEWEB)

    Xiong, Yuanqin; Xie, Yanyan [Institute of Polymer Science and Engineering, College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082 (China); Zhang, Fan [College of Chemistry and Chemical Engineering, Jishou University, Jishou 416000 (China); Ou, Encai; Jiang, Zhuojuan; Ke, Lili; Hu, Ding [Institute of Polymer Science and Engineering, College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082 (China); Xu, Weijian, E-mail: weijianxu59@gmail.com [Institute of Polymer Science and Engineering, College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082 (China)

    2012-08-20

    Highlights: Black-Right-Pointing-Pointer RGO/HO-SBS nanocomposites are prepared successfully. Black-Right-Pointing-Pointer The introduction of -OH improves the compatibility between RGO and HO-SBS. Black-Right-Pointing-Pointer RGO disperse homogeneously and form a compact continuous network in matrix (HO-SBS). Black-Right-Pointing-Pointer The percolation threshold of the nanocomposites is of 0.2-0.5 wt% (0.09-0.23 vol%) and its conductivity is up to 1.3 S/m. - Abstract: Flexible and electroconductive nanocomposites based on reduced graphene oxide (RGO) and hydroxylated styrene-butadiene-styrene tri-block copolymer (HO-SBS) were prepared by solution blending method. By the introduction of the groups of -OH and >C=O onto SBS, the compatibility between RGO and SBS was enhanced. Field emission scanning electron microscopy (FE-SEM) and high-resolution transmission electron microscopy (HR-TEM) showed that RGO dispersed homogeneously and formed a compact continuous network in matrix (HO-SBS). The addition of RGO improved the thermal stability of the RGO/HO-SBS nanocomposites while slightly lowered the mechanical property. Moreover, RGO gave the nanocomposites a maximum electrical conductivity up to 1.3 S/m.

  18. Nanoporous network channels from self-assembled triblock copolymer supramolecules.

    Science.gov (United States)

    du Sart, Gerrit Gobius; Vukovic, Ivana; Vukovic, Zorica; Polushkin, Evgeny; Hiekkataipale, Panu; Ruokolainen, Janne; Loos, Katja; ten Brinke, Gerrit

    2011-02-16

    Supramolecular complexes of a poly(tert-butoxystyrene)-block-polystyrene-block-poly(4-vinylpyridine) triblock copolymers and less than stoichiometric amounts of pentadecylphenol (PDP) are shown to self-assemble into a core-shell gyroid morphology with the core channels formed by the hydrogen-bonded P4VP(PDP)complexes. After structure formation, PDP was removed using a simple washing procedure, resulting in well-ordered nanoporous films that were used as templates for nickel plating. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Study of structural morphologies of thermoresponsive diblock AB and triblock BAB copolymers (A = poly(N-isopropylacrylamide), B = polystyrene)

    Science.gov (United States)

    Rodríguez-Hidalgo, María del Rosario; Soto-Figueroa, César; Vicente, Luis

    2018-03-01

    Structural morphologies of diblock AB and triblock BAB copolymers (A = poly(N-isopropylacrylamide), B = polystyrene) in aqueous environment have been investigated by dissipative particle dynamics (DPD). In triblock copolymers insoluble PS blocks contract while soluble pNIPAM blocks stay at the periphery forming looped chains as corona. As the temperature is increased there is a continuous morphological transition and micelles form ellipsoidal structures with segregated polymer zones. The phase transition of looped pNIPAM chains occurs at lower temperature than for linear chains and within broader temperature range. It is discussed how the chain topology of pNIPAM affects the phase transition.

  20. Temperature-dependent self-assembly and rheological behavior of a thermoreversible pmma-P n BA-PMMA triblock copolymer gel

    Energy Technology Data Exchange (ETDEWEB)

    Zabet, Mahla; Mishra, Satish; Boy, Ramiz; Walters, Keisha B.; Naskar, Amit K.; Kundu, Santanu (UO); (ORNL); (MSSU)

    2017-03-25

    Self-assembly and mechanical properties of triblock copolymers in a mid-block selective solvent are of interest in many applications. Herein, we report physical assembly of an ABA triblock copolymer, [PMMA–PnBA–PMMA] in two different mid-block selective solvents, n-butanol and 2-ethyl-1-hexanol. Gel formation resulting from end-block associations and the corresponding changes in mechanical properties have been investigated over a temperature range of -80 °C to 60 °C, from near the solvent melting points to above the gelation temperature. Shear-rheometry, thermal analysis, and small-angle neutron scattering data reveal formation and transition of structure in these systems from a liquid state to a gel state to a percolated cluster network with decrease in temperature. The aggregated PMMA end-blocks display a glass transition temperature. Our results provide new understanding into the structural changes of a self-assembled triblock copolymer gel over a large length scale and wide temperature range.

  1. Effect of planar extension on the structure and mechanical properties of polystyrene-poly(ethylene-¤co¤-butylene)-polystyrene triblock copolymers

    DEFF Research Database (Denmark)

    Daniel, C.; Hamley, I.W.; Mortensen, K.

    2000-01-01

    Two thermoplastic poly(styrene)-poly(ethylene-co-butylene) -poly(styrene) triblock copolymers containing either spherical or cylindrical poly(styrene) microdomains were pre-oriented through extensional flow. Small angle neutron scattering (SANS) measurements revealed that the pre-oriented triblock...

  2. One-Pot Synthesis of Charged Amphiphilic Diblock and Triblock Copolymers Via High-Throughput Cu(0-Mediated Polymerization

    Directory of Open Access Journals (Sweden)

    Lenny Voorhaar

    2017-07-01

    Full Text Available Block copolymers containing functionalized monomers, for example those containing charged groups, can be used for many purposes, one of which is the design of polymeric supramolecular materials based on electrostatic interactions. In this paper the synthesis of diblock copolymers and ABA-triblock copolymers containing poly(n-butyl acrylate as a first or middle block and poly(2-(dimethylaminoethyl acrylate, poly(1-ethoxyethyl acrylate and poly(1-ethoxyethyl-2-carboxyethyl acrylate as second or outer blocks, resulting in block copolymers that can contain positive or negative charges, is reported. The polymerizations were performed and optimized via one-pot sequential monomer addition reactions via Cu(0-mediated polymerization using an automated parallel synthesizer. Different initiators, monomer concentrations and polymerization times were tested. While a bromide-containing initiator led to the best results for most monomers, when polymerizing 2-(dimethylaminoethyl acrylate the use of a chloride-containing initiator was necessary. Due to the slower polymerization using this initiator, a longer polymerization time was needed before addition of the second monomer. Using the optimized conditions, the diblock and triblock copolymers could be synthesized with good control over molecular weight and dispersities around 1.1 were obtained.

  3. Morphology and Phase Transitions in Styrene-Butadiene-Styrene Triblock Copolymer Grafted with Isobutyl Substituted Polyhedral Oligomeric Silsesquioxanes (Postprint)

    National Research Council Canada - National Science Library

    Drazowski, Daniel B; Lee, Andre; Haddad, Timothy S

    2007-01-01

    Two symmetric triblock polystyrene-butadiene-polystyrene (SBS) copolymers with different styrene content were grafted with varying amounts of isobutyl-substituted polyhedral oligomeric silsesquioxane (POSS) molecules...

  4. Morphology and Phase Transitions in Styrene-Butadiene-Styrene Triblock Copolymer Grafted with Isobutyl Substituted Polyhedral Oligomeric Silsesquioxanes (preprint)

    National Research Council Canada - National Science Library

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

    2006-01-01

    Two symmetric triblock polystyrene-butadiene-polystyrene (SBS) copolymers with different styrene content were grafted with varying amounts of isobutyl-substituted polyhedral oligomeric silsesquioxane (POSS) molecules...

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

    International Nuclear Information System (INIS)

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

    2009-01-01

    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 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 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.

  6. Direct fabrication of ordered mesoporous carbons with super-micropore/small mesopore using mixed triblock copolymers.

    Science.gov (United States)

    Li, Peng; Song, Yan; Tang, Zhihong; Yang, Guangzhi; Yang, Junhe

    2014-01-01

    Ordered mesoporous carbons (OMCs) have been prepared by the strategy of evaporation-induced organic-organic self-assembly method by employing a mixture of amphiphilic triblock copolymers poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) (PEO-PPO-PEO) and reverse PPO-PEO-PPO as templates, with soluble in ethanol, low-molecular-weight phenolic resin as precursor, followed by carbonization. It has been found that the as prepared OMCs with porosity that combines super-micropore and small mesopore size distributed from 0.8 to 4 nm, which bridges the pore size from 2 to 3 nm and also for the diversification of the soft-templating synthesis of OMCs. Furthermore, the results showed that the OMCs obtained have mesophase transition from cylindrical p6 mm to centered rectangular c2 mm structure by simply tuning the ratio of PPO-PEO-PPO/PEO-PPO-PEO. Copyright © 2013 Elsevier Inc. All rights reserved.

  7. Design and Synthesis of Network-Forming Triblock Copolymers Using Tapered Block Interfaces

    OpenAIRE

    Kuan, Wei-Fan; Roy, Raghunath; Rong, Lixia; Hsiao, Benjamin S.; Epps, Thomas H.

    2012-01-01

    We report a strategy for generating novel dual-tapered poly(isoprene-b-isoprene/styrene-b-styrene-b-styrene/methyl methacrylate-b-methyl methacrylate) [P(I-IS-S-SM-M)] triblock copolymers that combines anionic polymerization, atom transfer radical polymerization (ATRP), and Huisgen 1,3-dipolar cycloaddition click chemistry. The tapered interfaces between blocks were synthesized via a semi-batch feed using programmable syringe pumps. This strategy allows us to manipulate the transition region ...

  8. Phase behavior of poly(dimethylsiloxane)-poly(ethylene oxide) amphiphilic block and graft copolymers in compressed carbon dioxide

    International Nuclear Information System (INIS)

    Stoychev, Ivan; Peters, Felix; Kleiner, Matthias; Sadowski, Gabriele; Clerc, Sebastien; Ganachaud, Francois; Chirat, Mathieu; Lacroix-Desmazes, Patrick; Fournel, Bruno

    2012-01-01

    The phase behavior of triblock and graft-type poly(dimethylsiloxane) (PDMS)-poly(ethylene oxide) (PEO) copolymer surfactants has been investigated in compressed carbon dioxide (CO 2 ). For this purpose, cloud-point pressures have been measured in the pressure and temperature range from P=10 to 40 MPa and from T= 293 to 338 K. The Perturbed-Chain Statistical Associating Fluid Theory (PC-SAFT) equation of state (EoS) has been applied to model the experimental data in order to better understand the influence of the structure of the copolymers on the phase behavior of the system. The pure-component parameters for PDMS have been fitted originally to PDMS/n-pentane system. These parameters are successfully applied for PDMS in CO 2 by adjusting a temperature-dependent binary interaction parameter. The phase behavior of the triblock copolymers was successfully predicted by PC-SAFT. In contrast, the phase behavior of the graft copolymers was difficult to predict accurately at this stage. (authors)

  9. Fabrication of Ordered Nanopattern by using ABC Triblock Copolymer with Salt in Toluene.

    Science.gov (United States)

    Huang, Hailiang; Zhong, Benbin; Zu, Xihong; Luo, Hongsheng; Lin, Wenjing; Zhang, Minghai; Zhong, Yazhou; Yi, Guobin

    2017-08-15

    Ordered nanopatterns of triblock copolymer polystyrene-block-poly(2-vinylpyridine)-block- poly (ethylene oxide)(PS-b-P2VP-b-PEO) have been achieved by the addition of lithium chloride (LiCl). The morphological and structural evolution of PS-b-P2VP-b-PEO/LiCl thin films were systematically investigated by varying different experimental parameters, including the treatment for polymer solution after the addition of LiCl, the time scale of ultrasonic treatment and the molar ratio of Li + ions to the total number of oxygen atoms (O) in PEO block and the nitrogen atoms (N) in P2VP block. When toluene was used as the solvent for LiCl, ordered nanopattern with cylinders or nanostripes could be obtained after spin-coating. The mechanism of nanopattern transformation was related to the loading of LiCl in different microdomains.

  10. Single-ion triblock copolymer electrolytes based on poly(ethylene oxide) and methacrylic sulfonamide blocks for lithium metal batteries

    Science.gov (United States)

    Porcarelli, Luca; Aboudzadeh, M. Ali; Rubatat, Laurent; Nair, Jijeesh R.; Shaplov, Alexander S.; Gerbaldi, Claudio; Mecerreyes, David

    2017-10-01

    Single-ion conducting polymer electrolytes represent the ideal solution to reduce concentration polarization in lithium metal batteries (LMBs). This paper reports on the synthesis and characterization of single-ion ABA triblock copolymer electrolytes comprising PEO and poly(lithium 1-[3-(methacryloyloxy)propylsulfonyl]-1-(trifluoromethylsulfonyl)imide) blocks, poly(LiMTFSI). Block copolymers are prepared by reversible addition-fragmentation chain transfer polymerization, showing low glass transition temperature (-55 to 7 °C) and degree of crystallinity (51-0%). Comparatively high values of ionic conductivity are obtained (up to ≈ 10-4 S cm-1 at 70 °C), combined with a lithium-ion transference number close to unity (tLi+ ≈ 0.91) and a 4 V electrochemical stability window. In addition to these promising features, solid polymer electrolytes are successfully tested in lithium metal cells at 70 °C providing long lifetime up to 300 cycles, and stable charge/discharge cycling at C/2 (≈100 mAh g-1).

  11. Nanoscale patterning of two metals on silicon surfaces using an ABC triblock copolymer template.

    Science.gov (United States)

    Aizawa, Masato; Buriak, Jillian M

    2006-05-03

    Patterning technologically important semiconductor interfaces with nanoscale metal films is important for applications such as metallic interconnects and sensing applications. Self-assembling block copolymer templates are utilized to pattern an aqueous metal reduction reaction, galvanic displacement, on silicon surfaces. Utilization of a triblock copolymer monolayer film, polystyrene-block-poly(2-vinylpyridine)-block-poly(ethylene oxide) (PS-b-P2VP-b-PEO), with two blocks capable of selective transport of different metal complexes to the surface (PEO and P2VP), allows for chemical discrimination and nanoscale patterning. Different regions of the self-assembled structure discriminate between metal complexes at the silicon surface, at which time they undergo the spontaneous reaction at the interface. Gold deposition from gold(III) compounds such as HAuCl4(aq) in the presence of hydrofluoric acid mirrors the parent block copolymer core structure, whereas silver deposition from Ag(I) salts such as AgNO3(aq) does the opposite, localizing exclusively under the corona. By carrying out gold deposition first and silver second, sub-100-nm gold features surrounded by silver films can be produced. The chemical selectivity was extended to other metals, including copper, palladium, and platinum. The interfaces were characterized by a variety of methods, including scanning electron microscopy, scanning Auger microscopy, X-ray photoelectron spectroscopy, and atomic force microscopy.

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

    Science.gov (United States)

    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.

  13. Synthesis of ABA Tri-Block Co-Polymer Magnetopolymersomes via Electroporation for Potential Medical Application

    Directory of Open Access Journals (Sweden)

    Jennifer Bain

    2015-12-01

    Full Text Available The ABA tri-block copolymer poly(2-methyloxazoline–poly(dimethylsiloxane–poly(2-methyloxazoline (PMOXA–PDMS–PMOXA is known for its capacity to mimic a bilayer membrane in that it is able to form vesicular polymersome structures. For this reason, it is the subject of extensive research and enables the development of more robust, adaptable and biocompatible alternatives to natural liposomes for biomedical applications. However, the poor solubility of this polymer renders published methods for forming vesicles unreproducible, hindering research and development of these polymersomes. Here we present an adapted, simpler method for the production of PMOXA–PDMS–PMOXA polymersomes of a narrow polydispersity (45 ± 5.8 nm, via slow addition of aqueous solution to a new solvent/polymer mixture. We then magnetically functionalise these polymersomes to form magnetopolymersomes via in situ precipitation of iron-oxide magnetic nanoparticles (MNPs within the PMOXA–PDMS–PMOXA polymersome core and membrane. This is achieved using electroporation to open pores within the membrane and to activate the formation of MNPs. The thick PMOXA–PDMS–PMOXA membrane is well known to be relatively non-permeable when compared to more commonly used di-block polymer membranes due a distinct difference in both size and chemistry and therefore very difficult to penetrate using standard biological methods. This paper presents for the first time the application of electroporation to an ABA tri-block polymersome membrane (PMOXA–PDMS–PMOXA for intravesicular in situ precipitation of uniform MNPs (2.6 ± 0.5 nm. The electroporation process facilitates the transport of MNP reactants across the membrane yielding in situ precipitation of MNPs. Further to differences in length and chemistry, a tri-block polymersome membrane structure differs from a natural lipid or di-block polymer membrane and as such the application and effects of electroporation on this type of

  14. Synthesis of triblock and random copolymers of 4- acetoxystyrene and styrene by living atom transfer radical polymerization

    DEFF Research Database (Denmark)

    Gao, Bo; Chen, Xianyi; Ivan, Bela

    1997-01-01

    Triblock copolymers containing polystyrene (PSt) and poly(4-acetoxystyrene) (PAcOSt) segments have been prepared by atom transfer radical polymerization (ATRP). In the first step one of the two monomers was polymerized in bulk using the initiating system alpha,alpha'-dibromo-p-xylene/CuBr/2,2'-bi...

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

    Science.gov (United States)

    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

  16. Self-assembly behavior of pH- and thermosensitive amphiphilic triblock copolymers in solution: experimental studies and self-consistent field theory simulations.

    Science.gov (United States)

    Cai, Chunhua; Zhang, Liangshun; Lin, Jiaping; Wang, Liquan

    2008-10-09

    We investigated, both experimentally and theoretically, the self-assembly behaviors of pH- and thermosensitive poly(L-glutamic acid)- b-poly(propylene oxide)-b-poly(L-glutamic acid) (PLGA-b-PPO-b-PLGA) triblock copolymers in aqueous solution by means of transmission electron microscopy (TEM), scanning electron microscopy (SEM), dynamic light scattering (DLS), circular dichroism (CD), and self-consistent field theory (SCFT) simulations. Vesicles were observed when the hydrophilic PLGA block length is shorter or the pH value of solution is lower. The vesicles were found to transform to spherical micelles when the PLGA block length increases or its conformation changes from helix to coil with increasing the pH value. In addition, increasing temperature gives rise to a decrease in the size of aggregates, which is related to the dehydration of the PPO segments at higher temperatures. The SCFT simulation results show that the vesicles transform to the spherical micelles with increasing the fraction or statistical length of A block in model ABA triblock copolymer, which corresponds to the increase in the PLGA length or its conformation change from helix to coil in experiments, respectively. The SCFT calculations also provide chain distribution information in the aggregates. On the basis of both experimental and SCFT results, the mechanism of the structure change of the PLGA- b-PPO- b-PLGA aggregates was proposed.

  17. Degradation and protein release properties of microspheres prepared from biodegradable poly(lactide-co-glycolide) and ABA triblock copolymers: influence of buffer media on polymer erosion and bovine serum albumin release.

    Science.gov (United States)

    Bittner, B; Witt, C; Mäder, K; Kissel, T

    1999-08-05

    The aim of the present study was to investigate the influence of the chemical insertion of poly(ethylene oxide), PEO, into a poly(lactide-co-glycolide), PLG, backbone on the mechanisms of in vitro degradation and erosion of the polymer. For this purpose microspheres prepared by a modified W/O/W double emulsion technique using ABA triblock copolymers, consisting of PLG A-blocks attached to central PEO B-blocks were compared with microspheres prepared from PLG. Due to their molecular architecture the ABA triblock copolymers differed in their erosion and degradation behavior from PLG. Degradation occurred faster in the ABA polymers by cleavage of ester bonds inside the polymer backbone. Even erosion was shown to start immediately after incubation in different buffer media. By varying pH and ionic strength of the buffer it was found that both mass loss and molecular weight decay were accelerated in alkaline and acidic pH in the case of the ABA triblock copolymers. Although the pH of the medium had a moderate influence on the degradation of PLG, the molecular weight decay was not accompanied by a mass loss during the observation time. In a second set of experiments we prepared bovine serum albumin, BSA, loaded microspheres from both polymers. The release of BSA from ABA microspheres under in vitro conditions parallels the faster swelling and erosion rates. This could be confirmed by electron paramagnetic resonance, EPR, measurements with spin labeled albumin where an influx of buffer medium into the ABA microspheres was already observed within a few minutes. In contrast, PLG microspheres revealed a burst release without any erosion. The current study shows that the environmental conditions affected the degradation and erosion of the pure polymer microspheres in the same way as the release of the model protein. This leads to the conclusion that the more favorable degradation profile of the ABA triblock copolymers was responsible for the improvement of the release profile.

  18. A Triblock Copolymer Design Leads to Robust Hybrid Hydrogels for High-Performance Flexible Supercapacitors.

    Science.gov (United States)

    Zhang, Guangzhao; Chen, Yunhua; Deng, Yonghong; Wang, Chaoyang

    2017-10-18

    We report here an intriguing hybrid conductive hydrogel as electrode for high-performance flexible supercapacitor. The key is using a rationally designed water-soluble ABA triblock copolymer (termed as IAOAI) containing a central poly(ethylene oxide) block (A) and terminal poly(acrylamide) (PAAm) block with aniline moieties randomly incorporated (B), which was synthesized by reversible additional fragment transfer polymerization. The subsequent copolymerization of aniline monomers with the terminated aniline moieties on the IAOAI polymer generates a three-dimensional cross-linking hybrid network. The hybrid hydrogel electrode demonstrates robust mechanical flexibility, remarkable electrochemical capacitance (919 F/g), and cyclic stability (90% capacitance retention after 1000 cycles). Moreover, the flexible supercapacitor based on this hybrid hydrogel electrode presents a large specific capacitance (187 F/g), superior to most reported conductive hydrogel-based supercapacitors. With the demonstrated additional favorable cyclic stability and excellent capacitive and rate performance, this hybrid hydrogel-based supercapacitor holds great promise for flexible energy-storage device.

  19. Tertiary-amine-containing thermo- and pH-sensitive hydrophilic ABA triblock copolymers: effect of different tertiary amines on thermally induced sol-gel transitions.

    Science.gov (United States)

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

    2014-03-11

    This Article reports on the synthesis of a series of well-defined, tertiary-amine-containing ABA triblock copolymers, composed of a poly(ethylene oxide) (PEO) central block and thermo- and pH-sensitive outer blocks, and the study of the effect of different tertiary amines on thermally induced sol-gel transition temperatures (T(sol-gel)) of their 10 wt % aqueous solutions. The doubly responsive ABA triblock copolymers were prepared from a difunctional PEO macroinitiator by atom transfer radical polymerization of methoxydi(ethylene glycol) methacrylate and ethoxydi(ethylene glycol) methacrylate at a feed molar ratio of 30:70 with ∼5 mol % of either N,N-diethylaminoethyl methacrylate (DEAEMA), N,N-diisopropylaminoethyl methacrylate, or N,N-di(n-butyl)aminoethyl methacrylate. The chain lengths of thermosensitive outer blocks and the molar contents of tertiary amines were very similar for all copolymers. Using rheological measurements, we determined the pH dependences of T(sol-gel) of 10 wt % aqueous solutions of these copolymers in a phosphate buffer. The T(sol-gel) versus pH curves of all polymers exhibited a sigmoidal shape. The T(sol-gel) increased with decreasing pH; the changes were small on both high and low pH sides. At a specific pH, the T(sol-gel) decreased with increasing the hydrophobicity of the tertiary amine, and upon decreasing pH the onset pH value for the T(sol-gel) to begin to increase noticeably was lower for the more hydrophobic tertiary amine-containing copolymer. In addition, we studied the effect of different tertiary amines on the release behavior of FITC-dextran from 10 wt % micellar gels in an acidic medium at 37 and 27 °C. The release profiles for three studied hydrogels at 37 °C were essentially the same, suggesting that the release was dominated by the diffusion of FITC-dextran. At 27 °C, the release was significantly faster for the DEAEMA-containing copolymer, indicating that both diffusion and gel dissolution contributed to the

  20. Self-consistent field theoretic simulations of amphiphilic triblock copolymer solutions: Polymer concentration and chain length effects

    Directory of Open Access Journals (Sweden)

    X.-G. Han

    2014-06-01

    Full Text Available Using the self-consistent field lattice model, polymer concentration φP and chain length N (keeping the length ratio of hydrophobic to hydrophilic blocks constant the effects on temperature-dependent behavior of micelles are studied, in amphiphilic symmetric ABA triblock copolymer solutions. When chain length is increased, at fixed φP, micelles occur at higher temperature. The variations of average volume fraction of stickers φcos and the lattice site numbers Ncols at the micellar cores with temperature are dependent on N and φP, which demonstrates that the aggregation of micelles depends on N and φP. Moreover, when φP is increased, firstly a peak appears on the curve of specific heat CV for unimer-micelle transition, and then in addition a primary peak, the secondary peak, which results from the remicellization, is observed on the curve of CV. For a long chain, in intermediate and high concentration regimes, the shape of specific heat peak markedly changes, and the peak tends to be a more broad peak. Finally, the aggregation behavior of micelles is explained by the aggregation way of amphiphilic triblock copolymer. The obtained results are helpful in understanding the micellar aggregation process.

  1. Directed Self-Assembly of Poly(2-vinylpyridine)-b-polystyrene-b-poly(2-vinylpyridine) Triblock Copolymer with Sub-15 nm Spacing Line Patterns Using a Nanoimprinted Photoresist Template.

    Science.gov (United States)

    Sun, Zhiwei; Chen, Zhenbin; Zhang, Wenxu; Choi, Jaewon; Huang, Caili; Jeong, Gajin; Coughlin, E Bryan; Hsu, Yautzong; Yang, XiaoMin; Lee, Kim Y; Kuo, David S; Xiao, Shuaigang; Russell, Thomas P

    2015-08-05

    Low molecular weight P2VP-b-PS-b-P2VP triblock copolymer (poly(2-vinlypyridine)-block-polystyrene-block-poly(2-vinylpyridine)] is doped with copper chloride and microphase separated into lamellar line patterns with ultrahigh area density. Salt-doped P2VP-b-PS-b-P2VP triblock copolymer is self-assembled on the top of the nanoimprinted photoresist template, and metallic nanowires with long-range ordering are prepared with platinum-salt infiltration and plasma etching. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. New thiol-responsive mono-cleavable block copolymer micelles labeled with single disulfides.

    Science.gov (United States)

    Sourkohi, Behnoush Khorsand; Schmidt, Rolf; Oh, Jung Kwon

    2011-10-18

    Thiol-responsive symmetric triblock copolymers having single disulfide linkages in the middle blocks (called mono-cleavable block copolymers, ss-ABP(2)) were synthesized by atom transfer radical polymerization in the presence of a disulfide-labeled difunctional Br-initiator. These brush-like triblock copolymers consist of a hydrophobic polyacrylate block having pendent oligo(propylene oxide) and a hydrophilic polymethacrylate block having pendent oligo(ethylene oxide). Gel permeation chromatography and (1)H NMR results confirmed the synthesis of well-defined mono-cleavable block copolymers and revealed that polymerizations were well controlled. Because of amphiphilic nature, these copolymers self-assembled to form colloidally stable micelles above critical micellar concentration of 0.032 mg · mL(-1). In response to reductive reactions, disulfides in thiol-responsive micelles were cleaved. Atomic force microscopy and dynamic light scattering analysis suggested that the cleavage of disulfides caused dissociation of micelles to smaller-sized assembled structures in water. Moreover, in a biomedical perspective, the mono-cleavable block copolymer micelles are not cytotoxic and thus biocompatible. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Silica reinforced triblock copolymer gels

    DEFF Research Database (Denmark)

    Theunissen, E.; Overbergh, N.; Reynaers, H.

    2004-01-01

    The effect of silica and polymer coated silica particles as reinforcing agents on the structural and mechanical properties of polystyrene-poly(ethylene/butylene)-polystyrene (PS-PEB-PS) triblock gel has been investigated. Different types of chemically modified silica have been compared in order...

  4. Influence of carbonate ions on the micellization behavior in triblock copolymer solution

    CERN Document Server

    Thiyagarajan, P

    2002-01-01

    SANS was used to investigate the micellization behavior of triblock copolymers (F68, F88 and F108) as functions of carbonate ion concentration and temperature. SANS data were fitted to determine the sizes of the core and corona, inter-micelle distance, association number and the volume fraction of the micelles. As the polymer molecular weight increases, the core radius and the radius of gyration (R sub g) of the corona and the inter-micelle distance increase. The carbonate ion concentration and polymer molecular weight have dramatic influence on the temperatures at which the micellization and spherical-to-cylindrical micelle transformation occur. The mechanism by which this phenomenon occurs in these solutions is through a gradual dehydration of polymers with increasing carbonate concentration and/or temperature. (orig.)

  5. The potential of Cu(I)Cl/2,2'-bipyridine catalysis in a triblock copolymer preparation by atom transfer radical polymerization

    Czech Academy of Sciences Publication Activity Database

    Masař, Bohumil; Vlček, Petr; Kříž, Jaroslav

    2001-01-01

    Roč. 81, č. 14 (2001), s. 3514-3522 ISSN 0021-8995 R&D Projects: GA MŠk OC P1.10; GA AV ČR KSK2050602 Institutional research plan: CEZ:AV0Z4050913 Keywords : atom transfer radical polymerization * triblock copolymers * sequential synthesis Subject RIV: CD - Macromolecular Chemistry Impact factor: 0.992, year: 2001

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

    Science.gov (United States)

    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." © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Formation of ordered microphase-separated pattern during spin coating of ABC triblock copolymer.

    Science.gov (United States)

    Huang, Weihuan; Luo, Chunxia; Zhang, Jilin; Han, Yanchun

    2007-03-14

    In this paper, the authors have systematically studied the microphase separation and crystallization during spin coating of an ABC triblock copolymer, polystyrene-b-poly(2-vinylpyridine)-b-poly(ethylene oxide) (PS-b-P2VP-b-PEO). The microphase separation of PS-b-P2VP-b-PEO and the crystallization of PEO blocks can be modulated by the types of the solvent and the substrate, the spinning speed, and the copolymer concentration. Ordered microphase-separated pattern, where PEO and P2VP blocks adsorbed to the substrate and PS blocks protrusions formed hexagonal dots above the P2VP domains, can only be obtained when PS-b-P2VP-b-PEO is dissolved in N,N-dimethylformamide and the films are spin coated onto the polar substrate, silicon wafers or mica. The mechanism of the formation of regular pattern by microphase separation is found to be mainly related to the inducement of the substrate (middle block P2VP wetting the polar substrate), the quick vanishment of the solvent during the early stage of the spin coating, and the slow evaporation of the remaining solvent during the subsequent stage. On the other hand, the probability of the crystallization of PEO blocks during spin coating decreases with the reduced film thickness. When the film thickness reaches a certain value (3.0 nm), the extensive crystallization of PEO is effectively prohibited and ordered microphase-separated pattern over large areas can be routinely prepared. When the film thickness exceeds another definite value (12.0 nm), the crystallization of PEO dominates the surface morphology. For films with thickness between these two values, microphase separation and crystallization can simultaneously occur.

  8. Stealth properties of poly(ethylene oxide)-based triblock copolymer micelles: a prerequisite for a pH-triggered targeting system.

    Science.gov (United States)

    Van Butsele, K; Morille, M; Passirani, C; Legras, P; Benoit, J P; Varshney, S K; Jérôme, R; Jérôme, C

    2011-10-01

    Evaluation of the biocompatibility of pH-triggered targeting micelles was performed with the goal of studying the effect of a poly(ethylene oxide) (PEO) coating on micelle stealth properties. Upon protonation under acidic conditions, pH-sensitive poly(2-vinylpyridine) (P2VP) blocks were stretched, exhibiting positive charges at the periphery of the micelles as well as being a model targeting unit. The polymer micelles were based on two different macromolecular architectures, an ABC miktoarm star terpolymer and an ABC linear triblock copolymer, which combined three different polymer blocks, i.e. hydrophobic poly(ε-caprolactone), PEO and P2VP. Neutral polymer micelles were formed at physiological pH. These systems were tested for their ability to avoid macrophage uptake, their complement activation and their pharmacological behavior after systemic injection in mice, as a function of their conformation (neutral or protonated). After protonation, complement activation and macrophage uptake were up to twofold higher than for neutral systems. By contrast, when P2VP blocks and the targeting unit were buried by the PEO shell at physiological pH, micelle stealth properties were improved, allowing their future systemic injection with an expected long circulation in blood. Smart systems responsive to pH were thus developed which therefore hold great promise for targeted drug delivery to an acidic tumoral environment. Copyright © 2011 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

  9. Nanosized amorphous calcium carbonate stabilized by poly(ethylene oxide)-b-poly(acrylic acid) block copolymers.

    Science.gov (United States)

    Guillemet, Baptiste; Faatz, Michael; Gröhn, Franziska; Wegner, Gerhard; Gnanou, Yves

    2006-02-14

    Particles of amorphous calcium carbonate (ACC), formed in situ from calcium chloride by the slow release of carbon dioxide by alkaline hydrolysis of dimethyl carbonate in water, are stabilized against coalescence in the presence of very small amounts of double hydrophilic block copolymers (DHBCs) composed of poly(ethylene oxide) (PEO) and poly(acrylic acid) (PAA) blocks. Under optimized conditions, spherical particles of ACC with diameters less than 100 nm and narrow size distribution are obtained at a concentration of only 3 ppm of PEO-b-PAA as additive. Equivalent triblock or star DHBCs are compared to diblock copolymers. The results are interpreted assuming an interaction of the PAA blocks with the surface of the liquid droplets of the concentrated CaCO3 phase, formed by phase separation from the initially homogeneous reaction mixture. The adsorption layer of the block copolymer protects the liquid precursor of ACC from coalescence and/or coagulation.

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

    International Nuclear Information System (INIS)

    Han, Xiang-Gang; Zhang, Xue-Feng

    2015-01-01

    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

  11. The state equation of aggregation behaviours for Poly(oxyethylene)-Poly(oxypropylene)-Poly(oxyethylene) tri-block copolymers in aqueous solution

    Science.gov (United States)

    Gao, Xuechao; Ji, Guozhao; Peng, Tiefeng

    2018-03-01

    In this work, the aggregation equation is developed to describe the aggregation number of copolymer molecules and micellar diameters from experimental data. Based on the regression parameters in the aggregation equation, it is concluded that the PO parts are beneficial to enlarge the micellar size and the EO parts suppress the formation of the micelles. By fitting the parameters with the EO and PO number, the aggregation equation was proposed to predict the aggregation behaviours of tri-block copolymers having EO units between 26 and 212, and with PO number between 30 and 70. By applying the equation to aqueous solution with salt additives, it can be extended to evaluate the impacts of the additives on the micelle formation.

  12. Study of the mechanical behavior of thermo reversible gels of PS-b-poly(ethylene/butylene)-b-PS triblock copolymers in a selective solvent for the middle block of the copolymer

    International Nuclear Information System (INIS)

    Hernaez, E.; Inchausti, I.; Quintana, J. R.; Katime, I.

    2001-01-01

    The thermo reversible gelation of three triblock copolymers polystyrene-b-poly(ethylene/butylene)-b-polystyrene, with different molar mass and a similar chemical composition, in n-octane was studied. The solvent is selective for the middle poly(ethylene/butylene) block of the copolymers. the influence of the molar mass of the three copolymers on the gelation and on the mechanical properties of the gels was analysed. The sol-gel transition temperatures. T g el have been determined and they increase with the copolymer concentration and the copolymer molar mass. On the other land, the mechanical properties of the different gels were examined through oscillatory shear and compressive stress relaxation measurements. The concentration dependence of the elastic storage modules, G' for the three copolymer studied fit a sole straight line in a double-logarithmic scale and its slope (2.22) is close to that expected for systems in good solvents (2.25). As the temperature is near to the sol-gel transition temperate, the elastic modulus are smaller and the relaxation rates are higher. (Author) 12 refs

  13. Synthesis of Novel Temperature- and pH-Sensitive ABA Triblock Copolymers P(DEAEMA-co-MEO2MA-co-OEGMA-b-PEG-b-P(DEAEMA-co-MEO2MA-co-OEGMA: Micellization, Sol–Gel Transitions, and Sustained BSA Release

    Directory of Open Access Journals (Sweden)

    Yanan Han

    2016-11-01

    Full Text Available Novel temperature- and pH-responsive ABA-type triblock copolymers, P(DEAEMA-co-MEO2MA-co-OEGMA-b-PEG-b-P(DEAEMA-co-MEO2MA-co-OEGMA, composed of a poly(ethylene glycol (PEG middle block and temperature- and pH-sensitive outer blocks, were synthesized by atom transfer radical polymerization (ATRP. The composition and structure of the copolymer were characterized by 1H NMR and gel permeation chromatography (GPC. The temperature- and pH-sensitivity, micellization, and the sol–gel transitions of the triblock copolymers in aqueous solutions were studied using transmittance measurements, surface tension, viscosity, fluorescence probe technique, dynamic light scattering (DLS, zeta-potential measurements, and transmission electron microscopy (TEM. The lower critical solution temperature (LCST of the triblock copolymer, which contains a small amount of a weak base group, (N,N-diethylamino ethyl methacrylate (DEAEMA, can be tuned precisely and reversibly by changing the solution pH. When the copolymer concentration was sufficiently high, increasing temperature resulted in the free-flowing solution transformation into a micellar gel. The sol-to-gel transition temperature (Tsol–gel in aqueous solution will continue to decrease as solution concentration increases.

  14. One-Pot Automated Synthesis of Quasi Triblock Copolymers for Self-Healing Physically Crosslinked Hydrogels.

    Science.gov (United States)

    Voorhaar, Lenny; De Meyer, Bernhard; Du Prez, Filip; Hoogenboom, Richard

    2016-10-01

    The preparation of physically crosslinked hydrogels from quasi ABA-triblock copolymers with a water-soluble middle block and hydrophobic end groups is reported. The hydrophilic monomer N-acryloylmorpholine is copolymerized with hydrophobic isobornyl acrylate via a one-pot sequential monomer addition through reversible addition fragmentation chain-transfer (RAFT) polymerization in an automated parallel synthesizer, allowing systematic variation of polymer chain length and hydrophobic-hydrophilic ratio. Hydrophobic interactions between the outer blocks cause them to phase-separate into larger hydrophobic domains in water, forming physical crosslinks between the polymers. The resulting hydrogels are studied using rheology and their self-healing ability after large strain damage is shown. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Synthesis and aqueous phase behavior of thermoresponsive biodegradable poly(D,L-3-methylglycolide)-block-poly(ethyelene glycol)-block-poly(D,L-3-methylglycolide) triblock copolymers

    NARCIS (Netherlands)

    Zhong, Zhiyuan; Dijkstra, Pieter J.; Feijen, Jan; Kwon, Young-Min; Bae, You Han; Kim, Sung Wan

    2002-01-01

    Novel biodegradable thermosensitive triblock copolymers of poly(D,L-3-methylglycolide)-block-poly(ethylene glycol)-block-poly(D,L-3-methylglycolide) (PMG-PEG-PMG) have been synthesized. Ring-opening polymerization of D,L-3-methyl-glycolide (MG) initiated with poly(ethylene glycol) (PEG) and

  16. Trilayered Morphology of an ABC Triple Crystalline Triblock Terpolymer

    KAUST Repository

    Palacios, Jordana K.

    2017-09-07

    Triple crystalline triblock terpolymers are materials with remarkable semicrystalline superstructures. In this work, we report for first time the alternating triple lamellar morphology that self-assembles inside spherulites of a triblock terpolymer composed of poly(ethylene oxide) (PEO), poly(ε-caprolactone) (PCL), and poly(l-lactide) (PLLA). The morphology of the PEO-b-PCL-b-PLLA triblock terpolymer is compared to an analogous PCL-b-PLLA diblock copolymer. Both diblock and triblock form a single phase in the melt. Two crystallization protocols were employed to create particular crystalline morphologies. In both cases, the isothermal crystallization of the PLA block is induced first (at 81 °C, a temperature above the melting points of both PCL and PEO blocks) and PLLA spherulites form a template, whereupon cooling the other two blocks can crystallize within the PLLA interlamellar spaces. WAXS analysis demonstrated the double crystalline and triple crystalline nature of the materials. The lamellar structure was evaluated by AFM observations and SAXS measurements. Moreover, theoretical SAXS curves of one-dimensional structural models were calculated. AFM micrographs of the triblock terpolymer evidenced the three different lamellae of PLLA, PCL and PEO that coexist together within the same spherulite. Three different lamellar thickness were determined, and their dimensions suggested that all blocks crystallized in chain-folded conformations. The evolution of the triple lamellar morphology during heating of tricrystalline samples was followed by in situ synchrotron SAXS measurements. The theoretical analysis of the SAXS curves of the triblock terpolymer allowed us to propose a stacking morphological model, in which a particular trilayer structure exists, where one lamella of PCL or one lamella of PEO is inserted randomly between two adjacent PLLA lamellae.

  17. Preparation, characterization, and in vitro activity evaluation of triblock copolymer-based polymersomes for drugs delivery

    Science.gov (United States)

    Besada, Lucas N.; Peruzzo, Pablo; Cortizo, Ana M.; Cortizo, M. Susana

    2018-03-01

    Polymersomes are polymer-based vesicles that form upon hydration of amphiphilic block copolymers and display high stability and durability, due to their mechanical and physical properties. They have hydrophilic reservoirs as well as thick hydrophobic membranes; allowing to encapsulate both water-soluble bioactive agent and hydrophobic drugs. In this study, poly ethylene glycol (PEG3350 and PEG6000) were used as hydrophilic part and poly(vinyl benzoate) (PVBz) as hydrophobic block to synthesize amphiphilic triblock copolymers (PVBz- b-PEG- b-PVBz). Different proportions of hydrophilic/hydrophobic part were assayed in order to obtain polymersomes by solvent injection method. For the synthesis of the copolymers, the initial block of PEG was derived to obtain a macroinitiator through a xanthate functional group (PEGX3 or PEGX6) and the polymerization of vinyl benzoate was carried out through reversible addition-fragmentation chain transfer polymerization (RAFT). The structure of PEGX and copolymers was confirmed by Infrared, 1H-NMR and UV-Vis spectrometry, while the average molecular weight (Mw) and polydispersity index (PI) were determined by size exclusion chromatography (SEC). The structures adopted by the copolymers in aqueous solution by self-assembly were investigated using transmission electron microscopy (TEM), dynamic light scattering (DLS) and small-angle X-ray scattering (SAXS). Both techniques confirm that polymersomes were obtained for a fraction of hydrophilic block ( f) ≈ 35 ± 10%, with a diameter of 38.3 ± 0.3 nm or 22.5 ± 0.7 nm, as determined by TEM and according to the M w of the precursor block copolymer. In addition, we analyzed the possible cytotoxicity in view of its potential application as biomedical nanocarrier. The results suggest that polymersomes seem not induce cytotoxicity during the periods of time tested.

  18. Preparation and Sustained-Release Property of Triblock Copolymer/Calcium Phosphate Nanocomposite as Nanocarrier for Hydrophobic Drug

    Directory of Open Access Journals (Sweden)

    Cao Shao-Wen

    2010-01-01

    Full Text Available Abstract The P123/ACP nanocomposite with sizes less than 100 nm consisting of triblock copolymer P123 and amorphous calcium phosphate (ACP has been prepared by using an aqueous solution containing CaCl2, (NH43PO4, and P123 at room temperature. The P123/ACP nanocomposite is used as the nanocarrier for hydrophobic drug ibuprofen, based on the combined advantages of both amphiphilic block copolymer and calcium phosphate delivery system. The P123/ACP nanocomposite has a much higher ibuprofen loading capacity (148 mg/g than the single-phase calcium phosphate nanostructures. The drug release percentage of the P123/ACP nanocomposite in simulated body fluid reaches about 100% in a period of 156 h, which is much slower than that of single-phase calcium phosphate nanostructures. It is expected that the P123/ACP nanocomposite is promising for the application in the controlled delivery of hydrophobic drugs.

  19. Controlling block copolymer phase behavior using ionic surfactant

    Energy Technology Data Exchange (ETDEWEB)

    Ray, D.; Aswal, V. K. [Solid State Physics Division, Bhabha Atomic Research Centre, Mumbai 400 085, India E-mail: debes.phys@gmail.com (India)

    2016-05-23

    The phase behavior of poly(ethylene oxide)-poly(propylene oxide-poly(ethylene oxide) PEO-PPO-PEO triblock copolymer [P85 (EO{sub 26}PO{sub 39}EO{sub 26})] 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. Fabrication of conductive metallized nanostructures from self-assembled amphiphilic triblock copolymer templates: Nanospheres, nanowires, nanorings

    International Nuclear Information System (INIS)

    Zhu Jintao; Jiang Wei

    2007-01-01

    Various metallized nanostructures (such as rings, wires with controllable lengths, spheres) have been successfully fabricated by coating metallic nanolayers onto soft nanotemplates through simple electroless methods. In particular, bimetallic nanostructures have been obtained by using simple methods. The multiple functional polymeric nanostructures were obtained through the self-assembly of polystyrene/poly(4-vinyl pyridine) triblock copolymer (P4VP-b-PS-b-P4VP) in selective media by changing the common solvent properties. By combining field emission scanning electron microscopy (SEM), atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS) characterization, it was confirmed that polymer/metal and bimetallic (Au at Ag) core-shell nanostructures could be achieved by chemical metal deposition method

  1. Self-Assembly of Rod-Coil Block Copolymers

    National Research Council Canada - National Science Library

    Jenekhe, S

    1999-01-01

    ... the self-assembly of new rod-coil diblock, rod- coil-rod triblock, and coil-rod-coil triblock copolymers from solution and the resulting discrete and periodic mesostmctares with sizes in the 100...

  2. Design strategy of pH-sensitive triblock copolymer micelles for efficient cellular uptake by computer simulations

    Science.gov (United States)

    Xia, Qiang-sheng; Ding, Hong-ming; Ma, Yu-qiang

    2018-03-01

    Efficient delivery of nanoparticles into specific cell interiors is of great importance in biomedicine. Recently, the pH-responsive micelle has emerged as one potential nanocarrier to realize such purpose since there exist obvious pH differences between normal tissues and tumors. Herein, by using dissipative particle dynamics simulation, we investigate the interaction of the pH-sensitive triblock copolymer micelles composed of ligand (L), hydrophobic block (C) and polyelectrolyte block (P) with cell membrane. It is found that the structure rearrangement of the micelle can facilitate its penetration into the lower leaflet of the bilayer. However, when the ligand-receptor specific interaction is weak, the micelles may just fuse with the upper leaflet of the bilayer. Moreover, the ionization degree of polyelectrolyte block and the length of hydrophobic block also play a vital role in the penetration efficiency. Further, when the sequence of the L, P, C beads in the copolymers is changed, the translocation pathways of the micelles may change from direct penetration to Janus engulfment. The present study reveals the relationship between the molecular structure of the copolymer and the uptake of the pH-sensitive micelles, which may give some significant insights into the experimental design of responsive micellar nanocarriers for highly efficient cellular delivery.

  3. Gel phase formation in dilute triblock copolyelectrolyte complexes

    Science.gov (United States)

    Srivastava, Samanvaya; Andreev, Marat; Levi, Adam E.; Goldfeld, David J.; Mao, Jun; Heller, William T.; Prabhu, Vivek M.; de Pablo, Juan J.; Tirrell, Matthew V.

    2017-02-01

    Assembly of oppositely charged triblock copolyelectrolytes into phase-separated gels at low polymer concentrations (simulations. Here we show that in contrast to uncharged, amphiphilic block copolymers that form discrete micelles at low concentrations and enter a phase of strongly interacting micelles in a gradual manner with increasing concentration, the formation of a dilute phase of individual micelles is prevented in polyelectrolyte complexation-driven assembly of triblock copolyelectrolytes. Gel phases form and phase separate almost instantaneously on solvation of the copolymers. Furthermore, molecular models of self-assembly demonstrate the presence of oligo-chain aggregates in early stages of copolyelectrolyte assembly, at experimentally unobservable polymer concentrations. Our discoveries contribute to the fundamental understanding of the structure and pathways of complexation-driven assemblies, and raise intriguing prospects for gel formation at extraordinarily low concentrations, with applications in tissue engineering, agriculture, water purification and theranostics.

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

    Science.gov (United States)

    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.

  5. Aqueous lubricating properties of charged (ABC) and neutral (ABA) triblock copolymer chains

    DEFF Research Database (Denmark)

    Røn, Troels; Javakhishvili, Irakli; Patil, Navin J.

    2014-01-01

    Application of charged polymer chains as additives for lubricating neutral surfaces in aqueous envi- ronment, especially via polymer physisorption, is generally impeded by the electrostatic repulsion be- tween adjacent polymers on the surface. In this study, we have investigated the adsorption an...... improvement compared to fully charged polymer chains, e.g. poly(acrylic acid)- block -poly(2-methoxyethyl acrylate) (PAA- b -PMEA), which is attributed to dilution of charged moieties on the surface and subsequent improvement of the lubricating fi lm stability......Application of charged polymer chains as additives for lubricating neutral surfaces in aqueous envi- ronment, especially via polymer physisorption, is generally impeded by the electrostatic repulsion be- tween adjacent polymers on the surface. In this study, we have investigated the adsorption...... and aqueous lubricating properties of an amphiphilic triblock copolymer, comprised of a neutral poly(ethylene glycol) (PEG) block, a hydrophobic poly(2-methoxyethyl acrylate) (PMEA) block, and a charged poly(methacrylic acid) (PMAA) block, namely PEG- b -PMEA- b -PMAA. After adsorption onto a nonpolar...

  6. Hydration of cations: a key to understanding of specific cation effects on aggregation behaviors of PEO-PPO-PEO triblock copolymers.

    Science.gov (United States)

    Lutter, Jacob C; Wu, Tsung-yu; Zhang, Yanjie

    2013-09-05

    This work reports results from the interactions of a series of monovalent and divalent cations with a triblock copolymer, poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) (PEO-PPO-PEO). Phase transition temperatures of the polymer in the presence of chloride salts with six monovalent and eight divalent cations were measured using an automated melting point apparatus. The polymer undergoes a two-step phase transition, consisting of micellization of the polymer followed by aggregation of the micelles, in the presence of all the salts studied herein. The results suggest that hydration of cations plays a key role in determining the interactions between the cations and the polymer. The modulation of the phase transition temperature of the polymer by cations can be explained as a balance between three interactions: direct binding of cations to the oxygen in the polymer chains, cations sharing one water molecule with the polymer in their hydration layer, and cations interacting with the polymer via two water molecules. Monovalent cations Na(+), K(+), Rb(+), and Cs(+) do not bind to the polymer, while Li(+) and NH4(+) and all the divalent cations investigated including Mg(2+), Ca(2+), Sr(2+), Ba(2+), Co(2+), Ni(2+), Cu(2+), and Cd(2+) bind to the polymer. The effects of the cations correlate well with their hydration thermodynamic properties. Mechanisms for cation-polymer interactions are discussed.

  7. Thermal Annealing to Modulate the Shape Memory Behavior of a Biobased and Biocompatible Triblock Copolymer Scaffold in the Human Body Temperature Range.

    Science.gov (United States)

    Merlettini, Andrea; Gigli, Matteo; Ramella, Martina; Gualandi, Chiara; Soccio, Michelina; Boccafoschi, Francesca; Munari, Andrea; Lotti, Nadia; Focarete, Maria Letizia

    2017-08-14

    A biodegradable and biocompatible electrospun scaffold with shape memory behavior in the physiological temperature range is here presented. It was obtained starting from a specifically designed, biobased PLLA-based triblock copolymer, where the central block is poly(propylene azelate-co-propylene sebacate) (P(PAz60PSeb40)) random copolymer. Shape memory properties are determined by the contemporary presence of the low melting crystals of the P(PAz60PSeb40) block, acting as switching segment, and of the high melting crystal phase of PLLA blocks, acting as physical network. It is demonstrated that a straightforward annealing process applied to the crystal phase of the switching element gives the possibility to tune the shape recovery temperature from about 25 to 50 °C, without the need of varying the copolymer's chemical structure. The thermal annealing approach here presented can be thus considered a powerful strategy for "ad hoc" programming the same material for applications requiring different recovery temperatures. Fibroblast culture experiments demonstrated scaffold biocompatibility.

  8. Anomalous Micellization of Pluronic Block Copolymers

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

  10. The melt rheological behavior of AB, ABA, BAB, and (AB)n block copolymers with monodisperse aramide segments

    NARCIS (Netherlands)

    Araichimani, A.; Dullaert, Konraad; Gaymans, R.J.

    2009-01-01

    The melt rheological behavior of segmented block copolymers with high melting diamide (A) hard segments (HS) and polyether (B) soft segments was studied. The block copolymers can be classified as B (monoblock), AB (diblock), ABA (triblock, diamide end segment), BAB (triblock, diamide mid-segment)

  11. Carboxylic Terminated Thermo-Responsive Copolymer Hydrogel and Improvement in Peptide Release Profile

    Directory of Open Access Journals (Sweden)

    Zi-Kun Rao

    2018-02-01

    Full Text Available To improve the release profile of peptide drugs, thermos-responsive triblock copolymer poly (ε-caprolactone-co-p-dioxanone-b-poly (ethylene glycol-b-poly (ε-caprolactone-co-p-dioxanone (PECP was prepared and end capped by succinic anhydride to give its carboxylic terminated derivative. Both PCEP block copolymer and its end group modified derivative showed temperature-dependent reversible sol-gel transition in water. The carboxylic end group could significantly decrease the sol-gel transition temperature by nearly 10 °C and strengthen the gel due to enhanced intermolecular force among triblock copolymer chains. Furthermore, compared with the original PECP triblock copolymer, HOOC–PECP–COOH copolymer displayed a retarded and sustained release profile for leuprorelin acetate over one month while effectively avoiding the initial burst. The controlled release was believed to be related to the formation of conjugated copolymer-peptide pair by ionic interaction and enhanced solubility of drug molecules into the hydrophobic domains of the hydrogel. Therefore, carboxyl terminated HOOC–PECP–COOH hydrogel was a promising and well-exhibited sustained release carrier for peptide drugs with the advantage of being able to develop injectable formulation by simple mixing.

  12. Influence of the content of hard segments on the properties of novel urethane-siloxane copolymers based on a poly(ε-caprolactone-b-poly(dimethylsiloxane-b-poly(ε- caprolactone triblock copolymer

    Directory of Open Access Journals (Sweden)

    Antić Vesna V.

    2011-01-01

    Full Text Available A series of novel thermoplastic urethane-siloxane copolymers (TPUSs based on a α,ω-dihydroxy-[poly(ε-caprolactone-bpoly( dimethylsiloxane-b-poly(ε-caprolactone] (α,ω-dihydroxy-PCLPDMS- PCL triblock copolymer, 4,4?-methylenediphenyl diisocyanate (MDI and 1,4-butanediol (BD was synthesized. The effects of the content (9-63 wt. % of hard urethane segments and their degree of polymerization on the properties of the segmented TPUSs were investigated. The structure, composition and hard segment degree of polymerization of the hard segments were examined using 1H- and quantitative 13C-NMR spectroscopy. The degree of crystallinity of the synthesized copolymers was determined using wide-angle X-ray scattering (WAXS. The surface properties were evaluated by measuring the water contact angle and water absorption. In the series of the TPUSs, the average degree of polymerization of the hard segments was varied from 1.2 to 14.4 MDI-BD units. It was found that average values from 3.8 to 14.4 MDI-BD units were effective segment lengths for crystallization of hard segments, which resulted in an increase in the degree of microphase separation of the copolymers. Spherulite-like superstructures were observed in copolymer films by scanning electron microscopy (SEM, which are believed to arise from the crystallization of the hard segments and/or PCL segments, depending on the content of the hard segments. The surface of the copolymers became more hydrophobic with increasing weight fraction of PDMS. The synthesized copolymers based on a PCL-PDMS-PCL segment showed good thermal stability, which increased with increasing content of soft PDMS segments, as was confirmed by the value of the starting temperature of thermal degradation.

  13. Renewable Pentablock Copolymers Containing Bulky Natural Rosin for Tough Bioplastics

    Science.gov (United States)

    Rahman, Md Anisur; Ganewatta, Mitra S.; Lokupitiya, Hasala N.; Liang, Yuan; Stefik, Morgan; Tang, Chuanbing

    Renewable polymers have received significant attention due to environmental concerns on petrochemical counterparts. One of the most abundant natural biomass is resin acids. However, most polymers derived from resin acids are low molecular weight and brittle because of the high chain entanglement molecular weight resulted from the bulky hydrophenanthrene pendant group. It is well established that the brittleness can be overcome by synthesizing multi-block copolymers with low entanglement molecular weight components. We investigated the effects of chain architecture and microdomain orientation on mechanical properties of both tri and pentablock copolymers. We synthesized rosin-containing A-B-A-B-A type pentablock and A-B-A type triblock copolymers to improve their mechanical properties. Pentablock copolymers showed higher strength and better toughness as compared to triblock copolymers, both superior to homopolymers. The greater toughness of pentablock copolymers is due to the presence of the rosin based midblock chains that act as bridging chains between two polynorbornene blocks.

  14. Tailored biodegradable triblock copolymer coatings obtained by MAPLE: a parametric study

    Science.gov (United States)

    Brajnicov, S.; Neacsu, P.; Moldovan, A.; Marascu, V.; Bonciu, A.; Ion, R.; Dinca, V.; Cimpean, A.; Dinescu, M.

    2017-11-01

    Biocompatible and biodegradable coatings with controllable and tailored chemical and physical characteristics (i.e. morphology and roughness) are of great interest in bone related research applications. Within this research direction, in this work, a series of novel biodegradable coatings based on triblock copolymers poly(lactide- co-caprolactone)-block-poly(ethylene-glycol)-block-poly(lactide- co-caprolactone) (PLCL-PEG-PLCL) were obtained by matrix-assisted pulsed laser evaporation (MAPLE) and their morphological characteristics and roughness were modulated by varying target composition and laser fluence. The coatings were used for preliminary in vitro testing with MC3T3-E1 pre-osteoblasts. It was found that for a specific range of fluences, the main functional groups in the MAPLE-deposited thin films, as determined by Fourier transform infrared spectroscopy, are similar to the molecular structures of the initial material. Depending on the deposition parameters, significant changes in morphologies, i.e. material accumulation in the form of droplets, wrinkles, or carpet-like structures were revealed by atomic force microscopy (AFM) and scanning electron microscopy. The optimized coating characteristics were further correlated to MC3T3-E1 pre-osteoblasts response. The ability to control the morphology and to maintain unaltered the chemistry of the deposited material through MAPLE is an important step in creating functional bio-interfaces in the field of biomedical research and tissue engineering.

  15. Boundary Lubrication of PEO-PPO-PEO Triblock Copolymer Physisorbed on Polypropylene, Polyethylene, and Cellulose Surfaces

    KAUST Repository

    Li, Yangyang

    2012-02-22

    In situ lateral force microscopy (LFM) and X-ray photoelectron spectroscopy (XPS) were used to probe the lubrication behavior of an aqueous solution of poly(oxyethylene)-poly(oxypropylene)-poly(oxyethylene) (PEO-PPO-PEO) symmetric triblock copolymer on thin films of polypropylene (PP), polyethylene (PE), and cellulose. LFM experiments were carried out while the substrates were immersed in water and in solutions of the copolymer. The friction coefficient on PP and PE was reduced after adsorption from the PEO-PPO-PEO aqueous solution while the opposite effect was observed for cellulose surfaces. A critical normal loading force, at which the friction coefficient of the lubricated and unlubricated surfaces is equal, was identified and related to the affinity of the polymer with the substrate. Further experiments were performed to mimic practical operations involving lubricant addition during manufacturing and postprocessing removal. XPS was used to verify the presence of the lubricant on the polymeric substrates and to evaluate its removal by water washing. The lubricant layer was easily removed by water from the PP and cellulose surfaces while a durable layer was found on PE. The XPS results were in agreement with the highest critical normal loading force measured for PE (52 nN for PE in contrast to a minimum of 10 nN for cellulose). While several reports exist on lubrication on hard surfaces, friction behavior on soft surfaces is still not well documented as the substrates usually deform under loading pressure. Therefore, we also propose a simple lubrication model for PP, PE, and cellulose and the use of critical normal loading force as a parameter to predict lubricity and durability of adsorbed nonionic block copolymers. © 2012 American Chemical Society.

  16. Synthesis and application of a thermo sensitive tri-block copolymer as an efficient sample treatment technique for preconcentration and ultra-trace detection of lead ions

    International Nuclear Information System (INIS)

    Behbahani, Mohammad; Abandansari, Hamid Sadeghi; Babapour, Meysam; Bagheri, Akbar; Nabid, Mohammad Reza; Salarian, Mani

    2014-01-01

    We have designed and synthesized a thermo sensitive tri-block copolymer for selective trace extraction of Pb(II) ions from biological and food samples. The polymer was characterized by Fourier transform IR and NMR spectroscopy, and by gel permeation chromatography. The critical aggregation concentration and lower critical solution temperature were determined via fluorescence and UV spectrophotometry, respectively. The effects of solution pH value, amount of copolymer, of the temperature on extraction and on phase separation, and of the matrix on the extraction of Pb(II) were optimized. Pb(II) ions were then quantified by FAAS. The use of this copolymer resulted in excellent figures of merit including a calibration plot extending from 0.5 to 160 μg L −1 (with an R 2 of >0.99), a limit of detection (LOD) as low as 90 pg L −1 , an extraction efficiency of >98 %, and relative standard deviations of <4 % for eight separate extraction experiments. (author)

  17. Multiblock copolymers synthesized in aqueous dispersions using multifunctional RAFT agents

    NARCIS (Netherlands)

    Bussels, R.; Bergman-Göttgens, C.M.; Meuldijk, J.; Koning, C.E.

    2005-01-01

    Triblock copolymers were synthesized in aqueous dispersions in two polymerization steps using a low molar mass difunctional dithiocarbamate-based RAFT agent, and in merely one polymerization step using a macromolecular difunctional dithiocarbamate-based RAFT agent. Segmented block copolymers

  18. Non-Covalent Microgel Particles Containing Functional Payloads: Coacervation of PEG-Based Triblocks via Microfluidics.

    Science.gov (United States)

    Wang, Cynthia X; Utech, Stefanie; Gopez, Jeffrey D; Mabesoone, Mathijs F J; Hawker, Craig J; Klinger, Daniel

    2016-07-06

    Well-defined microgel particles were prepared by combining coacervate-driven cross-linking of ionic triblock copolymers with the ability to control particle size and encapsulate functional cargos inherent in microfluidic devices. In this approach, the efficient assembly of PEO-based triblock copolymers with oppositely charged end-blocks allows for bioinspired cross-linking under mild conditions in dispersed aqueous droplets. This strategy enables the integration of charged cargos into the coacervate domains (e.g., the loading of anionic model compounds through electrostatic association with cationic end-blocks). Distinct release profiles can be realized by systematically varying the chemical nature of the payload and the microgel dimensions. This mild and noncovalent assembly method represents a promising new approach to tunable microgels as scaffolds for colloidal biomaterials in therapeutics and regenerative medicine.

  19. Dynamic photoinduced realignment processes in photoresponsive block copolymer films: effects of the chain length and block copolymer architecture.

    Science.gov (United States)

    Sano, Masami; Shan, Feng; Hara, Mitsuo; Nagano, Shusaku; Shinohara, Yuya; Amemiya, Yoshiyuki; Seki, Takahiro

    2015-08-07

    A series of block copolymers composed of an amorphous poly(butyl methacrylate) (PBMA) block connected with an azobenzene (Az)-containing liquid crystalline (PAz) block were synthesized by changing the chain length and polymer architecture. With these block copolymer films, the dynamic realignment process of microphase separated (MPS) cylinder arrays of PBMA in the PAz matrix induced by irradiation with linearly polarized light was studied by UV-visible absorption spectroscopy, and time-resolved grazing incidence small angle X-ray scattering (GI-SAXS) measurements using a synchrotron beam. Unexpectedly, the change in the chain length hardly affected the realignment rate. In contrast, the architecture of the AB-type diblock or the ABA-type triblock essentially altered the realignment feature. The strongly cooperative motion with an induction period before realignment was characteristic only for the diblock copolymer series, and the LPL-induced alignment change immediately started for triblock copolymers and the PAz homopolymer. Additionally, a marked acceleration in the photoinduced dynamic motions was unveiled in comparison with a thermal randomization process.

  20. Interstitial micelles in binary blends of A B A triblock copolymers and homopolymers

    Science.gov (United States)

    Wołoszczuk, S.; Banaszak, M.

    2018-01-01

    We investigate triblock-homopolymer blends of types A1BA2/A and A1BA2/B, using a lattice Monte Carlo method. While 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 and the A1BA2 solutions in selective solvent the phase behavior is relatively well known, including existence and stability of the interstitial micelles which were discovered in previous Monte Carlo simulations. In this paper we study the stability of the interstitial micelles as a function of triblock volume fraction in selective homopolymers of either type A or type B, using two significantly different homopolymer chain lengths. We found that adding selective homopolymer of type A shifts the stability of the interstitial micelles into significantly higher temperatures. We also obtained, via self-assembly, intriguing new nanostructures which can be identified as ordered truncated octahedra. Finally, we established that the phase behavior of the triblock-homopolymer blends depends relatively weakly on the chain length of the added homopolymer.

  1. Oxidation effect on templating of metal oxide nanoparticles within block copolymers

    International Nuclear Information System (INIS)

    Akcora, Pinar; Briber, Robert M.; Kofinas, Peter

    2009-01-01

    Amphiphilic norbornene-b-(norbornene dicarboxylic acid) diblock copolymers with different block ratios were prepared as templates for the incorporation of iron ions using an ion exchange protocol. The disordered arrangement of iron oxide particles within these copolymers was attributed to the oxidation of the iron ions and the strong interactions between iron oxide nanoparticles, particularly at high iron ion concentrations, which was found to affect the self-assembly of the block copolymer morphologies.

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

    Science.gov (United States)

    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. Copyright © 2016 Elsevier Ltd. All rights reserved.

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

    Directory of Open Access Journals (Sweden)

    Ahmed OAA

    2016-02-01

    Full Text Available Osama Abdelhakim Aly Ahmed,1,2 Ahmed Samir Zidan,1,3 Maan Khayat4 1Department of Pharmaceutics and Industrial Pharmacy, Faculty of Pharmacy, King Abdulaziz University, Jeddah, Saudi Arabia; 2Department of Pharmaceutics and Industrial Pharmacy, Faculty of Pharmacy, Minia University, Minia, Egypt; 3Department of Pharmaceutics and Industrial Pharmacy, Faculty of Pharmacy, Zagazig University, Zagazig, Egypt; 4Department of Pharmaceutical Chemistry, Faculty of Pharmacy, King Abdulaziz University, Jeddah, Saudi Arabia 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

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  5. Role of Synthetic and Dimensional Synthetic Organic Chemistry in Block Copolymer Micelle Nanosensor Engineering

    DEFF Research Database (Denmark)

    Ek, Pramod Kumar

    This thesis investigated the role of amphiphilic triblock copolymer micelle nanomaterials in nanosensors, with emphasis on the synthesis of micelle particle sensors. The thesis is focused on the role of synthetic and dimensional synthetic organic chemistry in amphiphilic triblock core-shellcorona...

  6. Novel fluorinated block copolymer architectures fuelled by atom transfer radical polymerization

    DEFF Research Database (Denmark)

    Jankova, Katja; Hvilsted, Søren

    2005-01-01

    Block copolymers based on poly(pentafluorostyrene), PFS, in various numbers and of different lengths, and polystyrene are prepared by atom transfer radical polymerization (ATRP). Di- and triblock copolymers with varying amounts of PFS were synthesized employing either I phenylethylbromide or 1,4-...

  7. Mesoscopic multiphase structures and the interfaces of block and graft copolymers in bulk

    International Nuclear Information System (INIS)

    Matsushita, Yushu

    1996-01-01

    Microphase-separated structures of copolymers with various architectures and their polymer/polymer interfaces were studied. They are SP diblock, PSP triblock, and SPP graft copolymers, where S and P denote polystyrene and poly(2-vinylpyridine), respectively. Morphological observations were carried out by means of transmission electron microscopy and small-angle X-ray scattering. Chain dimensions of component polymers were measured by small-angle neutron scattering and microphase-separated interfaces were observed by neutron reflectivity measurements using deuterium-labeled samples. It was clarified that morphological phase transitions among thermodynamically equilibrium structures for SP diblock and PSP triblock copolymers occur at almost the same compositions; however, those of SPP graft copolymers tend to occur at higher volume fraction of polystyrene, φ s , than those for block copolymers. As for alternating lamellar structures it turned out to be clear that lamellar domain spacings, D's, were scaled as the 2/3 power of the molecular weight of polymers irrespective of their architectures. S block chains of SP diblock and PSP triblock copolymers in lamellar structures were both confirmed to be deformed toward the direction perpendicular to the lamellar interfaces, but it revealed that their volumes were preserved. Further, S/P interfacial thicknesses of SP and PSP were essentially the same to each other and the values defined as the FWHM of the error functions which express the segment density distributions of the interfaces were determined to be about 4 nm. (author)

  8. Effects of nanoparticles on the compatibility of PEO-PMMA block copolymers.

    Science.gov (United States)

    Mu, Dan; Li, Jian-Quan; Li, Wei-Dong; Wang, Song

    2011-12-01

    The compatibility of six kinds of designed poly(ethylene oxide)-block-poly(methyl methacrylate) (PEO-b-PMMA) copolymers was studied at 270, 298 and 400 K via mesoscopic modeling. The values of the order parameters depended on both the structures of the block copolymers and the simulation temperature, while the values of the order parameters of the long chains were higher than those of the short ones; temperature had a more obvious effect on long chains than on the short ones. Plain copolymers doped with poly(ethylene oxide) (PEO) or poly(methyl methacrylate) (PMMA) homopolymer showed different order parameter values. When a triblock copolymer had the same component at both ends and was doped with one of its component polymers as a homopolymer (such as A5B6A5 doped with B6 or A5 homopolymer), the value of its order parameter depended on the simulation temperature. The highest order parameter values were observed for A5B6A5 doped with B6 at 400 K and for A5B6A5 doped with A5 at 270 K. A study of copolymers doped with nanoparticles showed that the mesoscopic phase was influenced by not only the properties of the nanoparticles, such as the size and density, but also the compositions of the copolymers. Increasing the size of the nanoparticles used as a dopant had the most significant effect on the phase morphologies of the copolymers.

  9. Simulation of 3D mesoscale structure formation in concentrated aqueous solution of the triblock polymer surfactants (ethylene oxide)(13)(propylene oxide)(30)(ethylene oxide)(13) and (propylene oxide)(19)(ethylene oxide)(33)(propylene oxide)(19). Application of dynamic mean-field density functional theory

    NARCIS (Netherlands)

    van Vlimmeren, BAC; Maurits, NM; Zvelindovsky, AV; Sevink, GJA; Fraaije, JGEM

    1999-01-01

    We simulate the microphase separation dynamics of aqueous solutions of the triblock polymer surfactants (ethylene oxide)(13)(propylene oxide)(30)(ethylene oxide)(13) and (propylene oxide)(19)(ethylene oxide)(33)(propylene oxide)(19) by a dynamic variant of mean-field density functional theory for

  10. Design of block-copolymer-based micelles for active and passive targeting

    NARCIS (Netherlands)

    Lebouille, Jérôme G J L; Leermakers, Frans A M; Cohen Stuart, Martien A.; Tuinier, Remco

    2016-01-01

    A self-consistent field study is presented on the design of active and passive targeting block-copolymeric micelles. These micelles form in water by self-assembly of triblock copolymers with a hydrophilic middle block and two hydrophobic outer blocks. A minority amount of diblock copolymers with the

  11. Design of block-copolymer-based micelles for active and passive targeting

    NARCIS (Netherlands)

    Lebouille, Jérôme G.J.L.; Leermakers, Frans A.M.; Cohen Stuart, Martien A.; Tuinier, Remco

    2016-01-01

    A self-consistent field study is presented on the design of active and passive targeting block-copolymeric micelles. These micelles form in water by self-assembly of triblock copolymers with a hydrophilic middle block and two hydrophobic outer blocks. A minority amount of diblock copolymers with

  12. Improving proton conduction pathways in di- and triblock copolymer membranes: Branched versus linear side chains

    Science.gov (United States)

    Dorenbos, G.

    2017-06-01

    Phase separation within a series of polymer membranes in the presence of water is studied by dissipative particle dynamics. Each polymer contains hydrophobic A beads and hydrophilic C beads. Three parent architectures are constructed from a backbone composed of connected hydrophobic A beads to which short ([C]), long ([A3C]), or symmetrically branched A5[AC][AC] side chains spring off. Three di-block copolymer derivatives are constructed by covalently bonding an A30 block to each parent architecture. Also three tri-blocks with A15 blocks attached to both ends of each parent architecture are modeled. Monte Carlo tracer diffusion calculations through the water containing pores for 1226 morphologies reveal that water diffusion for parent architectures is slowest and diffusion through the di-blocks is fastest. Furthermore, diffusion increases with side chain length and is highest for branched side chains. This is explained by the increase of water pore size with , which is the average number of bonds that A beads are separated from a nearest C bead. Optimization of within the amphiphilic parent architecture is expected to be essential in improving proton conduction in polymer electrolyte membranes.

  13. Designing block copolymer architectures for targeted membrane performance

    KAUST Repository

    Dorin, Rachel Mika; Phillip, William A.; Sai, Hiroaki; Werner, Jö rg; Elimelech, Menachem; Wiesner, Ulrich

    2014-01-01

    Using a combination of block copolymer self-assembly and non-solvent induced phase separation, isoporous ultrafiltration membranes were fabricated from four poly(isoprene-b-styrene-b-4-vinylpyridine) triblock terpolymers with similar block volume

  14. Stereocomplex mediated gelation of PEG-(PLA)2 and PEG(PLA)8 block copolymers

    NARCIS (Netherlands)

    Hiemstra, C.; Zhong, Zhiyuan; Dijkstra, Pieter J.; Feijen, Jan

    2005-01-01

    Stereocomplex mediated hydrogels have been prepared by mixing solutions of polymers of opposite chirality of either PEG-(PLA)2 triblock copolymers or PEG-(PLA)8 star block copolymers. The critical gel concentrations of the mixed enantiomer solutions were considerably lower compared to polymer

  15. Synthesis and Self-Assembly of Amphiphilic Triblock Terpolymers with Complex Macromolecular Architecture

    KAUST Repository

    Polymeropoulos, George; Zapsas, George; Hadjichristidis, Nikolaos; Avgeropoulos, Apostolos

    2015-01-01

    Two star triblock terpolymers (PS-b-P2VP-b-PEO)3 and one dendritic-like terpolymer [PS-b-P2VP-b-(PEO)2]3 of PS (polystyrene), P2VP (poly(2-vinylpyridine)), and PEO (poly(ethylene oxide)), never reported before, were synthesized by combining atom transfer radical and anionic polymerizations. The synthesis involves the transformation of the -Br groups of the previously reported Br-terminated 3-arm star diblock copolymers to one or two -OH groups, followed by anionic polymerization of ethylene oxide to afford the star or dendritic structure, respectively. The well-defined structure of the terpolymers was confirmed by static light scattering, size exclusion chromatography, and NMR spectroscopy. The self-assembly in solution and the morphology in bulk of the terpolymers, studied by dynamic light scattering and transmission electron microscopy, respectively, reveal new insights in the phase separation of these materials with complex macromolecular architecture. © 2015 American Chemical Society.

  16. Synthesis and Self-Assembly of Amphiphilic Triblock Terpolymers with Complex Macromolecular Architecture

    KAUST Repository

    Polymeropoulos, George

    2015-11-25

    Two star triblock terpolymers (PS-b-P2VP-b-PEO)3 and one dendritic-like terpolymer [PS-b-P2VP-b-(PEO)2]3 of PS (polystyrene), P2VP (poly(2-vinylpyridine)), and PEO (poly(ethylene oxide)), never reported before, were synthesized by combining atom transfer radical and anionic polymerizations. The synthesis involves the transformation of the -Br groups of the previously reported Br-terminated 3-arm star diblock copolymers to one or two -OH groups, followed by anionic polymerization of ethylene oxide to afford the star or dendritic structure, respectively. The well-defined structure of the terpolymers was confirmed by static light scattering, size exclusion chromatography, and NMR spectroscopy. The self-assembly in solution and the morphology in bulk of the terpolymers, studied by dynamic light scattering and transmission electron microscopy, respectively, reveal new insights in the phase separation of these materials with complex macromolecular architecture. © 2015 American Chemical Society.

  17. Cytotoxicity and cellular uptake of tri-block copolymer nanoparticles with different size and surface characteristics

    Directory of Open Access Journals (Sweden)

    Bhattacharjee Sourav

    2012-04-01

    Full Text Available Abstract Background Polymer nanoparticles (PNP are becoming increasingly important in nanomedicine and food-based applications. Size and surface characteristics are often considered to be important factors in the cellular interactions of these PNP, although systematic investigations on the role of surface properties on cellular interactions and toxicity of PNP are scarce. Results Fluorescent, monodisperse tri-block copolymer nanoparticles with different sizes (45 and 90 nm and surface charges (positive and negative were synthesized, characterized and studied for uptake and cytotoxicity in NR8383 and Caco-2 cells. All types of PNP were taken up by the cells. The positive smaller PNP45 (45 nm showed a higher cytotoxicity compared to the positive bigger PNP90 (90 nm particles including reduction in mitochondrial membrane potential (ΔΨm, induction of reactive oxygen species (ROS production, ATP depletion and TNF-α release. The negative PNP did not show any cytotoxic effect. Reduction in mitochondrial membrane potential (ΔΨm, uncoupling of the electron transfer chain in mitochondria and the resulting ATP depletion, induction of ROS and oxidative stress may all play a role in the possible mode of action for the cytotoxicity of these PNP. The role of receptor-mediated endocytosis in the intracellular uptake of different PNP was studied by confocal laser scanning microscopy (CLSM. Involvement of size and charge in the cellular uptake of PNP by clathrin (for positive PNP, caveolin (for negative PNP and mannose receptors (for hydroxylated PNP were found with smaller PNP45 showing stronger interactions with the receptors than bigger PNP90. Conclusions The size and surface characteristics of polymer nanoparticles (PNP; 45 and 90 nm with different surface charges play a crucial role in cellular uptake. Specific interactions with cell membrane-bound receptors (clathrin, caveolin and mannose leading to cellular internalization were observed to depend on

  18. Pressure jump kinetics of disorder to BCC ordering in diblock copolymer micelles in a selective solvent

    Czech Academy of Sciences Publication Activity Database

    Liu, Y.; Spring, J. D.; Steinhart, Miloš; Bansil, R.

    2012-01-01

    Roč. 45, č. 22 (2012), s. 9147-9154 ISSN 0024-9297 Institutional support: RVO:61389013 Keywords : X-ray-scattering * block-copolymer * triblock copolymer Subject RIV: CD - Macromolecular Chemistry Impact factor: 5.521, year: 2012

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

    Science.gov (United States)

    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.

  20. Fluorinated Amphiphilic Polymers and Their Blends for Fouling-Release Applications: The Benefits of a Triblock Copolymer Surface

    KAUST Repository

    Sundaram, Harihara S.

    2011-09-28

    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. © 2011 American Chemical Society.

  1. Associative, thermodynamic and thermo-kinetics behavior of di- and triblock copolymers of oxyethylene and oxybutylene in aqueous media

    International Nuclear Information System (INIS)

    Khan, Abbas; Siddiq, Mohammad

    2014-01-01

    Highlights: • Associative, thermodynamic and thermo-kinetics behavior was investigated. • Micellization of these copolymer is spontaneous, endothermic and entropy driven. • Micelles are spherical in shape and their nature depends on temperature. • Fusion/fission mechanism dominates over unimer entry/expulsion for micellar dynamics. • Micellar parameters depend on temperature and on the delicate hydrophobic–hydrophilic balance of the blocks. - Abstract: The associative, thermodynamic and thermo-kinetics properties of a diblock E 90 B 10 and three triblock copolymers based on polyoxyethylene and polyoxybutylene of the type E m B 10 E m water have been studied by surface tensiometry, light scattering and temperature-jump stopped-flow techniques. The data from surface tension was helpful to detect the critical micelle concentration (CMC) as well as to calculate the thermodynamic parameters of micellization. Dynamic light scattering (DLS) was employed to obtain the values of hydrodynamic radii (R h ), volume (υ h ) and hydrodynamic expansion parameter (δ h ) of the micelle at different temperatures. Similarly, static light scattering (SLS) measurements made us enable to find out various micellar parameters such as; weight-average molar (M w ), association number (N w ), thermodynamic radius (R t ), thermodynamic volume (υ t ), anhydrous volume (υ a ) and thermodynamic expansion parameter (δ t ) of the micelles. Likewise, the kinetics of micellar aggregation/dynamic was also investigated by using temperature-jump stopped-flow technique in the temperature range of 20–50 °C

  2. Nanostructured Polysulfone-Based Block Copolymer Membranes

    KAUST Repository

    Xie, Yihui

    2016-05-01

    The aim of this work is to fabricate nanostructured membranes from polysulfone-based block copolymers through self-assembly and non-solvent induced phase separation. Block copolymers containing polysulfone are novel materials for this purpose providing better mechanical and thermal stability to membranes than polystyrene-based copolymers, which have been exclusively used now. Firstly, we synthesized a triblock copolymer, poly(tert-butyl acrylate)-b-polsulfone-b-poly(tert-butyl acrylate) through polycondensation and reversible addition-fragmentation chain-transfer polymerization. The obtained membrane has a highly porous interconnected skin layer composed of elongated micelles with a flower-like arrangement, on top of the graded finger-like macrovoids. Membrane surface hydrolysis was carried out in a combination with metal complexation to obtain metal-chelated membranes. The copper-containing membrane showed improved antibacterial capability. Secondly, a poly(acrylic acid)-b-polysulfone-b-poly(acrylic acid) triblock copolymer obtained by hydrolyzing poly(tert-butyl acrylate)-b-polsulfone-b-poly(tert-butyl acrylate) formed a thin film with cylindrical poly(acrylic acid) microdomains in polysulfone matrix through thermal annealing. A phase inversion membrane was prepared from the same polymer via self-assembly and chelation-assisted non-solvent induced phase separation. The spherical micelles pre-formed in a selective solvent mixture packed into an ordered lattice in aid of metal-poly(acrylic acid) complexation. The space between micelles was filled with poly(acrylic acid)-metal complexes acting as potential water channels. The silver0 nanoparticle-decorated membrane was obtained by surface reduction, having three distinct layers with different particle sizes. Other amphiphilic copolymers containing polysulfone and water-soluble segments such as poly(ethylene glycol) and poly(N-isopropylacrylamide) were also synthesized through coupling reaction and copper0-mediated

  3. Temperature effects on the stability of gold nanoparticles in the presence of a cationic thermoresponsive copolymer

    Energy Technology Data Exchange (ETDEWEB)

    Pamies, Ramón [Technical University of Cartagena, Department of Material Engineering and Manufacturing (Spain); Zhu, Kaizheng [University of Oslo, Department of Chemistry (Norway); Kjøniksen, Anna-Lena, E-mail: anna.l.kjoniksen@hiof.no [Østfold University College, Faculty of Engineering (Norway); Nyström, Bo [University of Oslo, Department of Chemistry (Norway)

    2016-11-15

    New hybrid complexes composed by a thermoresponsive copolymer and gold nanoparticles (R{sub h} = 22 nm) have been characterized by dynamic light scattering (DLS) and UV-visible spectroscopy. A cationic thermoresponsive triblock copolymer, methoxy-poly(ethylene glycol)-block-poly(N-isopropylacrylamide)-block-poly((3-acrylamidopropyl) trimethyl ammonium chloride), abbreviated as MPEG-b-PNIPAAM-b-PN(+), has been synthesized by atom transfer radical polymerization (ATRP). We have evaluated the thermal response at low concentrations of this triblock copolymer in bulk solution and the effect of concentration on the interaction between this thermosensitive copolymer and the gold nanoparticles (AuNPs) to form new hybrid complexes (60–1000 nm) at different temperatures. The thermosensitive nature of the copolymer causes both aggregation and contraction of the aggregates at elevated temperatures. The AuNPs were found to be separately embedded in the hybrid complexes. Interestingly, the AuNPs prevent macroscopic phase separation of the system at high temperatures.

  4. Novel Pentablock Copolymers as Thermosensitive Self-Assembling Micelles for Ocular Drug Delivery

    Directory of Open Access Journals (Sweden)

    Mitra Alami-Milani

    2017-04-01

    Full Text Available Many studies have focused on how drugs are formulated in the sol state at room temperature leading to the formation of in situ gel at eye temperature to provide a controlled drug release. Stimuli-responsive block copolymer hydrogels possess several advantages including uncomplicated drug formulation and ease of application, no organic solvent, protective environment for drugs, site-specificity, prolonged and localized drug delivery, lower systemic toxicity, and capability to deliver both hydrophobic and hydrophilic drugs. Self-assembling block copolymers (such as diblock, triblock, and pentablock copolymers with large solubility variation between hydrophilic and hydrophobic segments are capable of making temperature-dependent micellar assembles, and with further increase in the temperature, of jellifying due to micellar aggregation. In general, molecular weight, hydrophobicity, and block arrangement have a significant effect on polymer crystallinity, micelle size, and in vitro drug release profile. The limitations of creature triblock copolymers as initial burst release can be largely avoided using micelles made of pentablock copolymers. Moreover, formulations based on pentablock copolymers can sustain drug release for a longer time. The present study aims to provide a concise overview of the initial and recent progresses in the design of hydrogel-based ocular drug delivery systems.

  5. Block copolymer lithography of rhodium nanoparticles for high temperature electrocatalysis.

    Science.gov (United States)

    Boyd, David A; Hao, Yong; Li, Changyi; Goodwin, David G; Haile, Sossina M

    2013-06-25

    We present a method for forming ordered rhodium nanostructures on a solid support. The approach makes use of a block copolymer to create and assemble rhodium chloride nanoparticles from solution onto a surface; subsequent plasma and thermal processing are employed to remove the polymer and fully convert the nanostructures to metallic rhodium. Films cast from a solution of the triblock copolymer poly(styrene-b-2-vinyl pyridine-b-ethylene oxide) dissolved in toluene with rhodium(III) chloride hydrate were capable of producing a monolayer of rhodium nanoparticles of uniform size and interparticle spacing. The nanostructures were characterized by scanning electron microscopy, X-ray photoelectron spectroscopy, and atomic force microscopy. The electrocatalytic performance of the nanoparticles was investigated with AC impedance spectroscopy. We observed that the addition of the particles to a model solid oxide fuel cell anode provided up to a 14-fold improvement in the anode activity as evidenced by a decrease in the AC impedance resistance. Examination of the anode after electrochemical measurement revealed that the basic morphology and distribution of the particles were preserved.

  6. Asymmetric PS-block-(PS-co-PB)-block-PS block copolymers: morphology formation and deformation behaviour

    International Nuclear Information System (INIS)

    Adhikari, Rameshwar; Huy, Trinh An; Buschnakowski, Matthias; Michler, Goerg H; Knoll, Konrad

    2004-01-01

    Morphology formation and deformation behaviour of asymmetric styrene/butadiene triblock copolymers (total polystyrene (PS) content ∼70%) consisting of PS outer blocks held apart by a styrene-co-butadiene random copolymer block (PS-co-PB) each were investigated. The techniques used were differential scanning calorimetry, transmission electron microscopy, uniaxial tensile testing and Fourier-transform infrared spectroscopy. A significant shift of the phase behaviour relative to that of a neat symmetric triblock copolymer was observed, which can be attributed to the asymmetric architecture and the presence of PS-co-PB as a soft block. The mechanical properties and the microdeformation phenomena were mainly controlled by the nature of their solid-state morphology. Independent of morphology type, the soft phase was found to deform to a significantly higher degree of orientation when compared with the hard phase

  7. Khảo sát sự tạo mixel của một số Copolyme Pluronic

    DEFF Research Database (Denmark)

    Hùng, Nguyễn Quốc; Hvidt, Søren; Batsberg, Walther

    2009-01-01

    The micellization of several Pluronics (PEO-PPO-PEO triblock copolymers) was investigated by Differential Scanning Calorimetry (DSC). These copolymers were also characterized and purified by liquid chromatography. The PEO/PPO compositions of Pluronics were determined by 1H-NMR. The thermograms from...

  8. Associative, thermodynamic and thermo-kinetics behavior of di- and triblock copolymers of oxyethylene and oxybutylene in aqueous media

    Energy Technology Data Exchange (ETDEWEB)

    Khan, Abbas [Department of Chemistry, Abdul Wali Khan University, Mardan 23200 (Pakistan); Department of Chemistry, Quaid-I-Azam University, Islamabad 45320 (Pakistan); Siddiq, Mohammad, E-mail: m_sidiq12@yahoo.com [Department of Chemistry, Quaid-I-Azam University, Islamabad 45320 (Pakistan)

    2014-11-10

    Highlights: • Associative, thermodynamic and thermo-kinetics behavior was investigated. • Micellization of these copolymer is spontaneous, endothermic and entropy driven. • Micelles are spherical in shape and their nature depends on temperature. • Fusion/fission mechanism dominates over unimer entry/expulsion for micellar dynamics. • Micellar parameters depend on temperature and on the delicate hydrophobic–hydrophilic balance of the blocks. - Abstract: The associative, thermodynamic and thermo-kinetics properties of a diblock E{sub 90}B{sub 10} and three triblock copolymers based on polyoxyethylene and polyoxybutylene of the type E{sub m}B{sub 10}E{sub m} water have been studied by surface tensiometry, light scattering and temperature-jump stopped-flow techniques. The data from surface tension was helpful to detect the critical micelle concentration (CMC) as well as to calculate the thermodynamic parameters of micellization. Dynamic light scattering (DLS) was employed to obtain the values of hydrodynamic radii (R{sub h}), volume (υ{sub h}) and hydrodynamic expansion parameter (δ{sub h}) of the micelle at different temperatures. Similarly, static light scattering (SLS) measurements made us enable to find out various micellar parameters such as; weight-average molar (M{sub w}), association number (N{sub w}), thermodynamic radius (R{sub t}), thermodynamic volume (υ{sub t}), anhydrous volume (υ{sub a}) and thermodynamic expansion parameter (δ{sub t}) of the micelles. Likewise, the kinetics of micellar aggregation/dynamic was also investigated by using temperature-jump stopped-flow technique in the temperature range of 20–50 °C.

  9. Importance of crystallinity of anchoring block of semi-solid amphiphilic triblock copolymers in stabilization of silicone nanoemulsions.

    Science.gov (United States)

    Le Kim, Trang Huyen; Jun, Hwiseok; Nam, Yoon Sung

    2017-10-01

    Polymer emulsifiers solidified at the interface between oil and water can provide exceptional dispersion stability to emulsions due to the formation of unique semi-solid interphase. Our recent works showed that the structural stability of paraffin-in-water emulsions highly depends on the oil wettability of hydrophobic block of methoxy poly(ethylene glycol)-block-poly(ε-caprolactone) (mPEG-b-PCL). Here we investigate the effects of the crystallinity of hydrophobic block of triblock copolymer-based emulsifiers, PCLL-b-PEG-b-PCLL, on the colloidal properties of silicone oil-in-water nanoemulsions. The increased ratio of l-lactide to ε-caprolactone decreases the crystallinity of the hydrophobic block, which in turn reduces the droplet size of silicone oil nanoemulsions due to the increased chain mobility at the interface. All of the prepared nanoemulsions are very stable for a month at 37°C. However, the exposure to repeated freeze-thaw cycles quickly destabilizes the nanoemulsions prepared using the polymer with the reduced crystallinity. This work demonstrates that the anchoring chain crystallization in the semi-solid interphase is critically important for the structural robustness of nanoemulsions under harsh physical stresses. Copyright © 2017 Elsevier Inc. All rights reserved.

  10. Self-Assembled CNT-Polymer Hybrids in Single-Walled Carbon Nanotubes Dispersed Aqueous Triblock Copolymer Solutions

    Science.gov (United States)

    Vijayaraghavan, D.; Manjunatha, A. S.; Poojitha, C. G.

    2018-04-01

    We have carried out scanning electron microscopy (SEM), differential scanning calorimetry (DSC), small angle X-ray scattering (SAXS), electrical conductivity, and 1H NMR studies as a function of temperature on single-walled carbon nanotubes (SWCNTs) dispersed aqueous triblock copolymer (P123) solutions. The single-walled carbon nanotubes in this system aggregate to form bundles, and the bundles aggregate to form net-like structures. Depending on the temperature and phases of the polymer, this system exhibits three different self-assembled CNT-polymer hybrids. We find CNT-unimer hybrid at low temperatures, CNT-micelle hybrid at intermediate temperatures wherein the polymer micelles are adsorbed in the pores of the CNT nets, and another type of CNT-micelle hybrid at high temperatures wherein the polymer micelles are adsorbed on the surface of the CNT bundles. Our DSC thermogram showed two peaks related to these structural changes in the CNT-polymer hybrids. Temperature dependence of the 1H NMR chemical shifts of the molecular groups of the polymer and the AC electrical conductivity of the composite also showed discontinuous changes at the temperatures at which the CNT-polymer hybrid's structural changes are seen. Interestingly, for a higher CNT concentration (0.5 wt.%) in the system, the aggregated polymer micelles adsorbed on the CNTs exhibit cone-like and cube-like morphologies at the intermediate and at high temperatures respectively.

  11. Functional Nanoporous Polymers from Block Copolymer Precursors

    DEFF Research Database (Denmark)

    Guo, Fengxiao

    Abstract Self-assembly of block copolymers provides well-defined morphologies with characteristic length scales in the nanometer range. Nanoporous polymers prepared by selective removal of one block from self-assembled block copolymers offer great technological promise due to their many potential...... functionalities remains a great challenge due to the limitation of available polymer synthesis and the nanoscale confinement of the porous cavities. The main topic of this thesis is to develop methods for fabrication of functional nanoporous polymers from block copolymer precursors. A method has been developed......, where living anionic polymerization and atom transfer radical polymerization (ATRP) are combined to synthesize a polydimethylsiloxane-b-poly(tert-butyl acrylate)-b-polystyrene (PDMS-b-PtBA-b-PS) triblock copolymer precursor. By using either anhydrous hydrogen fluoride or trifluoroacetic acid, PtBA block...

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

    Science.gov (United States)

    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

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

    Science.gov (United States)

    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)

  14. Poly(ethylene oxide)–Poly(propylene oxide)-Based Copolymers for ...

    African Journals Online (AJOL)

    Amphiphilic poly(ethylene oxide)–poly(propylene oxide) (PEO–PPO)-based copolymers are thermoresponsive materials having aggregation properties in aqueous medium. As hydrosolubilizers of poorly water-soluble drugs and improved stability of sensitive agents, these materials have been investigated for improvement ...

  15. Synthesis of single-crystal PbS nanorods via a simple hydrothermal process using PEO-PPO-PEO triblock copolymer as a structure-directing agent

    International Nuclear Information System (INIS)

    Bu Junfu; Nie Chageng; Liang Jinxia; Sun Lan; Xie Zhaoxiong; Wu Qi; Lin Changjian

    2011-01-01

    Single-crystal PbS nanorods were successfully synthesized through a simple hydrothermal route using PEO-PPO-PEO triblock copolymer (P123) as a structure-directing agent. The XRD pattern indicates that the crystal structure of the nanorods is face-centre-cubic rocksalt. A SEM image shows that the nanorods have a diameter of 40-70 nm and a length of 200-600 nm, and both tips exhibit taper-like structures. HRTEM and SAED images reveal the single-crystalline nature of the nanorods with the growth along the (111) direction. The experimental results indicated that the P123 concentration and reaction temperature played important roles in controlling the morphology of the PbS nanostructures. The optical property of PbS nanorods was investigated by UV-Vis absorption spectroscopy and the band structure was calculated by the B3LYP hybrid density functional theory.

  16. Morphological investigation of polydisperse asymmetric block copolymer systems of poly(styrene) and poly(methacrylic acid) in the strong segregation regime

    DEFF Research Database (Denmark)

    Asad Ayoubi, Mehran; Zhu, Kaizheng; Nyström, Bo

    2013-01-01

    Samples of compositionally (highly) asymmetric diblock copolymers and, also, mixtures of diblock and triblock copolymers (the latter obtained as end-coupling products of two diblock molecules of the mixture), composed of (a) monodisperse majority block(s) of poly(styrene) (PS) and a polydisperse...

  17. Doxorubicin-loaded micelles of reverse poly(butylene oxide)-poly(ethylene oxide)-poly(butylene oxide) block copolymers as efficient "active" chemotherapeutic agents.

    Science.gov (United States)

    Cambón, A; Rey-Rico, A; Mistry, D; Brea, J; Loza, M I; Attwood, D; Barbosa, S; Alvarez-Lorenzo, C; Concheiro, A; Taboada, P; Mosquera, V

    2013-03-10

    Five reverse poly(butylene oxide)-poly(ethylene oxide)-poly(butylene oxide) block copolymers, BOnEOmBOn, with BO ranging from 8 to 21 units and EO from 90 to 411 were synthesized and evaluated as efficient chemotherapeutic drug delivery nanocarriers and inhibitors of the P-glycoprotein (P-gp) efflux pump in a multidrug resistant (MDR) cell line. The copolymers were obtained by reverse polymerization of poly(butylene oxide), which avoids transfer reaction and widening of the EO block distribution, commonly found in commercial poly(ethylene oxide)-poly(propylene oxide) block copolymers (poloxamers). BOnEOmBOn copolymers formed spherical micelles of 10-40 nm diameter at lower concentrations (one order of magnitude) than those of equivalent poloxamers. The influence of copolymer block lengths and BO/EO ratios on the solubilization capacity and protective environment for doxorubicin (DOXO) was investigated. Micelles showed drug loading capacity ranging from ca. 0.04% to 1.5%, more than 150 times the aqueous solubility of DOXO, and protected the cargo from hydrolysis for more than a month due to their greater colloidal stability in solution. Drug release profiles at various pHs, and the cytocompatibility and cytotoxicity of the DOXO-loaded micelles were assessed in vitro. DOXO loaded in the polymeric micelles accumulated more slowly inside the cells than free DOXO due to its sustained release. All copolymers were found to be cytocompatible, with viability extents larger than 95%. In addition, the cytotoxicity of DOXO-loaded micelles was higher than that observed for free drug solutions in a MDR ovarian NCI-ADR-RES cell line which overexpressed P-gp. The inhibition of the P-gp efflux pump by some BOnEOmBOn copolymers, similar to that measured for the common P-gp inhibitor verapamil, favored the retention of DOXO inside the cell increasing its cytotoxic activity. Therefore, poly(butylene oxide)-poly(ethylene oxide) block copolymers offer interesting features as cell

  18. Ionization of amphiphilic acidic block copolymers.

    Science.gov (United States)

    Colombani, Olivier; Lejeune, Elise; Charbonneau, Céline; Chassenieux, Christophe; Nicolai, Taco

    2012-06-28

    The ionization behavior of an amphiphilic diblock copolymer poly(n-butyl acrylate(50%)-stat-acrylic acid(50%))(100)-block-poly(acrylic acid)(100) (P(nBA(50%)-stat-AA(50%))(100)-b-PAA(100), DH50) and of its equivalent triblock copolymer P(nBA(50%)-stat-AA(50%))(100)-b-PAA(200)-b-P(nBA(50%)-stat-AA(50%))(100) (TH50) were studied by potentiometric titration either in pure water or in 0.5 M NaCl. These polymers consist of a hydrophilic acidic block (PAA) connected to a hydrophobic block, P(nBA(50%)-stat-AA(50%))(100), whose hydrophobic character has been mitigated by copolymerization with hydrophilic units. We show that all AA units, even those in the hydrophobic block could be ionized. However, the AA units within the hydrophobic block were less acidic than those in the hydrophilic block, resulting in the preferential ionization of the latter block. The preferential ionization of PAA over that of P(nBA(50%)-stat-AA(50%))(100) was stronger at higher ionic strength. Remarkably, the covalent bonds between the PAA and P(nBA(50%)-stat-AA(50%))(100) blocks in the diblock or the triblock did not affect the ionization of each block, although the self-association of the block copolymers into spherical aggregates modified the environment of the PAA blocks compared to when PAA was molecularly dispersed.

  19. Visualization of the distribution of surface-active block copolymers in PDMS-based coatings

    DEFF Research Database (Denmark)

    Noguer, A. Camós; Latipov, R.; Madsen, F. B.

    2018-01-01

    the distribution and release of these block copolymers from PDMS-based coatings has been previously reported. However, the distribution and behaviour of these compounds in the bulk of the PDMS coating are not fully understood. A novel fluorescent-labelled triblock PEG-b-PDMS-b-PEG copolymer was synthesized...... results in non-specific protein adsorption and wettability issues. Poly(ethylene glycol)-based surface-active block copolymers and surfactants have been added to PDMS coatings and films to impart biofouling resistance and hydrophilicity to the PDMS surface with successful results. Information regarding...

  20. 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.

    Science.gov (United States)

    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.

  1. Boundary layers of aqueous surfactant and block copolymer solutions against hydrophobic and hydrophilic solid surfaces

    International Nuclear Information System (INIS)

    Steitz, Roland; Schemmel, Sebastian; Shi Hongwei; Findenegg, Gerhard H

    2005-01-01

    The boundary layer of aqueous surfactants and amphiphilic triblock copolymers against flat solid surfaces of different degrees of hydrophobicity was investigated by neutron reflectometry (NR), grazing incidence small angle neutron scattering (GISANS) and atomic force microscopy (AFM). Solid substrates of different hydrophobicities were prepared by appropriate surface treatment or by coating silicon wafers with polymer films of different chemical natures. For substrates coated with thin films (20-30 nm) of deuterated poly(styrene) (water contact angle θ w ∼ 90), neutron reflectivity measurements on the polymer/water interface revealed a water depleted liquid boundary layer of 2-3 nm thickness and a density about 90% of the bulk water density. No pronounced depletion layer was found at the interface of water against a less hydrophobic polyelectrolyte coating (θ w ∼ 63). It is believed that the observed depletion layer at the hydrophobic polymer/water interface is a precursor of the nanobubbles which have been observed by AFM at this interface. Decoration of the polymer coatings by adsorbed layers of nonionic C m E n surfactants improves their wettability by the aqueous phase at surfactant concentrations well below the critical micellar concentration (CMC) of the surfactant. Here, GISANS experiments conducted on the system SiO 2 /C 8 E 4 /D 2 O reveal that there is no preferred lateral organization of the C 8 E 4 adsorption layers. For amphiphilic triblock copolymers (PEO-PPO-PEO) it is found that under equilibrium conditions they form solvent-swollen brushes both at the air/water and the solid/water interface. In the latter case, the brushes transform to uniform, dense layers after extensive rinsing with water and subsequent solvent evaporation. The primary adsorption layers maintain properties of the precursor brushes. In particular, their thickness scales with the number of ethylene oxide units (EO) of the block copolymer. In the case of dip-coating without

  2. Surface modification of paclitaxel-loaded tri-block copolymer PLGA-b-PEG-b-PLGA nanoparticles with protamine for liver cancer therapy

    Energy Technology Data Exchange (ETDEWEB)

    Gao, Nansha [Chinese Academy of Science, Research Center for Human Tissues and Organs Degeneration, Shenzhen Institute of Advanced Technology (China); Chen, Zhihong [Guangdong Medical College, Analysis Centre (China); Xiao, Xiaojun [Shenzhen University, Institute of Allergy and Immunology, School of Medicine (China); Ruan, Changshun [Chinese Academy of Science, Research Center for Human Tissues and Organs Degeneration, Shenzhen Institute of Advanced Technology (China); Mei, Lin [Tsinghua University, The Shenzhen Key Lab of Gene and Antibody Therapy, and Division of Life and Health Sciences, Graduate School at Shenzhen (China); Liu, Zhigang, E-mail: lzg@szu.edu.cn [Shenzhen University, Institute of Allergy and Immunology, School of Medicine (China); Zeng, Xiaowei, E-mail: zeng.xiaowei@sz.tsinghua.edu.cn [Tsinghua University, The Shenzhen Key Lab of Gene and Antibody Therapy, and Division of Life and Health Sciences, Graduate School at Shenzhen (China)

    2015-08-15

    In order to enhance the therapeutic effect of chemotherapy on liver cancer, a biodegradable formulation of protamine-modified paclitaxel-loaded poly(lactide-co-glycolide)-b-poly(ethylene glycol)-b-poly(lactide-co-glycolide) (PLGA-b-PEG-b-PLGA) nanoparticles (PTX-loaded/protamine NPs) was prepared. Tri-block copolymer PLGA-b-PEG-b-PLGA was synthesized by ring-opening polymerization and characterized by {sup 1}H NMR spectroscopy and gel permeation chromatography. PTX-loaded and PTX-loaded/protamine NPs were characterized in terms of size, size distribution, zeta potential, surface morphology, drug encapsulation efficiency, and drug release. Confocal laser scanning microscopy showed that coumarin 6-loaded/protamine NPs were internalized by hepatocellular carcinoma cell line HepG2. The cellular uptake efficiency of NPs was obviously elevated after protamine modification. With commercial formulation Taxol{sup ®} as the reference, HepG2 cells were also used to study the cytotoxicity of the NPs. PTX-loaded/protamine NPs exhibited significantly higher cytotoxicity than PTX-loaded NPs and Taxol{sup ®} did. All the results suggested that surface modification of PTX-loaded PLGA-b-PEG-b-PLGA NPs with protamine boosted the therapeutic efficacy on liver cancer.

  3. Block copolymer micelles with a dual-stimuli-responsive core for fast or slow degradation.

    Science.gov (United States)

    Han, Dehui; Tong, Xia; Zhao, Yue

    2012-02-07

    We report the design and demonstration of a dual-stimuli-responsive block copolymer (BCP) micelle with increased complexity and control. We have synthesized and studied a new amphiphilic ABA-type triblock copolymer whose hydrophobic middle block contains two types of stimuli-sensitive functionalities regularly and repeatedly positioned in the main chain. Using a two-step click chemistry approach, disulfide and o-nitrobenzyle methyl ester groups are inserted into the main chain, which react to reducing agents and light, respectively. With the end blocks being poly(ethylene oxide), micelles formed by this BCP possess a core that can be disintegrated either rapidly via photocleavage of o-nitrobenzyl methyl esters or slowly through cleavage of disulfide groups by a reducing agent in the micellar solution. This feature makes possible either burst release of an encapsulated hydrophobic species from disintegrated micelles by UV light, or slow release by the action of a reducing agent, or release with combined fast-slow rate profiles using the two stimuli.

  4. Chain conformations of ABA triblock coplymers in microphase-separated structures for SANS

    International Nuclear Information System (INIS)

    Matsushita, Y.; Nomura, M.; Watanabe, J.; Mogi, Y.; Noda, I.; Han, C.C.

    1993-01-01

    Single chain conformations of center block, polystyrene, of poly(2-vinylpyridine-b-styrene-b-2-vinylpyridine)(PSP) triblock copolymers of the ABA type in bulk were measured by small angle neutron scattering (SANS), while microphase separation structures were studied by small angle X-ray Scattering (SAXS) and transmission electron microscopy (TEM). From the morphological observations, PSP block copolymers have confirmed to have alternating lamellar structure both when φs = 0.33 and φs = 0.5, where φs is the volume fraction of polystyrene blocks. It was also clarified that the chain dimension of center blocks of sample with φs = 0.33 is smaller than that of sample with φs = 0.5. This result may mean that the center blocks have bridge-righ conformation when φs = 0.33 while they have loop-rich conformation when φs = 0.5. (author)

  5. Study on Surface Modification of Glass Bead by a Block Copolymer Coupling Agent

    Institute of Scientific and Technical Information of China (English)

    LI Yin; ZHANG Bing; ZHOU Xiao-dong

    2008-01-01

    A tri-block copolymer coupling agent polystyrene biock-poly(n-butyl-acrylate)-block-poly(r-methacryloxypro pylt rimethoxysilane)(PS-b-PnBA-b-PMPS)was synthesized by atom transfer radical polymerization(ATRP),and its molecular structure was characterized by fourier-transform infrared spectra,hydrogen nuclear magnetic resonance and gel permeation chromatography.The glass bead was treated with the block copolymer coupling agent,and then studied by transmission electron microscopy.The result showed that strong interaction was formed between the block copolymer coupling agent and the surface of glass bead,and then the block of poly(n-butylacrylate)formed a layer of film on the surface.

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

    Science.gov (United States)

    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

  7. Synthesis and characterization of aba-type copolymers for encapsulation of bovine hemoglobin

    International Nuclear Information System (INIS)

    Lima, Felipe F.; Andrade, Cristina T.

    2012-01-01

    The use of biopolymers for the development of oxygen carriers has been extensively investigated. In this work, three different ABA triblock copolymers were synthesized and used to encapsulate purified bovine hemoglobin, using a double emulsion technique. The effect of polymer composition, homogenization velocity, and addition of a surfactant, on the protein entrapment was evaluated. These copolymers, which have a hydrophilic block, achieved higher values of encapsulation efficiency than the corresponding homopolymers. The increase in homogenization strength also promoted an increase in encapsulation efficiency. Capsules formation occurred even in the absence of PVA. (author)

  8. Synthesis and morphology of hydroxyapatite/polyethylene oxide nanocomposites with block copolymer compatibilized interfaces

    Science.gov (United States)

    Lee, Ji Hoon; Shofner, Meisha

    2012-02-01

    In order to exploit the promise of polymer nanocomposites, special consideration should be given to component interfaces during synthesis and processing. Previous results from this group have shown that nanoparticles clustered into larger structures consistent with their native shape when the polymer matrix crystallinity was high. Therefore in this research, the nanoparticles are disguised from a highly-crystalline polymer matrix by cloaking them with a matrix-compatible block copolymer. Specifically, spherical and needle-shaped hydroxyapatite nanoparticles were synthesized using a block copolymer templating method. The block copolymer used, polyethylene oxide-b-polymethacrylic acid, remained on the nanoparticle surface following synthesis with the polyethylene oxide block exposed. These nanoparticles were subsequently added to a polyethylene oxide matrix using solution processing. Characterization of the nanocomposites indicated that the copolymer coating prevented the nanoparticles from assembling into ordered clusters and that the matrix crystallinity was decreased at a nanoparticle spacing of approximately 100 nm.

  9. Oriented Structure of Pentablock Copolymers Induced by Solution Extrusion

    Science.gov (United States)

    Harada, Tamotsu; Bates, Frank S.; Lodge, Timothy P.

    2002-03-01

    Highly oriented structure of a poly(styrene-co-butadiene) pentablock copolymer (Mw; 104,700 g/mol, weight percentage of polybutadiene blocks; 29 wt of concentrated solutions. The pentablock copolymer was dissolved into mixtures of toluene and heptane, and the polymer concentration ranged from 40 wt extrusion, the pentablock copolymer was solidified either by coagulation in methanol or by evaporation of the solvent. Interestingly, a highly oriented lamellar structure was confirmed through the small angle X-ray scattering over a specific range of heptane composition, which is a good solvent for polybutadiene, although the hexagonal cylinder morphology was identified for the melt sample. The transition from the oriented lamellar to highly oriented cylinder structure was observed by annealing the samples at temperatures above the glass transition temperature of polystyrene. Moreover, a transition from parallel to perpendicular orientation in the lamellar state was observed with an increase of the extrusion shear rate. A comparison between pentablock and triblock copolymers will be also discussed.

  10. Silk-collagen-like block copolymers with charged blocks : self-assembly into nanosized ribbons and macroscopic gels

    NARCIS (Netherlands)

    Martens, A.A.

    2008-01-01

    The research described in this thesis concerns the design, biotechnological production, and physiochemical study of large water-soluble (monodisperse) protein triblock-copolymers with sequential blocks, some of which are positively or negatively charged and self-assemble in response to a change in

  11. Polystyrene-b-polyethylene oxide block copolymer membranes, methods of making, and methods of use

    KAUST Repository

    Peinemann, Klaus-Viktor; Karunakaran, Madhavan

    2015-01-01

    Embodiments of the present disclosure provide for polystyrene-b-polyethylene oxide (PS-b-PEO) block copolymer nanoporous membranes, methods of making a PS-b-PEO block copolymer nanoporous membrane, methods of using PS-b-PEO block copolymer nanoporous membranes, and the like.

  12. Polystyrene-b-polyethylene oxide block copolymer membranes, methods of making, and methods of use

    KAUST Repository

    Peinemann, Klaus-Viktor

    2015-04-16

    Embodiments of the present disclosure provide for polystyrene-b-polyethylene oxide (PS-b-PEO) block copolymer nanoporous membranes, methods of making a PS-b-PEO block copolymer nanoporous membrane, methods of using PS-b-PEO block copolymer nanoporous membranes, and the like.

  13. Gas-permeation properties of poly(ethylene oxide) poly(butylene terephthalate block copolymers

    NARCIS (Netherlands)

    Metz, S.J.; Mulder, M.H.V.; Wessling, Matthias

    2004-01-01

    This paper reports the gas-permeation properties of poly(ethylene oxide) (PEO) poly(butylene terephthalate) (PBT) segmented multiblock copolymers. These block copolymers allow a precise structural modification by the amount of PBT and the PEO segment length, enabling a systematic study of the

  14. Block copolymer self-assembly–directed synthesis of mesoporous gyroidal superconductors

    Science.gov (United States)

    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

  15. Block copolymer self-assembly-directed synthesis of mesoporous gyroidal superconductors.

    Science.gov (United States)

    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.

  16. Mesoporous Pt and Pt/Ru alloy electrocatalysts for methanol oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Franceschini, Esteban A. [Grupo de Celdas de Combustible, Departamento de Fisica de la Materia Condensada, Centro Atomico Constituyentes, CNEA. Av. General Paz 1499 (1650), San Martin, Buenos Aires (Argentina); Planes, Gabriel A. [Departamento de Quimica, Facultad de Ciencias Exactas, Fisicoquimicas y Naturales, Universidad Nacional de Rio Cuarto, Agencia Postal No 3, 5800, Rio Cuarto (Argentina); Williams, Federico J. [Departamento de Quimica Inorganica, Analitica y Quimica-Fisica, INQUIMAE CONICET, Facultad Ciencias Exactas y Naturales, Pabellon 2, Ciudad Universitaria, Buenos Aires (Argentina); Soler-Illia, Galo J.A.A. [Gerencia de Quimica, Centro Atomico Constituyentes, CNEA. Av. General Paz 1499 (1650), San Martin, Buenos Aires (Argentina); Corti, Horacio R. [Grupo de Celdas de Combustible, Departamento de Fisica de la Materia Condensada, Centro Atomico Constituyentes, CNEA. Av. General Paz 1499 (1650), San Martin, Buenos Aires (Argentina); Departamento de Quimica Inorganica, Analitica y Quimica-Fisica, INQUIMAE CONICET, Facultad Ciencias Exactas y Naturales, Pabellon 2, Ciudad Universitaria, Buenos Aires (Argentina)

    2011-02-15

    Mesoporous Pt and Pt/Ru catalysts with 2D-hexagonal mesostructure were synthesized using a triblock poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) copolymer (Pluronic F127 {sup registered}) template, on a gold support. Large electrochemical surface areas were observed for the catalysts prepared at high overpotentials. Compared to the Pt catalyst, the Pt/Ru alloy containing 3 at% of Ru exhibited lower onset potential and more than three times the limit mass activity for methanol oxidation. This behavior is assigned to the larger pore size of the mesoporous Pt and Pt/Ru catalysts obtained with this template that seems to improve the methanol accessibility to the active sites compared to those obtained using lyotropic liquid crystals. (author)

  17. Morphologies of ABC triblock terpolymer melts containing poly(Cyclohexadiene): Effects of conformational asymmetry

    KAUST Repository

    Kumar, Rajeev Senthil

    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. © 2012 American Chemical Society.

  18. Hierarchical self-assembly of two-length-scale multiblock copolymers

    International Nuclear Information System (INIS)

    Brinke, Gerrit ten; Loos, Katja; Vukovic, Ivana; Du Sart, Gerrit Gobius

    2011-01-01

    The self-assembly in diblock copolymer-based supramolecules, obtained by hydrogen bonding short side chains to one of the blocks, as well as in two-length-scale linear terpolymers results in hierarchical structure formation. The orientation of the different domains, e.g. layers in the case of a lamellar-in-lamellar structure, is determined by the molecular architecture, graft-like versus linear, and the relative magnitude of the interactions involved. In both cases parallel and perpendicular arrangements have been observed. The comb-shaped supramolecules approach is ideally suited for the preparation of nanoporous structures. A bicontinuous morphology with the supramolecular comb block forming the channels was finally achieved by extending the original approach to suitable triblock copolymer-based supramolecules.

  19. Disorder-order-crystalline state transitions of PEO-b-PPO-b-PEO copolymers and their blends: SAXS/WAXS/DSC study

    Czech Academy of Sciences Publication Activity Database

    Baldrian, Josef; Steinhart, M.; Amenitsch, H.; Bernstorff, S.

    2009-01-01

    Roč. 48, č. 1 (2009), s. 174-184 ISSN 0022-2348 Institutional research plan: CEZ:AV0Z40500505 Keywords : triblock copolymers * blends with homopolymer * structure development Subject RIV: CD - Macromolecular Chemistry Impact factor: 0.716, year: 2009

  20. pH-triggered reversible sol–gel transition in aqueous solutions of amphiphilic gradient copolymers

    Czech Academy of Sciences Publication Activity Database

    Borisova, O.; Billon, L.; Zaremski, M.; Grassl, B.; Bakaeva, Zulfiya; Lapp, A.; Štěpánek, Petr; Borisov, O.

    2011-01-01

    Roč. 7, č. 22 (2011), s. 10824-10833 ISSN 1744-683X R&D Projects: GA ČR GAP208/10/1600 Institutional research plan: CEZ:AV0Z40500505 Keywords : small angle neutron scattering * triblock copolymer * self-organized structure Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 4.390, year: 2011

  1. Thermoresponsive behavior of block copolymers of PEO and PNIPAm with different architecture in aqueous solutions: a study by NMR, FTIR, DSC and quantum-chemical calculations

    Czech Academy of Sciences Publication Activity Database

    Spěváček, Jiří; Konefal, Rafal; Dybal, Jiří; Čadová, Eva; Kovářová, Jana

    2017-01-01

    Roč. 94, September (2017), s. 471-483 ISSN 0014-3057 R&D Projects: GA ČR(CZ) GA15-13853S Institutional support: RVO:61389013 Keywords : thermoresponsive polymer * diblock copolymer PEO-b-PNIPAm * y-shape triblock copolymer PEO-b-(PNIPAm)2 Subject RIV: CD - Macromolecular Chemistry OBOR OECD: Polymer science Impact factor: 3.531, year: 2016

  2. Designing block copolymer architectures for targeted membrane performance

    KAUST Repository

    Dorin, Rachel Mika

    2014-01-01

    Using a combination of block copolymer self-assembly and non-solvent induced phase separation, isoporous ultrafiltration membranes were fabricated from four poly(isoprene-b-styrene-b-4-vinylpyridine) triblock terpolymers with similar block volume fractions but varying in total molar mass from 43 kg/mol to 115 kg/mol to systematically study the effect of polymer size on membrane structure. Small-angle X-ray scattering was used to probe terpolymer solution structure in the dope. All four triblocks displayed solution scattering patterns consistent with a body-centered cubic morphology. After membrane formation, structures were characterized using a combination of scanning electron microscopy and filtration performance tests. Membrane pore densities that ranged from 4.53 × 1014 to 1.48 × 1015 pores/m 2 were observed, which are the highest pore densities yet reported for membranes using self-assembly and non-solvent induced phase separation. Hydraulic permeabilities ranging from 24 to 850 L m-2 h-1 bar-1 and pore diameters ranging from 7 to 36 nm were determined from permeation and rejection experiments. Both the hydraulic permeability and pore size increased with increasing molar mass of the parent terpolymer. The combination of polymer characterization and membrane transport tests described here demonstrates the ability to rationally design macromolecular structures to target specific performance characteristics in block copolymer derived ultrafiltration membranes. © 2013 Elsevier Ltd. All rights reserved.

  3. Synthesis of DNA block copolymers with extended nucleic acid segments by enzymatic ligation : cut and paste large hybrid architectures

    NARCIS (Netherlands)

    Ayaz, Meryem S.; Kwak, Minseok; Alemdaroglu, Fikri E.; Wang, Jie; Berger, Ruediger; Herrmann, Andreas; Berger, Rüdiger

    2011-01-01

    Ultra-high molecular weight DNA/polymer hybrid materials were prepared employing molecular biology techniques. Nucleic acid restriction and ligation enzymes were used to generate linear DNA di- and triblock copolymers that contain up to thousands of base pairs in the DNA segments.

  4. Characterization of the binding of multivalent ions to modified pluronic micelles by isothermal titration calorimetry and modified conductometry

    NARCIS (Netherlands)

    Nispen, van S.F.G.M.; Custers, J.P.A.; Broeke, van den L.J.P.; Keurentjes, J.T.F.

    2010-01-01

    CAE surfactants (carboxylic acid end-standing triblock copolymers of poly(ethylene oxide)–poly(propylene oxide)–poly(ethylene oxide)) are amphiphiles that are able to bind multivalent cations thermoreversibly; a property that can be used to develop new environmentally friendly separation and ion

  5. Polymer association in a microemulsion system

    International Nuclear Information System (INIS)

    Fountain, L.E.; Shahidan Radiman; Toprakcioglu, C.

    1997-01-01

    Using small angle neutron scattering technique with appropriate contrast we have been able to elucidate some associations structures of polystyrene (PS) and triblock co-polymers of polyethylene oxide-polystyrene- polyethylene oxide (PEO-PS-PEO) in a water-in-oil microemulsion system

  6. Contrast variation SANS experiments to the study of detergent ...

    Indian Academy of Sciences (India)

    PEO-PPO-PEO triblock copolymer P85 [(EO)26 (PO)39 (EO)26] dissolves as unimers and detergent sodium dodecyl sulfate (SDS) forms micelles in aqueous solution at 20°C. The mixing of detergent with triblock copolymer induces the micellization of triblock copolymers. Contrast variation small-angle neutron scattering ...

  7. Tuning Structure and Properties of Graded Triblock Terpolymer-Based Mesoporous and Hybrid Films

    KAUST Repository

    Phillip, William A.

    2011-07-13

    Despite considerable efforts toward fabricating ordered, water-permeable, mesoporous films from block copolymers, fine control over pore dimensions, structural characteristics, and mechanical behavior of graded structures remains a major challenge. To this end, we describe the fabrication and performance characteristics of graded mesoporous and hybrid films derived from the newly synthesized triblock terpolymer, poly(isoprene-b-styrene-b-4-vinylpyridine). A unique morphology, unachievable in diblock copolymer systems, with enhanced mechanical integrity is evidenced. The film structure comprises a thin selective layer containing vertically aligned and nearly monodisperse mesopores at a density of more than 1014 per m2 above a graded macroporous layer. Hybridization via homopolymer blending enables tuning of pore size within the range of 16 to 30 nm. Solvent flow and solute separation experiments demonstrate that the terpolymer films have permeabilities comparable to commercial membranes, are stimuli-responsive, and contain pores with a nearly monodisperse diameter. These results suggest that moving to multiblock polymers and their hybrids may open new paths to produce high-performance graded membranes for filtration, separations, nanofluidics, catalysis, and drug delivery. © 2011 American Chemical Society.

  8. Block copolymer-nanoparticle hybrid self-assembly

    KAUST Repository

    Hoheisel, Tobias N.; Hur, Kahyun; Wiesner, Ulrich B.

    2015-01-01

    © 2014 Published by Elsevier Ltd. Polymer-inorganic hybrid materials provide exciting opportunities as they may display favorable properties from both constituents that are desired in applications including catalysis and energy conversion and storage. For the preparation of hybrid materials with well-defined morphologies, block copolymer-directed nanoparticle hybrids present a particularly promising approach. As will be described in this review, once the fundamental characteristics for successful nanostructure formation at or close to the thermodynamic equilibrium of these nanocomposites are identified, the approach can be generalized to various materials classes. In addition to the discussion of recent materials developments based on the use of AB diblock copolymers as well as ABC triblock terpolymers, this review will therefore emphasize progress in the fundamental understanding of the underlying formation mechanisms of such hybrid materials. To this end, critical experiments for, as well as theoretical progress in the description of these nanostructured block copolymer-based hybrid materials will be discussed. Rather than providing a comprehensive overview, the review will emphasize work by the Wiesner group at Cornell University, US, on block copolymer-directed nanoparticle assemblies as well as their use in first potential application areas. The results provide powerful design criteria for wet-chemical synthesis methodologies for the generation of functional nanomaterials for applications ranging from microelectronics to catalysis to energy conversion and storage.

  9. Pluronic-lysozyme conjugates as anti-adhesive and antibacterial bifunctional polymers for surface coating

    NARCIS (Netherlands)

    Muszanska, A.K.; Busscher, H.J.; Herrmann, A.; Mei, van der H.C.; Norde, W.

    2011-01-01

    This paper describes the preparation and characterization of polymer protein conjugates composed of a synthetic triblock copolymer with a central polypropylene oxide (PPO) block and two terminal polyethylene oxide (PEO) segments, Pluronic F-127, and the antibacterial enzyme lysozyme attached to the

  10. Synthesis and Functionalization of Poly(ethylene oxide-b-ethyloxazoline) Diblock Copolymers with Phosphonate Ions

    OpenAIRE

    Chen, Alfred Yuen-Wei

    2013-01-01

    Poly(ethylene oxide) (PEO) and poly(2-ethyl-2-oxazoline) (PEOX) are biocompatible polymers that act as hydrophilic "stealth" drug carriers. As block copolymers, the PEOX group offers a wider variety of functionalization. The goal of this project was to synthesize a poly(ethylene oxide)-b-poly(2-ethyl-2-oxazoline) (PEO-b-PEOX) block copolymer and functionalize pendent groups of PEOX with phosphonic acid. This was achieved through cationic ring opening polymerization (CROP) of 2-...

  11. Phase Separation and Elastic Properties of Poly(Trimethylene Terephthalate)-block-poly(Ethylene Oxide) Copolymers

    OpenAIRE

    Elżbieta Piesowicz; Sandra Paszkiewicz; Anna Szymczyk

    2016-01-01

    A series of poly(trimethylene terephthalate)-block-poly(ethylene oxide) (PTT-b-PEOT) copolymers with different compositions of rigid PTT and flexible PEOT segments were synthesized via condensation in the melt. The influence of the block length and the block ratio on the micro-separated phase structure and elastic properties of the synthesized multiblock copolymers was studied. The PEOT segments in these copolymers were kept constant at 1130, 2130 or 3130 g/mol, whereas the PTT content varied...

  12. Electrospinning synthesis of porous Al{sub 2}O{sub 3} nanofibers by pluronic P123 triblock copolymer surfactant and properties of uranium (VI)-sorption

    Energy Technology Data Exchange (ETDEWEB)

    Ren, Bo [The Key Laboratory of Superlight Materials and Surface Technology, Ministry of Education, Harbin 150001 (China); Department of Applied Chemistry Engineering, Jilin Vocational College of Industry and Technology, Jilin 132013 (China); Institute of Petrochemistry Heilongjiang Academy of Sciences, Harbin 150001 (China); Fan, Meiqing [The Key Laboratory of Superlight Materials and Surface Technology, Ministry of Education, Harbin 150001 (China); Department of Applied Chemistry Engineering, Jilin Vocational College of Industry and Technology, Jilin 132013 (China); Tan, Lichao [The Key Laboratory of Superlight Materials and Surface Technology, Ministry of Education, Harbin 150001 (China); Li, Rumin, E-mail: lirumin@hrbeu.edu.cn [The Key Laboratory of Superlight Materials and Surface Technology, Ministry of Education, Harbin 150001 (China); Song, Dalei; Liu, Qi [The Key Laboratory of Superlight Materials and Surface Technology, Ministry of Education, Harbin 150001 (China); Wang, Jun, E-mail: zhqw1888@sohu.com [The Key Laboratory of Superlight Materials and Surface Technology, Ministry of Education, Harbin 150001 (China); Institute of Advanced Marine Materials, Harbin Engineering University, Harbin 150001 (China); Zhang, Bin [Institute of Petrochemistry Heilongjiang Academy of Sciences, Harbin 150001 (China); Jing, Xiaoyan [The Key Laboratory of Superlight Materials and Surface Technology, Ministry of Education, Harbin 150001 (China)

    2016-07-01

    Porous Alumina (Al{sub 2}O{sub 3}) nanofibers were prepared by electrospinning process using pluronic P123 triblock copolymer surfactant as template. The characterizations of the adsorbent were investigated by X-ray diffraction (XRD) fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and nitrogen adsorption–desorption. The obtained nanofibers were used as adsorbents for the removal of Uranium (VI). The maximum adsorption occurred at pH 5, the equilibrium adsorption amount was about 87 mg/g, and the equilibrium time was 6.0 h. A pseudo-second order model could best describe adsorption kinetics. The adsorption equilibrium data fit Freundlich adsorption isotherm equation well. Thermodynamic parameters such as standard enthalpy (ΔH{sup 0}), standard entropy (ΔS{sup 0}), standard free energy (ΔG{sup 0}) and activation energy (E{sub a}) were calculated. The results predict an endothermic nature of adsorption and a spontaneous process. - Highlights: • The porous Al{sub 2}O{sub 3} nanofibers were used for U(VI)-sorption for the first time. • The adsorption process was endothermic and spontaneous. • The maximum adsorption capacity was 87 mg g{sup −1} at 25 °C.

  13. Adsorption of Poly(ethylene oxide)-Poly(lactide) Copolymers. Effects of Composition and Degradation.

    Science.gov (United States)

    Muller, Dries; Carlsson, Fredrik; Malmsten, Martin

    2001-04-01

    The effect of chemical degradation of two diblock copolymers of poly(ethylene oxide) (E) and poly(lactide) (L), E(39)L(5) and E(39)L(20), on their adsorption at silica and methylated silica was investigated with in situ ellipsometry. Steric stablization of polystyrene dispersions was investigated in relation to degradation. Hydrolysis of the poly(lactide) block of the copolymers was followed at different temperatures and pH by using HPLC to measure the occurrence of lactic acid in solution. The block copolymers were quite stable in pH-unadjusted solution at low temperature, whereas degradation was facilitated by increasing temperature or lowering of the pH. Lower degradation rates of E(39)L(20) where observed at low temperature in comparison with those of E(39)L(5), whereas the degradation rates of the copolymers were quantitatively similar at high temperature. The adsorption of the copolymers at methylated silica substrates decreased with increasing degree of degradation due to the reduction in the ability of hydrophobic block to anchor the copolymer layer at the surface. At silica the adsorption initially increased with increasing degradation, particularly for E(39)L(20) due to deposition of aggregates onto the surface. After extensive degradation the adsorption of the copolymers at both silica and methylated silica resembled that of the corresponding poly(ethylene oxide) homopolymer. Overall, it was found that the eventual reduction in adsorption occurred at a lower degree of degradation for E(39)L(5) than for E(39)L(20). Mean-field calculations showed a reduced anchoring for the block copolymers with decreasing poly(lactide) block length at hydrophobic surfaces. In accordance with this finding, it was observed that polystyrene dispersions were stabilized by E(39)L(20) or E(39)L(5) in a way that depended on both the lactide block length and the degree of degradation. Upon degradation of the hydrophobic block, stabilization of the polystyrene dispersions was

  14. Thermosensitive Self-Assembling Block Copolymers as Drug Delivery Systems

    Directory of Open Access Journals (Sweden)

    Giovanni Filippo Palmieri

    2011-04-01

    Full Text Available Self-assembling block copolymers (poloxamers, PEG/PLA and PEG/PLGA diblock and triblock copolymers, PEG/polycaprolactone, polyether modified poly(Acrylic Acid with large solubility difference between hydrophilic and hydrophobic moieties have the property of forming temperature dependent micellar aggregates and, after a further temperature increase, of gellifying due to micelle aggregation or packing. This property enables drugs to be mixed in the sol state at room temperature then the solution can be injected into a target tissue, forming a gel depot in-situ at body temperature with the goal of providing drug release control. The presence of micellar structures that give rise to thermoreversible gels, characterized by low toxicity and mucomimetic properties, makes this delivery system capable of solubilizing water-insoluble or poorly soluble drugs and of protecting labile molecules such as proteins and peptide drugs.

  15. Improved synthesis of polystyrene-poly(ethylene oxide)-heparin block copolymers

    NARCIS (Netherlands)

    Vulic, I.; Loman, A.J.B.; Feijen, Jan; Okano, T.; Kim, S.W.

    1990-01-01

    A novel procedure for the synthesis of block copolymers composed of a hydrophobic block of polystyrene, a hydrophilic block of poly(ethylene oxide) and a bioactive block of nitrous acid-degraded heparin was developed. Amino-semitelechelic polystyrene was prepared by anionic polymerization of styrene

  16. Aqueous-Based Fabrication of Low-VOC Nanostructured Block Copolymer Films as Potential Marine Antifouling Coatings.

    Science.gov (United States)

    Kim, Kris S; Gunari, Nikhil; MacNeil, Drew; Finlay, John; Callow, Maureen; Callow, James; Walker, Gilbert C

    2016-08-10

    The ability to fabricate nanostructured films by exploiting the phenomenon of microphase separation has made block copolymers an invaluable tool for a wide array of coating applications. Standard approaches to engineering nanodomains commonly involve the application of organic solvents, either through dissolution or annealing protocols, resulting in the release of volatile organic compounds (VOCs). In this paper, an aqueous-based method of fabricating low-VOC nanostructured block copolymer films is presented. The reported procedure allows for the phase transfer of water insoluble triblock copolymer, poly(styrene-block-2 vinylpyridine-block-ethylene oxide) (PS-b-P2VP-b-PEO), from a water immiscible phase to an aqueous environment with the assistance of a diblock copolymeric phase transfer agent, poly(styrene-block-ethylene oxide) (PS-b-PEO). Phase transfer into the aqueous phase results in self-assembly of PS-b-P2VP-b-PEO into core-shell-corona micelles, which are characterized by dynamic light scattering techniques. The films that result from coating the micellar solution onto Si/SiO2 surfaces exhibit nanoscale features that disrupt the ability of a model foulant, a zoospore of Ulva linza, to settle. The multilayered architecture consists of a pH-responsive P2VP-"shell" which can be stimulated to control the size of these features. The ability of these nanostructured thin films to resist protein adsorption and serve as potential marine antifouling coatings is supported through atomic force microscopy (AFM) and analysis of the settlement of Ulva linza zoospore. Field trials of the surfaces in a natural environment show the inhibition of macrofoulants for 1 month.

  17. Charged triblock copolymer self-assembly into charged micelles

    Science.gov (United States)

    Chen, Yingchao; Zhang, Ke; Zhu, Jiahua; Wooley, Karen; Pochan, Darrin; Department of Material Science; Engineering University of Delaware Team; Department of Chemistry Texas A&M University Collaboration

    2011-03-01

    Micelles were formed through the self-assembly of amphiphlic block copolymer poly(acrylic acid)-block-poly(methyl acrylate)-block-polystyrene (PAA-PMA-PS). ~Importantly, the polymer is complexed with diamine molecules in pure THF solution prior to water titration solvent processing-a critical aspect in the control of final micelle geometry. The addition of diamine triggers acid-base complexation ~between the carboxylic acid PAA side chains and amines. ~Remarkably uniform spheres were found to form close-packed patterns when forced into dried films and thin, solvated films when an excess of amine was used in the polymer assembly process. Surface properties and structural features of these hexagonal-packed spherical micelles with charged corona have been explored by various characterization methods including Transmission Electron Microscopy (TEM), cryogenic TEM, z-potential analysis and Dynamic Light Scattering. The forming mechanism for this pattern and morphology changes against external stimulate such as salt will be discussed.

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

    Science.gov (United States)

    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.

  19. Onion-like microspheres with tricomponent from gelable triblock copolymers.

    Science.gov (United States)

    Zhang, Ke; Gao, Lei; Chen, Yongming; Yang, Zhenzhong

    2010-06-01

    Onion-like functional microspheres with three alternate layers were obtained by aerosol-assisted self-assembly of a functional block copolymer, poly(3-(triethoxysilyl)propyl methacrylate)-block-polystyrene-block-poly(2-vinylpyridine) (PTEPM-b-PS-b-P2VP). Through self-gelation reaction occurred in the PTEPM layers, organic/inorganic hybrid functional spheres with highly ordered concentric curved lamellar structure were prepared. Using these hybrid onion-like microspheres as templates, gold ions were entrapped into the P2VP layers and then gold nanoparticles located in each P2VP layers were formed by a reduction. By dispersing in acidic water, the onion-like polymeric spheres were broken and, as a result, sandwich-like nanoplates with curved morphology were obtained. Copyright © 2010 Elsevier Inc. All rights reserved.

  20. Effects of PEO-PPO diblock impurities on the cubic structure of aqueous PEO-PPO-PEO pluronics micelles: fcc and bcc ordered structures in F127

    DEFF Research Database (Denmark)

    Mortensen, Kell; Pedersen, Walther Batsberg; Hvidt, S.

    2008-01-01

    We report on structural properties of PEO-PPO-PEO type of triblock block copolymers (Pluronics F127) with special emphasis on the effect of diblock PEO-PPO impurities on the ordered gel phase. Commercial F127 polymers contain as received roughly 20% PEO-PPO diblock and 80% PEO-PPO-PEO triblock...... copolymers. Aqueous solutions of F127 copolymers used as received form fee ordered micellar structure. Copolymers depleted with respect to the diblock impurity, resulting in a pure PEO-PPO-PEO triblock copolymer system, form bcc ordered micelles within the major parts of the gel phase. However, close...

  1. Poly(alkylene oxide) Copolymers for Nucleic Acid Delivery

    Science.gov (United States)

    2012-07-17

    Poly(alkylene oxide) Copolymers for Nucleic Acid Delivery Swati Mishra1,#, Lavanya Y. Peddada1,#, David I. Devore3,4, and Charles M. Roth1,2...Neil Raju for assistance with figures. Biographies Swati Mishra received her Ph.D. in Biomedical Engineering and Biotechnology from the University of...Kleiman N, Anderson RD, Gottlieb D, Karlsberg R, Snell J, Rocha- Singh K. Results from a phase II multicenter, double-blind placebo-controlled study of Del

  2. Adsorption of polyelectrolytes and charged block copolymers on oxides consequences for colloidal stability

    NARCIS (Netherlands)

    Hoogeveen, N.G.

    1996-01-01


    The aim of the study described in this thesis was to examine the adsorption properties of polyelectrolytes and charged block copolymers on oxides, and the effect of these polymers on the colloidal stability of oxidic dispersions. For this purpose the interaction of some well-characterised

  3. Sequential crystallization and morphology of triple crystalline biodegradable PEO-b-PCL-b-PLLA triblock terpolymers

    KAUST Repository

    Palacios, Jordana; Mugica, Agurtzane; Zubitur, Manuela; Iturrospe, Amaia; Arbe, A.; Liu, Guoming; Wang, Dujin; Zhao, Junpeng; Hadjichristidis, Nikolaos; Muller, Alejandro

    2016-01-01

    The sequential crystallization of poly(ethylene oxide)-b-poly(e-caprolactone)-b-poly(L-lactide) (PEO-b-PCL-b-PLLA) triblock terpolymers, in which the three blocks are able to crystallize separately and sequentially from the melt, is presented. Two

  4. Poly (ethylene oxide)-block-poly (n-butyl acrylate)-blockpoly (acrylic acid) triblock terpolymers with highly asymmetric hydrophilic blocks: synthesis and aqueous solution properties

    OpenAIRE

    Petrov, P. (Petar); Yoncheva, K. (Krassimira); Mokreva, P. (Pavlina); Konstantinov, S. (Spiro); Irache, J.M. (Juan Manuel); Müller, A.H.E. (Axel H.E.)

    2013-01-01

    The synthesis and aggregation behaviour in aqueous media of novel amphiphilic poly(ethylene oxide)- block-poly(n-butyl acrylate)-block-poly(acrylic acid) (PEO–PnBA–PAA) triblock terpolymers were studied. Terpolymers composed of two highly asymmetric hydrophilic PEO (113 monomer units) and PAA (10–17 units) blocks, and a longer soft hydrophobic PnBA block (163 or 223 units) were synthesized by atom transfer radical polymerisation (ATRP) of n-butyl acrylate and tert-butyl acrylate ...

  5. Shear-induced network-to-network transition in a block copolymer melt

    International Nuclear Information System (INIS)

    Cochran, Eric W.; Bates, Frank S.

    2004-01-01

    A tricontinuous (10,3)c network phase is documented in a poly(cyclohexylethylene-b-ethylethylene-b-ethylene) triblock copolymer melt based on small-angle x-ray scattering. Application of shear transforms the self-assembled soft material into a single crystal (10,3)d network while preserving the short-range threefold connector geometry. Long-range topological restructuring reduces the space group symmetry, from Fddd to Pnna, maintaining orthorhombic lattice symmetry. Both phases are stable to long time annealing, indicative of nearly degenerate free energies and prohibitive kinetic barriers

  6. (Electro)Mechanical Properties of Olefinic Block Copolymers

    Science.gov (United States)

    Spontak, Richard

    2014-03-01

    Conventional styrenic triblock copolymers (SBCs) swollen with a midblock-selective oil have been previously shown to exhibit excellent electromechanical properties as dielectric elastomers. In this class of electroactive polymers, compliant electrodes applied as active areas to opposing surfaces of an elastomer attract each other, and thus compress the elastomer due to the onset of a Maxwell stress, upon application of an external electric field. This isochoric process is accompanied by an increase in lateral area, which yields the electroactuation strain (measuring beyond 300% in SBC systems). Performance parameters such as the Maxwell stress, transverse strain, dielectric breakdown, energy density and electromechanical efficiency are determined directly from the applied electric field and resulting electroactuation strain. In this study, the same principle used to evaluate SBC systems is extended to olefinic block copolymers (OBCs), which can be described as randomly-coupled multiblock copolymers that consist of crystallizable polyethylene hard segments and rubbery poly(ethylene-co-octene) soft segments. Considerations governing the development of a methodology to fabricate electroresponsive OBC systems are first discussed for several OBCs differing in composition and bulk properties. Evidence of electroactuation in selectively-solvated OBC systems is presented and performance metrics measured therefrom are quantitatively compared with dielectric elastomers derived from SBC and related materials.

  7. Graphene oxide stabilized by PLA-PEG copolymers for the controlled delivery of paclitaxel.

    Science.gov (United States)

    Angelopoulou, A; Voulgari, E; Diamanti, E K; Gournis, D; Avgoustakis, K

    2015-06-01

    To investigate the application of water-dispersible poly(lactide)-poly(ethylene glycol) (PLA-PEG) copolymers for the stabilization of graphene oxide (GO) aqueous dispersions and the feasibility of using the PLA-PEG stabilized GO as a delivery system for the potent anticancer agent paclitaxel. A modified Staudenmaier method was applied to synthesize graphene oxide (GO). Diblock PLA-PEG copolymers were synthesized by ring-opening polymerization of dl-lactide in the presence of monomethoxy-poly(ethylene glycol) (mPEG). Probe sonication in the presence of PLA-PEG copolymers was applied in order to reduce the hydrodynamic diameter of GO to the nano-size range according to dynamic light scattering (DLS) and obtain nano-graphene oxide (NGO) composites with PLA-PEG. The composites were characterized by atomic force microscopy (AFM), thermogravimetric analysis (TGA), and DLS. The colloidal stability of the composites was evaluated by recording the size of the composite particles with time and the resistance of composites to aggregation induced by increasing concentrations of NaCl. The composites were loaded with paclitaxel and the in vitro release profile was determined. The cytotoxicity of composites against A549 human lung cancer cells in culture was evaluated by flow cytometry. The uptake of FITC-labeled NGO/PLA-PEG by A549 cells was also estimated with flow cytometry and visualized with fluorescence microscopy. The average hydrodynamic diameter of NGO/PLA-PEG according to DLS ranged between 455 and 534 nm, depending on the molecular weight and proportion of PLA-PEG in the composites. NGO/PLA-PEG exhibited high colloidal stability on storage and in the presence of high concentrations of NaCl (far exceeding physiological concentrations). Paclitaxel was effectively loaded in the composites and released by a highly sustained fashion. Drug release could be regulated by the molecular weight of the PLA-PEG copolymer and its proportion in the composite. The paclitaxel

  8. How the Complex Interplay between Different Blocks Determines the Isothermal Crystallization Kinetics of Triple-Crystalline PEO-b-PCL-b-PLLA Triblock Terpolymers

    KAUST Repository

    Palacios, Jordana K.

    2017-12-05

    PEO-b-PCL-b-PLLA triblock terpolymers are fascinating triple-crystalline materials. In this work, the isothermal crystallization kinetics of these terpolymers evaluated by differential scanning calorimetry (DSC) is presented for the first time and compared to analogous PCL-b-PLLA diblock copolymers and to PLLA, PCL, and PEO homopolymers. The results are complemented by in situ SAXS/WAXS synchrotron experiments. One-, two-, and three-step crystallization protocols were employed to study the crystallization kinetics of the blocks. At PLLA block crystallization temperatures, both PCL and PEO molten chains caused a strong plasticizing effect on the PLLA block crystallization, and the overall crystallization rate of the PLLA block in the terpolymers was higher than that in the PLLA-b-PCL diblock copolymers. In the case of the PCL block, the crystallization was followed after PLLA was fully crystallized (two-step crystallization). A nucleating effect induced by the previously formed PLLA crystals was observed. However, an antiplasticizing effect on PCL crystallization was detected if the sample is quenched directly from the melt to the PCL crystallization temperature (one-step crystallization). Finally, the crystallization of the PEO block was followed after PLLA and PCL had fully crystallized (three-step crystallization). The PEO crystallization rate highly decreased due to the confinement imposed by the previously formed PLLA and PCL crystals. Complex competitive effects such as plasticization, nucleation, antiplasticization, and confinement occurred during the isothermal crystallization of tricrystalline PEO-b-PCL-b-PLLA triblock terpolymers.

  9. How the Complex Interplay between Different Blocks Determines the Isothermal Crystallization Kinetics of Triple-Crystalline PEO-b-PCL-b-PLLA Triblock Terpolymers

    KAUST Repository

    Palacios, Jordana K.; Zhao, Junpeng; Hadjichristidis, Nikolaos; Mü ller, Alejandro J.

    2017-01-01

    PEO-b-PCL-b-PLLA triblock terpolymers are fascinating triple-crystalline materials. In this work, the isothermal crystallization kinetics of these terpolymers evaluated by differential scanning calorimetry (DSC) is presented for the first time and compared to analogous PCL-b-PLLA diblock copolymers and to PLLA, PCL, and PEO homopolymers. The results are complemented by in situ SAXS/WAXS synchrotron experiments. One-, two-, and three-step crystallization protocols were employed to study the crystallization kinetics of the blocks. At PLLA block crystallization temperatures, both PCL and PEO molten chains caused a strong plasticizing effect on the PLLA block crystallization, and the overall crystallization rate of the PLLA block in the terpolymers was higher than that in the PLLA-b-PCL diblock copolymers. In the case of the PCL block, the crystallization was followed after PLLA was fully crystallized (two-step crystallization). A nucleating effect induced by the previously formed PLLA crystals was observed. However, an antiplasticizing effect on PCL crystallization was detected if the sample is quenched directly from the melt to the PCL crystallization temperature (one-step crystallization). Finally, the crystallization of the PEO block was followed after PLLA and PCL had fully crystallized (three-step crystallization). The PEO crystallization rate highly decreased due to the confinement imposed by the previously formed PLLA and PCL crystals. Complex competitive effects such as plasticization, nucleation, antiplasticization, and confinement occurred during the isothermal crystallization of tricrystalline PEO-b-PCL-b-PLLA triblock terpolymers.

  10. Hard Pd Nanorods in the Soft Surfactant Mixture of CTAB and Pluronics: Seedless Synthesis and Their Self-Assembly.

    Science.gov (United States)

    Song, Hyon-Min; Zink, Jeffrey I

    2018-04-10

    Seedless synthesis of Pd nanorods and their self-assembly into the layered smectic ordering are described. Aqueous Pluronic triblock copolymers (14.3-35.7%) are used as a soft template along with cetyltrimethylammonium bromide for inducing one-dimensional growth of Pd nanorods. Pluronic triblock copolymers are probably the most used polymer surfactants, and they are composed of poly(ethylene oxide) (PEO)-poly(propylene oxide) (PPO)-PEO triblocks. Neither pH adjustment nor AgNO 3 and other additives, such as poly(vinyl pyrrolidone) and ethylene glycol, are required to obtain Pd nanorods. Sonochemical synthesis at 43 °C, followed by thermal annealing for 1 h at 65 °C produces Pd nanorods with the aspect ratio from 3.1 (17.9%, Pluronic L-64) to 6.7 (35.7%, Pluronic P-123). Two-dimensional self-assembly of the nanorods is observed, and both nematic ordering between the mesogens and smectic ordering between the layers is identified. Micellar hydrophobic PPO with hydrated PEO coronas are known to self-assemble into many crystalline orders, including cubic, hexagonal, lamellar, and inverse hexagonal mesophases, which extend into cylindrical micelles with increasing temperature. Relatively small size of Pluronic copolymers with regard to general polymers, but rather large size of their micelles and their tendency to organize into crystalline mesophases are thought to contribute to the anisotropic growth of Pd nanorods.

  11. Poly(ethylene oxide)/poly(butylene terephthalate) segmented block copolymers: the effect of copolymer composition on physical properties and degradation behavior

    NARCIS (Netherlands)

    Deschamps, A.A.; Grijpma, Dirk W.; Feijen, Jan

    2001-01-01

    In this study, the influence of copolymer composition on the physical properties and the degradation behavior of thermoplastic elastomers based on poly(ethylene oxide) (PEO) and poly(butylene terephthalate) (PBT) segments is investigated. These materials are intended to be used in medical

  12. Self-Assembly of Block and Graft Copolymers in Organic Solvents: An Overview of Recent Advances

    Directory of Open Access Journals (Sweden)

    Leonard Ionut Atanase

    2018-01-01

    Full Text Available This review is an attempt to update the recent advances in the self-assembly of amphiphilic block and graft copolymers. Their micellization behavior is highlighted for linear AB, ABC triblock terpolymers, and graft structures in non-aqueous selective polar and non-polar solvents, including solvent mixtures and ionic liquids. The micellar characteristics, such as particle size, aggregation number, and morphology, are examined as a function of the copolymers’ architecture and molecular characteristics.

  13. Synthesis and characterization of polystyrene-poly(ethylene oxide)-heparin block copolymers

    NARCIS (Netherlands)

    Vulić, I.; Okano, T.; Kim, S.W.; Feijen, Jan

    1988-01-01

    A procedure for the preparation of new block copolymers composed of a hydrophobic block of polystyrene, a hydrophilic spacer-block of poly(ethylene oxide) and a bioactive block of heparin was investigated. Polystyrene with one amino group per chain was synthesized by free radical oligomerization of

  14. Surface Self-Assembly and Properties of Monolayers Formed by Reverse Poly(butylene oxide)-poly(ethylene oxide)-poly(butylene oxide) Triblock Copolymers with Lengthy Hydrophilic Blocks

    DEFF Research Database (Denmark)

    Villar-Alvarez, Eva; Freire, Adriana Cambón; Blanco, Mateo

    2017-01-01

    for the former at low surface transfer pressures, evolving to continent-like structures first and then dewetted structures as the transfer pressure increases. Conversely, for BO20EO411BO20 and BO21EO385BO21 copolymers micelle formation is noted at lower transfer pressures than the shortest counterparts......, and the formed micelles appear to be elongated, interconnected and with larger thickness. As the transfer pressure increases, attractive micellar interactions are enhanced and then-lead to formation of a dense network of interconnected micelles, first followed by an evolvement to continent-like and dewetted...

  15. CO2 permeation properties of poly(ethylene oxide)-based segmented block copolymers

    NARCIS (Netherlands)

    Husken, D.; Visser, Tymen; Wessling, Matthias; Gaymans, R.J.

    2010-01-01

    This paper discusses the gas permeation properties of poly(ethylene oxide) (PEO)-based segmented block copolymers containing monodisperse amide segments. These monodisperse segments give rise to a well phase-separated morphology, comprising a continuous PEO phase with dispersed crystallised amide

  16. Square and Rectangular Arrays from Directed Assembly of Sphere-forming Diblock Copolymers in Thin Films

    Science.gov (United States)

    Ji, Shengxiang; Nagpal, Umang; Liao, Wen; de Pablo, Juan; Nealey, Paul

    2010-03-01

    Patterns of square and rectangular arrays with nanoscale dimensions are scientifically and technologically important. Fabrication of square array patterns in thin films has been demonstrated by directed assembly of cylinder-forming diblock copolymers on chemically patterned substrates, supramolecular assembly of diblock copolymers, and self-assembly of triblock terpolymers. However, a macroscopic area of square array patterns with long-range order has not been achieved, and the fabrication of rectangular arrays has not been reported so far. Here we report a facile approach for fabricating patterns of square and rectangular arrays by directing the assembly of sphere-forming diblock copolymers on chemically patterned substrates. On stripe patterns, a square arrangement of half spheres, corresponding to the (100) plane of the body-centred cubic (BCC) lattice, formed on film surfaces. When the underlying pattern periods mismatched with the copolymer period, the square pattern could be stretched (up to ˜60%) or compressed (˜15%) to form rectangular arrays. Monte Carlo simulations have been further used to verify the experimental results and the 3-dimensional arrangements of spheres.

  17. Easy and General Synthesis of Large-Sized Mesoporous Rare-Earth Oxide Thin Films by 'Micelle Assembly'.

    Science.gov (United States)

    Li, Yunqi; Bastakoti, Bishnu Prasad; Imura, Masataka; Dai, Pengcheng; Yamauchi, Yusuke

    2015-12-01

    Large-sized (ca. 40 nm) mesoporous Er2O3 thin films are synthesized by using a triblock copolymer poly(styrene-b-2-vinyl pyridine-b-ethylene oxide) (PS-b-P2VP-b-PEO) as a pore directing agent. Each block makes different contributions and the molar ratio of PVP/Er(3+) is crucial to guide the resultant mesoporous structure. An easy and general method is proposed and used to prepare a series of mesoporous rare-earth oxide (Sm2O3, Dy2O3, Tb2O3, Ho2O3, Yb2O3, and Lu2O3) thin films with potential uses in electronics and optical devices. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Mesoscopic Simulations of the Phase Behavior of Aqueous EO 19 PO 29 EO 19 Solutions Confined and Sheared by Hydrophobic and Hydrophilic Surfaces

    KAUST Repository

    Liu, Hongyi

    2012-01-25

    The MesoDyn method is used to investigate associative structures in aqueous solution of a nonionic triblock copolymer consisting of poly(propylene oxide) capped on both ends with poly(ethylene oxide) chains. The effect of adsorbing (hydrophobic) and nonadsorbing (hydrophilic) solid surfaces in contact with aqueous solutions of the polymer is elucidated. The macromolecules form self-assembled structures in solution. Confinement under shear forces is investigated in terms of interfacial behavior and association. The formation of micelles under confinement between hydrophilic surfaces occurs faster than in bulk aqueous solution while layered structures assemble when the polymers are confined between hydrophobic surfaces. Micelles are deformed under shear rates of 1 μs -1 and eventually break to form persistent, adsorbed layered structures. As a result, surface damage under frictional forces is prevented. Overall, this study indicates that aqueous triblock copolymers of poly(ethylene oxide) (PEO) and poly(propylene oxide) (PPO) (Pluronics, EO mPO nEO m) act as a boundary lubricant for hydrophobic surfaces but not for hydrophilic ones. © 2011 American Chemical Society.

  19. Mesoscopic Simulations of the Phase Behavior of Aqueous EO 19 PO 29 EO 19 Solutions Confined and Sheared by Hydrophobic and Hydrophilic Surfaces

    KAUST Repository

    Liu, Hongyi; Li, Yan; Krause, Wendy E.; Pasquinelli, Melissa A.; Rojas, Orlando J.

    2012-01-01

    The MesoDyn method is used to investigate associative structures in aqueous solution of a nonionic triblock copolymer consisting of poly(propylene oxide) capped on both ends with poly(ethylene oxide) chains. The effect of adsorbing (hydrophobic) and nonadsorbing (hydrophilic) solid surfaces in contact with aqueous solutions of the polymer is elucidated. The macromolecules form self-assembled structures in solution. Confinement under shear forces is investigated in terms of interfacial behavior and association. The formation of micelles under confinement between hydrophilic surfaces occurs faster than in bulk aqueous solution while layered structures assemble when the polymers are confined between hydrophobic surfaces. Micelles are deformed under shear rates of 1 μs -1 and eventually break to form persistent, adsorbed layered structures. As a result, surface damage under frictional forces is prevented. Overall, this study indicates that aqueous triblock copolymers of poly(ethylene oxide) (PEO) and poly(propylene oxide) (PPO) (Pluronics, EO mPO nEO m) act as a boundary lubricant for hydrophobic surfaces but not for hydrophilic ones. © 2011 American Chemical Society.

  20. Selective molecular annealing: in situ small angle X-ray scattering study of microwave-assisted annealing of block copolymers.

    Science.gov (United States)

    Toolan, Daniel T W; Adlington, Kevin; Isakova, Anna; Kalamiotis, Alexis; Mokarian-Tabari, Parvaneh; Dimitrakis, Georgios; Dodds, Christopher; Arnold, Thomas; Terrill, Nick J; Bras, Wim; Hermida Merino, Daniel; Topham, Paul D; Irvine, Derek J; Howse, Jonathan R

    2017-08-09

    Microwave annealing has emerged as an alternative to traditional thermal annealing approaches for optimising block copolymer self-assembly. A novel sample environment enabling small angle X-ray scattering to be performed in situ during microwave annealing is demonstrated, which has enabled, for the first time, the direct study of the effects of microwave annealing upon the self-assembly behavior of a model, commercial triblock copolymer system [polystyrene-block-poly(ethylene-co-butylene)-block-polystyrene]. Results show that the block copolymer is a poor microwave absorber, resulting in no change in the block copolymer morphology upon application of microwave energy. The block copolymer species may only indirectly interact with the microwave energy when a small molecule microwave-interactive species [diethylene glycol dibenzoate (DEGDB)] is incorporated directly into the polymer matrix. Then significant morphological development is observed at DEGDB loadings ≥6 wt%. Through spatial localisation of the microwave-interactive species, we demonstrate targeted annealing of specific regions of a multi-component system, opening routes for the development of "smart" manufacturing methodologies.

  1. Thermodynamic characterization of poly(4-hydroxystyrene)-g-[poly(propyleneoxide-b-ethylene oxide)] thermoresponsive brush copolymers

    Energy Technology Data Exchange (ETDEWEB)

    Thanassoulas, Angelos, E-mail: athanas@rrp.demokritos.gr [Biomolecuar Physics Laboratory, National Centre for Scientific Research “Demokritos”, 153 10 Aghia Paraskevi (Greece); Papadopoulos, Athanasios [Biomolecuar Physics Laboratory, National Centre for Scientific Research “Demokritos”, 153 10 Aghia Paraskevi (Greece); Pispas, Stergios [Theoretical and Physical Chemistry Institute, National Hellenic Research Foundation, 11635 Athens (Greece); Zhao, Junpeng; Zhang, Guangzhao [Faculty of Materials Science and Engineering, South China University of Technology, Guangzhou 510640 (China); Nounesis, George [Biomolecuar Physics Laboratory, National Centre for Scientific Research “Demokritos”, 153 10 Aghia Paraskevi (Greece)

    2016-08-20

    Highlights: • PPO-b-PEO core-shell brush copolymers exhibit thermoresponsive behavior in aqueous solutions. • Their thermal transitions strongly depend on their architecture and chemical composition. • These copolymer transitions follow a coil-to-globule mechanism. • It is possible to fine-tune their thermoresponsiveness to a wide range of temperatures. - Abstract: Thermoresponsive brush copolymers with poly(4-hydroxystyrene) backbones and poly(propyleneoxide-b-ethylene oxide) side chains were synthesized via a “grafting from” technique. The thermoresponsive behavior of four samples with different compositions has been investigated in dilute aqueous solutions by high-accuracy differential scanning calorimetry measurements. Thermal transitions involving both core contraction and intermolecular aggregation have been observed for all the copolymers in this study. The temperature where these thermal transitions occur is strongly associated to the architecture and chemical composition of the copolymers, allowing for fine-tuning of their thermoresponsiveness in a wide range of temperatures.

  2. Two-dimensional phase separated structures of block copolymers on solids

    Science.gov (United States)

    Sen, Mani; Jiang, Naisheng; Endoh, Maya; Koga, Tadanori; Ribbe, Alexander

    The fundamental, yet unsolved question in block copolymer (BCP) thin films is the self-organization process of BCPs at the solid-polymer melt interface. We here focus on the self-organization processes of cylinder-forming polystyrene-block-poly (4-vinylpyridine) diblock copolymer and lamellar-forming poly (styrene-block-butadiene-block-styrene) triblock copolymer on Si substrates as model systems. In order to reveal the buried interfacial structures, the following experimental protocols were utilized: the BCP monolayer films were annealed under vacuum at T>Tg of the blocks (to equilibrate the melts); vitrification of the annealed BCP films via rapid quench to room temperature; subsequent intensive solvent leaching (to remove unadsorbed chains) with chloroform, a non-selective good solvent for the blocks. The strongly bound BCP layers were then characterized by using atomic force microscopy, scanning electron microscopy, grazing incidence small angle X-ray scattering, and X-ray reflectivity. The results showed that both blocks lie flat on the substrate, forming the two-dimensional, randomly phase-separated structure irrespective of their microdomain structures and interfacial energetics. Acknowledgement of financial support from NSF Grant (CMMI -1332499).

  3. Core-shell-corona micelles by PS-b-P2VP-b-PEO copolymers: focus on the water-induced micellization process.

    Science.gov (United States)

    Willet, Nicolas; Gohy, Jean-François; Auvray, Loïc; Varshney, Sunil; Jérôme, Robert; Leyh, Bernard

    2008-04-01

    It is now well established that amphiphilic PS-b-P2VP-b-PEO linear triblock copolymers can form multilayered assemblies, thus core-shell-corona (CSC) micelles, in water. Micellization is triggered by addition of a small amount of water into a dilute solution of the PS-b-P2VP-b-PEO copolymer in a non-selective organic solvent. However, the phenomena that take place at the very beginning of this process are poorly documented. How these copolymer chains are perturbed by addition of water was investigated in this work by light and neutron scattering techniques and transmission electron microscopy. It was accordingly possible to determine the critical water concentration (CWC), the compactness of the nano-objects in solution, their number of aggregation, and their hydrodynamic diameter at each step of the micellization process.

  4. Chemical modification of biodegradable polymer poly(3-hydroxybutyrate) by poly(ethylene oxide)

    International Nuclear Information System (INIS)

    Almeida, Lilian L.; Rocha, Gisele A.; Hui, Wang S.

    2009-01-01

    Catalyzed transesterification in the melt was used to produce triblock copolymers from poly(3-hydroxybutyrate) (PHB) and poly(ethyleneoxide) (PEG), in a simplified process. PHB of high molecular weight was depolymerized by pyrolysis and transesterification with dihydroxy terminated PEG occurred through consecutive and partly simultaneous reactions. The effectiveness of the process was verified by the characterization of the formed copolymers by Hydrogen and Carbon-13 Nuclear Magnetic Resonance Spectroscopies (NMR) and solubility analysis in a series of solvents. (author)

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

    Energy Technology Data Exchange (ETDEWEB)

    Determan, Michael Duane [Iowa State Univ., Ames, IA (United States)

    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

  6. In-situ crosslinkable and self-assembling elastin-like polypeptide block copolymers for cartilage tissue repair

    Science.gov (United States)

    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

  7. Phase Separation and Elastic Properties of Poly(Trimethylene Terephthalate-block-poly(Ethylene Oxide Copolymers

    Directory of Open Access Journals (Sweden)

    Elżbieta Piesowicz

    2016-06-01

    Full Text Available A series of poly(trimethylene terephthalate-block-poly(ethylene oxide (PTT-b-PEOT copolymers with different compositions of rigid PTT and flexible PEOT segments were synthesized via condensation in the melt. The influence of the block length and the block ratio on the micro-separated phase structure and elastic properties of the synthesized multiblock copolymers was studied. The PEOT segments in these copolymers were kept constant at 1130, 2130 or 3130 g/mol, whereas the PTT content varied from 30 up to 50 wt %. The phase separation was assessed using differential scanning calorimetry (DSC and dynamic mechanical thermal analysis (DMTA. The crystal structure of the synthesised block copolymers and their microstructure on the manometer scale was evaluated by using WAXS and SAXS analysis. Depending on the PTT/PEOT ratio, but also on the rigid and flexible segment length in PTT-b-PEO copolymers, four different domains were observed i.e.,: a crystalline PTT phase, a crystalline PEO phase (which exists for the whole series based on three types of PEOT segments, an amorphous PTT phase (only at 50 wt % content of PTT rigid segments and an amorphous PEO phase. Moreover, the elastic deformability and reversibility of PTT-b-PEOT block copolymers were studied during a cyclic tensile test. Determined values of permanent set resultant from maximum attained stain (100% and 200% for copolymers were used to evaluate their elastic properties.

  8. Silicon containing copolymers

    CERN Document Server

    Amiri, Sahar; Amiri, Sanam

    2014-01-01

    Silicones have unique properties including thermal oxidative stability, low temperature flow, high compressibility, low surface tension, hydrophobicity and electric properties. These special properties have encouraged the exploration of alternative synthetic routes of well defined controlled microstructures of silicone copolymers, the subject of this Springer Brief. The authors explore the synthesis and characterization of notable block copolymers. Recent advances in controlled radical polymerization techniques leading to the facile synthesis of well-defined silicon based thermo reversible block copolymers?are described along with atom transfer radical polymerization (ATRP), a technique utilized to develop well-defined functional thermo reversible block copolymers. The brief also focuses on Polyrotaxanes and their great potential as stimulus-responsive materials which produce poly (dimethyl siloxane) (PDMS) based thermo reversible block copolymers.

  9. Differences in the adsorption behaviour of poly(ethylene oxide) copolymers onto model polystyrene nanoparticles assessed by isothermal titration microcalorimetry correspond to the biological differences.

    Science.gov (United States)

    Stolnik, S; Heald, C R; Garnett, M G; Illum, L; Davis, S S

    2005-01-01

    The adsorption behaviour of a tetrafunctional copolymer of poly (ethylene oxide)-poly (propylene oxide) ethylene diamine (commercially available as Poloxamine 908) and a diblock copolymer of poly (lactic acid)-poly (ethylene oxide) (PLA/PEG 2:5) onto a model colloidal drug carrier (156 nm sized polystyrene latex) is described. The adsorption isotherm, hydrodynamic thickness of the adsorbed layers and enthalpy of the adsorption were assessed. The close similarity in the conformation of the poly (ethylene oxide) (PEO) chains (molecular weight 5,000 Da) in the adsorbed layers of these two copolymers was demonstrated by combining the adsorption data with the adsorbed layer thickness data. In contrast, the results from isothermal titration microcalorimetry indicated a distinct difference in the interaction of the copolymers with the polystyrene colloid surface. Poloxamine 908 adsorption to polystyrene nanoparticles is dominated by an endothermic heat effect, whereas, PLA/PEG 2:5 adsorption is entirely an exothermic process. This difference in adsorption behaviour could provide an explanation for differences in the biodistribution of Poloxamine 908 and PLA/PEG 2:5 coated polystyrene nanoparticles observed in previous studies. A comparison with the interaction enthalpy for several other PEO-containing copolymers onto the same polystyrene colloid was made. The results demonstrate the importance of the nature of the anchoring moiety on the interaction of the adsorbing copolymer with the colloid surface. An endothermic contribution is found when an adsorbing molecule contains a poly (propylene oxide) (PPO) moiety (e.g. Poloxamine 908), whilst the adsorption is exothermic (i.e. enthalpy driven) for PEO copolymers with polylactide (PLA/PEG 2:5) or alkyl moieties.

  10. Triblock-Terpolymer-Directed Self-Assembly of Mesoporous TiO2: High-Performance Photoanodes for Solid-State Dye-Sensitized Solar Cells

    KAUST Repository

    Docampo, Pablo

    2012-04-30

    A new self-assembly platform for the fast and straightforward synthesis of bicontinuous, mesoporous TiO 2 films is presented, based on the triblock terpolymer poly(isoprene - b - styrene - b - ethylene oxide). This new materials route allows the co-assembly of the metal oxide as a fully interconnected minority phase, which results in a highly porous photoanode with strong advantages over the state-of-the-art nanoparticle-based photoanodes employed in solidstate dye-sensitized solar cells. Devices fabricated through this triblock terpolymer route exhibit a high availability of sub-bandgap states distributed in a narrow and low enough energy band, which maximizes photoinduced charge generation from a state-of-the-art organic dye, C220. As a consequence, the co-assembled mesoporous metal oxide system outperformed the conventional nanoparticle-based electrodes fabricated and tested under the same conditions, exhibiting solar power-conversion efficiencies of over 5%. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Triblock-Terpolymer-Directed Self-Assembly of Mesoporous TiO2: High-Performance Photoanodes for Solid-State Dye-Sensitized Solar Cells

    KAUST Repository

    Docampo, Pablo; Stefik, Morgan; Guldin, Stefan; Gunning, Robert; Yufa, Nataliya A.; Cai, Ning; Wang, Peng; Steiner, Ullrich; Wiesner, Ulrich; Snaith, Henry J.

    2012-01-01

    A new self-assembly platform for the fast and straightforward synthesis of bicontinuous, mesoporous TiO 2 films is presented, based on the triblock terpolymer poly(isoprene - b - styrene - b - ethylene oxide). This new materials route allows the co-assembly of the metal oxide as a fully interconnected minority phase, which results in a highly porous photoanode with strong advantages over the state-of-the-art nanoparticle-based photoanodes employed in solidstate dye-sensitized solar cells. Devices fabricated through this triblock terpolymer route exhibit a high availability of sub-bandgap states distributed in a narrow and low enough energy band, which maximizes photoinduced charge generation from a state-of-the-art organic dye, C220. As a consequence, the co-assembled mesoporous metal oxide system outperformed the conventional nanoparticle-based electrodes fabricated and tested under the same conditions, exhibiting solar power-conversion efficiencies of over 5%. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Drug-conjugated PLA-PEG-PLA copolymers: a novel approach for controlled delivery of hydrophilic drugs by micelle formation.

    Science.gov (United States)

    Danafar, H; Rostamizadeh, K; Davaran, S; Hamidi, M

    2017-12-01

    A conjugate of the antihypertensive drug, lisinopril, with triblock poly(lactic acid)-poly(ethylene glycol)-poly(lactic acid) (PLA-PEG-PLA) copolymer was synthesized by the reaction of PLA-PEG-PLA copolymer with lisinopril in the presence of dicyclohexylcarbodiimide and dimethylaminopyridine. The conjugated copolymer was characterized in vitro by hydrogen nuclear magnetic resonance (HNMR), Fourier transform infrared (FTIR), differential scanning calorimetry (DSC) and gel permeation chromatography (GPC) techniques. Then, the lisinopril conjugated PLA-PEG-PLA were self-assembled into micelles in aqueous solution. The resulting micelles were characterized further by various techniques such as dynamic light scattering (DLS) and atomic force microscopy (AFM). The results revealed that the micelles formed by the lisinopril-conjugated PLA-PEG-PLA have spherical structure with the average size of 162 nm. The release behavior of conjugated copolymer, micelles and micelles physically loaded by lisinopril were compared in different media. In vitro release study showed that in contrast to physically loaded micelles, the release rate of micelles consisted of the conjugated copolymer was dependent on pH of media where it was higher at lower pH compared to the neutral medium. Another feature of the conjugated micelles was their more sustained release profile compared to the lisinopril-conjugated copolymer and physically loaded micelles.

  13. SYNTHESIS OF BLOCK COPOLYMER BY INTEGRATED LIVING ANIONIC POLYMERIZATION-ATOM TRANSFER RADICAL POLYMERIZATION (ATRP)

    Institute of Scientific and Technical Information of China (English)

    Bing Liu; Feng Liu; Ning Luo; Sheng-kang Ying; Qing Liu

    2000-01-01

    Alpha-trichloroacetoxy terminated polystyrene oligomer (PS-CH2CH2OCOCCl3) and poly-(styrene-b-butadiene)oligomer [P(S-b-B)-CH2CH2OCOCCl3)] were synthesized by living anionic polymeri-zation using n-butyllithium as initiator.Then the PS-CH2CH2OCOCCl3 (PS-Cl3) or P(S-b-B)-CH2CH2O-COCCl3 (PSB-Cl3) was used as the macroinitiator in the polymerization of (meth)acrylates in the presence of CuX/bpy. AB diblock and ABC triblock copolymers were prepared by the integrated living anionic polymerization (LAP)-atom transfer radical polymerization (ATRP). The structures of the PSB-Cl3 and the P(S-b-MMA) were identified by FTIR and 1H-NMR spectrum, respectively. A new way to design block copolymers (the combination of LAP and ATRP) was developed.

  14. Directed Self-assembly of Block Copolymer with Sub-15 nm Domain Spacing Using Nanoimprinted Photoresist Templates

    Science.gov (United States)

    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.

  15. PLA-PEG-PLA copolymer-based polymersomes as nanocarriers for delivery of hydrophilic and hydrophobic drugs: preparation and evaluation with atorvastatin and lisinopril.

    Science.gov (United States)

    Danafar, H; Rostamizadeh, K; Davaran, S; Hamidi, M

    2014-10-01

    Tri-block poly(lactide)-poly(ethylene glycol)-poly(lactide) (PLA-PEG-PLA) copolymers were synthesized and used to prepare polymersomes loaded separately by the hydrophobic and hydrophilic model drugs, atorvastatin and lisinopril, respectively. The resulting nanostructures were characterized by various techniques such as FTIR, DSC, PCS and AFM. The polymersomes exhibited high encapsulation efficiencies of almost 78% and 70.8% for atorvastatin and lisinopril, respectively. Investigation on FTIR and DSC results revealed that such a high encapsulation efficiency is due to strong interaction between atorvastatin and the copolymer. The impact of drug/copolymer ratio and copolymer composition on drug-loading efficiency and drug release behavior were also studied. The results showed that in case of lisinopril, polymersomes exhibited a triphasic drug release, while for atorvastatin a biphasic release profile was obtained. Overall, the results indicated that PLA-PEG-PLA polymersomes can be considered as a promising carrier for both hydrophilic and hydrophobic drugs.

  16. Hydrophilic segmented block copolymers based on poly(ethylene oxide) and monodisperse amide segments

    NARCIS (Netherlands)

    Husken, D.; Feijen, Jan; Gaymans, R.J.

    2007-01-01

    Segmented block copolymers based on poly(ethylene oxide) (PEO) flexible segments and monodisperse crystallizable bisester tetra-amide segments were made via a polycondensation reaction. The molecular weight of the PEO segments varied from 600 to 4600 g/mol and a bisester tetra-amide segment (T6T6T)

  17. Triblock-terpolymer-directed self-assembly of mesoporous TiO{sub 2}: High-performance photoanodes for solid-state dye-sensitized solar cells

    Energy Technology Data Exchange (ETDEWEB)

    Docampo, Pablo; Gunning, Robert; Snaith, Henry J. [Clarendon Laboratory, Department of Physics, University of Oxford, Parks Road, Oxford OX1 3PU (United Kingdom); Stefik, Morgan; Wiesner, Ulrich [Department of Materials Science and Engineering, Cornell University, Ithaca, NY 14853 (United States); Guldin, Stefan; Yufa, Nataliya A.; Steiner, Ullrich [Department of Physics, University of Cambridge, J. J. Thomson Avenue, Cambridge CB3 0HE (United Kingdom); Cai, Ning; Wang, Peng [State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022 (China)

    2012-06-15

    A new self-assembly platform for the fast and straightforward synthesis of bicontinuous, mesoporous TiO{sub 2} films is presented, based on the triblock terpolymer poly(isoprene-b-styrene-b-ethylene oxide). This new materials route allows the co-assembly of the metal oxide as a fully interconnected minority phase, which results in a highly porous photoanode with strong advantages over the state-of-the-art nanoparticle-based photoanodes employed in solid-state dye-sensitized solar cells. Devices fabricated through this triblock terpolymer route exhibit a high availability of sub-bandgap states distributed in a narrow and low enough energy band, which maximizes photoinduced charge generation from a state-of-the-art organic dye, C220. As a consequence, the co-assembled mesoporous metal oxide system outperformed the conventional nanoparticle-based electrodes fabricated and tested under the same conditions, exhibiting solar power-conversion efficiencies of over 5%. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  18. Ion transport properties of mechanically stable symmetric ABCBA pentablock copolymers with quaternary ammonium functionalized midblock

    Energy Technology Data Exchange (ETDEWEB)

    Ertem, S. Piril [Department of Polymer Science and Engineering, University of Massachusetts Amherst, 120 Governors Drive Amherst Massachusetts 01003; Caire, Benjamin R. [Department of Chemical and Biological Engineering, Colorado School of Mines, Golden Colorado 80401; Tsai, Tsung-Han [Department of Polymer Science and Engineering, University of Massachusetts Amherst, 120 Governors Drive Amherst Massachusetts 01003; Zeng, Di [Department of Polymer Science and Engineering, University of Massachusetts Amherst, 120 Governors Drive Amherst Massachusetts 01003; Vandiver, Melissa A. [Department of Chemical and Biological Engineering, Colorado School of Mines, Golden Colorado 80401; Kusoglu, Ahmet [Energy Conversion Group, Energy Technologies Area, Lawrence Berkeley National Laboratory, Berkeley California 94720; Seifert, Soenke [Energy Conversion Group, Energy Technologies Area, Lawrence Berkeley National Laboratory, Berkeley California 94720; Hayward, Ryan C. [Department of Polymer Science and Engineering, University of Massachusetts Amherst, 120 Governors Drive Amherst Massachusetts 01003; Weber, Adam Z. [Energy Conversion Group, Energy Technologies Area, Lawrence Berkeley National Laboratory, Berkeley California 94720; Herring, Andrew M. [Department of Chemical and Biological Engineering, Colorado School of Mines, Golden Colorado 80401; Coughlin, E. Bryan [Department of Polymer Science and Engineering, University of Massachusetts Amherst, 120 Governors Drive Amherst Massachusetts 01003; Liberatore, Matthew W. [Department of Chemical Engineering Department, University of Toledo, 2801 W Bancroft Street MS305 Toledo Ohio 43606

    2017-02-07

    Anion exchange membranes (AEMs) are a promising class of materials for applications that require selective ion transport, such as fuel cells, water purification, and electrolysis devices. Studies of structure–morphology–property relationships of ion-exchange membranes revealed that block copolymers exhibit improved ion conductivity and mechanical properties due to their microphase-separated morphologies with well-defined ionic domains. While most studies focused on symmetric diblock or triblock copolymers, here, the first example of a midblock quaternized pentablock AEM is presented. A symmetric ABCBA pentablock copolymer was functionalized to obtain a midblock brominated polymer. Solution cast films were then quaternized to obtain AEMs with resulting ion exchange capacities (IEC) ranging from 0.4 to 0.9 mmol/g. Despite the relatively low IEC, the polymers were highly conductive (up to 60 mS/cm Br2 at 90 8C and 95%RH) with low water absorption (<25 wt %) and maintained adequate mechanical properties in both dry and hydrated conditions. Xray scattering and transmission electron microscopy (TEM) revealed formation of cylindrical non-ionic domains in a connected ionic phase.

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

    Science.gov (United States)

    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. Copyright © 2015 Elsevier Ltd. All rights reserved.

  20. Effect of block composition on thermal properties and melt viscosity of poly[2-(dimethylaminoethyl methacrylate], poly(ethylene oxide and poly(propylene oxide block co-polymers

    Directory of Open Access Journals (Sweden)

    2011-09-01

    Full Text Available To modify the rheological properties of certain commercial polymers, a set of block copolymers were synthesized through oxyanionic polymerization of 2-(dimethylaminoethyl methacrylate to the chain ends of commercial prepolymers, namely poly(ethylene oxide (PEO, poly(ethylene oxide-block-poly(propylene oxide-block-poly(ethylene oxide (PEO-PPO-PEO, and poly(propylene oxide (PPO. The formed block copolymers were analysed with size exclusion chromatography and nuclear magnetic resonance spectroscopy in order to confirm block formation. Thermal characterization of the resulting polymers was done with differential scanning calorimetry. Thermal transition points were also confirmed with rotational rheometry, which was primarily used to measure melt strength properties of the resulting block co-polymers. It was observed that the synthesised poly[2-(dimethylaminoethyl methacrylate]-block (PDM affected slightly the thermal transition points of crystalline PEO-block but the influence was stronger on amorphous PPO-blocks. Frequency sweeps measured above the melting temperatures for the materials confirmed that the pre-polymers (PEO and PEO-PPO-PEO behave as Newtonian fluids whereas polymers with a PDM block structure exhibit clear shear thinning behaviour. In addition, the PDM block increased the melt viscosity when compared with that one of the pre-polymer. As a final result, it became obvious that pre-polymers modified with PDM were in entangled form, in the melted state as well in the solidified form.

  1. Star block-copolymers: Enzyme-inspired catalysts for oxidation of alcohols in water

    KAUST Repository

    Mugemana, Clement

    2014-01-01

    A number of fluorous amphiphilic star block-copolymers containing a tris(benzyltriazolylmethyl)amine motif have been prepared. These polymers assembled into well-defined nanostructures in water, and their mode of assembly could be controlled by changing the composition of the polymer. The polymers were used for enzyme-inspired catalysis of alcohol oxidation. This journal is © the Partner Organisations 2014.

  2. Fluorinated 2-alkyl-2-oxazolines of high reactivity: spacer-length-induced acceleration for cationic ring-opening polymerization as a basis for triphilic block copolymer synthesis

    Czech Academy of Sciences Publication Activity Database

    Kaberov, Leonid; Verbraeken, B.; Riabtseva, Anna; Brus, Jiří; Talmon, Y.; Štěpánek, Petr; Hoogenboom, R.; Filippov, Sergey K.

    2018-01-01

    Roč. 7, č. 1 (2018), s. 7-10 ISSN 2161-1653 R&D Projects: GA ČR(CZ) GA17-00973S Grant - others:AV ČR(CZ) FWO-17-05 Program:Bilaterální spolupráce Institutional support: RVO:61389013 Keywords : poly(2-oxazoline)s * triblock copolymers * fluorinated Subject RIV: BO - Biophysics OBOR OECD: Biophysics Impact factor: 6.185, year: 2016

  3. Interaction between poly(vinyl pyridine) and poly(2,6-dimethyl-1,4-phenylene oxide) : A copolymer blend miscibility study

    NARCIS (Netherlands)

    de Wit, Joost; van Ekenstein, Gert Alberda; ten Brinke, Gerrit

    2007-01-01

    The phase behavior of blends of poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) with random copolymers of styrene and 2-vinyl pyridine, Poly(S-co-2VP), as well as with random copolymers of styrene and 4-vinyl pyridine, Poly(S-co-4VP), has been investigated in order to estimate the values of the

  4. Polyether-polyester graft copolymer

    Science.gov (United States)

    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.

  5. Morphology-properties relationship on nanocomposite films based on poly(styrene-block-diene-block-styrene copolymers and silver nanoparticles

    Directory of Open Access Journals (Sweden)

    2011-02-01

    Full Text Available A comparative study on the self-assembled nanostructured morphology and the rheological and mechanical properties of four different triblock copolymers, based on poly(styrene-block-diene-block-styrene and poly(styrene-block-diene-block-styrene matrices, and of their respective nanocomposites with 1 wt% silver nanoparticles, is reported in this work. In order to obtain well-dispersed nanoparticles in the block copolymer matrix, dodecanethiol was used as surfactant, showing good affinity with both nanoparticles and the polystyrene phase of the matrices as predicted by the solubility parameters calculated based on Hoftyzer and Van Krevelen theory. The block copolymer with the highest PS content shows the highest tensile modulus and tensile strength, but also the smallest elongation at break. When silver nanoparticles treated with surfactant were added to the block copolymer matrices, each system studied shows higher mechanical properties due to the good dispersion and the good interface of Ag nanoparticles in the matrices. Furthermore, it has been shown that semiempirical models such as Guth and Gold equation and Halpin-Tsai model can be used to predict the tensile modulus of the analyzed nanocomposites.

  6. Synthesis and luminescence properties of hybrid organic-inorganic transparent titania thin film activated by in-situ formed lanthanide complexes

    International Nuclear Information System (INIS)

    Wang Yige; Wang Li; Li Huanrong; Liu Peng; Qin Dashan; Liu Binyuan; Zhang Wenjun; Deng Ruiping; Zhang Hongjie

    2008-01-01

    Stable transparent titania thin films were fabricated at room temperature by combining thenoyltrifluoroacetone (TTFA)-modified titanium precursors with amphiphilic triblock poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO, P123) copolymers. The obtained transparent titania thin films were systematically investigated by IR spectroscopy, PL emission and excitation spectroscopy and transmission electron microscopy. IR spectroscopy indicates that TTFA coordinates the titanium center during the process of hydrolysis and condensation. Luminescence spectroscopy confirms the in-situ formation of lanthanide complexes in the transparent titania thin film. TEM image shows that the in-situ formed lanthanide complexes were homogeneously distributed throughout the whole thin film. The quantum yield and the number of water coordinated to lanthanide metal center have been theoretically determined based on the luminescence data. - Graphical abstract: Novel stable luminescent organic-inorganic hybrid titania thin film with high transparency activated by in-situ formed lanthanide complexes have been obtained at room temperature via a simple one-pot synthesis approach by using TTFA-modified titanium precursor with amphiphilic triblock copolymer P123. The obtained hybrid thin film displays bright red (or green), near-monochromatic luminescence due to the in-situ formed lanthanide complex

  7. Polyether/Polyester Graft Copolymers

    Science.gov (United States)

    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.

  8. Comprehensive two-dimensional liquid chromatographic analysis of poloxamers.

    Science.gov (United States)

    Malik, Muhammad Imran; Lee, Sanghoon; Chang, Taihyun

    2016-04-15

    Poloxamers are low molar mass triblock copolymers of poly(ethylene oxide) (PEO) and poly(propylene oxide) (PPO), having number of applications as non-ionic surfactants. Comprehensive one and two-dimensional liquid chromatographic (LC) analysis of these materials is proposed in this study. The separation of oligomers of both types (PEO and PPO) is demonstrated for several commercial poloxamers. This is accomplished at the critical conditions for one of the block while interaction for the other block. Reversed phase LC at CAP of PEO allowed for oligomeric separation of triblock copolymers with regard to PPO block whereas normal phase LC at CAP of PPO renders oligomeric separation with respect to PEO block. The oligomeric separation with regard to PEO and PPO are coupled online (comprehensive 2D-LC) to reveal two-dimensional contour plots by unconventional 2D IC×IC (interaction chromatography) coupling. The study provides chemical composition mapping of both PEO and PPO, equivalent to combined molar mass and chemical composition mapping for several commercial poloxamers. Copyright © 2016 Elsevier B.V. All rights reserved.

  9. Graphene oxide-enhanced sol-gel transition sensitivity and drug release performance of an amphiphilic copolymer-based nanocomposite

    Science.gov (United States)

    Hu, Huawen; Wang, Xiaowen; Lee, Ka I; Ma, Kaikai; Hu, Hong; Xin, John H.

    2016-01-01

    We report the fabrication of a highly sensitive amphiphilic copolymer-based nanocomposite incorporating with graphene oxide (GO), which exhibited a low-intensity UV light-triggered sol-gel transition. Non-cytotoxicity was observed for the composite gels after the GO incorporation. Of particular interest were the microchannels that were formed spontaneously within the GO-incorporated UV-gel, which expedited sustained drug release. Therefore, the present highly UV-sensitive, non-cytotoxic amphiphilic copolymer-based composites is expected to provide enhanced photothermal therapy and chemotherapy by means of GO’s unique photothermal properties, as well as through efficient passive targeting resulting from the sol-gel transition characteristic of the copolymer-based system with improved sensitivity, which thus promises the enhanced treatment of patients with cancer and other diseases. PMID:27539298

  10. Dependency of Anion and Chain Length of Imidazolium Based Ionic Liquid on Micellization of the Block Copolymer F127 in Aqueous Solution: An Experimental Deep Insight

    Directory of Open Access Journals (Sweden)

    Jignesh Lunagariya

    2017-07-01

    Full Text Available The non-ionic triblock copolymer, Pluronic® F127, has been selected to observe its interaction with ionic liquids (ILs in aqueous solutions by using DLS, surface tension, and viscosity measurements. The Critical Micelle Concentration (CMC of F127 increased with the addition of ILs, which appeared logical since it increases the solubility of PPO (and PEO moiety, making it behaves more like a hydrophilic block copolymer that is micellized at a higher copolymer concentration. The results from DLS data showed good agreement with those obtained from the surface tension measurements. Upon the addition of ILs, the tendency in micellar size reduction was demonstrated by viscosity results, and therefore, intrinsic viscosity decreased compared to pure F127 in aqueous solution. The results were discussed as a function of alkyl chain length and anions of imidazolium based ILs.

  11. Assembly of photosynthetic reaction center with ABA tri-block polymersomes: highlights on the protein localization.

    KAUST Repository

    Tangorra, Roberto Rocco

    2015-07-07

    The reconstitution of the integral membrane protein photosynthetic reaction center (RC) in polymersomes, i. e. artificial closed vesicles, was achieved by the micelle-to-vesicle transition technique, a very mild protocol based on size exclusion chromatography often used to drive the incorporation of proteins contemporarily to liposomes formation. An optimized protocol was used to successfully reconstitute the protein in a fully active state in polymersomes formed by the tri-block copolymers PMOXA22-PDMS61-PMOXA22. The RC is very sensitive to its solubilizing environment and was used to probe the positioning of the protein in the vesicles. According to charge-recombination experiments and to the enzymatic activity assay, the RC is found to accommodate in the PMOXA22 region of the polymersome, facing the water bulk solution, rather than in the PDMS61 transmembrane-like region. Furthermore, polymersomes were found to preserve protein integrity efficiently as the biomimetic lipid bilayers but show a much longer temporal stability than lipid based vesicles.

  12. Assembly of photosynthetic reaction center with ABA tri-block polymersomes: highlights on the protein localization.

    KAUST Repository

    Tangorra, Roberto Rocco; Operamolla, Alessandra; Milano, Francesco; Hassan Omar, Omar; Henrard, John; Comparelli, Roberto; Italiano, Francesca; Agostiano, Angela; De Leo, Vincenzo; Marotta, Roberto; Falqui, Andrea; Farinola, Gianluca; Trotta, Massimo

    2015-01-01

    The reconstitution of the integral membrane protein photosynthetic reaction center (RC) in polymersomes, i. e. artificial closed vesicles, was achieved by the micelle-to-vesicle transition technique, a very mild protocol based on size exclusion chromatography often used to drive the incorporation of proteins contemporarily to liposomes formation. An optimized protocol was used to successfully reconstitute the protein in a fully active state in polymersomes formed by the tri-block copolymers PMOXA22-PDMS61-PMOXA22. The RC is very sensitive to its solubilizing environment and was used to probe the positioning of the protein in the vesicles. According to charge-recombination experiments and to the enzymatic activity assay, the RC is found to accommodate in the PMOXA22 region of the polymersome, facing the water bulk solution, rather than in the PDMS61 transmembrane-like region. Furthermore, polymersomes were found to preserve protein integrity efficiently as the biomimetic lipid bilayers but show a much longer temporal stability than lipid based vesicles.

  13. Synthesis and Characterization of Novel Magnetite Nanoparticle Block Copolymer Complexes

    OpenAIRE

    Zhang, Qian

    2007-01-01

    Superparamagnetic Magnetite (Fe3O4) nanoparticles were synthesized and complexed with carboxylate-functionalized block copolymers, and aqueous dispersions of the complexes were investigated as functions of their chemical and morphological structures. The block copolymer dispersants possessed either poly(ethylene oxide), poly(ethylene oxide-co-propylene oxide), or poly(ethylene oxide-b-propylene oxide) outer blocks, and all contained a polyurethane center block with pendant carboxylate functi...

  14. Three-dimensional block copolymer nanostructures by the solvent-annealing-induced wetting in anodic aluminum oxide templates.

    Science.gov (United States)

    Chu, Chiang-Jui; Chung, Pei-Yun; Chi, Mu-Huan; Kao, Yi-Huei; Chen, Jiun-Tai

    2014-09-01

    Block copolymers have been extensively studied over the last few decades because they can self-assemble into well-ordered nanoscale structures. The morphologies of block copolymers in confined geometries, however, are still not fully understood. In this work, the fabrication and morphologies of three-dimensional polystyrene-block-polydimethylsiloxane (PS-b-PDMS) nanostructures confined in the nanopores of anodic aluminum oxide (AAO) templates are studied. It is discovered that the block copolymers can wet the nanopores using a novel solvent-annealing-induced nanowetting in templates (SAINT) method. The unique advantage of this method is that the problem of thermal degradation can be avoided. In addition, the morphologies of PS-b-PDMS nanostructures can be controlled by changing the wetting conditions. Different solvents are used as the annealing solvent, including toluene, hexane, and a co-solvent of toluene and hexane. When the block copolymer wets the nanopores in toluene vapors, a perpendicular morphology is observed. When the block copolymer wets the nanopores in co-solvent vapors (toluene/hexane = 3:2), unusual circular and helical morphologies are obtained. These three-dimensional nanostructures can serve as naontemplates for refilling with other functional materials, such as Au, Ag, ZnO, and TiO2 . © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Preparation and in vivo pharmacokinetics of curcumin-loaded PCL-PEG-PCL triblock copolymeric nanoparticles

    Directory of Open Access Journals (Sweden)

    Feng R

    2012-07-01

    Full Text Available Runliang Feng,1,* Zhimei Song,1,* Guangxi Zhai2 1Department of Pharmaceutical Engineering, College of Medicine and Life Science, University of Jinan, Jinan, Shandong Province, 2Department of Pharmaceutics, College of Pharmacy, Shandong University, Jinan, Shandong Province, People's Republic of China*These authors contributed equally to this workBackground: Curcumin (CUR has been linked with antioxidant, anti-inflammatory, antimicrobial, anti amyloid, and antitumor effects, but its application is limited because of its low aqueous solubility and poor oral bioavailability.Methods: To improve its bioavailability and water solubility, we synthesized two series of poly (ε-Caprolactone-poly (ethylene glycol-poly (ε-Caprolactone triblock copolymers by ring-opening polymerization of poly (ethylene glycol and ε-Caprolactone, with stannous 2-ethylhexanoate as the catalyst. Structure of the copolymers was characterized by proton nuclear magnetic resonance spectroscopy, Fourier transform infrared spectroscopy, and gel permeation chromatography. The nanoparticles (NPs were prepared using a probe-type ultrasonic emulsion and solvent evaporation method. To obtain an optimal delivery system, we explored the effect of the length of the copolymers' hydrophilic and hydrophobic chains on the encapsulation of hydrophobic CUR, performing entrapment efficiency and drug loading evaluations, as well as studying the particle distribution and in vitro release using the direct dispersion method. Finally, study of the in vivo pharmacokinetics of the CUR-loaded NPs was also carried out on selected copolymers in comparison with CUR solution formulations.Results: CUR was encapsulated with 94.3% and 95.5% efficiency in biodegradable nanoparticulate formulations based on NP43 and NP63, respectively. Dynamic laser light scattering and transmission electron microscopy indicated a particle diameter of 55.6 nm and 62.4 nm for NP43 and NP63, respectively. Fourier transform

  16. Tuning of Block Copolymer Membrane Morphology through Water Induced Phase Inversion Technique

    KAUST Repository

    Madhavan, Poornima

    2016-06-01

    surface and pore walls of PS-b-P4VP block copolymer membranes and then investigated the biocidal activity of the silver nanoparticles grown membranes. Finally, a novel photoresponsive nanostructured triblock copolymer membranes were developed by phase inversion technique. In addition, the photoresponsive behavior on irradiation with light and their membrane flux and retention properties were studied.

  17. Self-assembling of poly(ε-caprolactone)-b-poly(ethylene oxide) diblock copolymers in aqueous solution and at the silica-water interface

    International Nuclear Information System (INIS)

    Leyh, B.; Vangeyte, P.; Heinrich, M.; Auvray, L.; De Clercq, C.; Jerome, R.

    2004-01-01

    Small-angle neutron scattering is used to investigate the self-assembling behaviour of poly(ε-caprolactone)-b-poly(ethylene oxide) diblock copolymers with various block lengths (i) in aqueous solution, (ii) in aqueous solution with the addition of sodium dodecyl sulphate (SDS) and (iii) at the silica-water interface. Micelles are observed under our experimental conditions due to the very small critical micellar concentration of these copolymers (0.01 g/l). The poly(ε-caprolactone) core is surrounded by a poly(ethylene oxide) corona. The micellar form factors have been measured at low copolymer concentrations (0.2 wt%) under selected contrast matching conditions. The data have been fitted to various analytical models to extract the micellar core and corona sizes. SDS is shown to induce partial micelle disruption together with an increase of the poly(ethylene oxide) corona extension from 25% (without SDS) to 70% (with SDS) of a completely extended PEO 114 chain. Our data at the silica-water interface are compatible with the adsorption of micelles

  18. PEO-related block copolymer surfactants

    DEFF Research Database (Denmark)

    Mortensen, K.

    2001-01-01

    Non-ionic block copolymer systems based on hydrophilic poly(ethylene oxide) and more hydrophobic co-polymer blocks are used intensively in a variety of industrial and personal applications. A brief description on the applications is presented. The physical properties of more simple model systems...... of such PEG-based block copolymers in aqueous suspensions are reviewed. Based on scattering experiments using either X-ray or neutrons, the phase behavior is characterized, showing that the thermo-reversible gelation is a result of micellar ordering into mesoscopic crystalline phases of cubic, hexagonal...

  19. Block Copolymer Modified Epoxy Amine System for Reactive Rotational Molding: Structures, Properties and Processability

    Science.gov (United States)

    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.

  20. Amphiphilic block copolymers for biomedical applications

    Science.gov (United States)

    Zupancich, John Andrew

    Amphiphilic block copolymer self-assembly provides a versatile means to prepare nanoscale objects in solution. Control over aggregate shape is granted through manipulation of amphiphile composition and the synthesis of well-defined polymers offers the potential to produce micelles with geometries optimized for specific applications. Currently, polymer micelles are being investigated as vehicles for the delivery of therapeutics and attempts to increase efficacy has motivated efforts to incorporate bioactive ligands and stimuli-responsive character into these structures. This thesis reports the synthesis and self-assembly of biocompatible, degradable polymeric amphiphiles. Spherical, cylindrical, and bilayered vesicle structures were generated spontaneously by the direct dispersion of poly(ethylene oxide)-b-poly(gamma-methyl-ε-caprolactone) block copolymers in water and solutions were characterized with cryogenic transmission electron microscopy (cryo-TEM). The dependence of micelle structure on diblock copolymer composition was examined through the systematic variation of the hydrophobic block molecular weight. A continuous evolution of morphology was observed with coexistence of aggregate structures occurring in windows of composition intermediate to that of pure spheres, cylinders and vesicles. A number of heterobifunctional poly(ethylene oxide) polymers were synthesized for the preparation of ligand-functionalized amphiphilic diblock copolymers. The effect of ligand conjugation on block copolymer self-assembly and micelle morphology was also examined. An RGD-containing peptide sequence was efficiently conjugated to a set of well characterized poly(ethylene oxide)-b-poly(butadiene) copolymers. The reported aggregate morphologies of peptide-functionalized polymeric amphiphiles deviated from canonical structures and the micelle clustering, cylinder fragmentation, network formation, and multilayer vesicle generation documented with cryo-TEM was attributed to

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

    Science.gov (United States)

    Tripathi, Lakshmi; Wu, Lin-Ping; Chen, Jinchun; Chen, Guo-Qiang

    2012-04-05

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

  2. Poly(ortho-phenylenediamine-co-aniline) based copolymer with improved capacitance

    Science.gov (United States)

    Olmedo-Martínez, Jorge L.; Farías-Mancilla, Bárbara I.; Vega-Rios, Alejandro; Zaragoza-Contreras, E. Armando

    2017-10-01

    A poly(ortho-phenylenediamine-co-aniline) copolymer is synthesized via the oxidative route, using a 1:1 M ratio of aniline to ortho-phenylenediamine (oPDA) and ammonium persulfate as the oxidizing agent. Infrared spectroscopy indicates that the copolymer contains the functional groups typically present in polyaniline and poly(ortho-phenylenediamine); whereas UV-vis-NIR spectroscopy shows that the copolymer adopts a phenazine-type structure. Cyclic voltammetry evidences the copolymer synthesis, as a redox peak at -65 mV, different from those exhibited by polyaniline (160 mV and 600 mV) or poly(o-phenylenediamine) (-240 mV) is observed. Finally, electrochemical impedance spectroscopy and the charge/discharge test provide support to propose the copolymer application in electrodes for supercapacitors.

  3. Synthesis of defined polyhedral oligosilsesquioxane-containing diblock and triblock methacrylate copolymers by atom transfer radical polymerization

    Czech Academy of Sciences Publication Activity Database

    Janata, Miroslav; Sikora, Antonín; Látalová, Petra; Čadová, Eva; Raus, Vladimír; Matějka, Libor; Vlček, Petr

    2013-01-01

    Roč. 128, č. 6 (2013), s. 4294-4301 ISSN 0021-8995 R&D Projects: GA ČR GAP106/12/0844; GA ČR GAP108/12/1459 Institutional support: RVO:61389013 Keywords : copolymers * nanostructured polymers * radical polymerization Subject RIV: CD - Macromolecular Chemistry Impact factor: 1.640, year: 2013

  4. Biointerfacial impedance characterization of reduced graphene oxide supported carboxyl pendant conducting copolymer based electrode

    International Nuclear Information System (INIS)

    Puri, Nidhi; Niazi, Asad; Srivastava, Avanish Kumar; Rajesh

    2014-01-01

    We report, a comprehensive physical and biointerfacial electrochemical characteristics of electrodeposited poly(pyrrole-co-pyrrolepropylic acid) (PPy-PPa) copolymer film on the reduced graphene oxide (RGO) sheets attached over a silane modified indium-tin-oxide coated glass, for biosensing applications. The highly specific cardiac myoglobin protein antibody, Ab-cMb, has been covalently immobilized on the copolymer film through its pendent carboxyl group by carbodiimide coupling reaction. The factor ‘n’ describing divergence of the system from ideal capacitor characteristics exhibits a low value (n = 0.59) in a constant phase element of the impedance. This low value of ‘n’ showing a porous rough microstructure of PPy-PPa film on RGO exhibiting a diffusive characteristic that has been replaced by dominant charge transfer characteristic (R et ) with n = 0.78 on biomolecular immobilization and subsequent immunoreaction. The bioelectrode exhibits a linear impedance response to human cardiac cMb marker in the range of 10 ng mL −1 to 1 μg mL −1 in phosphate buffer solution (PBS; pH 7.4) at a low frequency region of et sensitivity of 70.30 Ω cm 2 per decade

  5. Poly(ester amide-Poly(ethylene oxide Graft Copolymers: Towards Micellar Drug Delivery Vehicles

    Directory of Open Access Journals (Sweden)

    Gregory J. Zilinskas

    2012-01-01

    Full Text Available Micelles formed from amphiphilic copolymers are promising materials for the delivery of drug molecules, potentially leading to enhanced biological properties and efficacy. In this work, new poly(ester amide-poly(ethylene oxide (PEA-PEO graft copolymers were synthesized and their assembly into micelles in aqueous solution was investigated. It was possible to tune the sizes of the micelles by varying the PEO content of the polymers and the method of micelle preparation. Under optimized conditions, it was possible to obtain micelles with diameters less than 100 nm as measured by dynamic light scattering and transmission electron microscopy. These micelles were demonstrated to encapsulate and release a model drug, Nile Red, and were nontoxic to HeLa cells as measured by an MTT assay. Overall, the properties of these micelles suggest that they are promising new materials for drug delivery systems.

  6. Amphiphilic brushes from metallo-supramolecular block copolymers

    NARCIS (Netherlands)

    Guillet, P.; Fustin, C.A.; Wouters, D.; Höppener, S.; Schubert, U.S.; Gohy, J.M.W.

    2009-01-01

    A novel strategy to control the formation of amphiphilic brushes from metallo-supramol. block copolymers is described. The investigated copolymer consists of a polystyrene block linked to a poly(ethylene oxide) one via a charged bis-terpyridine ruthenium(ii) complex (PS-[Ru]-PEO). The initial

  7. Effect of acid on the aggregation of poly(ethylene xide)-poly(propylene oxide)-poly(ethylene oxide) block copolymers.

    Science.gov (United States)

    Yang, Bin; Guo, Chen; Chen, Shu; Ma, Junhe; Wang, Jing; Liang, Xiangfeng; Zheng, Lily; Liu, Huizhou

    2006-11-23

    The acid effect on the aggregation of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) block copolymers EO(20)PO(70)EO(20) has been investigated by transmission electron microscopy (TEM), particle size analyzer (PSA), Fourier transformed infrared, and fluorescence spectroscopy. The critical micellization temperature for Pluronic P123 in different HCl aqueous solutions increases with the increase of acid concentration. Additionally, the hydrolysis degradation of PEO blocks is observed in strong acid concentrations at higher temperatures. When the acid concentration is low, TEM and PSA show the increase of the micelle mean diameter and the decrease of the micelle polydispersity at room temperature, which demonstrate the extension of EO corona and tendency of uniform micelle size because of the charge repulsion. When under strong acid conditions, the aggregation of micelles through the protonated water bridges was observed.

  8. Immunotheranostic Polymersomes Modularly Assembled from Tetrablock and Diblock Copolymers with Oxidation-Responsive Fluorescence.

    Science.gov (United States)

    Du, Fanfan; Liu, Yu-Gang; Scott, Evan Alexander

    2017-10-01

    Intracellular delivery is a key step for many applications in medicine and for investigations into cellular function. This is particularly true for immunotherapy, which often requires controlled delivery of antigen and adjuvants to the cytoplasm of immune cells. Due to the complex responses generated by the stimulation of diverse immune cell populations, it is critical to monitor which cells are targeted during treatment. To address this issue, we have engineered an immunotheranostic polymersome delivery system that fluorescently marks immune cells following intracellular delivery. N -(3-bromopropyl)phthalimide end-capped poly(ethylene glycol)-bl-poly(propylene sulfide) (PEG-PPS-PI) was synthesized by anionic ring opening polymerization and linked with PEG-PPS-NH 2 via a perylene bisimide (PBI) bridge to form a tetrablock copolymer (PEG-PPS-PBI-PPS-PEG). Block copolymers were assembled into polymersomes by thin film hydration in phosphate buffered saline and characterized by dynamic light scattering, cryogenic electron microscopy and fluorescence spectroscopy. Polymersomes were injected subcutaneously into the backs of mice, and draining lymph nodes were extracted for flow cytometric analysis of cellular uptake and disassembly. Modular self-assembly of tetrablock / diblock copolymers in aqueous solutions induced π-π stacking of the PBI linker that both red-shifted and quenched the PBI fluorescence. Reactive oxygen species within the endosomes of phagocytic immune cell populations oxidized the PPS blocks, which disassembled the polymersomes for dequenching and shifting of the PBI fluorescence from 640 nm to 550 nm emission. Lymph node resident macrophages and dendritic cells were found to increase in 550 nm emission over the course of 3 days by flow cytometry. Immunotheranostic polymersomes present a versatile platform to probe the contributions of specific cell populations during the elicitation of controlled immune responses. Flanking PBI with two oxidation

  9. Electrochemically oxidized electronic and ionic conducting nanostructured block copolymers for lithium battery electrodes.

    Science.gov (United States)

    Patel, Shrayesh N; Javier, Anna E; Balsara, Nitash P

    2013-07-23

    Block copolymers that can simultaneously conduct electronic and ionic charges on the nanometer length scale can serve as innovative conductive binder material for solid-state battery electrodes. The purpose of this work is to study the electronic charge transport of poly(3-hexylthiophene)-b-poly(ethylene oxide) (P3HT-PEO) copolymers electrochemically oxidized with lithium bis(trifluoromethanesulfonyl) imide (LiTFSI) salt in the context of a lithium battery charge/discharge cycle. We use a solid-state three-terminal electrochemical cell that enables simultaneous conductivity measurements and control over electrochemical doping of P3HT. At low oxidation levels (ratio of moles of electrons removed to moles of 3-hexylthiophene moieties in the electrode), the electronic conductivity (σe,ox) increases from 10(-7) S/cm to 10(-4) S/cm. At high oxidation levels, σe,ox approaches 10(-2) S/cm. When P3HT-PEO is used as a conductive binder in a positive electrode with LiFePO4 active material, P3HT is electrochemically active within the voltage window of a charge/discharge cycle. The electronic conductivity of the P3HT-PEO binder is in the 10(-4) to 10(-2) S/cm range over most of the potential window of the charge/discharge cycle. This allows for efficient electronic conduction, and observed charge/discharge capacities approach the theoretical limit of LiFePO4. However, at the end of the discharge cycle, the electronic conductivity decreases sharply to 10(-7) S/cm, which means the "conductive" binder is now electronically insulating. The ability of our conductive binder to switch between electronically conducting and insulating states in the positive electrode provides an unprecedented route for automatic overdischarge protection in rechargeable batteries.

  10. Solution small-angle x-ray scattering as a screening and predictive tool in the fabrication of asymmetric block copolymer membranes

    KAUST Repository

    Dorin, Rachel Mika; Marques, Debora S.; Sai, Hiroaki; Vainio, Ulla; Phillip, William A.; Peinemann, Klaus; Nunes, Suzana Pereira; Wiesner, Ulrich B.

    2012-01-01

    Small-angle X-ray scattering (SAXS) analysis of the diblock copolymer poly(styrene-b-(4-vinyl)pyridine) in a ternary solvent system of 1,4-dioxane, tetrahydrofuran, and N,N-dimethylformamide, and the triblock terpolymer poly(isoprene-b-styrene-b-(4-vinyl)-pyridine) in a binary solvent system of 1,4-dioxane and tetrahydrofuran, reveals a concentration-dependent onset of ordered structure formation. Asymmetric membranes fabricated from casting solutions with polymer concentrations at or slightly below this ordering concentration possess selective layers with the desired nanostructure. In addition to rapidly screening possible polymer solution concentrations, solution SAXS analysis also predicts hexagonal and square pore lattices of the final membrane surface structure. These results suggest solution SAXS as a powerful tool for screening casting solution concentrations and predicting surface structure in the fabrication of asymmetric ultrafiltration membranes from self-assembled block copolymers. (Figure presented) © 2012 American Chemical Society.

  11. Solution small-angle x-ray scattering as a screening and predictive tool in the fabrication of asymmetric block copolymer membranes

    KAUST Repository

    Dorin, Rachel Mika

    2012-05-15

    Small-angle X-ray scattering (SAXS) analysis of the diblock copolymer poly(styrene-b-(4-vinyl)pyridine) in a ternary solvent system of 1,4-dioxane, tetrahydrofuran, and N,N-dimethylformamide, and the triblock terpolymer poly(isoprene-b-styrene-b-(4-vinyl)-pyridine) in a binary solvent system of 1,4-dioxane and tetrahydrofuran, reveals a concentration-dependent onset of ordered structure formation. Asymmetric membranes fabricated from casting solutions with polymer concentrations at or slightly below this ordering concentration possess selective layers with the desired nanostructure. In addition to rapidly screening possible polymer solution concentrations, solution SAXS analysis also predicts hexagonal and square pore lattices of the final membrane surface structure. These results suggest solution SAXS as a powerful tool for screening casting solution concentrations and predicting surface structure in the fabrication of asymmetric ultrafiltration membranes from self-assembled block copolymers. (Figure presented) © 2012 American Chemical Society.

  12. CTAB assisted microwave synthesis of ordered mesoporous carbon supported Pt nanoparticles for hydrogen electro-oxidation

    International Nuclear Information System (INIS)

    Zhou, Jian-Hua; He, Jian-Ping; Ji, Ya-Jun; Dang, Wang-Juan; Liu, Xiao-Lei; Zhao, Gui-Wang; Zhang, Chuan-Xiang; Zhao, Ji-Shuang; Fu, Qing-Bin; Hu, Huo-Ping

    2007-01-01

    Mesoporous carbon with ordered hexagonal structure derived from the co-assembly of triblock copolymer F127 and resol was employed as the carbon support of Pt catalysts for hydrogen electro-oxidation. Structural characterizations revealed that the mesoporous carbon exhibited large surface area and uniform mesopores. The Pt nanoparticles supported on the novel mesoporous carbon were fabricated by a facile CTAB assisted microwave synthesis process, wherein CTAB was expected to improve the wettability of carbon support as well as the dispersion of Pt nanoparticles. X-ray diffraction and transmission electron microscopy were applied to characterize the Pt catalysts. It was found that the Pt nanoparticles were uniform in size and highly dispersed on the mesoporous carbon supports. The cyclic voltammograms in sulfuric acid demonstrated that the electrochemical active surface area of Pt catalysts prepared with CTAB was two times than that without CTAB

  13. Nanostructures and surface hydrophobicity of self-assembled thermosets involving epoxy resin and poly(2,2,2-trifluoroethyl acrylate)-block-poly(ethylene oxide) amphiphilic diblock copolymer.

    Science.gov (United States)

    Yi, Fangping; Zheng, Sixun; Liu, Tianxi

    2009-02-19

    Poly(2,2,2-trifluoroethyl acrylate)-block-poly(ethylene oxide) (PTFEA-b-PEO) amphiphilic diblock copolymer was synthesized via the reversible addition-fragmentation transfer polymerization of 2,2,2-triffluroethyl acrylate with dithiobenzoyl-terminated poly(ethylene oxide) as a chain-transfer agent. The amphiphilic diblock copolymer was incorporated into epoxy resin to prepare the nanostructured epoxy thermosets. The nanostructures were investigated by means of atomic force microscopy, small-angle X-ray scattering, and dynamic mechanical analysis. In terms of the miscibility of the subchains of the block copolymer with epoxy after and before curing reaction, it is judged that the formation of the nanostructures follows the mechanism of self-assembly. The static contact angle measurements indicate that the nanostructured thermosets containing PTFEA-b-PEO diblock copolymer displayed a significant enhancement in surface hydrophobicity as well as a reduction in surface free energy. The improvement in surface properties was ascribed to the enrichment of the fluorine-containing subchain (i.e., PTFEA block) of the amphiphilic diblock copolymer on the surface of the nanostructured thermosets, which was evidenced by surface atomic force microscopy and energy-dispersive X-ray spectroscopy.

  14. Regulation of Aquaporin Z osmotic permeability in ABA tri-block copolymer

    Directory of Open Access Journals (Sweden)

    Wenyuan Xie

    2015-08-01

    Full Text Available Aquaporins are transmembrane water channel proteins present in biological plasma membranes that aid in biological water filtration processes by transporting water molecules through at high speeds, while selectively blocking out other kinds of solutes. Aquaporin Z incorporated biomimetic membranes are envisaged to overcome the problem of high pressure needed, and holds great potential for use in water purification processes, giving high flux while keeping energy consumption low. The functionality of aquaporin Z in terms of osmotic permeability might be regulated by factors such as pH, temperature, crosslinking and hydrophobic thickness of the reconstituted bilayers. Hence, we reconstituted aquaporin Z into vesicles that are made from a series of amphiphilic block copolymers PMOXA-PDMS-PMOXAs with various hydrophobic molecular weights. The osmotic permeability of aquaporin Z in these vesicles was determined through a stopped-flow spectroscopy. In addition, the temperature and pH value of the vesicle solutions were adjusted within wide ranges to investigate the regulation of osmotic permeability of aquaporin Z through external conditions. Our results show that aquaporin Z permeability was enhanced by hydrophobic mismatch. In addition, the water filtration mechanism of aquaporin Z is significantly affected by the concentration of H+ and OH- ions.

  15. Self-assembly of Polystyrene- b -poly(2-vinylpyridine)- b -poly(ethylene oxide) Triblock Terpolymers

    KAUST Repository

    Musteata, Valentina-Elena; Sutisna, Burhannudin; Polymeropoulos, Georgios; Avgeropoulos, Apostolos; Meneau, Florian; Peinemann, Klaus-Viktor; Hadjichristidis, Nikolaos; Nunes, Suzana Pereira

    2017-01-01

    Polystyrene-b-poly(2-vinylpyridine)-b-poly(ethylene oxide) (PS-b-P2VP-b-PEO) terpolymer is a versatile polymer to form isoporous films and membranes, due to the possibility of self-assembly control and the properties of the different blocks, such as the P2VP ability of complexation, and H-bond formation, and the PEO biocompatibility. Copolymers with different block ratios and sizes were synthesized. The correlation between their equilibrium bulk morphology, the self-assembly in dilute and semi-dilute solutions and the non-equilibrium porous structures of membranes, obtained by non-solvent induced phase separation, was investigated and discussed in detail. The characterization was performed by small-angle X-ray scattering (SAXS), scanning (SEM) and transmission electron microscopy (TEM). Hexagonal, cubic and lamellar arrangements were observed. The preparation conditions were optimized and a regular, isoporous morphology, suitable for membrane application, was successfully obtained with PS80.5k-b-P2VP64.4k-b-PEO16.1k.

  16. Self-assembly of Polystyrene- b -poly(2-vinylpyridine)- b -poly(ethylene oxide) Triblock Terpolymers

    KAUST Repository

    Musteata, Valentina-Elena

    2017-11-08

    Polystyrene-b-poly(2-vinylpyridine)-b-poly(ethylene oxide) (PS-b-P2VP-b-PEO) terpolymer is a versatile polymer to form isoporous films and membranes, due to the possibility of self-assembly control and the properties of the different blocks, such as the P2VP ability of complexation, and H-bond formation, and the PEO biocompatibility. Copolymers with different block ratios and sizes were synthesized. The correlation between their equilibrium bulk morphology, the self-assembly in dilute and semi-dilute solutions and the non-equilibrium porous structures of membranes, obtained by non-solvent induced phase separation, was investigated and discussed in detail. The characterization was performed by small-angle X-ray scattering (SAXS), scanning (SEM) and transmission electron microscopy (TEM). Hexagonal, cubic and lamellar arrangements were observed. The preparation conditions were optimized and a regular, isoporous morphology, suitable for membrane application, was successfully obtained with PS80.5k-b-P2VP64.4k-b-PEO16.1k.

  17. The fabrication of highly ordered block copolymer micellar arrays: control of the separation distances of silicon oxide dots

    Science.gov (United States)

    Yoo, Hana; Park, Soojin

    2010-06-01

    We demonstrate the fabrication of highly ordered silicon oxide dotted arrays prepared from polydimethylsiloxane (PDMS) filled nanoporous block copolymer (BCP) films and the preparation of nanoporous, flexible Teflon or polyimide films. Polystyrene-block-poly(2-vinylpyridine) (PS-b-P2VP) films were annealed in toluene vapor to enhance the lateral order of micellar arrays and were subsequently immersed in alcohol to produce nano-sized pores, which can be used as templates for filling a thin layer of PDMS. When a thin layer of PDMS was spin-coated onto nanoporous BCP films and thermally annealed at a certain temperature, the PDMS was drawn into the pores by capillary action. PDMS filled BCP templates were exposed to oxygen plasma environments in order to fabricate silicon oxide dotted arrays. By addition of PS homopolymer to PS-b-P2VP copolymer, the separation distances of micellar arrays were tuned. As-prepared silicon oxide dotted arrays were used as a hard master for fabricating nanoporous Teflon or polyimide films by spin-coating polymer precursor solutions onto silicon patterns and peeling off. This simple process enables us to fabricate highly ordered nanoporous BCP templates, silicon oxide dots, and flexible nanoporous polymer patterns with feature size of sub-20 nm over 5 cm × 5 cm.

  18. The fabrication of highly ordered block copolymer micellar arrays: control of the separation distances of silicon oxide dots

    Energy Technology Data Exchange (ETDEWEB)

    Yoo, Hana; Park, Soojin, E-mail: spark@unist.ac.kr [Interdisciplinary School of Green Energy, Ulsan National Institute of Science and Technology, Banyeon-ri 100, Ulsan 689-798 (Korea, Republic of)

    2010-06-18

    We demonstrate the fabrication of highly ordered silicon oxide dotted arrays prepared from polydimethylsiloxane (PDMS) filled nanoporous block copolymer (BCP) films and the preparation of nanoporous, flexible Teflon or polyimide films. Polystyrene-block-poly(2-vinylpyridine) (PS-b-P2VP) films were annealed in toluene vapor to enhance the lateral order of micellar arrays and were subsequently immersed in alcohol to produce nano-sized pores, which can be used as templates for filling a thin layer of PDMS. When a thin layer of PDMS was spin-coated onto nanoporous BCP films and thermally annealed at a certain temperature, the PDMS was drawn into the pores by capillary action. PDMS filled BCP templates were exposed to oxygen plasma environments in order to fabricate silicon oxide dotted arrays. By addition of PS homopolymer to PS-b-P2VP copolymer, the separation distances of micellar arrays were tuned. As-prepared silicon oxide dotted arrays were used as a hard master for fabricating nanoporous Teflon or polyimide films by spin-coating polymer precursor solutions onto silicon patterns and peeling off. This simple process enables us to fabricate highly ordered nanoporous BCP templates, silicon oxide dots, and flexible nanoporous polymer patterns with feature size of sub-20 nm over 5 cm x 5 cm.

  19. Triblock copolymer-mediated synthesis of catalytically active gold nanostructures

    Science.gov (United States)

    Santos, Douglas C.; de Souza, Viviane C.; Vasconcelos, Diego A.; Andrade, George R. S.; Gimenez, Iara F.; Teixeira, Zaine

    2018-04-01

    The design of nanostructures based on poly(ethylene oxide)-poly(propylene)-poly(ethylene oxide) (PEO-PPO-PEO) and metal nanoparticles is becoming an important research topic due to their multiple functionalities in different fields, including nanomedicine and catalysis. In this work, water-soluble gold nanoparticles have been prepared through a green aqueous synthesis method using Pluronic F127 as both reducing and stabilizing agents. The size dependence (varying from 2 to 70 nm) and stability of gold nanoparticles were systematically studied by varying some parameters of synthesis, which were the polymer concentration, temperature, and exposure to UV-A light, being monitored by UV-Vis spectroscopy and TEM. Also, an elaborated study regarding to the kinetic of formation (nucleation and growth) was presented. Finally, the as-prepared Pluronic-capped gold nanoparticles have shown excellent catalytic activity towards the reduction of 4-nitrophenol to 4-aminophenol with sodium borohydride, in which a higher catalytic performance was exhibited when compared with gold nanoparticles prepared by classical reduction method using sodium citrate. [Figure not available: see fulltext.

  20. Preparation of curcumin-loaded PCL-PEG-PCL triblock copolymeric nanoparticles by a microchannel technology.

    Science.gov (United States)

    Guo, Fangyuan; Guo, Dingjia; Zhang, Wei; Yan, Qinying; Yang, Yan; Hong, Weiyong; Yang, Gensheng

    2017-03-01

    Biodegradable polymeric nanoparticles (NPs) have potential therapeutic applications; however, preparing NPs of a specific diameter and uniform size distribution is a challenge. In this work, we fabricated a microchannel system for the preparation of curcumin (Cur)-loaded NPs by the interfacial precipitation method, which rapidly and consistently generated stable NPs with a relatively smaller diameter, narrow size distribution, and higher drug-loading capacity and entrapment efficiency. Poly(ε-caprolactone)-poly(ethylene glycol)-poly (ε-caprolactone) triblock copolymers(PCEC) used as the carrier material was synthesized and characterized. Cur-loaded PCEC NPs had an average size of 167.2nm with a zeta potential of -29.23mV, and showed a loading capacity and drug entrapment efficiency of 15.28%±0.23% and 96.11%±0.13%, respectively. Meanwhile, the NPs demonstrated good biocompatibility and bioavailability, efficient cellular uptake, and long circulation time and a possible liver targeting effect in vivo. These results indicate that the Cur-loaded PCEC NPs can be used as drug carriers in controlled delivery systems and other biomedical applications. Copyright © 2017 Elsevier B.V. All rights reserved.

  1. All-acrylic superelastomers: facile synthesis and exceptional mechanical behavior

    Energy Technology Data Exchange (ETDEWEB)

    Lu, Wei; Goodwin, Andrew; Wang, Yangyang; Yin, Panchao; Wang, Weiyu; Zhu, Jiahua; Wu, Ting; Lu, Xinyi; Hu, Bin; Hong, Kunlun; Kang, Nam-Goo; Mays, Jimmy (Tennessee-K); (ORNL)

    2018-01-01

    All-acrylic multigraft copolymers made by a facile synthesis procedure exhibit elongation at break >1700% and strain recovery behavior far exceeding those of commercial acrylic and styrenic triblock copolymers.

  2. Preparation of silica-sustained electrospun polyvinylpyrrolidone fibers with uniform mesopores via oxidative removal of template molecules by H2O2 treatment

    International Nuclear Information System (INIS)

    Kang, Haigang; Zhu, Yihua; Shen, Jianhua; Yang, Xiaoling; Chen, Cheng; Cao, Huimin; Li, Chungzhong

    2010-01-01

    Silica-sustained electrospun PVP fibers with uniform mesopores were synthesized via facile oxidative removal of template molecules by H 2 O 2 extraction. Tetraethyl orthosilicate, polyvinylpyrrolidone (PVP), and triblock poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) copolymer pluronic P 123 compose the electrospinning sol to fabricate the silica-sustained PVP hybrid fibers. The effect of different post-treatment methods on the pore size distribution was investigated by calcination and extraction, respectively. Experimental results showed that oxidative removal of structure-directing agent P 123 in the hybrid fibers by H 2 O 2 treatment can easily form narrow pore size distribution, and the incorporation of 3D silica skeleton built by hot steam aging facilitated preserving the original cylindrical morphology of fibers. Scanning electron microscopy (SEM), N 2 adsorption-desorption isotherm, transmission electron microscopy (TEM), X-ray diffraction (XRD), FT-IR spectra and thermogravimetric analysis (TGA) were used to characterize the hybrid fibers. The hybrid fibers can be expected to have potential applications in drug release or tissue engineering because of their suitable pore size, large surface area and good biocompatibility.

  3. Effect of Perfluoroalkyl Endgroups on the Interactions of Tri-Block Copolymers with Monofluorinated F-DPPC Monolayers

    Directory of Open Access Journals (Sweden)

    Syed W. H. Shah

    2017-10-01

    Full Text Available We studied the interaction of amphiphilic and triphilic polymers with monolayers prepared from F-DPPC (1-palmitoyl-2-(16-fluoropalmitoyl-sn-glycero-3-phosphocholine, a phospholipid with a single fluorine atom at the terminus of the sn-2 chain, an analogue of dipalmitoyl-phosphatidylcholine (DPPC. The amphiphilic block copolymers contained a hydrophobic poly(propylene oxide block flanked by hydrophilic poly(glycerol monomethacrylate blocks (GP. F-GP was derived from GP by capping both termini with perfluoro-n-nonyl segments. We first studied the adsorption of GP and F-GP to lipid monolayers of F-DPPC. F-GP was inserted into the monolayer up to a surface pressure Π of 42.4 mN m−1, much higher than GP (32.5 mN m−1. We then studied isotherms of lipid-polymer mixtures co-spread at the air-water interface. With increasing polymer content in the mixture a continuous shift of the onset of the liquid-expanded (LE to liquid-condensed (LC transition towards higher molecular and higher area per lipid molecule was observed. F-GP had a larger effect than GP indicating that it needed more space. At a Π-value of 32 mN m−1, GP was excluded from the mixed monolayer, whereas F-GP stayed in F-DPPC monolayers up to 42 mN m−1. F-GP is thus more stably anchored in the monolayer up to higher surface pressures. Images of mixed monolayers were acquired using different fluorescent probes and showed the presence of perfluorinated segments of F-GP at LE-LC domain boundaries.

  4. Unique self-assembly behavior of a triblock copolymer and fabrication of catalytically active gold nanoparticle/polymer thin films at the liquid/liquid interface

    International Nuclear Information System (INIS)

    Shang, Ke; Geng, Yuanyuan; Xu, Xingtao; Wang, Changwei; Lee, Yong-Ill; Hao, Jingcheng; Liu, Hong-Guo

    2014-01-01

    Gold nanoparticle-doped poly(2-vinylpyridine)-block-polystyrene-block-poly(2-vinylpyridine) (P2VP-b-PS-b-P2VP) thin films were prepared at the planar liquid/liquid interface between the chloroform solution of the polymer and aqueous solution of HAuCl 4 . Transmission electron microscopic (TEM) investigations revealed that foam films composed of microcapsules as well as one-dimensional belts were formed, and numerous Au nanoparticles were incorporated in the walls of the microcapsules and the nanobelts. The walls and the belts have layered structure. The formation mechanism of the foams and the belts was attributed to adsorption of the polymer molecules, combination of the polymer molecules with AuCl 4 − ions, microphase separation and self-assembly of the composite molecules at the interface. This microstructure is different apparently from those formed in solutions, in casting or spin-coating thin films and at the air/water interface of this triblock copolymer, reflecting unique self-assembly behavior at the liquid/liquid interface. This microstructure is also different from those formed by homo-P2VP and P4VP-b-PS-b-P4VP at the liquid/liquid interface, indicating the effects of molecular structures on the self-assembly behaviors of the polymers. After further treatment by UV-light irradiation and KBH 4 aqueous solution, the gold species were reduced completely, as indicated by UV–vis spectra and X-ray photoelectron spectra (XPS). Thermogravimetric analysis indicated that the composite films have high thermal stability, and the content of gold was estimated to be about 9.1%. These composite films exhibited high catalytic activity for the reduction of 4-nitrophenol by KBH 4 in aqueous solutions. - Highlights: • P2VP-b-PS-b-P2VP formed microcapsules and nanobelts at the liquid/liquid interface. • Its self-assembly behavior differs from P4VP-b-PS-b-P4VP at the interface. • This behavior also differs from those in solution, in film and at air/water interface

  5. Unique self-assembly behavior of a triblock copolymer and fabrication of catalytically active gold nanoparticle/polymer thin films at the liquid/liquid interface

    Energy Technology Data Exchange (ETDEWEB)

    Shang, Ke; Geng, Yuanyuan; Xu, Xingtao [Key Laboratory for Colloid and Interface Chemistry of Education Ministry, Shandong University, Jinan 250100 (China); Wang, Changwei [Environmental Monitoring Center of Shandong Province, Jinan 250013 (China); Lee, Yong-Ill [Anastro Laboratory, Department of Chemistry, Changwon National University, Changwon 641-773 (Korea, Republic of); Hao, Jingcheng [Key Laboratory for Colloid and Interface Chemistry of Education Ministry, Shandong University, Jinan 250100 (China); Liu, Hong-Guo, E-mail: hgliu@sdu.edu.cn [Key Laboratory for Colloid and Interface Chemistry of Education Ministry, Shandong University, Jinan 250100 (China)

    2014-07-01

    Gold nanoparticle-doped poly(2-vinylpyridine)-block-polystyrene-block-poly(2-vinylpyridine) (P2VP-b-PS-b-P2VP) thin films were prepared at the planar liquid/liquid interface between the chloroform solution of the polymer and aqueous solution of HAuCl{sub 4}. Transmission electron microscopic (TEM) investigations revealed that foam films composed of microcapsules as well as one-dimensional belts were formed, and numerous Au nanoparticles were incorporated in the walls of the microcapsules and the nanobelts. The walls and the belts have layered structure. The formation mechanism of the foams and the belts was attributed to adsorption of the polymer molecules, combination of the polymer molecules with AuCl{sub 4}{sup −} ions, microphase separation and self-assembly of the composite molecules at the interface. This microstructure is different apparently from those formed in solutions, in casting or spin-coating thin films and at the air/water interface of this triblock copolymer, reflecting unique self-assembly behavior at the liquid/liquid interface. This microstructure is also different from those formed by homo-P2VP and P4VP-b-PS-b-P4VP at the liquid/liquid interface, indicating the effects of molecular structures on the self-assembly behaviors of the polymers. After further treatment by UV-light irradiation and KBH{sub 4} aqueous solution, the gold species were reduced completely, as indicated by UV–vis spectra and X-ray photoelectron spectra (XPS). Thermogravimetric analysis indicated that the composite films have high thermal stability, and the content of gold was estimated to be about 9.1%. These composite films exhibited high catalytic activity for the reduction of 4-nitrophenol by KBH{sub 4} in aqueous solutions. - Highlights: • P2VP-b-PS-b-P2VP formed microcapsules and nanobelts at the liquid/liquid interface. • Its self-assembly behavior differs from P4VP-b-PS-b-P4VP at the interface. • This behavior also differs from those in solution, in film and

  6. Electrode-Impregnable and Cross-Linkable Poly(ethylene oxide)-Poly(propylene oxide)-Poly(ethylene oxide) Triblock Polymer Electrolytes with High Ionic Conductivity and a Large Voltage Window for Flexible Solid-State Supercapacitors.

    Science.gov (United States)

    Han, Jae Hee; Lee, Jang Yong; Suh, Dong Hack; Hong, Young Taik; Kim, Tae-Ho

    2017-10-04

    We present cross-linkable precursor-type gel polymer electrolytes (GPEs) that have large ionic liquid uptake capability, can easily penetrate electrodes, have high ion conductivity, and are mechanically strong as high-performance, flexible all-solid-state supercapacitors (SC). Our polymer precursors feature a hydrophilic-hydrophobic poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) triblock main-chain structure and trifunctional silane end groups that can be multi-cross-linked with each other through a sol-gel process. The cross-linked solid-state electrolyte film with moderate IL content (200 wt %) shows a well-balanced combination of excellent ionic conductivity (5.0 × 10 -3 S cm -1 ) and good mechanical stability (maximum strain = 194%). Moreover, our polymer electrolytes have various advantages including high thermal stability (decomposition temperature > 330 °C) and the capability to impregnate electrodes to form an excellent electrode-electrolyte interface due to the very low viscosity of the precursors. By assembling our GPE-impregnated electrodes and solid-state GPE film, we demonstrate an all-solid-state SC that can operate at 3 V and provides an improved specific capacitance (112.3 F g -1 at 0.1 A g -1 ), better rate capability (64% capacity retention until 20 A g -1 ), and excellent cycle stability (95% capacitance decay over 10 000 charge/discharge cycles) compared with those of a reference SC using a conventional PEO electrolyte. Finally, flexible SCs with a high energy density (22.6 W h kg -1 at 1 A g -1 ) and an excellent flexibility (>93% capacitance retention after 5000 bending cycles) can successfully be obtained.

  7. Block-copolymer-assisted synthesis of hydroxyapatite nanoparticles with high surface area and uniform size

    Directory of Open Access Journals (Sweden)

    Yu-Tzu Huang, Masataka Imura, Yoshihiro Nemoto, Chao-Hung Cheng and Yusuke Yamauchi

    2011-01-01

    Full Text Available We report the synthesis of hydroxyapatite nanoparticles (HANPs by the coprecipitation method using calcium D-gluconate and potassium hydrogen phosphate as the sources of calcium and phosphate ions, respectively, and the triblock copolymer F127 as a stabilizer. The HANPs were characterized using scanning electron microscopy, x-ray diffraction, and nitrogen adsorption/desorption isotherms. Removal of F127 by solvent extraction or calcination alters the structure of HANPs. The solvent-extracted HANPs were single crystals with their lang001rang axis oriented along the rod axis of the HANP, whereas the calcined HANPs contained two crystal phases that resulted in a spherical morphology. The calcined HANPs had much higher surface area (127 m2 g−1 than the solvent-extracted HANPs (44 m2 g−1.

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

    Science.gov (United States)

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

    2017-06-07

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

  9. Structure and Properties of Nanocomposites based on PTT-block-PTMO Copolymer and Graphene Oxide prepared by in Situ Polymerization

    OpenAIRE

    Paszkiewicz, Sandra; Szymczyk, Anna; Špitalský, Zdenko; Mosnáček, Jaroslav; Kwiatkowski, Konrad; Rosłaniec, Zbigniew

    2014-01-01

    Poly(trimethylene terephthalate-block-tetramethylene oxide) (PTT-PTMO) copolymer/graphene oxide nanocomposites were prepared by in situ polymerization. From the SEM and TEM images of PTT-PTMO/GO nanocomposite, it can be seen that GO sheets are clearly well-dispersed in the PTT-PTMO matrix. TEM images also showed that graphene was well exfoliated into individual sheets, suggesting that in situ polymerization is a highly efficient method for preparing nanocomposites. The influence of GO on the ...

  10. Melt-processable, radiation cross-linkable E--CTFE copolymer compositions

    International Nuclear Information System (INIS)

    Robertson, A.B.; Schaffhauser, R.J.

    1976-01-01

    Melt-processable, radiation cross-linkable ethylene/chlorotrifluoroethylene copolymer compositions are provided which contain about 0.1 to 5 percent by weight of the copolymer of a radiation cross-linking promoter, about 0.01 to 5 percent by weight of an anti-oxidant and about 0.1 to 30 precent by weight of an acid scavenger. Such compositions do not give off odors when irradiated to cross-link the copolymer and do not develop bubbles after irradiation. 15 claims, no drawings

  11. 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

    International Nuclear Information System (INIS)

    Khoee, Sepideh; Hassanzadeh, Salman; Goliaie, Bahram

    2007-01-01

    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

  12. Photocrosslinked PLA-PEO-PLA Hydrogels from Self-Assembled Physical Networks: Mechanical Properties and Influence of Assumed Constitutive Relationships

    OpenAIRE

    Sanabria-DeLong, Naomi; Crosby, Alfred J.; Tew, Gregory N.

    2008-01-01

    Poly(lactide) – block – poly(ethylene oxide) – block – poly(lactide) [PLA-PEO-PLA] triblock copolymers are known to form physical hydrogels in water, due to the polymer's amphiphilicity. Their mechanical properties, biocompatibility, and biodegradability have made them attractive for use as soft tissue scaffolds. However, the network junction points are not covalently crosslinked and in a highly aqueous environment these hydrogels adsorb more water, transform from gel to sol, and lose the des...

  13. Meso-scale Modeling of Block Copolymers Self-Assembly in Casting Solutions for Membrane Manufacture

    KAUST Repository

    Moreno Chaparro, Nicolas

    2016-05-01

    the swelling of the B-rich domains. The B-C interactions control the curvature of the assemblies in these blends. Finally, we study the self-assembly triblock copolymers used for membranes fabrication. We show that the polymer concentration, the block-copolymer composition, and the swelling of the micelle are responsible for the formation of elongated micelles in the casting solution. The formation of nanoporous membranes arises from the network-like packing of those micelles.

  14. Surfactant-Assisted Hydrothermal Synthesis of Cobalt Oxide/Nitrogen-Doped Graphene Framework for Enhanced Anodic Performance in Lithium Ion Batteries

    International Nuclear Information System (INIS)

    Xing, Xia; Liu, Ruili; Liu, Shaoqing; Xiao, Suo; Xu, Yi; Wang, Chi; Wu, Dongqing

    2016-01-01

    In this work, the composites of nitrogen-doped graphene framework and Co 3 O 4 nanoparticles with adjustable morphologies (NG/Co 3 O 4 ) were fabricated via a surfactant-assisted hydrothermal route for first time. Three different surfactants including triblock copolymer F127, cetyltrimethyl ammonium bromide and sodium dodecyl sulfate are involved in the hybrid-assembly of graphene oxide, o-phthalonitrile and cobalt acetate in water/ethanol. Among the obtained samples, the one using F127 (NG/Co 3 O 4 -F127) manifests the most homogeneous distribution of Co 3 O 4 NPs with the size of ∼ 15 nm in the macropore-walls formed by NG. As the anode material in lithium ion battery (LIB), NG/Co 3 O 4 -F127 exhibits excellent electrochemical performance, which is superior to the other composites and most of the previously reported Co 3 O 4 based anode materials in LIBs.

  15. Biodegradable copolymers carrying cell-adhesion peptide sequences.

    Science.gov (United States)

    Proks, Vladimír; Machová, Lud'ka; Popelka, Stepán; Rypácek, Frantisek

    2003-01-01

    Amphiphilic block copolymers are used to create bioactive surfaces on biodegradable polymer scaffolds for tissue engineering. Cell-selective biomaterials can be prepared using copolymers containing peptide sequences derived from extracellular-matrix proteins (ECM). Here we discuss alternative ways for preparation of amphiphilic block copolymers composed of hydrophobic polylactide (PLA) and hydrophilic poly(ethylene oxide) (PEO) blocks with cell-adhesion peptide sequences. Copolymers PLA-b-PEO were prepared by a living polymerisation of lactide in dioxane with tin(II)2-ethylhexanoate as a catalyst. The following approaches for incorporation of peptides into copolymers were elaborated. (a) First, a side-chain protected Gly-Arg-Gly-Asp-Ser-Gly (GRGDSG) peptide was prepared by solid-phase peptide synthesis (SPPS) and then coupled with delta-hydroxy-Z-amino-PEO in solution. In the second step, the PLA block was grafted to it via a controlled polymerisation of lactide initiated by the hydroxy end-groups of PEO in the side-chain-protected GRGDSG-PEO. Deprotection of the peptide yielded a GRGDSG-b-PEO-b-PLA copolymer, with the peptide attached through its C-end. (b) A protected GRGDSG peptide was built up on a polymer resin and coupled with Z-carboxy-PEO using a solid-phase approach. After cleavage of the delta-hydroxy-PEO-GRGDSG copolymer from the resin, polymerisation of lactide followed by deprotection of the peptide yielded a PLA-b-PEO-b-GRGDSG block copolymer, in which the peptide is linked through its N-terminus.

  16. Preparation of gold microparticles using halide ions in bulk block copolymer phases via photoreduction

    International Nuclear Information System (INIS)

    Cha, Sang-Ho; Kim, Ki-Hyun; Lee, Won-Ki; Lee, Jong-Chan

    2009-01-01

    Gold microparticles were prepared from the gold salt in the solid bulk phase of a poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) block copolymer via a photoreduction process in the presence of halide ions. The shapes and sizes of the gold microparticles were found to be dependent on the types and amount of halide ions as well as the types of cations used due to the combined effects of the adsorption power and oxidative dissolution ability of the additives on gold surfaces. Gold nanorods were obtained when poly(ethylene oxide) was used instead of the block copolymer. This suggests that the poly(propylene oxide) (PPO) parts in the block copolymer are essential for the formation of gold microparticles, even though the degree of the direct interaction between the PPO blocks and gold salt is not significant. - Graphical abstract: Gold microparticles were successfully prepared using halide ions as additives in the polymeric bulk phase via photoreduction with the glow lamp irradiation.

  17. Synthesis and characterization of sulfonated bromo-poly(2,6-dimethyl-1,4-phenylene oxide)-co-(2,6-diphenyl-1,4-phenylene oxide) copolymer as proton exchange membrane

    Energy Technology Data Exchange (ETDEWEB)

    Jeong, Young-Gi; Seo, Dong-Wan; Lim, Young-Don; Jin, Hyun-Mi; Islam Mollah, M.S. [Department of Applied Chemistry, Konkuk University/RIC-ReSEM Chungju, 322 Danwol-dong, Chungbuk 380-701 (Korea, Republic of); Ur, Soon-Chul [Department of Materials Science and Engineering/RIC-ReSEM, Chungju National University, Chungju, Chungbuk 380-702 (Korea, Republic of); Pyun, Sang-Yong [Department of Chemistry, Pukyong National University, Pusan 608-737 (Korea, Republic of); Kim, Whan-Gi, E-mail: wgkim@kku.ac.k [Department of Applied Chemistry, Konkuk University/RIC-ReSEM Chungju, 322 Danwol-dong, Chungbuk 380-701 (Korea, Republic of)

    2010-01-25

    Novel polymer electrolyte membranes containing the sulfonic acid groups attached on polymer backbone and side group simultaneously were synthesized. The bromo-poly(2,6-dimethyl-1,4-phenylene oxide)-co-(2,6-diphenyl-1,4-phenylene oxide) copolymer (BrcoPPO) was prepared by oxidative coupling polymerization with 2,6-dimethyl phenol, 2,6-diphenyl phenol, CuCl(I) and pyridine, and followed by bromination with bromine. Copolymer was maintained in 2,6-diphenyl phenol 10 mol% and 2,6-dimethyl phenol 90 mol%. Sulfonation of BrcoPPO (S-BrcoPPO) was carried out in a chlorobenzene solvent using chlorosulfonic acid. The polymeric membranes were cast from dimethylsulfoxide solution. The membranes were studied by nuclear magnetic resonance (NMR), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). Sorption experiments were conducted to observe the interaction of sulfonated polymers with water and methanol. S-BrcoPPO membranes exhibited proton conductivities from 2.3 x 10{sup -3} to 1.4 x 10{sup -2} S/cm, water uptake from 7.00 to 49.43%, IEC from 0.58 to 1.38 mequiv./g, methanol permeability from 1.9 x 10{sup -7} to 3.5 x 10{sup -7} cm{sup 2}/S.

  18. Pressure-induced melting of micellar crystal

    DEFF Research Database (Denmark)

    Mortensen, K.; Schwahn, D.; Janssen, S.

    1993-01-01

    that pressure improves the solvent quality of water, thus resulting in decomposition of the micelles and consequent melting of the micellar crystal. The combined pressure and temperature dependence reveals that in spite of the apparent increase of order on the 100 angstrom length scale upon increasing......Aqueous solutions of triblock copolymers of poly(ethylene oxide) and poly(propylene oxide) aggregate at elevated temperatures into micelles which for polymer concentrations greater-than-or-equal-to 20% make a hard sphere crystallization to a cubic micellar crystal. Structural studies show...... temperature (decreasing pressure) the overall entropy increases through the inverted micellar crystallization characteristic....

  19. A concise review of dynamical processes in polymorphic ...

    Indian Academy of Sciences (India)

    TECS

    ... and gel phases. (normal as well as reverse) offer identical microscopic environment. Keywords. Block copolymer; critical micelle temperature; inverse melting transition; rotational diffu- ... carried out with water-soluble triblock copolymers in recent times. ..... DMDPP in nonpolar solvents such as n-hexane, ... and polymer-.

  20. Using Cyclohexanol as a Co-Surfactant in the Synthesis of New Mesoporous Silica Particles

    Directory of Open Access Journals (Sweden)

    Mohammad Ali Semsarzadeh

    2014-02-01

    Full Text Available In the synthesis of mesoporous silica particles, the geometry, pore size, and specific surface area and pore volume of the particles can be greatly influenced by selected media and method, selection of co-solvent and co-surfactant. In this study, new SPB particles (silicone mesoporous particles, prepared by sol-gel method using block copolymers as template were synthesized in a water/n-octane system from the mixture of two copolymers based on poly(ethylene oxide-b-poly (propylene oxide-b-poly(ethylene oxide (PEO-b-PPO-b-PEO and poly(propylene oxide-b-poly (ethylene oxide-b-poly(propylene oxide (PPO-b-PEO-b-PPO triblock copolymers. Tetraethyl orthosilicate (TEOS as precursor, cyclohexanol as co-surfactant, n-octane as co-solvent and citric acid catalyst were used. The specific surface area and pore volume, pore diameter, morphology, microstructure and porosity of the SPB particles were characterized by X-ray diffraction (XRD, nitrogen adsorption-desorption (BET method and scanning electron microscopy (SEM. The obtained results revealed that, using the mixture of two block copolymers in the synthesis of SPB1,2 particles, could produce mean pore diameters around 9 nm and control the pore size distribution of silica particles from non-normal to a normal distribution. Furthermore, the effect of chair conformation of cyclohexanol as a large co-surfactant on the mixed block copolymers due to increase in the uniformity and yield of the SPB1,2 mesoporous silica particles compared to the SPB1 particles, there is approximately a two fold increase in SPB1,2 particle yield. In this regard, the effect of cyclohexanol and the second block copolymer in making the new templates and micellization process were discussed.

  1. CAVITATION PROPERTIES OF BLOCK COPOLYMER STABILIZED PHASE-SHIFT NANOEMULSIONS USED AS DRUG CARRIERS

    OpenAIRE

    RAPOPORT, NATALYA; CHRISTENSEN, DOUGLAS A.; KENNEDY, ANNE M.; NAM, KWEONHO

    2010-01-01

    Cavitation properties of block copolymer stabilized perfluoropentane nanoemulsions have been investigated. The nanoemulsions were stabilized by two biodegradable amphiphilic block copolymers differing in the structure of the hydrophobic block, poly(ethylene oxide)-co-poly(L-lactide) (PEG-PLLA) and poly(ethylene oxide)-co-polycaprolactone (PEG-PCL). Cavitation parameters were measured in liquid emulsions and gels as a function of ultrasound pressure for unfocused or focused 1-MHz ultrasound. A...

  2. Synthesis and shape control of uniform polymer microparticles by tailored adsorption of poly(ethylene oxide)-b-Poly(ε-caprolactone) copolymer

    Energy Technology Data Exchange (ETDEWEB)

    Acter, Shahinur; Cho, Jang Woo; Kim, Jeong Won; Byun, Aram; Park, Kyoung Ho; Kim, Jin Woong [Hanyang University, Ahnsan (Korea, Republic of)

    2015-05-15

    This paper introduces a straightforward and robust polymerization method for the synthesis of uniform polymer microparticles having controlled surface chemistry as well as tailored particle shapes. Uniform polystyrene (PS) microparticles are produced by dispersion polymerization, in which amphiphilic poly(ethylene oxide)-b-poly(ε-caprolactone) (PEO-b-PCL) copolymers anchor on to the growing polymer particles and stabilize them by steric repulsion. We have observed that, when PEO-b-PCL copolymers are incorporated at the proper concentration range, the total number of particles remains unchanged after the formation of primary particles, which is essential for maintaining size uniformity. Otherwise, nonuniform PS microparticles are produced mainly as a result of the coagulation or secondary formation of particles. To show the diversity of our particle synthesis technology, shape-controlled microparticles, such as dimples and Janus particles, are also produced by using temperature-mediated swelling and phase separation. Finally, we show that PEO-b-PCL copolymers play a key role in regulating the surface wettability of the seed particles, thereby facilitating the formation of anisotropic microparticles.

  3. Lithium-Assisted Copolymerization of CO 2 /Cyclohexene Oxide: A Novel and Straightforward Route to Polycarbonates and Related Block Copolymers

    KAUST Repository

    Zhang, Dongyue

    2016-03-23

    A facile route toward alternating polycarbonates by anionic copolymerization of carbon dioxide (CO2) and cyclohexene oxide (CHO), using lithium halide or alkoxide as initiators and triisobutylaluminum (TiBA) as activator, is reported. α,ω-Heterobifunctional and α,ω-dihydroxypoly(cyclohexene carbonate)s (PCHC) as well as poly(CHC-co-CHO) copolymers with different carbonate composition could also be easily synthesized by adjusting the amount of TiBA or by adding inert lithium salts. The value of this initiating system also resides in the easy access to PSt-b-PCHC (PSt: polystyrene) and PI-b-PCHC (PI: polyisoprene) block copolymers which can be derived by mere one-pot sequential addition of styrene or dienes first and then of CO2 and CHO under the same experimental conditions. © 2016 American Chemical Society.

  4. Decontamination of solid substrates using supercritical carbon dioxide - Application with trade hydro-carbonated surfactants

    International Nuclear Information System (INIS)

    Galy, J.; Fournel, B.; Sawada, K.; Lacroix-Desmazes, P.; Lagerge, S.; Persin, M.

    2007-01-01

    The phase behavior of poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) tri-block copolymers (PEO-PPO-PEO Pluronics) in liquid and supercritical carbon dioxide has been studied by cloud point measurements. It shows that such trade hydro-carbonated surfactants are fairly soluble (0.1 wt.%) in carbon dioxide in relatively mild conditions of temperature and pressure (T ≤ 65 degrees C, P ≤ 30 MPa). An empirical model based on the molecular weight of the copolymer has been proposed to predict the pressure-temperature phase diagram for a series of Pluronics (10 wt.% of ethylene oxide). Furthermore, the water/CO 2 interfacial tension has been measured to investigate the interactions between water and the polar moieties of the surfactants (PEO blocks and hydroxyl end-groups) as well as the interactions between CO 2 and the 'CO 2 -philic' moiety of the surfactants (PPO block). An interfacial saturation concentration was evidenced and it was shown to depend on the temperature at a given pressure. The cloud point curves and interfacial tension data are fully consistent with a change in the affinity of the surfactant for CO 2 versus pressure and temperature. A correlation between CO 2 -philic characteristics and surface active properties of the copolymers is given. (authors)

  5. Triblock and pentablock terpolymers by sequential base-assisted living cationic copolymerization of functionalized vinyl ethers

    KAUST Repository

    Bouchekif, Hassen; Sulhami, A. I.; AlGhamdi, Rayed D.; Gnanou, Yves; Hadjichristidis, Nikolaos

    2015-01-01

    A series of novel, well-defined triblock (PnBVE-b-PCEVE-b-PSiDEGVE) and pentablock (PSiDEGVE-b-PCEVE-b-PnBVE-b-PCEVE-b-PSiDEGVE) terpolymers of n-butyl vinyl ether (nBVE), 2-chloroethyl vinyl ether (CEVE) and tert-butyldimethylsilyl ethylene glycol vinyl ether (SiEGVE) were synthesized by sequential base-assisted living cationic polymerization. The living character of the homopolymerization of the three VE monomers and the crossover reaction resulting in the formation of well-defined block copolymers were investigated in various solvents (toluene, dichloromethane and n-hexane) using either a monofunctional [nBVE-acetic acid adduct (nBEA), CEVE-acetic acid adduct (CEEA) and SiDEGVE-acetic acid adduct (SiDEGEA)] or a difunctional [1,4-cyclohexane-1,4-diyl bis(2-methoxyethyl acetate) (cHDMEA)] initiator. All initiators are structurally equivalent to the dormant species of the corresponding monomers in order to achieve fast initiation. The optimal conditions of polymerization were achieved in n-hexane at -20 °C, in the presence of 1 M AcOEt (base). Good control over the number average molecular weight (Mn) and the polydispersity index (PDI) was obtained only at [Et3Al2Cl3]0 = [Chain-end]0 ≤ 10 mM. 2,6-Di-tert-butylpyridine (DtBP) was used as a non-nucleophilic proton trap to suppress any protonic initiation from moisture (i.e., Et3Al2Cl3·H2O). Well-defined PnBVEn-b-PCEVEp-b-PSiDEGVEq and PSiDEGVEq-b-PCEVEp-b-PnBVEn-b-PCEVEp-b-PSiDEGVEq terpolymers with a high crossover efficiency, no PCEVE-induced physical gelation, and predictable Mn and PDI < 1.15 were synthesized successfully provided that the targeted DPCEVE/DPnBVE ratio (i.e., p/n) did not exceed 2 and 0.2, respectively. The quantitative desilylation of the PSiEGVE by n-Bu4N+F- in THF at 0 °C led to triblock and pentablock terpolymers in which the PCEVE is the central block and the polyalcohol is the outer block. The thermal properties of the synthesized materials were examined by differential scanning

  6. Amphiphilic block copolymers for drug delivery.

    Science.gov (United States)

    Adams, Monica L; Lavasanifar, Afsaneh; Kwon, Glen S

    2003-07-01

    Amphiphilic block copolymers (ABCs) have been used extensively in pharmaceutical applications ranging from sustained-release technologies to gene delivery. The utility of ABCs for delivery of therapeutic agents results from their unique chemical composition, which is characterized by a hydrophilic block that is chemically tethered to a hydrophobic block. In aqueous solution, polymeric micelles are formed via the association of ABCs into nanoscopic core/shell structures at or above the critical micelle concentration. Upon micellization, the hydrophobic core regions serve as reservoirs for hydrophobic drugs, which may be loaded by chemical, physical, or electrostatic means, depending on the specific functionalities of the core-forming block and the solubilizate. Although the Pluronics, composed of poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ethylene oxide), are the most widely studied ABC system, copolymers containing poly(L-amino acid) and poly(ester) hydrophobic blocks have also shown great promise in delivery applications. Because each ABC has unique advantages with respect to drug delivery, it may be possible to choose appropriate block copolymers for specific purposes, such as prolonging circulation time, introduction of targeting moieties, and modification of the drug-release profile. ABCs have been used for numerous pharmaceutical applications including drug solubilization/stabilization, alteration of the pharmacokinetic profile of encapsulated substances, and suppression of multidrug resistance. The purpose of this minireview is to provide a concise, yet detailed, introduction to the use of ABCs and polymeric micelles as delivery agents as well as to highlight current and past work in this area. Copyright 2003 Wiley-Liss, Inc. and the American Pharmacists Association

  7. Dye-sensitized PS-b-P2VP-templated nickel oxide films for photoelectrochemical applications.

    Science.gov (United States)

    Massin, Julien; Bräutigam, Maximilian; Kaeffer, Nicolas; Queyriaux, Nicolas; Field, Martin J; Schacher, Felix H; Popp, Jürgen; Chavarot-Kerlidou, Murielle; Dietzek, Benjamin; Artero, Vincent

    2015-06-06

    Moving from homogeneous water-splitting photocatalytic systems to photoelectrochemical devices requires the preparation and evaluation of novel p-type transparent conductive photoelectrode substrates. We report here on the sensitization of polystyrene-block-poly-(2-vinylpyridine) (PS-b-P2VP) diblock copolymer-templated NiO films with an organic push-pull dye. The potential of these new templated NiO film preparations for photoelectrochemical applications is compared with NiO material templated by F108 triblock copolymers. We conclude that NiO films are promising materials for the construction of dye-sensitized photocathodes to be inserted into photoelectrochemical (PEC) cells. However, a combined effort at the interface between materials science and molecular chemistry, ideally funded within a Global Artificial Photosynthesis Project, is still needed to improve the overall performance of the photoelectrodes and progress towards economically viable PEC devices.

  8. Preparations, Properties, and Applications of Periodic Nano Arrays using Anodized Aluminum Oxide and Di-block Copolymer

    Science.gov (United States)

    Noh, Kunbae

    2011-12-01

    Self-ordered arrangements observed in various materials systems such as anodic aluminum oxide, polystyrene nanoparticles, and block copolymer are of great interest in terms of providing new opportunities in nanofabrication field where lithographic techniques are broadly used in general. Investigations on self-assembled nano arrays to understand how to obtain periodic nano arrays in an efficient yet inexpensive way, and how to realize advanced material and device systems thereof, can lead to significant impacts on science and technology for many forefront device applications. In this thesis, various aspects of periodic nano-arrays have been discussed including novel preparations, properties and applications of anodized aluminum oxide (AAO) and PS-b-P4VP (S4VP) di-block copolymer self-assembly. First, long-range ordered AAO arrays have been demonstrated. Nanoimprint lithography (NIL) process allowed a faithful pattern transfer of the imprint mold pattern onto Al thin film, and interesting self-healing and pattern tripling phenomena were observed, which could be applicable towards fabrication of the NIL master mold having highly dense pattern over large area, useful for fabrication of a large-area substrate for predictable positioning of arrayed devices. Second, S4VP diblock copolymer self-assembly and S4VP directed AAO self-assembly have been demonstrated in the Al thin film on Si substrate. Such a novel combination of two dissimilar self-assembly techniques demonstrated a potential as a versatile tool for nanopatterning formation on a Si substrate, capable of being integrated into Si process technology. As exemplary applications, vertically aligned Ni nanowires have been synthesized into an S4VP-guided AAO membrane on a Si substrate in addition to anti-dot structured [Co/Pd]n magnetic multilayer using S4VP self assembly. Third, a highly hexagonally ordered, vertically parallel aluminum oxide nanotube array was successfully fabricated via hard anodization technique

  9. Redox-Stability of Alkoxy-BDT Copolymers and their Use for Organic Bioelectronic Devices

    KAUST Repository

    Giovannitti, Alexander

    2018-02-23

    Organic semiconductors can be employed as the active layer in accumulation mode organic electrochemical transistors (OECTs), where redox stability in aqueous electrolytes is important for long-term recordings of biological events. It is observed that alkoxy-benzo[1,2-b:4,5-b′]dithiophene (BDT) copolymers can be extremely unstable when they are oxidized in aqueous solutions. The redox stability of these copolymers can be improved by molecular design of the copolymer where it is observed that the electron rich comonomer 3,3′-dimethoxy-2,2′-bithiophene (MeOT2) lowers the oxidation potential and also stabilizes positive charges through delocalization and resonance effects. For copolymers where the comonomers do not have the same ability to stabilize positive charges, irreversible redox reactions are observed with the formation of quinone structures, being detrimental to performance of the materials in OECTs. Charge distribution along the copolymer from density functional theory calculations is seen to be an important factor in the stability of the charged copolymer. As a result of the stabilizing effect of the comonomer, a highly stable OECT performance is observed with transconductances in the mS range. The analysis of the decomposition pathway also raises questions about the general stability of the alkoxy-BDT unit, which is heavily used in donor-acceptor copolymers in the field of photovoltaics.

  10. Redox-Stability of Alkoxy-BDT Copolymers and their Use for Organic Bioelectronic Devices

    KAUST Repository

    Giovannitti, Alexander; Thorley, Karl J.; Nielsen, Christian B.; Li, Jun; Donahue, Mary J.; Malliaras, George G.; Rivnay, Jonathan; McCulloch, Iain

    2018-01-01

    Organic semiconductors can be employed as the active layer in accumulation mode organic electrochemical transistors (OECTs), where redox stability in aqueous electrolytes is important for long-term recordings of biological events. It is observed that alkoxy-benzo[1,2-b:4,5-b′]dithiophene (BDT) copolymers can be extremely unstable when they are oxidized in aqueous solutions. The redox stability of these copolymers can be improved by molecular design of the copolymer where it is observed that the electron rich comonomer 3,3′-dimethoxy-2,2′-bithiophene (MeOT2) lowers the oxidation potential and also stabilizes positive charges through delocalization and resonance effects. For copolymers where the comonomers do not have the same ability to stabilize positive charges, irreversible redox reactions are observed with the formation of quinone structures, being detrimental to performance of the materials in OECTs. Charge distribution along the copolymer from density functional theory calculations is seen to be an important factor in the stability of the charged copolymer. As a result of the stabilizing effect of the comonomer, a highly stable OECT performance is observed with transconductances in the mS range. The analysis of the decomposition pathway also raises questions about the general stability of the alkoxy-BDT unit, which is heavily used in donor-acceptor copolymers in the field of photovoltaics.

  11. A concise review of dynamical processes in polymorphic ...

    Indian Academy of Sciences (India)

    TECS

    This article describes our ongoing efforts to understand dynamical processes such as rota- tional diffusion and photoisomerization in polymorphic environments of a block copolymer. ... tional surfactants, these triblock copolymers do not possess a polar head group and nonpolar tail, but at- tain amphiphilic character as a ...

  12. Synthesis, characterization, and catalytic application of ordered mesoporous carbon–niobium oxide composites

    Energy Technology Data Exchange (ETDEWEB)

    Gao, Juan-Li; Gao, Shuang; Liu, Chun-Ling; Liu, Zhao-Tie; Dong, Wen-Sheng, E-mail: wsdong@snnu.edu.cn

    2014-11-15

    Graphical abstract: The ordered mesoporous carbon–niobium oxide composites have been synthesized by a multi-component co-assembly method associated with a carbonization process. - Highlights: • Ordered mesoporous carbon–niobium oxide composites were synthesized. • The content of Nb{sub 2}O{sub 5} in the composites could be tuned from 38 to 75%. • Niobium species were highly dispersed in amorphous carbon framework walls. • The composites exhibited good catalytic performance in the dehydration of fructose. - Abstract: Ordered mesoporous carbon–niobium oxide composites have been synthesized by a multi-component co-assembly method associated with a carbonization process using phenolic resol as carbon source, niobium chloride as precursor and amphiphilic triblock copolymer Pluronic F127 as template. The resulting materials were characterized using a combination of techniques including differential scanning calorimetry–thermogravimetric analysis, N{sub 2} physical adsorption, X-ray diffraction, transmission electron microscopy, and X-ray photoelectron spectroscopy. The results show that with increasing the content of Nb{sub 2}O{sub 5} from 38 to 75% the specific surface area decreases from 306.4 to 124.5 m{sup 2} g{sup −1}, while the ordered mesoporous structure is remained. Niobium species is well dispersed in the amorphous carbon framework. The mesoporous carbon–niobium oxide composites exhibit high catalytic activity in the dehydration of fructose to 5-hydroxymethylfurfural. A 100% conversion of fructose and a 76.5% selectivity of 5-hydroxymethylfurfural were obtained over the carbon–niobium oxide composite containing 75% Nb{sub 2}O{sub 5} under the investigated reaction conditions.

  13. Morphology and electrical properties of electrochemically synthesized pyrrole–formyl pyrrole copolymer

    Energy Technology Data Exchange (ETDEWEB)

    Gholami, Mehrdad, E-mail: mehrdad897@um.edu.my [Department of Chemistry, University of Malaya, Kuala Lumpur 50603 (Malaysia); Department of Chemistry, Marvdasht Branch, Islamic Azad University, P.O. Box 465, Marvdasht (Iran, Islamic Republic of); Nia, Pooria Moozarm, E-mail: pooriamn@yahoo.com [Department of Chemistry, University of Malaya, Kuala Lumpur 50603 (Malaysia); Alias, Yatimah, E-mail: yatimah70@um.edu.my [Department of Chemistry, University of Malaya, Kuala Lumpur 50603 (Malaysia)

    2015-12-01

    Graphical abstract: - Highlights: • The (Py–co-FPy) copolymer was synthesized electrochemically. • This copolymer has 1.6 times higher surface coverage compared to polypyrrole. • This copolymer showed 2.5 times lower resistance compared to polypyrrole. • The conjugated structure between Py and FPy causes enhancement of conductivity. • This conducting copolymer has a strong potential to be used in various applications. - Abstract: A direct electrochemical copolymerization of pyrrole–formyl pyrrole (Py–co-FPy) was carried out by oxidative copolymerization of formyl pyrrole and pyrrole in LiClO{sub 4} aqueous solution through galvanostatic method. The (Py–co-FPy) copolymer was characterized using Fourier-transform infrared spectroscopy (FT-IR), field emission scanning electron microscope (FESEM), energy-filtering transmission electron microscope (EFTEM), thermal gravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS), cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The FESEM images showed that the synthesized copolymer had a hollow whelk-like helixes structure, which justifies the enhancement of charge transportation through the copolymer film. Cyclic voltammetry studies revealed that the electrocatalytic activity of synthesized copolymer has improved and the surface coverage in copolymer enhanced 1.6 times compared to polypyrrole alone. Besides, (Py–co-FPy) copolymer showed 2.5 times lower electrochemical charge transfer resistance (R{sub ct}) value in impedance spectroscopy. Therefore, this copolymer has a strong potential to be used in several applications such as sensor applications.

  14. Well-Defined Cyclic Triblock Terpolymers: A Missing Piece of the Morphology Puzzle

    KAUST Repository

    Polymeropoulos, George; Bilalis, Panayiotis; Hadjichristidis, Nikolaos

    2016-01-01

    Two well-defined cyclic triblock terpolymers, missing pieces of the terpolymer morphology puzzle, consisting of poly(isoprene), polystyrene, and poly(2-vinylpyridine), were synthesized by combining the Glaser coupling reaction with anionic

  15. Self-oscillating AB diblock copolymer developed by post modification strategy

    Energy Technology Data Exchange (ETDEWEB)

    Ueki, Takeshi, E-mail: ueki@cross.t.u-tokyo.ac.jp, E-mail: ryo@cross.t.u-tokyo.ac.jp; Onoda, Michika; Tamate, Ryota; Yoshida, Ryo, E-mail: ueki@cross.t.u-tokyo.ac.jp, E-mail: ryo@cross.t.u-tokyo.ac.jp [Department of Materials Engineering, School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656 (Japan); Shibayama, Mitsuhiro [Institute for Solid State Physics, The University of Tokyo, 5-1-5 Kashiwano-ha, Kashiwa, Chiba 277-8581 (Japan)

    2015-06-15

    We prepared AB diblock copolymer composed of hydrophilic poly(ethylene oxide) segment and self-oscillating polymer segment. In the latter segment, ruthenium tris(2,2′-bipyridine) (Ru(bpy){sub 3}), a catalyst of the Belousov-Zhabotinsky reaction, is introduced into the polymer architecture based on N-isopropylacrylamide (NIPAAm). The Ru(bpy){sub 3} was introduced into the polymer segment by two methods; (i) direct random copolymerization (DP) of NIPAAm and Ru(bpy){sub 3} vinyl monomer and (ii) post modification (PM) of Ru(bpy){sub 3} with random copolymer of NIPAAm and N-3-aminopropylmethacrylamide. For both the diblock copolymers, a bistable temperature region (the temperature range; ΔT{sub m}), where the block copolymer self-assembles into micelle at reduced Ru(bpy){sub 3}{sup 2+} state whereas it breaks-up into individual polymer chain at oxidized Ru(bpy){sub 3}{sup 3+} state, monotonically extends as the composition of the Ru(bpy){sub 3} increases. The ΔT{sub m} of the block copolymer prepared by PM is larger than that by DP. The difference in ΔT{sub m} is rationalized from the statistical analysis of the arrangement of the Ru(bpy){sub 3} moiety along the self-oscillating segments. By using the PM method, the well-defined AB diblock copolymer having ΔT{sub m} (ca. 25 °C) large enough to cause stable self-oscillation can be prepared. The periodic structural transition of the diblock copolymer in a dilute solution ([Polymer] = 0.1 wt. %) is closely investigated in terms of the time-resolved dynamic light scattering technique at constant temperature in the bistable region. A macroscopic viscosity oscillation of a concentrated polymer solution (15 wt. %) coupled with the periodic microphase separation is also demonstrated.

  16. Effects of ethylene oxide sterilization on 82: 18 PLLA/PGA copolymer craniofacial fixation plates.

    Science.gov (United States)

    Pietrzak, William S

    2010-01-01

    Bioabsorbable devices are generally susceptible to some form of degradation or alteration of material properties in response to exposure to the terminal sterilization cycle. In addition to affecting the material strength, sterilization can also increase the rate of hydrolysis, both of which can impact clinical performance. The impact of sterilization on the material/device is unpredictable and must be empirically determined. This study examined the effects of ethylene oxide treatment on the material properties of LactoSorb 82:18 poly(L-lactic acid)-poly(glycolic acid) craniofacial plates. Compared with untreated control plates, there was no effect on the initial inherent viscosity (1.3 dL/g), the glass transition temperature (58 degrees C), or on the flexural mechanical properties. Furthermore, there was no effect on the in vitro rate of hydrolysis and mechanical strength loss profile. This provides evidence that the ethylene oxide sterilization cycle is compatible with these copolymer plates and that such treatment should not affect the clinical performance.

  17. Curcumin/poly(2-methyl-2-oxazoline-b-tetrahydrofuran-b-2-methyl-2-oxazoline) formulation: An improved penetration and biological effect of curcumin in F508del-CFTR cell lines.

    Science.gov (United States)

    Gonçalves, Cristine; Gomez, Jean-Pierre; Même, William; Rasolonjatovo, Bazoly; Gosset, David; Nedellec, Steven; Hulin, Philippe; Huin, Cécile; Le Gall, Tony; Montier, Tristan; Lehn, Pierre; Pichon, Chantal; Guégan, Philippe; Cheradame, Hervé; Midoux, Patrick

    2017-08-01

    Neutral amphiphilic triblock ABA copolymers are of great interest to solubilize hydrophobic drugs. We reported that a triblock ABA copolymer consisting of methyl-2-oxazoline (MeOx) and tetrahydrofuran (THF) (MeOx 6 -THF 19 -MeOx 6 ) (TBCP2) can solubilize curcumin (Cur) a very hydrophobic molecule exhibiting multiple therapeutic effects but whose insolubility and low stability in water is a major drawback for clinical applications. Here, we provide evidences by flow cytometry and confocal microscopy that Cur penetration in normal and ΔF508-CFTR human airway epithelial cell lines is facilitated by TBCP2. When used on ΔF508-CFTR cell lines, the Cur/TBCP2 formulation promotes the restoration of the expression of the CFTR protein in the plasma membrane. Furthermore, patch-clamp and MQAE fluorescence experiments show that this effect is associated with a correction of a Cl - selective current at the membrane surface of F508del-CFTR cells. The results show the great potential of the neutral amphiphilic triblock copolymer MeOx 6 -THF 19 -MeOx 6 as carrier for curcumin in a Cystic Fibrosis context. We anticipate that other MeOx n -THF m -MeOx n copolymers could have similar behaviours for other highly insoluble therapeutic drugs or cosmetic active ingredients. Copyright © 2017 Elsevier B.V. All rights reserved.

  18. Study of the role of β-adrenoceptors in the mechanisms of hemodynamic action and radioprotective activity of 2-methyl-5-vinylpyridine copolymer with 2-methyl-5-vinylpyridinium-N-oxide

    International Nuclear Information System (INIS)

    Korovkina, Eh.P.; Mikhajlov, P.P.; Tsorin, I.B.

    2000-01-01

    The effect of the new water soluble copolymer 2-methyl-5-vinylpyridine with 2-methyl-5-vinylpyridinium-N-oxide on the arterial pressure in dogs and cats is studied; the possibility of modifying the polymer hemodynamical activity under the impact of the β-propranolol blocking is investigated; the effect of the latter one on the copolymer in dogs is evaluated. The therapeutic antiradiation efficiency of the copolymer was judged by the irradiated dogs survival during 45 days. The dogs were subjected to the 137 Cs γ-radiation impact with the dose rate of 153 cGy in the 330 cGy. It is shown that the copolymer causes depression reaction in the anesthetized dogs and cats characteristic for the β-adrenomimetics This effect is leveled by the nonselective β-adrenoblocking - propranolol. The preliminary introduction of propranolol in dogs decreased the therapeutic antiradiation-efficiency of the given copolymer from 68.4 up to 8.3 % [ru

  19. Characterization of Lithium Polysulfide Salts in Homopolymers and Block Copolymers

    Science.gov (United States)

    Wang, Dunyang; Wujcik, Kevin; Balsara, Nitash

    Ion-conducting polymers are important for solid-state batteries due to the promise of better safety and the potential to produce higher energy density batteries. Nanostructured block copolymer electrolytes can provide high ionic conductivity and mechanical strength through microphase separation. One of the potential use of block copolymer electrolytes is in lithium-sulfur batteries, a system that has high theoretical energy density wherein the reduction of sulfur leads to the formation of lithium polysulfide intermediates. In this study we investigate the effect of block copolymer morphology on the speciation and transport properties of the polysulfides. The morphology and conductivities of polystyrene-b-poly(ethylene oxide) (SEO) containing lithium polysulfides were studies using small-angle X-ray scattering and ac impedance spectroscopy. UV-vis spectroscopy is being used to determine nature of the polysulfide species in poly(ethylene oxide) and SEO. Department of Energy, Soft Matter Electron Microscopy Program and Battery Materials Research Program.

  20. Thermal and radiochemical degradation of some PAN copolymers

    Energy Technology Data Exchange (ETDEWEB)

    Jipa, S. [INCDIE, ICPE CA, 313 Splaiul Unirii, P.O. Box 149, Bucharest 030138 (Romania); ' Valachia' University of Targoviste, 18-22 Unirii Av., Targoviste 130082 (Romania); Zaharescu, T. [' Valachia' University of Targoviste, 18-22 Unirii Av., Targoviste 130082 (Romania)], E-mail: traian_zaharescu@yahoo.com; Setnescu, R. [INCDIE, ICPE CA, 313 Splaiul Unirii, P.O. Box 149, Bucharest 030138 (Romania); ' Valachia' University of Targoviste, 18-22 Unirii Av., Targoviste 130082 (Romania); Dragan, E.S.; Dinu, M.V. [' Petru Poni' Institute of Macromolecular Chemistry, Iasi 700487 (Romania)

    2008-12-01

    Polyacrylonitrile (PAN) and some copolymers of acrylonitrile with divinylbenzene (AN-DVB) were investigated by the characterization of their thermal and radiation stabilities. The contribution of DVB to the thermal stability of PAN by the modification in the amount of unsaturated hydrocarbon between 6 and 20% was revealed by the evaluation of oxidation induction periods and required activation energies. The exposure of these materials to the action of {gamma}-radiation points out the higher stability of copolymers (AN-DVB) in comparison to the relative stability of PAN.

  1. Hydrophilic nanoporous polystyrenes and 1,2-polybutadienes

    DEFF Research Database (Denmark)

    Guo, Fengxiao; Jankova Atanasova, Katja; Vigild, Martin Etchells

    2008-01-01

    Nanoporous polymers from ordered block copolymers having hydrophilic cavity surfaces were successfully prepared by two methodologies: ' 1. Nanoporous polystyrenes fromPtBA-b-PS diblock or PDMS-b-PtBA-b-PS triblock copolymer precursors by atom transfer radical polymerization (ATRP), or combination...... of living anionic polymerization~ and ATRP r~spectively. The one, PtBA block, can be modified to the hydrophilic PAA, where the dther, polydimethysiloxane (PDMS) block, can be fully degraded. Deprotection of the tert-butyl groups in PtBA and the selective etching of PDMS· chains were accomplished...... by applying HF or TFA in one step. Thus both the di- and triblock copolymers after such a treatment resulted. in nanoporous polystyrenes with hexagonal cavities of different nanosizes (6-11 nm, Figure 1). 2. Nanoporous I,2-polybutadienes (I,2-PB) by grafting various acrylic monomers onto the pore. surfaces...

  2. Multifunctional triblock co-polymer mP3/4HB-b-PEG-b-lPEI for efficient intracellular siRNA delivery and gene silencing.

    Science.gov (United States)

    Zhou, Li; Chen, Zhifei; Wang, Feifei; Yang, Xiuqun; Zhang, Biliang

    2013-04-01

    A non-viral siRNA carrier composed of mono-methoxy-poly (3-hydroxybutyrate-co-4-hydroxybutyrate)-block-polyethylene glycol-block-linear polyethyleneimine (mP3/4HB-b-PEG-b-lPEI) was synthesized using 1800 Da linear polyethyleneimine and evaluated for siRNA delivery. Our study demonstrated that siRNA could be efficiently combined with mP3/4HB-b-PEG-b-lPEI (mAG) co-polymer and was protected from nuclease degradation. The combined siRNA were released from the complexes easily under heparin competition. The particle size of the mAG/siRNA complexes was 158 nm, with a ζ-potential of around 28 mV. Atomic force microscopy images displayed spherical and homogeneously distributed complexes. The mAG block co-polymer displayed low cytotoxicity and efficient cellular uptake of Cy3-siRNA in A549 cells by flow cytometry and confocal microscopy. In vitro transfection efficiency of the block co-polymer was assessed using siRNA against luciferase in cultured A549-Luc, HeLa-Luc, HLF-Luc, A375-Luc and MCF-7-Luc cells. A higher transfection efficiency and lower cytotoxicity was obtained by mAG block co-polymer in five cell lines. Furthermore, a remarkable improvement in luciferase gene silencing efficiency of the mAG complex (up to 90-95%) over that of Lipofectamine™ 2000 (70-82%) was observed in HLF-Luc and A375-Luc cells. Additionally, a mAG/p65-siRNA complex also showed a better capability than Lipofectamine™ 2000/p65-siRNA complex to drastically reduce the p65 mRNA level down to 10-16% in HeLa, U251 and HUVEC cells at an N/P ratio of 70. Crown Copyright © 2013. Published by Elsevier Ltd. All rights reserved.

  3. Design of block copolymer membranes using segregation strength trend lines

    KAUST Repository

    Sutisna, Burhannudin

    2016-05-18

    Block copolymer self-assembly and non-solvent induced phase separation are now being combined to fabricate membranes with narrow pore size distribution and high porosity. The method has the potential to be used with a broad range of tailor-made block copolymers to control functionality and selectivity for specific separations. However, the extension of this process to any new copolymer is challenging and time consuming, due to the complex interplay of influencing parameters, such as solvent composition, polymer molecular weights, casting solution concentration, and evaporation time. We propose here an effective method for designing new block copolymer membranes. The method consists of predetermining a trend line for the preparation of isoporous membranes, obtained by computing solvent properties, interactions and copolymer block sizes for a set of successful systems and using it as a guide to select the preparation conditions for new membranes. We applied the method to membranes based on poly(styrene-b-ethylene oxide) diblocks and extended it to newly synthesized poly(styrene-b-2-vinyl pyridine-b-ethylene oxide) (PS-b-P2VP-b-PEO) terpolymers. The trend line method can be generally applied to other new systems and is expected to dramatically shorten the path of isoporous membrane manufacture. The PS-b-P2VP-b-PEO membrane formation was investigated by in situ Grazing Incident Small Angle X-ray Scattering (GISAXS), which revealed a hexagonal micelle order with domain spacing clearly correlated to the membrane interpore distances.

  4. Single-molecule tracking studies of flow-induced microdomain alignment in cylinder-forming polystyrene-poly(ethylene oxide) diblock copolymer films.

    Science.gov (United States)

    Tran-Ba, Khanh-Hoa; Higgins, Daniel A; Ito, Takashi

    2014-09-25

    Flow-based approaches are promising routes to preparation of aligned block copolymer microdomains within confined spaces. An in-depth characterization of such nanoscale morphologies within macroscopically nonuniform materials under ambient conditions is, however, often challenging. In this study, single-molecule tracking (SMT) methods were employed to probe the flow-induced alignment of cylindrical microdomains (ca. 22 nm in diameter) in polystyrene-poly(ethylene oxide) diblock copolymer (PS-b-PEO) films. Films of micrometer-scale thicknesses were prepared by overlaying a benzene solution droplet on a glass coverslip with a rectangular glass plate, followed by solvent evaporation under a nitrogen atmosphere. The microdomain alignment was quantitatively assessed from SMT data exhibiting the diffusional motions of individual sulforhodamine B fluorescent probes that preferentially partitioned into cylindrical PEO microdomains. Better overall microdomain orientation along the flow direction was observed near the substrate interface in films prepared at a higher flow rate, suggesting that the microdomain alignment was primarily induced by shear flow. The SMT data also revealed the presence of micrometer-scale grains consisting of highly ordered microdomains with coherent orientation. The results of this study provide insights into shear-based preparation of aligned cylindrical microdomains in block copolymer films from solutions within confined spaces.

  5. High-concentration graphene dispersion stabilized by block copolymers in ethanol.

    Science.gov (United States)

    Perumal, Suguna; Lee, Hyang Moo; Cheong, In Woo

    2017-07-01

    This article describes a comprehensive study for the preparation of graphene dispersions by liquid-phase exfoliation using amphiphilic diblock copolymers; poly(ethylene oxide)-block-poly(styrene) (PEO-b-PS), poly(ethylene oxide)-block-poly(4-vinylpyridine) (PEO-b-PVP), and poly(ethylene oxide)-block-poly(pyrenemethyl methacrylate) (PEO-b-PPy) with similar block lengths. Block copolymers were prepared from PEO using the Steglich coupling reaction followed by reversible addition-fragmentation chain transfer (RAFT) polymerization. Graphite platelets (G) and reduced graphene oxide (rGO) were used as graphene sources. The dispersion stability of graphene in ethanol was comparatively investigated by on-line turbidity, and the graphene concentration in the dispersions was determined gravimetrically. Our results revealed that the graphene dispersions with PEO-b-PVP were much more stable and included graphene with fewer defects than that with PEO-b-PS or PEO-b-PPy, as confirmed by turbidity and Raman analyses. Gravimetry confirmed that graphene concentrations up to 1.7 and 1.8mg/mL could be obtained from G and rGO dispersions, respectively, using PEO-b-PVP after one week. Distinctions in adhesion forces of PS, VP, PPy block units with graphene surface and the variation in solubility of the block copolymers in ethanol medium significantly affected the stability of the graphene dispersion. Copyright © 2017 Elsevier Inc. All rights reserved.

  6. Thin Films of Novel Linear-Dendritic Diblock Copolymers

    Science.gov (United States)

    Iyer, Jyotsna; Hammond, Paula

    1998-03-01

    A series of diblock copolymers with one linear block and one dendrimeric block have been synthesized with the objective of forming ultrathin film nanoporous membranes. Polyethyleneoxide serves as the linear hydrophilic portion of the diblock copolymer. The hyperbranched dendrimeric block consists of polyamidoamine with functional end groups. Thin films of these materials made by spin casting and the Langmuir-Blodgett techniques are being studied. The effect of the polyethylene oxide block size and the number and chemical nature of the dendrimer end group on the nature and stability of the films formed willbe discussed.

  7. S-containing copolymer as cathode material in poly(ethylene oxide)-based all-solid-state Li-S batteries

    Science.gov (United States)

    Gracia, Ismael; Ben Youcef, Hicham; Judez, Xabier; Oteo, Uxue; Zhang, Heng; Li, Chunmei; Rodriguez-Martinez, Lide M.; Armand, Michel

    2018-06-01

    Inverse vulcanization copolymers (p(S-DVB)) from the radical polymerization of elemental sulfur and divinylbenzene (DVB) have been studied as cathode active materials in poly(ethylene oxide) (PEO)-based all-solid-state Li-S cells. The Li-S cell comprising the optimized p(S-DVB) cathode (80:20 w/w S/DVB ratio) and lithium bis(fluorosulfonyl)imide/PEO (LiFSI/PEO) electrolyte shows high specific capacity (ca. 800 mAh g-1) and high Coulombic efficiency for 50 cycles. Most importantly, polysulfide (PS) shuttle is highly mitigated due to the strong interactions of PS species with polymer backbone in p(S-DVB). This is demonstrated by the stable cycling of the p(S-DVB)-based cell using lithium bis(trifluoromethanesulfonyl)imide (LiTFSI)/PEO electrolyte, where successful charging cannot be achieved even at the first cycle with plain elemental S-based cathode material due to the severe PS shuttle phenomenon. These results suggest that inverse vulcanization copolymers are promising alternatives to elemental sulfur for enhancing the electrochemical performance of PEO-based all-solid-state Li-S cells.

  8. Self-assembling triblock proteins for biofunctional surface modification

    Science.gov (United States)

    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. Highly CO2-Selective Gas Separation Membranes Based on Segmented Copolymers of Poly(Ethylene oxide) Reinforced with Pentiptycene-Containing Polyimide Hard Segments.

    Science.gov (United States)

    Luo, Shuangjiang; Stevens, Kevin A; Park, Jae Sung; Moon, Joshua D; Liu, Qiang; Freeman, Benny D; Guo, Ruilan

    2016-01-27

    Poly(ethylene oxide) (PEO)-containing polymer membranes are attractive for CO2-related gas separations due to their high selectivity toward CO2. However, the development of PEO-rich membranes is frequently challenged by weak mechanical properties and a high crystallization tendency of PEO that hinders gas transport. Here we report a new series of highly CO2-selective, amorphous PEO-containing segmented copolymers prepared from commercial Jeffamine polyetheramines and pentiptycene-based polyimide. The copolymers are much more mechanically robust than the nonpentiptycene containing counterparts due to the molecular reinforcement mechanism of supramolecular chain threading and interlocking interactions induced by the pentiptycene structures, which also effectively suppresses PEO crystallization leading to a completely amorphous structure even at 60% PEO weight content. Membrane transport properties are sensitively affected by both PEO weight content and PEO chain length. A nonlinear correlation between CO2 permeability with PEO weight content was observed due to the competition between solubility and diffusivity contributions, whereby the copolymers change from being size-selective to solubility-selective when PEO content reaches 40%. CO2 selectivities over H2 and N2 increase monotonically with both PEO content and chain length, indicating strong CO2-philicity of the copolymers. The copolymer film with the longest PEO sequence (PEO2000) and highest PEO weight content (60%) showed a measured CO2 pure gas permeability of 39 Barrer, and ideal CO2/H2 and CO2/N2 selectivities of 4.1 and 46, respectively, at 35 °C and 3 atm, making them attractive for hydrogen purification and carbon capture.

  10. Influence of chemical crosslinks on the elastic behavior of segmented block copolymers

    NARCIS (Netherlands)

    van der Schuur, J.M.; Gaymans, R.J.

    2005-01-01

    Polyether(ester–amide)s (PEEA) segmented block copolymers with di- and tri-functional poly(propylene oxide)s and amide segments were synthesized and the elastic properties studied. The difunctional polyether used had a molecular weight of 2300 g/mol end capped with 20 wt% ethylene oxide. The

  11. Anionic polymerization of acrylates. Synthesis of (meth)acrylate di- and triblock copolymers using the Li ester-enolate/tert-alkoxide initiating system

    Czech Academy of Sciences Publication Activity Database

    Vlček, Petr; Otoupalová, Jaroslava; Janata, Miroslav; Látalová, Petra; Kurková, Dana; Toman, Luděk; Masař, Bohumil

    2004-01-01

    Roč. 37, č. 2 (2004), s. 344-351 ISSN 0024-9297 R&D Projects: GA ČR GA203/01/0513; GA AV ČR KSK4050111 Institutional research plan: CEZ:AV0Z4050913 Keywords : ligated anionic polymerization * block copolymers Subject RIV: CD - Macromolecular Chemistry Impact factor: 3.898, year: 2004

  12. Preparation and Properties of Triethoxyvinylsilane-Modified Styrene - Butyl Acrylate Emulsion Copolymers

    OpenAIRE

    NAGHASH, Hamid Javaherian; KARIMZADEH, Akram; MOMENI, Ahmad Reza; MASSAH, Ahmad Reza; ALIAN, Hamid

    2014-01-01

    The copolymers of triethoxyvinylsilane (TEVS) with styrene (St), butyl acrylate (BA), and methacrylic acid (MAA) were prepared by emulsion polymerization. The copolymerization was carried out by using auxiliary agents at 90 °C in the presence of potassium peroxodisulfate (KPS) as the initiator. Nonylphenol ethylene oxide -- 40 units (NP-40) and sodium lauryl sulfoacetate (SLSA) were used as nonionic and anionic emulsifiers, respectively. The resulting copolymers were characterized b...

  13. Controlled Synthesis of AB2 amphiphilic triarm star-shaped block copolymers by ring-opening polymerization

    OpenAIRE

    Petrova, Svetla; Riva, Raphaël; Jérôme, Christine; Lecomte, Philippe; Mateva, Rosa

    2009-01-01

    This paper describes the synthesis of a novel amphiphilic AB2 triarm star-shaped copolymer with A = non-toxic and biocompatible hydrophilic poly(ethylene oxide) (PEO) and B = biodegradable and hydrophobic poly(ε-caprolactone) (PCL). A series of AB2 triarm star-shaped copolymers with different molecular weights for the PCL block were successfully synthesized by a three-step procedure. α-methoxy-ω-epoxy-poly(ethylene oxide) (PEO-epoxide) was first synthesized by the nucleophilic substitution of...

  14. Preparation of Pt-mesoporous tungsten carbide/carbon composites via a soft-template method for electrochemical methanol oxidation

    International Nuclear Information System (INIS)

    Ma, Chun’an; Kang, Lingzhi; Shi, Meiqin; Lang, Xiaoling; Jiang, Yekun

    2014-01-01

    Highlights: • Mesoporous composite Pt-m(WC/C) is prepared by a soft template method. • The structure of phenolic gives a space limitation effect on the growth of WC. • Analysis of the effect of F127 on controlling the structure of composites. • Pt-m(WC/C) exhibits more than three times higher than Pt/C in catalytic activity. -- Abstract: This paper introduces a simple and reproducible chemical process for synthesis of Pt-mesoporous tungsten carbide/carbon composites composites Pt-m(WC/C) by means of a soft-template method. In this process, low-molecular-weight phenolic resol acted as the precursor both for carbon support and also the carbon resource of tungsten carbide. Tungsten hexachloride was used as a tungsten precursor along with different amount of triblock copolymer Pluronic F127 as pore-forming component. The best performance of Pt-m(WC/C) towards methanol oxidation is found when the mass ratios of WCl 6 :F127 is 1:0.6. The composite presents an improved methanol oxidation performance evidenced by a negative shift in onset potential, and increase of peak current density, compared with commercial Pt/C. The difference is explained by the adding of appropriate amount of F127 which facilitates the construction of mesoporous matrix structure of WC/C

  15. Encapsulation and release by star-shaped block copolymers as unimolecular nanocontainers

    NARCIS (Netherlands)

    Kul, D.; Renterghem, van L.M.; Meier, M.A.R.; Strandman, S.; Tenhu, H.; Yilmaz, S.S.; Schubert, U.S.; Du Prez, F.E.

    2008-01-01

    Five-arm star-shaped poly(ethylene oxide) (PEO) with terminal bromide groups was used as a macroinitiator for the atom transfer radical polymerization of tert-butyl acrylate (tBA), resulting in five-arm star-shaped poly(ethylene oxide)-block-poly(tert-butyl acrylate) block copolymers. The

  16. Electrosyntheses and characterizations of a new soluble conducting copolymer of 5-cyanoindole and 3,4-ethylenedioxythiophene

    International Nuclear Information System (INIS)

    Nie Guangming; Qu Liangyan; Xu Jingkun; Zhang Shusheng

    2008-01-01

    The copolymerization of 5-cyanoindole (CNIn) and 3,4-ethylenedioxythiophene (EDOT) was successfully performed electrochemically in acetonitrile containing tetrabutylammonium tetrafluoroborate by direct oxidation of monomer mixtures. The electrochemical properties of the copolymers were studied by cyclic voltammetry. The influence of applied polymerization potential on the synthesis of copolymer was investigated. This novel copolymer owns the advantages of poly(5-cyanoindole) (PCNIn) and poly(3,4-ethylenedioxythiophene) (PEDOT), i.e., good redox activity, good thermal stability and high conductivity. The copolymer was soluble in dimethyl sulfoxide. The fluorescence spectra indicate that the copolymer is a good blue-light emitter. The structure and morphology of the copolymers were investigated by UV-vis, infrared spectroscopy, 1 H NMR spectra and scanning electron microscopy (SEM), respectively

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

    NARCIS (Netherlands)

    Petit, Audrey|info:eu-repo/dai/nl/371748461; Redout, Everaldo M; van de Lest, Chris H|info:eu-repo/dai/nl/146063570; de Grauw, Janny C|info:eu-repo/dai/nl/304822469; Müller, Benno; Meyboom, Ronald; van Midwoud, Paul; Vermonden, Tina|info:eu-repo/dai/nl/275124517; Hennink, Wim E|info:eu-repo/dai/nl/070880409; van Weeren, René|info:eu-repo/dai/nl/074628550

    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

  18. Well-Defined Cyclic Triblock Terpolymers: A Missing Piece of the Morphology Puzzle

    KAUST Repository

    Polymeropoulos, George

    2016-10-27

    Two well-defined cyclic triblock terpolymers, missing pieces of the terpolymer morphology puzzle, consisting of poly(isoprene), polystyrene, and poly(2-vinylpyridine), were synthesized by combining the Glaser coupling reaction with anionic polymerization. An α,ω-dihydroxy linear triblock terpolymer (OH-PI1,4-b-PS-b-P2VP-OH) was first synthesized followed by transformation of the OH to alkyne groups by esterification with pentynoic acid and cyclization by Glaser coupling. The size exclusion chromatography (SEC) trace of the linear terpolymer precursor was shifted to lower elution time after cyclization, indicating the successful synthesis of the cyclic terpolymer. Additionally, the SEC trace of the cyclic terpolymer produced, after cleavage of the ester groups, shifted again practically to the position corresponding to the linear precursor. The first exploratory results on morphology showed the tremendous influence of the cyclic structure on the morphology of terpolymers. © 2016 American Chemical Society.

  19. Block Copolymers: Synthesis and Applications in Nanotechnology

    Science.gov (United States)

    Lou, Qin

    ring-opening crosslinking and can act as a negative-tone photoresist. The PGMA-b-PS thin films were also studied for phase separation with ˜25 nm patterns using transmission electron microscopy (TEM). Poly(styrene-block-4-vinyl pyridine) (PS-b-P4VP) block copolymer thin films are shown to form perpendicular cylinder phase separated structures, and these may be used to template the formation of ordered titania nanostructures with sub-50 nm diameters on either silicon or indium tin oxide (ITO) substrates. A study of the mechanism of TiO2 formation within the P4VP cylinder phase was developed and tested. It was found that the titania nanostructure morphology is affected by pH and deposition temperatures, and successful deposition required the cross-linking of the P4VP phase in order to obtain individual nanostructures.

  20. Investigating self-assembly and metal nanoclusters in aqueous di-block copolymers solutions

    CERN Document Server

    Lo Celso, F; Triolo, R; Triolo, A; Strunz, P; Bronstein, L; Zwanziger, J; Lin, J S

    2002-01-01

    Self-assembling properties of di-block copolymers/ surfactant hybrids in aqueous solution can be exploited to obtain metal nanoparticles stable dispersion. Results will be presented here for polystyrene-block-poly(ethylene oxide) solutions. A SANS structural investigation has been performed over different molecular weights of both hydrophilic and hydrophobic block, by varying temperature and concentration of the copolymer. A SAXS characterization of micellar systems containing Pt nanoparticles is reported. (orig.)

  1. Substrate tolerant direct block copolymer nanolithography

    DEFF Research Database (Denmark)

    Li, Tao; Wang, Zhongli; Schulte, Lars

    2016-01-01

    Block copolymer (BC) self-assembly constitutes a powerful platform for nanolithography. However, there is a need for a general approach to BC lithography that critically considers all the steps from substrate preparation to the final pattern transfer. We present a procedure that significantly sim...... plasma treatment enables formation of the oxidized PDMS hard mask, PS block removal and polymer or graphene substrate patterning....

  2. Patchy micelles based on coassembly of block copolymer chains and block copolymer brushes on silica particles.

    Science.gov (United States)

    Zhu, Shuzhe; Li, Zhan-Wei; Zhao, Hanying

    2015-04-14

    Patchy particles are a type of colloidal particles with one or more well-defined patches on the surfaces. The patchy particles with multiple compositions and functionalities have found wide applications from the fundamental studies to practical uses. In this research patchy micelles with thiol groups in the patches were prepared based on coassembly of free block copolymer chains and block copolymer brushes on silica particles. Thiol-terminated and cyanoisopropyl-capped polystyrene-block-poly(N-isopropylacrylamide) block copolymers (PS-b-PNIPAM-SH and PS-b-PNIPAM-CIP) were synthesized by reversible addition-fragmentation chain transfer polymerization and chemical modifications. Pyridyl disulfide-functionalized silica particles (SiO2-SS-Py) were prepared by four-step surface chemical reactions. PS-b-PNIPAM brushes on silica particles were prepared by thiol-disulfide exchange reaction between PS-b-PNIPAM-SH and SiO2-SS-Py. Surface micelles on silica particles were prepared by coassembly of PS-b-PNIPAM-CIP and block copolymer brushes. Upon cleavage of the surface micelles from silica particles, patchy micelles with thiol groups in the patches were obtained. Dynamic light scattering, transmission electron microscopy, and zeta-potential measurements demonstrate the preparation of patchy micelles. Gold nanoparticles can be anchored onto the patchy micelles through S-Au bonds, and asymmetric hybrid structures are formed. The thiol groups can be oxidized to disulfides, which results in directional assembly of the patchy micelles. The self-assembly behavior of the patchy micelles was studied experimentally and by computer simulation.

  3. Investigation of Molecular Structure and Thermal Properties of Thermo-Oxidative Aged SBS in Blends and Their Relations.

    Science.gov (United States)

    Xu, Xiong; Yu, Jianying; Xue, Lihui; Zhang, Canlin; Zha, Yagang; Gu, Yi

    2017-07-07

    Tri-block copolymer styrene-butadiene (SBS) is extensively applied in bituminous highway construction due to its high elasticity and excellent weather resistance. With the extension of time, tri-block structural SBS automatically degrades into bi-block structural SB- with some terminal oxygen-containing groups under the comprehensive effects of light, heat, oxygen, etc. In this paper, the effects of aging temperature, aging time and oxygen concentration on the molecular structure of thermo-oxidative aged SBS were mainly investigated using Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS), and the correlation between oxygen-containing groups and thermal properties (TG-DTG) was further discussed. The FTIR and XPS results show that rapid decomposition of SBS will occur with increments of aging temperature, aging time and oxygen concentration, and a large number of oxygen-containing groups such as -OH, C=O, -COOH, etc. will be formed during thermo-oxidative aging. In short-term aging, changes in aging temperature and oxygen concentration have a significant impact on the structural damage of SBS. However, in long-term aging, it has no further effect on the molecular structure of SBS or on increasing oxygen concentration. The TG and DTG results indicate that the concentration of substances with low molecular weight gradually increases with the improvement of the degree of aging of the SBS, while the initial decomposition rate increases at the beginning of thermal weightlessness and the decomposition rate slows down in comparison with neat SBS. From the relation between the XPS and TG results, it can be seen that the initial thermal stability of SBS rapidly reduces as the relative concentration of the oxygen-containing groups accumulates around 3%, while the maximum decomposition temperature slowly decreases when the relative concentration of the oxygen-containing groups is more than 3%, due to the difficult damage to strong bonds

  4. Synthesis and self-assembling of responsive polysaccharide-based copolymers in aqueous media

    Energy Technology Data Exchange (ETDEWEB)

    Marques, Nivia do N.; Balaban, Rosangela de C. [Universidade Federal do Rio Grande do Norte (UFRN), Natal, RN (Brazil); Halila, Sami; Borsali, Redouane, E-mail: borsali@cermav.cnrs.fr, E-mail: halila@cermav.cnrs.fr [Centre de Recherche sur les Macromolecules Vegetales (CERMAV), Grenoble (France)

    2015-07-01

    This work reports the synthesis and the thermoresponsive self-assembly behavior of carboxymethylcellulose-g-JeffamineM2070 and carboxymethylcellulose-g-JeffamineM600 copolymers in aqueous media. They were prepared through the grafting of two different types of amino-terminated poly(ethylene oxide-co-propylene oxide) chains onto the carboxylate groups of carboxymethylcellulose, by using water-soluble carbodiimide derivative and N-hydroxysuccinimide as coupling reagents. The grafting efficiency was confirmed by infrared and the degree of substitution by {sup 1}H NMR integrations. The salt effect on cloud point temperature was evaluated into different solvents (Milli-Q water, 0.5M NaCl, synthetic sea water (SSW) and 0.5M K{sub 2}CO{sub 3}) by UV-Vis and dynamic light scattering (DLS) measurements. Both copolymers showed lower cloud point temperature in 0.5M K2CO3 than in 0.5M NaCl and in SSW, which was attributed to the higher ionic strength for K{sub 2}CO{sub 3} combined to the ability of CO{sub 3}{sup 2-} to decrease polymer-water interactions. Copolymers chains displayed higher hydrodynamic radii than CMC precursor at 25 and 60 °C in saline solutions, and self-associations changed as a function of the environment and copolymer composition. (author)

  5. Synthesis and self-assembling of responsive polysaccharide-based copolymers in aqueous media

    International Nuclear Information System (INIS)

    Marques, Nivia do N.; Balaban, Rosangela de C.; Halila, Sami; Borsali, Redouane

    2015-01-01

    This work reports the synthesis and the thermoresponsive self-assembly behavior of carboxymethylcellulose-g-JeffamineM2070 and carboxymethylcellulose-g-JeffamineM600 copolymers in aqueous media. They were prepared through the grafting of two different types of amino-terminated poly(ethylene oxide-co-propylene oxide) chains onto the carboxylate groups of carboxymethylcellulose, by using water-soluble carbodiimide derivative and N-hydroxysuccinimide as coupling reagents. The grafting efficiency was confirmed by infrared and the degree of substitution by "1H NMR integrations. The salt effect on cloud point temperature was evaluated into different solvents (Milli-Q water, 0.5M NaCl, synthetic sea water (SSW) and 0.5M K_2CO_3) by UV-Vis and dynamic light scattering (DLS) measurements. Both copolymers showed lower cloud point temperature in 0.5M K2CO3 than in 0.5M NaCl and in SSW, which was attributed to the higher ionic strength for K_2CO_3 combined to the ability of CO_3"2"- to decrease polymer-water interactions. Copolymers chains displayed higher hydrodynamic radii than CMC precursor at 25 and 60 °C in saline solutions, and self-associations changed as a function of the environment and copolymer composition. (author)

  6. Diblock-copolymer-mediated self-assembly of protein-stabilized iron oxide nanoparticle clusters for magnetic resonance imaging.

    Science.gov (United States)

    Tähkä, Sari; Laiho, Ari; Kostiainen, Mauri A

    2014-03-03

    Superparamagnetic iron oxide nanoparticles (SPIONs) can be used as efficient transverse relaxivity (T2 ) contrast agents in magnetic resonance imaging (MRI). Organizing small (Doxide) diblock copolymer (P2QVP-b-PEO) to mediate the self-assembly of protein-cage-encapsulated iron oxide (γ-Fe2 O3 ) nanoparticles (magnetoferritin) into stable PEO-coated clusters. This approach relies on electrostatic interactions between the cationic N-methyl-2-vinylpyridinium iodide block and magnetoferritin protein cage surface (pI≈4.5) to form a dense core, whereas the neutral ethylene oxide block provides a stabilizing biocompatible shell. Formation of the complexes was studied in aqueous solvent medium with dynamic light scattering (DLS) and cryogenic transmission electron microcopy (cryo-TEM). DLS results indicated that the hydrodynamic diameter (Dh ) of the clusters is approximately 200 nm, and cryo-TEM showed that the clusters have an anisotropic stringlike morphology. MRI studies showed that in the clusters the longitudinal relaxivity (r1 ) is decreased and the transverse relaxivity (r2 ) is increased relative to free magnetoferritin (MF), thus indicating that clusters can provide considerable contrast enhancement. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Core-Shell-Corona Micelles with a Responsive Shell.

    Science.gov (United States)

    Gohy, Jean-François; Willet, Nicolas; Varshney, Sunil; Zhang, Jian-Xin; Jérôme, Robert

    2001-09-03

    A reactor for the synthesis of gold nanoparticles is one of the uses of a poly(styrene)-block-poly(2-vinylpyridine)-block-poly(ethylene oxide) triblock copolymer (PS-b-P2VP-b-PEO) which forms core-shell-corona micelles in water. Very low polydispersity spherical micelles are observed that consist of a PS core surrounded by a pH-sensitive P2VP shell and a corona of PEO chains end-capped by a hydroxyl group. The corona can act as a site for attaching responsive or sensing molecules. © 2001 WILEY-VCH Verlag GmbH, Weinheim, Fed. Rep. of Germany.

  8. Role of monomer sequence and backbone chemistry in polypeptoid copolymers for marine antifouling coatings

    Science.gov (United States)

    Patterson, Anastasia; Wenning, Brandon; Rizis, Georgios; Calabrese, David; Finlay, John; Franco, Sofia; Clare, Anthony; Kramer, Edward; Ober, Christopher; Segalman, Rachel

    The design rules elucidated in this work suggest that antifouling coatings bearing pendant peptoid side chains perform better overall in marine fouling tests than those with peptide side chains, with extremely low attachment of N. incerta and high removal of U. linza. This difference in performance is likely due to the lack of a hydrogen bond donor in the peptoid backbone. Furthermore, we show that the bulk polymer material of these hierarchical coatings (based on PEO or PDMS) plays a key role in determining both surface presentation and fouling release performance. We demonstrate these trends utilizing a modular coating based on a triblock copolymer consisting of polystyrene and a vinyl-containing midblock, to which sequence-defined pendant oligomers (peptides or peptoids with sequences of oligo-PEO and fluoroalkyl groups) are attached via thiol-ene ``click'' chemistry. Surface presentation was analyzed with X-ray photoelectron spectroscopy and captive bubble water contact angle, and antifouling performance was evaluated with attachment and removal bioassays of the marine macroalga U. linza and diatom N. incerta. NSF GRFP and ONR PECASE.

  9. Mechanical and Electrical Properties of Styrene-Isoprene-Styrene Copolymer Doped with Expanded Graphite Nanoplatelets

    Directory of Open Access Journals (Sweden)

    Zdenko Špitalský

    2015-01-01

    Full Text Available The molecular dynamics of a triblock copolymer and of expanded graphite nanoplatelets were investigated. Composites were prepared using the solution technique. The effects of filler addition and of filler-matrix interactions were investigated using dielectric relaxation spectroscopy (DRS and dynamic mechanical analysis (DMA. Only one relaxation was observed by DRS, which was associated with the relaxation of the main polymer chain. Both DRS and DMA demonstrated that the addition of the filler does not cause a significant change in either the temperature of the relaxation or its activation energy, which suggests the presence of weak interactions between the filler and matrix. The storage modulus of the composites increased with increasing filler content. The composite containing 8% filler exhibited a storage modulus increase of approximately 394% in the rubber area. Using the DC electrical conductivity measurements, the electrical percolation threshold was determined to be approximately 5%. The dielectric permittivity and conductivity in the microwave region were determined, confirming that percolating behavior and the critical threshold concentration.

  10. Synthesis and luminescence properties of hybrid organic-inorganic transparent titania thin film activated by in- situ formed lanthanide complexes

    Science.gov (United States)

    Wang, Yige; Wang, Li; Li, Huanrong; Liu, Peng; Qin, Dashan; Liu, Binyuan; Zhang, Wenjun; Deng, Ruiping; Zhang, Hongjie

    2008-03-01

    Stable transparent titania thin films were fabricated at room temperature by combining thenoyltrifluoroacetone (TTFA)-modified titanium precursors with amphiphilic triblock poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO, P123) copolymers. The obtained transparent titania thin films were systematically investigated by IR spectroscopy, PL emission and excitation spectroscopy and transmission electron microscopy. IR spectroscopy indicates that TTFA coordinates the titanium center during the process of hydrolysis and condensation. Luminescence spectroscopy confirms the in-situ formation of lanthanide complexes in the transparent titania thin film. TEM image shows that the in-situ formed lanthanide complexes were homogeneously distributed throughout the whole thin film. The quantum yield and the number of water coordinated to lanthanide metal center have been theoretically determined based on the luminescence data.

  11. Combinatorial and high-throughput screening of the effect of siloxane composition on the surface properties of crosslinked siloxane-polyurethane coatings.

    Science.gov (United States)

    Ekin, Abdullah; Webster, Dean C

    2007-01-01

    Libraries of siloxane-polyurethane coatings were designed, formulated, and screened using high-throughput experimentation. Four independent variables that were analyzed were the molecular weight of poly(dimethylsiloxane) (PDMS), presence or absence of poly(epsilon-caprolactone) (PCL) blocks attached to the PDMS backbone, the length of the PCL blocks, and the siloxane polymer level in the coating formulations. In addition to the siloxane libraries (3-aminopropyl-terminated PDMS and poly(epsilon-caprolactone)-poly(dimethylsiloxane)-poly(epsilon-caprolactone) (PCL-PDMS-PCL) triblock copolymers), the coating formulation included a trifunctional isocyanate crosslinker, trifunctional poly(epsilon-caprolactone) polyol, 2,4-pentanedione (pot-life extender), dibutyltin diacetate (catalyst), and a blend of solvents. The resulting coatings were analyzed for their surface energy and pseudobarnacle adhesion both before and after aging the coatings for 30 days in water. The water and methylene iodide contact angle averages increase with increasing molecular weight of PDMS. Coatings prepared from PCL-PDMS-PCL triblock copolymers have lower surface energies than coatings prepared from 3-aminopropyl-terminated PDMS; however, lower pseudobarnacle adhesion results were obtained for the coatings prepared from 3-aminopropyl-terminated PDMS than coatings prepared from PCL-PDMS-PCL triblock copolymers. The siloxane polymer level in the coating formulations does not have a significant effect on the surface energy of the coatings, but it resulted in higher pseudobarnacle adhesion.

  12. Copolymer adsorption and the effect on colloidal stability

    NARCIS (Netherlands)

    Bijsterbosch, H.D.

    1998-01-01

    The main aim of the work described in this thesis is to study the effect of different types of copolymers on the stability of aqueous oxide dispersions. Such dispersions are a major component in water-borne paints. In order to obtain a better insight in steric stabilisation we first investigated the

  13. Effects of supported metallocene catalyst active center multiplicity on antioxidant-stabilized ethylene homo- and copolymers

    KAUST Repository

    Atiqullah, Muhammad

    2014-10-09

    © 2014 Akadémiai Kiadó, Budapest, Hungary. A silica-supported bis(n-butylcyclopentadienyl) zirconium dichloride [( n BuCp)2ZrCl2] catalyst was synthesized. This was used to prepare an ethylene homopolymer and an ethylene-1-hexene copolymer. The active center multiplicity of this catalyst was modeled by deconvoluting the copolymer molecular mass distribution and chemical composition distribution. Five different active site types were predicted, which matched the successive self-nucleation and annealing temperature peaks. The thermo-oxidative melt stability, with and without Irganox 1010 and Irgafos 168, of the above polyethylenes was investigated using nonisothermal differential scanning calorimetric (DSC) experiments at 150 °C. This is a temperature that ensures complete melting of the samples and avoids the diffusivity of oxygen to interfere into polyethylene crystallinity and its thermo-oxidative melt degradation. The oxidation parameters such as onset oxidation temperature, induction period, protection factor, and S-factor were determined by combining theoretical modeling with the DSC experiments. Subsequently, these findings were discussed considering catalyst active center multiplicity and polymer microstructure, particularly average ethylene sequence length. Several insightful results, which have not been reported earlier in the literature, were obtained. The antioxidant effect, for each polymer, varied as (Irganox + Irgafos) ≈ Irganox > Irgafos > Neat polymer. The as-synthesized homopolymer turned out to be almost twice as stable as the corresponding copolymer. The antioxidant(s) in the copolymer showed higher antioxidant effectiveness (AEX) than those in the homopolymer. Irganox exhibited more AEX than Irgafos. To the best of our knowledge, such findings have not been reported earlier in the literature. However, mixed with Irganox or Irgafos, their melt oxidation stability was comparable. The homopolymer, as per the calculated S-factor, showed Irganox

  14. Phase behavior in blends of ethylene oxide-propylene oxide copolymer and poly(ether sulfone) studied by modulated-temperature DSC and NMR relaxometry.

    Science.gov (United States)

    Van Lokeren, Luk; Gotzen, Nicolaas-Alexander; Pieters, Ronny; Van Assche, Guy; Biesemans, Monique; Willem, Rudolph; Van Mele, Bruno

    2009-01-01

    The state diagram of a blend consisting of a copolymer containing ethylene oxide and propylene oxide, P(EO-ran-PO), and poly(ether sulfone), PES, is constructed by using modulated-temperature differential scanning calorimetry (MTDSC), T(2) NMR relaxometry, and light scattering. The apparent heat capacity signal in MTDSC is used for the characterization of polymer miscibility and morphology development. T(2) NMR relaxometry is used to detect the onset of phase separation, which is in good agreement with the onset of phase separation in the apparent heat capacity from MTDSC and the cloud-point temperature as determined from light scattering. The coexistence curve can be constructed from T(2) values at various temperatures by using a few blends with well-chosen compositions. These T(2) values also allow the detection of the boundary between the demixing zones with and without interference of partial vitrification and are in good agreement with stepwise quasi-isothermal MTDSC heat capacity measurements. Important interphases are detected in the heterogeneous P(EO-ran-PO)/PES blends.

  15. Synthesis and characterization of novel organotin carboxylate maleimide monomers and copolymers

    Directory of Open Access Journals (Sweden)

    2009-06-01

    Full Text Available Two novel tributyltin carboxylate maleimide monomers, tributyltin(maleimidoacetate and tributyltin(4-maleimidobenzoate, were synthesized by condensation reaction of maleimidoacetic acid or 4-maleimidobenzoic acid with bis(tributyltin oxide. Copolymerization of these monomers with styrene was carried in dioxane at 70°C using asobisisobutyronitrile as free radical initiator. The structures of monomers and copolymers were confirmed by FT-IR (Fourier Transform Infrared, 1H and 13C NMR (nuclear magnetic resonance spectroscopy and elemental analysis. The copolymers were characterized by solubility and thermal analysis.

  16. Self-assembled micelles based on pH-sensitive PAE-g-MPEG-cholesterol block copolymer for anticancer drug delivery

    Directory of Open Access Journals (Sweden)

    Zhang CY

    2014-10-01

    Full Text Available Can Yang Zhang, Di Xiong, Yao Sun, Bin Zhao, Wen Jing Lin, Li Juan Zhang School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou, Guangdong Province, People’s Republic of China Abstract: A novel amphiphilic triblock pH-sensitive poly(ß-amino ester-g-poly(ethylene glycol methyl ether-cholesterol (PAE-g-MPEG-Chol was designed and synthesized via the Michael-type step polymerization and esterification condensation method. The synthesized copolymer was determined with proton nuclear magnetic resonance and gel permeation chromatography. The grafting percentages of MPEG and cholesterol were determined as 10.93% and 62.02%, calculated from the area of the characteristic peaks, respectively. The amphiphilic copolymer was confirmed to self-assemble into core/shell micelles in aqueous solution at low concentrations. The critical micelle concentrations were 6.92 and 15.14 mg/L at pH of 7.4 and 6.0, respectively, obviously influenced by the changes of pH values. The solubility of pH-responsive PAE segment could be transformed depending on the different values of pH because of protonation–deprotonation of the amino groups, resulting in pH sensitivity of the copolymer. The average particle size of micelles increased from 125 nm to 165 nm with the pH decreasing, and the zeta potential was also significantly changed. Doxorubicin (DOX was entrapped into the polymeric micelles with a high drug loading level. The in vitro DOX release from the micelles was distinctly enhanced with the pH decreasing from 7.4 to 6.0. Toxicity testing proved that the DOX-loaded micelles exhibited high cytotoxicity in HepG2 cells, whereas the copolymer showed low toxicity. The results demonstrated how pH-sensitive PAE-g-MPEG-Chol micelles were proved to be a potential vector in hydrophobic drug delivery for tumor therapy. Keywords: micelle, pH-sensitive, cholesterol, poly(ß-amino ester, drug delivery

  17. Self-assembly in poly(dimethylsiloxane)-poly(ethylene oxide) block copolymer template directed synthesis of Linde type A zeolite.

    Science.gov (United States)

    Bonaccorsi, Lucio; Calandra, Pietro; Kiselev, Mikhail A; Amenitsch, Heinz; Proverbio, Edoardo; Lombardo, Domenico

    2013-06-11

    We describe the hydrothermal synthesis of zeolite Linde type A (LTA) submicrometer particles using a water-soluble amphiphilic block copolymer of poly(dimethylsiloxane)-b-poly(ethylene oxide) as a template. The formation and growth of the intermediate aggregates in the presence of the diblock copolymer have been monitored by small-angle X-ray scattering (SAXS) above the critical micellar concentration at a constant temperature of 45 °C. The early stage of the growth process was characterized by the incorporation of the zeolite LTA components into the surface of the block copolymer micellar aggregates with the formation of primary units of 4.8 nm with a core-shell morphology. During this period, restricted to an initial time of 1-3 h, the core-shell structure of the particles does not show significant changes, while a subsequent aggregation process among these primary units takes place. A shape transition of the SAXS profile at the late stage of the synthesis has been connected with an aggregation process among primary units that leads to the formation of large clusters with fractal characteristics. The formation of large supramolecular assemblies was finally verified by scanning electron microscopy, which evidenced the presence of submicrometer aggregates with size ranging between 100 and 300 nm, while X-ray diffraction confirmed the presence of crystalline zeolite LTA. The main finding of our results gives novel insight into the mechanism of formation of organic-inorganic mesoporous materials based on the use of a soft interacting nanotemplate as well as stimulates the investigation of alternative protocols for the synthesis of novel hybrid materials with new characteristics and properties.

  18. Internal nanoparticle structure of temperature-responsive self-assembled PNIPAM-b-PEG-b-PNIPAM triblock copolymers in aqueous solutions: NMR, SANS, and light scattering studies

    Czech Academy of Sciences Publication Activity Database

    Filippov, Sergey K.; Bogomolova, Anna; Kaberov, Leonid; Velychkivska, Nadiia; Starovoytova, Larisa; Černochová, Zulfiya; Rogers, S. E.; Lau, W. M.; Khutoryanskiy, V. V.; Cook, M. T.

    2016-01-01

    Roč. 32, č. 21 (2016), s. 5314-5323 ISSN 0743-7463 R&D Projects: GA ČR(CZ) GC15-10527J Institutional support: RVO:61389013 Keywords : nanoparticles * copolymers * NMP Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.833, year: 2016

  19. The effect of salt on the morphologies of compositionally asymmetric block copolymer electrolytes

    Science.gov (United States)

    Loo, Whitney; Maslyn, Jacqueline; Oh, Hee Jeung; Balsara, Nitash

    Block copolymer electrolytes are promising for applications in lithium metal solid-state batteries. Due to their ability to microphase separate into distinct morphologies, their ion transport and mechanical properties can be decoupled. The addition of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt to poly(styrene)-block-poly(ethylene oxide) (SEO) has been shown to increase microphase separation in symmetric block copolymer systems due to an increase in the effective interaction parameter (χeff) ; however the effect of block copolymer compositional asymmetry is not well-understood. The effect of compositional asymmetry on polymer morphology was investigated through small and wide angle X-ray scattering (SAXS/WAXS). The effective Flory-Huggins interaction parameter was extracted from the scattering profiles in order to construct a phase diagram to demonstrate the effect of salt and compositional asymmetry on block copolymer morphology.

  20. Preparation of Pt-mesoporous tungsten carbide/carbon composites via a soft-template method for electrochemical methanol oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Ma, Chun’an, E-mail: science@zjut.edu.cn; Kang, Lingzhi; Shi, Meiqin; Lang, Xiaoling; Jiang, Yekun

    2014-03-05

    Highlights: • Mesoporous composite Pt-m(WC/C) is prepared by a soft template method. • The structure of phenolic gives a space limitation effect on the growth of WC. • Analysis of the effect of F127 on controlling the structure of composites. • Pt-m(WC/C) exhibits more than three times higher than Pt/C in catalytic activity. -- Abstract: This paper introduces a simple and reproducible chemical process for synthesis of Pt-mesoporous tungsten carbide/carbon composites composites Pt-m(WC/C) by means of a soft-template method. In this process, low-molecular-weight phenolic resol acted as the precursor both for carbon support and also the carbon resource of tungsten carbide. Tungsten hexachloride was used as a tungsten precursor along with different amount of triblock copolymer Pluronic F127 as pore-forming component. The best performance of Pt-m(WC/C) towards methanol oxidation is found when the mass ratios of WCl{sub 6}:F127 is 1:0.6. The composite presents an improved methanol oxidation performance evidenced by a negative shift in onset potential, and increase of peak current density, compared with commercial Pt/C. The difference is explained by the adding of appropriate amount of F127 which facilitates the construction of mesoporous matrix structure of WC/C.

  1. Sustainable Elastomers from Renewable Biomass.

    Science.gov (United States)

    Wang, Zhongkai; Yuan, Liang; Tang, Chuanbing

    2017-07-18

    Sustainable elastomers have undergone explosive growth in recent years, partly due to the resurgence of biobased materials prepared from renewable natural resources. However, mounting challenges still prevail: How can the chemical compositions and macromolecular architectures of sustainable polymers be controlled and broadened? How can their processability and recyclability be enabled? How can they compete with petroleum-based counterparts in both cost and performance? Molecular-biomass-derived polymers, such as polymyrcene, polymenthide, and poly(ε-decalactone), have been employed for constructing thermoplastic elastomers (TPEs). Plant oils are widely used for fabricating thermoset elastomers. We use abundant biomass, such as plant oils, cellulose, rosin acids, and lignin, to develop elastomers covering a wide range of structure-property relationships in the hope of delivering better performance. In this Account, recent progress in preparing monomers and TPEs from biomass is first reviewed. ABA triblock copolymer TPEs were obtained with a soft middle block containing a soybean-oil-based monomer and hard outer blocks containing styrene. In addition, a combination of biobased monomers from rosin acids and soybean oil was formulated to prepare triblock copolymer TPEs. Together with the above-mentioned approaches based on block copolymers, multigraft copolymers with a soft backbone and rigid side chains are recognized as the first-generation and second-generation TPEs, respectively. It has been recently demonstrated that multigraft copolymers with a rigid backbone and elastic side chains can also be used as a novel architecture of TPEs. Natural polymers, such as cellulose and lignin, are utilized as a stiff, macromolecular backbone. Cellulose/lignin graft copolymers with side chains containing a copolymer of methyl methacrylate and butyl acrylate exhibited excellent elastic properties. Cellulose graft copolymers with biomass-derived polymers as side chains were

  2. Living cationic polymerization and polyhomologation: an ideal combination to synthesize functionalized polyethylene–polyisobutylene block copolymers

    KAUST Repository

    Zhang, Hefeng

    2015-12-17

    A series of hydroxyl-terminated polyisobutylene-b-polyethylene (PIB-b-PE-OH) copolymers were synthesized by combining living cationic polymerization and polyhomologation. Allyl-terminated PIBs, synthesized by living cationic polymerization, were hydroborated with BH3·THF to produce 3-arm boron-linked stars, PIB3B, which served as macroinitiators for the in situ polyhomologation of dimethylsulfoxonium methylide. The resulting 3-arm star block copolymers, (PIB-b-PE)3B, were oxidized/hydrolysed to afford PIB-b-PE-OH. Characterization of all intermediates and final products by high temperature gel permeation chromatography (HT-GPC) and proton nuclear magnetic resonance spectroscopy (1H NMR) revealed the well-defined character of the copolymers. The thermal properties of the copolymers were studied by differential scanning calorimetry (DSC).

  3. Metallic nickel nanorod arrays embedded into ordered block copolymer templates

    International Nuclear Information System (INIS)

    Seifarth, O.; Krenek, R.; Tokarev, I.; Burkov, Y.; Sidorenko, A.; Minko, S.; Stamm, M.; Schmeisser, D.

    2007-01-01

    We report on metallic Nickel nanorods prepared by utilizing a mask of ordered nanostructured hollow channels in a block copolymer matrix. These polymeric templates were formed by a self organized process in block copolymer supramolecular assemblies. Nickel was filled into with two different techniques, electrodeposition and washing in. We monitor the formation process of these nanorods by means of atomic force microscopy and synchrotron radiation soft X-ray based photoelectron emission microscopy. The oxidation state of the nickelrods is evaluated with X-ray absorption spectroscopy and X-ray photoelectron spectroscopy at the Ni L edges and lateral distributions of the Ni nanorods were detected with micrometer resolved X-ray absorption spectroscopy. The finding is that the Ni rods were metallic despite their preparation under ambient conditions, inside the particles no hints for NiO complexes were found. This indicates that the polymer protects Ni nanoparticles against oxidation

  4. White emission from liquid-crystalline copolymers containing oxadiazole moieties in the side chain

    Science.gov (United States)

    Kawamoto, Masuki; Tsukamoto, Takuji; Kinoshita, Motoi; Ikeda, Tomiki

    2006-09-01

    A liquid-crystalline polymer in the side chain was synthesized through copolymerization of a bipolar carrier-transporting monomer with a liquid-crystalline monomer containing oxadiazole moieties substituted with trifluoromethyl groups. A single-layer light-emitting diode of indium tin oxide (ITO)/copolymer/MgAg emitted white light with a maximum luminous efficiency of 0.1cd/A. The origin of the white emission in the copolymer is the electroplex between bipolar carrier-transporting moieties and strong electron-withdrawing moieties. Furthermore, a simple multilayer device with configuration of ITO/poly(3,4-ethylenedioxythiophene)/poly(styrenesulfonic acid)/copolymer/MgAg device showed white emission with CIE 1931 chromaticity coordinates (x,y): (0.30, 0.33).

  5. Facile preparation of pH-responsive polyurethane nanocarrier for oral delivery

    Energy Technology Data Exchange (ETDEWEB)

    Nabid, Mohammad Reza, E-mail: M-nabid@sbu.ac.ir; Omrani, Ismail

    2016-12-01

    This study reports a novel one pot synthesis of pH-responsive nanocarrier for oral delivery of hydrophobic drug under gastrointestinal tract. Triblock copolymer MPEG-HTPB-MPEG was synthesized coupling of MPEG and HTPB using hexamethylene diisocyanate(HDI) and pH-responsive carboxylic acid group was attached to polybuthadiene backbone by thiol-ene click reaction in a facile and convenient procedure. The MPEG-HTPB (g-COOH)-MPEG block copolymers were self-organized into micelle assemblies in the water. The size and shape of the micelle assemblies were confirmed by dynamic light scattering (DLS) and transmission electron microscopy (TEM). The nanocarriers have high drug loading ability for poorly water-soluble drug. The pH-responsive profile was demonstrated by pH-dependent swelling and in vitro drug release. < 10.0% IBU was released under artificial gastric fluid after 2 h, whereas an immediate release was observed under artificial intestinal fluid. The XTT assay indicated that the micelle obtained from PEG-HTPB (g-COOH)-PEG triblock copolymer are safe in a wide range of concentrations. The results show that pH-responsive PEG-HTPB (g-COOH)-PEG triblock copolymers are promising nanocarriers for the oral administration of hydrophobic drugs. - Highlights: • A facile method for synthesis of pH-responsive nanocarriers was developed. • pH-responsive amphiphilic polymer was synthesized using a rapid and one-pot procedure. • The nanocarriers have high drug loading ability for poorly water-soluble drug. • The nanocarriers show pH-dependent release profile. • The nanocarriers were stable in the gastric fluid and ruptured to release the loaded drug in intestinal fluid.

  6. Facile preparation of pH-responsive polyurethane nanocarrier for oral delivery

    International Nuclear Information System (INIS)

    Nabid, Mohammad Reza; Omrani, Ismail

    2016-01-01

    This study reports a novel one pot synthesis of pH-responsive nanocarrier for oral delivery of hydrophobic drug under gastrointestinal tract. Triblock copolymer MPEG-HTPB-MPEG was synthesized coupling of MPEG and HTPB using hexamethylene diisocyanate(HDI) and pH-responsive carboxylic acid group was attached to polybuthadiene backbone by thiol-ene click reaction in a facile and convenient procedure. The MPEG-HTPB (g-COOH)-MPEG block copolymers were self-organized into micelle assemblies in the water. The size and shape of the micelle assemblies were confirmed by dynamic light scattering (DLS) and transmission electron microscopy (TEM). The nanocarriers have high drug loading ability for poorly water-soluble drug. The pH-responsive profile was demonstrated by pH-dependent swelling and in vitro drug release. < 10.0% IBU was released under artificial gastric fluid after 2 h, whereas an immediate release was observed under artificial intestinal fluid. The XTT assay indicated that the micelle obtained from PEG-HTPB (g-COOH)-PEG triblock copolymer are safe in a wide range of concentrations. The results show that pH-responsive PEG-HTPB (g-COOH)-PEG triblock copolymers are promising nanocarriers for the oral administration of hydrophobic drugs. - Highlights: • A facile method for synthesis of pH-responsive nanocarriers was developed. • pH-responsive amphiphilic polymer was synthesized using a rapid and one-pot procedure. • The nanocarriers have high drug loading ability for poorly water-soluble drug. • The nanocarriers show pH-dependent release profile. • The nanocarriers were stable in the gastric fluid and ruptured to release the loaded drug in intestinal fluid.

  7. Synthesis and characterization of biocompatible multicomponent polymer systems as supports for cell cultures

    International Nuclear Information System (INIS)

    Porjazoska, Aleksandra; Cvetkovska, Maja; Yylmaz, Oksan Karal; Baysal, Kemal; Apohan, Nilhan Kayaman; Baysal, Bahattin M.

    2004-01-01

    Engineering living tissue for reconstructive surgery requires an appropriate cell source and optimal culture conditions, but also a suitable biodegradable scaffold as the basic elements. On the basis of the well known facts that scaffold chemistry and architecture can influence the fate and function of engrafted cells, a large number of polymers, as cell cultures supports, have been proposed. In this study, we report a synthesis, characterization and cell interactions with the following polymer systems: I. Poly[L- lactic acid / glycolic acid / poly(dimethylsiloxane)], copolymers; II. Poly(DL - lactic acid) / triblock PCL - PDMS - PCL copolymers; III. Blends of poly(DL - lactic - co - glycolic acid) and triblock PCL - PDMS - PCL copolymers. For the cell seeding experiments, Swiss 3T3 and/or L929 mouse fibroblasts were grown in RPMI 1640 and/or DMEM / F12 medium, and placed onto the bio polymer non porous or porous films, prepared using a particulate leaching technique. The amount of cells present on the surfaces of the scaffolds was quantified using a neutral red uptake assay. (Author)

  8. In-situ Polymerization of Polyaniline/Polypyrrole Copolymer using Different Techniques

    Science.gov (United States)

    Hammad, A. S.; Noby, H.; Elkady, M. F.; El-Shazly, A. H.

    2018-01-01

    The morphology and surface area of the poly(aniline-co-pyrrole) copolymer (PANPY) are important properties which improve the efficiency of the copolymer in various applications. In this investigation, different techniques were employed to produce PANPY in different morphologies. Aniline and pyrrole were used as monomers, and ammonium peroxydisulfate (APS) was used as an oxidizer with uniform molar ratio. Rapid mixing, drop-wise mixing, and supercritical carbon dioxide (ScCO2) polymerization techniques were appointed. The chemical structure, crystallinity, porosity, and morphology of the composite were distinguished by Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), Brunauer, Emmett and Teller (BET) analysis, and transmission electron microscopy (TEM) respectively. The characterization tests indicated that the polyaniline/polypyrrole copolymer was successfully prepared with different morphologies. Based on the obtained TEM, hollow nanospheres were formed using rapid mixing technique with acetic acid that have a diameter of 75 nm and thickness 26 nm approximately. Also, according to the XRD, the produced structures have a semi- crystalline structure. The synthesized copolymer with ScCO2-assisted polymerization technique showed improved surface area (38.1 m2/g) with HCl as dopant.

  9. Adsorption of copolymers at polymer/air and polymer/solid interfaces

    Science.gov (United States)

    Oslanec, Robert

    Using mainly low-energy forward recoil spectrometry (LE-FRES) and neutron reflectivity (NR), copolymer behavior at polymer/air and polymer/solid interfaces is investigated. For a miscible blend of poly(styrene-ran-acrylonitrile) copolymers, the volume fraction profile of the copolymer with lower acrylonitrile content is flat near the surface in contrast to mean field predictions. Including copolymer polydispersity into a self consistent mean field (SCMF) model does not account for this profile shape. LE-FRES and NR is also used to study poly(deuterated styrene-block-methyl-methacrylate) (dPS-b-PMMA) adsorption from a polymer matrix to a silicon oxide substrate. The interfacial excess, zsp*, layer thickness, L, and layer-matrix width, w, depend strongly on the number of matrix segments, P, for P 2N, the matrix chains are repelled from the adsorbed layer and the layer characteristics become independent of P. An SCMF model of block copolymer adsorption is developed. SCMF predictions are in qualitative agreement with the experimental behavior of zsp*, L, and w as a function of P. Using this model, the interaction energy of the MMA block with the oxide substrate is found to be -8ksb{B}T. In a subsequent experiment, the matrix/dPS interaction is made increasingly unfavorable by increasing the 4-bromostyrene mole fraction, x, in a poly(styrene-ran-4-bromostyrene) (PBrsbxS) matrix. Whereas experiments show that zsp* slightly decreases as x increases, the SCMF model predicts that zsp* should increase as the matrix becomes more unfavorable. Upon including a small matrix attraction for the substrate, the SCMF model shows that zsp* decreases with x because of competition between PBrsbxS and dPS-b-PMMA for adsorbing sites. In thin film dewetting experiments on silicon oxide, the addition of dPS-b-PMMA to PS coatings acts to slow hole growth and prevent holes from impinging. Dewetting studies show that longer dPS-b-PMMA chains are more effective stabilizing agents than shorter

  10. Olefin–Styrene Copolymers

    OpenAIRE

    Nunzia Galdi; Antonio Buonerba; Leone Oliva

    2016-01-01

    In this review are reported some of the most relevant achievements in the chemistry of the ethylene–styrene copolymerization and in the characterization of the copolymer materials. Focus is put on the relationship between the structure of the catalyst and that of the obtained copolymer. On the other hand, the wide variety of copolymer architecture is related to the properties of the material and to the potential utility.

  11. Hybrid, Nanoscale Phospholipid/Block Copolymer Vesicles

    Directory of Open Access Journals (Sweden)

    Bo Liedberg

    2013-09-01

    Full Text Available Hybrid phospholipid/block copolymer vesicles, in which the polymeric membrane is blended with phospholipids, display interesting self-assembly behavior, incorporating the robustness and chemical versatility of polymersomes with the softness and biocompatibility of liposomes. Such structures can be conveniently characterized by preparing giant unilamellar vesicles (GUVs via electroformation. Here, we are interested in exploring the self-assembly and properties of the analogous nanoscale hybrid vesicles (ca. 100 nm in diameter of the same composition prepared by film-hydration and extrusion. We show that the self-assembly and content-release behavior of nanoscale polybutadiene-b-poly(ethylene oxide (PB-PEO/1-palmitoyl-2-oleoyl-sn-glycero-3-phosphatidylcholine (POPC hybrid phospholipid/block copolymer vesicles can be tuned by the mixing ratio of the amphiphiles. In brief, these hybrids may provide alternative tools for drug delivery purposes and molecular imaging/sensing applications and clearly open up new avenues for further investigation.

  12. Amphiphilic block co-polymers: preparation and application in nanodrug and gene delivery.

    Science.gov (United States)

    Xiong, Xiao-Bing; Binkhathlan, Ziyad; Molavi, Ommoleila; Lavasanifar, Afsaneh

    2012-07-01

    Self-assembly of amphiphilic block co-polymers composed of poly(ethylene oxide) (PEO) as the hydrophilic block and poly(ether)s, poly(amino acid)s, poly(ester)s and polypropyleneoxide (PPO) as the hydrophobic block can lead to the formation of nanoscopic structures of different morphologies. These structures have been the subject of extensive research in the past decade as artificial mimics of lipoproteins and viral vectors for drug and gene delivery. The aim of this review is to provide an overview of the synthesis of commonly used amphiphilic block co-polymers. It will also briefly go over some pharmaceutical applications of amphiphilic block co-polymers as "nanodelivery systems" for small molecules and gene therapeutics. Copyright © 2012 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

  13. Modification of nylon-6 with semi-rigid poly (p-diphenyl oxide terephthalamide)

    International Nuclear Information System (INIS)

    Lin, M.F.; Wang, H.H.; Shu, Y.C.

    1994-01-01

    In this study, the flexible nylon-6 was reinforced by the semi-rigid aromatic polyamide, poly (p-diphenyl oxide terephthalamide) (POA), through physical polybending and chemical copolymerization using p-aminophenylacetic acid (P-APA) as a coupling agent. From the DSC measurements, it was shown that Tg of the polyblends was increased with the increase of POA content. The Tg and Tm of multiblock copolyamides were found to be higher than those of polyblends and triblock copolyamides. From the Rheovibron measurements, it was shown that the POA with nylon-6 poy-blends exhibited higher E' and Tg value than that of nylon-6, which increased with the increase of POA content. The Tg and E' values of multiblock copolyamides were higher than those of polyblends triblock copolyamides. Scanning electron microscopy revealed that the polyblends were a dispersed phase structure, although the multiblock copolyamides exhibited a homogeneous texture rather than an aggregated one. From the wide-angle x-ray diffraction pattern, the triblock copolyamides and polyblends had two diffraction peaks, i.e., 2 θ = 20.5 degrees and 24 degrees. However, the multiblock had only one at 2 θ = 20 degrees, which indicates that a different crystal structure of multiblock copolyamides. For the mechanical properties, it was found that the multiblock copolyamides had a more significant reinforcing effect than those of polyblends and triblock copolyamides. 21 refs., 11 figs., 5 tabs

  14. High performance co-polyimide nanofiber reinforced composites

    NARCIS (Netherlands)

    Yao, Jian; Li, Guang; Bastiaansen, Cees; Peijs, Ton

    2015-01-01

    Electrospun co-polyimide BPDA (3, 3′, 4, 4′-Biphenyltetracarboxylic dianhydride)/PDA (p-Phenylenediamine)/ODA (4, 4′-oxydianiline) nanofiber reinforced flexible composites were manufactured by impregnating these high performance nanofibers with styrene-butadiene-styrene (SBS) triblock copolymer

  15. Synthesis, characterization, and property of biodegradable PEG-PCL-PLA terpolymers with miktoarm star and triblock architectures as drug carriers.

    Science.gov (United States)

    Zhang, Yixin; Luo, Song; Liang, Yan; Zhang, Hai; Peng, Xinyu; He, Bin; Li, Sai

    2018-03-01

    A series of amphiphilic terpolymers with miktoarm star and triblock architectures of poly(ethylene glycol) (PEG), poly(ε-caprolactone) (PCL) and poly(l-lactide acid) (PLLA) or poly(DL-lactide acid) (PDLLA) terpolymers were synthesized as carriers for drug delivery. The architecture, molecular weight and crystallization behavior of the terpolymers were characterized. Anticancer drug doxorubicin was encapsulated in the micelles to investigate their drug loading properties. The miktoarm star terpolymers exhibited stronger crystallization capability, smaller size and better stability than that of triblock polymeric micelle, owing to the lower CMC values of miktoarm star polymeric micelle. Furthermore, the drug-loaded miktoarm star polymeric micelles showed the cumulative DOX release account of the micelles with PDLLA blocks was 65.3% while the release account of the corresponding micelles containing PLLA blocks was 45.2%. The IC 50 values of drug-loaded miktoarm star polymeric micelle were lower than triblock polymeric micelle. Meanwhile, Confocal laser scanning microscopy (CLSM) and Flow Cytometry results demonstrated that the miktoarm star micelles were more favorable for cellular internalization. The miktoarm star micelles with PDLLA blocks were promising carriers for anticancer drug delivery.

  16. High-frequency ultrasound-responsive block copolymer micelle.

    Science.gov (United States)

    Wang, Jie; Pelletier, Maxime; Zhang, Hongji; Xia, Hesheng; Zhao, Yue

    2009-11-17

    Micelles of a diblock copolymer composed of poly(ethylene oxide) and poly(2-tetrahydropyranyl methacrylate) (PEO-b-PTHPMA) in aqueous solution could be disrupted by high-frequency ultrasound (1.1 MHz). It was found that, upon exposure to a high-intensity focused ultrasound (HIFU) beam at room temperature, the pH value of the micellar solution decreased over irradiation time. The infrared spectroscopic analysis of solid block copolymer samples collected from the ultrasound irradiated micellar solution revealed the formation of carboxylic acid dimers and hydroxyl groups. These characterization results suggest that the high-frequency HIFU beam could induce the hydrolysis reaction of THPMA at room temperature resulting in the cleavage of THP groups. The disruption of PEO-b-PTHPMA micelles by ultrasound was investigated by using dynamic light scattering, atomic force microscopy, and fluorescence spectroscopy. On the basis of the pH change, it was found that the disruption process was determined by a number of factors such as the ultrasound power, the micellar solution volume and the location of the focal spot of the ultrasound beam. This study shows the potential to develop ultrasound-sensitive block copolymer micelles by having labile chemical bonds in the polymer structure, and to use the high-frequency HIFU to trigger a chemical reaction for the disruption of micelles.

  17. Crystallization in diblock copolymer thin films at different degrees of supercooling

    DEFF Research Database (Denmark)

    Darko, C.; Botiz, I.; Reiter, G.

    2009-01-01

    The crystalline structures in thin films of polystyrene-b-poly(ethylene oxide) (PS-b-PEO) diblock copolymers were studied in dependence on the degree of supercooling. Atomic force microscopy showed that the crystalline domains (lamellae) consist of grains, which are macroscopic at low and interme...

  18. Development and Characterization of Biocompatible Fullerene [C60]/Amphiphilic Block Copolymer Nanocomposite

    Directory of Open Access Journals (Sweden)

    Alok Chaurasia

    2015-01-01

    Full Text Available We report a supramolecular process for the synthesis of well-defined fullerene (C60/polymer colloid nanocomposites in an aqueous solution via complex formation. A biocompatible triblock poly(4-vinylpyridine-b-polyethylene-b-poly(4-vinylpyridine, P4VP8-b-PEO105-b-P4VP8, was synthesized by atom transfer radical polymerization. The block copolymer formed complexes with C60 in toluene and resulted in fullerene assembly in cluster form. Nanocomposite dispersion in an aqueous solution could be obtained using an aged solution of the polymer/C60/toluene solution by a solvent evaporation technique. The UV-Vis and FTIR spectroscopy confirmed the complex formation of fullerene with the polymer which plays a significant role in controlling the PDI and size of polymer/C60 micelles in the toluene solution. The particle size and morphology of P4VP8-b-PEO105-b-P4VP8 and P4VP8-b-PEO105-b-P4VP8/C60 mixture were studied by dynamic light scattering (DLS and transmission electron microscopy (TEM. In a cytotoxicity test, both pure polymer and the resulting polymer/C60 composite in water showed more than 90% cell viability at 1 mg/mL concentration.

  19. Photodegradable neutral-cationic brush block copolymers for nonviral gene delivery.

    Science.gov (United States)

    Hu, Xianglong; Li, Yang; Liu, Tao; Zhang, Guoying; Liu, Shiyong

    2014-08-01

    We report on the fabrication of a photodegradable gene-delivery vector based on PEO-b-P(GMA-g-PDMAEMA) neutral-cationic brush block copolymers that possess cationic poly(N,N-dimethylaminoethyl methacrylate) (PDMAEMA) brushes for DNA compaction, poly(ethylene oxide) (PEO) as a hydrophilic block, and poly(glycidyl methacrylate) (PGMA) as the backbone. The PEO-b-P(GMA-g-PDMAEMA) copolymers were synthesized through the combination of reversible addition-fragmentation transfer (RAFT) polymerization and postmodification. A photocleavable PEO-based macroRAFT agent was first synthesized; next, the PEO-b-PGMA block copolymer was prepared by RAFT polymerization of GMA; this was followed by a click reaction to introduce the RAFT initiators on the side chains of the PGMA block; then, RAFT polymerization of DMAEMA afforded the PEO-b-P(GMA-g-PDMAEMA) copolymer. The obtained neutral-cationic brush block copolymer could effectively complex plasmid DNA (pDNA) into nanoparticles at an N/P ratio (i.e., the number of nitrogen residues per DNA phosphate) of 4. Upon UV irradiation, pDNA could be released owing to cleavage of the pDNA-binding cationic PDMAEMA side chains as well as the nitrobenzyl ester linkages at the diblock junction point. In addition, in vitro gene transfection results demonstrated that the polyplexes could be effectively internalized by cells with good transfection efficiency, and the UV irradiation protocol could considerably enhance the efficiency of gene transfection. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Poly(ether amide) segmented block copolymers with adipicacid based tetra amide segments

    NARCIS (Netherlands)

    Biemond, G.J.E.; Feijen, Jan; Gaymans, R.J.

    2007-01-01

    Poly(tetramethylene oxide)-based poly(ether ester amide)s with monodisperse tetraamide segments were synthesized. The tetraamide segment was based on adipic acid, terephthalic acid, and hexamethylenediamine. The synthesis method of the copolymers and the influence of the tetraamide concentration,

  1. Printable, Degradable, and Biocompatible Ion Gels from a Renewable ABA Triblock Polyester and a Low Toxicity Ionic Liquid

    Energy Technology Data Exchange (ETDEWEB)

    Tang, Boxin; Schneiderman, Deborah K.; Bidoky, Fazel Zare; Frisbie, C.Daniel; Lodge, Timothy P. (UMM)

    2017-09-15

    We have designed printable, biocompatible, and degradable ion gels by combining a novel ABA triblock aliphatic polyester, poly(ε-decalactone)-b-poly(dl-lactide)-b-poly(ε-decalactone), and a low toxicity ionic liquid, 1-butyl-1-methylpyrrolidinium bistrifluoromethanesulfonylimide ([P14][TFSI]). Due to the favorable compatibility between amorphous poly(dl-lactide) and [P14][TFSI] and the insolubility of the poly(ε-decalactone), the triblock polymer forms self-assembled micellar cross-links similar to thermoplastic elastomers, which ensures similar processing conditions and mechanical robustness during the fabrication of printed electrolyte-gated organic transistor devices. Additionally, the ester backbone in the polymer structure enables efficient hydrolytic degradation of these ion gels compared to those made previously using carbon-backbone polymers.

  2. Synthesis of Inorganic Nanocomposites by Selective Introduction of Metal Complexes into a Self-Assembled Block Copolymer Template

    Directory of Open Access Journals (Sweden)

    Hiroaki Wakayama

    2015-01-01

    Full Text Available Inorganic nanocomposites have characteristic structures that feature expanded interfaces, quantum effects, and resistance to crack propagation. These structures are promising for the improvement of many materials including thermoelectric materials, photocatalysts, and structural materials. Precise control of the inorganic nanocomposites’ morphology, size, and chemical composition is very important for these applications. Here, we present a novel fabrication method to control the structures of inorganic nanocomposites by means of a self-assembled block copolymer template. Different metal complexes were selectively introduced into specific polymer blocks of the block copolymer, and subsequent removal of the block copolymer template by oxygen plasma treatment produced hexagonally packed porous structures. In contrast, calcination removal of the block copolymer template yielded nanocomposites consisting of metallic spheres in a matrix of a metal oxide. These results demonstrate that different nanostructures can be created by selective use of processes to remove the block copolymer templates. The simple process of first mixing block copolymers and magnetic nanomaterial precursors and then subsequently removing the block copolymer template enables structural control of magnetic nanomaterials, which will facilitate their applicability in patterned media, including next-generation perpendicular magnetic recording media.

  3. Main-chain supramolecular block copolymers.

    Science.gov (United States)

    Yang, Si Kyung; Ambade, Ashootosh V; Weck, Marcus

    2011-01-01

    Block copolymers are key building blocks for a variety of applications ranging from electronic devices to drug delivery. The material properties of block copolymers can be tuned and potentially improved by introducing noncovalent interactions in place of covalent linkages between polymeric blocks resulting in the formation of supramolecular block copolymers. Such materials combine the microphase separation behavior inherent to block copolymers with the responsiveness of supramolecular materials thereby affording dynamic and reversible materials. This tutorial review covers recent advances in main-chain supramolecular block copolymers and describes the design principles, synthetic approaches, advantages, and potential applications.

  4. Polystyrene-block-Poly(ionic liquid) Copolymers as Work Function Modifiers in Inverted Organic Photovoltaic Cells.

    Science.gov (United States)

    Park, Jong Baek; Isik, Mehmet; Park, Hea Jung; Jung, In Hwan; Mecerreyes, David; Hwang, Do-Hoon

    2018-02-07

    Interfacial layers play a critical role in building up the Ohmic contact between electrodes and functional layers in organic photovoltaic (OPV) solar cells. These layers are based on either inorganic oxides (ZnO and TiO 2 ) or water-soluble organic polymers such as poly[(9,9-dioctyl-2,7-fluorene)-alt-(9,9-bis(3'-(N,N-dimethylamino)propyl)-2,7-fluorene)] and polyethylenimine ethoxylated (PEIE). In this work, we have developed a series of novel poly(ionic liquid) nonconjugated block copolymers for improving the performance of inverted OPV cells by using them as work function modifiers of the indium tin oxide (ITO) cathode. Four nonconjugated polyelectrolytes (n-CPEs) based on polystyrene and imidazolium poly(ionic liquid) (PSImCl) were synthesized by reversible addition-fragmentation chain transfer polymerization. The ratio of hydrophobic/hydrophilic block copolymers was varied depending on the ratio of polystyrene to the PSImCl block. The ionic density, which controls the work function of the electrode by forming an interfacial dipole between the electrode and the block copolymers, was easily tuned by simply changing the PSImCl molar ratio. The inverted OPV device with the ITO/PS 29 -b-PSImCl 60 cathode achieved the best power conversion efficiency (PCE) of 7.55% among the synthesized block copolymers, exhibiting an even higher PCE than that of the reference OPV device with PEIE (7.30%). Furthermore, the surface properties of the block copolymers films were investigated by contact angle measurements to explore the influence of the controlled hydrophobic/hydrophilic characters on the device performances.

  5. Biodegradable nanocomposite hydrogel structures with enhanced mechanical properties prepared by photo-crosslinking solutions of poly(trimethylene carbonate)-poly(ethylene glycol)-poly(trimethylene carbonate) macromonomers and nanoclay particles

    NARCIS (Netherlands)

    Sharifi, Shahriar; Blanquer, Sebastien; van Kooten, T.G.; Grijpma, Dirk W.

    2012-01-01

    Soft hydrogels with elasticity modulus values lower than 100 kPa that are tough and biodegradable are of great interest in medicine and in tissue engineering applications. We have developed a series of soft hydrogel structures from different methacrylate-functionalized triblock copolymers of

  6. Ion conducting solid polymer electrolytes based on polypentafluorostyrene-b-polyether-b-polypentafluorostyrene prepared by atom transfer radical polymerization

    DEFF Research Database (Denmark)

    Jankova, Katja; Jannasch, P.; Hvilsted, Søren

    2004-01-01

    Novel triblock copolymers based on central poly( ethylene glycol) ( PEG) or poly( ethylene glycol-co-propylene glycol) (PEGPG) blocks with poly( pentafluorostyrene) (PFS) outer blocks were prepared by Atom Transfer Radical Polymerization (ATRP) with polydispersities on the order of 1.2 - 1...

  7. Order-Order Transition of C → sdG → sL → S in ABC Triblock Copolymer Thin Film Induced by Solvent Vapor.

    Science.gov (United States)

    Luo, Chunxia; Huang, Weihuan; Han, Yanchun

    2009-04-01

    The morphology transition of polystyrene-block-poly(butadiene)-block-poly(2-vinylpyridine) (SBV) triblock thin film induced in benzene vapor showing weak selectivity for PS is investigated. The order-order transitions (OOT) in the sequence of core-shell cylinders (C), sphere in 'diblock gyroid' (sdG), sphere in lamella (sL) and sphere (S) are observed. The projection along (111) direction in Gyroid phase (sdG(111)) is found to epitaxially grow from C(001) in the film. Instead of sdG(111), sdG(110)(0.1875) develops to the phase of sL. Consequently, the film experiences the transition sequence of sdG(111) → sdG(211) → sdG(110)(0.25)  → sdG(110)(0.1875) between C and sL. The mechanism is analyzed from the total surface area of the blocks. Copyright © 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Well-defined Polymethylene-Based Co/Terpolymers by Combining Anthracene/Maleimide Diels-Alder Reaction with Polyhomologation

    KAUST Repository

    Hadjichristidis, Nikolaos

    2015-05-26

    A novel strategy towards well-defined polymethylene-based co/terpolymers, by combining anthracene/maleimide Diels-Alder reaction with polyhomologation, is presented. For the synthesis of diblock copolymers the following approach was applied: a) synthesis of α-anthracene-ω-hydroxy- polymethylene by polyhomologation using tri (9-anthracene-methyl propyl ether) borane as initiator, b) synthesis of furan-protected-maleimide-terminated poly (ε-caprolactone) or polyethylene glycol and c). Diels-Alder reaction between the anthracene and maleimide-terminated polymers. In the case of triblock terpolymers the α-anthracene-ω-hydroxy-polymethylene was used as macroinitiator for the ring-opening polymerization of D, L-lactide to afford an anthracene-terminated PM-b-PLA copolymer, followed by Diels-Alder reaction with furan-protected maleimide-terminated poly (ε-caprolactone) or polyethylene glycol to give the triblock terpolymers. All intermediate and final products were characterized by SEC, 1H NMR, UV-VIS spectroscopy and DSC.

  9. [Complex formation between alpha-chymotrypsin and block copolymers based on ethylene and propylene oxide, induced by high pressure].

    Science.gov (United States)

    Topchieva, I N; Sorokina, E M; Kurganov, B I; Zhulin, V M; Makarova, Z G

    1996-06-01

    A new method of formation of non-covalent adducts based on an amphiphilic diblock copolymer of ethylene and propylene oxides with molecular mass of 2 kDa and alpha-chymotrypsin (ChT) under high pressure, has been developed. The composition of the complexes corresponds to seven polymer molecules per one ChT molecule in the pressure range of 1.1 to 400 MPa. The complexes fully retain the catalytic activity. Kinetic constants (Km and kcat) for enzymatic hydrolysis of N-benzoyl-L-tyrosine ethyl ester catalyzed by the complexes are identical with the corresponding values for native ChT. Analysis of kinetics of thermal inactivation of the complexes revealed that the constant of the rate of the slow inactivation step is markedly lower than for ChT.

  10. Application of reactive siloxane prepolymers for the synthesis of thermoplastic poly(ester–siloxanes and poly(ester–ether–siloxanes

    Directory of Open Access Journals (Sweden)

    VESNA V. ANTIC

    2007-02-01

    Full Text Available Thermoplastic poly(ester–siloxanes (TPES and poly(ester–ether–siloxane s, (TPEES, based on poly(butylene terephthalate (PBT as the hard segment and different siloxane-prepolymers as the soft segments, were prepared. The TPES and TPEES were synthesized by catalyzed two-step transesterification from dimethyl terephthalate, (DMT, 1,4-butanediol, (BD and a siloxane-prepolymer. Incorporation of dicarboxypropyl- or disilanol-terminated poly(dimethylsiloxanes (PDMS into the polar poly(butylene terephthalate chains resulted in rather inhomogeneous TPES copolymers, which was a consequence of a prononuced phase separation of the polar and non-polar reactants during synthesis. Two concepts were employed to avoid or reduce phase separation: 1 the use of siloxane-containing triblock prepolymers with hydrophilic terminal blocks, such as ethylene oxide (EO, poly(propylene oxide (PPO or poly(caprolactone (PLC when the terminal blocks serve as a compatibilizer between the extremely non-polar PDMS and the polar DMT and BD, and 2 the use of a high-boiling solvent (1,2,4-trichlorobenzene during the first phase of the reaction. Homogeneity was significantly improved in the case of copolymers based on PCL–PDMS–PCL.

  11. Improved flotation recovery via hydrophobicity adjustment

    Energy Technology Data Exchange (ETDEWEB)

    Philip Ofori; Graham O' Brien; Bruce Firth; Clint McNally; Anh Nguyen [University of Queensland, Qld. (Australia). CSIRO

    2009-03-15

    The main goal of this project was to examine a new approach to maximising the recovery of product specification coal during coal flotation using new generation reagents complemented by the use of the Coal Grain Analysis tool. Laboratory flotation experiments in which the novel reagents were employed as promoters by adding small amounts before adding conventional collector (diesel oil) showed that flotation recovery was significantly increased with only a small product quality (ash%) penalty. The groups of reagents used included surfactants from the group of tri-block copolymers of polyethylene oxide (PEO) and polypropylene oxide (PPO) often denoted as PEO/PPO/PEO or the reverse block copolymer PPO/PEO/PPO. Analysis of the flotation products using the grain analysis technique determined that whilst the recoveries of most grain types were improved, the coarse composite grains which were the components targeted for enhancement showed the most improvement. Plant scale test results confirmed the laboratory findings with remarkable improvements in recovery achieved for all components, especially for coarse inertite and composite grains. The difficult to float coals that are lost at this plant may be recovered without significant modification to the fines circuit by the use of targeted reagents.

  12. Metallo-supramolecular block copolymer micelles

    NARCIS (Netherlands)

    Gohy, J.M.W.

    2009-01-01

    Supramolecular copolymers have become of increasing interest in recent years in the search for new materials with tunable properties. In particular, metallo-supramolecular block copolymers in which metal-ligand complexes are introduced in block copolymer architectures, have known important progress,

  13. Multi-template synthesis of hierarchically porous carbon spheres with potential application in supercapacitors

    NARCIS (Netherlands)

    Zhou, Weizheng; Lin, Zhixing; Tong, Gangsheng; Stoyanov, Simeon D.; Yan, Deyue; Mai, Yiyong; Zhu, Xinyuan

    2016-01-01

    A new and simple multi-template approach towards hierarchical porous carbon (HPC) materials was reported. HPC spheres were prepared by using hierarchical silica capsules (HSCs) as the hard template and triblock copolymer Pluronic P123 as the soft template. Three types of pores were tunably

  14. Rheological Properties of Associative Star Polymers in Aqueous Solutions: Effect of Hydrophobe Length and Polymer Topology

    DEFF Research Database (Denmark)

    Hietala, Sami; Strandman, Satu; Jarvi, Paula

    2009-01-01

    triblock copolymer. These polymers, synthesized by atom transfer radical polymerization (ATRP), were found to form hydrogels due to intermolecular association originating from the PS blocks. The increasing length of the PS block was observed to lead to more elastic networks due to increased hydrophobic...

  15. Chimeric peptide beacons: a direct polypeptide analog of DNA molecular beacons†

    OpenAIRE

    Oh, Kenneth J.; Cash, Kevin J.; Lubin, Arica A.; Plaxco, Kevin W.

    2007-01-01

    We have developed a new biosensor architecture, which is comprised of a polypeptide–peptide nucleic acid tri-block copolymer and which we have termed chimeric peptide beacons (CPB), that generates an optical output via a mechanism analogous to that employed in DNA-based molecular beacons.

  16. A thermo-responsive and photo-polymerizable chondroitin sulfate-based hydrogel for 3D printing applications

    NARCIS (Netherlands)

    Abbadessa, A.; Blokzijl, M. M.; Mouser, V. H. M.; Marica, P.; Malda, J.; Hennink, W. E.; Vermonden, T.

    2016-01-01

    The aim ofthis study was to design a hydrogel system based on methacrylated chondroitin sulfate (CSMA) and a thermo-sensitive poly(N-(2-hydroxypropyl) methacrylamide-mono/dilactate)-polyethylene glycol triblock copolymer (M15P10) as a suitable material for additive manufacturing of scaffolds. CSMA

  17. Acute toxicity evaluation of in situ gel-forming controlled drug delivery system based on biodegradable poly(ε-caprolactone)-poly(ethylene glycol)-poly(ε-caprolactone) copolymer

    International Nuclear Information System (INIS)

    Fang Fang; Gong Changyang; Dong Pengwei; Fu Shaozhi; Gu Yingchun; Guo Gang; Zhao Xia; Wei Yuquan; Qian Zhiyong

    2009-01-01

    In this paper, biodegradable poly(ε-caprolactone)-poly(ethylene glycol)-poly(ε-caprolactone) (PCL-PEG-PCL) triblock copolymer was synthesized, and was characterized by FTIR, 1 H-NMR and GPC. The PCL-PEG-PCL/dimethyl sulfoxide (DMSO) solution displayed in situ gelling behavior when subcutaneously injected into the body. Toxicity tests and a histopathological study were performed in BALB/c mice. We focused mainly on acute organ toxicity of BALB/c mice by subcutaneous injection. In the acute toxicity test, the dose of subcutaneous injection was 5 g/kg body weight (b.w.), and the mice were observed continuously for 14 days. For the histopathological study, samples including heart, lung, liver, kidneys, spleen, stomach and intestine were histochemically prepared and stained with hematoxylin-eosin for histopathological examination. No mortality or significant signs of toxicity were observed during the whole observation period, and there is no significant lesion to be shown in histopathological study of major organs in the mice. Therefore, the maximal tolerance dose of dimethyl sulfoxide (DMSO) solution of PCL-PEG-PCL copolymer by subcutaneous injection was calculated to be higher than 5 g/kg b.w. Therefore, the PCL-PEG-PCL/DMSO system was thought to be non-toxic after subcutaneous injection, and it might be a candidate for an in situ gelling controlled drug delivery system.

  18. Mixed phase titania nanocomposite codoped with metallic silver and vanadium oxide: New efficient photocatalyst for dye degradation

    Energy Technology Data Exchange (ETDEWEB)

    Yang Xia [School of Urban and Environmental Sciences, Northeast Normal University, Changchun 130024 (China); School of Chemistry, Northeast Normal University, Changchun 130024 (China); Ma Fengyan; Li Kexin; Guo Yingna; Hu Jianglei; Li Wei [School of Chemistry, Northeast Normal University, Changchun 130024 (China); Huo Mingxin [School of Urban and Environmental Sciences, Northeast Normal University, Changchun 130024 (China); Guo Yihang, E-mail: guoyh@nenu.edu.cn [School of Chemistry, Northeast Normal University, Changchun 130024 (China)

    2010-03-15

    Titania nanocomposite codoped with metallic silver and vanadium oxide was prepared by a one-step sol-gel-solvothermal method in the presence of a triblock copolymer surfactant (P123). The resulting Ag/V-TiO{sub 2} three-component junction system exhibited an anatase/rutile (weight ratio of 73.8:26.2) mixed phase structure, narrower band gap (2.25 eV), and extremely small particle sizes (ca. 12 nm) with metallic Ag particles well distributed on the surface of the composite. The Ag/V-TiO{sub 2} nanocomposite was used as the visible- and UV-light-driven photocatalyst to degrade dyes rhodamine B (RB) and coomassie brilliant blue G-250 (CBB) in an aqueous solution. At 1.8% Ag and 4.9% V doping, the Ag/V-TiO{sub 2} system exhibited the highest visible- as well as UV-light photocatalytic activity; additionally, the activity of the three-component system exceeded that of Degussa P25, pure TiO{sub 2}, single-doped TiO{sub 2} system (Ag/TiO{sub 2} or V-TiO{sub 2}) as well as P123-free-Ag/V-TiO{sub 2} codoped system. The reasons for this enhanced photocatalytic activity were revealed.

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

    Science.gov (United States)

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

    2014-03-01

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

  20. Synthesis of an amphiphilic dendrimer-like block copolymer and its application on drug delivery

    KAUST Repository

    Wang, Shuaipeng

    2014-10-27

    Dendrimer-like amphiphilic copolymer is a kind of three-dimensional spherical structure polymer. An amphiphilic dendrimer-like diblock copolymer, PEEGE-G2-b-PEO(OH)12, constituted of a hydrophobic poly(ethoxyethyl glycidol ether) inner core and a hydrophilic poly(ethylene oxide) outer layer, has been successfully synthesized by the living anionic ring-opening polymerization method. The intermediates and targeted products were characterized with 1H NMR spectroscopy and gel permeation chromatography. The application on drug delivery of dendrimer-like diblock copolymer PEEGE-G2-b-PEO(OH)12 using DOX as a model drug was also studied. The drug loading content and encapsulation efficiency were found at 13.07% and 45.75%, respectively. In vitro release experiment results indicated that the drug-loaded micelles exhibited a sustained release behavior under acidic media.

  1. Electrochromic properties of a novel low band gap conductive copolymer

    Energy Technology Data Exchange (ETDEWEB)

    Yigitsoy, Basak; Varis, Serhat; Tanyeli, Cihangir; Akhmedov, Idris M.; Toppare, Levent [Department of Chemistry, Middle East Technical University, 06531 Ankara (Turkey)

    2007-07-10

    A copolymer of 2,5-di(thiophen-2-yl)-1-p-tolyl-1H-pyrrole (DTTP) with 3,4-ethylene dioxythiophene (EDOT) was electrochemically synthesized. The resultant copolymer P(DTTP-co-EDOT) was characterized via cyclic voltammetry, FTIR, SEM, conductivity measurements and spectroelectrochemistry. Copolymer film has distinct electrochromic properties. It has four different colors (chestnut, khaki, camouflage green, and blue). At the neutral state {lambda}{sub max} due to the {pi}-{pi}{sup *} transition was found to be 487 nm and E{sub g} was calculated as 1.65 eV. Double potential step chronoamperometry experiment shows that copolymer film has good stability, fast switching time (less than 1 s) and good optical contrast (20%). An electrochromic device based on P(DTTP-co-EDOT) and poly(3,4-ethylenedioxythiophene) (PEDOT) was constructed and characterized. The device showed reddish brown color at -0.6 V when the P(DTTP-co-EDOT) layer was in its reduced state; whereas blue color at 2.0 V when PEDOT was in its reduced state and P(DTTP-co-EDOT) layer was in its oxidized state. At 0.2 V intermediate green state was observed. Maximum contrast (%{delta}T) and switching time of the device were measured as 18% and 1 s at 615 nm. ECD has good environmental and redox stability. (author)

  2. Facile Synthesis of Well-Defined MDMO-PPV Containing (TriBlock—Copolymers via Controlled Radical Polymerization and CuAAC Conjugation

    Directory of Open Access Journals (Sweden)

    Neomy Zaquen

    2015-02-01

    Full Text Available A systematic investigation into the chain transfer polymerization of the so-called radical precursor polymerization of poly(p-phenylene vinylene (PPV materials is presented. Polymerizations are characterized by systematic variation of chain transfer agent (CTA concentration and reaction temperature. For the chain transfer constant, a negative activation energy of −12.8 kJ·mol−1 was deduced. Good control over molecular weight is achieved for both the sulfinyl and the dithiocarbamate route (DTC. PPVs with molecular weights ranging from thousands to ten thousands g·mol−1 were obtained. To allow for a meaningful analysis of the CTA influence, Mark–Houwink–Kuhn–Sakurada (MHKS parameters were determined for conjugated MDMO-PPV ([2-methoxy-5-(3',7'-dimethyloctyloxy]-1,4-phenylenevinylene to α = 0.809 and k = 0.00002 mL·g−1. Further, high-endgroup fidelity of the CBr4-derived PPVs was proven via chain extension experiments. MDMO-PPV-Br was successfully used as macroinitiator in atom transfer radical polymerization (ATRP with acrylates and styrene. A more polar PPV counterpart was chain extended by an acrylate in single-electron transfer living radical polymerization (SET-LRP. In a last step, copper-catalyzed azide alkyne cycloaddition (CuAAC was used to synthesize block copolymer structures. Direct azidation followed by macromolecular conjugation showed only partial success, while the successive chain extension via ATRP followed by CuAAC afforded triblock copolymers of the poly(p-phenylene vinylene-block-poly(tert-butyl acrylate-block-poly(ethylene glycol (PPV-b-PtBuA-b-PEG.

  3. Study of the therapeutic benefit of cationic copolymer administration to vascular endothelium under mechanical stress

    Science.gov (United States)

    Giantsos-Adams, Kristina; Lopez-Quintero, Veronica; Kopeckova, Pavla; Kopecek, Jindrich; Tarbell, John M.; Dull, Randal

    2015-01-01

    Pulmonary edema and the associated increases in vascular permeability continue to represent a significant clinical problem in the intensive care setting, with no current treatment modality other than supportive care and mechanical ventilation. Therapeutic compound(s) capable of attenuating changes in vascular barrier function would represent a significant advance in critical care medicine. We have previously reported the development of HPMA-based copolymers, targeted to endothelial glycocalyx that are able to enhance barrier function. In this work, we report the refinement of copolymer design and extend our physiological studies todemonstrate that the polymers: 1) reduce both shear stress and pressure-mediated increase in hydraulic conductivity, 2) reduce nitric oxide production in response to elevated hydrostatic pressure and, 3) reduce the capillary filtration coefficient (Kfc) in an isolated perfused mouse lung model. These copolymers represent an important tool for use in mechanotransduction research and a novel strategy for developing clinically useful copolymers for the treatment of vascular permeability. PMID:20932573

  4. MesoDyn simulation study on the phase morphologies of Miktoarm PEO-b-PMMA copolymer doped by nanoparticles

    Science.gov (United States)

    Mu, Dan; Li, Jian-Quan; Feng, Sheng-Yu

    2013-03-01

    The compatibility of six groups of 12 miktoarm poly(ethylene oxide)-block-poly(methyl methacrylate) (PEO-b-PMMA) copolymers is studied at 270, 298 and 400 K via mesoscopic modeling. The values of the order parameters depend on both the architectures of the block copolymers and the simulation temperature, while the tendency to change of the order parameters at low temperature, such as 270 and 298 K, is nearly the same. However, the values of order parameters of the copolymer in the same group are the same at high temperature, i.e. 400 K. Obviously, temperature has a more obvious effect on long and PEO-rich chains. A study of plain copolymers doped with nanoparticles shows that the microscopic phase is influenced by not only the properties of the nanoparticles, such as the size, number and density, but also the composition and architecture of copolymers. Increasing the size and the number of the nanoparticles used as a dopant plays the most significant role on determining the phase morphologies of the copolymers at lower and higher temperature, respectively. In paricular, the 23141 and 23241-type copolymers, which are both of PEO-rich composition, presents microscopic phase separation as perforated lamallae phase morphologies at 400 K, alternated with PEO and PMMA components.

  5. Micellization of symmetric PEP-PEO block copolymers in water molecular weight dependence

    CERN Document Server

    Kaya, H; Allgaier, J; Stellbrink, J; Richter, D

    2002-01-01

    The micellar behaviour of the amphiphilic block copolymer poly-(ethylene-propylene)-poly-(ethylene oxide) (PEP-PEO) in aqueous solution has been studied with small-angle neutron scattering. The polymer was studied over a wide range of molecular weights, always keeping the volume of the blocks equal. The scattering behaviour of the solutions showed that a morphological transition takes place upon lowering the molecular weight. The high molecular weight block copolymers all build spherical, monodisperse micelles with large aggregation numbers. At low molecular weights, however, cylindrical micelles are formed. An interesting intermediate case is represented by the PEP2-PEO2 system, in which a morphological transition occurs upon dilution. (orig.)

  6. Engineering with macromolecules : from supramolecular chemistry to defined nanomaterials

    NARCIS (Netherlands)

    Lohmeijer, B.G.G.; Gohy, J.M.W.; Schubert, U.S.

    2003-01-01

    By uniting concepts from polymer chem. and supramol. chem. we present a new approach for the prepn. of functional nano-materials. Amphiphilic diblock and triblock copolymers were constructed in such a way that a bisterpyridine ruthenium complex acts as the linker between the two constituting blocks.

  7. A thermo-responsive and photo-polymerizable chondroitin sulfate-based hydrogel for 3D printing applications

    NARCIS (Netherlands)

    Abbadessa, A|info:eu-repo/dai/nl/369480376; Blokzijl, M M; Mouser, V H M; Marica, P; Malda, J|info:eu-repo/dai/nl/412461099; Hennink, W E|info:eu-repo/dai/nl/070880409; Vermonden, T|info:eu-repo/dai/nl/275124517

    2016-01-01

    The aim of this study was to design a hydrogel system based on methacrylated chondroitin sulfate (CSMA) and a thermo-sensitive poly(N-(2-hydroxypropyl) methacrylamide-mono/dilactate)-polyethylene glycol triblock copolymer (M15P10) as a suitable material for additive manufacturing of scaffolds. CSMA

  8. Room-Temperature-Cured Copolymers for Lithium Battery Gel Electrolytes

    Science.gov (United States)

    Meador, Mary Ann B.; Tigelaar, Dean M.

    2009-01-01

    Polyimide-PEO copolymers (PEO signifies polyethylene oxide) that have branched rod-coil molecular structures and that can be cured into film form at room temperature have been invented for use as gel electrolytes for lithium-ion electric-power cells. These copolymers offer an alternative to previously patented branched rod-coil polyimides that have been considered for use as polymer electrolytes and that must be cured at a temperature of 200 C. In order to obtain sufficient conductivity for lithium ions in practical applications at and below room temperature, it is necessary to imbibe such a polymer with a suitable carbonate solvent or ionic liquid, but the high-temperature cure makes it impossible to incorporate and retain such a liquid within the polymer molecular framework. By eliminating the high-temperature cure, the present invention makes it possible to incorporate the required liquid.

  9. The radiation crosslinking of ethylene copolymers

    International Nuclear Information System (INIS)

    Burns, N.M.

    1979-01-01

    The enhanced radiation crosslinking tendency of ethylene-vinyl acetate and ethylene-ethyl acrylate copolymers over ethylene homopolymer is proportional to the comonomer content. This is caused by an increase in the amorphous polymer content and by structure-related factors. The copolymers crosslink by a random process that for ethylene-vinyl acetate copolymer involves some crosslinking through the acetoxy group of the comonomer. While knowledge of the process for the crosslinking of ethylene-ethyl acrylate copolymer is less certain, it is currently believed to occur primarily at the branch point on the polymer backbone. Data relating comonomer content and the molecular weight of the copolymers to the radiation crosslinking levels realized were developed to aid in resin selection by the formulator. Triallyl cyanurate cure accelerator was found to be less effective in ethylene-vinyl acetate copolymer than in homopolymer and to have no effect on gel development in ethylene-ethyl acrylate copolymer. (author)

  10. Structure and ionic conductivity of block copolymer electrolytes over a wide salt concentration range

    Science.gov (United States)

    Chintapalli, Mahati; Le, Thao; Venkatesan, Naveen; Thelen, Jacob; Rojas, Adriana; Balsara, Nitash

    Block copolymer electrolytes are promising materials for safe, long-lasting lithium batteries because of their favorable mechanical and ion transport properties. The morphology, phase behavior, and ionic conductivity of a block copolymer electrolyte, SEO mixed with LiTFSI was studied over a wide, previously unexplored salt concentration range using small angle X-ray scattering, differential scanning calorimetry and ac impedance spectroscopy, respectively. SEO exhibits a maximum in ionic conductivity at twice the salt concentration that PEO, the homopolymer analog of the ion-containing block, does. This finding is contrary to prior studies that examined a more limited range of salt concentrations. In SEO, the phase behavior of the PEO block and LiTFSI closely resembles the phase behavior of homopolymer PEO and LiTFSI. The grain size of the block copolymer morphology was found to decrease with increasing salt concentration, and the ionic conductivity of SEO correlates with decreasing grain size. Structural effects impact the ionic conductivity-salt concentration relationship in block copolymer electrolytes. SEO: polystyrene-block-poly(ethylene oxide); also PS-PEO LiTFSI: lithium bis(trifluoromethanesulfonyl imide

  11. Nanostructured synthetic carbons obtained by pyrolysis of spherical acrylonitrile/divinylbenzene copolymers.

    Directory of Open Access Journals (Sweden)

    Danish J Malik

    Full Text Available Novel carbon materials have been prepared by the carbonization of acrylonitrile (AN/divinylbenzene (DVB suspension porous copolymers having nominal crosslinking degrees in the range of 30-70% and obtained in the presence of various amounts of porogens. The carbons were obtained by pre-oxidation of AN/DVB copolymers at 250-350°C in air followed by pyrolysis at 850°C in an N(2 atmosphere. Both processes were carried out in one furnace and the resulting material needed no further activation. Resulting materials were characterized by XPS and low temperature nitrogen adsorption/desorption. It was found that maximum pyrolysis yield was ca. 50% depending on the oxidation conditions but almost independent of the crosslinking degree of the polymers. Porous structure of the carbons was characterized for the presence of micropores and macropores, when obtained from highly crosslinked polymers or polymers oxidized at 350°C and meso- and macropores in all other cases. The latter pores are prevailing in the structure of carbons obtained from less porous AN/DVB resins. Specific surface area (BET of polymer derived carbons can vary between 440 m(2/g and 250 m(2/g depending on the amount of porogen used in the synthesis of the AN/DVB polymeric precursors.

  12. A facile synthesis of poly(aniline-co-o-bromoaniline) copolymer: Characterization and application as semiconducting material

    Science.gov (United States)

    Mahudeswaran, A.; Vivekanandan, J.; Vijayanand, P. S.; Kojima, T.; Kato, S.

    2016-01-01

    Poly(aniline-co-o-bromoaniline) (p(an-co-o-BrAn)) copolymer has been synthesized using chemical oxidation method in the hydrochloric acid medium. Copolymerization of aniline with o-bromoaniline of different compositions, such as 1:1, 1:2, 2:1, 1:3 and 3:1 molar ratios were prepared. The synthesized copolymer is soluble in polar solvents like dimethyl sulphoxide (DMSO), dimethyl formamide (DMF), Tetrahydrofuran (THF) and 1-methyl 2-pyrrolidone (NMP). The copolymer is analyzed by various characterization techniques, such as FTIR, UV-Visible (UV-Vis) spectroscopy, X-ray diffraction (XRD), conductivity, Differential scanning calorimetry (DSC) and scanning electron microscopy (SEM). FTIR spectrum confirms the characteristic peaks of the copolymer containing benzenoid and quinoid ring stretching. UV spectrum reveals the formation of π-π∗ transition and n-π∗ transition between the energy levels. XRD peaks reveal that the copolymer possesses amorphous nature. Morphological study reveals that the agglomerated particles form globular structure and size of the each particle is about 100 nm. The electrical conductivity of the copolymers is found in the range of 10-5Scm-1. These organic semiconductor materials can be used to fabricate thinner and cheaper environmental friendly optoelectronic devices that will replace the conventional inorganic semiconductors.

  13. Preparations and characterizations of tunable and multicolored electrochromic copolymers derived from a novel star-shaped monomer and BEDOT-V

    International Nuclear Information System (INIS)

    Wang, Kai; Yang, Wenge; Hu, Yonghong; Kai, Yumei; Shi, Ying

    2014-01-01

    A novel star-shaped monomer 1,3,5-Tri[2-(3,4-ethylenedioxythien-2-yl)vin-1-yl]benzene (TEDOT-V-B) was synthesized by Wittig coupling reaction. The copolymers with BEDOT-V at different feed ratios were prepared onto the ITO-coated glass by cyclic voltammetry (CV) method and the electrochromic properties were reported. The influences of different feed ratios on the spectroelectrochemical and kinetic properties were investigated. Spectroelectrochemical studies indicated that the maximum absorption wavelengths of the copolymer films bathochromically shifted with feed ratios. In addition, the copolymers had tunable and low band gaps. When the feed ratio of BEDOT-V-B/BEDOT-V was 1:3, the copolymer film showed the fastest oxidation switching time of 0.9s (567 nm) and 0.9s (967 nm) and the fastest reduction switching time of 0.8s (567 nm) and 0.9s (967 nm). Compared with PBEDOT-V, the copolymers showed tunable and multicolored electrochromism through feed ratios and the RGB colors were achieved. Additionally, the surface morphology of the copolymer film was investigated by scanning electron microscope (SEM)

  14. N-containing carbons from styrene-divinylbenzene copolymer by urea treatment

    Energy Technology Data Exchange (ETDEWEB)

    Zhuravsky, Sergey V.; Kartel, Mykola T.; Tarasenko, Yuriy O. [Chuiko Institute of Surface Chemistry, National Academy of Sciences of Ukraine, 17 General Naumov Street, Kiev, 03164 (Ukraine); Villar-Rodil, Silvia [Instituto Nacional del Carbon, INCAR-CSIC, Apartado 73, 33080 Oviedo (Spain); Dobos, Gabor [Department of Atomic Physics, Budapest University of Technology and Economics, H-1521 Budapest (Hungary); Toth, Ajna [Department of Physical Chemistry and Materials Science, Budapest University of Technology and Economics, H-1521 Budapest, PO Box 92 (Hungary); Tascon, Juan M.D. [Instituto Nacional del Carbon, INCAR-CSIC, Apartado 73, 33080 Oviedo (Spain); Laszlo, Krisztina, E-mail: klaszlo@mail.bme.hu [Department of Physical Chemistry and Materials Science, Budapest University of Technology and Economics, H-1521 Budapest, PO Box 92 (Hungary)

    2012-01-15

    N-containing synthetic carbons with narrow porosity were prepared from a chlorinated styrene and divinylbenzene copolymer by a multistep method with a yield of 34 wt%. Surface chemical treatment and thermal carbonization of the starting copolymer was monitored by urea impregnation. Steam activation, oxidation and an additional heat treatment gave the final product. The synthesis route was designed in a cost-effective way. The porosity and the concentration of the introduced nitrogen atoms were determined at each step. The final product has a surface area of 1135 m{sup 2}/g. More than 70% of the pore volume comes from micropores with an average width of 0.7 nm. The 2.3 at.% surface nitrogen atoms are distributed among five detectable species, of which about 44% is quaternary nitrogen.

  15. Highly Efficient One-Pot Synthesis of COS-Based Block Copolymers by Using Organic Lewis Pairs.

    Science.gov (United States)

    Yang, Jia-Liang; Cao, Xiao-Han; Zhang, Cheng-Jian; Wu, Hai-Lin; Zhang, Xing-Hong

    2018-01-31

    A one-pot synthesis of block copolymer with regioregular poly(monothiocarbonate) block is described via metal-free catalysis. Lewis bases such as guanidine, quaternary onium salts, and Lewis acid triethyl borane (TEB) were equivalently combined and used as the catalysts. By using polyethylene glycol (PEG) as the macromolecular chain transfer agent (CTA), narrow polydispersity block copolymers were obtained from the copolymerization of carbonyl sulfide (COS) and propylene oxide (PO). The block copolymers had a poly(monothiocarbonate) block with perfect alternating degree and regioregularity. Unexpectedly, the addition of CTA to COS/PO copolymerization system could dramatically improve the turnover frequency (TOF) of PO (up to 240 h -1 ), higher than that of the copolymerization without CTA. In addition, the conversion of CTA could be up to 100% in most cases, as revealed by ¹H NMR spectra. Of consequence, the number-average molecular weights ( M n s) of the resultant block copolymers could be regulated by varying the feed ratio of CTA to PO. Oxygen-sulfur exchange reaction (O/S ER), which can generate randomly distributed thiocarbonate and carbonate units, was effectively suppressed in all of the cases in the presence of CTA, even at 80 °C. This work presents a versatile method for synthesizing sulfur-containing block copolymers through a metal-free route, providing an array of new block copolymers.

  16. In situ preparation of magnetic nanocomposites of goethite in a styrene-maleimide copolymer template

    International Nuclear Information System (INIS)

    Sepulveda-Guzman, S.; Perez-Camacho, O.; Rodriguez-Fernandez, O.; Garcia-Zamora, M.

    2005-01-01

    Magnetic composites were prepared by in situ precipitation of α-FeOOH (goethite) using a new styrene-co-N-4 carboxybutylmaleimide cross-linked copolymer as template. Thermogravimetric analysis showed iron oxide content in the composites up to 45%. The iron oxide phase was identified as goethite by X-ray diffraction analysis. Transmission electron microscopy revealed that the crosslinking extent of polymeric templates affected both the shape and dimension of the goethite particles, and consequently, the magnetic behavior of the polymer/iron oxide composites

  17. The influence of chain rigidity and the degree of sulfonation on the morphology of block copolymers as nano reactor

    Science.gov (United States)

    Hong, K.; Zhang, X.

    2005-03-01

    Polyelectrolyte block copolymer was used to form an ordered domain of ionic block as a ``nanoreactor'' due to its ability to bind oppositely charged metal ion, Zn^2+, Fe^2+ etc. The purpose of our research is to investigate the controllability of the size and morphology of domains (inorganic nano particles) by changing backbone stiffness, the charge density and the volume fraction of ionic block. Poly(styrene sulfonate) (PSS), which backbone is flexible, and poly(cyclohexadiene sulfonate) (PCHDS), which backbone is ``semiflexible'', were used as ionic blocks. We synthesized PtBS-PSS and PS-PCHDS with various degree of sulfonation and the volume fraction. Zinc oxide (ZnO) nano particles successfully formed in the ionic domain of microphase separated block copolymers. We used SANS to characterize the morphology of block copolymers and TEM for block copolymer containing ZnO nano particles. Our experimental results show that the chemistry of ``sulfonation'' of block copolymers can be successfully used to synthesize nano composite materials.

  18. Release behavior and intra-articular biocompatibility of celecoxib-loaded acetyl-capped PCLA-PEG-PCLA thermogels

    NARCIS (Netherlands)

    Petit, Audrey|info:eu-repo/dai/nl/371748461; Sandker, Marjan; Müller, Benno; Meyboom, Ronald; van Midwoud, Paul; Bruin, Peter; Redout, Everaldo M; Versluijs-Helder, Marjan|info:eu-repo/dai/nl/311472699; van der Lest, Chris H A; Buwalda, Sytze J|info:eu-repo/dai/nl/339146850; de Leede, Leo G J; Vermonden, Tina|info:eu-repo/dai/nl/275124517; Kok, Robbert Jan|info:eu-repo/dai/nl/170678326; Weinans, Harrie; Hennink, Wim E|info:eu-repo/dai/nl/070880409

    In this study, we investigated the in vitro and in vivo properties and performance of a celecoxib-loaded hydrogel based on a fully acetyl-capped PCLA-PEG-PCLA triblock copolymer. Blends of different compositions of celocoxib, a drug used for pain management in osteoarthritis, and the acetyl-capped

  19. ATRP of (meth)acrylates initiated with a bifunctional initiator bearing trichloromethyl functional groups and structural analysis of the formed polymer

    Czech Academy of Sciences Publication Activity Database

    Malinowska, A.; Vlček, Petr; Kříž, Jaroslav; Toman, Luděk; Látalová, Petra; Janata, Miroslav; Masař, Bohumil

    2005-01-01

    Roč. 46, č. 1 (2005), s. 5-14 ISSN 0032-3861 R&D Projects: GA ČR(CZ) GA203/01/0513 Institutional research plan: CEZ:AV0Z40500505 Keywords : ATRP * ABA triblock copolymers * methyl methacrylate Subject RIV: CD - Macromolecular Chemistry Impact factor: 2.849, year: 2005

  20. Synthesis of Medium-Chain-Length Polyhydroxyalkanoate Homopolymers, Random Copolymers, and Block Copolymers by an Engineered Strain of Pseudomonas entomophila.

    Science.gov (United States)

    Wang, Ying; Chung, Ahleum; Chen, Guo-Qiang

    2017-04-01

    Medium-chain-length polyhydroxyalkanoates (mcl-PHAs), widely used in medical area, are commonly synthesized by Pseudomonas spp. This study tries to use β-oxidation pathways engineered P. entomophila to achieve single source of a series of mcl-monomers for microbial production of PHA homopolymers. The effort is proven successful for the first time to obtain a wide range of mcl-PHA homopolymers from engineered P. entomophila LAC23 grown on various fatty acids, respectively, ranging from poly(3-hydroxyheptanoate) to poly(3-hydroxytetradecanoate). Effects of a PHA monomer chain length on thermal and crystallization properties including the changes of T m , T g , and T d5% are investigated. Additionally, strain LAC23 is used to synthesize random copolymers of 3-hydroxyoctanoate (3HO) and 3-hydroxydodecanoate (3HDD) or 3-hydroxytetradecanoates, their compositions could be controlled by adjusting the ratios of two related fatty acids. Meanwhile, block copolymer P(3HO)-b-P(3HDD) is synthesized by the same strain. It is found for the first time that even- and odd number mcl-PHA homopolymers have different physical properties. When the gene of the PHA synthase in the engineered P. entomophila is replaced by phaC from Aeromonas hydrophila 4AK4, poly(3-hydroxybutyrate-co-30 mol%-3-hydroxyhexanoate) is synthesized. Therefore, P. entomophila can be used to synthesize the whole range of PHA (C7-C14) homopolymers, random- and block copolymers. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Molecular Mobility in Phase Segregated Bottlebrush Block Copolymer Melts

    Science.gov (United States)

    Yavitt, Benjamin; Gai, Yue; Song, Dongpo; Winter, H. Henning; Watkins, James

    We investigate the linear viscoelastic behavior of poly(styrene)-block-poly(ethylene oxide) (PS-b-PEO) brush block copolymer (BBCP) materials over a range of vol. fractions and with side chain lengths below the entanglement molecular weights. The high chain mobility of the brush architecture results in rapid micro-phase segregation of the brush copolymer segments, which occurs during thermal annealing at mild temperatures. Master curves of the dynamic moduli were obtained by time-temperature superposition. The reduced degree of chain entanglements leads to a unique liquid-like rheology similar to that of bottlebrush homopolymers, even in the phase segregated state. We also explore the alignment of phase segregated domains at exceptionally low strain amplitudes (γ = 0.01) and mild processing temperatures using small angle X-ray scattering (SAXS). Domain orientation occurred readily at strains within the linear viscoelastic regime without noticeable effect on the moduli. This interplay of high molecular mobility and rapid phase segregation that are exhibited simultaneously in BBCPs is in contrast to the behavior of conventional linear block copolymer (LBCP) analogs and opens up new possibilities for processing BBCP materials for a wide range of nanotechnology applications. NSF Center for Hierarchical Manufacturing at the University of Massachusetts, Amherst (CMMI-1025020).

  2. Biosolar energy generation and harvesting from biomolecule-copolymer hybrid systems

    Science.gov (United States)

    Chu, Bong-Chieh Benjamin

    Alternative energy sources have become an increasingly important topic as energy needs outpace supply. Furthermore, as the world moves into the digital age of portable electronics, highly efficient and lightweight energy sources will need to be developed. Current technology, such as lithium ion batteries, provide enough power to run portable electronics for hours or days, but can still allow for improvement in their power density (W/kg). Utilizing energy-transducing membrane proteins, which are by nature highly efficient, it is possible to engineer biological-based energy sources with energy densities far greater than any solid-state systems. Furthermore, solar powered membrane proteins have the added benefit of a virtually unlimited supply of energy. This work has developed protein-polymer hybrid films and nanoscale vesicles for a variety of applications from fuel-cell technology to biological-based photovoltaics. Bacteriorhodopsin (BR), a light-activated proton pump, and Cytochrome C Oxidase (COX), a protein involved in the electron transport chain in mitochondria, were reconstituted into biomimetic triblock copolymer membranes. Block copolymer membranes mimic the amphiphilic nature of a natural lipid bilayer but exhibit greater mechanical stability due to UV-polymerizable endgroups. In BR/COX functionalized nanovesicles, proton gradients generated by the light-activated proton pumping of BR are used to drive COX in reverse to generate electrons, providing a hybrid biologically-active polymer to convert solar energy to chemical energy, and finally to electrical energy. This work has found protein activity in planar membranes through the photoelectric current generation by BR and the proton pumping activity of BR-functionalized polymer membranes deposited onto proton exchange membranes, as well as the coupled functionality of BR and COX through current generation in cyclic voltammetry and direct current measurements. Current switching between light and dark

  3. Radiation resistance of ethylene-styrene copolymers

    International Nuclear Information System (INIS)

    Matsumoto, Kaoru; Ikeda, Masaaki; Ohki, Yoshimichi; Kusama, Yasuo; Harashige, Masahiro; Yazaki, Fumihiko.

    1988-01-01

    In this paper, the radiation resistance of ethylene-styrene copolymer, a polymeric resin developed newly by the authors, is reported. Resin examined were five kinds of ethylene-styrene copolymers: three random and two graft copolymers with different styrene contents. Low-density polyethylene was used as a reference. The samples were irradiated by 60 Co γ-rays to total absorbed doses up to 10 MGy. The mechanical properties of the smaples were examined. Infrared spectroscopy, differential scanning calorimetry and X-ray scattering techniques were used to examine the morphology of the samples. The random copolymers are soft and easy to extend, because benzene rings which exisist highly at random hinder the crystallization. As for the radiation resistance, they are highly resistant to γ-rays in the aspects of carbonyl group formation, gel formation, and elongation. Further, they show even better radiation resistance when proper additives were compounded in. The graft copolymers are hard to extend, because they consist of segregated polystyrene and polyethylene regions which are connected with each other. The tensile strength of irradiated graft copolymers does not decrease below that of unirradiated copolymers, up to a total dose of 10 MGy. As a consequence, it can be said that ethylene-styrene copolymers have good radiation resistance owing to the so-called 'sponge' effect of benzene rings. (author)

  4. Tunable pores in mesoporous silica films studied using a pulsed slow positron beam

    International Nuclear Information System (INIS)

    He Chunqing; Muramatsu, Makoto; Ohdaira, Toshiyuki; Oshima, Nagayasu; Kinomura, Atsushi; Suzuki, Ryoichi; Kobayashi, Yoshinori

    2007-01-01

    Positron annihilation lifetime spectroscopy (PALS) based on a pulsed slow positron beam was applied to study mesoporous silica films, synthesized using amphiphilic PEO-PPO-PEO triblock copolymers as structure-directing agents. The pore size depends on the loading of different templates. Larger pores were formed in silica films templated by copolymers with higher molecular-weights. Using 2-dimensional PALS, open porosity of silica films was also found to be influenced by the molecular-weight as well as the ratio of hydrophobic PPO moiety of the templates

  5. Prediction of solvent dependent Beta-roll formation of a self-assembling silk-like protein domain

    NARCIS (Netherlands)

    Schor, M.; Martens, A.A.; Wolf, de F.A.; Cohen Stuart, M.A.; Bolhuis, P.G.

    2009-01-01

    Triblock copolymers consisting of a middle silk-like [(Gly-Ala)3-Gly-Glu]n block flanked by two hydrophilic end blocks that assume a random conformation in aqueous solution at all pH spontaneously assemble into micrometre long fibers at low pH. As elucidating the molecular structure of the stacked

  6. Prediction of solvent dependent beta-roll formation of a self-assembling silk-like protein domain

    NARCIS (Netherlands)

    Schor, M.; Martens, A.A.; de Wolf, F.A.; Cohen Stuart, M.A.; Bolhuis, P.G.

    2009-01-01

    Triblock copolymers consisting of a middle silk-like [(Gly - Ala)(3) - Gly - Glu](n) block flanked by two hydrophilic end blocks that assume a random conformation in aqueous solution at all pH spontaneously assemble into micrometre long fibers at low pH. As elucidating the molecular structure of the

  7. Polymeric micelle assembly for the smart synthesis of mesoporous platinum nanospheres with tunable pore sizes.

    Science.gov (United States)

    Li, Yunqi; Bastakoti, Bishnu Prasad; Malgras, Victor; Li, Cuiling; Tang, Jing; Kim, Jung Ho; Yamauchi, Yusuke

    2015-09-14

    A facile method for the fabrication of well-dispersed mesoporous Pt nanospheres involves the use of a polymeric micelle assembly. A core-shell-corona type triblock copolymer [poly(styrene-b-2-vinylpyridine-b-ethylene oxide), PS-b-P2VP-b-PEO] is employed as the pore-directing agent. Negatively charged PtCl4 (2-) ions preferably interact with the protonated P2VP(+) blocks while the free PEO chains prevent the aggregation of the Pt nanospheres. The size of the mesopores can be finely tuned by varying the length of the PS chain. Furthermore, it is demonstrated that the metallic mesoporous nanospheres thus obtained are promising candidates for applications in electrochemistry. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Block copolymer libraries: modular versatility of the macromolecular Lego system.

    Science.gov (United States)

    Lohmeijer, Bas G G; Wouters, Daan; Yin, Zhihui; Schubert, Ulrich S

    2004-12-21

    The synthesis and characterization of a new 4 x 4 library of block copolymers based on polystyrene and poly(ethylene oxide) connected by an asymmetrical octahedral bis(terpyridine) ruthenium complex at the block junction are described, while initial studies on the thin film morphology of the components of the library are presented by the use of Atomic Force Microscopy, demonstrating the impact of a library approach to derive structure-property relationships.

  9. Fabrication of supramolecular star-shaped amphiphilic copolymers for ROS-triggered drug release.

    Science.gov (United States)

    Zuo, Cai; Peng, Jinlei; Cong, Yong; Dai, Xianyin; Zhang, Xiaolong; Zhao, Sijie; Zhang, Xianshuo; Ma, Liwei; Wang, Baoyan; Wei, Hua

    2018-03-15

    release from the doxorubicin (DOX)-loaded supramolecular star-shaped micelles due to the oxidation-induced dissociation of β-CD/Fc pair and the consequent loss of the colloidal stability of the star-shaped micelles. Studies of the delivery efficacy by an in vitro cytotoxicity study further indicated that higher DBs and longer hydrophilic arm compromised the therapeutic efficacy of the DOX-loaded supramolecular star-shaped micelles, resulting in significantly reduced cytotoxicity, as measured by increased IC 50 value. Overall, our results revealed that the screening of hydrophilic block by DB and MW for an optimized star-shaped copolymer should balance the stability versus therapeutic efficacy tradeoff for a comprehensive consideration. Therefore, the 12-arm star-shaped copolymer with POEGMA 30 is the best formulation tested. Copyright © 2017 Elsevier Inc. All rights reserved.

  10. Ordered CdSe nanoparticles within self-assembled block copolymer domains on surfaces.

    Science.gov (United States)

    Zou, Shan; Hong, Rui; Emrick, Todd; Walker, Gilbert C

    2007-02-13

    Hierarchical, high-density, ordered patterns were fabricated on Si substrates by self-assembly of CdSe nanoparticles within approximately 20-nm-thick diblock copolymer films in a controlled manner. Surface-modified CdSe nanoparticles formed well-defined structures within microphase-separated polystyrene-b-poly(2-vinylpyridine) (PS-b-P2VP) domains. Trioctylphosphine oxide (TOPO)-coated CdSe nanoparticles were incorporated into PS domains and polyethylene glycol-coated CdSe nanoparticles were located primarily in the P2VP domains. Nearly close-packed CdSe nanoparticles were clearly identified within the highly ordered patterns on Si substrates by scanning electron microscopy (SEM). Contact angle measurements together with SEM results indicate that TOPO-CdSe nanoparticles were partially placed at the air/copolymer interface.

  11. Role of Hydrophobic/Aromatic Residues on the Stability of Double-Wall β-Sheet Structures Formed by a Triblock Peptide.

    Science.gov (United States)

    Ozgur, Beytullah; Sayar, Mehmet

    2017-04-27

    Bioinspired self-assembling peptides serve as powerful building blocks in the manufacturing of nanomaterials with tailored features. Because of their ease of synthesis, biocompatibility, and tunable activity, this emerging branch of biomolecules has become very popular. The triblock peptide architecture designed by the Hartgerink group is a versatile system that allows control over its assembly and has been shown to demonstrate tunable bioactivity. Three main forces, Coulomb repulsion, hydrogen bonding and hydrophobicity act together to guide the triblock peptides' assembly into one-dimensional objects and hydrogels. It was shown previously that both the nanofiber morphology (e.g., intersheet spacing, formation of antiparallel/parallel β-sheets) and hydrogel rheology strictly depend on the choice of the core residue where the triblock peptide fibers with aromatic cores in general form shorter fibers and yield poor hydrogels with respect to the ones with aliphatic cores. However, an elaborate understanding of the molecular reasons behind these changes remained unclear. In this study, by using carefully designed computer based free energy calculations, we analyzed the influence of the core residue on the formation of double-wall fibers and single-wall β-sheets. Our results demonstrate that the aromatic substitution impairs the fiber cores and this impairment is mainly associated with a reduced hydrophobic character of the aromatic side chains. Such weakening is most obvious in tryptophan containing peptides where the fiber core absorbs a significant amount of water. We also show that the ability of tyrosine to form side chain hydrogen bonds plays an indispensable role in the fiber stability. As opposed to the impairment of the fiber cores, single-wall β-sheets with aromatic faces become more stable compared to the ones with aliphatic faces suggesting that the choice of the core residue can also affect the underlying assembly mechanism. We also provide an in

  12. From micelles to fibers: balancing self-assembling and random coiling domains in pH-responsive silk-collagen-like protein-based polymers

    NARCIS (Netherlands)

    Beun, L.H.; Storm, I.M.; Werten, M.W.T.; Wolf, de F.A.; Cohen Stuart, M.A.; Vries, de R.J.

    2014-01-01

    We study the self-assembly of genetically engineered protein-based triblock copolymers consisting of a central pH-responsive silk-like middle block (SHn, where SH is a silk-like octapeptide, (GA)3GH and n is the number of repeats) flanked by hydrophilic random coil outer blocks (C2). Our previous

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

    Science.gov (United States)

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

    2016-07-05

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

  14. Organization of Gold Nanorods in Cylinder-Forming Block Copolymer Films

    Science.gov (United States)

    Jian, Guoquian; Riggleman, Robert; Composto, Russell

    2012-02-01

    The addition of gold nanorods (AuNRs) to copolymer films can impart unique optical and electrical properties. To take full advantage of this system, the AuNRs must be dispersed in a self-organizing copolymer that directs the orientation of the anisotropic particle. In the present work, AuNRs with aspect ratio 3.6 (8 nm x 29 nm) are grafted with poly(2-vinyl pyridine) (P2VP) brushes and dispersed in a cylindrical forming diblock copolymer of polystyrene-b-P2VP (180K-b-77K, 29.6 wt% P2VP). Films are spun cast and solvent annealed in chloroform to produce a perpendicular cylindrical morphology at the surface. Using TEM and UV-ozone etching combined with AFM, the AuNRs are well dispersed and co-locate (top down view) with the P2VP cylinders, ˜50nm diameter. However, the AuNRs mainly lie parallel to the surface indicating that they likely locate at the junction created at the intersection between P2VP cylinders and P2VP brush layer adjacent to the silicon oxide surface. Self-consistent field calculations of the Au:PS-b-P2VP morphology as well as the effect of adding P2VP homopolymer to the nanocomposite will be discussed.

  15. Lignin poly(lactic acid) copolymers

    Energy Technology Data Exchange (ETDEWEB)

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

    2017-02-14

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

  16. Assembly of Triblock Amphiphilic Peptides into One-Dimensional Aggregates and Network Formation.

    Science.gov (United States)

    Ozgur, Beytullah; Sayar, Mehmet

    2016-10-06

    Peptide assembly plays a key role in both neurological diseases and development of novel biomaterials with well-defined nanostructures. Synthetic model peptides provide a unique platform to explore the role of intermolecular interactions in the assembly process. A triblock peptide architecture designed by the Hartgerink group is a versatile system which relies on Coulomb interactions, hydrogen bonding, and hydrophobicity to guide these peptides' assembly at three different length scales: β-sheets, double-wall ribbon-like aggregates, and finally a highly porous network structure which can support gels with ≤1% by weight peptide concentration. In this study, by using molecular dynamics simulations of a structure based implicit solvent coarse grained model, we analyzed this hierarchical assembly process. Parametrization of our CG model is based on multiple-state points from atomistic simulations, which enables this model to represent the conformational adaptability of the triblock peptide molecule based on the surrounding medium. Our results indicate that emergence of the double-wall β-sheet packing mechanism, proposed in light of the experimental evidence, strongly depends on the subtle balance of the intermolecular forces. We demonstrate that, even though backbone hydrogen bonding dominates the early nucleation stages, depending on the strength of the hydrophobic and Coulomb forces, alternative structures such as zero-dimensional aggregates with two β-sheets oriented orthogonally (which we refer to as a cross-packed structure) and β-sheets with misoriented hydrophobic side chains are also feasible. We discuss the implications of these competing structures for the three different length scales of assembly by systematically investigating the influence of density, counterion valency, and hydrophobicity.

  17. Block copolymer membranes for aqueous solution applications

    KAUST Repository

    Nunes, Suzana Pereira

    2016-03-22

    Block copolymers are known for their intricate morphology. We review the state of the art of block copolymer membranes and discuss perspectives in this field. The main focus is on pore morphology tuning with a short introduction on non-porous membranes. The two main strategies for pore formation in block copolymer membranes are (i) film casting and selective block sacrifice and (ii) self-assembly and non-solvent induced phase separation (SNIPS). Different fundamental aspects involved in the manufacture of block copolymer membranes are considered, including factors affecting the equilibrium morphology in solid films, self-assembly of copolymer in solutions and macrophase separation by solvent-non-solvent exchange. Different mechanisms are proposed for different depths of the SNIPS membrane. Block copolymer membranes can be prepared with much narrower pore size distribution than homopolymer membranes. Open questions and indications of what we consider the next development steps are finally discussed. They include the synthesis and application of new copolymers and specific functionalization, adding characteristics to respond to stimuli and chemical environment, polymerization-induced phase separation, and the manufacture of organic-inorganic hybrids.

  18. Block copolymer membranes for aqueous solution applications

    KAUST Repository

    Nunes, Suzana Pereira

    2016-01-01

    Block copolymers are known for their intricate morphology. We review the state of the art of block copolymer membranes and discuss perspectives in this field. The main focus is on pore morphology tuning with a short introduction on non-porous membranes. The two main strategies for pore formation in block copolymer membranes are (i) film casting and selective block sacrifice and (ii) self-assembly and non-solvent induced phase separation (SNIPS). Different fundamental aspects involved in the manufacture of block copolymer membranes are considered, including factors affecting the equilibrium morphology in solid films, self-assembly of copolymer in solutions and macrophase separation by solvent-non-solvent exchange. Different mechanisms are proposed for different depths of the SNIPS membrane. Block copolymer membranes can be prepared with much narrower pore size distribution than homopolymer membranes. Open questions and indications of what we consider the next development steps are finally discussed. They include the synthesis and application of new copolymers and specific functionalization, adding characteristics to respond to stimuli and chemical environment, polymerization-induced phase separation, and the manufacture of organic-inorganic hybrids.

  19. Theoretical consideration on phase behaviors of poly(ethylene oxide-block-propylene oxide)/LiCF3SO3 systems in lithium battery

    International Nuclear Information System (INIS)

    Ko, Sung Jin; Kim, Sun Joon; Kong, Sung Ho; Bae, Young Chan

    2004-01-01

    A new thermodynamic model is developed based on the extended perturbed hard sphere chain (PHSC) model and melting point depression theory to describe the phase behaviors of copolymer electrolyte/salt systems. The phase behaviors of poly(ethylene oxide-block-propylene oxide)/LiCF 3 SO 3 systems are investigated by thermo-optical analysis (TOA) technique. Quantitative descriptions according to the proposed model are in good agreement with experimental data. The obtained results show that monomer ratio and sequence type of copolymers play a great role in determining eutectic points of the given systems

  20. Nanoparticle packing within block copolymer micelles prepared by the interfacial instability method.

    Science.gov (United States)

    Nabar, Gauri M; Winter, Jessica O; Wyslouzil, Barbara E

    2018-05-02

    The interfacial instability method has emerged as a viable approach for encapsulating high concentrations of nanoparticles (NPs) within morphologically diverse micelles. In this method, transient interfacial instabilities at the surface of an emulsion droplet guide self-assembly of block co-polymers and NP encapsulants. Although used by many groups, there are no systematic investigations exploring the relationship between NP properties and micelle morphology. Here, the effect of quantum dot (QD) and superparamagnetic iron oxide NP (SPION) concentration on the shape, size, and surface deformation of initially spherical poly(styrene-b-ethylene oxide) (PS-b-PEO) micelles was examined. Multi-NP encapsulation and uniform dispersion within micelles was obtained even at low NP concentrations. Increasing NP concentration initially resulted in larger numbers of elongated micelles and cylinders with tightly-controlled diameters smaller than those of spherical micelles. Beyond a critical NP concentration, micelle formation was suppressed; the dominant morphology became densely-loaded NP structures that were coated with polymer and exhibited increased polydispersity. Transmission electron microscopy (TEM) and small angle X-ray scattering (SAXS) revealed that NPs in densely-loaded structures can be well-ordered, with packing volume fractions of up to 24%. These effects were enhanced in magnetic composites, possibly by dipole interactions. Mechanisms governing phase transitions triggered by NP loading in the interfacial instability process were proposed. The current study helps establish and elucidate the active role played by NPs in directing block copolymer assembly in the interfacial instability process, and provides important guiding principles for the use of this approach in generating NP-loaded block copolymer composites.

  1. Synthesis of block copolymers with well-defined alternating chromophore and flexible spacer for electroluminescence application

    Energy Technology Data Exchange (ETDEWEB)

    Wang Haiqiao; Sun Qingjiang; Li Yongfang; Li Xiaoyu

    2003-02-24

    Two novel light-emitting block copolymers, poly[1,4,7,10-tetraoxadecane-1,10-diyl-1,4-naphthalene-1,2-ethenediyl-1,4- phenylene-1,2-ethenediyl-1,4-naphthalene] (TEO-DNVB) and poly[1,4,7,10-tetraoxadecane-1,10-diyl-1,4-naphthalene-1,2-ethenediyl- (2,5-dimethoxy-1,4-phenylene)-1,2-ethenediyl-1,4-naphthalene] (TEO-MDNVB), were synthesized by using the Wittig reaction. The block copolymers are composed of the fluorescent segments, 1,4-di[2-(1-naphthyl) vinyl] benzene (DNVB) or 2,5-dimethyloxy-1,4-di[2-(1-naphthyl) vinyl] benzene (MDNVB) and the flexible segments, tri(ethylene oxide) (TEO). The copolymers were characterized by Fourier transform infrared (FT-IR), {sup 1}H-nuclear magnetic resonance ({sup 1}H-NMR), ultraviolet-visible (UV-Vis), gel permeation chromatography (GPC) and cyclic voltammograms (CV). Thermal properties were investigated with differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) under nitrogen atmosphere. Cyclic voltammetric measurement reveals a reversible p-doping process. Efficient blue-green polymer light-emitting diodes (PLEDs) and polymer light-emitting electrochemical cells (PLECs) were successfully fabricated. The synthesis, characterization and the electroluminescent properties of the copolymers are reported in this paper.

  2. Functional materials derived from block copolymer self-assembly

    DEFF Research Database (Denmark)

    Li, Tao

    deposition methods, namely nanocasting and atomic layer deposition (ALD) will be applied to fabricate compact, inter-connected, and continuous metal oxide films. In this way, the structure integrity will be preserved after template removal during the annealing procedure. Another objective of this project......-casting, the block copolymer self-organizes into monolayer packed sphere pattern, without any surface treatment of the substrate and annealing process. Arrays of nano-pillars and nanowells of various materials are fabricated in dry etch processes over wafer scale without defects. We also show an in situ Al2O3 hard...

  3. Pramana – Journal of Physics | Indian Academy of Sciences

    Indian Academy of Sciences (India)

    Home; Journals; Pramana – Journal of Physics. P A Hassan. Articles written in Pramana – Journal of Physics. Volume 63 Issue 2 August 2004 pp 277-283 Contributed Papers : Small-angle neutron scattering. Sphere-to-rod transition of triblock copolymer micelles at room temperature · R Ganguly V K Aswal P A Hassan I K ...

  4. Macromolecular Architectures Designed by Living Radical Polymerization with Organic Catalysts

    Directory of Open Access Journals (Sweden)

    Miho Tanishima

    2014-01-01

    Full Text Available Well-defined diblock and triblock copolymers, star polymers, and concentrated polymer brushes on solid surfaces were prepared using living radical polymerization with organic catalysts. Polymerizations of methyl methacrylate, butyl acrylate, and selected functional methacrylates were performed with a monofunctional initiator, a difunctional initiator, a trifunctional initiator, and a surface-immobilized initiator.

  5. Water activity of aqueous solutions of ethylene oxide-propylene oxide block copolymers and maltodextrins

    Directory of Open Access Journals (Sweden)

    N. D. D. Carareto

    2010-03-01

    Full Text Available The water activity of aqueous solutions of EO-PO block copolymers of six different molar masses and EO/PO ratios and of maltodextrins of three different molar masses was determined at 298.15 K. The results showed that these aqueous solutions present a negative deviation from Raoult's law. The Flory-Huggins and UNIFAC excess Gibbs energy models were employed to model the experimental data. While a good agreement was obtained with the Flory-Huggins equation, discrepancies were observed when predicting the experimental behavior with the UNIFAC model. The water activities of ternary systems formed by a synthetic polymer, maltodextrin and water were also measured and used to test the predictive capability of both models.

  6. Hybrid titanium dioxide/PS-b-PEO block copolymer nanocomposites based on sol-gel synthesis

    International Nuclear Information System (INIS)

    Gutierrez, J; Tercjak, A; Garcia, I; Peponi, L; Mondragon, I

    2008-01-01

    The poly(styrene)-b-poly(ethylene oxide) (SEO) amphiphilic block copolymer, with two different molecular weights, has been used as a structure directing agent for generating nanocomposites of TiO 2 /SEO via the sol-gel process. SEO amphiphilic block copolymers are designed with a hydrophilic PEO-block which can interact with inorganic molecules, as well as a hydrophobic PS-block which builds the matrix. The addition of different amounts of sol-gel provokes strong variations in the self-assembled morphology of TiO 2 /SEO nanocomposites with respect to the neat block copolymer. As confirmed by atomic force microscopy (AFM), TiO 2 /PEO-block micelles get closer, forming well-ordered spherical domains, in which TiO 2 nanoparticles constitute the core surrounded by a corona of PEO-blocks. Moreover, for 20 vol% sol-gel the generated morphology changes to a hexagonally ordered structure for both block copolymers. The cylindrical structure of these nanocomposites has been confirmed by the two-dimensional Fourier transform power spectrum of the corresponding AFM height images. Affinity between titanium dioxide precursor and PEO-block of SEO allows us to generate hybrid inorganic/organic nanocomposites, which retain the optical properties of TiO 2 , as evaluated by UV-vis spectroscopy

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

    DEFF Research Database (Denmark)

    Tripathi, Lakshmi; Wu, Lin-Ping; Chen, Jinchun

    2012-01-01

    ), thermo- and mechanical analysis. NMR confirmed the existence of diblock copolymers consisting of 58 mol% PHB as the short chain length block with 42 mol% PHHx as the medium chain length block. The block copolymers had two glass transition temperatures (Tg) at 2.7°C and -16.4°C, one melting temperature...... (Tm) at 172.1°C and one cool crystallization temperature (Tc) at 69.1°C as revealed by differential scanning calorimetry (DSC), respectively. This is the first microbial short-chain-length (scl) and medium-chain-length (mcl) PHA block copolymer reported. CONCLUSIONS: It is possible to produce PHA......BACKGROUND: Block polyhydroxyalkanoates (PHA) were reported to be resistant against polymer aging that negatively affects polymer properties. Recently, more and more attempts have been directed to make PHA block copolymers. Diblock copolymers PHB-b-PHHx consisting of poly-3-hydroxybutyrate (PHB...

  8. Studies of P(VDF-HFP) copolymer applied to gamma dosimetry

    International Nuclear Information System (INIS)

    Liz, Otavio S.R.; Medeiros, Adriana S.

    2011-01-01

    When polymeric materials are irradiated by ionizing radiation, the effects are roughly divided into two types, degradation (chain scission) and chain link (crosslinking). These effects are normally identified by spectroscopic analysis in the UV-Vis and Infrared region. Recently, the intensities of optical absorption in the ultraviolet visible region (273 nm) due to radio-induction of conjugated C = C bonds in P(VDF-TrFE) copolymers have been successfully used for high dose gamma dosimetry, for doses ranging from 0.1 to 200 kGy. In this context, there is now an interest to conduct a similar systematic investigation of another fluorinated copolymer of PVDF, the poly(fluorovinylidene-co-hexafluoropropylene) [P(VDF-HFP)], not only in the UV-VIS region but also in the near and mid-infrared region. The copolymer used was obtained by randomly adding 10% molar of [CF2- CF-CF3] monomers in the [CH2-CF2]n main chain of PVDF homopolymer. Preliminary results have shown that the irradiated copolymer has characteristic absorption bands originated by irradiation in the FTIR spectrum. It was found that the 1852 cm -1 band, associated with C = O bonds, have a linear correlation with the absorbed dose for doses ranging from 10 to 750 kGy. The absorption band at 1729 cm -1 , associated to chain oxidation (C = O), has shown a similar behavior and can be used to measure doses from 100 to 1000 kGy. These results indicate that the FTIR absorption bands of gamma irradiated P (VDF-HFP) have great potential to be used in high dose dosimetry, without the addition of dyes. (author)

  9. Studies of P(VDF-HFP) copolymer applied to gamma dosimetry

    Energy Technology Data Exchange (ETDEWEB)

    Liz, Otavio S.R.; Medeiros, Adriana S. [Universidade Federal de Minas Gerais (DEN/UFMG), Belo Horizonte, MG (Brazil). Dept. de Engenharia Nuclear; Faria, Luiz O., E-mail: farialo@cdtn.b [Centro de Desenvolvimento da Tecnologia Nuclear (CDTN/CNEN-MG), Belo Horizonte, MG (Brazil)

    2011-07-01

    When polymeric materials are irradiated by ionizing radiation, the effects are roughly divided into two types, degradation (chain scission) and chain link (crosslinking). These effects are normally identified by spectroscopic analysis in the UV-Vis and Infrared region. Recently, the intensities of optical absorption in the ultraviolet visible region (273 nm) due to radio-induction of conjugated C = C bonds in P(VDF-TrFE) copolymers have been successfully used for high dose gamma dosimetry, for doses ranging from 0.1 to 200 kGy. In this context, there is now an interest to conduct a similar systematic investigation of another fluorinated copolymer of PVDF, the poly(fluorovinylidene-co-hexafluoropropylene) [P(VDF-HFP)], not only in the UV-VIS region but also in the near and mid-infrared region. The copolymer used was obtained by randomly adding 10% molar of [CF2- CF-CF3] monomers in the [CH2-CF2]n main chain of PVDF homopolymer. Preliminary results have shown that the irradiated copolymer has characteristic absorption bands originated by irradiation in the FTIR spectrum. It was found that the 1852 cm{sup -1} band, associated with C = O bonds, have a linear correlation with the absorbed dose for doses ranging from 10 to 750 kGy. The absorption band at 1729 cm{sup -1}, associated to chain oxidation (C = O), has shown a similar behavior and can be used to measure doses from 100 to 1000 kGy. These results indicate that the FTIR absorption bands of gamma irradiated P (VDF-HFP) have great potential to be used in high dose dosimetry, without the addition of dyes. (author)

  10. Block Copolymer Electrolytes: Thermodynamics, Ion Transport, and Use in Solid- State Lithium/Sulfur Cells

    Science.gov (United States)

    Teran, Alexander Andrew

    Nanostructured block copolymer electrolytes containing an ion-conducting block and a modulus-strengthening block are of interest for applications in solid-state lithium metal batteries. These materials can self-assemble into well-defined microstructures, creating conducting channels that facilitate ion transport. The overall objective of this dissertation is to gain a better understanding of the behavior of salt-containing block copolymers, and evaluate their potential for use in solid-state lithium/sulfur batteries. Anionically synthesized polystyrene-b-poly(ethylene oxide) (SEO) copolymers doped with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt were used as a model system. This thesis investigates the model system on several levels: from fundamental thermodynamic studies to bulk characterization and finally device assembly and testing. First, the thermodynamics of neat and salt-containing block copolymers was studied. The addition of salt to these materials is necessary to make them conductive, however even small amounts of salt can have significant effects on their phase behavior, and consequently their iontransport and mechanical properties. As a result, the effect of salt addition on block copolymer thermodynamics has been the subject of significant interest over the last decade. A comprehensive study of the thermodynamics of block copolymer/salt mixtures over a wide range of molecular weights, compositions, salt concentrations and temperatures was conducted. Next, the effect of molecular weight on ion transport in both homopolymer and copolymer electrolytes were studied over a wide range of chain lengths. Homopolymer electrolytes show an inverse relationship between conductivity and chain length, with a plateau in the infinite molecular weight limit. This is due to the presence of two mechanisms of ion conduction in homopolymers; the first mechanism is a result of the segmental motion of the chains surrounding the salt ions, 2 creating a liquid

  11. Lactosylated poly(ethylene oxide)-poly(propylene oxide) block copolymers for potential active targeting: synthesis and physicochemical and self-aggregation characterization

    Energy Technology Data Exchange (ETDEWEB)

    Cuestas, Maria L.; Glisoni, Romina J. [University of Buenos Aires, Group of Biomaterials and Nanotechnology for Improved Medicines (BIONIMED), Department of Pharmaceutical Technology, Faculty of Pharmacy and Biochemistry (Argentina); Mathet, Veronica L. [National Science Research Council (CONICET) (Argentina); Sosnik, Alejandro, E-mail: alesosnik@gmail.com [University of Buenos Aires, The Group of Biomaterials and Nanotechnology for Improved Medicines (BIONIMED), Department of Pharmaceutical Technology, Faculty of Pharmacy and Biochemistry (Argentina)

    2013-01-15

    Aiming to develop polymeric self-assembly nanocarriers with potential applications in active drug targeting to the liver, linear and branched poly(ethylene oxide)-poly(propylene oxide) amphiphiles were conjugated to lactobionic acid (LA), a disaccharide of galactose and gluconic acid, by the conventional Steglich esterification reaction. The conjugation was confirmed by ATR/FT-IR, {sup 1}H-NMR, and {sup 13}C-NMR spectroscopy. Elemental analysis and MALDI-TOF mass spectrometry were employed to elucidate the conjugation extent and the final molecular weight, respectively. The critical micellar concentration (CMC), the size and size distribution and zeta potential of the pristine and modified polymeric micelles under different conditions of pH and temperature were characterized by dynamic light scattering (DLS). Conjugation with LA favored the micellization process, leading to a decrease of the CMC with respect to the pristine counterpart, this phenomenon being independent of the pH and the temperature. At 37 Degree-Sign C, micelles made of pristine copolymers showed a monomodal size distribution between 12.8 and 24.4 nm. Conversely, LA-conjugated micelles showed a bimodal size pattern that comprised a main fraction of relatively small size (11.6-22.2 nm) and a second one with remarkably larger sizes of up to 941.4 nm. The former corresponded to single micelles, while the latter would indicate a secondary aggregation phenomenon. The spherical morphology of LA-micelles was visualized by transmission electron microscopy (TEM). Finally, to assess the ability of the LA-conjugated micelles to interact with lectin-like receptors, samples were incubated with concanavalin A at 37 Degree-Sign C and the size and size distribution were monitored by DLS. Findings indicated that regardless of the relatively weak affinity of this vegetal lectin for galactose, micelles underwent agglutination probably through the interaction of a secondary site in the lectin with the gluconic acid

  12. Tunable Mesoporous Bragg Reflectors Based on Block-Copolymer Self-Assembly

    KAUST Repository

    Guldin, Stefan; Kolle, Mathias; Stefik, Morgan; Langford, Richard; Eder, Dominik; Wiesner, Ulrich; Steiner, Ullrich

    2011-01-01

    Mesoporous Bragg reflectors are a promising materials platform for photovoltaics, light emission, and sensing. A fast and versatile fabrication route that relies on the self-assembly of the block copolymer poly(isoprene-b-ethylene oxide) in combination with simple sol-gel chemistry is reported. The method allows extended control over porosity and pore size in the resulting inorganic material and results in high-quality optical elements. © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Tunable Mesoporous Bragg Reflectors Based on Block-Copolymer Self-Assembly

    KAUST Repository

    Guldin, Stefan

    2011-07-06

    Mesoporous Bragg reflectors are a promising materials platform for photovoltaics, light emission, and sensing. A fast and versatile fabrication route that relies on the self-assembly of the block copolymer poly(isoprene-b-ethylene oxide) in combination with simple sol-gel chemistry is reported. The method allows extended control over porosity and pore size in the resulting inorganic material and results in high-quality optical elements. © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Copolymerization of Phenylselenide-Substituted Maleimide with Styrene and Its Oxidative Elimination Behavior

    Directory of Open Access Journals (Sweden)

    Qian Liu

    2018-03-01

    Full Text Available Selenium-containing monomer monophenyl maleimide selenide (MSM was synthesized and copolymerized with styrene (St using reversible addition-fragmentation chain transfer (RAFT polymerization. Copolymers with controlled molecular weight and narrow molecular weight distribution were obtained. The structure of the copolymer was characterized by nuclear magnetic resonance, matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF mass spectrum, Fourier transform infrared spectroscopy (FT-IR and Ultraviolet–visible spectroscopy (UV-vis spectroscopy. The copolymer can be oxidized by H2O2 to form carbon-carbon double bonds within the main chain due to the unique sensitivity of selenide groups in the presence of oxidants. Such structure changing resulted in an interesting concentration-related photoluminescence emission enhancement.

  15. Mechanical properties of weakly segregated block copolymers : 1. Synergism on tensile properties of poly(styrene-b-n-butylmethacrylate) diblock copolymers

    NARCIS (Netherlands)

    Weidisch, R.; Michler, G.H.; Fischer, H.; Arnold, M.; Hofmann, S.; Stamm, M.

    1999-01-01

    Mechanical properties of poly(styrene-b-n-butylmethacrylate) diblock copolymers, PS-b-PBMA, with different lengths of the polystyrene block were investigated. The copolymers display a composition range where the tensile strength of the block copolymers exceeds the values of the corresponding

  16. Oil recovery with vinyl sulfonic acid-acrylamide copolymers

    Energy Technology Data Exchange (ETDEWEB)

    Norton, C.J.; Falk, D.O.

    1973-12-18

    An aqueous polymer flood containing sulfomethylated alkali metal vinyl sulfonate-acrylamide copolymers was proposed for use in secondary or tertiary enhanced oil recovery. The sulfonate groups on the copolymers sustain the viscosity of the flood in the presence of brine and lime. Injection of the copolymer solution into a waterflooded Berea core, produced 30.5 percent of the residual oil. It is preferred that the copolymers are partially hydrolyzed.

  17. Role of pluronics on rheological, drying and crack initiation of 'suckable' gels of decontamination; Role des pluronics sur les proprietes rheologiques, de sechage et de fracturation des gels 'aspirables' de decontamination

    Energy Technology Data Exchange (ETDEWEB)

    Bousquet, C

    2007-12-15

    The aim of this work was to understand the role of an addition of pluronics on the rheological behaviour, the drying and the fracturing of 'suckable' gels used for nuclear decontamination. The system studied was an aqueous suspension of silica (100 g/L of Aerosil 380) in a strong acidic medium (HNO{sub 3}/H{sub 3}PO{sub 4} 1.5 mol/L/1.5 mol/L) in presence of pluronics. Pluronics are amphiphilic tri-blocks copolymers composed of ethylene poly-oxide blocks and of propylene poly-oxide. The first part of this study deals with the characterization of the rheological properties of the gels. From viscosity retaking measurements, flow rheo-grams analysis and the viscoelastic properties of the gels, have been determined an improvement of the rheological properties of the gels significant from the addition of 5 g/L of copolymer. In a second part, the determination of adsorption isotherms coupled to small angles neutrons diffusion measurements has revealed that copolymers are adsorbed flat on silica in bridging the aggregates between them and that the improvement of the rheological behaviour of the gels is due to the increase of the bonds density of the gelled lattice. Moreover, beyond 10 g/L, the adsorption saturation of copolymers at the surface of the silica prevents the bridging of the aggregates which induces the gel destabilization. The last part of this work deals with the characterization of characteristic values of drying and of crack initiation of gels. Then is revealed a relation between the drying kinetics and the formation of cracks in the gel layer. Moreover, the study of the evolution of stresses in the gel layer during time allows to reveal that the addition of pluronics to the formulation of gels allows to improve the gel resistance to the crack initiation and to the delamination. (O.M.)

  18. Role of pluronics on rheological, drying and crack initiation of 'suckable' gels of decontamination

    International Nuclear Information System (INIS)

    Bousquet, C.

    2007-12-01

    The aim of this work was to understand the role of an addition of pluronics on the rheological behaviour, the drying and the fracturing of 'suckable' gels used for nuclear decontamination. The system studied was an aqueous suspension of silica (100 g/L of Aerosil 380) in a strong acidic medium (HNO 3 /H 3 PO 4 1.5 mol/L/1.5 mol/L) in presence of pluronics. Pluronics are amphiphilic tri-blocks copolymers composed of ethylene poly-oxide blocks and of propylene poly-oxide. The first part of this study deals with the characterization of the rheological properties of the gels. From viscosity retaking measurements, flow rheo-grams analysis and the viscoelastic properties of the gels, have been determined an improvement of the rheological properties of the gels significant from the addition of 5 g/L of copolymer. In a second part, the determination of adsorption isotherms coupled to small angles neutrons diffusion measurements has revealed that copolymers are adsorbed flat on silica in bridging the aggregates between them and that the improvement of the rheological behaviour of the gels is due to the increase of the bonds density of the gelled lattice. Moreover, beyond 10 g/L, the adsorption saturation of copolymers at the surface of the silica prevents the bridging of the aggregates which induces the gel destabilization. The last part of this work deals with the characterization of characteristic values of drying and of crack initiation of gels. Then is revealed a relation between the drying kinetics and the formation of cracks in the gel layer. Moreover, the study of the evolution of stresses in the gel layer during time allows to reveal that the addition of pluronics to the formulation of gels allows to improve the gel resistance to the crack initiation and to the delamination. (O.M.)

  19. Synthesis of non-siliceous mesoporous oxides.

    Science.gov (United States)

    Gu, Dong; Schüth, Ferdi

    2014-01-07

    Mesoporous non-siliceous oxides have attracted great interest due to their unique properties and potential applications. Since the discovery of mesoporous silicates in 1990s, organic-inorganic assembly processes by using surfactants or block copolymers as soft templates have been considered as a feasible path for creating mesopores in metal oxides. However, the harsh sol-gel conditions and low thermal stabilities have limited the expansion of this method to various metal oxide species. Nanocasting, using ordered mesoporous silica or carbon as a hard template, has provided possibilities for preparing novel mesoporous materials with new structures, compositions and high thermal stabilities. This review concerns the synthesis, composition, and parameter control of mesoporous non-siliceous oxides. Four synthesis routes, i.e. soft-templating (surfactants or block copolymers as templates), hard-templating (mesoporous silicas or carbons as sacrificial templates), colloidal crystal templating (3-D ordered colloidal particles as a template), and super lattice routes, are summarized in this review. Mesoporous metal oxides with different compositions have different properties. Non-siliceous mesoporous oxides are comprehensively described, including a discussion of constituting elements, synthesis, and structures. General aspects concerning pore size control, atomic scale crystallinity, and phase control are also reviewed.

  20. Novel chiral core-shell silica microspheres with trans-(1R,2R)-diaminocyclohexane bridged in the mesoporous shell: synthesis, characterization and application in high performance liquid chromatography.

    Science.gov (United States)

    Wu, Xiabing; You, Linjun; Di, Bin; Hao, Weiqiang; Su, Mengxiang; Gu, Yu; Shen, Lingling

    2013-07-19

    Novel chiral core-shell silica microspheres with trans-(1R,2R)-diaminocyclohexane (DACH) moiety bridged in the mesoporous shell were synthesized using layer-by-layer method. The chiral mesoporous shell around the nonporous silica core was formed by the co-condensation of N,N'-bis-[(triethoxysilyl)propyl]-trans-(1R,2R)-bis-(ureido)-cyclohexane (DACH-BS) and tetraethoxysilane (TEOS) using octadecyltrimethylammonium chloride (C18TMACl) and triblock poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) copolymer (P123) as the templates. The functionalized core-shell silica microspheres were characterized and tested as chiral stationary phases for high performance liquid chromatography (HPLC). R/S-1,1'-bi-2,2'-naphthol, R/S-6,6'-dibromo-1,1'-bi-2-naphthol and R/S-1,1'-bi-2,2'-phenanthrol were enantioseparated rapidly on the column packed with the DACH core-shell silica particles. Moreover, the column packed with core-shell particles exhibited better performance than the column packed with the DACH functionalized periodic mesoporous organosilicas. Copyright © 2013 Elsevier B.V. All rights reserved.

  1. Data of PCL-b-P(MMA-DMAEMA2 characterization and related assays

    Directory of Open Access Journals (Sweden)

    Camila Franco

    2017-12-01

    Full Text Available The data presented here are related to the research paper entitled “PCL-b-P(MMA-co-DMAEMA2 new triblock copolymer for novel pH-sensitive nanocapsules intended for drug delivery to tumors” by Franco et al. [1]. Characterization data of PCL-diol, macroinitiator Br-PCL-Br, homopolymers (PMMA and PDMAEMA and copolymers (batch 1 and batch 2 analyzed by FTIR, SEC and NMR, as well as, characterization of PCL-NS formulation by laser diffraction and DLS analysis, initial nanocapsule formulations and 1C-NC and 2C-NC formulations, including hydrodynamic diameter at different pH media, and DMSO cytotoxicity. Keywords: Methacrylic copolymer, Polycaprolactone, Nanocapsules, pH-sensitive, Cell viability

  2. The self-assembly of particles with isotropic interactions: Using DNA coated colloids to create designer nanomaterials

    International Nuclear Information System (INIS)

    Thompson, R. B.; Dion, S.; Konigslow, K. von

    2014-01-01

    Self-consistent field theory equations are presented that are suitable for use as a coarse-grained model for DNA coated colloids, polymer-grafted nanoparticles and other systems with approximately isotropic interactions. The equations are generalized for arbitrary numbers of chemically distinct colloids. The advantages and limitations of such a coarse-grained approach for DNA coated colloids are discussed, as are similarities with block copolymer self-assembly. In particular, preliminary results for three species self-assembly are presented that parallel results from a two dimensional ABC triblock copolymer phase. The possibility of incorporating crystallization, dynamics, inverse statistical mechanics and multiscale modelling techniques are discussed

  3. The One-Pot Directed Assembly of Cylinder-Forming Block Copolymer on Adjacent Chemical Patterns for Bimodal Patterning.

    Science.gov (United States)

    Chang, Tzu-Hsuan; Xiong, Shisheng; Liu, Chi-Chun; Liu, Dong; Nealey, Paul F; Ma, Zhenqiang

    2017-09-01

    The direct self-assembly of cylinder-forming poly(styrene-block-methyl-methacrylate) (PS-b-PMMA) block copolymer is successfully assembled into two orientations, according to the underlying guiding pattern in different areas. Lying-down and perpendicular cylinders are formed, respectively, depending on the design of chemical pattern: sparse line/space pattern or hexagonal dot array. The first chemical pattern composed of prepatterned cross-linked polystyrene (XPS) line/space structure has a period (L S ) equal to twice the intercylinder period of the block copolymer (L 0 ). The PS-b-PMMA thin film on the prepared chemical template after thermal annealing forms a lying-down cylinder morphology when the width of the PS strips is less than the width of PS block in the PS-b-PMMA block copolymer. The morphology is only applicable at the discrete thickness of the PS-b-PMMA film. In addition to forming the lying-down cylinders directly on the XPS guiding pattern, the cylinder-forming block copolymer can also be assembled in a perpendicular way on the second guiding pattern (the hexagonal dot array). The block copolymer films are registered into two orientations in a single directed self-assembly process. The features of the assembled patterns are successfully transferred down to the silicon oxide substrate. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. The effect of the triblock properties on the morphologies and photophysical properties of nanoparticle loaded with carboxylic dendrimer phthalocyanine

    Science.gov (United States)

    Lv, Huafei; Chen, Zhe; Yu, Xinxin; Pan, Sujuan; Zhang, Tiantian; Xie, Shusen; Yang, Hongqin; Peng, Yiru

    2016-09-01

    Photodynamic therapy (PDT) is an emerging alternative treatment for various cancers and age-related macular degeneration. Phthalocyanines (Pcs) and their substituted derivatives are under intensive investigation as the second generation photosensitizers. A big challenge for the application of Pcs is poor solubility and limited accumulation in the tumor tissues, which severely reduced its PDT efficacy. Nano-delivery systems such as polymeric micelles are promising tools for increasing the solubility and improving delivery efficiency of Pcs for PDT application. In this paper, nanoparticles of amphiphilic triblock copolymer poly(L-lysine)-b-poly (ethylene glycol)-b-poly(L-lysine) were developed to encapsulate 1-2 generation carboxylic poly (benzyl aryl ether) dendrimer. The morphologies and photophysical properties of polymeric nanoparticles loaded with 1-2 generation dendritic phthalocyanines (G1-ZnPc(COOH)8/m and G2-ZnPc(COOH)16/m) were studied by AFM, UV/Vis and fluorescent spectroscopic method. The morphologies of self-assembled PLL-PEG-PLL aggregates exhibited concentration dependence. Its morphologies changed from cocoon-like to spheral. The diameters of G1-ZnPc(COOH)8/m and G2-ZnPc(COOH)16/m were in the range of 33-147 nm, increasing with the increase of the concentration of PLL-PEG-PLL. The morphologies of G2-ZnPc(COOH)16/m also changed from cocoon-like to sphere with the increase of the concentration of PLL-PEG-PLL. It was found that, the no obviously Q change was observed between the free phthalocyanines and nanoparticles. The fluorescence intensity of polymer nanoparticles were higher enhanced compared with free dendritic phthalocyanines. The dendrimer phthalocyanine loaded with poly(L-lysine)-b-poly (ethylene glycol)-b-poly(L-lysine) presented suitable physical stability, improved photophysical properties suggesting it may be considered as a promising formulation for PDT.

  5. Study of the interface solid/solutions containing PEO-PPO block copolymers and asphaltenes by FTIR/ATR; Estudo de solucoes de copolimeros em bloco de PEO-PPO contendo asfaltenos por FTIR/DTA

    Energy Technology Data Exchange (ETDEWEB)

    Aguiar, Janaina I.S.; Neto, Jessica S.G.; Mansur, Claudia R.E. [Universidade Federal do Rio de Janeiro, Instituto de Macromoleculas, Laboratorio de Macromoleculas e Coloides na Industria de Petroleo, Rio de Janeiro, RJ (Brazil)], E-mails: janaina_333@hotmail.com, kinha_dac_dm@hotmail.com; celias@ima.ufrj.br

    2011-07-01

    The formation of water/oil emulsions can cause problems in various stages of production, processing and refining of petroleum. In this study, the technique of Fourier transform infrared spectroscopy (FTIR) using the method of attenuated total reflectance (ATR) was applied to study the solid-solutions of block copolymers based on poly(ethylene oxide)-poly(propylene oxide) (PEO-PPO) interface and its interaction in this interface with asphaltenic fractions of petroleum. The solid is the crystal of the ATR. Initially, we determined the critical micelle concentration values of the copolymers, which were consistent those obtained by a tensiometer. Bottle Test was also performed to correlate the efficiency of PEO-PPO copolymers in the breaking of water/oil emulsions with its adsorption at the interfaces solutions. (author)

  6. Kinetic modelling of radiochemical ageing of ethylene-propylene copolymers

    International Nuclear Information System (INIS)

    Colin, Xavier; Richaud, Emmanuel; Verdu, Jacques; Monchy-Leroy, Carole

    2010-01-01

    A non-empirical kinetic model has been built for describing the general trends of radiooxidation kinetics of ethylene-propylene copolymers (EPR) at low γ dose rate and low temperature. It is derived from a radical chain oxidation mechanism composed of 30 elementary reactions: 19 relative to oxidation of methylene and methyne units plus 11 relative to their eventual cooxidation. The validity of this model has been already checked successfully elsewhere for one homopolymer: polyethylene (PE) (; ). In the present study, it is now checked for polypropylene (PP) and a series of three EPR differing essentially by their mole fraction of ethylene (37%, 73% and 86%) and their crystallinity degree (0%, 5% and 26%). Predicted values of radiation-chemical yields are in good agreement with experimental ones published in the last half past century.

  7. Unusual kinetics of poly(ethylene glycol) oxidation with cerium(IV) ions in sulfuric acid medium and implications for copolymer synthesis.

    Science.gov (United States)

    Szymański, Jan K; Temprano-Coleto, Fernando; Pérez-Mercader, Juan

    2015-03-14

    The cerium(IV)-alcohol couple in an acidic medium is an example of a redox system capable of initiating free radical polymerization. When the alcohol has a polymeric nature, the outcome of such a process is a block copolymer, a member of a class of compounds possessing many useful properties. The most common polymer with a terminal -OH group is poly(ethylene glycol) (PEG); however, the detailed mechanism of its reaction with cerium(IV) remains underexplored. In this paper, we report our findings for this reaction based on spectrophotometric measurements and kinetic modeling. We find that both the reaction order and the net rate constant for the oxidation process depend strongly on the nature of the acidic medium used. In order to account for the experimental observations, we postulate that protonation of PEG decreases its affinity for some of the cerium(IV)-sulfate complexes formed in the system.

  8. High-throughput preparation of complex multi-scale patterns from block copolymer/homopolymer blend films

    Science.gov (United States)

    Park, Hyungmin; Kim, Jae-Up; Park, Soojin

    2012-02-01

    A simple, straightforward process for fabricating multi-scale micro- and nanostructured patterns from polystyrene-block-poly(2-vinylpyridine) (PS-b-P2VP)/poly(methyl methacrylate) (PMMA) homopolymer in a preferential solvent for PS and PMMA is demonstrated. When the PS-b-P2VP/PMMA blend films were spin-coated onto a silicon wafer, PS-b-P2VP micellar arrays consisting of a PS corona and a P2VP core were formed, while the PMMA macrodomains were isolated, due to the macrophase separation caused by the incompatibility between block copolymer micelles and PMMA homopolymer during the spin-coating process. With an increase of PMMA composition, the size of PMMA macrodomains increased. Moreover, the P2VP blocks have a strong interaction with a native oxide of the surface of the silicon wafer, so that the P2VP wetting layer was first formed during spin-coating, and PS nanoclusters were observed on the PMMA macrodomains beneath. Whereas when a silicon surface was modified with a PS brush layer, the PS nanoclusters underlying PMMA domains were not formed. The multi-scale patterns prepared from copolymer micelle/homopolymer blend films are used as templates for the fabrication of gold nanoparticle arrays by incorporating the gold precursor into the P2VP chains. The combination of nanostructures prepared from block copolymer micellar arrays and macrostructures induced by incompatibility between the copolymer and the homopolymer leads to the formation of complex, multi-scale surface patterns by a simple casting process.A simple, straightforward process for fabricating multi-scale micro- and nanostructured patterns from polystyrene-block-poly(2-vinylpyridine) (PS-b-P2VP)/poly(methyl methacrylate) (PMMA) homopolymer in a preferential solvent for PS and PMMA is demonstrated. When the PS-b-P2VP/PMMA blend films were spin-coated onto a silicon wafer, PS-b-P2VP micellar arrays consisting of a PS corona and a P2VP core were formed, while the PMMA macrodomains were isolated, due to the

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

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Ethylene-ethyl acrylate copolymers. 177.1320... Basic Components of Single and Repeated Use Food Contact Surfaces § 177.1320 Ethylene-ethyl acrylate copolymers. Ethylene-ethyl acrylate copolymers may be safely used to produce packaging materials, containers...

  10. Sulfomethylated graft copolymers of xanthan gum and polyacrylamide

    Energy Technology Data Exchange (ETDEWEB)

    Cottrell, I.W.; Empey, R.A.; Racciato, J.S.

    1978-08-08

    A water-soluble anionic graft copolymer of xanthan gum and polyacrylamide is described in which at least part of the amide function of the acrylamide portion of the copolymer is sulfomethylated and the xanthan gum portion of the copolymer is unreacted with formaldehyde. The copolymer is sulfomethylated by reaction with formaldehyde and sodium metabisulfite. The formaldehyde does not cause any appreciable cross-linking between hydroxyl groups of the xanthan moieties. The sulfomethylation of the acrylamido group takes place at temperatures from 35 to 70 C. The pH is 10 or higher, typically from 12 to 13. The degree of anionic character may be varied by adjusting the molar ratio of formaldehyde and sodium metabisulfite with respect to the copolymer. 10 claims.

  11. Preparation of mesoporous silica thin films by photocalcination method and their adsorption abilities for various proteins

    Energy Technology Data Exchange (ETDEWEB)

    Kato, Katsuya, E-mail: katsuya-kato@aist.go.jp [National Institute of Advanced Industrial Science and Technology (AIST), 2266-98 Anagahora, Shimoshidami, Moriyama-ku, Nagoya 463-8560 (Japan); Nakamura, Hitomi [National Institute of Advanced Industrial Science and Technology (AIST), 2266-98 Anagahora, Shimoshidami, Moriyama-ku, Nagoya 463-8560 (Japan); Yamauchi, Yoshihiro; Nakanishi, Kazuma; Tomita, Masahiro [Department of Chemistry for Materials, Graduate School of Engineering, Mie University, 1577 Kurimamachiya-cho, Tsu, Mie 514-8570 (Japan)

    2014-07-01

    Mesoporous silica (MPS) thin film biosensor platforms were established. MPS thin films were prepared from tetraethoxysilane (TEOS) via using sol–gel and spin-coating methods using a poly-(ethylene oxide)-block-poly-(propylene oxide)-block-poly-(ethylene oxide) triblock polymer, such as P123 ((EO){sub 20}(PO){sub 70}(EO){sub 20}) or F127 ((EO){sub 106}(PO){sub 70}(EO){sub 106}), as the structure-directing agent. The MPS thin film prepared using P123 as the mesoporous template and treated via vacuum ultraviolet (VUV) irradiation to remove the triblock copolymer had a more uniform pore array than that of the corresponding film prepared via thermal treatment. Protein adsorption and enzyme-linked immunosorbent assay (ELISA) on the synthesized MPS thin films were also investigated. VUV-irradiated MPS thin films adsorbed a smaller quantity of protein A than the thermally treated films; however, the human immunoglobulin G (IgG) binding efficiency was higher on the former. In addition, protein A–IgG specific binding on MPS thin films was achieved without using a blocking reagent; i.e., nonspecific adsorption was inhibited by the uniform pore arrays of the films. Furthermore, VUV-irradiated MPS thin films exhibited high sensitivity for ELISA testing, and cytochrome c adsorbed on the MPS thin films exhibited high catalytic activity and recyclability. These results suggest that MPS thin films are attractive platforms for the development of novel biosensors. - Highlights: • VUV-treated MPS thin films with removed polymer had uniform pore. • VUV-treated MPS thin films exhibited high sensitivity by ELISA. • Cytochrome c showed the catalytic activity and recyclability on synthesized films.

  12. Preparation of mesoporous silica thin films by photocalcination method and their adsorption abilities for various proteins

    International Nuclear Information System (INIS)

    Kato, Katsuya; Nakamura, Hitomi; Yamauchi, Yoshihiro; Nakanishi, Kazuma; Tomita, Masahiro

    2014-01-01

    Mesoporous silica (MPS) thin film biosensor platforms were established. MPS thin films were prepared from tetraethoxysilane (TEOS) via using sol–gel and spin-coating methods using a poly-(ethylene oxide)-block-poly-(propylene oxide)-block-poly-(ethylene oxide) triblock polymer, such as P123 ((EO) 20 (PO) 70 (EO) 20 ) or F127 ((EO) 106 (PO) 70 (EO) 106 ), as the structure-directing agent. The MPS thin film prepared using P123 as the mesoporous template and treated via vacuum ultraviolet (VUV) irradiation to remove the triblock copolymer had a more uniform pore array than that of the corresponding film prepared via thermal treatment. Protein adsorption and enzyme-linked immunosorbent assay (ELISA) on the synthesized MPS thin films were also investigated. VUV-irradiated MPS thin films adsorbed a smaller quantity of protein A than the thermally treated films; however, the human immunoglobulin G (IgG) binding efficiency was higher on the former. In addition, protein A–IgG specific binding on MPS thin films was achieved without using a blocking reagent; i.e., nonspecific adsorption was inhibited by the uniform pore arrays of the films. Furthermore, VUV-irradiated MPS thin films exhibited high sensitivity for ELISA testing, and cytochrome c adsorbed on the MPS thin films exhibited high catalytic activity and recyclability. These results suggest that MPS thin films are attractive platforms for the development of novel biosensors. - Highlights: • VUV-treated MPS thin films with removed polymer had uniform pore. • VUV-treated MPS thin films exhibited high sensitivity by ELISA. • Cytochrome c showed the catalytic activity and recyclability on synthesized films

  13. Molecular Design of Sulfonated Triblock Copolymer Permselective Membranes

    Science.gov (United States)

    2008-07-03

    on DNA solvation in water [39] and simulations of polyacrylic acid with calcium counterion.[40] Mesoscale approaches to polyelectrolyte modeling...interacts strongly with both proton and potassium cation. Addition of three extra DMMP molecules does not change the nature of proton solvation. The ion...the potassium ion with K-O distance of 0.22nm. This does not mean a coordination of DMMP molecules by the ion. However, this result suggests a very

  14. A comprehensive study in triblock copolymer membrane interaction

    Czech Academy of Sciences Publication Activity Database

    Pembouong, G.; Morellet, N.; Kral, Teresa; Hof, Martin; Scherman, D.; Bureau, M.-F.; Mignet, N.

    2011-01-01

    Roč. 151, č. 1 (2011), s. 57-64 ISSN 0168-3659 R&D Projects: GA AV ČR IAA400400621; GA MŠk(CZ) LC06063 Institutional research plan: CEZ:AV0Z40400503 Keywords : poloxamer * pluronic * liposomes Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 5.732, year: 2011

  15. 21 CFR 177.1310 - Ethylene-acrylic acid copolymers.

    Science.gov (United States)

    2010-04-01

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

  16. 21 CFR 177.1312 - Ethylene-carbon monoxide copolymers.

    Science.gov (United States)

    2010-04-01

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

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

    Science.gov (United States)

    2010-04-01

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

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

    Science.gov (United States)

    2010-04-01

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

  19. Antimicrobial activity of poly(acrylic acid) block copolymers

    Energy Technology Data Exchange (ETDEWEB)

    Gratzl, Günther, E-mail: guenther.gratzl@jku.at [Johannes Kepler University Linz, Institute for Chemical Technology of Organic Materials, Altenberger Str. 69, 4040 Linz (Austria); Paulik, Christian [Johannes Kepler University Linz, Institute for Chemical Technology of Organic Materials, Altenberger Str. 69, 4040 Linz (Austria); Hild, Sabine [Johannes Kepler University Linz, Institute of Polymer Science, Altenberger Str. 69, 4040 Linz (Austria); Guggenbichler, Josef P.; Lackner, Maximilian [AMiSTec GmbH and Co. KG, Leitweg 13, 6345 Kössen, Tirol (Austria)

    2014-05-01

    The increasing number of antibiotic-resistant bacterial strains has developed into a major health problem. In particular, biofilms are the main reason for hospital-acquired infections and diseases. Once formed, biofilms are difficult to remove as they have specific defense mechanisms against antimicrobial agents. Antimicrobial surfaces must therefore kill or repel bacteria before they can settle to form a biofilm. In this study, we describe that poly(acrylic acid) (PAA) containing diblock copolymers can kill bacteria and prevent from biofilm formation. The PAA diblock copolymers with poly(styrene) and poly(methyl methacrylate) were synthesized via anionic polymerization of tert-butyl acrylate with styrene or methyl methacrylate and subsequent acid-catalyzed hydrolysis of the tert-butyl ester. The copolymers were characterized via nuclear magnetic resonance spectroscopy (NMR), size-exclusion chromatography (SEC), Fourier transform infrared spectroscopy (FTIR), elemental analysis, and acid–base titrations. Copolymer films with a variety of acrylic acid contents were produced by solvent casting, characterized by atomic force microscopy (AFM) and tested for their antimicrobial activity against Staphylococcus aureus, Escherichia coli, and Pseudomonas aeruginosa. The antimicrobial activity of the acidic diblock copolymers increased with increasing acrylic acid content, independent of the copolymer-partner, the chain length and the nanostructure. - Highlights: • Acrylic acid diblock copolymers are antimicrobially active. • The antimicrobial activity depends on the acrylic acid content in the copolymer. • No salts, metals or other antimicrobial agents are needed.

  20. Antimicrobial activity of poly(acrylic acid) block copolymers

    International Nuclear Information System (INIS)

    Gratzl, Günther; Paulik, Christian; Hild, Sabine; Guggenbichler, Josef P.; Lackner, Maximilian

    2014-01-01

    The increasing number of antibiotic-resistant bacterial strains has developed into a major health problem. In particular, biofilms are the main reason for hospital-acquired infections and diseases. Once formed, biofilms are difficult to remove as they have specific defense mechanisms against antimicrobial agents. Antimicrobial surfaces must therefore kill or repel bacteria before they can settle to form a biofilm. In this study, we describe that poly(acrylic acid) (PAA) containing diblock copolymers can kill bacteria and prevent from biofilm formation. The PAA diblock copolymers with poly(styrene) and poly(methyl methacrylate) were synthesized via anionic polymerization of tert-butyl acrylate with styrene or methyl methacrylate and subsequent acid-catalyzed hydrolysis of the tert-butyl ester. The copolymers were characterized via nuclear magnetic resonance spectroscopy (NMR), size-exclusion chromatography (SEC), Fourier transform infrared spectroscopy (FTIR), elemental analysis, and acid–base titrations. Copolymer films with a variety of acrylic acid contents were produced by solvent casting, characterized by atomic force microscopy (AFM) and tested for their antimicrobial activity against Staphylococcus aureus, Escherichia coli, and Pseudomonas aeruginosa. The antimicrobial activity of the acidic diblock copolymers increased with increasing acrylic acid content, independent of the copolymer-partner, the chain length and the nanostructure. - Highlights: • Acrylic acid diblock copolymers are antimicrobially active. • The antimicrobial activity depends on the acrylic acid content in the copolymer. • No salts, metals or other antimicrobial agents are needed

  1. Critical Conditions for Liquid Chromatography of Statistical Copolymers: Functionality Type and Composition Distribution Characterization by UP-LCCC/ESI-MS.

    Science.gov (United States)

    Epping, Ruben; Panne, Ulrich; Falkenhagen, Jana

    2017-02-07

    Statistical ethylene oxide (EO) and propylene oxide (PO) copolymers of different monomer compositions and different average molar masses additionally containing two kinds of end groups (FTD) were investigated by ultra high pressure liquid chromatography under critical conditions (UP-LCCC) combined with electrospray ionization time-of flight mass spectrometry (ESI-TOF-MS). Theoretical predictions of the existence of a critical adsorption point (CPA) for statistical copolymers with a given chemical and sequence distribution1 could be studied and confirmed. A fundamentally new approach to determine these critical conditions in a copolymer, alongside the inevitable chemical composition distribution (CCD), with mass spectrometric detection, is described. The shift of the critical eluent composition with the monomer composition of the polymers was determined. Due to the broad molar mass distribution (MMD) and the presumed existence of different end group functionalities as well as monomer sequence distribution (MSD), gradient separation only by CCD was not possible. Therefore, isocratic separation conditions at the CPA of definite CCD fractions were developed. Although the various present distributions partly superimposed the separation process, the goal of separation by end group functionality was still achieved on the basis of the additional dimension of ESI-TOF-MS. The existence of HO-H besides the desired allylO-H end group functionalities was confirmed and their amount estimated. Furthermore, indications for a MSD were found by UPLC/MS/MS measurements. This approach offers for the first time the possibility to obtain a fingerprint of a broad distributed statistical copolymer including MMD, FTD, CCD, and MSD.

  2. Copolymers at the solid - liquid interface

    NARCIS (Netherlands)

    Wijmans, C.M.

    1994-01-01

    Copolymers consisting of both adsorbing and nonadsorbing segments can show an adsorption behaviour which is very different from that of homopolymers. We have mainly investigated the adsorption of AB diblock copolymers, which have one adsorbing block (anchor) and one nonadsorbing block

  3. Synthesis and characterization of waterborne polyurethane acrylate copolymers

    International Nuclear Information System (INIS)

    Sultan, Misbah; Bhatti, Haq Nawaz; Zuber, Mohammad; Barikani, Mehdi

    2013-01-01

    Polyurethane acrylate copolymers were synthesized by emulsion polymerization process. To reduce the environmental hazards, organic solvents were replaced by eco-friendly aqueous system. Concentration of polyurethane and acrylate monomer was varied to investigate the effect of chemical composition on performance properties of copolymers. FTIR spectroscopy was used as a key tool to record the chemical synthesis route. The synthesized copolymer emulsions were characterized by evaluating their particle size, viscosity, dry weight content, chemical and water resistance. Thermal decomposition was studied by thermogravimetric analysis. Scanning electron microscope was used to visualize the morphological structure of copolymers. The experimental results indicate better polyurethane acrylate compatibility till the ratio of 30/70. However, these copolymers exhibited synergistic effects between the two polymers and revealed a remarkable improvement in numerous coating properties

  4. SYNTHESIS OF pH-RESPONSIVE AMPHIPHILIC DIBLOCK COPOLYMERS CONTAINING POLYISOBUTYLENE via OXYANION-INITIATED POLYMERIZATION AND THEIR MULTIPLE SELF-ASSEMBLY MORPHOLOGIES

    Institute of Scientific and Technical Information of China (English)

    Huai-chao Wang; Ming-zu Zhang; Pei-hong Ni; Jin-lin He; Ying Hao; Yi-xian Wu

    2013-01-01

    Two pH-responsive amphiphilic diblock copolymers,namely polyisobutylene-block-poly[2-(N,N-dimethylamino)ethyl methacrylate] (PIB-b-PDMAEMA) and polyisobutylene-block-poly(metharylic acid) (PIB-b-PMAA),were synthesized via oxyanion-initiated polymerization,and their multiple self-assembly behaviors have been studied.An exo-o1efin-terminated highly reactive polyisobutylene (HRPIB) was first changed to hydroxyl-terminated PIB (PIB-OH) via hydroboration-oxidation of C=C double bond in the chain end,and then reacted with KH to yield a potassium alcoholate of PIB (PIB-O-K+).PIB-O-K+ was immediately used as a macroinitiator to polymerize DMAEMA monomer,resulting in a cationic diblock copolymer PIB-b-PDMAEMA.With the similar synthesis procedure,the anionic diblock copolymer PIB-b-PMAA could be prepared via a combination of oxyanion-initiated polymerization of tert-butyl methacrylate (tBMA) and subsequent hydrolysis of tert-butyl ester groups in PtBMA block.The functional PIB and block copolymers have been fully characterized by 1H-NMR,FT-IR spectroscopy,and gel permeation chromatography (GPC).These samples allowed us to systematically investigate the effects of block composition on the pH responsivity and various self-assembled morphologies of the copolymers in THF/water mixed solvent.Transmission electron microscopy (TEM) images revealed that these diblock copolymers containing small amount of original PIB without exo-olefin-terminated group are able to self-assemble into micelles,vesicles with different particle sizes and cylindrical aggregates,depending on various factors including block copolymer composition,solvent polarity and pH value.

  5. The influence of chain stretching on the phase behavior of multiblock copolymer and comb copolymer melts

    NARCIS (Netherlands)

    Angerman, HJ; ten Brinke, G

    The subject of this paper is inspired by microphase-separated copolymer melts in which a small-scale structure is present inside one of the phases of a large-scale structure. Such a situation can arise in a diblock copolymer melt, if one of the blocks of the diblock is in itself a multiblock

  6. Polyketones as alternating copolymers of carbon monoxide

    International Nuclear Information System (INIS)

    Belov, Gennady P; Novikova, Elena V

    2004-01-01

    Characteristic features of the catalytic synthesis of alternating copolymers of carbon monoxide with various olefins, dienes, styrene and its derivatives are considered. The diversity of catalyst systems used for the copolymerisation of carbon monoxide is demonstrated and their influence on the structure and the molecular mass of the resulting copolymers is analysed. The data on the structure and physicochemical and mechanical properties of this new generation of functional copolymers are generalised and described systematically for the first time.

  7. 21 CFR 177.2470 - Polyoxymethylene copolymer.

    Science.gov (United States)

    2010-04-01

    ... Components of Articles Intended for Repeated Use § 177.2470 Polyoxymethylene copolymer. Polyoxymethylene copolymer identified in this section may be safely used as an article or component of articles intended for... are available from the Center for Food Safety and Applied Nutrition (HFS-200), Food and Drug...

  8. Nanoparticles based on novel amphiphilic polyaspartamide copolymers

    International Nuclear Information System (INIS)

    Craparo, Emanuela Fabiola; Teresi, Girolamo; Ognibene, Maria Chiara; Casaletto, Maria Pia; Bondi, Maria Luisa; Cavallaro, Gennara

    2010-01-01

    In this article, the synthesis of two amphiphilic polyaspartamide copolymers, useful to obtain polymeric nanoparticles without using surfactants or stabilizing agents, is described. These copolymers were obtained starting from α,β-poly-(N-2-hydroxyethyl)-dl-aspartamide (PHEA) by following a novel synthetic strategy. In particular, PHEA and its pegylated derivative (PHEA-PEG 2000 ) were functionalized with poly(lactic acid) (PLA) through 1,1'-carbonyldiimidazole (CDI) activation to obtain PHEA-PLA and PHEA-PEG 2000 -PLA graft copolymers, respectively. These copolymers were properly purified and characterized by 1 H-NMR, FT-IR, and Size Exclusion Chromatography (SEC) analyses, which confirmed that derivatization reactions occurred. Nanoparticles were obtained from PHEA-PLA and PHEA-PEG 2000 -PLA graft copolymers by using the high pressure homogenization-solvent evaporation method, avoiding the use of surfactants or stabilizing agents. Polymeric nanoparticles were characterized by dimensional analysis, before and after freeze-drying process, and Scanning Electron Microscopy (SEM). Zeta potential measurements and X-ray Photoelectron Spectroscopy (XPS) analysis demonstrated the presence of PEG and/or PHEA onto the PHEA-PEG 2000 -PLA and PHEA-PLA nanoparticle surface, respectively.

  9. Amphiphilic copolymers for fouling-release coatings

    DEFF Research Database (Denmark)

    Noguer, Albert Camós; Olsen, Stefan Møller; Hvilsted, Søren

    of the coatings [9,10,11]. This work shows the effect of an amphiphilic copolymer that induces hydrophilicity on the surface of the silicone-based fouling release coatings. The behaviour of these copolymers within the coating upon immersion and the interaction of these surface-active additives with other...

  10. Poly(ferrocenylsilane)-block-Polylactide Block Copolymers

    NARCIS (Netherlands)

    Roerdink, M.; van Zanten, Thomas S.; Hempenius, Mark A.; Zhong, Zhiyuan; Feijen, Jan; Vancso, Gyula J.

    2007-01-01

    A PFS/PLA block copolymer was studied to probe the effect of strong surface interactions on pattern formation in PFS block copolymer thin films. Successful synthesis of PFS-b-PLA was demonstrated. Thin films of these polymers show phase separation to form PFS microdomains in a PLA matrix, and

  11. Transport of Water in Semicrystalline Block Copolymer Membranes

    Science.gov (United States)

    Hallinan, Daniel; Oparaji, Onyekachi

    Poly(styrene)-block-poly(ethylene oxide) (PS- b-PEO) is a semicrystalline block copolymer (BCP) with interesting properties. It is mechanically tough, amphiphilic, and has a polar phase. The mechanical toughness is due to the crystallinity of PEO and the high glass transition temperature of PS, as well as the morphological structure of the BCP. The polymer has high CO2, water, and salt solubility that derive from the polar PEO component. Potential applications include CO2 separation, water purification, and lithium air batteries. In all of the aforementioned applications, water transport is an important parameter. The presence of water can also affect thermal and mechanical properties. Water transport and thermal and mechanical properties of a lamellar PS- b-PEO copolymer have been measured as a function of water activity. Water transport can be affected by the heterogeneous nature of a semicrystalline BCP. Therefore, Fourier transform infrared - attenuated total reflectance (FTIR-ATR) spectroscopy has been employed, because water transport and polymer swelling can be measured simultaneously. The effect of BCP structure on transport has been investigated by comparing water transport in PS- b-PEO to a PEO homopolymer. The crystalline content of the PEO and the presence of glassy PS lamellae will be used to explain the transport results.

  12. The pentafluorostyrene endeavours with atom transfer radical polymerization - quo vadis?

    DEFF Research Database (Denmark)

    Hvilsted, Søren

    2014-01-01

    The versatility of the atom transfer radical polymerization (ATRP) of pentafluorostyrene (FS) is comprehensively evaluated. The ATRP of a wide range of monomers derived from FS is likewise discussed with emphasis on the potential polymer applications. A large number of block and star copolymers...... centred around polypentafluorostyrene (PFS) and prepared primarily using the bromomacroinitiator concept is surveyed. Here the main emphasis is on the feasibility of the polymer design, but also the very many different applications are highlighted. The potential grafting onto PFS and PFS block copolymers...... by exploitation of the very labile para-fluorine demonstrates new material architecture possibilities through very mild reaction conditions. Finally the utility of PFS in various conducting materials is elaborated. The amphiphilic nature of PFS in triblock copolymers with polyethers has been exploited for Li+ ion...

  13. Chemical states and electronic properties of the interface between aluminium and a photoluminescent conjugated copolymer containing europium complex

    International Nuclear Information System (INIS)

    Cai, Q.J.; Ling, Q.D.; Li, S.; Zhu, F.R.; Huang, Wei; Kang, E.T.; Neoh, K.G.

    2004-01-01

    The chemical states and electronic properties of the interface between thermally evaporated aluminium and a photoluminescent conjugated copolymer containing 9,9'-dihexylfluorene and europium complex-chelated benzoate units in the main chain (PF6-Eu(dbm) 2 phen) were studied in situ by X-ray photoelectron spectroscopy (XPS) and ultraviolet photoelectron spectroscopy (UPS). The changes in C 1s, Eu 3d, N 1s, and Al 2p core-level lineshapes with progressive deposition of aluminium atoms were carefully monitored. Aluminium was found to interact with the conjugated backbone of the copolymer to form the Al carbide, Al-O-C complex, and Al(III)-N chelate at the interface. In addition, the europium ions were reduced to the metallic state by the deposited aluminium atoms, which were oxidized and chelated by the 1,10-phenanthroline ligands (phen). The changes in chemical states at the interface suggest that the intramolecular energy transfer process in this copolymer had been affected. Moreover, aluminium also interacted with the bulk-adsorbed oxygen, which migrates to the surface in response to the deposition of aluminium atoms, to form a layer of metal oxides. On the other hand, the evolution of the UPS spectra suggests that the π-states of the conjugated system were affected and an unfavorable dipole layer was induced by the deposited aluminium atoms

  14. Micellization and Dynamics of a Block Copolymer

    DEFF Research Database (Denmark)

    Hvidt, Søren

    2006-01-01

    and copolymer mixtures, and evidence in favor of a multi-equilibria unimer-micelle model will be presented. Results obtained by liquid chromatographic methods will be shown and it will be demonstrated that commercial EPE copolymers are inhomogeneous at several levels and many of their unusual properties reflect...... ratios and temperature. The micellization process with increasing temperature has been followed by a number of techniques including differential scanning calorimetry, liquid chromatography, and surface tension measurements. Different micellization models have been tested for purified copolymers...

  15. Acrylonitrile-methyl Methacrylate Copolymer Films Containing Microencapsulated n-Octadecane

    Institute of Scientific and Technical Information of China (English)

    LI Jun; HAN Na; ZHANG Xing-xiang

    2006-01-01

    Acrylonitrile-methyl methacrylate copolymer was synthesized in aqueous solution by Redox. The copolymer was mixed with 10 - 40 wt% of microencapsulated n-octadecane (MicroPCMs) in water. Copolymer films containing MicroPCMs were cast at room temperature in N, N-Dimethylformamide solution. The copolymer of acrylonitrile-methyl methacrylate and the copolymer films containing MicroPCMs were characterized by using Fourier Transform Infrared Spectroscopy (FTIR), Differential Scanning Calorimetry (DSC), Thermogravimetric Analyzer (TG), X-ray Diffrac tion (XRD) and Scanning Electron Microscopy (SEM), etc.The microcapsules in the films are evenly distributed in the copolymer matrix. The heat-absorbing temperatures and heat-evolving temperatures of the films are almost the same as that of the MicroPCMs, respectively, and fluctuate in a slight range. In addition, the enthalpy efficiency of MicroPCMs rises with the contents of MicroPCMs increasing.The crystallinity of the film increases with the contents of MicroPCMs increasing.

  16. Morphological studies on block copolymer modified PA 6 blends

    Energy Technology Data Exchange (ETDEWEB)

    Poindl, M., E-mail: marcus.poindl@ikt.uni-stuttgart.de, E-mail: christian.bonten@ikt.uni-stuttgart.de; Bonten, C., E-mail: marcus.poindl@ikt.uni-stuttgart.de, E-mail: christian.bonten@ikt.uni-stuttgart.de [Institut für Kunststofftechnik, University of Stuttgart (Germany)

    2014-05-15

    Recent studies show that compounding polyamide 6 (PA 6) with a PA 6 polyether block copolymers made by reaction injection molding (RIM) or continuous anionic polymerization in a reactive extrusion process (REX) result in blends with high impact strength and high stiffness compared to conventional rubber blends. In this paper, different high impact PA 6 blends were prepared using a twin screw extruder. The different impact modifiers were an ethylene propylene copolymer, a PA PA 6 polyether block copolymer made by reaction injection molding and one made by reactive extrusion. To ensure good particle matrix bonding, the ethylene propylene copolymer was grafted with maleic anhydride (EPR-g-MA). Due to the molecular structure of the two block copolymers, a coupling agent was not necessary. The block copolymers are semi-crystalline and partially cross-linked in contrast to commonly used amorphous rubbers which are usually uncured. The combination of different analysis methods like atomic force microscopy (AFM), transmission electron microscopy (TEM) and scanning electron microscopy (SEM) gave a detailed view in the structure of the blends. Due to the partial cross-linking, the particles of the block copolymers in the blends are not spherical like the ones of ethylene propylene copolymer. The differences in molecular structure, miscibility and grafting of the impact modifiers result in different mechanical properties and different blend morphologies.

  17. Photo-Induced Micellization of Block Copolymers

    Directory of Open Access Journals (Sweden)

    Satoshi Kuwayama

    2010-11-01

    Full Text Available We found novel photo-induced micellizations through photolysis, photoelectron transfer, and photo-Claisen rearrangement. The photolysis-induced micellization was attained using poly(4-tert-butoxystyrene-block-polystyrene diblock copolymer (PBSt-b-PSt. BSt-b-PSt showed no self-assembly in dichloromethane and existed as isolated copolymers. Dynamic light scattering demonstrated that the copolymer produced spherical micelles in this solvent due to irradiation with a high-pressure mercury lamp in the presence of photo-acid generators, such as bis(alkylphenyliodonium hexafluorophosphate, diphenyliodonium hexafluorophosphate, and triphenylsulfonium triflate. The 1H NMR analysis confirmed that PBSt-b-PSt was converted into poly(4-vinylphenol-block-PSt by the irradiation, resulting in self-assembly into micelles. The irradiation in the presence of the photo-acid generator also induced the micellization of poly(4-pyridinemethoxymethylstyrene-block-polystyrene diblock copolymer (PPySt-b-PSt. Micellization occurred by electron transfer from the pyridine to the photo-acid generator in their excited states and provided monodispersed spherical micelles with cores of PPySt blocks. Further, the photo-Claisen rearrangement caused the micellization of poly(4-allyloxystyrene-block-polystyrene diblock copolymer (PASt-b-PSt. Micellization was promoted in cyclohexane at room temperature without a catalyst. During micellization, the elimination of the allyl groups competitively occurred along with the photorearrangement of the 4-allyloxystyrene units into the 3-allyl-4-hydroxystyrene units.

  18. Synthesis of a large-sized mesoporous phosphosilicate thin film through evaporation-induced polymeric micelle assembly.

    Science.gov (United States)

    Li, Yunqi; Bastakoti, Bishnu Prasad; Imura, Masataka; Suzuki, Norihiro; Jiang, Xiangfen; Ohki, Shinobu; Deguchi, Kenzo; Suzuki, Madoka; Arai, Satoshi; Yamauchi, Yusuke

    2015-01-01

    A triblock copolymer, poly(styrene-b-2-vinyl pyridine-b-ethylene oxide) (PS-b-P2VP-b-PEO) was used as a soft template to synthesize large-sized mesoporous phosphosilicate thin films. The kinetically frozen PS core stabilizes the micelles. The strong interaction of the inorganic precursors with the P2VP shell enables the fabrication of highly robust walls of phosphosilicate and the PEO helps orderly packing of the micelles during solvent evaporation. The molar ratio of phosphoric acid and tetraethyl orthosilicate is crucial to achieve the final mesostructure. The insertion of phosphorus species into the siloxane network is studied by (29) Si and (31) P MAS NMR spectra. The mesoporous phosphosilicate films exhibit steady cell adhesion properties and show great promise as excellent materials in bone-growth engineering applications. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Fast & scalable pattern transfer via block copolymer nanolithography

    DEFF Research Database (Denmark)

    Li, Tao; Wang, Zhongli; Schulte, Lars

    2015-01-01

    A fully scalable and efficient pattern transfer process based on block copolymer (BCP) self-assembling directly on various substrates is demonstrated. PS-rich and PDMS-rich poly(styrene-b-dimethylsiloxane) (PS-b-PDMS) copolymers are used to give monolayer sphere morphology after spin-casting of s......A fully scalable and efficient pattern transfer process based on block copolymer (BCP) self-assembling directly on various substrates is demonstrated. PS-rich and PDMS-rich poly(styrene-b-dimethylsiloxane) (PS-b-PDMS) copolymers are used to give monolayer sphere morphology after spin...... on long range lateral order, including fabrication of substrates for catalysis, solar cells, sensors, ultrafiltration membranes and templating of semiconductors or metals....

  20. Investigation of a new thermosensitive block copolymer micelle: hydrolysis, disruption, and release.

    Science.gov (United States)

    Pelletier, Maxime; Babin, Jérôme; Tremblay, Luc; Zhao, Yue

    2008-11-04

    Thermosensitive polymer micelles are generally obtained with block copolymers in which one block exhibits a lower critical solution temperature in aqueous solution. We investigate a different design that is based on the use of one block bearing a thermally labile side group, whose hydrolysis upon heating shifts the hydrophilic-hydrophobic balance toward the destabilization of block copolymer micelles. Atom transfer radical polymerization was utilized to synthesize a series of diblock copolymers composed of hydrophilic poly(ethylene oxide) (PEO) and hydrophobic poly(2-tetrahydropyranyl methacrylate) (PTHPMA). We show that micelles of PEO-b-PTHPMA in aqueous solution can be destabilized as a result of the thermosensitive hydrolytic cleavage of tetrahydropyranyl (THP) groups that transforms PTHPMA into hydrophilic poly(methacrylic acid). The three related processes occurring in aqueous solution, namely, hydrolytic cleavage of THP, destabilization of micelles, and release of loaded Nile Red (NR), were investigated simultaneously using 1H NMR, dynamic light scattering, and fluorescence spectroscopy, respectively. At 80 degrees C, the results suggest that the three events proceed with a similar kinetics. Although slower than at elevated temperatures, the disruption of PEO-b-PTHPMA micelles can take place at the body temperature (approximately 37 degrees C), and the release kinetics of NR can be adjusted by changing the relative lengths of the two blocks or the pH of the solution.

  1. Sequential polymerization of ethylene oxide, ε-caprolactone and l-lactide: A one-pot metal-free route to tri- and pentablock terpolymers

    KAUST Repository

    Zhao, Junpeng

    2014-01-01

    Metal-free polymerization of ethylene oxide (EO) catalyzed by a relatively mild phosphazene base (t-BuP2) was proven feasible, which enabled the one-pot sequential polymerization of EO, ε-caprolactone, and l-lactide. Using either 3-phenyl-1-propanol or water as an initiator, the corresponding triblock or pentablock terpolymers were easily prepared. © 2014 the Partner Organisations.

  2. Large strain deformation behavior of polymeric gels in shear- and cavitation rheology

    Science.gov (United States)

    Hashemnejad, Seyed Meysam; Kundu, Santanu

    Polymeric gels are used in many applications including in biomedical and in food industries. Investigation of mechanical responses of swollen polymer gels and linking that to the polymer chain dynamics are of significant interest. Here, large strain deformation behavior of two different gel systems and with different network architecture will be presented. We consider biologically relevant polysaccharide hydrogels, formed through ionic and covalent crosslinking, and physically associating triblock copolymer gels in a midblock selective solvent. Gels with similar low-strain shear modulus display distinctly different non-linear rheological behavior in large strain shear deformation. Both these gels display strain-stiffening behavior in shear-deformation prior to macroscopic fracture of the network, however, only the alginate gels display negative normal stress. The cavitation rheology data show that the critical pressure for cavitation is higher for alginate gels than that observed for triblock gels. These distinctly different large-strain deformation behavior has been related to the gel network structure, as alginate chains are much stiffer than the triblock polymer chains.

  3. An Electrochemical Study of Two Self-Dopable Water-Soluble Aniline Derivatives: Electrochemical Deposition of Copolymers

    Directory of Open Access Journals (Sweden)

    Loredana Vacareanu

    2012-01-01

    Full Text Available An electrochemical study of two water-soluble aniline derivatives, N-(3-sulfopropyl aniline (AnPS and N-(3-sulfopropyl p-aminodiphenylamine (DAnPS, in aqueous acidic electrolytic solutions containing different kinds of doping anions (Cl −, SO4 2−, and ClO4 − was carried out. At sufficiently high anodic potential, the sulfonated aniline derivatives undergo oxidation processes yielding cation-radical and dimer intermediates, but no polymer deposition was observed on the working electrode surface. Experimental results showed that both aniline derivatives are electroactive compounds exhibiting redox behaviour in the range of potential of −0.2 V–1.6 V. Due to the self-doping effect induced by sulfonic groups, AnPS and DAnPS compounds have good electroactivity even in neat water solution. By adding a small amount of aniline into electrolytic system, thin layers of copolymers were deposited on the working electrode surface. The copolymer layers formed on the electrodes show a highly orientational and positional order, confirmed by AFM and XRD spectroscopic techniques. During the anodic oxidation processes some distinct colour changes were observed.

  4. Strong adsorbability of mercury ions on aniline/sulfoanisidine copolymer nanosorbents.

    Science.gov (United States)

    Li, Xin-Gui; Feng, Hao; Huang, Mei-Rong

    2009-01-01

    The highest Hg-ion adsorbance so far, namely up to 2063 mg g(-1), has been achieved by poly(aniline-co-5-sulfo-2-anisidine) nanosorbents. Sorption of Hg ions occurs mainly by redox and chelation mechanisms (see scheme), but also by ion exchange and physisorption.Poly(aniline (AN)-co-5-sulfo-2-anisidine (SA)) nanoparticles were synthesized by chemical oxidative copolymerization of AN and SA monomers, and their extremely strong adsorption of mercury ions in aqueous solution was demonstrated. The reactivity ratios of AN and SA comonomers were found to be 2.05 and 0.02, respectively. While AN monomer tends to homopolymerize, SA monomer tends to copolymerize with AN monomer because of the great steric hindrance and electron-attracting effect of the sulfo groups, despite the effect of conjugation of the methoxyl group with the benzene ring. The effects of initial mercury(II) concentration, sorption time, sorption temperature, ultrasonic treatment, and sorbent dosage on mercury-ion sorption onto AN/SA (50/50) copolymer nanoparticles with a number-average diameter of around 120 nm were significantly optimized. The results show that the maximum Hg-ion sorption capacity on the particulate nanosorbents can even reach 2063 mg of Hg per gram of sorbent, which would be the highest Hg-ion adsorbance so far. The sorption data fit to the Langmuir isotherm, and the process obeys pseudo-second-order kinetics. The IR and UV/Vis spectral data of the Hg-loaded copolymer particles suggest that some mercury(II) was directly reduced by the copolymer to mercury(I) and even mercury(0). A mechanism of sorption between the particles and Hg ions in aqueous solution is proposed, and a physical/ion exchange/chelation/redox sorption ratio of around 2/3/45/50 was found. Copolymer nanoparticles may be one of the most powerful and cost-effective sorbents of mercury ions, with a wide range of potential applications for the efficient removal and even recovery of the mercury ions from aqueous solution.

  5. 21 CFR 177.1340 - Ethylene-methyl acrylate copolymer resins.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Ethylene-methyl acrylate copolymer resins. 177.1340... Basic Components of Single and Repeated Use Food Contact Surfaces § 177.1340 Ethylene-methyl acrylate copolymer resins. Ethylene-methyl acrylate copolymer resins may be safely used as articles or components of...

  6. POLYCAPROLACTONE-POLY (ETHYLENE GLYCOL) BLOCK COPOLYMER Ⅲ DRUG RELEASE BEHAVIOR

    Institute of Scientific and Technical Information of China (English)

    BEI Jianzhong; WANG Zhifeng; WANG Shenguo

    1995-01-01

    The drug release behavior of degradable polymer - polycaprolactone-poly (ethylene glycol)block copolymer(PCE) in vitro was investigated by using 5-Fluoro-uracil (5-Fu) as a model drug under a condition of pH 7.4 at 37℃. It is found that the release rate of 5-Fu from PCE increased with increasing polyether content of the copolymer. The results show that the increasing polyether content of the copolymer caused increasing hydrophilicity and decreasing crystallinity of the PCE copolymer. Thus, the drug release behavior and the degradable property of the PCE can be controlled by adjusting the composition of the copolymer.

  7. Tailored Design of Bicontinuous Gyroid Mesoporous Carbon and Nitrogen-Doped Carbon from Poly(ethylene oxide-b-caprolactone) Diblock Copolymers.

    Science.gov (United States)

    Chu, Wei-Cheng; Bastakoti, Bishnu Prasad; Kaneti, Yusuf Valentino; Li, Jheng-Guang; Alamri, Hatem R; Alothman, Zeid A; Yamauchi, Yusuke; Kuo, Shiao-Wei

    2017-10-04

    Highly ordered mesoporous resol-type phenolic resin and the corresponding mesoporous carbon materials were synthesized by using poly(ethylene oxide-b-caprolactone) (PEO-b-PCL) diblock copolymer as a soft template. The self-assembled mesoporous phenolic resin was found to form only in a specific resol concentration range of 40-70 wt % due to an intriguing balance of hydrogen-bonding interactions in the resol/PEO-b-PCL mixtures. Furthermore, morphological transitions of the mesostructures from disordered to gyroid to cylindrical and finally to disordered micelle structure were observed with increasing resol concentration. By calcination under nitrogen atmosphere at 800 °C, the bicontinuous mesostructured gyroid phenolic resin could be converted to mesoporous carbon with large pore size without collapse of the original mesostructure. Furthermore, post-treatment of the mesoporous gyroid phenolic resin with melamine gave rise to N-doped mesoporous carbon with unique electronic properties for realizing high CO 2 adsorption capacity (6.72 mmol g -1 at 0 °C). © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. "Non-equilibrium" block copolymer micelles with glassy cores: a predictive approach based on theory of equilibrium micelles.

    Science.gov (United States)

    Nagarajan, Ramanathan

    2015-07-01

    Micelles generated in water from most amphiphilic block copolymers are widely recognized to be non-equilibrium structures. Typically, the micelles are prepared by a kinetic process, first allowing molecular scale dissolution of the block copolymer in a common solvent that likes both the blocks and then gradually replacing the common solvent by water to promote the hydrophobic blocks to aggregate and create the micelles. The non-equilibrium nature of the micelle originates from the fact that dynamic exchange between the block copolymer molecules in the micelle and the singly dispersed block copolymer molecules in water is suppressed, because of the glassy nature of the core forming polymer block and/or its very large hydrophobicity. Although most amphiphilic block copolymers generate such non-equilibrium micelles, no theoretical approach to a priori predict the micelle characteristics currently exists. In this work, we propose a predictive approach for non-equilibrium micelles with glassy cores by applying the equilibrium theory of micelles in two steps. In the first, we calculate the properties of micelles formed in the mixed solvent while true equilibrium prevails, until the micelle core becomes glassy. In the second step, we freeze the micelle aggregation number at this glassy state and calculate the corona dimension from the equilibrium theory of micelles. The condition when the micelle core becomes glassy is independently determined from a statistical thermodynamic treatment of diluent effect on polymer glass transition temperature. The predictions based on this "non-equilibrium" model compare reasonably well with experimental data for polystyrene-polyethylene oxide diblock copolymer, which is the most extensively studied system in the literature. In contrast, the application of the equilibrium model to describe such a system significantly overpredicts the micelle core and corona dimensions and the aggregation number. The non-equilibrium model suggests ways to

  9. A new method to analyze copolymer based superplasticizer traces in cement leachates.

    Science.gov (United States)

    Guérandel, Cyril; Vernex-Loset, Lionel; Krier, Gabriel; De Lanève, Michel; Guillot, Xavier; Pierre, Christian; Muller, Jean François

    2011-03-15

    Enhancing the flowing properties of fresh concrete is a crucial step for cement based materials users. This is done by adding polymeric admixtures. Such additives have enabled to improve final mechanicals properties and the development of new materials like high performance or self compacting concrete. Like this, the superplasticizers are used in almost cement based materials, in particular for concrete structures that can have a potential interaction with drinking water. It is then essential to have suitable detection techniques to assess whether these organic compounds are dissolved in water after a leaching process or not. The main constituent of the last generation superplasticizer is a PolyCarboxylate-Ester copolymer (PCE), in addition this organic admixture contains polyethylene oxide (free PEO) which constitutes a synthesis residue. Numerous analytical methods are available to characterize superplasticizer content. Although these techniques work well, they do not bring suitable detection threshold to analyze superplasticizer traces in solution with high mineral content such as leachates of hardened cement based materials formulated with superplasticizers. Moreover those techniques do not enable to distinguish free PEO from PCE in the superplasticizer. Here we discuss two highly sensitive analytical methods based on mass spectrometry suitable to perform a rapid detection of superplasticizer compounds traces in CEM I cement paste leachates: MALDI-TOF mass spectrometry, is used to determine the free PEO content in the leachate. However, industrial copolymers (such as PCE) are characterized by high molecular weight and polymolecular index. These two parameters lead to limitation concerning analysis of copolymers by MALDI-TOFMS. In this study, we demonstrate how pyrolysis and a Thermally assisted Hydrolysis/Methylation coupled with a triple-quadrupole mass spectrometer, provides good results for the detection of PCE copolymer traces in CEM I cement paste

  10. Novel thermo-responsive double-hydrophilic and hydrophobic MPEO-b-PEtOx-b-PCL triblock terpolymers: synthesis, characterization and self-assembly studies

    Czech Academy of Sciences Publication Activity Database

    Petrova, Svetlana; Venturini, Cristina Garcia; Jäger, Alessandro; Jäger, Eliezer; Černoch, Peter; Kereiche, S.; Kováčik, L.; Raška, I.; Štěpánek, Petr

    2015-01-01

    Roč. 59, 24 February (2015), s. 215-225 ISSN 0032-3861 R&D Projects: GA ČR GAP208/10/1600; GA MŠk(CZ) 7F14009 Institutional support: RVO:61389013 Keywords : MPEO-b-PEtOx-b-PCL triblock terpolymers * light-scattering * thermo-responsive nanoparticles Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.586, year: 2015

  11. Polystyrene-poly(vinylphenol) copolymers as compatibilzers for organic-inorganic composites

    International Nuclear Information System (INIS)

    Landry, C.J.T.; Coltrain, B.K.; Teegarden, D.M.

    1996-01-01

    Random, graft, and block copolymers of polystyrene (PS) and poly(4-vinylphenol) (PVPh), and PVPh homopolymer are shown to act as compatibilizers for incompatible organic-inorganic composite materials. The VPh component reacts, or interacts strongly with the polymerizing inorganic (titanium or zirconium) alkoxide. The organic components studied were PS, poly(vinyl methyl ether), and poly(styrene-co-acrylonitrile). The use of such compatibilizers provides a means of combining in situ polymerized inorganic oxides and hydrophobic polymers. This is seen as a reduction in the size of the dispersed inorganic phase and results in improved optical and mechanical properties

  12. Self-assembled nanoformulation of methylprednisolone succinate with carboxylated block copolymer for local glucocorticoid therapy.

    Science.gov (United States)

    Kamalov, Marat I; Đặng, Trinh; Petrova, Natalia V; Laikov, Alexander V; Luong, Duong; Akhmadishina, Rezeda A; Lukashkin, Andrei N; Abdullin, Timur I

    2018-04-01

    A new self-assembled formulation of methylprednisolone succinate (MPS) based on a carboxylated trifunctional block copolymer of ethylene oxide and propylene oxide (TBC-COOH) was developed. TBC-COOH and MPS associated spontaneously at increased concentrations in aqueous solutions to form almost monodisperse mixed micelles (TBC-COOH/MPS) with a hydrodynamic diameter of 19.6 nm, zeta potential of -27.8 mV and optimal weight ratio ∼1:6.3. Conditions for the effective formation of TBC-COOH/MPS were elucidated by comparing copolymers and glucocorticoids with different structure. The micellar structure of TBC-COOH/MPS persisted upon dilution, temperature fluctuations and interaction with blood serum components. TBC-COOH increased antiradical activity of MPS and promoted its intrinsic cytotoxicity in vitro attributed to enhanced cellular availability of the mixed micelles. Intracellular transportation and hydrolysis of MPS were analyzed using optimized liquid chromatography tandem mass spectrometry with multiple reaction monitoring which showed increased level of both MPS and methylprednisolone in neuronal cells treated with the formulated glucocorticoid. Our results identify TBC-COOH/MPS as an advanced in situ prepared nanoformulation and encourage its further investigation for a potential local glucocorticoid therapy. Copyright © 2018 Elsevier B.V. All rights reserved.

  13. Iodinated glycidyl methacrylate copolymer as a radiopaque material for biomedical applications.

    Science.gov (United States)

    Dawlee, S; Jayabalan, M

    2013-07-01

    Polymeric biomaterial was synthesized by copolymerizing 50:50 mol% of monomers, glycidyl methacrylate and methyl methacrylate. Iodine atoms were then grafted to the epoxide groups of glycidyl methacrylate units, rendering the copolymer radiopaque. The percentage weight of iodine in the present copolymer was found to be as high as 23%. The iodinated copolymer showed higher glass transition temperature and thermal stability in comparison with unmodified polymer. Radiographic analysis showed that the copolymer possessed excellent radiopacity. The iodinated copolymer was cytocompatible to L929 mouse fibroblast cells. The in vivo toxicological evaluation by intracutaneous reactivity test of the copolymer extracts has revealed that the material was nontoxic. Subcutaneous implantation of iodinated copolymer in rats has shown that the material was well tolerated. Upon explantation and histological examination, no hemorrhage, infection or necrosis was observed. The samples were found to be surrounded by a vascularized capsule consisting of connective tissue cells. The results indicate that the iodinated copolymer is biocompatible and may have suitable applications as implantable materials.

  14. Block copolymer with simultaneous electric and ionic conduction for use in lithium ion batteries

    Science.gov (United States)

    Javier, Anna Esmeralda K; Balsara, Nitash Pervez; Patel, Shrayesh Naran; Hallinan, Jr., Daniel T

    2013-10-08

    Redox reactions that occur at the electrodes of batteries require transport of both ions and electrons to the active centers. Reported is the synthesis of a block copolymer that exhibits simultaneous electronic and ionic conduction. A combination of Grignard metathesis polymerization and click reaction was used successively to synthesize the block copolymer containing regioregular poly(3-hexylthiophene) (P3HT) and poly(ethylene oxide) (PEO) segments. The P3HT-PEO/LiTFSI mixture was then used to make a lithium battery cathode with LiFePO.sub.4 as the only other component. All-solid lithium batteries of the cathode described above, a solid electrolyte and a lithium foil as the anode showed capacities within experimental error of the theoretical capacity of the battery. The ability of P3HT-PEO to serve all of the transport and binding functions required in a lithium battery electrode is thus demonstrated.

  15. Generation of toxic degradation products by sonication of Pluronic® dispersants: implications for nanotoxicity testing

    OpenAIRE

    Wang, Ruhung; Hughes, Tyler; Beck, Simon; Vakil, Samee; Li, Synyoung; Pantano, Paul; Draper, Rockford K.

    2012-01-01

    Poloxamers (known by the trade name Pluronic®) are triblock copolymer surfactants that contain two polyethylene glycol blocks and one polypropylene glycol block of various sizes. Poloxamers are widely used as nanoparticle dispersants for nanotoxicity studies wherein nanoparticles are sonicated with a dispersant to prepare suspensions. It is known that poloxamers can be degraded during sonication and that reactive oxygen species contribute to the degradation process. However, the possibility t...

  16. In vitro evaluation of antioxidant and neuroprotective effects of curcumin loaded in Pluronic micelles

    OpenAIRE

    Cvetelina Gorinova; Denitsa Aluani; Yordan Yordanov; Magdalena Kondeva-Burdina; Virginia Tzankova; Cvetelina Popova; Krassimira Yoncheva

    2016-01-01

    Curcumin is a polyphenolic substance with attractive pharmacological activities (e.g. antioxidant, anti-inflammatory, anticancer). Incorporation of curcumin in polymeric micelles could overcome the problems associated with its instability and low aqueous solubility. The aim of this study was to load curcumin in polymeric micelles based on Pluronic® P 123 or Pluronic® F 127 triblock copolymers and evaluate the antioxidant and neuroprotective effects after micellization. The micelles were prepa...

  17. 78 FR 20032 - Styrene-Ethylene-Propylene Block Copolymer; Tolerance Exemption

    Science.gov (United States)

    2013-04-03

    ...-Ethylene-Propylene Block Copolymer; Tolerance Exemption AGENCY: Environmental Protection Agency (EPA... for residues of styrene-ethylene-propylene block copolymer (CAS Reg. No. 108388-87-0) when used as an...-ethylene-propylene block copolymer on food or feed commodities. DATES: This regulation is effective April 3...

  18. Crystalline Ethylene Oxide and Propylene Oxide Triblock Copolymer Solid Dispersion Enhance Solubility, Stability and Promoting Time- Controllable Release of Curcumin.

    Science.gov (United States)

    Alves, Thais F R; das Neves Lopes, Franciely C C; Rebelo, Marcia A; Souza, Juliana F; da Silva Pontes, Katiusca; Santos, Carolina; Severino, Patricia; Junior, Jose M O; Komatsu, Daniel; Chaud, Marco V

    2018-01-01

    The design and development of an effective medicine are, however, often faced with a number of challenges. One of them is the close relationship of drug's bioavailability with solubility, dissolution rate and permeability. The use of curcumin's (CUR) therapeutic potential is limited by its poor water solubility and low chemical stability. The purpose was to evaluate the effect of polymer and solid dispersion (SD) preparation techniques to enhance the aqueous solubility, dissolution rate and stability of the CUR. The recent patents on curcumin SD were reported as (i) curcumin with polyvinylpyrrolidone (CN20071 32500 20071214, WO2006022012 and CN20151414227 20150715), (ii) curcumin-zinc/polyvinylpyrrolidone (CN20151414227 20150715), (iii) curcumin-poloxamer 188 (CN2008171177 20080605), (iv) curcumin SD prepared by melting method (CN20161626746-20160801). SD obtained by co-preciptation or microwave fusion and the physical mixture of CUR with Poloxamer-407 (P-407), Hydroxypropylmetylcellulose-K4M (HPMC K4M) and Polyvinylpyrrolidone-K30 (PVP-K30) were prepared at the ratios of 1:2; 1:1 and 2:1. The samples were evaluated by solubility, stability, dissolution rate and characterized by SEM, PXRD, DSC and FTIR. The solubility, stability (pH 7.0) and dissolution rate were significantly greater for SD (CUR:P-407 1:2). The PXRD,SEM and DSC indicated a change in the crystalline state of CUR. The enhancement of solubility was dependent on a combination of factors including the weight ratio, preparation techniques and carrier properties. The drug release data fitted well with the Weibull equation, indicating that the drug release was controlled by diffusion, polymer relaxation and erosion occurring simultaneously. Thus, these SDs, specifically CUR:P-407 1:2 w/w, can overcome the barriers of poor bioavailability to reap many beneficial properties. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

  19. Polyethylene-Based Tadpole Copolymers

    KAUST Repository

    Alkayal, Nazeeha

    2017-02-15

    Novel well-defined polyethylene-based tadpole copolymers ((c-PE)-b-PS, PE: polyethylene, PS: polystyrene) with ring PE head and linear PS tail are synthesized by combining polyhomologation, atom transfer radical polymerization (ATRP), and Glaser coupling reaction. The -OH groups of the 3-miktoarm star copolymers (PE-OH)-b-PS, synthesized by polyhomologation and ATRP, are transformed to alkyne groups by esterification with propiolic acid, followed by Glaser cyclization and removal of the unreacted linear with Merrifield\\'s resin-azide. The characterization results of intermediates and final products by high-temperature size exclusion chromatography, H NMR spectroscopy, and differential scanning calorimetry confirm the tadpole topology.

  20. Fabrication of periodic arrays of metallic nanoparticles by block copolymer templates on HfO_2 substrates

    International Nuclear Information System (INIS)

    Frascaroli, Jacopo; Seguini, Gabriele; Spiga, Sabina; Perego, Michele; Boarino, Luca

    2015-01-01

    Block copolymer-based templates can be exploited for the fabrication of ordered arrays of metal nanoparticles (NPs) with a diameter down to a few nanometers. In order to develop this technique on metal oxide substrates, we studied the self-assembly of polymeric templates directly on the HfO_2 surface. Using a random copolymer neutralization layer, we obtained an effective HfO_2 surface neutralization, while the effects of surface cleaning and annealing temperature were carefully examined. Varying the block copolymer molecular weight, we produced regular nanoporous templates with feature size variable between 10 and 30 nm and a density up to 1.5 × 10"1"1 cm"−"2. With the adoption of a pattern transfer process, we produced ordered arrays of Pt and Pt/Ti NPs with diameters of 12, 21 and 29 nm and a constant size dispersion (σ) of 2.5 nm. For the smallest template adopted, the NP diameter is significantly lower than the original template dimension. In this specific configuration, the granularity of the deposited film probably influences the pattern transfer process and very small NPs of 12 nm were achieved without a significant broadening of the size distribution. (paper)