Sample records for sbs triblock copolymer

  1. 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


    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...

  2. Silica reinforced triblock copolymer gels

    DEFF Research Database (Denmark)

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


    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...... to evaluate the influence of the compatibility between gel and filler. Time-resolved SANS and small-angle X-ray scattering (SAXS) shows that the presence of silica particles affects the ordering of the polystyrene domains during gelsetting. The scattering pattern of silica-reinforced gels reveals strong...... scattering at very low q, but no structure and formfactor information. However, on heating above the viscoelastic to plastic transition, the 'typical' scattering pattern of the copolymer gel builds-up. All reinforced gels are strengthened by the addition of the reinforcing agent. The transitions from...

  3. Hydrogel networks based on ABA triblock copolymers. (United States)

    Tartivel, Lucile; Behl, Marc; Schroeter, Michael; Lendlein, Andreas


    Triblock copolymers from hydrophilic oligo(ethylene glycol) segment A and oligo(propylene glycol) segment B, providing an ABA structure (OEG-OPG-OEG triblock), are known to be biocompatible and are used as self-solidifying gels in drug depots. A complete removal of these depots would be helpful in cases of undesired side effects of a drug, but this remains a challenge as they liquefy below their transition temperature. Therefore we describe the synthesis of covalently cross-linked hydrogel networks. Triblock copolymer-based hydrogels were created by irradiating aqueous solutions of the corresponding macro-dimethacrylates with UV light. The degree of swelling, swelling kinetics, mechanical properties and morphology of the networks were investigated. Depending on precursor concentration, equilibrium degree of swelling of the films ranged between 500% and 880% and was reached in 1 hour. In addition, values for storage and loss moduli of the hydrogel networks were in the 100 Pa to 10 kPa range. Although OEG-OPG-OEG triblocks are known for their micellization, which could hamper polymer network formation, reactive OEG-OPG-OEG triblock oligomers could be successfully polymerized into hydrogel networks. The degree of swelling of these hydrogels depends on their molecular weight and on the oligomer concentration used for hydrogel preparation. In combination with the temperature sensitivity of the ABA triblock copolymers, it is assumed that such hydrogels might be beneficial for future medical applications - e.g., removable drug release systems.

  4. Ordering phenomena in ABA triblock copolymer gels

    DEFF Research Database (Denmark)

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


    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...... crystalline lattice with close-packed spheres or with cubic (presumably BCC) equilibrium morphology. The appearance of the latter is never detected in the gels with a stretched conformation of the midblock....

  5. Sustainable Triblock Copolymers for Application as Thermoplastic Elastomers (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.

  6. Chain exchange in triblock copolymer micelles (United States)

    Lu, Jie; Lodge, Timothy; Bates, Frank


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

  7. Self-assembly of ABA triblock copolymers under soft confinement (United States)

    Sheng, Yuping; An, Jian; Zhu, Yutian


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

  8. Perfluorocyclobutyl Aryl Ether-Based ABC Amphiphilic Triblock Copolymer (United States)

    Xu, Binbin; Yao, Wenqiang; Li, Yongjun; Zhang, Sen; Huang, Xiaoyu


    A series of fluorine-containing amphiphilic ABC triblock copolymers comprising hydrophilic poly(ethylene glycol) (PEG) and poly(methacrylic acid) (PMAA), and hydrophobic poly(p-(2-(4-biphenyl)perfluorocyclobutoxy)phenyl methacrylate) (PBPFCBPMA) segments were synthesized by successive atom transfer radical polymerization (ATRP). First, PEG-Br macroinitiators bearing one terminal ATRP initiating group were prepared by chain-end modification of monohydroxy-terminated PEG via esterification reaction. PEG-b-PBPFCBPMA-Br diblock copolymers were then synthesized via ATRP of BPFCBPMA monomer initiated by PEG-Br macroinitiator. ATRP polymerization of tert-butyl methacrylate (tBMA) was directly initiated by PEG-b-PBPFCBPMA-Br to provide PEG-b-PBPFCBPMA-b-PtBMA triblock copolymers with relatively narrow molecular weight distributions (Mw/Mn ≤ 1.43). The pendant tert-butyoxycarbonyls were hydrolyzed to carboxyls in acidic environment without affecting other functional groups for affording PEG-b-PBPFCBPMA-b-PMAA amphiphilic triblock copolymers. The critical micelle concentrations (cmc) were determined by fluorescence spectroscopy using N-phenyl-1-naphthylamine as probe and the self-assembly behavior in aqueous media were investigated by transmission electron microscopy. Large compound micelles and bowl-shaped micelles were formed in neutral aqueous solution. Interestingly, large compound micelles formed by triblock copolymers can separately or simultaneously encapsulate hydrophilic Rhodamine 6G and hydrophobic pyrene agents.

  9. Stimuli-Responsive Peptide-based Triblock and Star Copolymers (United States)

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


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

  10. Acrylic Triblock Copolymers Incorporating Isosorbide for Pressure Sensitive Adhesives

    Energy Technology Data Exchange (ETDEWEB)

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


    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.

  11. Supramolecular association of a triblock copolymer in water. (United States)

    Gente, Giacomo; Iovino, Alessandro; La Mesa, Camillo


    Solutions of a poly(oxyethylene)-poly(oxypropylene)-poly(oxyethylene) triblock copolymer, Pluronic F(68), were investigated in isothermal and isopleth mode. Surface tension, sigma, dynamic shear viscosity, n(omega), QELS experiments, and volumetric, colligative, and refractive index measurements characterize the system behavior in a wide range of compositions and temperatures. The thermodynamic properties associated with micelle formation, above the critical micellar temperature, were determined by different experimental methods. The large entropic contributions to the system stability are ascribed to significant dehydration of the oxypropylene portion in the copolymer, consequent to micelle formation. Temperature has a pronounced effect on the association features of F(68). It gives rise to abrupt changes in QELS and rheological properties when the critical micellar temperature is approached. Such effects are explained in terms of thermally driven micellization processes and interconnection between micelles.

  12. Directed assembly of non-equilibrium ABA triblock copolymer morphologies on nanopatterned substrates. (United States)

    Ji, Shengxiang; Nagpal, Umang; Liu, Guoliang; Delcambre, Sean P; Müller, Marcus; de Pablo, Juan J; Nealey, Paul F


    The majority of past work on directed assembly of block copolymers on chemically nanopatterned surfaces (or chemical patterns) has focused on AB diblock copolymers, and the resulting morphologies have generally corresponded to equilibrium states. Here we report a study on directed assembly of ABA triblock copolymers. Directed assembly of thin films of symmetric poly(methyl methacrylate-b-styrene-b-methyl methacrylate) (PMMA-b-PS-b-PMMA) triblock copolymers is shown to be capable of achieving a high degree of perfection, registration, and accuracy on striped patterns having periods, L(s), commensurate with the bulk period of the copolymer, L(o). When L(s) is incommensurate with L(o), the triblock copolymer domains can reach dimensions up to 55% larger or 13% smaller than L(o). The range over which triblock copolymers tolerate departures from a commensurate L(s) is significantly larger than that accessible with the corresponding diblock copolymer material on analogous directed assembly systems. The assembly kinetics of the triblock copolymer is approximately 3 orders of magnitude slower than observed in the diblock system. Theoretically informed simulations are used to interpret our experimental observations; a thermodynamic analysis reveals that triblocks can form highly ordered, non-equilibrium metastable structures that do not arise in the diblock.

  13. Thermoplastic Dielectric Elastomer of Triblock Copolymer with High Electromechanical Performance. (United States)

    Ma, Zipeng; Xie, Yuhan; Mao, Jie; Yang, Xuxu; Li, Tiefeng; Luo, Yingwu


    Dielectric elastomer (DE) actuators have been shown to have promising applications as soft electromechanical transducers in many emerging technologies. The DE actuators, which are capable of large actuation strain over a wide range of excitation frequencies, are highly desirable. Here, the first single-component DE of a triblock copolymer with attractive electromechanical performance is reported. Symmetric poly(styrene-b-butyl acrylate-b-styrene) (SBAS) is designed and synthesized. The SBAS actuator exhibits about 100% static actuation area strain and excellent dynamic performance, as evidenced by a wide half bandwidth of 300 Hz and a very high specific power of 1.2 W g-1 within the excitation frequency range of 300-800 Hz. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. A neutron scattering study of triblock copolymer micelles

    Energy Technology Data Exchange (ETDEWEB)

    Gerstenberg, M.C.


    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

  15. Impact of triblock copolymers on the biophysical function of naturally-derived lung surfactant. (United States)

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


    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 of triblock copolymers in A549 cells demonstrated some cytotoxicity, dependent on the hydrophobicity and dose of the substance applied (effective at ≥0.1mg/ml). Supplementing triblock copolymers onto Alveofact® had an obvious influence on the aggregation state and surface activity (>25 and >5mN/m during adsorption and bubble pulsation, respectively) of the lung surfactant. Interestingly, Pluronic® F127, a rather hydrophilic triblock copolymer, showed the most intense effect on the microstructure and biophysical performance of Alveofact®. This is likely due to the synergistic interplay of its low critical micelle concentration and rather high molecular weight, leading to the penetration of lung surfactant film/vesicles and accompanied by a partial replacement of relevant surfactant components from the air/liquid interface. Overall, suitable compositions and concentrations of triblock copolymers were identified with respect to compatibility with the physiological environment of the deep lungs. Copyright © 2017 Elsevier B.V. All rights reserved.

  16. Morphology of biaxially stretched triblock copolymer gels using SAXS (United States)

    Krishnan, Arjun; Ghosh, Tushar; Spontak, Richard


    Gels of styrenic triblock copolymers swollen by a low-volatility, midblock-selective oil behave as high-strain, low-field dielectric elastomers in the design of electroactive polymeric actuators. A standard configuration of such devices involves stretching, or ``prestraining,'' the elastomer film biaxially. However, little is known about the effect of biaxial prestrain on copolymer morphology. In this study, small-angle X-ray scattering (SAXS) is used to probe the nanostructure of gels composed of poly[styrene-b-(ethylene-co-butylene)-b-styrene] and mineral oil by systematically changing the concentration of polymer from 5 to 30 wt% and the biaxial prestrain from 0 to 300%. In the azimuthally integrated intensity profiles, the form factor due to scattering from polystyrene microdomains correlates strongly with polymer concentration and does not change with the applied prestrain, indicating that the polystyrene crosslinks remain as polydisperse spheres. The structure factor data correlates with prestrain, and is fitted using the Percus-Yevick approximation for interacting spheres. While a hard sphere interaction model is sufficient for unstrained gels, we resort to a square shoulder hard sphere potential for strained samples.

  17. 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


    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...

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

    NARCIS (Netherlands)

    Güney, Aysun; Malda, Jos|info:eu-repo/dai/nl/412461099; Dhert, Wouter J A|info:eu-repo/dai/nl/10261847X; 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

  19. Double-bond-containing polyallene-based triblock copolymers via phenoxyallene and (meth)acrylate (United States)

    Ding, Aishun; Lu, Guolin; Guo, Hao; Huang, Xiaoyu


    A series of ABA triblock copolymers, consisting of double-bond-containing poly(phenoxyallene) (PPOA), poly(methyl methacrylate) (PMMA), or poly(butyl acrylate) (PBA) segments, were synthesized by sequential free radical polymerization and atom transfer radical polymerization (ATRP). A new bifunctional initiator bearing azo and halogen-containing ATRP initiating groups was first prepared followed by initiating conventional free radical homopolymerization of phenoxyallene with cumulated double bond to give a PPOA-based macroinitiator with ATRP initiating groups at both ends. Next, PMMA-b-PPOA-b-PMMA and PBA-b-PPOA-b-PBA triblock copolymers were synthesized by ATRP of methyl methacrylate and n-butyl acrylate initiated by the PPOA-based macroinitiator through the site transformation strategy. These double-bond-containing triblock copolymers are stable under UV irradiation and free radical circumstances.

  20. Determination of Loops to Bridges Ratio in Triblock Copolymers by Dielectric Relaxation Spectroscopy^# (United States)

    Karatasos, K.; Anastasiadis, S. H.; Kremer, F.; Watanabe, H.


    Dielectric spectroscopy over a broad frequency (10-2 Hz to 10^6 Hz) and temperature (-160 to 300^circC) range has been used to investigate the loops to bridges ratio in ordered triblock copolymers. We have utilized a specifically synthesized poly(styrene-b-1,4-isoprene-styrene) triblock having symmetrically inverted dipoles along the chain backbone of the middle block and the respective diblock precursor. The relaxation process observed for the triblock, with relaxation times identical to the block end-to-end vector relaxation of the diblock, corresponds to relaxation of the loop conformation in the ordered triblock. The weight fraction of loops in the ordered triblock, w_loops, is estimated from comparison of the dielectric loss and/or the dielectric strength of this process in the triblock to that in the diblock. This fraction is being investigated as a function of the sample history. Besides, the very slow relaxation, recently observed in ordered diblocks and attributed to relaxation of the conformal interfaces formed in the ordered state, is also clearly observed for ordered triblocks. # Part of this research was sponsored by NATO's Scientific Affairs Division in the framework of the Science for Stability Programme

  1. Bentonite-based organoclays as innovative flame retardants agents for SBS copolymer. (United States)

    Franchini, M Comes; Fabbri, P; Frache, A; Ori, G; Messori, M; Siligardi, C; Ricci, A


    Two organophilic bentonites, based on nitrogen-containing compounds, have been synthesised via ion exchange starting from pristine bentonite with octadecyltrimethylammonium bromide (OTAB) and with synthetic melamine-derived N2,N4-dihexadecyl-1,3,5-triazine-2,4,6-triamine (DEDMEL). The chemical and morphological characterization of the organoclays was based on XRD, TEM, Laser Granulometry, X-Ray Fluorescence and CEC capacity. Copoly(styrene-butadiene-styrene)-nanocomposites (SBS-nanocomposites) were obtained by intercalation of the SBS-copolymer into these new organoclays by melt intercalation method. XRD and TEM analysis of the organoclays and of the micro/nano-composites obtained are presented. The effect of the organoclays on the SBS-nanocomposite's flammability properties was investigated using cone calorimeter. An encouraging decrease of 20% in the peak heat released rate (PHRR) has been obtained confirming the important role of melamine's based skeleton and its derived organoclays to act as effective fire retardants and for the improvement of this important functional property in SBS copolymers.

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

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


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

  3. Surface charge-specific cytotoxicity and cellular uptake of tri-block copolymer nanoparticles

    NARCIS (Netherlands)

    Bhattacharjee, S.; Ershov, D.S.; Gucht, van der J.; Alink, G.M.; Rietjens, I.; Zuilhof, H.; Marcelis, A.T.M.


    A series of monodisperse (45 ± 5 nm) fluorescent nanoparticles from tri-block copolymers (polymeric nanoparticles (PNPs)) bearing different surface charges were synthesised and investigated for cytotoxicity in NR8383 and Caco-2 cells. The positive PNPs were more cytotoxic and induced a higher

  4. Synthesis of SAN-PB-SAN triblock copolymers via a ''living'' copolymerization with macro-photoiniferters

    NARCIS (Netherlands)

    Kroeze, E; de Boer, B.; ten Brinke, G.; Hadziioannou, G


    A technique is described for the synthesis of poly((styrene-co-acrylonitrile)-block-butadiene-block-(styrene-co-acrylonitrile)) (SAN-PB-SAN) triblock copolymers through polybutadiene-based photo-iniferters. Dihydroxy- and dicarboxy-terminated polybutadienes were transformed into the

  5. Effects of pH and additives on aqueous wetting films stabilized by a triblock copolymer

    NARCIS (Netherlands)

    Eliseeva, O.V.; Besseling, N.A.M.; Koopal, L.K.; Stuart, M.A.C.


    Effects of pH and additives (NaCl, Na2SO4, NaSCN and urea) on the adsorption of an ABA triblock copolymer (F127) with polyethylene oxide as the A blocks and polypropylene oxide as the B blocks, at the interfaces of wetting films, on film drainage and on the interaction forces in these films are

  6. Photoresponsive Polymeric Reversible Nanoparticles via Self-Assembly of Reactive ABA Triblock Copolymers and Their Transformation to Permanent Nanostructures

    Directory of Open Access Journals (Sweden)

    Liang Ding


    Full Text Available Azobenzene-functionalized ABA triblock copolymers with controlled molecular weights are prepared first via a sequential ring-opening metathesis polymerization and acyclic diene metathesis polymerization in one-pot, which are readily converted, by a facile esterification, to the modified ABA triblock copolymers. Then, these reactive triblock copolymers can spontaneously self-assemble in a selective solvent to form reproducible and reversible polymeric core-shell nanoparticles. Finally, the stable and permanent shell-crosslinked nanoparticles are obtained by an intramolecular crosslinking reaction in dilute solution under UV light irradiation. These as-prepared polymeric nanoparticles and their precursor incorporating azobenzene chromophores exhibit distinct photoresponsive performance and morphological variation.

  7. Effect of ionic surfactant on the self-assembly of triblock copolymer (United States)

    Ray, D.; Kohlbrecher, J.; Aswal, V. K.


    The effect of anionic surfactant sodium dodecyl sulfate (SDS) on the self-assembly of PEO-PPO-PEO triblock copolymer in aqueous solution has been studied using small-angle neutron scattering (SANS). The measurements have been carried out for fixed concentrations (1 wt%) of block copolymer and surfactant, and at varying temperatures between 20 to 80°C. Micelles of pure ionic surfactants show little change in their sizes with increasing temperature, whereas structures of the non-ionic micelles increase significantly (sphere-to-rod transition for some block copolymers). Contrast variation SANS measurement suggests addition of SDS to aqueous copolymer solutions leads to the formation of mixed micelles. Interestingly, the self-assembly of block copolymer is found to get completely arrested by the ionic surfactant in the mixed micelles which gives a control over the block copolymer phase behavior.

  8. Synthesis of tri-block copolymers through reverse atom transfer radical polymerization of methyl methacrylate using polyurethane macroiniferter

    Directory of Open Access Journals (Sweden)


    Full Text Available Reverse atom transfer radical polymerization was successfully used for the first time to synthesis tri-block copolymers. Poly (methyl methacrylate-block-polyurethane-block-poly (methyl methacrylate tri-block copolymers were synthesized using tetraphenylethane-based polyurethane as a macroiniferter, copper(II halide as a catalyst and N, N, N′, N″, N″-pentamethyldiethylenetriamine as a ligand. Controlled nature of the polymerization was confirmed by the linear increase of number average molecular weight with increasing conversion. Mole contents of poly (methyl methacrylate present in the tri-block copolymers were calculated using proton nuclear magnetic resonance spectroscopy and the results were comparable with the gel permeation chromatography results. Differential scanning calorimetric results confirmed the presence of two different types of blocks in the tri-block copolymers.

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

    Energy Technology Data Exchange (ETDEWEB)

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


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

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

    Energy Technology Data Exchange (ETDEWEB)

    Lee, S.H.; Koberstein, J.T. (Univ. of Connecticut, Storrs, CT (United States). Dept. of Chemical Engineering); Quan, X. (AT T Bell Labs., Murray Hill, NJ (United States)); Gancarz, I. (Technical Univ. of Wroclaw (Poland)); Wignall, G.D. (Oak Ridge National Lab., TN (United States)); Wilson, F.C. (E.I. Du Pont de Nemours, Inc., Wilmington, DE (United States))


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

  11. Tailoring the LCST of PNIPAAM-b-PLA-b-PNIPAAM triblock copolymers via stereocomplexation. (United States)

    Zhang, Xing; Tan, Beng H; He, Chaobin


    Poly(N-isopropylacrylamide)-block-poly(l-lactic acid)-block-poly(N-isopropylacrylamide) (PNIPAAM-b-PLLA-b-PNIPAAM) and PNIPAAM-b-PDLA-b-PNIPAAM triblock copolymers with varying polylactic acid (PLA) lengths are synthesized using a combination of ring-opening polymerization and atom-transfer radical polymerization. Results of (1) H NMR and gel permeation chromatography analyses show that the copolymers have a well-defined triblock structure and the PLA segment lengths can be readily controlled with monomer feed ratio. Stereocomplexation between the enantiomeric PLA segments is confirmed with differential scanning calorimetry and wide-angle X-ray scattering. Dynamic light scattering experiments show that (1) the LCST of PNIPAAM in water could be tailored from 32 °C up to 38.5 °C by increasing the length of PLA segments and mixing copolymers of similar molecular weight with enantiomeric PLA segments to induce stereocomplexation, and (2) the LCST of each mixed copolymer system could be tailored within a 2-3 °C range of body temperature by manipulating the ratio of the enantiomeric copolymers in solution. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. 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


    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.

  13. ABC Triblock Copolymer Worms: Synthesis, Characterization, and Evaluation as Pickering Emulsifiers for Millimeter-Sized Droplets


    Mable, C.J.; Thompson, K. L.; Derry, M. J.; Mykhaylyk, O.O.; Binks, B P; Armes, S. P.


    Polymerization-induced self-assembly (PISA) is\\ud used to prepare linear poly(glycerol monomethacrylate)−\\ud poly(2-hydroxypropyl methacrylate)−poly(benzyl methacrylate)\\ud [PGMA−PHPMA−PBzMA] triblock copolymer nanoobjects\\ud in the form of a concentrated aqueous dispersion via a\\ud three-step synthesis based on reversible addition−fragmentation\\ud chain transfer (RAFT) polymerization. First, GMA is\\ud polymerized via RAFT solution polymerization in ethanol,\\ud then HPMA is polymerized via RA...

  14. Nanostructured DPA-MPC-DPA triblock copolymer gel for controlled drug release of ketoprofen and spironolactone. (United States)

    Azmy, Bahaa; Standen, Guy; Kristova, Petra; Flint, Andrew; Lewis, Andrew L; Salvage, Jonathan P


    Uncontrolled rapid release of drugs can reduce their therapeutic efficacy and cause undesirable toxicity; however, controlled release from reservoir materials helps overcome this issue. The aims of this study were to determine the release profiles of ketoprofen and spironolactone from a pH-responsive self-assembling DPA-MPC-DPA triblock copolymer gel and elucidate underlying physiochemical properties. Drug release profiles from DPA50 -MPC250 -DPA50 gel (pH 7.5), over 32 h (37 °C), were determined using UV-Vis spectroscopy. Nanoparticle size was measured by dynamic light scattering (DLS) and critical micelle concentration (CMC) by pyrene fluorescence. Polymer gel viscosity was examined via rheology, nanoparticle morphology investigated using scanning transmission electron microscopy (STEM) and the gel matrix observed using cryo-scanning electron microscopy (Cryo-SEM). DPA50 -MPC250 -DPA50 copolymer (15% w/v) formed a free-standing gel (pH 7.5) that controlled drug release relative to free drugs. The copolymer possessed a low CMC, nanoparticle size increased with copolymer concentration, and DLS data were consistent with STEM. The gel displayed thermostable viscosity at physiological temperatures, and the gel matrix was a nanostructured aggregation of smaller nanoparticles. The DPA50 -MPC250 -DPA50 copolymer gel could be used as a drug delivery system to provide the controlled drug release of ketoprofen and spironolactone. © 2017 Royal Pharmaceutical Society.

  15. Segmental chain dynamics of ABA triblock copolymer micelles in aqueous solution (United States)

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

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

  16. Temperature-dependent optical properties of gold nanoparticles coated with a charged diblock copolymer and an uncharged triblock copolymer. (United States)

    Volden, Sondre; Kjøniksen, Anna-Lena; Zhu, Kaizheng; Genzer, Jan; Nyström, Bo; Glomm, Wilhelm R


    We demonstrate that the optical properties of gold nanoparticles can be used to detect and follow stimuli-induced changes in adsorbed macromolecules. Specifically, we investigate thermal response of anionic diblock and uncharged triblock copolymers based on poly(N-isopropylacrylamide) (PNIPAAM) blocks adsorbed onto gold nanoparticles and planar gold surfaces in a temperature range between 25 and 60 degrees C. By employing a palette of analytical probes, including UV-visible spectroscopy, dynamic light scattering, fluorescence, and quartz crystal microbalance with dissipation monitoring, we establish that while the anionic copolymer forms monolayers at both low and high temperature, the neutral copolymer adsorbs as a monolayer at low temperatures and forms multilayers above the cloud point (T(C)). Raising the temperature above T(C) severely affects the optical properties of the gold particle/polymer composites, expelling associated water and altering the immediate surroundings of the gold nanoparticles. This effect, stronger for the uncharged polymer, is related to the amount of polymer adsorbed on the surface, where a denser shell influences the surface plasmon band to a greater degree. This is corroborated with light scattering experiments, which reveal that flocculation of the neutral polymer-coated particles occurs at high temperatures. The flocculation behavior of the neutral copolymer on planar gold surfaces results in multilayer formation. The observed effects are discussed within the framework of the Mie-Drude theory.

  17. Mimicking conjugated polymer thin-film photophysics with a well-defined triblock copolymer in solution. (United States)

    Brazard, Johanna; Ono, Robert J; Bielawski, Christopher W; Barbara, Paul F; Vanden Bout, David A


    Conjugated polymers (CPs) are promising materials for use in electronic applications, such as low-cost, easily processed organic photovoltaic (OPV) devices. Improving OPV efficiencies is hindered by a lack of a fundamental understanding of the photophysics in CP-based thin films that is complicated by their heterogeneous nanoscale morphologies. Here, we report on a poly(3-hexylthiophene)-block-poly(tert-butyl acrylate)-block-poly(3-hexylthiophene) rod-coil-rod triblock copolymer. In good solvents, this polymer resembles solutions of P3HT; however, upon the addition of a poor solvent, the two P3HT chains within the triblock copolymer collapse, affording a material with electronic spectra identical to those of a thin film of P3HT. Using this new system as a model for thin films of P3HT, we can attribute the low fluorescence quantum yield of films to the presence of a charge-transfer state, providing fundamental insights into the condensed phase photophysics that will help to guide the development of the next generation of materials for OPVs.

  18. 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


    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...... weights and narrow molecular weight distributions. Polymerization of a mixture of equal molar amounts of the two monomers yielded a random copolymer with narrow molecular weight distribution....

  19. Stereocomplex formation in ABA triblock copolymers of poly(lactide)(A) and poly(ethylene glycol)(B)

    NARCIS (Netherlands)

    Stevels, W.M.; Ankone, Martinus J.K.; Dijkstra, Pieter J.; Feijen, Jan


    Two series of triblock copolymers of poly(ethylene glycol) (PEG, number-average molecular weight [bar M ]n = 6000) and poly(L-lactide) (PLLA) or poly(D-lactide) (PDLA) were prepared by ring-opening polymerization of lactide initiated by PEG end groups using stannous octoate as a catalyst, either in

  20. Temperature-induced aggregation in aqueous solutions of pluronic F68 triblock copolymer containing small amount of o-xylene

    DEFF Research Database (Denmark)

    Borbely, S.; Pedersen, J.S.


    The temperature- and concentration-dependent aggregation of EO(78)PO(30)EO(78) triblock copolymer in aqueous solutions has been studied in the concentration range from 5 to 200 g/dm(3) at 25 degrees C, 45 degrees C and 60 degrees C. The influence of o-xylene on the micellization was measured...

  1. Thermoplastic elastomers based on poly(lactide)-poly(trimethylene carbonate-co-caprolactone)-poly(lactide) triblock copolymers and their stereocomplexes

    NARCIS (Netherlands)

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


    Triblock copolymers of poly(l-lactide)–poly(trimethylene carbonate-co-caprolactone)–poly(l-lactide) and poly(d-lactide)–poly(trimethylene carbonate-co-caprolactone)–poly(d-lactide) were prepared by sequential ring-opening polymerizations. These polymers are thermoplastic elastomers (TPEs) with good

  2. Modeling and self-assembly behavior of PEG-PLA-PEG triblock copolymers in aqueous solution (United States)

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


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

  3. 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.


    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...

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

    Energy Technology Data Exchange (ETDEWEB)

    Edelstein, A.; Fink, D.; Musch, M.; Valuckaite, V.; Zabornia, O.; Grubjesic, S.; Firestone, M. A.; Matthews, J. B.; Alverdy, J. C. (Materials Science Division); (Univ. of Chicago)


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

  5. One-Pot Automated Synthesis of Quasi Triblock Copolymers for Self-Healing Physically Crosslinked Hydrogels. (United States)

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


    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.

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

    CERN Document Server

    Thiyagarajan, P


    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.)

  7. Diverse 2D structures obtained by adsorption of charged ABA triblock copolymer on different surfaces (United States)

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


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

  8. Surface modification with well-defined biocompatible triblock copolymers Improvement of biointerfacial phenomena on a poly(dimethylsiloxane) surface. (United States)

    Iwasaki, Yasuhiko; Takamiya, Mika; Iwata, Ryoko; Yusa, Shin-Ichi; Akiyoshi, Kazunari


    To improve interfacial phenomena of poly(dimethylsiloxane) (PDMS) as biomaterials, well-defined triblock copolymers were prepared as coating materials by reversible addition-fragmentation chain transfer (RAFT) controlled polymerization. Hydroxy-terminated poly(vinylmethylsiloxane-co-dimethylsiloxane) (HO-PV(l)D(m)MS-OH) was synthesized by ring-opening polymerization. The copolymerization ratio of vinylmethylsiloxane to dimethylsiloxane was 1/9. The molecular weight of HO-PV(l)D(m)MS-OH ranged from (1.43 to 4.44)x10(4), and their molecular weight distribution (M(w)/M(n)) as determined by size-exclusion chromatography equipped with multiangle laser light scattering (SEC-MALS) was 1.16. 4-Cyanopentanoic acid dithiobenzoate was reacted with HO-PV(l)D(m)MS-OH to obtain macromolecular chain transfer agents (macro-CTA). 2-Methacryloyloxyethyl phosphorylcholine (MPC) was polymerized with macro-CTAs. The gel-permeation chromatography (GPC) chart of synthesized polymers was a single peak and M(w)/M(n) was relatively narrow (1.3-1.6). Then the poly(MPC) (PMPC)-PV(l)D(m)MS-PMPC triblock copolymers were synthesized. The molecular weight of PMPC in a triblock copolymer was easily controllable by changing the polymerization time or the composition of the macro-CTA to a monomer in the feed. The synthesized block copolymers were slightly soluble in water and extremely soluble in ethanol and 2-propanol. Surface modification was performed via hydrosilylation. The block copolymer was coated on the PDMS film whose surface was pretreated with poly(hydromethylsiloxane). The surface wettability and lubrication of the PDMS film were effectively improved by immobilization with the block copolymers. In addition, the number of adherent platelets from human platelet-rich plasma (PRP) was dramatically reduced by surface modification. Particularly, the triblock copolymer having a high composition ratio of MPC units to silicone units was effective in improving the surface properties of PDMS. By

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

    Directory of Open Access Journals (Sweden)

    Jennifer Bain


    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

  10. Stereocomplexes of enantiomeric lactic acid and sebacic acid ester-anhydride triblock copolymers. (United States)

    Slivniak, Raia; Domb, Abraham J


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

  11. Flexible Epoxy Resin Formed Upon Blending with a Triblock Copolymer through Reaction-Induced Microphase Separation (United States)

    Chu, Wei-Cheng; Lin, Wei-Sheng; Kuo, Shiao-Wei


    In this study, we used diglycidyl ether bisphenol A (DGEBA) as a matrix, the ABA block copolymer poly(ethylene oxide–b–propylene oxide–b–ethylene oxide) (Pluronic F127) as an additive, and diphenyl diaminosulfone (DDS) as a curing agent to prepare flexible epoxy resins through reaction-induced microphase separation (RIMPS). Fourier transform infrared spectroscopy confirmed the existence of hydrogen bonding between the poly(ethylene oxide) segment of F127 and the OH groups of the DGEBA resin. Small-angle X-ray scattering, atomic force microscopy, and transmission electron microscopy all revealed evidence for the microphase separation of F127 within the epoxy resin. Glass transition temperature (Tg) phenomena and mechanical properties (modulus) were determined through differential scanning calorimetry and dynamic mechanical analysis, respectively, of samples at various blend compositions. The modulus data provided evidence for the formation of wormlike micelle structures, through a RIMPS mechanism, in the flexible epoxy resin upon blending with the F127 triblock copolymer. PMID:28773571

  12. 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.


    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...

  13. Gas-tight triblock-copolymer membranes are converted to CO₂ permeable by insertion of plant aquaporins. (United States)

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


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

  14. Effect of adding of the styrene-butadiene-styrene (SBS) copolymer in chemical and rheological properties of the brazilian asphalt; Efeito da adicao de SBS nas propriedades quimicas e reologicas de asfalto oriundo de petroleo brasileiro

    Energy Technology Data Exchange (ETDEWEB)

    Lucena, M.C.C.; Soares, S.A. [Ceara Univ., Fortaleza, CE (Brazil). Dept. de Quimica Organica e Inorganica]. E-mail:;; Soares, J.B. [Ceara Univ., Fortaleza, CE (Brazil). Dept. de Engenharia de Transportes]. E-mail:


    Chemical and rheological characterization of the asphalt cement (AC) from the Fazenda Alegre petroleum, and the effect of adding 4.5% of the styrene-butadiene-styrene (SBS) copolymer were investigated. Structural characteristics were analyzed by infrared spectroscopy (FTIR) and nuclear magnetic resonance (NMR). A structure similar to the Arabian and Venezuelan petroleum was observed. The simulated aging led to structural modification noticed by the increment in the carbonyl and sulphoxide groups. Thermogravimetry (TGA) showed that SBS did not affect the AC thermal decomposition at both inert and oxidative atmosphere. However, the differential scanning calorimetry (DSC) showed a decrease in the glass transition temperature of the material when SBS was added. The effect of SBS on the absolute viscosity revealed that SBS is not an inert additive and causes an increase in viscosity, in a nonlinear fashion. The commonly found Newtonian behavior of asphalt binders under high temperatures was also found on the SBS modified binder. Dynamic mechanical tests have shown that SBS increases the binder performance grade. (author)

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

    KAUST Repository

    Li, Yangyang


    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. Micelles based on amphiphilic PCL-PEO triblock and star-shaped diblock copolymers: Potential in drug delivery applications. (United States)

    Quaglia, Fabiana; Ostacolo, Luisanna; Nese, Giuseppe; Canciello, Mariarosaria; De Rosa, Giuseppe; Ungaro, Francesca; Palumbo, Rosario; La Rotonda, Maria Immacolata; Maglio, Giovanni


    In this work, the potential in drug nanodelivery of micelles made from poly(epsilon-caprolactone) (PCL) and poly (ethyleneoxide) (PEO) copolymers with triblock and star-diblock architectures was explored. Linear and 4-arm star-shaped PCL macromers with two or four --OH end groups were prepared by ring-opening polymerization of CL and condensed with alpha-methoxy-omega-carboxy-PEO. The resulting amphiphilic copolymers were characterized by (1)H NMR, size exclusion chromatography, and differential scanning calorimetry. Separate PCL and PEO crystalline phases were observed for both copolymers. Copolymers self-assembled in water giving critical association concentrations in the range 0.010-0.023 mg/mL. Micelles with a size of 32-45 nm were prepared by dialysis and characterized for hydrodynamic diameter and surface charge. Their potential as nanocarriers in drug delivery applications was evaluated too. Micelles were nontoxic to both Red blood cells and HeLa cells. Complement activation experiments indicated that micelles can escape the reticuloendothelial system once intravenously injected. Finally, a different uptake on HeLa cells was found for micelles obtained from triblock and star-shaped copolymers. (c) 2008 Wiley Periodicals, Inc. J Biomed Mater Res, 2008.

  17. Time-composition superpositioning in the rheological behavior of triblock copolymer/selective co-solvent blends (United States)

    Krishnan, Arjun; Bukovnik, Rudolf; Spontak, Richard


    Thermoplastic elastomers composed of styrenic triblock copolymers are of great importance in applications such as adhesives and vibration dampening due to their 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. In this study we consider a ternary blend of a poly[styrene-b-(ethylene-co-butylene)-b-styrene] triblock copolymer and mixtures of two midblock selective co-solvents: a mineral oil that is liquid at ambient temperature, and a glassy tackifier resin that exhibits limited solubility in the midblock matrix. We use dynamic rheology to study the viscoelastic response of a wide variety of systems under oscillatory shear. The copolymer concentration is varied between 15 to 35 wt%, while the resin/oil ratio in the midblock-solvent matrix is independently varied. Frequency spectra acquired at ambient temperature display viscoelastic behavior that shifts in the frequency domain depending on the resin/oil ratio. At high oil loadings, the materials behave as physical gels. For each copolymer concentration, all the frequency data can be shifted by time-composition superpositioning to yield a single master-curve.

  18. ABC Triblock Copolymer Worms: Synthesis, Characterization, and Evaluation as Pickering Emulsifiers for Millimeter-Sized Droplets. (United States)

    Mable, C J; Thompson, K L; Derry, M J; Mykhaylyk, O O; Binks, B P; Armes, S P


    Polymerization-induced self-assembly (PISA) is used to prepare linear poly(glycerol monomethacrylate)-poly(2-hydroxypropyl methacrylate)-poly(benzyl methacrylate) [PGMA-PHPMA-PBzMA] triblock copolymer nano-objects in the form of a concentrated aqueous dispersion via a three-step synthesis based on reversible addition-fragmentation chain transfer (RAFT) polymerization. First, GMA is polymerized via RAFT solution polymerization in ethanol, then HPMA is polymerized via RAFT aqueous solution polymerization, and finally BzMA is polymerized via "seeded" RAFT aqueous emulsion polymerization. For certain block compositions, highly anisotropic worm-like particles are obtained, which are characterized by small-angle X-ray scattering (SAXS) and transmission electron microscopy (TEM). The design rules for accessing higher order morphologies (i.e., worms or vesicles) are briefly explored. Surprisingly, vesicular morphologies cannot be accessed by targeting longer PBzMA blocks-instead, only spherical nanoparticles are formed. SAXS is used to rationalize these counterintuitive observations, which are best explained by considering subtle changes in the relative enthalpic incompatibilities between the three blocks during the growth of the PBzMA block. Finally, the PGMA-PHPMA-PBzMA worms are evaluated as Pickering emulsifiers for the stabilization of oil-in-water emulsions. Millimeter-sized oil droplets can be obtained using low-shear homogenization (hand-shaking) in the presence of 20 vol % n-dodecane. In contrast, control experiments performed using PGMA-PHPMA diblock copolymer worms indicate that these more delicate nanostructures do not survive even these mild conditions.

  19. Tailored biodegradable triblock copolymer coatings obtained by MAPLE: a parametric study (United States)

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


    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.

  20. Improving proton conduction pathways in di- and triblock copolymer membranes: Branched versus linear side chains (United States)

    Dorenbos, G.


    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.

  1. Structure of PS/PMMA Blends with Interfacially Active Janus Particles Derived from ABC Triblock Copolymers (United States)

    Bryson, Kyle; Löbling, Tina; Müller, Axel; Hayward, Ryan; Russell, Thomas


    Kinetic trapping of bicontinuous polymer morphologies on submicron length scales through the interfacial adsorption of nanoparticles is of interest due to the unique combination of the properties of each component provided by such structures, and their potential for use as membranes and composite materials. However, this strategy is challenging to realize in polymeric systems, due to the difficulties in preparing particles that are neutrally wetted by the two polymer phases. Janus particles afford a route to circumvent the necessity of neutral wettability. Both theory and experiment have shown enhanced interfacial adsorption energies for Janus particles, as well as greater flexibility in controlling particle orientation at the interface, in comparison to homogeneous particles. Janus particles with polystyrene and poly(methyl methacrylate) (PS/PMMA) hemispheres and a crosslinked polybutadiene core were prepared from triblock copolymers. Using blends of PS and PMMA homopolymers and the Janus particles, we examined structures produced by phase separation during solvent casting and thermodynamic demixing transitions via TEM and small-angle light scattering. The results elucidate the role of particle wettability on interfacial behavior and the structure of stabilized emulsions.

  2. Triblock copolymer-templated synthesis of porous TiO{sub 2} and its photocatalytic activity

    Energy Technology Data Exchange (ETDEWEB)

    Suwanchawalit, Cheewita [Silpakorn University, Department of Chemistry, Faculty of Science (Thailand); Wongnawa, Sumpun, E-mail: [Prince of Songkla University, Department of Chemistry and Center for Innovation in Chemistry, Faculty of Science (Thailand)


    Mixed amorphous and anatase-type titania particles were synthesized using non-ionic triblock copolymer as surfactant template and TiOSO{sub 4} as inorganic precursor through sol-gel process. The as-prepared materials were characterized by X-ray diffraction spectroscopy, scanning and transmission electron microscopy, specific surface area, Fourier-transformed infrared spectroscopy, and diffuse reflectance ultraviolet-visible spectroscopy. The template material could be easily removed by extracting with dichloromethane and was confirmed by infrared spectroscopy. X-ray diffraction pattern reveals the crystalline part of as-prepared product as a framework of anatase phase. From the N{sub 2} adsorption-desorption analysis, the as-prepared sample has a surface area of 301 m{sup 2}/g with pore size distribution narrowly centered around 6 nm. The photodegradation of indigo carmine including kinetics, effect of pH, and recyclability of the product were investigated. The photocatalytic results showed that the as-synthesized titania could efficiently degrade indigo carmine under ultraviolet irradiation and showed higher photocatalytic activity than the commercial Degussa P25-TiO{sub 2}.

  3. Triblock copolymer-templated synthesis of porous TiO2 and its photocatalytic activity (United States)

    Suwanchawalit, Cheewita; Wongnawa, Sumpun


    Mixed amorphous and anatase-type titania particles were synthesized using non-ionic triblock copolymer as surfactant template and TiOSO4 as inorganic precursor through sol-gel process. The as-prepared materials were characterized by X-ray diffraction spectroscopy, scanning and transmission electron microscopy, specific surface area, Fourier-transformed infrared spectroscopy, and diffuse reflectance ultraviolet-visible spectroscopy. The template material could be easily removed by extracting with dichloromethane and was confirmed by infrared spectroscopy. X-ray diffraction pattern reveals the crystalline part of as-prepared product as a framework of anatase phase. From the N2 adsorption-desorption analysis, the as-prepared sample has a surface area of 301 m2/g with pore size distribution narrowly centered around 6 nm. The photodegradation of indigo carmine including kinetics, effect of pH, and recyclability of the product were investigated. The photocatalytic results showed that the as-synthesized titania could efficiently degrade indigo carmine under ultraviolet irradiation and showed higher photocatalytic activity than the commercial Degussa P25-TiO2.

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

    DEFF Research Database (Denmark)

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


    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...

  5. Amphiphilic PEO-b-PBLG diblock and PBLG-b-PEO-b-PBLG triblock copolymer based nanoparticles: doxorubicin loading and in vitro evaluation. (United States)

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


    Huisgen's 1,3-dipolar cycloaddition ("Click Chemestry") has been used to prepare amphiphilic PEO-b-PBLG diblock and PBLG-b-PEO-b-PBLG triblock copolymers as potential carriers of anticancer drugs. Spherical and flower shaped micelles (D ≈ 100 nm) were obtained from diblock and triblock copolymers respectively. DOX was effectively encapsulated up to 18 wt.% and 50-60% of it was steadily released from the micelles over a period of 7 d. Flow cytometry and fluorescence microscopy confirmed the effective intracellular uptake as well as the sustained release of DOX from micelles. These results suggest that the diblock as well as triblock copolymers are promising carriers for intra-cellular drug delivery. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Poly(ethylene glycol-poly(tetrahydrofuran-poly(ethylene glycol triblock copolymer : Synthesis, crystallization behavior and novel morphology

    Directory of Open Access Journals (Sweden)

    X. Q. Liao


    Full Text Available Poly(ethylene glycol-poly(tetrahydrofuran-poly(ethylene glycol (PEG-PTHF-PEG triblock copolymer was synthesized by ring-opening polymerization of ethylene oxide using sodium alcoholate of PTHF as the macroinitiator. Its crystallization behavior and formation mechanisms of different crystal structures were studied. The study showed that the molecular weight of PEG-PTHF-PEG exhibited a significant effect on its crystallization: that is, with the increase of the copolymer’s molecular weight, the crystallizability of PTHF blocks decreased gradually, which led to the transition of copolymer from crystalline-crystalline to crystalline-amorphous. By adjusting the total molecular weight of triblock copolymer, the crystallization process can be effectively controlled, and as a result, different spherulite structures were obtained. Particularly, when PTHF blocks became amorphous, novel double concentric spherulites were observed. The morphological structures were studied by differential scanning calorimetry (DSC, Fourier transform infrared spectroscopy (FTIR, scanning electron microscope (SEM, polarized optical microscopy (POM, and its crystalline process was investigated.

  7. Adsorption and association of a symmetric PEO-PPO-PEO triblock copolymer on polypropylene, polyethylene, and cellulose surfaces. (United States)

    Li, Yan; Liu, Hongyi; Song, Junlong; Rojas, Orlando J; Hinestroza, Juan P


    The association of a symmetric polyoxyethylene-polyoxypropylene-polyoxyethylene (PEO(19)-PPO(29)-PEO(19)) triblock copolymer adsorbed from aqueous solutions onto polypropylene (PP), polyethylene (PE), and cellulose surfaces was probed using Atomic Force Microscopy (AFM). Significant morphological differences between the polyolefin substrates (PP and PE) and the cellulose surfaces were observed after immersion of the films in the PEO(19)-PPO(29)-PEO(19) solutions. When the samples were scanned, while immersed in solutions of the triblock copolymer, it was revealed that the structures adsorbed on the polyolefin surfaces were smoothed by the adsorbed PEO(19)-PPO(29)-PEO(19). In contrast, those structures on the hydrophilic cellulose surfaces were sharpened. These observations were related to the roughness of the substrate and the energy of interaction between the surfaces and the PEO and PPO polymer segments. The interaction energy between each of the blocks and the surface was calculated using molecular dynamics simulations. It is speculated that the associative structures amply reported in aqueous solution at concentrations above the critical micelle concentration, CMC, are not necessarily preserved upon adsorption; instead, it appears that molecular arrangements of the anchor-buoy type and hemimicelles prevail. The reported data suggests that the roughness of the surface, as well as its degree of hydrophobicity, have a large influence on the nature of the resulting adsorbed layer. The reported observations are valuable in explaining the behavior of finishing additives and lubricants commonly used in textile and fiber processing, as well as the effect of the morphology of the boundary layers on friction and wear, especially in the case of symmetric triblock copolymers, which are commonly used as antifriction, antiwear additives.

  8. Stereocomplex formation in ABA triblock copolymers of poly(lactide)(A) and poly(ethylene glycol)(B)


    Stevels, W.M.; Ankone, Martinus J.K.; Dijkstra, Pieter J.; Feijen, Jan


    Two series of triblock copolymers of poly(ethylene glycol) (PEG, number-average molecular weight [bar M ]n = 6000) and poly(L-lactide) (PLLA) or poly(D-lactide) (PDLA) were prepared by ring-opening polymerization of lactide initiated by PEG end groups using stannous octoate as a catalyst, either in refluxing toluene or in the melt at 175°C. The weight percentage of PLA in the polymers varied between 15 and 75 wt.-%. Blends of polymers containing blocks of opposite chirality were prepared by c...

  9. Evolution of entanglements during the response to a uniaxial deformation of lamellar triblock copolymers and polymer glasses. (United States)

    Léonforte, F


    Using coarse-grained molecular-dynamics simulations, a generic styrene-block-butadiene-block-styrene triblock copolymer under lamellar conformation is used in order to investigate the mutual entanglement evolution when a structure of alternating glassy (S)/rubbery (B) layers is submitted to an imposed deformation. By varying the amount of loop chains between each phase, i.e., noncrossing chains, it is possible to generate different types of S/B interface definitions. A specific boundary driven tensile strain protocol has been developed in order to mimic "real" experiments and measure the stress-strain curve. The same protocol is also applied to a reference state consisting in a directed glassy homopolymers, as well as to an isotropic glassy polymer. The evolution of initial mutual entanglements from the undeformed samples during the whole deformation process is monitored. It is shown for all considered systems that initial entanglements mostly participate to the preyield regime of the stress-strain curve and that this network is debonded during the strain-hardening regime. For triblocks with a non-null amount of crossing chains, the lower the amount is, the longer the memory effect of the initial entanglement network in the postyield regime is. On the fly distributions of entanglements, which depart from the postyield regime, depict memory effects and long-time correlations during the strain-hardening regime. For triblocks, loop chains reinforce these effects.

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

    KAUST Repository

    Hadjichristidis, Nikolaos


    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.

  11. 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


    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.

  12. ABC triblock surface active block copolymer with grafted ethoxylated fluoroalkyl amphiphilic side chains for marine antifouling/fouling-release applications. (United States)

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


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

  13. Triblock copolymer anion exchange membranes bearing alkyl-tethered cycloaliphatic quaternary ammonium-head-groups for fuel cells (United States)

    Lin, Chen Xiao; Wang, Xiu Qin; Li, Ling; Liu, Fang Hua; Zhang, Qiu Gen; Zhu, Ai Mei; Liu, Qing Lin


    To explore highly conductive and alkaline stable anion exchange membrane (AEM) materials, triblock copolymers bearing alkyl-tethered cycloaliphatic quaternary ammonium-head-groups are prepared via nucleophilic substitution, Friedel-Crafts acylation, ketone reduction and Menshutkin reaction. The designed triblock copolymers composed of quaternized poly(phenylene oxide) segments and poly(ether sulfone) segments are responsible for the microphase separated morphology and well-connected ion domains, as confirmed by transmission electron microscopy. The highest conductivity, up to 105.1 mS cm-1 at 80 °C is achieved for the AEM with ionic exchange capacity (IEC) of 1.81 meq g-1. Furthermore, the AEMs show robust alkaline stability due to the alkyl-tethered cation-head-groups structure. High retention of hydroxide conductivity (88.9%) and IEC (91.2%) is observed for the AEMs via degradation test in a 1 M aqueous KOH solution at 80 °C for 480 h. Based on the AEM with high conductivity, a H2/O2 fuel cell achieves a peak power density of 176.5 mW cm-2 (80 °C) at a current density of 500 mA cm-2.

  14. Nanostructured Organic-Inorganic Hybrid Films Prepared by the Sol-Gel Method from Self-Assemblies of PS-b-PAPTES-b-PS Triblock Copolymers


    Gamys, Ce Guinto; Beyou, Emmanuel; Bourgeat-Lami, Elodie; Alcouffe, Pierre; David, Laurent


    International audience; ABA-based triblock copolymers of styrene as block ends and gelable 3-acryloxypropyltriethoxysilane (APTES) as the middle block were successfully prepared through nitroxide-medi- ated polymerization (NMP). The copolymers were bulk self- assembled into films and the degree of phase separation between the two blocks was evaluated by differential scanning calorimetry (DSC). Their morphology was examined through small angle X-ray scattering (SAXS) and transmission electron ...

  15. Simultaneous determination of the styrene unit content and assessment of molecular weight of triblock copolymers in adhesives by a size exclusion chromatography method. (United States)

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


    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.

  16. Low molecular weight linear polyethylenimine-b-poly(ethylene glycol)-b-polyethylenimine triblock copolymers: synthesis, characterization, and in vitro gene transfer properties

    NARCIS (Netherlands)

    Zhong, Zhiyuan; Feijen, Jan; Christensen, L.


    Novel ABA triblock copolymers consisting of low molecular weight linear polyethylenimine (PEI) as the A block and poly(ethylene glycol) (PEG) as the B block were prepared and evaluated as polymeric transfectant. The cationic polymerization of 2-methyl-2-oxazoline (MeOZO) using PEG−bis(tosylate) as a

  17. Structural Properties of Bulk and Aqueous Systems of PEO-PIB-PEO Triblock Copolymers as Studied by Small-Angle Neutron Scattering and Cryo-Transmission Electron Microscopy

    DEFF Research Database (Denmark)

    Mortensen, Kell; Talmon, Yeshayahu; Gao, Bo


    The phase behavior of a low molecular weight (M-w = 6000) symmetric triblock copolymer of poly(ethylene oxide) and poly(isobutylene), PEO-PIB-PEO, in the bulk as well in aqueous, D2O, solutions has been studied using small-angle neutron scattering and cryo-transmission electron microscopy...

  18. Hydrogen Bonding-Mediated Microphase Separation during the Formation of Mesoporous Novolac-Type Phenolic Resin Templated by the Triblock Copolymer, PEO-b-PPO-b-PEO. (United States)

    Chu, Wei-Cheng; Chiang, Shih-Fan; Li, Jheng-Guang; Kuo, Shiao-Wei


    After blending the triblock copolymer, poly(ethylene oxide-b-propylene oxide-b-ethylene oxide) (PEO-b-PPO-b-PEO) with novolac-type phenolic resin, Fourier transform infrared spectroscopy revealed that the ether groups of the PEO block were stronger hydrogen bond acceptors for the OH groups of phenolic resin than were the ether groups of the PPO block. Thermal curing with hexamethylenetetramine as the curing agent resulted in the triblock copolymer being incorporated into the phenolic resin, forming a nanostructure through a mechanism involving reaction-induced microphase separation. Mild pyrolysis conditions led to the removal of the PEO-b-PPO-b-PEO triblock copolymer and formation of mesoporous phenolic resin. This approach provided a variety of composition-dependent nanostructures, including disordered wormlike, body-centered-cubic spherical and disorder micelles. The regular mesoporous novolac-type phenolic resin was formed only at a phenolic content of 40-60 wt %, the result of an intriguing balance of hydrogen bonding interactions among the phenolic resin and the PEO and PPO segments of the triblock copolymer.

  19. 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


    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

  20. Hydrogen Bonding-Mediated Microphase Separation during the Formation of Mesoporous Novolac-Type Phenolic Resin Templated by the Triblock Copolymer, PEO-b-PPO-b-PEO

    Directory of Open Access Journals (Sweden)

    Wei-Cheng Chu


    Full Text Available After blending the triblock copolymer, poly(ethylene oxide-b-propylene oxide-b-ethylene oxide (PEO-b-PPO-b-PEO with novolac-type phenolic resin, Fourier transform infrared spectroscopy revealed that the ether groups of the PEO block were stronger hydrogen bond acceptors for the OH groups of phenolic resin than were the ether groups of the PPO block. Thermal curing with hexamethylenetetramine as the curing agent resulted in the triblock copolymer being incorporated into the phenolic resin, forming a nanostructure through a mechanism involving reaction-induced microphase separation. Mild pyrolysis conditions led to the removal of the PEO-b-PPO-b-PEO triblock copolymer and formation of mesoporous phenolic resin. This approach provided a variety of composition-dependent nanostructures, including disordered wormlike, body-centered-cubic spherical and disorder micelles. The regular mesoporous novolac-type phenolic resin was formed only at a phenolic content of 40–60 wt %, the result of an intriguing balance of hydrogen bonding interactions among the phenolic resin and the PEO and PPO segments of the triblock copolymer.

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

    NARCIS (Netherlands)

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


    Stereo-complexes (poly(ST–TMC–ST)) of enantiomeric triblock copolymers based on 1,3-trimethylene carbonate (TMC) and L- or D-lactide (poly(LLA–TMC–LLA) and poly(DLA–TMC–DLA)) were prepared. Films of poly(ST–TMC–ST) could be prepared by solvent casting mixtures of equal amounts of poly(LLA–TMC–LLA)

  2. Adsorption of non-ionic ABC triblock copolymers: Surface modification of TiO2 suspensions in aqueous and non-aqueous medium (United States)

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


    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.

  3. Surface Film Adsorption and Lubricity of Soybean Oil In-Water Emulsion and Triblock Copolymer Aqueous Solution: A Comparative Study

    Directory of Open Access Journals (Sweden)

    Reza Taheri


    Full Text Available This paper investigates the surface film adsorption and lubricity of two different types of potential environmentally friendly cold metal forming lubricants: soybean vegetable oil in water VO/W emulsions and triblock copolymer aqueous solutions. The lubricants have different visual appearance, surface film adsorption characteristic, lubricity and surface cleaning behaviour. The effects of concentration, temperature and emulsification ultrasonic energy (for VO/W emulsion are studied. The result shows that the soybean VO/W emulsions have stronger adsorption, superior lubricity and anti-wear property compared to the copolymer solutions. The effect of temperature is investigated at 30 °C and 65 °C which are below and above cloud point of the aqueous copolymer solutions. Both lubricants show improved friction and anti-wear property at 65 °C. However, tenacious residual film remained on the discs surface after surface cleaning indicates lower cleanability of the soybean VO/W emulsions compared to the copolymer solutions, postulating the need for extra post-processing cleaning operations after cold forming process with VO/W emulsion lubricant.

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

    Directory of Open Access Journals (Sweden)

    Bhattacharjee Sourav


    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

  5. Effect of interfaces on the melting of PEO confined in triblock PS-b-PEO-b-PS copolymers. (United States)

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


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

  6. Mesoscopic Simulations of Adsorption and Association of PEO-PPO-PEO Triblock Copolymers on a Hydrophobic Surface: From Mushroom Hemisphere to Rectangle Brush. (United States)

    Song, Xianyu; Zhao, Shuangliang; Fang, Shenwen; Ma, Yongzhang; Duan, Ming


    The dissipative particle dynamics (DPD) method is used to investigate the adsorption behavior of PEO-PPO-PEO triblock copolymers at the liquid/solid interface. The effect of molecular architecture on the self-assembled monolayer adsorption of PEO-PPO-PEO triblock copolymers on hydrophobic surfaces is elucidated by the adsorption process, film properties, and adsorption morphologies. The adsorption thicknesses on hydrophobic surfaces and the diffusion coefficient as well as the aggregation number of Pluronic copolymers in aqueous solution observed in our simulations agree well with previous experimental and numerical observations. The radial distribution function revealed that the ability of self-assembly on hydrophobic surfaces is P123 > P84 > L64 > P105 > F127, which increased with the EO ratio of the Pluronic copolymers. Moreover, the shape parameter and the degree of anisotropy increase with increasing molecular weight and mole ratio of PO of the Pluronic copolymers. Depending on the conformation of different Pluronic copolymers, the morphology transition of three regimes on hydrophobic surfaces is present: mushroom or hemisphere, progressively semiellipsoid, and rectangle brush regimes induced by decreasing molecular weight and mole ratio of EO of Pluronic copolymers.

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

    Energy Technology Data Exchange (ETDEWEB)

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


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

  8. 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


    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.

  9. A Near-Infrared Light-Responsive Hybrid Hydrogel Based on UCST Triblock Copolymer and Gold Nanorods

    Directory of Open Access Journals (Sweden)

    Hu Zhang


    Full Text Available We report a near-infrared (NIR light-responsive hydrogel that is capable of undergoing the gel to sol transition upon 785 nm light exposure based on a photothermal effect. The new hydrogel design relies on loading gold nanorods (AuNRs in an ABA-type triblock copolymer, namely P(AAm–co–AN–b–PDMA–b–P(AAm–co–AN, where P(AAm–co–AN stands for a random copolymer of acrylamide and acrylonitrile that exhibits an upper critical solution temperature (UCST in aqueous solution and PDMA is water-soluble polydimethylacrylamide. At solution temperature below UCST, the insoluble P(AAm–co–AN blocks lead to formation of hydrogel of flower-like micelles. When the hydrogel is exposed to 785 nm NIR light, the absorption due to the longitudinal surface plasmon resonance of loaded AuNRs generates heat that raises the hydrogel temperature above UCST and, consequently, the gel-to-sol transition. The NIR light-triggered release of a protein loaded in the hydrogel was found to display a switchable fashion.

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

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


    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. 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)


    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.

  12. Thermo-responsive diblock and triblock cationic copolymers at the silica/aqueous interface: A QCM-D and AFM study

    DEFF Research Database (Denmark)

    Moghaddam, Saeed Zajforoushan; Zhu, Kaizheng; Nyström, Bo


    The properties of synthesized diblock poly(N-isopropylacrylamide)-poly((3-acrylamidopropyl)trimethylammonium chloride) and triblock methoxy-poly(ethylene glycol)-poly(N-isopropylacrylamide)-poly((3-acrylamidopropyl)trimethylammonium chloride) cationic copolymers at the silica/aqueous interface...... suggests a comparable layer thickness for the copolymers on the silica surface, the AFM imaging and colloidal probe measurements reveal significant differences in surface coverage and thickness of the layers, which are discussed and compared with respect to the stabilization effect by the hydrophilic poly...

  13. Triblock copolymers encapsulated poly (aryl benzyl ether) dendrimer zinc(II) phthalocyanine nanoparticles for enhancement in vitro photodynamic efficacy. (United States)

    Huang, Yide; Yu, Huizhen; Lv, Huafei; Zhang, Hong; Ma, Dongdong; Yang, Hongqin; Xie, Shusen; Peng, Yiru


    A novel series of nanoparticles formed via an electrostatic interaction between the periphery of negatively charged 1-2 generation aryl benzyl ether dendrimer zinc (II) phthalocyanines and positively charged poly(L-lysin) segment of triblock copolymer, poly(L-lysin)-block-poly(ethylene glycol)-block-poly(L-lysin), was developed for the use as an effective photosensitizers in photodynamic therapy. The dynamic light scattering, atomic force microscopy showed that two nanoparticles has a relevant size of 80-150nm. The photophysical properties and singlet oxygen quantum yields of free dendrimer phthalocyanines and nanoparticles exhibited generation dependence. The intracellular uptake of dendrimer phthalocyanines in Hela cells was significantly elevated as they were incorporated into the micelles, but was inversely correlated with the generation of dendrimer phthalocyanines. The photocytotoxicity of dendrimer phthalocyanines incorporated into polymeric micelles was also increased. The presence of nanoparticles induced efficient cell death. Using a mitochondrial-sepcific dye rhodamine 123 (Rh123), our fluorescence microscopic result indicated that nanoparticles localized to the mitochondria. Copyright © 2016 Elsevier B.V. All rights reserved.

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

    KAUST Repository

    Sundaram, Harihara S.


    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.

  15. Thermosensitive in situ hydrogel based on the hybrid of hyaluronic acid and modified PCL/PEG triblock copolymer. (United States)

    Lv, Zesheng; Chang, Longlong; Long, Xingwen; Liu, Jianping; Xiang, Yuzhang; Liu, Jinjian; Liu, Jianfeng; Deng, Hongzhang; Deng, Liandong; Dong, Anjie


    In this work, a new hydrogel was constructed using poly(ɛ-caprolactone-co-1,4,8-trioxa[4.6]spiro-9-undecanone)-poly(ethylene glycol)-poly(ɛ-caprolactone-co-1,4,8-trioxa[4.6]spiro-9-undecanone) tri-block copolymers (PECT) with hyaluronic acid (HA) in order to expand application scopes of PECT hydrogel. The rheological and sol-gel phase transition behaviors were investigated by rheometer and test tube inversion method, and the interior morphologies of hydrogel systems were observed by scanning electron microscope (SEM). With the introduction of HA, certain properties of PECT hydrogel, such as viscosity and morphology, have present trends with regularity. Furthermore, with the participation of HA, the degradation and release of acetylsalicylic acid was slightly affected, however, the drug release mechanism of hydrogel has not been changed. PECT/HA hydrogel is confirmed to be non-toxic through a test to NIH3T3 cells. In conclusion, blending with HA is a feasible and safe method to tune properties of PECT hydrogel. Copyright © 2014 Elsevier Ltd. All rights reserved.

  16. Importance of crystallinity of anchoring block of semi-solid amphiphilic triblock copolymers in stabilization of silicone nanoemulsions. (United States)

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


    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.

  17. Experimental and theoretical study of bifunctionalized PEO–PPO–PEO triblock copolymers with applications as dehydrating agents for heavy crude oil

    Directory of Open Access Journals (Sweden)

    César A. Flores-Sandoval


    Full Text Available A series of α,ω-diamines of polyoxyethylene–polyoxypropylene–polyoxyethylene (POE–POP–POE triblock copolymer was synthesized and experimentally evaluated as dewatering agents for heavy crude oil. A quantitative structure–activity relationship (QSAR study of the effect of the secondary amine structure over the yield of nucleophilic substitution reactions with α,ω-ditosylate ester of PEO–PPO–PEO triblock copolymer was performed exclusively at the DFT level. Multiple linear regression (MLR analysis including softness or hardness parameters gave R2 = 0.9062, producing an equation with an acceptable rm(test2 value. Furthermore, in order to understand the physicochemical interaction between the functionalizing copolymers and water, QSAR models based on AM1 semiempirical and DFT (B3LYP functional descriptors were carried out for comparative purposes. For the MLR analysis at the AM1 level, R2 = 0.9058, whereas at the DFT level, R2 = 0.9879. 2-(Methylaminoethanol was employed to evaluate the equations obtained. The residual of the logERcalc SN2 reaction was −0.0043, showing a good correlation with experimental efficiency. Regarding water removal efficiency, the residuals of logWRcalc at the AM1 and DFT levels were of 0.0220 and 0.0041, respectively. Even though, DFT produced a better correlation, a QSAR study at the AM1 level could be employed to study the behavior of α,ω-diamines of PEO–PPO–PEO triblock copolymer and to destabilize water/oil emulsions, with a computational cost relatively low compared to DFT calculations.

  18. Effect of reinforcement nanoparticles addition on mechanical properties of SBS/curaua fiber composites

    Energy Technology Data Exchange (ETDEWEB)

    Borba, Patricia M. [Servico Nacional de Aprendizagem Industrial (CETEPO/SENAI/RS), Sao Leopoldo, RS (Brazil). Centro Tecnologico de Polimeros; Tedesco, Adriana [Braskem S. A., III Polo Petroquimico, Triunfo, RS (Brazil); Lenz, Denise M., E-mail: [Universidade Luterana do Brasil (ULBRA), Canoas, RS (Brazil). Programa de Pos-graduacao em Engenharia de Materiais e Processos Sustentaveis


    Composites of styrene-butadiene-styrene triblock copolymer (SBS) matrix with curauá fiber and/or a nanoparticulated mineral (montmorillonite clay - MMT) used as reinforcing agents were prepared by melt-mixing. The influence of clay addition on properties like tensile and tear strength, rebound resilience, flex fatigue life, abrasion loss, hardness and water absorption of composites with 5, 10 and 20 wt% of curauá fiber was evaluated in presence of maleic anhydride grafted styrene-(ethylene-co-butylene)-styrene triblock copolymer (MA-g-SEBS) coupling agent. Furthermore, the effect of mineral plasticizer loading on tensile strength of selected composites was investigated. The hybrid SBS composite that showed the best overall mechanical performance was composed by 2 wt% of MMT and 5 wt% of curauá fiber. Increasing fiber content up to 20 wt% resulted in a general decrease in all mechanical properties as well as incorporation of 5 wt% MMT caused a decrease in the tensile strength in all fiber contents. The hybrid composites showed clay agglomerates (tactoids) poorly dispersed that could explain the poor mechanical performance of composites at higher concentrations of curauá fiber and MMT nanoparticles. The addition of plasticizer further decreased the tensile strength while the addition of MMT nanoparticles decreased water absorption for all SBS composites. (author)

  19. Amphiphilic triblock copolymers with PEGylated hydrocarbon structures as environmentally friendly marine antifouling and fouling-release coatings. (United States)

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


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

  20. Cooperative preassociation stages of PEO-PPO-PEO triblock copolymers: NMR and theoretical study. (United States)

    Kríz, Jaroslav; Dybal, Jirí


    Using (1)H and (13)C 1D and 2D NMR spectra, pulsed field-gradient (PFG) diffusion measurements, and (13)C relaxations supported by density functional theory (DFT) calculations, the temperature-dependent behavior of (EO)(m)(PO)(n)(EO)(m) block copolymers (m/n = 31/14, 31/72, and 17/1) in D(2)O below and at the critical micellar temperature (CMT) was investigated in order to understand the nature of primary self-association acts and their true driving force. It was shown that a conformation change of the PO block followed by mild and reversible association with other PO blocks and eventually with the inner parts of EO blocks starts at temperatures 10-12 K below the CMT. The primary process is the entropy-driven disintegration of the PPO hydration envelope based on cooperation of hydrophobic hydration and hydrogen bonding. The partial dehydration of PPO is followed by its conformation change. Both processes are cooperative and reversible with a correlation time of the order 0.01 s and an activation energy of 51.3 kJ/mol. The PPO chain in a staggered conformation is prone to self-association starting at temperatures 5-6 K below CMT. In (EO)(m)(PO)(n)(EO)(m) block copolymers, this process is complicated by the stripping of PEO chains of a part of hydrogen-bound water and entwining them with PPO. It is shown that only inner (PPO-near) parts of PEO take part in the process, the end-groups remaining free.

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

    Energy Technology Data Exchange (ETDEWEB)

    Enlow, Drew Lenzen [Iowa State Univ., Ames, IA (United States)


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

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

    Directory of Open Access Journals (Sweden)

    Wenyuan Xie


    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.

  3. Experimental and computational study of the effect of alcohols on the solution and adsorption properties of a nonionic symmetric triblock copolymer. (United States)

    Liu, Xiaomeng; He, Feng; Salas, Carlos; Pasquinelli, Melissa A; Genzer, Jan; Rojas, Orlando J


    This study investigates the effect of alcohols on the solution and adsorption properties of symmetric triblock nonionic copolymers comprising blocks of ethylene oxide (EO) and propylene oxide (PO) (EO(37)PO(56)EO(37)). The cloud point, surface tension, critical micelle concentration (CMC), and maximum packing at the air-water interface are determined, and the latter is compared to the amount of polymer that adsorbs from solution onto polypropylene (PP) and cellulose surfaces. The interaction energy and radius of micelles are calculated by using molecular dynamics (MD) simulations. Equivalent MD bead parameters were used in dynamic density functional theory (DDFT) simulations to study the influence of alcohols on the phase behavior of EO(37)PO(56)EO(37) and its adsorption on PP from aqueous solutions. The simulation results agree qualitatively with the experimental observations. Ethanol acts as a good cosolvent for EO(37)PO(56)EO(37) and reduces the amount of EO(37)PO(56)EO(37) that adsorbs on PP surfaces; however, little or no influence is observed on the adsorption on cellulose. Interestingly, longer chain alcohols, such as 1-pentanol, produce the opposite effect. Overall, the solution and adsorption properties of nonionic symmetric triblock copolymers in the presence of alcohols are rationalized by changes in solvency and the hydrophobic effect.

  4. New triblock copolymer templates, PEO-PB-PEO, for the synthesis of titania films with controlled mesopore size, wall thickness, and bimodal porosity. (United States)

    Ortel, Erik; Fischer, Anna; Chuenchom, Laemthong; Polte, Jörg; Emmerling, Franziska; Smarsly, Bernd; Kraehnert, Ralph


    The synthesis and properties of a series of new structure-directing triblock copolymers with PEO-PB-PEO structure (PEO = poly(ethylene oxide) and PB = polybutadiene) and their application as superior pore-templates for the preparation of mesoporous titania coatings are reported. Starting from either TiCl4 or from preformed TiO2 nanocrystalline building blocks, mesoporous crystalline titanium oxide films with a significant degree of mesoscopic ordered pores are derived, and the pore size can be controlled by the molecular mass of the template polymer. Moreover, the triblock copolymers form stable micelles already at very low concentration, i.e., prior to solvent evaporation during the evaporation-induced self-assembly process (EISA). Consequently, the thickness of pore walls can be controlled independently of pore size by changing the polymer-to-precursor ratio. Thus, unprecedented control of wall thickness in the structure of mesoporous oxide coatings is achieved. In addition, the micelle formation of the new template polymers is sufficiently distinct from that of typical commercial PPO-PEO-PPO polymers (Pluronics; PPO = poly(propylene oxide)), so that a combination of both polymers facilitates bimodal porosity via dual micelle templating. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    Directory of Open Access Journals (Sweden)

    Qiu-Sheng Shi


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

  6. Biodegradable Nanoparticles of mPEG-PLGA-PLL Triblock Copolymers as Novel Non-Viral Vectors for Improving siRNA Delivery and Gene Silencing (United States)

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


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

  7. Nature of interactions between PEO-PPO-PEO triblock copolymers and lipid membranes: (I) effect of polymer hydrophobicity on its ability to protect liposomes from peroxidation. (United States)

    Wang, Jia-Yu; Marks, Jeremy; Lee, Ka Yee C


    PEO-PPO-PEO triblock copolymers have opposing effects on lipid membrane integrity: they can behave either as membrane sealants or as membrane permeabilizers. To gain insights into their biomembrane activities, the fundamental interactions between a series of PEO-based polymers and phospholipid vesicles were investigated. Specifically, the effect of copolymer hydrophobicity on its ability to prevent liposomes from peroxidation was evaluated, and partitioning free energy and coefficient involved in the interactions were derived. Our results show that the high degree of hydrophilicity is a key feature of the copolymers that can effectively protect liposomes from peroxidation and the protective effect of the copolymers stems from their adsorption at the membrane surface without penetrating into the bilayer core. The origin of this protective effect induced by polymer absorption is attributed to the retardation of membrane hydration dynamics, which is further illustrated in the accompanying study on dynamic nuclear polarization (DNP)-derived hydration dynamics (Cheng, C.-Y.; Wang, J.-Y.; Kausik, R.; Lee, K. Y. C.; Han S. Biomacromolecules, 2012, DOI: 10.1021/bm300848c).

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

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


    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

  9. Thermal Annealing to Modulate the Shape Memory Behavior of a Biobased and Biocompatible Triblock Copolymer Scaffold in the Human Body Temperature Range. (United States)

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


    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.

  10. Surface structures of an amphiphilic tri-block copolymer in air and in water probed using sum frequency generation vibrational spectroscopy. (United States)

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


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

  11. 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.


    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.

  12. A-B-C Triblock Copolymer Micelles for Intracellular Delivery of Cancer-Targeted siRNA (United States)

    Gary, Dana Jeanine

    Successful clinical use of synthetic siRNAs for gene therapy via a pathway called RNA interference (RNAi) is still limited by a variety of factors in the delivery process. These factors include recognition and uptake by the targeted cell type, efficient escape from the intracellular endosomal cavities, and release of the siRNA payload into the cytosol where the RNAi mechanism can be initiated. siRNA on its own is incapable of enduring this journey intact and thus various protective vehicles have been designed for the safe and efficient delivery of siRNA for gene silencing. Among the most promising of the non-viral vectors studied thus far in the literature are synthetic polymers, designed to protect and deliver the siRNA cargo intracellularly with minimal toxicity to the host. In this work, we will explore the A-B-C triblock copolymer PEG-PnBA-PDMAEMA, which forms micelle-like aggregates in aqueous buffer, providing an unconventional architectural platform for studying siRNA delivery properties. The in vitro and in vivo performance (toxicity, gene silencing, biodistribution, tumor accumulation, etc.) of the PEG-PnBA-PDMAEMA micelle/siRNA complexes (micelleplexes) are compared relative to more traditional polycation-based systems (e.g., PDMAEMA, PEG-PDMAEMA) to determine the role of nano-carrier architecture on delivery behavior. These three systems are very similar chemically but are expected to have distinct delivery behaviors due to their architectural dissimilarities and differing degrees of PEGylation. We observed an overall improvement in the gene silencing and tumor accumulation efficiencies with the micelleplex system with no additional toxicity than the PDMAEMA and PEG-PDMAEMA complexes under the same conditions. This proves that the micelleplex concept affords net-positive benefits to the nano-carrier based on its architecture which the PDMAEMA and PEG-PDMAEMA systems are not able to provide. However, in spite of its obvious edge over basic polyctations

  13. Interaction of poly (ethylene oxide)-poly (propylene oxide)-poly (ethylene oxide) triblock copolymer of molecular weight 2800 with sodium dodecylsulfate (SDS) micelles: some physicochemical studies

    Energy Technology Data Exchange (ETDEWEB)

    James, Jilly [Chemical Laboratory, Physical and Inorganic Chemistry Division, Central Leather Research Institute, Adyar, Chennai 600 020 (India); Vellaichami, S. [Chemical Laboratory, Physical and Inorganic Chemistry Division, Central Leather Research Institute, Adyar, Chennai 600 020 (India); Krishnan, Ramya S.G. [Chemical Laboratory, Physical and Inorganic Chemistry Division, Central Leather Research Institute, Adyar, Chennai 600 020 (India); Samikannu, S. [Department of Chemistry, Loyola College, Chennai 600 034 (India); Mandal, Asit Baran [Chemical Laboratory, Physical and Inorganic Chemistry Division, Central Leather Research Institute, Adyar, Chennai 600 020 (India)]. E-mail:


    The interaction of water insoluble poly (ethylene oxide)-poly (propylene oxide)-poly (ethylene oxide) triblock copolymer (mol. wt. 2800) micelles with sodium dodecylsulfate (SDS) micelles has been studied for the first time. The critical micelle concentrations (cmc) and counter ion association of SDS in aqueous and in presence of this triblock copolymer were determined by using conductance and surface tension methods. The cmc values obtained by these methods are in good agreement with each other and dependent on temperature. The aggregation numbers obtained by fluorescence method for polymer and polymer-SDS mixed micellar systems are 15 and 141, respectively at 25 {sup o}C. Using the monophasic micellization concept, the association constant (K{sub A}) for the polymer-SDS mixed micellar systems was determined [A.B. Mandal, S. Ray, S.P. Moulik, Indian J. Chem. 19A (1980) 620]. The positive values of {delta}G{sup 0}, {delta}H{sup 0} and {delta}S{sup 0} suggest that the polymer must have interacted with SDS with the increase in the freedom of the system as a whole. Using biphasic model, the thermodynamic parameters viz; {delta}G{sub m}{sup 0},{delta}H{sub m}{sup 0}and{delta}S{sub m}{sup 0} for SDS-H{sub 2}O and polymer-SDS mixed micellar systems were estimated and the results are in good agreement with the monophasic model. Using biphasic micellar model, the standard free energy for transfer of SDS from aqueous to polymer additive environments is also calculated at various temperatures and found to be negative. These results suggest that the SDS is more stable in micellized form in the SDS-water-polymer ternary systems compared to the situation in the corresponding SDS-water binary systems.

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

    Directory of Open Access Journals (Sweden)

    Xiong Xu


    Full Text Available 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

  15. RGD Peptides-Conjugated Pluronic Triblock Copolymers Encapsulated with AP-2α Expression Plasmid for Targeting Gastric Cancer Therapy in Vitro and in Vivo. (United States)

    Wang, Wei; Liu, Zhimin; Sun, Peng; Fang, Cheng; Fang, Hongwei; Wang, Yueming; Ji, Jiajia; Chen, Jun


    Gastric cancer, a high-risk malignancy, is a genetic disease developing from a cooperation of multiple gene mutations and a multistep process. Gene therapy is a novel treatment method for treating gastric cancer. Here, we developed a novel Arg-Gly-Asp (RGD) peptides conjugated copolymers nanoparticles-based gene delivery system in order to actively targeting inhibit the growth of gastric cancer cells. These transcription factor (AP-2α) expression plasmids were also encapsulated into pluronic triblock copolymers nanoparticles which was constituted of poly(ethylene glycol)-block-poly(propylene glycol)- block-poly(ethylene glycol) (PEO-block-PPO-block-PEO, P123). The size, morphology and composition of prepared nanocomposites were further characterized by nuclear magnetic resonance (NMR), transmission electron microscopy (TEM) and dynamic light scattering (DLS). In MTT (3-(4,5-dimethyl-2-thiazolyl)-2,5-diphenyltetrazolium bromide) analysis, these nanocomposites have minor effects on the proliferation of GES-1 cells but significantly decreased the viability of MGC-803, suggesting they own low cytotoxicity but good antitumor activity. The following in vivo evaluation experiments confirmed that these nanocomposites could prevent the growth of gastric cancer cells in the tumor xenograft mice model. In conclusion, these unique RGD peptides conjugated P123 encapsulated AP-2α nanocomposites could selectively and continually kill gastric cancer cells by over-expression of AP-2α in vitro and in vivo; this exhibits huge promising applications in clinical gastric cancer therapy.

  16. RGD Peptides-Conjugated Pluronic Triblock Copolymers Encapsulated with AP-2α Expression Plasmid for Targeting Gastric Cancer Therapy in Vitro and in Vivo

    Directory of Open Access Journals (Sweden)

    Wei Wang


    Full Text Available Gastric cancer, a high-risk malignancy, is a genetic disease developing from a cooperation of multiple gene mutations and a multistep process. Gene therapy is a novel treatment method for treating gastric cancer. Here, we developed a novel Arg-Gly-Asp (RGD peptides conjugated copolymers nanoparticles-based gene delivery system in order to actively targeting inhibit the growth of gastric cancer cells. These transcription factor (AP-2α expression plasmids were also encapsulated into pluronic triblock copolymers nanoparticles which was constituted of poly(ethylene glycol-block-poly(propylene glycol- block-poly(ethylene glycol (PEO-block-PPO-block-PEO, P123. The size, morphology and composition of prepared nanocomposites were further characterized by nuclear magnetic resonance (NMR, transmission electron microscopy (TEM and dynamic light scattering (DLS. In MTT (3-(4,5-dimethyl-2-thiazolyl-2,5-diphenyltetrazolium bromide analysis, these nanocomposites have minor effects on the proliferation of GES-1 cells but significantly decreased the viability of MGC-803, suggesting they own low cytotoxicity but good antitumor activity. The following in vivo evaluation experiments confirmed that these nanocomposites could prevent the growth of gastric cancer cells in the tumor xenograft mice model. In conclusion, these unique RGD peptides conjugated P123 encapsulated AP-2α nanocomposites could selectively and continually kill gastric cancer cells by over-expression of AP-2α in vitro and in vivo; this exhibits huge promising applications in clinical gastric cancer therapy.

  17. Adsorption of a PEO-PPO-PEO triblock copolymer on metal oxide surfaces with a view to reducing protein adsorption and further biofouling. (United States)

    Yang, Y; Poleunis, C; Románszki, L; Telegdi, J; Dupont-Gillain, C C


    Abstract Biomolecule adsorption is the first stage of biofouling. The aim of this work was to reduce the adsorption of proteins on stainless steel (SS) and titanium surfaces by modifying them with a poly(ethylene oxide) (PEO)-poly(propylene oxide) (PPO)-PEO triblock copolymer. Anchoring of the central PPO block of the copolymer is known to be favoured by hydrophobic interaction with the substratum. Therefore, the surfaces of metal oxides were first modified by self-assembly of octadecylphosphonic acid. PEO-PPO-PEO preadsorbed on the hydrophobized surfaces of titanium or SS was shown to prevent the adsorption of bovine serum albumin (BSA), fibrinogen and cytochrome C, as monitored by quartz crystal microbalance (QCM). Moreover, X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry were used to characterize the surfaces of the SS and titanium after competitive adsorption of PEO-PPO-PEO and BSA. The results show that the adsorption of BSA is well prevented on hydrophobized surfaces, in contrast to the surfaces of native metal oxides.

  18. Folate-decorated PEGylated triblock copolymer as a pH/reduction dual-responsive nanovehicle for targeted intracellular co-delivery of doxorubicin and Bcl-2 siRNA. (United States)

    Suo, Aili; Qian, Junmin; Xu, Minghui; Xu, Weijun; Zhang, Yaping; Yao, Yu


    Co-delivery of chemotherapeutic drug and small interfering RNA (siRNA) within a single nanovehicle has emerged as a promising combination therapy approach to treating cancers because of their synergistic effect. Nanocarrier delivery systems with low cytotoxicity and high efficiency are needed for such a purpose. In this study, a novel folate-conjugated PEGylated cationic triblock copolymer, poly(acrylhydrazine)-block-poly(3-dimethylaminopropyl methacrylamide)-block-poly(acrylhydrazine) (PAH-b-PDMAPMA-b-PAH), was synthesized and evaluated as a stimuli-sensitive vehicle for the targeted co-delivery of doxorubicin (DOX) and Bcl-2 siRNA into breast cancer MCF-7 cells. The synthetic process of the PEGylated triblock copolymer involved sequential reversible addition-fragmentation chain transfer polymerization, PEGylation and removal of tert-butoxy carbamate protecting groups. Folate-conjugated and/or -unconjugated poly(ethylene glycol) segments were grafted onto PAH-b-PDMAPMA-b-PAH via a reduction-sensitive disulfide linkage. The synthetic polymers were characterized by 1 H NMR and gel permeation chromatography. The PEGylated triblock copolymer could chemically conjugate DOX onto PAH blocks via pH-responsive hydrazone bonds and simultaneously complex negatively charged Bcl-2 siRNA with cationic PDMAPMA blocks through electrostatic interactions at N/P ratios≥32:1 to form multifunctional nanomicelleplexes. The nanomicelleplexes exhibited spherical shape, possessed a positively charged surface with a zeta potential of +22.5mV and had a desirable and uniform particle size of 187nm. In vitro release studies revealed that the nanomicelleplexes could release DOX and Bcl-2 siRNA in a reduction and pH dual-sensitive manner and the payload release was significantly enhanced in a reductive acidic environment mimicking the endosomes/lysosomes of cancer cells compared to under physiology conditions. Furthermore, the release of both DOX and siRNA was found to follow Higuchi kinetic

  19. Spontaneous Enhancement of Packing Regularity of Spherical Microdomains in the Body-Centered Cubic Lattice upon Uniaxial Stretching of Elastomeric Triblock Copolymers

    Directory of Open Access Journals (Sweden)

    Shinichi Sakurai


    Full Text Available Block copolymers forming glassy spheres in the matrix of rubbery chains can exhibit elastomeric properties. It is well known that the spherical microdomains are arranged in the body-center cubic (bcc lattice. However, recently, we have found packing in the face-centered cubic (fcc lattice, which is easily transformed into the bcc lattice upon uniaxial stretching. In the same time, the packing regularity of the spheres in the bcc lattice was found to be enhanced for samples completely recovered from the stretched state. This reminds us that a cycle of stretching-and-releasing plays an important role from analogy of densification of the packing in granules upon shaking. In the current paper, we quantify the enhancement of packing regularity of spherical microdomains in the bcc lattice upon uniaxial stretching of the same elastomeric triblock copolymer as used in our previous work by conducting small-angle X-ray scattering (SAXS measurements using high brilliant synchrotron radiation. Isotropically circular rings of the lattice peaks observed for the unstretched sample turned into deformed ellipsoidal rings upon the uniaxial stretching, with sharpening of the peaks in the direction parallel to the stretching direction and almost disappearing of the peaks in the perpendicular direction. By quantitatively analyzing the SAXS results, it was found that the packing regularity of the spherical microdomains was enhanced in the parallel direction while it was spoiled in the perpendicular direction under the stretched state. The enhanced regularity of packing was unchanged even if the stretching load was completely removed.

  20. Surface modification of paclitaxel-loaded tri-block copolymer PLGA- b-PEG- b-PLGA nanoparticles with protamine for liver cancer therapy (United States)

    Gao, Nansha; Chen, Zhihong; Xiao, Xiaojun; Ruan, Changshun; Mei, Lin; Liu, Zhigang; Zeng, Xiaowei


    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 1H 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® 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® 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.

  1. Magnetic solid-phase extraction of phthalate esters (PAEs) in apparel textile by core-shell structured Fe3O4@silica@triblock-copolymer magnetic microspheres. (United States)

    Xu, Mei; Liu, Minhua; Sun, Meirong; Chen, Kun; Cao, Xiujun; Hu, Yaoming


    In this paper, novel core-shell structured magnetic Fe3O4/silica nanocomposites with triblock-copolymer grafted on their surface (Fe3O4@SiO2@MDN) were successfully fabricated by combining a sol-gel method with a seeded aqueous-phase radical copolymerization approach. Owing to the excellent characteristics of the strong magnetic responsivity, outstanding hydrophilicity and abundant π-electron system, the obtained core-shell structured microspheres showed great potential as a magnetic solid phase extraction (MSPE) adsorbent. Several kinds of phthalate esters (PAEs) were selected as model analytes to systematically evaluate the applicability of adsorbents for extraction followed by gas chromatography-mass spectrometry (GC-MS) analyses. Various parameters, including adsorbents amounts, adsorption time, species of eluent, and desorption time were optimized. Under the optimized conditions, Validation experiments such as recovery, reproducibility, and limit of detection were carried on and showed satisfactory results. The analysis method showed excellent linearity with a wide range of 0.2-10mg/kg (R(2)>0.9974) and low limits of detection (LOD) of 0.02-0.09 mg/kg (S/N=3). Ultimately, the novel magnetic adsorbents were successfully employed to detect the PAEs in apparel textile samples. And the results indicated that this novel approach brought forward in the present work offered an attractive alternative for rapid, efficient and sensitive MSPE for PAEs compounds. Copyright © 2015 Elsevier B.V. All rights reserved.

  2. 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: [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: [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)


    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.

  3. 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: [Shenzhen University, Institute of Allergy and Immunology, School of Medicine (China); Zeng, Xiaowei, E-mail: [Tsinghua University, The Shenzhen Key Lab of Gene and Antibody Therapy, and Division of Life and Health Sciences, Graduate School at Shenzhen (China)


    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.

  4. Hydration of cations: a key to understanding of specific cation effects on aggregation behaviors of PEO-PPO-PEO triblock copolymers. (United States)

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


    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.

  5. Analysis of P (VdCl-co-AN-co-MMA)-LiClO 4-EC triblock copolymer ...

    Indian Academy of Sciences (India)

    The lithium ion conducting copolymer electrolytes based on poly(vinylidene chloride-co-acrylonitrileco- methyl methacrylate) P(VdCl-co-AN-co-MMA)-lithium per chlorate (LiClO4) (P(VdCl-co-AN-co-MMA): LiClO4) and poly(vinylidene chloride-co-acrylonitrile-co-methyl methacrylate)P(VdCl-co-AN-co-MMA)-lithium per ...

  6. 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


    at the same time part of the nanoporosity, and PDMS was quantitatively etched to provide additional nanoporosity. Both the deprotection of the PtBA block and the etching of PDMS were realized by one-step operations using either anhydrous hydrogen fluoride (HF) or trifluoroacetic acid (TFA). The finding......, and scanning electron microscopy. In contact with water, all the prepared nanoporous polymers showed spontaneous water uptake close to the amounts expected from the precursor block copolymer compositions....

  7. Use of the Flory-Huggins theory to predict the solubility of nifedipine and sulfamethoxazole in the triblock, graft copolymer Soluplus. (United States)

    Altamimi, Mohammad A; Neau, Steven H


    Drug dispersed in a polymer can improve bioavailability; dispersed amorphous drug undergoes recrystallization. Solid solutions eliminate amorphous regions, but require a measure of the solubility. Use the Flory-Huggins Theory to predict crystalline drugs solubility in the triblock, graft copolymer Soluplus® to provide a solid solution. Physical mixtures of the two drugs with similar melting points but different glass forming ability, sulfamethoxazole and nifedipine, were prepared with Soluplus® using a quick technique. Drug melting point depression (MPD) was measured using differential scanning calorimetry. The Flory-Huggins Theory allowed: (1) interaction parameter, χ, calculation using MPD data to provide a measure of drug-polymer interaction strength and (2) estimation of the free energy of mixing. A phase diagram was constructed with the MPD data and glass transition temperature (Tg) curves. The interaction parameters with Soluplus® and the free energy of mixing were estimated. Drug solubility was calculated by the intersection of solubility equations and that of MPD and Tg curves in the phase diagram. Negative interaction parameters indicated strong drug-polymer interactions. The phase diagram and solubility equations provided comparable solubility estimates for each drug in Soluplus®. Results using the onset of melting rather than the end of melting support the use of the onset of melting. The Flory-Huggins Theory indicates that Soluplus® interacts effectively with each drug, making solid solution formation feasible. The predicted solubility of the drugs in Soluplus® compared favorably across the methods and supports the use of the onset of melting.

  8. 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


    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.

  9. 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: [Key Laboratory for Colloid and Interface Chemistry of Education Ministry, Shandong University, Jinan 250100 (China)


    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

  10. Influence of triblock copolymer (pluronic F127) on enhancing the physico-chemical properties and photocatalytic response of mesoporous TiO{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Samsudin, Emy Marlina; Hamid, Sharifah Bee Abd, E-mail:; Juan, Joon Ching; Basirun, Wan Jefrey


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

  11. Synthesis of Novel π-Conjugated Rod-Rod-Rod Triblock Copolymers Containing Poly(3-hexylthiophene and Polyacetylene Segments by Combination of Quasi-Living GRIM and Living Anionic Polymerization

    Directory of Open Access Journals (Sweden)

    Tomoya Higashihara


    Full Text Available The first successful synthesis of a new rod-rod-rod triblock copolymer, polyacetylene(PA-b-poly(3-hexylthiophene(P3HT-b-PA could be synthesized by a combination of quasi-living Grignard metathesis (GRIM and living anionic polymerization. We first confirmed that poly(4-tolyl vinyl sulfoxide (PTVS, which is a soluble precursor for PA, could be synthesized by living anionic polymerization in THF at −78 °C, initiated with 3-methyl-1,1-diphenylpentyllithium as the initiator in the presence of in situ-generated lithium enolate. The molecular weights (MWs and polydispersities (PDIs were well controlled (MW = 5,200–27,000, PDI = 1.10–1.22, respectively. A coil-rod-coil triblock copolymer, PTVS-b-P3HT-b-PTVS, (6,000-12,500-6,000 could also be synthesized, initiated with a P3HT-based difunctional macroinitiator in the presence of lithium enolate. GPC-RALLS and 1H NMR analyses confirmed a high degree of structural homogeneity of PTVS-b-P3HT-b-PTVS. A thermal transformation reaction of the polymer was carried out in the film state at 170 °C for 2 h to afford PA-b-P3HT-b-PA quantitatively, as monitored by TGA and FT-IR analyses. The optical and electronic properties as well as the morphological behavior of the block copolymers were investigated by UV-vis spectroscopy, conductivity measurement, and AFM observation.

  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; Estudio del comportamiento mecanico de geles fisicos termoreversibles obtenidos a partir de copolimeros tribloques de PS-b-poli(etileno/butileno)-PS en un disolvente selectivo del bloque central

    Energy Technology Data Exchange (ETDEWEB)

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


    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{sub 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. Biodegradable Tri-Block Copolymer Poly(lactic acid-poly(ethylene glycol-poly(L-lysine(PLA-PEG-PLL as a Non-Viral Vector to Enhance Gene Transfection

    Directory of Open Access Journals (Sweden)

    Na Zhang


    Full Text Available Low cytotoxicity and high gene transfection efficiency are critical issues in designing current non-viral gene delivery vectors. The purpose of the present work was to synthesize the novel biodegradable poly (lactic acid-poly(ethylene glycol-poly(L-lysine (PLA-PEG-PLL copolymer, and explore its applicability and feasibility as a non-viral vector for gene transport. PLA-PEG-PLL was obtained by the ring-opening polymerization of Lys(Z-NCA onto amine-terminated NH2-PEG-PLA, then acidolysis to remove benzyloxycarbonyl. The tri-block copolymer PLA-PEG-PLL combined the characters of cationic polymer PLL, PLA and PEG: the self-assembled nanoparticles (NPs possessed a PEG loop structure to increase the stability, hydrophobic PLA segments as the core, and the primary ε-amine groups of lysine in PLL to electrostatically interact with negatively charged phosphate groups of DNA to deposit with the PLA core. The physicochemical properties (morphology, particle size and surface charge and the biological properties (protection from nuclease degradation, plasma stability, in vitro cytotoxicity, and in vitro transfection ability in HeLa and HepG2 cells of the gene-loaded PLA-PEG-PLL nanoparticles (PLA-PEG-PLL NPs were evaluated, respectively. Agarose gel electrophoresis assay confirmed that the PLA-PEG-PLL NPs could condense DNA thoroughly and protect DNA from nuclease degradation. Initial experiments showed that PLA-PEG-PLL NPs/DNA complexes exhibited almost no toxicity and higher gene expression (up to 21.64% in HepG2 cells and 31.63% in HeLa cells than PEI/DNA complexes (14.01% and 24.22%. These results revealed that the biodegradable tri-block copolymer PLA-PEG-PLL might be a very attractive candidate as a non-viral vector and might alleviate the drawbacks of the conventional cationic vectors/DNA complexes for gene delivery in vivo.

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

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


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

  15. Solubilisation of griseofulvin, quercetin and rutin in micellar formulations of triblock copolymers E62P39E62 and E137S18E137. (United States)

    Ribeiro, Maria Elenir N P; Vieira, Icaro G P; Cavalcante, Igor Marques; Ricardo, Nágila M P S; Attwood, David; Yeates, Stephen G; Booth, Colin


    The solubilisation of two poorly soluble flavonoids, quercetin and rutin, in micellar solutions of mixtures of a block copolymer of ethylene oxide and styrene oxide (E(137)S(18)E(137)) with one of ethylene oxide and propylene oxide (E(62)P(39)E(62)) has been studied at 25 and 37 degrees C. Solubilisation capacities were higher than those for the model poorly water-soluble drug griseofulvin and comparable with published values for the solubilisation of rutin by beta-cyclodextrin.

  16. Combining reactive triblock copolymers with functional cross-linkers: A versatile pathway to disulfide stabilized-polyplex libraries and their application as pDNA vaccines. (United States)

    Heller, Philipp; Hobernik, Dominika; Lächelt, Ulrich; Schinnerer, Meike; Weber, Benjamin; Schmidt, Manfred; Wagner, Ernst; Bros, Matthias; Barz, Matthias


    Therapeutic nucleic acids such as pDNA hold great promise for the treatment of multiple diseases. These therapeutic interventions are, however, compromised by the lack of efficient and safe non-viral delivery systems, which guarantee stability during blood circulation together with high transfection efficiency. To provide these desired properties within one system, we propose the use of reactive triblock copolypept(o)ides, which include a stealth-like block for efficient shielding, a hydrophobic block based on reactive disulfides for cross-linking and a cationic block for complexation of pDNA. After the complexation step, bifunctional cross-linkers can be employed to bio-reversibly stabilize derived polyplexes by disulfide bond formation and to introduce endosomolytic moieties at the same time. Cross-linked polyplexes show no aggregation in human blood serum. Upon cellular uptake and cleavage of disulfide bonds, the cross-linkers can interact with the endosomal membrane, leading to lysis and efficient endosomal translocation. In principal, the approach allows for the combination of one polymer with various different cross-linkers and thus enables the fast forward creation of a polyplex library. Here, we provide a first insight into the potential of this concept and use a screening strategy to identify a lead candidate, which is able to transfect dendritic cells with a model DNA vaccine. Copyright © 2017. Published by Elsevier B.V.

  17. Effects of Bile Salt Sodium Glycodeoxycholate on the Self-Assembly of PEO-PPO-PEO Triblock Copolymer P123 in Aqueous Solution. (United States)

    Bayati, Solmaz; Galantini, Luciano; Knudsen, Kenneth D; Schillén, Karin


    A comprehensive experimental study on the interaction between the PEO-PPO-PEO block copolymer P123 (EO20PO68EO20) and the anionic bile salt sodium glycodeoxycholate (NaGDC) in water has been performed. The work was aimed at investigating the suitability of using P123 as bile salt sequestrant beside the fundamental aspects of PEO-PPO-PEO block copolymer-bile salt interactions. Various experimental techniques including dynamic and static light scattering, small-angle X-ray scattering, and differential scanning calorimetry (DSC) were employed in combination with electrophoretic mobility measurements. The system was investigated at a constant P123 concentration of 1.74 mM and with varying bile salt concentrations up to approximately 250 mM NaGDC (or a molar ratio n(NaGDC)/n(P123) = 144). In the mixed P123-NaGDC solutions, the endothermic process related to the self-assembly of P123 was observed to gradually decrease in enthalpy and shift to higher temperatures upon progressive addition of NaGDC. To explain this effect, the formation of NaGDC micelles carrying partly dehydrated P123 unimers was proposed and translated into a stoichiometric model, which was able to fit the experimental DSC data. In the mixtures at low molar ratios, NaGDC monomers associated with the P123 micelle forming a charged "P123 micelle-NaGDC" complex with a dehydrated PPO core. These complexes disintegrated upon increasing NaGDC concentration to form small "NaGDC-P123" complexes visualized as bile salt micelles including one or a few P123 copolymer chains.

  18. Novel polymeric micelles for insect pest control: encapsulation of essential oil monoterpenes inside a triblock copolymer shell for head lice control

    Directory of Open Access Journals (Sweden)

    Alejandro Lucia


    Full Text Available Background Essential oil components (EOCs are molecules with interesting application in pest control, these have been evaluated against different insect pest from more than 100 years, but their practical use is rather limited. Thus, the enhancement of their bioavailability and manageability due to their dispersion in water can open new perspective for the preparation of formulations for the control of insect pest. In this work, we studied the encapsulation of different monoterpenes in a poloxamer shell in order to prepare aqueous formulations that can be used for the development of platforms used in pest control. Methods Micellar systems containing a 5 wt% of poloxamer 407 and 1.25 wt% of the different monoterpenes were prepared. Dynamic Light Scattering (DLS experiments were carried out to characterize the dispersion of the EOCs in water. The pediculicidal activity of these micellar systems was tested on head lice using an ex vivo immersion test. Results The poloxamers allowed the dispersion of EOCs in water due to their encapsulation inside the hydrophobic core of the copolymer micelles. From this study, we concluded that it is possible to make stable micellar systems containing water (>90 wt%, 1.25 wt% of different monoterpenes and a highly safe polymer (5wt% Poloxamer 407. These formulations were effective against head lice with mortality ranging from 30 to 60%, being the most effective emulsions those containing linalool, 1,8-cineole, α-terpineol, thymol, eugenol, geraniol and nonyl alcohol which lead to mortalities above 50%. Discussion Since these systems showed good pediculicidal activity and high physicochemical stability, they could be a new route for the green fabrication of biocompatible and biosustainable insecticide formulations.

  19. Novel polymeric micelles for insect pest control: encapsulation of essential oil monoterpenes inside a triblock copolymer shell for head lice control. (United States)

    Lucia, Alejandro; Toloza, Ariel Ceferino; Guzmán, Eduardo; Ortega, Francisco; Rubio, Ramón G


    Essential oil components (EOCs) are molecules with interesting application in pest control, these have been evaluated against different insect pest from more than 100 years, but their practical use is rather limited. Thus, the enhancement of their bioavailability and manageability due to their dispersion in water can open new perspective for the preparation of formulations for the control of insect pest. In this work, we studied the encapsulation of different monoterpenes in a poloxamer shell in order to prepare aqueous formulations that can be used for the development of platforms used in pest control. Micellar systems containing a 5 wt% of poloxamer 407 and 1.25 wt% of the different monoterpenes were prepared. Dynamic Light Scattering (DLS) experiments were carried out to characterize the dispersion of the EOCs in water. The pediculicidal activity of these micellar systems was tested on head lice using an ex vivo immersion test. The poloxamers allowed the dispersion of EOCs in water due to their encapsulation inside the hydrophobic core of the copolymer micelles. From this study, we concluded that it is possible to make stable micellar systems containing water (>90 wt%), 1.25 wt% of different monoterpenes and a highly safe polymer (5wt% Poloxamer 407). These formulations were effective against head lice with mortality ranging from 30 to 60%, being the most effective emulsions those containing linalool, 1,8-cineole, α-terpineol, thymol, eugenol, geraniol and nonyl alcohol which lead to mortalities above 50%. Since these systems showed good pediculicidal activity and high physicochemical stability, they could be a new route for the green fabrication of biocompatible and biosustainable insecticide formulations.

  20. Gel phase formation in dilute triblock copolyelectrolyte complexes

    Energy Technology Data Exchange (ETDEWEB)

    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.


    Assembly of oppositely charged triblock copolyelectrolytes into phase-separated gels at low polymer concentrations (<1% by mass) has been observed in scattering experiments and molecular dynamics 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.

  1. Gel phase formation in dilute triblock copolyelectrolyte complexes (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.


    Assembly of oppositely charged triblock copolyelectrolytes into phase-separated gels at low polymer concentrations (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.

  2. [The sick building syndrome (SBS)]. (United States)

    Ezratty, Véronique


    AN INCREASINGLY COMMON ENVIRONMENTAL HEALTH PROBLEM: Complaints related to indoor environment represent one of the most frequent problems that environmental health practitioners are confronted with. Hence the incidence of the Sick Building Syndrome (SBS) has been increasing since the Seventies. DIFFERING DEFINITIONS AND CLINICAL PRESENTATIONS: The WHO defines SBS as an excess of complaints and symptoms occurring in certain occupants of non-industrial buildings. The syndrome can only be evoked after elimination in the person concerned of a disease related to the building, the aetiological agent of which is identifiable. The symptoms described during SBS (headaches, concentration problems, asthenia, irritation of the skin or nasal mucosa, of the eyes and upper respiratory tract.) are non specific and frequently observed in the general population. AN UNKNOWN CASE, BUT NUMEROUS AETIOLOGICAL FACTORS SUSPECTED: There is no unanimously accepted definition nor physio-pathological theory to explain the occurrence of SBS in a particular building. Many favouring factors, including the type and rate of ventilation, volatile organic compounds, particles and humidity have been suspected. TECHNICAL, SOCIAL, AND MEDICAL MANAGEMENT IS REQUIRED: Although the symptoms are benign, they can be uncomfortable or even handicapping and prevent the functioning of workplaces. The SBS, the social and economical costs of which are high, requires multidisciplinary management.

  3. 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.


    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)

  4. Trilayered Morphology of an ABC Triple Crystalline Triblock Terpolymer

    KAUST Repository

    Palacios, Jordana K.


    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.

  5. pH-sensitive micelles self-assembled from multi-arm star triblock co-polymers poly(ε-caprolactone)-b-poly(2-(diethylamino)ethyl methacrylate)-b-poly(poly(ethylene glycol) methyl ether methacrylate) for controlled anticancer drug delivery. (United States)

    Yang, You Qiang; Zhao, Bin; Li, Zhen Dong; Lin, Wen Jing; Zhang, Can Yang; Guo, Xin Dong; Wang, Ju Fang; Zhang, Li Juan


    A series of amphiphilic 4- and 6-armed star triblock co-polymers poly(ε-caprolactone)-b-poly(2-(diethylamino)ethyl methacrylate)-b-poly(poly(ethylene glycol) methyl ether methacrylate) (4/6AS-PCL-b-PDEAEMA-b-PPEGMA) were developed by a combination of ring opening polymerization and continuous activators regenerated by electron transfer atom transfer radical polymerization. The critical micelle concentration values of the star co-polymers in aqueous solution were extremely low (2.2-4.0mgl(-1)), depending on the architecture of the co-polymers. The self-assembled blank and doxorubicin (DOX)-loaded three layer micelles were spherical in shape with an average size of 60-220nm determined by scanning electron microscopy and dynamic light scattering. The in vitro release behavior of DOX from the three layer micelles exhibited pH-dependent properties. The DOX release rate was significantly accelerated by decreasing the pH from 7.4 to 5.0, due to swelling of the micelles at lower pH values caused by the protonation of tertiary amine groups in DEAEMA in the middle layer of the micelles. The in vitro cytotoxicity of DOX-loaded micelles to HepG2 cells suggested that the 4/6AS-PCL-b-PDEAEMA-b-PPEGMA micelles could provide equivalent or even enhanced anticancer activity and bioavailability of DOX and thus a lower dosage is sufficient for the same therapeutic efficacy. The results demonstrate that the pH-sensitive multilayer micelles could have great potential application in delivering hydrophobic anticancer drugs for improved cancer therapy. Copyright © 2013 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

  6. 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


    The surface behavior and properties of several reverse poly(butylene oxide)-poly(ethylene oxide)-poly(butylene oxide) block copolymers, BO8EO90BO8, BO12EO227BO12, BO14EO378BO14, BO20EO411BO20, and BO21EO385BO21 at the air/water interface have been analyzed by drop tensiometry, Langmuir film balan...

  7. Renewable Pentablock Copolymers Containing Bulky Natural Rosin for Tough Bioplastics (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.

  8. Mechanistic analysis of Zein nanoparticles/PLGA triblock in situ forming implants for glimepiride (United States)

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


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

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

    NARCIS (Netherlands)

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


    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

  10. Controlled Functionalization of Olefin/styrene Copolymers through Free Radical Processes

    NARCIS (Netherlands)

    Passaglia, Elisa; Aglietto, Mauro; Ciardelli, Francesco; Picchioni, Francesco


    The functionalization of styrene-b-(ethylene-co-1-butene)-b-styrene triblock copolymer (SEBS) and styrene-co-butadiene (SBR) random copolymer by free radical processes is presented. SEBS was functionalized in the melt with diethyl maleate (DEM) and dicumyl peroxide (DCP) as initiator. The

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

    DEFF Research Database (Denmark)

    Jankova, Katja; Hvilsted, Søren


    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-...

  12. Overview of the SBS 2016 Mining Track

    DEFF Research Database (Denmark)

    Bogers, Toine; Hendrickx, Iris; Koolen, Marijn


    In this paper we present an overview of the mining track in the Social Book Search (SBS) lab 2016. The mining track addressed two tasks: (1) classifying forum posts as book search requests, and (2) linking book title mentions in forum posts to unique book IDs in a database. Both tasks are important...

  13. Controlled block copolymer micelle formation for encapsulation of hydrophobic ingredients

    NARCIS (Netherlands)

    Lebouille, G.J.L.; Vleugels, L.F.W.; Dias, A.A.; Leermakers, F.A.M.; Cohen Stuart, M.A.; Tuinier, R.


    We report on the formation of polymeric micelles in water using triblock copolymers with a polyethylene glycol middle block and various hydrophobic outer blocks prepared with the precipitation method. We form micelles in a reproducible manner with a narrow size distribution. This suggests that

  14. POE-PEG-POE triblock copolymeric microspheres containing protein. I. Preparation and characterization. (United States)

    Yang, Y Y; Wan, J P; Chung, T S; Pallathadka, P K; Ng, S; Heller, J


    Poly(ortho ester) (POE)-poly (ethylene glycol) (PEG) triblock copolymers (POE-PEG-POE) with different PEG contents were synthesised as carriers for controlled protein delivery. POE-PEG-POE microspheres containing bovine serum albumin (BSA) were prepared using a double-emulsion (water-in-oil-in-water) process. In this first paper of a two-part series, we report the fundamentals of the fabrication and characterization of POE-PEG-POE microspheres. Because the triblock copolymer is more hydrophilic than neat poly(ortho ester), the triblock copolymer yields a more stable first emulsion (water-in-oil) and a greater BSA encapsulation efficiency (90% vs. 30%). No BSA is found on POE-PEG-POE microsphere surfaces measured by X-ray photoelectron spectroscopy, while uniform BSA distributions are observed within the microspheres by confocal microscopy. SEM pictures show that an increase in PEG content results in microspheres with a denser cross-section because of a more stable first emulsion and better affinity between the copolymer and water. POE-PEG(20%)-POE suffers significant swelling during the fabrication process and yields the biggest microspheres. However, the POE-PEG(30%)-POE microspheres are much smaller since the dissolution loss of POE-PEG(30%)-POE in the external water phase may be much higher than that of POE-PEG(20%)-POE. The salt concentration in the external water phase significantly affects the morphology of the resultant microspheres. Microspheres with a dense wall are produced when using pure water as the external water phase. Polymer concentration has less impact on BSA encapsulation efficiency but has a considerable effect on microsphere size and morphology. Increasing the concentration of the polyvinyl alcohol emulsifier does not cause an obvious decrease in microsphere size. However, increased BSA loading results in bigger microspheres.

  15. Ternary and quaternary nanocomposites based on polystyrene, SBS, organically modified clay and silicone-polyether;Compositos e/ou nanocompositos ternarios e quaternarios de poliestireno, SBS, argila e silicona-polieter

    Energy Technology Data Exchange (ETDEWEB)

    Kaneko, Manuela L.Q.A.; Lourenco, Emerson; Paiva, Raphael E.F.; Felisberti, Maria I.; Yoshida, Inez V.P., E-mail: valeria@iqm.unicamp.b [Universidade Estadual de Campinas (IQ/UNICAMP), SP (Brazil). Inst. de Quimica


    This work aims the study of toughened nanocomposites based on polystyrene (PS), poly(styrene-b-butadiene-b-styrene) (SBS), organically modified clay (C20A) and silicone-polyether, PDMS-POE. The intercalation of the copolymer PDMS-POE into the clay galleries increased the interlamellar distance, improving the exfoliation of the clay during the extrusion process of the materials. C20A/PDMS-POE nanocomposite, MC20A, was prepared by mechanical mixture using 1:1 wt% ratio. MC20A was incorporated into PS and PS/SBS blends using an extruder. The materials were characterized by X-ray diffraction and stress-strain mechanical tests. MC20A/PS/SBS, prepared by extrusion, showed an increase in the interlamellar distance, suggesting the intercalation of PS or SBS into the clay galleries. The PDMSPOE acted as a 'plasticizer' for PS and PS/SBS blend. However, this effect was not reverted by the clay addition. On the contrary, the 'plasticizer' effect was intensified by the clay maybe due to the slip characteristics of PDMS-POE associated with the lamella orientation. (author)

  16. Dual responsive physical networks from asymmetric biosynthetic triblock copolymers

    NARCIS (Netherlands)

    Pham, T.H.T.


      The aim of the project is to develop biosynthetically produced amino acid polymers which are composed of three distinct blocks A-C-B, each with a separate function. A is a first self-assembling block capable of ‘recognizing’ (upon a trigger) other A blocks; C is an inert, random

  17. Molecular Design of Sulfonated Triblock Copolymer Permselective Membranes (United States)


    on DNA solvation in water [39] and simulations of polyacrylic acid with calcium counterion.[40] Mesoscale approaches to polyelectrolyte modeling...vacuum and is unstable in the RHF minimization of a single DMMP. Replacement of ammonium cation by sodium leads to an increase in the DMMP activity...polyamine and sodium counterions: diffusion and averaged binding of water and cations. Nucleic Acids Research, 2003. 31(20): p. 5971-5981. 49. Korolev, N

  18. Mechanical and thermal properties of PP/PBT blends compatibilized with triblock thermoplastic elastomer

    Directory of Open Access Journals (Sweden)

    Ignaczak Wojciech


    Full Text Available A linear triblock copolymer, poly(styrene-b-etylene/butylene-b-styrene(SEBS thermoplastic elastomer (TPE grafted with maleic anhydride was used for compatibilization of PP/PBT blends. PP/PBT blends of different mass ratios 60/40, 50/50, 40/60 were mixed with 2.5, 5.0 and 7.5 wt.% of SEBS copolymer in a twin screw extruder. Differential scanning calorimetry and dynamic mechanical analysis were performed to define the phase structure of PP/PBT blends. TPE with a rubbery mid-block shifted the glass transition of PP/PBT blend towards lower temperatures, and significant decrease the crystallization temperature of a crystalline phase of PP component was observed. The influence of the amount of compatibilizer and the blend composition on the mechanical properties (tensile and flexural strengths, toughness and moduli was determined. Addition of 5 wt.% of a triblock TPE led to a three-fold increase of PP/PBT toughness. A significant increase of impact properties was observed for all materials compatibilized with the highest amount of SEBS copolymer.

  19. Polysiloxane-based block copolymers with marine bacterial anti-adhesion properties. (United States)

    Duong, The Hy; Briand, Jean-François; Margaillan, André; Bressy, Christine


    Di- and triblock copolymers based on tert-butyldimethylsilyl methacrylate (MASi) and poly(dimethylsiloxane) (PDMS) macro-RAFT agents were synthesized resulting in copolymers with predictable molar masses and low dispersities (Đ marine bacteria (Pseudoalteromonas sp. and Shewanella sp.) isolated from the Mediterranean Sea. Coatings based on PDMS-based block copolymers demonstrated anti-adhesive performances against the two strains better than that of the coating containing only PMASi-based polymers. Coatings based on diblock copolymers demonstrated antifouling performances in the field that were better than those of the corresponding coatings containing triblock copolymers. Results of both lab and field assays showed that the antifouling properties were related to coatings possessing the highest receding water contact angle.

  20. Molecular Interaction Control in Diblock Copolymer Blends and Multiblock Copolymers with Opposite Phase Behaviors (United States)

    Cho, Junhan


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

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

    Energy Technology Data Exchange (ETDEWEB)

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


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

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

    KAUST Repository

    Kumar, Rajeev Senthil


    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.

  3. Bicomponent Block Copolymers Derived from One or More Random Copolymers as an Alternative Route to Controllable Phase Behavior

    Energy Technology Data Exchange (ETDEWEB)

    Ashraf, Arman R. [Corporate Research and Development, The Procter and Gamble Company, Cincinnati OH 45224 USA; Ryan, Justin J. [Department of Materials Science and Engineering, North Carolina State University, Raleigh NC 27695 USA; Satkowski, Michael M. [Corporate Research and Development, The Procter and Gamble Company, Cincinnati OH 45224 USA; Lee, Byeongdu [Advanced Photon Source, Argonne National Laboratory, Argonne IL 60439 USA; Smith, Steven D. [Corporate Research and Development, The Procter and Gamble Company, Cincinnati OH 45224 USA; Spontak, Richard J. [Department of Materials Science and Engineering, North Carolina State University, Raleigh NC 27695 USA; Department of Chemical and Biomolecular Engineering, North Carolina State University, Raleigh NC 27695 USA


    Block copolymers have been extensively studied due to their ability to spontaneously self-organize into a wide variety of morphologies that are valuable in energy-, medical- and conservation-related (nano)technologies. While the phase behavior of bicomponent diblock and triblock copolymers is conventionally governed by temperature and individual block masses, we demonstrate that their phase behavior can alternatively be controlled through the use of blocks with random monomer sequencing. Block random copolymers (BRCs), i.e., diblock copolymers wherein one or both blocks is a random copolymer comprised of A and B repeat units, have been synthesized, and their phase behavior, expressed in terms of the order-disorder transition (ODT), has been investigated. Our results establish that, depending on the block composition contrast and molecular weight, BRCs can microphase-separate. We also report that the predicted ODT can be generated at relatively constant molecular weight and temperature with these new soft materials. This sequence-controlled synthetic strategy is extended to thermoplastic elastomeric triblock copolymers differing in chemistry and possessing a random-copolymer midblock.

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

    DEFF Research Database (Denmark)

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


    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...

  5. Overview of the SBS 2016 Suggestion Track

    DEFF Research Database (Denmark)

    Koolen, Marijn; Bogers, Toine; Jaap, Kamps


    The goal of the SBS 2016 Suggestion Track is to evaluate approaches for supporting users in searching collections of books who express their information needs both in a query and through example books. The track investigates the complex nature of relevance in book search and the role of traditional...... and user-generated book metadata in retrieval. We consolidated last year’s investigation into the nature of book suggestions from the LibraryThing forums and how they compare to book relevance judgements. Participants were encouraged to incorporate rich user profiles of both topic creators and other...... LibraryThing users to explore the relative value of recommendation and retrieval paradigms for book search....

  6. The self-assembly mechanism of fibril-forming silk-based block copolymers

    NARCIS (Netherlands)

    Schor, M.; Bolhuis, P.G.


    Triblock copolymers consisting of a silk-based ((Gly-Ala)3Gly-Glu) repeat flanked by hydrophilic outer blocks self-assemble into micrometer long fibrils in response to a trigger. Since the exact mechanism of the fibril formation remains unclear, we employ a multiscale modelling approach in

  7. Emulsions stabilized with PEO-PPO-PEO block copolymers and silica

    NARCIS (Netherlands)

    Uricanu, V.I.; Gosa, Kristiana-Lisette


    The specific behavior of poly(ethylene oxide)–poly(propylene oxide)–poly(ethylene oxide) (PEO–PPO–PEO) tri-block copolymers in aqueous solutions was studied in the presence of vinyl acetate (VAc) and colloidal silica. Several factors controlling specific interactions were investigated, the block

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

    Directory of Open Access Journals (Sweden)

    Zi-Kun Rao


    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.

  9. Asfalto modificado com polimero SBS para pavimentos drenantes


    Ronaldo Zamiro Machado


    Resumo: O polímero SBS - Estireno-Butadieno-Estireno tem sido muito empregado para modificar o asfalto, tanto para pavimentação como para aplicações industrial. Nessa pesquisa foi abordado o estudo do asfalto modificado com polímeros SBS, apresentando comportamento melhor que asfalto convencional, mostrando-se como o polímero se comporta ao ser misturado com o asfalto e quais características são melhoradas. O asfalto modificado com polímero SBS tem uma vida útil muito superior ao asfalto conv...

  10. Radiation-induced crosslinking of poly(styrene–butadiene–styrene) block copolymers and their sulfonation

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Sun-Young [Advanced Radiation Technology Institute, Korea Atomic Energy Research Institute, 29 Geumgu-gil, Jeongeup-si, Jeollabuk-do 580-185 (Korea, Republic of); Department of Chemical and Biomolecular Engineering, Yonsei University, 50 Yonsei-ro, Seodaemun-gu, Seoul 120-749 (Korea, Republic of); Song, Ju-Myung; Sohn, Joon-Yong [Advanced Radiation Technology Institute, Korea Atomic Energy Research Institute, 29 Geumgu-gil, Jeongeup-si, Jeollabuk-do 580-185 (Korea, Republic of); Shul, Yong-Gun [Department of Chemical and Biomolecular Engineering, Yonsei University, 50 Yonsei-ro, Seodaemun-gu, Seoul 120-749 (Korea, Republic of); Shin, Junhwa, E-mail: [Advanced Radiation Technology Institute, Korea Atomic Energy Research Institute, 29 Geumgu-gil, Jeongeup-si, Jeollabuk-do 580-185 (Korea, Republic of)


    Highlights: • The c-SBS films were prepared using a gamma ray or electron beam. • The crosslinking degree of the c-SBS films were increased with the irradiation dose. • The prepared c-SBS films were sulfonated with various concentration of CSA. • The sulfonation of the c-SBS film is largely dependent on the concentration of CSA. • The sulfonation process is progressed from the surface to the inner part of c-SBS film. -- Abstract: Several crosslinked poly(styrene–butadiene–styrene) (c-SBS) block copolymer films were prepared using a gamma ray or electron beam with various irradiation doses and the prepared c-SBS film was then subjected to sulfonation using a chlorosulfonic acid (CSA) solution to introduce a sulfonic acid group. To estimate the degree of crosslinking, the gel fractions and FT-IR spectra of the c-SBS films were used and the results indicate that the degree of crosslinking is increased with an increase in the radiation dose. The surface morphology and mechanical property of the c-SBS films were observed using SEM and UTM instruments, respectively. The sulfonated c-SBS films were investigated by measuring the ion exchange capacity (IEC) and by observing the cross-sectional distribution patterns of sulfonic acid group using an SEM-EDX instrument. The IEC and SEM-EDX studies indicate that the sulfonated c-SBS membranes can be successfully prepared through the radiation crosslinking of the SBS film and the subsequent sulfonation with a diluted CSA solution.

  11. On the Use of Self-Assembling Block Copolymers to Toughen A Model Epoxy (United States)

    Chen, Yilin

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

  12. Experimental investigation of the behaviour and fate of block copolymers in fouling-release coatings

    DEFF Research Database (Denmark)

    Noguer, Albert Camós

    Fouling-release coatings (FRC) were developed as an environmentally friendly alternative after the ban of highly toxic antifouling coatings based on tributyltin. Poly(dimethylsiloxane) (PDMS) has been the most widely used polymer for FRC, and its fouling-inhibition properties have been enhanced...... the distribution and behaviour of PEG-b-PDMS-b-PEG copolymers in PDMS coatings by fluorescence means. Chapter 5 investigates the degradation of PDMS-PEG-based copolymers in FRC immersed in seawater. Chapter 6 consists of a long-term field study regarding the release/loss of these block copolymers from fouling...... and stability of the copolymer on the surface of the coating are proven to be a central aspect of the performance of these FRC. A novel fluorescent-labelled triblock PEG-b-PDMS-b-PEG copolymer was synthesized in this project to visualize the distribution and behaviour of PDMS-PEG-based copolymers in PDMS...

  13. Efeito da adição de diferentes copolímeros em blendas HDPE/HIPS pós-consumo: morfologia de fases e propriedades térmicas The effect of different block copolymers on post consumer HDPE/HIPS Blends: phase morphology and thermal properties

    Directory of Open Access Journals (Sweden)

    Igor S. B. Perez


    Full Text Available Blendas de poliolefinas/HIPS têm sido exploradas para obter filmes especiais com determinadas propriedades desejadas, tornando imperativo desenvolver vários estudos para um melhor conhecimento do comportamento desses materiais. Neste trabalho, efeitos da adição dos copolímeros comerciais de estireno-butadieno multibloco (SBS e de estireno-(etileno-co-butileno-estireno (SEBS tribloco linear em blendas pós-consumo de HDPE e HIPS são reportados. A diminuição nas dimensões da microfase dispersa, aliada à rugosidade superficial da fase HDPE após extração seletiva do HIPS, independentemente de a fase matriz ser HIPS ou HDPE, mostraram mais eficiência do SEBS como modificador interfacial de tensão ou como surfactante entre os diferentes domínios quando comparado com o SBS. Os resultados das caracterizações térmicas, por exemplo, menor Tm e menor grau de cristalinidade do HDPE, e maior Tg do poliestireno na presença de SEBS corroboraram esta conclusão, como será discutido posteriormente.Blending of post-consumer polyolefins/HIPS has been exploited for obtaining special films with a desired set of properties, which has required studies to understand the behavior of these materials. In this work the effects of commercial multiblock styrene-butadiene (SBS and linear triblock styrene-(ethylene-co-butylene-styrene (SEBS copolymers in blends of post-consumer high density polyethylene (HDPE and HIPS are reported. Thermal properties and phase morphology were comparatively analyzed for the additives aiming at verifying possible correlations between them. Decreased dimensions of the minor micro phase along with HDPE surface roughness after HIPS selective extraction, independently of the matrix being HIPS or HDPE, showed better effectiveness for SEBS as interfacial tension modifier or as surfactant at the different domains interface when compared with SBS. The results of thermal characterizations, e.g. lower HDPE melting temperature, lower

  14. Hydrazone-Containing Triblock Copolymeric Micelles for pH-Controlled Drug Delivery

    Directory of Open Access Journals (Sweden)

    Peilan Qi


    Full Text Available In this study, the structure–activity relationship of amphiphilic block copolymer micelles as nanosized drug delivery system was revealed. Firstly, a biodegradable triblock polymers PEG-DiHyd-PLA containing hydrazone bond was synthesized through the ring-opening polymerization. In this method, PEG-DiHyd-Phenol was used as the initiator and L-lactide as the monomer. Then, the polymeric micelles were formed and used as nano-drug carriers with pH sensitivity. The structure and composition of the polymer were characterized by infrared (IR, nuclear magnetic resonance (1H-NMR, and gel permeation chromatography (GPC, we characterized the self-assembling process of the triblock polymers and the pH sensitivity of the micelles by the means of transmission electron microscopy (TEM, dynamic light scattering method (DLS. Doxorubicin (DOX acts as the model drug, and we researched the capacities of drug loading and release in vitro of the micelles. MTT experiments showed that the blank micelles of PEG-DiHyd-PLA were not cytotoxic to tumor cells (HepG-2, MCF-7 and normal cell (L-02 cells, but the DOX loaded ones displayed more toxicity than the ones without hydrazone, which was consistent to the further confocal laser scanning microscopy and flow cytometry study.

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

    NARCIS (Netherlands)

    Martens, A.A.


    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

  16. Symptom definitions for SBS (sick building syndrome) in residential dwellings. (United States)

    Wang, Bing-Ling; Takigawa, Tomoko; Yamasaki, Yukie; Sakano, Noriko; Wang, Da-Hong; Ogino, Keiki


    The potential risk factors for sick building syndrome (SBS) in newly built dwellings were investigated. Two different definitions for SBS were used, a narrow definition (symptoms related to home environment and continuously occurring in the last 3 months were regarded as positive) and another relatively broad definition (symptoms related to home environment and either continuously or sporadically occurring in the last 3 months were regarded as positive). With both definitions indoor air chemicals, especially TVOC, and high stress during work were found to be significantly associated with SBS symptoms. Allergic history was more associated with narrow-sense symptoms and odor perception with broad-sense symptoms. The results indicate that the broad definition be preferred to find more potential risk factors.

  17. Dynamic photoinduced realignment processes in photoresponsive block copolymer films: effects of the chain length and block copolymer architecture. (United States)

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


    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.

  18. Hierarchical Sol-Gel Transition Induced by Thermosensitive Self-Assembly of an ABC Triblock Polymer in an Ionic Liquid

    Energy Technology Data Exchange (ETDEWEB)

    Kitazawa, Yuzo; Ueki, Takeshi; McIntosh, Lucas D.; Tamura, Saki; Niitsuma, Kazuyuki; Imaizumi, Satoru; Lodge, Timothy P.; Watanabe, Masayoshi (U of Tokyo); (UMM); (Yokohama)


    Here we investigate a hierarchical morphology change and accompanying sol–gel transition using a doubly thermosensitive ABC-triblock copolymer in an ionic liquid (IL). The triblock copolymer contains two different lower critical solution temperature (LCST) thermosensitive polymers, poly(benzyl methacrylate) (PBnMA) and poly(2-phenylethyl methacrylate) (PPhEtMA), as the end blocks and poly(methyl methacrylate) (PMMA) as the middle block (PBnMA-b-PMMA-b-PPhEtMA: BMP). BMP undergoes a hierarchical phase transition corresponding to the self-assembly of each of the thermosensitive blocks in the IL, and a sol–gel transition was observed in concentrated, above 10 wt %, polymer solutions. The gelation behavior was affected by polymer concentration, and at 20 wt %, the BMP/IL composite showed a phase transition, with increasing temperature, from solution through a jammed micelle suspension to a physically cross-linked gel. For each phase was formed reversibly and rapidly over the corresponding temperature range. Finally, the jammed micelle and cross-linked gel states were characterized using viscoelastic measurements and small-angle X-ray scattering (SAXS).

  19. Structure and Self-Assembly of Oligocarbonate-Fluorene End Functionalized Poly (ethylene glycol) ABA Triblock Polymer (United States)

    Wei, Guangmin; Prabhu, Vivek; Venkataraman, Shrinivas; Yang, Yi Yan; Hedrick, James; Vivek Prabhu Team; Shrinivas Venkataraman, Yi Yan Yang Collaboration; James Hedrick Collaboration

    Hierarchical structures of oligocarbonate-fluorene end-functionalized poly(ethylene glycol) triblock copolymer (P(F-TMC)m-PEG444-P(F-TMC)m) were characterized by light scattering, atomic force microscopy, and Ultraviolet-visible spectroscopy in dilute regime in water, a poor solvent of F-TMC block. The evidence for pai-pai stacked of F-TMC block in self-assembled structure was provided. The self-assembly behavior is highly dependent on concentration and F-TMC block length, m. The presence of clusters dominates the population of scatterers once m is larger than 2, where there is no clear evidence of a separation of micelles and clusters. The molecular aggregation driven by F-TMC groups appears too strong to permit labile micelle-cluster dynamics as observed with m = 2 and 1.2. The non-mean field scaling of the aggregation number, when compared to models for triblock copolymers, highlights the need for a molecular-based model to predict the self-assembly at low end-group numbers. In our case, the end-groups are oligomers, so the comparison to Flory scaling may not be justified.

  20. Laboratory Evaluation of Aging Behaviour of SBS Modified Asphalt

    Directory of Open Access Journals (Sweden)

    Jie Wang


    Full Text Available To study the effect of aging SBS modified asphalt on the performance of asphalt pavement, aging at various times and temperatures was conducted with thin film oven, and then tests were made about the penetration, softening point, ductility, viscosity, toughness, and fluorescence microscopy of modified asphalt with different aging levels. The results show that, with the increasing of aging time, the penetration and ductility of modified asphalt decrease while its softening point and viscosity increase, and the variation trend of the toughness and tenacity is related to the aging temperature; the aging dynamic model with viscosity as parameter can well characterize the aging process of modified asphalt; at microlevel, with the decreasing of SBS particle size, the uniformity of particle size is better. Analysis of macroscopic properties, microscopic characteristics, and significance shows that the SBS particle area ratio has a significant correlation with tenacity as the aging temperature changes. When the aging temperature is 163°C, the SBS particle area ratio still has a significant correlation with tenacity as the aging time changes.

  1. Nucleon form factors program with SBS at JLAB

    Energy Technology Data Exchange (ETDEWEB)

    Wojtsekhowski, Bogdan B. [JLAB


    The physics of the nucleon form factors is the basic part of the Jefferson Laboratory program. We review the achievements of the 6-GeV era and the program with the 12- GeV beam with the SBS spectrometer in Hall A, with a focus on the nucleon ground state properties.

  2. Poly(phenylene ether Based Amphiphilic Block Copolymers

    Directory of Open Access Journals (Sweden)

    Edward N. Peters


    Full Text Available Polyphenylene ether (PPE telechelic macromonomers are unique hydrophobic polyols which have been used to prepare amphiphilic block copolymers. Various polymer compositions have been synthesized with hydrophilic blocks. Their macromolecular nature affords a range of structures including random, alternating, and di- and triblock copolymers. New macromolecular architectures can offer tailored property profiles for optimum performance. Besides reducing moisture uptake and making the polymer surface more hydrophobic, the PPE hydrophobic segment has good compatibility with polystyrene (polystyrene-philic. In general, the PPE contributes to the toughness, strength, and thermal performance. Hydrophilic segments go beyond their affinity for water. Improvements in the interfacial adhesion between polymers and polar substrates via hydrogen bonding and good compatibility with polyesters (polyester-philic have been exhibited. The heterogeneity of domains in these PPE based block copolymer offers important contributions to diverse applications.

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

    Directory of Open Access Journals (Sweden)

    Mitra Alami-Milani


    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.

  4. Nanostructured Polysulfone-Based Block Copolymer Membranes

    KAUST Repository

    Xie, Yihui


    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

  5. 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


    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

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

    KAUST Repository

    Phillip, William A.


    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.

  7. Crosslinkable surfactants based on linoleic acid-functionalized block copolymers of ethylene oxide and e-caprolactone for the preparation of stable PMMA latices

    NARCIS (Netherlands)

    Tan, B.H.; Grijpma, Dirk W.; Nabuurs, Tijs; Feijen, Jan


    Amphiphilic diblock and triblock copolymers consisting of poly(ethylene oxide) (PEO) as (central) hydrophilic segment and poly(ε-caprolactone) (PCL) as hydrophobic segment(s) were prepared by ring opening polymerization. The length of the PEO segment was kept constant View the MathML source, whereas

  8. All solid-state SBS phase conjugate mirror (United States)

    Dane, C.B.; Hackel, L.A.


    A stimulated Brillouin scattering (SBS) phase conjugate laser mirror uses a solid-state nonlinear gain medium instead of the conventional liquid or high pressure gas medium. The concept has been effectively demonstrated using common optical-grade fused silica. An energy threshold of 2.5 mJ and a slope efficiency of over 90% were achieved, resulting in an overall energy reflectivity of >80% for 15 ns, 1 um laser pulses. The use of solid-state materials is enabled by a multi-pass resonant architecture which suppresses transient fluctuations that would otherwise result in damage to the SBS medium. This all solid state phase conjugator is safer, more reliable, and more easily manufactured than prior art designs. It allows nonlinear wavefront correction to be implemented in industrial and defense laser systems whose operating environments would preclude the introduction of potentially hazardous liquids or high pressure gases. 8 figs.

  9. Using Nonuniform Fiber to Generate Slow Light via SBS

    Directory of Open Access Journals (Sweden)

    Wenhai Li


    Full Text Available The data pulse delay based on slow light induced by stimulated Brillouin scattering (SBS in a nonuniform dispersion decreasing fiber (DDF is demonstrated experimentally, and the distortions of data pulses at different beat frequencies are studied. We found that a delay exceeding a pulse width can be achieved at particular beat frequency, and the DDF has larger delay versus gain slope coefficient with much better output pulse quality than single-mode fiber.

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

    Directory of Open Access Journals (Sweden)

    Leonard Ionut Atanase


    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.

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

  12. Rheology and Relaxation Timescales of ABA Triblock Polymer Gels (United States)

    Peters, Andrew; Lodge, Timothy

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

  13. Formation and structural properties of multi-block copolymer vesicles (United States)

    Wang, Rong; Ma, Shiying


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

  14. 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: (India)


    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.

  15. PEO-PPO Diblock Copolymers Protect Myoblasts from Hypo-Osmotic Stress In Vitro Dependent on Copolymer Size, Composition, and Architecture. (United States)

    Kim, Mihee; Haman, Karen J; Houang, Evelyne M; Zhang, Wenjia; Yannopoulos, Demetris; Metzger, Joseph M; Bates, Frank S; Hackel, Benjamin J


    Poloxamer 188, a triblock copolymer of poly(ethylene oxide) (PEO) and poly(propylene oxide) (PPO), protects cellular membranes from various stresses. Though numerous block copolymer variants exist, evaluation of alternative architecture, composition, and size has been minimal. Herein, cultured murine myoblasts are exposed to the stresses of hypotonic shock and isotonic recovery, and membrane integrity was evaluated by quantifying release of lactate dehydrogenase. Comparative evaluation of a systematic set of PEO-PPO diblock and PEO-PPO-PEO triblock copolymers demonstrates that the diblock architecture can be protective in vitro. Short PPO blocks hinder protection with >9 PPO units needed for protection at 150 μM and >16 units needed at 14 μM. Addition of a tert-butyl end group enhances protection at reduced concentration. When the end group and PPO length are fixed, increasing the PEO length improves protection. This systematic evaluation establishes a new in vitro screening tool for evaluating membrane-sealing amphiphiles and provides mechanistic insight to guide future copolymer design for membrane stabilization in vivo.

  16. 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.


    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.

  17. A triblock fluorous surfactant as a specific gelator for perfluorocarbons. (United States)

    Gan, Jiaan; El Bakkari, Mounir; Belin, Colette; Margottin, Chrystèle; Godard, Pascale; Pozzo, Jean-Luc; Vincent, Jean-Marc


    The fluorinated double-tailed triblock surfactant 1-Na represents a new type of gelator for perfluorocarbons which can gelate at low concentration (1.5 wt%) both bromoperfluorooctane and perfluorodecalin, two of the most appealing perfluorinated fluids for pharmaceutical applications.

  18. Modeling of triblock terpolymer micelles with a segregated corona

    NARCIS (Netherlands)

    Charlaganov, M.; Borisov, O.V.; Leermakers, F.A.M.


    We report on self-consistent field predictions for the formation of spherical micelles by ANBMCN triblock terpolymers in a selective solvent, that is, a good solvent for the AN and CN blocks and a poor solvent for the middle BM block. Above some threshold value for the repulsion between the A and C

  19. Designing block copolymer architectures for targeted membrane performance

    KAUST Repository

    Dorin, Rachel Mika


    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.

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


    Martens, A.A.


    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 pH or co-assemble in response to oppositely charged polyelectrolytes (including each other). Such molecules displaying controlled self-assembly may lead to new biocompatible nano-structured material...

  1. Acid-Labile Amphiphilic PEO-b-PPO-b-PEO Copolymers: Degradable Poloxamer Analogs. (United States)

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


    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.

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

    KAUST Repository

    Polymeropoulos, George


    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.

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

    KAUST Repository

    Tangorra, Roberto Rocco


    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.

  4. Characteristics of SBS dynamics in single-mode optical fibres

    Energy Technology Data Exchange (ETDEWEB)

    Gordeev, A A; Efimkov, V F; Zubarev, I G; Mikhailov, S I; Sobolev, V B [P N Lebedev Physics Institute, Russian Academy of Sciences, Moscow (Russian Federation)


    The characteristics of the gain of Stokes pulses in single-mode optical fibres by stimulated Brillouin scattering (SBS) of monochromatic and nonmonochromatic pump signals have been investigated by numerical simulation using a spectral approach. Conditions under which 'slow light' (caused by a group delay) can be implemented are found (it is reasonable to apply this term to a process in which a pulse is delayed with conservation of its shape). The plane-wave interaction model is shown to describe adequately the dynamics of this process in single-mode fibres. A number of gain modes are investigated for Stokes pulses with different time structures upon monochromatic and nonmonochromatic excitation. A new data transfer technique is proposed, which is based on the conversion of stepwise phase modulation of the input Stokes signal into amplitude modulation of the output signal. (nonlinear optical phenomena)

  5. Peptide surface modification of P(HEMA-co-MMA)-b-PIB-b-P(HEMA-co-MMA) block copolymers. (United States)

    Ojha, Umaprasana; Feng, Dingsong; Chandekar, Amol; Whitten, James E; Faust, Rudolf


    Peptide surface modification of poly[(methyl methacrylate-co-hydroxyethyl methacrylate)-b-isobutylene-b-(methyl methacrylate-co-hydroxyethyl methacrylate)] P(MMA-co-HEMA)-b-PIB-b-P(MMA-co-HEMA) triblock copolymers with different HEMA/MMA ratios has been accomplished using an efficient synthetic procedure. The triblock copolymers were reacted with 4-fluorobenzenesulfonyl chloride (fosyl chloride) in pyridine to obtain the activated polymers [poly{(methyl methacrylate-co-fosyloxyethyl methacrylate)-b-isobutylene-b-(methyl methacrylate-co-fosyloxyethyl methacrylate)}] P(MMA-co-FEMA)-b-PIB-b-P(MMA-co-FEMA), with an activating efficiency of 80-90%. The resulting polymers were soluble in chloroform, and their solutions were used to coat thin uniform films with a predetermined thickness on smooth steel surfaces. The presence of reactive activating groups on the film surface was confirmed by X-ray photoelectron spectroscopy (XPS), dye labeling, and confocal laser scanning microscopic studies. Activation of the triblock copolymer films was also achieved under heterogeneous conditions in polar (acetonitrile) and nonpolar (hexanes) media. The extent of activation was controlled by varying the dipping time and polarity of the medium. Peptide attachment was accomplished by immersing the coated steel strips into aqueous buffer solution of Gly-Gly or GYIGSR. XPS and solubility studies revealed successful attachment of peptides to the polymer surface. Virtually all remaining activating groups were successfully replaced in the subsequent step by a treatment with Tris(hydroxymethyl)amino methane in a buffered methanol/water mixture.

  6. Fabrication of Bioactive Surfaces by Functionalization of Electroactive and Surface-Active Block Copolymers

    Directory of Open Access Journals (Sweden)

    Omotunde Olubi


    Full Text Available Biofunctional block copolymers are becoming increasingly attractive materials as active components in biosensors and other nanoscale electronic devices. We have described two different classes of block copolymers with biofuctional properties. Biofunctionality for block copolymers is achieved through functionalization with appropriate biospecific ligands. We have synthesized block copolymers of electroactive poly(3-decylthiophene and 2-hydroxyethyl methacrylate by atom transfer radical polymerization. The block copolymers were functionalized with the dinitrophenyl (DNP groups, which are capable of binding to Immunoglobulin E (IgE on cell surfaces. The block copolymers were shown to be redox active. Additionally, the triblock copolymer of α, ω-bi-biotin (poly(ethylene oxide-b-poly (styrene-b-poly(ethylene oxide was also synthesized to study their capacity to bind fluorescently tagged avidin. The surface-active property of the poly(ethylene oxide block improved the availability of the biotin functional groups on the polymer surfaces. Fluorescence microscopy observations confirm the specific binding of biotin with avidin.

  7. Effects of SBS Configuration on Performance of High Modulus Bitumen Based on Dynamic Mechanical Analysis

    Directory of Open Access Journals (Sweden)

    Ming Liang


    Full Text Available High modulus bitumens modified by polystyrene-block-polybutadiene-block-polystyrene (SBS with different molecular structure were investigated on dynamic shear rheometer and fluorescence microscopy to evaluate viscoelastic properties and morphology of binders. The results shows that storage modulus (G’ is obviously less than loss modulus (G”, which means viscous behaviour of bitumen is dominant, and anti-rutting factor (G* ⁄ sin δ is markedly enhanced by star SBS than by linear SBS. The morphology indicated that star SBS improved the softening point more obviously, tending to form a cross-linked network in bitumen. As for linear SBS, it is dispersed in bitumen in the form of globules and enhances the ductility of binder.

  8. Block copolymer-nanoparticle hybrid self-assembly

    KAUST Repository

    Hoheisel, Tobias N.


    © 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. Hemocompatibility of styrenic block copolymers for use in prosthetic heart valves. (United States)

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


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

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

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


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

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

    KAUST Repository

    Bouchekif, Hassen


    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

  12. Gain optimization in fiber optical parametric amplifiers by combining standard and high-SBS threshold highly nonlinear fibers

    DEFF Research Database (Denmark)

    Da Ros, Francesco; Rottwitt, Karsten; Peucheret, Christophe


    Combining Al-doped and Ge-doped HNLFs as gain media in FOPAs is proposed and optimized, resulting in efficient SBS mitigation while circumventing the additional loss of the high SBS threshold Al-doped fiber.......Combining Al-doped and Ge-doped HNLFs as gain media in FOPAs is proposed and optimized, resulting in efficient SBS mitigation while circumventing the additional loss of the high SBS threshold Al-doped fiber....

  13. Morphological Consequences of Frustration in ABC Triblock Polymers

    Energy Technology Data Exchange (ETDEWEB)

    Radlauer, Madalyn R.; Sinturel, Christophe; Asai, Yusuke; Arora, Akash; Bates, Frank S.; Dorfman, Kevin D.; Hillmyer, Marc A. (UMM); (Nagoya); (Orleans)


    Three poly(styrene)-block-poly(isoprene)-block-poly(lactide) (PS-b-PI-b-PLA, SIL) triblock terpolymers were synthesized and characterized in the bulk and as thin films. The pronounced incompatibility of the covalently connected PI and PLA led to significant frustration and the tendency to minimize their intermaterial dividing surface area. This resulted in the formation of a core–shell cylinder morphology with exaggerated nonconstant mean curvature from triblock polymers with equal block volume fractions rather than the more typical lamellar morphology. The effect of frustration was magnified in thin films by both confinement and interfacial interactions such that the PI domains became discontinuous. Self-consistent field theory (SCFT) calculations emphasize that the marked difference in the PS/PI and PI/PLA interaction parameters promotes the formation of nonlamellar morphologies. However, SCFT predicts that lamellar morphology is more stable than the observed cylindrical morphology, demonstrating a limitation that arises from the underlying assumptions.

  14. Morphology and property studies of ABA and A(A/B)B copolymers, blends and gels (United States)

    Laurer, Jonathan Harold

    A comprehensive examination of midblock influences on morphological and property development in triblock copolymer blends with either a parent homopolymer or a non-parent, midblock-selective solvent is presented. Both traditional ABA triblock copolymers and novel A(A/B)B extended block copolymers, in which the midblock is a random A/B copolymer, are employed to identify and enhance midblock-controlled morphologies. Changes in solvent affinity, chain conformation, morphology and properties were found to be highly sensitive to midblock type, monomer sequencing, and concentration. In blends with parent homopolymer, monomer sequencing demonstrated a profound effect in A(A/B)B/hA blends, enhancing bilayer development in dilute block copolymer systems. Microstructures previously observed only in (co)surfactant solutions, including the symmetric Lsb3 (sponge) bicontinuous morphology, are found to develop in these blends. Transitions among micelles, vesicles and sponge morphologies exhibit identical composition dependencies as their low-molar-mass surfactant analogs, indicating that these systems are fundamentally related in the dilute regime. At all compositions, the random midblock was found to exhibit a dominant, multi-faceted role by (i) compatibilizing the repulsive A and B endblocks, (ii) rigidifying the interphase between microdomains, and (iii) screening homopolymer interactions. While another bicontinuous morphology, the gyroid, was observed for the first time in a neat, compositionally-asymmetric ABA copolymer, blends with mineral oil (a non-parent midblock-selective solvent) produced lamellar, cylindrical and micellar morphologies. Upon midblock hydrogenation, transitions occurred at different blend compositions, representing an adjustment in midblock/solvent affinity. Gel networks form in these blends if bridged midblocks exist uniformly throughout the specimen, resulting in thermoplastic elastomer gel (TPEG) materials. Gels were produced in both symmetric (ca

  15. Comparison of ELG and UV Galaxies from the SBS Survey (United States)

    Gyulzadian, Marieta V.

    This paper discusses the optical spectroscopic properties and comparison of the emission line galaxies (ELG) and galaxies with UV-excess (UV galaxies) from the Second Byurakan Survey (SBS). 155 galaxies spectra have been examined over the wavelength range 3500-57A. These objects are expected to be very rare, representing the possible ?tail? of the epoch of galaxy formation, or, rather, accidental ?secondary? galaxy formation from ultimate primeval material clouds at last submitted to astration because of interactive processes triggering coalescence into protogalaxies (G.Comte, 1998, Astrofizika, 41, 138). We investigate the relation between the observed emission-line widths, relative line intensity, the blue continuum colorant continuum properties for these galaxies. This includes investigating correlation between the various lines. We find anticorrelation between the equivalent width for the Hb and EW[OIII]/EW(Hb); EW[OIII] and EW[OIII]/EW(Hb). Anticorrelation for [OIII]/Hb and C3727-C4861 is also present. We find no correlation between a and relative intensive lines. There is faint correlation between a3727-4861 and C3727-C4861.

  16. Crystallization of bifonazole and acetaminophen within the matrix of semicrystalline, PEO-PPO-PEO triblock copolymers. (United States)

    Chen, Zhen; Liu, Zhengsheng; Qian, Feng


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

  17. Sphere-to-rod transition of triblock copolymer micelles at room ...

    Indian Academy of Sciences (India)

    (PEO)20 micelles have been observed in aqueous medium under the influence of ethanol and sodium chloride. Addition of 5–10% ethanol induces a high temperature sphere-to- rod transition of the micelles, .... Further evidence of growth of micelles with the addition of NaCl is produced by a comparative analysis of the ...

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

    DEFF Research Database (Denmark)

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


    in a mixture of aliphatic and alicyclic compounds constitute such a network system. Using a Rheometrics RSA-2 instrument modified for in situ measurements of small-angle neutron scattering and rheology provides a unique possibility far detailed understanding thermodynamics of such a gel. The self...

  19. Cytotoxicity and cellular uptake of triblock copolymer nanoparticles with different size and surface characteristics

    NARCIS (Netherlands)

    Bhattacharjee, S.; Ershov, D.S.; Fytioanos, K.; Gucht, van der J.; Alink, G.M.; Rietjens, I.M.C.M.; Marcelis, A.T.M.; Zuilhof, H.


    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

  20. 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)


    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

  1. Preparation and evaluation of a linoleic-acid-modified amphiphilic polypeptide copolymer as a carrier for controlled drug release. (United States)

    Tian, Zhen; Zhang, Ai-Ying; Ye, Lin; Wang, Meng; Feng, Zeng-guo


    In the present study, we describe the synthesis, characterization and self-assembly of a novel amphiphilic linoleic acid (LA)-modified polypeptide copolymer and its drug release behavior in vitro as well. Initially, an amphiphilic ABA triblock copolymer comprising polytetrahydrofuran (PTHF) as a central hydrophobic block and poly(L-lysine)s as outer hydrophilic blocks was prepared via the ring-opening polymerization of epsilon-benzyloxycarbonyl-L-lysine N-carboxyanhydride with a distal amine-terminated PTHF as a macroinitiator, followed by the removal of the protecting group. The resulting triblock copolymer was then reacted with linoleic acid in the presence of N-ethyl-N'-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDCHCl)/N-hydroxysuccinimide (HOSu) to give rise to a target LA-modified polypeptide copolymer. It was found to self-assemble into nanoparticles in water. Its critical aggregation concentration was assessed by fluorescence measurement with N-phenyl-1-naphthylamine employed as a molecular probe. The particle sizes of the aggregates were determined by dynamic light scattering, and the aggregate morphologies were evidenced by transmission electron microscopy measurements. Finally, the drug-loading capacity and release behavior in vitro were investigated by using doxorubicin as a model drug.

  2. Unraveling the electrolyte properties of Na3SbS4 through computation and experiment (United States)

    Rush, Larry E.; Hood, Zachary D.; Holzwarth, N. A. W.


    Solid-state sodium electrolytes are expected to improve next-generation batteries on the basis of favorable energy density and reduced cost. Na3SbS4 represents a new solid-state ion conductor with high ionic conductivities in the mS/cm range. Here, we explore the tetragonal phase of Na3SbS4 and its interface with metallic sodium anode using a combination of experiments and first-principles calculations. The computed Na-ion vacancy migration energies of 0.1 eV are smaller than the value inferred from experiment, suggesting that grain boundaries or other factors dominate the experimental systems. Analysis of symmetric cells of the electrolyte—Na/Na 3SbS4/Na —show that a conductive solid electrolyte interphase forms. Computer simulations infer that the interface is likely to be related to Na3SbS3 , involving the conversion of the tetrahedral SbS43 - ions of the bulk electrolyte into trigonal pyramidal SbS33 - ions at the interface.

  3. SBS symptoms in relation to dampness and ventilation in inspected single-family houses in Sweden. (United States)

    Smedje, Greta; Wang, Juan; Norbäck, Dan; Nilsson, Håkan; Engvall, Karin


    To investigate the relationships between symptoms compatible with the sick building syndrome (SBS) in adults and building dampness and ventilation in single-family houses. Within the Swedish BETSI study, a national sample of single-family houses were inspected by professional building experts, and adults living in the houses answered a questionnaire on SBS. Relationships between building factors and SBS were analysed using logistic regression. Of the respondents, 23% reported having had weekly SBS symptoms during the last three months. A large proportion of houses exhibited building or construction problems. In total, 40% of houses had dampness problems in the foundation, and this was related to a higher prevalence of both mucous and dermal symptoms, and any SBS symptoms. Furthermore, high air humidity was related to more symptoms, with the relationship with absolute humidity being stronger than that with relative humidity or moisture load. Symptoms were also more prevalent in houses with a high U value, reflecting a poor thermal insulation. Compared to natural ventilation, living in a house with mechanical supply and exhaust ventilation was related to a lower prevalence of general symptoms and any SBS symptoms, but there were only weak associations between measured air exchange rate and symptoms. A large proportion of single-family houses have dampness problems in the foundation, and pollutants may enter the living space of the house and affect the health of the occupants. Furthermore, absolute air humidity should be measured more often in indoor air studies.

  4. The structure of P85 pluronic block copolymer micelles determined by small-angle neutron scattering

    DEFF Research Database (Denmark)

    Pedersen, J.S.; Gerstenberg, M.C.


    The symmetric triblock copolymer Pluronic P85 with EO(25)PO(40)EO(25) has been studied by small-angle neutron scattering (SANS) at 50 and 60 degreesC at concentrations of 0.25-10 wt.% in D(2)O. The data are analyzed by a model based on Monte Carlo simulations. The micelles are modeled as having...... a spherical core of poly(propylene oxide) (PPO) with some water surrounded by a corona of the poly(ethylene oxide) (PEO) block. The latter are non-interacting and obey Gaussian statistics, but are expelled from the core region. The analysis shows that the micelles are fairly concentration and temperature...

  5. Hydrogel formation by the 'topological conversion' of cyclic PLA-PEO block copolymers


    Yamamoto, Takuya; Inoue, Kotaro; TEZUKA, YASUYUKI


    An amphiphilic cyclic block copolymer consisting of poly(L- or D-lactide) and poly(ethylene oxide), that is, PLLA-PEO or PDLA-PEO, was synthesized from its corresponding linear triblock precursor, PLLA-PEO-PLLA or PDLA-PEO-PDLA, respectively, with alkenyl end groups. A mixture of the micellar dispersions of linear PLLA-PEO-PLLA and linear PDLA-PEO-PDLA formed a gel upon heating, whereas a mixture of the cyclic counterparts did not undergo this phase transition. These results suggest that the ...

  6. Well-defined ABA- and BAB-type block copolymers of PDMAEMA and PCL

    DEFF Research Database (Denmark)

    Bruce, Carl; Javakhishvili, Irakli; Fogelstrom, Linda


    Triblock copolymers of ABA- and BAB-type consisting of poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA, A) and poly(epsilon-caprolactone) (PCL, B) have successfully been prepared. PDMAEMA-b-PCL-b-PDMAEMA (ABA) and PCL-b-PDMAEMA-b-PCL (BAB) were synthesised by a combination of ring...... as the outer block (ABA), the inherent crystallinity of PCL was destroyed while with PCL as the outer block (BAB), the degree of crystallinity was in the same proximity as for a PCL homopolymer....

  7. Transparent nanostructured cellulose acetate films based on the self assembly of PEO-b-PPO-b-PEO block copolymer. (United States)

    Gutierrez, Junkal; Carrasco-Hernandez, Sheyla; Barud, Hernane S; Oliveira, Rafael L; Carvalho, Renata A; Amaral, André C; Tercjak, Agnieszka


    In this study fabrication and characterization of transparent nanostructured composite films based on cellulose triacetate (CTA) and poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) (EPE) triblock copolymer were presented. The effect of the addition of EPE triblock copolymer on the thermal stability, morphology, and mechanical properties of cellulose triacetate films was investigated. The triblock EPE was chosen since PEO blocks interact favorably with CTA, whereas, PPO blocks remain immiscible which provokes a microphase separation. This allows to obtain EPE/CTA composite films with ordered microphase-separated structures where PPO spherical microdomains are well-dispersed in PEO/CTA matrix by simple solvent-evaporation process. During this process, PEO block chains selectively interact with CTA by strong interpolymer hydrogen-bonding while PPO block microseparated. The addition even 40wt% of EPE leads to nanostructured EPE/CTA composite. The cytotoxicity assay of CTA and EPE/CTA composite films confirm non-toxic character of designed transparent nanostructured composites based on sustainable matrices. Copyright © 2017 Elsevier Ltd. All rights reserved.

  8. Avaliação dos efeitos da radiação ultravioleta sobre propriedades reológicas de ligantes asfálticos modificados com PPA e copolímeros SBS e SBR

    Directory of Open Access Journals (Sweden)

    Thalita Cristina Brito Nascimento


    Full Text Available The aging process suffered by asphalt binders interferes directly with the mechanical properties of HMA mixes. In order to avoid an excessive hardening of the asphalt binder, the specifications limit certain aging indices or aging param-eters. However, asphalt binder specifications do not take account of the effect of the ultraviolet radiation (UV on the rheo-logical properties of such materials. The objectives of this work are (i to quantify the effects of the UV radiation on the rheological properties of a 50/70 pen-grade asphalt binder and five asphalt binders modified with polyphosphoric acid and the SBS and SBR copolymers (binder+PPA, binder+SBS, binder+SBS+PPA, binder+SBR and binder+SBR+PPA and (ii to compare the aging levels caused by UV radiation with the aging level in the PAV. The samples aged in the PAV and in the wetherometer were previously aged in the RTFO oven. The use of modifiers increased the resistance to long-term aging of the materials, either in the PAV or in the wetherometer. The binder+SBR+PPA showed the best performance in terms of aging resistance.

  9. Triblock Terpolymers by Simultaneous Tandem Block Polymerization (STBP). (United States)

    Freudensprung, Ines; Klapper, Markus; Müllen, Klaus


    A route of synthesizing triblock terpolymers in a one-pot, "one-step" polymerization approach is presented. The combination of two distinct polymerization techniques through orthogonal catalyst/initiator functionalities attached to a polymeric linker furnishes novel pathways to ABC-terpolymers. Both polymerizations have to be compatible regarding mechanisms, chosen monomers, and solvents. Here, an α,ω-heterobifunctional poly(ethylene glycol) serves as poly-meric catalyst/initiator to obtain triblock terpolymers of poly(norbornene)-b-poly(ethylene glycol)-b-poly(L-lactic acid) PNB-PEG-PLLA via simultaneous ring opening metathesis poly-merization and ring opening polymerization in a fast one-pot polymerization. Structural characterization of the polymers is provided via (1)H-, DOSY-, and (1)H,(1)H-COSY-NMR, while solution and thin film self-assembly are investigated by dynamic light scattering and atomic force microscopy. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Recent Advances of Poly(ether-ether) and Poly(ether-ester) Block Copolymers in Biomedical Applications. (United States)

    He, Zhi-Yao; Shi, Kun; Wei, Yu-Quan; Qian, Zhi-Yong


    Poly(ether-ether) and poly(ether-ester) block copolymers have been widely applied in biomedical fields over two decades due to their good safety and biocompatibility. Poly(ethylene glycol), poly(ethylene glycol)-poly(propylene glycol) and poly(lactic-co-glycolic acid) have been approved as excipients by Food and Drug Administration. Because of the broad perspective in biomedical fields, many novel poly(etherether) and poly(ether-ester) block copolymers have been developed for drug delivery, gene therapy and tissue engineering in recent years. This review focuses on active targeting theranostic systems, gene delivery systems and tissue engineering based on poly(ether-ether) and poly(ether-ester) block copolymers. We perform a structured search of bibliographic databases for peer-reviewed scientific reports using a focused review question and inclusion/exclusion criteria. The literatures related to the topics of this review are cataloged according to the developed copolymers or their applications such as active targeting theranostic systems, gene delivery systems and tissue engineering. Some important advances and new trends are summarized in this review. Some commercial poly(ether-ether) copolymers have been used as excipients for drug research and development. Amphiphilic and biodegradable poly(ether-ester) diblock copolymers are capable of formulating biomedical nanoparticulate theranostic systems, and targeting moiety-functionalized poly(ether-ester) diblock copolymers will be further developed and applied in biomedical nanotechnology fields in the near future. Meanwhile, triblock or multiblock poly(ether-ether) and poly(ether-ester) copolymers with environmentsensitive properties are suitable for gene delivery and tissue engineering. Poly(ether-ether) and poly(ether-ester) copolymers are being extensively applied in active targeting theranostic systems, gene delivery systems and tissue engineering. Biodegradable, environment-sensitive and targeting moiety

  11. Classification of SBS Mathematics Questions between 2008-2013 years with Respect to PISA Competency Levels

    Directory of Open Access Journals (Sweden)

    Tuğba Aydoğdu İskenderoğlu


    Full Text Available One of the main objectives of the education is students are ready to make the conditions of the age in which they live. From this perspective approach of mathematics education changed in our age looking for answers to the question as instead of "what we teach them?", "How they use our teaching which their life?". In other words, the main purpose of education is our students collected under the mathematical literacy. Then teach them which students' knowledge which use in everyday life, to make logical inferences, interpret and solve problems related to the various situations. The purpose of this study was implemented in our country between the years of 2008-2013 SBS questions examined and categorized according to the scale which PISA mathematics proficiency. In this study, data was collected using qualitative research techniques, document analysis methods of data collection. The results of the study, the questions examined in this study all levels of math exams in 2008-2013 SBS was not appropriate questions. Questions in general 2, 3 and 4 levels of which they are located, exams include just one question which is the highest level of 5 and there have not been any questions level 6. SBS administered by the Ministry of National Education thought-provoking the absence of the upper levels questions. For this reason, math questions of SBS should be every level and be prepared questions reconsideration measurement is recommended.Key Words: PISA, Mathematics competency levels, Mathematics competency scale, Mathematics problems of SBS

  12. Synthesis, crystal structure, electronic structure, and photoelectric response properties of KCu2SbS3. (United States)

    Wang, Ruiqi; Zhang, Xian; He, Jianqiao; Zheng, Chong; Lin, Jianhua; Huang, Fuqiang


    Copper thioantimonates have received enormous attention due to their potential for applications in photovoltaic devices. In this work, a new layered compound KCu2SbS3 was synthesized via a reactive flux method using thiourea as a reactive flux. The compound crystallizes in the triclinic space group P1[combining macron]. The structure features two-dimensional [Cu2SbS3](-) layers stacking along the c axis with K(+) ions intercalated between the layers. Each [Cu2SbS3](-) layer is composed of two single graphene-like layers connected via interlayer Cu-S bonds and CuSb contacts. The optical measurements indicate that the compound has a band gap of 1.7 eV. The Hall effect measurement shows that KCu2SbS3 is a p-type semiconductor with a carrier concentration of 7 × 10(16) cm(-3). First-principles calculations reveal that the direct transition occurs between Cu-3d-S-3p orbitals (VBM) to Sb-5p-S-3p orbitals (CBM). The photoelectric response properties of KCu2SbS3 under visible light irradiation were analyzed. The photocurrent is 3.7 μA cm(-2) at 10 V bias, demonstrating its potential for applications in photoelectric devices.

  13. Probe And Enhancement Of SBS Based Phonons In Infrared Fibers Using Waveguide Coupled External Radiation (United States)

    Yu, Chung; Chong, Yat C.; Fong, Chee K.


    Interaction of GHz and MHz radiation with CO2 laser propagation in a silver halide fiber using sBs based phonon coupling is furthet investigated. The external signal serves to both probe and enhance laser generated sBs phonons in the fiber. Efficient coupling of microwave radiation into the fiber is accomplished by placing the fiber in a hollow metallic waveguide, designed and constructed to transmit the dominant mode in the 0.9-2.0 GHz band. MHz radiation is conveniently coupled into the fiber using the guided microwave radiation as carrier. Phonon emissions from the fiber under CO2 laser pumping are first established on a spectrum analyzer; low frequency generators ale then tuned to match these frequencies and their maximum interaction recorded. Such interactions are systematically studied by monitoring the amplitude and waveform of the reflected and transmitted laser pulse at various power levels and frequencies of the externally coupled radiation. A plot of reflected laser power versus incident laser power reveals a distinct sBs generated phonon threshold. Variouslaunch directions of the GHz and MHz radiation with respect to the direction of laser propagation are realized to verify theory governing sBs interactions. The MHz radiation and its associated phonons in the fiber are convenient tools for probing sBs related phenomenon in infrared fibers.

  14. Formation of microphase-separated structure with half pitch less than 5.0nm formed by multiblock copolymers for nanolithographic application (United States)

    Kosaka, T.; Kawaguchi, Y.; Himi, T.; Shimizu, T.; Hirahara, K.; Takano, A.; Matsushita, Y.


    In this study, we have successfully synthesized polystyrene-b-poly(4-hydroxystyrene) (SH) with molecular weight of 14k and with narrow molecular weight distribution by living anionic polymerization, and the obtained SH diblock copolymer has formed the definite alternative lamellar structure with the half pitch of 10.4nm. In order to achieve narrow half pitch pattern, diblock copolymer (XY) with stronger segregated polymer components with high chi (X and Y) was used, and it was confirmed that the high-chi XY diblock copolymer having molecular weight of 6k showed the clear lamellar structure with the half pitch of 5.5nm. Furthermore syntheses of multiblock copolymers with high chi such as YXY (where X is Si contained polymer) triblock and XYXY (where XYXY is Si contained high χ polymer) tetrablock copolymers were attempted to achieve the narrower half pitch pattern less than 5 nm, and the multiblock copolymers with aimed molecular weight and narrow molecular weight distribution have been successfully obtained. From the highchi multiblock copolymers, it was confirmed that the formation of the definite microphase-separated structure with the half pitch of 4.8nm was observed by TEM and SAXS measurements. Moreover we have developed a large-scale living anionic polymerization apparatus for the preparation of well-defined block copolymers scaled over 3kg.

  15. Silicone/Acrylate Copolymers (United States)

    Dennis, W. E.


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

  16. Responsive Hydrogels from Associative Block Copolymers: Physical Gelling through Polyion Complexation

    Directory of Open Access Journals (Sweden)

    Christine M. Papadakis


    Full Text Available The present review article highlights a specific class of responsive polymer-based hydrogels which are formed through association of oppositely charged polyion segments. The underpinning temporary three-dimensional network is constituted of hydrophilic chains (either ionic or neutral physically crosslinked by ion pair formation arising from intermolecular polyionic complexation of oppositely charged repeating units (polyacid/polybase ionic interactions. Two types of hydrogels are presented: (i hydrogels formed by triblock copolymers bearing oppositely charged blocks (block copolyampholytes, forming self-assembled networks; and (ii hydrogels formed by co-assembly of oppositely charged polyelectrolyte segments belonging to different macromolecules (either block copolymers or homopolyelectrolytes. Due to the weak nature of the involved polyions, these hydrogels respond to pH and are sensitive to the presence of salts. Discussing and evaluating their solution, rheological and structural properties in dependence on pH and ionic strength, it comes out that the hydrogel properties are tunable towards potential applications.

  17. Utilization of Network-Forming Block Copolymers and Ionomers in the Development of Novel Nanostructures and Responsive Media (United States)

    Mineart, Kenneth

    Network forming block copolymers, i.e. thermoplastic elastomers (TPEs), are one of the highest commodity forms of block copolymers due to their competitive elasticity and extendability as well as their ability to be melt and solution processed. TPEs owe many of their advantages to a combination of hard and soft blocks. The soft blocks, which must be covalently bound at both ends to hard blocks, connect adjacent hard domains resulting in physically cross-linked systems. Herein, simulations and theory are used to provide a molecular-level depiction of the evolution from diblock copolymers, which do not contain the ability to form physical cross-links, to network forming triblock copolymers. In addition, systems with high interblock incompatibility that are within the diblock-to-triblock transition (i.e. having high molecular asymmetry) are identified to form three component (ABC triblock copolymer) phases from copolymer containing only two chemically distinct blocks. Following this work, which emphasizes the fundamental principle of TPEs, the dissertation shifts focus to physically- and chemically-modified triblock and pentablock copolymer TPEs. Recent progress has sought to broaden TPEs to include properties that are above and beyond their inherent mechanical benefits, including responsiveness to external stimuli. The first examples presented here consist of TPEs prepared in combination with amorphous hydrocarbon additives to yield TPE gels (TPEGs). The resulting TPEGs, which maintain the beneficial processing properties of TPEs, are subsequently molded into 1- and 2-D arrays of microchannels that are filled with liquid metal. The final devices exhibit strain-sensitive electrical conductivity to at least 600% strain, have tunable compliance (ease of stretching), and are fully recyclable. The substitution of the amorphous hydrocarbon component for crystalline analogues with melting points molded composites filled with liquid metal. These shape-memory TPECs can also

  18. Silicon containing copolymers

    CERN Document Server

    Amiri, Sahar; Amiri, Sanam


    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.

  19. The impact of microfluidic mixing of triblock micelleplexes on in vitro / in vivo gene silencing and intracellular trafficking (United States)

    Feldmann, Daniel P.; Xie, Yuran; Jones, Steven K.; Yu, Dongyue; Moszczynska, Anna; Merkel, Olivia M.


    The triblock copolymer polyethylenimine-polycaprolactone-polyethylene glycol (PEI-PCL-PEG) has been shown to spontaneously assemble into nano-sized particulate carriers capable of complexing with nucleic acids for gene delivery. The objective of this study was to investigate micelleplex characteristics, their in vitro and in vivo fate following microfluidic preparation of siRNA nanoparticles compared to the routinely used batch reactor mixing technique. Herein, PEI-PCL-PEG nanoparticles were prepared with batch reactor or microfluidic mixing techniques and characterized by various biochemical assays and in cell culture. Microfluidic nanoparticles showed a reduction of overall particle size as well as a more uniform size distribution when compared to batch reactor pipette mixing. Confocal microscopy, flow cytometry and qRT-PCR displayed the subcellular delivery of the microfluidic formulation and confirmed the ability to achieve mRNA knockdown. Intratracheal instillation of microfluidic formulation resulted in a significantly more efficient (p batch reactor formulation. The use of microfluidic mixing techniques yields an overall smaller and more uniform PEG-PCL-PEI nanoparticle that is able to more efficiently deliver siRNA in vivo. This preparation method may prove to be useful when a scaled up production of well-defined polyplexes is required.

  20. Effect of streamer plasma air purifier on sbs symptoms and performance of office work

    DEFF Research Database (Denmark)

    Zhang, X.J.; Fang, Lei; Wargocki, Pawel


    Subjective experiments were conducted to evaluate the effect of a streamer plasma air purifier on perceived air quality, SBS symptoms and performance of office work during 5-hour exposure of 32 recruited subjects in field laboratory in which real materials were used to establishing a realistic...... level of air pollution. Intensity of SBS symptoms were indicated using visual-analogue scales. Subjects’ performance was evaluated with several computer tasks. The results show that operation of the air purifiers improved perceived air quality and reduced the odor intensity of indoor air. Eye dryness...... symptom was found significantly improved when the air purifiers were used but no other SBS symptoms or performance of office work were improved when the air purifiers were in operation compared to the condition when they were off....

  1. An assessment of SBS modified asphalt concrete pavements performance features performing numerical analysis (United States)

    Karakas, Ahmet Sertac; Bozkurt, Tarik Serhat; Sayin, Baris; Ortes, Faruk


    In passenger and freight traffic on the roads, which has the largest share of the hot mix asphalt (HMA) prepared asphalt concrete pavement is one of the most preferred type of flexible superstructure. During the service life of the road, they must provide the performance which is expected to show. HMA must be high performance mix design, comfortable, safe and resistance to degradation. In addition, it becomes a critical need to use various additives materials for roads to be able to serve long-term against environmental conditions such as traffic and climate due to the fact that the way of raw materials is limited. Styrene Butadiene Styrene (SBS) polymers are widely used among additives. In this study, the numerical analysis of SBS modified HMA designed asphalt concrete coatings prepared with different thicknesses with SBS modified HMA is performed. After that, stress and deformation values of the three pavement models are compared and evaluated.

  2. pF3D Simulations of SBS and SRS in NIF Hohlraum Experiments (United States)

    Langer, Steven; Strozzi, David; Amendt, Peter; Chapman, Thomas; Hopkins, Laura; Kritcher, Andrea; Sepke, Scott


    We present simulations of stimulated Brillouin scattering (SBS) and stimulated Raman scattering (SRS) for NIF experiments using high foot pulses in cylindrical hohlraums and for low foot pulses in rugby-shaped hohlraums. We use pF3D, a massively-parallel, paraxial-envelope laser plasma interaction code, with plasma profiles obtained from the radiation-hydrodynamics codes Lasnex and HYDRA. We compare the simulations to experimental data for SBS and SRS power and spectrum. We also show simulated SRS and SBS intensities at the target chamber wall and report the fraction of the backscattered light that passes through and misses the lenses. Work performed under the auspices of the U.S. Department of Energy by LLNL under Contract DE-AC52-07NA27344. Release number LLNL-ABS-697482.

  3. Building Asphalt Pavement with SBS-based Compound Added Using a Dry Process in Greenland

    DEFF Research Database (Denmark)

    Lee, Hosin; Kim, Yongjoo; Geisler, Nivi


    PMA where it is formulated to melt and blend with asphalt quickly during a batch mixing process. The main objectives of this study are to (1) build asphalt pavement using asphalt mixtures with SBS-based compound added using a “dry” process at the batch plant and (2) evaluate its performance under......-based compound seemed to affect the asphalt mix to become more flexible under the heavy loads. By adding SBS-based compound to asphalt mixtures using a “dry” process, it is expected that the pavement would become more resistant to rutting than a typical asphalt mixture used in Greenland while enduring its arctic...

  4. Modification of poly(styrene-block-butadiene-block-styrene) [SBS] with phosphorus containing fire retardants

    DEFF Research Database (Denmark)

    Chernyy, Sergey; Ullah, Saif; Jomaas, Grunde


    An elaborate survey of the chemical modification methods for endowing highly flammable SBS with increased fire resistant properties by means of chemical modification of the polymer backbone with phosphorus containing fire retardant species is presented. Optimal conditions for free radical additio...... application of the H3PO4 modified SBS as a fire retardant additive for bitumen material, in combination with synergetic melamine species, offered 25% better self-extinguishing properties of such formulation already at a low loading level of the fire retardant components (3.5 wt.%)....

  5. Fabrication of triblock ABA type peptide dendrimer based on glutamic acid dimethyl ester and PEG as a potential nano drug delivery agent (United States)

    Namazi, Hassan; Toomari, Yousef; Abbaspour, Hassan


    Introduction: Peptide dendrimers build up from amino acids and they simulate to artificial proteins with globular architecture. These characteristics furnish peptide dendrimers with best biodegradability and biocompatibility in drug delivery systems. Methods: A barbell-like dendrimer from glutamic acid dimethyl ester-poly (ethylene glycol)-glutamic acid dimethyl ester as ABA-type triblock copolymer (PG-PEG-PG) was prepared with liquid-phase peptide synthesis via a divergent approach. PEG 600 diacid (PEG-A) and glutamic acid dimethyl ester were used as the core and the monomeric building blocks, respectively. Linear-dendritic copolymer was prepared in the presence of DCC in pyridine. Transmission electron microscope (TEM) was used for measuring the size of first generation (G1-COOH) and second generation (G2-COOH) of dendrimer compounds. Thermal behavior of the synthesized dendrimers was investigated using DSC. Results: The desired generations G1-COOH, G2-COOH and G3-COOH were prepared by divergent method using PEG diacid 600 as a core compound. The size range of the resulted particles was found to be 20-100 nm for various generations. The isolated dendrimer was examined as the drug-delivery agent and the controlled release was carried out for drug molecule in pH 7.4. Conclusion: Based on the obtained results, the synthesized biocompatible dendrimers could potentially be utilized as a drug carrier agent. PMID:25671173

  6. Development and validation of the disease-specific Short Bowel Syndrome-Quality of Life (SBS-QoL) scale

    DEFF Research Database (Denmark)

    Berghöfer, P; Fragkos, K C; Baxter, J P


    Subjects with short bowel syndrome (SBS) have impaired quality of life (QoL). No disease-specific instrument has been available to measure treatment-induced changes in QoL over time. Therefore, the aim was to develop and validate an SBS-specific QoL scale....

  7. Rheological and chemical evaluation on the ageing properties of SBS polymer modified bitumen: From the laboratory to the field

    NARCIS (Netherlands)

    Liu, G.; Nielsen, E.; Komacka, J.; Greet, L.; Ven, M.V.D.


    This study investigated the ageing properties of the styrene-butadiene- styrene polymer modified bitumen (SBS PMB) from the laboratory to the field. The virgin SBS PMB had been kept for 23 years and its field-aged binder was extracted from the reclaimed stone matrix asphalt (SMA) after the 22-year

  8. Personal computers pollute indoor air: effects on perceived air quality, SBS symptoms and productivity in offices

    DEFF Research Database (Denmark)

    Bako-Biro, Zsolt; Wargocki, Pawel; Weschler, Charles J.


    Perceived air quality and Sick Building Syndrome (SBS) symptoms were studied in a low-polluting office space ventilated at an air change rate of 2 h-1 (10 L/s per person with 6 people present) with and without personal computers (PCs). Other environmental parameters were kept constant. Thirty...

  9. SBS Suppression and Coherent Combination of Fiber MOPAs via Chirped Diode Lasers (United States)


    preliminary data with a higher power amplifier at Nufern, but SBS continued to pop up at the transition point between the SDL and the ChDL, for...reasons that we did not understand at the time. The technique had the additional practical disadvantage that the coherence length of the SDL is far too

  10. Association of ventilation system type with SBS symptoms in office workers

    Energy Technology Data Exchange (ETDEWEB)

    Seppanen, Olli; Fisk, William J.


    This paper provides a review and synthesis of current knowledge about the associations of ventilation system types in office buildings with sick building syndrome symptoms and discusses potential explanations for the associations. Relative to natural ventilation, air conditioning, with or without humidification, was consistently associated with a statistically significant increase in the prevalence of one or more SBS symptoms. Prevalences were typically higher by approximately 30% to 200% in the air conditioned buildings. In two of three assessments from a single study, symptom prevalences were also significantly higher in air conditioned buildings than in buildings with simple mechanical ventilation and no humidification. In approximately half of assessments, SBS symptom prevalences were significantly higher in buildings with simple mechanical ventilation than in buildings with natural ventilation. Insufficient information was available for conclusions about the potential increased risk of SBS symptoms with humidification. The statistically significant associations of mechanical ventilation and air conditioning with SBS symptoms are much more frequent than expected from chance and also not likely to be a consequence of confounding by several potential personal, job, or building related confounders. The reasons for the increases in symptom prevalences with mechanical ventilation and particularly with air conditioning remain unclear. Multiple deficiencies in HVAC system design, construction, operation, or maintenance, including some which cause pollutant emissions from HVAC systems, may contribute to the increases in symptom prevalences.

  11. Selectivity of the surface binding site (SBS) on barley starch synthase I

    DEFF Research Database (Denmark)

    Wilkens, Casper; Cuesta-Seijo, Jose A.; Palcic, Monica


    Starch synthase I (SSI) from various sources has been shown to preferentially elongate branch chains of degree of polymerisation (DP) from 6–7 to produce chains of DP 8–12. In the recently determined crystal structure of barley starch synthase I (HvSSI) a so-called surface binding site (SBS) was ...

  12. Interface Oscillation in the Side-by-Side (SBS) Tape Casting of Functionally Graded Ceramics (FGCs)

    DEFF Research Database (Denmark)

    Jabbari, Masoud; Bulatova, Regina; Hattel, Jesper Henri


    slurries. The rheological behavior of the slurries are extracted from experiments and used in the ANSYS FLUENT commercial code to develop a fluid flow model for the non-Newtonian ceramic slurries and evaluate the interface oscillation between the stripes in SBS tape casting. The Numerical results show...

  13. Mussel-Inspired Thermoresponsive Polypeptide-Pluronic Copolymers for Versatile Surgical Adhesives and Hemostasis. (United States)

    Lu, Dedai; Wang, Hongsen; Li, Ting'e; Li, Yunfei; Dou, Fajuan; Sun, Shaobo; Guo, Hongyun; Liao, Shiqi; Yang, Zhiwang; Wei, Qiangbing; Lei, Ziqiang


    Inspired by marine mussel adhesive proteins, polymers with catechol side groups have been extensively explored in industrial and academic research. Here, Pluronic L-31 alcoholate ions were used as the initiator to prepare a series of polypeptide-Pluronic-polypeptide triblock copolymers via ring-opening polymerization of l-DOPA-N-carboxyanhydride (DOPA-NCA), l-arginine-NCA (Arg-NCA), l-cysteine-NCA (Cys-NCA), and ε-N-acryloyl lysine-NCA (Ac-Lys-NCA). These copolymers demonstrated good biodegradability, biocompatibility, and thermoresponsive properties. Adhesion tests using porcine skin and bone as adherends demonstrated lap-shear adhesion strengths up to 106 kPa and tensile adhesion strengths up to 675 kPa. The antibleeding activity and tissue adhesive ability were evaluated using a rat model. These polypeptide-Pluronic copolymer glues showed superior hemostatic properties and superior effects in wound healing and osteotomy gaps. Complete healing of skin incisions and remodeling of osteotomy gaps were observed in all rats after 14 and 60 days, respectively. These copolymers have potential uses as tissue adhesives, antibleeding, and tissue engineering materials.

  14. 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


    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.

  15. Multicompartment Core Micelles of Triblock Terpolymers in Organic Media

    Energy Technology Data Exchange (ETDEWEB)

    Schacher, Felix [University of Bayreuth; Walther, Andreas [Helsinki University of Technology, Helsinki, Finland; Ruppel, Markus A [ORNL; Drechsler, Markus [Universitat Bayreuth; Muller, Axel [Universitat Bayreuth


    The formation of multicompartment micelles featuring a spheres on sphere core morphology in acetone as a selective solvent is presented. The polymers investigated are ABC triblock terpolymers, polybutadieneb-poly(2-vinyl pyridine)-b-poly(tert-butyl methacrylate) (BVT), which were synthesized via living sequential anionic polymerization in THF. Two polymers with different block lengths of the methacrylate moiety were studied with respect to the formation of multicompartmental aggregates. The micelles were analyzed by static and dynamic light scattering as well as by transmission electron microscopy. Cross-linking of the polybutadiene compartment could be accomplished via two different methods, cold vulcanization and with photopolymerization after the addition of a multifunctional acrylate. In both cases, the multicompartmental character of the micellar core is fully preserved, and the micelles could be transformed into core-stabilized nanoparticles. The successful cross-linking of the polybutadiene core is indicated by 1H NMR and by the transfer of the aggregates into nonselective solvents such as THF or dioxane.

  16. Development of a kilojoule channel for Nd-glass laser systems with a 70-ns pulse SBS compressor (United States)

    Sirazetdinov, Vladmir S.; Alekseev, V. N.; Charukhchev, A. V.; Kotilev, V. N.; Liber, V. I.; Serebryakov, Victor A.


    An optical scheme for a kJ channel of a neodymium glass laser system with SBS-compressor for a 70 ns pulse has been described. The use of a pump pulse of long duration - 70 ns - makes it possible to operate a near-steady SBS mode in compressed gasses. An experimental study of the SBS oscillator-compressor stage with pump focusing and a two- pass pattern has been carried out and a 70 ns, 8 J pump pulse has been compressed down to 1 ns.

  17. Investigation on Using SBS and Active Carbon Filler to Reduce the VOC Emission from Bituminous Materials. (United States)

    Cui, Peiqiang; Wu, Shaopeng; Li, Fuzhou; Xiao, Yue; Zhang, Honghua


    Bituminous materials are playing a vital role in pavement design and the roofing industry because of outstanding properties. Unfortunately, bituminous materials will release volatile organic compounds (VOC), making them non-environmentally friendly. Therefore, technologies that can be used to decrease the VOC emission are urgently required. In this research, the VOC emission and material behaviors were analyzed and compared to investigate the possibility of adding styrene butadiene styrene (SBS) and active carbon filler into bituminous materials to develop environmentally-friendly materials. Thermal gravimetric analysis-mass spectrometry (TG-MS) and ultraviolet-visible spectroscopy testing (UV-Vis) were employed to characterize the VOC emission process. Temperature sweep testing and frequency sweep testing were conducted to evaluate the rheological properties of bituminous materials. Research results indicated that the combined introduction of 4 wt% styrene butadiene styrene (SBS) and 4 wt% active carbon filler cannot only significantly lower the VOC emission speed and amount, but also improve the deformation resistance behavior at a higher temperature. SBS and active carbon filler can be used to reduce the VOC emission form bituminous materials.

  18. Theoretical analysis and experiment performance of slow-light based on stimulated Brillouin scattering (SBS) (United States)

    Zhou, Hongyan; Zhong, Kun; Zhang, Ru; Lang, Peilin


    Slow light technology will play a key role in future all-optical communication. The slow-light technology based on stimulated Brillouin scattering has become a research highlight because of its additional advantages, such as compatibility of the devices with existing telecommunication systems, room-temperature operation, and tunable at arbitrary wavelengths. According to the propagation of a cw pulse through a Brillouin fiber amplifier, whose frequency is near the Stokes resonance, via three-wave coupling equations, both pump depletion and fiber losses taken into consideration, the principle of how slow-light effect based on stimulated Brillouin scattering produced and the mathematical expression of time delay are strictly deduced. A delay of 8 ns is obtained when the input Stokes pulse is 200ns and the SBS (stimulated Brillouin scattering) gain G is ~18 in our designed experiment of SBS slow-light system. Then the extent of transformation from pump waves to Stokes waves is measured using MATLAB numerical simulation according to the experiment dates, based on the relation between output pump light power and input pump light power and also the relation between output Stokes light power and input pump light power. And the relation between the input light power and propagation distance is discussed as well. Finally the relation between slow light pulse delay and SBS gain is also obtained.

  19. The Prevelence of SBS and Absenteeism among Children in Urban Refurbished Private Preshools

    Directory of Open Access Journals (Sweden)

    Salleh Naziah Muhamad


    Full Text Available The preschool education is compulsory to children in Malaysia. This regulation has encouraged more premises to be refurbished as a pre-school building. This paper examines the pupils’ absenteeism and the prevalence of Sick Building Symptoms (SBS initiated in congested private preschool with different ventilation strategies. The study analysed data from the attendance record of 10 classrooms and the questionnaire surveys administered to 151 parents about their children health symptoms once they were leaving the schools building. Questions on SBS used 5-point likert scale with symptoms concern on nose, eye, head, throat, skin, breath and tiredness. The descriptive and chi-square test applied to obtain the association of SBS and ventilation strategies in the classrooms. With quantitative and qualitative explanation, the unhealthy environment in refurbished pre-schools explained. Running nose, coughing and sore throat frequently reported in air-conditioning (AC classrooms. The higher absent rate found in AC classrooms. These symptoms show there were weaknesses in ventilation performance and environment in the selected preschools. Further analyses on objective measurements in future research are strongly recommended.

  20. Al/Ge co-doped large mode area fiber with high SBS threshold. (United States)

    Li, Ming-Jun; Chen, Xin; Wang, Ji; Gray, Stuart; Liu, Anping; Demeritt, Jeffrey A; Ruffin, A B; Crowley, Alana M; Walton, Donnell T; Zenteno, Luis A


    We propose a novel approach of making large effective area laser fiber with higher threshold for the stimulated Brillouin scattering (SBS) using Al/Ge co-doping in the fiber core. The increased SBS threshold is achieved by reducing the acoustic-optic overlap integral while keeping the optical refractive index profile with a step structure. The manipulation of the overlap integral is done by adjusting the relative doping level between Al(2)O(3) and GeO(2) in the core. The mechanism is validated by detailed examples of numerical modeling. An Yb-doped double clad fiber with the core co-doped with Al(2)O(3) and GeO(2) was fabricated by the OVD process. Measured acoustic velocity profile using a scanning acoustic microscope verified that the acoustic velocity in the fiber core changes with the design. An amplifier utilizing the fiber demonstrated that the proposed fiber yielded 6 dB higher SBS threshold than a fiber without using the co-doping scheme.

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

    KAUST Repository

    Madhavan, Poornima


    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.

  2. Efeito do SBS epoxidado como um agente compatibilizante para obtenção de nanocompósitos de SBS/argila cloisite 10A

    Directory of Open Access Journals (Sweden)

    Patrícia Alves da Silva


    Full Text Available Atualmente, cargas nanométricas são utilizadas para desenvolver novos materiais poliméricos com melhor desempenho mecânico. Neste trabalho, foi empregada uma mistura de borracha termoplástica de poli(estireno-b-butadieno-b-estireno (SBS e de argila Montmorilonita (Cloisite 10A via intercalação por fusão. Uma suspensão de Cloisite 10A em ciclohexano foi adicionada a SBS em solução. Para maior compatibilidade entre a argila e a borracha termoplástica utilizou-se uma borracha termoplástica epoxidada como agente compatibilizante. Neste estudo, a proporção argila compatibilizante foi de 0,6 até 3,0 para verificar a influência desta proporção nas propriedades mecânicas dos nanocompósitos. As propriedades morfológicas e mecânicas dos nanocompósitos foram avaliadas através da difração de raios X, microscopia eletrônica de transmissão, ensaio de tração, análise dinâmico-mecânica (DMA e avaliação do torque final da mistura. A combinação de argila/conpatibilizante favoreceu a formação de estruturas mais alongadas de argila que promoveram o ganho de módulo e tensão com pequena redução de alongamento.

  3. Mixed micellization between natural and synthetic block copolymers: β-casein and Lutrol F-127. (United States)

    Portnaya, Irina; Khalfin, Rafail; Kesselman, Ellina; Ramon, Ory; Cogan, Uri; Danino, Dganit


    Amphiphilic block copolymers and mixtures of amphiphiles find broad applications in numerous technologies, including pharma, food, cosmetic and detergency. Here we report on the interactions between a biological charged diblock copolymer, β-casein, and a synthetic uncharged triblock copolymer, Lutrol F-127 (EO(101)PO(56)EO(101)), on their mixed micellization characteristics and the micelles' structure and morphology. Isothermal titration calorimetry (ITC) experiments indicate that mixed micelles form when Lutrol is added to monomeric as well as to assembled β-casein. The main driving force for the mixed micellization is the hydrophobic interactions. Above β-casein CMC, strong perturbations caused by penetration of the hydrophobic oxypropylene sections of Lutrol into the protein micellar core lead to disintegration of the micelles and reformation of mixed Lutrol/β-casein micelles. The negative enthalpy of micelle formation (ΔH) and cooperativity increase with raising β-casein concentration in solution. ζ-potential measurements show that Lutrol interacts with the protein micelles to form mixed micelles even below its critical micellization temperature (CMT). They further indicate that Lutrol effectively masks the protein charges, probably by forming a coating layer of the ethyleneoxide rich chains. Small-angle X-ray scattering (SAXS) and cryogenic-transmission electron microscopy (cryo-TEM) indicate relatively small changes in the oblate micellar shape, but do show swelling along the small axis of β-casein micelles in the presence of Lutrol, thereby confirming the formation of mixed micelles.

  4. 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


    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.

  5. Surface-phase separation of PEO-containing biodegradable PLLA blends and block copolymers (United States)

    Lee, Joo-Woon; Jeong, Euh Duck; Cho, Eun Jeong; Gardella, Joseph A.; Hicks, Wesley; Hard, Robert; Bright, Frank V.


    The surface chemistry of two series of poly(ethylene oxide) (PEO)-containing biodegradable poly( L-lactic acid) (PLLA) matrix systems has been investigated using time-of-flight SIMS (ToF-SIMS) and XPS. The two systems are (1) PLLA blend matrices with an amphiphilic Pluronic ® P-104 surfactant, P(EO) 27- b-P(PO) 61- b-P(EO) 27, and (2) PLLA- b-PEO diblock and PLLA- b-PEO- b-PLLA triblock copolymers. The phase separation is analyzed in determining the surface enrichment of the component and chemical composition at the polymer-air interface. The PEO component is surface-dominant in the blend system in contrast to the surface excess of poly(propylene oxide) (PPO) in pure Pluronic ® P-104. The block copolymer system shows the surface enrichment of PLLA component. These results can be explained in terms of the change in surface free energy for the block copolymers and the better miscibility of PLLA and PPO against amphiphilic PEO for the blends, respectively.

  6. New amphiphilic glycopolymers by click functionalization of random copolymers – application to the colloidal stabilisation of polymer nanoparticles and their interaction with concanavalin A lectin

    Directory of Open Access Journals (Sweden)

    Otman Otman


    Full Text Available Glycopolymers with mannose units were readily prepared by click chemistry of an azido mannopyranoside derivative and a poly(propargyl acrylate-co-N-vinyl pyrrolidone. These glycopolymers were used as polymer surfactants, in order to obtain glycosylated polycaprolactone nanoparticles. Optimum stabilization for long time storage was achieved by using a mixture of glycopolymers and the non-ionic triblock copolymer Pluronic® F-68. The mannose moieties are accessible at the surface of nanoparticles and available for molecular recognition by concanavalin A lectin. Interaction of mannose units with the lectin were evaluated by measuring the changes in nanoparticles size by dynamic light scattering in dilute media.

  7. Microphase Separation in Thin Films of Block Copolymer Supramolecular Assemblies: Composition Dependent Morphological Transitions and Molecular Architecture Effect (United States)

    Nandan, Bhanu; Stamm, Manfred


    Block copolymer based supramolecular assemblies (SMAs) recently have attracted lot of attention because of their potential application as nanotemplates. These SMAs are prepared by attaching small molecules selectively to one of the blocks of the copolymer through physical interactions. In the present study, the phase behavior of SMAs formed by polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) with 2-(4'-hydroxybenzeneazo)benzoic acid (HABA) was investigated with respect to the molar ratio (X) between HABA and 4VP monomer unit in bulk as well as in thin films. It will be shown that these SMAs show some interesting composition dependent and solvent induced pathway dependent phase transitions. Moreover, the orientation of cylindrical or lamellar microdomains of P4VP(HABA) depends on the selectivity of the solvent as well as on the degree of swelling of the thin film. Furthermore, it will be shown that the molecular architecture of the block copolymer influences the orientation and ordering of microdomains in the SMA. Hence, whereas, the cylindrical and lamellar microdomains of SMA composed of a P4VP-b-PS-b-P4VP triblock copolymer were perpendicular to the substrate, those composed from a PS-b-P4VP diblock of similar composition had in-plane orientation of the microdomains.

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

    Directory of Open Access Journals (Sweden)


    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.

  9. Relationship between the affinity of PEO-PPO-PEO block copolymers for biological membranes and their cellular effects. (United States)

    Redhead, Martin; Mantovani, Giuseppe; Nawaz, Selina; Carbone, Paola; Gorecki, Dariusz C; Alexander, Cameron; Bosquillon, Cynthia


    The interactions of poly(ethylene oxide)-co-poly(propylene oxide) tri-block copolymers (PEO-PPO-PEO block copolymers, Pluronics®, Synperonics®, Poloxamers) of differing chemical composition with cell membranes were systematically investigated in order to clarify the mechanisms behind their previously reported various cellular responses. Relationships between the structural components of a defined series of PEO-PPO-PEO block copolymers and i) their interactions with biological membranes; ii) their cytotoxic potential were probed using a combination of haemolysis studies and cytotoxicity assays in the Caco-2 and HMEC-1 cell lines. The length of the PPO block as well as the PEO/PPO ratio were determinants of their membrane binding constant and cytotoxicity endpoints measured in the MTS and LDH assays. Similar 2D parabolic relationships were found between polymer composition and their affinity for membranes or their cytotoxicity potential. Cytotoxicity was related to the ability of the copolymers to form ion transversable pores within the cell membrane. The data suggest a link between the affinity of certain Pluronics for biological membranes and their cellular adverse effects. This first cell-based investigation of the interactions of Pluronics with biological membranes is an important step towards unravelling the complex mechanisms which govern the biological effects of widely used amphiphilic materials.

  10. 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


    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.

  11. The effect of a personalized ventilation system on perceived air quality and SBS symptoms

    DEFF Research Database (Denmark)

    Kaczmarczyk, Jan; Zeng, Q.; Melikov, Arsen Krikor


    Perceived air quality, SBS symptoms and performance were studied with 30 human subjects. Experiments were performed in an office set-up with six workplaces, each equipped with a Personalized Ventilation System (PVS). Each PVS allowed the amount of supply air and its direction to be controlled....... Subjects participated in four experiments: (1) PVS supplying outdoor air at 20 deg.C; (2) PVS supplying outdoor air at 23 deg.C; (3) PVS supplying recirculated room air; and (4) mixing ventilation. Room temperature was kept constant at 23 deg.C and relative humidity at 30%. Results showed that the best...

  12. Water soluble poly(styrene sulfonate)-b-poly(vinylidene fluoride)-b-poly(styrene sulfonate) triblock copolymer nanoparticles

    Czech Academy of Sciences Publication Activity Database

    Černoch, Peter; Černochová, Zulfiya; Petrova, Svetlana; Kaňková, Dana; Kim, J.-S.; Vasu, V.; Asandei, A. D.


    Roč. 6, č. 60 (2016), s. 55374-55381 ISSN 2046-2069 R&D Projects: GA MŠk(CZ) LH14038 Institutional support: RVO:61389013 Keywords : polystyrenesulfonate * poly(neopentyl styrenesulfonate) * PVDF Subject RIV: CD - Macromolecular Chemistry Impact factor: 3.108, year: 2016

  13. De Novo Synthesis of Phosphorylated Triblock Copolymers with Pathogen Virulence-Suppressing Properties That Prevent Infection-Related Mortality

    Energy Technology Data Exchange (ETDEWEB)

    Mao, Jun; Zaborin, Alexander; Poroyko, Valeriy; Goldfeld, David; Lynd, Nathaniel A. [McKetta; Chen, Wei [Institute; Tirrell, Matthew V. [Institute; Zaborina, Olga; Alverdy, John C.


    Phosphate is a key and universal "cue" in response to which bacteria either enhance their virulence when local phosphate is scarce or downregulate it when phosphate is adundant. Phosphate becomes depleted in the mammalian gut following physiologic stress and serves as a major trigger for colonizing bacteria to express virulence. This process cannot be reversed with oral supplementation of inorganic phosphate because it is nearly completely absorbed in the proximal small intestine. In the present study, we describe the de novo synthesis of phosphorylated polyethylene glycol compounds with three defined ABA (hydrophilic/-phobic/-philic) structures, ABA-PEG10k-Pi10, ABA-PEG16k-Pi14, and ABA-PEG20k-Pi20, and linear polymer PEG20k-Pi20 absent of the hydrophobic block. The 10k, 16k, and 20k demonstrate the molecular weights of the poly(ethylene glycol) block, and Pi10, Pi14, and Pi20 represent the repeating units of phosphate. Polymers were tested for their efficacy against Pseudomonas aeruginosa virulence in vitro and in vivo by assessing the expression of the phosphate sensing protein PstS, the production of key virulence factor pyocyanin, and Caenorhabditis elegans killing assays. Results indicate that all phosphorylated polymers suppressed phosphate sensing, virulence expression, and lethality in P. aeruginosa. Among all of the phosphorylated polymers, ABA-PEG20kPi20 displayed the greatest degree of protection against P. aeruginosa. To define the role of the hydrophobic core in ABA-PEG20k-Pi20 in the above response, we synthesized PEG20k-Pi20 in which the hydrophobic core is absent. Results indicate that the hypdrophobic core of ABA-PEG20k-Pi20 is a key structure in its protective effect against P. aeruginosa, in part due to its ability to coat the surface of bacteria. Taken together, the synthesis of novel polymers with defined structures and levels of phosphorylation may elucidate their antivirulence action against clinically important and lethal pathogens such as P. aeruginosa

  14. Transport Properties of Sulfonated Poly (Styrene-b-isobutylene-b-styrene) Triblock Copolymers at High Ion-Exchange Capacities

    National Research Council Canada - National Science Library

    Winey, Karen I; Elabd, Yossef A; Napadensky, Eugene; Walker, Charles W


    ... (IEC), specifically at high IECs (up to -2 mequiv/g). The proton conductivity of S-SIBS was -1 order of magnitude higher than sulfonated polystyrene at similar IECs and 3-fold higher than Nafion 117 at an IEC of 2 mequiv/g...

  15. Block copolymer investigations (United States)

    Yufa, Nataliya A.

    The research presented in this thesis deals with various aspects of block copolymers on the nanoscale: their behavior at a range of temperatures, their use as scaffolds, or for creation of chemically striped surfaces, as well as the behavior of metals on block copolymers under the influence of UV light, and the healing behavior of copolymers. Invented around the time of World War II, copolymers have been used for decades due to their macroscopic properties, such as their ability to be molded without vulcanization, and the fact that, unlike rubber, they can be recycled. In recent years, block copolymers (BCPs) have been used for lithography, as scaffolds for nano-objects, to create a magnetic hard drive, as well as in photonic and other applications. In this work we used primarily atomic force microscopy (AFM) and transmission electron microscopy (TEM), described in Chapter II, to conduct our studies. In Chapter III we demonstrate a new and general method for positioning nanoparticles within nanoscale grooves. This technique is suitable for nanodots, nanocrystals, as well as DNA. We use AFM and TEM to demonstrate selective decoration. In Chapters IV and V we use AFM and TEM to study the structure of polymer surfaces coated with metals and self-assembled monolayers. We describe how the surfaces were created, exhibit their structure on the nanoscale, and prove that their macroscopic wetting properties have been altered compared to the original polymer structures. Finally, Chapters VI and VII report out in-situ AFM studies of BCP at high temperatures, made possible only recently with the invention of air-tight high-temperature AFM imaging cells. We locate the transition between disordered films and cylinders during initial ordering. Fluctuations of existing domains leading to domain coarsening are also described, and are shown to be consistent with reptation and curvature minimization. Chapter VII deals with the healing of PS-b-PMMA following AFM-tip lithography or

  16. Dynamics of entangled rod-coil block copolymers (United States)

    Wang, Muzhou; Timachova, Ksenia; Alexander-Katz, Alfredo; Likhtman, Alexei E.; Olsen, Bradley D.


    Polymer science is exploring advanced materials which combine functional domains such as proteins and semiconducting polymers with traditional flexible polymers onto the same molecule. While many studies have focused on equilibrium structure-property relationships, little is known about how the conformational restrictions of rigid domains affect dynamical phenomena such as mechanical properties, processing pathways, and self-assembly kinetics. We have recently introduced a reptation theory for entangled rod-coil block copolymers as a model for this wider class of functional polymeric materials. The theory hypothesizes that the motion of rod-coils is slowed relative to rod and coil homopolymers because of a mismatch between the curvature of the rod and coil entanglement tubes. This effect leads to activated reptation and arm retraction as two relaxation mechanisms that govern the short and long rod regimes, respectively. These results were verified by tracer diffusion measurements using molecular dynamics simulation and forced Rayleigh scattering in both the rod-coil diblock and coil-rod-coil triblock configurations. The tracer diffusion results were then compared to experimental self-diffusion measurements which require a consideration of the motion of the surrounding chains.

  17. Dynamics of Chain Exchange in Block Copolymer Micelles (United States)

    Lodge, Timothy

    Block copolymer micelles are rarely at equilibrium. The primary reason is the large number of repeat units in the insoluble block, Ncore, which makes the thermodynamic penalty for extracting a single chain (``unimer exchange'') substantial. As a consequence, the critical micelle concentration (CMC) is rarely accessed experimentally; however, in the proximity of a critical micelle temperature (CMT), equilibration is possible. We have been using time-resolved small angle neutron scattering (TR-SANS) to obtain a detailed picture of the mechanisms and time scales for chain exchange, at or near equilibrium. Our model system is poly(styrene)-block-poly(ethylene-alt-propylene)) (PS-PEP), in the PEP-selective solvent squalane (C30H62) . Equivalent micelles with either normal (hPS) or perdeuterated (dPS) cores are initially mixed in a blend of isotopically substituted squalane, designed to contrast-match a 50:50 hPS:dPS core. Samples are then annealed at a target temperature, and chain exchange is revealed quantitatively by the temporal decay in scattered intensity. The rate of exchange as function of concentration, temperature, Ncore, Ncorona, and chain architecture (diblock versus triblock) will be discussed.

  18. Perceived air quality, thermal comfort, and SBS symptoms at low air temperature and increased radiant temperature

    DEFF Research Database (Denmark)

    Toftum, Jørn; Reimann, Gregers Peter; Foldbjerg, P.


    This study investigated if low air temperature, which is known to improve the perception of air quality, also can reduce the intensity of some SBS symptoms. In a low-polluting office, human subjects were exposed to air at two temperatures 23 deg.C and 18 deg.C both with and without a pollution so.......C suggested an improvement of the perceived air quality, while no systematic effect on symptom intensity was observed. The overall indoor environment was evaluated equally acceptable at both temperatures due to local thermal discomfort at the low air temperature.......This study investigated if low air temperature, which is known to improve the perception of air quality, also can reduce the intensity of some SBS symptoms. In a low-polluting office, human subjects were exposed to air at two temperatures 23 deg.C and 18 deg.C both with and without a pollution...... source present at the low temperature. To maintain overall thermal neutrality, the low air temperature was partly compensated for by individually controlled radiant heating, and partly by allowing subjects to modify clothing insulation. A reduction of the air temperature from 23 deg.C to 18 deg...

  19. Orbit and attitude determination results during launch support operations for SBS-5 (United States)

    Hartman, K. R.; Iano, P. J.


    Presented are orbit and attitude determination results from the launch of Satellite Business Systems (SBS)-5 satellite on September 8, 1988 by Arianespace. SBS-5 is a (HS-376) spin stabilized spacecraft. The launch vehicle injected the spacecraft into a low inclination transfer orbit. Apogee motor firing (AMF) attitude was achieved with trim maneuvers. An apogee kick motor placed the spacecraft into drift orbit. Postburn, reorientation and spindown maneuvers were performed during the next 25 hours. The spacecraft was on-station 19 days later. The orbit and attitude were determined by both an extended Kalman filter and a weighted least squares batch processor. Although the orbit inclination was low and the launch was near equinox, post-AMF analysis indicated an attitude declination error of 0.034 deg., resulting in a saving of 8.5 pounds of fuel. The AMF velocity error was 0.4 percent below nominal. The post-AMF drift rate was determined with the filter only 2.5 hours after motor firing. The filter was used to monitor and retarget the reorientation to orbit normal in real time.

  20. Qualitative analysis of SBS modifier in asphalt pavements using field samples (United States)

    Chi, Fengxia; Liu, Zhifei


    Series of tests are implemented to analysis the related characteristics of common asphalt and unknown asphalt mainly using Fourier Transform Infrared (FTIR) and Dynamic Shear Rheometer (DSR) for chemical compositions and rheological properties of asphalt, respectively. In addition, a series of mechanical properties were performed on asphalt mixtures, including indirect tensile strength test and three point bending test at low temperature. Experimental results indicated that compared with common asphalt, the characteristic absorption peak of the unknown asphalt are appeared at 966cm-1and 699cm-1, which are accordant with the SBS modifier. The results of DSR indicated that the unknown asphalt’s complex modulus is higher and the phase angle is lower. The mechanical tests indicated that some properties of the unknown mixture samples are increased by 24.7%∼41.8% compared with common pavement sample, like the indirect tensile strength, the bending test at low temperature and indirect tensile resilient modulus. Comprehensive analysis indicates that SBS modifier is existed in the unknown asphalt pavement.

  1. Elimination of the reactivation process in the adhesion of chlorinated SBS rubber with polychloroprene adhesives

    Directory of Open Access Journals (Sweden)


    Full Text Available Chlorination treatment of a thermoplastic styrene-butadiene-styrene rubber (SBS with a 3 wt% solution of trichloroisocyanuric acid (TCI in methyl ethyl ketone (MEK introduces chlorinated and oxidized moieties on the rubber surface which increase its surface energy and produces surface microroughness. Consequently adhesion properties, evaluated by T-peel strength measurements in chlorinated SBS/solvent based-polyurethane adhesive/leather joints, are enhanced. In this study, two solvent-based polychloroprene adhesives (PCP0 and PCP30R have been considered as an alternative to the commonly used solvent-based polyurethane adhesive (PU. A thermoreactive phenolic resin was added to one of the polychloroprene adhesive formulations (PCP30R. This tackifier resin favors chlorination of the adhesive and reinforces the interface between the chlorinated adhesive and the chlorinated rubber surface. Besides, PCP30R adhesive does not need adhesive reactivation and considerable high T-peel strength value (5.7±0.3 kN/m was obtained. Elimination of the reactivation process implies a considerable improvement of the manufacturing process in the footwear industry.

  2. 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


    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.

  3. Large size GEM for Super Bigbite Spectrometer (SBS) polarimeter for Hall A 12 GeV program at JLab (United States)

    Gnanvo, Kondo; Liyanage, Nilanga; Nelyubin, Vladimir; Saenboonruang, Kiadtisak; Sacher, Seth; Wojtsekhowski, Bogdan


    We report on the R&D effort in the design and construction of a large size Gas Electron Multiplier (GEM) for the Proton Polarimeter Back Tracker (BT) of the Super Bigbite Spectrometer (SBS) in Hall A at Thomas Jefferson National Laboratory (JLab). The SBS BT GEM trackers consist of two sets of five large GEM chambers of size 60×200 cm2. The GEM chamber is a vertical stack of four GEM modules, each with an active area of 60×50 cm2. We have built and tested several prototypes and the construction of GEM modules for SBS BT is ongoing. We describe in this paper the design and construction of the GEM module prototype as well as the preliminary results on performance from tests carried out in our detector lab and during test beam at Fermi National Laboratory (Fermilab).

  4. Large size GEM for Super Bigbite Spectrometer (SBS) polarimeter for Hall A 12 GeV program at JLab

    Energy Technology Data Exchange (ETDEWEB)

    Gnanvo, Kondo, E-mail: [University of Virginia, Department of Physics, Charlottesville, VA 22904 (United States); Liyanage, Nilanga; Nelyubin, Vladimir; Saenboonruang, Kiadtisak; Sacher, Seth [University of Virginia, Department of Physics, Charlottesville, VA 22904 (United States); Wojtsekhowski, Bogdan [Thomas Jefferson National Accelerator Facility, Newport News, VA 23606 (United States)


    We report on the R&D effort in the design and construction of a large size Gas Electron Multiplier (GEM) for the Proton Polarimeter Back Tracker (BT) of the Super Bigbite Spectrometer (SBS) in Hall A at Thomas Jefferson National Laboratory (JLab). The SBS BT GEM trackers consist of two sets of five large GEM chambers of size 60×200 cm{sup 2}. The GEM chamber is a vertical stack of four GEM modules, each with an active area of 60×50 cm{sup 2}. We have built and tested several prototypes and the construction of GEM modules for SBS BT is ongoing. We describe in this paper the design and construction of the GEM module prototype as well as the preliminary results on performance from tests carried out in our detector lab and during test beam at Fermi National Laboratory (Fermilab)

  5. Evaluation of triblock copolymeric micelles of δ- valerolactone and poly (ethylene glycol as a competent vector for doxorubicin delivery against cancer

    Directory of Open Access Journals (Sweden)

    Kumar G S Vinod


    Full Text Available Abstract Background Specific properties of amphiphilic copolymeric micelles like small size, stability, biodegradability and prolonged biodistribution have projected them as promising vectors for drug delivery. To evaluate the potential of δ-valerolactone based micelles as carriers for drug delivery, a novel triblock amphiphilic copolymer poly(δ-valerolactone/poly(ethylene glycol/poly(δ-valerolactone (VEV was synthesized and characterized using IR, NMR, GPC, DTA and TGA. To evaluate VEV as a carrier for drug delivery, doxorubicin (DOX entrapped VEV micelles (VEVDMs were prepared and analyzed for in vitro antitumor activity. Results VEV copolymer was successfully synthesized by ring opening polymerization and the stable core shell structure of VEV micelles with a low critical micelle concentration was confirmed by proton NMR and fluorescence based method. Doxorubicin entrapped micelles (VEVDMs prepared using a modified single emulsion method were obtained with a mean diameter of 90 nm and high encapsulation efficiency showing a pH dependent sustained doxorubicin release. Biological evaluation in breast adenocarcinoma (MCF7 and glioblastoma (U87MG cells by flow cytometry showed 2-3 folds increase in cellular uptake of VEVDMs than free DOX. Block copolymer micelles without DOX were non cytotoxic in both the cell lines. As evaluated by the IC50 values VEVDMs induced 77.8, 71.2, 81.2% more cytotoxicity in MCF7 cells and 40.8, 72.6, 76% more cytotoxicity in U87MG cells than pristine DOX after 24, 48, 72 h treatment, respectively. Moreover, VEVDMs induced enhanced apoptosis than free DOX as indicated by higher shift in Annexin V-FITC fluorescence and better intensity of cleaved PARP. Even though, further studies are required to prove the efficacy of this formulation in vivo the comparable G2/M phase arrest induced by VEVDMs at half the concentration of free DOX confirmed the better antitumor efficacy of VEVDMs in vitro. Conclusions Our studies

  6. Thermodynamics of coil-hyperbranched poly(styrene-b-acrylated epoxidized soybean oil) block copolymers (United States)

    Lin, Fang-Yi; Hohmann, Austin; Hernández, Nacú; Cochran, Eric

    Here we present the phase behavior of a new type of coil-hyperbranched diblock copolymer: poly(styrene- b-acrylated epoxidized soybean oil), or PS-PAESO. PS-PAESO is an example of a biorenewable thermoplastic elastomer (bio-TPE). To date, we have shown that bio-TPEs can be economical commercial substitutes for their petrochemically derived analogues--such as poly(styrene- b-butadiene- b-styrene) (SBS)--in a range of applications including pressure sensitive adhesives and bitumen modification. From a polymer physics perspective, PS-PAESO is an interesting material in that it couples a linear coil-like block with a highly branched block. Thus in contrast to the past five decades of studies on linear AB diblock copolymers, coil-hyperbranched block copolymers are relatively unknown to the community and can be expected to deviate substantially from the standard ``universal'' phase behavior in the AB systems. To explore these new materials, we have constructed a library of PS-PAESO materials spanning a range of molecular weight and composition values. The phase transition behavior and the morphology information will be interpreted by isochronal temperature scanning in dynamic shear rheology, small angle X-ray scattering and the corresponding transmission electron microscopy.

  7. Synthesis of ABCBA penta stereoblock polylactide copolymers by two-step ring-opening polymerization of L- and D-lactides with poly(3-methyl-1,5-pentylene succinate) as macroinitiator (C): development of flexible stereocomplexed polylactide materials. (United States)

    Hirata, Masayuki; Masutani, Kazunari; Kimura, Yoshiharu


    BCB triblock copolymers consisting of poly-L-lactide (PLLA: B) and poly(3-methy-1,5-pentylene succinate) (SA/MPD: C) were first synthesized by ring-opening polymerization (ROP) of L-lactide by using a dihydroxyl-terminated SA/MPD (Mn≈20k) and tin octoate as the macroinitiator and catalyst, respectively. The telechelic dihydroxyl-terminated SA/MPD was readily synthesized by the controlled melt-polycondensation of succinic acid and 3-methyl-1,5-pentandiol (MPD). The resultant triblock copolymers, dihydroxyl-terminated, were subsequently utilized as the macroinitiators in the second-step ROP of D-lactide to obtain ABCBA penta-block copolymers (penta-sb-PLA) consisting of poly-D-lactide (PDLA), PLLA, and SA/MPD as the A, B, and C blocks, respectively. The weight-average molecular weights of the resultant penta-sb-PLAs became higher than 150 kDa. The cast films of these penta-sb-PLAs exhibited flexible nature due to the presence of the SA/MPD soft block as well as excellent heat-stability owing to the easy stereocomplex formation of the neighboring enantiomeric PLLA and PDLA blocks.

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

    KAUST Repository

    Polymeropoulos, George


    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.

  9. Human Perception, SBS Sympsoms and Performance of Office Work during Exposure to Air Polluted by Building Materials and Personal Computers

    DEFF Research Database (Denmark)

    Bako-Biro, Zsolt

    The present thesis deals with the impact of polluted air from building materials and personal computers on human perception, Sick Building Syndrome (SBS) symptoms and performance of office work. These effects have been studies in a series of experiments that are described in two different chapters...

  10. Sick building syndrome (SBS) and sick house syndrome (SHS) in relation to psychosocial stress at work in the Swedish workforce. (United States)

    Runeson-Broberg, Roma; Norbäck, Dan


    Medical symptoms called sick building syndrome (SBS) and sick house syndrome (SHS) are usually investigated separately: in this study, SBS and SHS were explored simultaneously. The significance of personal factors, perceptions of air quality, and psychosocial work situation in explaining SBS and SHS were investigated. A random sample of 1,000 subjects (20-65 year) received a postal questionnaire including questions on personal factors, medical symptoms, and the psychosocial demand-control-support model. The response rate was 70 % (n = 695), of which 532 were occupationally active. In logistic regression models, atopy, poor air quality at work, and low social support, especially low supervisor support, were associated with both SBS and SHS when age, gender, smoking, and BMI were introduced. The general work-related symptoms (headache, tiredness, nausea, and sensation of a cold) were also related to low control over work. The perception of poor physical environmental conditions is associated with common medical symptoms that are both work and home related. The associations between medical symptoms and poor air quality are still present, even when controlling for the psychosocial environment.

  11. 293 W, GHz narrow-linewidth, polarization maintaining nanosecond fiber amplifier with SBS suppression employing simultaneous phase and intensity modulation. (United States)

    Ran, Yang; Su, Rongtao; Ma, Pengfei; Wang, Xiaolin; Lv, Haibin; Zhou, Pu; Si, Lei


    We present a new method of SBS suppression in fiber amplifier system by employing simultaneously phase and intensity modulation. In this way, a GHz narrow-linewidth polarization-maintaining (PM) all-fiber pulsed laser is obtained based on a master oscillator power amplifier (MOPA) configuration. The pulsed seed is generated from a single-frequency continuous wave (CW) laser at 1064 nm by simultaneous modulation using an electro-optic intensity modulator (EOIM) and an electro-optic phase modulator (EOPM). Theoretical model is built and simulation framework has been established to estimate the SBS threshold of the pulsed amplifier system before and after modulation. In experiment, in order to suppress SBS effectively, the pulse width is set to be 4 ns and the phase modulation voltage is set to be 5 V. After amplifying by the amplifier chain, a ~3.5 ns pulsed laser with average/peak power of 293 W/3.9 kW is obtained at intensity repetition rate of 20 MHz and phase repetition rate of 100MHz, showing good agreement with simulation results. The linewidth of the output laser is ~4.5 GHz, the M(2) factor at maximal output power is measured to be ~1.1 and the slope efficiency is ~86%.This method provides some references to suppress the SBS in narrow linewidth pulsed amplifier systems.

  12. Bitumen nanocomposites with improved performance

    KAUST Repository

    Kosma, Vasiliki


    Bitumen-clay nanocomposite binders with styrene-butadienestyrene triblock copolymer, SBS, and combinations of SBS and crumb rubber (CR) with different CR/SBS ratios have been synthesized and characterized. In addition to the binder, samples containing the binder and concrete sand (with a weight ratio 1:9) were prepared. The modified binders were studied in terms of filler dispersion, storage stability, mechanical performance and water susceptibility. We demonstrate that the samples containing nanoclays consistently outperform those based only on the polymer additives. We also find that nanocomposite samples based on a combination of SBS and CR are best, since in addition to other improvements they show excellent storage stability. Our work shows that substituting CR with SBS as a bitumen additive and combining it with inexpensive nanoclays leads to new materials with enhanced performance and improved stability for practical asphalt applications.

  13. Interactions between bovine serum albumin and Langmuir films composed of charged and uncharged poly(N-isopropylacrylamide) block copolymers. (United States)

    Volden, Sondre; Ese, Marit-Helen G; Zhu, Kaizheng; Yasuda, Masahiro; Nyström, Bo; Glomm, Wilhelm R


    The thermoresponsive poly(N-isopropylacrylamide) (PNIPAAM) and NIPAAM block copolymer derivatives are attractive for drug delivery applications as they contract reversibly at lower critical solution temperatures (LCST) close to physiological conditions. In order to investigate biomaterial-protein compatibility, we have studied the interaction between PNIPAAM copolymer films spread at the air-water surface and bovine serum albumin (BSA) injected below the precompressed polymer films, using the Langmuir technique coupled with Brewster angle microscopy (BAM). A PNIPAAM homopolymer was applied together with a number of PNIPAAM-based di- and triblock copolymers, to assess effects of e.g., charge and hydrophobicity on protein-polymer interactions. The nature and strength of protein-polymer interaction was found to be tunable, ranging from complex formation (PNIPAAM homopolymer) to mixed monolayers and electrostatic cross-linking, according to the nature of the co-monomer. Results show that intercalation versus adsorption can be controlled through polymer composition. Copyright © 2012 Elsevier B.V. All rights reserved.

  14. The self-assembly mechanism of fibril-forming silk-based block copolymers. (United States)

    Schor, Marieke; Bolhuis, Peter G


    Triblock copolymers consisting of a silk-based ((Gly-Ala)(3)Gly-Glu) repeat flanked by hydrophilic outer blocks self-assemble into micrometer long fibrils in response to a trigger. Since the exact mechanism of the fibril formation remains unclear, we employ a multiscale modelling approach in combination with rare event simulations to elucidate key processes. Atomistic scale simulations on the silk-based block suggest a mechanism in which a polypeptide prefolded into a β-roll structure docks to the growing end of a fibril through the formation of Glu-Glu sidechain contacts. Subsequently it can slide to the optimal position before water is expelled to form a dry interface between the fibril end and the attaching block copolymer. In addition, we find that the folded state of the silk-based block is further stabilised through interactions with its neighboring block. Templated folding may also play a role in case a partially folded polypeptide attaches. The coarse-grained simulations indicate that the attachment and subsequent sliding is mediated by the hydrophilic flanks in a size dependent manner. The hydrophilic blocks prevent random aggregation and allow growth only at the end of the fibril. Our multiscale approach may be used for other fibril-forming peptides. This journal is © the Owner Societies 2011

  15. Polydispersity-Driven Block Copolymer Amphiphile Self-Assembly into Prolate-Spheroid Micelles

    Energy Technology Data Exchange (ETDEWEB)

    Schmitt, Andrew L.; Repollet-Pedrosa, Milton H.; Mahanthappa, Mahesh K. (UW)


    The aqueous self-assembly behavior of polydisperse poly(ethylene oxide-b-1,4-butadiene-b-ethylene oxide) (OBO) macromolecular triblock amphiphiles is examined to discern the implications of continuous polydispersity in the hydrophobic block on the resulting aqueous micellar morphologies of otherwise monodisperse polymer surfactants. The chain length polydispersity and implicit composition polydispersity of these samples furnishes a distribution of preferred interfacial curvatures, resulting in dilute aqueous block copolymer dispersions exhibiting coexisting spherical and rod-like micelles with vesicles in a single sample with a O weight fraction, w{sub O}, of 0.18. At higher w{sub O} = 0.51-0.68, the peak in the interfacial curvature distribution shifts and we observe the formation of only American football-shaped micelles. We rationalize the formation of these anisotropically shaped aggregates based on the intrinsic distribution of preferred curvatures adopted by the polydisperse copolymer amphiphiles and on the relief of core block chain stretching by chain-length-dependent intramicellar segregation.

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

    KAUST Repository

    Moreno Chaparro, Nicolas


    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.

  17. Improved slow-light performance of 10 Gb/s NRZ, PSBT and DPSK signals in fiber broadband SBS. (United States)

    Yi, Lilin; Jaouen, Yves; Hu, Weisheng; Su, Yikai; Bigo, Sébastien


    We have demonstrated error-free operations of slow-light via stimulated Brillouin scattering (SBS) in optical fiber for 10-Gb/s signals with different modulation formats, including non-return-to-zero (NRZ), phase-shaped binary transmission (PSBT) and differential phase-shiftkeying (DPSK). The SBS gain bandwidth is broadened by using current noise modulation of the pump laser diode. The gain shape is simply controlled by the noise density function. Super-Gaussian noise modulation of the Brillouin pump allows a flat-top and sharp-edge SBS gain spectrum, which can reduce slow-light induced distortion in case of 10-Gb/s NRZ signal. The corresponding maximal delay-time with error-free operation is 35 ps. Then we propose the PSBT format to minimize distortions resulting from SBS filtering effect and dispersion accompanied with slow light because of its high spectral efficiency and strong dispersion tolerance. The sensitivity of the 10-Gb/s PSBT signal is 5.2 dB better than the NRZ case with a same 35-ps delay. The maximal delay of 51 ps with error-free operation has been achieved. Futhermore, the DPSK format is directly demodulated through a Gaussian-shaped SBS gain, which is achieved using Gaussian-noise modulation of the Brillouin pump. The maximal error-free time delay after demodulation of a 10-Gb/s DPSK signal is as high as 81.5 ps, which is the best demonstrated result for 10-Gb/s slow-light.

  18. Effect of chain length of PEO on the gelation and micellization of the pluronic F127 copolymer aqueous system. (United States)

    Pragatheeswaran, Abhinav Maheswaran; Chen, Shing Bor


    The effect of adding homopolymer poly(ethylene oxide) (PEO) on the sol/gel behavior of amphiphilic triblock copolymer Pluronic F127 ((EO)98(PO)67(EO)98) in aqueous media is explored. Emphasis is placed on the influence of the PEO molecular weight and concentration on micellization and gelation and the exploration of their correlation. PEO is always found to lower the critical micellization temperature modestly. However, short PEO chains promote the gelation of F127, and long chains delay or even curb gel formation. Micelle size measurements and cryo-TEM micrographs provide evidence for micellar aggregation via the bridging of long PEO chains or depletion flocculation, thereby impeding the ordering of micelles for gel formation.

  19. Expression and cytosolic assembly of the S-layer fusion protein mSbsC-EGFP in eukaryotic cells

    Directory of Open Access Journals (Sweden)

    Veenhuis Marten


    Full Text Available Abstract Background Native as well as recombinant bacterial cell surface layer (S-layer protein of Geobacillus (G. stearothermophilus ATCC 12980 assembles to supramolecular structures with an oblique symmetry. Upon expression in E. coli, S-layer self assembly products are formed in the cytosol. We tested the expression and assembly of a fusion protein, consisting of the mature part (aa 31–1099 of the S-layer protein and EGFP (enhanced green fluorescent protein, in eukaryotic host cells, the yeast Saccharomyces cerevisiae and human HeLa cells. Results Upon expression in E. coli the recombinant mSbsC-EGFP fusion protein was recovered from the insoluble fraction. After denaturation by Guanidine (Gua-HCl treatment and subsequent dialysis the fusion protein assembled in solution and yielded green fluorescent cylindric structures with regular symmetry comparable to that of the authentic SbsC. For expression in the eukaryotic host Saccharomyces (S. cerevisiae mSbsC-EGFP was cloned in a multi-copy expression vector bearing the strong constitutive GPD1 (glyceraldehyde-3-phosophate-dehydrogenase promoter. The respective yeast transfomants were only slightly impaired in growth and exhibited a needle-like green fluorescent pattern. Transmission electron microscopy (TEM studies revealed the presence of closely packed cylindrical structures in the cytosol with regular symmetry comparable to those obtained after in vitro recrystallization. Similar structures are observed in HeLa cells expressing mSbsC-EGFP from the Cytomegalovirus (CMV IE promoter. Conclusion The mSbsC-EGFP fusion protein is stably expressed both in the yeast, Saccharomyces cerevisiae, and in HeLa cells. Recombinant mSbsC-EGFP combines properties of both fusion partners: it assembles both in vitro and in vivo to cylindrical structures that show an intensive green fluorescence. Fusion of proteins to S-layer proteins may be a useful tool for high level expression in yeast and HeLa cells of

  20. 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.


    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.

  1. Detection of Amitraz Resistance in Rhipicephalus (Boophilus) microplus from SBS Nagar, Punjab, India (United States)

    Singh, N. K.; Jyoti; Rath, S. S.


    The resistance status of Rhipicephalus (Boophilus) microplus collected from SBS Nagar, Punjab, was evaluated against amitraz by Adult Immersion Test (AIT). The regression graph of probit mortality of ticks plotted against log values of progressively increasing concentrations of amitraz revealed the slope of mortality (95% CI) as 2.36 ± 0.61 (0.38 to 4.33). The LC50 (95% CI) and LC95 (95% CI) values were recorded as 332.52 ppm (305.06–362.44) and 1646.93 ppm (1383.97–1959.84), respectively, and the resistance factor (RF) was 13.17 which indicated level II resistance status. The dose response curves for egg mass weight, reproductive index, and percentage inhibition of oviposition were also validated by AIT and the slopes (95% CI) were −7.17 ± 2.41 (−14.85 to 0.50), −0.009 ± 0.02 (−0.16 to −0.031), and 19.99 ± 4.77 (4.81 to 35.17), respectively. The current study reports the development of resistance in R. (B.) microplus to amitraz from Punjab state and the data generated would be useful in formulation of effective control strategies against ticks of this region. PMID:24683347

  2. Composites copolymer-nanoparticule : courbure (United States)

    Hamdoun, B.; Ausserré, D.; Joly, S.


    The compression coefficient and the mean curvature coefficient of a composite of an A-B diblock copolymer charged with nanoparticles depend on the concentration of nanoparticles and on the dissymmetry of the copolymer chains. Concerning the curvature coefficient, a distinction must be done between an adiabatic and an isotherm coefficient when the copolymer chains are not symmetric or when Φ is not zero. Finally, the AB interfaces of the composite film present a spontaneous curvature that we calculate in the approximation of “small” nanoparticles. Les coefficients de compression et de courbure moyenne d'un composite de copolymères diblocs A-B et de nanoparticules dépendent de la concentration Φ en nanoparticules et de la dissymétrie du copolymères. Pour la courbure, on doit faire une distinction entre un coefficient adiabatique et un coefficient isotherme dès que le polymère n'est plus symétrique ou que Φ n'est plus nulle. Enfin, et surtout, les interfaces AB du composite présentent une courbure spontanée que nous calculons dans l'approximation des “petites” nanoparticules.

  3. Evaluating Welfare Effects of Rice Import Quota in Japan: Based on Measuring Non-Tariff Barriers of SBS Rice Imports

    Directory of Open Access Journals (Sweden)

    Qianhui Gao


    Full Text Available The principal objective of this study is to analyze welfare effects of Japan’s rice import quota focusing on the simultaneous buy and sell (SBS of the rice importation minimum access (MA policy. Based on the utility function specified in this study, the constructed model is adopted to measure consumption patterns through estimating elasticity of substitution between imported rice and Japan’s domestic rice, and consumers’ preference parameters for different kinds of rice. The results showed that Japanese households prefer domestic rice to the imported rice. Besides, three scenarios of adjusting rice quota volumes were carried out to examine the changes in consumer prices of imported rice and Japanese consumers’ welfares. The results revealed that tariff equivalents of the SBS import quota almost doubled the scale of the mark-up, and the intervention by the Ministry of Agriculture of Japan did cause non-tariff barriers to trade (NTBs. Finally, if the SBS rice quota quantity was fixed at or larger than 180 thousand tons every fiscal year, the consumer prices of imported rice in Japan’s market would decrease to be less than the prices of Japan’s domestic rice, and therefore the imported rice would have more price advantages in this scenario.

  4. Shape Memory Polymer Composites of Poly(styrene-b-butadiene-b-styrene Copolymer/Liner Low Density Polyethylene/Fe3O4 Nanoparticles for Remote Activation

    Directory of Open Access Journals (Sweden)

    Yongkun Wang


    Full Text Available Magnetically sensitive shape memory poly(styrene-b-butadiene-b-styrene copolymer (SBS/liner low density polyethylene (LLDPE composites filled with various contents of Fe3O4 nanoparticles were prepared. The influence of the Fe3O4 nanoparticles content on the thermal properties, mechanical properties, fracture morphology, magnetic behavior, and shape memory effect of SBS/LLDPE/Fe3O4 composites was systematically studied in this paper. The results indicated that homogeneously dispersed Fe3O4 nanoparticles ensured the uniform heat generation and transfer in the alternating magnetic field, and endowed the SBS/LLDPE/Fe3O4 composites with an excellent magnetically responsive shape memory effect. When the shape memory composites were in the alternating magnetic field (f = 60 kHz, H = 21.21 kA·m−1, the best shape recovery ratio reached 99%, the shape retention ratio reached 99.4%, and the shape recovery speed increased significantly with the increment of Fe3O4 nanoparticles. It is anticipated that tagging products with this novel shape memory composite is helpful for the purpose of an intravascular delivery system in Micro-Electro-Mechanical System (MEMS devices.

  5. Polyethylene-Based Tadpole Copolymers

    KAUST Repository

    Alkayal, Nazeeha


    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.

  6. Composites copolymer-nanoparticule : courbure


    Hamdoun, B.; Ausserré, D.; Joly, S.


    Les coefficients de compression et de courbure moyenne d'un composite de copolymères diblocs A-B et de nanoparticules dépendent de la concentration Φ en nanoparticules et de la dissymétrie du copolymères. Pour la courbure, on doit faire une distinction entre un coefficient adiabatique et un coefficient isotherme dès que le polymère n'est plus symétrique ou que Φ n'est plus nulle. Enfin, et surtout, les interfaces AB du composite présentent une courbure spontanée que nous calculons dans l'appr...

  7. Main-chain supramolecular block copolymers. (United States)

    Yang, Si Kyung; Ambade, Ashootosh V; Weck, Marcus


    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.

  8. A novel method for recovery of acidic sludge of used-motor oil reprocessing industries to bitumen using bentonite and SBS

    National Research Council Canada - National Science Library

    Ahmad Jonidi Jafari; malek hassanpour; Mitra Gholam; Mehdi Farzadkia


    .... The acidic sludge contains unsaturated compounds that are polar and asphaltene. The bitumen under certain conditions is produced from mixing of bentonite, polymer styrene – butadiene – styrene (SBS), and acidic sludge...

  9. Short bowel syndrome results in increased gene expression associated with proliferation, inflammation, bile acid synthesis and immune system activation: RNA sequencing a zebrafish SBS model. (United States)

    Schall, Kathy A; Thornton, Matthew E; Isani, Mubina; Holoyda, Kathleen A; Hou, Xiaogang; Lien, Ching-Ling; Grubbs, Brendan H; Grikscheit, Tracy C


    Much of the morbidity associated with short bowel syndrome (SBS) is attributed to effects of decreased enteral nutrition and administration of total parenteral nutrition (TPN). We hypothesized that acute SBS alone has significant effects on gene expression beyond epithelial proliferation, and tested this in a zebrafish SBS model. In a model of SBS in zebrafish (laparotomy, proximal stoma, distal ligation, n = 29) or sham (laparotomy alone, n = 28) surgery, RNA-Seq was performed after 2 weeks. The proximal intestine was harvested and RNA isolated. The three samples from each group with the highest amount of RNA were spiked with external RNA controls consortium (ERCC) controls, sequenced and aligned to reference genome with gene ontology (GO) enrichment analysis performed. Gene expression of ctnnb1, ccnb1, ccnd1, cyp7a1a, dkk3, ifng1-2, igf2a, il1b, lef1, nos2b, saa1, stat3, tnfa and wnt5a were confirmed to be elevated in SBS by RT-qPCR. RNA-seq analysis identified 1346 significantly upregulated genes and 678 significantly downregulated genes in SBS zebrafish intestine compared to sham with Ingenuity analysis. The upregulated genes were involved in cell proliferation, acute phase response signaling, innate and adaptive immunity, bile acid regulation, production of nitric oxide and reactive oxygen species, cellular barrier and coagulation. The downregulated genes were involved in folate synthesis, gluconeogenesis, glycogenolysis, fatty-acid oxidation and activation and drug and steroid metabolism. RT-qPCR confirmed gene expression differences from RNA-Sequencing. Changes of gene expression after 2 weeks of SBS indicate complex and extensive alterations of multiple pathways, some previously implicated as effects of TPN. The systemic sequelae of SBS alone are significant and indicate multiple targets for investigating future therapies.

  10. Influence of water-insoluble nonionic copolymer E(6)P(39)E(6) on the microstructure and self-aggregation dynamics of aqueous SDS solution-NMR and SANS investigations. (United States)

    Prameela, G K S; Phani Kumar, B V N; Aswal, V K; Mandal, Asit Baran


    The influence of water-insoluble nonionic triblock copolymer PEO-PPO-PEO [poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide)] i.e., E6P39E6 with molecular weight 2800, on the microstructure and self-aggregation dynamics of anionic surfactant sodium dodecylsulfate (SDS) in aqueous solution (D2O) were investigated using high resolution nuclear magnetic resonance (NMR) and small-angle neutron scattering (SANS) measurements. Variable concentration and temperature proton ((1)H), carbon ((13)C) NMR chemical shifts, (1)H self-diffusion coefficients, (1)H spin-lattice and spin-spin relaxation rates data indicate that the higher hydrophobic nature of copolymer significantly influenced aggregation characteristics of SDS. The salient features of the NMR investigations include (i) the onset of mixed micelles at lower SDS concentrations (SDS free micelles at higher SDS concentrations (~30 mM), (ii) disintegration of copolymer-SDS mixed aggregate at moderate SDS concentrations (~10 mM) and still binding of a copolymer with SDS and (iii) preferential localization of the copolymer occurred at the SDS micelle surface. SANS investigations indicate prolate ellipsoidal shaped mixed aggregates with an increase in SDS aggregation number, while a contrasting behavior in the copolymer aggregation is observed. The aggregation features of SDS and the copolymer, the sizes of mixed aggregates and the degree of counterion dissociation (α) extracted from SANS data analysis corroborate reasonably well with those of (1)H NMR self-diffusion and sodium ((23)Na) spin-lattice relaxation data.

  11. Micelles based on HPMA copolymers

    NARCIS (Netherlands)

    Talelli, M.; Rijcken, C.J.F.; Nostrum, C.F. van; Storm, G.; Hennink, W.E.

    Polymeric micelles have been under extensive investigation during the past years as drug delivery systems, particularly for anticancer drugs. They are formed by the self-assembly of amphiphilic block copolymers in aqueous solutions and have a spherical shape and a size in the nano-range (<200 nm).

  12. Impacts of Repeat Unit Structure and Copolymer Architecture on Thermal and Solution Properties in Homopolymers, Copolymers, and Copolymer Blends (United States)

    Marrou, Stephen Raye

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

  13. Non-fouling biomaterials based on blends of polyethylene oxide copolymers and polyurethane: simultaneous measurement of platelet adhesion and fibrinogen adsorption from flowing whole blood. (United States)

    Tan, J; McClung, W G; Brash, J L


    Measurements of platelet adhesion and fibrinogen adsorption from flowing whole blood to a series of polyethylene oxide (PEO)-based materials were carried out. A unique experimental design was used in which both quantities were measured in the same experiment. The materials consisted of a polyurethane (PU) as a matrix into which various triblock copolymers of general structure PEO-PU-PEO were blended; the PU block was the same in all materials but the PEO blocks ranged in molecular weight from 550 to 5000. Platelets were isolated from fresh human blood and labeled with (51)Cr; purified fibrinogen was labeled with (125)I. A whole blood preparation containing these labeled species was used for the adhesion/adsorption studies. The surfaces were exposed to the flowing blood in a cone and plate device at a wall shear rate of 300 s(-1). It was found that both platelet adhesion and fibrinogen adsorption decreased with increasing copolymer content in the blends and with decreasing PEO block size for a given copolymer content. The block size effect was due probably to higher PEO surface coverage for the lower molecular weight blocks. Fibrinogen adsorption and platelet adhesion were linearly and strongly correlated. The best performing materials showed very low fibrinogen adsorption of the order of 25 ng/cm(2), and correspondingly low platelet densities around 10,000 per cm(2), i.e. fractional platelet coverage in the vicinity of 0.2%.

  14. Strategies for Inorganic Incorporation using Neat Block Copolymer Thin Films for Etch Mask Function and Nanotechnological Application. (United States)

    Cummins, Cian; Ghoshal, Tandra; Holmes, Justin D; Morris, Michael A


    Block copolymers (BCPs) and their directed self-assembly (DSA) has emerged as a realizable complementary tool to aid optical patterning of device elements for future integrated circuit advancements. Methods to enhance BCP etch contrast for DSA application and further potential applications of inorganic nanomaterial features (e.g., semiconductor, dielectric, metal and metal oxide) are examined. Strategies to modify, infiltrate and controllably deposit inorganic materials by utilizing neat self-assembled BCP thin films open a rich design space to fabricate functional features in the nanoscale regime. An understanding and overview on innovative ways for the selective inclusion/infiltration or deposition of inorganic moieties in microphase separated BCP nanopatterns is provided. Early initial inclusion methods in the field and exciting contemporary reports to further augment etch contrast in BCPs for pattern transfer application are described. Specifically, the use of evaporation and sputtering methods, atomic layer deposition, sequential infiltration synthesis, metal-salt inclusion and aqueous metal reduction methodologies forming isolated nanofeatures are highlighted in di-BCP systems. Functionalities and newly reported uses for electronic and non-electronic technologies based on the inherent properties of incorporated inorganic nanostructures using di-BCP templates are highlighted. We outline the potential for extension of incorporation methods to triblock copolymer features for more diverse applications. Challenges and emerging areas of interest for inorganic infiltration of BCPs are also discussed. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Efeito da adição de material vegetal (fibra da castanha de cutia e polímero (SBS nas propriedades do ligante asfáltico (CAP 50/70 Effect of addition of plant material (fiber of cutia chesnut and polymer (SBS on the properties of asphalt binder (CAP 50/70

    Directory of Open Access Journals (Sweden)

    Tayana M. F. Cunha


    Full Text Available Tendo em vista a necessidade do mercado brasileiro por ligantes que minimizem a prematura falência estrutural dos revestimentos nas vias urbanas, a modificação do cimento asfáltico de petróleo (CAP 50/70 constitui uma excelente opção tecnológica. Nesta pesquisa utilizou-se 2% p/p do copolímero de estireno-butadieno-estireno (SBS e 2% p/p de fibra natural da casca dos frutos de Couepia edulis (Prance, conhecida como castanha de cutia, material vegetal com característica de reforço e biodisponibilidade na região Amazônica. Os efeitos oxidativos e térmicos, bem como as características físicas dos materiais asfálticos modificados, foram estudados e comparados ao ligante convencional, utilizando-se ensaios estabelecidos pela Agência Nacional de Petróleo, Gás Natural e Biocombustíveis (ANP e análise térmica - termogravimetria (TG, a fim de determinar as propriedades de degradação e estabilização térmica. Os resultados para os ligantes modificados, confrontados ao ligante tradicional, apresentaram: maior resistência ao envelhecimento, melhorias evidenciadas pelo aumento da consistência, ponto de amolecimento, além da excelente estabilidade térmica em toda faixa de temperatura de utilização (10 ºC a 80 ºC e aplicação (130 ºC a 170 ºC dos cimentos asfálticos de petróleo, fornecendo uma opção ao pavimento regional.There is a need in the Brazilian market for asphalt binders that minimize premature structural failure of the coatings on urban roads, and the modification of asphalt cement oil (CAP 50/70 is an excellent option. In this research we used 2% w/w of the styrene - butadiene-styrene (SBS copolymer and 2% w/w of natural fiber from Couepia edulis (Prance, known as cutia chesnut, which is a plant from the Amazon region with strengthening properties. The oxidative and thermal effects, as well as the physical characteristics of the asphalt modified materials, were studied and compared to the conventional binder

  16. Human Response to Ductless Personalized Ventilation with Local Air Cleaning: Air Quality and Prevalence of SBS Symptoms

    DEFF Research Database (Denmark)

    Dalewski, Mariusz; Bivolarova, Maria; Fillon, Maelys


    The impact of local air cleaning and cooling of the head region by ductless personalized ventilation (DPV) on perceived air quality (PAQ) and Sick Building Syndrome (SBS) symptoms was studied. Thirty subjects participated in experiments performed in a test room with displacement ventilation (DV...... with air filter and 29 °C with DPV without filter. During the experiments the subjects simulated office work and answered on computerized questionnaires. At warm environment PAQ and air freshness significantly improved when DPV was used. Eye dryness increased significantly with time but was not influenced...

  17. Linking experiment and theory for three-dimensional networked binary metal nanoparticle–triblock terpolymer superstructures

    KAUST Repository

    Li, Zihui


    © 2014 Macmillan Publishers Limited. Controlling superstructure of binary nanoparticle mixtures in three dimensions from self-assembly opens enormous opportunities for the design of materials with unique properties. Here we report on how the intimate coupling of synthesis, in-depth electron tomographic characterization and theory enables exquisite control of superstructure in highly ordered porous three-dimensional continuous networks from single and binary mixtures of metal nanoparticles with a triblock terpolymer. Poly(isoprene-block-styrene-block-(N,N-dimethylamino)ethyl methacrylate) is synthesized and used as structure-directing agent for ligand-stabilized platinum and gold nanoparticles. Quantitative analysis provides insights into short-and long-range nanoparticle-nanoparticle correlations, and local and global contributions to structural chirality in the networks. Results provide synthesis criteria for next-generation mesoporous network superstructures from binary nanoparticle mixtures for potential applications in areas including catalysis.

  18. Validação transcultural da Escala de Avaliação de Limitações no Comportamento Social - SBS-BR Transcultural validation of the Social Behaviour Schedule (SBS

    Directory of Open Access Journals (Sweden)

    Lúcia Abelha Lima


    Full Text Available Este trabalho apresenta os resultados referentes à validação da versão brasileira daSocial Behaviour Schedule - SBS, escala que avalia as limitações no comportamento social de pacientes psiquiátricos. O estudo de tradução e adaptação transcultural do instrumento foi realizado pelo Núcleo de Pesquisa do Instituto Municipal de Assistência à Saúde Juliano Moreira (IMASJM, RJ, e a coleta de dados foi feita nas Unidades Assistenciais do IMASJM. Análise das propriedades psicométricas da escala foi feita no Núcleo de Ensino e Saúde Coletiva (NESC da UFRJ. A Escala de Avaliação do Comportamento Social foi submetida a uma backtranslation, assim como a um estudo piloto sendo avaliada por uma comissão de especialistas, para que fosse feita sua adaptação ao nosso contexto. A SBS-BR mostrou-se uma escala com qualidades psicométricas de validade e fidedignidade satisfatórias, no que se refere à consistência interna da escala, bem como à sua validade discriminante e de construto. A análise da estrutura fatorial da escala nos permitiu a identificação de quatro síndromes comportamentais bem definidas. Estudos futuros deverão aprofundar a investigação das qualidades psicométricas da presente escala, no que se refere à sua confiabilidade com relação a interentrevistados e interentrevistadores. A Escala SBS-BR tem muito a contribuir na avaliação do impacto dos novos programas de saúde mental, principalmente no que diz respeito aos pacientes psiquiátricos com distúrbios severos e persistentes.This article describes the psychometric properties of the Brazilian version of the Social Behaviour Schedule - SBS, developed to provide global assessments of functional living skills of chronically mentally ill individuals. Núcleo de Pesquisa do Instituto Municipal de Assistência à Saúde Juliano Moreira (IMASJM, RJ, has conducted the questionnaires translation and adaptation and the data collection took place in the health care

  19. Polystyrene Chain Growth from Di-End-Functional Polyolefins for Polystyrene-Polyolefin-Polystyrene Block Copolymers

    Directory of Open Access Journals (Sweden)

    Chung Sol Kim


    Full Text Available Triblock copolymers of polystyrene (PS and a polyolefin (PO, e.g., PS-block-poly(ethylene-co-1-butene-block-PS (SEBS, are attractive materials for use as thermoplastic elastomers and are produced commercially by a two-step process that involves the costly hydrogenation of PS-block-polybutadiene-block-PS. We herein report a one-pot strategy for attaching PS chains to both ends of PO chains to construct PS-block-PO-block-PS directly from olefin and styrene monomers. Dialkylzinc compound containing styrene moieties ((CH2=CHC6H4CH2CH22Zn was prepared, from which poly(ethylene-co-propylene chains were grown via “coordinative chain transfer polymerization” using the pyridylaminohafnium catalyst to afford di-end functional PO chains functionalized with styrene and Zn moieties. Subsequently, PS chains were attached at both ends of the PO chains by introduction of styrene monomers in addition to the anionic initiator Me3SiCH2Li·(pmdeta (pmdeta = pentamethyldiethylenetriamine. We found that the fraction of the extracted PS homopolymer was low (~20% and that molecular weights were evidently increased after the styrene polymerization (ΔMn = 27–54 kDa. Transmission electron microscopy showed spherical and wormlike PS domains measuring several tens of nm segregated within the PO matrix. Optimal tensile properties were observed for the sample containing a propylene mole fraction of 0.25 and a styrene content of 33%. Finally, in the cyclic tensile test, the prepared copolymers exhibited thermoplastic elastomeric properties with no breakage up over 10 cycles, which is comparable to the behavior of commercial-grade SEBS.

  20. Cage-like mesoporous organosilicas with isocyanurate bridging groups synthesized by soft templating with poly(ethylene oxide)-poly(butylene oxide)-poly(ethylene oxide) block copolymer. (United States)

    Grudzien, Rafal M; Blitz, Jonathan P; Pikus, Stanislaw; Jaroniec, Mietek


    Ordered large-pore organosilicas with isocyanurate bridging groups were synthesized via co-condensation of tetraethyl orthosilicate (TEOS) and tris[3-(trimethoxysilyl)propyl]isocyanurate (ICS) in the presence of poly(ethylene oxide)-poly(butylene oxide)-poly(ethylene oxide) (EO(39)BO(47)EO(39)) B50-6600 template under acidic conditions. It was shown that the extraction of the B60-5500 triblock copolymer with acidified ethanol solution was insufficient to remove completely the template; however, calcination of as-synthesized and extracted samples under air atmosphere at 200 degrees C, 250 degrees C and 300 degrees C caused not only the removal of the polymer but also a substantial decomposition of the ICS groups. In contrast, the heat treatment of extracted organosilicas at 360 degrees C in flowing nitrogen was able to fully remove the residual template without degradation of the ICS bridging groups. Characterization of the resulting materials by small angle X-ray scattering (SAXS) and X-ray powder diffraction (XRD) revealed that isocyanurate-containing organosilicas have a body-centered cubic symmetry (Im3m). Argon adsorption-desorption isotherms of these organosilicas revealed cage-like mesopores, high surface areas and large pore volumes. The diameters of spherical cages were found to be very uniform in the range of 12-14 nm. A complete removal of triblock copolymer was confirmed by high-resolution thermogravimetry (TG), Fourier transform infrared spectroscopy (FT-IR) and CHNS elemental analysis (EA). The latter showed that the isocyanurate rings are intact in the framework and their loading is up to 1 mmol g(-1). Moreover, these organosilicas were also synthesized using low acid concentration, double amount of polymer and sodium chloride; in this case the template was completely extracted and there was no need for additional heat treatment.

  1. Development and Characterization of Biocompatible Fullerene [C60]/Amphiphilic Block Copolymer Nanocomposite

    Directory of Open Access Journals (Sweden)

    Alok Chaurasia


    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.

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

    Directory of Open Access Journals (Sweden)

    Zdenko Špitalský


    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.

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

  4. 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)


    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.

  5. Drug targeting to tumors using HPMA copolymers

    NARCIS (Netherlands)

    Lammers, T.G.G.M.


    Copolymers based on N-(2-hydroxypropyl)methacrylamide (HPMA) are prototypic and well-characterized polymeric drug carriers that have been broadly implemented in the delivery of anticancer agents. HPMA copolymers circulate for prolonged periods of time, and by means of the Enhance Permeability and

  6. Recycling Matter in the Universe. X-Ray observations of SBS1150+599A (PN 6135.9+55.9) (United States)

    Tovmassian, Gagik; Tomsick, John; Napiwotzki, Ralf; Yungelson, Lev; Stasinska, Grazyna; Pena, Miriam; Richer, Michael


    We present X-ray observations of the close binary nucleus of the planetary nebula SBS 1150+599A obtained with the XMM-Newton satellite. Only one component of the binary can be observed in optical-UV. New X-ray observations show that the previously invisible component is a very hot compact star. This finding allows us to deduce rough values for the basic parameters of the binary. With a high probability the total mass of the system exceeds Chandrasekhar limit and makes the SBS1150+599A one of the best candidate for a supernova type Ia progenitor.

  7. Block copolymer membranes for aqueous solution applications

    KAUST Repository

    Nunes, Suzana Pereira


    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.

  8. The Sick Building Syndrome (SBS) in office workers. A case-referent study of personal, psychosocial and building-related risk indicators. (United States)

    Stenberg, B; Eriksson, N; Höög, J; Sundell, J; Wall, S


    The Office Illness Project in Northern Sweden, comprising both a screening questionnaire study of 4943 office workers and a case-referent study of Sick Building Syndrome (SBS) in 464 subjects was recently completed. Previously published results from the survey showed that female gender asthma/rhinitis, high psychosocial work load, paper and visual display terminal (VDT) work were related to an increased prevalence of SBS symptoms. The case-referent study presented in this paper used data from the questionnaire supplemented with information from a clinical examination, a survey of psychosocial factors at work building data from inspection and measurements taken at the work sites. Personal factors such as atopy and photosensitive skin, psychosocial conditions and physical exposure factors influencing indoor air quality (IAQ), such as outdoor air flow rates and the presence of photocopiers were related to an increased prevalence of the reported SBS symptoms. The results were established using multivariate analysis. The rate response relationship between actually measured ventilation rates and the prevalence of perceived SBS symptoms presents strong evidence for the association between IAQ factors and health.

  9. Electrical transport and optical properties of the incommensurate intergrowth compounds (SbS)(1.15)(TiS2)(n) with n=1 and 2

    NARCIS (Netherlands)

    Ren, Y; Ruscher, CH; Haas, C; Wiegers, GA


    The in-plane electrical transport and optical properties of the incommensurate intergrowth compounds (SbS)(1.15)(TiS2)(n) with n = 1, 2 have been investigated by means of measurements of the electrical resistivity, Hall coefficient and thermopower in the temperature range from 4.2 to 350 K, and by

  10. Determination of the electron temperature in the modified ionosphere over HAARP using the HF pumped Stimulated Brillouin Scatter (SBS emission lines

    Directory of Open Access Journals (Sweden)

    P. A. Bernhardt


    Full Text Available An ordinary mode electromagnetic wave can decay into an ion acoustic wave and a scattered electromagnetic wave by a process called stimulated Brillouin scatter (SBS. The first detection of this process during ionospheric modification with high power radio waves was reported by Norin et al. (2009 using the HAARP transmitter in Alaska. Subsequent experiments have provided additional verification of this process and quantitative interpretation of the scattered wave frequency offsets to yield measurements of the electron temperatures in the heated ionosphere. Using the SBS technique, electron temperatures between 3000 and 4000 K were measured over the HAARP facility. The matching conditions for decay of the high frequency pump wave show that in addition to the production of an ion-acoustic wave, an electrostatic ion cyclotron wave may also be produced by the generalized SBS processes. Based on the matching condition theory, the first profiles of the scattered wave amplitude are produced using the stimulated Brillouin scatter (SBS matching conditions. These profiles are consistent with maximum ionospheric interactions at the upper-hybrid resonance height and at a region just below the plasma resonance altitude where the pump wave electric fields reach their maximum values.

  11. The Effect of Recreational Activities on the Elimination of State-Trait Anxiety of the Students Who Will Take the SBS Placement Test (United States)

    Birtürk, Atilay; Karagün, Elif


    The purpose of this study is to examine whether recreational activities have an effect on the elimination of state-trait anxiety of the students who will take the "SBS Placement Test" which is an exam for transition from secondary school to high school. For this purpose, as well as an information survey which determined the…

  12. Pump spectral linewidth influence on stimulated Brillouin scattering (SBS) and stimulated Raman scattering (SRS) and self-termination behavior of SRS in liquids

    Energy Technology Data Exchange (ETDEWEB)

    He, Guang S.; Kuzmin, Andrey; Prasad, Paras N. [The Institute for Lasers, Photonics and Biophotonics, State University of New York, Buffalo, NY (United States)


    The threshold, temporal behavior, and conversion efficiency of stimulated Brillouin scattering (SBS) and stimulated Raman scattering (SBS) in three liquids (benzene, hexane, and dimethyl sulfoxide) and two crystals (calcite and barium nitrate) have been investigated under three largely different spectral linewidth conditions. Pumped with 532-nm and nanosecond duration laser pulses of ≤ 0.01 cm{sup -1} linewidth, only SBS can be generated in all tested liquids with a high nonlinear reflectivity. However when the pump spectral linewidth is ∝0.07 cm{sup -1} or ∝0.8 cm{sup -1}, both SBS and SRS can be observed in benzene while only SRS can be generated in dimethyl sulfoxide; in all these cases SRS is the dominant contribution to the stimulated scattering but the efficiency values are drastically decreased due to the self-termination behavior of SRS in liquids, which arises from the thermal self-defocusing of both pump beam and SRS beam owing to Stokes-shift related opto-heating effect. In contrast, for SRS process in the two crystals, the thermal self-defocusing influence is negligible benefitting from their much greater thermal conductivity, and a higher conversion efficiency of SRS generation can be retained under all three pump conditions. (copyright 2016 by WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  13. Preparation and Characterization of Amphiphilic Triblock Terpolymer-Based Nanofibers as Antifouling Biomaterials

    KAUST Repository

    Cho, Youngjin


    Antifouling surfaces are critical for the good performance of functional materials in various applications including water filtration, medical implants, and biosensors. In this study, we synthesized amphiphilic triblock terpolymers (tri-BCPs, coded as KB) and fabricated amphiphilic nanofibers by electrospinning of solutions prepared by mixing the KB with poly(lactic acid) (PLA) polymer. The resulting fibers with amphiphilic polymer groups exhibited superior antifouling performance to the fibers without such groups. The adsorption of bovine serum albumin (BSA) on the amphiphilic fibers was about 10-fold less than that on the control surfaces from PLA and PET fibers. With the increase of the KB content in the amphiphilic fibers, the resistance to adsorption of BSA was increased. BSA was released more easily from the surface of the amphiphilic fibers than from the surface of hydrophobic PLA or PET fibers. We have also investigated the structural conformation of KB in fibers before and after annealing by contact angle measurements, transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDX), and coarse-grained molecular dynamics (CGMD) simulation to probe the effect of amphiphilic chain conformation on antifouling. The results reveal that the amphiphilic KB was evenly distributed within as-spun hybrid fibers, while migrated toward the core from the fiber surface during thermal treatment, leading to the reduction in antifouling. This suggests that the antifouling effect of the amphiphilic fibers is greatly influenced by the arrangement of amphiphilic groups in the fibers. © 2012 American Chemical Society.

  14. Understanding the structure and performance of self-assembled triblock terpolymer membranes

    KAUST Repository

    Pendergast, MaryTheresa M.


    Nanoporous membranes represent a possible route towards more precise particle and macromolecular separations, which are of interest across many industries. Here, we explored membranes with vertically-aligned nanopores formed from a poly(isoprene-. b-styrene-. b-4 vinyl pyridine) (ISV) triblock terpolymer via a hybrid self-assembly/nonsolvent induced phase separation process (S-NIPS). ISV concentration, solvent composition, and evaporation time in the S-NIPS process were varied to tailor ordering of the selective layer and produce enhanced water permeability. Here, water permeability was doubled over previous versions of ISV membranes. This was achieved by increasing volatile solvent concentration, thereby decreasing the evaporation period required for self-assembly. Fine-tuning was required, however, since overly-rapid evaporation did not yield the desired pore structure. Transport models, used to relate the in-. situ structure to the performance of these materials, revealed narrowing of pores and blocking by the dense region below. It was shown that these vertically aligned nanoporous membranes compare favorably with commercial ultrafiltration membranes formed by NIPS and track-etching processes, which suggests that there is practical value in further developing and optimizing these materials for specific industrial separations. © 2013 Elsevier B.V.

  15. Injectible bodily prosthetics employing methacrylic copolymer gels

    Energy Technology Data Exchange (ETDEWEB)

    Mallapragada, Surya K.; Anderson, Brian C.


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

  16. Novel polymeric micelles for insect pest control: encapsulation of essential oil monoterpenes inside a triblock copolymer shell for head lice control


    Alejandro Lucia; Ariel Ceferino Toloza; Eduardo Guzmán; Francisco Ortega; Rubio, Ramón G.


    Background Essential oil components (EOCs) are molecules with interesting application in pest control, these have been evaluated against different insect pest from more than 100 years, but their practical use is rather limited. Thus, the enhancement of their bioavailability and manageability due to their dispersion in water can open new perspective for the preparation of formulations for the control of insect pest. In this work, we studied the encapsulation of different monoterpenes in a polo...

  17. Immobilizing PEO-PPO-PEO triblock copolymers on hydrophobic surfaces and its effect on protein and platelet: a combined study using QCM-D and DPI. (United States)

    Jin, Jing; Huang, Fujian; Hu, Yu; Jiang, Wei; Ji, Xiangling; Liang, Haojun; Yin, Jinghua


    Dual polarization interferometry was used to monitor the immobilization dynamics of four Pluronics on hydrophobic surfaces and to elucidate the effect of Pluronic conformation on protein adsorption. The proportion of hydrophobic chain segments and not the length of the hydrophobic chain can influence the chain densities of the Pluronics. The immobilized densities of the Pluronics resulted from competition between the hydration of polyethylene oxide (PEO) in the aqueous solution and the hydrophobic interaction of polypropylene oxide on the substrate. P-123 obtained the largest graft mass (2.89±0.25 ng/mm2) because of the dominant effect of hydrophobic interactions. Hydrophobic segments of P-123 were anchored slowly and step-wise on the C18 substrate. P-123 exhibited the largest hydrophobic chain segment proportion (propylene oxide/ethylene oxide=3.63) and formed a brush chain conformation, indicating excellent protein and platelet resistance. The result of quartz crystal microbalance with dissipation further confirmed that the PEO conformation in P-123 on the substrate exhibited a relatively extended brush chain, and that L-35 showed relatively loose and pancake-like structures. The PEO in P-123 regulated the conformation to maintain the native conformation and resist the adsorption of bovine serum albumin (BSA). Thus, the hemocompatibilities of the immobilized Pluronics were influenced by the proportion of hydrophobic chain segments and their PEO conformations. Crown Copyright © 2014. Published by Elsevier B.V. All rights reserved.

  18. Micellization and Dynamics of a Block Copolymer

    DEFF Research Database (Denmark)

    Hvidt, Søren


    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...

  19. Electrostatic control of block copolymer morphology (United States)

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


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

  20. Block copolymer structures in nano-pores (United States)

    Pinna, Marco; Guo, Xiaohu; Zvelindovsky, Andrei


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

  1. Gyroid Membranes made from Nanoporous Blck Copolymers

    DEFF Research Database (Denmark)

    Szewczykowski, Piotr Plzemystaw; Vigild, Martin Etchells; Ndoni, Sokol


    Nanoporous materials are interesting and exciting materials in view of their many potential applications, especially as ultrafiltration membranes. One way of preparing nanoporous polymeric materials is to use block copolymers. Block copolymers have the great advantage that they organize them......-selves into different morphologies on the nano scale. Block copolymer synthesis controls the molecular weight and volume fraction of blocks, which determine the resulting nano-structures. From a membrane application point of view one very suitable morphology is the bicontinuous gyroid. Mechanical stability...... of the membrane and its nanoporosity is e.g. obtained by cross-linking the majority blocks and selectively etching the minority blocks. Here we report on ultrafiltration membranes prepared from a 1,2-polybutadiene-b-polydimethylsiloxane diblock copolymer with gyroid structure. Different experimental methods...

  2. Sick building syndrome (SBS) and exposure to water-damaged buildings: time series study, clinical trial and mechanisms. (United States)

    Shoemaker, Ritchie C; House, Dennis E


    Occupants of water-damaged buildings (WDBs) with evidence of microbial amplification often describe a syndrome involving multiple organ systems, commonly referred to as "sick building syndrome" (SBS), following chronic exposure to the indoor air. Studies have demonstrated that the indoor air of WDBs often contains a complex mixture of fungi, mycotoxins, bacteria, endotoxins, antigens, lipopolysaccharides, and biologically produced volatile compounds. A case-series study with medical assessments at five time points was conducted to characterize the syndrome after a double-blinded, placebo-controlled clinical trial conducted among a group of study participants investigated the efficacy of cholestyramine (CSM) therapy. The general hypothesis of the time series study was that chronic exposure to the indoor air of WDBs is associated with SBS. Consecutive clinical patients were screened for diagnosis of SBS using criteria of exposure potential, symptoms involving at least five organ systems, and the absence of confounding factors. Twenty-eight cases signed voluntary consent forms for participation in the time-series study and provided samples of microbial contaminants from water-damaged areas in the buildings they occupied. Twenty-six participants with a group-mean duration of illness of 11 months completed examinations at all five study time points. Thirteen of those participants also agreed to complete a double-blinded, placebo-controlled clinical trial. Data from Time Point 1 indicated a group-mean of 23 out of 37 symptoms evaluated; and visual contrast sensitivity (VCS), an indicator of neurological function, was abnormally low in all participants. Measurements of matrix metalloproteinase 9 (MMP9), leptin, alpha melanocyte stimulating hormone (MSH), vascular endothelial growth factor (VEGF), immunoglobulin E (IgE), and pulmonary function were abnormal in 22, 13, 25, 14, 1, and 7 participants, respectively. Following 2 weeks of CSM therapy to enhance toxin elimination

  3. Acute toxicity evaluation of in situ gel-forming controlled drug delivery system based on biodegradable poly(epsilon-caprolactone)-poly(ethylene glycol)-poly(epsilon-caprolactone) copolymer

    Energy Technology Data Exchange (ETDEWEB)

    Fang Fang; Gong Changyang; Dong Pengwei; Fu Shaozhi; Gu Yingchun; Guo Gang; Zhao Xia; Wei Yuquan; Qian Zhiyong, E-mail:, E-mail: [State Key Laboratory of Biotherapy, West China Hospital, West China Medical School, Sichuan University, Chengdu, 610041 (China)


    In this paper, biodegradable poly(epsilon-caprolactone)-poly(ethylene glycol)-poly(epsilon-caprolactone) (PCL-PEG-PCL) triblock copolymer was synthesized, and was characterized by FTIR, {sup 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.

  4. Comparative study of aluminum phthalocyanine incorporating into two types of block copolymer: photo-physical property, size, and in vitro photodynamic therapy efficacy

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Yide [Fujian Normal University, College of Life Sciences (China); Ma, Dongdong; Pan, Sujuan; Lin, Pingping [Fujian Normal University, College of Chemistry & Engineering, Fujian Provincial Key Laboratory of Polymer Materials (China); Lin, Yao [Fujian Normal University, College of Life Sciences (China); Yang, Hongqin [Fujian Normal University, College of Photonic & Electronic Engineering (China); Peng, Yiru, E-mail: [Fujian Normal University, College of Chemistry & Engineering, Fujian Provincial Key Laboratory of Polymer Materials (China)


    Nanoparticles of amphiphilic triblock copolymer poly(l-lysine)-b-poly(ethylene glycol)-b-poly(l-lysine) and diblock copolymer methoxy-poly(ethylene glycol)-b-poly(l-lysine) were developed to encapsulate tetra(4-sulfoazophenyl-4′-aminosulfonyl) chloride aluminum phthalocyanine, a new photosensitizer used in photodynamic therapy. The mean nanoparticle sizes varied from 10 to 70 nm, and the encapsulation efficacy ranged from 56 to 73 % due to electrostatic self-assembly induced by two types of polymer. The characteristic photophysical parameters including the absorption spectrum profile, fluorescence quantum yield, and fluorescence decay curves for free and encapsulated phthalocyanine were analyzed. The cellular uptake amount and photoactivity of S-AlPc were improved by encapsulation. The aluminum phthalocyanine loaded with poly(l-lysine)-b-poly(ethylene glycol)-b-poly(l-lysine) presented suitable physical stability, improved photophysical properties, and enhanced phototoxicity in vitro, suggesting it may be considered as a promising formulation for PDT.

  5. Comparative study of aluminum phthalocyanine incorporating into two types of block copolymer: photo-physical property, size, and in vitro photodynamic therapy efficacy (United States)

    Huang, Yide; Ma, Dongdong; Pan, Sujuan; Lin, Pingping; Lin, Yao; Yang, Hongqin; Peng, Yiru


    Nanoparticles of amphiphilic triblock copolymer poly( l-lysine)- b-poly(ethylene glycol)- b-poly( l-lysine) and diblock copolymer methoxy-poly(ethylene glycol)- b-poly( l-lysine) were developed to encapsulate tetra(4-sulfoazophenyl-4'-aminosulfonyl) chloride aluminum phthalocyanine, a new photosensitizer used in photodynamic therapy. The mean nanoparticle sizes varied from 10 to 70 nm, and the encapsulation efficacy ranged from 56 to 73 % due to electrostatic self-assembly induced by two types of polymer. The characteristic photophysical parameters including the absorption spectrum profile, fluorescence quantum yield, and fluorescence decay curves for free and encapsulated phthalocyanine were analyzed. The cellular uptake amount and photoactivity of S-AlPc were improved by encapsulation. The aluminum phthalocyanine loaded with poly( l-lysine)- b-poly(ethylene glycol)- b-poly( l-lysine) presented suitable physical stability, improved photophysical properties, and enhanced phototoxicity in vitro, suggesting it may be considered as a promising formulation for PDT.

  6. Responsive Copolymers for Enhanced Petroleum Recovery

    Energy Technology Data Exchange (ETDEWEB)

    McCormick, C.; Hester, R.


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

  7. Chitosan/polyanion surface modification of styrene–butadiene–styrene block copolymer membrane for wound dressing

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Jen Ming, E-mail: [Department of Chemical and Materials Engineering, Chang Gung University, Kwei-Shan, Tao-Yuan 333, Taiwan (China); Yang, Jhe-Hao [Department of Electronic Engineering, Chang Gung University, Kwei-Shan, Tao-Yuan 333, Taiwan (China); Huang, Huei Tsz [Department of Chemical and Materials Engineering, Chang Gung University, Kwei-Shan, Tao-Yuan 333, Taiwan (China)


    The surface of styrene–butadiene–styrene block copolymer (SBS) membrane is modified with tri-steps in this study. At first, two step modified SBS membrane (MSBS) was prepared with epoxidation and ring opening reaction with maleated ionomer. Then chitosan was used as the polycation electrolyte and sodium alginate, poly(γ-glutamic acid) (PGA) and poly(aspartic acid) (PAsp) were selected as polyanion electrolytes to deposit on the surfaces of MSBS membrane by the layer-by-layer self-assembly (LbL) deposition technique to get three [chitosan/polyanion] LbL modified SBS membranes, ([CS/Alg], [CS/PGA] and [CS/PAsp]). From the quantitative XPS analysis and water contact angle measurement, it is found that the order of wettability and the content of functional group percentages of COO{sup −} and -O=C-N- on the three [CS/polyanion] systems are [CS/Alg] > [CS/PGA] > [CS/PAsp]. Performances of water vapor transmission rates, fibronectin adsorption, antibacterial assessment and 3T3 fibroblast cell growth on [CS/Alg], [CS/PGA] and [CS/PAsp] membranes were also evaluated. With the evaluation of water vapor transmission rate, these [CS/Alg], [CS/PGA] and [CS/PAsp] membranes are sterile semipermeable with water evaporation at about 82 ± 8 g/day · m{sup 2}. It is found that the amount of fibronectin adsorption on the three [CS/polyanion] systems is significantly determined by the sum of the functional group of COO{sup −} and -O=C-N- on the surfaces of [CS/Alg], [CS/PGA] and [CS/PAsp] systems. The results are inverse with the sum of the functional group of COO{sup −} and -O=C-N- on the three [CS/polyanion]. From the cytotoxicity test and cell adhesion and proliferation assay of 3T3 fibroblasts on the three [CS/polyanion] systems, it revealed that the cells not only remained viable but they also proliferated on the surfaces of [CS/Alg], [CS/PGA] and [CS/PAsp]. The bactericidal activity was found on [CS/Alg], [CS/PGA] and [CS/PAsp]. The transport of bacterial through

  8. Order and Disorder in High χ/Low N , Broad Dispersity ABA Triblock Polymers

    Energy Technology Data Exchange (ETDEWEB)

    Schmitt, Adam K.; Mahanthappa, Mahesh K. (UW); (UMM)


    Using a combination of small-angle X-ray scattering (SAXS) and transmission electron microscopy (TEM), we document the composition-dependent morphologies of 39 new poly(lactide-block-1,4-butadiene-block-lactide) (LBL) block polymers, comprising a broad dispersity B segment (Mn = 4.5–17.7 kg/mol; $\\def\\eth{{\\specialfont\\char238}}$ = Mw/Mn = 1.72–1.88) and narrow dispersity L end blocks (Mn = 0.6–15.3 kg/mol; $\\def\\eth{{\\specialfont\\char238}}$ = 1.10–1.21) with volume fractions 0.26 ≤ fB ≤ 0.95. A subset of these samples undergo melt self-assembly into cylindrical, lamellar, and apparently bicontinuous morphologies. By assessing the states of order and disorder in these triblock polymer melts using temperature-dependent SAXS, we find that broad B segment dispersity increases the minimum segregation strength χN ≳ 27 required for LBL triblock self-assembly relative to the self-consistent mean-field theory prediction χN ≥ 17.9 for narrow dispersity analogues. While B segment dispersity has previously been shown to thermodynamically stabilize the self-assembled morphologies of low χ/high N ABA triblocks, the present study indicates that broad B block dispersity in related high χ/low N systems destabilizes the microphase-separated melt. These observations are rationalized in terms of recent theories that suggest that broad segmental dispersity substantially enhances fluctuation effects at low N, thus disfavoring melt segregation.

  9. 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

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

    KAUST Repository

    Palacios, Jordana


    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 terpolymers with identical PEO and PCL block lengths and two different PLLA block lengths were prepared, thus the effect of increasing PLLA content on the crystallization behavior and morphology was evaluated. Wide angle X-Ray scattering (WAXS) experiments performed on cooling from the melt confirmed the triple crystalline nature of these terpolymers and revealed that they crystallize in sequence: the PLLA block crystallizes first, then the PCL block, and finally the PEO block. Differential scanning calorimetry (DSC) analysis further demonstrated that the three blocks can crystallize from the melt when a low cooling rate is employed. The crystallization process takes place from a homogenous melt as indicated by small angle X-Ray scattering (SAXS) experiments. The crystallization and melting enthalpies and temperatures of both PEO and PCL blocks decrease as PLLA content in the terpolymer increases. Polarized light optical microscopy (PLOM) demonstrated that the PLLA block templates the morphology of the terpolymer, as it forms spherulites upon cooling from the melt. The subsequent crystallization of PCL and PEO blocks occurs inside the interlamellar regions of the previously formed PLLA block spherulites. In this way, unique triple crystalline mixed spherulitic superstructures have been observed for the first time. As the PLLA content in the terpolymer is reduced the superstructural morphology changes from spherulites to a more axialitic-like structure.

  11. VLT/MUSE illuminates possible channels for Lyman continuum escape in the halo of SBS 0335-52E (United States)

    Herenz, E. C.; Hayes, M.; Papaderos, P.; Cannon, J. M.; Bik, A.; Melinder, J.; Östlin, G.


    We report on the discovery of ionised gas filaments in the circum-galactic halo of the extremely metal-poor compact starburst SBS 0335-052E in a 1.5 h integration with the MUSE integral-field spectrograph. We detect these features in Hα and [O iii] emission down to a limiting surface-brightness of 5 × 10-19 erg s-1 cm-2 arcsec-2. The filaments have projected diameters of 2.1 kpc and extend more than 9 kpc to the north and north-west from the main stellar body. We also detect extended nebular He ii λ4686 emission that brightens towards the north-west at the rim of a starburst driven super-shell. We also present a velocity field of the ionised gas. The filaments appear to connect seamlessly in velocity space to the kinematical disturbances caused by the shell. Similar to high-z star-forming galaxies, the ionised gas in this galaxy is dispersion dominated. We argue that the filaments were created via feedback from the starburst and that these ionised structures in the halo may act as escape channels for Lyman continuum radiation in this gas-rich system. Based on observations collected at the European Organisation for Astronomical Research in the Southern Hemisphere under ESO programme 096.B-0690.

  12. Simulations of drastically reduced SBS with laser pulses composed of a Spike Train of Uneven Duration and Delay (STUD pulses

    Directory of Open Access Journals (Sweden)

    Hüller Stefan


    Full Text Available By comparing the impact of established laser smoothing techniques like Random Phase Plates (RPP and Smoothing by Spectral Dispersion (SSD to the concept of “Spike Trains of Uneven Duration and Delay” (STUD pulses on the amplification of parametric instabilities in laser-produced plasmas, we show with the help of numerical simulations, that STUD pulses can drastically reduce instability growth by orders of magnitude. The simulation results, obtained with the code Harmony in a nonuniformly flowing mm-size plasma for the Stimulated Brillouin Scattering (SBS instability, show that the efficiency of the STUD pulse technique is due to the fact that successive re-amplification in space and time of parametrically excited plasma waves inside laser hot spots is minimized. An overall mean fluctuation level of ion acoustic waves at low amplitude is established because of the frequent change of the speckle pattern in successive spikes. This level stays orders of magnitude below the levels of ion acoustic waves excited in hot spots of RPP and SSD laser beams.

  13. Polyamide copolymers having 2,5-furan dicarboxamide units

    Energy Technology Data Exchange (ETDEWEB)

    Chisholm, Bret Ja; Samanta, Satyabrata


    Polyamide copolymers, and methods of making and using polyamide copolymers, having 2,5-furan dicarboxamide units are disclosed herein. Such polymers can be useful for engineering thermoplastics having advantageous physical and/or chemical properties.

  14. Recycling cycle of materials applied to acrylonitrile-butadiene-styrene/policarbonate blends with styrene-butadiene-styrene copolymer addition (United States)

    Cândido, L. H. A.; Ferreira, D. B.; Júnior, W. Kindlein; Demori, R.; Mauler, R. S.


    The scope of this research is the recycling of polymers from mobile phones hulls discarded and the performance evaluation when they are submitted to the Recycling Cycle of Materials (RCM). The studied material was the ABS/PC blend in a 70/30 proportion. Different compositions were evaluated adding virgin material, recycled material and using the copolymer SBS as impact modifier. In order to evaluate the properties of material's composition, the samples were characterized by TGA, FTIR, SEM, IZOD impact strength and tensile strength tests. At the first stage, the presented results suggest the composition containing 25% of recycled material and 5% of SBS combines good mechanical performance to the higher content of recycled material and lower content of impact modifier providing major benefits to recycling plans. Five cycles (RCM) were applied in the second stage; they evidenced a decrease trend considering the impact strength. At first and second cycle the impact strength was higher than reference material (ABS/PC blend) and from the fourth cycle it was lower. The superiority impact strength in the first and second cycles can be attributed to impact modifier effect. The thermal tests and the spectrometry didn't show the presence of degradation process in the material and the TGA curves demonstrated the process stability. The impact surface of each sample was observed at SEM. The microstructures are not homogeneous presenting voids and lamellar appearance, although the outer surface presents no defects, demonstrating good moldability. The present work aims to assess the life cycle of the material from the successive recycling processes.

  15. Oil recovery with vinyl sulfonic acid-acrylamide copolymers

    Energy Technology Data Exchange (ETDEWEB)

    Norton, C.J.; Falk, D.O.


    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.

  16. A novel method for recovery of acidic sludge of used-motor oil reprocessing industries to bitumen using bentonite and SBS


    Ahmad Jonidi Jafari; malek hassanpour; Mitra Gholam; Mehdi Farzadkia


    ABSTRACT Acidic sludge is a by-product from used motor oil reprocessing industries, which thousand tons of this sludge are disposed into the environment as a hazardous waste material daily. The acidic sludge contains unsaturated compounds that are polar and asphaltene. The bitumen under certain conditions is produced from mixing of bentonite, polymer styrene – butadiene – styrene (SBS), and acidic sludge. Context and purpose: The objective of this study was the recovery of acidic sludge...

  17. Charge Transport in Conjugated Block Copolymers (United States)

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

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

  18. Photo-Induced Micellization of Block Copolymers

    Directory of Open Access Journals (Sweden)

    Satoshi Kuwayama


    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.

  19. PEO-related block copolymer surfactants

    DEFF Research Database (Denmark)

    Mortensen, K.


    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 ...... or lamellar nature. Shear has major effect on the crystalline texture, but seems not to change the thermodynamic stable phases significantly. (C) 2001 Elsevier Science B.V. All rights reserved.......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...

  20. Chain exchange in block copolymer micelles (United States)

    Lu, Jie; Bates, Frank; Lodge, Timothy


    Block copolymer micelles are aggregates formed by self-assembly of amphiphilic copolymers dispersed in a selective solvent, driven by unfavorable interactions between the solvent and the core-forming block. Due to the relatively long chains being subject to additional thermodynamic and dynamic constraints (e.g., entanglements, crystallinity, vitrification), block copolymer micelles exhibit significantly slower equilibration kinetics than small molecule surfactants. As a result, details of the mechanism(s) of equilibration in block copolymer micelles remain unclear. This present works focuses on the chain exchange kinetics of poly(styrene-b-ethylenepropylene) block copolymers in squalane (C30H62) using time-resolved small angle neutron scattering (TR-SANS). A mixture of h-squalane and d-squalane is chosen so that it contrast matches a mixed 50/50 h/d polystyrene micelle core. When the temperature is appropriate and isotopically labeled chains undergo mixing, the mean core contrast with respect to the solvent decreases, and the scattering intensity is therefore reduced. This strategy allows direct probing of chain exchange rate from the time dependent scattering intensity I(q, t).

  1. 21 CFR 177.1980 - Vinyl chloride-propylene copolymers. (United States)


    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Vinyl chloride-propylene copolymers. 177.1980... Basic Components of Single and Repeated Use Food Contact Surfaces § 177.1980 Vinyl chloride-propylene copolymers. The vinyl chloride-propylene copolymers identified in paragraph (a) of this section may be safely...

  2. 78 FR 6213 - Styrene-2-Ethylhexyl Acrylate Copolymer; Tolerance Exemption (United States)


    ... AGENCY 40 CFR Part 180 Styrene-2-Ethylhexyl Acrylate Copolymer; Tolerance Exemption AGENCY: Environmental...; also known as styrene-2-ethylhexyl acrylate copolymer when used as an inert ingredient in a pesticide...-risk polymers are described in 40 CFR 723.250(d). Styrene-2-ethylhexyl acrylate copolymer conforms to...

  3. 21 CFR 177.1312 - Ethylene-carbon monoxide copolymers. (United States)


    ... 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...

  4. 21 CFR 177.1320 - Ethylene-ethyl acrylate copolymers. (United States)


    ... 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...

  5. 21 CFR 177.1350 - Ethylene-vinyl acetate copolymers. (United States)


    ... 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...

  6. 21 CFR 177.1950 - Vinyl chloride-ethylene copolymers. (United States)


    ... 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...

  7. 21 CFR 177.1310 - Ethylene-acrylic acid copolymers. (United States)


    ... 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...

  8. 21 CFR 177.1211 - Cross-linked polyacrylate copolymers. (United States)


    ... polyacrylate copolymers consist of: (1) The grafted copolymer of cross-linked sodium polyacrylate identified as... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Cross-linked polyacrylate copolymers. 177.1211... Basic Components of Single and Repeated Use Food Contact Surfaces § 177.1211 Cross-linked polyacrylate...

  9. 21 CFR 181.32 - Acrylonitrile copolymers and resins. (United States)


    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Acrylonitrile copolymers and resins. 181.32 Section... Ingredients § 181.32 Acrylonitrile copolymers and resins. (a) Acrylonitrile copolymers and resins listed in this section, containing less than 30 percent acrylonitrile and complying with the requirements of...

  10. Evaluating structure in thin block copolymer films with soft x-rays (Conference Presentation) (United States)

    Sunday, Daniel; Liman, Christopher; Hannon, Adam F.; Ren, Jiaxing; Chen, Xuanxuan; Suh, Hyo Seon; de Pablo, Juan J.; Nealey, Paul F.; Kline, R. Joseph


    The semiconductor industry is evaluating a variety of approaches for the cost efficient production of future processing and memory generations. Amongst the technologies being explored are multiple patterning steps, extreme ultraviolet (EUV) lithography, multiple-beam electron beam lithography and the directed self-assembly (DSA) of block copolymers (BCPs). BCP DSA utilizes a chemical or topographical template to induce long range order in a thin film of BCP which enhances the resolution of the original pattern. The characterization of buried structure within a DSA BCP film is challenging due to the lack of contrast between the organic materials. Critical-dimension small angle x-ray scattering (CDSAXS) measurements were performed on DSA BCP films, using soft X-rays to tune the contrast, in order to understand the relationship between template structure and film morphology.1 The results of these measurements show that as the width of the guiding stripe widens the arrangement of the BCP on the guiding stripe inverts, shifting from the A block being centered on the guiding stripe to the B block being centered on the guiding stripe. The initial results of integration of mean field simulations into the analysis of scattering data will also be discussed. In addition to examining the BCP structure with CDSAXS, soft X-ray reflectivity2 measurements were performed on BCP to better understand the relationship between interface width for systems with alternative architectures (triblocks) and additives (polymers/ionic liquids). The addition of a selectively associating additive increases the interaction parameter between the two blocks, resulting in the reduction of the interface width and access to smaller pitches. The use of soft X-ray reflectivity allows the evaluation of the distribution of the additive. (1) Sunday, D. F.; Hammond, M. R.; Wang, C.; Wu, W.; Delongchamp, D. M.; Tjio, M.; Cheng, J. Y.; Kline, R. J.; Pitera, J. W. Determination of the Internal Morphology of

  11. Functional Nanoporous Polymers from Block Copolymer Precursors

    DEFF Research Database (Denmark)

    Guo, Fengxiao

    applications as, e.g., membranes for separation and purification, templates for nanostructured materials, sensors, substrates for catalysis, low dielectric constant materials, photonic materials, and depots for controlled drug delivery. The development of nanoporous polymers with well controlled pore wall......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...

  12. Functionalization of Block Copolymer Vesicle Surfaces

    Directory of Open Access Journals (Sweden)

    Wolfgang Meier


    Full Text Available In dilute aqueous solutions certain amphiphilic block copolymers self-assemble into vesicles that enclose a small pool of water with a membrane. Such polymersomes have promising applications ranging from targeted drug-delivery devices, to biosensors, and nanoreactors. Interactions between block copolymer membranes and their surroundings are important factors that determine their potential biomedical applications. Such interactions are influenced predominantly by the membrane surface. We review methods to functionalize block copolymer vesicle surfaces by chemical means with ligands such as antibodies, adhesion moieties, enzymes, carbohydrates and fluorophores. Furthermore, surface-functionalization can be achieved by self-assembly of polymers that carry ligands at their chain ends or in their hydrophilic blocks. While this review focuses on the strategies to functionalize vesicle surfaces, the applications realized by, and envisioned for, such functional polymersomes are also highlighted.

  13. High SBS-Threshold Er/Yb Co-Doped Phosphate Glass Fiber Amplifiers for High Power, Sub-us Pulsed, Narrow Linewidth, All Fiber-Based Laser Transmitter Project (United States)

    National Aeronautics and Space Administration — In Phase I, NP Photonics has achieved 1.2 kW peak power for 105 ns fiber laser pulses, and successfully demonstrated the feasibility to produce monolithic high SBS...

  14. Time Delay and Accretion Disk Size Measurements in the Lensed Quasar SBS 0909+532 from Multiwavelength Microlensing Analysis (United States)

    Hainline, Laura J.; Morgan, Christopher W.; MacLeod, Chelsea L.; Landaal, Zachary D.; Kochanek, C. S.; Harris, Hugh C.; Tilleman, Trudy; Goicoechea, L. J.; Shalyapin, V. N.; Falco, Emilio E.


    We present three complete seasons and two half-seasons of Sloan Digital Sky Survey (SDSS) r-band photometry of the gravitationally lensed quasar SBS 0909+532 from the U.S. Naval Observatory, as well as two seasons each of SDSS g-band and r-band monitoring from the Liverpool Robotic Telescope. Using Monte Carlo simulations to simultaneously measure the system's time delay and model the r-band microlensing variability, we confirm and significantly refine the precision of the system's time delay to \\Delta t_{AB} = 50^{+2}_{-4}\\,{days}, where the stated uncertainties represent the bounds of the formal 1σ confidence interval. There may be a conflict between the time delay measurement and a lens consisting of a single galaxy. While models based on the Hubble Space Telescope astrometry and a relatively compact stellar distribution can reproduce the observed delay, the models have somewhat less dark matter than we would typically expect. We also carry out a joint analysis of the microlensing variability in the r and g bands to constrain the size of the quasar's continuum source at these wavelengths, obtaining log {(r s, r /cm)[cos i/0.5]1/2} = 15.3 ± 0.3 and log {(r s, g /cm)[cos i/0.5]1/2} = 14.8 ± 0.9, respectively. Our current results do not formally constrain the temperature profile of the accretion disk but are consistent with the expectations of standard thin disk theory.

  15. A longitudinal study of sick building syndrome (SBS) among pupils in relation to SO2, NO2, O3 and PM10 in schools in China. (United States)

    Zhang, Xin; Li, Fan; Zhang, Li; Zhao, Zhuohui; Norback, Dan


    There are fewer longitudinal studies from China on symptoms as described for the sick building syndrome (SBS). Here, we performed a two-year prospective study and investigated associations between environmental parameters such as room temperature, relative air humidity (RH), carbon dioxide (CO2), nitrogen dioxide (NO2), sulphur dioxide (SO2), ozone (O3), particulate matter (PM10), and health outcomes including prevalence, incidence and remission of SBS symptoms in junior high schools in Taiyuan, China. Totally 2134 pupils participated at baseline, and 1325 stayed in the same classrooms during the study period (2010-2012). The prevalence of mucosal symptoms, general symptoms and symptoms improved when away from school (school-related symptoms) was 22.7%, 20.4% and 39.2%, respectively, at baseline, and the prevalence increased during follow-up (P<0.001). At baseline, both indoor and outdoor SO2 were found positively associated with prevalence of school-related symptoms. Indoor O3 was shown to be positively associated with prevalence of skin symptoms. At follow-up, indoor PM10 was found to be positively associated with new onset of skin, mucosal and general symptoms. CO2 and RH were positively associated with new onset of mucosal, general and school-related symptoms. Outdoor SO2 was positively associated with new onset of skin symptoms, while outdoor NO2 was positively associated with new onset of skin, general and mucosal symptoms. Outdoor PM10 was found to be positively associated with new onset of skin, general and mucosal symptoms as well as school-related symptoms. In conclusion, symptoms as described for SBS were commonly found in school children in Taiyuan City, China, and increased during the two-year follow-up period. Environmental pollution, including PM10, SO2 and NO2, could increase the prevalence and incidence of SBS and decrease the remission rate. Moreover, parental asthma and allergy (heredity) and pollen or pet allergy (atopy) can be risk factors for

  16. A longitudinal study of sick building syndrome (SBS among pupils in relation to SO2, NO2, O3 and PM10 in schools in China.

    Directory of Open Access Journals (Sweden)

    Xin Zhang

    Full Text Available There are fewer longitudinal studies from China on symptoms as described for the sick building syndrome (SBS. Here, we performed a two-year prospective study and investigated associations between environmental parameters such as room temperature, relative air humidity (RH, carbon dioxide (CO2, nitrogen dioxide (NO2, sulphur dioxide (SO2, ozone (O3, particulate matter (PM10, and health outcomes including prevalence, incidence and remission of SBS symptoms in junior high schools in Taiyuan, China. Totally 2134 pupils participated at baseline, and 1325 stayed in the same classrooms during the study period (2010-2012. The prevalence of mucosal symptoms, general symptoms and symptoms improved when away from school (school-related symptoms was 22.7%, 20.4% and 39.2%, respectively, at baseline, and the prevalence increased during follow-up (P<0.001. At baseline, both indoor and outdoor SO2 were found positively associated with prevalence of school-related symptoms. Indoor O3 was shown to be positively associated with prevalence of skin symptoms. At follow-up, indoor PM10 was found to be positively associated with new onset of skin, mucosal and general symptoms. CO2 and RH were positively associated with new onset of mucosal, general and school-related symptoms. Outdoor SO2 was positively associated with new onset of skin symptoms, while outdoor NO2 was positively associated with new onset of skin, general and mucosal symptoms. Outdoor PM10 was found to be positively associated with new onset of skin, general and mucosal symptoms as well as school-related symptoms. In conclusion, symptoms as described for SBS were commonly found in school children in Taiyuan City, China, and increased during the two-year follow-up period. Environmental pollution, including PM10, SO2 and NO2, could increase the prevalence and incidence of SBS and decrease the remission rate. Moreover, parental asthma and allergy (heredity and pollen or pet allergy (atopy can be risk

  17. Dynamics of Block Copolymer Nanocomposites

    Energy Technology Data Exchange (ETDEWEB)

    Mochrie, Simon G. J.


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

  18. A dose-equivalent comparison of the effects of continuous subcutaneous glucagon-like peptide 2 (GLP-2) infusions versus meal related GLP-2 injections in the treatment of short bowel syndrome (SBS) patients

    DEFF Research Database (Denmark)

    Naimi, R M; Madsen, K B; Askov-Hansen, C


    Glucagon-like peptide 2 (GLP-2), secreted endogenously from L-cells in the distal bowel in relation to meals, modulates intestinal absorption by adjusting gastric emptying and secretion and intestinal growth. Short bowel syndrome (SBS) patients with distal intestinal resections have attenuated en...... effects of continuous, subcutaneous (s.c.), exogenous GLP-2 infusion (CONT-GLP-2) versus three daily s.c. GLP-2 injections (TID-GLP-2) on intestinal absorption in SBS patients....

  19. Co-polymer Films for Sensors (United States)

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


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

  20. Electrochemical and spectroscopic characterization of poly (bithiophene + 2-methylfuran) copolymer (United States)

    Lamiri, Leila; Nessark, Belkacem; Habelhames, Farid; Sibous, Lakhdar


    In this work, Poly(bithiophene + 2-methylfuran) copolymer was successfully synthetized by an electrochemical polymerization of two monomers, bithiophene and 2-methylfuran in acetonitrile containing lithium perchlorate. The obtained copolymer was characterized via cyclic voltammetry, impedance spectroscopy, UV-visible, scanning electron microscope, conductivity and photocurrent measurements. The cyclic voltammetry study showed two redox couples characteristic of Poly (bithiophene + 2-methylfuran) copolymer. The impedance spectroscopy study revealed that the resistance of the copolymer film increases with the addition of 2-methylfuran. The photocurrent measurement showed good photoelectrochemical properties, making this copolymer an ideal candidate for photovoltaic cell applications.

  1. Synthesis of amphiphilic diblock copolymer for surface modification of Ethylene-Norbornene copolymers

    DEFF Research Database (Denmark)

    Levinsen, Simon; Svendsen, Winnie Edith; Horsewell, Andy


    consisting of a bulk material compatible block and a hydrophilic block. To utilize the possibility of incorporating diblock copolymers into ethylenenorbornene copolymers, we have in this work developed a model poly(ethylene-1-butene) polymer compatible with the commercial available ethylene......-norbornene copolymer TOPAS. Through matching of the radius of gyration for the model polymer and TOPAS the miscibility was achieved. The poly(ethylene-1-butene) polymer was synthesized from a hydrogenated anionic polymerized polybutadiene polymer. As hydrophilic block poly(ethylene oxide) was subsequently added also......The aim of this work is to produce polymer modifiers in order to develop hydrophilic polymeric surfaces for use in microfluidics. The use of hydrophilic polymers in microfluidics will have many advantages e.g. preventing protein absorbance. Here we present an amphiphilic diblock copolymer...

  2. Glycine/Glycolic acid based copolymers

    NARCIS (Netherlands)

    in 't Veld, P.J.A.; in 't Veld, Peter J.A.; Shen, Zheng-Rong; Shen, Z.; Takens, Gijsbert A.J.; Takens, G.A.J.; Dijkstra, Pieter J.; Feijen, Jan


    Glycine/glycolic acid based biodegradable copolymers have been prepared by ring-opening homopolymerization of morpholine-2,5-dione, and ring-opening copolymerization of morpholine-2,5-dione and glycolide. The homopolymerization of morpholine-2,5-dione was carried out in the melt at 200°C for 3 min

  3. Restructuring in block copolymer thin films

    DEFF Research Database (Denmark)

    Posselt, Dorthe; Zhang, Jianqi; Smilgies, Detlef-M.


    Block copolymer (BCP) thin films have been proposed for a number of nanotechnology applications, such as nanolithography and as nanotemplates, nanoporous membranes and sensors. Solvent vapor annealing (SVA) has emerged as a powerful technique for manipulating and controlling the structure of BCP ...

  4. Synthesis of fluorescent diblock copolymer nanoparticle supported ...

    Indian Academy of Sciences (India)


    Jun 9, 2017 ... using different techniques. The diblock copolymer (DBC) of. PCL is reviewed in this paper. In 2005, PCL-based liquid crys- talline DBC was synthesized and characterized thoroughly. [3]. A RAFT technique was adopted for the synthesis of PCL- based DBC [4]. A DBC between PCL and MMA was prepared.

  5. Nylon 46-polytetramethylene oxide segmented block copolymers

    NARCIS (Netherlands)

    Gaymans, R.J.; Schwering, P.; de Haan, J.L.


    Block copolymers were synthesized from amine-terminated polytetramethylene oxide (PMTO) (Mw 800 and 1130) and polyamide 4,6 salt. First prepolymers were prepared at 200–210°C in the presence of a solvent (pyrrolidone). The prepolymers were postcondensed at 255°C (where possible in the solid state)


    NARCIS (Netherlands)

    Hilberer, A; Gill, R.E; Herrema, J.K; Malliaras, G.G; Wildeman, J.; Hadziioannou, G

    In this article we review results obtained in our laboratory on the design and study of new light-emitting polymers. We are interested in the synthesis and characterisation of block copolymers with regularly alternating conjugated and non conjugated sequences. The blocks giving rise to luminescence

  7. Preparation of amphiphilic block copolymer containing triazene ...

    Indian Academy of Sciences (India)

    The lower rate constant in film state (film = 1.3 × 10−3 s-1), shows that the higher mobility of polymeric chains in solution allow a more rapid orientation, favourable to the triazene bond cleavage. The capability of block copolymer to form micelles in aqueous environment and implicitly, its critical micelle concentration (CMC) ...

  8. 21 CFR 177.1970 - Vinyl chloride-lauryl vinyl ether copolymers. (United States)


    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Vinyl chloride-lauryl vinyl ether copolymers. 177...-lauryl vinyl ether copolymers. The vinyl chloride-lauryl vinyl ether copolymers identified in paragraph... section vinyl chloride-lauryl vinyl ether copolymers consist of basic copolymers produced by the...

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

    KAUST Repository

    Musteata, Valentina-Elena


    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.

  10. A novel method for recovery of acidic sludge of used-motor oil reprocessing industries to bitumen using bentonite and SBS

    Directory of Open Access Journals (Sweden)

    Ahmad Jonidi Jafari


    Full Text Available ABSTRACT Acidic sludge is a by-product from used motor oil reprocessing industries, which thousand tons of this sludge are disposed into the environment as a hazardous waste material daily. The acidic sludge contains unsaturated compounds that are polar and asphaltene. The bitumen under certain conditions is produced from mixing of bentonite, polymer styrene – butadiene – styrene (SBS, and acidic sludge. Context and purpose: The objective of this study was the recovery of acidic sludge to bitumen using additives such as bentonite and SBS. Also, the effect of additives with different weight percentages (wt%(on the performance parameters of bitumen was evaluated. At first, spilled oil was separated from the acidic sludge by a centrifugal concentrator. Then, concentrated acidic sludge and additives were mixed in together. Finally, the performance tests were carried out to compare the quality of acidic sludge with the obtained products.The results indicated that performance parameters such as softening point (SP, weight loss, penetration degree, PI, Frass breaking point, and temperature susceptibility (TS were promoted from 37°C, 1.3%, 230 dmm, -0.07854, -5°C and 0.0451 to 54°C, 1%, 130 dmm, 2.7094, -11°C , 0.02721, respectively. According to the paired sample t-test analysis, a significant difference was found between the bentonite dosage and the improved performance parameters from concentrated acidic sludge and obtained products (pvalue ≤.001. The bentonite and SBS with 2 and 4 wt%, respectively were determined as the suitable additives in the recovery of acidic sludge to bitumen.

  11. 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 ...

  12. Airborne molds and bacteria, microbial volatile organic compounds (MVOC), plasticizers and formaldehyde in dwellings in three North European cities in relation to sick building syndrome (SBS). (United States)

    Sahlberg, Bo; Gunnbjörnsdottir, Maria; Soon, Argo; Jogi, Rain; Gislason, Thorarinn; Wieslander, Gunilla; Janson, Christer; Norback, Dan


    There are few studies on associations between airborne microbial exposure, formaldehyde, plasticizers in dwellings and the symptoms compatible with the sick building syndrome (SBS). As a follow-up of the European Community Respiratory Health Survey (ECRHS II), indoor measurements were performed in homes in three North European cities. The aim was to examine whether volatile organic compounds of possible microbial origin (MVOCs), and airborne levels of bacteria, molds, formaldehyde, and two plasticizers in dwellings were associated with the prevalence of SBS, and to study associations between MVOCs and reports on dampness and mold. The study included homes from three centers included in ECRHS II. A total of 159 adults (57% females) participated (19% from Reykjavik, 40% from Uppsala, and 41% from Tartu). A random sample and additional homes with a history of dampness were included. Exposure measurements were performed in the 159 homes of the participants. MVOCs were analyzed by GCMS with selective ion monitoring (SIM). Symptoms were reported in a standardized questionnaire. Associations were analyzed by multiple logistic regression. In total 30.8% reported any SBS (20% mucosal, 10% general, and 8% dermal symptoms) and 41% of the homes had a history of dampness and molds There were positive associations between any SBS and levels of 2-pentanol (P=0.002), 2-hexanone (P=0.0002), 2-pentylfuran (P=0.009), 1-octen-3-ol (P=0.002), formaldehyde (P=0.05), and 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (Texanol) (P=0.05). 1-octen-3-ol (P=0.009) and 3-methylfuran (P=0.002) were associated with mucosal symptoms. In dwellings with dampness and molds, the levels of total bacteria (P=0.02), total mold (P=0.04), viable mold (P=0.02), 3-methylfuran (P=0.008) and ethyl-isobutyrate (P=0.02) were higher. In conclusion, some MVOCs like 1-octen-3-ol, formaldehyde and the plasticizer Texanol, may be a risk factor for sick building syndrome. Moreover, concentrations of airborne molds

  13. Sick building syndrome (SBS) among office workers in a Malaysian university--Associations with atopy, fractional exhaled nitric oxide (FeNO) and the office environment. (United States)

    Lim, Fang-Lee; Hashim, Zailina; Md Said, Salmiah; Than, Leslie Thian-Lung; Hashim, Jamal Hisham; Norbäck, Dan


    There are few studies on sick building syndrome (SBS) including clinical measurements for atopy and fractional exhaled nitric oxide (FeNO). Our aim was to study associations between SBS symptoms, selected personal factors, office characteristics and indoor office exposures among office workers from a university in Malaysia. Health data were collected by a questionnaire (n=695), skin prick test (SPT) (n=463) and FeNO test (n=460). Office settled dust was vacuumed and analyzed for endotoxin, (1,3)-β-glucan and house dust mites (HDM) allergens group 1 namely Dermatophagoides pteronyssinus (Der p 1) and Dermatophagoides farinae (Der f 1). Office indoor temperature, relative air humidity (RH), carbon monoxide (CO) and carbon dioxide (CO2) were measured by a direct reading instrument. Associations were studied by two-levels multiple logistic regression with mutual adjustment and stratified analysis. The prevalence of weekly dermal, mucosal and general symptoms was 11.9%, 16.0% and 23.0% respectively. A combination of SPT positivity (allergy to HDM or cat) and high FeNO level (≥25 ppb) was associated with dermal (p=0.002), mucosal (p<0.001) and general symptoms (p=0.05). Der f1 level in dust was associated with dermal (p<0.001), mucosal (p<0.001) and general (p=0.02) symptoms. Among those with allergy to D. farinae, associations were found between Der f 1 levels in dust and dermal (p=0.003), mucosal (p=0.001) and general symptoms (p=0.007). Office-related symptoms were associated with Der f 1 levels in dust (p=0.02), low relative air humidity (p=0.04) and high office temperature (p=0.05). In conclusion, a combination of allergy to cat or HDM and high FeNO is a risk factor for SBS symptoms. Der f 1 allergen in dust can be a risk factor for SBS in the office environment, particularly among those sensitized to Der f 1 allergen. Copyright © 2015 Elsevier B.V. All rights reserved.

  14. Optical nanoimaging for block copolymer self-assembly. (United States)

    Yan, Jie; Zhao, Ling-Xi; Li, Chong; Hu, Zhe; Zhang, Guo-Feng; Chen, Ze-Qiang; Chen, Tao; Huang, Zhen-Li; Zhu, Jintao; Zhu, Ming-Qiang


    One approach toward optical nanoimaging involves sequential molecular localization of photoswitchable fluorophores to achieve high resolution beyond optical limit of diffraction. Block copolymer micelles assembled from polystryrene-block-poly(ethylene oxide) block copolymers (PSt-b-PEO) are visualized in optical nanoimaging by staining the polystyrene blocks with spiropyrans (SPs). SPs localized in hydrophobic phase of block copolymer micelles exhibit reversible fluorescence on-off switching at alternating irradiation of UV and visible light. Phase-selective distribution of SPs in block copolymer micelles enables optical nanoimaging of microphase structures of block copolymer self-assembly at 50-nm resolution. To date, this is the sturdiest realization of optical nanoimaging with subdiffraction resolution for solution self-assembly of block copolymers.

  15. Preparation of Proteoglycan Mimetic Graft Copolymers. (United States)

    Kipper, Matt J; Place, Laura W


    Proteoglycans are proteins with pendant glycosaminoglycan polysaccharide side chains. The method described here enables the preparation of graft copolymers with glycosaminoglycan side chains, which mimic the structure and composition of proteoglycans. By controlling the stoichiometry, graft copolymers can be obtained with a wide range of glycosaminoglycan side-chain densities. The method presented here uses a three-step reaction mechanism to first functionalize a hyaluronic acid backbone, followed by reductive amination to couple the glycosaminoglycan side chain to the backbone, by the reducing end. Proteoglycan mimics like the ones proposed here could be used to study the structure-property relationships of proteoglycans and to introduce the biochemical and biomechanical properties of proteoglycans into biomaterials and therapeutic formulations.

  16. Hybrid, Nanoscale Phospholipid/Block Copolymer Vesicles

    Directory of Open Access Journals (Sweden)

    Bo Liedberg


    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.

  17. Phase-Segregated Dendrigraft Copolymer Architectures

    Directory of Open Access Journals (Sweden)

    Lorena-Eugenia Sanchez Cadena


    Full Text Available Dendrigraft polymers have a multi-level branched architecture resulting from the covalent assembly of macromolecular building blocks. Most of these materials are obtained in divergent (core-first synthetic procedures whereby the molecule grows outwards in successive grafting reactions or generations. Two main types of dendrigraft polymers can be identified depending on the distribution of reactive sites over the grafting substrate: Arborescent polymers have a large and variable number of more or less uniformly distributed sites, while dendrimer-like star polymers have a lower but well-defined number of grafting sites strictly located at the ends of the substrate chains. An overview of the synthesis and the characterization of dendrigraft copolymers with phase-segregated morphologies is provided in this review for both dendrigraft polymer families. The tethering of side-chains with a different composition onto branched substrates confers unusual physical properties to these copolymers, which are highlighted through selected examples.

  18. Rapid ordering of block copolymer thin films. (United States)

    Majewski, Pawel W; Yager, Kevin G


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

  19. A Cationic Smart Copolymer for DNA Binding

    Directory of Open Access Journals (Sweden)

    Tânia Ribeiro


    Full Text Available A new block copolymer with a temperature-responsive block and a cationic block was prepared by reversible addition-fragmentation chain transfer (RAFT polymerization, with good control of its size and composition. The first block is composed by di(ethylene glycol methyl ether methacrylate (DEGMA and oligo(ethylene glycol methyl ether methacrylate (OEGMA, with the ratio DEGMA/OEGMA being used to choose the volume phase transition temperature of the polymer in water, tunable from ca. 25 to above 90 °C. The second block, of trimethyl-2-methacroyloxyethylammonium chloride (TMEC, is positively charged at physiological pH values and is used for DNA binding. The coacervate complexes between the block copolymer and a model single strand DNA are characterized by fluorescence correlation spectroscopy and fluorescence spectroscopy. The new materials offer good prospects for biomedical application, for example in controlled gene delivery.

  20. Mechanism of Molecular Exchange in Copolymer Micelles (United States)

    Choi, Soo-Hyung; Lodge, Timothy; Bates, Frank


    Compared to thermodynamic structure, much less has been known about the kinetics of block copolymer micelles which should underlay the attainment of thermodynamic equilibrium. In this presentation, molecular exchange between spherical micelles formed by isotopically labeled diblock copolymers was investigated using time-resolved small-angle neutron scattering. Two pairs of structurally matched poly(styrene-b-ethylene-alt-propylene) (PS-PEP) were synthesized and dispersed in isotopic mixture of squalane, highly selective to PEP block. Each pair includes polymers with fully deuterated (dPS-PEP) and a normal (hPS-PEP) PS blocks. Temperature dependence of the micelle exchange rate R(t) is consistent with melt dynamics for the core polymer. Furthermore, R(t) is significantly sensitive to the core block length N due to the thermodynamic penalty associated with ejecting a core block into the solvent. This hypersensitivity, combined with modest polydispersity in N, leads to an approximately logarithmic decay in R(t).

  1. Critical adsorption of copolymer tethered on selective surfaces (United States)

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


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

  2. Adsorption-like Collapse of Diblock Copolymers


    Orlandini, E.; Seno, F.; Stella, A. L.


    A linear copolymer made of two reciprocally attracting N-monomer blocks collapses to a compact phase through a novel transition, whose exponents are determined with extensive MC simulations in two and three dimensions. In the former case, an identification with the statistical geometry of suitable percolation paths allows to predict that the number of contacts between the blocks grows like $N^{9/16}$. In the compact phase the blocks are mixed and, in two dimensions, also zipped, in such a way...

  3. 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


    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.

  4. Fracture behavior of block copolymer and graphene nanoplatelet modified epoxy and fiber reinforced/epoxy polymer composites (United States)

    Kamar, Nicholas T.

    Glass and carbon fiber reinforced/epoxy polymer composites (GFRPs and CFRPs) have high strength-to-weight and stiffness-to-weight ratios. Thus, GFRPs and CFRPs are used to lightweight aircraft, marine and ground vehicles to reduce transportation energy utilization and cost. However, GFRP and CFRP matrices have a low resistance to crack initiation and propagation; i.e. they have low fracture toughness. Current methods to increase fracture toughness of epoxy and corresponding GFRP and CFRPs often reduce composite mechanical and thermomechanical properties. With the advent of nanotechnology, new methods to improve the fracture toughness and impact properties of composites are now available. The goal of this research is to identify the fracture behavior and toughening mechanisms of nanoparticle modified epoxy, GFRPs and CFRPs utilizing the triblock copolymer poly(styrene)-block-poly(butadiene)-block-poly(methylmethacrylate) (SBM) and graphene nanoplatelets (GnPs) as toughening agents. The triblock copolymer SBM was used to toughen the diglycidyl ether of bisphenol-A (DGEBA) resin cured with m-phenylenediamine (mPDA) and corresponding AS4-12k CFRPs. SBM self assembled in epoxy to form nanostructured domains leading to larger increases in fracture toughness, KQ (MPa*m 1/2) than the traditional, phase separating carboxyl-terminated butadiene-acrylonitrile (CTBN) rubber. Additionally, SBM increased the mode-I fracture toughness, GIc (J/m2) of CFRPs without corresponding reductions in composite three-point flexural properties and glass transition temperature (Tg). Fractography of SBM modified epoxy and CFRPs via scanning electron microscopy (SEM) showed that sub 100 nm spherical micelles cavitated to induce void growth and matrix shear yielding toughening mechanisms. Furthermore, SBM did not suppress epoxy Tg, while CTBN decreased Tg with both increasing concentration and acrylonitrile content. Graphene nanoplatelets (GnPs) consist of a few layers of graphene sheets, which

  5. LEGO-inspired drug design: Discovery of novel fungal Plasma membrane H+-ATPase (Pma1) inhibitors from small molecule libraries: An introduction of HFSA-SBS_DOS-RD strategy in drug discovery

    DEFF Research Database (Denmark)

    Tung, Truong Thanh; Dao, Trong Tuan; Palmgren, Michael B.

    Fungal plasma membrane H+-ATPase (Pma1) has recently emerged as a potential target for the discovery of new antifungal agents. This p-type pump which localized on the surface of fungal cells plays a crucial role in many physiol. functions and processes inside the cell. Esp., by pumping proton......, we have identified the need for small mol. library of high quality for targeting Pma1. The LEGO-inspired hypothesis encouraged us to first develop new strategy from the combination of hypothesis-based fragment selection and assembly (HFSA), specific biol. relevance scaffold based diversity......-oriented synthesis (SBS_DOS) and rational design (RD), so called HFSA-SBS_DOS-RD strategy in drug discovery and development process. Using HFSA-SBS_DOS-RD, our group successfully designed, synthesized, and performed SAR studies of novel compds. potent Pma1 inhibitors. An expeditious, high yield and scalable...

  6. Mistura PAni.DBSA/SBS Obtida por Polimerização "In Situ": Propriedades Elétrica, Dielétrica e Dinâmico-Mecânica

    Directory of Open Access Journals (Sweden)

    Leyva María E.


    Full Text Available Misturas elastoméricas condutoras de eletricidade envolvendo copolímero tribloco poli(estireno-b-butadieno-b-estireno (SBS e polianilina dopada com ácido dodecilbenzenosulfônico (Pani.DBSA foram obtidas por polimerização "in situ". Os filmes obtidos por moldagem por compressão mostraram baixo limiar de percolação, apresentando valores de condutividade semelhantes aos encontrados para o polímero condutor puro com cerca de 20 % em massa de Pani.DBSA. A caracterização das misturas por análise termodinâmico-mecânica (DMTA evidenciou uma ligeira interação da Pani.DBSA com ambas fases do copolímero SBS. Na região borrachosa, o módulo da mistura aumenta com o aumento do conteúdo de Pani. No entanto, existe uma progressiva queda no fator de amortecimento ("damping" com o aumento da concentração de Pani. A energia de ativação, Ea, do processo de transição vítreo-borrachoso de ambas fases do SBS foi calculada, utilizando a equação de Arrhenius com os dados obtidos tanto por DMTA como por análise termodielétrica (DETA. A caracterização dielétrica não proporcionou informações a respeito da localização da Pani.DBSA na matriz de SBS. No entanto, observou-se o fenômeno de polarização interfacial entre a Pani e o SBS. Uma morfologia do tipo microtubos foi observada para Pani.DBSA na mistura SBS/Pani.DBSA, utilizando-se a técnica de microscopia eletrônica de varredura.

  7. Convenient synthetic method of starch/lactic acid graft copolymer ...

    Indian Academy of Sciences (India)

    Copolymer of starch grafted with lactic acid (LA) could be directly prepared by reaction of cornstarch with lactic acid and with sodium hydroxide (NaOH) as the catalyst. The structure of starch/LA copolymer was characterized by IR, XRD, SEM and 1H-NMR. The effects of NaOH concentration, ratios of starch and LA, reaction ...

  8. Micellar structure of amphiphilic poly(2-oxazoline) diblock copolymers

    DEFF Research Database (Denmark)

    Papadakis, C.M.; Ivanova, R.; Lüdtke, K.


    Amphiphilic diblock copolymers from poly(2-oxazoline)s in aqueous solution can form micelles. By means of small-angle neutron scattering, we have found that poly[(n-nonyl-2-oxazoline)-b-(methyl-2-oxazoline)] {P[(NOx)-b-(MOx)]} diblock copolymers in aqueous solution form micelles of core-shell typ...

  9. Cryoelectron microscopy of block-copolymers in an organic solvent

    NARCIS (Netherlands)

    Oostergetel, G.T.; Esselink, F.J; Hadziioannou, G


    Solutions of the diblock copolymer polystyrene/poly-2-vinylpyridine (PS/P2VP) in toluene were studied by cryo-transmission electron microscopy following fast freezing of a thin film of the solution in liquid nitrogen. The block copolymer forms spherical micelles which can be visualized using phase

  10. Positively charged co-polymers for use as antimicrobial agents

    DEFF Research Database (Denmark)


    The present invention provides a positively charged co-polymer for use as an antimicrobial agent, wherein said positively charged co-polymer is composed of amino acids and/or derivatives thereof and wherein at least 75 molar percent of said amino acids are selected from the group consisting...

  11. Rheological Behavior of Entangled Polystyrene-Polyhedral Oligosilsesquioxane (POSS) Copolymer

    National Research Council Canada - National Science Library

    Wu, Jian; Mather, Patrick T; Haddad, Timothy S; Kim, Gyeong-Man


    ...: random copolymers of polystyrene (PS) and styryl-based polyhedral oligosilsesquioxane (POSS), R7(Si8O12)(C6H4CH=CH2), with R = isobutyl (iBu). A series of styrene-styryl POSS random copolymers with 0, 6, 15, 30, 50 wt...

  12. From Block Copolymers to Nano-porous Materials

    DEFF Research Database (Denmark)

    Vigild, Martin Etchells; Ndoni, Sokol; Berg, Rolf Henrik


    Quantitative etching of the polydimethylsiloxane block in a series of polystyrene-polydimethylsiloxane (PS-PDMS) block copolymers is reported. Reacting the block copolymer with anhydrous hydrogen fluoride (HF) renders a nanoporous material with the remaining PS maintaining the original morphology...

  13. Block Copolymer Directed Assembly for Nanomaterials and Nanodevices (United States)

    Kim, Sang


    Block copolymer nanopatterning is a promising technology that can complement the inherent limitations of conventional photolithography. The spontaneous and parallel assembly of block copolymers may generate densely packed, periodic 10-nm-scale nanodomains in a scalable way. Furthermore, laterally ordered, device-oriented nanostructures are attainable by the directed self-assembly principles employing prepatterned substrates. In this presentation, the overview of my research achievements associated to block copolymer nanopatterning will be presented. My research group demonstrated the world-first successful integration of block copolymer nanopatterning with 193 nm ArF lithography. We also developed soft-graphoepitaxy, which generates highly aligned nanoscale metal and semiconductor nanostructures without any trace of structure-directing topographic pattern. Soft-graphoepitaxy could be further developed to ultralarge-area nanopatterning, where micrometer scale photoresist pattern can be completely transformed into large-area block copolymer nanopattern. My research group also developed various pattern transfer methods for block copolymer nanopatterning. Mussel-inspired block copolymer nanopatterning exploiting universal natural adhesive of mussel polydopamine enables the nanopatterning of low surface energy materials, such as gold, Teflon and graphene. Our recent transferrable and flexible nanopatterning employing chemically modified graphene films as pattern substrates makes it possible to apply block copolymer nanopatterning onto arbitrary nonplanar and flexible geometries and generates ideal three-dimensional assembly of carbon nanotubes and graphene.

  14. How PEO-PPO-PEO triblock polymer micelles control the synthesis of gold nanoparticles: temperature and hydrophobic effects. (United States)

    Khullar, Poonam; Mahal, Aabroo; Singh, Vijender; Banipal, Tarlok Singh; Kaur, Gurinder; Bakshi, Mandeep Singh


    Aqueous micellar solutions of F68 (PEO(78)-PPO(30)-PEO(78)) and P103 (PEO(17)-PPO(60)-PEO(17)) triblock polymers were used to synthesize gold (Au) nanoparticles (NPs) at different temperatures. All reactions were monitored with respect to reaction time and temperature by using UV-visible studies to understand the growth kinetics of NPs and the influence of different micellar states on the synthesis of NPs. The shape, size, and locations of NPs in the micellar assemblies were determined with the help of TEM, SEM, and EDS analyses. The results explained that all reactions were carried out with the PEO-PPO-PEO micellar surface cavities present at the micelle-solution interface and were precisely controlled by the micellar assemblies. Marked differences were detected when predominantly hydrophilic F68 and hydrophobic P103 micelles were employed to conduct the reactions. The UV-visible results demonstrated that the reduction of gold ions into nucleating centers was channeled through the ligand-metal charge-transfer complex (LMCT) and carried out by the surface cavities. Excessive hydration of the surface cavities in the case of F68 micelles produced a few small NPs, but their yield and size increased as the micelles were dehydrated under the effect of increasing temperature. The results concluded that the presence of well-defined predominantly hydrophobic micelles with a compact micelle-solution interfacial arrangement of surface cavities ultimately controlled the reaction.

  15. Compatibility of Functionalized Graphene with Polyethylene and Its Copolymers

    Directory of Open Access Journals (Sweden)

    Hyeon Myeong Seo


    Full Text Available The compatibility of polyethylene (PE with a functionalized graphene sheet (FGS, which was prepared by the thermal reduction of graphite oxide, was examined in this study. The dispersion of the FGS in the PE was improved as the molecular weight of the PE was decreased. The PE copolymers containing polar comonomers such as maleic anhydride or acrylic acid exhibited better compatibility with FGS than the PE homopolymers. The compatibility of the FGS with PE copolymers containing small amounts of comonomers, which have a solubility parameter slightly larger [up to approximately 0.5 (J/cm31/2] than that of PE itself, was better than the compatibility of both the PE and PE copolymers containing larger amounts of comonomers. The morphology, electric conductivity, and tensile properties of FGS/PE copolymer/PE nanocomposites showed that the copolymers with a solubility parameter slightly larger than that of PE effectively served as a compatibilizer in FGS/PE nanocomposites.

  16. Sulfomethylated graft copolymers of xanthan gum and polyacrylamide

    Energy Technology Data Exchange (ETDEWEB)

    Cottrell, I.W.; Empey, R.A.; Racciato, J.S.


    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.

  17. 21 CFR 177.1990 - Vinylidene chloride/methyl acrylate copolymers. (United States)


    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Vinylidene chloride/methyl acrylate copolymers. 177... chloride/methyl acrylate copolymers. The vinylidene chloride/methyl acrylate copolymers (CAS Reg. No. 25038...) Identity. For the purposes of this section vinylidene chloride/methyl acrylate copolymers consist of basic...

  18. 21 CFR 177.1570 - Poly-1-butene resins and butene/ethylene copolymers. (United States)


    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Poly-1-butene resins and butene/ethylene copolymers... resins and butene/ethylene copolymers. The poly-1-butene resins and butene/ethylene copolymers identified... the catalytic polymerization of 1-butene liquid monomer. Butene/ethylene copolymers are produced by...

  19. Small domain-size multiblock copolymer electrolytes (United States)

    Pistorino, Jonathan; Eitouni, Hany Basam


    New block polymer electrolytes have been developed which have higher conductivities than previously reported for other block copolymer electrolytes. The new materials are constructed of multiple blocks (>5) of relatively low domain size. The small domain size provides greater protection against formation of dendrites during cycling against lithium in an electrochemical cell, while the large total molecular weight insures poor long range alignment, which leads to higher conductivity. In addition to higher conductivity, these materials can be more easily synthesized because of reduced requirements on the purity level of the reagents.

  20. Nucleation of Ordered Phases in Block Copolymers (United States)

    Cheng, Xiuyuan; Lin, Ling; E, Weinan; Zhang, Pingwen; Shi, An-Chang


    Nucleation of various ordered phases in block copolymers is studied by examining the free-energy landscape within the self-consistent field theory. The minimum energy path (MEP) connecting two ordered phases is computed using a recently developed string method. The shape, size, and free-energy barrier of critical nuclei are obtained from the MEP, providing information about the emergence of a stable ordered phase from a metastable phase. In particular, structural evolution of embryonic gyroid nucleus is predicted to follow two possible MEPs, revealing an interesting transition pathway with an intermediate perforated layered structure.

  1. Functional Nanoparticles Enabled by Block Copolymer Templates: from Precision Synthesis of Block Copolymers to Properties and Applications of Nanoparticles. (United States)

    Li, Xiao; Iocozzia, James; Chen, Yihuang; Zhao, Shiqiang; Cui, Xun; Wang, Wei; Yu, Haifeng; Lin, Shaoliang; Lin, Zhiqun


    Inorganic nanoparticles have become a research focus in numerous fields because of their unique properties that distinguish them from their bulk counterparts. Controlling the size and shape of nanoparticles is an essential aspect of nanoparticle synthesis. Preparing inorganic nanoparticles via block copolymer templates is one of the most reliable routes for tuning the size and shape of nanoparticles with a high degree of precision. In this review, we discuss recent progress in block copolymer template design and implementation in the crafting of spherical inorganic nanoparticles including plain, hollow and core@shell varieties. The templates, also known as nanoreactors, are divided into two categories: micelles self-assembled from linear block copolymers and unimolecular star-like block copolymers. The precise control of size and morphology of nanoparticles is highlighted. The useful properties and applications of inorganic nanoparticles prepared from block copolymer templates are also addressed. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Kinetic assembly of block copolymers in solution helical cylindrical micelles and patchy nanoparticles (United States)

    Zhong, Sheng

    There is always an interest to understand how molecules behave under different conditions. One application of this knowledge is to self-assemble molecules into increasingly complex structures in a simple fashion. Self-assembly of amphiphilic block copolymer in solution has produced a large variety of nanostructures through the manipulation in polymer chemistry, assembly environment, and additives. Moreover, some reports suggest the formation of many polymeric assemblies is driven by kinetic process. The goal of this dissertation is to study the influence of kinetics on the assembly of block copolymer. The study shows kinetic control can be a very effective way to make novel polymeric nanostructures. Two examples discussed here are helical cylindrical micelles and patchy nanoparticles. Helical cylindrical micelles are made from the co-assembly of amphiphilic triblock copolymer poly(acrylic acid)-block-poly(methyl acrylate)- block-polystyrene and organoamine molecules in a mixture of tetrahydrofuran (THF) and water (H2O). This system has already shown promise of achieving many assembled structures. The unique aspects about this system are the use of amine molecules to complex with acid groups and the existence of cosolvent system. Application of amine molecules offers a convenient control over assembled morphology and the introduction of PMA-PS selective solvent, THF, promotes the mobility of the polymer chains. In this study, multivalent organoamine molecules, such as diethylenetriamine and triethylenetetramine, are used to interact with block copolymer in THF/water mixture. As expected, the assembled morphologies are dependent on the polymer architecture, selection and quantity of the organoamine molecules, and solution composition. Under the right conditions, unprecedented, multimicrometer-long, supramolecular helical cylindrical micelles are formed. Both single-stranded and double-stranded helices are found in the same system. These helical structures share

  3. Acute effects of continuous infusions of glucagon-like peptide (GLP)-1, GLP-2 and the combination (GLP-1+GLP-2) on intestinal absorption in short bowel syndrome (SBS) patients. A placebo-controlled study

    DEFF Research Database (Denmark)

    Madsen, K B; Askov-Hansen, C; Naimi, R M


    The ileocolonic brake is impaired in short bowel syndrome (SBS) patients with distal bowel resections. An attenuated meal-stimulated hormone secretion may cause gastric hypersecretion, rapid gastric and intestinal transit and a poor adaptation. Attempting to restore this ileocolonic brake...

  4. Benzodithiophene and Imide-Based Copolymers for Photovoltaic; Applications

    Energy Technology Data Exchange (ETDEWEB)

    Braunecker, W. A.; Owczarczyk, Z. R.; Garcia, A.; Kopidakis, N.; Larsen, R. E.; Hammond, S. R.; Ginley, D. S.; Olson, D. C.


    Conjugated alternating copolymers were designed with low optical band gaps for organic photovoltaic (OPV) applications by considering quinoid resonance stabilization. Copolymers of thienoisoindoledione (TID) and benzodithiophene (BDT) had appreciably lower band gaps (by {approx}0.4 eV) than copolymers of thienopyrroledione (TPD) and BDT. In addition to intramolecular charge transfer stabilization (i.e., the 'push-pull' effect), the former copolymer's quinoid resonance structure is stabilized by a gain in aromatic resonance energy in the isoindole unit. Additionally, the HOMO levels of the copolymers could be tuned with chemical modifications to the BDT monomer, resulting in open circuit voltages of greater than 1 V in photovoltaic devices. Despite the optimized band gap, TID containing polymers displayed lower photoconductance, as determined by time-resolved microwave conductivity, and decreased device efficiency (2.1% vs 4.8%) as compared with TPD analogues. These results were partially attributed to morphology, as computational modeling suggests TID copolymers have a twisted backbone, and X-ray diffraction data indicate the polymer films do not form ordered domains, whereas TPD copolymers are considerably more planar and are shown to form partially ordered domains.

  5. Synthesis and morphological characterization of block copolymers for improved biomaterials

    Energy Technology Data Exchange (ETDEWEB)

    Schricker, Scott, E-mail: [Restorative and Prosthetic Dentistry Section, College of Dentistry, The Ohio State University, Columbus, OH 43210 (United States); Palacio, Manuel [Nanoprobe Laboratory for Bio- and Nanotechnology and Biomimetics, The Ohio State University, Columbus, OH 43210 (United States); Thirumamagal, B.T.S. [Restorative and Prosthetic Dentistry Section, College of Dentistry, The Ohio State University, Columbus, OH 43210 (United States); Bhushan, Bharat [Nanoprobe Laboratory for Bio- and Nanotechnology and Biomimetics, The Ohio State University, Columbus, OH 43210 (United States)


    Biocompatible polymers are known to act as scaffolds for the regeneration and growth of bone. Block copolymers are of interest as scaffold materials because a number of the blocks are biocompatible, and their nanostructure is easily tunable with synthetic techniques. In this paper, we report the synthesis of a novel class of biomaterials from block copolymers containing a hydrophobic block of methyl methacrylate and a hydrophilic block of either acrylic acid, dimethyl acrylamide, or 2-hydroxyethyl methacrylate. The block copolymers were synthesized using a combination of reversible addition-fragmentation chain transfer (RAFT) polymerization and click chemistry. Since the surface morphology is critical for successful cell growth, atomic force microscopy (AFM) studies were conducted for selected block copolymers. The topography, phase angle and friction maps were obtained in dry and physiological buffer environments to study the morphology. Results of AFM imaging identified the presence of polymer domains corresponding to the copolymer components. The distribution of nanoscale features in these block copolymers is comparable to those found on other surfaces that exhibit favorable cell adhesion and growth. In physiological buffer medium, the hydrophilic component of the block copolymer (acrylic acid or hydroxyethyl methacrylate) appears to be present in greater amounts on the surface as a consequence of water absorption and swelling.

  6. Synthesis and characterization of diblock copolymer templated iron oxide nanoparticles (United States)

    Akcora, Pinar


    Templating ordered assemblies of magnetic oxide nanoparticles within self-assembled diblock copolymers of varying morphologies is an important problem with a wide applicability such as in electromagnetics, optical devices, metal catalysts, medicine and biology. In this thesis, the effects of different polymer structures on particle ordering and resultant magnetic properties have been investigated using various microstructure and magnetic characterization tools. Ring-opening metathesis polymerization (ROMP) of norbornene and functionalized norbornene monomers has been used to synthesize diblock copolymers of narrow polydispersities using Grubbs' catalyst. These block copolymers can be used as templates to form inorganic nanoparticles. In this research, the structural and physical understanding of the inorganic-copolymer system was studied by small-angle neutron and x-ray scattering techniques and transmission electron microscopy. Synthesis of gamma-Fe2O3 nanoparticles has been achieved within novel block copolymers of (norbornene)-b-(deuterated norbornene dicarboxylic) acid and (norbornene methanol-(norbornene dicarboxylic acid). The polymer morphologies were controlled by varying the volume fractions of the constituent blocks. The pure norbornene based diblock copolymer morphologies were demonstrated by electron microscopy for the first tune. Spherical, cylindrical and lamellar morphologies of these novel diblock copolymers were reported. The block ratios of the synthesized polymers were determined using gel permeation chromatography-light scattering, elemental analysis and UV-VIS spectroscopy. Solution phase doping and submersion of thin films in metal salt solutions were employed as metal doping methods and the observed nanoparticle structures were compared to those of the undoped copolymer morphologies. This project reports on the types of templating structures and dispersion of the nanoparticles. The effects of particle, interactions on the microphase

  7. Nanoparticle Network Formation in Nanostructured and Disordered Block Copolymer Matrices

    Directory of Open Access Journals (Sweden)

    Khan Saad


    Full Text Available Abstract Incorporation of nanoparticles composed of surface-functionalized fumed silica (FS or native colloidal silica (CS into a nanostructured block copolymer yields hybrid nanocomposites whose mechanical properties can be tuned by nanoparticle concentration and surface chemistry. In this work, dynamic rheology is used to probe the frequency and thermal responses of nanocomposites composed of a symmetric poly(styrene-b-methyl methacrylate (SM diblock copolymer and varying in nanoparticle concentration and surface functionality. At sufficiently high loading levels, FS nanoparticle aggregates establish a load-bearing colloidal network within the copolymer matrix. Transmission electron microscopy images reveal the morphological characteristics of the nanocomposites under these conditions.

  8. Patchy micelles based on coassembly of block copolymer chains and block copolymer brushes on silica particles. (United States)

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


    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.

  9. Methacrylamide Copolymer Resists For Electron Beam Lithography (United States)

    Namaste, Y. M. N.; Obendorf, S. K.; Rodriguez, F.


    Polymethacrylamide (PMAAm) and copolymers of MAAm with methyl methacrylate were synthesized and evaluated for their applicability to electron beam lithography. The sensitivity of PMAAm has previously been reported as less than 1 μC/cm2, with thermal stability at temperatures up to 330°C.' Despite these claims, further lithographic evaluation of this resist system is apparently absent from the literature. This research was conducted to further investigate the lithographic performance of these resists and to determine their sensitivity using current definitions. Using PMAAm homopolymer (Mw = 8.1 x 105), with a 15 minute prebake at 200°C, the lithographic results were much poorer than expected. Patterns exposed to doses of 10 μC/cm2 or lower could not be developed using water as the developing solvent. Forced developing with Na2SiO3 solution (pH=10) developed lower doses than water, but much greater thinning was observed. An unexposed thinning of 10% occurred when developing exposures of 15 μC/cm2 with water, and 40 μC/cm2 with Na2SiO3 solution (20 KV). Swelling of the unexposed polymer and some adhesion problems were observed. The high sensitivity previously reported for PMAAm' can not be attributed solely to chain scission efficiency (Gs), which has been reported to be only 1.5 times that of PMMA (Gs determined by Y-irradiation). An induction period in the dissolution of unexposed polymer has also been sugggested as contributing to the sensitivity of this resist. In the present work, dissolution induction periods were observed with laser interferometry for the unexposed films, but the magnitude of these induction periods could not account for a large enhancement of sensitivity. Imide crosslink formation may have been responsible for the previously reported sensitivity of PMAAm.' In the present work, imid formation was not observed, either after prebaking coated wafers at 180 to 240°C or heating of polymer solutions for 7 hours at 80°C. Apparently, the

  10. Synthesis and interfacial behavior of polystyrene-polysaccharide diblock copolymers

    NARCIS (Netherlands)

    Bosker, W.T.E.; Ágoston, K.; Cohen Stuart, M.A.; Norde, W.; Timmermans, J.W.; Slaghek, T.M.


    Linear block copolymers of polystyrene and polysaccharide were synthesized using a block synthesis method with amino-terminated polystyrene and sodium cyanoborohydride as reducing agent. Different types of polysaccharides, dextrans, and maltodextrins with various molecular weights were used. IR

  11. Controlled Synthesis of Fluorinated Copolymers with Pendant Sulfonates

    DEFF Research Database (Denmark)

    Dimitrov, Ivaylo; Jankova Atanasova, Katja; Hvilsted, Søren


    Novel fluorinated copolymers of different architectures and bearing sulfopropyl groups were synthesized by atom transfer radical polymerization (ATRP) of aromatic fluorinated monomers and two modification reactions performed on the polymer chain - demethylation followed by sulfopropylation. As a ...

  12. Opto-electronic devices from block copolymers and their oligomers.

    NARCIS (Netherlands)

    Hadziioannou, G


    This paper presents research activities towards the development of polymer materials and devices for optoelectronics, An approach to controlling the conjugation length and transferring the luminescence properties of organic molecules to polymers through black copolymers containing well-defined

  13. Composition fluctuations in homopolymer blends and diblock copolymers

    DEFF Research Database (Denmark)

    Frielinghaus, H.; Mortensen, K.; Almdal, K.


    The thermal composition fluctuations of a deuterogenous polystyrene/polyethyleneoxide (dPS/PEO) homopolymer blend and corresponding diblock copolymer have been investigated by small angle neutron scattering (SANS). The measured susceptibilities could be described by theories, which take strong...

  14. HPMA and HEMA copolymer bead interactions with eukaryotic cells

    Directory of Open Access Journals (Sweden)

    Cristina D. Vianna-Soares


    Full Text Available Two different hydrophilic acrylate beads were prepared via aqueous suspension polymerization. Beads produced of a hydroxypropyl methacrylate (HPMA and ethyleneglycol methacrylate (EDMA copolymer were obtained using a polyvinyl alcohol suspending medium. Copolymers of 2hydroxyethyl methacrylate (HEMA, methyl methacrylate (MMA and ethyleneglycol methacrylate (EDMA beads were obtained using magnesium hydroxide as the suspending agent. Following characterization by scanning electron microscopy (SEM, nitrogen sorption analysis (NSA and mercury intrusion porosimetry (MIP, the beads were cultured with monkey fibroblasts (COS7 to evaluate their ability to support cell growth, attachment and adhesion. Cell growth behavior onto small HPMA/EDMA copolymer beads and large HEMA/MMA/EDMA copolymer beads is evaluated regarding their hidrophilicity/hidrophobicity and surface roughness.

  15. Surface morphology of PS-PDMS diblock copolymer films

    DEFF Research Database (Denmark)

    Andersen, T.H.; Tougaard, S.; Larsen, N.B.


    Spin coated thin films (∼400 Å) of poly(styrene)–poly(dimethylsiloxane) (PS–PDMS) diblock copolymers have been investigated using X-ray Photoelectron Spectroscopy and Atomic Force Microscopy. Surface segregation of the poly(dimethylsiloxane) blocks was studied for five diblock copolymers which...... by use of peak shape analysis of the X-ray Photoelectron Spectra via the Tougaard Method. The amount of dimethylsiloxane in the uppermost part of the films was quantified as a function of annealing time and temperature. For annealing above the PS glass transition temperature, surface segregation...... of the dimethylsiloxane chain-ends occurs for all the studied PS–PDMS diblock copolymers. At room temperature, surface segregation takes place only when the amount of dimethylsiloxane in the diblock copolymers is small....

  16. Blends of caprolactam/caprolactone copolymers and chlorinated polymers

    NARCIS (Netherlands)

    Alberda van Ekenstein, G.O.R.; Deuring, H.; ten Brinke, G.; Ellis, T.S.

    The phase behaviour of blends of chlorinated polyethylene, polyvinyl chloride (PVC) and chlorinated PVC with random copolymers of caprolactone and caprolactam has been investigated and the results correlated with a binary interaction model. The known miscibility of polycaprolactone in the

  17. Nanopatterned articles produced using reconstructed block copolymer films (United States)

    Russell, Thomas P.; Park, Soojin; Wang; , Jia-Yu; Kim, Bokyung


    Nanopatterned surfaces are prepared by a method that includes forming a block copolymer film on a substrate, annealing and surface reconstructing the block copolymer film to create an array of cylindrical voids, depositing a metal on the surface-reconstructed block copolymer film, and heating the metal-coated block copolymer film to redistribute at least some of the metal into the cylindrical voids. When very thin metal layers and low heating temperatures are used, metal nanodots can be formed. When thicker metal layers and higher heating temperatures are used, the resulting metal structure includes nanoring-shaped voids. The nanopatterned surfaces can be transferred to the underlying substrates via etching, or used to prepare nanodot- or nanoring-decorated substrate surfaces.

  18. Concentration Dependent Structure of Block Copolymer Solutions (United States)

    Choi, Soohyung; Bates, Frank S.; Lodge, Timothy P.


    Addition of solvent molecules into block copolymer can induce additional interactions between the solvent and both blocks, and therefore expands the range of accessible self-assembled morphologies. In particular, the distribution of solvent molecules plays a key role in determining the microstructure and its characteristic domain spacing. In this study, concentration dependent structures formed by poly(styrene-b-ethylene-alt-propylene) (PS-PEP) solution in squalane are investigated using small-angle X-ray scattering. This reveals that squalane is essentially completely segregated into the PEP domains. In addition, the conformation of the PS block changes from stretched to nearly fully relaxed (i.e., Gaussian conformation) as amounts of squalane increases. NRF

  19. Interfacial properties of semifluorinated alkane diblock copolymers (United States)

    Pierce, Flint; Tsige, Mesfin; Borodin, Oleg; Perahia, Dvora; Grest, Gary S.


    The liquid-vapor interfacial properties of semifluorinated linear alkane diblock copolymers of the form F3C(CF2)n-1(CH2)m-1CH3 are studied by fully atomistic molecular dynamics simulations. The chemical composition and the conformation of the molecules at the interface are identified and correlated with the interfacial energies. A modified form of the Optimized Parameter for Liquid Simulation All-Atom (OPLS-AA) force field of Jorgensen and co-workers [J. Am. Chem. Soc. 106, 6638 (1984); 118, 11225 (1996); J. Phys. Chem. A 105, 4118 (2001)], which includes specific dihedral terms for H-F blocks-and corrections to the H-F nonbonded interaction, is used together with a new version of the exp-6 force field developed in this work. Both force fields yield good agreement with the available experimental liquid density and surface tension data as well as each other over significant temperature ranges and for a variety of chain lengths and compositions. The interfacial regions of semifluorinated alkanes are found to be rich in fluorinated groups compared to hydrogenated groups, an effect that decreases with increasing temperature but is independent of the fractional length of the fluorinated segments. The proliferation of fluorine at the surface substantially lowers the surface tension of the diblock copolymers, yielding values near those of perfluorinated alkanes and distinct from those of protonated alkanes of the same chain length. With decreasing temperatures within the liquid state, chains are found to preferentially align perpendicular to the interface, as previously seen.

  20. Multicompartmental Microcapsules from Star Copolymer Micelles

    Energy Technology Data Exchange (ETDEWEB)

    Choi, Ikjun; Malak, Sidney T.; Xu, Weinan; Heller, William T.; Tsitsilianis, Constantinos; Tsukruk, Vladimir V.


    We present the layer-by-layer (LbL) assembly of amphiphilic heteroarm pH-sensitive star-shaped polystyrene-poly(2-pyridine) (PSnP2VPn) block copolymers to fabricate porous and multicompartmental microcapsules. Pyridine-containing star molecules forming a hydrophobic core/hydrophilic corona unimolecular micelle in acidic solution (pH 3) were alternately deposited with oppositely charged linear sulfonated polystyrene (PSS), yielding microcapsules with LbL shells containing hydrophobic micelles. The surface morphology and internal nanopore structure of the hollow microcapsules were comparatively investigated for shells formed from star polymers with a different numbers of arms (9 versus 22) and varied shell thickness (5, 8, and 11 bilayers). The successful integration of star unimers into the LbL shells was demonstrated by probing their buildup, surface segregation behavior, and porosity. The larger arm star copolymer (22 arms) with stretched conformation showed a higher increment in shell thickness due to the effective ionic complexation whereas a compact, uniform grainy morphology was observed regardless of the number of deposition cycles and arm numbers. Small-angle neutron scattering (SANS) revealed that microcapsules with hydrophobic domains showed different fractal properties depending upon the number of bilayers with a surface fractal morphology observed for the thinnest shells and a mass fractal morphology for the completed shells formed with the larger number of bilayers. Moreover, SANS provides support for the presence of relatively large pores (about 25 nm across) for the thinnest shells as suggested from permeability experiments. The formation of robust microcapsules with nanoporous shells composed of a hydrophilic polyelectrolyte with a densely packed hydrophobic core based on star amphiphiles represents an intriguing and novel case of compartmentalized microcapsules with an ability to simultaneously store different hydrophilic, charged, and hydrophobic

  1. Supramolecular Multiblock Copolymers Featuring Complex Secondary Structures. (United States)

    Elacqua, Elizabeth; Manning, Kylie B; Lye, Diane S; Pomarico, Scott K; Morgia, Federica; Weck, Marcus


    This contribution introduces main-chain supramolecular ABC and ABB'A block copolymers sustained by orthogonal metal coordination and hydrogen bonding between telechelic polymers that feature distinct secondary structure motifs. Controlled polymerization techniques in combination with supramolecular assembly are used to engineer heterotelechelic π-sheets that undergo high-fidelity association with both helical and coil-forming synthetic polymers. Our design features multiple advances to achieve our targeted structures, in particular, those emulating sheet-like structural aspects using poly(p-phenylenevinylene)s (PPVs). To engineer heterotelechelic PPVs in a sheet-like design, we engineer an iterative one-pot cross metathesis-ring-opening metathesis polymerization (CM-ROMP) strategy that affords functionalized Grubbs-II initiators that subsequently polymerize a paracyclophanediene. Supramolecular assembly of two heterotelechelic PPVs is used to realize a parallel π-sheet, wherein further orthogonal assembly with helical motifs is possible. We also construct an antiparallel π-sheet, wherein terminal PPV blocks are adjacent to a flexible coil-like poly(norbornene) (PNB). The PNB is designed, through supramolecular chain collapse, to expose benzene and perfluorobenzene motifs that promote a hairpin turn via charge-transfer-aided folding. We demonstrate that targeted helix-(π-sheet)-helix and helix-(π-sheet)-coil assemblies occur without compromising intrinsic helicity, while both parallel and antiparallel β-sheet-like structures are realized. Our main-chain orthogonal assembly approach allows the engineering of multiblock copolymer scaffolds featuring diverse secondary structures via the directional assembly of telechelic building blocks. The targeted assemblies, a mix of sequence-defined helix-sheet-coil and helix-sheet-helix architectures, are Nature-inspired synthetic mimics that expose α/β and α+β protein classes via de novo design and cooperative assembly

  2. Novel block, graft and random copolymers for biomedical applications

    DEFF Research Database (Denmark)

    Javakhishvili, Irakli; Jankova Atanasova, Katja; Tanaka, Masaru

    Despite the simple structure, poly(2-methoxyethyl acrylate) (PMEA) shows excellent blood compatibility [1]. Both the freezing-bound water (intermediate water: preventing the biocomponents from directly contacting the polymer surface) and non-freezing water on the polymer surface play important ro...... copolymers with MMA [4] utilizing ATRP. Here we present other block, graft and random copolymers of MEA intended for biomedical applications. These macromolecular architectures have been constructed by employing controlled radical polymerization methods such as RAFT and ATRP....

  3. Microbial production of polyhydroxyalkanoate block copolymer by recombinant Pseudomonas putida. (United States)

    Li, Shi Yan; Dong, Cui Ling; Wang, Shen Yu; Ye, Hai Mu; Chen, Guo-Qiang


    Polyhydroxyalkanoate (PHA) synthesis genes phaPCJ(Ac) cloned from Aeromonas caviae were transformed into Pseudomonas putida KTOY06ΔC, a mutant of P. putida KT2442, resulting in the ability of the recombinant P. putida KTOY06ΔC (phaPCJ(A.c)) to produce a short-chain-length and medium-chain-length PHA block copolymer consisting of poly-3-hydroxybutyrate (PHB) as one block and random copolymer of 3-hydroxyvalerate (3HV) and 3-hydroxyheptanoate (3HHp) as another block. The novel block polymer was studied by differential scanning calorimetry (DSC), nuclear magnetic resonance, and rheology measurements. DSC studies showed the polymer to possess two glass transition temperatures (T(g)), one melting temperature (T(m)) and one cool crystallization temperature (T(c)). Rheology studies clearly indicated a polymer chain re-arrangement in the copolymer; these studies confirmed the polymer to be a block copolymer, with over 70 mol% homopolymer (PHB) of 3-hydroxybutyrate (3HB) as one block and around 30 mol% random copolymers of 3HV and 3HHp as the second block. The block copolymer was shown to have the highest tensile strength and Young's modulus compared with a random copolymer with similar ratio and a blend of homopolymers PHB and PHVHHp with similar ratio. Compared with other commercially available PHA including PHB, PHBV, PHBHHx, and P3HB4HB, the short-chain- and medium-chain-length block copolymer PHB-b-PHVHHp showed differences in terms of mechanical properties and should draw more attentions from the PHA research community. © Springer-Verlag 2010

  4. Fast & scalable pattern transfer via block copolymer nanolithography

    DEFF Research Database (Denmark)

    Li, Tao; Wang, Zhongli; Schulte, Lars


    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...... on long range lateral order, including fabrication of substrates for catalysis, solar cells, sensors, ultrafiltration membranes and templating of semiconductors or metals....

  5. Self-Assembled Antimicrobial and biocompatible copolymer films on Titanium


    Pfaffenroth, Cornelia; Winkel, Andreas; Dempwolf, Wibke; Gamble, Lara J.; Castner, David G.; Stiesch, Meike; Menzel, Henning


    Biofilm formation on biomedical devices such as dental implants can result in serious infections and finally in device failure. Polymer coatings which provide antimicrobial action to surfaces without compromising the compatibility with human tissue are of great interest. Copolymers of 4-vinyl-N-hexylpyridinium bromide and dimethyl(2-methacryloyloxyethyl) phosphonate are interesting candidates in this respect. These copolymers form ultrathin polycationic layers on titanium surfaces. As the cop...

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

    KAUST Repository

    Docampo, Pablo


    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.

  7. Method of forming oriented block copolymer line patterns, block copolymer line patterns formed thereby, and their use to form patterned articles

    Energy Technology Data Exchange (ETDEWEB)

    Russell, Thomas P.; Hong, Sung Woo; Lee, Dong Hyun; Park, Soojin; Xu, Ting


    A block copolymer film having a line pattern with a high degree of long-range order is formed by a method that includes forming a block copolymer film on a substrate surface with parallel facets, and annealing the block copolymer film to form an annealed block copolymer film having linear microdomains parallel to the substrate surface and orthogonal to the parallel facets of the substrate. The line-patterned block copolymer films are useful for the fabrication of magnetic storage media, polarizing devices, and arrays of nanowires.

  8. Real-time monitoring of the penetration of amphiphilic acrylate copolymer in leather using a fluorescent copolymer as tracer. (United States)

    Du, Jin-Xia; Shi, Lu; Peng, Bi-Yu


    A fluorescent tracer, poly (acrylic-co-stearyl acrylate-co-3-acryloyl fluorescein) [poly (AA-co-SA-co-Ac-Flu)], used for real-time monitoring the penetration of amphiphilic acrylate copolymer, poly (acrylic-co-stearyl acrylate) [poly (AA-co-SA)], in leather was synthesized by radical polymerization of acrylic, stearyl acrylate and fluorescent monomer, 3-acryloyl fluorescein (Ac-Flu). The structure, molecular weight, introduced fluorescent group content and fluorescent characteristics of the fluorescent tracer and target copolymer, amphiphilic acrylate copolymer, were also characterized. The results show that the tracer presents the similar structural characteristics to the target and enough fluorescence intensity with 1.68 wt % of the fluorescent monomer introduced amount. The vertical section of the leather treated with the target copolymer mixing with 7% of the tracer exhibits evident fluorescence, and the change of fluorescence intensity along with the vertical section with treating time increasing can reflect the penetration depth of the target copolymer. The introduction of the fluorescent group in polymer structure through copolymerization with a limited amount of fluorescent monomer, Ac-Flu, is an effective way to make a tracer to monitor the penetration of the target in leather, which provides a new thought for the penetration research of syntans such as vinyl copolymer materials in leather manufacture. © 2015 Wiley Periodicals, Inc.

  9. High Precision NO2 and NO measurements with the ICAD instrument during s-b-s campaign Hohenpeißenberg 2016 (United States)

    Pöhler, Denis; Lutz, Erik; Horbanski, Martin; Lampel, Johannes; Platt, Ulrich


    Nitrogen Oxides (NOx = NO2 + NO) play a major role in air pollution and atmospheric chemistry. Beside health effects they influence e.g. acid rain, ozone and oxidation capacity. But precise NO2 and NO measurements are still difficult. State of the art NO2 / NO instruments show significant interferences e.g. to H2O and HONO, problems of zero point and calibration drifts, temperature and also vibration influences. Other systems, especially low cost sensors, feature significant problems in terms of measurement accuracy and reliability. To overcome these problems we developed a direct spectroscopic NO2 / NOx ICAD instrument (Iterative Cavity Enhanced DOAS). It feature high accuracy, is relatively small, mobile and requires only low power consumption. During a side by side (s-b-s) inter-comparison campaign at the Meteorological Observatory Hohenpeißenberg (DWD) 2016 the performance of different instruments for NO2, NO and NOx were investigated under natural and artificial conditions. The concentration ranged from few ppt up to 100ppb. The inter-comparison demonstrates excellent performance of our ICAD in terms of accuracy and drift. In comparison to other techniques it features no interferences to different humidity's, temperatures and interfering gases. Also the zero point and calibration is absolutely stable. As the instrument is also much simpler and easier to operate, it has many advantages in comparison to other instruments. The characteristics of the instruments and results of the campaign will be presented.

  10. New ALMA constraints on the star-forming interstellar medium at low metallicity: a 50 pc view of the blue compact dwarf galaxy SBS 0335-052 (United States)

    Cormier, D.; Bendo, G. J.; Hony, S.; Lebouteiller, V.; Madden, S. C.; Galliano, F.; Glover, S. C. O.; Klessen, R. S.; Abel, N. P.; Bigiel, F.; Clark, P. C.


    Properties of the cold interstellar medium of low-metallicity galaxies are not well known due to the faintness and extremely small scale on which emission is expected. We present deep ALMA band 6 (230 GHz) observations of the nearby, low-metallicity (12 + log (O/H) = 7.25) blue compact dwarf galaxy SBS 0335-052 at an unprecedented resolution of 0.2 arcsec (52 pc). The 12CO J = 2→1 line is not detected and we report a 3σ upper limit of LCO(2-1) = 3.6 × 104 K km s-1 pc2. Assuming that molecular gas is converted into stars with a given depletion time, ranging from 0.02 to 2 Gyr, we find lower limits on the CO-to-H2 conversion factor αCO in the range 102-104 M⊙ pc-2 (K km s-1)-1. The continuum emission is detected and resolved over the two main super star clusters. Re-analysis of the IR-radio spectral energy distribution suggests that the mm-fluxes are not only free-free emission but are most likely also associated with a cold dust component coincident with the position of the brightest cluster. With standard dust properties, we estimate its mass to be as large as 105 M⊙. Both line and continuum results suggest the presence of a large cold gas reservoir unseen in CO even with ALMA.

  11. New adhesive systems based on functionalized block copolymers

    Energy Technology Data Exchange (ETDEWEB)

    Kent, M.; Saunders, R.; Hurst, M.; Small, J.; Emerson, J.; Zamora, D.


    The goal of this work was to evaluate chemically-functionalized block copolymers as adhesion promoters for metal/thermoset resin interfaces. Novel block copolymers were synthesized which contain pendant functional groups reactive toward copper and epoxy resins. In particular, imidazole and triazole functionalities that chelate with copper were incorporated onto one block, while secondary amines were incorporated onto the second block. These copolymers were found to self-assemble from solution onto copper surfaces to form monolayers. The structure of the adsorbed monolayers were studied in detail by neutron reflection and time-of-flight secondary ion mass spectrometry. The monolayer structure was found to vary markedly with the solution conditions and adsorption protocol. Appropriate conditions were found for which the two blocks form separate layers on the surface with the amine functionalized block exposed at the air surface. Adhesion testing of block copolymer-coated copper with epoxy resins was performed in both lap shear and peel modes. Modest enhancements in bond strengths were observed with the block copolymer applied to the native oxide. However, it was discovered that the native oxide is the weak link, and that by simply removing the native oxide, and then applying an epoxy resin before the native oxide can reform, excellent bond strength in the as-prepared state as well as excellent retention of bond strength after exposure to solder in ambient conditions are obtained. It is recommended that long term aging studies be performed with and without the block copolymer. In addition, the functionalized block copolymer method should be evaluated for another system that has inherently poor bonding, such as the nickel/silicone interface, and for systems involving metals and alloys which form oxides very rapidly, such as aluminum and stainless steel, where bonding strategies involve stabilizing the native oxide.

  12. Disulfide-Functionalized Diblock Copolymer Worm Gels. (United States)

    Warren, Nicholas J; Rosselgong, Julien; Madsen, Jeppe; Armes, Steven P


    Two strategies for introducing disulfide groups at the outer surface of RAFT-synthesized poly(glycerol monomethacrylate)-poly(2-hydroxypropyl methacrylate) (PGMA-PHPMA, or Gx-Hy for brevity) diblock copolymer worms are investigated. The first approach involved statistical copolymerization of GMA with a small amount of disulfide dimethacrylate (DSDMA, or D) comonomer to afford a G54-D0.50 macromolecular chain transfer agent (macro-CTA); this synthesis was conducted in relatively dilute solution in order to ensure mainly intramolecular cyclization and hence the formation of linear chains. Alternatively, a new disulfide-based bifunctional RAFT agent (DSDB) was used to prepare a G45-S-S-G45 (or (G45-S)2) macro-CTA. A binary mixture of a non-functionalized G55 macro-CTA was utilized with each of these two disulfide-based macro-CTAs in turn for the RAFT aqueous dispersion polymerization of 2-hydroxypropyl methacrylate (HPMA). By targeting a PHPMA DP of 130 and systematically varying the molar ratio of the two macro-CTAs, a series of disulfide-functionalized diblock copolymer worm gels were obtained. For both formulations, oscillatory rheology studies confirmed that higher disulfide contents led to stronger gels, presumably as a result of inter-worm covalent bond formation via disulfide/thiol exchange. Using the DSDB-based macro-CTA led to the strongest worm gels, and this formulation also proved to be more effective in suppressing the thermosensitive behavior that is observed for the nondisulfide-functionalized control worm gel. However, macroscopic precipitation occurred when the proportion of DSDB-based macro-CTA was increased to 50 mol %, whereas the DSDMA-based macro-CTA could be utilized at up to 80 mol %. Finally, the worm gel modulus could be reduced to that of a nondisulfide-containing worm gel by reductive cleavage of the inter-worm disulfide bonds using excess tris(2-carboxyethyl)phosphine (TCEP) to yield thiol groups. These new biomimetic worm gels are

  13. Monte Carlo simulations of the phase separation of a copolymer blend in a thin film

    KAUST Repository

    Wang, Zhexiao


    Monte Carlo simulations were carried out to study the phase separation of a copolymer blend comprising an alternating copolymer and/or block copolymer in a thin film, and a phase diagram was constructed with a series of composed recipes. The effects of composition and segregation strength on phase separation were discussed in detail. The chain conformation of the block copolymer and alternating copolymer were investigated with changes of the segregation strength. Our simulations revealed that the segment distribution along the copolymer chain and the segregation strength between coarse-grained beads are two important parameters controlling phase separation and chain conformation in thin films of a copolymer blend. A well-controlled phase separation in the copolymer blend can be used to fabricate novel nanostructures.

  14. Chromatographic examination of the chemical composition and sequence distribution of copolymers from ethyl and benzyl diazoacetate

    NARCIS (Netherlands)

    Reingruber, E.M.; Chojnacka, A.; Jellema, E.; de Bruin, B.; Buchberger, W.; Schoenmakers, P.J.


    Polymers, especially copolymers, are highly complex samples and, therefore, require various setups for their thorough characterization. In this work, one- and two-dimensional chromatographic approaches were applied to characterize two homopolymers and two dissimilar copolymers prepared by

  15. Tough and Sustainable Graft Block Copolymer Thermoplastics

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Jiuyang; Li, Tuoqi; Mannion, Alexander M.; Schneiderman, Deborah K.; Hillmyer, Marc A.; Bates, Frank S. (UMM)


    Fully sustainable poly[HPMC-g-(PMVL-b-PLLA)] graft block copolymer thermoplastics were prepared from hydroxypropyl methylcellulose (HPMC), β-methyl-δ-valerolactone (MVL), and l-lactide (LLA) using a facile two-step sequential addition approach. In these materials, rubbery PMVL functions as a bridge between the semirigid HPMC backbone and the hard PLLA end blocks. This specific arrangement facilitates PLLA crystallization, which induces microphase separation and physical cross-linking. By changing the backbone molar mass or side chain composition, these thermoplastic materials can be easily tailored to access either plastic or elastomeric behavior. Moreover, the graft block architecture can be utilized to overcome the processing limitations inherent to linear block polymers. Good control over molar mass and composition enables the deliberate design of HPMC-g-(PMVL-b-PLLA) samples that are incapable of microphase separation in the melt state. These materials are characterized by relatively low zero shear viscosities in the melt state, an indication of easy processability. The simple and scalable synthetic procedure, use of inexpensive and renewable precursors, and exceptional rheological and mechanical properties make HPMC-g-(PMVL-b-PLLA) polymers attractive for a broad range of applications.

  16. Molecular Exchange in Ordered Diblock Copolymer Micelles (United States)

    Choi, Soo-Hyung; Lodge, Timothy; Bates, Frank


    Previously, molecular exchange between spherical micelles in dilute solution (1 vol% polymer) was investigated using time-resolved small-angle neutron scattering (TR-SANS). As the concentration of spherical micelles formed by the diblock copolymers increases, the micelles begin to overlap and eventually pack onto body-centered cubic (BCC) lattice. In this study, concentrated, ordered micelles (15 vol% polymers) prepared by dispersing isotopically labeled poly(styrene- b -ethylene-alt-propylene) in an isotopic squalane mixture was investigated to understand the micellar concentration dependence of the molecular exchange. Perfectly random mixing of isotopically labeled micelles on the BCC lattice was confirmed by SANS patterns where the interparticle contribution vanishes, resulting in an intensity that directly relates to the exchange kinetics. The measured molecular exchange process for the concentrated, ordered system is qualitatively consistent with the previous observations, but the rate is more than an order of magnitude slower than that for the dilute, disordered system. Infineum(IPrime), MRSEC(NSF), NIST.

  17. Molecular Exchange Dynamics in Block Copolymer Micelles (United States)

    Bates, Frank; Lu, Jie; Choi, Soohyung; Lodge, Timothy


    Poly(styrene-b-ethylene propylene) (PS-PEP) diblock copolymers were mixed with squalane (C30H62) at 1% by weight resulting in the formation of spherical micelles. The structure and dynamics of molecular exchange were characterized by synchrotron small-angle x-ray scattering (SAXS) and time resolved small-angle neutron scattering (TR-SANS), respectively, between 100 C and 160 C. TR-SANS measurements were performed with solutions initially containing deuterium labeled micelle cores and normal cores dispersed in a contrast matched squalane. Monitoring the reduction in scattering intensity as a function of time at various temperatures revealed molecular exchange dynamics highly sensitive to the core molecular weight and molecular weight distribution. Time-temperature superposition of data acquired at different temperatures produced a single master curve for all the mixtures. Experiments conducted with isotopically labeled micelle cores, each formed from two different but relatively mondisperse PS blocks, confirmed a simple dynamical model based on first order kinetics and core Rouse single chain relaxation. These findings demonstrate a dramatic transition to nonergodicity with increasing micelle core molecular weight and confirm the origins of the logarithmic exchange kinetics in such systems.

  18. Synthesis, characterization and antimicrobial activity of important heterocyclic acrylic copolymers

    Directory of Open Access Journals (Sweden)


    Full Text Available The acrylate monomer, 7-acryloyloxy-4-methyl coumarin (AMC has been synthesized by reacting 7-hydroxy-4-methyl coumarin, with acryloyl chloride in the presence of NaOH at 0–5°C. Copolymers of 7-acryloyloxy-4-methyl coumarin (AMC with vinyl acetate (VAc were synthesized in DMF (dimethyl formamide solution at 70±1°C using 2,2′-azobisisobutyronitrile (AIBN as an initiator with different monomer-to-monomer ratios in the feed. The copolymers were characterized by Fourier transform infra red (FTIR spectroscopy. The copolymer composition was evaluated by 1H-NMR (proton nuclear magnetic resonance and was further used to determine reactivity ratios. The monomer reactivity ratios for AMC (M1-VAc (M2 pair were determined by the application of conventional linearization methods such as Fineman-Ross (r1 = 0.6924; r2 = 0.6431, Kelen-Tüdõs (r1 = 0.6776; r2 = 0.6374 and extended Kelen-Tüdõs (r1 = 0.6657; r2 = 0.6256. Thermo gravimetric analysis showed that thermal decomposition of the copolymers occurred in single stage in the temperature range of 263–458°C. The molecular weights of the polymers were determined using gel permeation chromatography. The homo and copolymers were tested for their antimicrobial properties against selected microorganisms.

  19. Relaxation processes in a lower disorder order transition diblock copolymer

    Energy Technology Data Exchange (ETDEWEB)

    Sanz, Alejandro; Ezquerra, Tiberio A.; Nogales, Aurora, E-mail: [Instituto de Estructura de la Materia, IEM-CSIC. C/ Serrano 121, Madrid 28006 (Spain); Hernández, Rebeca [Instituto de Ciencia y Tecnología de Polímeros, ICTP-CSIC. C/ Juan de la Cierva 3, Madrid 28006 (Spain); Sprung, Michael [Petra III at DESY, Notkestr. 85, 22607 Hamburg (Germany)


    The dynamics of lower disorder-order temperature diblock copolymer leading to phase separation has been observed by X ray photon correlation spectroscopy. Two different modes have been characterized. A non-diffusive mode appears at temperatures below the disorder to order transition, which can be associated to compositional fluctuations, that becomes slower as the interaction parameter increases, in a similar way to the one observed for diblock copolymers exhibiting phase separation upon cooling. At temperatures above the disorder to order transition T{sub ODT}, the dynamics becomes diffusive, indicating that after phase separation in Lower Disorder-Order Transition (LDOT) diblock copolymers, the diffusion of chain segments across the interface is the governing dynamics. As the segregation is stronger, the diffusive process becomes slower. Both observed modes have been predicted by the theory describing upper order-disorder transition systems, assuming incompressibility. However, the present results indicate that the existence of these two modes is more universal as they are present also in compressible diblock copolymers exhibiting a lower disorder-order transition. No such a theory describing the dynamics in LDOT block copolymers is available, and these experimental results may offer some hints to understanding the dynamics in these systems. The dynamics has also been studied in the ordered state, and for the present system, the non-diffusive mode disappears and only a diffusive mode is observed. This mode is related to the transport of segment in the interphase, due to the weak segregation on this system.

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

    KAUST Repository

    Sutisna, Burhannudin


    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.

  1. Perpendicularly Aligned, Anion Conducting Nanochannels in Block Copolymer Electrolyte Films

    Energy Technology Data Exchange (ETDEWEB)

    Arges, Christopher G.; Kambe, Yu; Suh, Hyo Seon; Ocola, Leonidas E.; Nealey, Paul F.


    Connecting structure and morphology to bulk transport properties, such as ionic conductivity, in nanostructured polymer electrolyte materials is a difficult proposition because of the challenge to precisely and accurately control order and the orientation of the ionic domains in such polymeric films. In this work, poly(styrene-block-2-vinylpyridine) (PSbP2VP) block copolymers were assembled perpendicularly to a substrate surface over large areas through chemical surface modification at the substrate and utilizing a versatile solvent vapor annealing (SVA) technique. After block copolymer assembly, a novel chemical vapor infiltration reaction (CVIR) technique selectively converted the 2-vinylpyridine block to 2-vinyl n-methylpyridinium (NMP+ X-) groups, which are anion charge carriers. The prepared block copolymer electrolytes maintained their orientation and ordered nanostructure upon the selective introduction of ion moieties into the P2VP block and post ion-exchange to other counterion forms (X- = chloride, hydroxide, etc.). The prepared block copolymer electrolyte films demonstrated high chloride ion conductivities, 45 mS cm(-1) at 20 degrees C in deionized water, the highest chloride ion conductivity for anion conducting polymer electrolyte films. Additionally, straight-line lamellae of block copolymer electrolytes were realized using chemoepitaxy and density multiplication. The devised scheme allowed for precise and accurate control of orientation of ionic domains in nanostructured polymer electrolyte films and enables a platform for future studies that examines the relationship between polymer electrolyte structure and ion transport.

  2. Highly conductive side chain block copolymer anion exchange membranes. (United States)

    Wang, Lizhu; Hickner, Michael A


    Block copolymers based on poly(styrene) having pendent trimethyl styrenylbutyl ammonium (with four carbon ring-ionic group alkyl linkers) or benzyltrimethyl ammonium groups with a methylene bridge between the ring and ionic group were synthesized by reversible addition-fragmentation radical (RAFT) polymerization as anion exchange membranes (AEMs). The C4 side chain polymer showed a 17% increase in Cl(-) conductivity of 33.7 mS cm(-1) compared to the benzyltrimethyl ammonium sample (28.9 mS cm(-1)) under the same conditions (IEC = 3.20 meq. g(-1), hydration number, λ = ∼7.0, cast from DMF/1-propanol (v/v = 3 : 1), relative humidity = 95%). As confirmed by small angle X-ray scattering (SAXS), the side chain block copolymers with tethered ammonium cations showed well-defined lamellar morphologies and a significant reduction in interdomain spacing compared to benzyltrimethyl ammonium containing block copolymers. The chemical stabilities of the block copolymers were evaluated under severe, accelerated conditions, and degradation was observed by (1)H NMR. The block copolymer with C4 side chain trimethyl styrenylbutyl ammonium motifs displayed slightly improved stability compared to that of a benzyltrimethyl ammonium-based AEM at 80 °C in 1 M NaOD aqueous solution for 30 days.

  3. 78 FR 20032 - Styrene-Ethylene-Propylene Block Copolymer; Tolerance Exemption (United States)


    ... AGENCY 40 CFR Part 180 Styrene-Ethylene-Propylene Block Copolymer; Tolerance Exemption AGENCY... from the requirement of a tolerance for residues of styrene-ethylene-propylene block copolymer (CAS Reg... permissible level for residues of styrene-ethylene-propylene block copolymer on food or feed commodities...

  4. 21 CFR 177.1480 - Nitrile rubber modified acrylonitrile-methyl acrylate copolymers. (United States)


    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Nitrile rubber modified acrylonitrile-methyl... Nitrile rubber modified acrylonitrile-methyl acrylate copolymers. Nitrile rubber modified acrylonitrile... rubber modified acrylonitrile-methyl acrylate copolymers consist of basic copolymers produced by the...

  5. 40 CFR 721.10101 - Copolymer of alkyl acrylate and ethyleneglycol dimethacrylate (generic). (United States)


    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Copolymer of alkyl acrylate and... Significant New Uses for Specific Chemical Substances § 721.10101 Copolymer of alkyl acrylate and...) The chemical substance identified generically as copolymer of alkyl acrylate and ethyleneglycol...

  6. 21 CFR 177.1340 - Ethylene-methyl acrylate copolymer resins. (United States)


    ... 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...

  7. 21 CFR 177.1360 - Ethylene-vinyl acetate-vinyl alcohol copolymers. (United States)


    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Ethylene-vinyl acetate-vinyl alcohol copolymers... for Use as Basic Components of Single and Repeated Use Food Contact Surfaces § 177.1360 Ethylene-vinyl acetate-vinyl alcohol copolymers. Ethylene-vinyl acetate-vinyl alcohol copolymers (CAS Reg. No. 26221-27-2...

  8. 40 CFR 180.1162 - Acrylate polymers and copolymers; exemption from the requirement of a tolerance. (United States)


    ... 40 Protection of Environment 23 2010-07-01 2010-07-01 false Acrylate polymers and copolymers... RESIDUES IN FOOD Exemptions From Tolerances § 180.1162 Acrylate polymers and copolymers; exemption from the requirement of a tolerance. (a) Acrylate polymers and copolymers are exempt from the requirement of a...

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

    KAUST Repository

    Peinemann, Klaus-Viktor


    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.

  10. 21 CFR 177.1040 - Acrylonitrile/styrene copoly-mer. (United States)


    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Acrylonitrile/styrene copoly-mer. 177.1040 Section... Basic Components of Single and Repeated Use Food Contact Surfaces § 177.1040 Acrylonitrile/styrene copoly-mer. Acrylonitrile/styrene copolymers identified in this section may be safely used as a component...

  11. Responsive copolymers for enhanced petroleum recovery. Quarterly technical progress report, March 22, 1994--June 21, 1994

    Energy Technology Data Exchange (ETDEWEB)

    McCormick, C.; Hester, R.


    In this report, the authors consider the synthesis of copolymers of interest in the enhanced recovery of petroleum. Acrylamide and N,N-dimethyl-N-dodecyl-N-(2-amidoethyl) ammonium bromide copolymers were synthesized and characterized by various instrumental methods. The rheological properties of this copolymer were investigated using a porous media elongation rheometer.

  12. 76 FR 42613 - National Emission Standards for Hazardous Air Pollutants for Polyvinyl Chloride and Copolymers... (United States)


    ... Polyvinyl Chloride and Copolymers Production; Extension of Comment Period AGENCY: Environmental Protection... for Hazardous Air Pollutants for Polyvinyl Chloride and Copolymers Production is being extended for 14... extend the public comment period for the May 20, 2011, Proposed Polyvinyl Chloride and Copolymers...

  13. Solubility of dense CO2 in two biocompatible acrylate copolymers

    Directory of Open Access Journals (Sweden)

    A. R. C. Duarte


    Full Text Available Biocompatible polymers and copolymers are frequently being used as part of controlled delivery systems. These systems can be prepared using a "clean and environment friendly" technology like supercritical fluids. One great advantage of this process is that compressed carbon dioxide has excellent plasticizing properties and can swell most biocompatible polymeric matrixes, thus promoting drug impregnation processes. Mass sorption of two acrylate biocompatible copolymers contact with supercritical carbon dioxide is reported. Equilibrium solubility of dense carbon dioxide in poly(methylmethacrylate-co-ethylhexylacrylate and poly(methylmethacrylate-co-ethylhexylacrylate-co-ethyleneglycoldimethacrylate was studied by a static method at 10.0 MPa and 313 K. The reticulated copolymer had Fickean behavior and its diffusion coefficient was calculated, under operating conditions.

  14. Universality between Experiment and Simulation of a Diblock Copolymer Melt (United States)

    Beardsley, T. M.; Matsen, M. W.

    The equivalent behavior among analogous block copolymer systems involving chemically distinct molecules or mathematically different models has long hinted at an underlying universality, but only recently has it been rigorously demonstrated by matching results from different simulations. The profound implication of universality is that simple coarse-grained models can be calibrated so as to provide quantitatively accurate predictions to experiment. Here, we provide the first compelling demonstration of this by simulating a polyisoprene-polylactide diblock copolymer melt using a previously calibrated lattice model. The simulation successfully predicts the peak in the disordered-state structure function, the position of the order-disorder transition and the latent heat of the transition in excellent quantitative agreement with experiment. This could mark a new era of precision in the field of block copolymer research. This work was funded by NSF under the Center for Sustainable Polymers (CHE-1413862), and computer resources were provided by SHARCNET of Compute Canada.

  15. Performance behavior of modified cellulosic fabrics using polyurethane acrylate copolymer. (United States)

    Zuber, Mohammad; Shah, Sayyed Asim Ali; Jamil, Tahir; Asghar, Muhammad Irfan


    The surface of the cellulosic fabrics was modified using self-prepared emulsions of polyurethane acrylate copolymers (PUACs). PUACs were prepared by varying the molecular weight of polycaprolactone diol (PCL). The PCL was reacted with isophorone diisocyanate (IPDI) and chain was extended with 2-hydroxy ethyl acrylate (HEA) to form vinyl terminated polyurethane (VTPU) preploymer. The VTPU was further co-polymerized through free radical polymerization with butyl acrylate in different proportions. The FT-IR spectra of monomers, prepolymers and copolymers assured the formation of proposed PUACs structure. The various concentrations of prepared PUACs were applied onto the different fabric samples using dip-padding techniques. The results revealed that the application of polyurethane butyl acrylate copolymer showed a pronounced effect on the tear strength and pilling resistance of the treated fabrics. Copyright © 2014 Elsevier B.V. All rights reserved.

  16. Modification of ethylene-norbornene copolymer by Gamma irradiation

    Directory of Open Access Journals (Sweden)

    Kačarević-Popović Zorica M.


    Full Text Available The possibility of modifying polyethylene and many other polymers with high energy radiation has led to many useful applications. Due to their new combination of properties and the shortage of experimental data, the radiolysis of a new class of materials, cyclo-olefin copolymers (COC, polymerised from norbornene and ethylene using metallocene catalysts, is of great interest to the study of radiation chemistry and the physics of polymeric systems. Ethylenenorbornene copolymer, pristine and containing an antioxidant were subjected to gamma irradiation in the presence of air and in water. The irradiated copolymer was studied using IR and UV-vis spectrophotometric analysis. The radiation-induced changes in the molecular structure were correlated to changes in the glass transition temperature measured by the DSC method.

  17. Block copolymer/homopolymer dual-layer hollow fiber membranes

    KAUST Repository

    Hilke, Roland


    We manufactured the first time block copolymer dual-layer hollow fiber membranes and dual layer flat sheet membranes manufactured by double solution casting and phase inversion in water. The support porous layer was based on polystyrene and the selective layer with isopores was formed by micelle assembly of polystyrene-. b-poly-4-vinyl pyridine. The dual layers had an excellent interfacial adhesion and pore interconnectivity. The dual membranes showed pH response behavior like single layer block copolymer membranes with a low flux for pH values less than 3, a fast increase between pH4 and pH6 and a constant high flux level for pH values above 7. The dry/wet spinning process was optimized to produce dual layer hollow fiber membranes with polystyrene internal support layer and a shell block copolymer selective layer.

  18. Responsive copolymers for enhanced petroleum recovery. Second annual report

    Energy Technology Data Exchange (ETDEWEB)

    McCormick, C.; Hester, R.


    The authors describe second year efforts in synthesis, characterization, and rheology to develop polymers with significantly improved efficiency in mobility control and conformance. These advanced polymer systems would maintain high viscosities or behave as virtual gels under low shear conditions and at elevated electrolyte concentrations. At high fluid shear rates, associates would deaggregate yielding low viscosity solutions, reducing problems of shear degradation or face plugging during injection. Polymeric surfactants were also developed with potential for use in higher salt, higher temperature reservoirs for mobilization of entrapped oil. Chapters include: Ampholytic terpolymers of acrylamide with sodium 3-acrylamido-3-methylbutanoate and 2-acrylamido-2-methylpropanetrimethylammonium chloride; Hydrophilic sulfobetaine copolymers of acrylamide and 3-(2-acrylamido-methylpropane-dimethylammonio)-1-propanesulfonate; Copolymerization of maleic anhydride and N-vinylformamide; Reactivity ratio of N-vinylformamide with acrylamide, sodium acrylate, and n-butyl acrylate; Effect of the distribution of the hydrophobic cationic monomer dimethyldodecyl(2-acrylamidoethyl)ammonium bromide on the solution behavior of associating acrylamide copolymers; Effect of surfactants on the solution properties of amphipathic copolymers of acrylamide and N,N-dimethyl-N-dodecyl-N-(2-acrylamidoethyl)ammonium bromide; Associative interactions and photophysical behavior of amphiphilic terpolymers prepared by modification of maleic anhydride/ethyl vinyl ether copolymers; Copolymer compositions of high-molecular-weight functional acrylamido water-soluble polymers using direct-polarization magic-angle spinning {sup 13}C NMR; Use of factorial experimental design in static and dynamic light scattering characterization of water soluble polymers; and Porous medium elongational rheometer studies of NaAMB/AM copolymer solutions.

  19. Structure-Property Relationships in Polyolefin Block Copolymers (United States)

    Mansour, Ameara Salah

    Poly(cyclohexylethylene) (PCHE for a homopolymer or C in a block copolymer) is created by hydrogenating polystyrene, and this polymer exhibits interesting properties, such as a high glass transition temperature (147 °C), high flexural modulus (2.8 GPa), low stress optical coefficient (-0.2 * 10-9 Pa-1), and low cost. However, the inherently brittle nature of PCHE prevents it from being used in applications that simultaneously require high modulus, ductility, thermal stability, and optical clarity. Previous research has shown that incorporating PCHE into a block copolymer with rubbery poly(ethylene-alt-propylene) (P) or poly(ethylethylene) (EE) or semicrystalline polyethylene (E) results in a tough material. In some cases, applications also require specific mechanical or optical properties. In order to tune these properties, this research examined tuning crystallinity using two methods: (1) by controlling the microstructure of the soft block by synthesizing a random copolymer of E and EE, and (2) by blending high C content pentablock copolymers with semicrystalline and rubbery minority components. In the first study, diblock copolymers of C(EcoEE) also were used to understand how the microstructure of the random copolymer affects the thermodynamics of the system. In the second study, CECEC and CPCPC, designed to form the same morphology (hexagonally packed cylinders with glassy C matrices), and have similar order-to-disorder transition temperatures and domain spacings, were blended together. Isothermal crystallization experiments were used to determine how the confining E and P in one domain affects the crystallization process. The effect of architecture, the state of the minority component, and the percent crystallinity on the mechanical properties of high glass content materials was also examined. These results were compared to the mechanical properties of homopolymer PCHE, polystyrene, and polycarbonate. The processing conditions needed to create smooth films of

  20. Charge-Reversible Multifunctional HPMA Copolymers for Mitochondrial Targeting. (United States)

    Wang, Fengling; Sun, Wei; Li, Lian; Li, Lijia; Liu, Yuanyuan; Zhang, Zhi-Rong; Huang, Yuan


    Mitochondrial-oriented delivery of anticancer drugs has been considered as a promising strategy to improve the antitumor efficiency of chemotherapeutics. However, the physiological and biological barriers from the injection site to the final mitochondrial action site remain great challenges. Herein, a novel mitochondrial-targeted multifunctional nanocomplex based on N-(2-hydroxypropyl) methacrylamide (HPMA) copolymers (MPC) is designed to enhance drug accumulation in mitochondria. MPC possesses various functions such as extracellular pH response, superior cellular uptake, lysosomal escape, and mitochondrial targeting. In detail, MPC was formed by two oppositely charged HPMA copolymers, that is, positively charged mitochondrial-targeting guanidine group-modified copolymers and charge-reversible 2,3-dimethylmaleic anhydride (DMA)-modified copolymers (P-DMA). It was validated that MPC could remain stable in the blood circulation (pH 7.4) but could be cleaved to expose the positive charge of the guanidine group immediately in response to the mild acidity of tumor tissues (pH 6.5). The gradual exposure of positively charged guanidine will simultaneously facilitate endocytosis, endosomal/lysosomal escape, and mitochondrial targeting. The in vitro experiments showed that compared with copolymers without guanidine modification, the cellular uptake and mitochondrial-targeting ability of MPC in the simulated tumor environment (MPC@pH6.5) separately increased 4.3- and 23.8-fold, respectively. The in vivo experiments were processed on B16F10 tumor-bearing C57 mice, and MPC showed the highest accumulation in the tumor site and a peak tumor inhibition rate of 82.9%. In conclusion, multifunctional mitochondrial-targeting HPMA copolymers provide a novel and versatile approach for cancer therapy.

  1. Functional Block Copolymers as Compatibilizers for Nanoclays in Polypropylene Nanocomposites

    DEFF Research Database (Denmark)

    Jankova Atanasova, Katja; Daugaard, Anders Egede; Stribeck, Norbert

    With the aim of creating tough nanocomposits (NC) [1] based on polypropylene (PP) and nanoclay (NCl) in the framework of the 7th EU program NANOTOUGH we have designed amphiphilic block copolymers utilizing Atom Transfer Radical Polymerization (ATRP) [2]. They consist of a hydrophobic block...... for the exchange of the Na+ ions of the used NCl (3.8 wt.-% aq. dispersion of montmorillonite, MMT from Laviosa Chimica Mineralia, Italy) by the synthesized charged block copolymer, which was performed in water. Modified nanoclays with 2.5 to 8.0 wt.-% of the quaternized PEB-b-PDMAEMA35 were prepared...

  2. Synthesis and Characterization of Organotin Containing Copolymers: Reactivity Ratio Studies

    Directory of Open Access Journals (Sweden)

    Mohamed H. El-Newehy


    Full Text Available Organotin monomers containing dibutyltin groups – dibutyltin citraconate (DBTC as a new monomer and dibutyltin maleate (DBTM – were synthesized. Free radical copolymerizations of the organotin monomers with styrene (ST and butyl acrylate (BA were performed. The overall conversion was kept low (≤15% wt/wt for all studied samples and the copolymers composition was determined from tin analysis using the Gillman and Rosenberg method. The reactivity ratios were calculated from the copolymer composition using the Fineman-Ross (FR method. The synthesized monomers were characterized by elemental analysis, 1H-, 13C-NMR and FTIR spectroscopy.

  3. Polymers and block copolymers of fluorostyrenes by ATRP

    DEFF Research Database (Denmark)

    Hvilsted, Søren; Borkar, Sachin; Abildgaard, Lillian


    Fully or partly fluorinated polymers have many desirable and intriguing properties. In the framework of a larger program on design and control of new functional block copolymers we recently employed the Atom Transfer Radical Polymerization (ATRP) protocol on 2,3,4,5,6-pentafluorostyrene (FS). We...... materials based on 2,3,5,6-tetrafiuoro-4-methoxy-styrene (TFMS). TFMS homopolymers as well as diblock copolymers with FS are produced by ATRP. Both types of novel polymers were subsequently demethylated and different side chains introduced on the resulting hydroxy sites....

  4. HPMA based amphiphilic copolymers mediate central nervous effects of domperidone. (United States)

    Hemmelmann, Mirjam; Knoth, Christiane; Schmitt, Ulrich; Allmeroth, Mareli; Moderegger, Dorothea; Barz, Matthias; Koynov, Kaloian; Hiemke, Christoph; Rösch, Frank; Zentel, Rudolf


    In this study we give evidence that domperidone encapsulated into amphiphilic p(HPMA)-co-p(laurylmethacrylate) (LMA) copolymer aggregates is able to cross the blood-brain barrier, since it affected motor behaviour in animals, which is a sensitive measure for CNS actions. Carefully designed copolymers based on the clinically approved p(HPMA) were selected and synthesized by a combination of controlled radical polymerization and post-polymerization modification. The hydrodynamic radii (R(h) ) of amphiphilic p(HPMA)-co-p(LMA) alone and loaded with domperidone were determined by fluorescence correlation spectroscopy. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Pressure and temperature effects in homopolymer blends and diblock copolymers

    DEFF Research Database (Denmark)

    Frielinghaus, H.; Schwahn, D.; Mortensen, K.


    contribution of the Flory-Huggins parameter at larger pressure fields. This gives rise to a shift of the phase boundaries to higher temperatures and to a strong reduction of the Ginzburg parameter. Diblock copolymers show a different behavior. Neither the entropic term of the Flory-Huggins parameter nor......Thermal composition fluctuations in homopolymer mer blends and diblock copolymers were studied with SANS in varying pressure and temperature fields. For homopolymers we find a quite consistent behavior: The dominating effect of compressibility or packing leads to a reduction of the entropic...

  6. Chlorine resistant desalination membranes based on directly sulfonated poly(arylene ether sulfone) copolymers (United States)

    McGrath, James E [Blacksburg, VA; Park, Ho Bum [Austin, TX; Freeman, Benny D [Austin, TX


    The present invention provides a membrane, kit, and method of making a hydrophilic-hydrophobic random copolymer membrane. The hydrophilic-hydrophobic random copolymer membrane includes a hydrophilic-hydrophobic random copolymer. The hydrophilic-hydrophobic random copolymer includes one or more hydrophilic monomers having a sulfonated polyarylsulfone monomer and a second monomer and one or more hydrophobic monomers having a non-sulfonated third monomer and a fourth monomer. The sulfonated polyarylsulfone monomer introduces a sulfonate into the hydrophilic-hydrophobic random copolymer prior to polymerization.

  7. Micellization of St/MMA gradient copolymers: a general picture of structural transitions in gradient copolymer micelles. (United States)

    Zheng, Chao; Huang, Haiying; He, Tianbai


    In this work, a gradient copolymer of styrene (St) and methyl methacrylate (MMA) is synthesized via reversible addition-fragmentation chain transfer living radical polymerization and its micellization behaviors in an acetone and water mixture are investigated by transmission electron microscopy, light scattering, and NMR spectroscopy. Three different kinds of transitions were found to coexist in a single system for the first time: a unimers to micelles transition, a star-like micelles to crew-cut micelles transition resulting from the shrinkage of micelles, and morphological transitions from spherical micelles to cylindrical micelles to vesicles. Our findings provide a general picture of structural transitions and relaxation processes in gradient copolymer micelles, which can lead to the development of novel materials and applications based on gradient copolymers. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Studies on Preparation of Poly(3,4-Dihydroxyphenylalanine-Polylactide Copolymers and the Effect of the Structure of the Copolymers on Their Properties

    Directory of Open Access Journals (Sweden)

    Dongjian Shi


    Full Text Available Properties of copolymers are generally influenced by the structure of the monomers and polymers. For the purpose of understanding the effect of polymer structure on the properties, two kinds of copolymers, poly(3,4-dihydroxyphenylalanine-g-polylactide and poly(3,4-dihydroxyphenylalanine-b-polylactide (PDOPA-g-PLA and PDOPA-b-PLA were designed and prepared by ring-opening polymerization of lactide with pre-prepared PDOPA as the initiator and the amidation of the functional PLA and PDOPA oligomer, respectively. The molecular weight and composition of the copolymers could be adjusted by changing the molar ratio of LA and DOPA and were confirmed by gel permeation chromatography (GPC and proton nuclear magnetic resonance (1H NMR spectra. The obtained copolymers with graft and block structures showed high solubility even in common organic solvents. The effects of the graft and block structures on the thermal and degradation properties were also detected. The PDOPA-g-PLA copolymers showed higher thermal stability than the PDOPA-b-PLA copolymers, due to the PDOPA-g-PLA copolymers with regular structure and strong π-π stacking interactions among the intermolecular and intramolecular chains. In addition, the degradation results showed that the PDOPA-g-PLA copolymers and the copolymers with higher DOPA composition had quicker degradation speeds. Interestingly, both two kinds of copolymers, after degradation, became undissolved in the organic solvents because of the oxidation and crosslinking formation of the catechol groups in the DOPA units during degradation in alkaline solution. Moreover, fluorescent microscopy results showed good biocompatibility of the PDOPA-g-PLA and PDOPA-b-PLA copolymers. The PDOPA and PLA copolymers have the potential applications to the biomedical and industrial fields.

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

    Energy Technology Data Exchange (ETDEWEB)

    Gholami, Mehrdad, E-mail: [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: [Department of Chemistry, University of Malaya, Kuala Lumpur 50603 (Malaysia); Alias, Yatimah, E-mail: [Department of Chemistry, University of Malaya, Kuala Lumpur 50603 (Malaysia)


    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.

  10. Anhydric maleic functionalization and polyethylene glycol grafting of lactide-co-trimethylene carbonate copolymers

    Energy Technology Data Exchange (ETDEWEB)

    Díaz, A.; Valle, L.; Franco, L. del [Departament d' Enginyeria Química, Universitat Politècnica de Catalunya, Av. Diagonal 647, Barcelona E-08028 (Spain); Sarasua, J.R. [Department of Mining-Metallurgy Engineering and Materials Science, University of the Basque Country (UPV/EHU), Bilbao (Spain); Estrany, F. [Departament d' Enginyeria Química, Universitat Politècnica de Catalunya, Av. Diagonal 647, Barcelona E-08028 (Spain); Puiggalí, J., E-mail: [Department of Mining-Metallurgy Engineering and Materials Science, University of the Basque Country (UPV/EHU), Bilbao (Spain)


    Lactide and trimethylene carbonate copolymers were successfully grafted with polyethylene glycol via previous functionalization with maleic anhydride and using N,N′-diisopropylcarbodiimide as condensing agent. Maleinization led to moderate polymer degradation. Specifically, the weight average molecular weight decreased from 36,200 to 30,200 g/mol for the copolymer having 20 mol% of trimethylene carbonate units. Copolymers were characterized by differential scanning calorimetry, thermogravimetry and X-ray diffraction. Morphology of spherulites and lamellar crystals was evaluated with optical and atomic force microscopies, respectively. The studied copolymers were able to crystallize despite the randomness caused by the trimethylene carbonate units and the lateral groups. Contact angle measurements indicated that PEG grafted copolymers were more hydrophilic than parent copolymers. This feature justified that enzymatic degradation in lipase medium and proliferation of both epithelial-like and fibroblast-like cells were enhanced. Grafted copolymers were appropriate to prepare regular drug loaded microspheres by the oil-in-water emulsion method. Triclosan release from loaded microspheres was evaluated in two media. - Highlights: • Pegylated copolymers of lactide and trimethylene carbonate have been synthesized. • Grafting with polyethylene glycol was able via maleic anhydride functionalization. • Drug-loaded microspheres could be prepared from new pegylated copolymers. • Hydrophilicity of lactide/trimethylene carbonate copolymers increased by pegylation. • New pegylated copolymers supported cell adhesion and proliferation.

  11. Biocompatibility of poly(DL-lactic acid/glycine) copolymers

    NARCIS (Netherlands)

    Schakenraad, J.M.; Dijkstra, Pieter J.


    In this review the authors discuss the polymer chemical, physical and cell biological aspects of poly (DL-lactic acid/glycine) copolymers, both in vitro and in vivo. The mechanism and rate of degradation and the degree of foreign body reaction were evaluated as a function of the molecular


    NARCIS (Netherlands)



    The hydrogels described here are copolymers of acrylamide and methacrylamide highly cross-linked with piperazine diacrylamide or 4,7,10-trioxa-1,13-tridecanediamine diacrylamide by radical polymerisation in highly concentrated aqueous and aqueous gelatin solutions. The hydrogels were characterised

  13. Unexpected phase behavior of an asymmetric diblock copolymer

    DEFF Research Database (Denmark)

    Papadakis, Christine Maria; Almdal, Kristoffer; Mortensen, Kell


    We report on measurements of the transmitted depolarized light intensity and on small-angle neutron scattering (SANS) measurements on a compositionally asymmetric poly(ethylene propylene)-poly(dimethylsiloxane) diblock copolymer studied in the bulk. SANS measurements were made both on isotropic a...

  14. Tough, semiconducting polyethylene-poly(3-hexylthiophene) diblock copolymers

    DEFF Research Database (Denmark)

    Müller, C.; Goffri, S.; Breiby, Dag Werner


    10(-2) cm(2)V(-1)s(-1) and ON-OFF ratios, I-on/I-off similar to 10(5) at contents of the insulating PE moiety as high as 90 wt %. In addition, the diblock copolymers display outstanding flexibility and toughness with elongations at break exceeding 600 % and true tensile strengths around 70 MPa...

  15. Fibronectin fixation on poly(ethyl acrylate)-based copolymers. (United States)

    Briz, N; Antolinos-Turpin, C M; Alió, J; Garagorri, N; Ribelles, J L Gómez; Gómez-Tejedor, J A


    The aim of this paper is to quantify the adhered fibronectin (FN; by adsorption and/or grafting) and the exposure of its cell adhesive motifs (RGD and FNIII7-10) on poly(ethyl acrylate) (PEA) copolymers whose chemical composition has been designed to increase wettability and to introduce acid functional groups. FN was adsorbed to PEA, poly(ethyl acrylate-co-hydroxyethyl acrylate), poly(ethyl acrylate-co-acrylic acid), and poly(ethyl acrylate-co-methacrylic acid) copolymers, and covalently cross-linked to poly(ethyl acrylate-co-acrylic acid) and poly(ethyl acrylate-co-methacrylic acid) copolymers. Amount of adhered FN and exhibition of RGD and FNIII7- 10 fragments involved in cell adhesion were quantified with enzyme-linked immunosorbent assay tests. Even copolymers with a lower content of the hydrophilic component showed a decrease in water contact angle. In addition, FN was successfully fixed on all surfaces, especially on the hydrophobic surfaces. However, it was demonstrated that exposure of its cell adhesion sequences, which is the key factor in cell adhesion and proliferation, was higher for hydrophilic surfaces. Copyright © 2013 Wiley Periodicals, Inc.

  16. In vivo biocompatibility of radiation crosslinked acrylamide copolymers

    Energy Technology Data Exchange (ETDEWEB)

    Saraydin, Dursun E-mail:; Uenver-Saraydin, Serpil; Karadag, Erdener; Koptagel, Emel; Gueven, Olgun


    In vitro swelling and in vivo biocompatibility of radiation crosslinked acrylamide copolymers such as acrylamide/crotonic acid (AAm/CA) and acrylamide/itaconic acid (AAm/IA) were studied. The swelling kinetics of acrylamide copolymers were performed in distilled water, human serum and some simulated physiological fluids such as phosphate buffer, pH 7.4, glycine-HCl buffer, pH 1.1, physiological saline solution, and some swelling and diffusion parameters have been calculated. AAm/CA and AAm/IA hydrogels were subcutaneously implanted in rats for up to 10 weeks and the immediate short- and long-term tissue response to these implants were investigated. Histological analysis indicated that tissue reaction at the implant site progressed from an initial acute inflammatory response. No necrosis, tumorigenesis or infection was observed at the implant site up to 10 weeks. The radiation crosslinked AAm/CA and AAm/IA copolymers were found well tolerated, non-toxic and highly biocompatible. However, AAm/IA copolymer was not found to be compatible biomaterials, because one of the AAm/IA samples was disintegrated into small pieces in the rat.

  17. Functional materials derived from block copolymer self-assembly

    DEFF Research Database (Denmark)

    Li, Tao

    The main objective of this project is to explore block copolymer self-assembly for generating functional materials with well-defined morphology on sub-20 nanometer length scale, which can be utilized in many important applications such as solar cells and nanolithography. One of the specific targe...

  18. Optical fibre Bragg grating recorded in TOPAS cyclic olefin copolymer

    DEFF Research Database (Denmark)

    Johnson, I.P.; Yuan, Scott Wu; Stefani, Alessio


    A report is presented on the inscription of a fibre Bragg grating into a microstructured polymer optical fibre fabricated from TOPAS cyclic olefin copolymer. This material offers two important advantages over poly (methyl methacrylate), which up to now has formed the basis for polymer fibre Bragg...

  19. Copolymer adsorption and the effect on colloidal stability

    NARCIS (Netherlands)

    Bijsterbosch, H.D.


    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

  20. Characterization and micellization of a poloxamer block copolymer

    DEFF Research Database (Denmark)

    Hvidt, S.; Pedersen, Walther Batsberg


    Several poloxamers that are symmetrical EPE block copolymers (E and P are ethylene and propylene oxide, respectively) have been characterized by size exclusion chromatography on Superose columns in water. The poloxamers contain between 12 and 26 wt% of smaller-size UV-absorbing impurities...