WorldWideScience

Sample records for three-armed star-shaped copolymer

  1. Synthesis and characterization of a star shaped supramolecular block copolymer

    NARCIS (Netherlands)

    Meier, M.A.R.; Schubert, U.S.

    2004-01-01

    A novel 5-arm star shaped block copolymer consisting of an poly(ethylene glycol) inner block and an poly(e-caprolactone) outer block was prepd. by utilizing an 5-arm star shaped poly(ethylene glycol) macroinitiator for the controlled ring opening polymn. of e-caprolactone. Furthermore, the resulting

  2. Three Arm Star Homo- And Co-Polymers Via Atom Transfer Radical Polymerization

    International Nuclear Information System (INIS)

    Amin, A.; Sobh, R.A.; Ayoub, M.M.H.

    2005-01-01

    Star homo and co-polymers of some vinyl monomers such as methylmethacrylate, butylmethacrylate and styrene (MMA, BMA, St.) were prepared using N, N, N', N' tetramethylethylenediamine ligand/ CuBr catalytic system via atom transfer radical polymerization (ATRP). Three armed benzene based core was successfully used as initiator. Low polydispersities and regular molecular weight values were obtained in most cases especially at low conversions. MMA and BuMA showed comparable behavior where controlled and true ATRP was observed even at the high conversions. However, styrene monomer recorded irregular high polydispersities at high conversions in spite of the relatively low molecular weight values. 1HNMR confirmed the structures of the resulting polymers. Transmission Electron microscope (TEM) proved the nano-structure of the star polymers. The thermal behavior of the MMA star homo and copolymers was studied. The effect of the star shape on the thermal behavior was very clear with respect to the linear ones

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

    NARCIS (Netherlands)

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

    2008-01-01

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

  4. Fabrication of supramolecular star-shaped amphiphilic copolymers for ROS-triggered drug release.

    Science.gov (United States)

    Zuo, Cai; Peng, Jinlei; Cong, Yong; Dai, Xianyin; Zhang, Xiaolong; Zhao, Sijie; Zhang, Xianshuo; Ma, Liwei; Wang, Baoyan; Wei, Hua

    2018-03-15

    Star-shaped copolymers with branched structures can form unimolecular micelles with better stability than the micelles self-assembled from conventional linear copolymers. However, the synthesis of star-shaped copolymers with precisely controlled degree of branching (DB) suffers from complicated sequential polymerizations and multi-step purification procedures, as well as repeated optimizations of polymer compositions. The use of a supramolecular host-guest pair as the block junction would significantly simplify the preparation. Moreover, the star-shaped copolymer-based unimolecular micelle provides an elegant solution to the tradeoff between extracellular stability and intracellular high therapeutic efficacy if the association/dissociation of the supramolecular host-guest joint can be triggered by the biologically relevant stimuli. For this purpose, in this study, a panel of supramolecular star-shaped amphiphilic block copolymers with 9, 12, and 18 arms were designed and fabricated by host-guest complexations between the ring-opening polymerization (ROP)-synthesized star-shaped poly(ε-caprolactone) (PCL) with 3, 4, and 6 arms end-capped with ferrocene (Fc) (PCL-Fc) and the atom transfer radical polymerization (ATRP)-produced 3-arm poly(oligo ethylene glycol) methacrylates (POEGMA) with different degrees of polymerization (DPs) of 24, 30, 47 initiated by β-cyclodextrin (β-CD) (3Br-β-CD-POEGMA). The effect of DB and polymer composition on the self-assembled properties of the five star-shaped copolymers was investigated by dynamic light scattering (DLS), transmission electron microscopy (TEM), and fluorescence spectrometery. Interestingly, the micelles self-assembled from 12-arm star-shaped copolymers exhibited greater stability than the 9- and 18-arm formulations. The potential of the resulting supramolecular star-shaped amphiphilic copolymers as drug carriers was evaluated by an in vitro drug release study, which confirmed the ROS-triggered accelerated drug

  5. Phase behavior of diblock copolymer/star-shaped polymer thin film mixtures.

    Science.gov (United States)

    Zhao, Junnan; Sakellariou, Georgios; Green, Peter F

    2016-05-07

    We investigated the phase behavior of thin film, thickness h≈ 100 nm, mixtures of a polystyrene-b-poly(2-vinylpyridine) (PS-b-P2VP) diblock copolymer with star-shaped polystyrene (SPS) molecules of varying functionalities f, where 4 ≤f≤ 64, and molecular weights per arm Marm. The miscibility of the system and the surface composition varied appreciably with Marm and f. For large values of Marm, regardless of f, the miscibility of the system was qualitatively similar to that of linear chain PS/PS-b-P2VP mixtures - the copolymer chains aggregate to form micelles, each composed of an inner P2VP core and PS corona, which preferentially segregate to the free surface. On the other hand, for large f and small Marm, SPS molecules preferentially resided at the free surface. Moreover, blends containing SPS molecules with the highest values of f and lowest values of Marm were phase separated. These observations are rationalized in terms of competing entropic interactions and the dependence of the surface tension of the star-shaped molecules on Marm and f.

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

    OpenAIRE

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

    2009-01-01

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

  7. Structure-directing star-shaped block copolymers: supramolecular vesicles for the delivery of anticancer drugs.

    Science.gov (United States)

    Yang, Chuan; Liu, Shao Qiong; Venkataraman, Shrinivas; Gao, Shu Jun; Ke, Xiyu; Chia, Xin Tian; Hedrick, James L; Yang, Yi Yan

    2015-06-28

    Amphiphilic polycarbonate/PEG copolymer with a star-like architecture was designed to facilitate a unique supramolecular transformation of micelles to vesicles in aqueous solution for the efficient delivery of anticancer drugs. The star-shaped amphipilic block copolymer was synthesized by initiating the ring-opening polymerization of trimethylene carbonate (TMC) from methyl cholate through a combination of metal-free organo-catalytic living ring-opening polymerization and post-polymerization chain-end derivatization strategies. Subsequently, the self-assembly of the star-like polymer in aqueous solution into nanosized vesicles for anti-cancer drug delivery was studied. DOX was physically encapsulated into vesicles by dialysis and drug loading level was significant (22.5% in weight) for DOX. Importantly, DOX-loaded nanoparticles self-assembled from the star-like copolymer exhibited greater kinetic stability and higher DOX loading capacity than micelles prepared from cholesterol-initiated diblock analogue. The advantageous disparity is believed to be due to the transformation of micelles (diblock copolymer) to vesicles (star-like block copolymer) that possess greater core space for drug loading as well as the ability of such supramolecular structures to encapsulate DOX. DOX-loaded vesicles effectively inhibited the proliferation of 4T1, MDA-MB-231 and BT-474 cells, with IC50 values of 10, 1.5 and 1.0mg/L, respectively. DOX-loaded vesicles injected into 4T1 tumor-bearing mice exhibited enhanced accumulation in tumor tissue due to the enhanced permeation and retention (EPR) effect. Importantly, DOX-loaded vesicles demonstrated greater tumor growth inhibition than free DOX without causing significant body weight loss or cardiotoxicity. The unique ability of the star-like copolymer emanating from the methyl cholate core provided the requisite modification in the block copolymer interfacial curvature to generate vesicles of high loading capacity for DOX with significant

  8. Reduction-responsive interlayer-crosslinked micelles prepared from star-shaped copolymer via click chemistry for drug controlled release

    Science.gov (United States)

    Dai, Yu; Wang, Hongquan; Zhang, Xiaojin

    2017-12-01

    To improve the stability of polymeric micelles, here we describe interlayer-crosslinked micelles prepared from star-shaped copolymer via click chemistry. The formation of interlayer-crosslinked micelles was investigated and confirmed by proton nuclear magnetic resonance, Fourier-transform infrared spectroscopy, and fluorescence spectroscopy. The morphology of un-crosslinked micelles and crosslinked micelles observed by transmission electron microscope is both uniform nano-sized spheres (approximately 20 nm). The crosslinking enhances the stability of polymeric micelles and improves the drug loading capacity of polymeric micelles. The interlayer-crosslinked micelles prepared from star-shaped copolymer and a crosslinker containing a disulfide bond are reduction-responsive and can release the drug quickly in the presence of the reducing agents such as glutathione (GSH).

  9. Star-shaped poly[(trimethylene carbonate)-co-(epsilon-caprolactone)] and its block copolymers with lactide/glycolide : synthesis, characterization and properties

    NARCIS (Netherlands)

    Joziasse, CAP; Grablowitz, H; Pennings, AJ

    Linear and star-shaped copolymers of trimethylene carbonat/epsilon-caprolactone were synthesized using different polyol initiators and catalysts. Unexpectedly, when dipentaerythritol was used as an initiator cross-linked rubbers were obtained, that swell in chlorofonn. This network formation can be

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

    Science.gov (United States)

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

    2016-07-18

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

  11. Preparations and characterizations of tunable and multicolored electrochromic copolymers derived from a novel star-shaped monomer and BEDOT-V

    International Nuclear Information System (INIS)

    Wang, Kai; Yang, Wenge; Hu, Yonghong; Kai, Yumei; Shi, Ying

    2014-01-01

    A novel star-shaped monomer 1,3,5-Tri[2-(3,4-ethylenedioxythien-2-yl)vin-1-yl]benzene (TEDOT-V-B) was synthesized by Wittig coupling reaction. The copolymers with BEDOT-V at different feed ratios were prepared onto the ITO-coated glass by cyclic voltammetry (CV) method and the electrochromic properties were reported. The influences of different feed ratios on the spectroelectrochemical and kinetic properties were investigated. Spectroelectrochemical studies indicated that the maximum absorption wavelengths of the copolymer films bathochromically shifted with feed ratios. In addition, the copolymers had tunable and low band gaps. When the feed ratio of BEDOT-V-B/BEDOT-V was 1:3, the copolymer film showed the fastest oxidation switching time of 0.9s (567 nm) and 0.9s (967 nm) and the fastest reduction switching time of 0.8s (567 nm) and 0.9s (967 nm). Compared with PBEDOT-V, the copolymers showed tunable and multicolored electrochromism through feed ratios and the RGB colors were achieved. Additionally, the surface morphology of the copolymer film was investigated by scanning electron microscope (SEM)

  12. Structural studies of three-arm star block copolymers exposed to extreme stretch suggests persistent polymer tube

    DEFF Research Database (Denmark)

    Garvey, Christopher J.; Almdal, Kristoffer; Dorokhin, Andriy

    2018-01-01

    We present structural SANS-studies of a three-armed polystyrene star polymer with short deuterated segments at the end of each arm. We show that the form factor of the three-armed star molecules in the relaxed state agrees with that of the random phase approximation of Gaussian chains. Upon...

  13. Structural Studies of Three-Arm Star Block Copolymers Exposed to Extreme Stretch Suggests a Persistent Polymer Tube

    Science.gov (United States)

    Mortensen, Kell; Borger, Anine L.; Kirkensgaard, Jacob J. K.; Garvey, Christopher J.; Almdal, Kristoffer; Dorokhin, Andriy; Huang, Qian; Hassager, Ole

    2018-05-01

    We present structural small-angle neutron scattering studies of a three-armed polystyrene star polymer with short deuterated segments at the end of each arm. We show that the form factor of the three-armed star molecules in the relaxed state agrees with that of the random phase approximation of Gaussian chains. Upon exposure to large extensional flow conditions, the star polymers change conformation resulting in a highly stretched structure that mimics a fully extended three-armed tube model. All three arms are parallel to the flow, one arm being either in positive or negative stretching direction, while the two other arms are oriented parallel, right next to each other in the direction opposite to the first arm.

  14. Solid-state NMR study of stereocomplexes formed by enantiomeric star-shaped PEG-PLA copolymers in water

    NARCIS (Netherlands)

    Calucci, Lucia; Forte, Claudia; Buwalda, S.J.; Dijkstra, Pieter J.

    2011-01-01

    Solid-state NMR was applied to samples obtained by freeze-drying hydrogels of 1:1 (PEG65-NHCO-PLLA13)8/(PEG65-NHCO-PDLA13)8 or (PEG65-NHCO-PDLA13)8 only star block copolymers (where PEG, PLLA, and PDLA stand for poly(ethylene glycol), poly(l-lactide), and poly(d-lactide), respectively) in order to

  15. Star-shaped poly(oligoethylene glycol) copolymer-based gels: Thermo-responsive behaviour and bioapplicability for risedronate intranasal delivery.

    Science.gov (United States)

    Soliman, Mahmoud E; Elmowafy, Enas; Casettari, Luca; Alexander, Cameron

    2018-05-30

    The aim of this work was to obtain an intranasal delivery system with improved mechanical and mucoadhesive properties that could provide prolonged retention time for the delivery of risedronate (RS). For this, novel in situ forming gels comprising thermo-responsive star-shaped polymers, utilizing either polyethylene glycol methyl ether (PEGMA-ME 188, Mn 188) or polyethylene glycol ethyl ether (PEGMA-EE 246, Mn 246), with polyethylene glycol methyl ether (PEGMA-ME 475, Mn 475), were synthesized and characterized. RS was trapped in the selected gel-forming solutions at a concentration of 0.2% w/v. The pH, rheological properties, in vitro drug release, ex vivo permeation as well as mucoadhesion were also examined. MTT assays were conducted to verify nasal tolerability of the developed formulations. Initial in vivo studies were carried out to evaluate anti-osteoporotic activity in a glucocorticoid induced osteoporosis model in rats. The results showed successful development of thermo-sensitive formulations with favorable mechanical properties at 37 °C, which formed non-irritant, mucoadhesive porous networks, facilitating nasal RS delivery. Moreover, sustained release of RS, augmented permeability and marked anti-osteoporotic efficacy as compared to intranasal (IN) and intravenous (IV) RS solutions were realized. The combined results show that the in situ gels should have promising application as nasal drug delivery systems. Copyright © 2018 Elsevier B.V. All rights reserved.

  16. Fluidic Manufacture of Star-Shaped Gold Nanoparticles.

    Science.gov (United States)

    Silvestri, Alessandro; Lay, Luigi; Psaro, Rinaldo; Polito, Laura; Evangelisti, Claudio

    2017-07-21

    Star-shaped gold nanoparticles (StarAuNPs) are extremely attractive nanomaterials, characterized by localized surface plasmon resonance which could be potentially employed in a large number of applications. However, the lack of a reliable and reproducible synthetic protocols for the production of StarAuNPs is the major limitation to their spreading. For the first time, here we present a robust protocol to manufacture reproducible StarAuNPs by exploiting a fluidic approach. Star-shaped AuNPs have been synthesized by means of a seed-less protocol, employing ascorbic acid as reducing agent at room temperature. Moreover, the versatility of the bench-top microfluidic protocol has been exploited to afford hydrophilic, hydrophobic and solid-supported engineered StarAuNPs, by avoiding intermediate NP purifications. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Nano-Star-Shaped Polymers for Drug Delivery Applications.

    Science.gov (United States)

    Yang, Da-Peng; Oo, Ma Nwe Nwe Linn; Deen, Gulam Roshan; Li, Zibiao; Loh, Xian Jun

    2017-11-01

    With the advancement of polymer engineering, complex star-shaped polymer architectures can be synthesized with ease, bringing about a host of unique properties and applications. The polymer arms can be functionalized with different chemical groups to fine-tune the response behavior or be endowed with targeting ligands or stimuli responsive moieties to control its physicochemical behavior and self-organization in solution. Rheological properties of these solutions can be modulated, which also facilitates the control of the diffusion of the drug from these star-based nanocarriers. However, these star-shaped polymers designed for drug delivery are still in a very early stage of development. Due to the sheer diversity of macromolecules that can take on the star architectures and the various combinations of functional groups that can be cross-linked together, there remain many structure-property relationships which have yet to be fully established. This review aims to provide an introductory perspective on the basic synthetic methods of star-shaped polymers, the properties which can be controlled by the unique architecture, and also recent advances in drug delivery applications related to these star candidates. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Integral LQR Control of a Star-Shaped Octorotor

    Directory of Open Access Journals (Sweden)

    Adrian M. STOICA

    2012-06-01

    Full Text Available The paper starts by presenting the model of the star-shaped octorotor. LQR control is chosen to stabilize the attitude and altitude of the vehicle. Waypoint navigation is also implemented. Numerical simulations demonstrate the effectiveness of the control strategy under nominal conditions. However, in practice mass related uncertainties can occur. In this case the results are unsatisfactory. Thus the improvement of the applied LQR control strategy is proposed. It is shown that after adding integral action to the altitude controller the issue is solved.

  19. The origin of star-shaped oscillations of Leidenfrost drops

    Science.gov (United States)

    Ma, Xiaolei; Burton, Justin C.

    We experimentally investigate the oscillations of Leidenfrost drops of water, liquid nitrogen, ethanol, methanol, acetone and isopropyl alcohol. The drops levitate on a cushion of evaporated vapor over a hot, curved surface which keeps the drops stationary. We observe star-shaped modes along the periphery of the drop, with mode numbers n = 2 to 13. The number of observed modes is sensitive to the properties of the liquid. The pressure oscillation frequency in the vapor layer under the drop is approximately twice that of the drop frequency, which is consistent with a parametric forcing mechanism. However, the Rayleigh and thermal Marangoni numbers are of order 10,000, indicating that convection should play a dominating role as well. Surprisingly, we find that the wavelength and frequency of the oscillations only depend on the thickness of the liquid, which is twice the capillary length, and do not depend on the mode number, substrate temperature, or the substrate curvature. This robust behavior suggests that the wavelength for the oscillations is set by thermal convection inside the drop, and is less dependent on the flow in the vapor layer under the drop

  20. Design of Star-Shaped Flextensional Stator for Ultrasonic Motor

    Directory of Open Access Journals (Sweden)

    Lien-Kai Chang

    2014-05-01

    Full Text Available When a driving voltage opposite to the piezoelectric polarity is applied on the flextensional stator, it will generate the normal force, of which the operating voltage range of piezoelectric actuators will decrease. This paper presents a novel stator design for producing the normal force in which the driving voltage has the same piezoelectric polarity, which is based on the structure of two multilayer piezoelectric actuators clamped in a star-shaped shell. To obtain the two close resonance frequencies of flexural and translation modes, a genetic algorithm combined with the finite element analysis is employed to find the optimal dimensions for the geometry of the stator. The importance of each design parameter is evaluated through a proposed sensitivity analysis method. A prototype resulting from the optimal design was fabricated and the experimental results are given to show that the stator can generate, in practice, the required coupling resonance mode between 35.15 kHz and 36.49 kHz.

  1. Vortex distribution in small star-shaped Mo{sub 80}Ge{sub 20} plate

    Energy Technology Data Exchange (ETDEWEB)

    Vu, The Dang, E-mail: vu-dang@pe.osakafu-u.ac.jp [Department of Physics and Electronics, Osaka Prefecture University, Sakai, Osaka 599-8531 (Japan); Department of Physics and Electronics, University of Sciences, Vietnam National University HCMC (Viet Nam); Matsumoto, Hitoshi; Miyoshi, Hiroki [Department of Physics and Electronics, Osaka Prefecture University, Sakai, Osaka 599-8531 (Japan); Huy, Ho Thanh [Department of Physics and Electronics, Osaka Prefecture University, Sakai, Osaka 599-8531 (Japan); Department of Physics and Electronics, University of Sciences, Vietnam National University HCMC (Viet Nam); Shishido, Hiroaki [Department of Physics and Electronics, Osaka Prefecture University, Sakai, Osaka 599-8531 (Japan); Institute for Nanofabrication Research, Osaka Prefecture University, Sakai, Osaka 599-8531 (Japan); Kato, Masaru [Institute for Nanofabrication Research, Osaka Prefecture University, Sakai, Osaka 599-8531 (Japan); Department of Mathematical Science, Osaka Prefecture University, Sakai, Osaka 599-8531 (Japan); Ishida, Takekazu [Department of Physics and Electronics, Osaka Prefecture University, Sakai, Osaka 599-8531 (Japan); Institute for Nanofabrication Research, Osaka Prefecture University, Sakai, Osaka 599-8531 (Japan)

    2017-02-15

    Highlights: • We found the general feature of vortex configuration in small star-shaped Mo{sub 80}Ge{sub 20} plates such as the appearance of symmetric line, the rule of shell filling and the existence of a magic number in both theoretical predictions and experimental results. • We found that the vortex distribution in a concave decagon tends to adapt to one of the five symmetric axes of the star-shaped plate expected in confining vortices in a restricted sample geometry. • The numerical results of Ginzburg–Landau equation confirmed that the filling rules for a vortex configuration and the existence of a magic number for small star-shaped plates are in good agreement with experiment results. - Abstract: We investigated vortex states in small star-shaped Mo{sub 80}Ge{sub 20} plates both theoretically and experimentally. The numerical calculations of the Ginzburg–Landau equation have been carried out with the aid of the finite element method, which is convenient to treat an arbitrarily shaped superconductor. The experimental results were observed by using a scanning SQUID microscope. Through systematic measurements, we figured out how vortices form symmetric configuration with increasing the magnetic field. The vortex distribution tends to adapt to one of five mirror symmetric lines when vortices were located at the five triangular horns of a star-shaped plate. The crystalline homogeneity of a sample was confirmed by the X-ray diffraction and the superconducting properties so that vortices are easily able to move for accommodating vortices in the geometric symmetry of the star-shaped plate. The experimental vortex configurations obtained for a star-shaped plate are in good agreement with theoretical predictions from the nonlinear Ginzburg–Landau equation.

  2. Hybrid gas separation membranes containing star-shaped polystyrene with the fullerene (C60) core

    Czech Academy of Sciences Publication Activity Database

    Pulyalina, A. Y.; Rostovtseva, V. A.; Pientka, Zbyněk; Vinogradova, L. V.; Polotskaya, G. A.

    2018-01-01

    Roč. 58, č. 4 (2018), s. 296-303 ISSN 0965-5441 Institutional support: RVO:61389013 Keywords : gas separation * hybrid membranes * star-shaped macromolecules Subject RIV: CD - Macromolecular Chemistry OBOR OECD: Polymer science Impact factor: 0.493, year: 2016

  3. Ultrafast Charge Generation Pathways in Photovoltaic Blends Based on Novel Star-Shaped Conjugated Molecules

    NARCIS (Netherlands)

    Kozlov, Oleg V.; Luponosov, Yuriy N.; Ponomarenko, Sergei A.; Kausch-Busies, Nina; Paraschuk, Dmitry Yu; Olivier, Yoann; Beljonne, David; Cornil, Jerome; Pshenichnikov, Maxim S.

    2015-01-01

    The quest for new materials is one of the main factors propelling recent advances in organic photovoltaics. Star-shaped small molecules (SSMs) have been proven promising candidates as perspective donor material due to the increase in numbers of excitation pathways caused by the degeneracy of the

  4. Star-shaped Poly(2-oxazoline)s by Dendrimer Endcapping

    NARCIS (Netherlands)

    Lambermont-Thijs, H.M.L.; Fijten, M.W.M.; Schubert, U.S.; Hoogenboom, R.

    2011-01-01

    The synthesis of star-shaped poly(2-ethyl-2-oxazoline) is reported by direct end-capping of the living polymer chains with dendritic multiamines. The end-capping kinetics after addition of a first generation polypropylenimine dendrimer are discussed based on monitoring by size exclusion

  5. Exploring Redox States, Doping and Ordering of Electroactive Star-Shaped Oligo(aniline)s.

    Science.gov (United States)

    Mills, Benjamin M; Fey, Natalie; Marszalek, Tomasz; Pisula, Wojciech; Rannou, Patrice; Faul, Charl F J

    2016-11-14

    We have prepared a simple star-shaped oligo(aniline) (TDPB) and characterised it in detail by MALDI-TOF MS, UV/Vis/NIR spectroscopy, time-dependent DFT, cyclic voltammetry and EPR spectroscopy. TDPB is part of an underdeveloped class of π-conjugated molecules with great potential for organic electronics, display and sensor applications. It is redox active and reacts with acids to form radical cations. Acid-doped TDPB shows behaviour similar to discotic liquid crystals, with X-ray scattering investigations revealing columnar self-assembled arrays. The combination of unpaired electrons and supramolecular stacking suggests that star-shaped oligo(aniline)s like TDPB have the potential to form conducting nanowires and organic magnetic materials. © 2016 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

  6. Star-shaped tetrathiafulvalene oligomers towards the construction of conducting supramolecular assembly.

    Science.gov (United States)

    Iyoda, Masahiko; Hasegawa, Masashi

    2015-01-01

    The construction of redox-active supramolecular assemblies based on star-shaped and radially expanded tetrathiafulvalene (TTF) oligomers with divergent and extended conjugation is summarized. Star-shaped TTF oligomers easily self-aggregate with a nanophase separation to produce supramolecular structures, and their TTF units stack face-to-face to form columnar structures using the fastener effect. Based on redox-active self-organizing supramolecular structures, conducting nanoobjects are constructed by doping of TTF oligomers with oxidants after the formation of such nanostructures. Although radical cations derived from TTF oligomers strongly interact in solution to produce a mixed-valence dimer and π-dimer, it seems to be difficult to produce nanoobjects of radical cations different from those of neutral TTF oligomers. In some cases, however, radical cations form nanostructured fibers and rods by controlling the supramolecular assembly, oxidation states, and counter anions employed.

  7. Star-shaped ladder-type ter(p-phenylene)s for efficient multiphoton absorption.

    Science.gov (United States)

    Guo, Lei; Li, King Fai; Wong, Man Shing; Cheah, Kok Wai

    2013-05-04

    Star-shaped ladder-type ter(p-phenylene)s exhibit remarkably efficient multiphoton absorption properties with 2PA cross-section up to 2579 GM at 700 nm and 3PA cross-section up to 3.35 × 10(-76) cm(6) s(2) in the femtosecond regime for a blue-emissive molecule despite having such a short π-conjugated framework.

  8. Simulations of vortices in a star-shaped plate with an artificial pin

    Science.gov (United States)

    Miyoshi, Hiroki; Ito, Atsuki; Dang, Vu The; Thanh Huy, Ho; Hayashi, Masahiko; Kato, Masaru; Ishida, Takekazu

    2017-07-01

    Although a triangular vortex lattice is stable in a bulk type-II superconductor, exotic vortex configurations are expected to appear in a small superconducting plate. Theoretical calculations on vortex structures in a star-shaped superconducting plate have been given in our preceding work. In this work, we extended our theoretical studies to the case of having an artificial pin. We performed the Ginzburg-Landau (GL) calculations systematically to compare with the pin-free case by using the finite element method. We found that a vortex tends to accommodate preferentially in an aritificial pin in the star-shaped plate. We found a systematic evolution of vortex structure with increaseing magnetic field. We compare our theoretical calculations with vortices in a star-shaped Mo80Ge20 plate with an artificial pin and without an artificial pin obtained by a scanning SQUID microscope. We reconstructed the vortex image on the sample surface by using the inverse Biot-Savart law and the Fourier transformation.

  9. Synthesis and Performance of Highly Stable Star-Shaped Polyaniline Electrochromic Materials with Triphenylamine Core

    Science.gov (United States)

    Xiong, Shanxin; Li, Shuaishuai; Zhang, Xiangkai; Wang, Ru; Zhang, Runlan; Wang, Xiaoqin; Wu, Bohua; Gong, Ming; Chu, Jia

    2018-02-01

    The molecular architecture of conducting polymers has a significant impact on their conjugated structure and electrochemical properties. We have investigated the influence of star-shaped structure on the electrochemical and electrochromic properties of polyaniline (PANI). Star-shaped PANI (SPANI) was prepared by copolymerization of aniline with triphenylamine (TPA) using an emulsion polymerization method. With addition of less than 4.0 mol.% TPA, the resulting SPANI exhibited good solubility in xylene with dodecylbenzenesulfonic acid (DBSA) as doping acid. The structure and thermal stability of the SPANI were characterized using Fourier-transform infrared spectroscopy, Raman spectroscopy, and thermogravimetric analysis, and the electrochemical behavior was analyzed by cyclic voltammetry (CV). The electrochromic properties of SPANI were tested using an electrochemical workstation combined with an ultraviolet-visible (UV-Vis) spectrometer. The results show that, with increasing TPA loading, the thermal stability of SPANI increased. With addition of 4.0 mol.% TPA, the weight loss of SPANI was 36.9% at 700°C, much lower than the value of 71.2% for PANI at the same temperature. The low oxidation potential and large enclosed area of the CV curves indicate that SPANI possesses higher electrochemical activity than PANI. Enhanced electrochromic properties including higher optical contrast and better electrochromic stability of SPANI were also obtained. SPANI with 1.6 mol.% TPA loading exhibited the highest optical contrast of 0.71, higher than the values of 0.58 for PANI, 0.66 for SPANI-0.4%, or 0.63 for SPANI-4.0%. Overdosing of TPA resulted in slow switching speed due to slow ion transport in short branched chains of star-shaped PANI electrochromic material. Long-term stability testing confirmed that all the SPANI-based devices exhibited better stability than the PANI-based device.

  10. Synthesis and properties of novel star-shaped oligofluorene conjugated systems with BODIPY cores

    Directory of Open Access Journals (Sweden)

    Clara Orofino-Pena

    2014-11-01

    Full Text Available Star-shaped conjugated systems with varying oligofluorene arm length and substitution patterns of the central BODIPY core have been synthesised, leading to two families of compounds, T-B1–T-B4 and Y-B1–Y-B4, with T- and Y-shaped motifs, respectively. Thermal stability, cyclic voltammetry, absorption and photoluminescence spectroscopy of each member of these two families were studied in order to determine their suitability as emissive materials in photonic applications.

  11. Formation of nanophases in epoxy thermosets containing amphiphilic block copolymers with linear and star-like topologies.

    Science.gov (United States)

    Wang, Lei; Zhang, Chongyin; Cong, Houluo; Li, Lei; Zheng, Sixun; Li, Xiuhong; Wang, Jie

    2013-07-11

    In this work, we investigated the effect of topological structures of block copolymers on the formation of the nanophase in epoxy thermosets containing amphiphilic block copolymers. Two block copolymers composed of poly(ε-caprolactone) (PCL) and poly(2,2,2-trifluoroethyl acrylate) (PTFEA) blocks were synthesized to possess linear and star-shaped topologies. The star-shaped block copolymer composed a polyhedral oligomeric silsesquioxane (POSS) core and eight poly(ε-caprolactone)-block-poly(2,2,2-trifluoroethyl acrylate) (PCL-b-PTFEA) diblock copolymer arms. Both block copolymers were synthesized via the combination of ring-opening polymerization and reversible addition-fragmentation chain transfer/macromolecular design via the interchange of xanthate (RAFT/MADIX) process; they were controlled to have identical compositions of copolymerization and lengths of blocks. Upon incorporating both block copolymers into epoxy thermosets, the spherical PTFEA nanophases were formed in all the cases. However, the sizes of PTFEA nanophases from the star-like block copolymer were significantly lower than those from the linear diblock copolymer. The difference in the nanostructures gave rise to the different glass transition behavior of the nanostructured thermosets. The dependence of PTFEA nanophases on the topologies of block copolymers is interpreted in terms of the conformation of the miscible subchain (viz. PCL) at the surface of PTFEA microdomains and the restriction of POSS cages on the demixing of the thermoset-philic block (viz. PCL).

  12. Li7(BH)5(+): a new thermodynamically favored star-shaped molecule.

    Science.gov (United States)

    Torres-Vega, Juan J; Vásquez-Espinal, Alejandro; Beltran, Maria J; Ruiz, Lina; Islas, Rafael; Tiznado, William

    2015-07-15

    The potential energy surfaces (PESs) of Lin(BH)5(n-6) systems (where n = 5, 6, and 7) were explored using the gradient embedded genetic algorithm (GEGA) program, in order to find their global minima conformations. This search predicts that the lowest-energy isomers of Li6(BH)5 and Li7(BH)5(+) contain a (BH)5(6-) pentagonal fragment, which is isoelectronic and structurally analogous to the prototypical aromatic hydrocarbon anion C5H5(-). Li7(BH)5(+), along with Li7C5(+), Li7Si5(+) and Li7Ge5(+), joins a select group of clusters that adopt a seven-peak star-shape geometry, which is favored by aromaticity in the central five-membered ring, and by the preference of Li atoms for bridging positions. The theoretical analysis of chemical bonding, based on magnetic criteria, supports the notion that electronic delocalization is an important stabilization factor in all these star-shaped clusters.

  13. Parking simulation of three-dimensional multi-sized star-shaped particles

    International Nuclear Information System (INIS)

    Zhu, Zhigang; Chen, Huisu; Xu, Wenxiang; Liu, Lin

    2014-01-01

    The shape and size of particles may have a great impact on the microstructure as well as the physico-properties of particulate composites. However, it is challenging to configure a parking system of particles to a geometrical shape that is close to realistic grains in particulate composites. In this work, with the assistance of x-ray tomography and a spherical harmonic series, we present a star-shaped particle that is close to realistic arbitrary-shaped grains. To realize such a hard particle parking structure, an inter-particle overlapping detection algorithm is introduced. A serial sectioning approach is employed to visualize the particle parking structure for the purpose of justifying the reliability of the overlapping detection algorithm. Furthermore, the validity of the area and perimeter of solids in any arbitrary section of a plane calculated using a numerical method is verified by comparison with those obtained using an image analysis approach. This contribution is helpful to further understand the dependence of the micro-structure and physico-properties of star-shaped particles on the realistic geometrical shape. (paper)

  14. A star-shaped polythiophene dendrimer coating for solid-phase microextraction of triazole agrochemicals.

    Science.gov (United States)

    Abolghasemi, Mir Mahdi; Habibiyan, Rahim; Jaymand, Mehdi; Piryaei, Marzieh

    2018-02-14

    A nanostructured star-shaped polythiophene dendrimer was prepared and used as a fiber coating for headspace solid phase microextraction of selected triazolic pesticides (tebuconazole, hexaconazole, penconazole, diniconazole, difenoconazole, triticonazole) from water samples. The dendrimer with its large surface area was characterized by thermogravimetric analysis, UV-Vis spectroscopy and field emission scanning electron microscopy. It was placed on a stainless steel wire for use in SPME. The experimental conditions for fiber coating, extraction, stirring rate, ionic strength, pH value, desorption temperature and time were optimized. Following thermal desorption, the pesticides were quantified by GC-MS. Under optimum conditions, the repeatability (RSD) for one fiber (for n = 3) ranges from 4.3 to 5.6%. The detection limits are between 8 and 12 pg mL -1 . The method is fast, inexpensive (in terms of equipment), and the fiber has high thermal stability. Graphical abstract Schematic presentation of a nanostructured star-shaped polythiophene dendrimer for use in headspace solid phase microextraction of the triazolic pesticides (tebuconazole, hexaconazole, penconazole, diniconazole, difenoconazole, triticonazole). They were then quantified by gas chromatography-mass spectrometry.

  15. Nanofibers-based nanoweb promise superhydrophobic polyaniline: from star-shaped to leaf-shaped structures.

    Science.gov (United States)

    Fan, Haosen; Wang, Hao; Guo, Jing; Zhao, Ning; Xu, Jian

    2013-11-01

    Star-shaped and leaf-shaped polyaniline (PANI) hierarchical structures with interlaced nanofibers on the surface were successfully prepared by chemical polymerization of aniline in the presence of lithium triflate (LT). Chemical structure and composition of the star-like PANI obtained were characterized by FTIR and UV-vis spectra. PANI 2D architectures can be tailored from star-shaped to leaf-shaped structures by change the concentration of LT. The synthesized star-like and leaf-like polyaniline show good superhydrophobicity with water contact angles of both above 150° due to the combination of the rough nanoweb structure and the low surface tension of fluorinated chain of dopant. This method is a facile and applicable strategy for a large-scale fabrication of 2D PANI micro/nanostructures. Many potential applications such as self-cleaning and antifouling coating can be expected based on the superhydrophobic PANI micro/nanostructures. Crown Copyright © 2013. Published by Elsevier Inc. All rights reserved.

  16. Glutathione-assisted synthesis of star-shaped zinc oxide nanostructures and their photoluminescence behavior

    International Nuclear Information System (INIS)

    Kavita; Singh, Karamjit; Kumar, Sunil; Bhatti, H.S.

    2014-01-01

    Star-shaped ZnO nanostructures have been synthesized by facile chemical co-precipitation method in the presence of glutathione. Glutathione, a reducing agent, shape modifier and an entirely benign antioxidant; acts as a capping agent in the present study. The powder X-ray diffraction patterns indicate that the novel star-shaped ZnO nanostructures exhibit hexagonal structure. Fourier transform infra-red spectroscopic studies confirmed the anchoring of glutathione on ZnO nanocrystals. Transmission electron microscopy and field emission scanning electron microscopy revealed the star and cube-shaped shaped morphology of the glutathione modified nanocrystals. Optical characterization of synthesized nanocrystals has been done by UV–vis absorption spectroscopy and steady state photoluminescence spectroscopy. Recorded Photoluminescence spectra confirm the multi-chromatic photoluminescence behavior of the synthesized nanostructures. - Highlights: • Morphology has been investigated as a function of capping agent concentration. • Comparison between capped and uncapped ZnO nanoparticles has been examined. • Diffraction scans show the crystalline wurtzite structure of synthesized product. • Recorded PL spectra show the multichromatic behavior of synthesized nanostructures

  17. Synthesis and self-assembly of Chitosan-g-Polystyrene copolymer: A new route for the preparation of heavy metal nanoparticles

    KAUST Repository

    Francis, Raju S.; Baby, Deepa K.; Gnanou, Yves

    2015-01-01

    Amphiphilic graft copolymers made of a Chitosan (CS) backbone and three arm polystyrene (PS) grafts were prepared by "grafting onto" strategy using Toluene Diisocyanate. IR spectroscopy and SEC show the successful grafting process. SEM pictures

  18. Fabrication of hexagonal star-shaped and ring-shaped patterns arrays by Mie resonance sphere-lens-lithography

    Science.gov (United States)

    Liu, Xianchao; Wang, Jun; Li, Ling; Gou, Jun; Zheng, Jie; Huang, Zehua; Pan, Rui

    2018-05-01

    Mie resonance sphere-lens-lithography has proved to be a good candidate for fabrication of large-area tunable surface nanopattern arrays. Different patterns on photoresist surface are obtained theoretically by adjusting optical coupling among neighboring spheres with different gap sizes. The effect of light reflection from the substrate on the pattern produced on the photoresist with a thin thickness is also discussed. Sub-micron hexagonal star-shaped and ring-shaped patterns arrays are achieved with close-packed spheres arrays and spheres arrays with big gaps, respectively. Changing of star-shaped vertices is induced by different polarization of illumination. Experimental results agree well with the simulation. By using smaller resonance spheres, sub-400 nm star-shaped and ring-shaped patterns can be realized. These tunable patterns are different from results of previous reports and have enriched pattern morphology fabricated by sphere-lens-lithography, which can find application in biosensor and optic devices.

  19. Star-shaped Polymers through Simple Wavelength-Selective Free-Radical Photopolymerization.

    Science.gov (United States)

    Eibel, Anna; Fast, David E; Sattelkow, Jürgen; Zalibera, Michal; Wang, Jieping; Huber, Alex; Müller, Georgina; Neshchadin, Dmytro; Dietliker, Kurt; Plank, Harald; Grützmacher, Hansjörg; Gescheidt, Georg

    2017-11-06

    Star-shaped polymers represent highly desired materials in nanotechnology and life sciences, including biomedical applications (e.g., diagnostic imaging, tissue engineering, and targeted drug delivery). Herein, we report a straightforward synthesis of wavelength-selective multifunctional photoinitiators (PIs) that contain a bisacylphosphane oxide (BAPO) group and an α-hydroxy ketone moiety within one molecule. By using three different wavelengths, these photoactive groups can be selectively addressed and activated, thereby allowing the synthesis of ABC-type miktoarm star polymers through a simple, highly selective, and robust free-radical polymerization method. The photochemistry of these new initiators and the feasibility of this concept were investigated in unprecedented detail by using various spectroscopic techniques. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. A new representative of star-shaped fungi: Astraeus sirindhorniae sp. nov. from Thailand.

    Science.gov (United States)

    Phosri, Cherdchai; Watling, Roy; Suwannasai, Nuttika; Wilson, Andrew; Martín, María P

    2014-01-01

    Phu Khieo Wildlife Sanctuary (PKWS) is a major hotspot of biological diversity in Thailand but its fungal diversity has not been thouroughly explored. A two-year macrofungal study of this remote locality has resulted in the recognition of a new species of a star-shaped gasteroid fungus in the genus Astraeus. This fungus has been identified based on a morphological approach and the molecular study of five loci (LSU nrDNA, 5.8S nrDNA, RPB1, RPB2 and EF1-a). Multigene phylogenetic analysis of this new species places it basal relative to other Astraeus, providing additional evidence for the SE Asian origin of the genus. The fungus is named in honour of Her Majesty Princess Sirindhorn on the occasion the 84th birthday of her father, who have both been supportive of natural heritage studies in Thailand.

  1. BODIPY star-shaped molecules as solid state colour converters for visible light communications

    Energy Technology Data Exchange (ETDEWEB)

    Vithanage, D. A.; Manousiadis, P. P.; Sajjad, M. T.; Samuel, I. D. W., E-mail: idws@st-andrews.ac.uk, E-mail: gat@st-andrews.ac.uk; Turnbull, G. A., E-mail: idws@st-andrews.ac.uk, E-mail: gat@st-andrews.ac.uk [Organic Semiconductor Centre, SUPA, School of Physics and Astronomy, University of St Andrews, St. Andrews KY16 9SS (United Kingdom); Rajbhandari, S. [School of Computing, Electronics and Mathematics, Coventry University, Coventry, West Midlands CV1 2JH (United Kingdom); Department of Engineering Science, University of Oxford, Oxford OX1 3PJ (United Kingdom); Chun, H.; Faulkner, G.; O' Brien, D. C. [Department of Engineering Science, University of Oxford, Oxford OX1 3PJ (United Kingdom); Orofino, C.; Cortizo-Lacalle, D.; Findlay, N. J.; Skabara, P. J. [WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, Glasgow G1 1XL (United Kingdom); Kanibolotsky, A. L. [WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, Glasgow G1 1XL (United Kingdom); Institute of Physical-Organic Chemistry and Coal Chemistry, 02160 Kyiv (Ukraine)

    2016-07-04

    In this paper, we study a family of solid-state, organic semiconductors for visible light communications. The star-shaped molecules have a boron-dipyrromethene (BODIPY) core with a range of side arm lengths which control the photophysical properties. The molecules emit red light with photoluminescence quantum yields ranging from 22% to 56%. Thin films of the most promising BODIPY molecules were used as a red colour converter for visible light communications. The film enabled colour conversion with a modulation bandwidth of 73 MHz, which is 16 times higher than that of a typical phosphor used in LED lighting systems. A data rate of 370 Mbit/s was demonstrated using On-Off keying modulation in a free space link with a distance of ∼15 cm.

  2. Star-Shaped Polypeptides: Synthesis and Opportunities for Delivery of Therapeutics.

    Science.gov (United States)

    Byrne, Mark; Murphy, Robert; Kapetanakis, Antonios; Ramsey, Joanne; Cryan, Sally-Ann; Heise, Andreas

    2015-09-17

    Significant advances in the synthesis of polypeptides by N-carboxyanhydride (NCA) polymerisation over the last decade have enabled the design of advanced polypeptide architectures such as star-shaped polypeptides. These materials combine the functionality offered by amino acids with the flexibility of creating stable nanoparticles with adjustable cargo space for therapeutic delivery. This review highlights recent advances in the synthesis of star polypeptides by NCA polymerisation followed by a critical review of the applications of this class of polymer in the delivery of therapeutic agents. This includes examples of traditional small-molecule drugs as well as the emerging class of biologics such as genetic therapeutics (gene delivery). © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Star-shaped ZnO/Ag hybrid nanostructures for enhanced photocatalysis and antibacterial activity

    Energy Technology Data Exchange (ETDEWEB)

    Andrade, George R.S., E-mail: grsandrade@hotmail.com [Postgraduate Program in Materials Science and Engineering, Federal University of Sergipe, São Cristóvão, SE (Brazil); Nascimento, Cristiane C. [Postgraduate Program in Materials Science and Engineering, Federal University of Sergipe, São Cristóvão, SE (Brazil); Federal Institute of Education, Science and Technology of Sergipe, Glória Campus, Nossa Senhora da Glória, SE (Brazil); Lima, Zenon M. [Postgraduate Program in Industrial Biochemistry, Tiradentes University, Aracaju, SE (Brazil); Teixeira-Neto, Erico [LNNano − Brazilian Nanotechnology National Laboratory, Brazilian Center for Research in Energy and Materials, Campinas, SP (Brazil); Costa, Luiz P. [Postgraduate Program in Industrial Biochemistry, Tiradentes University, Aracaju, SE (Brazil); ITPS − Technological and Research Institute of Sergipe, Aracaju, SE (Brazil); Gimenez, Iara F. [Postgraduate Program in Materials Science and Engineering, Federal University of Sergipe, São Cristóvão, SE (Brazil); Department of Chemistry, Federal University of Sergipe, São Cristóvão, SE (Brazil)

    2017-03-31

    Highlights: • A new and simple one-pot method for preparing star-shaped ZnO particles was reported. • ZnO particles were decorated with Ag nanoparticles (SNPs) by a photodeposition method. • The presence of SNC{sup −} ions on ZnO surface prevented uncontrollable growth of SNPs. • ZnO/Ag particles showed plasmon-enhanced photocatalytic activity toward an AZO dye. • SNP improved 16 times the antibacterial activity of ZnO toward 4 bacterial strains. - Abstract: Zinc oxide (ZnO) particles with a star-shaped morphology have been synthesized by a novel and simple room-temperature method and decorated with silver nanoparticles (SNPs) for enhanced photocatalysis and bactericide applications. The presence of thiourea during the precipitation of ZnO in alkaline conditions allowed the control of morphological features (e.g. average size and shape) and the surface functionalization with thiocyanate ions (SCN{sup −}). SNPs were deposited into the ZnO surface by a photoreduction method and their sizes could be easily controlled by changing the ZnO/AgNO{sub 3} ratio. The presence of SCN{sup −} on the semiconductor surface prevents uncontrollable growth of Ag nanoparticles into different morphologies and high degrees of polydispersity. XRD, SEM, TEM, FTIR, UV-vis-NIR and PL were employed for characterizing the structure, morphology and optical properties of the as-obtained pure and hybrid nanostructures. Finally, the hybrid ZnO/Ag particles have shown plasmon-enhanced performance for applications in photocatalysis and antibacterial activity compared to the pure ZnO counterpart. In this work, evaluation of the photodegradation of an aqueous methylene blue solution under UV-A irradiation and the antibacterial activity toward 4 bacterial strains, including Gram-positive bacteria Staphylococcus aureus (ATCC 43300, ATCC 25923 and ATCC 33591) and Gram-negative bacteria Pseudomonas aeruginosa (ATCC 27853).

  4. A studentized permutation test for three-arm trials in the 'gold standard' design.

    Science.gov (United States)

    Mütze, Tobias; Konietschke, Frank; Munk, Axel; Friede, Tim

    2017-03-15

    The 'gold standard' design for three-arm trials refers to trials with an active control and a placebo control in addition to the experimental treatment group. This trial design is recommended when being ethically justifiable and it allows the simultaneous comparison of experimental treatment, active control, and placebo. Parametric testing methods have been studied plentifully over the past years. However, these methods often tend to be liberal or conservative when distributional assumptions are not met particularly with small sample sizes. In this article, we introduce a studentized permutation test for testing non-inferiority and superiority of the experimental treatment compared with the active control in three-arm trials in the 'gold standard' design. The performance of the studentized permutation test for finite sample sizes is assessed in a Monte Carlo simulation study under various parameter constellations. Emphasis is put on whether the studentized permutation test meets the target significance level. For comparison purposes, commonly used Wald-type tests, which do not make any distributional assumptions, are included in the simulation study. The simulation study shows that the presented studentized permutation test for assessing non-inferiority in three-arm trials in the 'gold standard' design outperforms its competitors, for instance the test based on a quasi-Poisson model, for count data. The methods discussed in this paper are implemented in the R package ThreeArmedTrials which is available on the comprehensive R archive network (CRAN). Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

  5. Pd-Catalyzed Consecutive C-H Arylation Triggered Cyclotrimerization: Synthesis of Star-shaped Benzotristhiazoles and Benzotrisoxazoles.

    Science.gov (United States)

    Xu, Zhanqiang; Oniwa, Kazuaki; Kikuchi, Hiromasa; Bao, Ming; Yamamoto, Yoshinori; Jin, Tienan; Terada, Masahiro

    2018-05-18

    Star-shaped π-extended molecules comprising discotic aromatic cores and peripheral π-conjugated arms have attracted significant attention as diverse optoelectronic materials in terms of their large π-surface, tunable self-assembly, enhanced charge transport and fluorescence, and liquid crystallinity. Although many efforts have been made in construction of various aromatic discotic cores, a new class of C3-symmetric star-shaped discotic π-molecules consisting of electron-deficient benzotristhiazole and benzotrisoxazole cores remains unexplored owing to the unachievable synthetic approaches, which are expected to exhibit distinct optoelectronic properties. Herein, we report a novel and highly efficient Pd-catalyzed cyclotrimerization of the functionalized thiazoles or oxazoles for the construction of a new class of discotic molecules of benzotristhiazole and benzotrisoxazole central cores with star-shaped π-conjugated arms. The combination of Pd2(dba)3/XPhos catalyst systems with the 4-bromo-substituted thiazole enables the formation of a sufficiently stable thiazole-Pd species that participates in the subsequent C-H arylations consecutively to form the corresponding cyclic trimer products. This new class of star-shaped discotic π-extended products showed tunable energy levels and high fluorescence quantum yields that make them promising candidates in optoelectronic application. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Polystyrene star-shaped polymers made by the new In-Inmethod

    International Nuclear Information System (INIS)

    Fazeli, N.; Afshar Toromi, F.

    2002-01-01

    Three main methods are usually used for the synthesis of star-shaped polymers, where each one has its own advantages and disadvantages. Among these techniques, i n-out m ethod is the best one to produce hetero arm star polymers with narrow molecular weight distribution and long arms with active sites at the end of the second-generation arms. This method, however, has some difficulties during the synthesis of hetero-arm star polymers with styrene or dienes as the second monomers. The reason is that in the o ut s tep, the carbanions of the growing chain attack the existing double bonds of the other cores and produce an irreversible gel. The new i n-in m ethod mentioned in this paper, is used to synthesize double-star polystyrene polymers with relatively narrow molecular weight distribution and without occurrence of any gelation during the process. With the monomers, which are able to attack the existing double bonds of the cores of the star polymers, it is also possible to produce-hetero-arm star polymers using this new method

  7. Maximal qubit violation of n-locality inequalities in a star-shaped quantum network

    Science.gov (United States)

    Andreoli, Francesco; Carvacho, Gonzalo; Santodonato, Luca; Chaves, Rafael; Sciarrino, Fabio

    2017-11-01

    Bell's theorem was a cornerstone for our understanding of quantum theory and the establishment of Bell non-locality played a crucial role in the development of quantum information. Recently, its extension to complex networks has been attracting growing attention, but a deep characterization of quantum behavior is still missing for this novel context. In this work we analyze quantum correlations arising in the bilocality scenario, that is a tripartite quantum network where the correlations between the parties are mediated by two independent sources of states. First, we prove that non-bilocal correlations witnessed through a Bell-state measurement in the central node of the network form a subset of those obtainable by means of a local projective measurement. This leads us to derive the maximal violation of the bilocality inequality that can be achieved by arbitrary two-qubit quantum states and arbitrary local projective measurements. We then analyze in details the relation between the violation of the bilocality inequality and the CHSH inequality. Finally, we show how our method can be extended to the n-locality scenario consisting of n two-qubit quantum states distributed among n+1 nodes of a star-shaped network.

  8. Electroplex light emission based on BCP and a novel star-shaped hexafluorenylbenzene

    Science.gov (United States)

    Ma, Tao; Yu, Junsheng; Lou, Shuangling; Jiang, Yadong; Zhang, Qing

    2009-05-01

    Organic light emitting diode (OLEDs) are fabricated using a novel star-shaped hexafluorenylbenzene with a simple structure of indium-tin-oxide (ITO)/1,2,3,4,5,6-hexakis(9,9-diethyl-9H-fluoren-2-yl)benzene (HKEthFLYPh):N, N'-bis-(1-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine (NPB)/2,9-dimenthyl-4,7-diphenyl-1,10-phenanthroline (BCP)/tris(8-hydroxyquinoline) aluminum (Alq3)/Mg:Ag by spin coating method. The electroluminescent properties of the device are characterized. The results show that there is a new peak at 600 nm, which is no appearance in PL spectra. This new emission is proposed to be electroplex that occurred at the solid-state interface between HKEthFLYPh and BCP in addition to the exciton emission from NPB. The Commissions Internationale De L'Eclairage (CIE) coordinates of the device are (x=0.33, y=0.29) at 10 V, which obviously belongs to white light emission.

  9. MOVEMENT SIMULATION OF THREE ARMED ROBOT BY BEING USED AutoLISP

    Directory of Open Access Journals (Sweden)

    Mustafa BOZDEMİR

    2000-01-01

    Full Text Available Development of a suitable robot for desired aim and duty is very important for design enginers. On the other hand, designed robots may be unsuccesful in functioning inspite of many efforts. For this reason, before the production of considered robot systems, having prepared a simulation program, investigation of work field, getting done path plan and mistakes could be eliminated before robot production. In this study, movement simulation of a three armed robot has been realized by using AutoLIPS programing language which is supplied with AutoCAD. Analytical and matrix solution methods have been used in simulation equations.

  10. Sample size determination for a three-arm equivalence trial of Poisson and negative binomial responses.

    Science.gov (United States)

    Chang, Yu-Wei; Tsong, Yi; Zhao, Zhigen

    2017-01-01

    Assessing equivalence or similarity has drawn much attention recently as many drug products have lost or will lose their patents in the next few years, especially certain best-selling biologics. To claim equivalence between the test treatment and the reference treatment when assay sensitivity is well established from historical data, one has to demonstrate both superiority of the test treatment over placebo and equivalence between the test treatment and the reference treatment. Thus, there is urgency for practitioners to derive a practical way to calculate sample size for a three-arm equivalence trial. The primary endpoints of a clinical trial may not always be continuous, but may be discrete. In this paper, the authors derive power function and discuss sample size requirement for a three-arm equivalence trial with Poisson and negative binomial clinical endpoints. In addition, the authors examine the effect of the dispersion parameter on the power and the sample size by varying its coefficient from small to large. In extensive numerical studies, the authors demonstrate that required sample size heavily depends on the dispersion parameter. Therefore, misusing a Poisson model for negative binomial data may easily lose power up to 20%, depending on the value of the dispersion parameter.

  11. Synthesis of star-shaped lead sulfide (PbS) nanomaterials and theirs gas-sensing properties

    Energy Technology Data Exchange (ETDEWEB)

    Song, Chengwen; Sun, Menghan; Yin, Yanyan; Xiao, Jingkun; Dong, Wei; Li, Chen; Zhang, Li, E-mail: chengwensong@dlmu.edu.cn [College of Environmental Science and Engineering, Dalian Maritime University, Dalian(China)

    2016-11-15

    Star-shaped PbS nanomaterials are synthesized by a hydrothermal method. Morphology and structure of the PbS nanomaterials are analyzed by SEM, HRTEM and XRD. Gas-sensing properties of the as-prepared PbS sensor are also systematically investigated. The results show star-shaped PbS nanostructure consists of four symmetric arms in the same plane and demonstrate good crystallinity. With the increase of ethanol concentration, the sensitivity of the PbS sensor significantly increases and demonstrates an almost linear relationship at the optimal operating temperature of 400 deg C. Moreover, the fast response-recovery towards ethanol is also observed, which indicates its great potential on ethanol detection. (author)

  12. Synthesis of star-shaped lead sulfide (PbS) nanomaterials and theirs gas-sensing properties

    International Nuclear Information System (INIS)

    Song, Chengwen; Sun, Menghan; Yin, Yanyan; Xiao, Jingkun; Dong, Wei; Li, Chen; Zhang, Li

    2016-01-01

    Star-shaped PbS nanomaterials are synthesized by a hydrothermal method. Morphology and structure of the PbS nanomaterials are analyzed by SEM, HRTEM and XRD. Gas-sensing properties of the as-prepared PbS sensor are also systematically investigated. The results show star-shaped PbS nanostructure consists of four symmetric arms in the same plane and demonstrate good crystallinity. With the increase of ethanol concentration, the sensitivity of the PbS sensor significantly increases and demonstrates an almost linear relationship at the optimal operating temperature of 400 deg C. Moreover, the fast response-recovery towards ethanol is also observed, which indicates its great potential on ethanol detection. (author)

  13. Green Thermosetting Factory: Novel Star-Shaped Biobased Systems and Their Thermosetting Resins; Synthesis and Characterization

    Science.gov (United States)

    Jahandideh, Arash

    Increasing attentions toward sustainable development, economic and environmental issues have led to many attempts at replacing the petroleum-based materials with renewables. Substitution of petroleum-based platforms with green alternative technologies is beneficiary in different ways. Using bio-renewables reduces the dependency of the national plastic industry to the petroleum resources and substantially promotes the environmental profile and sustainability of the product. It is expected that the emergence of the corn-based thermosetting industry generates substantial profits for the corn production sector. Developments in the emerging biobased thermosets are spectacular from a technological point of view. However, there are still several disadvantages associated with the current biobased thermosetting resins, e.g. low processability, environmental issues, expensive sources and poor thermomechanical properties. Use of natural fibers not only contributes to the production of a more environmentally friendly product, but also has advantages such as low-weight product and low manufacturing costs. The results of this study show a possibility of production of biocomposites made from natural fibers and star-shaped resin, synthesized from corn-based materials (lactic acid and itaconic acid) and different multihydroxyl core molecules. These resins were synthesized via two-steps strategy: polycondensation of the monomers with the core molecules followed by end-functionalization of the branches by methacrylic anhydride or itaconic acid. The results have shown that these resin are capable of competing with or even surpassing fossil fuel based resins in terms of cost and eco-friendliness aspect. Inexpensive biobased raw material, better environmental profile, low viscosity, and better processability of the matrix along with better thermomechanical properties of the produced biocomposites are of advantages expected for these systems.

  14. Interactions of Fluorescein Dye with Spherical and Star Shaped Gold Nanoparticles.

    Science.gov (United States)

    Pal, Gopa Dutta; Paul, Somnath; Bardhan, Munmun; Ganguly, Tapan

    2018-04-01

    UV-vis absorption, FT-IR, steady state fluorescence and fluorescence lifetime measurements were made on Fluorescein dye (Fl dye) molecules in presence of gold nanoparticles of different morphologies: spherical gold nanoparticles (GNP) and star shaped gold nanoparticles (GNS). The experimental observations demonstrate that Fl dye molecules form dimers when adsorbed on nanosurface of spherical gold particles. On the other hand possibly due to lack of adsorption on the surface of GNS the dye molecules were unable to form dimers. The projected tips on the surface of GNS may possibly hinder the dyes to adsorb on the surface of this nanoparticle. From the spectral analysis and measurements of thermodynamic parameters it is inferred that two different types of ground state interactions occur between Fl-dye-GNP and Fl dye-GNS systems. Both the observed negative values of the thermodynamic parameters ΔH and ΔS in the case of the former system predict the possibility of occurrences of hydrogen bonding interactions between two neighboring Fl dye molecules when adsorbed on the nanosurface of GNP. On the other hand in Fl dye-GNS system electrostatic interactions appear to occur, as evidenced from negative ΔH and positive value of ΔS, between the positive charges residing on the tips of the nanoparticles and anionic form of Fl dye. It has been concluded that as the adsorption of organic dyes on solid surfaces is prerequisite for the degradation of dye pollutants, the present experimental observations demonstrate that GNP could be used as a better candidate than GNS in degradation mechanism of the xanthenes dyes.

  15. Synthesis and crystal structures of multifunctional tosylates as basis for star-shaped poly(2-ethyl-2-oxazolines

    Directory of Open Access Journals (Sweden)

    Richard Hoogenboom

    2010-09-01

    Full Text Available The synthesis of well-defined polymer architectures is of major importance for the development of complex functional materials. In this contribution, we discuss the synthesis of a range of multifunctional star-shaped tosylates as potential initiators for the living cationic ring-opening polymerization (CROP of 2-oxazolines resulting in star-shaped polymers. The synthesis of the tosylates was performed by esterification of the corresponding alcohols with tosyl chloride. Recrystallization of these tosylate compounds afforded single crystals, and the X-ray crystal structures of di-, tetra- and hexa-tosylates are reported. The use of tetra- and hexa-tosylates, based on (dipentaerythritol as initiators for the CROP of 2-ethyl-2-oxazoline, resulted in very slow initiation and ill-defined polymers, which is most likely caused by steric hindrance in these initiators. As a consequence, a porphyrin-cored tetra-tosylate initiator was prepared, which yielded a well-defined star-shaped poly(2-ethyl-2-oxazoline by CROP as demonstrated by SEC with RI, UV and diode-array detectors, as well as by 1H NMR spectroscopy.

  16. Silica-covered star-shaped Au-Ag nanoparticles as new electromagnetic nanoresonators for Raman characterisation of surfaces.

    Science.gov (United States)

    Krajczewski, Jan; Kołątaj, Karol; Pietrasik, Sylwia; Kudelski, Andrzej

    2018-03-15

    One of the tools used for determining the composition of surfaces of various materials is shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS). SHINERS is a modification of "standard" surface-enhanced Raman spectroscopy (SERS), in which, before Raman spectra are recorded, the surfaces analysed are covered with a layer of plasmonic nanoparticles protected by a very thin layer of a transparent dielectric. The plasmonic cores of the core-shell nanoparticles used in SHINERS measurements generate a local enhancement of the electric field of the incident electromagnetic radiation, whereas the transparent coatings prevent the metal cores from coming into direct contact with the material being analysed. In this contribution, we propose a new type of SHINERS nanoresonators that contain spiky, star-shaped metal cores (produced from a gold/silver alloy). These spiky, star-shaped Au-Ag nanoparticles have been covered by a layer of silica. The small radii of the ends of the tips of the spikes of these plasmonic nanostructures make it possible to generate a very large enhancement of the electromagnetic field there, with the result that such SHINERS nanoresonators are significantly more efficient than the standard semi-spherical nanostructures. The Au-Ag alloy nanoparticles were synthesised by the reduction of a solution containing silver nitrate and chloroauric acid by ascorbic acid. The final geometry of the nanostructures thus formed was controlled by changing the ratio between the concentrations of AuCl 4 - and Ag + ions. The shape of the synthesised star-shaped Au-Ag nanoparticles does not change significantly during the two standard procedures for depositing a layer of silica (by the decomposition of sodium silicate or the decomposition of tetraethyl orthosilicate). Copyright © 2017 Elsevier B.V. All rights reserved.

  17. Silica-covered star-shaped Au-Ag nanoparticles as new electromagnetic nanoresonators for Raman characterisation of surfaces

    Science.gov (United States)

    Krajczewski, Jan; Kołątaj, Karol; Pietrasik, Sylwia; Kudelski, Andrzej

    2018-03-01

    One of the tools used for determining the composition of surfaces of various materials is shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS). SHINERS is a modification of "standard" surface-enhanced Raman spectroscopy (SERS), in which, before Raman spectra are recorded, the surfaces analysed are covered with a layer of plasmonic nanoparticles protected by a very thin layer of a transparent dielectric. The plasmonic cores of the core-shell nanoparticles used in SHINERS measurements generate a local enhancement of the electric field of the incident electromagnetic radiation, whereas the transparent coatings prevent the metal cores from coming into direct contact with the material being analysed. In this contribution, we propose a new type of SHINERS nanoresonators that contain spiky, star-shaped metal cores (produced from a gold/silver alloy). These spiky, star-shaped Au-Ag nanoparticles have been covered by a layer of silica. The small radii of the ends of the tips of the spikes of these plasmonic nanostructures make it possible to generate a very large enhancement of the electromagnetic field there, with the result that such SHINERS nanoresonators are significantly more efficient than the standard semi-spherical nanostructures. The Au-Ag alloy nanoparticles were synthesised by the reduction of a solution containing silver nitrate and chloroauric acid by ascorbic acid. The final geometry of the nanostructures thus formed was controlled by changing the ratio between the concentrations of AuCl4- and Ag+ ions. The shape of the synthesised star-shaped Au-Ag nanoparticles does not change significantly during the two standard procedures for depositing a layer of silica (by the decomposition of sodium silicate or the decomposition of tetraethyl orthosilicate).

  18. Electropolymerized Star-Shaped Benzotrithiophenes Yield π-Conjugated Hierarchical Networks with High Areal Capacitance

    KAUST Repository

    Ringk, Andreas

    2016-03-30

    High-surface-area π-conjugated polymeric networks have the potential to lend outstanding capacitance to supercapacitors because of the pronounced faradaic processes that take place across the dense intimate interface between active material and electrolytes. In this report, we describe how benzo[1,2-b:3,4-b’:5,6-b’’]trithiophene (BTT) and tris-EDOT-benzo[1,2-b:3,4-b’:5,6-b’’]trithiophene (TEBTT) can serve as 2D (trivalent) building blocks in the development of electropolymerized hierarchical π-conjugated frameworks with particularly high areal capacitance. In comparing electropolymerized networks of BTT, TEBTT, and their copolymers with EDOT, we show that P(TEBTT/EDOT)-based frameworks can achieve higher areal capacitance (e.g., as high as 443.8 mF cm-2 at 1 mA cm-2) than those achieved by their respective homopolymers (PTEBTT and PEDOT) in the same experimental conditions of electrodeposition (PTEBTT: 271.1 mF cm-2 (at 1 mA cm-2) and PEDOT: 12.1 mF cm-2 (at 1 mA cm-2)). For example, P(TEBTT/EDOT)-based frameworks synthesized in a 1:1 monomer-to-comonomer ratio show a ca. 35x capacitance improvement over PEDOT. The high areal capacitance measured for P(TEBTT/EDOT) copolymers can be explained by the open, highly porous hierarchical morphologies formed during the electropolymerization step. With >70% capacitance retention over 1,000 cycles (up to 89% achieved), both PTEBTT- and P(TEBTT/EDOT)-based frameworks are resilient to repeated electrochemical cycling and can be considered promising systems for high life cycle capacitive electrode applications.

  19. Electropolymerized Star-Shaped Benzotrithiophenes Yield π-Conjugated Hierarchical Networks with High Areal Capacitance

    KAUST Repository

    Ringk, Andreas; Lignie, Adrien; Hou, Yuanfang; Alshareef, Husam N.; Beaujuge, Pierre

    2016-01-01

    High-surface-area π-conjugated polymeric networks have the potential to lend outstanding capacitance to supercapacitors because of the pronounced faradaic processes that take place across the dense intimate interface between active material and electrolytes. In this report, we describe how benzo[1,2-b:3,4-b’:5,6-b’’]trithiophene (BTT) and tris-EDOT-benzo[1,2-b:3,4-b’:5,6-b’’]trithiophene (TEBTT) can serve as 2D (trivalent) building blocks in the development of electropolymerized hierarchical π-conjugated frameworks with particularly high areal capacitance. In comparing electropolymerized networks of BTT, TEBTT, and their copolymers with EDOT, we show that P(TEBTT/EDOT)-based frameworks can achieve higher areal capacitance (e.g., as high as 443.8 mF cm-2 at 1 mA cm-2) than those achieved by their respective homopolymers (PTEBTT and PEDOT) in the same experimental conditions of electrodeposition (PTEBTT: 271.1 mF cm-2 (at 1 mA cm-2) and PEDOT: 12.1 mF cm-2 (at 1 mA cm-2)). For example, P(TEBTT/EDOT)-based frameworks synthesized in a 1:1 monomer-to-comonomer ratio show a ca. 35x capacitance improvement over PEDOT. The high areal capacitance measured for P(TEBTT/EDOT) copolymers can be explained by the open, highly porous hierarchical morphologies formed during the electropolymerization step. With >70% capacitance retention over 1,000 cycles (up to 89% achieved), both PTEBTT- and P(TEBTT/EDOT)-based frameworks are resilient to repeated electrochemical cycling and can be considered promising systems for high life cycle capacitive electrode applications.

  20. A star-shaped poly(2-methyl-2-oxazoline)-based antifouling coating: Application in investigation of the interaction between acetaminophen and bovine serum albumin by frontal analysis capillary electrophoresis.

    Science.gov (United States)

    Du, Haiqin; Zhang, Chong; Mao, Ke; Wang, Yanmei

    2017-08-01

    In this work, an antifouling capillary modified with star-shaped poly(2-methyl-2-oxazoline)-based copolymer was used to study the interaction between acetaminophen (APAP) and bovine serum albumin (BSA) by frontal analysis capillary electrophoresis (FACE). The star-shaped copolymer, poly(ethylene imine)-graft-poly(2-methyl-2-oxazoline) (PEI-g-PMOXA), was immobilized onto the fused-silica capillary inner wall via dopamine-assisted co-deposition strategy, yielding a PEI-g-PMOXA/polydopamine (PDA)-coated antifouling capillary, i.e., an antifouling capillary coated with the PEI-g-PMOXA/PDA co-deposited film. Electroosmotic flow (EOF) mobility of the PEI-g-PMOXA/PDA-coated capillary was almost zero in a wide pH range (3.0-10.0), while the EOF mobility of bare capillary was much larger and increased significantly with pH increasing. When the PEI-g-PMOXA/PDA-coated capillary was exploited to separate a protein mixture including cytochrome c, lysozyme, ribonuclease A and α-chymotrypsinogen A, the theoretical plate numbers were of five orders of magnitude which were about ten-fold higher over those obtained with bare capillary; in addition, the RSD values of migration time were mostly less than 0.7% (30 consecutive runs) which were much smaller than those of bare capillary (c.a. 5.7%). The protein-resistant PEI-g-PMOXA/PDA-coated capillary was then used to investigate the interaction between APAP and BSA by FACE, the binding constant and number of binding sites at 25°C and pH 7.4 (Tris/HCl buffer of 25mM) were 1.39×10 4 M -1 and 1.08, respectively, which were comparable to the results determined by fluorescence spectroscopic measurement (3.18×10 4 M -1 and 1.19, respectively). Copyright © 2017 Elsevier B.V. All rights reserved.

  1. A soluble star-shaped silsesquioxane-cored polymer-towards novel stabilization of pH-dependent high internal phase emulsions.

    Science.gov (United States)

    Xing, Yuxiu; Peng, Jun; Xu, Kai; Gao, Shuxi; Gui, Xuefeng; Liang, Shengyuan; Sun, Longfeng; Chen, Mingcai

    2017-08-30

    A well-defined pH-responsive star-shaped polymer containing poly(N,N-dimethylaminoethyl methacrylate) (PDMA) arms and a cage-like methacryloxypropyl silsesquioxane (CMSQ-T 10 ) core was used as an interfacial stabilizer for emulsions consisting of m-xylene and water. We explored the properties of the CMSQ/PDMA star-shaped polymer using the characteristic results of nuclear magnetic resonance (NMR) spectroscopy, size exclusion chromatography (SEC), dynamic light scattering (DLS), and zeta potential and conductivity measurements. The interfacial tension results showed that the CMSQ/PDMA star-shaped polymer reduced the interfacial tension between water and oil in a pH-dependent manner. Gelled high internal phase emulsions (HIPEs) including o/w and w/o types were formed in the pH ranges of 1.2-5.8 and 9.1-12.3 with the CMSQ/PDMA star-shaped polymer as a stabilizer, when the oil fractions were 80-90 vol% and 10-20 vol%, respectively. The soluble star-shaped polymer aggregated spontaneously to form a microgel that adsorbed to the two immiscible phases. Images of the fluorescently labeled polymers demonstrated that there was a star-shaped polymer in the continuous phase, and the non-Pickering stabilization based on the percolating network of the star-shaped polymer also contributed to the stabilization of the HIPE. This pH-dependent HIPE was prepared with a novel stabilization mechanism consisting of microgel adsorption and non-Pickering stabilization. Moreover, the preparation of HIPEs provided the possibility of their application in porous materials and responsive materials.

  2. Influence of Polyplex Formation on the Performance of Star-Shaped Polycationic Transfection Agents for Mammalian Cells

    Directory of Open Access Journals (Sweden)

    Alexander Raup

    2016-06-01

    Full Text Available Genetic modification (“transfection” of mammalian cells using non-viral, synthetic agents such as polycations, is still a challenge. Polyplex formation between the DNA and the polycation is a decisive step in such experiments. Star-shaped polycations have been proposed as superior transfection agents, yet have never before been compared side-by-side, e.g., in view of structural effects. Herein four star-shaped polycationic structures, all based on (2-dimethylamino ethyl methacrylate (DMAEMA building blocks, were investigated for their potential to deliver DNA to adherent (CHO, L929, HEK-293 and non-adherent (Jurkat, primary human T lymphocytes mammalian cells. The investigated vectors included three structures where the PDMAEMA arms (different arm length and grafting densities had been grown from a center silsesquioxane or silica-coated γ-Fe2O3-core and one micellar structure self-assembled from poly(1,2-butadiene-block PDMAEMA polymers. All nano-stars combined high transfection potential with excellent biocompatibility. The micelles slightly outperformed the covalently linked agents. For method development and optimization, the absolute amount of polycation added to the cells was more important than the N/P-ratio (ratio between polycation nitrogen and DNA phosphate, provided a lower limit was passed and enough polycation was present to overcompensate the negative charge of the plasmid DNA. Finally, the matrix (NaCl vs. HEPES-buffered glucose solution, but also the concentrations adjusted during polyplex formation, affected the results.

  3. White polymer light-emitting diodes based on star-shaped polymers with an orange dendritic phosphorescent core.

    Science.gov (United States)

    Zhu, Minrong; Li, Yanhu; Cao, Xiaosong; Jiang, Bei; Wu, Hongbin; Qin, Jingui; Cao, Yong; Yang, Chuluo

    2014-12-01

    A series of new star-shaped polymers with a triphenylamine-based iridium(III) dendritic complex as the orange-emitting core and poly(9,9-dihexylfluorene) (PFH) chains as the blue-emitting arms is developed towards white polymer light-emitting diodes (WPLEDs). By fine-tuning the content of the orange phosphor, partial energy transfer and charge trapping from the blue backbone to the orange core is realized to achieve white light emission. Single-layer WPLEDs with the configuration of ITO (indium-tin oxide)/poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS)/polymer/CsF/Al exhibit a maximum current efficiency of 1.69 cd A(-1) and CIE coordinates of (0.35, 0.33), which is very close to the pure white-light point of (0.33, 0.33). To the best of our knowledge, this is the first report on star-shaped white-emitting single polymers that simultaneously consist of fluorescent and phosphorescent species. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Origin of three-armed rifts in volcanic islands: the case of El Hierro (Canary Islands)

    Science.gov (United States)

    Galindo Jiménez, Inés; Becerril Carretero, Laura; Martí Molist, Joan; Gudmundsson, Agust

    2015-04-01

    Rifts zones in volcanic oceanic islands are common structures that have been explained through several theories/models. However, despite all these models it is as yet unclear whether it is the intense intrusive activity or the sector collapses that actually control the structural evolution and geometry of oceanic-island rift zones. Here we provide a new hypothesis to explain the origin and characteristics of the feeding system of oceanic-island rift zones based on the analysis of more than 1700 surface, subsurface (water galleries), and submarine structural data from El Hierro (Canary Islands). El Hierro's geological structure is primarily controlled by a three-armed rift-zone, the arms striking NE, WSW and S. Between the rift axes there are three valleys formed during huge landslides: El Golfo, El Julan, and Las Playas. Our results show: (1) a predominant NE-SW strike of structural elements, which coincides with the main regional trend of the Canary Archipelago as a whole; (2) a clear radial strike distribution of structural elements for the whole volcanic edifice (including submarine flanks) with respect to the centre of the island; (3) that the rift zones are mainly subaerial structures and do not propagate through the submarine edifice; (4) that it is only in the NE rift that structures have a general strike similar to that of the rift as a whole, and; (5) that in the W and S rifts there is not clear main direction, showing the structural elements in the W rift a fan distribution coinciding with the general radial pattern in the island as a whole. Based on these data, we suggest that the radial-striking structures reflect comparatively uniform stress fields that operated during the constructive episodes, mainly conditioned by the combination of overburden pressure, gravitational spreading, and magma-induced stresses. By contrast, in the shallower parts of the edifice, that is, the NE-SW, N-S and WNW-ESE-striking structures, reflect local stress fields related

  5. Pulsatile dry cupping in chronic low back pain - a randomized three-armed controlled clinical trial.

    Science.gov (United States)

    Teut, M; Ullmann, A; Ortiz, M; Rotter, G; Binting, S; Cree, M; Lotz, F; Roll, S; Brinkhaus, B

    2018-04-02

    We aimed to investigate the effectiveness of two different forms of dry pulsatile cupping in patients with chronic low back pain (cLBP) compared to medication on demand only in a three-armed randomized trial. 110 cLBP patients were randomized to regular pulsatile cupping with 8 treatments plus paracetamol on demand (n = 37), minimal cupping with 8 treatments plus paracetamol on demand (n = 36) or the control group with paracetamol on demand only (n = 37). Primary outcome was the pain intensity on a visual analogue scale (VAS, 0-100 mm) after 4 weeks, secondary outcome parameter included VAS pain intensity after 12 weeks, back function as measured with the 'Funktionsfragebogen Hannover Rücken' (FFbH-R) and health related quality of life questionnaire Short form 36 (SF-36) after 4 and 12 weeks. The mean baseline-adjusted VAS after 4 weeks was 34.9 mm (95% CI: 28.7; 41.2) for pulsatile cupping, 40.4 (34.2; 46.7) for minimal cupping and 56.1 (49.8; 62.4) for control group, resulting in statistically significant differences between pulsatile cupping vs. control (21.2 (12.2; 30.1); p back function after 4 weeks, but not after 12 weeks (- 5.4 (- 11.7;0.8); p = 0.088), pulsatile cupping also showed better improvements on SF-36 physical component scale compared to control at 4 and 12 weeks (- 5.6 (- 9.3;-2.0); p = 0.003; - 6.1 (- 9.9;-2.4); p = 0.002). For back function and quality of life minimal cupping group was not statistically different to control after 4 and 12 weeks. Paracetamol intake did not differ between the groups (cupping vs. control (7.3 (- 0.4;15.0); p = 0.063); minimal cupping vs. control (6.3 (- 2.0;14.5); p = 0.133). Both forms of cupping were effective in cLBP without showing significant differences in direct comparison after four weeks, only pulsatile cupping showed effects compared to control after 12 weeks. The study was registered at ClinicalTrials.gov (identifier: NCT02090686 ).

  6. A Versatile Approach to Unimolecular Water-Soluble Carriers: ATRP of PEGMA with Hydrophobic Star-Shaped Polymeric Core Molecules as an Alternative for PEGylation

    NARCIS (Netherlands)

    Schramm, O.G.; Pavlov, G.M.; Erp, van H.H.P; Meier, M.A.R.; Hoogenboom, R.; Schubert, U.S.

    2009-01-01

    New amphiphilic star-shaped architectures with dense hydrophilic shells were synthesized by a combination of ring-opening polymerization (ROP) of e-caprolactone (CL) and atom transfer radical polymerization (ATRP) of different poly(ethylene glycol) methacrylates (PEGMAs). The PCL hydrophobic cores

  7. Effects of electron-withdrawing group and electron-donating core combinations on physical properties and photovoltaic performance in D-pi-A star-shaped small molecules

    NARCIS (Netherlands)

    Luponosov, Yuriy N.; Min, Jie; Solodukhin, Alexander N.; Kozlov, Oleg V.; Obrezkova, Marina A.; Peregudova, Svetlana M.; Ameri, Tayebeh; Chvalun, Sergei N.; Pshenichnikov, Maxim S.; Brabec, Christoph J.; Ponomarenko, Sergei A.

    The first representatives of star-shaped molecules having 3-alkylrhodanine (alkyl-Rh) electron-withdrawing groups, linked through bithiophene pi-spacer with electron-donating either triphenylamine (TPA) or tris(2-methoxyphenyl)amine (m-TPA) core were synthesized. The physical properties and

  8. γ-Ray radiolysis and theoretical study on radical ions of star-shaped oligofluorenes having a truxene or isotruxene as a core

    International Nuclear Information System (INIS)

    Fujitsuka, Mamoru; Tojo, Sachiko; Yang, Jye-Shane; Majima, Tetsuro

    2013-01-01

    Highlights: ► Radiolysis provides absorption spectra of radical ions of star-shaped oligofluorenes. ► Absorption spectroscopic properties depend on oligomer size extensively. ► TDDFT provides reasonable assignments to the visible and near-IR absorption bands. ► Extensive charge delocalization was indicated by planarization of oligomers. - Abstract: Poly- and oligofluorenes have been intensively studied for years, because of their excellent properties as photo- and electro-functional materials. Especially, star-shaped oligofluorenes as two-dimensional oligomers are interesting materials for wide researchers. To understand their electronic properties in charged states, absorption spectra of radical cation and radical anion of star-shaped oligomers with varied size were investigated by means of γ-ray radiolysis. The absorption spectra of their radical ions ranged from the visible to near-IR regions were successfully obtained. By using the theoretical calculation, the observed peaks were assigned. It is indicated that the transition between HOMO and LUMO of the original neutral state plays a significant role in the visible region. Furthermore, it is indicated that the star-shaped oligofluorenes tend to take a planar structure upon oxidation and reduction

  9. Rubber toughened linear and star-shaped poly(d,l-lactide-co-glycolide) : synthesis, properties and in vitro degradation

    NARCIS (Netherlands)

    Joziasse, CAP; Veenstra, H; Topp, MDC; Grijpma, DW; Pennings, AJ

    Blends of D,L-lactide/glycolide copolymers were synthesized and their properties and in vitro degradation behaviour were evaluated as a function of chain architecture and blend composition. Tensile and impact properties of the blends are hardly influenced by matrix composition and chain

  10. [Endocarditis due to Aggregatibacter (formerly: Actinobacillus) actinomycetemcomitans, a bacterium that grows in characteristic star-shaped colonies].

    Science.gov (United States)

    Lampe, A S; Schroijen, M A; Smith, S J

    2008-04-05

    A 72-year-old man, having had an artificial valve for almost 20 years now, presented with tiredness that had persisted for several weeks and reported weight loss of 5 kg. In more recent days he experienced fever and cold shivers, and an associated dry cough. Bearing in mind the potential for endocarditis, blood cultures were grown. In this, we identified a small, Gram-negative rod with a small, smooth, raised colony that grew slowly. We considered a micro-organism from the 'HACEK group', which is a group of micro-organisms including Haemophilus aphrophilus, Haemophilus paraphrophilus, Cardiobacterium hominis, Eikenella corrodens, Kingella kingae and Aggregatibacter (formerly: Actinobacillus) actinomycetemcomitans. More careful observation revealed that the bacteria formed star-shaped colonies, proving that A. actinomycetemcomitans was the cause of this non-acute endocarditis. The patient received antibiotic treatment. Because non-acute endocarditis is often caused by hidden abnormalities in the mouth or teeth and A. actinomycetemcomitans plays an important role in severe cases of peridontitis, a dental surgeon was consulted. The dental surgeon diagnosed multifocal peridontitis and treated the patient, who was able to leave the hospital after 6 weeks of antibiotic treatment.

  11. Isolation of a star-shaped uranium(V/VI) cluster from the anaerobic photochemical reduction of uranyl(VI)

    International Nuclear Information System (INIS)

    Chatelain, Lucile; White, Sarah; Scopelliti, Rosario; Mazzanti, Marinella

    2016-01-01

    Actinide oxo clusters are an important class of compounds due to their impact on actinide migration in the environment. The photolytic reduction of uranyl(VI) has potential application in catalysis and spent nuclear fuel reprocessing, but the intermediate species involved in this reduction have not yet been elucidated. Here we show that the photolysis of partially hydrated uranyl(VI) in anaerobic conditions leads to the reduction of uranyl(VI), and to the incorporation of the resulting U V species into the stable mixed-valent star-shaped U VI /U V oxo cluster [U(UO 2 ) 5 (μ 3 -O) 5 (PhCOO) 5 (Py) 7 ]. This cluster is only the second example of a U VI /U V cluster and the first one associating uranyl groups to a non-uranyl(V) center. The U V center in 1 is stable, while the reaction of uranyl(V) iodide with potassium benzoate leads to immediate disproportionation and formation of the U 12 IV U 4 V O 24 cluster {[K(Py) 2 ] 2 [K(Py)] 2 [U 16 O 24 (PhCOO) 24 (Py) 2 ]}.

  12. Synthesis,thermal property and hydrolytic degradation of a novel star-shaped hexa[p-(carbonylglycinomethylester)phenoxy]cyclotriphosphazene

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    A novel star-shaped cyclotriphosphazene substituted by glycinomethylesterphenoxy and its intermediates are synthesized from hexachlorocyclotriphosphazene (HCCP). The structures are characterized by 1H NMR,13C NMR,31P NMR,FTIR and elemental analysis. Their thermal properties are clarified by thermogravimetric analysis (TGA),differential scanning calorimentry (DSC) and FTIR,while hydrolytic degradation behaviour is studied with UV-vis spectrophotometer and by measuring the weight loss,and the phosphorus content of residue. According to hydrolysis behaviour of hexa[p-(carbonylglycinomethylester)phenoxy]cyclotriphosphazene (HGPCP) under different conditions,it is easy to hydrolyze in hydrochloric acid (pH 1.0) than in phosphate buffer (pH 7.4) at 37℃. And the sample hydrolytic degradation still remains at the stage of side groups’ break. The TGA data show that the thermal stability of the hexa[p-(aldehyde)phenoxy]cyclotriphosphazene (HAPCP),hexa[p-(carboxyl) phenoxy]cyclotriphosphazene (HCPCP) and HGPCP is so high that their char residues are 75%,47% and 47% at 800℃,respectively,probably due to cross-linking between molecules.

  13. Isolation of a star-shaped uranium(V/VI) cluster from the anaerobic photochemical reduction of uranyl(VI)

    Energy Technology Data Exchange (ETDEWEB)

    Chatelain, Lucile; White, Sarah; Scopelliti, Rosario; Mazzanti, Marinella [Ecole Polytechnique Federale de Lausanne (EPFL) (Switzerland). Inst. de Sciences et Ingenierie Chimiques

    2016-11-07

    Actinide oxo clusters are an important class of compounds due to their impact on actinide migration in the environment. The photolytic reduction of uranyl(VI) has potential application in catalysis and spent nuclear fuel reprocessing, but the intermediate species involved in this reduction have not yet been elucidated. Here we show that the photolysis of partially hydrated uranyl(VI) in anaerobic conditions leads to the reduction of uranyl(VI), and to the incorporation of the resulting U{sup V} species into the stable mixed-valent star-shaped U{sup VI}/U{sup V} oxo cluster [U(UO{sub 2}){sub 5}(μ{sub 3}-O){sub 5}(PhCOO){sub 5}(Py){sub 7}]. This cluster is only the second example of a U{sup VI}/U{sup V} cluster and the first one associating uranyl groups to a non-uranyl(V) center. The U{sup V} center in 1 is stable, while the reaction of uranyl(V) iodide with potassium benzoate leads to immediate disproportionation and formation of the U{sub 12}{sup IV}U{sub 4}{sup V}O{sub 24} cluster {[K(Py)_2]_2[K(Py)]_2[U_1_6O_2_4(PhCOO)_2_4(Py)_2]}.

  14. One-pot synthesis of star-shaped macromolecules containing polyglycidol and poly(ethylene oxide) arms.

    Science.gov (United States)

    Lapienis, Grzegorz; Penczek, Stanislaw

    2005-01-01

    Synthesis of fully hydrophilic star-shaped macromolecules with different kinds of arms (A(x)B(y)C(z)) based on polyglycidol (PGL, A(x)) and poly(ethylene oxide) (PEO, C(z)) arms and diepoxy compounds (diglycidyl ethers of ethylene glycol (DGEG) or neopentyl glycol (DGNG) in the core, B(y)) forming the core is described. Precursors of arms were prepared by polymerization of glycidol with protected -OH groups. The first-generation stars were formed in the series of consecutive-parallel reactions of arms A(x) with diepoxy compounds (B). These first-generation stars (A(x)B(y)), having approximately O-, Mt+ groups on the cores, were used as multianionic initiators for the second generation of arms (C(z)) built by polymerization of ethylene oxide. The products with M(n) up to 10(5) and having up to approximately 40 arms were obtained. The number of arms (f) was determined by direct measurements of M(n) of the first-generation stars (M(n) of arms A(x) is known), compared with f calculated from the branching index g, determined from R(g) measured with size-exclusion chromatography (SEC) triple detection with TriSEC software. The progress of the star formation was monitored by 1H NMR and SEC. These novel water-soluble stars, having a large number of hydroxyl groups, both at the ends of PEO arms as well as within the PGL arms, can be functionalized and further used for attaching compounds of interest. This approach opens, therefore, a new way of "multiPEGylation".

  15. Comparison of the cellular transport mechanism of cationic, star-shaped polymers and liposomes in HaCat cells

    Directory of Open Access Journals (Sweden)

    Luo H

    2017-02-01

    Full Text Available Heng-Cong Luo,1,2,* Na Li,1,* Li Yan,1 Kai-jin Mai,3 Kan Sun,1 Wei Wang,1 Guo-Juan Lao,1 Chuan Yang,1 Li-Ming Zhang,3 Meng Ren1 1Department of Endocrinology, Sun Yat-Sen Memorial Hospital, Guangdong Provincial Key Laboratory of Malignant Tumor Epigenetics and Gene Regulation Medical Research Center, Sun Yat-Sen University, Guangzhou, People’s Republic of China; 2Department of Endocrinology, The Third Affiliated Hospital of Guangzhou Medical University, Guangzhou, People’s Republic of China; 3School of Materials Science and Engineering, School of Chemistry, Sun Yat-Sen University, Guangzhou, People’s Republic of China *These authors contributed equally to this work Abstract: Several biological barriers must be overcome to achieve efficient nonviral gene delivery. These barriers include target cell uptake, lysosomal degradation, and dissociation from the carrier. In this study, we compared the differences in the uptake mechanism of cationic, star-shaped polymer/MMP-9siRNA complexes (β-CD-(D37/MMP-9siRNA complexes: polyplexes and commercial liposome/MMP-9siRNA complexes (Lipofectamine® 2000/MMP-9siRNA complexes: liposomes. The uptake pathway and transfection efficiency of the polyplexes and liposomes were determined by fluorescence microscopy, flow cytometry, and reverse transcriptase-polymerase chain reaction. The occurrence of intracellular processing was assessed by confocal laser scanning microscopy. Endosomal acidification inhibitors were used to explore the endosomal escape mechanisms of the polyplexes and lysosomes. We concluded that the polyplexes were internalized by non-caveolae- and non-clathrin-mediated pathways, with no lysosomal trafficking, thereby inducing successful transfection, while the majority of liposomes were internalized by clathrin-dependent endocytosis (CDE, caveolae-mediated endocytosis, and macropinocytosis, and only CDE induced successful transfection. Liposomes might escape more quickly than polyplexes, and

  16. Endocytosis Pathways of the Folate Tethered Star-Shaped PEG-PCL Micelles in Cancer Cell Lines

    Directory of Open Access Journals (Sweden)

    Yu-Lun Li

    2014-03-01

    Full Text Available This study reports on the cellular uptake of folate tethered micelles using a branched skeleton of poly(ethylene glycol and poly(ε-caprolactone. The chemical structures of the copolymers were characterized by proton nuclear magnetic resonance spectroscopy, and Fourier transform infrared spectroscopy. Doxorubicin (DOX was utilized as an anticancer drug. The highest drug loading efficiencies of DOX in the folate decorated micelle (DMCF and folate-free micelle (DMC were found to be 88.5% and 88.2%, respectively, depending on the segment length of the poly(ε-caprolactone in the copolymers. A comparison of fluorescent microscopic images of the endocytosis pathway in two cell lines, human breast cancer cells (MCF-7 and human oral cavity carcinoma cells (KB, revealed that the micelles were engulfed by KB and MCF-7 cells following in vitro incubation for one hour. Flow cytometric analysis revealed that free folic acid can inhibit the uptake of DOX by 48%–57% and 26%–39% in KB cells and MCF-7 cells, respectively. These results prove that KB cells are relatively sensitive to folate-tethered micelles. Upon administering methyl-β-cyclodextrin, an inhibitor of the caveolae-mediated endocytosis pathway, the uptake of DOX by KB cells was reduced by 69% and that by MCF-7 cells was reduced by 56%. This finding suggests that DMCF enters cells via multiple pathways, thus implying that the folate receptor is not the only target of tumor therapeutics.

  17. Olefin–Styrene Copolymers

    OpenAIRE

    Nunzia Galdi; Antonio Buonerba; Leone Oliva

    2016-01-01

    In this review are reported some of the most relevant achievements in the chemistry of the ethylene–styrene copolymerization and in the characterization of the copolymer materials. Focus is put on the relationship between the structure of the catalyst and that of the obtained copolymer. On the other hand, the wide variety of copolymer architecture is related to the properties of the material and to the potential utility.

  18. Entropic effects, shape, and size of mixed micelles formed by copolymers with complex architectures

    Science.gov (United States)

    Kalogirou, Andreas; Gergidis, Leonidas N.; Moultos, Othonas; Vlahos, Costas

    2015-11-01

    The entropic effects in the comicellization behavior of amphiphilic A B copolymers differing in the chain size of solvophilic A parts were studied by means of molecular dynamics simulations. In particular, mixtures of miktoarm star copolymers differing in the molecular weight of solvophilic arms were investigated. We found that the critical micelle concentration values show a positive deviation from the analytical predictions of the molecular theory of comicellization for chemically identical copolymers. This can be attributed to the effective interactions between copolymers originated from the arm size asymmetry. The effective interactions induce a very small decrease in the aggregation number of preferential micelles triggering the nonrandom mixing between the solvophilic moieties in the corona. Additionally, in order to specify how the chain architecture affects the size distribution and the shape of mixed micelles we studied star-shaped, H-shaped, and homo-linked-rings-linear mixtures. In the first case the individual constituents form micelles with preferential and wide aggregation numbers and in the latter case the individual constituents form wormlike and spherical micelles.

  19. Silicon containing copolymers

    CERN Document Server

    Amiri, Sahar; Amiri, Sanam

    2014-01-01

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

  20. Electroacupuncture to alleviate postoperative pain after a laparoscopic appendectomy: study protocol for a three-arm, randomised, controlled trial.

    Science.gov (United States)

    Lee, Seunghoon; Nam, Dongwoo; Kwon, Minsoo; Park, Won Seo; Park, Sun Jin

    2017-08-04

    The purpose of this study is to evaluate the efficacy and safety of electroacupuncture (EA) for postoperative pain after laparoscopic appendectomy compared with sham electroacupuncture (SEA) and no acupuncture treatment. This study is a protocol for a three-arm, randomised, patient-assessor-blinded (to the type of acupuncture treatment), controlled, parallel trial. 138 participants diagnosed with appendicitis and scheduled for laparoscopic appendectomy will be randomly assigned to the EA group (n=46), SEA group (n=46) or control group (n=46). The EA group will receive acupuncture treatment at both regional and distal acupuncture points with electrostimulation. The SEA group will receive sham acupuncture treatment with mock electrostimulation. Both EA and SEA groups will receive a total of four treatments 1 hour preoperative, 1 hour postoperative and during the morning and afternoon the day after surgery with the same routine postoperative pain control. The control group will receive only routine postoperative pain control. The primary outcome is the 11-point Pain Intensity Numerical Rating Scale (PI-NRS) at 24 hours after surgery. The secondary outcomes are the PI-NRS, analgesic consumption, opioid-related side effects, time to first passing flatus, quality of life and adverse events evaluated 6, 12, 24 and 36 hours and 7 days after surgery. The study was planned in accordance with the Helsinki Declaration and the Korean Good Clinical Practice Guidelines to protect the participants and was approved by the institutional review board (IRB) of Kyung Hee University Medical Center (KMC IRB-1427-02). The results will be disseminated in peer-reviewed journals and presented at international conferences. Clinical Research Information Service (KCT0001328). © Article author(s) (or their employer(s) unless otherwise stated in the text of the article) 2017. All rights reserved. No commercial use is permitted unless otherwise expressly granted.

  1. Evaluation of novel biodegradable three-armed- and hyper-branched tissue adhesives in a meniscus explant model.

    Science.gov (United States)

    Bochyńska, A I; Hannink, G; Verhoeven, R; Grijpma, D W; Buma, P

    2017-05-01

    Current treatment methods to repair meniscal tears do not bring fully satisfactory results. Tissue adhesives are considered promising alternatives, since they are easy to apply and cause minimal tissue trauma. The first aim of this study was to analyze the adhesive properties of and tissue response to two recently developed biodegradable block copolymeric three-armed- and hyper-branched tissue adhesives. The second aim was to investigate if tissue surface modification with collagenase improves the attachment of the adhesives and increases the healing potential of the tissue. Cylindrical explants were harvested from bovine menisci. The central core of the explants was removed and glued back into the defect, with or without incubation in collagenase solution prior to gluing, using one of the novel glues, Dermabond® or fibrin glue. The repair constructs were cultured in vitro for 1 and 28 days. Adhesion tests and histology were performed to analyze the effects of the glue in combination with the additional treatment. The adhesive strength of the novel glues was 40-50 kPa, which was significantly higher than that of fibrin glue (15 kPa). Cells were present in direct contact with the glues, and the tissue remained vital during the whole culture period. Increased cellularity around the tear in the collagenase treated explants was observed after 1 day. The two newly developed tissue adhesives are attractive materials to be used for repair of meniscal tears. The beneficial influence of collagenase treatment in treating meniscal tears with glues still needs to be confirmed in more clinical relevant studies. © 2017 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 105A: 1405-1411, 2017. © 2017 Wiley Periodicals, Inc.

  2. In Vitro and In Vivo Characterization of Biodegradable Reactive Isocyanate-Terminated Three-Armed- and Hyperbranched Block Copolymeric Tissue Adhesives

    NARCIS (Netherlands)

    Bochynska, Agnieszka I.; Hannink, Gerjon; Rongen, Jan J.; Grijpma, Dirk W.; Buma, Pieter

    2017-01-01

    Tissue adhesives are an attractive class of biomaterials, which can serve as a treatment for meniscus tears. In this study, physicochemical and adhesive properties of novel biodegradable three-armed- and hyperbranched block copolymeric adhesives are evaluated. Additionally, their degradation in

  3. Data feedback and behavioural change intervention to improve primary care prescribing safety (EFIPPS): multicentre, three arm, cluster randomised controlled trial.

    Science.gov (United States)

    Guthrie, Bruce; Kavanagh, Kimberley; Robertson, Chris; Barnett, Karen; Treweek, Shaun; Petrie, Dennis; Ritchie, Lewis; Bennie, Marion

    2016-08-18

     To evaluate the effectiveness of feedback on safety of prescribing compared with moderately enhanced usual care.  Three arm, highly pragmatic cluster randomised trial.  262/278 (94%) primary care practices in three Scottish health boards.  Practices were randomised to: "usual care," consisting of emailed educational material with support for searching to identify patients (88 practices at baseline, 86 analysed); usual care plus feedback on practice's high risk prescribing sent quarterly on five occasions (87 practices, 86 analysed); or usual care plus the same feedback incorporating a behavioural change component (87 practices, 86 analysed).  The primary outcome was a patient level composite of six prescribing measures relating to high risk use of antipsychotics, non-steroidal anti-inflammatories, and antiplatelets. Secondary outcomes were the six individual measures. The primary analysis compared high risk prescribing in the two feedback arms against usual care at 15 months. Secondary analyses examined immediate change and change in trend of high risk prescribing associated with implementation of the intervention within each arm.  In the primary analysis, high risk prescribing as measured by the primary outcome fell from 6.0% (3332/55 896) to 5.1% (2845/55 872) in the usual care arm, compared with 5.9% (3341/56 194) to 4.6% (2587/56 478) in the feedback only arm (odds ratio 0.88 (95% confidence interval 0.80 to 0.96) compared with usual care; P=0.007) and 6.2% (3634/58 569) to 4.6% (2686/58 582) in the feedback plus behavioural change component arm (0.86 (0.78 to 0.95); P=0.002). In the pre-specified secondary analysis of change in trend within each arm, the usual care educational intervention had no effect on the existing declining trend in high risk prescribing. Both types of feedback were associated with significantly more rapid decline in high risk prescribing after the intervention compared with before.  Feedback of prescribing safety data

  4. Electroacupuncture to treat painful diabetic neuropathy: study protocol for a three-armed, randomized, controlled pilot trial.

    Science.gov (United States)

    Lee, Seunghoon; Kim, Joo-Hee; Shin, Kyung-Min; Kim, Jung-Eun; Kim, Tae-Hun; Kang, Kyung-Won; Lee, Minhee; Jung, So-Young; Shin, Mi-Suk; Kim, Ae-Ran; Park, Hyo-Ju; Hong, Kwon-Eui; Choi, Sun-Mi

    2013-07-18

    The purpose of this study is to conduct a basic analysis of the effectiveness and safety of electroacupuncture in the treatment of painful diabetic neuropathy (PDN) as compared to placebo and usual care and to evaluate the feasibility of large-scale clinical research. This study is a protocol for a three-armed, randomized, patient-assessor-blinded (to the type of treatment), controlled pilot trial. Forty-five participants with a ≥ six month history of PDN and a mean weekly pain score of ≥ 4 on the 11-point Pain Intensity Numerical Rating Scale (PI-NRS) will be assigned to the electroacupuncture group (n = 15), sham group (n = 15) or usual care group (n = 15). The participants assigned to the electroacupuncture group will receive electroacupuncture (remaining for 30 minutes with a mixed current of 2 Hz/120 Hz and 80% of the bearable intensity) at 12 standard acupuncture points (bilateral ST36, GB39, SP9, SP6, LR3 and GB41) twice per week for eight weeks (a total of 16 sessions) as well as the usual care. The participants in the sham group will receive sham electroacupuncture (no electrical current will be passed to the needle, but the light will be seen, and the sound of the pulse generator will be heard by the participants) at non-acupuncture points as well as the usual care. The participants in the usual care group will not receive electroacupuncture treatment during the study period and will receive only the usual care. The follow-up will be in the 5th, 9th and 17th weeks after random allocation. The PI-NRS score assessed at the ninth week will be the primary outcome measurement used in this study. The Short-Form McGill Pain Questionnaire (SF-MPQ), a sleep disturbance score (11-point Likert scale), the Short-Form 36v2 Health Survey (SF-36), the Beck Depression Inventory (BDI) and the Patient Global Impression of Change (PGIC) will be used as outcome variables to evaluate the effectiveness of the acupuncture. Safety will be assessed at every visit. The result

  5. Enhanced optical transmission through a star-shaped bull's eye at dual resonant-bands in UV and the visible spectral range.

    Science.gov (United States)

    Nazari, Tavakol; Khazaeinezhad, Reza; Jung, Woohyun; Joo, Boram; Kong, Byung-Joo; Oh, Kyunghwan

    2015-07-13

    Dual resonant bands in UV and the visible range were simultaneously observed in the enhanced optical transmission (EOT) through star-shaped plasmonic structures. EOTs through four types of polygonal bull's eyes with a star aperture surrounded by the concentric star grooves were analyzed and compared for 3, 4, 5, and 6 corners, using finite difference time domain (FDTD) method. In contrast to plasmonic resonances in the visible range, the UV-band resonance intensity was found to scale with the number of corners, which is related with higher order multipole interactions. Spectral positions and relative intensities of the dual resonances were analyzed parametrically to find optimal conditions to maximize EOT in UV-visible dual bands.

  6. Comparison of Coatings from Reactive Star Shaped PEG-stat-PPG Prepolymers and Grafted Linear PEG for Biological and Medical Applications

    DEFF Research Database (Denmark)

    Groll, J.; Ademovic, Z.; Klee, D.

    2005-01-01

    ). In an alternative approach, surfaces were modified with layers prepared from isocyanate terminated, star shaped poly(ethylene glycol-stat-propylene glycol) prepolymers (80% ethylene glycol, six arms, M. = 3000, 12 000, and 18 000; this compound will be referred to as "Star PEG" in the text). Due to the highly......Grafting of poly(ethylene glycol) (PEG) is a common strategy for reducing nonspecific interactions of surfaces with proteins. We have used grafting at "cloud point" solution conditions that ensures maximum grafting density of linear methoxy terminated PEG-aldehyde (mPEG-ald, M-W = 5000 and 30000....... Protein adsorption was monitored by surface MALDI-TOF MS and fluorescence microscopy. No protein adsorption could be detected on Star PEG coatings and on mPEG-ald 5000, whereas mPEG-ald 30 000 could only prevent adsorption of lysozyme but not of the smaller insulin....

  7. Theoretical Investigations of the Photophysical Properties of Star-Shaped π-Conjugated Molecules with Triarylboron Unit for Organic Light-Emitting Diodes Applications

    Directory of Open Access Journals (Sweden)

    Ruifa Jin

    2017-10-01

    Full Text Available The density functional theory (DFT and time-dependent DFT (TD-DFT methodologies have been applied to explore on a series of star-shaped π-conjugated organoboron systems for organic light-emitting diode (OLED materials. The compounds under investigation consist of benzene as π-bridge and different core units and triarylboron end groups. Their geometry structures, frontier molecular orbital (FMO energies, absorption and fluorescence spectra, and charge transport properties have been investigated systematically. It turned out that the FMO energy levels, the band gaps, and reorganization energies optical are affected by the introduction of different core units and triarylboron end groups. The results suggest that the designed compounds are expected to be promising candidates for luminescent materials. Furthermore, they can also serve as hole and/or electron transport materials for OLEDs.

  8. Treating Depression and Adherence (CBT-AD) in Patients with HIV in Care: A Three-arm Randomized Controlled Trial

    Science.gov (United States)

    Safren, Steven A.; Bedoya, C. Andres; O’Cleirigh, Conall; Biello, Katie B.; Pinkston, Megan M.; Stein, Michael D.; Traeger, Lara; Kojic, Erna; Robbins, Gregory K.; Lerner, Jonathan A.; Herman, Debra S.; Mimiaga, Matthew J.; Mayer, Kenneth H.

    2016-01-01

    Summary Background Depression, highly prevalent in HIV, is consistently associated with worse ART adherence. Integrating CBT for depression with adherence counseling using the “Life-Steps” approach (CBT-AD) has an emerging evidence base. The aim of the current study was to test the efficacy of CBT-AD. Methods We conducted a three-arm RCT (N=240 HIV-positive adults with depression), comparing CBT-AD to Life-Steps integrated with information and supportive psychotherapy (ISP-AD) (both 12 sessions), and to ETAU (1 session Life-Steps). Participants were recruited from three sites in New England area, two being hospital settings, and one being a community health center. Randomization was done via a 2:2:1 ratio, using random allocation software by the data manager, in pairs, stratified by three variables: site, whether or not the participant was prescribed antidepressant medications, and history of injection drug use. The primary outcome was adherence assessed via electronic pill caps (MEMs) with correction for “pocketed” doses. Secondary outcomes included depression, plasma HIV RNA and CD4. Follow-ups occurred at 4, 8 and 12 months. We used intent-to treat analyses with ANCOVA for independent-assessor pre-post assessments of depression and mixed effects modeling for longitudinal assessments. Clinical Trial Registration: NCT00951028, https://clinicaltrials.gov/ct2/show/NCT00951028), closed to new participants. Findings The period of recruitment was February 26, 2009 to June 21, 2012, with the 12-month follow-up period extending until April 29, 2013. There were no study-related adverse events. CBT-AD (n=94 randomized, 83 retained) had greater improvements in adherence (Est.=1·00, CI=0·34, 1·66, p=0·003) and depression (CES-D Est.=−0·41, CI=−0·66, −0·16, p=0·001; MADRS Est.=−4·69, CI=−8·09, −1·28, p=0·007; CGI Est.=−0·66, CI=−1·11,-0·21, p=0·005) than ETAU (49 randomized, 46 retained) at post-treatment (4-month). Over follow-ups, CBT

  9. Synthesis of Well-Defined Three-Arm Star-Branched Polystyrene through Arm-First Coupling Approach by Atom Transfer Radical Polymerization

    OpenAIRE

    Shahabuddin, Syed; Hamime Ismail, Fatem; Mohamad, Sharifah; Muhamad Sarih, Norazilawati

    2015-01-01

    Here we describe a simple route to synthesize three-arm star-branched polystyrene. Atom transfer radical polymerization technique has been utilized to yield branched polystyrene involving Williamson coupling strategy. Initially a linear polymeric chain of predetermined molecular weight has been synthesized which is further end-functionalized into a primary alkyl bromide moiety, a prime requisition for Williamson reaction. The end-functionalized polymer is then coupled using 1,1,1-tris(4-hydro...

  10. Synthesis of Well-Defined Three-Arm Star-Branched Polystyrene through Arm-First Coupling Approach by Atom Transfer Radical Polymerization

    Directory of Open Access Journals (Sweden)

    Syed Shahabuddin

    2015-01-01

    Full Text Available Here we describe a simple route to synthesize three-arm star-branched polystyrene. Atom transfer radical polymerization technique has been utilized to yield branched polystyrene involving Williamson coupling strategy. Initially a linear polymeric chain of predetermined molecular weight has been synthesized which is further end-functionalized into a primary alkyl bromide moiety, a prime requisition for Williamson reaction. The end-functionalized polymer is then coupled using 1,1,1-tris(4-hydroxyphenylethane, a trifunctional core molecule, to give well-defined triple-arm star-branched polystyrene.

  11. Spontaneous improvement in randomised clinical trials: meta-analysis of three-armed trials comparing no treatment, placebo and active intervention

    DEFF Research Database (Denmark)

    Krogsbøll, Lasse Theis; Hróbjartsson, Asbjørn; Gøtzsche, Peter C

    2009-01-01

    were psychological in 17 trials, physical in 15 trials, and pharmacological in 5 trials. Overall, across all conditions and interventions, there was a statistically significant change from baseline in all three arms. The standardized mean difference (SMD) for change from baseline was -0.24 (95...... uncertainty, as indicated by the confidence intervals for the three SMDs. The conditions that had the most pronounced spontaneous improvement were nausea (45%), smoking (40%), depression (35%), phobia (34%) and acute pain (25%). CONCLUSION: Spontaneous improvement and effect of placebo contributed importantly...

  12. Block coordination copolymers

    Science.gov (United States)

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

    2012-11-13

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

  13. Utilization of star-shaped polymer architecture in the creation of high-density polymer brush coatings for the prevention of platelet and bacteria adhesion

    Science.gov (United States)

    Totani, Masayasu; Terada, Kayo; Terashima, Takaya; Kim, Ill Yong; Ohtsuki, Chikara; Xi, Chuanwu; Tanihara, Masao

    2014-01-01

    We demonstrate utilization of star-shaped polymers as high-density polymer brush coatings and their effectiveness to inhibit the adhesion of platelets and bacteria. Star polymers consisting of poly(2-hydroxyethyl methacrylate) (PHEMA) and/or poly(methyl methacrylate) (PMMA), were synthesized using living radical polymerization with a ruthenium catalyst. The polymer coatings were prepared by simple drop casting of the polymer solution onto poly(ethylene terephthalate) (PET) surfaces and then dried. Among the star polymers prepared in this study, the PHEMA star polymer (star-PHEMA) and the PHEMA/PMMA (mol. ratio of 71/29) heteroarm star polymer (star-H71M29) coatings showed the highest percentage of inhibition against platelet adhesion (78–88% relative to noncoated PET surface) and Escherichia coli (94–97%). These coatings also showed anti-adhesion activity against platelets after incubation in Dulbecco's phosphate buffered saline or surfactant solution for 7 days. In addition, the PMMA component of the star polymers increased the scratch resistance of the coating. These results indicate that the star-polymer architecture provides high polymer chain density on PET surfaces to prevent adhesion of platelets and bacteria, as well as coating stability and physical durability to prevent exposure of bare PET surfaces. The star polymers provide a simple and effective approach to preparing anti-adhesion polymer coatings on biomedical materials against the adhesion of platelets and bacteria. PMID:25485105

  14. Rosettes, Engrailed Edges, and Star-Shaped Patterns: Between Rediscovery and Forgetfulness in the Early Accounts of Vibrating Liquid Drops Floating over Hot Surfaces.

    Science.gov (United States)

    Stewart, Seán M

    2017-12-01

    Small drops of liquid brought into contact with very hot surfaces float above it as beautiful, slightly flattened spheroids without coming to the boil. An example of film boiling, drops that are sessile can often suddenly and quite unexpectedly start to oscillate forming highly symmetric patterns of surprising pulchritude. The rim of these oscillating drops take on "star-shaped" patterns with many different modes of vibration possible. Still an object of study today, their discovery, early accounts, rediscovery and ensuing controversies over claims of priority, before quietly slipping away from the collective memory of the scientific community to become all but forgotten makes for a compelling story in the early history of film boiling. The episode serves not only as a valuable reminder of the importance the history of science can play in highlighting past achievements that would otherwise remain unknown to the modern practitioner. It also provides an example of how external pressures and personal ambition can often influence the work of a scientist in their pursuit of self-recognition and acclaim amongst their peers. Copyright © 2017 Elsevier Ltd. All rights reserved.

  15. Anti-lymphoma efficacy comparison of anti-Cd20 monoclonal antibody-targeted and non-targeted star-shaped polymer-prodrug conjugates

    Czech Academy of Sciences Publication Activity Database

    Lidický, Ondřej; Janoušková, Olga; Strohalm, Jiří; Alam, M.; Klener, P.; Etrych, Tomáš

    2015-01-01

    Roč. 20, č. 11 (2015), s. 19849-19864 ISSN 1420-3049 R&D Projects: GA MŠk(CZ) ED1.1.00/02.0109; GA ČR(CZ) GA15-02986S; GA MŠk(CZ) LO1507 Institutional support: RVO:61389013 Keywords : HPMA copolymers * drug delivery systems * doxorubicin Subject RIV: CD - Macromolecular Chemistry Impact factor: 2.465, year: 2015

  16. Block copolymer battery separator

    Science.gov (United States)

    Wong, David; Balsara, Nitash Pervez

    2016-04-26

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

  17. Bioinspired Star-Shaped Poly(l-lysine) Polypeptides: Efficient Polymeric Nanocarriers for the Delivery of DNA to Mesenchymal Stem Cells.

    Science.gov (United States)

    Walsh, David P; Murphy, Robert D; Panarella, Angela; Raftery, Rosanne M; Cavanagh, Brenton; Simpson, Jeremy C; O'Brien, Fergal J; Heise, Andreas; Cryan, Sally-Ann

    2018-05-07

    The field of tissue engineering is increasingly recognizing that gene therapy can be employed for modulating in vivo cellular response thereby guiding tissue regeneration. However, the field lacks a versatile and biocompatible gene delivery platform capable of efficiently delivering transgenes to mesenchymal stem cells (MSCs), a cell type often refractory to transfection. Herein, we describe the extensive and systematic exploration of three architectural variations of star-shaped poly(l-lysine) polypeptide (star-PLL) with varying number and length of poly(l-lysine) arms as potential nonviral gene delivery vectors for MSCs. We demonstrate that star-PLL vectors are capable of self-assembling with pDNA to form stable, cationic nanomedicines. Utilizing high content screening, live cell imaging, and mechanistic uptake studies we confirm the intracellular delivery of pDNA by star-PLLs to MSCs is a rapid process, which likely proceeds via a clathrin-independent mechanism. We identify a star-PLL composition with 64 poly(l-lysine) arms and five l-lysine subunits per arm as a particularly efficient vector that is capable of delivering both reporter genes and the therapeutic transgenes bone morphogenetic protein-2 and vascular endothelial growth factor to MSCs. This composition facilitated a 1000-fold increase in transgene expression in MSCs compared to its linear analogue, linear poly(l-lysine). Furthermore, it demonstrated comparable transgene expression to the widely used vector polyethylenimine using a lower pDNA dose with significantly less cytotoxicity. Overall, this study illustrates the ability of the star-PLL vectors to facilitate efficient, nontoxic nucleic acid delivery to MSCs thereby functioning as an innovative nanomedicine platform for tissue engineering applications.

  18. Synthesis and Characterization of Biodegradable Amphiphilic Star and Y-Shaped Block Copolymers as Potential Carriers for Vinorelbine

    Directory of Open Access Journals (Sweden)

    Fatemeh Bahadori

    2014-01-01

    Full Text Available Two amphiphilic block copolymers using hydrophobic poly(ε-caprolactone (PCL and hydrophilic poly(ethylene glycol (PEG were successfully synthesized. One of them is an (A-b-B4 type star polymer [(PCL-b-PEG4] and the other one is a Y-shaped PEG–(PCL2. A star-shaped polymer (PCL-b-PEG4 was prepared by ring-opening polymerization (ROP of ε-caprolactone continued by click reaction of (PCL-azide4 and PEG-alkyne. The synthesis of Y-shaped PEG–(PCL2 block copolymer was carried out via Diels-Alder click reaction of a furan protected maleimide end-functionalized PEG (PEG-MI with an anthracene end-functionalized PCL following the ROP of ε-caprolactone. The characterization of micelles is carried out using both materials in aqueous media as drug delivery vehicles, which showed satisfying results and enhanced the cytotoxic effect of the anti-cancer drug vinorelbine (VLB. However, micelles consisted of Y-shaped unimers were found to be more convenient for delivery of hydrophobic drugs such as VLB because they formed in lower concentration, carrying a higher amount of drugs and owing a monomodal distribution. We concluded that the free tails of hydrophobic chains in Y-shaped block copolymer facilitate the assembly of amphiphilic material in water to form micelles.

  19. Polyether/Polyester Graft Copolymers

    Science.gov (United States)

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

    1986-01-01

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

  20. To reveal the nature of interactions of human hemoglobin with gold nanoparticles having two different morphologies (sphere and star-shaped) by using various spectroscopic techniques.

    Science.gov (United States)

    Chakraborty, Madhurima; Paul, Somnath; Mitra, Ishani; Bardhan, Munmun; Bose, Mridul; Saha, Abhijit; Ganguly, Tapan

    2018-01-01

    The nature of interactions between heme protein human hemoglobin (HHb) and gold nanoparticles of two different morphologies that is GNP (spherical) and GNS (star-shaped) have been investigated by using UV-vis absorption, steady state fluorescence, synchronous fluorescence, resonance light scattering (RLS), time resolved fluorescence, FT-IR, and circular dichroism (CD) techniques under physiological condition of pH ~7 at ambient and different temperatures. Analysis of the steady state fluorescence quenching of HHb in aqueous solution in the presence of GNP and GNS suggests that the nature of the quenching is of static type. The static nature of the quenching is also confirmed from time resolved data. The static type of quenching also indicates the possibility of formation of ground state complex for both HHb-GNP and HHb-GNS systems. From the measurements of Stern-Volmer (SV) constants K SV and binding constants, K A and number of binding sites it appears that HHb forms stronger binding with GNP relative to GNS. Analysis of the thermodynamic parameters indicates that the formation of HHb-GNP and HHb-GNS complexes are spontaneous molecular interaction processes (∆G<0). In both cases hydrogen bonding and van der Waals interactions play a dominant role (∆H<0, ∆S<0). Synchronous fluorescence spectroscopy further reveals that the ground state complex formations of HHb-GNP and HHb-GNS preferably occur by binding with the amino acid tyrosine through hydrogen bonding interactions. Moreover the α-helicity contents of the proteins as obtained from the circular dichroism (CD) spectra appears to be marginally reduced by increasing concentrations of GNP and GNS and the α-helical structures of HHb retain its identity as native secondary structure in spite of complex formations with GNP or GNS. These findings demonstrate the efficiency of biomedical applications of GNP and GNS nanoparticles as well as in elucidating their mechanisms of action as drugs or drug delivery

  1. Cationic star-shaped polymer as an siRNA carrier for reducing MMP-9 expression in skin fibroblast cells and promoting wound healing in diabetic rats

    Directory of Open Access Journals (Sweden)

    Li N

    2014-07-01

    Full Text Available Na Li,1,* Heng-Cong Luo,1,* Chuan Yang,1 Jun-Jie Deng,2 Meng Ren,1 Xiao-Ying Xie,1 Diao-Zhu Lin,1 Li Yan,1 Li-Ming Zhang2 1Department of Endocrinology, Sun Yat-sen Memorial Hospital, Sun Yat-sen University, Guangzhou, People’s Republic of China; 2DSAPM Lab and PCFM Lab, Institute of Polymer Science, Department of Polymer and Materials Science, School of Chemistry and Chemical Engineering, Sun Yat-sen University, Guangzhou, People’s Republic of China *These authors contributed equally to this work Background: Excessive expression of matrix metalloproteinase-9 (MMP-9 is deleterious to the cutaneous wound-healing process in the context of diabetes. The aim of the present study was to explore whether a cationic star-shaped polymer consisting of ß-cyclodextrin (ß-CD core and poly(amidoamine dendron arms (ß-CD-[D3]7 could be used as the gene carrier of small interfering RNA (siRNA to reduce MMP-9 expression for enhanced diabetic wound healing. Methods: The cytotoxicity of ß-CD-(D37 was investigated by 3-(4,5-Dimethylthiazol-2-yl-2,5-diphenyltetrazolium bromide assay (MMT method in the rat CRL1213 skin fibroblast cell line. The transfection efficiency of ß-CD-(D37/MMP-9-small interfering RNA (siRNA complexes was determined by confocal microscopy and flow cytometry. Quantitative real time (RT polymerase chain reaction was performed to measure the gene expression of MMP-9 after the transfection by ß-CD-(D37/MMP-9-siRNA complexes. The ß-CD-(D37/MMP-9-siRNA complexes were injected on the wounds of streptozocin-induced diabetic rats. Wound closure was measured on days 4 and 7 post-wounding. Results: ß-CD-(D37 exhibited low cytotoxicity in fibroblast cells, and easily formed the complexes with MMP-9-siRNA. The ß-CD-(D37/MMP-9-siRNA complexes were readily taken up by fibroblast cells, resulting in the downregulation of MMP-9 gene expression (P<0.01. Animal experiments revealed that the treatment by ß-CD-(D37/MMP-9-siRNA complexes enhanced wound

  2. Polyethylene-Based Tadpole Copolymers

    KAUST Repository

    Alkayal, Nazeeha; Zhang, Zhen; Bilalis, Panayiotis; Gnanou, Yves; Hadjichristidis, Nikolaos

    2017-01-01

    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

  3. Comparison of two theory-based, fully automated telephone interventions designed to maintain dietary change in healthy adults: study protocol of a three-arm randomized controlled trial.

    Science.gov (United States)

    Wright, Julie A; Quintiliani, Lisa M; Turner-McGrievy, Gabrielle M; Migneault, Jeffrey P; Heeren, Timothy; Friedman, Robert H

    2014-11-10

    Health behavior change interventions have focused on obtaining short-term intervention effects; few studies have evaluated mid-term and long-term outcomes, and even fewer have evaluated interventions that are designed to maintain and enhance initial intervention effects. Moreover, behavior theory has not been developed for maintenance or applied to maintenance intervention design to the degree that it has for behavior change initiation. The objective of this paper is to describe a study that compared two theory-based interventions (social cognitive theory [SCT] vs goal systems theory [GST]) designed to maintain previously achieved improvements in fruit and vegetable (F&V) consumption. The interventions used tailored, interactive conversations delivered by a fully automated telephony system (Telephone-Linked Care [TLC]) over a 6-month period. TLC maintenance intervention based on SCT used a skills-based approach to build self-efficacy. It assessed confidence in and barriers to eating F&V, provided feedback on how to overcome barriers, plan ahead, and set goals. The TLC maintenance intervention based on GST used a cognitive-based approach. Conversations trained participants in goal management to help them integrate their newly acquired dietary behavior into their hierarchical system of goals. Content included goal facilitation, conflict, shielding, and redundancy, and reflection on personal goals and priorities. To evaluate and compare the two approaches, a sample of adults whose F&V consumption was below public health goal levels were recruited from a large urban area to participate in a fully automated telephony intervention (TLC-EAT) for 3-6 months. Participants who increase their daily intake of F&V by ≥1 serving/day will be eligible for the three-arm randomized controlled trial. A sample of 405 participants will be randomized to one of three arms: (1) an assessment-only control, (2) TLC-SCT, and (3) TLC-GST. The maintenance interventions are 6 months. All 405

  4. A phase III randomized three-arm trial of physical therapist delivered pain coping skills training for patients with total knee arthroplasty: the KASTPain protocol

    Directory of Open Access Journals (Sweden)

    Riddle Daniel L

    2012-08-01

    Full Text Available Abstract Background Approximately 20% of patients report persistent and disabling pain following total knee arthroplasty (TKA despite an apparently normally functioning prosthesis. One potential risk factor for unexplained persistent pain is high levels of pain catastrophizing. We designed a three-arm trial to determine if a pain coping skills training program, delivered prior to TKA, effectively reduces function-limiting pain following the procedure in patients with high levels of pain catastrophizing. Methods/design The trial will be conducted at four University-based sites in the US. A sample of 402 patients with high levels of pain catastrophizing will be randomly assigned to either a pain coping skills training arm, an arthritis education control arm or usual care. Pain coping skills will be delivered by physical therapists trained and supervised by clinical psychologist experts. Arthritis education will be delivered by nurses trained in the delivery of arthritis-related content. The primary outcome will be change in Western Ontario and McMaster Universities Osteoarthritis Index (WOMAC Pain scale score 12 months following surgery. A variety of secondary clinical and economic outcomes also will be evaluated. Discussion The trial will be conducted at four University-based sites in the US. A sample of 402 patients with high levels of pain catastrophizing will be randomly assigned to either a pain coping skills training arm, an arthritis education control arm or usual care. Pain coping skills will be delivered by physical therapists trained and supervised by clinical psychologist experts. Arthritis education will be delivered by nurses trained in the delivery of arthritis-related content. The primary outcome will be change in Western Ontario and McMaster Universities Osteoarthritis Index (WOMAC Pain scale score 12 months following surgery. A variety of secondary clinical and economic outcomes also will be evaluated. Trial Registration NCT

  5. Electronic medication complete communication strategy for opioid prescriptions in the emergency department: Rationale and design for a three-arm provider randomized trial.

    Science.gov (United States)

    McCarthy, Danielle M; Courtney, D Mark; Lank, Patrick M; Cameron, Kenzie A; Russell, Andrea M; Curtis, Laura M; Kim, Kwang-Youn A; Walton, Surrey M; Montague, Enid; Lyden, Abbie L; Gravenor, Stephanie J; Wolf, Michael S

    2017-08-01

    Thousands of people die annually from prescription opioid overdoses; however there are few strategies to ensure patients receive medication risk information at the time of prescribing. To compare the effectiveness of the Emergency Department (ED) Electronic Medication Complete Communication (EMC 2 ) Opioid Strategy (with and without text messaging) to promote safe medication use and improved patient knowledge as compared to usual care. The ED EMC 2 Opioid Strategy consists of 5 automated components to promote safe medication use: 1) physician reminder to counsel, 2) inbox message sent on to the patient's primary care physician, 3) pharmacist message on the prescription to counsel, 4) MedSheet supporting prescription information, and 5) patient-centered Take-Wait-Stop wording of prescription instructions. This strategy will be assessed both with and without the addition of text messages via a three-arm randomized trial. The study will take place at an urban academic ED (annual volume>85,000) in Chicago, IL. Patients being discharged with a new prescription for hydrocodone-acetaminophen will be enrolled and randomized (based on their prescribing physician). The primary outcome of the study is medication safe use as measured by a demonstrated dosing task. Additionally actual safe use, patient knowledge and provider counseling will be measured. Implementation fidelity as well as costs will be reported. The ED EMC 2 Opioid Strategy embeds a risk communication strategy into the electronic health record and promotes medication counseling with minimal workflow disruption. This trial will evaluate the strategy's effectiveness and implementation fidelity as compared to usual care. This trial is registered on clinicaltrials.gov with identifier NCT02431793. Copyright © 2017 Elsevier Inc. All rights reserved.

  6. Efficacy and safety of bilateral continuous theta burst stimulation (cTBS for the treatment of chronic tinnitus: design of a three-armed randomized controlled trial

    Directory of Open Access Journals (Sweden)

    Plontke Stefan K

    2009-08-01

    Full Text Available Abstract Background Tinnitus, the perception of sound and noise in absence of an auditory stimulus, has been shown to be associated with maladaptive neuronal reorganization and increased activity of the temporoparietal cortex. Transient modulation of tinnitus by repetitive transcranial magnetic stimulation (rTMS indicated that these areas are critically involved in the pathophysiology of tinnitus and suggested new treatment strategies. However, the therapeutic efficacy of rTMS in tinnitus is still unclear, individual response is variable, and the optimal stimulation area disputable. Recently, continuous theta burst stimulation (cTBS has been put forward as an effective rTMS protocol for the reduction of pathologically enhanced cortical excitability. Methods 48 patients with chronic subjective tinnitus will be included in this randomized, placebo controlled, three-arm trial. The treatment consists of two trains of cTBS applied bilaterally to the secondary auditory cortex, the temporoparietal associaction cortex, or to the lower occiput (sham condition every working day for four weeks. Primary outcome measure is the change of tinnitus distress as quantified by the Tinnitus Questionnaire (TQ. Secondary outcome measures are tinnitus loudness and annoyance as well as tinnitus change during and after treatment. Audiologic and speech audiometric measurements will be performed to assess potential side effects. The aim of the present trail is to investigate effectiveness and safety of a four weeks cTBS treatment on chronic tinnitus and to compare two areas of stimulation. The results will contribute to clarify the therapeutic capacity of rTMS in tinnitus. Trial registration The trial was registered with the clinical trials register of http://www.clinicaltrials.gov (NCT00518024.

  7. Lignin poly(lactic acid) copolymers

    Energy Technology Data Exchange (ETDEWEB)

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

    2017-02-14

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

  8. A Comparative Study on Micellar and Solubilizing Behavior of Three EO-PO Based Star Block Copolymers Varying in Hydrophobicity and Their Application for the In Vitro Release of Anticancer Drugs

    Directory of Open Access Journals (Sweden)

    Bijal Vyas

    2018-01-01

    Full Text Available The temperature and pH dependent self-assembly of three star shaped ethylene oxide-propylene oxide (EO-PO block copolymers (Tetronics® 304, 904 and 908 with widely different hydrophobicity was examined in aqueous solutions. Physico-chemical methods viz. viscosity, cloud point, solubilization along with thermal, scattering and spectral techniques shows strongly temperature and salt dependent solution behavior. T304 possessing low molecular weight did not form micelles; moderately hydrophilic T904 remained as micelles at ambient temperature and showed micellar growth while very hydrophilic T908 formed micelles at elevated temperatures. The surface activity/micellization/solubilization power was favored in the presence of salt. The copolymers turn more hydrophilic in acidic pH due to protonation of central ethylene diamine moiety that hinders micelle formation. The solubilization of a model insoluble azo dye 1-(o-Tolylazo-2-naphthol (Orange OT and hydrophobic drugs (quercetin and curcumin for copolymer solutions in aqueous and salt solutions are also reported. Among the three copolymers, T904 showed maximum solubility of dye and drugs, hence the in vitro release of drugs from T904 micelles was estimated and the effect on cytotoxicity of loading the drugs in T904 micelles was compared with the cytotoxicity of free drugs on the CHO-K1 cells. The results from the present work provide a better insight in selection of Tetronics® for their application in different therapeutic applications.

  9. Metallo-supramolecular block copolymer micelles

    NARCIS (Netherlands)

    Gohy, J.M.W.

    2009-01-01

    Supramolecular copolymers have become of increasing interest in recent years in the search for new materials with tunable properties. In particular, metallo-supramolecular block copolymers in which metal-ligand complexes are introduced in block copolymer architectures, have known important progress,

  10. Brain-Computer Interface-based robotic end effector system for wrist and hand rehabilitation: results of a three-armed randomized controlled trial for chronic stroke

    Directory of Open Access Journals (Sweden)

    Kai Keng eAng

    2014-07-01

    Full Text Available The objective of this study was to investigate the efficacy of an Electroencephalography (EEG-based Motor Imagery (MI Brain-Computer Interface (BCI coupled with a Haptic Knob (HK robot for arm rehabilitation in stroke patients. In this three-arm, single-blind, randomized controlled trial; 21 chronic hemiplegic stroke patients (Fugl-Meyer Motor Assessment (FMMA score 10-50, recruited after pre-screening for MI BCI ability, were randomly allocated to BCI-HK, HK or Standard Arm Therapy (SAT groups. All groups received 18 sessions of intervention over 6 weeks, 3 sessions per week, 90 minutes per session. The BCI-HK group received 1 hour of BCI coupled with HK intervention, and the HK group received 1 hour of HK intervention per session. Both BCI-HK and HK groups received 120 trials of robot-assisted hand grasping and knob manipulation followed by 30 minutes of therapist-assisted arm mobilization. The SAT group received 1.5 hours of therapist-assisted arm mobilization and forearm pronation-supination movements incorporating wrist control and grasp-release functions. In all, 14 males, 7 females, mean age 54.2 years, mean stroke duration 385.1 days, with baseline FMMA score 27.0 were recruited. The primary outcome measure was upper-extremity FMMA scores measured mid-intervention at week 3, end-intervention at week 6, and follow-up at weeks 12 and 24. Seven, 8 and 7 subjects underwent BCI-HK, HK and SAT interventions respectively. FMMA score improved in all groups, but no intergroup differences were found at any time points. Significantly larger motor gains were observed in the BCI-HK group compared to the SAT group at weeks 3, 12 and 24, but motor gains in the HK group did not differ from the SAT group at any time point. In conclusion, BCI-HK is effective, safe, and may have the potential for enhancing motor recovery in chronic stroke when combined with therapist-assisted arm mobilization.

  11. Baseline characteristics of study sites and women enrolled in a three-arm cluster randomized controlled trial: PMTCT uptake and retention (pure) Malawi.

    Science.gov (United States)

    van Lettow, Monique; Tweya, Hannock; Rosenberg, Nora E; Trapence, Clement; Kayoyo, Virginia; Kasende, Florence; Kaunda, Blessings; Hosseinipour, Mina C; Eliya, Michael; Cataldo, Fabian; Gugsa, Salem; Phiri, Sam

    2017-07-11

    Malawi introduced an ambitious public health program known as "Option B+" which provides all HIV-infected pregnant and breastfeeding women with lifelong combination antiretroviral therapy, regardless of WHO clinical stage or CD4 cell count. The PMTCT Uptake and REtention (PURE) study aimed at evaluating the effect of peer-support on care-seeking and retention in care. PURE Malawi was a three-arm cluster randomized controlled trial that compared facility-based and community-based models of peer support to standard of care under Option B+ strategy. Each arm was expected to enroll a minimum of 360 women with a total minimum sample size of 1080 participants. 21 sites (clusters) were selected for inclusion in the study. This paper describes the site selection, recruitment, enrollment process and baseline characteristics of study sites and women enrolled in the trial. Study implementation was managed by 3 partner organizations; each responsible for 7 study sites. The trial was conducted in the South East, South West, and Central West zones of Malawi, the zones where the implementing partners operate. Study sites included 2 district hospitals, 2 mission hospitals, 2 rural hospitals, 13 health centers and 1 private clinic. Enrollment occurred from November 2013 to November 2014, over a median period of 31 weeks (range 17-51) by site. A total of 1269 HIV-infected pregnant (1094) and breastfeeding (175) women, who were eligible to initiate ART under Option B+, were enrolled. Each site reached or surpassed the minimum sample size. Comparing the number of women enrolled versus antenatal cohort reports, sites recruited a median of 90% (IQR 75-100) of eligible reported women. In the majority of sites the ratio of pregnant and lactating women enrolled in the study was similar to the ratio of reported pregnant and lactating women starting ART in the same sites. The median age of all women was 27 (IQR 22-31) years. All women have ≥20 months of possible follow-up time; 96%

  12. Brain-computer interface-based robotic end effector system for wrist and hand rehabilitation: results of a three-armed randomized controlled trial for chronic stroke.

    Science.gov (United States)

    Ang, Kai Keng; Guan, Cuntai; Phua, Kok Soon; Wang, Chuanchu; Zhou, Longjiang; Tang, Ka Yin; Ephraim Joseph, Gopal J; Kuah, Christopher Wee Keong; Chua, Karen Sui Geok

    2014-01-01

    The objective of this study was to investigate the efficacy of an Electroencephalography (EEG)-based Motor Imagery (MI) Brain-Computer Interface (BCI) coupled with a Haptic Knob (HK) robot for arm rehabilitation in stroke patients. In this three-arm, single-blind, randomized controlled trial; 21 chronic hemiplegic stroke patients (Fugl-Meyer Motor Assessment (FMMA) score 10-50), recruited after pre-screening for MI BCI ability, were randomly allocated to BCI-HK, HK or Standard Arm Therapy (SAT) groups. All groups received 18 sessions of intervention over 6 weeks, 3 sessions per week, 90 min per session. The BCI-HK group received 1 h of BCI coupled with HK intervention, and the HK group received 1 h of HK intervention per session. Both BCI-HK and HK groups received 120 trials of robot-assisted hand grasping and knob manipulation followed by 30 min of therapist-assisted arm mobilization. The SAT group received 1.5 h of therapist-assisted arm mobilization and forearm pronation-supination movements incorporating wrist control and grasp-release functions. In all, 14 males, 7 females, mean age 54.2 years, mean stroke duration 385.1 days, with baseline FMMA score 27.0 were recruited. The primary outcome measure was upper extremity FMMA scores measured mid-intervention at week 3, end-intervention at week 6, and follow-up at weeks 12 and 24. Seven, 8 and 7 subjects underwent BCI-HK, HK and SAT interventions respectively. FMMA score improved in all groups, but no intergroup differences were found at any time points. Significantly larger motor gains were observed in the BCI-HK group compared to the SAT group at weeks 3, 12, and 24, but motor gains in the HK group did not differ from the SAT group at any time point. In conclusion, BCI-HK is effective, safe, and may have the potential for enhancing motor recovery in chronic stroke when combined with therapist-assisted arm mobilization.

  13. A randomised, single-blind, single-dose, three-arm, parallel-group study in healthy subjects to demonstrate pharmacokinetic equivalence of ABP 501 and adalimumab.

    Science.gov (United States)

    Kaur, Primal; Chow, Vincent; Zhang, Nan; Moxness, Michael; Kaliyaperumal, Arunan; Markus, Richard

    2017-03-01

    To demonstrate pharmacokinetic (PK) similarity of biosimilar candidate ABP 501 relative to adalimumab reference product from the USA and European Union (EU) and evaluate safety, tolerability and immunogenicity of ABP 501. Randomised, single-blind, single-dose, three-arm, parallel-group study; healthy subjects were randomised to receive ABP 501 (n=67), adalimumab (USA) (n=69) or adalimumab (EU) (n=67) 40 mg subcutaneously. Primary end points were area under the serum concentration-time curve from time 0 extrapolated to infinity (AUC inf ) and the maximum observed concentration (C max ). Secondary end points included safety and immunogenicity. AUC inf and C max were similar across the three groups. Geometrical mean ratio (GMR) of AUC inf was 1.11 between ABP 501 and adalimumab (USA), and 1.04 between ABP 501 and adalimumab (EU). GMR of C max was 1.04 between ABP 501 and adalimumab (USA) and 0.96 between ABP 501 and adalimumab (EU). The 90% CIs for the GMRs of AUC inf and C max were within the prespecified standard PK equivalence criteria of 0.80 to 1.25. Treatment-related adverse events were mild to moderate and were reported for 35.8%, 24.6% and 41.8% of subjects in the ABP 501, adalimumab (USA) and adalimumab (EU) groups; incidence of antidrug antibodies (ADAbs) was similar among the study groups. Results of this study demonstrated PK similarity of ABP 501 with adalimumab (USA) and adalimumab (EU) after a single 40-mg subcutaneous injection. No new safety signals with ABP 501 were identified. The safety and tolerability of ABP 501 was similar to the reference products, and similar ADAb rates were observed across the three groups. EudraCT number 2012-000785-37; Results. Published by the BMJ Publishing Group Limited. For permission to use (where not already granted under a licence) please go to http://www.bmj.com/company/products-services/rights-and-licensing/.

  14. Incentives in Diabetic Eye Assessment by Screening (IDEAS): study protocol of a three-arm randomized controlled trial using financial incentives to increase screening uptake in London.

    Science.gov (United States)

    Judah, Gaby; Vlaev, Ivo; Gunn, Laura; King, Dominic; King, Derek; Valabhji, Jonathan; Darzi, Ara; Bicknell, Colin

    2016-03-18

    Diabetes is an increasing public health problem in the UK and globally. Diabetic retinopathy is a microvascular complication of diabetes, and is one of the leading causes of blindness in the UK working age population. The diabetic eye screening programme in England aims to invite all people with diabetes aged 12 or over for retinal photography to screen for the presence of diabetic retinopathy. However, attendance rates are only 81 %, leaving many people at risk of preventable sight loss. This is a three arm randomized controlled trial to investigate the impact of different types of financial incentives (based on principles from behavioral economics) on increasing attendance at diabetic eye screening appointments in London. Eligible participants will be aged 16 or over, and are those who have been invited to screening appointments annually, but who have not attended, or telephoned to rearrange an appointment, within the last 24 months. Eligible participants will be randomized to one of three conditions: 1. Control condition (usual invitation letter) 2. Fixed incentive condition (usual invitation letter, including a voucher for £10 if they attend their appointment) 3. Probabilistic incentive condition (invitation letter, including a voucher for a 1 in 100 chance of winning £1000 if they attend their appointment). Participants will be sent invitation letters, and the primary outcome will be whether or not they attend their appointment. One thousand participants will be included in total, randomized with a ratio of 1.4:1:1. In order to test whether the incentive scheme has a differential impact on patients from different demographic or socio-economic groups, information will be recorded on age, gender, distance from screening center, socio-economic status and length of time since they were last screened. A cost-effectiveness analysis will also be performed. This study will be the first trial of financial incentives for improving uptake of diabetic eye screening. If

  15. Synthesis and self-assembly of Chitosan-g-Polystyrene copolymer: A new route for the preparation of heavy metal nanoparticles

    KAUST Repository

    Francis, Raju S.

    2015-01-01

    Amphiphilic graft copolymers made of a Chitosan (CS) backbone and three arm polystyrene (PS) grafts were prepared by "grafting onto" strategy using Toluene Diisocyanate. IR spectroscopy and SEC show the successful grafting process. SEM pictures of Chitosan-g-Polystyrene (CS-g-PS) indicate a spherulite like surface and exhibit properties that result from the disappearance of Chitosan crystallinity. The introduced polystyrene star grafts units improve hydrophobic properties considerably as confirmed by the very high solubility of (CS-g-PS) in organic solvents. The graft copolymer which self-assembles into polymeric micelles in organic media demonstrates much better adsorption of transition and inner transition metal ions than pure Chitosan whose amine groups are not necessarily available due to crystallinity.

  16. Polyethylene-Based Tadpole Copolymers

    KAUST Repository

    Alkayal, Nazeeha

    2017-02-15

    Novel well-defined polyethylene-based tadpole copolymers ((c-PE)-b-PS, PE: polyethylene, PS: polystyrene) with ring PE head and linear PS tail are synthesized by combining polyhomologation, atom transfer radical polymerization (ATRP), and Glaser coupling reaction. The -OH groups of the 3-miktoarm star copolymers (PE-OH)-b-PS, synthesized by polyhomologation and ATRP, are transformed to alkyne groups by esterification with propiolic acid, followed by Glaser cyclization and removal of the unreacted linear with Merrifield\\'s resin-azide. The characterization results of intermediates and final products by high-temperature size exclusion chromatography, H NMR spectroscopy, and differential scanning calorimetry confirm the tadpole topology.

  17. Main-chain supramolecular block copolymers.

    Science.gov (United States)

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

    2011-01-01

    Block copolymers are key building blocks for a variety of applications ranging from electronic devices to drug delivery. The material properties of block copolymers can be tuned and potentially improved by introducing noncovalent interactions in place of covalent linkages between polymeric blocks resulting in the formation of supramolecular block copolymers. Such materials combine the microphase separation behavior inherent to block copolymers with the responsiveness of supramolecular materials thereby affording dynamic and reversible materials. This tutorial review covers recent advances in main-chain supramolecular block copolymers and describes the design principles, synthetic approaches, advantages, and potential applications.

  18. The radiation crosslinking of ethylene copolymers

    International Nuclear Information System (INIS)

    Burns, N.M.

    1979-01-01

    The enhanced radiation crosslinking tendency of ethylene-vinyl acetate and ethylene-ethyl acrylate copolymers over ethylene homopolymer is proportional to the comonomer content. This is caused by an increase in the amorphous polymer content and by structure-related factors. The copolymers crosslink by a random process that for ethylene-vinyl acetate copolymer involves some crosslinking through the acetoxy group of the comonomer. While knowledge of the process for the crosslinking of ethylene-ethyl acrylate copolymer is less certain, it is currently believed to occur primarily at the branch point on the polymer backbone. Data relating comonomer content and the molecular weight of the copolymers to the radiation crosslinking levels realized were developed to aid in resin selection by the formulator. Triallyl cyanurate cure accelerator was found to be less effective in ethylene-vinyl acetate copolymer than in homopolymer and to have no effect on gel development in ethylene-ethyl acrylate copolymer. (author)

  19. Modeling of emulsion copolymer microstructure

    NARCIS (Netherlands)

    van Doremaele, G.H.J.; Herk, van A.M.; German, A.L.

    1992-01-01

    A model is developed to describe stages II and III of batch emulsion copolymn., and its predictive capabilities are investigated by application to the system styrene-Me acrylate. The main reaction site is the monomer-swollen polymer particle. Copolymn. rate and copolymer microstructure (molar

  20. Polyether-polyester graft copolymer

    Science.gov (United States)

    Bell, Vernon L. (Inventor)

    1987-01-01

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

  1. Thermo-responsive block copolymers

    NARCIS (Netherlands)

    Mocan Cetintas, Merve

    2017-01-01

    Block copolymers (BCPs) are remarkable materials because of their self-assembly behavior into nano-sized regular structures and high tunable properties. BCPs are in used various applications such as surfactants, nanolithography, biomedicine and nanoporous membranes. In these thesis, we aimed to

  2. Feasibility of mobile health game "Fume" in supporting tobacco-related health literacy among early adolescents: A three-armed cluster randomized design.

    Science.gov (United States)

    Parisod, Heidi; Pakarinen, Anni; Axelin, Anna; Löyttyniemi, Eliisa; Smed, Jouni; Salanterä, Sanna

    2018-05-01

    New interventions supporting health literacy and a tobacco-free lifestyle in adolescence are needed to narrow the widening gap in existing health inequalities. Health games offer potential and could be utilized for example in school healthcare, but more research is needed to increase the understanding of the effects of game elements in health interventions. The aim of this feasibility study is to determine the short-term effectiveness of the tobacco-related mobile health game Fume and a non-gamified website in comparison with a no-intervention control group, regarding tobacco-related health literacy among 10-13-year-old early adolescents. In addition, we compare the demand for and acceptability of Fume to that of the website. In total, 151 early adolescents participated in this single-blinded, three-armed cluster randomized trial. The participants from three municipalities in southwest Finland were randomly allocated between a group with access to the health game Fume (n = 61), a group with access to the website (n = 47), and a group with no intervention (n = 43). The intervention groups first participated in a 20-min training session with Fume/the website, and then had two weeks to use Fume/the website based on their own interest. Short-term effectiveness was measured by primary (anti-smoking self-efficacy) and secondary (smoking outcome expectations, attitudes towards tobacco use, tobacco-use motives, motivation to decline tobacco use in the future, and knowledge about tobacco) outcomes derived from the theory-based determinants of tobacco-related health literacy and evaluated with self-assessment questionnaires at baseline and post-intervention (after a two-week follow-up). For evaluating the demand, the actual use of Fume/the website was tracked during the two-week period. Regarding acceptability, the raised interest towards Fume/the website and opinions about the interventions were evaluated post-intervention. Differences were tested with the Mc

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

    NARCIS (Netherlands)

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

    2002-01-01

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

  4. Polyketones as alternating copolymers of carbon monoxide

    International Nuclear Information System (INIS)

    Belov, Gennady P; Novikova, Elena V

    2004-01-01

    Characteristic features of the catalytic synthesis of alternating copolymers of carbon monoxide with various olefins, dienes, styrene and its derivatives are considered. The diversity of catalyst systems used for the copolymerisation of carbon monoxide is demonstrated and their influence on the structure and the molecular mass of the resulting copolymers is analysed. The data on the structure and physicochemical and mechanical properties of this new generation of functional copolymers are generalised and described systematically for the first time.

  5. Copolymers of fluorinated polydienes and sulfonated polystyrene

    Science.gov (United States)

    Mays, Jimmy W [Knoxville, TN; Gido, Samuel P [Hadley, MA; Huang, Tianzi [Knoxville, TN; Hong, Kunlun [Knoxville, TN

    2009-11-17

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

  6. Synthesis of biodegradable styrene copolymers

    OpenAIRE

    Gevers, Dries; Kobben, Stephan; Junkers, Tanja; Copinet, Alain; Buntinx, Mieke; Peeters, Roos

    2017-01-01

    Polystyrene (PS), a versatile polymer with many applications (e.g. packaging) representing about 10% of the total annual polymer consumption, shows practically no biodegradability. In this study a styrene (ST) based copolymer is synthesized and examined regarding its ability to degrade in a composting test. As second monomer, to introduce biodegradable ester groups, 5,6-benzo-2-metylene-dioxepane (BMDO) has been used in radical copolymerization reactions performed in inert and stirred 10 m...

  7. Stereocomplexation, Thermal and Mechanical Properties of Conetworks Composed of Star-Shaped l-Lactide, d-Lactide and ε-Caprolactone Oligomers Utilizing Sugar Alcohols as Core Molecules

    Directory of Open Access Journals (Sweden)

    Kaito Sugane

    2017-11-01

    Full Text Available It is important to develop tailor-made biodegradable/biocompatible polymer networks usable for biomaterials whose thermal and mechanical properties are easily controlled by changing the composition. We synthesized sugar-alcohol-based polymer networks (SPN-mscLAO/3CLO, m = 4, 5 or 6 by the crosslinking reactions of erythritol, xylitol or sorbitol-based m-armed star-shaped l-lactide and d-lactide oligomers (HmSLLAO and HmSDLAO, a glycerol-based 3-armed star-shaped ε-caprolactone oligomer (H3SCLO and hexamethylene diisocyanate (HDI at the weight ratios of HmSLLAO/HmSDLAO = 1/1 and (HmSLLAO + HmSDLAO/H3CLO = 100/0, 75/25, 50/50, 25/75 or 0/100. The influence of the arm number on the crystallization behavior, thermal and mechanical properties of SPN-mscLAO/3CLOs were systematically investigated by comparing with those of sugar-alcohol-based homochiral polymer network (SPN-mLLAO, m = 4, 5 or 6 prepared by the reaction of HmSLLAO and HDI. Stereocomplex (sc crystallites are dominantly formed for SPN-mscLAO/3CLOs 100/0–25/75, whereas SPN-mLLAOs were amorphous. The higher order of melting temperature of sc-crystals for SPN-mscLAO/3CLOs 100/0–25/75 was m = 5 > m = 6 > m = 4. The sc-crystallinities of SPN-4scLAO/3CLOs 100/0–50/50 were significantly lower than those of SPN-mscLAO/3CLOs 100/0–50/50 (m = 5 and 6. The larger order of the sc-spherulite size at crystallization temperature of 110 °C was m = 5 > m = 6 > m = 4 for SPN-mscLAO/3CLO 100/0. The size and number of sc-spherulites decreased with increasing crystallization temperature over the range of 110–140 °C and with increasing CLO fraction. Among all the networks, SPN-5scLAO/3CLOs 75/25 and 50/50 exhibited the highest and second highest tensile toughnesses (21.4 and 20.3 MJ·m−3, respectively.

  8. Biodegradable shape-memory block co-polymers for fast self-expandable stents.

    Science.gov (United States)

    Xue, Liang; Dai, Shiyao; Li, Zhi

    2010-11-01

    Block co-polymers PCTBVs (M(n) of 36,300-65,300 g/mol, T(m) of 39-40 and 142 degrees C) containing hyperbranched three-arm poly(epsilon-caprolactone) (PCL) as switching segment and microbial polyester PHBV as crystallizable hard segment were designed as biodegradable shape-memory polymer (SMP) for fast self-expandable stent and synthesized in 96% yield by the reaction of three-arm PCL-triol (M(n) of 4200 g/mol, T(m) of 47 degrees C) with methylene diphenyl 4,4'-diisocyanate isocynate (MDI) to form the hyperbrached MDI-linked PCL (PTCM; M(n) of 25,400 g/mol and a T(m) of 38 degrees C), followed by further polymerization with PHBV-diol (M(n) of 2200 g/mol, T(m) of 137 and 148 degrees C). The polymers were characterized by (1)H NMR, GPC, DSC, tensile test, and cyclic thermomechanical tensile test. PCTBVs showed desired thermal properties, mechanical properties, and ductile nature. PCTBV containing 25 wt% PHBV (PCTBV-25) demonstrated excellent shape-memory property at 40 degrees C, with R(f) of 94%, R(r) of 98%, and shape recovery within 25s. PCTBV-25 was also shown as a safe material with good biocompatibility by cytotoxicity tests and cell growth experiments. The stent made from PCTBV-25 film showed nearly complete self-expansion at 37 degrees C within only 25 s, which is much better and faster than the best known self-expandable stents. Copyright (c) 2010 Elsevier Ltd. All rights reserved.

  9. 21 CFR 177.2470 - Polyoxymethylene copolymer.

    Science.gov (United States)

    2010-04-01

    ... Components of Articles Intended for Repeated Use § 177.2470 Polyoxymethylene copolymer. Polyoxymethylene copolymer identified in this section may be safely used as an article or component of articles intended for... are available from the Center for Food Safety and Applied Nutrition (HFS-200), Food and Drug...

  10. Radiation resistance of ethylene-styrene copolymers

    International Nuclear Information System (INIS)

    Matsumoto, Kaoru; Ikeda, Masaaki; Ohki, Yoshimichi; Kusama, Yasuo; Harashige, Masahiro; Yazaki, Fumihiko.

    1988-01-01

    In this paper, the radiation resistance of ethylene-styrene copolymer, a polymeric resin developed newly by the authors, is reported. Resin examined were five kinds of ethylene-styrene copolymers: three random and two graft copolymers with different styrene contents. Low-density polyethylene was used as a reference. The samples were irradiated by 60 Co γ-rays to total absorbed doses up to 10 MGy. The mechanical properties of the smaples were examined. Infrared spectroscopy, differential scanning calorimetry and X-ray scattering techniques were used to examine the morphology of the samples. The random copolymers are soft and easy to extend, because benzene rings which exisist highly at random hinder the crystallization. As for the radiation resistance, they are highly resistant to γ-rays in the aspects of carbonyl group formation, gel formation, and elongation. Further, they show even better radiation resistance when proper additives were compounded in. The graft copolymers are hard to extend, because they consist of segregated polystyrene and polyethylene regions which are connected with each other. The tensile strength of irradiated graft copolymers does not decrease below that of unirradiated copolymers, up to a total dose of 10 MGy. As a consequence, it can be said that ethylene-styrene copolymers have good radiation resistance owing to the so-called 'sponge' effect of benzene rings. (author)

  11. Copolymers at the solid - liquid interface

    NARCIS (Netherlands)

    Wijmans, C.M.

    1994-01-01

    Copolymers consisting of both adsorbing and nonadsorbing segments can show an adsorption behaviour which is very different from that of homopolymers. We have mainly investigated the adsorption of AB diblock copolymers, which have one adsorbing block (anchor) and one nonadsorbing block

  12. Amphiphilic copolymers for fouling-release coatings

    DEFF Research Database (Denmark)

    Noguer, Albert Camós; Olsen, Stefan Møller; Hvilsted, Søren

    of the coatings [9,10,11]. This work shows the effect of an amphiphilic copolymer that induces hydrophilicity on the surface of the silicone-based fouling release coatings. The behaviour of these copolymers within the coating upon immersion and the interaction of these surface-active additives with other...

  13. Poly(ferrocenylsilane)-block-Polylactide Block Copolymers

    NARCIS (Netherlands)

    Roerdink, M.; van Zanten, Thomas S.; Hempenius, Mark A.; Zhong, Zhiyuan; Feijen, Jan; Vancso, Gyula J.

    2007-01-01

    A PFS/PLA block copolymer was studied to probe the effect of strong surface interactions on pattern formation in PFS block copolymer thin films. Successful synthesis of PFS-b-PLA was demonstrated. Thin films of these polymers show phase separation to form PFS microdomains in a PLA matrix, and

  14. Revisiting the Acanthamoeba species that form star-shaped cysts (genotypes T7, T8, T9, and T17): characterization of seven new Brazilian environmental isolates and phylogenetic inferences.

    Science.gov (United States)

    Magliano, Ana C M; Teixeira, Marta M G; Alfieri, Silvia C

    2012-01-01

    Free-living amoebae of the genus Acanthamoeba are the agents of both opportunistic and non-opportunistic infections and are frequently isolated from the environment. Of the 17 genotypes (T1-T17) identified thus far, 4 (T7, T8, T9, and T17) accommodate the rarely investigated species of morphological group I, those that form large, star-shaped cysts. We report the isolation and characterization of 7 new Brazilian environmental Acanthamoeba isolates, all assigned to group I. Phylogenetic analyses based on partial (~1200 bp) SSU rRNA gene sequences placed the new isolates in the robustly supported clade composed of the species of morphological group I. One of the Brazilian isolates is closely related to A. comandoni (genotype T9), while the other 6, together with 2 isolates recently assigned to genotype T17, form a homogeneous, well-supported group (2·0% sequence divergence) that likely represents a new Acanthamoeba species. Thermotolerance, osmotolerance, and cytophatic effects, features often associated with pathogenic potential, were also examined. The results indicated that all 7 Brazilian isolates grow at temperatures up to 40°C, and resist under hyperosmotic conditions. Additionally, media conditioned by each of the new Acanthamoeba isolates induced the disruption of SIRC and HeLa cell monolayers.

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

    Science.gov (United States)

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

    2016-07-05

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

  16. Block copolymer membranes for aqueous solution applications

    KAUST Repository

    Nunes, Suzana Pereira

    2016-03-22

    Block copolymers are known for their intricate morphology. We review the state of the art of block copolymer membranes and discuss perspectives in this field. The main focus is on pore morphology tuning with a short introduction on non-porous membranes. The two main strategies for pore formation in block copolymer membranes are (i) film casting and selective block sacrifice and (ii) self-assembly and non-solvent induced phase separation (SNIPS). Different fundamental aspects involved in the manufacture of block copolymer membranes are considered, including factors affecting the equilibrium morphology in solid films, self-assembly of copolymer in solutions and macrophase separation by solvent-non-solvent exchange. Different mechanisms are proposed for different depths of the SNIPS membrane. Block copolymer membranes can be prepared with much narrower pore size distribution than homopolymer membranes. Open questions and indications of what we consider the next development steps are finally discussed. They include the synthesis and application of new copolymers and specific functionalization, adding characteristics to respond to stimuli and chemical environment, polymerization-induced phase separation, and the manufacture of organic-inorganic hybrids.

  17. Block copolymer membranes for aqueous solution applications

    KAUST Repository

    Nunes, Suzana Pereira

    2016-01-01

    Block copolymers are known for their intricate morphology. We review the state of the art of block copolymer membranes and discuss perspectives in this field. The main focus is on pore morphology tuning with a short introduction on non-porous membranes. The two main strategies for pore formation in block copolymer membranes are (i) film casting and selective block sacrifice and (ii) self-assembly and non-solvent induced phase separation (SNIPS). Different fundamental aspects involved in the manufacture of block copolymer membranes are considered, including factors affecting the equilibrium morphology in solid films, self-assembly of copolymer in solutions and macrophase separation by solvent-non-solvent exchange. Different mechanisms are proposed for different depths of the SNIPS membrane. Block copolymer membranes can be prepared with much narrower pore size distribution than homopolymer membranes. Open questions and indications of what we consider the next development steps are finally discussed. They include the synthesis and application of new copolymers and specific functionalization, adding characteristics to respond to stimuli and chemical environment, polymerization-induced phase separation, and the manufacture of organic-inorganic hybrids.

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

    Science.gov (United States)

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

    2014-03-01

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

  19. Micellization and Dynamics of a Block Copolymer

    DEFF Research Database (Denmark)

    Hvidt, Søren

    2006-01-01

    and copolymer mixtures, and evidence in favor of a multi-equilibria unimer-micelle model will be presented. Results obtained by liquid chromatographic methods will be shown and it will be demonstrated that commercial EPE copolymers are inhomogeneous at several levels and many of their unusual properties reflect...... ratios and temperature. The micellization process with increasing temperature has been followed by a number of techniques including differential scanning calorimetry, liquid chromatography, and surface tension measurements. Different micellization models have been tested for purified copolymers...

  20. PEO-related block copolymer surfactants

    DEFF Research Database (Denmark)

    Mortensen, K.

    2001-01-01

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

  1. Star-Shaped Intense Uptake of ¹³¹I on Whole Body Scans Can Reflect Good Therapeutic Effects of Low-Dose Radioactive Iodine Treatment of 1.1 GBq.

    Science.gov (United States)

    Kong, Sung Hye; Lim, Jung Ah; Song, Young Shin; Moon, Shinje; Kim, Ye An; Kim, Min Joo; Cho, Sun Wook; Moon, Jae Hoon; Yi, Ka Hee; Park, Do Joon; Cho, Bo Youn; Park, Young Joo

    2018-05-04

    After initial radioactive iodine (RAI) treatment in differentiated thyroid cancer patients, we sometimes observe a star-shaped region of intense uptake of ¹³¹I on whole body scans (WBSs), called a 'star artifact.' We evaluated the clinical implications of star artifacts on the success rate of remnant ablation and long-term prognosis. Total 636 patients who received ¹³¹I dose of 1.1 GBq for the initial RAI therapy and who did not show distant metastasis at the time of diagnosis were retrospectively evaluated. A negative second WBS was used for evaluating the ablation efficacy of the RAI therapy. Among them, 235 patients (36.9%) showed a star artifact on their first WBS. In patients with first stimulated thyroglobulin (sTg) levels ≤2 ng/mL, patients with star artifacts had a higher rate of negative second WBS compared with those without star artifacts (77.8% vs. 63.9%, P=0.044), and showed significantly higher recurrence-free survival (P=0.043) during the median 8.0 years (range, 1.0 to 10.0) of follow-up. The 5- and 10-year recurrence rates (5YRR, 10YRR) were also significantly lower in patients with star artifacts compared with those without (0% vs. 4.9%, respectively, P=0.006 for 5YRR; 0% vs. 6.4%, respectively, P=0.005 for 10YRR). However, ablation success rate or recurrence-free survival was not different among patients whose first sTg levels >2 ng/mL regardless of star artifacts. Therefore, star artifacts at initial RAI therapy imply a good ablation efficacy or a favorable long-term prognosis in patients with sTg levels ≤2 ng/mL. Copyright © 2018 Korean Endocrine Society.

  2. Functional Nanoporous Polymers from Block Copolymer Precursors

    DEFF Research Database (Denmark)

    Guo, Fengxiao

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

  3. Block Copolymers: Synthesis and Applications in Nanotechnology

    Science.gov (United States)

    Lou, Qin

    This study is focused on the synthesis and study of (block) copolymers using reversible deactivation radical polymerizations (RDRPs), including atom transfer radical polymerization (ATRP) and reversible addition-fragmentation chain transfer (RAFT) polymerization. In particular, two primary areas of study are undertaken: (1) a proof-of-concept application of lithographic block copolymers, and (2) the mechanistic study of the deposition of titania into block copolymer templates for the production of well-ordered titania nanostructures. Block copolymers have the ability to undergo microphase separation, with an average size of each microphase ranging from tens to hundreds of nanometers. As such, block copolymers have been widely considered for nanotechnological applications over the past two decades. The development of materials for various nanotechnologies has become an increasingly studied area as improvements in many applications, such as those found in the semiconductor and photovoltaic industries are constantly being sought. Significant growth in developments of new synthetic methods ( i.e. RDRPs) has allowed the production of block copolymers with molecular (and sometimes atomic) definition. In turn, this has greatly expanded the use of block copolymers in nanotechnology. Herein, we describe the synthesis of statistical and block copolymers of 193 nm photolithography methacrylate and acrylate resist monomers with norbornyl and adamantyl moieties using RAFT polymerization.. For these resist (block) copolymers, the phase separation behaviors were examined by atomic force microscopy (AFM). End groups were removed from the polymers to avoid complications during the photolithography since RAFT end groups absorb visible light. Poly(glycidyl methacrylate-block-polystyrene) (PGMA-b-PS) was synthesize by ATRP and demonstrated that this block copolymer acts as both a lithographic UV (365 nm) photoresist and a self-assembly material. The PGMA segments can undergo cationic

  4. Responsive Copolymers for Enhanced Petroleum Recovery

    Energy Technology Data Exchange (ETDEWEB)

    McCormick, C.; Hester, R.

    2001-02-27

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

  5. Reactivity Ratios for Organotin Copolymer Systems

    Directory of Open Access Journals (Sweden)

    Mohamed H. El-Newehy

    2010-04-01

    Full Text Available Di(tri-n-butyltin itaconate (DTBTI and monoethyl tributyltin fumarate (METBTF were synthesized as organotin monomers. The organotin monomers were copolymerized with styrene (ST and methyl methacrylate (MMA via a free radical polymerization technique. The overall conversion was kept low (£15% wt/wt for all studied samples and the copolymer composition was determined from tin analysis. The synthesized monomers and copolymers were characterized by elemental analysis, 1H- and 13C-NMR, and FTIR spectroscopy.

  6. 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

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

    NARCIS (Netherlands)

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

    2005-01-01

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

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

    Science.gov (United States)

    Chisholm, Bret Ja; Samanta, Satyabrata

    2017-09-19

    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.

  9. Oil recovery with vinyl sulfonic acid-acrylamide copolymers

    Energy Technology Data Exchange (ETDEWEB)

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

    1973-12-18

    An aqueous polymer flood containing sulfomethylated alkali metal vinyl sulfonate-acrylamide copolymers was proposed for use in secondary or tertiary enhanced oil recovery. The sulfonate groups on the copolymers sustain the viscosity of the flood in the presence of brine and lime. Injection of the copolymer solution into a waterflooded Berea core, produced 30.5 percent of the residual oil. It is preferred that the copolymers are partially hydrolyzed.

  10. Photo-Induced Micellization of Block Copolymers

    Directory of Open Access Journals (Sweden)

    Satoshi Kuwayama

    2010-11-01

    Full Text Available We found novel photo-induced micellizations through photolysis, photoelectron transfer, and photo-Claisen rearrangement. The photolysis-induced micellization was attained using poly(4-tert-butoxystyrene-block-polystyrene diblock copolymer (PBSt-b-PSt. BSt-b-PSt showed no self-assembly in dichloromethane and existed as isolated copolymers. Dynamic light scattering demonstrated that the copolymer produced spherical micelles in this solvent due to irradiation with a high-pressure mercury lamp in the presence of photo-acid generators, such as bis(alkylphenyliodonium hexafluorophosphate, diphenyliodonium hexafluorophosphate, and triphenylsulfonium triflate. The 1H NMR analysis confirmed that PBSt-b-PSt was converted into poly(4-vinylphenol-block-PSt by the irradiation, resulting in self-assembly into micelles. The irradiation in the presence of the photo-acid generator also induced the micellization of poly(4-pyridinemethoxymethylstyrene-block-polystyrene diblock copolymer (PPySt-b-PSt. Micellization occurred by electron transfer from the pyridine to the photo-acid generator in their excited states and provided monodispersed spherical micelles with cores of PPySt blocks. Further, the photo-Claisen rearrangement caused the micellization of poly(4-allyloxystyrene-block-polystyrene diblock copolymer (PASt-b-PSt. Micellization was promoted in cyclohexane at room temperature without a catalyst. During micellization, the elimination of the allyl groups competitively occurred along with the photorearrangement of the 4-allyloxystyrene units into the 3-allyl-4-hydroxystyrene units.

  11. Nanoparticles based on novel amphiphilic polyaspartamide copolymers

    International Nuclear Information System (INIS)

    Craparo, Emanuela Fabiola; Teresi, Girolamo; Ognibene, Maria Chiara; Casaletto, Maria Pia; Bondi, Maria Luisa; Cavallaro, Gennara

    2010-01-01

    In this article, the synthesis of two amphiphilic polyaspartamide copolymers, useful to obtain polymeric nanoparticles without using surfactants or stabilizing agents, is described. These copolymers were obtained starting from α,β-poly-(N-2-hydroxyethyl)-dl-aspartamide (PHEA) by following a novel synthetic strategy. In particular, PHEA and its pegylated derivative (PHEA-PEG 2000 ) were functionalized with poly(lactic acid) (PLA) through 1,1'-carbonyldiimidazole (CDI) activation to obtain PHEA-PLA and PHEA-PEG 2000 -PLA graft copolymers, respectively. These copolymers were properly purified and characterized by 1 H-NMR, FT-IR, and Size Exclusion Chromatography (SEC) analyses, which confirmed that derivatization reactions occurred. Nanoparticles were obtained from PHEA-PLA and PHEA-PEG 2000 -PLA graft copolymers by using the high pressure homogenization-solvent evaporation method, avoiding the use of surfactants or stabilizing agents. Polymeric nanoparticles were characterized by dimensional analysis, before and after freeze-drying process, and Scanning Electron Microscopy (SEM). Zeta potential measurements and X-ray Photoelectron Spectroscopy (XPS) analysis demonstrated the presence of PEG and/or PHEA onto the PHEA-PEG 2000 -PLA and PHEA-PLA nanoparticle surface, respectively.

  12. 21 CFR 177.1310 - Ethylene-acrylic acid copolymers.

    Science.gov (United States)

    2010-04-01

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

  13. 21 CFR 177.1312 - Ethylene-carbon monoxide copolymers.

    Science.gov (United States)

    2010-04-01

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

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

    Science.gov (United States)

    2010-04-01

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

  15. 21 CFR 177.1320 - Ethylene-ethyl acrylate copolymers.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Ethylene-ethyl acrylate copolymers. 177.1320... Basic Components of Single and Repeated Use Food Contact Surfaces § 177.1320 Ethylene-ethyl acrylate copolymers. Ethylene-ethyl acrylate copolymers may be safely used to produce packaging materials, containers...

  16. 21 CFR 177.1950 - Vinyl chloride-ethylene copolymers.

    Science.gov (United States)

    2010-04-01

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

  17. Functionalization of Block Copolymer Vesicle Surfaces

    Directory of Open Access Journals (Sweden)

    Wolfgang Meier

    2011-01-01

    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.

  18. Amphiphilic block copolymers for biomedical applications

    Science.gov (United States)

    Zupancich, John Andrew

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

  19. Dynamics of Block Copolymer Nanocomposites

    Energy Technology Data Exchange (ETDEWEB)

    Mochrie, Simon G. J.

    2014-09-09

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

  20. Co-polymer Films for Sensors

    Science.gov (United States)

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

    2012-01-01

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

  1. Ordering phenomena in ABA triblock copolymer gels

    DEFF Research Database (Denmark)

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

    1997-01-01

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

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

    Science.gov (United States)

    Cho, Junhan

    2014-03-01

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

  3. Shear instability of a gyroid diblock copolymer

    DEFF Research Database (Denmark)

    Eskimergen, Rüya; Mortensen, Kell; Vigild, Martin Etchells

    2005-01-01

    -induced destabilization is discussed in relation to analogous observations on shear-induced order-to-order and disorder-to-order transitions observed in related block copolymer systems and in microemulsions. It is discussed whether these phenomena originate in shear-reduced fluctuations or shear-induced dislocations....

  4. CONJUGATED BLOCK-COPOLYMERS FOR ELECTROLUMINESCENT DIODES

    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

  5. Substrate tolerant direct block copolymer nanolithography

    DEFF Research Database (Denmark)

    Li, Tao; Wang, Zhongli; Schulte, Lars

    2016-01-01

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

  6. Micellization and Characterization of Block Copolymer Detergents

    DEFF Research Database (Denmark)

    Hvidt, Søren

    and different models have been proposed. Results obtained by a range of liquid chromatographic methods will be shown and it will be demonstrated that commercial EPE copolymers are inhomogeneous at several levels and many of their unusual properties reflect the presence of impurities....

  7. Cyclic olefin copolymer-silica nanocomposites foams

    Czech Academy of Sciences Publication Activity Database

    Pegoretti, A.; Dorigato, A.; Biani, A.; Šlouf, Miroslav

    2016-01-01

    Roč. 51, č. 8 (2016), s. 3907-3916 ISSN 0022-2461 R&D Projects: GA MŠk(CZ) LO1507 Institutional support: RVO:61389013 Keywords : cyclic olefin copolymer * nanocomposites * silica Subject RIV: CD - Macromolecular Chemistry Impact factor: 2.599, year: 2016

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

    OpenAIRE

    Yunqi Li; Bishnu Prasad Bastakoti; Yusuke Yamauchi

    2016-01-01

    This review focuses on the application of triblock copolymers as designed templates to synthesize nanoporous materials with various compositions. Asymmetric triblock copolymers have several advantages compared with symmetric triblock copolymers and diblock copolymers, because the presence of three distinct domains can provide more functional features to direct the resultant nanoporous materials. Here we clearly describe significant contributions of asymmetric triblock copolymers, especially p...

  9. A Novel Highly Bioavailable Curcumin Formulation Improves Symptoms and Diagnostic Indicators in Rheumatoid Arthritis Patients: A Randomized, Double-Blind, Placebo-Controlled, Two-Dose, Three-Arm, and Parallel-Group Study.

    Science.gov (United States)

    Amalraj, Augustine; Varma, Karthik; Jacob, Joby; Divya, Chandradhara; Kunnumakkara, Ajaikumar B; Stohs, Sidney J; Gopi, Sreeraj

    2017-10-01

    Rheumatoid arthritis (RA) is an autoimmune, chronic systemic inflammatory disorder. The long-term use of currently available drugs for the treatment of RA has many potential side effects. Natural phytonutrients may serve as alternative strategies for the safe and effective treatment of RA, and curcuminoids have been used in Ayurvedic medicine for the treatment of inflammatory conditions for centuries. In this study, a novel, highly bioavailable form of curcumin in a completely natural turmeric matrix was evaluated for its ability to improve the clinical symptoms of RA. A randomized, double-blind, placebo-controlled, three-arm, parallel-group study was conducted to evaluate the comparative efficacy of two different doses of curcumin with that of a placebo in active RA patients. Twelve patients in each group received placebo, 250 or 500 mg of the curcumin product twice daily for 90 days. The responses of the patients were assessed using the American College of Rheumatology (ACR) response, visual analog scale (VAS), C-reactive protein (CRP), Disease Activity Score 28 (DAS28), erythrocyte sedimentation rate (ESR), and rheumatoid factor (RF) values. RA patients who received the curcumin product at both low and high doses reported statistically significant changes in their clinical symptoms at the end of the study. These observations were confirmed by significant changes in ESR, CPR, and RF values in patients receiving the study product compared to baseline and placebo. The results indicate that this novel curcumin in a turmeric matrix acts as an analgesic and anti-inflammatory agent for the management of RA at a dose as low as 250 mg twice daily as evidenced by significant improvement in the ESR, CRP, VAS, RF, DAS28, and ACR responses compared to placebo. Both doses of the study product were well tolerated and without side effects.

  10. Impact of body weight, low energy diet and gastric bypass on drug bioavailability, cardiovascular risk factors and metabolic biomarkers: protocol for an open, non-randomised, three-armed single centre study (COCKTAIL).

    Science.gov (United States)

    Hjelmesæth, Jøran; Åsberg, Anders; Andersson, Shalini; Sandbu, Rune; Robertsen, Ida; Johnson, Line Kristin; Angeles, Philip Carlo; Hertel, Jens Kristoffer; Skovlund, Eva; Heijer, Maria; Ek, Anna-Lena; Krogstad, Veronica; Karlsen, Tor-Ivar; Christensen, Hege; Andersson, Tommy B; Karlsson, Cecilia

    2018-05-29

    Roux-en-Y gastric bypass (GBP) is associated with changes in cardiometabolic risk factors and bioavailability of drugs, but whether these changes are induced by calorie restriction, the weight loss or surgery per se, remains uncertain. The COCKTAIL study was designed to disentangle the short-term (6 weeks) metabolic and pharmacokinetic effects of GBP and a very low energy diet (VLED) by inducing a similar weight loss in the two groups. This open, non-randomised, three-armed, single-centre study is performed at a tertiary care centre in Norway. It aims to compare the short-term (6 weeks) and long-term (2 years) effects of GBP and VLED on, first, bioavailability and pharmacokinetics (24 hours) of probe drugs and biomarkers and, second, their effects on metabolism, cardiometabolic risk factors and biomarkers. The primary outcomes will be measured as changes in: (1) all six probe drugs by absolute bioavailability area under the curve (AUC oral /AUC iv ) of midazolam (CYP3A4 probe), systemic exposure (AUC oral ) of digoxin and rosuvastatin and drug:metabolite ratios for omeprazole, losartan and caffeine, levels of endogenous CYP3A biomarkers and genotypic variation, changes in the expression and activity data of the drug-metabolising, drug transport and drug regulatory proteins in biopsies from various organs and (2) body composition, cardiometabolic risk factors and metabolic biomarkers. The COCKTAIL protocol was reviewed and approved by the Regional Committee for Medical and Health Research Ethics (Ref: 2013/2379/REK sørøst A). The results will be disseminated to academic and health professional audiences and the public via presentations at conferences, publications in peer-reviewed journals and press releases and provided to all participants. NCT02386917. © Article author(s) (or their employer(s) unless otherwise stated in the text of the article) 2018. All rights reserved. No commercial use is permitted unless otherwise expressly granted.

  11. A Three-arm Randomized Clinical Trial Comparing Continuous Femoral Plus Single-injection Sciatic Peripheral Nerve Blocks versus Periarticular Injection with Ropivacaine or Liposomal Bupivacaine for Patients Undergoing Total Knee Arthroplasty.

    Science.gov (United States)

    Amundson, Adam W; Johnson, Rebecca L; Abdel, Matthew P; Mantilla, Carlos B; Panchamia, Jason K; Taunton, Michael J; Kralovec, Michael E; Hebl, James R; Schroeder, Darrell R; Pagnano, Mark W; Kopp, Sandra L

    2017-06-01

    Multimodal analgesia is standard practice for total knee arthroplasty; however, the role of regional techniques in improved perioperative outcomes remains unknown. The authors hypothesized that peripheral nerve blockade would result in lower pain scores and opioid consumption than two competing periarticular injection solutions. This three-arm, nonblinded trial randomized 165 adults undergoing unilateral primary total knee arthroplasty to receive (1) femoral catheter plus sciatic nerve blocks, (2) ropivacaine-based periarticular injection, or (3) liposomal bupivacaine-based periarticular injection. Primary outcome was maximal pain during postoperative day 1 (0 to 10, numerical pain rating scale) in intention-to-treat analysis. Additional outcomes included pain scores and opioid consumption for postoperative days 0 to 2 and 3 months. One hundred fifty-seven study patients received peripheral nerve block (n = 50), ropivacaine (n = 55), or liposomal bupivacaine (n = 52) and reported median maximal pain scores on postoperative day 1 of 3, 4, and 4.5 and on postoperative day 0 of 1, 4, and 5, respectively (average pain scores for postoperative day 0: 0.6, 1.7, and 2.4 and postoperative day 1: 2.5, 3.5, and 3.7). Postoperative day 1 median maximal pain scores were significantly lower for peripheral nerve blockade compared to liposomal bupivacaine-based periarticular injection (P = 0.016; Hodges-Lehmann median difference [95% CI] = -1 [-2 to 0]). After postanesthesia care unit discharge, postoperative day 0 median maximal and average pain scores were significantly lower for peripheral nerve block compared to both periarticular injections (ropivacaine: maximal -2 [-3 to -1]; P bupivacaine: maximal -3 [-4 to -2]; P bupivacaine over ropivacaine in periarticular injections for total knee arthroplasty.

  12. Internet-based treatment for panic disorder: A three-arm randomized controlled trial comparing guided (via real-time video sessions) with unguided self-help treatment and a waitlist control. PAXPD study results.

    Science.gov (United States)

    Ciuca, Amalia M; Berger, Thomas; Crişan, Liviu G; Miclea, Mircea

    2018-05-01

    A growing body of evidence suggests that Internet-based cognitive behavioral treatments (ICBT) are effective to treat anxiety disorders. However, the effect of therapist guidance in ICBT is still under debate and guided ICBT offered in a real-time audio-video communication format has not yet been systematically investigated. This three-arm RCT compared the efficacy of guided with unguided ICBT (12 weeks intervention) and a waitlist (WL). A total of 111 individuals meeting the diagnostic criteria for panic disorder (PD) were randomly assigned to one of three conditions. Primary outcomes were the severity of self-report panic symptoms and diagnostic status. Secondary outcomes were symptoms of depression, functional impairment, catastrophic cognitions, fear of sensations and body vigilance. At post-treatment, both active conditions showed superior outcomes regarding PD and associated symptoms (guided ICBT vs. WL: d = 1.04-1.36; unguided ICBT vs. WL: d = 0.70-1.06). At post-treatment, the two active conditions did not differ significantly in self-reported symptom reduction (d = 0.21-0.54, all ps > 0.05), but the guided treatment was superior to the unguided treatment in terms of diagnostic status (χ 2 (1) = 13.15, p < 0.01). Treatment gains were maintained at successive follow-ups and the guided treatment became superior to the unguided treatment at 6 months follow-up (d = 0.72-1.05, all ps < 0.05). Copyright © 2018 Elsevier Ltd. All rights reserved.

  13. Financial disincentives? A three-armed randomised controlled trial of the effect of financial Incentives  in Diabetic Eye Assessment  by Screening (IDEAS) trial.

    Science.gov (United States)

    Judah, Gaby; Darzi, Ara; Vlaev, Ivo; Gunn, Laura; King, Derek; King, Dominic; Valabhji, Jonathan; Bicknell, Colin

    2018-05-23

    Conflicting evidence exists regarding the impact of financial incentives on encouraging attendance at medical screening appointments. The primary aim was to determine whether financial incentives increase attendance at diabetic eye screening in persistent non-attenders. A three-armed randomised controlled trial was conducted in London in 2015. 1051 participants aged over 16 years, who had not attended eye screening appointments for 2 years or more, were randomised (1.4:1:1 randomisation ratio) to receive the usual invitation letter (control), an offer of £10 cash for attending screening (fixed incentive) or a 1 in 100 chance of winning £1000 (lottery incentive) if they attend. The primary outcome was the proportion of invitees attending screening, and a comparative analysis was performed to assess group differences. Pairwise comparisons of attendance rates were performed, using a conservative Bonferroni correction for independent comparisons. 34/435 (7.8%) of control, 17/312 (5.5%) of fixed incentive and 10/304 (3.3%) of lottery incentive groups attended. Participants who received any incentive were significantly less likely to attend their appointment compared with controls (risk ratio (RR)=0.56; 95% CI 0.34 to 0.92). Those in the probabilistic incentive group (RR=0.42; 95% CI 0.18 to 0.98), but not the fixed incentive group (RR=1.66; 95% CI 0.65 to 4.21), were significantly less likely to attend than those in the control group. Financial incentives, particularly lottery-based incentives, attract fewer patients to diabetic eye screening than standard invites in this population. Financial incentives should not be used to promote screening unless tested in context, as they may negatively affect attendance rates. © Article author(s) (or their employer(s) unless otherwise stated in the text of the article) 2018. All rights reserved. No commercial use is permitted unless otherwise expressly granted.

  14. Phase behavior of model ABC triblock copolymers

    Science.gov (United States)

    Chatterjee, Joon

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

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

    Science.gov (United States)

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

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

  16. Ion Transport in Nanostructured Block Copolymer/Ionic Liquid Membranes

    OpenAIRE

    Hoarfrost, Megan Lane

    2012-01-01

    Incorporating an ionic liquid into one block copolymer microphase provides a platform for combining the outstanding electrochemical properties of ionic liquids with a number of favorable attributes provided by block copolymers. In particular, block copolymers thermodynamically self-assemble into well-ordered nanostructures, which can be engineered to provide a durable mechanical scaffold and template the ionic liquid into continuous ion-conducting nanochannels. Understanding how the additio...

  17. Reporting funding source or conflict of interest in abstracts of randomized controlled trials, no evidence of a large impact on general practitioners' confidence in conclusions, a three-arm randomized controlled trial.

    Science.gov (United States)

    Buffel du Vaure, Céline; Boutron, Isabelle; Perrodeau, Elodie; Ravaud, Philippe

    2014-04-28

    Systematic reporting of funding sources is recommended in the CONSORT Statement for abstracts. However, no specific recommendation is related to the reporting of conflicts of interest (CoI). The objective was to compare physicians' confidence in the conclusions of abstracts of randomized controlled trials of pharmaceutical treatment indexed in PubMed. We planned a three-arm parallel-group randomized trial. French general practitioners (GPs) were invited to participate and were blinded to the study's aim. We used a representative sample of 75 abstracts of pharmaceutical industry-funded randomized controlled trials published in 2010 and indexed in PubMed. Each abstract was standardized and reported in three formats: 1) no mention of the funding source or CoI; 2) reporting the funding source only; and 3) reporting the funding source and CoI. GPs were randomized according to a computerized randomization on a secure Internet system at a 1:1:1 ratio to assess one abstract among the three formats. The primary outcome was GPs' confidence in the abstract conclusions (0, not at all, to 10, completely confident). The study was planned to detect a large difference with an effect size of 0.5. Between October 2012 and June 2013, among 605 GPs contacted, 354 were randomized, 118 for each type of abstract. The mean difference (95% confidence interval) in GPs' confidence in abstract findings was 0.2 (-0.6; 1.0) (P = 0.84) for abstracts reporting the funding source only versus no funding source or CoI; -0.4 (-1.3; 0.4) (P = 0.39) for abstracts reporting the funding source and CoI versus no funding source and CoI; and -0.6 (-1.5; 0.2) (P = 0.15) for abstracts reporting the funding source and CoI versus the funding source only. We found no evidence of a large impact of trial report abstracts mentioning funding sources or CoI on GPs' confidence in the conclusions of the abstracts. ClinicalTrials.gov identifier: NCT01679873.

  18. Hybrid, Nanoscale Phospholipid/Block Copolymer Vesicles

    Directory of Open Access Journals (Sweden)

    Bo Liedberg

    2013-09-01

    Full Text Available Hybrid phospholipid/block copolymer vesicles, in which the polymeric membrane is blended with phospholipids, display interesting self-assembly behavior, incorporating the robustness and chemical versatility of polymersomes with the softness and biocompatibility of liposomes. Such structures can be conveniently characterized by preparing giant unilamellar vesicles (GUVs via electroformation. Here, we are interested in exploring the self-assembly and properties of the analogous nanoscale hybrid vesicles (ca. 100 nm in diameter of the same composition prepared by film-hydration and extrusion. We show that the self-assembly and content-release behavior of nanoscale polybutadiene-b-poly(ethylene oxide (PB-PEO/1-palmitoyl-2-oleoyl-sn-glycero-3-phosphatidylcholine (POPC hybrid phospholipid/block copolymer vesicles can be tuned by the mixing ratio of the amphiphiles. In brief, these hybrids may provide alternative tools for drug delivery purposes and molecular imaging/sensing applications and clearly open up new avenues for further investigation.

  19. Rapid ordering of block copolymer thin films

    International Nuclear Information System (INIS)

    Majewski, Pawel W; Yager, Kevin G

    2016-01-01

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

  20. Nanostructured Polysulfone-Based Block Copolymer Membranes

    KAUST Repository

    Xie, Yihui

    2016-05-01

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

  1. A Cationic Smart Copolymer for DNA Binding

    Directory of Open Access Journals (Sweden)

    Tânia Ribeiro

    2017-11-01

    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.

  2. SANS study of coated block copolymer micelles

    Czech Academy of Sciences Publication Activity Database

    Pleštil, Josef; Kříž, Jaroslav; Koňák, Čestmír; Pospíšil, Herman; Kadlec, Petr; Sedláková, Zdeňka; Grillo, I.; Cubitt, R.

    2005-01-01

    Roč. 206, č. 12 (2005), s. 1206-1215 ISSN 1022-1352 R&D Projects: GA ČR GA203/03/0600; GA AV ČR IAA1050201; GA AV ČR KSK4050111 Institutional research plan: CEZ:AV0Z40500505 Keywords : block copolymer micelles * core-shell polymers * nanoparticles Subject RIV: CD - Macromolecular Chemistry Impact factor: 2.111, year: 2005

  3. Increased radiation degradation in methyl methacrylate copolymers

    International Nuclear Information System (INIS)

    Helbert, J.N; Wagner, G.E.; Caplan, P.J.; Poindexter, E.H.

    1975-01-01

    The effect of polar substituents at the quaternary carbon on degradation processes in several polymers and 10 to 20 percent copolymers of methyl methacrylate was explored. EPR was used to monitor radiation degradation products and to determine radiation G values. Irradiations were carried out at 77 0 K in a gamma irradiator at a dose rate of 0.3 Mrad/hr. (U.S.)

  4. Surface morphology of PS-PDMS diblock copolymer films

    DEFF Research Database (Denmark)

    Andersen, T.H.; Tougaard, S.; Larsen, N.B.

    2001-01-01

    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 ra...

  5. 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

    2006-01-01

    ...: 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...

  6. Adsorption of charged diblock copolymers : effect on colloidal stability

    NARCIS (Netherlands)

    Israels, R.

    1994-01-01

    In this thesis we present Scheutjens-Fleer (SF) calculations on the adsorption of diblock copolymers. More specifically, we restrict ourselves to adsorption at uncharged surfaces, while the specific type of block copolymers we consider have one uncharged adsorbing "anchor" block and one

  7. Amphiphilic brushes from metallo-supramolecular block copolymers

    NARCIS (Netherlands)

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

    2009-01-01

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

  8. Polyether based segmented copolymers with uniform aramid units

    NARCIS (Netherlands)

    Niesten, M.C.E.J.

    2000-01-01

    Segmented copolymers with short, glassy or crystalline hard segments and long, amorphous soft segments (multi-block copolymers) are thermoplastic elastomers (TPE’s). The hard segments form physical crosslinks for the amorphous (rubbery) soft segments. As a result, this type of materials combines

  9. Morphological studies on block copolymer modified PA 6 blends

    Energy Technology Data Exchange (ETDEWEB)

    Poindl, M., E-mail: marcus.poindl@ikt.uni-stuttgart.de, E-mail: christian.bonten@ikt.uni-stuttgart.de; Bonten, C., E-mail: marcus.poindl@ikt.uni-stuttgart.de, E-mail: christian.bonten@ikt.uni-stuttgart.de [Institut für Kunststofftechnik, University of Stuttgart (Germany)

    2014-05-15

    Recent studies show that compounding polyamide 6 (PA 6) with a PA 6 polyether block copolymers made by reaction injection molding (RIM) or continuous anionic polymerization in a reactive extrusion process (REX) result in blends with high impact strength and high stiffness compared to conventional rubber blends. In this paper, different high impact PA 6 blends were prepared using a twin screw extruder. The different impact modifiers were an ethylene propylene copolymer, a PA PA 6 polyether block copolymer made by reaction injection molding and one made by reactive extrusion. To ensure good particle matrix bonding, the ethylene propylene copolymer was grafted with maleic anhydride (EPR-g-MA). Due to the molecular structure of the two block copolymers, a coupling agent was not necessary. The block copolymers are semi-crystalline and partially cross-linked in contrast to commonly used amorphous rubbers which are usually uncured. The combination of different analysis methods like atomic force microscopy (AFM), transmission electron microscopy (TEM) and scanning electron microscopy (SEM) gave a detailed view in the structure of the blends. Due to the partial cross-linking, the particles of the block copolymers in the blends are not spherical like the ones of ethylene propylene copolymer. The differences in molecular structure, miscibility and grafting of the impact modifiers result in different mechanical properties and different blend morphologies.

  10. Antimicrobial activity of poly(acrylic acid) block copolymers

    Energy Technology Data Exchange (ETDEWEB)

    Gratzl, Günther, E-mail: guenther.gratzl@jku.at [Johannes Kepler University Linz, Institute for Chemical Technology of Organic Materials, Altenberger Str. 69, 4040 Linz (Austria); Paulik, Christian [Johannes Kepler University Linz, Institute for Chemical Technology of Organic Materials, Altenberger Str. 69, 4040 Linz (Austria); Hild, Sabine [Johannes Kepler University Linz, Institute of Polymer Science, Altenberger Str. 69, 4040 Linz (Austria); Guggenbichler, Josef P.; Lackner, Maximilian [AMiSTec GmbH and Co. KG, Leitweg 13, 6345 Kössen, Tirol (Austria)

    2014-05-01

    The increasing number of antibiotic-resistant bacterial strains has developed into a major health problem. In particular, biofilms are the main reason for hospital-acquired infections and diseases. Once formed, biofilms are difficult to remove as they have specific defense mechanisms against antimicrobial agents. Antimicrobial surfaces must therefore kill or repel bacteria before they can settle to form a biofilm. In this study, we describe that poly(acrylic acid) (PAA) containing diblock copolymers can kill bacteria and prevent from biofilm formation. The PAA diblock copolymers with poly(styrene) and poly(methyl methacrylate) were synthesized via anionic polymerization of tert-butyl acrylate with styrene or methyl methacrylate and subsequent acid-catalyzed hydrolysis of the tert-butyl ester. The copolymers were characterized via nuclear magnetic resonance spectroscopy (NMR), size-exclusion chromatography (SEC), Fourier transform infrared spectroscopy (FTIR), elemental analysis, and acid–base titrations. Copolymer films with a variety of acrylic acid contents were produced by solvent casting, characterized by atomic force microscopy (AFM) and tested for their antimicrobial activity against Staphylococcus aureus, Escherichia coli, and Pseudomonas aeruginosa. The antimicrobial activity of the acidic diblock copolymers increased with increasing acrylic acid content, independent of the copolymer-partner, the chain length and the nanostructure. - Highlights: • Acrylic acid diblock copolymers are antimicrobially active. • The antimicrobial activity depends on the acrylic acid content in the copolymer. • No salts, metals or other antimicrobial agents are needed.

  11. Antimicrobial activity of poly(acrylic acid) block copolymers

    International Nuclear Information System (INIS)

    Gratzl, Günther; Paulik, Christian; Hild, Sabine; Guggenbichler, Josef P.; Lackner, Maximilian

    2014-01-01

    The increasing number of antibiotic-resistant bacterial strains has developed into a major health problem. In particular, biofilms are the main reason for hospital-acquired infections and diseases. Once formed, biofilms are difficult to remove as they have specific defense mechanisms against antimicrobial agents. Antimicrobial surfaces must therefore kill or repel bacteria before they can settle to form a biofilm. In this study, we describe that poly(acrylic acid) (PAA) containing diblock copolymers can kill bacteria and prevent from biofilm formation. The PAA diblock copolymers with poly(styrene) and poly(methyl methacrylate) were synthesized via anionic polymerization of tert-butyl acrylate with styrene or methyl methacrylate and subsequent acid-catalyzed hydrolysis of the tert-butyl ester. The copolymers were characterized via nuclear magnetic resonance spectroscopy (NMR), size-exclusion chromatography (SEC), Fourier transform infrared spectroscopy (FTIR), elemental analysis, and acid–base titrations. Copolymer films with a variety of acrylic acid contents were produced by solvent casting, characterized by atomic force microscopy (AFM) and tested for their antimicrobial activity against Staphylococcus aureus, Escherichia coli, and Pseudomonas aeruginosa. The antimicrobial activity of the acidic diblock copolymers increased with increasing acrylic acid content, independent of the copolymer-partner, the chain length and the nanostructure. - Highlights: • Acrylic acid diblock copolymers are antimicrobially active. • The antimicrobial activity depends on the acrylic acid content in the copolymer. • No salts, metals or other antimicrobial agents are needed

  12. Radiation crosslinked block copolymer blends with improved impact resistance

    International Nuclear Information System (INIS)

    Saunders, F.L.; Pelletier, R.R.

    1976-01-01

    Polymer blends having high impact resistance after mechanical working are produced by blending together a non-elastomeric monovinylidene aromatic polymer such as polystyrene with an elastomeric copolymer, such as a block copolymer of styrene and butadiene, in the form of crosslinked, colloidal size particles

  13. Characteristics of immobilized aminoacylase from Aspergillus oryzae on macroporous copolymers.

    Science.gov (United States)

    He, B L; Jiang, P; Qiu, Y B

    1990-01-01

    Aminoacylase from Aspergillus oryzae was adsorbed on functionallized macroporous copolymers where the enzyme showed excellent catalyzing activity and operation stability. Various factors which effect the activity of the immobilized aminoacylase such as temperature, pH and ionic strength were investigated. The continuous operation of the enzyme immobilized on macroporous copolymers was compared with that of the enzyme immobilized on DEAE-Sephadex.

  14. Synthesis and characterization of waterborne polyurethane acrylate copolymers

    International Nuclear Information System (INIS)

    Sultan, Misbah; Bhatti, Haq Nawaz; Zuber, Mohammad; Barikani, Mehdi

    2013-01-01

    Polyurethane acrylate copolymers were synthesized by emulsion polymerization process. To reduce the environmental hazards, organic solvents were replaced by eco-friendly aqueous system. Concentration of polyurethane and acrylate monomer was varied to investigate the effect of chemical composition on performance properties of copolymers. FTIR spectroscopy was used as a key tool to record the chemical synthesis route. The synthesized copolymer emulsions were characterized by evaluating their particle size, viscosity, dry weight content, chemical and water resistance. Thermal decomposition was studied by thermogravimetric analysis. Scanning electron microscope was used to visualize the morphological structure of copolymers. The experimental results indicate better polyurethane acrylate compatibility till the ratio of 30/70. However, these copolymers exhibited synergistic effects between the two polymers and revealed a remarkable improvement in numerous coating properties

  15. Sulfomethylated graft copolymers of xanthan gum and polyacrylamide

    Energy Technology Data Exchange (ETDEWEB)

    Cottrell, I.W.; Empey, R.A.; Racciato, J.S.

    1978-08-08

    A water-soluble anionic graft copolymer of xanthan gum and polyacrylamide is described in which at least part of the amide function of the acrylamide portion of the copolymer is sulfomethylated and the xanthan gum portion of the copolymer is unreacted with formaldehyde. The copolymer is sulfomethylated by reaction with formaldehyde and sodium metabisulfite. The formaldehyde does not cause any appreciable cross-linking between hydroxyl groups of the xanthan moieties. The sulfomethylation of the acrylamido group takes place at temperatures from 35 to 70 C. The pH is 10 or higher, typically from 12 to 13. The degree of anionic character may be varied by adjusting the molar ratio of formaldehyde and sodium metabisulfite with respect to the copolymer. 10 claims.

  16. Process of irradiating an ethylene-vinyl acetate copolymer to produce low melt index copolymers, and products of said process

    International Nuclear Information System (INIS)

    Potts, J.E.

    1976-01-01

    Application of ionizing radiation in a dose between 0.5 and 1.5 megareps to copolymers of ethylene and vinyl acetate lowers the melt index and increases the toughness and flexibility of the copolymers without substantially decreasing solubility or thermoplasticity. The increased toughness and flexibility carries over into blends with wax or polyethylene. (author)

  17. Ionization of amphiphilic acidic block copolymers.

    Science.gov (United States)

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

    2012-06-28

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

  18. Amphiphilic block copolymers for drug delivery.

    Science.gov (United States)

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

    2003-07-01

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

  19. 21 CFR 177.1570 - Poly-1-butene resins and butene/ethylene copolymers.

    Science.gov (United States)

    2010-04-01

    ... 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...

  20. Anomalous Micellization of Pluronic Block Copolymers

    Science.gov (United States)

    Leonardi, Amanda; Ryu, Chang Y.

    2014-03-01

    Poly(ethylene oxide) - poly(propylene oxide) - poly(ethylene oxide) (PEO-PPO-PEO) block copolymers, commercially known as Pluronics, are a unique family of amphiphilic triblock polymers, which self-assemble into micelles in aqueous solution. These copolymers have shown promise in therapeutic, biomedical, cosmetic, and nanotech applications. As-received samples of Pluronics contain low molecular weight impurities (introduced during the manufacturing and processing), that are ignored in most applications. It has been observed, however, that in semi-dilute aqueous solutions, at concentrations above 1 wt%, the temperature dependent micellization behavior of the Pluronics is altered. Anomalous behavior includes a shift of the critical micellization temperature and formation of large aggregates at intermediate temperatures before stable sized micelles form. We attribute this behavior to the low molecular weight impurities that are inherent to the Pluronics which interfere with the micellization process. Through the use of Dynamic Light Scattering and HPLC, we compared the anomalous behavior of different Pluronics of different impurity levels to their purified counterparts.

  1. Responsive linear-dendritic block copolymers.

    Science.gov (United States)

    Blasco, Eva; Piñol, Milagros; Oriol, Luis

    2014-06-01

    The combination of dendritic and linear polymeric structures in the same macromolecule opens up new possibilities for the design of block copolymers and for applications of functional polymers that have self-assembly properties. There are three main strategies for the synthesis of linear-dendritic block copolymers (LDBCs) and, in particular, the emergence of click chemistry has made the coupling of preformed blocks one of the most efficient ways of obtaining libraries of LDBCs. In these materials, the periphery of the dendron can be precisely functionalised to obtain functional LDBCs with self-assembly properties of interest in different technological areas. The incorporation of stimuli-responsive moieties gives rise to smart materials that are generally processed as self-assemblies of amphiphilic LDBCs with a morphology that can be controlled by an external stimulus. Particular emphasis is placed on light-responsive LDBCs. Furthermore, a brief review of the biomedical or materials science applications of LDBCs is presented. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Bactericidal and Hemocompatible Coating via the Mixed-Charged Copolymer.

    Science.gov (United States)

    Fan, Xiao-Li; Hu, Mi; Qin, Zhi-Hui; Wang, Jing; Chen, Xia-Chao; Lei, Wen-Xi; Ye, Wan-Ying; Jin, Qiao; Ren, Ke-Feng; Ji, Jian

    2018-03-28

    Cationic antibacterial coating based on quaternary ammonium compounds, with an efficient and broad spectrum bactericidal property, has been widely used in various fields. However, the high density of positive charges tends to induce weak hemocompatibility, which hinders the application of the cationic antibacterial coating in blood-contacting devices and implants. It has been reported that a negatively charged surface can reduce blood coagulation, showing improved hemocompatibility. Here, we describe a strategy to combine the cationic and anionic groups by using mixed-charged copolymers. The copolymers of poly (quaternized vinyl pyridine- co- n-butyl methacrylate- co-methacrylate acid) [P(QVP- co- nBMA- co-MAA)] were synthesized through free radical copolymerization. The cationic group of QVP, the anionic group of MAA, and the hydrophobic group of nBMA were designed to provide bactericidal capability, hemocompatibility, and coating stability, respectively. Our findings show that the hydrophilicity of the copolymer coating increased, and its zeta potential decreased from positive charge to negative charge with the increase of the anionic/cationic ratio. Meanwhile, the bactericidal property of the copolymer coating was kept around a similar level compared with the pure quaternary ammonium copolymer coating. Furthermore, the coagulation time, platelet adhesion, and hemolysis tests revealed that the hemocompatibility of the copolymer coating improved with the addition of the anionic group. The mixed-charged copolymer combined both bactericidal property and hemocompatibility and has a promising potential in blood-contacting antibacterial devices and implants.

  3. Incorporation of fluconazole in copolymer PMMA-g-PEG derivatives

    International Nuclear Information System (INIS)

    Silveira, B.M.; Santos, V.M.R. dos; Novack, K.M.; Lopes, S.A.

    2014-01-01

    The graft copolymer PMMA-g-PEG went through chemical transformations in its chain through acetylation, halogenation, methylation and esterification followed by hydrolysis reactions. Subsequently, the copolymer PMMA-g-PEG derivatives passed through the process of emulsification and incorporation of the drug fluconazole. Derivatives copolymers were characterized by infrared spectroscopy (FTIR), X-ray diffraction (XRD) and scanning electron microscopy (SEM) after incorporation in order to evaluate their effectiveness. The efficiency of incorporation was observed and it was also verified that the complexity of polymer chain influence in the incorporated fluconazole content. (author)

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

    Science.gov (United States)

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

    2015-04-14

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

  5. Mechanical properties of weakly segregated block copolymers : 1. Synergism on tensile properties of poly(styrene-b-n-butylmethacrylate) diblock copolymers

    NARCIS (Netherlands)

    Weidisch, R.; Michler, G.H.; Fischer, H.; Arnold, M.; Hofmann, S.; Stamm, M.

    1999-01-01

    Mechanical properties of poly(styrene-b-n-butylmethacrylate) diblock copolymers, PS-b-PBMA, with different lengths of the polystyrene block were investigated. The copolymers display a composition range where the tensile strength of the block copolymers exceeds the values of the corresponding

  6. Synthesis of graft copolymers onto starch and its semiconducting properties

    Directory of Open Access Journals (Sweden)

    Nevin Çankaya

    Full Text Available Literature review has revealed that, although there are studies about grafting on natural polymers, especially on starch, few of them are about electrical properties of graft polymers. Starch methacrylate (St.met was obtained by esterification of OH groups on natural starch polymer for this purpose. Grafting of synthesized N-cyclohexyl acrylamide (NCA and commercial methyl methacrylate (MMA monomers with St.met was done by free radical polymerization method. The graft copolymers were characterized with FT-IR spectra, thermal and elemental analysis. Thermal stabilities of the graft copolymers were determined by TGA (thermo gravimetric analysis method and thermal stability of the copolymers is decreased via grafting. The electrical conductivity of the polymers was measured as a function of temperature and it has been observed that electrical conductivity increases with increasing temperature. The absorbance and transmittance versus wavelength of the polymers have been measured. Keywords: Starch, Graft copolymer, Semiconducting, Thermal stability, Starch methacrylate

  7. HPMA and HEMA copolymer bead interactions with eukaryotic cells

    Directory of Open Access Journals (Sweden)

    Cristina D. Vianna-Soares

    2004-09-01

    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.

  8. Controlled Synthesis of Fluorinated Copolymers with Pendant Sulfonates

    DEFF Research Database (Denmark)

    Dimitrov, Ivaylo; Jankova Atanasova, Katja; Hvilsted, Søren

    2008-01-01

    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 ...

  9. Fast & scalable pattern transfer via block copolymer nanolithography

    DEFF Research Database (Denmark)

    Li, Tao; Wang, Zhongli; Schulte, Lars

    2015-01-01

    A fully scalable and efficient pattern transfer process based on block copolymer (BCP) self-assembling directly on various substrates is demonstrated. PS-rich and PDMS-rich poly(styrene-b-dimethylsiloxane) (PS-b-PDMS) copolymers are used to give monolayer sphere morphology after spin-casting of s......A fully scalable and efficient pattern transfer process based on block copolymer (BCP) self-assembling directly on various substrates is demonstrated. PS-rich and PDMS-rich poly(styrene-b-dimethylsiloxane) (PS-b-PDMS) copolymers are used to give monolayer sphere morphology after spin...... on long range lateral order, including fabrication of substrates for catalysis, solar cells, sensors, ultrafiltration membranes and templating of semiconductors or metals....

  10. Self-Assembly of Rod-Coil Block Copolymers

    National Research Council Canada - National Science Library

    Jenekhe, S

    1999-01-01

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

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

    KAUST Repository

    Sutisna, Burhannudin; Polymeropoulos, Georgios; Musteata, Valentina-Elena; Peinemann, Klaus-Viktor; Avgeropoulos, Apostolos; Smilgies, Detlef-M.; Hadjichristidis, Nikolaos; Nunes, Suzana Pereira

    2016-01-01

    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

  12. Opto-electronic devices from block copolymers and their oligomers.

    NARCIS (Netherlands)

    Hadziioannou, G

    1997-01-01

    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. 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

  14. Molecular weight and its distribution of tetrafluoroethylene and propylene copolymer

    International Nuclear Information System (INIS)

    Watanabe, Hiromasa; Okamoto, Jiro; Yamaguchi, Koichi.

    1978-04-01

    In comparison of molecular structure of tetrafluoroethylene and propylene copolymer produced by radiation and chemical initiators respectively, both were fractionated by elution method and fine structure was examined. For the fractionated sample by radiation, the relation between molecular weight anti Mn and intrinsic viscosity ( eta] is ( eta] = 3.97 x 10 -4 anti Mnsup(0.630) The result is not in agreement with that of the unfractionated sample by radiation, and similar to those of samples by chemical initiators. There is no difference, however, in the elution method of GPC between both these copolymers; the elution behavior agrees with that of standard polystyrene. Long chain branching thus exists little in the copolymer of tetrafluoroethylene and propylene. To reveal the relations between reaction conditions and molecular weight and its distribution of the copolymer produced by flow apparatus, the molecular weight distribution was measured by GPC. The method of analysis could evaluate molecular weight distribution changing constantly. (auth.)

  15. Designing block copolymer architectures for targeted membrane performance

    KAUST Repository

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

    2014-01-01

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

  16. Block copolymer/homopolymer dual-layer hollow fiber membranes

    KAUST Repository

    Hilke, Roland; Neelakanda, Pradeep; Behzad, Ali Reza; Nunes, Suzana Pereira; Peinemann, Klaus-Viktor

    2014-01-01

    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

  17. Fluctuations, conformational asymmetry and block copolymer phase behaviour

    DEFF Research Database (Denmark)

    Bates, F.S.; Schulz, M.F.; Khandpur, A.K.

    1994-01-01

    Phase behaviour near the order-disorder transition (ODT) of 58 model hydrocarbon diblock copolymers, representing four different systems, is summarized. Six distinct ordered-state microstructures are reported, including hexagonally modulated lamellae (HML), hexagonally perforated layers (HPL) and...

  18. Surface dynamics of micellar diblock copolymer films

    Science.gov (United States)

    Song, Sanghoon; Cha, Wonsuk; Kim, Hyunjung; Jiang, Zhang; Narayanan, Suresh

    2011-03-01

    We studied the structure and surface dynamics of poly(styrene)-b-poly(dimethylsiloxane) (PS-b-PDMS) diblock copolymer films with micellar PDMS surrounded by PS shells. By `in-situ' high resolution synchrotron x-ray reflectivity and diffuse scattering, we obtained exact thickness, electron density and surface tension. A segregation layer near the top surface was appeared with increasing temperature Surface dynamics were measured as a function of film thickness and temperature by x-ray photon correlation spectroscopy. The best fit to relaxation time constants as a function of in-plane wavevectors were analyzed with a theory based on capillary waves with hydrodynamics with bilayer model Finally the viscosities for the top segregated layer as well as for the bottom layer are obtained at given temperatures This work was supported by National Research Foundation of Korea (R15-2008-006-01001-0), Seoul Research and Business Development Program (10816), and Sogang University Research Grant (2010).

  19. Restructuring in block copolymer thin films

    DEFF Research Database (Denmark)

    Posselt, Dorthe; Zhang, Jianqi; Smilgies, Detlef-M.

    2017-01-01

    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...... thin films, e.g., by healing defects, by altering the orientation of the microdomains and by changing the morphology. Due to high time resolution and compatibility with SVA environments, grazing-incidence small-angle X-ray scattering (GISAXS) is an indispensable technique for studying the SVA process......, providing information of the BCP thin film structure both laterally and along the film normal. Especially, state-of-the-art combined GISAXS/SVA setups at synchrotron sources have facilitated in situ and real-time studies of the SVA process with a time resolution of a few seconds, giving important insight...

  20. Thin Film Assembly of Spider Silk-like Block Copolymers

    Science.gov (United States)

    2011-01-01

    Shipley, N. H.; Lewis, R. V. Int. J. Biol.Macromol. 1999, 24, 271. (c) Thiel, B. L.; Guess, K. B.; Viney, C. Biopolymers 1997, 41, 703. (13) Silk ...Film Assembly of Spider Silk -like Block Copolymers Sreevidhya T. Krishnaji,†,‡ Wenwen Huang,§ Olena Rabotyagova,†,‡ Eugenia Kharlampieva, ) Ikjun Choi...Received November 26, 2010 We report the self-assembly of monolayers of spider silk -like block copolymers. Langmuir isotherms were obtained for a series of

  1. Theory of Primary Photoexcitations in Donor-Acceptor Copolymers

    OpenAIRE

    Aryanpour, Karan; Dutta, Tirthankar; Huynh, Uyen N. V.; Vardeny, Zeev Valy; Mazumdar, Sumit

    2015-01-01

    We present a generic theory of primary photoexcitations in low band gap donor-acceptor conjugated copolymers. Because of the combined effects of strong electron correlations and broken symmetry, there is considerable mixing between a charge-transfer exciton and an energetically proximate triplet-triplet state with an overall spin singlet. The triplet-triplet state, optically forbidden in homopolymers, is allowed in donor-acceptor copolymers. For an intermediate difference in electron affiniti...

  2. Biodegradable copolymers carrying cell-adhesion peptide sequences.

    Science.gov (United States)

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

    2003-01-01

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

  3. Microbial production of polyhydroxyalkanoate block copolymer by recombinant Pseudomonas putida.

    Science.gov (United States)

    Li, Shi Yan; Dong, Cui Ling; Wang, Shen Yu; Ye, Hai Mu; Chen, Guo-Qiang

    2011-04-01

    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. 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...... 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....

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

    OpenAIRE

    Zhang, Qian

    2007-01-01

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

  6. Electrorheological Properties of Suspensions Prepared from Polystyrene- Block- Polyisoprene Copolymer

    OpenAIRE

    YAVUZ, Mustafa

    2014-01-01

    Considerable scientific and industrial interest is currently being focused on a class of materials known as electrorheological (ER) fluids, which display remarkable rheological behaviour, being able to convert rapidly and repeatedly from a liquid to solid when an electric field (E) is applied or removed. In this article, the synthesis, characterization, partial hydrolysis and ER properties of polystyrene- block}-polyisoprene copolymer (COP) were investigated. The block copolymer was ...

  7. Self-assembled Block Copolymer Membranes with Bioinspired Artificial Channels

    KAUST Repository

    Sutisna, Burhannudin

    2018-04-01

    Nature is an excellent design that inspires scientists to develop smart systems. In the realm of separation technology, biological membranes have been an ideal model for synthetic membranes due to their ultrahigh permeability, sharp selectivity, and stimuliresponse. In this research, fabrications of bioinspired membranes from block copolymers were studied. Membranes with isoporous morphology were mainly prepared using selfassembly and non-solvent induced phase separation (SNIPS). An effective method that can dramatically shorten the path for designing new isoporous membranes from block copolymers via SNIPS was first proposed by predetermining a trend line computed from the solvent properties, interactions and copolymer block sizes of previously-obtained successful systems. Application of the method to new copolymer systems and fundamental studies on the block copolymer self-assembly were performed. Furthermore, the manufacture of bioinspired membranes was explored using (1) poly(styrene-b-4-hydroxystyrene-b-styrene) (PS-b-PHS-b-PS), (2) poly(styrene-bbutadiene- b-styrene) (PS-b-PB-b-PS) and (3) poly(styrene-b-γ-benzyl-L-glutamate) (PSb- PBLG) copolymers via SNIPS. The structure formation was investigated using smallangle X-ray scattering (SAXS) and time-resolved grazing-Incidence SAXS. The PS-b- PHS-b-PS membranes showed preferential transport for proteins, presumably due to the hydrogen bond interactions within the channels, electrostatic attraction, and suitable pore dimension. Well-defined nanochannels with pore sizes of around 4 nm based on PS-b- PB-b-PS copolymers could serve as an excellent platform to fabricate bioinspired channels due to the modifiable butadiene blocks. Photolytic addition of thioglycolic acid was demonstrated without sacrificing the self-assembled morphology, which led to a five-fold increase in water permeance compared to that of the unmodified. Membranes with a unique feather-like structure and a lamellar morphology for dialysis and

  8. A Study on Copolymer Systems of Styrene with Diethanolamine Side Group and Methyl Methacrylate

    Directory of Open Access Journals (Sweden)

    Aslisah Acikses

    2018-01-01

    Full Text Available 4-Diethanolaminomethyl styrene (DEAMSt monomer was prepared by the modification of 4-chloromethyl styrene with diethanolamine. The copolymers in different combinations (0.11, 0.19, and 0.30 by mole of DEAMSt and methyl methacrylate (MMA were prepared by free radical polymerization method at 60°C in the presence of 1,4-dioxane and AIBN as initiator. The structures of DEAMSt and DEAMSt-MMA copolymer were characterized by FT-IR and 1H-NMR. The glass transition temperature (Tg of the copolymers was measured by DSC. Thermal decomposition behavior of the copolymers was investigated by TGA. The average molecular weights of the copolymers were determined by GPC. The dye uptaking properties of the copolymers were investigated using bromocresol green. Then, the dielectric constant, dielectric loss factor, and conductivity of copolymers were investigated as a function of temperature and frequency. The activation energies (Ea of the copolymers were determined by impedance analyzer.

  9. Tuning the Optoelectronic Properties of Vinylene-Linked Donor−Acceptor Copolymers for Organic Photovoltaics

    KAUST Repository

    Ko, Sangwon; Mondal, Rajib; Risko, Chad; Lee, Jung Kyu; Hong, Sanghyun; McGehee, Michael D.; Brédas, Jean-Luc; Bao, Zhenan

    2010-01-01

    -property relationships in organic photovoltaic devices. Both alternating (P) and random copolymers (P1-P4) were prepared via Suzuki and Stille polycondensations, respectively. The cyclopentadithiophene copolymers (P2 and P4) have smaller electrochemical band gaps (1

  10. Monte Carlo simulations of the phase separation of a copolymer blend in a thin film

    KAUST Repository

    Wang, Zhexiao

    2014-12-11

    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.

  11. Triplet State Formation in Photovoltaic Blends of DPP-Type Copolymers and PC71BM

    KAUST Repository

    Ochsmann, Julian R.; Chandran, Deepak; Gehrig, Dominik W.; Anwar, Husna; Madathil, Pramod Kandoth; Lee, Kwang-Sup; Laquai, Fré dé ric

    2015-01-01

    The exciton dynamics in pristine films of two structurally related low-bandgap diketopyrrolopyrrole (DPP)-based donor–acceptor copolymers and the photophysical processes in bulk heterojunction solar cells using DPP copolymer:PC71BM blends

  12. CO2-Philic Thin Film Composite Membranes: Synthesis and Characterization of PAN-r-PEGMA Copolymer

    KAUST Repository

    Karunakaran, Madhavan; Kumar, Mahendra; Shevate, Rahul; Akhtar, Faheem Hassan; Peinemann, Klaus-Viktor

    2017-01-01

    amounts of PEG content was synthesized by free radical polymerization in presence of AIBN initiator and the obtained copolymers were used for the fabrication of composite membranes. The synthesized copolymers show high molecular weights in the range of 44

  13. Incomplete copolymer degradation of in situ chemotherapy.

    Science.gov (United States)

    Bourdillon, Pierre; Boissenot, Tanguy; Goldwirt, Lauriane; Nicolas, Julien; Apra, Caroline; Carpentier, Alexandre

    2018-02-17

    In situ carmustine wafers containing 1,3-bis(2-chloroethyl)-1-nitrosourea (BCNU) are commonly used for the treatment of recurrent glioblastoma to overcome the brain-blood barrier. In theory, this chemotherapy diffuses into the adjacent parenchyma and the excipient degrades in maximum 8 weeks but no clinical data confirms this evolution, because patients are rarely operated again. A 75-year-old patient was operated twice for recurrent glioblastoma, and a carmustine wafer was implanted during the second surgery. Eleven months later, a third surgery was performed, revealing unexpected incomplete degradation of the wafer. 1H-Nuclear Magnetic Resonance was performed to compare this wafer to pure BCNU and to an unused copolymer wafer. In the used wafer, peaks corresponding to hydrophobic units of the excipient were no longer noticeable, whereas peaks of the hydrophilic units and traces of BCNU were still present. These surprising results could be related to the formation of a hydrophobic membrane around the wafer, thus interfering with the expected diffusion and degradation processes. The clinical benefit of carmustine wafers in addition to the standard radio-chemotherapy remains limited, and in vivo behavior of this treatment is not completely elucidated yet. We found that the wafer may remain after several months. Alternative strategies to deal with the blood-brain barrier, such as drug-loaded liposomes or ultrasound-opening, must be explored to offer larger drug diffusion or allow repetitive delivery.

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

    KAUST Repository

    Sutisna, Burhannudin

    2016-05-18

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

  15. SANS and SAXS study of block copolymer/homopolymer mixtures

    International Nuclear Information System (INIS)

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

    1991-01-01

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

  16. Relaxation processes in a lower disorder order transition diblock copolymer

    International Nuclear Information System (INIS)

    Sanz, Alejandro; Ezquerra, Tiberio A.; Nogales, Aurora; Hernández, Rebeca; Sprung, Michael

    2015-01-01

    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 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

  17. Highly conductive side chain block copolymer anion exchange membranes.

    Science.gov (United States)

    Wang, Lizhu; Hickner, Michael A

    2016-06-28

    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.

  18. Synthesis, characterization and antimicrobial activity of important heterocyclic acrylic copolymers

    Directory of Open Access Journals (Sweden)

    2008-10-01

    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. Controlling block copolymer phase behavior using ionic surfactant

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-05-23

    The phase behavior of poly(ethylene oxide)-poly(propylene oxide-poly(ethylene oxide) PEO-PPO-PEO triblock copolymer [P85 (EO{sub 26}PO{sub 39}EO{sub 26})] in presence of anionic surfactant sodium dodecyl sulfate (SDS) in aqueous solution as a function of temperature has been studied using dynamic light scattering (DLS) and small-angle neutron scattering (SANS). The measurements have been carried out for fixed concentrations (1 wt%) of block copolymer and surfactants. Each of the individual components (block copolymer and surfactant) and the nanoparticle–surfactant mixed system have been examined at varying temperature. The block copolymer P85 forms spherical micelles at room temperature whereas shows sphere-to-rod like micelle transition at higher temperatures. On the other hand, SDS surfactant forms ellipsoidal micelles over a wide temperature range. Interestingly, it is found that phase behavior of mixed micellar system (P85 + SDS) as a function of temperature is drastically different from that of P85, giving the control over the temperature-dependent phase behavior of block copolymers.

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

    KAUST Repository

    Peinemann, Klaus-Viktor; Karunakaran, Madhavan

    2015-01-01

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

  1. 78 FR 20032 - Styrene-Ethylene-Propylene Block Copolymer; Tolerance Exemption

    Science.gov (United States)

    2013-04-03

    ...-Ethylene-Propylene Block Copolymer; Tolerance Exemption AGENCY: Environmental Protection Agency (EPA... for residues of styrene-ethylene-propylene block copolymer (CAS Reg. No. 108388-87-0) when used as an...-ethylene-propylene block copolymer on food or feed commodities. DATES: This regulation is effective April 3...

  2. 21 CFR 177.1360 - Ethylene-vinyl acetate-vinyl alcohol copolymers.

    Science.gov (United States)

    2010-04-01

    ... 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...

  3. 21 CFR 177.1340 - Ethylene-methyl acrylate copolymer resins.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Ethylene-methyl acrylate copolymer resins. 177.1340... Basic Components of Single and Repeated Use Food Contact Surfaces § 177.1340 Ethylene-methyl acrylate copolymer resins. Ethylene-methyl acrylate copolymer resins may be safely used as articles or components of...

  4. Realization of an integrated VDF/TrFE copolymer-on-silicon pyroelectric sensor

    NARCIS (Netherlands)

    Setiadi, D.; Setiadi, D.; Regtien, Paulus P.L.; Sarro, P.M.

    1995-01-01

    An integrated pyroelectric sensor based on a vinylidene fluoride trifluoroethylene (VDF/TrFE) copolymer is presented. A silicon substrate that contains FET readout electronics is coated with the VDF/TrFE copolymer film using a spin-coating technique. On-chip poling of the copolymer has been applied

  5. 40 CFR 180.1162 - Acrylate polymers and copolymers; exemption from the requirement of a tolerance.

    Science.gov (United States)

    2010-07-01

    ... 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...

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

    KAUST Repository

    Peinemann, Klaus-Viktor

    2015-04-16

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

  7. 21 CFR 177.1020 - Acrylonitrile/butadiene/sty-rene co-polymer.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Acrylonitrile/butadiene/sty-rene co-polymer. 177... SERVICES (CONTINUED) FOOD FOR HUMAN CONSUMPTION (CONTINUED) INDIRECT FOOD ADDITIVES: POLYMERS Substances.../butadiene/sty-rene co-polymer. Acrylonitrile/butadiene/styrene copolymer identified in this section may be...

  8. Block copolymer/homopolymer dual-layer hollow fiber membranes

    KAUST Repository

    Hilke, Roland

    2014-12-01

    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.

  9. Morphologies of precise polyethylene-based acid copolymers and ionomers

    Science.gov (United States)

    Buitrago, C. Francisco

    Acid copolymers and ionomers are polymers that contain a small fraction of covalently bound acidic or ionic groups, respectively. For the specific case of polyethylene (PE), acid and ionic pendants enhance many of the physical properties such as toughness, adhesion and rheological properties. These improved properties result from microphase separated aggregates of the polar pendants in the non-polar PE matrix. Despite the widespread industrial use of these materials, rigorous chemical structure---morphology---property relationships remain elusive due to the inevitable structural heterogeneities in the historically-available acid copolymers and ionomers. Recently, precise acid copolymers and ionomers were successfully synthesized by acyclic diene metathesis (ADMET) polymerization. These precise materials are linear, high molecular weight PEs with pendant acid or ionic functional groups separated by a precisely controlled number of carbon atoms. The morphologies of nine precise acid copolymers and eleven precise ionomers were investigated by X-ray scattering, solid-state 13C nuclear magnetic resonance (NMR) and differential scanning calorimetry (DSC). For comparison, the morphologies of linear PEs with pseudo-random placement of the pendant groups were also studied. Previous studies of precise copolymers with acrylic acid (AA) found that the microstructural precision produces a new morphology in which PE crystals drive the acid aggregates into layers perpendicular to the chain axes and presumably at the interface between crystalline and amorphous phases. In this dissertation, a second new morphology for acid copolymers is identified in which the aggregates arrange on cubic lattices. The fist report of a cubic morphology was observed at room and elevated temperatures for a copolymer functionalized with two phosphonic acid (PA) groups on every 21st carbon atom. The cubic lattice has been identified as face-centered cubic (FCC). Overall, three morphology types have been

  10. Low molecular weight block copolymers as plasticizers for polystyrene

    DEFF Research Database (Denmark)

    Hansen, Kristoffer Karsten; Nielsen, Charlotte Juel; Hvilsted, Søren

    2005-01-01

    /mol and minimum polystyrene content of 50 w/w%, which by us is predicted as the limits for solubility of polystyrene-b-alkyl in polystyrene. DSC showed polystyrene was plasticized, as seen by a reduction in glass transition temperature, by block copolymers consisting of a polystyrene block with molecular weight...... of approximately 1 kg/mol and an alkyl block with a molecular weight of approximately of 0.3 kg/mol. The efficiency of the block copolymers as plasticizers increases with decreasing molecular weight and polystyrene content. In addition, polystyrene-b-alkyl is found to be an efficient plasticizer also...... for polystyrene-b-polyisoprene-b-polystyrene (SIS) block copolymers. The end use properties of SIS plasticized with polystyrene-b-alkyl, measured as tensile strength, is higher than for SIS plasticized with dioctyl adipate. The polystyrene-b-polybutadiene-b-polystyrene and polystyrene-bpoly(propylene glycol...

  11. Water stale and structure analysis of Konjac irradiation copolymer

    International Nuclear Information System (INIS)

    Geng Shengrong; Xia Hezhou; Chen Xueling; Ye Lixiu; Hua Yuejin

    2011-01-01

    To study the absorption performance of Konjac-AA copolymer prepared by using irradiation, the water absorption capacity, sorbent speed and water keeping ability were determined, DSC and TEM analysis were used to investigate the water content and structure characters. The results showed that the largest water absorption speed was 16 g · -1 · min -1 at room temperature, and the largest water absorption was 400 times within 60 minutes. The water absorption was affected by granularity, temperature, ion content and ion type, especially the ion type. The water keeping ability was affected by temperature and time, which was up to 35% of absorbed water when the fully water absorbed copolymer was kept under room temperature for 15 d. The free and bounder water content which could be assimilated by the plants was 99.617%. The water stale copolymer has a three-dimensional spiral structure. (authors)

  12. Thermoresponsive behavior of chitosan-g-N-isopropylacrylamide copolymer solutions.

    Science.gov (United States)

    Recillas, Maricarmen; Silva, Luisa L; Peniche, Carlos; Goycoolea, Francisco M; Rinaudo, Marguerite; Argüelles-Monal, Waldo M

    2009-06-08

    Chitosan-g-N-isopropylacrylamide (NIPAm) water-soluble copolymers were synthesized and characterized by FTIR and (1)H NMR spectroscopies combined with conductometric and potentiometric titrations. Their thermoresponsive, fully reversible, behavior in aqueous solutions was characterized by means of microcalorimetry and rheology. During heating of copolymer solutions there is a well-known endothermic effect, which coincides with a marked increase in G' and a moderate decrement in G'' due to the formation of a hydrophobic network at the expense of the net amount of sol fraction. It was also found that a straight dependence between the values of G' above the LCST and the enthalpies associated with the transition reflecting that the connectivity in the gel network is governed by the net number of formed enthalpic-hydrophobic driven-junctions. Both the LCST and the enthalpy change vary with the ionic strength of copolymer solutions, but no dependence was found with the neutralization of the polyelectrolyte chain.

  13. Pressure and temperature effects in homopolymer blends and diblock copolymers

    DEFF Research Database (Denmark)

    Frielinghaus, H.; Schwahn, D.; Mortensen, K.

    1997-01-01

    Thermal composition fluctuations in a homogeneous binary polymer blend and in a diblock copolymer were measured by small-angle neutron scattering as a function of temperature and pressure. The experimental data were analyzed with theoretical expressions, including the important effect of thermal...... fluctuations. Phase boundaries, the Flory-Huggins interaction parameter and the Ginzburg number were obtained. The packing of the molecules changes with pressure. Therefore, the degree of thermal fluctuation as a function of packing and temperature was studied. While in polymer blends packing leads, in some...... respects, to a universal behaviour, such behaviour is not found in diblock copolymers. It is shown that the Ginzburg number decreases with pressure sensitively in blends, while it is constant in diblock copolymers. The Ginzburg number is an estimation of the transition between the universality classes...

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

    Science.gov (United States)

    Wang, Dunyang; Wujcik, Kevin; Balsara, Nitash

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

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

    Science.gov (United States)

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

    2011-01-25

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

  16. Modification of ethylene-norbornene copolymer by Gamma irradiation

    Directory of Open Access Journals (Sweden)

    Kačarević-Popović Zorica M.

    2006-01-01

    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. Preparation and icephobic properties of polymethyltrifluoropropylsiloxane–polyacrylate block copolymers

    Energy Technology Data Exchange (ETDEWEB)

    Li, Xiaohui; Zhao, Yunhui [School of Materials Science and Engineering, and Tianjin Key Laboratory of Composite and Functional Materials, Tianjin University, Tianjin 300072 (China); Li, Hui [School of Chemistry and Chemical Engineering, Shandong Key Laboratory of Fluorine Chemistry and Chemical Engineering Materials, University of Jinan, Jinan 250022 (China); Yuan, Xiaoyan, E-mail: xyuan28@yahoo.com [School of Materials Science and Engineering, and Tianjin Key Laboratory of Composite and Functional Materials, Tianjin University, Tianjin 300072 (China)

    2014-10-15

    Highlights: • PMTFPS–b-polyacrylate copolymers in five different compositions were synthesized. • Enrichment of PMTFPS amounts at the surface made high F/Si value. • Icing delay time was related to the surface roughness. • Ice shear strength was decreased by the synergistic effect of silicone and fluorine. - Abstract: Five polymethyltrifluoropropylsiloxane (PMTFPS)–polyacrylate block copolymers (PMTFPS–b-polyacrylate) were synthesized by free radical polymerization of methyl methacrylate, n-butyl acrylate and hydroxyethyl methacrylate using PMTFPS macroazoinitiator (PMTFPS-MAI) in range of 10–50 mass percentages. The morphology, surface chemical composition and wettability of the prepared copolymer films were investigated by transmission electron microscopy, atomic force microscopy, X-ray photoelectron spectroscopy, and water contact angle measurement. Delayed icing time and ice shear strength of the films were also detected for the icephobic purpose. The surface morphologies of the copolymers were different from those of the bulk because of the migration of the PMTFPS segments to the air interface during the film formation. Maximal delayed icing time (186 s at −15 °C) and reduction of the ice shear strength (301 ± 10 kPa) which was significantly lower than that of polyacrylates (804 ± 37 kPa) were achieved when the content of PMTFPS-MAI was 20 wt%. The icephobicity of the copolymers was attributed primarily to the enrichment of PMTFPS on the film surface and synergistic effect of both silicone and fluorine. Thus, the results show that the PMTFPS–b-polyacrylate copolymer can be used as icephobic coating materials potentially.

  18. Responsive copolymers for enhanced petroleum recovery. Second annual report

    Energy Technology Data Exchange (ETDEWEB)

    McCormick, C.; Hester, R.

    1995-05-01

    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. Synthesis and Characterization of Organotin Containing Copolymers: Reactivity Ratio Studies

    Directory of Open Access Journals (Sweden)

    Mohamed H. El-Newehy

    2010-03-01

    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.

  20. Thin Films of Novel Linear-Dendritic Diblock Copolymers

    Science.gov (United States)

    Iyer, Jyotsna; Hammond, Paula

    1998-03-01

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

  1. Polymers and block copolymers of fluorostyrenes by ATRP

    DEFF Research Database (Denmark)

    Hvilsted, Søren; Borkar, Sachin; Abildgaard, Lillian

    2002-01-01

    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....

  2. Chemical etching of fission tracks in ethylene-tetrafluoroethylene copolymer

    International Nuclear Information System (INIS)

    Komaki, Y.; Tsujimura, S.; Seguchi, T.

    1979-01-01

    The chemical etching of fission tracks in ethylene-tetrafluoroethylene copolymer was studied. Etched holes 3000 to 4000 A in diameter were recognized by electron microscopy for a film bombarded by fission fragments in oxygen and etched in a 12N sodium hydroxide solution at 125 0 C. The radial etching rate at 125 0 C was 6 to 8 A/hr, which is less than 17 A/hr for polyvinylidene fluoride in the same sodium hydroxide concentration at 85 0 C. The smaller rate is a reflection of the larger chemical resistivity of ethylene-tetrafluoroethylene copolymer than polyvinylidene fluoride. (author)

  3. Organisation and shape of micellar solutions of block copolymers

    Science.gov (United States)

    Gaspard, J. P.; Creutz, S.; Bouchat, Ph.; Jérôme, R.; Cohen Stuart, M.

    1997-02-01

    Diblock copolymers of polymethacrylic acid sodium salt, forming the hair, and styrene derivatives have been studied in aqueous solutions by SANS and SAXS. The influence of both the chemical nature and the length of the hydrophobic bloxk on the size and shape of micelles have been investigated. The micellar core size is in agreement with the theoretical evaluation for copolymers with a short hydrophobic sequence. In contrast, in case of larger hydrophobic blocks, the measured size is incompatible with a star-like model. Various hypotheses are presented for the latter.

  4. Thermal and radiochemical degradation of some PAN copolymers

    Energy Technology Data Exchange (ETDEWEB)

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

    2008-12-01

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

  5. Nanoporous Crosslinked Polyisoprene from Polyisoprene-Polydimethylsiloxane Block Copolymer

    DEFF Research Database (Denmark)

    Hansen, Michael Steffen; Vigild, Martin Etchells; Berg, Rolf Henrik

    2004-01-01

    The polyisoprene block of a polyisoprene-polydimethylsiloxane (PI-PDMS) diblock copolymer with 0.68 volume fraction of PI was tightly crosslinked with dicumylperoxide. The PDMS part of the obtained glassy material was subsequently quantitatively etched with anhydrous hydrogen fluoride or tetrabut......The polyisoprene block of a polyisoprene-polydimethylsiloxane (PI-PDMS) diblock copolymer with 0.68 volume fraction of PI was tightly crosslinked with dicumylperoxide. The PDMS part of the obtained glassy material was subsequently quantitatively etched with anhydrous hydrogen fluoride...

  6. POLYCAPROLACTONE-POLY (ETHYLENE GLYCOL) BLOCK COPOLYMER Ⅲ DRUG RELEASE BEHAVIOR

    Institute of Scientific and Technical Information of China (English)

    BEI Jianzhong; WANG Zhifeng; WANG Shenguo

    1995-01-01

    The drug release behavior of degradable polymer - polycaprolactone-poly (ethylene glycol)block copolymer(PCE) in vitro was investigated by using 5-Fluoro-uracil (5-Fu) as a model drug under a condition of pH 7.4 at 37℃. It is found that the release rate of 5-Fu from PCE increased with increasing polyether content of the copolymer. The results show that the increasing polyether content of the copolymer caused increasing hydrophilicity and decreasing crystallinity of the PCE copolymer. Thus, the drug release behavior and the degradable property of the PCE can be controlled by adjusting the composition of the copolymer.

  7. STUDIES ON POLY (ETHYLENE TEREPHTHALATE)- POLY ( TETRAMETHYLENE ETHER ) MULTIBLOCK COPOLYMER.Ⅰ. COM POSITIONAL HOMOGENEITY

    Institute of Scientific and Technical Information of China (English)

    ZHAN Yongjian; YING Qicong; WU Meiyan; QIAN Renyuan

    1991-01-01

    The compositional homogeneity of a poly (ethylene terephthalate )-poly (tetramethylene ether)multiblock copolymer sample with low content of hard segment was examined by GPC, TLC, and solubility method. The copolymer sample was found to have a uniform composition as a function of elution volume over the major portion of sample from GPC method. However within one elution fraction, the copolymer chains, although having the same hydrodynamic volume, may have some difference in composition. Two fractions with different composition were obtained by precipitation in ethanol. Some low molar mass copolymers were also separated by a TLC technique from the copolymer sample.

  8. SYNTHESIS OF STYRENE-METHYL METHACRYLATE BLOCK COPOLYMER BY POLYAZOAMIDE AS INITIATOR

    Institute of Scientific and Technical Information of China (English)

    WANG Zhongyi; WEI Jeqing

    1996-01-01

    Polyazoamide(PAA) was used as initiator to prepare block copolymer P(MMA-b-St) by free radical polymerization. The fraction of block copolymer was about 50%. The structure of the block-copolymer was characterized by IR and the results of 1H-NMR and GPC showed that the content of the block and the molecular weight (-Mw) of the prepolymer and block copolymer could be controlled by varying the mol ratio of styrene/PAA and MMA/prepolymer. DSC and TEM results revealed that the block copolymer has two separated glass transition temperatures and phase separation within the domain structure.

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

    Directory of Open Access Journals (Sweden)

    Yunqi Li

    2016-04-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-12-01

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

  11. 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: Jordi.Puiggali@upc.es [Department of Mining-Metallurgy Engineering and Materials Science, University of the Basque Country (UPV/EHU), Bilbao (Spain)

    2014-09-01

    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.

  12. Inhomogeneity of block copolymers at the interface of an immiscible polymer blend

    Science.gov (United States)

    Ryu, Ji Ho; Kim, YongJoo; Lee, Won Bo

    2018-04-01

    We present the effects of structure and stiffness of block copolymers on the interfacial properties of an immiscible homopolymer blend. Diblock and two-arm grafted copolymers with variation in stiffness are modeled using coarse-grained molecular dynamics to compare the compatibilization efficiency, i.e., reduction of interfacial tension. Overall, grafted copolymers are located more compactly at the interface and show better compatibilization efficiency than diblock copolymers. In addition, an increase in the stiffness for one of the blocks of the diblock copolymers causes unusual inhomogeneous interfacial coverage due to bundle formation. However, an increase in the stiffness for one of blocks of the grafted copolymers prevents the bundle formation due to the branched chain. As a result, homogeneous interfacial coverage of homopolymer blends is realized with significant reduction of interfacial tension which makes grafted copolymer a better candidate for the compatibilizer of immiscible homopolymer blend.

  13. Monte Carlo simulation of AB-copolymers with saturating bonds

    DEFF Research Database (Denmark)

    Chertovich, A.C.; Ivanov, V.A.; Khokhlov, A.R.

    2003-01-01

    Structural transitions in a single AB-copolymer chain where saturating bonds can be formed between A- and B-units are studied by means of Monte Carlo computer simulations using the bond fluctuation model. Three transitions are found, coil-globule, coil-hairpin and globule-hairpin, depending...

  14. Asymmetric block copolymers confined in a thin film

    NARCIS (Netherlands)

    Huinink, HP; Brokken-Zijp, JCM; van Dijk, MA; Sevink, GJA

    2000-01-01

    We have used a dynamic density functional theory (DDFT) for polymeric systems, to simulate the formation of micro phases in a melt of an asymmetric block copolymer, A(n)B(m)(f(A) = 1/3), both in the bulk and in a thin film. In the DDFT model a polymer is represented as a chain of springs and beads.

  15. Diblock Copolymer/Layered Silicate Nanocomposite Thin Film Stability

    Science.gov (United States)

    Limary, Ratchana; Green, Peter

    2000-03-01

    The stability of thin film symmetric diblock copolymers blended with layered silicate nanocomposites were examined using a combination of optical microscopy, atomic force microscopy (AFM), and X-ray diffraction (XRD). Two cases were examined PS-b-PMMA (polystyrene-b-polymethylacrylate) blended with montmorillonite stoichiometrically loaded with alkyl ammonium ions, OLS(S), and PS-b-PMMA blended with montmorillonite loaded with excess alkyl ammonium ions, OLS(E). XRD spectra show an increase in the gallery spacing of the OLSs, indicating that the copolymer chains have intercalated the layered silicates. AFM images reveal a distinct difference between the two nanocomposite thin films: regions in the vicinity of OLS(S) aggregates were depleted of material, while in the vicinity of OLS(E) aggregates, dewetting of the substrate occurred. We show that the stability of the copolymer/OLS nanocomposite films is determined by the enthalpic driving force associated with intercalation of the copolymer chains into the galleries of the modified OLS layers and by the substrate/organic modifier interactions.

  16. Functional (co)polymers from carbenes: scope, mechanism & polymer properties

    NARCIS (Netherlands)

    Franssen, N.M.G.

    2012-01-01

    Polymerization of carbenes is a valuable alternative to traditional olefin polymerization with regard to the formation of high molecular-weight functional copolymers in a stereoregular way. The versatility of this reaction with respect to different carbene precursors allows the formation of a large

  17. Linear low density polyethylene/cycloolefin copolymer blends

    Czech Academy of Sciences Publication Activity Database

    Dorigato, A.; Pegoretti, A.; Fambri, L.; Lonardi, C.; Šlouf, Miroslav; Kolařík, Jan

    2011-01-01

    Roč. 5, č. 1 (2011), s. 23-37 ISSN 1788-618X R&D Projects: GA ČR GA106/09/1348 Institutional research plan: CEZ:AV0Z40500505 Keywords : polymer blends * cycloolefin copolymer * creep Subject RIV: JI - Composite Materials Impact factor: 1.769, year: 2011

  18. Epoxy-crosslinked sulfonated poly (phenylene) copolymer proton exchange membranes

    Science.gov (United States)

    Hibbs, Michael; Fujimoto, Cy H.; Norman, Kirsten; Hickner, Michael A.

    2010-10-19

    An epoxy-crosslinked sulfonated poly(phenylene) copolymer composition used as proton exchange membranes, methods of making the same, and their use as proton exchange membranes (PEM) in hydrogen fuel cells, direct methanol fuel cell, in electrode casting solutions and electrodes, and in sulfur dioxide electrolyzers. These improved membranes are tougher, have higher temperature capability, and lower SO.sub.2 crossover rates.

  19. Tough, semiconducting polyethylene-poly(3-hexylthiophene) diblock copolymers

    DEFF Research Database (Denmark)

    Müller, C.; Goffri, S.; Breiby, Dag Werner

    2007-01-01

    Semiconducting diblock copolymers of polyethylene (PE) and regioregular poly(3-hexylthiophene) (P3HT) are demonstrated to exhibit a rich phase behaviour, judicious use of which permitted us to fabricate field-effect transistors that show saturated charge carrier mobilities, mu(FET), as high as 2 x...

  20. Poly(bisphenol A carbonate) - poly(dimethylsiloxane) multiblock copolymers

    NARCIS (Netherlands)

    Aert, van H.A.M.; Nelissen, L.N.I.H.; Lemstra, P.J.; Brunelle, D.J.

    2001-01-01

    A versatile technique for the synthesis of multiblock copolymers of polydimethylsiloxane (PDMS) and poly(bisphenol A carbonate) (PC) is described. Specific reaction of the phenol end groups of a,¿-bis(bisphenol A)-terminated PDMS with the activated end groups of

  1. Isotropic Lifshitz behavior in block copolymer-homopolymer blends

    DEFF Research Database (Denmark)

    Bates, F.S.; Maurer, W.; Lodge, T.P.

    1995-01-01

    A series of mixtures composed of a symmetric A-B diblock copolymer and a symmetric blend of A and B homopolymers was investigated by small-angle neutron scattering. Mean-field theory predicts that a line of lamellar-disorder transitions with wave-vector instability q* > 0 will meet a line of crit...

  2. 21 CFR 175.210 - Acrylate ester copolymer coating.

    Science.gov (United States)

    2010-04-01

    ... ester copolymer coating may safely be used as a food-contact surface of articles intended for packaging..., and methacrylic acid applied in emulsion form to molded virgin fiber and heat-cured to an insoluble... application of the emulsion may include substances named in this paragraph, in an amount not to exceed that...

  3. Block copolymer-nanoparticle hybrid self-assembly

    KAUST Repository

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

    2015-01-01

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

  4. Spectral Signatures of Polarons in Conjugated Co-polymers

    NARCIS (Netherlands)

    Wiebeler, Christian; Tautz, Raphael; Feldmann, Jochen; von Hauff, Elizabeth; Da Como, Enrico; Schumacher, Stefan

    2013-01-01

    We study electronic and optical properties of the low-bandgap co-polymer PCPDT-BT (poly-cyclopentadithiophene-co-benzothiadiazole) and compare it with the corresponding homo-polymer PCPDT (poly-cyclopentadithiophene). We investigate the linear absorptivity in these systems for neutral molecules and

  5. Influence of Chirality in Ordered Block Copolymer Phases

    Science.gov (United States)

    Prasad, Ishan; Grason, Gregory

    2015-03-01

    Block copolymers are known to assemble into rich spectrum of ordered phases, with many complex phases driven by asymmetry in copolymer architecture. Despite decades of study, the influence of intrinsic chirality on equilibrium mesophase assembly of block copolymers is not well understood and largely unexplored. Self-consistent field theory has played a major role in prediction of physical properties of polymeric systems. Only recently, a polar orientational self-consistent field (oSCF) approach was adopted to model chiral BCP having a thermodynamic preference for cholesteric ordering in chiral segments. We implement oSCF theory for chiral nematic copolymers, where segment orientations are characterized by quadrupolar chiral interactions, and focus our study on the thermodynamic stability of bi-continuous network morphologies, and the transfer of molecular chirality to mesoscale chirality of networks. Unique photonic properties observed in butterfly wings have been attributed to presence of chiral single-gyroid networks, this has made it an attractive target for chiral metamaterial design.

  6. Fast assembly of ordered block copolymer nanostructures through microwave annealing.

    Science.gov (United States)

    Zhang, Xiaojiang; Harris, Kenneth D; Wu, Nathanael L Y; Murphy, Jeffrey N; Buriak, Jillian M

    2010-11-23

    Block copolymer self-assembly is an innovative technology capable of patterning technologically relevant substrates with nanoscale precision for a range of applications from integrated circuit fabrication to tissue interfacing, for example. In this article, we demonstrate a microwave-based method of rapidly inducing order in block copolymer structures. The technique involves the usage of a commercial microwave reactor to anneal block copolymer films in the presence of appropriate solvents, and we explore the effect of various parameters over the polymer assembly speed and defect density. The approach is applied to the commonly used poly(styrene)-b-poly(methyl methacrylate) (PS-b-PMMA) and poly(styrene)-b-poly(2-vinylpyridine) (PS-b-P2VP) families of block copolymers, and it is found that the substrate resistivity, solvent environment, and anneal temperature all critically influence the self-assembly process. For selected systems, highly ordered patterns were achieved in less than 3 min. In addition, we establish the compatibility of the technique with directed assembly by graphoepitaxy.

  7. Oriented Structure of Pentablock Copolymers Induced by Solution Extrusion

    Science.gov (United States)

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

    2002-03-01

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

  8. Protein resistance of dextran and dextran-PEG copolymer films

    Science.gov (United States)

    Kozak, Darby; Chen, Annie; Bax, Jacinda; Trau, Matt

    2011-01-01

    The protein resistance of dextran and dextran-poly(ethylene glycol) (PEG) copolymer films was examined on an organosilica particle-based assay support. Comb-branched dextran-PEG copolymer films were synthesized in a two step process using the organosilica particle as a solid synthetic support. Particles modified with increasing amounts (0.1-1.2 mg m−2) of three molecular weights (10 000, 66 900, 400 000 g mol−1) of dextran were found to form relatively poor protein-resistant films compared to dextran-PEG copolymers and previously studied PEG films. The efficacy of the antifouling polymer films was found to be dependent on the grafted amount and its composition, with PEG layers being the most efficient, followed by dextran-PEG copolymers, and dextran alone being the least efficient. Immunoglobulin gamma (IgG) adsorption decreased from ~ 5 to 0.5 mg m−2 with increasing amounts of grafted dextran, but bovine serum albumin (BSA) adsorption increased above monolayer coverage (to ~2 mg m−2) indicating ternary adsorption of the smaller protein within the dextran layer. PMID:21614699

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

    NARCIS (Netherlands)

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

    2011-01-01

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

  10. Resonant soft x-ray GISAXS on block copolymer films

    Science.gov (United States)

    Wang, Cheng; Araki, T.; Watts, B.; Ade, H.; Hexemer, A.; Park, S.; Russell, T. P.; Schlotter, W. F.; Stein, G. E.; Tang, C.; Kramer, E. J.

    2008-03-01

    Ordered block copolymer thin films may have important applications in modern device fabrication. Current characterization methods such as conventional GISAXS have fixed electron density contrast that can be overwhelmed by surface scattering. However, soft x-rays have longer wavelength, energy dependent contrast and tunable penetration, making resonant GISAXS a very promising tool for probing nanostructured polymer thin films. Our preliminary investigation was performed using PS-b-P2VP block copolymer films on beam-line 5-2 SSRL, and beam-line 6.3.2 at ALS, LBNL. The contrast/sensitivity of the scattering pattern varies significantly with photon energy close to the C K-edge (˜290 eV). Also, higher order peaks are readily observed, indicating hexagonal packing structure in the sample. Comparing to the hard x-ray GISAXS data of the same system, it is clear that resonant GISAXS has richer data and better resolution. Beyond the results on the A-B diblock copolymers, results on ABC block copolymers are especially interesting.

  11. Multiple ordered phases in a block copolymer melt

    DEFF Research Database (Denmark)

    Almdal, K.; Koppi, K.A.; Bates, F.S.

    1992-01-01

    A poly(ethylenepropylene)-poly(ethylethylene) (PEP-PEE) diblock copolymer containing 65% by volume PEP was investigated using small-angle neutron scattering (SANS) and rheological measurements. Four distinct phases have been identified as a function of temperature: three ordered phases at low...

  12. Copolymer adsorption and the effect on colloidal stability

    NARCIS (Netherlands)

    Bijsterbosch, H.D.

    1998-01-01

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

  13. Responsive copolymers for enhanced petroleum recovery. Annual report

    Energy Technology Data Exchange (ETDEWEB)

    McCormick, C.; Hester, R.

    1994-08-01

    A coordinated research program involving synthesis, characterization, and rheology has been undertaken to develop advanced polymer system which should be significantly more efficient than polymers presently used for mobility control and conformance. Unlike the relatively inefficient, traditional EOR polymers, these advanced polymer systems possess microstructural features responsive to temperature, electrolyte concentration, and shear conditions. Contents of this report include the following chapters. (1) First annual report responsive copolymers for enhanced oil recovery. (2) Copolymers of acrylamide and sodium 3-acrylamido-3-methylbutanoate. (3) Terpolymers of NaAMB, Am, and n-decylacrylamide. (4) Synthesis and characterization of electrolyte responsive terpolymers of acrylamide, N-(4-butyl)phenylacrylamide, and sodium acrylate, sodium-2-acrylamido-2-methylpropanesulphonate or sodium-3-acrylamido-3-methylbutanoate. (5) Synthesis and solution properties of associative acrylamido copolymers with pyrensulfonamide fluorescence labels. (6) Photophysical studies of the solution behavior of associative pyrenesulfonamide-labeled polyacrylamides. (7) Ampholytic copolymers of sodium 2-(acrylamido)-2-methylpropanesulfonate with [2-(acrylamido)-2-methypropyl]trimethylammonium chloride. (8) Ampholytic terpolymers of acrylamide with sodium 2-acrylamido-2-methylpropanesulphoante and 2-acrylamido-2-methylpropanetrimethyl-ammonium chloride and (9) Polymer solution extensional behavior in porous media.

  14. Electrochromic properties of a novel low band gap conductive copolymer

    Energy Technology Data Exchange (ETDEWEB)

    Yigitsoy, Basak; Varis, Serhat; Tanyeli, Cihangir; Akhmedov, Idris M.; Toppare, Levent [Department of Chemistry, Middle East Technical University, 06531 Ankara (Turkey)

    2007-07-10

    A copolymer of 2,5-di(thiophen-2-yl)-1-p-tolyl-1H-pyrrole (DTTP) with 3,4-ethylene dioxythiophene (EDOT) was electrochemically synthesized. The resultant copolymer P(DTTP-co-EDOT) was characterized via cyclic voltammetry, FTIR, SEM, conductivity measurements and spectroelectrochemistry. Copolymer film has distinct electrochromic properties. It has four different colors (chestnut, khaki, camouflage green, and blue). At the neutral state {lambda}{sub max} due to the {pi}-{pi}{sup *} transition was found to be 487 nm and E{sub g} was calculated as 1.65 eV. Double potential step chronoamperometry experiment shows that copolymer film has good stability, fast switching time (less than 1 s) and good optical contrast (20%). An electrochromic device based on P(DTTP-co-EDOT) and poly(3,4-ethylenedioxythiophene) (PEDOT) was constructed and characterized. The device showed reddish brown color at -0.6 V when the P(DTTP-co-EDOT) layer was in its reduced state; whereas blue color at 2.0 V when PEDOT was in its reduced state and P(DTTP-co-EDOT) layer was in its oxidized state. At 0.2 V intermediate green state was observed. Maximum contrast (%{delta}T) and switching time of the device were measured as 18% and 1 s at 615 nm. ECD has good environmental and redox stability. (author)

  15. Optical fibre Bragg grating recorded in TOPAS cyclic olefin copolymer

    DEFF Research Database (Denmark)

    Johnson, I.P.; Yuan, Scott Wu; Stefani, Alessio

    2011-01-01

    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...

  16. Characterisation of polyhydroxyalkanoate copolymers with controllable four-monomer composition.

    Science.gov (United States)

    Dai, Yu; Lambert, Lynette; Yuan, Zhiguo; Keller, Jurg

    2008-03-20

    Polyhydroxyalkanoate (PHA) copolymers comprising the four monomers 3-hydroxybutyrate (3HB), 3-hydroxyvalerate (3HV), 3-hydroxy-2-methylvalerate (3HMV) and 3-hydroxy-2-methylbutyrate (3HMB) were generated using the recently discovered Defluviicoccus vanus-related glycogen accumulating organisms (DvGAOs) under anaerobic conditions without applying any nutrient limitations. The composition could be manipulated in a defined range by modifying the ratio of propionate and acetate provided in the feed stream. The PHAs produced were characterised as random copolymers (from propionate alone) or a mixture of random copolymers (from mixture of propionate and acetate) through microstructure analysis using 13C NMR spectroscopy. The sequence distribution of all eight comonomer pairs in the carbonyl region of 3HB and 3HV was identified and assigned with confidence utilising two-dimensional heteronuclear multiple bond coherence (HMBC) spectroscopy. Weight average molecular weights were in the range 390-560 kg/mol. Differential scanning calorimetry (DSC) traces showed that the melting temperature (Tm) varied between 70 and 161 degrees C and glass transition temperature (Tg) ranged from -8 to 0 degrees C. The incorporation of considerable amounts of 3HMV and 3HMB monomer units introduced additional "defects" into the PHBV copolymer structure and hence greatly lowered the crystallinity. The data indicate the potential of these four-monomer PHAs to be employed for practical applications, considering their favourable properties and the cost-effective production process using a mixed culture and simple carbon sources.

  17. Segmented block copolymers with monodisperse aramide end-segments

    NARCIS (Netherlands)

    Araichimani, A.; Gaymans, R.J.

    2008-01-01

    Segmented block copolymers were synthesized using monodisperse diaramide (TT) as hard segments and PTMO with a molecular weight of 2 900 g · mol-1 as soft segments. The aramide: PTMO segment ratio was increased from 1:1 to 2:1 thereby changing the structure from a high molecular weight multi-block

  18. 21 CFR 177.1830 - Styrene-methyl methacrylate copolymers.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Styrene-methyl methacrylate copolymers. 177.1830 Section 177.1830 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD FOR HUMAN CONSUMPTION (CONTINUED) INDIRECT FOOD ADDITIVES: POLYMERS Substances for Use as Basic Components of Single and Repeated Us...

  19. Synthesis and photooxidation of styrene copolymer bearing camphorquinone pendant groups

    Science.gov (United States)

    Moszner, Norbert; Lukáč, Ivan

    2012-01-01

    Summary (±)-10-Methacryloyloxycamphorquinone (MCQ) was synthesized from (±)-10-camphorsulfonic acid either by a known seven-step synthetic route or by a novel, shorter five-step synthetic route. MCQ was copolymerized with styrene (S) and the photochemical behavior of the copolymer MCQ/S was compared with that of a formerly studied copolymer of styrene with monomers containing the benzil (BZ) moiety (another 1,2-dicarbonyl). Irradiation (λ > 380 nm) of aerated films of styrene copolymers with monomers containing the BZ moiety leads to the insertion of two oxygen atoms between the carbonyl groups of BZ and to the formation of benzoyl peroxide (BP) as pendant groups on the polymer backbone. An equivalent irradiation of MCQ/S led mainly to the insertion of only one oxygen atom between the carbonyl groups of camphorquinone (CQ) and to the formation of camphoric anhydride (11) covalently bound to the polymer backbone. While the decomposition of pendant BP groups formed in irradiated films of styrene copolymers with pendant BZ groups leads to crosslinking, only small molecular-weight changes in irradiated MCQ/S were observed. PMID:22509202

  20. Styrene-divinylbenzene copolymer grafted with phosphonic acid dialkylesters

    Directory of Open Access Journals (Sweden)

    SMARANDA ILIESCU

    2004-12-01

    Full Text Available The functionalization of a crosslinked chloromethylated polystyrene 8% divinylbenzene copolymer with phosphonic ester groups is detailed. The reacton conditions were studied in order to determine the optimal conditions for obtaining only diesters. A statistical method for the calculation of the fraction of repetive units for the inited and final resin is proposed.

  1. Features of radiation chemical processes in ethylene-styrene copolymers

    International Nuclear Information System (INIS)

    Leshchenko, S.S.; Mal'tseva, A.P.; Iskakov, L.I.; Karpov, V.L.

    1976-01-01

    A study was made of statistical copolymers of ethylene with styrene to determine their structure and properties and radio-chemical transformations. The styrene content of the copolymers ranged from 1 to 85 mole%. The investigation covered non-irradiated copolymers and those irradiated with doses of 1-1000Mrad at room temperature and at liquid nitrogen temperature. It is shown that styrene units present in the CES inhibited all radio-chemical processes compared with PE irradiated under similar conditions. It is suggested that the radiation resistance of CES with styrene contents up to 10 mole % increases in the course of irradiation as a result of the formation of structures with a high degree of conjugation which are more capable of scattering absorbed energy than in the case of phenyl rings by themselves. The most promising of the CES examined is the one with a styrene content of 5 mole %. The mechanical properties of this copolymer are similar to those of PE, and its radiation resistance rises under service conditions in the presence of ionizing radiation

  2. 21 CFR 177.1820 - Styrene-maleic anhydride copolymers.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Styrene-maleic anhydride copolymers. 177.1820 Section 177.1820 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD FOR HUMAN CONSUMPTION (CONTINUED) INDIRECT FOOD ADDITIVES: POLYMERS Substances for Use as Basic Components of Single and Repeated Use...

  3. Quantification of branching in model three-arm star polyethylene

    KAUST Repository

    Ramachandran, Ramnath; Beaucage, Gregory B.; Rai, Durgesh K.; Lohse, David J.; Sun, Thomas; Tsou, Andy; Norman, Alexander Iain; Hadjichristidis, Nikolaos

    2012-01-01

    The versatility of a novel scaling approach in quantifying the structure of model well-defined 3-arm star polyethylene molecules is presented. Many commercial polyethylenes have long side branches, and the nature and quantity of these branches varies widely among the various forms. For instance, low-density polyethylene (LDPE) is typically a highly branched structure with broad distributions in branch content, branch lengths and branch generation (in hyperbranched structures). This makes it difficult to accurately quantify the structure and the inherent structure-property relationships. To overcome this drawback, model well-defined hydrogenated polybutadiene (HPB) structures have been synthesized via anionic polymerization and hydrogenation to serve as model analogues to long-chain branched polyethylene. In this article, model 3-arm star polyethylene molecules are quantified using the scaling approach. Along with the long-chain branch content in polyethylene, the approach also provides unique measurements of long-chain branch length and hyperbranch content. Such detailed description facilitates better understanding of the effect of branching on the physical properties of polyethylene. © 2012 American Chemical Society.

  4. Quantification of branching in model three-arm star polyethylene

    KAUST Repository

    Ramachandran, Ramnath

    2012-01-24

    The versatility of a novel scaling approach in quantifying the structure of model well-defined 3-arm star polyethylene molecules is presented. Many commercial polyethylenes have long side branches, and the nature and quantity of these branches varies widely among the various forms. For instance, low-density polyethylene (LDPE) is typically a highly branched structure with broad distributions in branch content, branch lengths and branch generation (in hyperbranched structures). This makes it difficult to accurately quantify the structure and the inherent structure-property relationships. To overcome this drawback, model well-defined hydrogenated polybutadiene (HPB) structures have been synthesized via anionic polymerization and hydrogenation to serve as model analogues to long-chain branched polyethylene. In this article, model 3-arm star polyethylene molecules are quantified using the scaling approach. Along with the long-chain branch content in polyethylene, the approach also provides unique measurements of long-chain branch length and hyperbranch content. Such detailed description facilitates better understanding of the effect of branching on the physical properties of polyethylene. © 2012 American Chemical Society.

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

    Science.gov (United States)

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

    2015-08-07

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

  6. Anomalous Behaviors of Block Copolymers at the Interface of an Immiscible Polymer Blend

    Science.gov (United States)

    Ryu, Ji Ho; Lee, Won Bo

    We investigate the effects of structure and stiffness of block copolymers on the interface of an immiscible polymer blend using coarse-grained molecular dynamics (CGMD) simulation. The diblock and grafted copolymers, which are described by Kremer and Grest bead spring model, are used to compare the compatibilization efficiency, that is, reduction of the interfacial tension. It is found that, overall, the grafted copolymers are located more compactly at the interface and show better compatibilization efficiency than diblock copolymers. In addition, it is noted that an increase in the stiffness of one block of diblock copolymer causes inhomogeneous interfacial coverage due to bundle formation among the stiff blocks and orientational constraint on bundled structures near the interface, which makes copolymers poor compatibilizers. The dependence of anomalous orientational constraint on the chain length of homopolymers is also investigated. Theoretical and Computational Soft Matters Lab.

  7. Topology and Shape Control for Assemblies of Block Copolymer Blends in Solution

    KAUST Repository

    Moreno Chaparro, Nicolas; Nunes, Suzana Pereira; Peinemann, Klaus-Viktor; Calo, Victor M.

    2015-01-01

    We study binary blends of asymmetric diblock copolymers (AB/AC) in selective solvents with a mesoscale model. We investigate the morphological transitions induced by the concentration of the AC block copolymer and the difference in molecular weight between the AB and AC copolymers, when segments B and C exhibit hydrogen-bonding interactions. To the best of our knowledge, this is the first work modeling mixtures of block copolymers with large differences in molecular weight. The coassembly mechanism localizes the AC molecules at the interface of A and B domains and induces the swelling of the B-rich domains. The coil size of the large molecular weight block copolymer depends only on the concentration of the short block copolymer (AC or AB), regardless of the B–C interactions. However, the B–C interactions control the morphological transitions that occur in these blends.

  8. Microtome Sliced Block Copolymers and Nanoporous Polymers as Masks for Nanolithography

    DEFF Research Database (Denmark)

    Shvets, Violetta; Schulte, Lars; Ndoni, Sokol

    2014-01-01

    Introduction. Block copolymers self-assembling properties are commonly used for creation of very fine nanostructures [1]. Goal of our project is to test new methods of the block-copolymer lithography mask preparation: macroscopic pieces of block-copolymers or nanoporous polymers with cross...... PDMS can be chemically etched from the PB matrix by tetrabutylammonium fluoride in tetrahydrofuran and macroscopic nanoporous PB piece is obtained. Both block-copolymer piece and nanoporous polymer piece were sliced with cryomicrotome perpendicular to the axis of cylinder alignment and flakes...... of etching patterns appear only under the certain parts of thick flakes and are not continuous. Although flakes from block copolymer are thinner and more uniform in thickness than flakes from nanoporous polymer, quality of patterns under nanoporous flakes appeared to be better than under block copolymer...

  9. Topology and Shape Control for Assemblies of Block Copolymer Blends in Solution

    KAUST Repository

    Moreno Chaparro, Nicolas

    2015-10-27

    We study binary blends of asymmetric diblock copolymers (AB/AC) in selective solvents with a mesoscale model. We investigate the morphological transitions induced by the concentration of the AC block copolymer and the difference in molecular weight between the AB and AC copolymers, when segments B and C exhibit hydrogen-bonding interactions. To the best of our knowledge, this is the first work modeling mixtures of block copolymers with large differences in molecular weight. The coassembly mechanism localizes the AC molecules at the interface of A and B domains and induces the swelling of the B-rich domains. The coil size of the large molecular weight block copolymer depends only on the concentration of the short block copolymer (AC or AB), regardless of the B–C interactions. However, the B–C interactions control the morphological transitions that occur in these blends.

  10. Immobilization of trichoderma REESEI (QM 9414) cells with paper covered with ionic copolymer by radiation polymerization

    International Nuclear Information System (INIS)

    Lu Zhaoxin

    1992-01-01

    Cationic-hydrophobic copolymer and anionic-hydrophobic copolymer was covered onto surface of paper by radiation polymerization. The paper covered with ionic copolymer was used as carrier of immobilizing Trichoderma reesei cells. Results showed that the cells were immobilized firmly on the carriers and not dislocated from the carriers by shaking. All of FPA of the cells immobilized with the carriers covered with cationic copolymer were higher than that of un-immobilized free cells. The carriers covered with anionic copolymer showed good effect on immobilization of the cells. The weight of immobilized cells increase as increasing the component of DEAEMA in poly (DEAEMA-ATMPT) or decreasing the component of AA in poly (AA-ATMPT). It also increase with the increase of water absorption in poly (DEAEMA-ATMPT) or decrease of water absorption in poly (AA-ATMPT). It shows the static interaction play an important role in the immobilization of cells with ionic copolymer materials

  11. SYNTHESIS OF AMPHIPHILIC COMB-SHAPED COPOLYMERS USED FOR SURFACE MODIFICATION OF PVDF MEMBRANES

    Institute of Scientific and Technical Information of China (English)

    徐又一

    2009-01-01

    The synthesis of a novel amphiphilic comb-shaped copolymer consisting of a main chain of styrene-(N-(4- hydroxyphenyl) maleimide)(SHMI) copolymer and poly(ethylene glycol) methyl ether methacrylate(PEGMA) side groups was achieved by atom transfer radical polymerization(ATRP).The amphiphilic copolymers were characterized by ~1H-NMR, Fourier transform infrared(FTIR) spectroscopy and gel permeation chromatography(GPC).From thermogravimetric analysis (TGA),the decomposition temperature of SHMI-g-PEGMA is low...

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

    OpenAIRE

    Elżbieta Piesowicz; Sandra Paszkiewicz; Anna Szymczyk

    2016-01-01

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

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

    International Nuclear Information System (INIS)

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

    2009-01-01

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

  14. Structural and chemical aspects of HPMA copolymers as drug carriers.

    Science.gov (United States)

    Ulbrich, Karel; Subr, Vladimír

    2010-02-17

    Synthetic strategies and chemical and structural aspects of the synthesis of HPMA copolymer conjugates with various drugs and other biologically active molecules are described and discussed in this chapter. The discussion is held from the viewpoint of design and structure of the polymer backbone and biodegradable spacer between a polymer and drug, structure and methods of attachment of the employed drugs to the carrier and structure and methods of conjugation with targeting moieties. Physicochemical properties of the water-soluble polymer-drug conjugates and polymer micelles including mechanisms of drug release are also discussed. Detailed description of biological behavior of the polymer-drug conjugates as well as application of the copolymers for surface modification and targeting of gene delivery vectors are not included, they are presented and discussed in separate chapters of this issue. Copyright 2009 Elsevier B.V. All rights reserved.

  15. Pathway-engineering for highly-aligned block copolymer arrays.

    Science.gov (United States)

    Choo, Youngwoo; Majewski, Paweł W; Fukuto, Masafumi; Osuji, Chinedum O; Yager, Kevin G

    2017-12-21

    While the ultimate driving force in self-assembly is energy minimization and the corresponding evolution towards equilibrium, kinetic effects can also play a very strong role. These kinetic effects, such as trapping in metastable states, slow coarsening kinetics, and pathway-dependent assembly, are often viewed as complications to be overcome. Here, we instead exploit these effects to engineer a desired final nano-structure in a block copolymer thin film, by selecting a particular ordering pathway through the self-assembly energy landscape. In particular, we combine photothermal shearing with high-temperature annealing to yield hexagonal arrays of block copolymer cylinders that are aligned in a single prescribed direction over macroscopic sample dimensions. Photothermal shearing is first used to generate a highly-aligned horizontal cylinder state, with subsequent thermal processing used to reorient the morphology to the vertical cylinder state in a templated manner. Finally, we demonstrate the successful transfer of engineered morphologies into inorganic replicas.

  16. Cylindrical-confinement-induced phase behaviours of diblock copolymer melts

    International Nuclear Information System (INIS)

    Mei-Jiao, Liu; Shi-Ben, Li; Lin-Xi, Zhang; Xiang-Hong, Wang

    2010-01-01

    The phase behaviours of diblock copolymers under cylindrical confinement are studied in two-dimensional space by using the self-consistent field theory. Several phase parameters are adjusted to investigate the cylindrical-confinement-induced phase behaviours of diblock copolymers. A series of lamella-cylinder mixture phases, such as the mixture of broken-lamellae and cylinders and the mixture of square-lamellae and cylinders, are observed by varying the phase parameters, in which the behaviours of these mixture phases are discussed in the corresponding phase diagrams. Furthermore, the free energies of these mixture phases are investigated to illustrate their evolution processes. Our results are compared with the available observations from the experiments and simulations respectively, and they are in good agreement and provide an insight into the phase behaviours under cylindrical confinement. (cross-disciplinary physics and related areas of science and technology)

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

    Directory of Open Access Journals (Sweden)

    Giovanni Filippo Palmieri

    2011-04-01

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

  18. Biocompatibility of epoxidized styrene-butadiene-styrene block copolymer membrane

    International Nuclear Information System (INIS)

    Yang, Jen Ming; Tsai, Shih Chang

    2010-01-01

    Styrene-butadiene-styrene block copolymer (SBS) membrane was prepared by solution casting method and then was epoxidized with peroxyformic acid generated in situ to yield the epoxidized styrene-butadiene-styrene block copolymer membrane (ESBS). The structure and properties of ESBS were characterized with infrared spectroscopy, Universal Testing Machine, differential scanning calorimetry (DSC), and thermogravimetry analysis (TGA). The performances of contact angle, water content, protein adsorption, and water vapor transmission rate on ESBS membrane were determined. After epoxidation, the hydrophilicity of the membrane increased. The water vapor transmission rate of ESBS membrane is similar to human skin. The biocompatibility of ESBS membrane was evaluated with the cell culture of fibroblasts on the membrane. It revealed that the cells not only remained viable but also proliferated on the surface of the various ESBS membranes and the population doubling time for fibroblast culture decreased.

  19. Theory of Primary Photoexcitations in Donor-Acceptor Copolymers.

    Science.gov (United States)

    Aryanpour, Karan; Dutta, Tirthankar; Huynh, Uyen N V; Vardeny, Zeev Valy; Mazumdar, Sumit

    2015-12-31

    We present a generic theory of primary photoexcitations in low band gap donor-acceptor conjugated copolymers. Because of the combined effects of strong electron correlations and broken symmetry, there is considerable mixing between a charge-transfer exciton and an energetically proximate triplet-triplet state with an overall spin singlet. The triplet-triplet state, optically forbidden in homopolymers, is allowed in donor-acceptor copolymers. For an intermediate difference in electron affinities of the donor and the acceptor, the triplet-triplet state can have a stronger oscillator strength than the charge-transfer exciton. We discuss the possibility of intramolecular singlet fission from the triplet-triplet state, and how such fission can be detected experimentally.

  20. Metallic nickel nanorod arrays embedded into ordered block copolymer templates

    International Nuclear Information System (INIS)

    Seifarth, O.; Krenek, R.; Tokarev, I.; Burkov, Y.; Sidorenko, A.; Minko, S.; Stamm, M.; Schmeisser, D.

    2007-01-01

    We report on metallic Nickel nanorods prepared by utilizing a mask of ordered nanostructured hollow channels in a block copolymer matrix. These polymeric templates were formed by a self organized process in block copolymer supramolecular assemblies. Nickel was filled into with two different techniques, electrodeposition and washing in. We monitor the formation process of these nanorods by means of atomic force microscopy and synchrotron radiation soft X-ray based photoelectron emission microscopy. The oxidation state of the nickelrods is evaluated with X-ray absorption spectroscopy and X-ray photoelectron spectroscopy at the Ni L edges and lateral distributions of the Ni nanorods were detected with micrometer resolved X-ray absorption spectroscopy. The finding is that the Ni rods were metallic despite their preparation under ambient conditions, inside the particles no hints for NiO complexes were found. This indicates that the polymer protects Ni nanoparticles against oxidation

  1. Synthesis and characterization of acrylate copolymer containing fluorescein functional group

    Energy Technology Data Exchange (ETDEWEB)

    Hui, Guodong; Huang, Weiyun; Song, Yunzhao; Chen, Deben; Zhong, Anyong [Sichuan University, Chengdu (China)

    2013-08-15

    We report a novel method to fabricate fluorescent polymer (F-CPA) based on the esterification between acrylate copolymer (CPA) and fluorescein using N, N-dicyclohexylcarbodiimide (DCC)/4-dimethylaminopyridine (DMAP) as catalyst. The resulting copolymer was characterized by Fourier transform-infrared spectroscopy (FT-IR), gel permeation chromatography (GPC), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), ultraviolet-visible spectroscopy (UV-Vis) and fluorescence spectroscopy. In addition, the influences of concentration, solvents, pH and metal cations (Cu{sup 2+}, Fe{sup 3+} and Zn{sup 2+}) on the fluorescent behaviors of F-CPA are discussed in detail. All those observations suggest that the synthesized F-CPA is an excellent luminescent macromolecular material with simple synthesis method and excellent solubility. Moreover, its sensitive fluorescence response behaviors to solvents, pH and metal cations make it to become a polymer-based probe.

  2. Synthesis and characterization of acrylate copolymer containing fluorescein functional group

    International Nuclear Information System (INIS)

    Hui, Guodong; Huang, Weiyun; Song, Yunzhao; Chen, Deben; Zhong, Anyong

    2013-01-01

    We report a novel method to fabricate fluorescent polymer (F-CPA) based on the esterification between acrylate copolymer (CPA) and fluorescein using N, N-dicyclohexylcarbodiimide (DCC)/4-dimethylaminopyridine (DMAP) as catalyst. The resulting copolymer was characterized by Fourier transform-infrared spectroscopy (FT-IR), gel permeation chromatography (GPC), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), ultraviolet-visible spectroscopy (UV-Vis) and fluorescence spectroscopy. In addition, the influences of concentration, solvents, pH and metal cations (Cu"2"+, Fe"3"+ and Zn"2"+) on the fluorescent behaviors of F-CPA are discussed in detail. All those observations suggest that the synthesized F-CPA is an excellent luminescent macromolecular material with simple synthesis method and excellent solubility. Moreover, its sensitive fluorescence response behaviors to solvents, pH and metal cations make it to become a polymer-based probe

  3. Barite formation in the presence of a commercial copolymer

    Science.gov (United States)

    Ruiz-Agudo, Cristina; Putnis, Christine; Ruiz-Agudo, Encarnacion; Putnis, Andrew

    2015-04-01

    Fluid composition can significantly modify the mechanisms of mineral formation. Particularly, the presence of organic additives in the aqueous media has been shown to alter the precipitation of minerals substantially (e.g. calcium carbonate, barium carbonate and barium sulfate). Despite the numerous studies dealing with barite precipitation and the influence of organic additives (e.g. Benton et al. 1993, Qi et al., 2000, Wang and Cölfen, 2006, Mavredaki et al., 2011), the details of the mechanism of barite formation in the presence of organic additives, particularly at the early stages of this process, are yet to be fully resolved. Here, we present observations on the initial stages of barite formation from aqueous solutions, as well as the alterations induced by a commercial copolymer (maleic acid/allyl sulfonic acid copolymer with phosphonate groups), commonly used as a scale inhibitor in oil recovery. Most synthetic commercial additives contain the same functional groups (e.g. carboxylate, phosphonate and/or sulfonate groups). Thus our work may help to understand the mechanism by which copolymers modify crystallization processes and aid in the selection of the most appropriate inhibitors for hindering or controlling barite scale formation. Barite scaling is one of the main problems in many industrial processes (such as, paper-making, chemical manufacturing, cement operations, off-shore oil extraction, geothermal energy production). Using Atomic Force Microscopy (AFM), we show that barite growth is significantly influenced by the presence of the copolymer. In its absence, barium sulfate growth occurs by 2D island nucleation and spreading. The addition of small amounts (0.1 ppm and 0.5 ppm) of the copolymer enhances 2D nucleation but blocks growth. Just 1 ppm of inhibitor is enough to block barite nucleation and growth by adsorption of a copolymer layer onto the barite surface. Transmission electron microscopy (TEM) was also used to gain better insights into the

  4. Magnetic Alignment of Block Copolymer Microdomains by Intrinsic Chain Anisotropy.

    Science.gov (United States)

    Rokhlenko, Yekaterina; Gopinadhan, Manesh; Osuji, Chinedum O; Zhang, Kai; O'Hern, Corey S; Larson, Steven R; Gopalan, Padma; Majewski, Paweł W; Yager, Kevin G

    2015-12-18

    We examine the role of intrinsic chain susceptibility anisotropy in magnetic field directed self-assembly of a block copolymer using in situ x-ray scattering. Alignment of a lamellar mesophase is observed on cooling across the disorder-order transition with the resulting orientational order inversely proportional to the cooling rate. We discuss the origin of the susceptibility anisotropy, Δχ, that drives alignment and calculate its magnitude using coarse-grained molecular dynamics to sample conformations of surface-tethered chains, finding Δχ≈2×10^{-8}. From field-dependent scattering data, we estimate that grains of ≈1.2  μm are present during alignment. These results demonstrate that intrinsic anisotropy is sufficient to support strong field-induced mesophase alignment and suggest a versatile strategy for field control of orientational order in block copolymers.

  5. Water state and TEM analysis of Konjac irradiation copolymer

    International Nuclear Information System (INIS)

    Geng Shengrong; Xia Hezhou; Chen Xueling; Ye Lixiu; Hua Yuejin

    2012-01-01

    To study the absorption performance of Konjac-AA copolymer prepared by irradiation, the water absorbent capacity, sorbent speed and water keeping ability was determined and DSC and TEM analysis were used to explore the water content and structure characters. The results showed that on room temperature the largest water absorption speed was 16 g · g -1 · min -1 at, and the largest water absorption was 400 times at 60 min. The water absorption was affected by granularity, temperature, ion content and ion type, especially the ion type, the water keeping ability was affected by temperature and time, which was up to 35% while the fully water absorbed copolymer was kept under room temperature for 15 d. The free and bounder water content which was assimilated by the plants was 99.617%. The gel stale co polymer has a three-dimensional structure of spiral, which was constituted by spherical objects of varying sizes. (authors)

  6. Radiation degradation of α-substituted acrylate polymers and copolymers

    International Nuclear Information System (INIS)

    Helbert, J.N.; Caplan, P.J.; Poindexter, E.H.

    1977-01-01

    Radiation degradation is observed in poly(methyl α-chloroacrylate), poly(methyl α-cyanoacrylate), and poly (α-chloroacrylonitrile) homopolymers and their respective MMA copolymers when γ-irradiated in vacuo. Polymer degradation susceptibilities are quantified in terms of G(scission radicals) and G(scission) -- G(crosslinks), measured by EPR and membrane osmometry, respectively; values by these two methods are compared. Higher G(rads) values ranging from 2 to 6 and [G(s) -- G(x)] values ranging from 2 to 11 are obtained for the substituted polymers and copolymers relative to the values for PMMA (1.6; 1.9), a standard e-beam positive resist, which suggests that these modified polymers are more sensitive e-beam resists than PMMA

  7. Room-Temperature-Cured Copolymers for Lithium Battery Gel Electrolytes

    Science.gov (United States)

    Meador, Mary Ann B.; Tigelaar, Dean M.

    2009-01-01

    Polyimide-PEO copolymers (PEO signifies polyethylene oxide) that have branched rod-coil molecular structures and that can be cured into film form at room temperature have been invented for use as gel electrolytes for lithium-ion electric-power cells. These copolymers offer an alternative to previously patented branched rod-coil polyimides that have been considered for use as polymer electrolytes and that must be cured at a temperature of 200 C. In order to obtain sufficient conductivity for lithium ions in practical applications at and below room temperature, it is necessary to imbibe such a polymer with a suitable carbonate solvent or ionic liquid, but the high-temperature cure makes it impossible to incorporate and retain such a liquid within the polymer molecular framework. By eliminating the high-temperature cure, the present invention makes it possible to incorporate the required liquid.

  8. Creating surfactant nanoparticles for block copolymer composites through surface chemistry.

    Science.gov (United States)

    Kim, Bumjoon J; Bang, Joona; Hawker, Craig J; Chiu, Julia J; Pine, David J; Jang, Se Gyu; Yang, Seung-Man; Kramer, Edward J

    2007-12-04

    A simple strategy to tailor the surface of nanoparticles for their specific adsorption to and localization at block copolymer interfaces was explored. Gold nanoparticles coated by a mixture of low molecular weight thiol end-functional polystyrene (PS-SH) (Mn = 1.5 and 3.4 kg/mol) and poly(2-vinylpyridine) homopolymers (P2VP-SH) (Mn = 1.5 and 3.0 kg/mol) were incorporated into a lamellar poly(styrene-b-2-vinylpyridine) diblock copolymer (PS-b-P2VP) (Mn = 196 kg/mol). A library of nanoparticles with varying PS and P2VP surface compositions (FPS) and high polymer ligand areal chain densities was synthesized. The location of the nanoparticles in the PS-b-P2VP block copolymer was determined by transmission electron microscopy. Sharp transitions in particle location from the PS domain to the PS/P2VP interface, and subsequently to the P2VP domain, were observed at FPS = 0.9 and 0.1, respectively. This extremely wide window of FPS values where the polymer-coated gold nanoparticles adsorb to the interface suggests a redistribution of PS and P2VP polymers on the Au surface, inducing the formation of amphiphilic nanoparticles at the PS/P2VP interface. In a second and synthetically more challenging approach, gold nanoparticles were covered with a thiol terminated random copolymer of styrene and 2-vinylpyridine synthesized by RAFT polymerization. Two different random copolymers were considered, where the molecular weight was fixed at 3.5 kg/mol and the relative incorporation of styrene and 2-vinylpyridine repeat units varied (FPS = 0.52 and 0.40). The areal chain density of these random copolymers on Au is unfortunately not high enough to preclude any contact between the P2VP block of the block copolymer and the Au surface. Interestingly, gold nanoparticles coated by the random copolymer with FPS = 0.4 were dispersed in the P2VP domain, while those with FPS = 0.52 were located at the interface. A simple calculation for the adsorption energy to the interface of the nanoparticles

  9. Dynamics of interacting edge defects in copolymer lamellae

    Science.gov (United States)

    Dalnoki-Veress, Kari; McGraw, Joshua D.; Rowe, Ian D. W.

    2011-03-01

    It is known that terraces at the interface of lamella forming diblock copolymers do not make discontinuous jumps in height. Rather, their profiles are smoothly varying. The width of the transition region between two lamellar heights is typically several hundreds of nanometres, resulting from a balance between surface tension, chain stretching penalties, and the enthalpy of mixing. What is less well known in these systems is what happens when two transition regions approach one another. In this study, we show that time dependent experimental data of interacting copolymer lamellar edges is consistent with a model that assumes a repulsion between adjacent edges. The range of the interaction between edge defects is consistent with the profile width of noninteracting diblock terraces. Financial support from NSERC of Canada is gratefully acknowledged.

  10. Copolymers for soft hydrophilic contact lenses: development and investigations

    International Nuclear Information System (INIS)

    Schwach, G.W.

    1978-05-01

    Low esters of methacrylic acid which may be polymerized by different methods are used predominantly for producing soft hydrophilic contact lenses. Compounds of the vinyl-type often are added to improve the optical and mechanical qualities. Composition as well as possibilities of polymerization by irradiation were tested so long until copolymers were found which finally allowed the production of soft hydrophilic contact lenses. Swelling characteristics and permeability of the different elastomeres are to be investigated in order to guarantee sufficient compatibility of contact lenses. Contamination of the lens materials by microorganisms is also a point of special interest. The effects on the hydrophilic contact lens-copolymers by different substances used for cleaning and storage solutions have been investigated as well. (author)

  11. Investigation of some copolymers based on acrylic salts as circulation loss control agents

    Directory of Open Access Journals (Sweden)

    Ahmed Mohamed Alsabagh

    2013-12-01

    The prepared copolymers were investigated as loss circulation control materials by measuring different filtration parameters such as; spurt loss, fluid loss and permeability plugging tester value according to the American Petroleum Institute (API standard. From the obtained data, it was found that the 0.6% from the poly[PA-co-AM](0.4:0.6 exhibited the best results of the filtration parameters among the other copolymers. At the same time all the studied copolymers enhanced the rheological properties of the drilling mud. These results were discussed on the light of the swelling capacity of the copolymers.

  12. Molecular architecture of electroactive and biodegradable copolymers composed of polylactide and carboxyl-capped aniline trimer.

    Science.gov (United States)

    Guo, Baolin; Finne-Wistrand, Anna; Albertsson, Ann-Christine

    2010-04-12

    Two-, four-, and six-armed branched copolymers with electroactive and biodegradable properties were synthesized by coupling reactions between poly(l-lactides) (PLLAs) with different architecture and carboxyl-capped aniline trimer (CCAT). The aniline oligomer CCAT was prepared from amino-capped aniline trimer and succinic anhydride. FT-IR, NMR, and SEC analyses confirmed the structure of the branched copolymers. UV-vis spectra and cyclic voltammetry of CCAT and copolymer solution showed good electroactive properties, similar to those of polyaniline. The water contact angle of the PLLAs was the highest, followed by the undoped copolymer and the doped copolymers. The values of doped four-armed copolymers were 54-63 degrees . Thermal properties of the polymers were studied by DSC and TGA. The copolymers had better thermal stability than the pure PLLAs, and the T(g) between 48-58 degrees C and T(m) between 146-177 degrees C of the copolymers were lower than those of the pure PLLA counterparts. This kind of electroactive and biodegradable copolymer has a great potential for applications in cardiovascular or neuronal tissue engineering.

  13. Infrared and ultraviolet spectroscopic studies of low-temperature radiolysis of ethylene - styrene copolymers

    International Nuclear Information System (INIS)

    Mal'tseva, A.P.; Golikov, V.P.; Leshchenko, S.S.; Karpov, V.L.

    1977-01-01

    Certain features of low-temperature radiolysis of statistic ethylene-styrene copolymers have been studied by infrared and ultraviolet spectroscopy. It is shown that the nature of the accumulation and decay of trans-vinylene, vinyl and vinylidene double bonds in an ethylene-styrene copolymer is essentially influenced by both the dose absorbed and copolymer composition. A suggestion is made that the ethylene-styrene copolymer is formed when structures are irradiated containing double bonds conjugated with the phenyl rings of styrene groups - which more effectively dissipate the absorbed energy than solitary phenyl rings

  14. Thermodynamics of Surfactants, Block Copolymers and Their Mixtures in Water: The Role of the Isothermal Calorimetry

    Science.gov (United States)

    De Lisi, Rosario; Milioto, Stefania; Muratore, Nicola

    2009-01-01

    The thermodynamics of conventional surfactants, block copolymers and their mixtures in water was described to the light of the enthalpy function. The two methodologies, i.e. the van’t Hoff approach and the isothermal calorimetry, used to determine the enthalpy of micellization of pure surfactants and block copolymers were described. The van’t Hoff method was critically discussed. The aqueous copolymer+surfactant mixtures were analyzed by means of the isothermal titration calorimetry and the enthalpy of transfer of the copolymer from the water to the aqueous surfactant solutions. Thermodynamic models were presented to show the procedure to extract straightforward molecular insights from the bulk properties. PMID:19742173

  15. Functional Block Copolymers as Compatibilizers for Nanoclays in Polypropylene Nanocomposites

    DEFF Research Database (Denmark)

    Jankova Atanasova, Katja; Daugaard, Anders Egede; Stribeck, Norbert

    2011-01-01

    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...... crystallites) is replaced by alien-reinforcement (of the MMT). Furthermore, the results from the impact strength and cyclic test of the prepared PP nanocomposites [3] are promicing....

  16. Rapid transitions between defect configurations in a block copolymer melt.

    Science.gov (United States)

    Tsarkova, Larisa; Knoll, Armin; Magerle, Robert

    2006-07-01

    With in situ scanning force microscopy, we image the ordering of cylindrical microdomains in a thin film of a diblock copolymer melt. Tracking the evolution of individual defects reveals elementary steps of defect motion via interfacial undulations and repetitive transitions between distinct defect configurations on a time scale of tens of seconds. The velocity of these transitions suggests a cooperative movement of clusters of chains. The activation energy for the opening/closing of a connection between two cylinders is estimated.

  17. Styrene-Based Copolymer for Polymer Membrane Modifications

    OpenAIRE

    Harsha Srivastava; Harshad Lade; Diby Paul; G. Arthanareeswaran; Ji Hyang Kweon

    2016-01-01

    Poly(vinylidene fluoride) (PVDF) was modified with a styrene-based copolymer. The crystalline behavior, phase, thermal stability, and surface morphology of the modified membranes were analyzed. The membrane surface roughness showed a strong dependence on the styrene-acrylonitrile content and was reduced to 34% for a PVDF/styrene-acrylonitrile blend membrane with a 40/60 ratio. The thermal and crystalline behavior confirmed the blend miscibility of both polymers. It was observed in X-ray diffr...

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

    Science.gov (United States)

    2012-07-17

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

  19. Process for producing a novel copolymer. [electron beams

    Energy Technology Data Exchange (ETDEWEB)

    Oiwa, M; Matsumoto, A; Tojima, M; Matsumoto, K; Sasaki, H

    1970-11-27

    Diaryl oxalate present in a polymer not only decomposes at lower temperatures, but also provides for stronger free radicals initiating polymerization than diaryl oxalate present in a monomer. A copolymer of vinyl monomers is produced by providing a diaryl oxalate polymer or a diaryl oxalate monomer-co-vinyl monomer, decomposing them to release the diaryl oxalate units by heating or irradiating with radiation thereby copolymerizing the vinyl monomer with the polymer radicals by utilizing the diaryl oxalate unit. For example, a single diaryl oxalate polymer or a copolymer containing the diaryl oxalate polymer as a constituent of the copolymer are irradiated or heated with a vinyl monomer, i.e. methyl methacrylate, acrylnitrile, vinyl acetate, styrene etc., to form a copolymer without difficulty. In one of the examples, 500 g of diaryl oxalate monomer, 1,200 ml of benzene and 0.2 mol/l of benzoil peroxide as an initiator were mixed and polymerized in nitrogen gas at 70/sup 0/C for 8 hrs. From this polymerized solution, a polymer was deposited in methanol. The produced polymer had an iodin value of 77.7 with a yield of 35%. The gel content of the produced polymer was 98.9% for 10 Mrad. This polymer was dissolved in methyl methacrylate, thereafter filled in a mold and irradiated with electron beams of 2 MeV in nitrogen gas to harden it. The advantage of this process is that the polymerization is effected with low energy radiations at room temperature without requiring any catalyst.

  20. Ethylene vinylacetate copolymer and nanographite composite as chemical vapour sensor

    International Nuclear Information System (INIS)

    Stepina, Santa; Sakale, Gita; Knite, Maris

    2013-01-01

    Polymer-nanostructured carbon composite as chemical vapour sensor is described, made by the dissolution method of a non-conductive polymer, ethylene vinylacetate copolymer, mixed with conductive nanographite particles (carbon black). Sensor exhibits relative electrical resistance change in chemical vapours, like ethanol and toluene. Since the sensor is relatively cheap, easy to fabricate, it can be used in air quality monitoring and at industries to control hazardous substance concentration in the air, for example, to protect workers from exposure to chemical spills

  1. Block copolymer micelles as switchable templates for nanofabrication

    OpenAIRE

    Krishnamoorthy, S; Pugin, R; Brugger, J; Heinzelmann, H; Hoogerwerf, A C; Hinderling, C

    2006-01-01

    Block copolymer inverse micelles from polystyrene-block-poly-2-vinylpyridine (PS-b-P2VP) deposited as monolayer films onto surfaces show responsive behavior and are reversibly switchable between two states of different topography and surface chemistry. The as-coated films are in the form of arrays of nanoscale bumps, which can be transformed into arrays of nanoscale holes by switching through exposure to methanol. The use of these micellar films to act as switchable etch masks for the structu...

  2. Block copolymer libraries: modular versatility of the macromolecular Lego system.

    Science.gov (United States)

    Lohmeijer, Bas G G; Wouters, Daan; Yin, Zhihui; Schubert, Ulrich S

    2004-12-21

    The synthesis and characterization of a new 4 x 4 library of block copolymers based on polystyrene and poly(ethylene oxide) connected by an asymmetrical octahedral bis(terpyridine) ruthenium complex at the block junction are described, while initial studies on the thin film morphology of the components of the library are presented by the use of Atomic Force Microscopy, demonstrating the impact of a library approach to derive structure-property relationships.

  3. Localization of a random copolymer at an interface

    International Nuclear Information System (INIS)

    Madras, N; Whittington, S G

    2003-01-01

    We investigate the nature of the phase diagram for a self-avoiding walk model of a random copolymer at an interface between two immiscible solvents, when one monomer prefers to be in one solvent, the other monomer prefers to be in the other solvent, and both types of monomer have an attractive or repulsive interaction with the interface. Our results are all rigorous, and extend previous work of Maritan et al (1999) and Martin et al (2000)

  4. Donor-Acceptor Block Copolymers: Synthesis and Solar Cell Applications

    Directory of Open Access Journals (Sweden)

    Kazuhiro Nakabayashi

    2014-04-01

    Full Text Available Fullerene derivatives have been widely used for conventional acceptor materials in organic photovoltaics (OPVs because of their high electron mobility. However, there are also considerable drawbacks for use in OPVs, such as negligible light absorption in the visible-near-IR regions, less compatibility with donor polymeric materials and high cost for synthesis and purification. Therefore, the investigation of non-fullerene acceptor materials that can potentially replace fullerene derivatives in OPVs is increasingly necessary, which gives rise to the possibility of fabricating all-polymer (polymer/polymer solar cells that can deliver higher performance and that are potentially cheaper than fullerene-based OPVs. Recently, considerable attention has been paid to donor-acceptor (D-A block copolymers, because of their promising applications as fullerene alternative materials in all-polymer solar cells. However, the synthesis of D-A block copolymers is still a challenge, and therefore, the establishment of an efficient synthetic method is now essential. This review highlights the recent advances in D-A block copolymers synthesis and their applications in all-polymer solar cells.

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

    Science.gov (United States)

    Zhang, Jingwen; Sides, Scott; Bates, Frank

    2013-03-01

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

  6. Molecular Mobility in Phase Segregated Bottlebrush Block Copolymer Melts

    Science.gov (United States)

    Yavitt, Benjamin; Gai, Yue; Song, Dongpo; Winter, H. Henning; Watkins, James

    We investigate the linear viscoelastic behavior of poly(styrene)-block-poly(ethylene oxide) (PS-b-PEO) brush block copolymer (BBCP) materials over a range of vol. fractions and with side chain lengths below the entanglement molecular weights. The high chain mobility of the brush architecture results in rapid micro-phase segregation of the brush copolymer segments, which occurs during thermal annealing at mild temperatures. Master curves of the dynamic moduli were obtained by time-temperature superposition. The reduced degree of chain entanglements leads to a unique liquid-like rheology similar to that of bottlebrush homopolymers, even in the phase segregated state. We also explore the alignment of phase segregated domains at exceptionally low strain amplitudes (γ = 0.01) and mild processing temperatures using small angle X-ray scattering (SAXS). Domain orientation occurred readily at strains within the linear viscoelastic regime without noticeable effect on the moduli. This interplay of high molecular mobility and rapid phase segregation that are exhibited simultaneously in BBCPs is in contrast to the behavior of conventional linear block copolymer (LBCP) analogs and opens up new possibilities for processing BBCP materials for a wide range of nanotechnology applications. NSF Center for Hierarchical Manufacturing at the University of Massachusetts, Amherst (CMMI-1025020).

  7. Controlled Assembly of Fibronectin Nanofibrils Triggered by Random Copolymer Chemistry.

    Science.gov (United States)

    Mnatsakanyan, Hayk; Rico, Patricia; Grigoriou, Eleni; Candelas, Aarón Maturana; Rodrigo-Navarro, Aleixandre; Salmeron-Sanchez, Manuel; Sabater i Serra, Roser

    2015-08-19

    Fibronectin fibrillogenesis is the physiological process by which cells elaborate a fibrous FN matrix. Poly(ethyl acrylate), PEA, has been described to induce a similar process upon simple adsorption of fibronectin (FN) from a protein solution-in the absence of cells-leading to the so-called material-driven fibronectin fibrillogenesis. Poly(methyl acrylate), PMA, is a polymer with very similar chemistry to PEA, on which FN is adsorbed, keeping the globular conformation of the protein in solution. We have used radical polymerization to synthesize copolymers with controlled EA/MA ratio, seeking to modulate the degree of FN fibrillogenesis. The physicochemical properties of the system were studied using dynamic-mechanical analysis, differential scanning calorimetry, and water contact angle. Both the degree of FN fibrillogenesis and the availability of the integrin binding region of FN directly depend on the percentage of EA in the copolymer, whereas the same total amount of FN was adsorbed regardless the EA/MA ratio. Cell morphology adhesion and differentiation of murine C2C12 were shown to depend on the degree of FN fibrillogenesis previously attained on the material surface. Myogenic differentiation was enhanced on the copolymers with higher EA content, i.e. more interconnected FN fibrils.

  8. Formation and Characterization of Anisotropic Block Copolymer Gels

    Science.gov (United States)

    Liaw, Chya Yan; Joester, Derk; Burghardt, Wesley; Shull, Kenneth

    2012-02-01

    Cylindrical micelles formed from block copolymer solutions closely mimic biological fibers that are presumed to guide mineral formation during biosynthesis of hard tissues like bone. The goal of our work is to use acrylic block copolymers as oriented templates for studying mineral formation reactions in model systems where the structure of the underlying template is well characterized and reproducible. Self-consistent mean field theory is first applied to investigate the thermodynamically stable micellar morphologies as a function of temperature and block copolymer composition. Small-angle x-ray scattering, optical birefringence and shear rheometry are used to study the morphology development during thermal processing. Initial experiments are based on a thermally-reversible alcohol-soluble system that can be converted to an aqueous gel by hydrolysis of a poly(t-butyl methacrylate) block to a poly(methacrylic acid) block. Aligned cylindrical domains are formed in the alcohol-based system when shear is applied in an appropriate temperature regime, which is below the critical micelle temperature but above the temperature at which the relaxation time of the gels becomes too large. Processing strategies for producing the desired cylindrical morphologies are being developed that account for both thermodynamic and kinetic effects.

  9. High-frequency ultrasound-responsive block copolymer micelle.

    Science.gov (United States)

    Wang, Jie; Pelletier, Maxime; Zhang, Hongji; Xia, Hesheng; Zhao, Yue

    2009-11-17

    Micelles of a diblock copolymer composed of poly(ethylene oxide) and poly(2-tetrahydropyranyl methacrylate) (PEO-b-PTHPMA) in aqueous solution could be disrupted by high-frequency ultrasound (1.1 MHz). It was found that, upon exposure to a high-intensity focused ultrasound (HIFU) beam at room temperature, the pH value of the micellar solution decreased over irradiation time. The infrared spectroscopic analysis of solid block copolymer samples collected from the ultrasound irradiated micellar solution revealed the formation of carboxylic acid dimers and hydroxyl groups. These characterization results suggest that the high-frequency HIFU beam could induce the hydrolysis reaction of THPMA at room temperature resulting in the cleavage of THP groups. The disruption of PEO-b-PTHPMA micelles by ultrasound was investigated by using dynamic light scattering, atomic force microscopy, and fluorescence spectroscopy. On the basis of the pH change, it was found that the disruption process was determined by a number of factors such as the ultrasound power, the micellar solution volume and the location of the focal spot of the ultrasound beam. This study shows the potential to develop ultrasound-sensitive block copolymer micelles by having labile chemical bonds in the polymer structure, and to use the high-frequency HIFU to trigger a chemical reaction for the disruption of micelles.

  10. Removal of Industrial Pollutants From Wastewater's By Graft Copolymers

    International Nuclear Information System (INIS)

    Hegazy El-Sayed, A.; El-Nagar Abdel-Wahab, M.; Senna Magdy, M.; Zahran Abdel-Hamid, H.

    1999-01-01

    Graft copolymers that obtained by radiation grafting of acrylic acid and acrylamide onto LDPE film were converted to N-hydroxy ethyl amide and hydroxamic acid derivatives respectively. The possible application for the different prepared chemical derivatives of LDPE graft copolymers in metal adsorption from solutions containing a single cation or simulated medium active waste has been investigated. The results showed that the adsorption of Cu(II) metal by different chemical derivatives was greatly affected by different factors such as graft yield, ph value, concentration of metal in the feed solution, immersion time and treatment temperature. The affinity of N-hydroxy ethyl amide derivative toward the different metals was found to be in the order of; Cu(II) >Pd(II) > Cd(II)> Co(II). However, for hydroxamic acid derivative , the affinity order was: Cd(II) > Cu(II) > Co(II). The ESR and IR analysis revealed that the metal ions are chelated through the lone pair of electrons on the -OH and -NH- groups forming a ring structure. The measured metal ion uptake from simulated medium active waste mixture by N-hydroxy ethyl amide derivative was found to follow the following order: Fe> U> Ni> Zr> Zn> Cr. On the other hand, the measured metal uptake by hydroxamic acid derivative was found to follow: Fe>U> Zr> Ca. It is concluded that the prepared grafted copolymers are of interest for metal chelation and could be applied in the field of waste treatment

  11. PTCR effect in carbon black/copolymer composites

    International Nuclear Information System (INIS)

    Costa, L.C.; Chakki, A.; Achour, M.E.; Graca, M.P.F.

    2011-01-01

    Some materials show an abrupt increase in resistivity when the temperature changes only over a few degrees. This phenomenon, known as PTCR effect (positive temperature coefficient of resistivity), has been largely studied in the last few years, due to its potential applications in industry. Particularly, it can be used in auto controlled heaters, temperature sensors, protection circuits and in security systems for power electronic circuits. In this work we present the study of the electrical properties of the percolating system carbon black particles filled with ethylene butylacrylate copolymer composite (EBA), in the temperature range from -100 to 100 o C and in frequencies between 10 Hz and 100 kHz. The PTCR effect was observed at temperatures slightly above the room temperature, for concentrations higher than that of the percolation critical concentration. The mechanism responsible for the change in resistivity, at this stage, is predominantly tunnelling, wherein the conductive filler particles are not in physical contact, and the electrons tunnel through the insulating gap between them. At low temperatures, such as below and close to the glass transition temperature, the DC conductivity obeys the Arrhenius law. The calculated activation energy values are independent of carbon black contents inside the copolymer matrix, suggesting that these particles do not interact significantly with the chain segments of the macromolecules in the EBA copolymer.

  12. PTCR effect in carbon black/copolymer composites

    Energy Technology Data Exchange (ETDEWEB)

    Costa, L.C., E-mail: kady@fis.ua.p [I3N and Physics Department, University of Aveiro, 3810-193 Aveiro (Portugal); Chakki, A.; Achour, M.E. [LASTID, Physics Department, Faculty of Sciences, Ibn Tofail University, BP 133, 14000 Kenitra (Morocco); Graca, M.P.F. [I3N and Physics Department, University of Aveiro, 3810-193 Aveiro (Portugal)

    2011-01-15

    Some materials show an abrupt increase in resistivity when the temperature changes only over a few degrees. This phenomenon, known as PTCR effect (positive temperature coefficient of resistivity), has been largely studied in the last few years, due to its potential applications in industry. Particularly, it can be used in auto controlled heaters, temperature sensors, protection circuits and in security systems for power electronic circuits. In this work we present the study of the electrical properties of the percolating system carbon black particles filled with ethylene butylacrylate copolymer composite (EBA), in the temperature range from -100 to 100 {sup o}C and in frequencies between 10 Hz and 100 kHz. The PTCR effect was observed at temperatures slightly above the room temperature, for concentrations higher than that of the percolation critical concentration. The mechanism responsible for the change in resistivity, at this stage, is predominantly tunnelling, wherein the conductive filler particles are not in physical contact, and the electrons tunnel through the insulating gap between them. At low temperatures, such as below and close to the glass transition temperature, the DC conductivity obeys the Arrhenius law. The calculated activation energy values are independent of carbon black contents inside the copolymer matrix, suggesting that these particles do not interact significantly with the chain segments of the macromolecules in the EBA copolymer.

  13. Application of Bottlebrush Block Copolymers as Photonic Crystals.

    Science.gov (United States)

    Liberman-Martin, Allegra L; Chu, Crystal K; Grubbs, Robert H

    2017-07-01

    Brush block copolymers are a class of comb polymers that feature polymeric side chains densely grafted to a linear backbone. These polymers display interesting properties due to their dense functionality, low entanglement, and ability to rapidly self-assemble to highly ordered nanostructures. The ability to prepare brush polymers with precise structures has been enabled by advancements in controlled polymerization techniques. This Feature Article highlights the development of brush block copolymers as photonic crystals that can reflect visible to near-infrared wavelengths of light. Fabrication of these materials relies on polymer self-assembly processes to achieve nanoscale ordering, which allows for the rapid preparation of photonic crystals from common organic chemical feedstocks. The characteristic physical properties of brush block copolymers are discussed, along with methods for their preparation. Strategies to induce self-assembly at ambient temperatures and the use of blending techniques to tune photonic properties are emphasized. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. (Electro)Mechanical Properties of Olefinic Block Copolymers

    Science.gov (United States)

    Spontak, Richard

    2014-03-01

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

  15. Acrylic Triblock Copolymers Incorporating Isosorbide for Pressure Sensitive Adhesives

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-05-10

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

  16. Ductile electroactive biodegradable hyperbranched polylactide copolymers enhancing myoblast differentiation.

    Science.gov (United States)

    Xie, Meihua; Wang, Ling; Guo, Baolin; Wang, Zhong; Chen, Y Eugene; Ma, Peter X

    2015-12-01

    Myotube formation is crucial to restoring muscular functions, and biomaterials that enhance the myoblast differentiation into myotubes are highly desirable for muscular repair. Here, we report the synthesis of electroactive, ductile, and degradable copolymers and their application in enhancing the differentiation of myoblasts to myotubes. A hyperbranched ductile polylactide (HPLA) was synthesized and then copolymerized with aniline tetramer (AT) to produce a series of electroactive, ductile and degradable copolymers (HPLAAT). The HPLA and HPLAAT showed excellent ductility with strain to failure from 158.9% to 42.7% and modulus from 265.2 to 758.2 MPa. The high electroactivity of the HPLAAT was confirmed by UV spectrometer and cyclic voltammogram measurements. These HPLAAT polymers also showed improved thermal stability and controlled biodegradation rate compared to HPLA. Importantly, when applying these polymers for myotube formation, the HPLAAT significantly improved the proliferation of C2C12 myoblasts in vitro compared to HPLA. Furthermore, these polymers greatly promoted myogenic differentiation of C2C12 cells as measured by quantitative analysis of myotube number, length, diameter, maturation index, and gene expression of MyoD and TNNT. Together, our study shows that these electroactive, ductile and degradable HPLAAT copolymers represent significantly improved biomaterials for muscle tissue engineering compared to HPLA. Copyright © 2015 Elsevier Ltd. All rights reserved.

  17. Functionalized and graft copolymers of chitosan and its pharmaceutical applications.

    Science.gov (United States)

    Bhavsar, Chintan; Momin, Munira; Gharat, Sankalp; Omri, Abdelwahab

    2017-10-01

    Chitosan is the second most abundant natural polysaccharide. It belongs a family of polycationic polymers comprised of repetitive units of glucosamine and N-acetylglucosamine. Its biodegradability, nontoxicity, non-immunogenicity and biocompatibility along with properties like mucoadhesion, fungistatic and bacteriogenic have made chitosan an appreciated polymer with numerous applications in the pharmaceutical, comestics and food industry. However, the limited solubility of chitosan at alkaline and neutral pH limits its widespread commercial use. This can be circumvented by fabrication of chitosan by graft copolymerization with acyl, alkyl, monomeric and polymeric moieties. Areas covered: Modifications like quarterization, thiolation, acylation and grafting result in copolymers with higher mucoadhesion strength, increased hydrophobic interactions (advantageous in hydrophobic drug entrapment), and increased solubility in alkaline pH, the ability for adsorption of metal ions, protein and peptide delivery and nutrient delivery. Insights on methods of polymerization, including atomic transfer radical polymerization and click chemistry are discussed. Applications of such modified chitosan copolymers in medical and surgical, and drug delivery, including nasal, oral and buccal delivery have also been covered. Expert opinion: Despite a number of successful investigations, commercialization of chitosan copolymers still remains a challenge. Further advancements in polymerization techniques may address the unmet needs of the healthcare industry.

  18. Synthesis and thermal behavior of polyacrylonitrile/vinylidene chloride copolymer

    Directory of Open Access Journals (Sweden)

    Robson Fleming

    2014-06-01

    Full Text Available Polyacrylonitrile fiber encompasses a broad range of products based on acrylonitrile (AN which is readily copolymerized with a wide range of ethylenic unsaturated monomers giving rise to polymers with different characteristics and applications. Such products can be designed for cost-effective, flame and heat resistant solutions for the textile industry, aircraft and automotive markets. In the present work acrylonitrile was copolymerized with vinylidene chloride (VDC by conventional suspension polymerization process via redox system, with an initial content of 10%/mass of the VDC monomer. The copolymer average molecular weight was obtained by Gel Permeation Chromatography (GPC and by intrinsic viscosity analysis. To control the polymerization process continuously, qualitative and quantitative analysis of the chloride content in the PAN AN/VDC copolymer structure was accomplished by using X-ray fluorescence and potentiometric titration techniques. A good correlation was found between these two techniques, leading to a straightforward verification of VDC in the polymer structure. The thermal behavior of PAN AN/VDC copolymer was performed by Differential Scanning Calorimetry (DSC and Thermogravimetric Analysis (TGA. The results showed that VDC monomers exhibited a nearly stoichiometric reaction with acrylonitrile, copolymerizing about 90% of its initial mass. VDC changed significantly the polyacrylonitrile thermal behavior, decreasing the polymer degradation temperature by about 40-50°C.

  19. Morphology evolution of PS-b-PDMS block copolymer and its hierarchical directed self-assembly on block copolymer templates

    DEFF Research Database (Denmark)

    Rasappa, Sozaraj; Schulte, Lars; Borah, Dipu

    2018-01-01

    Cylinder-forming polystyrene-block-polydimethylsiloxane (PS-b-PDMS, 27.2k-b-11.7k, SD39) block copolymer having a total molecular weight of 39 kg mol−1 was exploited to achieve in-plane morphologies of lines, dots and antidots. Brush-free self-assembly of the SD39 on silicon substrates was invest...... substrates provides a simplified method for surface nanopatterning, templated growth of nanomaterials and nanofabrication....... the pattern into the underlying substrate. Directed self-assembly and hierarchical directed self-assembly on block copolymer templates for confinement of dots was successfully demonstrated. The strategy for achieving multiple morphologies using one BCP by mere choice of the annealing solvents on unmodified...

  20. Coarse-grained modeling of hybrid block copolymer system

    Science.gov (United States)

    Su, Yongrui

    This thesis is comprised of three major projects of my research. In the first project, I proposed a nanoparticle model and combined it with the Theoretically Informed Coarse Grained (TICG) model for pure polymer systems and the grand canonical slip springs model developed in our group to build a new model for entangled nanocomposites. With Molecule Dynamics(MD) simulation, I studied the mechanic properties of the nanocomposites, for example the influence of nanoparticles size and volume fraction on entanglements, the diffusion of polymers and nanoparticles, and the influence of nanoparticles size and volume fraction on viscosity et al.. We found that the addition of small-size nanoparticles reduces the viscosity of the nanocomposites, which is in contrary to what Einstein predicted a century ago. However, when particle increases its size to micrometers the Einstein predictions is recovered. From our simulation, we believe that small-size nanoparticles can more effectively decrease the entanglements of nanocomposites than larger particles. The free volume effect introduced by small-size nanoparticles also helps decrease the viscosity of the whole system. In the second project, I combined the Ohta-Kawasaki (OK) model [3] and the Covariance Matrix Adaptation Evolutionary Strategy(CMA-ES) to optimize the block copolymer blends self-assembly in the hole-shrink process. The aim is to predict the optimal composition and the optimal surface energy to direct the block copolymer blends self-assembly process in the confined hole. After optimization in the OK model, we calibrated the optimal results by the more reliable TICG model and got the same morphology. By comparing different optimization process, we found that the homopolymers which are comprised of the same monomers as either block of the block copolymer can form a perfect perforated hole and might have better performance than the pure block copolymer. While homopolymers which are comprised of a third-party monomers

  1. Self-Assembled Structures of PMAA-PMMA Block Copolymers : Synthesis, Characterization, and Self-Consistent Field Computations

    NARCIS (Netherlands)

    Li, Feng; Schellekens, Mike; de Bont, Jens; Peters, Ron; Overbeek, Ad; Leermakers, Frans A. M.; Tuinier, Remco

    2015-01-01

    Block copolymers composed of methacrylic acid (MAA) and methyl methacrylate (MMA) blocks are interesting candidates for replacing surfactants in emulsion polymerization methods. Here the synthesis and experimental characterization of well-defined PMAA-PMMA block copolymers made via RAFT

  2. Self-assembled structures of PMAA-PMMA block copolymers: Synthesis, characterization, and self-consistent field computations

    NARCIS (Netherlands)

    Li, F.; Schellekens, J.; Bont, de J.A.M.; Peters, R.; Overbeek, A.; Leermakers, F.A.M.; Tuinier, R.

    2015-01-01

    Block copolymers composed of methacrylic acid (MAA) and methyl methacrylate (MMA) blocks are interesting candidates for replacing surfactants in emulsion polymerization methods. Here the synthesis and experimental characterization of well-defined PMAA–PMMA block copolymers made via RAFT

  3. Microspheres for protein delivery prepared from amphiphilic multiblock copolymers. 1. influence of preparation techniques on particle characteristics and protein delivery

    NARCIS (Netherlands)

    Bezemer, J.M.; Radersma, R.; Grijpma, Dirk W.; Dijkstra, Pieter J.; van Blitterswijk, Clemens; Feijen, Jan

    2000-01-01

    The entrapment of lysozyme in amphiphilic multiblock copolymer microspheres by emulsification and subsequent solvent removal processes was studied. The copolymers are composed of hydrophilic poly(ethylene glycol) (PEG) blocks and hydrophobic poly(butylene terephthalate) (PBT) blocks. Direct solvent

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2005-12-17

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

  5. Study of the molecular mobility of methyl-methacrylate and methacrylic acid copolymers by solid state NMR

    International Nuclear Information System (INIS)

    Tavares, Maria Ines B.; Mansur, Claudia R.E.; Monteiro, Elisabeth E.C.

    1997-01-01

    Several methyl-methacrylate/methacrylic acid copolymers were prepared in the presence of concentrated nitric acid. The obtained copolymers were characterized by molecular weigh determination and hydrolization degree. The molecular mobility of these copolymers was studied by solid state nuclear magnetic resonance. Results are presented

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

    DEFF Research Database (Denmark)

    Jankova, Katja; Hvilsted, Søren

    2005-01-01

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

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

    Czech Academy of Sciences Publication Activity Database

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

    2012-01-01

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

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

    NARCIS (Netherlands)

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

    2004-01-01

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

  9. Light scattering from block copolymer melts near the order-disorder transition

    Czech Academy of Sciences Publication Activity Database

    Štěpánek, Petr; Lodge, T. P.; Bates, F. S.

    1994-01-01

    Roč. 2, - (1994), s. 110 ISSN 0009-2347. [Symposium Block Copolymer Dynamics, Chain Dynamics of Block Copolymers: Dynamics near the Ordering Transition. San Diego, 13.03.1994-18.03.1994] R&D Projects: GA AV ČR IA45023 Impact factor: 0.331, year: 1994

  10. About morphology in ethylene-propylene(-diene) copolymers-based latexes

    NARCIS (Netherlands)

    Tillier, D.L.; Meuldijk, J.; Hoehne, G.W.H.; Frederik, P.M.; Regev, O.; Koning, C.E.

    2005-01-01

    Coatings and engineering plastics often require high impact strength. This property can be achieved with tougheners. For the present paper, core-shell impact modifiers were synthesized using ethylene–propylene copolymers (EPM), ethylene–propylene-diene copolymers (EPDM) or a mixture of both types

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

    DEFF Research Database (Denmark)

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

    2009-01-01

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

  12. Vertical vs Lateral Macrophase Separation in Thin Films of Block Copolymer Mixtures

    DEFF Research Database (Denmark)

    Berezkin, Anatoly V.; Jung, Florian; Posselt, Dorthe

    2017-01-01

    Mixtures of two diblock copolymers of very different lengths may feature both macro- and microphase separation; however, not much is known about the mechanisms of separation in diblock copolymer thin films. In the present work, we study thin films of mixtures of two compositionally symmetric bloc...

  13. Poly(4-vinylpyridine)-block-poly(N-acryloylpiperidine) diblock copolymers: synthesis, self-assembly and interaction

    NARCIS (Netherlands)

    Hofman, Anton H.; Alberda van Ekenstein, Gerhard; Woortman, Albert; ten Brinke, Gerrit; Loos, Katja

    2015-01-01

    Controlled radical polymerization of 4-vinylpyridine (4VP) and N-acryloylpiperidine (API) by the RAFT process allowed preparation of well-defined double hydrogen bond accepting P4VP-b-PAPI diblock copolymers. The miscibility of this new monomer pair was studied via a random copolymer blend approach

  14. 21 CFR 177.1030 - Acrylonitrile/butadiene/styrene/methyl methacrylate copolymer.

    Science.gov (United States)

    2010-04-01

    ... methacrylate copolymer identified in this section may be safely used as an article or component of articles... monomer content of the finished copolymer articles is not more than 11 parts per million as determined by... available from the Center for Food Safety and Applied Nutrition (HFS-200), Food and Drug Administration...

  15. Self-Assembled Asymmetric Block Copolymer Membranes: Bridging the Gap from Ultra- to Nanofiltration

    KAUST Repository

    Yu, Haizhou; Qiu, Xiaoyan; Moreno, Nicolas; Ma, Zengwei; Calo, Victor M.; Nunes, Suzana Pereira; Peinemann, Klaus-Viktor

    2015-01-01

    -assembled block copolymer membranes to below 5 nm without post-treatment. It is now reported that the self-assembly of blends of two chemically interacting copolymers can lead to highly porous membranes with pore diameters as small as 1.5 nm. The membrane

  16. 21 CFR 177.1315 - Ethylene-1, 4-cyclohexylene dimethylene terephthalate copolymers.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Ethylene-1, 4-cyclohexylene dimethylene... Ethylene-1, 4-cyclohexylene dimethylene terephthalate copolymers. Ethylene-1, 4-cyclohexylene dimethylene... purposes of this section, ethylene-1,4-cyclohexylene dimethylene terephthalate copolymers (1,4-benzene...

  17. Rheological Behavior of Entangled Polystyrene-Polyhedral Oligosilsesquioxane (POSS) Copolymer (Postprint)

    National Research Council Canada - National Science Library

    Wu, Jian; Mather, Patrick T; Haddad, Timothy S; Kim, Gyeong-Man

    2006-01-01

    ...: 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...

  18. 21 CFR 175.365 - Vinylidene chloride copolymer coatings for polycarbonate film.

    Science.gov (United States)

    2010-04-01

    ... polycarbonate film. 175.365 Section 175.365 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH... chloride copolymer coatings for polycarbonate film. Vinylidene chloride copolymer coatings identified in this section and applied on polycarbonate film may be safely used as food-contact surfaces, in...

  19. Monte Carlo simulation of diblock copolymer microphases by means of a 'fast' off-lattice model

    DEFF Research Database (Denmark)

    Besold, Gerhard; Hassager, O.; Mouritsen, Ole G.

    1999-01-01

    We present a mesoscopic off-lattice model for the simulation of diblock copolymer melts by Monte Carlo techniques. A single copolymer molecule is modeled as a discrete Edwards chain consisting of two blocks with vertices of type A and B, respectively. The volume interaction is formulated in terms...

  20. Effect of cationic grafted copolymer structure on the encapsulation of bovine serum albumin

    International Nuclear Information System (INIS)

    Flynn, Nicholas; Topal, Ç. Özge; Hikkaduwa Koralege, Rangika S.; Hartson, Steve; Ranjan, Ashish; Liu, Jing; Pope, Carey; Ramsey, Joshua D.

    2016-01-01

    The aim of the present study was to evaluate a library of poly-L-lysine (PLL)-graft (g)-polyethylene glycol (PEG) copolymers for the ability to encapsulate effectively a model protein, bovine serum albumin (BSA), and to characterize the stability and protein function of the resulting nanoparticle. A library of nine grafted copolymers was produced by varying PLL molecular weight and PEG grafting ratio. Electrostatic self-assembly of the protein and the grafted copolymer drove encapsulation. The formation of protein/polymer nanoparticles with a core/shell structure was confirmed using PAGE, dynamic light scattering, and electron microscopy. Encapsulation of the BSA into nanoparticles was strongly dependent on the copolymer-to-protein mass ratio, PEG grafting ratio, and PLL molecular weight. A copolymer-to-protein mass ratio of 7:1 and higher was generally required for high levels of encapsulation, and under these conditions, no loss of protein activity was observed. Copolymer characteristics also influenced nanoparticle resistance to polyanions and protease degradation. The results indicate that a copolymer of 15–30 kDa PLL, with a PEG grafting ratio of 10:1, is most promising for protein delivery. - Highlights: • A 4–70 kDa range of PLL-g-PEG copolymers was able to encapsulate BSA into NPs. • Encapsulation of BSA by PLL-g-PEG not only retained but increased esterolytic activity. • NPs were stable against protease degradation and polyanion dissociation.

  1. Block copolymer adsorption from a homopolymer melt to an amine-terminated surface

    Czech Academy of Sciences Publication Activity Database

    Costa, A. C.; Composto, R. J.; Vlček, Petr; Geoghegan, M.

    2005-01-01

    Roč. 18, č. 2 (2005), s. 159-166 ISSN 1292-8941 R&D Projects: GA ČR GA203/01/0513 Grant - others:Americal Chemical Society, The Petroleum Research Fund(US) 38027/34081 Keywords : copolymer adsorption * neutron reflectometry * diblock copolymers Subject RIV: CD - Macromolecular Chemistry Impact factor: 2.503, year: 2005

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

    NARCIS (Netherlands)

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

    2016-01-01

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

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

    NARCIS (Netherlands)

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

    2016-01-01

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

  4. Synthesis, characterization and photoinduction of optical anisotropy in liquid crystalline diblock azo-copolymers

    NARCIS (Netherlands)

    Forcen, P.; Oriol, L.; Sanchez, S.; Alcala, R.; Hvilsted, S.; Jankova, K.; Loos, J.

    2007-01-01

    Diblock copolymers with polymethyl methacrylate and side chain liquid crystalline (LC) azopolymethacrylate blocks were synthesized by atom transfer radical polymerization (ATRP). The azobenzene content in these copolymers ranges from 52 to 7 wt %. For an azo content down to 20% they exhibit a LC

  5. Self-assembling block copolymer systems involving competing length scales : A route toward responsive materials

    NARCIS (Netherlands)

    Nap, R; Erukhimovich, [No Value; ten Brinke, G; Erukhimovich, Igor

    2004-01-01

    The phase behavior of block copolymers melts involving competing length scales, i.e., able to microphase separate on two different length scales, is theoretically investigated using a self-consistent field approach. The specific block copolymers studied consist of a linear A-block linked to an

  6. Polarizability of DNA Block Copolymer Nanoparticles Observed by Electrostatic Force Microscopy

    NARCIS (Netherlands)

    Sowwan, Mukhles; Faroun, Maryam; Mentovich, Elad; Ibrahim, Imad; Haboush, Shayma; Alemdaroglu, Fikri Emrah; Kwak, Minseok; Richter, Shachar; Herrmann, Andreas

    2010-01-01

    In this study, DNA block copolymer (DBC) micelles with a polystyrene (PS) core and a single-stranded (ss) DNA shell were doped with ferrocene (Fc) molecules. Tapping mode atomic force microscopy (AFM) was used to study the morphology of the doped and undoped block copolymer aggregates. We show that

  7. A 3x1 integrated pyroelectric sensor based on VDF/TrFE copolymer

    NARCIS (Netherlands)

    Setiadi, D.; Setiadi, D.; Sarro, P.M.; Regtien, Paulus P.L.

    1996-01-01

    This paper presents an integrated pyroelectric sensor based on a vinylidene fluoride¿trifluoroethylene (VDF/TrFE) copolymer. A silicon substrate that contains field-effect transistor (FET) readout electronics is coated with the VDF/TrFE copolymer film using a spin-coating technique. On-chip poling

  8. Swelling dynamics of zwitterionic copolymers: The effects of concentration and type of anion and cation

    NARCIS (Netherlands)

    de Grooth, Joris; Ogieglo, Wojciech; de Vos, Wiebe Matthijs; Girones nogue, Miriam; Nijmeijer, Dorothea C.; Benes, Nieck Edwin

    2014-01-01

    The effect of different salts and their concentration on the swelling of zwitterionic copolymers has been investigated for bulk polymer samples as well as for thin films. Relatively low ratios of the zwitterionic monomer already radically change the swelling properties of the copolymer. Increasing

  9. Adsorption kinetics of diblock copolymers from a micellar solution on silica and titania.

    NARCIS (Netherlands)

    Bijsterbosch, H.D.; Cohen Stuart, M.A.; Fleer, G.J.

    1998-01-01

    The solution and adsorption behavior of a series of diblock copolymers of hydrophobic poly(dimethyl siloxane) and hydrophilic poly(2-ethyl-2-oxazoline) was studied. These block copolymers formed large polydisperse micelles in an aqueous solution. The critical micelle concentration was lower than 2

  10. Iodinated glycidyl methacrylate copolymer as a radiopaque material for biomedical applications.

    Science.gov (United States)

    Dawlee, S; Jayabalan, M

    2013-07-01

    Polymeric biomaterial was synthesized by copolymerizing 50:50 mol% of monomers, glycidyl methacrylate and methyl methacrylate. Iodine atoms were then grafted to the epoxide groups of glycidyl methacrylate units, rendering the copolymer radiopaque. The percentage weight of iodine in the present copolymer was found to be as high as 23%. The iodinated copolymer showed higher glass transition temperature and thermal stability in comparison with unmodified polymer. Radiographic analysis showed that the copolymer possessed excellent radiopacity. The iodinated copolymer was cytocompatible to L929 mouse fibroblast cells. The in vivo toxicological evaluation by intracutaneous reactivity test of the copolymer extracts has revealed that the material was nontoxic. Subcutaneous implantation of iodinated copolymer in rats has shown that the material was well tolerated. Upon explantation and histological examination, no hemorrhage, infection or necrosis was observed. The samples were found to be surrounded by a vascularized capsule consisting of connective tissue cells. The results indicate that the iodinated copolymer is biocompatible and may have suitable applications as implantable materials.

  11. Effect of cationic grafted copolymer structure on the encapsulation of bovine serum albumin

    Energy Technology Data Exchange (ETDEWEB)

    Flynn, Nicholas [School of Chemical Engineering, Oklahoma State University, Stillwater, OK 74078 (United States); Topal, Ç. Özge [School of Mechanical and Aerospace Engineering, Oklahoma State University, Stillwater, OK 74078 (United States); Hikkaduwa Koralege, Rangika S. [School of Chemical Engineering, Oklahoma State University, Stillwater, OK 74078 (United States); Hartson, Steve [Department of Biochemistry and Molecular Biology, Oklahoma State University, Stillwater, OK 74078 (United States); Ranjan, Ashish; Liu, Jing; Pope, Carey [Department of Physiological Sciences, Oklahoma State University, Stillwater, OK 74078 (United States); Ramsey, Joshua D., E-mail: josh.ramsey@okstate.edu [School of Chemical Engineering, Oklahoma State University, Stillwater, OK 74078 (United States)

    2016-05-01

    The aim of the present study was to evaluate a library of poly-L-lysine (PLL)-graft (g)-polyethylene glycol (PEG) copolymers for the ability to encapsulate effectively a model protein, bovine serum albumin (BSA), and to characterize the stability and protein function of the resulting nanoparticle. A library of nine grafted copolymers was produced by varying PLL molecular weight and PEG grafting ratio. Electrostatic self-assembly of the protein and the grafted copolymer drove encapsulation. The formation of protein/polymer nanoparticles with a core/shell structure was confirmed using PAGE, dynamic light scattering, and electron microscopy. Encapsulation of the BSA into nanoparticles was strongly dependent on the copolymer-to-protein mass ratio, PEG grafting ratio, and PLL molecular weight. A copolymer-to-protein mass ratio of 7:1 and higher was generally required for high levels of encapsulation, and under these conditions, no loss of protein activity was observed. Copolymer characteristics also influenced nanoparticle resistance to polyanions and protease degradation. The results indicate that a copolymer of 15–30 kDa PLL, with a PEG grafting ratio of 10:1, is most promising for protein delivery. - Highlights: • A 4–70 kDa range of PLL-g-PEG copolymers was able to encapsulate BSA into NPs. • Encapsulation of BSA by PLL-g-PEG not only retained but increased esterolytic activity. • NPs were stable against protease degradation and polyanion dissociation.

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

    DEFF Research Database (Denmark)

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

    1998-01-01

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

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

    NARCIS (Netherlands)

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

    2005-01-01

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

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

    Science.gov (United States)

    Bowman, Michelle Kathleen

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

  15. Understanding the ordering mechanisms of self-assembled nanostructures of block copolymers during zone annealing

    Energy Technology Data Exchange (ETDEWEB)

    Cong, Zhinan; Zhang, Liangshun, E-mail: zhangls@ecust.edu.cn, E-mail: jlin@ecust.edu.cn; Wang, Liquan; Lin, Jiaping, E-mail: zhangls@ecust.edu.cn, E-mail: jlin@ecust.edu.cn [Shanghai Key Laboratory of Advanced Polymeric Materials, State Key Laboratory of Bioreactor Engineering, Key Laboratory for Ultrafine Materials of Ministry of Education, School of Materials Science and Engineering, East China University of Science and Technology, Shanghai 200237 (China)

    2016-03-21

    A theoretical method based on dynamic version of self-consistent field theory is extended to investigate directed self-assembly behaviors of block copolymers subjected to zone annealing. The ordering mechanisms and orientation modulation of microphase-separated nanostructures of block copolymers are discussed in terms of sweep velocity, wall preference, and Flory-Huggins interaction parameter. The simulated results demonstrate that the long-range ordered nanopatterns are achieved by lowering the sweep velocity of zone annealing due to the incorporation of templated ordering of block copolymers. The surface enrichment by one of the two polymer species induces the orientation modulation of defect-free nanostructures through finely tuning the composition of block copolymers and the preference of walls. Additionally, the Flory-Huggins interaction parameters of block copolymers in the distinct regions are main factors to design the zone annealing process for creating the highly ordered nanostructures with single orientation.

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

    Science.gov (United States)

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

    2017-10-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-08-20

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

  18. Synthesis, Characterization and Photoinduction of Optical Anisotropy in Liquid Crystalline Diblock Azo-Copolymers

    DEFF Research Database (Denmark)

    Forcén, P; Oriol, L; Sánchez, C

    2007-01-01

    Diblock copolymers with polymethyl methacrylate and side chain liquid crystalline WC) azopolymethacrylate blocks were synthesized by atom transfer radical polymerization (ATRP). The azobeazene content in these copolymers ranges from 52 to 7 wt %. For an azo conteat dowri to 20% they exhibit a LC...... anisotropy induced in these films by illumination with linearly polarized 488 nm light was studied and the resuits compared with those of the azo homopolymer and of a random copolymer with a similar composition. The formation of azo aggregates inside the azo blocks is strongly reduced in going from...... the homopolymer to the copolymers. Photoinduced azo orientation perpendicular to the 488 nm light polarization was found in aH the polymers. The orientational order parameter is very similar in the homopolymer and in the block copolymers with an azo content down to 20 wt %, while it is much lower in the random...

  19. The Preparation and Characterization of Tourmaline-Containing Functional Copolymer p (VST/MMA/BA

    Directory of Open Access Journals (Sweden)

    Yingmo Hu

    2018-01-01

    Full Text Available Tourmaline was modified with vinyl triethoxysilane containing double bond to prepare the polymerizable organic vinylsiliconoxyl tourmaline (VST and then copolymerized with methyl methacrylate (MMA and butyl acrylate (BA to produce the tourmaline-containing functional copolymer p (VST/MMA/BA. The structures and morphologies of VST and p (VST/MMA/BA copolymer were characterized by IR, SEM, and EDX. The experimental results indicated that tourmaline was introduced into the copolymer via surface modification and the tourmaline-containing functional copolymer was obtained by a copolymerization process with MMA and BA. The prepared p (VST/MMA/BA copolymer displayed excellent storage stabilities, high far-infrared radiation and negative ion releasing performances, and good mechanical properties.

  20. PREPARATION AND PROPERTIES OF MMA/1-PROPYLMETHACRYLATE-POSS COPOLYMER WITH ATOM TRANSFER RADICAL POLYMERIZATION

    Institute of Scientific and Technical Information of China (English)

    He-xin Zhang; Ho-young Lee; Young-jun Shin; Dong-ho Lee; Seok Kyun Noh

    2008-01-01

    The methyl methacrylate(MMA)/1-propylmethacrylate-polyhedral oligomeric silsesquioxane(PM-POSS) copolymers were synthesized via atom transfer radical polymerization with CuBr as catalyst.The unreacted PM-POSS monomer could be removed completely by washing the copolymerization product with n-hexane.The copolymers were characterized with 1H-NMR,X-ray diffraction,difierential scanning calorimetry,thermogravimetric analysis and gel permeatlon chromatography.With increasing PM-POSS feed ratio.the total conversion increased while the glass transition temperatures of copolymer decreased.The thermogravimetric analysis demonstrated that the thermal stability of copolymer improved slightly with PM-POSS addition.The molecular weight of copolymers increased with incorporation of PM-POSS.

  1. Facile synthesis and characterization of novel biodegradable amphiphilic block copolymers bearing pendant hydroxyl groups

    Energy Technology Data Exchange (ETDEWEB)

    Hu, Gaicen; Fan, Xiaoshan; Xu, Bingcan; Zhang, Delong; Hu, Zhiguo, E-mail: zghu@htu.cn

    2014-10-01

    Novel amphiphilic block copolymers bearing pendant hydroxyl groups polylactide-b–poly(3,3-bis(Hydroxymethyl–triazolylmethyl) oxetane)-b–polylactide (PLA-b–PHMTYO-b–PLA) were synthesized via a facile and efficient method. First, the block copolymer intermediates polylactide-b–poly(3,3-Diazidomethyloxetane)-b–polylactide (PLA-b–PBAMO-b–PLA) were synthesized through ring-opening polymerization of lactide using PBAMO as a macroinitiator. Following “Click” reaction of PLA-b–PBAMO-b–PLA with propargyl alcohol provided the targeted amphiphilic block copolymers PLA-b–PHMTYO-b–PLA with pendant hydroxyl groups. The composition and structure of prepared copolymers were characterized by {sup 1}H nuclear magnetic resonance ({sup 1}H NMR) spectroscopy, Fourier transform infrared (FT-IR) and gel permeation chromatography (GPC). The self-assembly behavior of the copolymers in water was investigated by transmission electron microscope (TEM), dynamic light scattering (DLS) and static light scattering (SLS). The results showed that the novel copolymers PLA-b–PHMTYO-b–PLA self-assembled into spherical micelles with diameters ranging from 100 nm to 200 nm in aqueous solution. These copolymers also exhibited low critical micellar concentrations (CMC: 6.9 × 10{sup −4} mg/mL and 3.9 × 10{sup −5} mg/mL, respectively). In addition, the in vitro cytotoxicity of these copolymers was determined in the presence of L929 cells. The results showed that the block copolymers PLA-b–PHMTYO-b–PLA exhibited better biocompatibility. Therefore, these well-defined copolymers are expected to find some applications in drug delivery or tissue engineering. - Highlights: • The method to synthesize PLA-b–PHMTYO-b–PLA is relatively facile and efficient. • PLA-b–PHMTYO-b–PLA self-assembles into spherical micelles with low CMC in water. • PLA-b–PHMTYO-b–PLA exhibits better biocompatibility and biodegradability.

  2. Facile synthesis and characterization of novel biodegradable amphiphilic block copolymers bearing pendant hydroxyl groups

    International Nuclear Information System (INIS)

    Hu, Gaicen; Fan, Xiaoshan; Xu, Bingcan; Zhang, Delong; Hu, Zhiguo

    2014-01-01

    Novel amphiphilic block copolymers bearing pendant hydroxyl groups polylactide-b–poly(3,3-bis(Hydroxymethyl–triazolylmethyl) oxetane)-b–polylactide (PLA-b–PHMTYO-b–PLA) were synthesized via a facile and efficient method. First, the block copolymer intermediates polylactide-b–poly(3,3-Diazidomethyloxetane)-b–polylactide (PLA-b–PBAMO-b–PLA) were synthesized through ring-opening polymerization of lactide using PBAMO as a macroinitiator. Following “Click” reaction of PLA-b–PBAMO-b–PLA with propargyl alcohol provided the targeted amphiphilic block copolymers PLA-b–PHMTYO-b–PLA with pendant hydroxyl groups. The composition and structure of prepared copolymers were characterized by 1 H nuclear magnetic resonance ( 1 H NMR) spectroscopy, Fourier transform infrared (FT-IR) and gel permeation chromatography (GPC). The self-assembly behavior of the copolymers in water was investigated by transmission electron microscope (TEM), dynamic light scattering (DLS) and static light scattering (SLS). The results showed that the novel copolymers PLA-b–PHMTYO-b–PLA self-assembled into spherical micelles with diameters ranging from 100 nm to 200 nm in aqueous solution. These copolymers also exhibited low critical micellar concentrations (CMC: 6.9 × 10 −4 mg/mL and 3.9 × 10 −5 mg/mL, respectively). In addition, the in vitro cytotoxicity of these copolymers was determined in the presence of L929 cells. The results showed that the block copolymers PLA-b–PHMTYO-b–PLA exhibited better biocompatibility. Therefore, these well-defined copolymers are expected to find some applications in drug delivery or tissue engineering. - Highlights: • The method to synthesize PLA-b–PHMTYO-b–PLA is relatively facile and efficient. • PLA-b–PHMTYO-b–PLA self-assembles into spherical micelles with low CMC in water. • PLA-b–PHMTYO-b–PLA exhibits better biocompatibility and biodegradability

  3. Self-assembly in casting solutions of block copolymer membranes

    KAUST Repository

    Marques, Debora S.; Vainio, Ulla; Moreno Chaparro, Nicolas; Calo, Victor M.; Bezahd, Ali Reza; Pitera, Jed W.; Peinemann, Klaus; Nunes, Suzana Pereira

    2013-01-01

    Membranes with exceptional pore regularity and high porosity were obtained from block copolymer solutions. We demonstrate by small-angle X-ray scattering that the order which gives rise to the pore morphology is already incipient in the casting solution. Hexagonal order was confirmed in PS-b-P4VP 175k-b-65k solutions in DMF/THF/dioxane with concentrations as high as 24 wt%, while lamellar structures were obtained in more concentrated solutions in DMF or DMF/dioxane. The change in order has been understood with the support of dissipative particle dynamic modeling. © 2013 The Royal Society of Chemistry.

  4. Thermal stability of homo- and copolymers of vinyl fluoride

    International Nuclear Information System (INIS)

    Raucher, D.; Levy, M.

    1979-01-01

    The thermal stability of poly(vinyl fluoride)(PVF) was studied by thermal gravimetry and mass spectrometry (TGA and TGA-MS). In low-molecular-weight polymers a two-step decomposition pattern was observed. It consisted of the dehydrofluorination to a polyene chain followed by decomposition of the resulting polyene at higher temperatures. Copolymers of vinyl fluoride-vinyl acetate (VF-VAc) and vinyl fluoride-vinyl chloride (VF-VCl) showed a simultaneous evolution of hydrofluoric acid and acetic acid and hydrofluoric acid and hydrochloric acid, respectively. This suggests that after the elimination of the weakest link a spontaneous elimination of neighboring HF molecules takes place

  5. Study on reactive extrusion processes of block copolymer

    International Nuclear Information System (INIS)

    Wu Lili; Jia Yuxi; Sun Sheng; Zhang Guofang; Zhao Guoqun; An Lijia

    2007-01-01

    The anionic copolymerization process of styrene-butadiene (S/B) block copolymer in a closely intermeshing co-rotating twin screw extruder with butyl-lithium initiator was studied. According to the anionic copolymerization mechanism and the reactive extrusion characteristics, the mathematical models of monomer conversion, average molecular weight and fluid viscosity during the anionic copolymerization of S/B were constructed, and then the reactive extrusion process was simulated by means of the finite volume method and the uncoupled semi-implicit iterative algorithm. Finally, the influence of the feeding mixture composition on conversion was discussed. The simulated results were nearly in agreement with the experimental results

  6. Ion Correlation Effects in Salt-Doped Block Copolymers

    Science.gov (United States)

    Brown, Jonathan R.; Seo, Youngmi; Hall, Lisa M.

    2018-03-01

    We apply classical density functional theory to study how salt changes the microphase morphology of diblock copolymers. Polymers are freely jointed and one monomer type favorably interacts with ions, to account for the selective solvation that arises from different dielectric constants of the microphases. By including correlations from liquid state theory of an unbound reference fluid, the theory can treat chain behavior, microphase separation, ion correlations, and preferential solvation, at the same coarse-grained level. We show good agreement with molecular dynamics simulations.

  7. Functional materials derived from block copolymer self-assembly

    DEFF Research Database (Denmark)

    Li, Tao

    deposition methods, namely nanocasting and atomic layer deposition (ALD) will be applied to fabricate compact, inter-connected, and continuous metal oxide films. In this way, the structure integrity will be preserved after template removal during the annealing procedure. Another objective of this project......-casting, the block copolymer self-organizes into monolayer packed sphere pattern, without any surface treatment of the substrate and annealing process. Arrays of nano-pillars and nanowells of various materials are fabricated in dry etch processes over wafer scale without defects. We also show an in situ Al2O3 hard...

  8. Photoresponsive Block Copolymers Containing Azobenzenes and Other Chromophores

    Directory of Open Access Journals (Sweden)

    Takaomi Kobayashi

    2010-01-01

    Full Text Available Photoresponsive block copolymers (PRBCs containing azobenzenes and other chromophores can be easily prepared by controlled polymerization. Their photoresponsive behaviors are generally based on photoisomerization, photocrosslinking, photoalignment and photoinduced cooperative motions. When the photoactive block forms mesogenic phases upon microphase separation of PRBCs, supramolecular cooperative motion in liquid-crystalline PRBCs enables them to self-organize into hierarchical structures with photoresponsive features. This offers novel opportunities to photocontrol microphase-separated nanostructures of well-defined PRBCs and extends their diverse applications in holograms, nanotemplates, photodeformed devices and microporous films.

  9. ABC Triblock Copolymer Vesicles with Mesh-like Morphology

    Science.gov (United States)

    Zhao, Wei; Russell, Thomas; Grason, Gregory

    2010-03-01

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

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

    Science.gov (United States)

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

    2011-02-16

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

  11. Block copolymer micelles as switchable templates for nanofabrication.

    Science.gov (United States)

    Krishnamoorthy, Sivashankar; Pugin, Raphaël; Brugger, Juergen; Heinzelmann, Harry; Hoogerwerf, Arno C; Hinderling, Christian

    2006-04-11

    Block copolymer inverse micelles from polystyrene-block-poly-2-vinylpyridine (PS-b-P2VP) deposited as monolayer films onto surfaces show responsive behavior and are reversibly switchable between two states of different topography and surface chemistry. The as-coated films are in the form of arrays of nanoscale bumps, which can be transformed into arrays of nanoscale holes by switching through exposure to methanol. The use of these micellar films to act as switchable etch masks for the structuring of the underlying material to form either pillars or holes depending on the switching state is demonstrated.

  12. Characterization and Some Properties of Functionalized Graft Copolymer

    International Nuclear Information System (INIS)

    Hegazy El-Sayed, A.; Kamal, H.; Mahmoud, Gh.A.; Khalifa, N.A.

    2000-01-01

    The study involved the investigation and characterization of membranes prepared by graft copolymerization of acrylonitrile (AN) and vinyl acetate (VAc) binary monomers onto low density polyethylene (LDPE) and isotactic polypropylene (IPP). The mutual gamma-irradiation method was used as a grafting technique. The effects of grafting and chemical treatments on the thermal properties and crystallinity of prepared graft copolymer have been investigated using DSC, TGA and XRD. IR spectra recorded before and after grafting and also for the chemically treated membranes to elucidate the structural changes occurred due to grafting and chemical treatments

  13. 78 FR 6213 - Styrene-2-Ethylhexyl Acrylate Copolymer; Tolerance Exemption

    Science.gov (United States)

    2013-01-30

    ...This regulation establishes an exemption from the requirement of a tolerance for residues of 2-propenoic acid, 2-ethylhexyl ester, polymer with ethenylbenzene; also known as styrene-2-ethylhexyl acrylate copolymer when used as an inert ingredient in a pesticide chemical formulation. H. B. Fuller Company submitted a petition to EPA under the Federal Food, Drug, and Cosmetic Act (FFDCA), requesting an exemption from the requirement of a tolerance. This regulation eliminates the need to establish a maximum permissible level for residues of 2-propenoic acid, 2-Ethylhexyl Ester, Polymer with Ethenylbenzene on food or feed commodities.

  14. Ellipsometry measurements of glass transition breadth in bulk films of random, block, and gradient copolymers.

    Science.gov (United States)

    Mok, M M; Kim, J; Marrou, S R; Torkelson, J M

    2010-03-01

    Bulk films of random, block and gradient copolymer systems were studied using ellipsometry to demonstrate the applicability of the numerical differentiation technique pioneered by Kawana and Jones for studying the glass transition temperature (T (g)) behavior and thermal expansivities of copolymers possessing different architectures and different levels of nanoheterogeneity. In a series of styrene/n -butyl methacrylate (S/nBMA) random copolymers, T (g) breadths were observed to increase from approximately 17( degrees ) C in styrene-rich cases to almost 30( degrees ) C in nBMA-rich cases, reflecting previous observations of significant nanoheterogeneity in PnBMA homopolymers. The derivative technique also revealed for the first time a substantial increase in glassy-state expansivity with increasing nBMA content in S/nBMA random copolymers, from 1.4x10(-4) K-1 in PS to 3.5x10(-4) K-1 in PnBMA. The first characterization of block copolymer T (g) 's and T (g) breadths by ellipsometry is given, examining the impact of nanophase-segregated copolymer structure on ellipsometric measurements of glass transition. The results show that, while the technique is effective in detecting the two T (g) 's expected in certain block copolymer systems, the details of the glass transition can become suppressed in ellipsometry measurements of a rubbery minor phase under conditions where the matrix is glassy; meanwhile, both transitions are easily discernible by differential scanning calorimetry. Finally, broad glass transition regions were measured in gradient copolymers, yielding in some cases extraordinary T (g) breadths of 69- 71( degrees ) C , factors of 4-5 larger than the T (g) breadths of related homopolymers and random copolymers. Surprisingly, one gradient copolymer demonstrated a slightly narrower T (g) breadth than the S/nBMA random copolymers with the highest nBMA content. This highlights the fact that nanoheterogeneity relevant to the glass transition response in selected

  15. Synthesis of Medium-Chain-Length Polyhydroxyalkanoate Homopolymers, Random Copolymers, and Block Copolymers by an Engineered Strain of Pseudomonas entomophila.

    Science.gov (United States)

    Wang, Ying; Chung, Ahleum; Chen, Guo-Qiang

    2017-04-01

    Medium-chain-length polyhydroxyalkanoates (mcl-PHAs), widely used in medical area, are commonly synthesized by Pseudomonas spp. This study tries to use β-oxidation pathways engineered P. entomophila to achieve single source of a series of mcl-monomers for microbial production of PHA homopolymers. The effort is proven successful for the first time to obtain a wide range of mcl-PHA homopolymers from engineered P. entomophila LAC23 grown on various fatty acids, respectively, ranging from poly(3-hydroxyheptanoate) to poly(3-hydroxytetradecanoate). Effects of a PHA monomer chain length on thermal and crystallization properties including the changes of T m , T g , and T d5% are investigated. Additionally, strain LAC23 is used to synthesize random copolymers of 3-hydroxyoctanoate (3HO) and 3-hydroxydodecanoate (3HDD) or 3-hydroxytetradecanoates, their compositions could be controlled by adjusting the ratios of two related fatty acids. Meanwhile, block copolymer P(3HO)-b-P(3HDD) is synthesized by the same strain. It is found for the first time that even- and odd number mcl-PHA homopolymers have different physical properties. When the gene of the PHA synthase in the engineered P. entomophila is replaced by phaC from Aeromonas hydrophila 4AK4, poly(3-hydroxybutyrate-co-30 mol%-3-hydroxyhexanoate) is synthesized. Therefore, P. entomophila can be used to synthesize the whole range of PHA (C7-C14) homopolymers, random- and block copolymers. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Copolymer semiconductors comprising thiazolothiazole or benzobisthiazole, or benzobisoxazole electron acceptor subunits, and electron donor subunits, and their uses in transistors and solar cells

    Science.gov (United States)

    Jenekhe, Samson A; Subramaniyan, Selvam; Ahmed, Eilaf; Xin, Hao; Kim, Felix Sunjoo

    2014-10-28

    The inventions disclosed, described, and/or claimed herein relate to copolymers comprising copolymers comprising electron accepting A subunits that comprise thiazolothiazole, benzobisthiazole, or benzobisoxazoles rings, and electron donating subunits that comprise certain heterocyclic groups. The copolymers are useful for manufacturing organic electronic devices, including transistors and solar cells. The invention also relates to certain synthetic precursors of the copolymers. Methods for making the copolymers and the derivative electronic devices are also described.

  17. Methacrylate-Based Copolymers for Polymer Optical Fibers

    Directory of Open Access Journals (Sweden)

    Daniel Zaremba

    2017-01-01

    Full Text Available Waveguides made of poly-methyl-methacrylate (PMMA play a major role in the homogeneous distribution of display backlights as a matrix for solid-state dye lasers and polymer optical fibers (POFs. PMMA is favored because of its transparency in the visible spectrum, low price, and well-controlled processability. Nevertheless, technical drawbacks, such as its limited temperature stability, call for new materials. In this work, the copolymerization technique is used to modify the properties of the corresponding homopolymers. The analytical investigation of fourteen copolymers made of methyl-methacrylate (MMA or ethyl-methacrylate (EMA as the basis monomer is summarized. Their polymerization behaviors are examined by NMR spectroscopy with subsequent copolymerization parameter evaluation according to Fineman-Ross and Kelen-Tüdös. Therefore, some r-parameter sets are shown to be capable of copolymerizations with very high conversions. The first applications as high-temperature resistant (HT materials for HT-POFs are presented. Copolymers containing isobornyl-methacrylate (IBMA as the comonomer are well-suited for this demanding application.

  18. Ethylene-Octene Copolymers/Organoclay Nanocomposites: Preparation and Properties

    Directory of Open Access Journals (Sweden)

    Alice Tesarikova

    2016-01-01

    Full Text Available Two ethylene-octene copolymers with 17 and 45 wt.% of octene (EOC-17 and EOC-45 were compared in nanocomposites with Cloisite 93A. EOC-45 nanocomposites have a higher elongation at break. Dynamical mechanical analysis (DMA showed a decrease of tan⁡δ with frequency for EOC-17 nanocomposites, but decrease is followed by an increase for EOC-45 nanocomposites; DMA showed also increased modulus for all nanocomposites compared to pure copolymers over a wide temperature range. Barrier properties were improved about 100% by addition of organoclay; they were better for EOC-17 nanocomposites due to higher crystallinity. X-ray diffraction (XRD together with transmission electron microscopy (TEM showed some intercalation for EOC-17 but much better dispersion for EOC-45 nanocomposites. Differential scanning calorimetry (DSC showed increased crystallization temperature Tc for EOC-17 nanocomposite (aggregates acted as nucleation agents but decrease Tc for EOC-45 nanocomposite together with greatly influenced melting peak. Accelerated UV aging showed smaller C=O peak for EOC-45 nanocomposites.

  19. Effect of solvents on the enzyme mediated degradation of copolymers

    International Nuclear Information System (INIS)

    Banerjee, Aditi; Chatterjee, Kaushik; Madras, Giridhar

    2015-01-01

    The biodegradation of polycaprolactone (PCL), polylactic acid (PLA), polyglycolide (PGA) and their copolymers, poly (lactide-co-glycolide) and poly (D, L-lactide-co-caprolactone) (PLCL) was investigated. The influence of different solvents on the degradation of these polymers at 37 °C in the presence of two different lipases namely Novozym 435 and the free lipase of porcine pancreas was investigated. The rate coefficients for the polymer degradation and enzyme deactivation were determined using continuous distribution kinetics. Among the homopolymers, the degradation of PGA was nearly an order of magnitude lower than that for PCL and PLA. The overall rate coefficients of the copolymers were higher than their respective homopolymers. Thus, PLCL degraded faster than either PCL or PLA. The degradation was highly dependent on the viscosity of the solvent used with the highest degradation observed in acetone. The degradation of the polymers in acetone was nearly twice that observed in dimethyl sulfoxide indicating that the degradation decreases with increase in the solvent viscosity. The degradation of the polymers in water-solvent mixtures indicated an optimal water content of 2.5 wt% of water. (paper)

  20. Dynamics of Disordered PI-PtBS Diblock Copolymer

    Science.gov (United States)

    Watanabe, Hiroshi

    2009-03-01

    Viscoelastic (G^*) and dielectric (ɛ'') data were examined for a LCST-type diblock copolymer composed of polyisoprene (PI; M = 53K) and poly(p-tert- butyl styrene) (PtBS; M = 42K) blocks disordered at T PtBS block at low T and the dynamic heterogeneity due to PtBS was effectively quenched to give a frictional nonuniformity for the PI block relaxation. The ɛ'' data were thermo-rheologically complex at low T, partly due to this nonuniformity. However, the block connectivity could have also led to the complexity. For testing this effect, the ɛ'' data were reduced at the iso- frictional state defined with respect to bulk PI. In this state, the ɛ'' data of the copolymer at low and high T, respectively, were close to the data for the star-branched and linear bulk PI. Thus, the PI block appeared to be effectively tethered in space at low T thereby behaving similarly to the star arm while the PI block tended to move cooperatively with the PtBS block at high T to behave similarly to the linear PI, which led to the complexity of the ɛ'' data. The PtBS block also exhibited the complexity (noted from the G^* data), which was well correlated with the complexity of the PI block.

  1. Rapid synthesis of graft copolymers from natural cellulose fibers.

    Science.gov (United States)

    Thakur, Vijay Kumar; Thakur, Manju Kumari; Gupta, Raju Kumar

    2013-10-15

    Cellulose is the most abundant natural polysaccharide polymer, which is used as such or its derivatives in a number of advanced applications, such as in paper, packaging, biosorption, and biomedical. In present communication, in an effort to develop a proficient way to rapidly synthesize poly(methyl acrylate)-graft-cellulose (PMA-g-cellulose) copolymers, rapid graft copolymerization synthesis was carried out under microwave conditions using ferrous ammonium sulfate-potassium per sulfate (FAS-KPS) as redox initiator. Different reaction parameters such as microwave radiation power, ratio of monomer, solvent and initiator concentrations were optimized to get the highest percentage of grafting. Grafting percentage was found to increase with increase in microwave power up to 70%, and maximum 36.73% grafting was obtained after optimization of all parameters. Fourier transforms infrared spectroscopy (FT-IR), scanning electron microscopy (SEM) and thermogravimetric analysis (TGA/DTA/DTG) analysis were used to confirm the graft copolymerization of poly(methyl acrylate) (PMA) onto the mercerized cellulose. The grafted cellulosic polymers were subsequently subjected to the evaluation of different physico-chemical properties in order to access their application in everyday life, in a direction toward green environment. The grafted copolymers demonstrated increased chemical resistance, and higher thermal stability. Published by Elsevier Ltd.

  2. Monte Carlo simulation of AB-copolymers with saturating bonds

    CERN Document Server

    Chertovich, A V; Khokhlov, A R; Bohr, J

    2003-01-01

    Structural transitions in a single AB-copolymer chain where saturating bonds can be formed between A-and B-units are studied by means of Monte Carlo computer simulations using the bond fluctuation model. Three transitions are found, coil-globule, coil-hairpin and globule-hairpin, depending on the nature of a particular AB-sequence: statistical random sequence, diblock sequence and 'random-complementary' sequence (one-half of such an AB-sequence is random with Bernoulli statistics while the other half is complementary to the first one). The properties of random-complementary sequences are closer to those of diblock sequences than to the properties of random sequences. The model (although quite rough) is expected to represent some basic features of real RNA molecules, i.e. the formation of secondary structure of RNA due to hydrogen bonding of corresponding bases and stacking interactions of the base pairs in helixes. We introduce the notation of RNA-like copolymers and discuss in what sense the sequences studie...

  3. Amphiphilic Copolymers Shuttle Drugs Across the Blood-Brain Barrier.

    Science.gov (United States)

    Clemens-Hemmelmann, Mirjam; Kuffner, Christiane; Metz, Verena; Kircher, Linda; Schmitt, Ulrich; Hiemke, Christoph; Postina, Rolf; Zentel, Rudolf

    2016-05-01

    Medical treatment of diseases of the central nervous system requires transport of drugs across the blood-brain barrier (BBB). Here, it is extended previously in vitro experiments with a model compound to show that the non-water-soluble and brain-impermeable drug domperidone (DOM) itself can be enriched in the brain by use of an amphiphilic copolymer as a carrier. This carrier consists of poly(N-(2-hydroxypropyl)-methacrylamide), statistically copolymerized with 10 mol% hydrophobic lauryl methacrylate, into whose micellar aggregates DOM is noncovalently absorbed. As tested in a BBB model efficient transport of DOM across, the BBB is achievable over a wide range of formulations, containing 0.8 to 35.5 wt% domperidone per copolymer. In neither case, the polymer itself is translocated across the BBB model. In vivo experiments in mice show that already 10 min after intraperitoneal injection of the polymer/domperidone (PolyDOM) formulation, domperidone can be detected in blood and in the brain. Highest serum and brain levels of domperidone are detected 40 min after injection. At that time point serum domperidone is increased 48-fold. Most importantly, domperidone is exclusively detectable in high amounts in the brain of PolyDOM injected mice and not in mice injected with bare domperidone. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Hollow ZIF-8 Nanoworms from Block Copolymer Templates

    Science.gov (United States)

    Yu, Haizhou; Qiu, Xiaoyan; Neelakanda, Pradeep; Deng, Lin; Khashab, Niveen M.; Nunes, Suzana P.; Peinemann, Klaus-Viktor

    2015-10-01

    Recently two quite different types of “nano-containers” have been recognized as attractive potential drug carriers; these are wormlike filamenteous micelles (“filomicelles”) on the one hand and metal organic frameworks on the other hand. In this work we combine these two concepts. We report for the first time the manufacturing of metal organic framework nanotubes with a hollow core. These worm-like tubes are about 200 nm thick and several μm long. The preparation is simple: we first produce long and flexible filament-shaped micelles by block copolymer self-assembly. These filomicelles serve as templates to grow a very thin layer of interconnected ZIF-8 crystals on their surface. Finally the block copolymer is removed by solvent extraction and the hollow ZIF-8 nanotubes remain. These ZIF-NTs are surprisingly stable and withstand purification by centrifugation. The synthesis method is straightforward and can easily be applied for other metal organic framework materials. The ZIF-8 NTs exhibit high loading capacity for the model anti cancer drug doxorubicin (DOX) with a pH-triggered release. Hence, a prolonged circulation in the blood stream and a targeted drug release behavior can be expected.

  5. Removable polytetrafluoroethylene template based epitaxy of ferroelectric copolymer thin films

    Science.gov (United States)

    Xia, Wei; Chen, Qiusong; Zhang, Jian; Wang, Hui; Cheng, Qian; Jiang, Yulong; Zhu, Guodong

    2018-04-01

    In recent years ferroelectric polymers have shown their great potentials in organic and flexible electronics. To meet the requirements of high-performance and low energy consumption of novel electronic devices and systems, structural and electrical properties of ferroelectric polymer thin films are expected to be further optimized. One possible way is to realize epitaxial growth of ferroelectric thin films via removable high-ordered polytetrafluoroethylene (PTFE) templates. Here two key parameters in epitaxy process, annealing temperature and applied pressure, are systematically studied and thus optimized through structural and electrical measurements of ferroelectric copolymer thin films. Experimental results indicate that controlled epitaxial growth is realized via suitable combination of both parameters. Annealing temperature above the melting point of ferroelectric copolymer films is required, and simultaneously moderate pressure (around 2.0 MPa here) should be applied. Over-low pressure (around 1.0 MPa here) usually results in the failure of epitaxy process, while over-high pressure (around 3.0 MPa here) often results in residual of PTFE templates on ferroelectric thin films.

  6. Responsive block copolymer photonics triggered by protein-polyelectrolyte coacervation.

    Science.gov (United States)

    Fan, Yin; Tang, Shengchang; Thomas, Edwin L; Olsen, Bradley D

    2014-11-25

    Ionic interactions between proteins and polyelectrolytes are demonstrated as a method to trigger responsive transitions in block copolymer (BCP) photonic gels containing one neutral hydrophobic block and one cationic hydrophilic block. Poly(2-vinylpyridine) (P2VP) blocks in lamellar poly(styrene-b-2-vinylpyridine) block copolymer thin films are quaternized with primary bromides to yield swollen gels that show strong reflectivity peaks in the visible range; exposure to aqueous solutions of various proteins alters the swelling ratios of the quaternized P2VP (QP2VP) gel layers in the PS-QP2VP materials due to the ionic interactions between proteins and the polyelectrolyte. Parameters such as charge density, hydrophobicity, and cross-link density of the QP2VP gel layers as well as the charge and size of the proteins play significant roles on the photonic responses of the BCP gels. Differences in the size and pH-dependent charge of proteins provide a basis for fingerprinting proteins based on their temporal and equilibrium photonic response. The results demonstrate that the BCP gels and their photonic effect provide a robust and visually interpretable method to differentiate different proteins.

  7. Process for producing a new copolymer. [Patent in Japanese

    Energy Technology Data Exchange (ETDEWEB)

    Tojima, M; Matsumoto, K; Sasaki, H

    1970-12-11

    A new process for copolymerization is given by using either a diaryl oxalate single polymer or a diaryl oxalate copolymer with at least one vinyl monomer as a source of free radicals, and adding a conventional radical initiator to them when irradiated with light or particle radiations. The function of the free radicals generated from the diaryl oxalate monomer is quite different from the free radicals generated from the conventional initiators. The addition of the conventional radical initiators is to accelerate the copolymerization reaction. The advantage of this process is that low energy light at room temperature can be used like high energy radiation. In one of the examples, 500 g of diaryl oxalate monomer, 1200ml of benzene and 0.2 mol/l of benzoil peroxide were mixed and underwent a polymerization reaction in nitrogen gas at 70/sup 0/C for 8 hrs. A polymer was isolated from their methanol solution. The polymer had an iodine value of 77.7 and a yield of 35%. The polymer was dissolved in vinyl acetate, methacrylate or acrylic acid with or without benzoil peroxides. The produced viscous solutions were molded and irradiated with a 450 Watt mercury lamp. Experiments revealed that the products obtained in the presence of benzoil peroxides could reduce by as much as one half to one third the time required to harden the copolymer.

  8. Insolubilisation of biologically active materials with novel radiation graft copolymers

    International Nuclear Information System (INIS)

    Garnett, J.L.; Jankiewicz, S.V.; Levot, R.; Sangster, D.F.

    1984-01-01

    The use of radiation grafting to immobilise a typical enzyme, trypsin, is reported. The technique involves radiation grafting to a backbone polymer a monomer containing an appropriate functional group to which the enzyme is bonded. In the present work, p-nitrostyrene has been grafted to representative trunk polymers, polypropylene and PVC, the nitro group in the resulting copolymer converted to the isothiocyanato derivative to which trypsin is attached. Of importance to this insolubilisation process, especially for radiation sensitive backbone polymers, is the inclusion of additives which enhance grafting. A new class of additives which increase the grafting yields is reported using as representative backbone polymers, naturally occurring cellulose and synthetic low density polyethylene. The new additives are specific metal salts such as LiClO 4 . The reactivity of these salts in grafting enhancement has been compared with that of mineral acid which has previously been used as an additive to increase grafting yields in both preirradiation and simultaneous techniques. A new model for grafting enhancement in the presence of the metal salts as well as acids is proposed whereby increased grafting yields are attributed to increased partitioning of monomer into the graft region in the presence of ionic solutes. The value of these additives in preparing copolymers suitable for general reagent insolubilisation reactions is discussed

  9. Transport of Water in Semicrystalline Block Copolymer Membranes

    Science.gov (United States)

    Hallinan, Daniel; Oparaji, Onyekachi

    Poly(styrene)-block-poly(ethylene oxide) (PS- b-PEO) is a semicrystalline block copolymer (BCP) with interesting properties. It is mechanically tough, amphiphilic, and has a polar phase. The mechanical toughness is due to the crystallinity of PEO and the high glass transition temperature of PS, as well as the morphological structure of the BCP. The polymer has high CO2, water, and salt solubility that derive from the polar PEO component. Potential applications include CO2 separation, water purification, and lithium air batteries. In all of the aforementioned applications, water transport is an important parameter. The presence of water can also affect thermal and mechanical properties. Water transport and thermal and mechanical properties of a lamellar PS- b-PEO copolymer have been measured as a function of water activity. Water transport can be affected by the heterogeneous nature of a semicrystalline BCP. Therefore, Fourier transform infrared - attenuated total reflectance (FTIR-ATR) spectroscopy has been employed, because water transport and polymer swelling can be measured simultaneously. The effect of BCP structure on transport has been investigated by comparing water transport in PS- b-PEO to a PEO homopolymer. The crystalline content of the PEO and the presence of glassy PS lamellae will be used to explain the transport results.

  10. Sustainable Triblock Copolymers for Application as Thermoplastic Elastomers

    Science.gov (United States)

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

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

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

    Science.gov (United States)

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

    2013-06-25

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

  12. Indirect rapid prototyping of antibacterial acid anhydride copolymer microneedles

    International Nuclear Information System (INIS)

    Boehm, Ryan D; Miller, Philip R; Singh, Ritika; Narayan, Roger J; Shah, Akash; Stafslien, Shane; Daniels, Justin

    2012-01-01

    Microneedles are needle-like projections with microscale features that may be used for transdermal delivery of a variety of pharmacologic agents, including antibacterial agents. In the study described in this paper, an indirect rapid prototyping approach involving a combination of visible light dynamic mask micro-stereolithography and micromolding was used to prepare microneedle arrays out of a biodegradable acid anhydride copolymer, Gantrez® AN 169 BF. Fourier transform infrared spectroscopy, energy dispersive x-ray spectrometry and nanoindentation studies were performed to evaluate the chemical and mechanical properties of the Gantrez® AN 169 BF material. Agar plating studies were used to evaluate the in vitro antimicrobial performance of these arrays against Bacillus subtilis, Candida albicans, Enterococcus faecalis, Escherichia coli, Pseudomonas aeruginosa and Staphylococcus aureus. Large zones of growth inhibition were noted for Escherichia coli, S. aureus, Enterococcus faecalis and B. subtilis. The performance of Gantrez® AN 169 BF against several bacteria suggests that biodegradable acid anhydride copolymer microneedle arrays prepared using visible light dynamic mask micro-stereolithography micromolding may be useful for treating a variety of skin infections. (communication)

  13. Thermally Stable Gold Nanoparticles with a Crosslinked Diblock Copolymer Shell

    Science.gov (United States)

    Jang, Se Gyu; Khan, Anzar; Hawker, Craig J.; Kramer, Edward J.

    2010-03-01

    The use of polymer-coated Au nanoparticles prepared using oligomeric- or polymeric-ligands tethered by Au-S bonds for incorporation into block copolymer templates under thermal processing has been limited due to dissociation of the Au-S bond at T > 100^oC where compromises their colloidal stability. We report a simple route to prepare sub-5nm gold nanoparticles with a thermally stable polymeric shell. An end-functional thiol ligand consisting of poly(styrene-b-1,2&3,4-isoprene-SH) is synthesized by anionic polymerization. After a standard thiol ligand synthesis of Au nanoparticles, the inner PI block is cross-linked through reaction with 1,1,3,3-tetramethyldisiloxane. Gold nanoparticles with the cross-linked shell are stable in organic solvents at 160^oC as well as in block copolymer films of PS-b-P2VP annealed in vacuum at 170^oC for several days. These nanoparticles can be designed to strongly segregate to the PS-P2VP interface resulting in very large Au nanoparticle volume fractions φp without macrophase separation as well as transitions between lamellar and bicontinuous morphologies as φp increases.

  14. Designing block copolymer architectures for targeted membrane performance

    KAUST Repository

    Dorin, Rachel Mika

    2014-01-01

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

  15. Loess clay based copolymer for removing Pb(II) ions

    International Nuclear Information System (INIS)

    He, Yu-Feng; Zhang, Ling; Wang, Rong-Min; Li, Hui-Ru; Wang, Yan

    2012-01-01

    Highlights: ► The loess clay based copolymer was prepared using functional monomers. ► Characterization of the polymer adsorbent and the raw material were carried out. ► The adsorption behavior of the complex for Pb(II) ions was evaluated. ► The removal rate of Pb(II) got to 99% and the adsorption capacity got to 356.9 mg/g. - Abstract: Functional monomers, such as acrylic acid and 2-hydroxyethyl methacrylate were supported into loess clay in situ polymerization, which afforded loess clay based copolymer (LC/PAAHM), a new kind of polymer adsorbent for removing Pb(II) ions from aqueous solution. Characterization of the polymer adsorbent was carried out by different sophisticated methods, such as Fourier transformation infrared spectrometry (FTIR), scanning electron microscopy (SEM), X-ray diffractometry (XRD), thermogravimetric analysis (TGA), and Zetasizer. Batch experiments were carried out to evaluate the factors affecting the removal efficiency, in which the pH, the adsorbent dosage, temperature and initial Pb(II) concentration all found in positive relevance to the increase of Pb(II) removal efficiency. The removal rate of Pb(II) got to 99% at room temperature and the adsorption capacity got to 356.9 mg/g. The pseudo-first-order and pseudo-second-order kinetic models were applied to test the experimental data, and Langmuir and Freundlich models have been applied to study the adsorption equilibrium, respectively.

  16. Hollow ZIF-8 Nanoworms from Block Copolymer Templates

    KAUST Repository

    Yu, Haizhou; Qiu, Xiaoyan; Neelakanda, Pradeep; Deng, Lin; Khashab, Niveen M.; Nunes, Suzana Pereira; Peinemann, Klaus-Viktor

    2015-01-01

    Recently two quite different types of “nano-containers” have been recognized as attractive potential drug carriers; these are wormlike filamenteous micelles (“filomicelles”) on the one hand and metal organic frameworks on the other hand. In this work we combine these two concepts. We report for the first time the manufacturing of metal organic framework nanotubes with a hollow core. These worm-like tubes are about 200 nm thick and several μm long. The preparation is simple: we first produce long and flexible filament-shaped micelles by block copolymer self-assembly. These filomicelles serve as templates to grow a very thin layer of interconnected ZIF-8 crystals on their surface. Finally the block copolymer is removed by solvent extraction and the hollow ZIF-8 nanotubes remain. These ZIF-NTs are surprisingly stable and withstand purification by centrifugation. The synthesis method is straightforward and can easily be applied for other metal organic framework materials. The ZIF-8 NTs exhibit high loading capacity for the model anti cancer drug doxorubicin (DOX) with a pH-triggered release. Hence, a prolonged circulation in the blood stream and a targeted drug release behavior can be expected.

  17. Hollow ZIF-8 Nanoworms from Block Copolymer Templates

    KAUST Repository

    Yu, Haizhou

    2015-10-16

    Recently two quite different types of “nano-containers” have been recognized as attractive potential drug carriers; these are wormlike filamenteous micelles (“filomicelles”) on the one hand and metal organic frameworks on the other hand. In this work we combine these two concepts. We report for the first time the manufacturing of metal organic framework nanotubes with a hollow core. These worm-like tubes are about 200 nm thick and several μm long. The preparation is simple: we first produce long and flexible filament-shaped micelles by block copolymer self-assembly. These filomicelles serve as templates to grow a very thin layer of interconnected ZIF-8 crystals on their surface. Finally the block copolymer is removed by solvent extraction and the hollow ZIF-8 nanotubes remain. These ZIF-NTs are surprisingly stable and withstand purification by centrifugation. The synthesis method is straightforward and can easily be applied for other metal organic framework materials. The ZIF-8 NTs exhibit high loading capacity for the model anti cancer drug doxorubicin (DOX) with a pH-triggered release. Hence, a prolonged circulation in the blood stream and a targeted drug release behavior can be expected.

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

    KAUST Repository

    Giovannitti, Alexander

    2018-02-23

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

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

    KAUST Repository

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

    2018-01-01

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

  20. Highly fluorinated comb-shaped copolymer as proton exchange membranes (PEMs): Fuel cell performance

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Dae Sik; Guiver, Michael D.; Ding, Jianfu [Institute for Chemical Process and Environmental Technology, National Research Council, 1200 Montreal Road, Ottawa, Ontario K1A 0R6 (Canada); Kim, Yu.Seung; Pivovar, Bryan S. [Materials Physics and Applications, Sensors and Electrochemical Devices Group, Los Alamos National Laboratory, Los Alamos, NM 87545 (United States)

    2008-07-15

    The fuel cell performance (DMFC and H{sub 2}/air) of highly fluorinated comb-shaped copolymer is reported. The initial performance of membrane electrode assemblies (MEAs) fabricated from comb-shaped copolymer containing a side-chain weight fraction of 22% are compared with those derived from Nafion and sulfonated polysulfone (BPSH-35) under DMFC conditions. The low water uptake of comb copolymer enabled an increase in proton exchange site concentrations in the hydrated polymer, which is a desirable membrane property for DMFC application. The comb-shaped copolymer architecture induces phase separated morphology between the hydrophobic fluoroaromatic backbone and the polysulfonic acid side chains. The initial performance of the MEAs using BPSH-35 and Comb 22 copolymer were comparable and higher than that of the Nafion MEA at all methanol concentrations. For example, the power density of the MEA using Comb 22 copolymer at 350 mA cm{sup -2} and 0.5 M methanol was 145 mW cm{sup -2}, whereas the power densities of MEAs using BPSH-35 were 136 mW cm{sup -2}. The power density of the MEA using Comb 22 copolymer at 350 mA cm{sup -2} and 2.0 M methanol was 144.5 mW cm{sup -2}, whereas the power densities of MEAs using BPSH-35 were 143 mW cm{sup -2}. (author)

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

    Science.gov (United States)

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

    2011-12-01

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

  2. Synthesis of biodegradable and electroactive multiblock polylactide and aniline pentamer copolymer for tissue engineering applications.

    Science.gov (United States)

    Huang, Lihong; Zhuang, Xiuli; Hu, Jun; Lang, Le; Zhang, Peibiao; Wang, Yu; Chen, Xuesi; Wei, Yen; Jing, Xiabin

    2008-03-01

    To obtain one biodegradable and electroactive polymer as the scaffold for tissue engineering, the multiblock copolymer PLAAP was designed and synthesized with the condensation polymerization of hydroxyl-capped poly( l-lactide) (PLA) and carboxyl-capped aniline pentamer (AP). The PLAAP copolymer exhibited excellent electroactivity, solubility, and biodegradability. At the same time, as one scaffold material, PLAAP copolymer possesses certain mechanical properties with the tensile strength of 3 MPa, tensile Young 's modulus of 32 MPa, and breaking elongation rate of 95%. We systematically studied the compatibility of PLAAP copolymer in vitro and proved that the electroactive PLAAP copolymer was innocuous, biocompatible, and helpful for the adhesion and proliferation of rat C6 cells. Moreover, the PLAAP copolymer stimulated by electrical signals was demonstrated as accelerating the differentiation of rat neuronal pheochromocytoma PC-12 cells. This biodegradable and electroactive PLAAP copolymer thus possessed the properties in favor of the long-time application in vivo as nerve repair scaffold materials in tissue engineering.

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

    International Nuclear Information System (INIS)

    Zhang Qiyi; Yang Wenyan; Hu Kaiyan

    2016-01-01

    The self-assembly of diblock copolymers confined around one square-shaped particle is studied systematically within two-dimensional self-consistent field theory (SCFT). In this model, we assume that the thin block copolymer film is confined in the vicinity of a square-shaped particle by a homopolymer melt, which is equivalent to the poor solvents. Multiple sequences of square-shaped particle-induced copolymer aggregates with different shapes and self-assembled internal morphologies are predicted as functions of the particle size, the structural portion of the copolymer, and the volume fraction of the copolymer. A rich variety of aggregates are found with complex internal self-assembled morphologies including complex structures of the vesicle, with one or several inverted micelle surrounded by the outer monolayer with the particle confined in the core. These results demonstrate that the assemblies of diblock copolymers formed around the square-shaped particle in poor solvents are of immediate interest to the assembly of copolymer and the morphology of biomembrane in the confined environment, as well as to the transitions of vesicles to micelles. (paper)

  4. Sorption of Aromatic Compounds with Copolymer Sorbent Materials Containing β-Cyclodextrin

    Directory of Open Access Journals (Sweden)

    Lee D. Wilson

    2011-08-01

    Full Text Available Urethane copolymer sorbent materials that incorporate β-cyclodextrin (CD have been prepared and their sorption properties with chlorinated aromatic compounds (i.e., pentachlorophenol, 2,4-dichlorophenol and 2,4-dichlorophenoxy acetic acid have been evaluated. The sorption properties of granular activated carbon (GAC were similarly compared in aqueous solution at variable pH conditions. The sorbents displayed variable BET surface areas as follows: MDI-X copolymers (< 101 m2/g, CDI-X copolymers (< 101 m2/g, and granular activated carbon (GAC ~103 m2/g. The sorption capacities for the copolymers sorbents are listed in descending order, as follows: GAC > CDI-3 copolymer ≈ MDI-3 copolymer. The sorption capacity for the aromatic adsorbates with each sorbent are listed in descending order, as follows: 2,4-dichlorophenol > 2,4-dichlorophenoxy acetic acid > pentachlorophenol. In general, the differences in the sorption properties of the copolymer sorbents with the chlorinated organics were related to the following factors: (i surface area of the sorbent; (ii CD content and accessibility; and (iii and the chemical nature of the sorbent material.

  5. A semiflexible alternating copolymer chain adsorption on a flat and a fluctuating surface

    International Nuclear Information System (INIS)

    Mishra, Pramod Kumar

    2010-01-01

    A lattice model of a directed self-avoiding walk is used to investigate adsorption properties of a semiflexible alternating copolymer chain on an impenetrable flat and fluctuating surface in two (square, hexagonal and rectangular lattice) and three dimensions (cubic lattice). In the cubic lattice case the surface is two-dimensional impenetrable flat and in two dimensions the surface is a fluctuating impenetrable line (hexagonal lattice) and also flat impenetrable line (square and rectangular lattice). Walks of the copolymer chains are directed perpendicular to the plane of the surface and at a suitable value of monomer surface attraction, the copolymer chain gets adsorbed on the surface. To calculate the exact value of the monomer surface attraction, the directed walk model has been solved analytically using the generating function method to discuss results when one type of monomer of the copolymer chain has attractive, repulsive or no interaction with the surface. Results obtained in the flat surface case show that, for a stiffer copolymer chain, adsorption transition occurs at a smaller value of monomer surface attraction than a flexible copolymer chain while in the case of a fluctuating surface, the adsorption transition point is independent of bending energy of the copolymer chain. These features are similar to that of a semiflexible homopolymer chain adsorption.

  6. A semiflexible alternating copolymer chain adsorption on a flat and a fluctuating surface.

    Science.gov (United States)

    Mishra, Pramod Kumar

    2010-04-21

    A lattice model of a directed self-avoiding walk is used to investigate adsorption properties of a semiflexible alternating copolymer chain on an impenetrable flat and fluctuating surface in two (square, hexagonal and rectangular lattice) and three dimensions (cubic lattice). In the cubic lattice case the surface is two-dimensional impenetrable flat and in two dimensions the surface is a fluctuating impenetrable line (hexagonal lattice) and also flat impenetrable line (square and rectangular lattice). Walks of the copolymer chains are directed perpendicular to the plane of the surface and at a suitable value of monomer surface attraction, the copolymer chain gets adsorbed on the surface. To calculate the exact value of the monomer surface attraction, the directed walk model has been solved analytically using the generating function method to discuss results when one type of monomer of the copolymer chain has attractive, repulsive or no interaction with the surface. Results obtained in the flat surface case show that, for a stiffer copolymer chain, adsorption transition occurs at a smaller value of monomer surface attraction than a flexible copolymer chain while in the case of a fluctuating surface, the adsorption transition point is independent of bending energy of the copolymer chain. These features are similar to that of a semiflexible homopolymer chain adsorption.

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

    Directory of Open Access Journals (Sweden)

    Elżbieta Piesowicz

    2016-06-01

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

  8. DupuytrEn Treatment EffeCtiveness Trial (DETECT): a protocol for prospective, randomised, controlled, outcome assessor-blinded, three-armed parallel 1:1:1, multicentre trial comparing the effectiveness and cost of collagenase clostridium histolyticum, percutaneous needle fasciotomy and limited fasciectomy as short-term and long-term treatment strategies in Dupuytren's contracture.

    Science.gov (United States)

    Räisänen, Mikko P; Karjalainen, Teemu; Göransson, Harry; Reito, Aleksi; Kautiainen, Hannu; Malmivaara, Antti; Leppänen, Olli V

    2018-03-28

    Dupuytren's contracture (DC) is a chronic fibroproliferative disorder of the palmar fascia which leads to flexion contracture in one or more fingers. There is no definitive cure for DC, and treatment aims at relieving symptoms by releasing the contracture using percutaneous or operative techniques. We planned a prospective, randomised, controlled, outcome assessor-blinded, three-armed parallel 1:1:1, multicentre trial comparing the effectiveness and cost of (1) collagenase clostridium histolyticum injection followed by limited fasciectomy in non-responsive cases, (2) percutaneous needle fasciotomy followed by limited fasciectomy in non-responsive cases and (3) primary limited fasciectomy during short-term and long-term follow-up for Tubiana I-III stages DC. We will recruit participants from seven national centres in Finland. Primary outcome is the rate of success in the treatment arm at 5 years after recruitment. Success is a composite outcome comprising (1) at least 50% contracture release from the date of recruitment and (2) participants in a patient-accepted symptom state (PASS). Secondary outcomes are (1) angle of contracture, (2) quick disabilities of the arm, a shoulder and hand outcome measure (QuickDASH), (3) perceived hand function, (4) EQ-5D-3L, (5) rate of major adverse events, (6) patient's trust of the treatment, (7) global rating, (8) rate of PASS, (9) rate of minimal clinically important improvement, (10) expenses, (11) progression of disease, (12) progression-free survival, (13) favoured treatment modality, (14) patients achieving full contracture release and >50% improvement and (15) patient satisfaction with the treatment effect. Predictive factors for achieving the PASS will also be analysed. The protocol was approved by the Tampere University Hospital Institutional Review Board and Finnish Medicine Agency. The study will be performed according to the principles of good clinical practice. The results of the trial will be disseminated as

  9. Fluorosilicone multi-block copolymers tethering quaternary ammonium salt groups for antimicrobial purpose

    Energy Technology Data Exchange (ETDEWEB)

    Zhou, Fang; Qin, Xiaoshuai; Li, Yancai; Ren, Lixia; Zhao, Yunhui, E-mail: zhaoyunhui@tju.edu.cn; Yuan, Xiaoyan

    2015-08-30

    Highlights: • QAS-containing fluorosilicone multi-block copolymers were synthesized. • The block length of PHFBMA in the copolymers was tailored via RAFT polymerization. • Surface roughness of the copolymers decreased with the increased PHFBMA content. • A certain length of PHFBMA block enhanced C−N{sup +} percentage on the surface. - Abstract: Symmetrically structured fluorosilicone multi-block copolymers containing poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) and poly(hexafluorobutyl methacrylate) (PHFBMA) were sequentially synthesized via reversible addition–fragmentation chain transfer polymerization, using a polydimethylsiloxane (PDMS) chain transfer agent with dithiocarbonate groups at both ends. Then, the CBABC-type block copolymers were quaternized with n-octyliodide to tether quaternary ammonium salt (QAS) groups in the PDMAEMA blocks for the antimicrobial use. The obtained fluorosilicone copolymers showed clear variations in the C-N{sup +} composition and surface morphology on their films depending on the content of the PHFBMA blocks, which were characterized by X-ray photoelectron spectroscopy and atomic force microscopy, respectively. The results indicated that the symmetrical CBABC structure favored PDMS and QAS tethered blocks migrating to the film surface. With the mass percentage of the PHFBMA increased from 0 to 32.5%, the surface roughness of the copolymer film decreased gradually with a tendency to form a smooth surface. Owing to the surface properties, fluorosilicone multi-block copolymers containing a certain amount of PHFBMA with higher C-N{sup +} content and relatively smooth morphology demonstrated obvious antimicrobial activity against Gram-positive bacteria, Bacillus subtilis and Gram-negative bacteria, Escherichia coli. The functionalized multi-block copolymers based on fluorosilicone and QAS groups would have potential applications in antimicrobial coatings.

  10. Fluorosilicone multi-block copolymers tethering quaternary ammonium salt groups for antimicrobial purpose

    International Nuclear Information System (INIS)

    Zhou, Fang; Qin, Xiaoshuai; Li, Yancai; Ren, Lixia; Zhao, Yunhui; Yuan, Xiaoyan

    2015-01-01

    Highlights: • QAS-containing fluorosilicone multi-block copolymers were synthesized. • The block length of PHFBMA in the copolymers was tailored via RAFT polymerization. • Surface roughness of the copolymers decreased with the increased PHFBMA content. • A certain length of PHFBMA block enhanced C−N + percentage on the surface. - Abstract: Symmetrically structured fluorosilicone multi-block copolymers containing poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) and poly(hexafluorobutyl methacrylate) (PHFBMA) were sequentially synthesized via reversible addition–fragmentation chain transfer polymerization, using a polydimethylsiloxane (PDMS) chain transfer agent with dithiocarbonate groups at both ends. Then, the CBABC-type block copolymers were quaternized with n-octyliodide to tether quaternary ammonium salt (QAS) groups in the PDMAEMA blocks for the antimicrobial use. The obtained fluorosilicone copolymers showed clear variations in the C-N + composition and surface morphology on their films depending on the content of the PHFBMA blocks, which were characterized by X-ray photoelectron spectroscopy and atomic force microscopy, respectively. The results indicated that the symmetrical CBABC structure favored PDMS and QAS tethered blocks migrating to the film surface. With the mass percentage of the PHFBMA increased from 0 to 32.5%, the surface roughness of the copolymer film decreased gradually with a tendency to form a smooth surface. Owing to the surface properties, fluorosilicone multi-block copolymers containing a certain amount of PHFBMA with higher C-N + content and relatively smooth morphology demonstrated obvious antimicrobial activity against Gram-positive bacteria, Bacillus subtilis and Gram-negative bacteria, Escherichia coli. The functionalized multi-block copolymers based on fluorosilicone and QAS groups would have potential applications in antimicrobial coatings

  11. Peculiarity of counterion - polyion interactions in aqueous solutions of copolymers of acrylamide with cadmium acrylate

    Energy Technology Data Exchange (ETDEWEB)

    Myagchenkov, V A; Kurenkov, V F; Akhmed' yanova, R A [Kazanskij Khimiko-Tekhnologicheskij Inst. (USSR)

    1984-02-01

    Binding of Cd/sup 2 +/ ions in aqueous solutions of statistical copolymers of acrylamide with cadmium acrylate with different content of ionogenic groups in copolymers was investigated by polarography, conductometry, viscometry and dialysis. It is shown that the degree of binding of Cd/sup 2 +/ ions increases with increasing of the content of ionogenic groups in the copolymer and with decreasing of ionic strength of the solution. The values of the degree of binding of Cd/sup 2 +/ ions obtained by polarography and dialysis show satisfactory agreement.

  12. Electrochemical and visco metric studies on some copolymer/ homopolymer poly electrolytes and transition metal ion interaction

    International Nuclear Information System (INIS)

    Rajabi, F. H.; Frahani, B. V.

    2003-01-01

    Some random three-component copolymers have been prepared by condensing of formaldehyde with various aromatic amines. The compositions of the copolymers have been determined by known methods. selective complexation of copolymers have been carried out with PAA, PEI, PVP and some transition metal ions (e.g., Cu 2+ )by adding the components in various sequences. The relative complexation ability of different -NH 2 groups, associated with the various comonomer units, has been interpreted in terms of the these complexes has been studied by conductometry. potentiometry and viscometry techniques. A scheme has presented to explain the mode of interaction of the various components

  13. Non-immunogenic, hydrophilic/cationic block copolymers and uses thereof

    Science.gov (United States)

    Scales, Charles W.; Huang, Faqing; McCormick, Charles L.

    2010-05-18

    The present invention provides novel non-immunogenic, hydrophilic/cationic block copolymers comprising a neutral-hydrophilic polymer and a cationic polymer, wherein both polymers have well-defined chain-end functionality. A representative example of such a block copolymer comprises poly(N-(2-hydroxypropyl)methacrylamide) (PHPMA) and poly(N-[3-(dimethylamino)propyl]methacrylamide) (PDMAPMA). Also provided is a synthesis method thereof in aqueous media via reversible addition fragmentation chain transfer (RAFT) polymerization. Further provided are uses of these block copolymers as drug delivery vehicles and protection agents.

  14. Optimisation of Silicone-based Dielectric Elastomer Transducers by Means of Block Copolymers - Synthesis and Compounding

    DEFF Research Database (Denmark)

    A Razak, Aliff Hisyam

    through the use of a multi-walled carbon nanotube (MWCNT) in a PDMS-PEG matrix as a compliant electrode of dielectric elastomers. The conductive PDMS-PEG copolymer was incorporated with surface-treated MWCNT, in order to obtain highly conductive elastomer. The prepared sample with 4 parts per hundred...... enhancing the electrical breakdown strength of silicone by using an aromatic voltage stabiliser. Here, polyphenylmethylsiloxane (PPMS), which contained aromatic voltage stabilisers, was bonded covalently to PDMS through a hydrosilylation reaction obtaining PDMS-PPMS copolymers. The synthesised copolymers...

  15. Small angle neutron scattering study of the micelle structure of amphiphilic block copolymers

    International Nuclear Information System (INIS)

    Yamaoka, H.; Matsuoka, H.; Sumaru, K.; Hanada, S.

    1994-01-01

    The amphiphilic block copolymers of vinyl ether were prepared by living cationic polymerization. The partially deuterated copolymers for SANS experiments were especially synthesized by introducing deuterated phenyl units in the hydrophobic chain. SANS measurements were performed for aqueous solutions of these copolymers by changing H 2 O/D 2 O ratios. The SANS profiles indicate that the micelles in the present system exhibit a core-shell structure and that the size and shape of micelles are largely dependent on the length of hydrophobic chain. The micelle of shorter hydrophobic chain was found to be nearly spherical, whereas the micelle of longer hydrophobic chain was confirmed to have an ellipsoidal shape

  16. Mechanically compliant electrodes and dielectric elastomers from PEG-PDMS copolymers

    DEFF Research Database (Denmark)

    A Razak, Aliff Hisyam; Madsen, Frederikke Bahrt; Skov, Anne Ladegaard

    2016-01-01

    Soft conducting elastomers have been prepared from polydimethylsiloxane-polyethyleneglycol (PDMS-PEG) copolymer and surfactant-stabilized multi-walled carbon nanotubes (MWCNTs). The copolymer was chain-extended with PDMS of molecular weight 17.2 kg mol-1 in order to obtain a crosslinkable PDMS...... showed high conductivity combined with inherent softness. The high conductivity and softness, PDMS-PEG copolymers with incorporated MWCNTs hold great promises as compliant and highly stretchable electrodes for stretchable devices such as electro-mechanical transducers....

  17. Microphase separation behavior on the surfaces of PEG-MDI-PDMS multiblock copolymer coatings

    International Nuclear Information System (INIS)

    Fang Hongxia; Zhou Shuxue; Wu Limin

    2006-01-01

    A series of poly(ethylene glycol)(PEG)-4,4'-diphenylmethanediisocyanate(MDI)-poly(dimethylsiloxane) (PDMS) multiblock copolymers were synthesized by employing two-step growth polymerization technique. Atomic force microscopy (AFM) observed nanoscopically well-organized phase-separated surfaces consisting of hydrophilic domain from PEG and MDI segments and hydrophobic domain from PDMS segments even with 50 wt.% PDMS in the copolymer, and the multiblock copolymer coatings presented a surface free energy of as low as 6-8 mN m -1

  18. POTENTIAL USE OF GRAFT COPOLYMERS OF MERCERIZED FLAX AS FILLER IN POLYSTYRENE COMPOSITE MATERIALS

    Directory of Open Access Journals (Sweden)

    Susheel Kalia

    2008-11-01

    Full Text Available Graft copolymerization of binary vinyl monomers onto mercerized flax fiber was carried out for the enhancement of mechanical properties of polystyrene composites. Binary vinyl monomer mixture of AA+AN has been found to show maximum grafting (33.55% onto mercerized flax. Graft copolymers thus synthesized were characterized with FT-IR spectroscopy, SEM, and TGA techniques. Mercerized flax (MF showed maximum thermal stability in comparison to graft copolymers. It has been found that polystyrene composites reinforced with graft copolymers showed improvement in mechanical properties such as wear resistance, compressive strength, and tensile strength.

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

    DEFF Research Database (Denmark)

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

    2018-01-01

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

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

    International Nuclear Information System (INIS)

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

    1976-01-01

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

  1. Self-Assembly and Crystallization of Conjugated Block Copolymers

    Science.gov (United States)

    Davidson, Emily Catherine

    This dissertation demonstrates the utility of molecular design in conjugated polymers to create diblock copolymers that robustly self-assemble in the melt and confine crystallization upon cooling. This work leverages the model conjugated polymer poly(3-(2'-ethyl)hexylthiophene) (P3EHT), which features a branched side chain, resulting in a dramatically reduced melting temperature (Tm 80°C) relative to the widely-studied poly(3-hexylthiophene) (P3HT) (Tm 200°C). This reduced melting temperature permits an accessible melt phase, without requiring that the segregation strength (chiN) be dramatically increased. Thus, diblock copolymers containing P3EHT demonstrate robust diblock copolymer self-assembly in the melt over a range of compositions and morphologies. Furthermore, confined crystallization in the case of both glassy (polystyrene (PS) matrix block) and soft (polymethylacrylate (PMA) matrix block) confinement is studied, with the finding that even in soft confinement, crystallization is constrained within the diblock microdomains. This success demonstrates the strategy of leveraging molecular design to decrease the driving force for crystallization as a means to achieving robust self-assembly and confined crystallization in conjugated block copolymers. Importantly, despite the relatively flexible nature of P3EHT in the melt, the diblock copolymer phase behavior appears to be significantly impacted by the stiffness (persistence length of 3 nm) of the P3EHT chain compared to the coupled amorphous blocks (persistence length 0.7 nm). In particular, it is shown that the synthesized morphologies are dominated by a very large composition window for lamellar geometries (favored at high P3EHT volume fractions); cylindrical geometries are favored when P3EHT is the minority fraction. This asymmetry of the composition window is attributed to impact of conformational asymmetry (the difference in chain stiffness, as opposed to shape) between conjugated and amorphous blocks

  2. Monte Carlo studies on the interfacial properties and interfacial structures of ternary symmetric blends with gradient copolymers.

    Science.gov (United States)

    Sun, Dachuan; Guo, Hongxia

    2012-08-09

    Using Monte Carlo simulation methods, the effects of the comonomer sequence distribution on the interfacial properties (including interfacial tension, interfacial thickness, saturated interfacial area per copolymer, and bending modulus) and interfacial structures (including chain conformations and comonomer distributions of the simulated copolymers at the interfaces) of a ternary symmetric blend containing two immiscible homopolymers and one gradient copolymer are investigated. We find that copolymers with a larger composition gradient width have a broader comonomer distribution along the interface normal, and hence more pronouncedly enlarge the interfacial thickness and reduce the interfacial tension. Furthermore, the counteraction effect, which arises from the tendency of heterogeneous segments in gradient copolymers to phase separate and enter their miscible phases to reduce the local enthalpy, decreases the stretching of copolymers along the interface normal direction. As a result, copolymers with a larger width of gradient composition can occupy a larger interfacial area and form softer monolayers at saturation and are more efficient in facilitating the formation of bicontinuous microemulsions. Additionally, chain length ratio, segregation strength, and interactions between homopolymers and copolymers can alter the interfacial character of gradient copolymers. There exists a strong coupling between the comonomer sequence distribution, chain conformation, and interfacial properties. Especially, bending modulus is mainly determined by the complicated interplay of interfacial copolymer density and interfacial chain conformation.

  3. Overview on the Preparation and Characterization of some Itaconic Acid Chelating Copolymers

    International Nuclear Information System (INIS)

    Abd El-Ghaffar, M.A.; Youssef, E.A.; El-Halawany, N.R.

    2005-01-01

    Itaconic acid (IA) was copolymerised by an emulsion process with butyl acrylate (BuA), butyl methacrylate (BuMA) and styrene (St) using potassium persulphate/sodium meta bisulphite as a redox initiation system and sodium dodecyl benzene sulfonate as an emulsifier. The rate of copolymerization was found to decrease with increasing (IA) content . The prepared copolymers were characterized by spectrophotometric analysis (IR and lINMR), thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) . The monomer reactivity ratios (r1and r2) for the prepared copolymers were determined and discussed . The copolymers having the best properties were incorporated in latex paint formulations. The Ac.. conductivity of the binary itaconic copolymers have been investigated and studied at room temperature and showed semiconducting properties

  4. Design, synthesis, and characterization of lightly sulfonated multigraft acrylate-based copolymer superelastomers

    Energy Technology Data Exchange (ETDEWEB)

    Misichronis, Konstantinos [Univ. of Tennessee, Knoxville, TN (United States). Dept. of Chemistry; Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division; Wang, Weiyu [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science (CNMS); Cheng, Shiwang [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division; Wang, Yangyang [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science (CNMS); Shrestha, Umesh [Univ. of Tennessee, Knoxville, TN (United States). Dept. of Chemistry; Dadmun, Mark D. [Univ. of Tennessee, Knoxville, TN (United States). Dept. of Chemistry; Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division; Mays, Jimmy W. [Univ. of Tennessee, Knoxville, TN (United States). Dept. of Chemistry; Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division; Saito, Tomonori [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division

    2018-01-29

    Multigraft copolymer superelastomers consisting of a poly(n-butyl acrylate) backbone and polystyrene side chains were synthesized and the viscoelastic properties of the non-sulfonated and sulfonated final materials were investigated using extensional rheology (SER3). The non-linear viscoelastic experiments revealed significantly increased true stresses (up to 10 times higher) after sulfonating only 2–3% of the copolymer while the materials maintained high elongation (<700%). The linear viscoelastic experiments showed that the storage and loss modulus are increased by sulfonation and that the copolymers can be readily tuned and further improved by increasing the number of branching points and the molecular weight of the backbone. Here, in this way, we show that by tuning not only the molecular characteristics of the multigraft copolymers but also their architecture and chemical interaction, we can acquire thermoplastic superelastomer materials with desired viscoelastic properties.

  5. Distributions of chain ends and junction points in ordered block copolymers

    International Nuclear Information System (INIS)

    Mayes, A.M.; Johnson, R.D.; Russell, T.P.; Smith, S.D.; Satija, S.K.; Majkrzak, C.F.

    1993-01-01

    Chain configurations in ordered symmetric poly(styrene-b-methyl methacrylate) diblock copolymers were examined by neutron reflectively. In a thin-film geometry the copolymers organize into lamellar microdomains oriented parallel to the substrate surface. The copolymers organize into lamellar microdomains oriented parallel to the substrate surface. The copolymers were synthesized with small fractions of deuterated segments at either the chain ends or centers. This selective labeling permitted characterization of the spatial distribution of chain ends and junction points normal to the plane of the film. From the reflectivity analysis, the junction points are found to be confined to the PS/PMMA interfacial regions. The chain ends, however, are well distributed through their respective domains, exhibiting only a weak maximum in concentration at the center of the domains

  6. Reversible Copolymer Materials for FDM 3-D Printing of Non-Standard Plastics, Phase II

    Data.gov (United States)

    National Aeronautics and Space Administration — Cornerstone Research Group Inc. (CRG) proposes to continue efforts from the 2015 NASA SBIR Phase I topic H14.03 ?Reversible Copolymer Materials for FDM 3D Printing...

  7. Self-assembled block copolymer membranes: From basic research to large-scale manufacturing

    KAUST Repository

    Nunes, Suzana Pereira; Behzad, Ali Reza; Peinemann, Klaus-Viktor

    2013-01-01

    Order and porosity of block copolymer membranes have been controlled by solution thermodynamics, self-assembly, and macrophase separation. We have demonstrated how the film manufacture with long-range order can be up-scaled with the use

  8. Anionic polymerization and polyhomologation: An ideal combination to synthesize polyethylene-based block copolymers

    KAUST Repository

    Zhang, H.; Alkayal, N.; Gnanou, Yves; Hadjichristidis, Nikolaos

    2013-01-01

    A novel one-pot methodology combining anionic polymerization and polyhomologation, through a "bridge" molecule (BF3OEt 2), was developed for the synthesis of polyethylene (PE)-based block copolymers. The anionically synthesized macroanion reacts

  9. Micellar aggregates of amylose-block-polystyrene rod-coil block copolymers in water and THF

    NARCIS (Netherlands)

    Loos, Katja; Böker, Alexander; Zettl, Heiko; Zhang, Mingfu; Krausch, Georg; Müller, Axel H.E.; Boker, A.; Zhang, A.F.

    2005-01-01

    Amylose-block-polystyrenes with various block copolymer compositions were investigated in water and in THF solution. Fluorescence correlation spectroscopy, dynamic light, scattering (DLS), and asymmetric flow field-flow fractionation with multiangle light scattering detection indicate the presence

  10. Kinetics of directed self-assembly of block copolymers on chemically patterned substrates

    International Nuclear Information System (INIS)

    Müller, Marcus; Li, Weihua; Rey, Juan Carlos Orozco; Welling, Ulrich

    2015-01-01

    Chemically patterned surfaces have been successfully employed to direct the kinetics of self-assembly of block copolymers into dense, periodic morphologies (”chemoepitaxy”). Significant efforts have been directed towards understanding the kinetics of structure formation and, particularly, the formation and annihilation of defects. In the present manuscript we use computer simulations of a soft, coarse-grained polymer model to study the kinetics of structure formation of lamellar-forming block copolymer thin films on a chemical pattern of lines and spaces. The case where the copolymer material replicates the surface pattern and the more subtle scenario of sparse guiding patterns are considered. Our simulation results highlight (1) the importance of the early stages of pattern-directed self-assembly that template the subsequent morphology and (2) the dependence of the free-energy landscape on the incompatibility between the two blocks of the copolymer. (paper)

  11. Optimization of components in high-yield synthesis of block copolymer-mediated gold nanoparticles

    International Nuclear Information System (INIS)

    Ray, Debes; Aswal, Vinod Kumar

    2012-01-01

    The optimization to achieve stable and high-yield gold nanoparticles in block copolymer-mediated synthesis has been examined. Gold nanoparticles are synthesized using block copolymer P85 in gold salt HAuCl 4 ·3H 2 O solution. This method usually has a very limited yield which does not simply increase with the increase in the gold salt concentration. We show that the yield can be enhanced by increasing the block copolymer concentration but is limited to the factor by which the concentration is increased. On the other hand, the presence of an additional reductant (trisodium citrate) in 1:1 molar ratio with gold salt enhances the yield by manyfold. In this case (with additional reductant), the stable and high-yield nanoparticles having size about 14 nm can be synthesized at very low block copolymer concentrations. These nanoparticles thus can be efficiently used for their application such as for adsorption of proteins.

  12. Controlled disulfonated poly(arylene ether sulfone) multiblock copolymers for direct methanol fuel cells.

    Science.gov (United States)

    Li, Qing; Chen, Yu; Rowlett, Jarrett R; McGrath, James E; Mack, Nathan H; Kim, Yu Seung

    2014-04-23

    Structure-property-performance relationships of disulfonated poly(arylene ether sulfone) multiblock copolymer membranes were investigated for their use in direct methanol fuel cell (DMFC) applications. Multiple series of reactive polysulfone, polyketone, and polynitrile hydrophobic block segments having different block lengths and molecular composition were synthesized and reacted with a disulfonated poly(arylene ether sulfone) hydrophilic block segment by a coupling reaction. Large-scale morphological order of the multiblock copolymers evolved with the increase of block size that gave notable influence on mechanical toughness, water uptake, and proton/methanol transport. Chemical structural changes of the hydrophobic blocks through polar group, fluorination, and bisphenol type allowed further control of the specific properties. DMFC performance was analyzed to elicit the impact of structural variations of the multiblock copolymers. Finally, DMFC performances of selected multiblock copolymers were compared against that of the industrial standard Nafion in the DMFC system.

  13. 21 CFR 177.1480 - Nitrile rubber modified acrylonitrile-methyl acrylate copolymers.

    Science.gov (United States)

    2010-04-01

    ...-methyl acrylate copolymers identified in this section may be safely used as components of articles... Applied Nutrition (HFS-200), Food and Drug Administration, 5100 Paint Branch Pkwy., College Park, MD 20740...

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

    KAUST Repository

    Moreno Chaparro, Nicolas

    2016-01-01

    Isoporous membranes manufactured from diblock copolymer are successfully produced at laboratory scale under controlled conditions. Because of the complex phenomena involved, membrane preparation requires trial and error methodologies to find

  15. Living cationic polymerization and polyhomologation: an ideal combination to synthesize functionalized polyethylene–polyisobutylene block copolymers

    KAUST Repository

    Zhang, Hefeng

    2015-12-17

    A series of hydroxyl-terminated polyisobutylene-b-polyethylene (PIB-b-PE-OH) copolymers were synthesized by combining living cationic polymerization and polyhomologation. Allyl-terminated PIBs, synthesized by living cationic polymerization, were hydroborated with BH3·THF to produce 3-arm boron-linked stars, PIB3B, which served as macroinitiators for the in situ polyhomologation of dimethylsulfoxonium methylide. The resulting 3-arm star block copolymers, (PIB-b-PE)3B, were oxidized/hydrolysed to afford PIB-b-PE-OH. Characterization of all intermediates and final products by high temperature gel permeation chromatography (HT-GPC) and proton nuclear magnetic resonance spectroscopy (1H NMR) revealed the well-defined character of the copolymers. The thermal properties of the copolymers were studied by differential scanning calorimetry (DSC).

  16. Nonlinear optical measurements of conducting copolymers of aniline under CW laser excitation

    Science.gov (United States)

    Pramodini, S.; Poornesh, P.

    2015-08-01

    Synthesis and measurements of third-order optical nonlinearity and optical limiting of conducting copolymers of aniline are presented. Single beam z-scan technique was employed for the nonlinear optical studies. Continuous wave He-Ne laser operating at 633 nm was used as the source of excitation. Copolymer samples exhibited reverse saturable absorption (RSA) process. The nonlinear refraction studies depict that the copolymers exhibit self-defocusing property. The estimated values of βeff, n2 and χ(3) were found to be of the order of 10-2 cm/W, 10-5 esu and 10-7 esu respectively. Self-diffraction rings were observed due to refractive index change when exposed to the laser beam. A good optical limiting and clamping of power of ∼0.9 mW and ∼0.05 mW was observed. Therefore, copolymers of aniline emerge as a potential candidate for photonic device applications.

  17. Nanocomposite photoactuators based on an ethylene vinyl acetate copolymer filled with carbon nanotubes

    Czech Academy of Sciences Publication Activity Database

    Czaniková, K.; Torras, N.; Esteve, J.; Krupa, I.; Kasák, P.; Pavlova, Ewa; Račko, D.; Chodák, I.; Omastová, M.

    2013-01-01

    Roč. 186, September (2013), s. 701-710 ISSN 0925-4005 Institutional support: RVO:61389013 Keywords : actuator * carbon nanotubes * ethylene vinyl acetate copolymer Subject RIV: CD - Macromolecular Chemistry Impact factor: 3.840, year: 2013

  18. Photoinduced optical anisotropy in azobenzene methacrylate block copolymers: Influence of molecular weight and irradiation conditions

    DEFF Research Database (Denmark)

    Gimeno, Sofia; Forcen, Patricia; Oriol, Luis

    2009-01-01

    The photoinduced anisotropy in a series of azomethacrylate block copolymers with different Molecular weights and azo contents has been investigated under several irradiation conditions. Depending on molecular weight and composition, different microstructures (disordered, lamellar, spherical) appe...

  19. Study of the Pyrrol/Diphenylamine Copolymer by FT-IR spectroscopy and conductivity

    Directory of Open Access Journals (Sweden)

    Carlos Alberto Perez

    2004-01-01

    Full Text Available The main goal of this study was to analyze the physical properties of the copolymer formed by the electrochemical deposition of the polydiphenylamine (PDPA on polypyrrole (Ppy and Ppy on PDPA, in different conditions, through the characterization of the materials formed by the resonant Raman, FT-IR and conductivity techniques. The interactions among the species which are present in the new copolymer structure and the changes in electronic conductivity, were verified. The copolymer was also synthesized electrochemically in the presence of iodide species and the material was characterized by FT-IR spectroscopy and conductivity. The role of the dopant was studied in the process of charge transfer between the copolymer-dopant, acting in the stabilization of the species in the polymer backbone and the increase of the electronic conductivity.

  20. Synthesis and characterization of functional acrylic copolymers via RAFT mini-emulsion polymerization

    Science.gov (United States)

    Yılmaz, Onur; Özkan, ćiǧdem Kılıçarislan; Yılmaz, Catalina N.; Yorgancıoǧlu, Ali; Özgünay, Hasan; Karavana, Hüseyin Ata

    2017-12-01

    Copolymers bearing reactive functional groups with controlled molecular weights are of importance since they can be used in many fields such as composites, coatings, membranes, catalysis, biology, optoelectronics, pharmaceuticals, etc. In the present study low molecular weight copolymers based on butyl acrylate (BA) and methyl methacrylate (MMA) in combination with reactive functional monomers of vinyl trietoxysilane (VTES), 3-trimetoxysilylpropyl methacrylate (TMSPMA) and glycidyl methacrylate (GMA) were synthesized via RAFT mini-emulsion technique using 2-cyano 2-propyldodecyldithiocarbonate as CTA agent. The results showed that the average molecular weights of copolymers were close to the theoretical values. On the other hand, PDI values were found to be higher than conventional RAFT polymers. The particle sizes of the latexes were small with very homogenous distributions and good stability. FTIR, H-NMR and TGA results verified the success of copolymer syntheses.

  1. Diketopyrrolopyrrole-diketopyrrolopyrrole-based conjugated copolymer for high-mobility organic field-effect transistors

    KAUST Repository

    Kanimozhi, Catherine K.

    2012-10-10

    In this communication, we report the synthesis of a novel diketopyrrolopyrrole-diketopyrrolopyrrole (DPP-DPP)-based conjugated copolymer and its application in high-mobility organic field-effect transistors. Copolymerization of DPP with DPP yields a copolymer with exceptional properties such as extended absorption characteristics (up to ∼1100 nm) and field-effect electron mobility values of >1 cm 2 V -1 s -1. The synthesis of this novel DPP-DPP copolymer in combination with the demonstration of transistors with extremely high electron mobility makes this work an important step toward a new family of DPP-DPP copolymers for application in the general area of organic optoelectronics. © 2012 American Chemical Society.

  2. Study of the therapeutic benefit of cationic copolymer administration to vascular endothelium under mechanical stress

    Science.gov (United States)

    Giantsos-Adams, Kristina; Lopez-Quintero, Veronica; Kopeckova, Pavla; Kopecek, Jindrich; Tarbell, John M.; Dull, Randal

    2015-01-01

    Pulmonary edema and the associated increases in vascular permeability continue to represent a significant clinical problem in the intensive care setting, with no current treatment modality other than supportive care and mechanical ventilation. Therapeutic compound(s) capable of attenuating changes in vascular barrier function would represent a significant advance in critical care medicine. We have previously reported the development of HPMA-based copolymers, targeted to endothelial glycocalyx that are able to enhance barrier function. In this work, we report the refinement of copolymer design and extend our physiological studies todemonstrate that the polymers: 1) reduce both shear stress and pressure-mediated increase in hydraulic conductivity, 2) reduce nitric oxide production in response to elevated hydrostatic pressure and, 3) reduce the capillary filtration coefficient (Kfc) in an isolated perfused mouse lung model. These copolymers represent an important tool for use in mechanotransduction research and a novel strategy for developing clinically useful copolymers for the treatment of vascular permeability. PMID:20932573

  3. The effect of salt on the morphologies of compositionally asymmetric block copolymer electrolytes

    Science.gov (United States)

    Loo, Whitney; Maslyn, Jacqueline; Oh, Hee Jeung; Balsara, Nitash

    Block copolymer electrolytes are promising for applications in lithium metal solid-state batteries. Due to their ability to microphase separate into distinct morphologies, their ion transport and mechanical properties can be decoupled. The addition of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt to poly(styrene)-block-poly(ethylene oxide) (SEO) has been shown to increase microphase separation in symmetric block copolymer systems due to an increase in the effective interaction parameter (χeff) ; however the effect of block copolymer compositional asymmetry is not well-understood. The effect of compositional asymmetry on polymer morphology was investigated through small and wide angle X-ray scattering (SAXS/WAXS). The effective Flory-Huggins interaction parameter was extracted from the scattering profiles in order to construct a phase diagram to demonstrate the effect of salt and compositional asymmetry on block copolymer morphology.

  4. Ionic Liquids As Self-Assembly Guide for the Formation of Nanostructured Block Copolymer Membranes

    KAUST Repository

    Madhavan, Poornima; Sougrat, Rachid; Behzad, Ali Reza; Peinemann, Klaus-Viktor; Nunes, Suzana Pereira

    2015-01-01

    Nanostructured block copolymer membranes were manufactured by water induced phase inversion, using ionic liquids (ILs) as cosolvents. The effect of ionic liquids on the morphology was investigated, by using polystyrene-b-poly(4-vinyl pyridine) (PS

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

    Science.gov (United States)

    Lee, Ji Hoon; Shofner, Meisha

    2012-02-01

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

  6. Identifying the nature of surface chemical modification for directed self-assembly of block copolymers

    Directory of Open Access Journals (Sweden)

    Laura Evangelio

    2017-09-01

    Full Text Available In recent years, block copolymer lithography has emerged as a viable alternative technology for advanced lithography. In chemical-epitaxy-directed self-assembly, the interfacial energy between the substrate and each block copolymer domain plays a key role on the final ordering. Here, we focus on the experimental characterization of the chemical interactions that occur at the interface built between different chemical guiding patterns and the domains of the block copolymers. We have chosen hard X-ray high kinetic energy photoelectron spectroscopy as an exploration technique because it provides information on the electronic structure of buried interfaces. The outcome of the characterization sheds light onto key aspects of directed self-assembly: grafted brush layer, chemical pattern creation and brush/block co-polymer interface.

  7. Phase transition of LB films of mixed diblock copolymer at the air/water interface

    Science.gov (United States)

    Seo, Y. S.; Kim, K. S.; Samuilov, V.; Rafailovich, M. H.; Sokolov, J.; Lammertink, Rob G. H.; Vancso, G. J.

    2000-03-01

    We have studied the morphology of Langmuir blodgett films at the air/water interface of mixed diblock copolymer films. Solutions of poly(styrene-b-ferrocenyldimethylsilane) and PS-b-P2VP mixed in a ratio of 20/80 in chloroform were spread at the air/water interface. The morphology of the films was studied with AFM as a function of the surface pressure and the diblock copolymer molecular weight. The results show that the two diblock copolymers can be induced to mix at the air/water interface with increasing surface pressure. A reversible transition from spherical to cylindrical morphologies is induced in the mixture which can not be observed in films formed of the two components separately. The effective surface phase diagram as a function of block copolymer composition and pressure will be presented.

  8. Dual hydrophilic and salt responsive schizophrenic block copolymers – synthesis and study of self-assembly

    NARCIS (Netherlands)

    Vasantha, Vivek Arjunan; Jana, Satyasankar; Lee, Serina Siew Chen; Lim, Chin-Sing; Teo, Serena Lay Ming; Parthiban, Anbanandam; Vancso, Gyula J.

    2015-01-01

    A new class of dual hydrophilic diblock copolymers (BCPs) possessing poly(ethylene glycol) (PEG) and zwitterionic polysulfabetaine (PSB) was synthesized by reversible addition–fragmentation chain transfer (RAFT) polymerization. These BCPs formed schizophrenic micelles undergoing core–shell

  9. Precision design of ethylene- and polar-monomer-based copolymers by organometallic-mediated radical polymerization

    Science.gov (United States)

    Kermagoret, Anthony; Debuigne, Antoine; Jérôme, Christine; Detrembleur, Christophe

    2014-03-01

    The copolymerization of ethylene with polar monomers is a major challenge when it comes to the manufacture of materials with potential for a wide range of commercial applications. In the chemical industry, free-radical polymerization is used to make a large proportion of such copolymers, but the forcing conditions result in a lack of fine control over the architecture of the products. Herein we introduce a synthetic tool, effective under mild experimental conditions, for the precision design of unprecedented ethylene- and polar-monomer-based copolymers. We demonstrate how an organocobalt species can control the growth of the copolymer chains, their composition and the monomer distribution throughout the chain. By fine tuning the ethylene pressure during polymerization and by exploiting a unique reactive mode of the end of the organometallic chain, novel block-like copolymer structures can be prepared. This highly versatile synthetic platform provides access to a diverse range of polymer materials.

  10. Molecular changes in copolymers of styrene and methyl methacrylate caused by radiation

    International Nuclear Information System (INIS)

    Busfield, W.K.; O'Donnell, J.H.; Smith, C.A.

    1976-01-01

    Homopolymers of styrene and methyl methacrylate and copolymers of these monomers were irradiated in vacuo at room temperature using 60 Co γ-radiation to various doses. The gaseous radiolysis products of the polymers were analysed by gas chromatography. The radiation chemical yield, G values, of the gaseous and liquid products were calculated for the homopolymers and copolymers. The G values obtained for the homopolymers were compared with those obtained by previous workers. The graphs of G value versus composition (% Styrene) showed a marked deviation from linearity which indicated that the styrene in the copolymer had a greater effect on the behaviour than did the methyl methacrylate units. It has been postulated that the benzene ring on the styrene unit acts in some way as an energy sink, and hence protects the copolymer from radiation damage in an analogous way to that suggested for hydrocarbon mixtures. Mechanisms for the process are discussed. (author)

  11. General Syntheses of Nanotubes Induced by Block Copolymer Self-Assembly

    DEFF Research Database (Denmark)

    Zhao, Jianming; Huang, Wei; Si, Pengchao

    2018-01-01

    Amphiphilic block copolymer templating strategies are extensively used for syntheses of mesoporous materials. However, monodisperse tubular nanostructures are limited. Here, a general method is developed to synthesize monodisperse nanotubes with narrow diameter distribution induced by self...

  12. Diketopyrrolopyrrole-diketopyrrolopyrrole-based conjugated copolymer for high-mobility organic field-effect transistors

    KAUST Repository

    Kanimozhi, Catherine K.; Yaacobi-Gross, Nir; Chou, Kang Wei; Amassian, Aram; Anthopoulos, Thomas D.; Patil, Satish P.

    2012-01-01

    In this communication, we report the synthesis of a novel diketopyrrolopyrrole-diketopyrrolopyrrole (DPP-DPP)-based conjugated copolymer and its application in high-mobility organic field-effect transistors. Copolymerization of DPP with DPP yields a

  13. Biomimetic block copolymer particles with gated nanopores and ultrahigh protein sorption capacity

    KAUST Repository

    Yu, Haizhou; Qiu, Xiaoyan; Nunes, Suzana Pereira; Peinemann, Klaus-Viktor

    2014-01-01

    . The tiny and, in most cases, hollow spheres are used as vehicles for transport and controlled administration of pharmaceutical drugs or nutrients. Here we report a simple strategy to fabricate microspheres by block copolymer self-assembly. The microsphere

  14. Ultraporous films with uniform nanochannels by block copolymer micelles assembly

    KAUST Repository

    Nunes, Suzana Pereira

    2010-10-12

    Films with high pore density and regularity that are easy to manufacture by conventional large-scale technology are key components aimed for fabrication of new generations of magnetic arrays for storage media, medical scaffolds, and artificial membranes. However, potential manufacture strategies like the self-assembly of block copolymers, which lead to amazing regular patterns, could be hardly reproduced up to now using commercially feasible methods. Here we report a unique production method of nanoporous films based on the self-assembly of copper(II) ion-polystyrene-b-poly(4-vinylpyridine) complexes and nonsolvent induced phase separation. Extremely high pore densities and uniformity were achieved. Water fluxes of 890 L m-2 h-1 bar-1 were obtained, which are at least 1 order of magnitude higher than those of commercially available membranes with comparable pore size. The pores are also stimuli (pH)-responsive. © 2010 American Chemical Society.

  15. Intradomain Textures in Block Copolymers: Multizone Alignment and Biaxiality

    Science.gov (United States)

    Prasad, Ishan; Seo, Youngmi; Hall, Lisa M.; Grason, Gregory M.

    2017-06-01

    Block copolymer (BCP) melt assembly has been studied for decades, focusing largely on self-organized spatial patterns of periodically ordered segment density. Here, we demonstrate that underlying the well-known composition profiles (i.e., ordered lamella, cylinders, spheres, and networks) are generic and heterogeneous patterns of segment orientation that couple strongly to morphology, even in the absence of specific factors that promote intra or interchain segment alignment. We employ both self-consistent field theory and coarse-grained simulation methods to measure polar and nematic order parameters of segments in a freely jointed chain model of diblock melts. We show that BCP morphologies have a multizone texture, with segments predominantly aligned normal and parallel to interdomain interfaces in the respective brush and interfacial regions of the microdomain. Further, morphologies with anisotropically curved interfaces (i.e., cylinders and networks) exhibit biaxial order that is aligned to the principal curvature axes of the interface.

  16. Lamplighter model of a random copolymer adsorption on a line

    Directory of Open Access Journals (Sweden)

    L.I. Nazarov

    2014-09-01

    Full Text Available We present a model of an AB-diblock random copolymer sequential self-packaging with local quenched interactions on a one-dimensional infinite sticky substrate. It is assumed that the A-A and B-B contacts are favorable, while A-B are not. The position of a newly added monomer is selected in view of the local contact energy minimization. The model demonstrates a self-organization behavior with the nontrivial dependence of the total energy, E (the number of unfavorable contacts, on the number of chain monomers, N: E ~ N^3/4 for quenched random equally probable distribution of A- and B-monomers along the chain. The model is treated by mapping it onto the "lamplighter" random walk and the diffusion-controlled chemical reaction of X+X → 0 type with the subdiffusive motion of reagents.

  17. Stabilization of liquid crystal dispersions with acrylamide copolymers

    Energy Technology Data Exchange (ETDEWEB)

    Park, S.J.; Kim, M.H.; Lee, J.R. [Korea Research Institute of Chemical Technology, Taejon (Korea, Republic of)

    1999-03-01

    The effects of hydrophobic moieties(styrene and methyl methacrylate) on the stability of a liquid crystal(LC, E-7)-in-water dispersion stabilized by copolymers of hydrophilic acrylamide with hydrophobic monomers have been studied in terms of nematic curvilinear aligned phase(NCAP) system. It was observed that the preferential adsorption hydrophobic moieties onto LC droplet surface resulted in steric stabilization of the dispersion, due to increasing the interfacial tension of LC and reducing the LC droplet size. According to the interfacial tension, coalescence time, and sedimented layer thickness measurements, it was proposed that the presence of hydrophobic moieties allows to form the apolar microenvironment in the round of LC droplet and finally reduces the anchoring effect between LC and the polymeric wall. 16 refs., 10 figs.

  18. Silver-enhanced block copolymer membranes with biocidal activity

    KAUST Repository

    Madhavan, Poornima

    2014-11-12

    Silver nanoparticles were deposited on the surface and pore walls of block copolymer membranes with highly ordered pore structure. Pyridine blocks constitute the pore surfaces, complexing silver ions and promoting a homogeneous distribution. Nanoparticles were then formed by reduction with sodium borohydride. The morphology varied with the preparation conditions (pH and silver ion concentration), as confirmed by field emission scanning and transmission electron microscopy. Silver has a strong biocide activity, which for membranes can bring the advantage of minimizing the growth of bacteria and formation of biofilm. The membranes with nanoparticles prepared under different pH values and ion concentrations were incubated with Pseudomonas aeruginosa and compared with the control. The strongest biocidal activity was achieved with membranes containing membranes prepared under pH 9. Under these conditions, the best distribution with small particle size was observed by microscopy.

  19. Block Copolymer Micellization as a Protection Strategy for DNA Origami.

    Science.gov (United States)

    Agarwal, Nayan P; Matthies, Michael; Gür, Fatih N; Osada, Kensuke; Schmidt, Thorsten L

    2017-05-08

    DNA nanotechnology enables the synthesis of nanometer-sized objects that can be site-specifically functionalized with a large variety of materials. For these reasons, DNA-based devices such as DNA origami are being considered for applications in molecular biology and nanomedicine. However, many DNA structures need a higher ionic strength than that of common cell culture buffers or bodily fluids to maintain their integrity and can be degraded quickly by nucleases. To overcome these deficiencies, we coated several different DNA origami structures with a cationic poly(ethylene glycol)-polylysine block copolymer, which electrostatically covered the DNA nanostructures to form DNA origami polyplex micelles (DOPMs). This straightforward, cost-effective, and robust route to protect DNA-based structures could therefore enable applications in biology and nanomedicine where unprotected DNA origami would be degraded. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Charged triblock copolymer self-assembly into charged micelles

    Science.gov (United States)

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

    2011-03-01

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