WorldWideScience

Sample records for block copolymer micelles

  1. Bactericidal block copolymer micelles.

    Science.gov (United States)

    Vyhnalkova, Renata; Eisenberg, Adi; van de Ven, Theo

    2011-05-12

    Block copolymer micelles with bactericidal properties were designed to deactivate pathogens such as E. coli bacteria. The micelles of PS-b-PAA and PS-b-P4VP block copolymers were loaded with biocides TCMTB or TCN up to 20 or 30 wt.-%, depending on the type of antibacterial agent. Bacteria were exposed to loaded micelles and bacterial deactivation was evaluated. The micelles loaded with TCN are bactericidal; bacteria are killed in less than two minutes of exposure. The most likely interpretation of the data is that the biocide is transferred to the bacteria by repeated micelle/bacteria contacts, and not via the solution. PMID:21275041

  2. Skin delivery by block copolymer nanoparticles (block copolymer micelles).

    Science.gov (United States)

    Laredj-Bourezg, Faiza; Bolzinger, Marie-Alexandrine; Pelletier, Jocelyne; Valour, Jean-Pierre; Rovère, Marie-Rose; Smatti, Batoule; Chevalier, Yves

    2015-12-30

    Block copolymer nanoparticles often referred to as "block copolymer micelles" have been assessed as carriers for skin delivery of hydrophobic drugs. Such carriers are based on organic biocompatible and biodegradable materials loaded with hydrophobic drugs: poly(lactide)-block-poly(ethylene glycol) copolymer (PLA-b-PEG) nanoparticles that have a solid hydrophobic core made of glassy poly(d,l-lactide), and poly(caprolactone)-block-poly(ethylene glycol) copolymer (PCL-b-PEG) nanoparticles having a liquid core of polycaprolactone. In vitro skin absorption of all-trans retinol showed a large accumulation of retinol in stratum corneum from both block copolymer nanoparticles, higher by a factor 20 than Polysorbate 80 surfactant micelles and by a factor 80 than oil solution. Additionally, skin absorption from PLA-b-PEG nanoparticles was higher by one order of magnitude than PCL-b-PEG, although their sizes (65nm) and external surface (water-swollen PEG layer) were identical as revealed by detailed structural characterizations. Fluorescence microscopy of histological skin sections provided a non-destructive picture of the storage of Nile Red inside stratum corneum, epidermis and dermis. Though particle cores had a different physical states (solid or liquid as measured by (1)H NMR), the ability of nanoparticles for solubilization of the drug assessed from their Hildebrand solubility parameters appeared the parameter of best relevance regarding skin absorption.

  3. Chain exchange in block copolymer micelles

    Science.gov (United States)

    Lu, Jie; Bates, Frank; Lodge, Timothy

    2014-03-01

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

  4. Molecular Exchange Dynamics in Block Copolymer Micelles

    Science.gov (United States)

    Bates, Frank; Lu, Jie; Choi, Soohyung; Lodge, Timothy

    2012-02-01

    Poly(styrene-b-ethylene propylene) (PS-PEP) diblock copolymers were mixed with squalane (C30H62) at 1% by weight resulting in the formation of spherical micelles. The structure and dynamics of molecular exchange were characterized by synchrotron small-angle x-ray scattering (SAXS) and time resolved small-angle neutron scattering (TR-SANS), respectively, between 100 C and 160 C. TR-SANS measurements were performed with solutions initially containing deuterium labeled micelle cores and normal cores dispersed in a contrast matched squalane. Monitoring the reduction in scattering intensity as a function of time at various temperatures revealed molecular exchange dynamics highly sensitive to the core molecular weight and molecular weight distribution. Time-temperature superposition of data acquired at different temperatures produced a single master curve for all the mixtures. Experiments conducted with isotopically labeled micelle cores, each formed from two different but relatively mondisperse PS blocks, confirmed a simple dynamical model based on first order kinetics and core Rouse single chain relaxation. These findings demonstrate a dramatic transition to nonergodicity with increasing micelle core molecular weight and confirm the origins of the logarithmic exchange kinetics in such systems.

  5. Multicompartment Micelles From π-Shaped ABC Block Copolymers

    Institute of Scientific and Technical Information of China (English)

    XIA Jun; ZHONG Chong-Li

    2007-01-01

    Dissipative particle dynamics simulations were performed on the morphology and structure of multicompartment micelles formed from n-shaped ABC block copolymers in water. The influences of chain architectures were studied in a systematic way, and a rich variety of morphologies were observed, such as spherical, wormlike,X-shaped, Y-shaped, ribbon-like, layered rod-like, layered disk-like, as well as network morphologies. The simulations show that the distance between the two grafts plays an important role in control of the morphology. Since π-shaped ABC block copolymers can be reduced to linear ABC and star ABC block copolymers, they are good model copolymers for studying the self-assembly of complex block copolymers into micelles. The knowledge obtained in this work as well as the new morphologies identified provide useful information for future rational design and synthesis of novel multicompartment micelles.

  6. Dynamics of Chain Exchange in Block Copolymer Micelles

    Science.gov (United States)

    Lodge, Timothy

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

  7. Molecular exchange in block copolymer micelles: when corona chains overlap

    Science.gov (United States)

    Lu, Jie; Lodge, Timothy; Bates, Frank; Choi, Soohyung

    2013-03-01

    The chain exchange kinetics of poly(styrene-b-ethylenepropylene) (PS-PEP) diblock copolymer micelles in squalane (C30H62) was investigated using time-resolved small angle neutron scattering (TR-SANS). The solvent is a mixture of h-squalane and d-squalane that contrast-matches a mixed 50/50 h/d PS micelle core. As isotope labeled chains exchange, the core contrast decreases, leading to a reduction in scattering intensity. This strategy therefore allows direct probing of the chain exchange rate. Separate copolymer micellar solutions containing either deuterium labeled (dPS) or normal (hPS) poly(styrene) core blocks were prepared and mixed at room temperature, below the core glass transition temperature. The samples were heated to several temperatures (around 100 °C) and monitored by TR-SANS every 5 min. As polymer concentration was increased from 1% to 15% by volume, we observed a significant slowing down of chain exchange rate. Similar retarded kinetics was found when part of the solvent in the 1% solution was replaced by homopolymer PEP (comparable size as corona block). Furthermore, if all the solvent is replaced with PEP, no exchange was detected for up to 3hr at 200 °C. These results will be discussed in terms of a molecular model for chain exchange Infineum, Iprime, NIST, ORNL

  8. Mechano-responsive hydrogels crosslinked by reactive block copolymer micelles

    Science.gov (United States)

    Xiao, Longxi

    Hydrogels are crosslinked polymeric networks that can swell in water without dissolution. Owing to their structural similarity to the native extracelluar matrices, hydrogels have been widely used in biomedical applications. Synthetic hydrogels have been designed to respond to various stimuli, but mechanical signals have not incorporated into hydrogel matrices. Because most tissues in the body are subjected to various types of mechanical forces, and cells within these tissues have sophisticated mechano-transduction machinery, this thesis is focused on developing hydrogel materials with built-in mechano-sensing mechanisms for use as tissue engineering scaffolds or drug release devices. Self-assembled block copolymer micelles (BCMs) with reactive handles were employed as the nanoscopic crosslinkers for the construction of covalently crosslinked networks. BCMs were assembled from amphiphilic diblock copolymers of poly(n-butyl acrylate) and poly(acrylic acid) partially modified with acrylate. Radical polymerization of acrylamide in the presence of micellar crosslinkers gave rise to elastomeric hydrogels whose mechanical properties can be tuned by varying the BCM composition and concentration. TEM imaging revealed that the covalently integrated BCMs underwent strain-dependent reversible deformation. A model hydrophobic drug, pyrene, loaded into the core of BCMs prior to the hydrogel formation, was dynamically released in response to externally applied mechanical forces, through force-induced reversible micelle deformation and the penetration of water molecules into the micelle core. The mechano-responsive hydrogel has been studied for tissue repair and regeneration purposes. Glycidyl methacrylate (GMA)-modified hyaluronic acid (HA) was photochemically crosslinked in the presence of dexamethasone (DEX)-loaded crosslinkable BCMs. The resultant HA gels (HAxBCM) contain covalently integrated micellar compartments with DEX being sequestered in the hydrophobic core. Compared

  9. ADVANCES IN MICROEMULSION PHASE ON SELF-ASSEMBLY AND MICELLE EXTRACTION WITH BLOCK COPOLYMERS

    Institute of Scientific and Technical Information of China (English)

    Chen Guo; Hao Wen; Huizhou Liu

    2005-01-01

    In this paper we review our work on self-assembly of the system, poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) block copolymers, which is a kind of macromolecular complex fluids. The control of self-assembly could be obtained by adding inorganic salts or aliphatic alcohols. By self-assembly of amphiphilic block copolymers, a microemulsion phase is formed, which could be applied in micelle extraction, such as hollow-fiber membrane micelle extraction, magnetic micelle extraction and immobilized micelle extraction.

  10. High intensity focused ultrasound responsive metallo-supramolecular block copolymer micelles.

    Science.gov (United States)

    Liang, Bo; Tong, Rui; Wang, Zhenhua; Guo, Shengwei; Xia, Hesheng

    2014-08-12

    The metal-supramolecular diblock copolymer containing mechano-labile bis(terpyridine)-Cu(II) complex linkage in the junction point was synthesized. These metal-ligand containing amphiphilic copolymers are able to self-assemble in aqueous solution to form spherical micelles with poly(propylene glycol) block forming the hydrophobic core. It is found that high intensity focused ultrasound can open the copolymer micelles and trigger the release of the payload in the micelle. The micellar properties and release kinetics of encapsulated guest molecule in response to ultrasound stimuli were investigated. The weak Cu(II)-terpyridine dynamic bond in the copolymer chain can be cleaved under ultrasound and thus leads to the disruption of the copolymer micelle and the release of loaded cargo. This study will open up a new way for the molecular design of ultrasound modulated drug delivery systems. PMID:25072274

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

    Science.gov (United States)

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

    2014-02-01

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

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

    DEFF Research Database (Denmark)

    Ek, Pramod Kumar

    This thesis investigated the role of amphiphilic triblock copolymer micelle nanomaterials in nanosensors, with emphasis on the synthesis of micelle particle sensors. The thesis is focused on the role of synthetic and dimensional synthetic organic chemistry in amphiphilic triblock core...... micelles. Shell cross-linking on PEG-b-PAEMA-b-PS micelles was performed by amidation reactions between the amino groups of PAEMA blocks using a di-carboxylic acid cross-linker. Also a dendritic cross-linker based click chemistry was used to stabilize the PEG-b-PAEMA-b-PES micelle having click readied PES...

  13. Effective repair of traumatically injured spinal cord by nanoscale block copolymer micelles

    Science.gov (United States)

    Shi, Yunzhou; Kim, Sungwon; Huff, Terry B.; Borgens, Richard B.; Park, Kinam; Shi, Riyi; Cheng, Ji-Xin

    2010-01-01

    Spinal cord injury results in immediate disruption of neuronal membranes, followed by extensive secondary neurodegenerative processes. A key approach for repairing injured spinal cord is to seal the damaged membranes at an early stage. Here, we show that axonal membranes injured by compression can be effectively repaired using self-assembled monomethoxy poly(ethylene glycol)-poly(D,L-lactic acid) di-block copolymer micelles. Injured spinal tissue incubated with micelles (60 nm diameter) showed rapid restoration of compound action potential and reduced calcium influx into axons for micelle concentrations much lower than the concentrations of polyethylene glycol, a known sealing agent for early-stage spinal cord injury. Intravenously injected micelles effectively recovered locomotor function and reduced the volume and inflammatory response of the lesion in injured rats, without any adverse effects. Our results show that copolymer micelles can interrupt the spread of primary spinal cord injury damage with minimal toxicity.

  14. The Organization of Nanoporous Structure Using Controlled Micelle Size from MPEG-b-PDLLA Block Copolymers

    Energy Technology Data Exchange (ETDEWEB)

    Chang, Jeong Ho; Kim, Kyung Ja [Ceramic Engineering and Technology, Seoul (Korea, Republic of); Shin, Young Kook [Chungbuk National University, Jeongju (Korea, Republic of)

    2004-03-15

    Selected MPEG-b-PDLLA block copolymers have been synthesized by ring-opening polymerization with systematic variation of the chain lengths of the resident hydrophilic and hydrophobic blocks. The size and shape of the micelles that spontaneously form in solution are then controlled by the characteristics of the block copolymer template. All the materials prepared in this study showed the tunable pore size of 20-80 A with the increase of hydrophobic chain lengths and up to 660 m{sup 2}/g of specific surface area. The formation mechanism of these nanoporous structures obtained by controlling the micelle size has been confirmed using both liquid and solid state {sup 13}C and {sup 29}Si NMR techniques. This work verifies the formation mechanism of nanoporous structures in which the pore size and wall thickness are closely dependent on the size of hydrophobic cores and hydrophilic shells of the block copolymer templates

  15. Influencing the structure of block copolymer micelles with small molecule additives

    Science.gov (United States)

    Robertson, Megan; Singh, Avantika; Cooksey, Tyler; Kidd, Bryce; Piemonte, Rachele; Wang, Shu; Mai Le, Kim; Madsen, Louis

    Amphiphilic block copolymer micelles in water are under broad exploration for drug delivery applications due to their high loading capacity and targeted drug delivery. We aim to understand the kinetic and thermodynamic processes that underlie the self-assembly of diblock copolymer micelle systems. The present work focuses on diblock copolymers containing poly(ethylene oxide) (a hydrophilic polymer) and polycaprolactone (a hydrophobic polymer), which spontaneously self-assemble into spherical micelles in water. Addition of a common good solvent (a co-solvent) for both of the constituting blocks, such as tetrahydrofuran (THF), reduces the interfacial tension at the core-corona interface. We are currently investigating the effect of this phenomenon on the micelle structural properties, using small-angle scattering and nuclear magnetic resonance. We have characterized the hydrodynamic radius, core radius, corona thickness, aggregation number, degree of swelling of the micelle core with the co-solvent, and unimer (free chain) concentration, as a function of the co-solvent concentration. Fundamental knowledge from these studies will inform design of drug delivery systems by allowing us to tailor micelle properties for optimal cargo loading.

  16. Hydrogen-bonded multilayers of micelles of a dually responsive dicationic block copolymer

    OpenAIRE

    Erel, İrem; Karahan, H. Enis; Demirel, A. Levent; Tuncer, Cansel; Bütün, Vural

    2012-01-01

    We report the fabrication of hydrogen-bonded multilayers of micelles of a dually responsive, dicationic block copolymer, poly[2-(N-morpholino)ethyl methacrylate-block-2-(diisopropylamino)ethyl methacrylate] (PMEMA-b-PDPA). By taking advantage of the difference in the hydrophilicity of PMEMA and PDPA blocks, micelles with a PMEMA-corona and a PDPA-core were obtained above pH 6.5 and were assembled layer-by-layer at the surface with tannic acid (TA) at pH 7.4 through hydrogen bonding interactio...

  17. Cooperative catalysis with block copolymer micelles: A combinatorial approach

    KAUST Repository

    Bukhryakov, Konstantin V.

    2015-02-09

    A rapid approach to identifying complementary catalytic groups using combinations of functional polymers is presented. Amphiphilic polymers with "clickable" hydrophobic blocks were used to create a library of functional polymers, each bearing a single functionality. The polymers were combined in water, yielding mixed micelles. As the functional groups were colocalized in the hydrophobic microphase, they could act cooperatively, giving rise to new modes of catalysis. The multipolymer "clumps" were screened for catalytic activity, both in the presence and absence of metal ions. A number of catalyst candidates were identified across a wide range of model reaction types. One of the catalytic systems discovered was used to perform a number of preparative-scale syntheses. Our approach provides easy access to a range of enzyme-inspired cooperative catalysts.

  18. Cooperative catalysis with block copolymer micelles: a combinatorial approach.

    Science.gov (United States)

    Bukhryakov, Konstantin V; Desyatkin, Victor G; O'Shea, John-Paul; Almahdali, Sarah R; Solovyeva, Vera; Rodionov, Valentin O

    2015-02-01

    A rapid approach to identifying complementary catalytic groups using combinations of functional polymers is presented. Amphiphilic polymers with "clickable" hydrophobic blocks were used to create a library of functional polymers, each bearing a single functionality. The polymers were combined in water, yielding mixed micelles. As the functional groups were colocalized in the hydrophobic microphase, they could act cooperatively, giving rise to new modes of catalysis. The multipolymer "clumps" were screened for catalytic activity, both in the presence and absence of metal ions. A number of catalyst candidates were identified across a wide range of model reaction types. One of the catalytic systems discovered was used to perform a number of preparative-scale syntheses. Our approach provides easy access to a range of enzyme-inspired cooperative catalysts.

  19. Small angle neutron scattering study of doxorubicin–surfactant complexes encapsulated in block copolymer micelles

    Indian Academy of Sciences (India)

    Jayita Bhattacharjee; Gunjan Verma; V K Aswal; P A Hassan

    2008-11-01

    Self-assembling behaviour of block copolymers and their ability to evade the immune system through polyethylene oxide stealth makes it an attractive candidate for drug encapsulation. Micelles formed by polyethylene oxide–polypropylene oxide–polyethylene oxide triblock copolymers (PEO–PPO–PEO), pluronic P123, have been employed for encapsulating the anti-cancer drug doxorubicin hydrochloride. The binding affinity of doxorubicin within the micelle carrier is enhanced through complex formation of drug and anionic surfactant, aerosol OT (AOT). Electrostatic binding of doxorubicin with negatively charged surfactants leads to the formation of hydrophobic drug–surfactant complexes. Surfactant-induced partitioning of the anti-cancer drug into nonpolar solvents such as chloroform is investigated. SANS measurements were performed on pluronic P123 mi-celles in the presence of drug–surfactant complex. No significant changes in the structure of the micelles are observed upon drug encapsulation. This demonstrates that surfactant–drug complexes can be encapsulated in block copolymer micelles without disrupting the structure of aggregates.

  20. 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.

  1. Structural changes in block copolymer micelles induced by cosolvent mixtures

    Energy Technology Data Exchange (ETDEWEB)

    Kelley, Elizabeth G.; Smart, Thomas P.; Jackson, Andrew J.; Sullivan, Millicent O.; Epps, III, Thomas H. (Delaware)

    2012-11-26

    We investigated the influence of tetrahydrofuran (THF) addition on the structure of poly(1,2-butadiene-b-ethylene oxide) [PB-PEO] micelles in aqueous solution. Our studies showed that while the micelles remained starlike, the micelle core-corona interfacial tension and micelle size decreased upon THF addition. The detailed effects of the reduction in interfacial tension were probed using contrast variations in small angle neutron scattering (SANS) experiments. At low THF contents (high interfacial tensions), the SANS data were fit to a micelle form factor that incorporated a radial density distribution of corona chains to account for the starlike micelle profile. However, at higher THF contents (low interfacial tensions), the presence of free chains in solution affected the scattering at high q and required the implementation of a linear combination of micelle and Gaussian coil form factors. These SANS data fits indicated that the reduction in interfacial tension led to broadening of the core-corona interface, which increased the PB chain solvent accessibility at intermediate THF solvent fractions. We also noted that the micelle cores swelled with increasing THF addition, suggesting that previous assumptions of the micelle core solvent content in cosolvent mixtures may not be accurate. Control over the size, corona thickness, and extent of solvent accessible PB in these micelles can be a powerful tool in the development of targeting delivery vehicles.

  2. Tuning Cationic Block Copolymer Micelle Size by pH and Ionic Strength.

    Science.gov (United States)

    Sprouse, Dustin; Jiang, Yaming; Laaser, Jennifer E; Lodge, Timothy P; Reineke, Theresa M

    2016-09-12

    The formation, morphology, and pH and ionic strength responses of cationic block copolymer micelles in aqueous solutions have been examined in detail to provide insight into the future development of cationic micelles for complexation with polyanions such as DNA. Diblock polymers composed of a hydrophilic/cationic block of N,N-dimethylaminoethyl methacrylate (DMAEMA) and a hydrophobic/nonionic block of n-butyl methacrylate (BMA) were synthesized [denoted as DMAEMA-b-BMA (X-Y), where X = DMAEMA molecular weight and Y = molecular weight of BMA in kDa]. Four variants were created with block molecular weights of 14-13, 14-23, 27-14, 27-29 kDa and low dispersities less than 1.10. The amphiphilic polymers self-assembled in aqueous conditions into core-shell micelles that ranged in size from 25-80 nm. These cationic micelles were extensively characterized in terms of size and net charge in different buffers over a wide range of ionic strength (0.02-1 M) and pH (5-10) conditions. The micelle core is kinetically trapped, and the corona contracts with increasing pH and ionic strength, consistent with previous work on micelles with glassy polystyrene cores, indicating that the corona properties are independent of the dynamics of the micelle core. The contraction and extension of the corona scales with solution ionic strength and charge fraction of the amine groups. The aggregation numbers of the micelles were obtained by static light scattering, and the Rg/Rh ratios are close to that of a hard sphere. The zeta potentials of the micelles were positive up to two pH units above the corona pKa, suggesting that applications relying on micelle charge for stability should be viable over a wide range of solution conditions. PMID:27487088

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

    Science.gov (United States)

    Mortensen, Kell

    1997-03-01

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

  4. Histological study on side effects and tumor targeting of a block copolymer micelle on rats.

    Science.gov (United States)

    Kawaguchi, Takanori; Honda, Takashi; Nishihara, Masamichi; Yamamoto, Tatsuhiro; Yokoyama, Masayuki

    2009-06-19

    Histological examinations were performed with polymeric micelle-injected rats for evaluations of possible toxicities of polymeric micelle carriers. Weight of major organs as well as body weight of rats was measured after multiple intravenous injections of polymeric micelles forming from poly(ethylene glycol)-b-poly(aspartate) block copolymer. No pathological toxic side effects were observed at two different doses, followed only by activation of the mononuclear phagocyte system (MPS) in the spleen, liver, lung, bone marrow, and lymph node. This finding confirms the absence of--or the very low level of--in vivo toxicity of the polymeric micelle carriers that were reported in previous animal experiments and clinical results. Then, immunohistochemical analyses with a biotinylated polymeric micelle confirmed specific accumulation of the micelle in the MPS. The immunohistochemical analyses also revealed, first, very rapid and specific accumulation of the micelle in the vasculatures of tumor capsule of rat ascites hepatoma AH109A, and second, the micelle's scanty infiltration into tumor parenchyma. This finding suggests a unique tumor-accumulation mechanism that is very different from simple EPR effect-based tumor targeting.

  5. pH and ionic strength responsive polyelectrolyte block copolymer micelles prepared by ring opening metathesis polymerization

    NARCIS (Netherlands)

    Stubenrauch, K.; Voets, I.K.; Popovski, G.F.; Trimmel, G.

    2009-01-01

    Well-defined amphiphilic block copolymers were prepared by ring opening metathesis polymerization and their stimuli responsive behavior of formed micelles in aqueous solution was investigated. The hydrophobic core of the micelles consists of either a poly[5,6-bis(ethoxymethyl)bicyclo[2.2.1]hept-2-en

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2013-09-26

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

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

    OpenAIRE

    Ek, Pramod Kumar; Andresen, Thomas Lars; Almdal, Kristoffer

    2012-01-01

    This thesis investigated the role of amphiphilic triblock copolymer micelle nanomaterials in nanosensors, with emphasis on the synthesis of micelle particle sensors. The thesis is focused on the role of synthetic and dimensional synthetic organic chemistry in amphiphilic triblock core-shellcorona micelle based ratiometric fluorescence pH nanosensor fabrications. Two synthetic strategies such as post micelle modification and mixed micellisation (co-micellisation) were employed for pH nanosenso...

  8. Enhanced gene expression promoted by hybrid magnetic/cationic block copolymer micelles.

    Science.gov (United States)

    Haladjova, E; Rangelov, S; Tsvetanov, Ch B; Posheva, V; Peycheva, E; Maximova, V; Momekova, D; Mountrichas, G; Pispas, S; Bakandritsos, A

    2014-07-15

    We report on novel gene delivery vector systems based on hybrid polymer-magnetic micelles. The hybrid micelles were prepared by codissolution of hydrophobically surface modified iron oxide and amphiphilic polystyrene-b-poly(quaternized 2-vinylpyridine) block copolymer (PS-b-P2QVP) in organic solvent. After extensive dialysis against water, micelles with positively charged hydrophilic corona of PQVP and hydrophobic PS core were prepared, in which magnetic nanoparticles were randomly distributed. The hybrid micelles were used to form complexes with linear (salmon sperm, 2000 bp, corresponding to M(w) of 1.32 × 10(6) Da) and plasmid (pEGFP-N1, 4730 bp, corresponding to M(w) of 3.12 × 10(6) Da) DNA. The resulting magnetopolyplexes of phosphate:amine (P/N) ratios in the 0.05-20 range were characterized by light scattering, ζ-potential measurements, and transmission electron microscopy as well as cytotoxicity and gel retardation assays. The investigated systems displayed a narrow size distribution, particle dimensions below 360 nm, whereas their ζ-potential values varied from positive to negative depending of the P/N ratio. The resulting vector nanosystems exhibited low toxicity. They were able to introduce pEGFP-N1 molecules into the cells. The application of a magnetic field markedly boosted the transgene expression efficiency of the magnetopolyplexes, which was even superior to those of commercial transfectants such as Lipofectamine and dendritic polyethylenimine. PMID:24945823

  9. Coexistence of crew-cut and starlike spherical micelles composed of copolymers with an annealed polyelectrolyte block.

    NARCIS (Netherlands)

    Lauw, Y.; Leermakers, F.A.M.; Cohen Stuart, M.A.; Borisov, O.V.; Zhulina, E.B.

    2006-01-01

    The self-assembly of block copolymer AmBn into spherical micelles is analyzed using a numerical self-consistent-field theory. A is the hydrophilic annealed polyacid and B the Hydrophobic part. The degree of polymerization for the polar moiety is fixed (m = 100), whereas that of the tail is varied (n

  10. Preparation and Characterization of Copolymer Micelles Formed by Poly(ethylene glycol)-Polylactide Block Copolymers as Novel Drug Carriers

    Institute of Scientific and Technical Information of China (English)

    姜维; 王运东; 甘泉; 张建铮; 赵秀文; 费维扬; 贝建中; 王身国

    2006-01-01

    Diblock copolymer poly(ethylene glycol) methyl ether-polylactide (MePEG-PLA) micelles were prepared by dialysis against water. Indomethacin (IMC) as a model drug was entrapped into the micelles by dialysis method. The critical micelle concentration (CMC) of the prepared micelles in distilled water investigated by fluorescence spectroscopy was 0.0051mg/mL which is lower than that of common low molecular weight surfactants. The diameters of MePEG-PLA micelles and IMC loaded MePEG-PLA micelles in a number-averaged scale measured by dynamic light scattering were 52.4 and 53.7 nm respectively. The observation with transmission electron microscope and scanning electron microscope showed that the appearance of MePEG-PLA micelles was in a spherical shape. The content of IMC incorporated in the core portion of the micelles was 18% (ω). The effects of the synthesis method of the copolymer on the polydispersity of the micelles and the yield of the micelles formation were discussed.

  11. PEE-PEO block copolymer exchange rate between micelles is detergent and temperature activated

    Science.gov (United States)

    Schantz, Allen; Saboe, Patrick; Lee, Hee-Young; Sines, Ian; Butler, Paul; Bishop, Kyle; Maranas, Janna; Kumar, Manish

    We examine the kinetics of polymer chain exchange between polymer/detergent micelles, a system relevant to the synthesis of protein-containing biomimetic membranes. Although chain exchange between polymer aggregates in water is too slow to observe, adding detergent allows us to determine chain exchange rates using time-resolved small-angle neutron scattering (TR-SANS). We examine a membrane-protein-relevant, vesicle-forming ultra-short polymer, Poly(ethyl ethylene)20-Poly(ethylene oxide)18 (PEE20-PEO18). PEE20-PEO18 is solubilized in mixed micelles with the membrane-protein-compatible non-ionic detergent octyl- β -D-glucoside (OG). We show that OG activates block copolymer exchange, and obtain rate constants at two detergent concentrations above the CMC (critical micellar concentration) of OG. We find that chain exchange increases two orders of magnitude when temperature increases from 308 to 338 K, and that even a 1 mg/mL increase in OG concentration leads to a noticeable increase in exchange rate. We also calculate the activation energy for chain exchange and find that it is much higher than for lipid exchange. These findings explain the need for high detergent concentration and/or temperature to synthesize densely packed polymer/protein membranes.

  12. Switchable pH-responsive polymeric membranes prepared via block copolymer micelle assembly

    KAUST Repository

    Nunes, Suzana Pereira

    2011-05-24

    A process is described to manufacture monodisperse asymmetric pH-responsive nanochannels with very high densities (pore density >2 × 10 14 pores per m2), reproducible in m2 scale. Cylindric pores with diameters in the sub-10 nm range and lengths in the 400 nm range were formed by self-assembly of metal-block copolymer complexes and nonsolvent-induced phase separation. The film morphology was tailored by taking into account the stability constants for a series of metal-polymer complexes and confirmed by AFM. The distribution of metal-copolymer micelles was imaged by transmission electron microscopy tomography. The pH response of the polymer nanochannels is the strongest reported with synthetic pores in the nm range (reversible flux increase of more than 2 orders of magnitude when switching the pH from 2 to 8) and could be demonstrated by cryo-field emission scanning electron microscopy, SAXS, and ultra/nanofiltration experiments. © 2011 American Chemical Society.

  13. Micelles and gels of oxyethylene-oxybutylene diblock copolymers in aqueous solution: The effect of oxyethylene-block length

    DEFF Research Database (Denmark)

    Derici, L.; Ledger, S.; Mai, S.M.;

    1999-01-01

    Block copolymer E(90)B(10) (E = oxyethylene, B = oxybutylene) was synthesised and characterised by gel permeation chromatography and (13)C NMR spectroscopy. Dynamic light scattering (DLS) and static light scattering (SLS) were used to characterise the micelles in solution (both in water and in aq......Block copolymer E(90)B(10) (E = oxyethylene, B = oxybutylene) was synthesised and characterised by gel permeation chromatography and (13)C NMR spectroscopy. Dynamic light scattering (DLS) and static light scattering (SLS) were used to characterise the micelles in solution (both in water...... and in aqueous 0.2 mol dm(-3) K(2)SO(4)), yielding the micellar association numbers, the hydrodynamic and thermodynamic radii, and related expansion factors. Micellar parameters were also obtained by small-angle neutron scattering (SANS) for solutions of a similar copolymer, E(86)B(10), in water, i...... of water in the micelle core. Moderately concentrated solutions of copolymer E(90)B(10) were studied in the gel state by small-angle X-ray scattering (SAXS) in tandem with rheology (oscillatory shear). Values for the dynamic elastic modulus (G') of the gels significantly exceeded 10(4) Pa across the range...

  14. Effect of polyoxypropylene chain length on the critical micelle concentration of propylene oxide-ethylene oxide block copolymers

    Institute of Scientific and Technical Information of China (English)

    ZHANG Zhi-guo; YIN Hong

    2005-01-01

    In this work, the surface activity of block copolymer nonionic surfactants (RPE) has been determined, i.e., critical micelle concentration (CMC), surface excess concentration (Γ), surface area demand per molecule (A), surface tension at CMC (yCMC). A linear decrease of ln[CMC] vs number of oxypropylene units in copolymer molecule was observed. The change in the work of cohesion per oxypropylene group when passing from molecular into micellar state, calculated from the Shinoda equation, was 0.43kT for the studied compounds.

  15. pH-responsive layer-by-layer films of zwitterionic block copolymer micelles

    OpenAIRE

    Demirel, Adem Levent; Yusan, Pelin; Tuncel, İrem; Bütün, Vural; Erel-Goktepe, İrem

    2014-01-01

    We report a strategy to incorporate micelles of poly[3-dimethyl (methacryloyloxyethyl) ammonium propane sulfonate]-block-poly[2-(diisopropylamino) ethyl methacrylate] (beta PDMA-b-PDPA) into electrostatic layer-by-layer (LbL) films. We obtained micelles with pH-responsive PDPA-cores and zwitterionic bPDMA-coronae at pH 8.5 through pH-induced self-assembly of bPDMA-b-PDPA in aqueous solution. To incorporate bPDMA-b-PDPA micelles into LbL films, we first obtained a net electrical charge on bPDM...

  16. Dynamic Processes in Diblock Copolymer Micelles

    Science.gov (United States)

    Robertson, Megan; Singh, Avantika

    2013-03-01

    Diblock copolymers, which form micelle structures in selective solvents, offer advantages of robustness and tunability of micelle characteristics as compared to small molecule surfactants. Diblock copolymer micelles in water have been a subject of great interest in drug delivery applications based on their high loading capacity and targeted drug delivery. The aim of this work is to understand the dynamic processes which underlie the self-assembly of diblock copolymer micelle systems which have a semi-crystalline core. Due to the large size of the molecules, the self-assembly of block copolymer micelles occurs on significantly longer time scales than small molecule analogues. The present work focuses on amphiphilic diblock copolymers containing blocks of poly(ethylene oxide) (a hydrophilic polymer) and polycaprolactone (a hydrophobic, semi-crystalline polymer), which spontaneously self-assemble into spherical micelles in water. A variety of experimental techniques are used to probe the kinetic processes relevant to micelle self-assembly, including time-resolved neutron scattering, dynamic light scattering, pulsed field gradient nuclear magnetic resonance, and fluorescence resonance energy transfer experiments.

  17. From charge-mosaic to micelle self-assembly: Block copolymer membranes in the last 40 years

    KAUST Repository

    Nunes, Suzana Pereira

    2013-01-23

    Different strategies for membrane preparation based on block copolymers are reviewed in this paper, starting from early papers on charge-mosaic membranes and following with dense membranes for gas separation for applications like CO2 separation, pervaporation of aqueous solutions containing organic pollutants, low-fouling surfaces and finally tailoring porous membranes with very sharp pore size distribution. The approaches for manufacture of nanoporous films are summarized, including etching and preferential dissolution. The advantages of a new process based on micelle assembly and phase inversion are emphasized, confirming its perspective of up-scale and application at large scale. © 2012 American Chemical Society.

  18. Passive targeting of thermosensitive diblock copolymer micelles to the lungs: synthesis and characterization of poly(N-isopropylacrylamide)-block-poly(ε-caprolactone)

    OpenAIRE

    Lee, Ren-Shen; Lin, Chih-Hung; Aljuffali, Ibrahim A.; Hu, Kai-Yin; Fang, Jia-You

    2015-01-01

    Background Amphiphilic poly(N-isopropylacrylamide)-block-poly(ε-caprolactone) (PNiPAAm-b-PCL) copolymers were synthesized by ring-opening polymerization to form thermosensitive micelles as nanocarriers for bioimaging and carboplatin delivery. Results The critical micelle concentration increased from 1.8 to 3.5 mg/l following the decrease of the PNiPAAm chain length. The copolymers revealed a lower critical solution temperature (LCST) between 33 and 40°C. The copolymers self-assembled to form ...

  19. Influence of formulation variables on the biodistribution of multifunctional block copolymer micelles.

    Science.gov (United States)

    Fonge, Humphrey; Huang, Huang; Scollard, Deborah; Reilly, Raymond M; Allen, Christine

    2012-02-10

    The physico-chemical characteristics and composition of block copolymer micelles (BCMs) may influence the pharmacokinetics and consequently, the desired delivery characteristics. In this study the influence of formulation variables such as size, density of targeting ligand [i.e. epidermal growth factor (hEGF)] and the bifunctional chelator (BFC) used for labelling the BCMs with (111)In, on the pharmacokinetics and biodistribution in mice were evaluated. BCMs were prepared from Me-PEG(x)-b-PCL(y) (x=2.5 k, y=1.2 k for 15 nm BCMs and x=5 k, y=5 k for 60 nm BCMs) with (targeted, 1 or 5 mol% hEGF) or without (non-targeted) hEGF-PEG(x)-b-PCL(y). To investigate the effect of the BFC on the pharmacokinetics, the BCMs were labelled with (111)In using p-SCN-Bn-DOTA (Bn-DOTA-PEG(x)-b-PCL(y)), H(2)N-DOTA (DOTA-PEG(x)-b-PCL(y)), DTPA anhydride (DTPA-PEG(x)-b-PCL(y)) or p-SCN-Bn-DTPA (Bn-DTPA-PEG(x)-b-PCL(y)). The resulting 15 nm or 60 nm non-targeted or targeted (1 or 5 mol% hEGF) were injected via a tail vein to mice bearing MDA-MB-468 human breast cancer xenograft that overexpress EGFR, followed by pharmacokinetics and biodistribution studies. Pharmacokinetic parameters were determined by fitting the blood concentration vs time data using a two compartment model with i.v. bolus input. Pharmacokinetic parameters were found to depend on BCM size, the BFC used as well as the density of hEGF on the surface of the BCMs. BCMs labelled with p-SCN-Bn-DTPA ((111)In-Bn-BCMs) showed improved pharmacokinetics (i.e. extended circulation lifetime) and tumor uptake compared to those labelled with DOTA-PEG(x)-b-PCL(y), p-SCN-Bn-DOTA or DTPA dianhydride. Formulations with a high density of hEGF (5 mol% hEGF) had short circulation half-lives. BCMs labelled with (111)In via p-SCN-Bn-DTPA showed highest accumulation in the liver and spleen and slower whole body elimination. Smaller sized BCMs were rapidly cleared from the circulation. Increasing the density of hEGF on the surface did not

  20. Structures of PEP–PEO Block Copolymer Micelles: Effects of Changing Solvent and PEO Length and Comparison to a Thermodynamic Model

    DEFF Research Database (Denmark)

    Jensen, Grethe Vestergaard; Shi, Qing; Deen, G. Roshan;

    2012-01-01

    Structures of poly(ethylene propylene)–poly(ethylene oxide) (PEP–PEO) block copolymer micelles were determined from small-angle X-ray scattering and static light scattering and compared to predictions from a thermodynamic model. Both the corona block length and the solvent water–ethanol ratio were...

  1. Atomistic molecular dynamics simulations of the structure of symmetric Polyelectrolyte block copolymer micelle in salt-free aqueous solution

    Science.gov (United States)

    Chockalingam, Rajalakshmi; Natarajan, Upendra

    2014-03-01

    The structure of a symmetric polystyrene- b - poly(acrylic acid) (PS- b - PAA) micelle in salt-free aqueous solution as a function of degree-of-neutralization (or ionization, f) of the PAA is studied via explicit-atom-ion MD simulations, for the first time for a polyelectrolyte block copolymer in a polar solvent. Micelle size increases with fin agreement with experimental observations in literature, due to extension of PAA at higher ionization. Pair RDF's with respect to water oxygens show that corona-water interaction becomes stronger with f due to an increase in number density of carboxylate (COO-) groups on the chain. Water-PAA coordination (carboxylate O's) increases with ionization. H-bonding between PAA and water increases with f due to greater extent of corona-water affinity. With increase in f, atom and counter-ion ρ profiles confirm extension of corona blocks and micelle existing in the ``osmotic regime,'' and a decrease in scattering peak intensity, in agreement with neutron scattering experiments and mean-field theory in literature. Inter-chain distance in PS core is found to decrease with ionization. Macromolecular Simulation and Modeling Laboratory, Dept. of Chemical Engineering, Indian Institute of Technology Madras, Chennai 600036.

  2. Mechanism of Molecular Exchange in Copolymer Micelles

    Science.gov (United States)

    Choi, Soo-Hyung; Lodge, Timothy; Bates, Frank

    2010-03-01

    Compared to thermodynamic structure, much less has been known about the kinetics of block copolymer micelles which should underlay the attainment of thermodynamic equilibrium. In this presentation, molecular exchange between spherical micelles formed by isotopically labeled diblock copolymers was investigated using time-resolved small-angle neutron scattering. Two pairs of structurally matched poly(styrene-b-ethylene-alt-propylene) (PS-PEP) were synthesized and dispersed in isotopic mixture of squalane, highly selective to PEP block. Each pair includes polymers with fully deuterated (dPS-PEP) and a normal (hPS-PEP) PS blocks. Temperature dependence of the micelle exchange rate R(t) is consistent with melt dynamics for the core polymer. Furthermore, R(t) is significantly sensitive to the core block length N due to the thermodynamic penalty associated with ejecting a core block into the solvent. This hypersensitivity, combined with modest polydispersity in N, leads to an approximately logarithmic decay in R(t).

  3. The morphology of block copolymer micelles in supercritical carbon dioxide by small-angle neutron and X-ray scattering

    International Nuclear Information System (INIS)

    Above its critical point, carbon dioxide forms a supercritical fluid, which promises to be an environmentally responsible replacement for the organic solvents traditionally used in polymerizations. Many lipophilic polymers such as polystyrene (PS) are insol- uble in CO2, though polymerizations may be accomplished via the use of PS-fluoropolymer stabilizers, which act as emulsifying agents. Small-angle neutron and X-ray scattering have been used to show that these molecules form micelles with a CO2-phobic PS core and a CO2-philic fluoropolymer corona. When the PS block was fixed in length and the fluorinated corona block was varied, the number of block copolymer molecules per micelle (six to seven) remained constant. Thus, the coronal block molecular weight exerts negligible influence on the aggregation number, in accordance with the theoretical predictions of Halperin, Tirrell and Lodge [Adv. Polym. Sci. (1992), 100, 31-46]. These observations are relevant to understanding the mechanisms of micellization and solubilization in supercritical fluids. (orig.)

  4. The morphology of block copolymer micelles in supercritical carbon dioxide by small-angle neutron and X-ray scattering

    Energy Technology Data Exchange (ETDEWEB)

    Londono, J.D.; Dharmapurikar, R.; Cochran, H.D.; Wignall, G.D. [Oak Ridge National Lab., TN (United States); McClain, J.B.; Betts, D.E.; Canelas, D.A.; DeSimone, J.M.; Samulski, E.T.; Chillura-Martino, D.; Triolo, R.

    1997-10-01

    Above its critical point, carbon dioxide forms a supercritical fluid, which promises to be an environmentally responsible replacement for the organic solvents traditionally used in polymerizations. Many lipophilic polymers such as polystyrene (PS) are insol- uble in CO{sub 2}, though polymerizations may be accomplished via the use of PS-fluoropolymer stabilizers, which act as emulsifying agents. Small-angle neutron and X-ray scattering have been used to show that these molecules form micelles with a CO{sub 2}-phobic PS core and a CO{sub 2}-philic fluoropolymer corona. When the PS block was fixed in length and the fluorinated corona block was varied, the number of block copolymer molecules per micelle (six to seven) remained constant. Thus, the coronal block molecular weight exerts negligible influence on the aggregation number, in accordance with the theoretical predictions of Halperin, Tirrell and Lodge [Adv. Polym. Sci. (1992), 100, 31-46]. These observations are relevant to understanding the mechanisms of micellization and solubilization in supercritical fluids. (orig.). 24 refs.

  5. Role of Amphiphilic Block Copolymer Composition on Pore Characteristics of Micelle-Templated Mesoporous Cobalt Oxide Films.

    Science.gov (United States)

    Wang, Siyang; Tangvijitsakul, Pattarasai; Qiang, Zhe; Bhaway, Sarang M; Lin, Kehua; Cavicchi, Kevin A; Soucek, Mark D; Vogt, Bryan D

    2016-04-26

    Block copolymer templating is a versatile approach for the generation of well-defined porosity in a wide variety of framework chemistries. Here, we systematically investigate how the composition of a poly(methoxy poly[ethylene glycol] methacrylate)-block-poly(butyl acrylate) (PMPEG-PBA) template impacts the pore characteristics of mesoporous cobalt oxide films. Three templates with a constant PMPEG segment length and different hydrophilic block volume fractions of 17%, 51%, and 68% for the PMPEG-PBA are cooperatively assembled with cobalt nitrate hexahydrate and citric acid. Irrespective of template composition, a spherical nanostructure is templated and elliptical mesostructures are obtained on calcination due to uniaxial contraction of the film. The average pore size increases from 11.4 ± 2.8 to 48.5 ± 4.3 nm as the length of the PBA segment increases as determined from AFM. For all three templates examined, a maximum in porosity (∼35% in all cases) and surface area is obtained when the precursor solids contain 35-45 wt % PMPEG-PBA. This invariance suggests that the total polymer content drives the structure through interfacial assembly. The composition for maximizing porosity and surface area with the micelle-templating approach results from a general decrease in porosity with increasing cobalt nitrate hexahydrate content and the increasing mechanical integrity of the framework to resist collapse during template removal/crystallization as the cobalt nitrate hexahydrate content increases. Unlike typical evaporation induced self-assembly with sol-gel chemistry, the hydrophilic/hydrophobic composition of the block copolymer template is not a critical component to the mesostructure developed with micelle-templating using metal nitrate-citric acid as the precursor. PMID:27040316

  6. Large Amplitude Oscillatory Shear of Block Copolymer Spheres on a Body-Centered Cubic Lattice: Are Micelles Like Metals?

    Energy Technology Data Exchange (ETDEWEB)

    Torija, Maria A.; Choi, Soo-Hyung; Lodge, Timothy P.; Bates, Frank S. (UMM)

    2013-03-07

    Small-angle X-ray diffraction experiments have uncovered a remarkable mechanism of grain alignment during plastic deformation of ordered sphere-forming diblock copolymer micelles when subjected to large amplitude dynamic shearing. A nearly monodisperse poly(styrene-b-ethylene-alt-propylene) (SEP) diblock copolymer with block molecular weights of 42,000 and 60,000 was mixed with squalane (C{sub 30}H{sub 62}), an EP selective solvent, at a concentration of 10 wt %. After high temperature annealing, the sample formed an ordered polydomain morphology containing glassy S cores at room temperature. SAXS powder patterns confirm body-centered cubic (BCC) symmetry and reveal the development of a complex array of two-dimensionally resolved Bragg reflections following the application, and cessation, of oscillatory shearing. These diffraction results are interpreted on the basis of the classic mechanism of crystalline slip, which accounts for plastic deformation of ductile materials such as metals. Four distinct slip systems are shown to be active in this work, suggesting a robust basis for deforming and mixing of soft ordered solids.

  7. Micellization and Dynamics of a Block Copolymer

    DEFF Research Database (Denmark)

    Hvidt, Søren

    2006-01-01

    Triblock copolymers of the type EPE, where E and P denote ethylene oxide and propylene oxide blocks, respectively, are industrially important copolymers often called Pluronics or Poloxamers. EPE copolymers form micelles with a core of P blocks and different micellar shapes depending on block length...... 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...

  8. Unimolecular micelles of amphiphilic cyclodextrin-core star-like block copolymers for anticancer drug delivery.

    Science.gov (United States)

    Xu, Zhigang; Liu, Shiying; Liu, Hui; Yang, Cangjie; Kang, Yuejun; Wang, Mingfeng

    2015-11-11

    Well-defined star-like amphiphilic polymers composed of a β-cyclodextrin core, from which 21 hydrophobic poly(lactic acid) arms and hydrophilic poly(ethylene glycol) arms are grafted sequentially, form robust and uniform unimolecular micelles that are biocompatible and efficient in the delivery of anticancer drugs. PMID:26121632

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

    DEFF Research Database (Denmark)

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

    2003-01-01

    independent at the conditions studied. The micelles are slightly polydisperse in the aggregation number and have aggregation numbers in the range 40 - 50. The core contains about 40% water and has a radius of about 40 Angstrom. The corona extends out to about 80-100 Angstrom and has a fairly low volume...

  10. Block copolymer micelles target Auger electron radiotherapy to the nucleus of HER2-positive breast cancer cells.

    Science.gov (United States)

    Hoang, Bryan; Reilly, Raymond M; Allen, Christine

    2012-02-13

    Intracellular trafficking of Auger electron emitting radionuclides to perinuclear and nuclear regions of cells is critical to realizing their full therapeutic potential. In the present study, block copolymer micelles (BCMs) were labeled with the Auger electron emitter indium-111 ((111)In) and loaded with the radiosensitizer methotrexate. HER2 specific antibodies (trastuzumab fab) and nuclear localization signal (NLS; CGYGPKKKRKVGG) peptides were conjugated to the surface of the BCMs to direct uptake in HER2 expressing cells and subsequent localization in the cell nucleus. Cell uptake and intracellular distribution of the multifunctional BCMs were evaluated in a panel of breast cancer cell lines with different levels of HER2 expression. Indeed cell uptake was found to be HER2 density dependent, confirming receptor-mediated internalization of the BCMs. Importantly, conjugation of NLS peptides to the surface of BCMs was found to result in a significant increase in nuclear uptake of the radionuclide (111)In. Successful nuclear targeting was shown to improve the antipoliferative effect of the Auger electrons as measured by clonogenic assays. In addition, a significant radiation enhancement effect was observed by concurrent delivery of low-dose MTX and (111)In in all breast cancer cell lines evaluated.

  11. Novel 4-Arm Poly(Ethylene Glycol-Block-Poly(Anhydride-Esters Amphiphilic Copolymer Micelles Loading Curcumin: Preparation, Characterization, and In Vitro Evaluation

    Directory of Open Access Journals (Sweden)

    Li Lv

    2013-01-01

    Full Text Available A novel 4-arm poly(ethylene glycol-block-poly(anhydride-esters amphiphilic copolymer (4-arm PEG-b-PAE was synthesized by esterization of 4-arm poly(ethylene glycol and poly(anhydride-esters which was obtained by melt polycondensation of α-, ω-acetic anhydride terminated poly(L-lactic acid. The obtained 4-arm PEG-b-PAE was characterized by 1H-NMR and gel permeation chromatography. The critical micelle concentration of 4-arm PEG-b-PAE was 2.38 μg/mL. The curcumin-loaded 4-arm PEG-b-PAE micelles were prepared by a solid dispersion method and the drug loading content and encapsulation efficiency of the micelles were 7.0% and 85.2%, respectively. The curcumin-loaded micelles were spherical with a hydrodynamic diameter of 151.9 nm. Curcumin was encapsulated within 4-arm PEG-b-PAE micelles amorphously and released from the micelles, faster in pH 5.0 than pH 7.4, presenting one biphasic drug release pattern with rapid release at the initial stage and slow release later. The hemolysis rate of the curcumin-loaded 4-arm PEG-b-PAE micelles was 3.18%, which was below 5%. The IC50 value of the curcumin-loaded micelles against Hela cells was 10.21 μg/mL, lower than the one of free curcumin (25.90 μg/mL. The cellular uptake of the curcumin-loaded micelles in Hela cell increased in a time-dependent manner. The curcumin-loaded micelles could induce G2/M phase cell cycle arrest and apoptosis of Hela cells.

  12. Chain exchange in triblock copolymer micelles

    Science.gov (United States)

    Lu, Jie; Lodge, Timothy; Bates, Frank

    2015-03-01

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

  13. Novel 4-Arm Poly(Ethylene Glycol)-Block-Poly(Anhydride-Esters) Amphiphilic Copolymer Micelles Loading Curcumin: Preparation, Characterization, and In Vitro Evaluation

    OpenAIRE

    Li Lv; Yuanyuan Shen; Min Li; Xiaofen Xu; Mingna Li; Shengrong Guo; Shengtang Huang

    2013-01-01

    A novel 4-arm poly(ethylene glycol)-block-poly(anhydride-esters) amphiphilic copolymer (4-arm PEG-b-PAE) was synthesized by esterization of 4-arm poly(ethylene glycol) and poly(anhydride-esters) which was obtained by melt polycondensation of α -, ω -acetic anhydride terminated poly(L-lactic acid). The obtained 4-arm PEG-b-PAE was characterized by 1H-NMR and gel permeation chromatography. The critical micelle concentration of 4-arm PEG-b-PAE was 2.38  μ g/mL. The curcumin-loaded 4-arm PEG-b-PA...

  14. Photo-Induced Micellization of Block Copolymers

    OpenAIRE

    Satoshi Kuwayama; Eri Yoshida

    2010-01-01

    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 ...

  15. Structure of strongly interacting polyelectrolyte diblock copolymer micelles

    OpenAIRE

    Korobko, A.V.; Jesse, W.; Lapp, A.; Egelhaaf, S. U.; van der Maarel, J. R. C.

    2004-01-01

    The structure of spherical micelles of the diblock poly(styrene-block-acrylic acid) [PS-b-PA] copolymer in water was investigated up to concentrations where the polyelectrolyte coronal layers have to shrink and/or interpenetrate in order to accommodate the micelles in the increasingly crowded volume. We obtained the partial structure factors pertaining to the core and corona density correlations with small angle neutron scattering (SANS) and contrast matching in the water. The counterion stru...

  16. Metallo-supramolecular block copolymers : from synthesis to smart nanomaterials

    OpenAIRE

    Guillet, Pierre

    2008-01-01

    Supramolecular copolymers have become of increasing interest in recent years for the search of new materials with tunable properties. In particular, metallo-supramolecular block copolymers have seen important progresses since the last five years. In this thesis, a library of metallo-supramolecular amphiphilic block copolymers containing a hydrophilic block, linked to a hydrophobic block, through a metal-ligand complex has been investigated. The micelles formed in water from these copolymers...

  17. Self-assembled micelles based on pH-sensitive PAE-g-MPEG-cholesterol block copolymer for anticancer drug delivery.

    Science.gov (United States)

    Zhang, Can Yang; Xiong, Di; Sun, Yao; Zhao, Bin; Lin, Wen Jing; Zhang, Li Juan

    2014-01-01

    A novel amphiphilic triblock pH-sensitive poly(β-amino ester)-g-poly(ethylene glycol) methyl ether-cholesterol (PAE-g-MPEG-Chol) was designed and synthesized via the Michael-type step polymerization and esterification condensation method. The synthesized copolymer was determined with proton nuclear magnetic resonance and gel permeation chromatography. The grafting percentages of MPEG and cholesterol were determined as 10.93% and 62.02%, calculated from the area of the characteristic peaks, respectively. The amphiphilic copolymer was confirmed to self-assemble into core/shell micelles in aqueous solution at low concentrations. The critical micelle concentrations were 6.92 and 15.14 mg/L at pH of 7.4 and 6.0, respectively, obviously influenced by the changes of pH values. The solubility of pH-responsive PAE segment could be transformed depending on the different values of pH because of protonation-deprotonation of the amino groups, resulting in pH sensitivity of the copolymer. The average particle size of micelles increased from 125 nm to 165 nm with the pH decreasing, and the zeta potential was also significantly changed. Doxorubicin (DOX) was entrapped into the polymeric micelles with a high drug loading level. The in vitro DOX release from the micelles was distinctly enhanced with the pH decreasing from 7.4 to 6.0. Toxicity testing proved that the DOX-loaded micelles exhibited high cytotoxicity in HepG2 cells, whereas the copolymer showed low toxicity. The results demonstrated how pH-sensitive PAE-g-MPEG-Chol micelles were proved to be a potential vector in hydrophobic drug delivery for tumor therapy. PMID:25364250

  18. Self-assembled materials from thermosensitive and biohybrid block copolymers

    NARCIS (Netherlands)

    de Graaf, A.J.

    2012-01-01

    In this research, several block copolymers were synthesized and characterized with regard to possible pharmaceutical applications. All block copolymers were thermosensitive and self-assembled at 37 °C into structures like micelles and hydrogels, which can be used for innovative drug delivery purpose

  19. Self-assembled micelles based on pH-sensitive PAE-g-MPEG-cholesterol block copolymer for anticancer drug delivery

    Directory of Open Access Journals (Sweden)

    Zhang CY

    2014-10-01

    Full Text Available Can Yang Zhang, Di Xiong, Yao Sun, Bin Zhao, Wen Jing Lin, Li Juan Zhang School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou, Guangdong Province, People’s Republic of China Abstract: A novel amphiphilic triblock pH-sensitive poly(ß-amino ester-g-poly(ethylene glycol methyl ether-cholesterol (PAE-g-MPEG-Chol was designed and synthesized via the Michael-type step polymerization and esterification condensation method. The synthesized copolymer was determined with proton nuclear magnetic resonance and gel permeation chromatography. The grafting percentages of MPEG and cholesterol were determined as 10.93% and 62.02%, calculated from the area of the characteristic peaks, respectively. The amphiphilic copolymer was confirmed to self-assemble into core/shell micelles in aqueous solution at low concentrations. The critical micelle concentrations were 6.92 and 15.14 mg/L at pH of 7.4 and 6.0, respectively, obviously influenced by the changes of pH values. The solubility of pH-responsive PAE segment could be transformed depending on the different values of pH because of protonation–deprotonation of the amino groups, resulting in pH sensitivity of the copolymer. The average particle size of micelles increased from 125 nm to 165 nm with the pH decreasing, and the zeta potential was also significantly changed. Doxorubicin (DOX was entrapped into the polymeric micelles with a high drug loading level. The in vitro DOX release from the micelles was distinctly enhanced with the pH decreasing from 7.4 to 6.0. Toxicity testing proved that the DOX-loaded micelles exhibited high cytotoxicity in HepG2 cells, whereas the copolymer showed low toxicity. The results demonstrated how pH-sensitive PAE-g-MPEG-Chol micelles were proved to be a potential vector in hydrophobic drug delivery for tumor therapy. Keywords: micelle, pH-sensitive, cholesterol, poly(ß-amino ester, drug delivery

  20. Block copolymer battery separator

    Energy Technology Data Exchange (ETDEWEB)

    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.

  1. Polyplex Micelles with Double-Protective Compartments of Hydrophilic Shell and Thermoswitchable Palisade of Poly(oxazoline)-Based Block Copolymers for Promoted Gene Transfection.

    Science.gov (United States)

    Osawa, Shigehito; Osada, Kensuke; Hiki, Shigehiro; Dirisala, Anjaneyulu; Ishii, Takehiko; Kataoka, Kazunori

    2016-01-11

    Improving the stability of polyplex micelles under physiological conditions is a critical issue for promoting gene transfection efficiencies. To this end, hydrophobic palisade was installed between the inner core of packaged plasmid DNA (pDNA) and the hydrophilic shell of polyplex micelles using a triblock copolymer consisting of hydrophilic poly(2-ethyl-2-oxazoline), thermoswitchable amphiphilic poly(2-n-propyl-2-oxazoline) (PnPrOx) and cationic poly(L-lysine). The two-step preparation procedure, mixing the triblock copolymer with pDNA below the lower critical solution temperature (LCST) of PnPrOx, followed by incubation above the LCST to form a hydrophobic palisade of the collapsed PnPrOx segment, induced the formation of spatially aligned hydrophilic-hydrophobic double-protected polyplex micelles. The prepared polyplex micelles exhibited significant tolerance against attacks from nuclease and polyanions compared to those without hydrophobic palisades, thereby promoting gene transfection. These results corroborated the utility of amphiphilic poly(oxazoline) as a molecular thermal switch to improve the stability of polyplex gene carriers relevant for physiological applications. PMID:26682466

  2. Structure of PEP-PEO block copolymer micelles: Exploiting the complementarity of small-angle X-ray scattering and static light scattering

    DEFF Research Database (Denmark)

    Jensen, Grethe Vestergaard; Shi, Qing; Hernansanz, María J.;

    2011-01-01

    )-b-poly(ethylene oxide) (PEP-PEO) in a 70% ethanol solution are investigated. The polymers have identical PEP blocks of 5.0 kDa and varying PEO blocks of 2.8-49 kDa. The SLS contrasts of PEP and PEO are similar, providing a homogeneous contrast, making SLS ideal for determining the overall micelle morphology. The SAXS...

  3. Surface tension of micellar block copolymer films

    International Nuclear Information System (INIS)

    Surface tensions of micellar block copolymers of poly(styrene-b-dimethylsiloxane) (PS-b-PDMS) films are obtained by X-ray diffuse scattering. PS-b-PDMS films on Si substrates with the thicknesses from 36 to 588 nm were investigated at temperatures of 30 - 215 .deg. C. The surface tension reflects the concentration of PDMS micelles which are preferably located at the surface. The molar fraction of PDMS micelles near the surface is estimated by using angle-resolved X-ray photoelectron spectroscopy.

  4. New amphiphilic diblock copolymers: surfactant properties and solubilization in their micelles.

    Science.gov (United States)

    Garnier, Sébastien; Laschewsky, André

    2006-04-25

    Several series of amphiphilic diblock copolymers are investigated as macrosurfactants in comparison to reference low-molar-mass and polymeric surfactants. The various copolymers share poly(butyl acrylate) as a common hydrophobic block but are distinguished by six different hydrophilic blocks (one anionic, one cationic, and four nonionic hydrophilic blocks) with various compositions. Dynamic light scattering experiments indicate the presence of micelles over the whole concentration range from 10(-4) to 10 g x L(-1). Accordingly, the critical micellization concentrations are very low. Still, the surface tension of aqueous solutions of block copolymers decreases slowly but continuously with increasing concentration, without exhibiting a plateau. The longer the hydrophobic block, the shorter the hydrophilic block, and the less hydrophilic the monomer of the hydrophilic block is, the lower the surface tension is. However, the effects are small, and the copolymers reduce the surface tension much less than standard low-molar-mass surfactants. Also, the copolymers foam much less and even act as anti-foaming agents in classical foaming systems composed of standard surfactants. The copolymers stabilize O/W emulsions made of methyl palmitate as equally well as standard surfactants but are less efficient for O/W emulsions made of tributyrine. However, the copolymer micelles exhibit a high solubilization power for hydrophobic dyes, probably at their core-corona interface, in dependence on the initial geometry of the micelles and the composition of the block copolymers. Whereas micelles of copolymers with strongly hydrophilic blocks are stable upon solubilization, solubilization-induced micellar growth is observed for copolymers with moderately hydrophilic blocks. PMID:16618143

  5. Micellization and Characterization of Block Copolymer Detergents

    DEFF Research Database (Denmark)

    Hvidt, Søren

    Triblock copolymers of the type EPE, where E and P denote ethylene oxide and propylene oxide blocks, respectively, are used widely in industry as emulsifiers, anti-foaming agents, and in delayed drug release. EPE copolymers form micelles with a core of P blocks and different micellar shapes...... depending on block length ratios and temperature. The micellization process with increasing temperature or concentration has been followed by a number of techniques including differential scanning calorimetry and surface tension measurements. The detailed micellar mechanism is not well understood 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....

  6. Molecular Exchange in Ordered Diblock Copolymer Micelles

    Science.gov (United States)

    Choi, Soo-Hyung; Lodge, Timothy; Bates, Frank

    2011-03-01

    Previously, molecular exchange between spherical micelles in dilute solution (1 vol% polymer) was investigated using time-resolved small-angle neutron scattering (TR-SANS). As the concentration of spherical micelles formed by the diblock copolymers increases, the micelles begin to overlap and eventually pack onto body-centered cubic (BCC) lattice. In this study, concentrated, ordered micelles (15 vol% polymers) prepared by dispersing isotopically labeled poly(styrene- b -ethylene-alt-propylene) in an isotopic squalane mixture was investigated to understand the micellar concentration dependence of the molecular exchange. Perfectly random mixing of isotopically labeled micelles on the BCC lattice was confirmed by SANS patterns where the interparticle contribution vanishes, resulting in an intensity that directly relates to the exchange kinetics. The measured molecular exchange process for the concentrated, ordered system is qualitatively consistent with the previous observations, but the rate is more than an order of magnitude slower than that for the dilute, disordered system. Infineum(IPrime), MRSEC(NSF), NIST.

  7. Nanopatterning of Co/Pt-multilayers via self-assembled block-copolymer micelles; Magnetische Nanostrukturen basierend auf Co/Pt-Multilagen, hergestellt mittels selbstorganisierter Masken aus Blockcopolymer-Micellen

    Energy Technology Data Exchange (ETDEWEB)

    Stillrich, H.

    2007-07-01

    The production and characterization of magnetic nanostructures based on Co/Ptmultilayers are described in this thesis. Nanostructure arrays of Co/Pt multilayer films are generated utilizing the self-assembly of block copolymer micelles with a few 10nm diameter. For an understanding of the magnetic properties of nanostructures the properties of Co/Pt-multilayer films are examined first. The films are grown via different sputter techniques. The structural and magnetic properties are investigated depending on the deposition technique. The sources of magnetic anisotropy are discussed based on these investigations. One major topic concerning Co/Pt-multilayers is the reorientation of the easy axis of magnetization from perpendicular to in-plane as a function of the cobalt and platinum layer thicknesses. Combining averaging magnetization measurements and high resolution magnetic imaging, the canting of magnetization within the reorientation transition and a canted domain structure were found. The basis for magnetic nanostructures are Co/Pt-multilayers that were optimized for strong magnetic anisotropy. Magnetic antidot and dot arrays are generated from Co/Pt-multilayers via novel methods utilizing block copolymer micelle masks and ion milling. The generation of nanostructure arrays is proven by the morphologic and topographic properties, combined with the evolution of magneto-optic signals. Two different approaches for the generation of antidot arrays are shown. The magnetic properties of antidot arrays with perpendicular and in-plane easy magnetization are investigated. Magnetic dot arrays are produced utilizing the cores of SiO{sub 2} filled block copolymer micelles. The dot arrays consist of single domain particles. The switching field distribution of the dot arrays is analysed and described using the size distribution of the magnetic particles. Magnetic nanostructures in the region of the superparamagnetic limit are investigated. (orig.)

  8. A free-standing, sheet-shaped, "hydrophobic" biomaterial containing polymeric micelles formed from poly(ethylene glycol)-poly(lactic acid) block copolymer for possible incorporation/release of "hydrophilic" compounds.

    Science.gov (United States)

    Moroishi, Hitomi; Yoshida, Chikara; Murakami, Yoshihiko

    2013-02-01

    Sheet-shaped materials with a large contact area relative to the drug targeting site lead to advantages over conventional particle-shaped drug carriers and have several advantages for their biomedical applications. The present study proposes a methodology for preparing a novel sheet-shaped "hydrophobic" and biocompatible biomaterial in which polymeric micelles are uniformly dispersed for the incorporation of "hydrophilic" compounds into the sheet. The methoxy-terminated poly(ethylene glycol)-block-poly(lactic acid) block copolymer (CH(3)O-PEG-b-PLA) was successfully synthesized by means of the anionic ring-opening polymerization of both ethylene oxide and dl-lactide. CH(3)O-PEG-b-PLA was self-assembled and formed stable micelle-like w/o emulsion with a hydrophilic inner core in organic solvents. A sheet-shaped material containing a hydrophilic inner space for incorporating hydrophilic compounds was obtained by spin-coating both the micelle solution and a sheet-forming polymer. Fluorescent images of the sheet proved that polymeric micelles providing hydrophilic spaces were uniformly dispersed in the hydrophobic sheet. The facile technique presented in this paper can be a tool for fabricating sheet-shaped biomaterials that have a hydrophilic inner core and, consequently, that are suitable for the sustained release of hydrophilic compounds.

  9. Hydrolytic Degradation of Poly (ethylene oxide)-block-Polycaprolactone Worm Micelles

    OpenAIRE

    Geng, Yan; Discher, Dennis E.

    2005-01-01

    Spherical micelles and nanoparticles made with degradable polymers have been of great interest for therapeutic application, but degradation induced changes in a spherical morphology can be subtle and mechanism/kinetics appears poorly understood. Here, we report the first preparation of giant and flexible worm micelles self-assembled from degradable copolymer poly (ethylene oxide)-block-polycaprolactone. Such worm micelles spontaneously shorten to generate spherical micelles, triggered by poly...

  10. Self-assembled materials from thermosensitive and biohybrid block copolymers

    OpenAIRE

    De Graaf, A.J.

    2012-01-01

    In this research, several block copolymers were synthesized and characterized with regard to possible pharmaceutical applications. All block copolymers were thermosensitive and self-assembled at 37 °C into structures like micelles and hydrogels, which can be used for innovative drug delivery purposes. Some of the synthesized polymers were biohybrid, in the sense that they contained peptide segments which enabled their cleavage by enzymes that are upregulated in diseased tissues. First, method...

  11. Block copolymer patterns and templates

    Directory of Open Access Journals (Sweden)

    Mingqi Li

    2006-09-01

    Full Text Available This review describes the chemical and physical aspects of patternable block copolymers and their use for nanostructure fabrication. The patternability of block copolymers results from their ability to self-assemble into microdomains and the manipulation of these patterns by a variety of physical and chemical means. Procedures for achieving long-range lateral order, as well as orientation order of microdomain patterns, are discussed. The level of control that these strategies afford has enabled block copolymers to be used as templates for fabricating a variety of nanostructures.

  12. Redox-controlled micellization of organometallic block copolymers.

    Science.gov (United States)

    Rider, David A; Winnik, Mitchell A; Manners, Ian

    2007-11-21

    Polystyrene-block-polyferrocenylsilane (PS-b-PFS) diblock copolymers were stoichiometrically oxidized in solution using salts of the one-electron oxidant tris(4-bromophenyl)ammoniumyl. Due to a redox-induced polarity change for the PFS block, self-assembly into well-defined spherical micelles occurs. The micelles are composed of a core of partially oxidized PFS segments and a corona of PS. When the micellar solutions were treated with the reducing agent decamethylcobaltocene, the spherical micelles disassemble and regenerate unassociated and pristine PS-b-PFS free chains. PMID:17971963

  13. Structure of Poly(styrene-b-ethylene-alt-propylene) Diblock Copolymer Micelles in Squalane

    Energy Technology Data Exchange (ETDEWEB)

    Choi, Soo-Hyung; Bates, Frank S.; Lodge, Timothy P.; (UMM)

    2009-11-04

    The temperature dependence of the micellar structures formed by poly(styrene-b-ethylene-alt-propylene) (SEP) diblock copolymers in squalane, a highly selective solvent for the PEP blocks, has been studied using dynamic light scattering (DLS) and small-angle X-ray scattering (SAXS). Four SEP diblock copolymers were prepared by sequential anionic polymerization of styrene and isoprene, followed by hydrogenation of the isoprene blocks, to yield SEP(17-73), SEP(26-66), SEP(36-69), and SEP(42-60), where the numbers indicate block molecular weights in kDa. All four polymers formed well-defined spherical micelles. In dilute solution, DLS provided the temperature-dependent mean hydrodynamic radius, R{sub h}, and its distribution, while detailed fitting of the SAXS profiles gave the core radius, R{sub c}, the equivalent hard sphere radius, R{sub hs}, and an estimate of the aggregation number, N{sub agg}. In general, the micelles became smaller as the critical micelle temperature (CMT) was approached, which was well above the glass transition of the core block. As concentration increased the micelles packed onto body centered cubic lattices for all four copolymers, which underwent order-disorder transitions upon heating near the dilute solution CMTs. The results are discussed in terms of current understanding of block copolymer solution self-assembly, and particular attention is paid to the issue of equilibration, given the high glass transition temperature of the core block.

  14. Structure of poly(styrene-b-ethylene-alt-propylene) diblock copolymer micelles in squalane.

    Science.gov (United States)

    Choi, Soo-Hyung; Bates, Frank S; Lodge, Timothy P

    2009-10-22

    The temperature dependence of the micellar structures formed by poly(styrene-b-ethylene-alt-propylene) (SEP) diblock copolymers in squalane, a highly selective solvent for the PEP blocks, has been studied using dynamic light scattering (DLS) and small-angle X-ray scattering (SAXS). Four SEP diblock copolymers were prepared by sequential anionic polymerization of styrene and isoprene, followed by hydrogenation of the isoprene blocks, to yield SEP(17-73), SEP(26-66), SEP(36-69), and SEP(42-60), where the numbers indicate block molecular weights in kDa. All four polymers formed well-defined spherical micelles. In dilute solution, DLS provided the temperature-dependent mean hydrodynamic radius, R(h), and its distribution, while detailed fitting of the SAXS profiles gave the core radius, R(c), the equivalent hard sphere radius, R(hs), and an estimate of the aggregation number, N(agg). In general, the micelles became smaller as the critical micelle temperature (CMT) was approached, which was well above the glass transition of the core block. As concentration increased the micelles packed onto body centered cubic lattices for all four copolymers, which underwent order-disorder transitions upon heating near the dilute solution CMTs. The results are discussed in terms of current understanding of block copolymer solution self-assembly, and particular attention is paid to the issue of equilibration, given the high glass transition temperature of the core block.

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

    Science.gov (United States)

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

    2014-01-01

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

  16. Structural and Mechanical Hysteresis at the Order-Order Transition of Block Copolymer Micellar Crystals

    Directory of Open Access Journals (Sweden)

    Theresa A. LaFollette

    2011-01-01

    Full Text Available Concentrated solutions of a water-soluble block copolymer (PEO20-(PPO70-(PEO20 show a thermoreversible transition from a liquid to a gel. Over a range of concentration there also exists an order-order transition (OOT between cubically-packed spherical micelles and hexagonally-packed cylindrical micelles. This OOT displays a hysteresis between the heating and cooling transitions that is observed at both the macroscale through rheology and nanoscale through small angle neutron scattering (SANS. The hysteresis is caused by the persistence of the cubically-packed spherical micelle phase into the hexagonally-packed cylindrical micelle phase likely due to the hindered realignment of the spherical micelles into cylindrical micelles and then packing of the cylindrical micelles into a hexagonally-packed cylindrical micelle phase. This type of hysteresis must be fully characterized, and possibly avoided, for these block copolymer systems to be used as templates in nanocomposites.

  17. Controlling block copolymer phase behavior using ionic surfactant

    Science.gov (United States)

    Ray, D.; Aswal, V. K.

    2016-05-01

    The phase behavior of poly(ethylene oxide)-poly(propylene oxide-poly(ethylene oxide) PEO-PPO-PEO triblock copolymer [P85 (EO26PO39EO26)] in presence of anionic surfactant sodium dodecyl sulfate (SDS) in aqueous solution as a function of temperature has been studied using dynamic light scattering (DLS) and small-angle neutron scattering (SANS). The measurements have been carried out for fixed concentrations (1 wt%) of block copolymer and surfactants. Each of the individual components (block copolymer and surfactant) and the nanoparticle-surfactant mixed system have been examined at varying temperature. The block copolymer P85 forms spherical micelles at room temperature whereas shows sphere-to-rod like micelle transition at higher temperatures. On the other hand, SDS surfactant forms ellipsoidal micelles over a wide temperature range. Interestingly, it is found that phase behavior of mixed micellar system (P85 + SDS) as a function of temperature is drastically different from that of P85, giving the control over the temperature-dependent phase behavior of block copolymers.

  18. Grafted block complex coacervate core micelles and their effect on protein adsorption on silica and polystyrene

    NARCIS (Netherlands)

    Brzozowska, Agata M.; de Keizer, Arie; Norde, Willem; Detrembleur, Christophe; Stuart, Martien Cohen

    2010-01-01

    We have studied the formation and the stability of grafted block complex coacervate core micelles (C3Ms) in solution and the influence of grafted block C3M coatings on the adsorption of the proteins beta-lactoglobulin, bovine serum albumin, and lysozyme. The C3Ms consist of a grafted block copolymer

  19. Grafted block complex coacervate core micelles and their effect on protein adsorption on silica and polystyrene

    NARCIS (Netherlands)

    Brzozowska, A.M.; Keizer, de A.; Norde, W.; Detrembleur, C.; Cohen Stuart, M.A.

    2010-01-01

    We have studied the formation and the stability of grafted block complex coacervate core micelles (C3Ms) in solution and the influence of grafted block C3M coatings on the adsorption of the proteins ß-lactoglobulin, bovine serum albumin, and lysozyme. The C3Ms consist of a grafted block copolymer PA

  20. Self-Assembly of Amphiphilic Block Copolymers Containing Poly(n-octadecyl acrylate) Block in Aqueous Solution

    Energy Technology Data Exchange (ETDEWEB)

    Akiba, Isamu; Akino, Yusuke; Masunaga, Hiroyasu; Sakurai, Kazuo, E-mail: akiba@env.kitakyu-u.ac.jp

    2010-11-15

    Synchrotron small-angle X-ray scattering (SAXS) experiments were carried out for poly(acrylic acid)-block-poly(n-octadecyl acrylate) (PAA-b-PODA) and PAA-b-PODA-b-PAA micelles in aqueous solutions. SAXS results indicated that PAA-b-PODA and PAA-b-PODA-b-PAA formed core-shell micelles with disk-like morphology below melting temperature of PODA in aqueous solutions. The thickness of PAA-b-PODA (diblock copolymer) micelle was larger than that of PAA-b-PODA-b-PAA (triblock copolymer) micelle. The difference of sizes between these micelles was related to difference of molecular architectures of PAA-b-PODA and PAA-b-PODA-b-PAA. PAA-b-PODA micelle showed morphological transition from disk to spherical shape with elevating temperature. On the contrary, PAA-b-PODA-b-PAA micelle maintained disk-like shape above melting temperature, although enlargement of micelle thickness is caused.

  1. Self-Assembly of Amphiphilic Block Copolymers Containing Poly(n-octadecyl acrylate) Block in Aqueous Solution

    Science.gov (United States)

    Akiba, Isamu; Akino, Yusuke; Masunaga, Hiroyasu; Sakurai, Kazuo

    2010-11-01

    Synchrotron small-angle X-ray scattering (SAXS) experiments were carried out for poly(acrylic acid)-block-poly(n-octadecyl acrylate) (PAA-b-PODA) and PAA-b-PODA-b-PAA micelles in aqueous solutions. SAXS results indicated that PAA-b-PODA and PAA-b-PODA-b-PAA formed core-shell micelles with disk-like morphology below melting temperature of PODA in aqueous solutions. The thickness of PAA-b-PODA (diblock copolymer) micelle was larger than that of PAA-b-PODA-b-PAA (triblock copolymer) micelle. The difference of sizes between these micelles was related to difference of molecular architectures of PAA-b-PODA and PAA-b-PODA-b-PAA. PAA-b-PODA micelle showed morphological transition from disk to spherical shape with elevating temperature. On the contrary, PAA-b-PODA-b-PAA micelle maintained disk-like shape above melting temperature, although enlargement of micelle thickness is caused.

  2. Nanostructured Polysulfone-Based Block Copolymer Membranes

    KAUST Repository

    Xie, Yihui

    2016-05-01

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

  3. Block coordination copolymers

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-11-11

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

  4. 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.

  5. Rheological and Mechanical behaviour of Block copolymers, Multigraft copolymers and Block copolymer Nanocomposites

    OpenAIRE

    Thunga, Mahendra

    2009-01-01

    Block copolymers are commercially significant and fundamentally interesting class of polymeric materials. The ability to undergo interfacial thermodynamics-controlled microphase separation from a completely disordered state in the melt to a specifically defined ordered structure through self-organization makes the block copolymers based materials unique. Block copolymer are strongly replacing many of the commercially available polymers due to their unique microstructure and properties. The mo...

  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. DEFORMATION OF COPOLYMER MICELLES INDUCED BY AMPHIPHILIC DIMER PARTICLES

    Institute of Scientific and Technical Information of China (English)

    Xiao-chun Qin; Chun-lai Ren

    2012-01-01

    Combining self-consistent-field theory and density-functional theory,we systematically study the deformation of copolymer micelles induced by the presence of amphiphilic dimer particles.Due to the amphiphilic nature,dimer particles tend to accumulate onto the interface of the copolymer micelle.With increasing concentration of the symmetric dimer particles,which are made of two identical spherical particles,the micelle deforms from the initial sphere to ellipse,dumbbell,and finally separates into two micelles.Furthermore,asymmetric dimer particles,composed by two particles with different sizes,are considered to investigate the influence of geometry of dimer particles on the deformation of the micelle.It is found that the micelle inclines to deform into dumbbell due to the additional curvature originating in the gathering of asymmetric dimer particles onto the interface of the micelle.The present study on the deformation of micelles is useful to understand the possible shape variation in the course of cell division/fusion.

  8. Crystalline free energies of micelles of diblock copolymer solutions

    CERN Document Server

    D'Adamo, Giuseppe; 10.1063/1.3509391

    2012-01-01

    We report a characterization of the relative stability and structural behavior of various micellar crystals of an athermal model of AB-diblock copolymers in solution. We adopt a previously devel- oped coarse-graining representation of the chains which maps each copolymer on a soft dumbbell. Thanks to this strong reduction of degrees of freedom, we are able to investigate large aggregated systems, and for a specific length ratio of the blocks f = MA/(MA + MB) = 0.6, to locate the order-disorder transition of the system of micelles. Above the transition, mechanical and thermal properties are found to depend on the number of particles per lattice site in the simulation box, and the application of a recent methodology for multiple occupancy crystals (B.M. Mladek et al., Phys. Rev. Lett. 99, 235702 (2007)) is necessary to correctly define the equilibrium state. Within this scheme we have performed free energy calculations at two reduced density {\\rho}/{\\rho}\\ast = 4,5 and for several cubic structures as FCC,BCC,A1...

  9. Analysis of the aggregation structure from amphiphilic block copolymers in solutions by small-angle x-ray scattering

    CERN Document Server

    Rong Li Xia; Wang Jun; Wei Liu He; Li Fu Mian; Li Zi Chen

    2002-01-01

    The aggregation structure of polystyrene-p vinyl benzoic amphiphilic block copolymers which were prepared in different conditions was investigated by synchrotron radiation small-angle x-ray scattering (SAXS). The micelle was self-assembled in selective solvents of the block copolymers. Authors' results demonstrate that the structure of the micelle depends on the factors, such as the composition of the copolymers, the nature of the solvent and the concentration of the solution

  10. Stereocomplex micelle from nonlinear enantiomeric copolymers efficiently transports antineoplastic drug

    Science.gov (United States)

    Wang, Jixue; Shen, Kexin; Xu, Weiguo; Ding, Jianxun; Wang, Xiaoqing; Liu, Tongjun; Wang, Chunxi; Chen, Xuesi

    2015-05-01

    Nanoscale polymeric micelles have attracted more and more attention as a promising nanocarrier for controlled delivery of antineoplastic drugs. Herein, the doxorubicin (DOX)-loaded poly(D-lactide)-based micelle (PDM/DOX), poly(L-lactide)-based micelle (PLM/DOX), and stereocomplex micelle (SCM/DOX) from the equimolar mixture of the enantiomeric four-armed poly(ethylene glycol)-polylactide (PEG-PLA) copolymers were successfully fabricated. In phosphate-buffered saline (PBS) at pH 7.4, SCM/DOX exhibited the smallest hydrodynamic diameter ( D h) of 90 ± 4.2 nm and the slowest DOX release compared with PDM/DOX and PLM/DOX. Moreover, PDM/DOX, PLM/DOX, and SCM/DOX exhibited almost stable D hs of around 115, 105, and 90 nm at above normal physiological condition, respectively, which endowed them with great potential in controlled drug delivery. The intracellular DOX fluorescence intensity after the incubation with the laden micelles was different degrees weaker than that incubated with free DOX · HCl within 12 h, probably due to the slow DOX release from micelles. As the incubation time reached to 24 h, all the cells incubated with the laden micelles, especially SCM/DOX, demonstrated a stronger intracellular DOX fluorescence intensity than free DOX · HCl-cultured ones. More importantly, all the DOX-loaded micelles, especially SCM/DOX, exhibited potent antineoplastic efficacy in vitro, excellent serum albumin-tolerance stability, and satisfactory hemocompatibility. These encouraging data indicated that the loading micelles from nonlinear enantiomeric copolymers, especially SCM/DOX, might be promising in clinical systemic chemotherapy through intravenous injection.

  11. NANOSTRUCTURES OF FUNCTIONAL BLOCK COPOLYMERS

    Institute of Scientific and Technical Information of China (English)

    Guojun Liu

    2000-01-01

    Nanostructure fabrication from block copolymers in my group normally involves polymer design, synthesis, selfassembly, selective domain crosslinking, and sometimes selective domain removal. Preparation of thin films with nanochannels was used to illustrate the strategy we took. In this particular case, a linear triblock copolymer polyisopreneblock-poly(2-cinnamoylethyl methacrylate)-block-poly(t-butyl acrylate), PI-b-PCEMA-b-PtBA, was used. Films, 25 to50μm thick, were prepared from casting on glass slides a toluene solution of PI-b-PCEMA-b-PtBA and PtBA homopolymer,hPtBA, where hPtBA is shorter than the PtBA block. At the hPtBA mass fraction of 20% relative to the triblock or the total PtBA (hPtBA and PtBA block) volume fraction of 0.44, hPtBA and PtBA formed a seemingly continuous phase in the matrix of PCEMA and PI. Such a block segregation pattern was locked in by photocrosslinking the PCEMA domain. Nanochannels were formed by extracting out hPtBA with solvent. Alternatively, larger channels were obtained from extracting out hPtBA and hydrolyzing the t-butyl groups of the PtBA block. Such membranes were not liquid permeable but had gas permeability constants ~6 orders of magnitude higher than that of low-density polyethylene films.

  12. Characterization and micellization of a poloxamer block copolymer

    DEFF Research Database (Denmark)

    Hvidt, S.; Pedersen, Walther Batsberg

    2007-01-01

    Several poloxamers that are symmetrical EPE block copolymers (E and P are ethylene and propylene oxide, respectively) have been characterized by size exclusion chromatography on Superose columns in water. The poloxamers contain between 12 and 26 wt% of smaller-size UV-absorbing impurities....... Poloxamer P94 (E28P48E28) forms micelles with increasing temperature, and micellization was investigated by eluent gel permeation chromatography (EGPC). EGPC results demonstrate that P94 impurities are not incorporated into the micelles up to 38°C. The importance of poloxamer heterogeneity for thermodynamic...

  13. 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.

  14. A neutron scattering study of triblock copolymer micelles

    International Nuclear Information System (INIS)

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

  15. Kinking mechanisms in block copolymers

    Science.gov (United States)

    Polis, Daniel L.; Winey, Karen I.

    1998-03-01

    Two of the primary models proposed for kink formation are fixed hinge rotation and boundary migration. Our results regarding steady shear induced kink bands in an aligned lamellar poly(styrene-b-ethylene propylene) diblock copolymer are consistent with a fixed hinge rotation mechanism. When the shear strain is above a critical strain, a range of kink widths and kink angles are produced at each shear rate studied. Moreover, the kink widths are independent of rate and strain, having a characteristic size similar to that of remaining defects in the initially aligned block copolymer. Rounded folds, similar in size, shape, and orientation to kink bands, are produced at these residual defects at shear strains below the critical stain. These rounded folds may sharpen into angular folds or kink bands with additional strain.

  16. 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.

  17. Curvature-coupled hydration of Semicrystalline Polymer Amphiphiles yields flexible Worm Micelles but favors rigid Vesicles: polycaprolactone-based block copolymers

    OpenAIRE

    Rajagopal, Karthikan; Mahmud, Abdullah; Christian, David A.; Pajerowski, J. David; Brown, Andre E. X.; Sharon M Loverde; Discher, Dennis E.

    2010-01-01

    Crystallization processes are in general sensitive to detailed conditions, but our present understanding of underlying mechanisms is insufficient. A crystallizable chain within a diblock copolymer assembly is expected to couple curvature to crystallization and thereby impact rigidity as well as preferred morphology, but the effects on dispersed phases have remained unclear. The hydrophobic polymer polycaprolactone (PCL) is semi-crystalline in bulk (Tm = 60°C) and is shown here to generate fle...

  18. 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.

  19. 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...

  20. STUDY ON POLYSULFONE-POLYESTER BLOCK COPOLYMERS

    Institute of Scientific and Technical Information of China (English)

    DING Youjun; QI Daquan

    1988-01-01

    Synthesis and characterization of a series of Polysulfone (PSF)-Polyester (PEs) block copolymers were studied.The degree of randomness (B) of these block copolymers was calculated from the intensities of their proton signals in 1H NMR spectra and lies in the region of 0 < B < 1. It was shown that the degree of randomness (B) and the average sequence length (L) in block copolymers were relatively dependent on the reaction conditions, various feed ratios and structure of diols.The phenomenon was observed, when the PSF-PEs block copolymers dissolved in different solvents they had different viscosities and molecular conformations.The PSF-PEs block copolymers had better solvent resistance than homo-polysulfone.

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

    Science.gov (United States)

    Hoarfrost, Megan Lane

    Incorporating an ionic liquid into one block copolymer microphase provides a platform for combining the outstanding electrochemical properties of ionic liquids with a number of favorable attributes provided by block copolymers. In particular, block copolymers thermodynamically self-assemble into well-ordered nanostructures, which can be engineered to provide a durable mechanical scaffold and template the ionic liquid into continuous ion-conducting nanochannels. Understanding how the addition of an ionic liquid affects the thermodynamic self-assembly of block copolymers, and how the confinement of ionic liquids to block copolymer nanodomains affects their ion-conducting properties is essential for predictable structure-property control. The lyotropic phase behavior of block copolymer/ionic liquid mixtures is shown to be reminiscent of mixtures of block copolymers with selective molecular solvents. A variety of ordered microstructures corresponding to lamellae, hexagonally close-packed cylinders, body-centered cubic, and face-centered cubic oriented micelles are observed in a model system composed of mixtures of imidazolium bis(trifluoromethylsulfonyl)imide ([Im][TFSI]) and poly(styrene- b-2-vinyl pyridine) (PS-b-P2VP). In contrast to block copolymer/molecular solvent mixtures, the interfacial area occupied by each PS-b-P2VP chain decreases upon the addition of [Im][TFSI], indicating a considerable increase in the effective segregation strength of the PS-b-P2VP copolymer with ionic liquid addition. The relationship between membrane structure and ionic conductivity is illuminated through the development of scaling relationships that describe the ionic conductivity of block copolymer/ionic liquid mixtures as a function of membrane composition and temperature. It is shown that the dominant variable influencing conductivity is the overall volume fraction of ionic liquid in the mixture, which means there is incredible freedom in designing the block copolymer architecture

  2. Functional Nanoporous Polymers from Block Copolymer Precursors

    OpenAIRE

    Guo, Fengxiao

    2010-01-01

    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 applications as, e.g., membranes for separation and purification, templates for nanostructured materials, sensors, substrates for catalysis, low dielectric constant materials, photonic materials, and...

  3. Grafted block complex coacervate core micelles and their effect on protein adsorption on silica and polystyrene

    OpenAIRE

    Brzozowska, A.M.; Keizer, de, O.; Norde, W; Detrembleur, C.; Cohen Stuart, M. A.

    2010-01-01

    We have studied the formation and the stability of grafted block complex coacervate core micelles (C3Ms) in solution and the influence of grafted block C3M coatings on the adsorption of the proteins beta-lactoglobulin, bovine serum albumin, and lysozyme. The C3Ms consist of a grafted block copolymer PAA(21)-b-PAPEO(14) (poly(acrylic acid)-b-poly(acrylate methoxy poly(ethylene oxide)), with a negatively charged PAA block and a neutral PAPEO block and a positively charged homopolymer P2MVPI (po...

  4. 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.

  5. Structural and Mechanical Hysteresis at the Order-Order Transition of Block Copolymer Micellar Crystals

    OpenAIRE

    LaFollette, Theresa A.; Lynn M. Walker Walker

    2011-01-01

    Concentrated solutions of a water-soluble block copolymer (PEO)20-(PPO)70-(PEO)20 show a thermoreversible transition from a liquid to a gel. Over a range of concentration there also exists an order-order transition (OOT) between cubically-packed spherical micelles and hexagonally-packed cylindrical micelles. This OOT displays a hysteresis between the heating and cooling transitions that is observed at both the macroscale through rheology and nanoscale through small angle neutron scattering (S...

  6. Structural properties of self-assembled polymeric micelles

    DEFF Research Database (Denmark)

    Mortensen, K.

    1998-01-01

    At present, the thermodynamic understanding of complex copolymer systems is undergoing important developments. Block copolymers aggregate in selective solvents into micelles of various form and size depending on molecular architecture and interaction parameters. The micelles constitute the basis ...

  7. Prediction of solvent-induced morphological changes of polyelectrolyte diblock copolymer micelles.

    Science.gov (United States)

    Li, Nan K; Fuss, William H; Tang, Lei; Gu, Renpeng; Chilkoti, Ashutosh; Zauscher, Stefan; Yingling, Yaroslava G

    2015-11-14

    Self-assembly processes of polyelectrolyte block copolymers are ubiquitous in industrial and biological processes; understanding their physical properties can also provide insights into the design of polyelectrolyte materials with novel and tailored properties. Here, we report systematic analysis on how the ionic strength of the solvent and the length of the polyelectrolyte block affect the self-assembly and morphology of the polyelectrolyte block copolymer materials by constructing a salt-dependent morphological phase diagram using an implicit solvent ionic strength (ISIS) method for dissipative particle dynamics (DPD) simulations. This diagram permits the determination of the conditions for the morphological transition into a specific shape, namely vesicles or lamellar aggregates, wormlike/cylindrical micelles, and spherical micelles. The scaling behavior for the size of spherical micelles is predicted, in terms of radius of gyration (R(g,m)) and thickness of corona (Hcorona), as a function of solvent ionic strength (c(s)) and polyelectrolyte length (NA), which are R(g,m) ∼ c(s)(-0.06)N(A)(0.54) and Hcorona ∼ c(s)(-0.11)N(A)(0.75). The simulation results were corroborated through AFM and static light scattering measurements on the example of the self-assembly of monodisperse, single-stranded DNA block-copolynucleotides (polyT50-b-F-dUTP). Overall, we were able to predict the salt-responsive morphology of polyelectrolyte materials in aqueous solution and show that a spherical-cylindrical-lamellar change in morphology can be obtained through an increase in solvent ionic strength or a decrease of polyelectrolyte length. PMID:26315065

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

    Science.gov (United States)

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

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

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  10. Block copolymer self-assembly and co-assembly : shape function and application

    NARCIS (Netherlands)

    Li, F.

    2009-01-01

    Amphiphilic block copolymers can, in selective solvents such as water, assemble into various shapes and architectures. Among those, polymer vesicles, polymer micelles and polymer fibers are very popular structures in current nanotechnology. These objects each have their own particular properties and

  11. Time-resolved GISAXS and cryo-microscopy characterization of block copolymer membrane formation

    KAUST Repository

    Marques, Debora S.

    2014-03-01

    Time-resolved grazing-incidence small-angle X-ray scattering (GISAXS) and cryo-microscopy were used for the first time to understand the pore evolution by copolymer assembly, leading to the formation of isoporous membranes with exceptional porosity and regularity. The formation of copolymer micelle strings in solution (in DMF/DOX/THF and DMF/DOX) was confirmed by cryo field emission scanning electron microscopy (cryo-FESEM) with a distance of 72 nm between centers of micelles placed in different strings. SAXS measurement of block copolymer solutions in DMF/DOX indicated hexagonal assembly with micelle-to-micelle distance of 84-87 nm for 14-20 wt% copolymer solutions. GISAXS in-plane peaks were detected, revealing order close to hexagonal. The d-spacing corresponding to the first peak in this case was 100-130 nm (lattice constant 115-150 nm) for 17 wt% copolymer solutions evaporating up to 100 s. Time-resolved cryo-FESEM showed the formation of incipient pores on the film surface after 4 s copolymer solution casting with distances between void centers of 125 nm. © 2014 Elsevier Ltd. All rights reserved.

  12. 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.

  13. 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.

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

  15. Self-assembling Behavior of Amphiphilic Copolymer Containing Cross-linked Hydrophilic Block in Ethanol

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    The self-assembly behavior of the amphiphilic block copolymer poly( methyl methacrylate)-block-poly( lead dimethacrylate) (PMMA-b-PLDMA) with cross-linked hydrophilic block (PLDMA) in ethanol was investigated. The results show that the size and morphology of the resulting micelle or micellar aggregates are ascribed to the content of ethanol and the nature of the solvent mixture. PbS nanoparticles were formed in the micelle by in situ reaction with H2S gas. The morphology and size of the self-assembly objects were investigated using scanning electron microscopy (SEM) and transmission electron microscopy (TEM).

  16. CONJUGATED BLOCK-COPOLYMERS FOR ELECTROLUMINESCENT DIODES

    NARCIS (Netherlands)

    Hilberer, A; Gill, R.E; Herrema, J.K; Malliaras, G.G; Wildeman, J.; Hadziioannou, G

    1995-01-01

    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

  17. Ion and temperature sensitive polypeptide block copolymer.

    Science.gov (United States)

    Joo, Jae Hee; Ko, Du Young; Moon, Hyo Jung; Shinde, Usha Pramod; Park, Min Hee; Jeong, Byeongmoon

    2014-10-13

    A poly(ethylene glycol)/poly(L-alanine) multiblock copolymer incorporating ethylene diamine tetraacetic acid ([PA-PEG-PA-EDTA(m)) was synthesized as an ion/temperature dual stimuli-sensitive polymer, where the effect of different metal ions (Cu(2+), Zn(2+), and Ca(2+)) on the thermogelation of the polymer aqueous solution was investigated. The dissociation constants between the metal ions and the multiblock copolymer were calculated to be 1.2 × 10(-7), 6.6 × 10(-6), and 1.2 × 10(-4) M for Cu(2+), Zn(2+), and Ca(2+), respectively, implying that the binding affinity of the multiblock copolymer for Cu(2+) is much greater than that for Zn(2+) or Ca(2+). Atomic force microscopy and dynamic light scattering of the multiblock copolymer containing metal ions suggested micelle formation at low temperature, which aggregated as the temperature increased. Circular dichroism spectra suggested that changes in the α-helical secondary structure of the multiblock copolymer were more pronounced by adding Cu(2+) than other metal ions. The thermogelation of the multiblock copolymer aqueous solution containing Cu(2+) was observed at a lower temperature, and the modulus of the gel was significantly higher than that of the system containing Ca(2+) or Zn(2+), in spite of the same concentration of the metal ions and their same ionic valence of +2. The above results suggested that strong ionic complexes between Cu(2+) and the multiblock copolymer not only affected the secondary structure of the polymer but also facilitated the thermogelation of the polymer aqueous solution through effective salt-bridge formation even in a millimolar range of the metal ion concentration. Therefore, binding affinity of metal ions for polymers should be considered first in designing an effective ion/temperature dual stimuli-sensitive polymer. PMID:25178662

  18. Conjugation of Lectin to Poly(ε-caprolactone-block-glycopolymer Micelles for In Vitro Intravesical Drug Delivery

    Directory of Open Access Journals (Sweden)

    Ning Ning Li

    2016-10-01

    Full Text Available Amphiphilic poly(ε-caprolactone-block-poly[2-(α-d-mannopyranosyloxy ethyl acrylamide] (PCL-b-PManEA block copolymers were synthesized via a combination of ring-opening polymerization (ROP, reversible addition-fragmentation chain transfer (RAFT polymerization and reactive ester-amine reaction. The PCL-b-PManEA block copolymers can self-assemble into micelles and encapsulate anticancer drug doxorubicin (DOX. To enhance mucoadhesive property of the resulting DOX-loaded PCL-b-PManEA micelles, Concanavalin A (ConA lectin was further conjugated with the micelles. Turbidimetric assay using mucin shows that the DOX-loaded PCL-b-PManEA@ConA micelles are mucoadhesive. DOX release from the DOX-loaded PCL-b-PManEA@ConA micelles in artificial urine at 37 °C exhibits an initial burst release, followed by a sustained and slow release over three days. Confocal laser scanning microscope (CLSM images indicate that the DOX-loaded PCL-b-PManEA@ConA micelles can be effectively internalized by UMUC3 human urothelial carcinoma cells. The DOX-loaded PCL-b-PManEA@ConA micelles exhibit significant cytotoxicity to these cells.

  19. Janus Micelles

    OpenAIRE

    Erhardt, R.; Böker, A.; Zettl, H; H. KAYA; PYCKHOUT-HINTZEN, W.; Krausch, G.; Abetz, V.; A. Müller

    2001-01-01

    A novel strategy to synthesize amphiphilic surface-compartmentalized nanoparticles based on linear ABC triblock copolymers is presented. These so-called Janus micelles consist of a cross-linked core and a corona with a "northern" and a "southern" hemisphere. Selectively cross-linking spherical domains of the polybutadiene middle block in a well-ordered bulk morphology of a polystyrene-block-polybutadiene-block-poly( methyl methacrylate) triblock copolymer (SBM) leads to the conservation of th...

  20. 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....... simplifies the main stream BC lithography process, showing a broad substrate tolerance and allowing for efficient pattern transfer over wafer scale. PDMS-rich poly(styrene-b-dimethylsiloxane) (PS-b-PDMS) copolymers are directly applied on substrates including polymers, silicon and graphene. A single oxygen...

  1. Facile synthesis and characterization of novel biodegradable amphiphilic block copolymers bearing pendant hydroxyl groups

    International Nuclear Information System (INIS)

    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 1H nuclear magnetic resonance (1H 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

  2. 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.

  3. Small angle neutron scattering study of complex coacervate micelles and hydrogels formed from ionic diblock and triblock copolymers.

    Science.gov (United States)

    Krogstad, Daniel V; Choi, Soo-Hyung; Lynd, Nathaniel A; Audus, Debra J; Perry, Sarah L; Gopez, Jeffrey D; Hawker, Craig J; Kramer, Edward J; Tirrell, Matthew V

    2014-11-13

    A complex coacervate is a fluid phase that results from the electrostatic interactions between two oppositely charged macromolecules. The nature of the coacervate core structure of hydrogels and micelles formed from complexation between pairs of diblock or triblock copolymers containing oppositely charged end-blocks as a function of polymer and salt concentration was investigated. Both ABA triblock copolymers of poly[(allyl glycidyl ether)-b-(ethylene oxide)-b-(allyl glycidyl ether)] and analogous poly[(allyl glycidyl ether)-b-(ethylene oxide)] diblock copolymers, which were synthesized to be nearly one-half of the symmetrical triblock copolymers, were studied. The poly(allyl glycidyl ether) blocks were functionalized with either guanidinium or sulfonate groups via postpolymerization modification. Mixing of oppositely charged block copolymers resulted in the formation of nanometer-scale coacervate domains. Small angle neutron scattering (SANS) experiments were used to investigate the size and spacing of the coacervate domains. The SANS patterns were fit using a previously vetted, detailed model consisting of polydisperse core-shell micelles with a randomly distributed sphere or body-centered cubic (BCC) structure factor. For increasing polymer concentration, the size of the coacervate domains remained constant while the spatial extent of the poly(ethylene oxide) (PEO) corona decreased. However, increasing salt concentration resulted in a decrease in both the coacervate domain size and the corona size due to a combination of the electrostatic interactions being screened and the shrinkage of the neutral PEO blocks. Additionally, for the triblock copolymers that formed BCC ordered domains, the water content in the coacervate domains was calculated to increase from approximately 16.8% to 27.5% as the polymer concentration decreased from 20 to 15 wt %.

  4. Micellization kinetics in block copolymer solutions : Scaling model

    NARCIS (Netherlands)

    Dormidontova, EE

    1999-01-01

    The kinetics of micelle evolution of diblock copolymers from unimers toward the equilibrium state is studied analytically on the basis of consideration of the kinetic equations. The association/dissociation rate constants for unimer insertion/expulsion and micelle fusion/fission are calculated by ap

  5. Manipulating the morphologies of poly(vinyl alcohol) block copolymer surfactants

    Science.gov (United States)

    Repollet-Pedrosa, Milton H.

    Amphiphilic block copolymers (ABCs) are macromolecules containing well-defined hydrophilic and hydrophobic segments that self-assemble into nanoscale aggregates such as spherical and cylindrical micelles and vesicles, when dispersed in block-selective solvents. ABCs possess a miniscule critical micelle concentration, which results in kinetically trapped and persistent assemblies in solution with slow chain exchange between aggregates. This makes them useful as rheological modifiers for personal care products, enhanced oil recovery, and drug delivery formulations. Their utility in many of these applications is crucially dependent on the ability to control the micellar morphologies that they adopt in selective solvents. Triggering ABC micellar morphological transformations, i.e. from spherical to cylindrical micelles, is important for generating "on-demand" stimuli-responsive morphologies that control the aggregate morphology and the bulk solution properties in any given application. In this thesis, we develop the straightforward synthesis of biodegradable and biocompatible ABCs comprised of poly(vinyl acetate) (PVAc) and poly(vinyl alcohol) (PVA), with narrow molecular distributions and variable yet well-defined compositions. These block copolymer amphiphiles readily form spherical micelles in aqueous dispersions. We demonstrate that the addition of a water-soluble poly(ethylene oxide) (PEO) homopolymer to these dispersions results in a rapid transformation of these spherical micelles into cylindrical micelles. Dilution of these cylindrical micelles with water induces their reversion to spherical micelles. Our results indicate that the reversible morphology change depends sensitively on the PEO homopolymer concentration and molecular weight, as well as the length of the PVA corona block of the micelles. Through a series of quantitative 1H NMR studies, we found that the preferential partitioning of PEO homopolymer into the PVAc micellar core drives this morphological

  6. Fabrication and study of properties of magnetite nanoparticles in hybrid micelles of polystyrene-block-polyethylene oxide and sodium dodecyl sulfate

    Energy Technology Data Exchange (ETDEWEB)

    Loginova, T. P., E-mail: tlg@ineos.ac.ru; Timofeeva, G. I.; Lependina, O. L.; Shandintsev, V. A. [Russian Academy of Sciences, Nesmeyanov Institute of Organoelement Compounds (Russian Federation); Matyushin, A. A. [Ministry of Public Health of the Russian Federation, First Moscow State Medical University (Russian Federation); Khotina, I. A. [Russian Academy of Sciences, Nesmeyanov Institute of Organoelement Compounds (Russian Federation); Shtykova, E. V. [Russian Academy of Sciences, Shubnikov Institute of Crystallography (Russian Federation)

    2016-01-15

    Magnetite nanoparticles have been formed for the first time in hybrid micelles of polystyrene-block-polyethylene oxide and sodium dodecyl sulfate in water by ultrasonic treatment at room temperature. An analysis by small-angle X-ray scattering and transmission electron microscopy (TEM) showed that magnetite nanoparticles in hybrid micelles of block copolymer and sodium dodecyl sulfate are polydesperse (have sizes from 0.5 to 20 nm). The specific magnetization of solid samples has been measured.

  7. Fabrication and study of properties of magnetite nanoparticles in hybrid micelles of polystyrene- block-polyethylene oxide and sodium dodecyl sulfate

    Science.gov (United States)

    Loginova, T. P.; Timofeeva, G. I.; Lependina, O. L.; Shandintsev, V. A.; Matyushin, A. A.; Khotina, I. A.; Shtykova, E. V.

    2016-01-01

    Magnetite nanoparticles have been formed for the first time in hybrid micelles of polystyrene- block-polyethylene oxide and sodium dodecyl sulfate in water by ultrasonic treatment at room temperature. An analysis by small-angle X-ray scattering and transmission electron microscopy (TEM) showed that magnetite nanoparticles in hybrid micelles of block copolymer and sodium dodecyl sulfate are polydesperse (have sizes from 0.5 to 20 nm). The specific magnetization of solid samples has been measured.

  8. Synthesis of Functional Block Copolymers Carrying One Poly( p -phenylenevinylene) and One Nonconjugated Block in a Facile One-Pot Procedure

    KAUST Repository

    Menk, Florian

    2016-02-29

    Block copolymers composed of a MEH-PPV block and a nonconjugated functional block (molecular weights between 5 and 90 kg/mol) were synthesized in a facile one-pot procedure via ROMP. This one-pot procedure permits the synthesis of numerous block copolymers with little effort. Amphiphilic block copolymers were obtained via incorporation of oxanorbornene carrying a PEG side chain as well as via postpolymerization modification of a reactive ester carrying norbornene derivative with methoxypoly(ethylene glycol)amine. These amphiphilic block copolymers can be self-assembled into micelles exhibiting different sizes (60-95 nm), morphologies (micelles or fused, caterpillar-like micelles), and optical properties depending on the polymer composition and the micellization procedure. Furthermore, the reactive ester carrying block copolymers enabled the introduction of anchor groups which facilitated the preparation of nanocomposites with CdSe/CdZnS core-shell QDs. The obtained composites were studied using time-resolved photoluminescence measurements. The results revealed an increased interaction based on an accelerated decay of the QD emission for composites as compared to the mixture of the QDs with unfunctionalized polymers. © 2016 American Chemical Society.

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

    KAUST Repository

    Moreno Chaparro, Nicolas

    2016-05-01

    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 the optimal conditions, leading to a considerable demand of resources. Experimental insights demonstrate that the self-assembly of the block copolymers in solution has an effect on the final membrane structure. Nevertheless, the complete understanding of these multi-scale phenomena is elusive. Herein we use the coarse-grained method Dissipative Particle Dynamics to study the self-assembly of block copolymers that are used for the preparation of the membranes. To simulate representative time and length scales, we introduce a framework for model reduction of polymer chain representations for dissipative particle dynamics, which preserves the properties governing the phase equilibria. We reduce the number of degrees of freedom by accounting for the correlation between beads in fine-grained models via power laws and the consistent scaling of the simulation parameters. The coarse-graining models are consistent with the experimental evidence, showing a morphological transition of the aggregates as the polymer concentration and solvent affinity change. We show that hexagonal packing of the micelles can occur in solution within different windows of polymer concentration depending on the solvent affinity. However, the shape and size dispersion of the micelles determine the characteristic arrangement. We describe the order of crew-cut micelles using a rigid-sphere approximation and propose different phase parameters that characterize the emergence of monodisperse-spherical micelles in solution. Additionally, we investigate the effect of blending asymmetric diblock copolymers (AB/AC) over the properties of the membranes. We observe that the co-assembly mechanism localizes the AC molecules at the interface of A and B domains, and induces

  10. Polyelectrolyte complex micelles by self-assembly of polypeptide-based triblock copolymer for doxorubicin delivery

    Directory of Open Access Journals (Sweden)

    Jeong Hwan Kim

    2014-08-01

    Full Text Available Polyelectrolyte complex micelles were prepared by self-assembly of polypeptide-based triblock copolymer as a new drug carrier for cancer chemotherapy. The triblock copolymer, poly(l-aspartic acid-b-poly(ethylene glycol-b-poly(l-aspartic acid (PLD-b-PEG-b-PLD, spontaneously self-assembled with doxorubicin (DOX via electrostatic interactions to form spherical micelles with a particle size of 60–80 nm (triblock ionomer complexes micelles, TBIC micelles. These micelles exhibited a high loading capacity of 70% (w/w at a drug/polymer ratio of 0.5 at pH 7.0. They showed pH-responsive release patterns, with higher release at acidic pH than at physiological pH. Furthermore, DOX-loaded TBIC micelles exerted less cytotoxicity than free DOX in the A-549 human lung cancer cell line. Confocal microscopy in A-549 cells indicated that DOX-loaded TBIC micelles were transported into lysosomes via endocytosis. These micelles possessed favorable pharmacokinetic characteristics and showed sustained DOX release in rats. Overall, these findings indicate that PLD-b-PEG-b-PLD polypeptide micelles are a promising approach for anti-cancer drug delivery.

  11. 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.

  12. 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.

  13. 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.

  14. Contrast variation SANS experiments to the study of detergent-induced micellization of block copolymers

    Indian Academy of Sciences (India)

    V K Aswal; J Kohlbrecher

    2004-08-01

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

  15. 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

  16. Facile synthesis and characterization of novel biodegradable amphiphilic block copolymers bearing pendant hydroxyl groups.

    Science.gov (United States)

    Hu, Gaicen; Fan, Xiaoshan; Xu, Bingcan; Zhang, Delong; Hu, Zhiguo

    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 (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. PMID:25175206

  17. Use of Superparamagnetic Nanoparticle/Block Copolymer Electrostatic Complexes as Contrast Agents in Magnetic Resonance Imaging

    OpenAIRE

    Berret, Jean-Francois; Cartier, Regis

    2007-01-01

    During the past years we have investigated the complexation between nanocolloids and oppositely charged polymers. The nanocolloids examined were ionic surfactant micelles and inorganic oxide nanoparticles. For the polymers, we used homopolyelectrolytes and block copolymers with linear and comb architectures. In general, the attractive interactions between oppositely charged species are strong and as such, the simple mixing of solutions containing dispersed constituents yield to a precipitatio...

  18. Self-Assembled Polymeric Micelles Based on Hyaluronic Acid-g-Poly(d,l-lactide-co-glycolide Copolymer for Tumor Targeting

    Directory of Open Access Journals (Sweden)

    Gyung Mo Son

    2014-09-01

    Full Text Available Graft copolymer composed hyaluronic acid (HA and poly(d,l-lactide-co-glycolide (PLGA (HAgLG was synthesized for antitumor targeting via CD44 receptor of tumor cells. The carboxylic end of PLGA was conjugated with hexamethylenediamine (HMDA to have amine end group in the end of chain (PLGA-amine. PLGA-amine was coupled with carboxylic acid of HA. Self-assembled polymeric micelles of HAgLG have spherical morphologies and their sizes were around 50–200 nm. Doxorubicin (DOX-incorporated polymeric micelles were prepared by dialysis procedure. DOX was released over 4 days and its release rate was accelerated by the tumoric enzyme hyaluronidase. To assess targetability of polymeric micelles, CD44-positive HepG2 cells were employed treated with fluorescein isothiocyanate (FITC-labeled polymeric micelles. HepG2 cells strongly expressed green fluorescence at the cell membrane and cytosol. However, internalization of polymeric micelles were significantly decreased when free HA was pretreated to block the CD44 receptor. Furthermore, the CD44-specific anticancer activity of HAgLG polymeric micelles was confirmed using CD44-negative CT26 cells and CD44-positive HepG2 cells. These results indicated that polymeric micelles of HaLG polymeric micelles have targetability against CD44 receptor of tumor cells. We suggest HAgLG polymeric micelles as a promising candidate for specific drug targeting.

  19. A concise review of dynamical processes in polymorphic environments of a block copolymer: Rotational diffusion and photoisomerization

    Indian Academy of Sciences (India)

    K S Mali; G B Dutt

    2007-03-01

    This article describes our ongoing efforts to understand dynamical processes such as rotational diffusion and photoisomerization in polymorphic environments of a block copolymer. The objective is to explore how the typical properties of a block copolymer solution such as critical micelle temperature (CMT) and temperature-induced sol-gel transition influence the rotational diffusion of hydrophobic solute molecules. Rotational diffusion of solute molecules differs significantly below and above the CMT of a block copolymer solution, while there is no influence of sol-gel transition on solute rotation. This is rationalized on the basis of the site of solubilization of the solute molecules which is the palisade layer of the micelles in both phases and unaffected by gelation. A similar result has been obtained in case of photoisomerization studies carried out with a carbocyanine derivative in the sol and gel phases of the block copolymer. The isomerization studies have been extended to the reverse phases (sol and gel phases) of the block copolymer to explore the nature of the water present in the cores of the reverse micelles. Our results provide evidence for the existence of water droplets with properties resembling bulk water. In essence, we show that despite having vastly differing bulk properties, both the solution and gel phases (normal as well as reverse) offer identical microscopic environment.

  20. 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 AB 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. PMID:26651715

  1. Self-consistent field predictions for quenched spherical biocompatible triblock copolymer micelle

    NARCIS (Netherlands)

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

    2013-01-01

    We have used the Scheutjens–Fleer self-consistent field (SF-SCF) method to predict the self-assembly of triblock copolymers with a solvophilic middle block and sufficiently long solvophobic outer blocks. We model copolymers consisting of polyethylene oxide (PEO) as the solvophilic block and poly(lac

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

    Indian Academy of Sciences (India)

    R Ganguly; V K Aswal; P A Hassan; I K Gopalakrishnan; J V Yakhmi

    2004-08-01

    A room temperature sphere-to-rod transition of the polyethylene oxide-polypropylene oxide-polyethylene oxide-based triblock copolymer, (PEO)20 (PPO)70 (PEO)20 micelles have been observed in aqueous medium under the influence of ethanol and sodium chloride. Addition of 5-10% ethanol induces a high temperature sphere-to-rod transition of the micelles, which is brought to room temperature upon addition of NaCl. The inference about the change in the shape of the micelles has been drawn from small-angle neutron scattering (SANS) and viscosity studies.

  3. Concentration Dependent Structure of Block Copolymer Solutions

    Science.gov (United States)

    Choi, Soohyung; Bates, Frank S.; Lodge, Timothy P.

    2015-03-01

    Addition of solvent molecules into block copolymer can induce additional interactions between the solvent and both blocks, and therefore expands the range of accessible self-assembled morphologies. In particular, the distribution of solvent molecules plays a key role in determining the microstructure and its characteristic domain spacing. In this study, concentration dependent structures formed by poly(styrene-b-ethylene-alt-propylene) (PS-PEP) solution in squalane are investigated using small-angle X-ray scattering. This reveals that squalane is essentially completely segregated into the PEP domains. In addition, the conformation of the PS block changes from stretched to nearly fully relaxed (i.e., Gaussian conformation) as amounts of squalane increases. NRF

  4. From Block Copolymers to Nano-porous Materials

    DEFF Research Database (Denmark)

    Vigild, Martin Etchells; Ndoni, Sokol; Berg, Rolf Henrik

    2003-01-01

    Quantitative etching of the polydimethylsiloxane block in a series of polystyrene-polydimethylsiloxane (PS-PDMS) block copolymers is reported. Reacting the block copolymer with anhydrous hydrogen fluoride (HF) renders a nanoporous material with the remaining PS maintaining the original morphology...

  5. 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...

  6. Reversible Micro- and Nano- Phase Programming of Anthraquinone Thermochromism Using Blended Block Copolymers.

    Science.gov (United States)

    Zhang, Yumiao; Lovell, Jonathan F

    2015-12-22

    Here, we present an approach to generate materials with programmable thermochromic transition temperatures (TTTs), based on the reversible microcrystallization of anthraquinone dyes with the assistance of blended Pluronic block copolymers. At temperatures above block copolymer critical micellization temperature (CMT), hydrophobic anthraquinone dyes, including Sudan blue II, were dispersed in copolymer micelles, whereas at lower temperature, the dyes formed microcrystals driven by dye-dye and dye-Pluronic molecular interactions. The crystallization process altered the optical properties of the dye with bathochromatic shifts detectable by eye and the thermochromic process was fully reversible. Not only could Pluronic reversibly incorporate the anthraquinone dyes into micelles at elevated temperatures, but it also modulated the crystallization process and resulting morphology of microcrystals via tuning the molecular interactions when the temperature was lowered. Crystal melting transition points (and TTTs) were in agreement with the CMTs, demonstrating that the thermochromism was dependent on block copolymer micellization. Thermochromism could be readily programmed over a broad range of temperatures by changing the CMT by using different types and concentrations of Pluronics and combinations thereof. PMID:26626998

  7. Comparing Fluid and Elastic Block Copolymer Shells

    Science.gov (United States)

    Rozairo, Damith; Croll, Andrew B.

    2014-03-01

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

  8. Preparation and self-assembly behavior of polystyrene-block-poly (dimethylaminoethyl methacrylate amphiphilic block copolymer using atom transfer radical polymerization

    Directory of Open Access Journals (Sweden)

    2008-03-01

    Full Text Available Asymmetric and semi-symmetric amphiphilic diblock copolymers polystyrene-block-poly (dimethylaminoethyl methacrylate (PS-b-PDMAEMA with the same PS block length of 62 repeat units and quite short (3 repeat units or equivalent (47 repeat units length of PDMAEMA have been prepared simply by varying the ratio of the bromine-terminated macroinitiator polystyrene (PS-Br to DMAEMA using atom transfer radical polymerization (ATRP. The chemical structures and compositions of the PS-b-PDMAEMA block copolymers are studied by nuclear magnetic resonance (NMR spectroscopy, gel permeation chromatography (GPC, and elementary analysis (EA. The self-assembly behaviors of copolymers in N,N-dimethyl formamide (DMF with different pH and dioxane/water binary solvent mixture by direct dissolution method (DD, are studied by transmission electron microscopy (TEM, electron diffracting analysis (EDA, and energy-dispersive analysis of X-rays (EDAX techniques. Transmission electron microscopy results suggest that asymmetric block copolymer PS62-b-PDMAEMA3 (the numbers in the form of footnotes represent repeated units of each monomer in the copolymer can form spherical core-shell micelles, large compound reverse micelles (LCRMs, hexagonal/rhombic phases, reverse hexagonal/rhombic phases, vesicles, reverse vesicles and necklace-like reverse micelles, controlled by common or selective solvent and pH, while most of the aggregates of semi-symmetric PS62-b-PDMAEMA47 are simply spherical, such as spherical core-shell micelles and reverse spherical core-shell micelles, besides hexagonal/rhombic phases. All above structures are controlled by three components of the free energy of aggregation: core-chain stretching, interfacial energy and intercoronal chain interaction.

  9. Spherocylindrical coacervate core micelles formed by a supramolecular coordination polymer and a diblock copolymer

    NARCIS (Netherlands)

    Yan, Y.; Harnau, L.; Besseling, N.A.M.; Keizer, de A.; Ballauff, M.; Rosenfeldt, S.; Cohen Stuart, M.A.

    2008-01-01

    We investigated the hierarchical structure of complex coacervate core micelles formed by mixing a supramolecular coordination polymer and a diblock copolymer. Cryogenic transmission electron microscopy (cryo-TEM) on those systems was only possible for very dilute samples and suggested the existence

  10. Organisation and shape of micellar solutions of block-copolymers

    NARCIS (Netherlands)

    Gaspard, J.P.; Creutz, S.; Bouchat, P.; Jerome, R.; Cohen Stuart, M.A.

    1997-01-01

    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 m

  11. Micellar cathodes from self-assembled nitroxide-containing block copolymers in battery electrolytes.

    Science.gov (United States)

    Hauffman, Guillaume; Maguin, Quentin; Bourgeois, Jean-Pierre; Vlad, Alexandru; Gohy, Jean-François

    2014-01-01

    This contribution describes the synthesis of block copolymers containing electrochemically active blocks, their micellization, and finally their use as micellar cathodes in a lithium battery. The self-assembly of the synthesized poly(styrene)-block-poly(2,2,6,6-tetramethylpiperidinyloxy-4-yl methacrylate) (PS-b-PTMA) diblock copolymers is realized in a typical battery electrolyte made of 1 m lithium trifluoromethanesulfonate dissolved in a mixture of ethylene carbonate/diethyl carbonate/dimethyl carbonate(1:1:1, in volume). Dynamic light scattering and atomic force micro-scopy indicate the formation of well-defined spherical micelles with a PS core and a PTMA corona. The electrochemical properties of those micelles are further investigated. Cyclic voltammograms show a reversible redox reaction at 3.6 V (vs Li(+) /Li). The charge/discharge profiles indicate a flat and reversible plateau around 3.6 V (vs Li(+) /Li). Finally, the cycling performances of the micellar cathodes are demonstrated. Such self-assembled block copolymers open new opportunities for nanostructured organic radical batteries. PMID:24127365

  12. Piezoelectric Properties of Non-Polar Block Copolymers

    Energy Technology Data Exchange (ETDEWEB)

    Pester, Christian [RWTH Aachen University; Ruppel, Markus A [ORNL; Schoberth, Heiko [University of Bayreuth; Schmidt, K. [Universitat Bayreuth; Liedel, Clemens [RWTH Aachen University; Van Rijn, Patrick [RWTH Aachen University; Littrell, Ken [ORNL; Schindler, Kerstin [RWTH Aachen University; Hiltl, Stephanie [RWTH Aachen University; Czubak, Thomas [RWTH Aachen University; Mays, Jimmy [ORNL; Urban, Volker S [ORNL; Boker, Alexander [RWTH Aachen University

    2011-01-01

    Piezoelectric properties in non-polar block copolymers are a novelty in the field of electroactive polymers. The piezoelectric susceptibility of poly(styrene-b-isoprene) block copolymer lamellae is found to be up to an order of magnitude higher when compared to classic piezoelectric materials. The electroactive response increases with temperature and is found to be strongest in the disordered phase.

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

    OpenAIRE

    Zhang, Qian

    2007-01-01

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

  14. Electric Field Induced Selective Disordering in Lamellar Block Copolymers

    Energy Technology Data Exchange (ETDEWEB)

    Ruppel, Markus A [ORNL; Pester, Christian W [ORNL; Langner, Karol M [Leiden Institute of Chemistry, Leiden University, The Netherlands; Sevink, Geert [Leiden Institute of Chemistry, Leiden University, The Netherlands; Schoberth, Heiko [University of Bayreuth; Schmidt, Kristin [ORNL; Urban, Volker S [ORNL; Mays, Jimmy [ORNL; Boker, Alexander [RWTH Aachen University

    2013-01-01

    External electric fields align nanostructured block copolymers by either rotation of grains or nucleation and growth depending on how strongly the chemically distinct block copolymer components are segregated. In close vicinity to the orderdisorder transition, theory and simulations suggest a third mechanism: selective disordering. We present a time-resolved small-angle X-ray scattering study that demonstrates how an electric field can indeed selectively disintegrate ill-aligned lamellae in a lyotropic block copolymer solution, while lamellae with interfaces oriented parallel to the applied field prevail. The present study adds an additional mechanism to the experimentally corroborated suite of mechanistic pathways, by which nanostructured block copolymers can align with an electric field. Our results further unveil the benefit of electric field assisted annealing for mitigating orientational disorder and topological defects in block copolymer mesophases, both in close vicinity to the orderdisorder transition and well below it.

  15. Complex coacervate core micelles.

    Science.gov (United States)

    Voets, Ilja K; de Keizer, Arie; Cohen Stuart, Martien A

    2009-01-01

    In this review we present an overview of the literature on the co-assembly of neutral-ionic block, graft, and random copolymers with oppositely charged species in aqueous solution. Oppositely charged species include synthetic (co)polymers of various architectures, biopolymers - such as proteins, enzymes and DNA - multivalent ions, metallic nanoparticles, low molecular weight surfactants, polyelectrolyte block copolymer micelles, metallo-supramolecular polymers, equilibrium polymers, etcetera. The resultant structures are termed complex coacervate core/polyion complex/block ionomer complex/interpolyelectrolyte complex micelles (or vesicles); i.e., in short C3Ms (or C3Vs) and PIC, BIC or IPEC micelles (and vesicles). Formation, structure, dynamics, properties, and function will be discussed. We focus on experimental work; theory and modelling will not be discussed. Recent developments in applications and micelles with heterogeneous coronas are emphasized.

  16. Block copolymer ion gels for gas separation

    Science.gov (United States)

    Gu, Yuanyan; Lodge, Timothy

    2012-02-01

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

  17. Chemoenzymatic Synthesis of Amphiphilic Core-Shell TMP-(PCL-b-PGMA2)3 Star-Block Copolymer.

    Science.gov (United States)

    Wang, Shuwei; Li, Yapeng; Zhang, Xiaonan; Chen, Xuesi; Wang, Jingyuan; Zhang, He-Xin; Yoon, Keun-Byoung

    2015-06-01

    A novel well-defined amphiphilic Core-Shell star-block copolymer was synthesized from trimethylolpropane, ε-caprolactone, and glycidyl methacrylate by a combination of enzymatic ring-opening polymerization and atom transfer radical polymerization. The structure and molecular weight of the macroinitiator and the star-block copolymer were confirmed by means of nuclear magnetic resonance and gel permeation chromatography. The effects of the glycidyl methacrylate sequence length on the hydrodynamic diameter and morphology of the polymer micelles were investigated by dynamic light scattering and transmission electron microscopy, respectively. PMID:26369103

  18. Complexation-tailored morphology of asymmetric block copolymer membranes

    KAUST Repository

    Madhavan, Poornima

    2013-08-14

    Hydrogen-bond formation between polystyrene-b-poly (4-vinylpyridine) (PS-b-P4VP) block copolymer (BCP) and -OH/-COOH functionalized organic molecules was used to tune morphology of asymmetric nanoporous membranes prepared by simultaneous self-assembly and nonsolvent induced phase separation. The morphologies were characterized by field emmision scanning electron microscopy (FESEM) and atomic force microscopy (AFM). Hydrogen bonds were confirmed by infrared (IR), and the results were correlated to rheology characterization. The OH-functionalized organic molecules direct the morphology into hexagonal order. COOH-functionalized molecules led to both lamellar and hexagonal structures. Micelle formation in solutions and their sizes were determined using dynamic light scattering (DLS) measurements and water fluxes of 600-3200 L/m 2·h·bar were obtained. The pore size of the plain BCP membrane was smaller than with additives. The following series of additives led to pores with hexagonal order with increasing pore size: terephthalic acid (COOH-bifunctionalized) < rutin (OH-multifunctionalized) < 9-anthracenemethanol (OH-monofunctionalized) < 3,5-dihydroxybenzyl alcohol (OH-trifunctionalized). © 2013 American Chemical Society.

  19. Heparin-containing block copolymers, Part I: Surface characterization

    NARCIS (Netherlands)

    Vulić, I.; Pijpers, A.P.; Okano, T.; Kim, S.W.; Feijen, J.

    1993-01-01

    Newly synthesized heparin-containing block copolymers, consisting of a hydrophobic block of polystyrene (PS), a hydrophilic spacer-block of poly(ethylene oxide) (PEO) and covalently bound heparin (Hep) as bioactive block, were coated on aluminium, glass, polydimethylsiloxane (PDMS), PS or Biomer sub

  20. 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.

  1. Micellar Self-Assembly of Block Copolymers for Fabrication of Nanostructured Membranes

    KAUST Repository

    Marques, Debora S.

    2013-11-01

    This research work examines the process of block copolymer membrane fabrication by self-assembly combined by non-solvent induced phase separation. Self-assembly takes place from the preparation of the primordial solution until the moment of immersion in a non-solvent bath. These mechanisms are driven thermodynamically but are limited by kinetic factors. It is shown in this work how the ordering of the assembly of micelles is improved by the solution parameters such as solvent quality and concentration of block copolymer. Order transitions are detected, yielding changes in the morphology. The evaporation of the solvents after casting is demonstrated to be essential to reach optimum membrane structure. The non-solvent bath stops the phase separation at an optimum evaporation time.

  2. Preparation of amphiphilic block copolymer containing triazene moieties and fluorescence study

    Indian Academy of Sciences (India)

    Emil C Buruiana; Andreea L Chibac; Violeta Melinte; Tinca Buruiana

    2013-01-01

    The present study describes the synthesis via microwave accelerated reversible additionfragmentation chain transfer (RAFT) polymerization of an amphiphilic block copolymer poly(acrylic acid)-b-poly(dodecylacrylamide-co-1-(phenyl)-3-(2-methacryloyloxyethyl carbamoyloxyethyl)-3-methyltriazene-1) [PAA-b-(PDA-co-PUMA-T)]. The structure and the chemical composition of the block copolymer were confirmed by spectral/thermal analysis. The photoreactivity of the triazene sequences from PAA-b-(PDA-co-PUMA-T) was quantified by UV/vis irradiation in chloroform/dimethylformamide solutions and in thin film, indicating that the solvent polarity modifies with an order of magnitude the rate constant values. The lower rate constant in film state (film = 1.3 × 10−3 s-1), shows that the higher mobility of polymeric chains in solution allow a more rapid orientation, favourable to the triazene bond cleavage. The capability of block copolymer to form micelles in aqueous environment and implicitly, its critical micelle concentration (CMC) was evidenced through fluorescence measurements using pyrene probe (10-6 M), the CMC value being of 4.64 × 10−3 g L-1 PAA--(PDA--PUMA-T) (3.27 × 10−7 M). Experiments of fluorescence quenching with various metal cations (UO$^{2+}_{2}$, Fe2+, Fe3+, Ni2+, Cu2+, Co2+, Pb2+ and Hg2+) suggested that such a block copolymer could find applications as fluorescence-based chemosensor for the detection of iron cations in homogeneous organic solutions or aqueous environments by thin films.

  3. 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...

  4. Functional Block Copolymers via Anionic Polymerization for Electroactive Membranes

    OpenAIRE

    Schultz, Alison

    2013-01-01

           Ion-containing block copolymers blend ionic liquid properties with well-defined polymer architectures. This provides conductive materials with robust mechanical stability, efficient processability, and tunable macromolecular design. Conventional free radical polymerization and anion exchange achieved copolymers containing n-butyl acrylate and phosphonium ionic liquids. These compositions incorporated vinylbenzyl triphenyl phosphonium and vinylbenzyl tricyclohexyl phosphonium cations be...

  5. Stereo block copolymers of L- and D-lactides

    NARCIS (Netherlands)

    Yui, Nobuhiko; Dijkstra, Pieter J.; Feijen, Jan

    1990-01-01

    Sequential diblock copolymers composed of L- and D-lactic acid residues were synthesized through a living ring-opening polymerization of L- and D-lactide initiated by aluminium tris(2-propanolate). The composition of the block copolymers was varied by changing the reaction conditions and monomer ove

  6. Structure of Block Copolymer Hydrogel Formed by Complex Coacervate Process

    Science.gov (United States)

    Choi, Soohyung; Ortony, Julia; Krogstad, Daniel; Spruell, Jason; Lynd, Nathaniel; Han, Songi; Kramer, Edward

    2012-02-01

    Complex coacervation occurs when oppositely charged polyelectrolytes associate in solution, forming dense micron-sized droplets. Hydrogels with coacervate block domains were formed by mixing two ABA and A'BA' triblock copolymer solutions in water where the A and A' blocks are oppositely charged. Small-angle neutron scattering (SANS) was used to investigate the structure of hydrogels formed by ABA triblock copolymers (A block: poly(allyl glycidyl ether) functionalized with guanidinium (A) or sulfonate (A'), B block: poly(ethylene oxide)). By using an appropriate fitting model, structural information such as coacervate core block radius and water volume fraction w can be extracted from SANS data. The results reveal that w in the coacervate core block was significantly higher than in conventional triblock copolymer hydrogels where microphase separation is driven by the hydrophobicity of the core-forming blocks.

  7. Bioreducible unimolecular micelles based on amphiphilic multiarm hyperbranched copolymers for triggered drug release

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    A novel type of bioreducible amphiphilic multiarm hyperbranched copolymer (H40-star-PLA-SS-PEG) based on Boltorn H40 core,poly(L-lactide) (PLA) inner-shell,and poly(ethylene glycol) (PEG) outer-shell with disulfide-linkages between the hydrophobic and hydrophilic moieties was developed as unimolecular micelles for controlled drug release triggered by reduction.The obtained H40-star-PLA-SS-PEG was characterized in detail by nuclear magnetic resonance (NMR),Fourier transform infrared (FTIR),gel permeation chromatography (GPC),differential scanning calorimeter (DSC),and thermal gravimetric analysis (TGA).Transmission electron microscopy (TEM) and dynamic light scattering (DLS) analyses suggested that H40-star-PLA-SS-PEG formed stable unimolecular micelles in aqueous solution with an average diameter of 19 nm.Interestingly,these micelles aggregated into large particles rapidly in response to 10 mM dithiothreitol (DTT),most likely due to shedding of the hydrophilic PEG outer-shell through reductive cleavage of the disulfide bonds.As a hydrophobic anticancer model drug,doxorubicin (DOX) was encapsulated into these reductive unimolecular micelles.In vitro release studies revealed that under the reduction-stimulus,the detachment of PEG outer-shell in DOX-loaded micelles resulted in a rapid drug release.Flow cytometry and confocal laser scanning microscopy (CLSM) measurements indicated that these DOX-loaded micelles were easily internalized by living cells.Methyl tetrazolium (MTT) assay demonstrated a markedly enhanced drug efficacy of DOX-loaded H40-star-PLA-SS-PEG micelles as compared to free DOX.All of these results show that these bioreducible unimolecular micelles are promising carriers for the triggered intracellular delivery of hydrophobic anticancer drugs.

  8. Micelle assembly. Multidimensional hierarchical self-assembly of amphiphilic cylindrical block comicelles.

    Science.gov (United States)

    Qiu, Huibin; Hudson, Zachary M; Winnik, Mitchell A; Manners, Ian

    2015-03-20

    Self-assembly of molecular and block copolymer amphiphiles represents a well-established route to micelles with a wide variety of shapes and gel-like phases. We demonstrate an analogous process, but on a longer length scale, in which amphiphilic P-H-P and H-P-H cylindrical triblock comicelles with hydrophobic (H) or polar (P) segments that are monodisperse in length are able to self-assemble side by side or end to end in nonsolvents for the central or terminal segments, respectively. This allows the formation of cylindrical supermicelles and one-dimensional (1D) or 3D superstructures that persist in both solution and the solid state. These assemblies possess multiple levels of structural hierarchy in combination with existence on a multimicrometer-length scale, features that are generally only found in natural materials. PMID:25792323

  9. Nanopatterned articles produced using surface-reconstructed block copolymer films

    Energy Technology Data Exchange (ETDEWEB)

    Russell, Thomas P.; Park, Soojin; Wang, Jia-Yu; Kim, Bokyung

    2016-06-07

    Nanopatterned surfaces are prepared by a method that includes forming a block copolymer film on a substrate, annealing and surface reconstructing the block copolymer film to create an array of cylindrical voids, depositing a metal on the surface-reconstructed block copolymer film, and heating the metal-coated block copolymer film to redistribute at least some of the metal into the cylindrical voids. When very thin metal layers and low heating temperatures are used, metal nanodots can be formed. When thicker metal layers and higher heating temperatures are used, the resulting metal structure includes nanoring-shaped voids. The nanopatterned surfaces can be transferred to the underlying substrates via etching, or used to prepare nanodot- or nanoring-decorated substrate surfaces.

  10. Synthesis of Amylose-b-P2 VP Block Copolymers.

    Science.gov (United States)

    Kumar, Kamlesh; Woortman, Albert J J; Loos, Katja

    2015-12-01

    A new class of rod-coil block copolymers is synthesized by chemoenzymatic polymerization. In the first step, maltoheptaose, which acts as a primer for the synthesis of amylose, is attached to poly(2-vinyl pyridine) (P2 VP). The enzymatic polymerization of maltoheptaose is carried out by phosphorylase to obtain amylose-b-P2 VP block copolymers. The block copolymer is characterized by Fourier transform infrared spectroscopy, nuclear magnetic resonance, gel permeation chromatography, and wide-angle X-ray scattering techniques. The designed molecules combine the inclusion complexation ability of amylose with the supramolecular complexation ability of P2 VP and therefore this kind of rod-coil block copolymers can be used to generate well-organized novel self-assembled structures. PMID:26437256

  11. New adhesive systems based on functionalized block copolymers

    Energy Technology Data Exchange (ETDEWEB)

    Kent, M.; Saunders, R.; Hurst, M.; Small, J.; Emerson, J.; Zamora, D.

    1997-05-01

    The goal of this work was to evaluate chemically-functionalized block copolymers as adhesion promoters for metal/thermoset resin interfaces. Novel block copolymers were synthesized which contain pendant functional groups reactive toward copper and epoxy resins. In particular, imidazole and triazole functionalities that chelate with copper were incorporated onto one block, while secondary amines were incorporated onto the second block. These copolymers were found to self-assemble from solution onto copper surfaces to form monolayers. The structure of the adsorbed monolayers were studied in detail by neutron reflection and time-of-flight secondary ion mass spectrometry. The monolayer structure was found to vary markedly with the solution conditions and adsorption protocol. Appropriate conditions were found for which the two blocks form separate layers on the surface with the amine functionalized block exposed at the air surface. Adhesion testing of block copolymer-coated copper with epoxy resins was performed in both lap shear and peel modes. Modest enhancements in bond strengths were observed with the block copolymer applied to the native oxide. However, it was discovered that the native oxide is the weak link, and that by simply removing the native oxide, and then applying an epoxy resin before the native oxide can reform, excellent bond strength in the as-prepared state as well as excellent retention of bond strength after exposure to solder in ambient conditions are obtained. It is recommended that long term aging studies be performed with and without the block copolymer. In addition, the functionalized block copolymer method should be evaluated for another system that has inherently poor bonding, such as the nickel/silicone interface, and for systems involving metals and alloys which form oxides very rapidly, such as aluminum and stainless steel, where bonding strategies involve stabilizing the native oxide.

  12. Theory for dynamical self arrest and gelation in microemulsions and the block copolymer systems

    Energy Technology Data Exchange (ETDEWEB)

    Wu, Sangwook [Iowa State Univ., Ames, IA (United States)

    2005-01-01

    The main purpose of this work is to investigate the glassy behavior of microemulsions and block copolymers. The origin of glassy behavior in microemulsions and block copolymers is frustration due to a competition between short-range interaction and long range interaction. According to the charge frustrated Ising model, the competition between ferromagnetic interaction and antiferromagnetic interaction is the origin of frustration in microemulsions. The competition between entropic effects and stoichiometric constraints responsible for the formation of micelles in microemulsions can lead to the emergence of a self generated glassy behavior in these systems. In the block copolymer, the competition between the repulsive short range interaction between monomers in polymer chains and the long range interaction by chemical bonds can lead to the emergence of a self generated glassy behavior. The criteria for the fluctuation induced first order transition and our microemulsion and block copolymer glasses are essentially the same. Both are a consequence of the large phase space of low energy excitations (14) (62) (all states with momenta q which fulfill |q| = qm) and are of at the most a moderate supercooling of the liquid state is required. This is strongly supported by the observation in Ref. (14) that the metastable states which are first to appear at a fluctuation induced first order transition are the ones build by a superposition of large amplitude waves of wavenumber qm, but with random orientations and phases, i.e. just the ones which form the metastable states of our microemulsion and block copolymer glass. (38)

  13. Theory for dynamical self arrest and gelation in microemulsions and the block copolymer systems

    Energy Technology Data Exchange (ETDEWEB)

    Wu, Sangwook

    2005-05-01

    The main purpose of this work is to investigate the glassy behavior of microemulsions and block copolymers. The origin of glassy behavior in microemulsions and block copolymers is frustration due to a competition between short-range interaction and long range interaction. According to the charge frustrated Ising model, the competition between ferromagnetic interaction and antiferromagnetic interaction is the origin of frustration in microemulsions. The competition between entropic effects and stoichiometric constraints responsible for the formation of micelles in microemulsions can lead to the emergence of a self generated glassy behavior in these systems. In the block copolymer, the competition between the repulsive short range interaction between monomers in polymer chains and the long range interaction by chemical bonds can lead to the emergence of a self generated glassy behavior. The criteria for the fluctuation induced first order transition and our microemulsion and block copolymer glasses are essentially the same. Both are a consequence of the large phase space of low energy excitations (14) (62) (all states with momenta q which fulfill |q| = q{sub m}) and are of at the most a moderate supercooling of the liquid state is required. This is strongly supported by the observation in Ref. (14) that the metastable states which are first to appear at a fluctuation induced first order transition are the ones build by a superposition of large amplitude waves of wavenumber q{sub m}, but with random orientations and phases, i.e. just the ones which form the metastable states of our microemulsion and block copolymer glass. (38)

  14. Perpendicularly Aligned, Anion Conducting Nanochannels in Block Copolymer Electrolyte Films

    Energy Technology Data Exchange (ETDEWEB)

    Arges, Christopher G.; Kambe, Yu; Suh, Hyo Seon; Ocola, Leonidas E.; Nealey, Paul F.

    2016-03-08

    Connecting structure and morphology to bulk transport properties, such as ionic conductivity, in nanostructured polymer electrolyte materials is a difficult proposition because of the challenge to precisely and accurately control order and the orientation of the ionic domains in such polymeric films. In this work, poly(styrene-block-2-vinylpyridine) (PSbP2VP) block copolymers were assembled perpendicularly to a substrate surface over large areas through chemical surface modification at the substrate and utilizing a versatile solvent vapor annealing (SVA) technique. After block copolymer assembly, a novel chemical vapor infiltration reaction (CVIR) technique selectively converted the 2-vinylpyridine block to 2-vinyl n-methylpyridinium (NMP+ X-) groups, which are anion charge carriers. The prepared block copolymer electrolytes maintained their orientation and ordered nanostructure upon the selective introduction of ion moieties into the P2VP block and post ion-exchange to other counterion forms (X- = chloride, hydroxide, etc.). The prepared block copolymer electrolyte films demonstrated high chloride ion conductivities, 45 mS cm(-1) at 20 degrees C in deionized water, the highest chloride ion conductivity for anion conducting polymer electrolyte films. Additionally, straight-line lamellae of block copolymer electrolytes were realized using chemoepitaxy and density multiplication. The devised scheme allowed for precise and accurate control of orientation of ionic domains in nanostructured polymer electrolyte films and enables a platform for future studies that examines the relationship between polymer electrolyte structure and ion transport.

  15. Block Copolymers of Ethylene Oxide and Styrene Oxide.New Copolymer Surfactants(Ⅱ)

    Institute of Scientific and Technical Information of China (English)

    Zhuo Yang; David Attwood; Colin Booth

    2003-01-01

    @@ 3.2. Association Number Figure 5 shows the dependence of the weight-average association number (Nw,measured by static light scattering, solution temperature 30 °C) on hydrophobe block length for ES and ESEblock copolymers.

  16. New routes to the synthesis of amylose-block-polystyrene rod-coil block copolymers

    NARCIS (Netherlands)

    Loos, Katja; Müller, Axel H.E.

    2002-01-01

    Hybrid block copolymers amylose-block-polystyrene were synthesized by covalent attachment of maltoheptaose derivatives to end-functionalized polystyrene and subsequent enzymatic grafting from polymerization. The maltoheptaose derivatives were attached by reductive amination or hydrosilation to amino

  17. 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 o

  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. Preparation of shell cross-linked nano-objects from hybrid-peptide block copolymers.

    Science.gov (United States)

    Rodríguez-Hernández, Juan; Babin, Jérôme; Zappone, Bruno; Lecommandoux, Sébastien

    2005-01-01

    Supramolecular structures formed by self-assembly of diblock copolymers in solution are stable over restricted environmental conditions: concentration, temperature, pH, or ion strength among others. To enlarge their domain of application, it appears necessary to develop stabilization strategies. We report here different strategies to stabilize the shell of micelles formed by self-assembly of amphiphilic polydiene-b-polypeptide diblock copolymers. For this purpose, covalent bonds can be formed between either amine or carboxylic acid groups distributed along the soluble peptide block and a cross-linking agent that contains respectively aldehyde or amine functions. Shell stabilization affords systems with unique properties that combine three main advantages: shape persistence, control of the porosity, and stimuli-responsive behavior. The covalent capture of such macromolecular objects has been studied by light scattering, AFM, and conductimetry measurements.

  20. Solubility and self-assembly of amphiphilic gradient and block copolymers in supercritical CO2

    International Nuclear Information System (INIS)

    This work aims at demonstrating the interest of gradient copolymers in supercritical CO2 in comparison with block copolymers. Gradient copolymers exhibit a better solubility in supercritical CO2 than block copolymers, as attested by cloud point data. The self-assembly of gradient and block copolymers in dense CO2 has been characterized by Small-Angle Neutron Scattering (SANS); and it is shown that it is not fundamentally modified when changing from block copolymers to gradient copolymers. Therefore, gradient copolymers are advantageous thanks to their easier synthesis and their solubility at lower pressure while maintaining a good ability for self-organization in dense CO2. (authors)

  1. Block Copolymer Nanocomposites in Electric Fields: Kinetics of Alignment

    Energy Technology Data Exchange (ETDEWEB)

    Liedel, Clemens [RWTH Aachen University; Pester, Christian [RWTH Aachen University; Ruppel, Markus A [ORNL; Lewin, Christian [RWTH Aachen University; Pavan, Mariela J. [Hebrew University of Jerusalem; Urban, Volker S [ORNL; Shenhar, Roy [Hebrew University of Jerusalem; Bosecke, Peter [European Synchrotron Radiation Facility (ESRF); Boker, Alexander [RWTH Aachen University

    2013-01-01

    We investigate the kinetics of block copolymer/nanoparticle composite alignment in an electric field using in situ transmission small-angle X-ray scattering. As a model system, we employ a lamellae forming polystyrene-block-poly(2-vinyl pyridine) block copolymer with different contents of gold nanoparticles in thick films under solvent vapor annealing. While the alignment improves with increasing nanoparticle fraction, the kinetics slows down. This is explained by changes in the degree of phase separation and viscosity. Our findings provide extended insights into the basics of nanocomposite alignment.

  2. Synthesis and characterization of an elastin-mimetic amphiphilic block copolymer protein

    Science.gov (United States)

    Lee, Terrence Anita-Talley

    2000-10-01

    The overall goal in material science is to be able to control the molecular architecture of a material and thus its end properties. There is no method that offers greater control than the biological synthesis of proteins. From the DNA sequence to the final synthesized protein, the entire process is finitely controlled. This present work describes methods developed and used to synthesize protein polymers by manipulating this process. From the initial DNA sequence chosen, the end properties that the protein polymer will have are dictated. An amphiphilic diblock copolymer was designed based on environmentally responsive elastin-mimetic peptide sequences [(Val/Ile)-Pro-Gly-Xaa-Gly] (Xaa = Ala or Glu for the hydrophilic block, Val or Phe for the hydrophobic block) and synthesized using a genetic engineering approach. Differential scanning calorimetry measurements in aqueous solution revealed that reversible hydrophobic folding and assembly of the copolymer occurs above the inverse temperature transition, Tt, of the hydrophobic block. This process results in the formation of 50 nm protein-based micellar aggregates, which were characterized by electron microscopy and temperature-dependent dynamic light scattering techniques. The distribution of micellar aggregates can be altered reproducibly through variation of environmental conditions including pH and temperature. The uniform and defined macromolecular architecture of this protein copolymer permits greater control over the physical properties of the micelles, which therefore may facilitate applications in controlled release of small molecules.

  3. Contrast enhanced diffusion NMR: quantifying impurities in block copolymers for DSA

    Science.gov (United States)

    Wojtecki, Rudy; Porath, Ellie; Vora, Ankit; Nelson, Alshakim; Sanders, Daniel

    2016-03-01

    Block-copolymers (BCPs) offer the potential to meet the demands of next generation lithographic materials as they can self-assemble into scalable and tailorable nanometer scale patterns. In order for these materials to find wide spread adoption many challenges remain, including reproducible thin film morphology, for which the purity of block copolymers is critical. One of the sources of impurities are reaction conditions used to synthesize block copolymers that may result in the formation of homopolymer as a side product, which can impact the quality and the morphology of self-assembled features. Detection and characterization of these homopolymer impurities can be challenging by traditional methods of polymer characterization. We will discuss an alternate NMR-based method for the detection of homopolymer impurities in block copolymers - contrast enhanced diffusion ordered spectroscopy (CEDOSY). This experimental technique measures the diffusion coefficient of polymeric materials in the solution allowing for the `virtual' or spectroscopic separation of BCPs that contain homopolymer impurities. Furthermore, the contrast between the diffusion coefficient of mixtures containing BCPs and homopolymer impurities can be enhanced by taking advantage of the chemical mismatch of the two blocks to effectively increase the size of the BCP (and diffusion coefficient) through the formation of micelles using a cosolvent, while the size and diffusion coefficient of homopolymer impurities remain unchanged. This enables the spectroscopic separation of even small amounts of homopolymer impurities that are similar in size to BCPs. Herein, we present the results using the CEDOSY technique with both first generation BCP system, poly(styrene)-b-poly(methyl methacrylate), as well as a second generation high-χ system.

  4. 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. PMID:27216558

  5. Amphiphilic block copolymers bearing six-membered ortho ester ring in side chains as potential drug carriers: synthesis, characterization, and in vivo toxicity evaluation.

    Science.gov (United States)

    Luo, Shi; Tao, Yangyang; Tang, Rupei; Wang, Rui; Ji, Weihang; Wang, Chun; Zhao, Youliang

    2014-07-01

    A new type of amphiphilic block copolymers, poly(ethylene glycol)-block-poly(2-methyl-acrylicacid 2-methoxy-5-methyl-[1,3]dioxin-5-ylmethyl ester) (PEG-b-PMME), bearing acid-labile six-membered ortho ester rings in side chains was synthesized by reversible addition-fragmentation chain-transfer polymerization, and the influence of chain length of the hydrophobic PMME block on micelle properties was investigated. The PEG-b-PMME micelles were stable in aqueous buffer at physiological pH with a low critical micelle concentration. Nile Red as a model drug was encapsulated into the micelles to explore the release profiles. The Nile Red-loaded polymeric micelles showed rapid release of Nile Red in weakly acidic environments (pH 5) but slow release under physiological condition (pH 7.4), due to different hydrolysis rate of ortho ester side chains of PEG-b-PMME. The Paclitaxel (PTX)-loaded micelles retained potency in killing lung cancer cells (A549), compared with the free PTX. No obvious toxicity was found in vitro and in vivo after intraperitoneal injection of the micelles, which confirms that the PEG-b-PMME micelles with unique acid-labile characteristic have great potential as nano-scaled carriers for drug delivery.

  6. LEDs based on conjugated PPV block copolymers

    NARCIS (Netherlands)

    Brouwer, H.J.; Hilberer, A.; Krasnikov, V.V.; Werts, M.; Wildeman, J.; Hadziioannou, G.

    1997-01-01

    A way to control the bandgap in semi-conducting polymers is by preparing polymers with a partially conjugated backbone. In our laboratory, three conjugated copolymers containing PPV trimers as light emitting chromophores have been synthesized, which emit in the blue, green and orange wavelength regi

  7. 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.

  8. Biodegradable amphiphilic block copolymers containing functionalized PEO blocks:Controlled synthesis and biomedical potentials

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    A series of controllable amphiphilic block copolymers composed of poly(ethylene oxide)(PEO) as the hydrophilic block and poly(ε-caprolactone)(PCL) as the hydrophobic block with the amino terminal group at the end of the PEO chain(PCL-b-PEO-NH2) were synthesized.Based on the further reaction of reactive amino groups,diblock copolymers with functional carboxyl groups(PCL-b-PEO-COOH) and functional compounds RGD(PCL-b-PEO-RGD) as well as the triblock copolymers with thermosensitive PNIPAAm blocks(PCL-b-PEO-b-PNIPAAM) were synthesized.The well-controlled structures of these copolymers with functional groups and blocks were characterized by gel permeation chromatography(GPC) and 1H NMR spectroscopy.These copolymers with functionalized hydrophilic blocks were fabricated into microspheres for the examination of biofunctions via cell culture experiments and in vitro drug release.The results indicated the significance of introducing functional groups(e.g.,NH2,COOH and RGD) into the end of the hydrophilic block of amphiphilic block copolymers for biomedical potentials in tissue engineering and controlled drug release.

  9. Novel block, graft and random copolymers for biomedical applications

    DEFF Research Database (Denmark)

    Javakhishvili, Irakli; Jankova Atanasova, Katja; Tanaka, Masaru;

    roles for this [2]. An artificial lung (oxygenator), already in use, is coated with high MW PMEA prepared by radical polymerization with AIBN [2]. To broaden the possibilities for designing biomedical devices [3] and inspired from these findings we first prepared homo polymers of MEA and their block...... 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....

  10. Synthesis of Amphiphilic Block Copolymers for Use in Biomedical Applications

    OpenAIRE

    Carmichael-Baranauskas, Anita Yvonne

    2010-01-01

    The research presented in this thesis focuses on the synthesis of three amphiphilic block copolymer systems containing poly(ethylene oxide) (PEO) blocks. The polymer systems were developed for use in biomedical applications. The first of these is a series of poly(ethylene oxide-b¬-oxazoline) (PEO-b-POX) diblock copolymers for use in the progress towards novel non-viral gene transfer vectors. Poly(ethylene oxide-b¬-2-ethyl-2-oxazoline) (PEO-b-PEOX) and poly(ethylene oxide-b¬-2-methyl-2-o...

  11. PEG-detachable and acid-labile cross-linked micelles based on orthoester linked graft copolymer for paclitaxel release

    Energy Technology Data Exchange (ETDEWEB)

    Yuan Zhefan; Huang Jingyi; Liu Jing; Cheng Sixue; Zhuo Renxi; Li Feng, E-mail: lfsj2004@hotmail.com [Key Laboratory of Biomedical Polymers of Ministry of Education, College of Chemistry and Molecular Science, Wuhan University, Wuhan, 430072 (China)

    2011-08-19

    Polyethylene glycol detachable graft copolymer, mPEG-g-p(NAS-co-BMA), was synthesized by grafting 2-({omega}-methoxy)PEGyl-1,3-dioxan-5-ylamine onto poly(N-(acryloyloxy)succinimide-co-butyl methacrylate). Pseudo in situ cross-linking of the mPEG-g-p(NAS-co-BMA) was performed in dimethylformamide phosphate buffer (v/v = 1/1) by an acid-labile diamine cross-linker bearing two symmetrical cyclic orthoesters. The cross-linked (CL) micelles with different contents of mPEG segments represented different morphologies. The CL micelles containing approximately one mPEG segment exhibited 'echini' morphology whereas the CL micelle with approximately three mPEG segments formed nanowires. The hydrolysis rate of the CL micelles is highly pH-dependent and much more rapid at mild acid than physiological conditions. Hydrolyzates of the CL micelles formed vesicles because new amphiphilic copolymers were formed. Paclitaxel (PTX) was successfully loaded into the CL micelles and a controlled and pH-dependent release behavior was observed. No obvious cytotoxicity was found for the CL micelles at concentration as high as 800 mg l{sup -1}.

  12. PEG-detachable and acid-labile cross-linked micelles based on orthoester linked graft copolymer for paclitaxel release

    Science.gov (United States)

    Yuan, Zhefan; Huang, Jingyi; Liu, Jing; Cheng, Sixue; Zhuo, Renxi; Li, Feng

    2011-08-01

    Polyethylene glycol detachable graft copolymer, mPEG-g-p(NAS-co-BMA), was synthesized by grafting 2-(ω-methoxy)PEGyl-1,3-dioxan-5-ylamine onto poly(N-(acryloyloxy)succinimide-co-butyl methacrylate). Pseudo in situ cross-linking of the mPEG-g-p(NAS-co-BMA) was performed in dimethylformamide phosphate buffer (v/v = 1/1) by an acid-labile diamine cross-linker bearing two symmetrical cyclic orthoesters. The cross-linked (CL) micelles with different contents of mPEG segments represented different morphologies. The CL micelles containing approximately one mPEG segment exhibited 'echini' morphology whereas the CL micelle with approximately three mPEG segments formed nanowires. The hydrolysis rate of the CL micelles is highly pH-dependent and much more rapid at mild acid than physiological conditions. Hydrolyzates of the CL micelles formed vesicles because new amphiphilic copolymers were formed. Paclitaxel (PTX) was successfully loaded into the CL micelles and a controlled and pH-dependent release behavior was observed. No obvious cytotoxicity was found for the CL micelles at concentration as high as 800 mg l - 1.

  13. Block and Graft Copolymers of Polyhydroxyalkanoates

    Science.gov (United States)

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

    2004-03-01

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

  14. Self-Assembly of Amphiphilic Block Copolypeptoids – Micelles, Worms and Polymersomes

    Science.gov (United States)

    Fetsch, Corinna; Gaitzsch, Jens; Messager, Lea; Battaglia, Giuseppe; Luxenhofer, Robert

    2016-01-01

    Polypeptoids are an old but recently rediscovered polymer class with interesting synthetic, physico-chemical and biological characteristics. Here, we introduce new aromatic monomers, N-benzyl glycine N-carboxyanhydride and N-phenethyl glycine N-carboxyanhydride and their block copolymers with the hydrophilic polysarcosine. We compare their self-assembly in water and aqueous buffer with the self-assembly of amphiphilic block copolypeptoids with aliphatic side chains. The aggregates in water were investigated by dynamic light scattering and electron microscopy. We found a variety of morphologies, which were influenced by the polymer structure as well as by the preparation method. Overall, we found polymersomes, worm-like micelles and oligo-lamellar morphologies as well as some less defined aggregates of interconnected worms and vesicles. Such, this contribution may serve as a starting point for a more detailed investigation of the self-assembly behavior of the rich class of polypeptoids and for a better understanding between the differences in the aggregation behavior of non-uniform polypeptoids and uniform peptoids. PMID:27666081

  15. Synergistic dual-pH responsive copolymer micelles for pH-dependent drug release

    Science.gov (United States)

    Deng, Hongzhang; Zhao, Xuefei; Liu, Jinjian; Zhang, Jianhua; Deng, Liandong; Liu, Jianfeng; Dong, Anjie

    2016-01-01

    The tuning of the structure of nanocarriers with fast acidic-degradation rate and high stability in physiological conditions or during storage is under intensive study. In this context, a kind of dual-pH responsive micelles with well-balanced stability, that is, fast hydrolysis in acidic environment and stability towards blood drug release at 7.4 were developed. This is achieved by the self-assembly of micelles of poly(ethylene glycol)-b-(poly ε-caprolactone-g-poly(2,2-dimethyl-1,3-dioxolane-4-yl)methylacrylate-co-2(dimethylamino)ethyl methacrylate) (mPEG-b-(PCL-g-P(DA-co-DMAEMA))) copolymers with two inert pH responsive moieties of DA and DMAEMA. The fast synergistic acid-triggered disassembly and high stability at physiological condition of the mPEG-b-(PCL-g-P(DA-co-DMAEMA)) micelles was verified by 1H NMR, particle size and optical stability measurements, which was induced and mediated by the synergistic pH responses of the hydrolysis of the ketal in DA moieties and the switch in solubility of tertiary amino moieties (DMAEMA) under mild acid conditions. It was observed that the hydrolysis rate of the ketal could be promoted by increasing the content of DMAEMA moieties. The fast intracellular disassembly of the micelles depending on the contents of DMAEMA moieties was also traced by fluorescence resonance energy transfer (FRET). The in vitro release studies showed that the release of DOX from mPEG-b-(PCL-g-P(DA-co-DMAEMA)) micelles at mild acid condition was significantly accelerated by increasing the content of DMAEMA moieties, while greatly impeding drug release in physiological conditions. The antitumor activity of DOX-loaded micelles was studied in MCF-7 and 4T1 cells in vitro and in 4T1 tumor-bearing Balb-c mice in vivo. The results indicated the DOX-loaded micelles with higher content of DMAEMA moieties exhibited enhanced anticancer activity. Collectively, the synergistic dual-pH responsive design of mPEG-b-(PCL-g-P(DA-co-DMAEMA)) micelles provided a new

  16. STRUCTURE OF CRYSTALLINE DOMAINS IN SEMICRYSTALLINE BLOCK COPOLYMER THIN FILMS

    Institute of Scientific and Technical Information of China (English)

    Guo-dong Liang; Jun-ting Xu; Zhi-qiang Fan

    2006-01-01

    Thin film morphology of a symmetric semicrystalline oxyethylene/oxybutylene diblock copolymer (E76B38) on silicon was investigated by tapping mode atomic force microscopy (AFM). It is found that the nascent thin film is composed of multiple polymer layers having mixed thicknesses of L ≈ L0 and L ≈ L0/2 (L0 is the long period of the block copolymer in bulk) besides the first layer near the substrate. This shows that the crystalline domain in the block copolymer consists of double poly(oxyethylene) layers. Annealing leads to disappearance of the polymer layers with thickness L ≈ L0/2, indicating that such polymer layers are metastable.

  17. Synthesis of biodegradable amphiphilic Y-shaped block co-polymers via ring-opening polymerization for drug delivery.

    Science.gov (United States)

    Jia, Lin; Yan, Lifeng; Li, Yang

    2011-01-01

    A series of novel Y-shaped biodegradable block co-polymers of poly(ε-caprolactone) (PCL) and poly(ethyl ethylene phosphate) (PEEP) (PCL-(PEEP)2) were synthesized via ring-opening polymerization (ROP) of EEP with bis-hydroxy-functional ROP initiator (init-PCL-(OH)2). The init-PCL-(OH)2 was synthesized by ROP of CL using 4-hydroxybutyl acrylate (HBA) as initiator and L-tartaric acid as catalyst in bulk, and subsequently the resulting vinyl-terminated PCL was end-capped by acetyl chloride, followed by Michael addition using excess diethanolamine. The Y-shaped co-polymers and their intermediates were characterized by (1)H-, (13)C-, (31)P-NMR, FT-IR and gel-permeation chromatography. The results indicated that the molecular weight of the Y-shaped co-polymers increased with the increasing of the molar ratios of EEP to init-PCL-(OH)2 in the feed, while the PCL chain length was kept constant. The amphiphilic block co-polymers could self-assemble into micelles in aqueous solution, which was demonstrated by dynamic light scattering, (1)H-NMR and atomic force microscopy. A study of controlled release of indomethacin indicated that the amphiphilic block co-polymers could potentially provide novel vehicles for drug delivery.

  18. Stability of ordered phases in block copolymer melts and solutions

    Indian Academy of Sciences (India)

    Kell Mortensen

    2008-11-01

    Block copolymer melts and solutions assemble into nanosized objects that order into a variety of phases, depending on molecular parameters and mutual interactions. Beyond the classical phases of lamella ordered sheets, hexagonally ordered cylinders and cubic ordered spheres, the complex bicontinuous gyroid phase and the modulated lamellar phase are observed near the phase boundaries. The stability of these phases has been discussed on the basis of theoretical calculations. Here, we will discuss new experimental results showing that the given ordered phase depends critically on both molecular purity and mechanical treatment of the sample. While a variety of block copolymer micellar systems have been shown to undergo the liquid-to-bcc-to-fcc phase sequence upon varying micellar parameters (or temperature), we find for a purified system a different sequence, namely liquid-to-fcc-to-bcc [1]. The latter sequence is by the way the one predicted for pure block copolymer melts. External fields like shear or stress may also affect the ordered phase. Applying well-controlled large-amplitude oscillatory shear can be used to effectively control the texture of soft materials in the ordered states. As an example, we present results on a body-centred-cubic phase of a block copolymer system, showing how a given texture can be controlled with the application of specific shear rate and shear amplitude [2,3]. Shear may however also affect the thermodynamic ground state, causing shear-induced ordering and disordering (melting), and shear-induced order–order transitions. We will present data showing that the gyroid state of diblock copolymer melts is unstable when exposed to large amplitude/frequency shear, transforming into the hexagonal cylinder phase [4]. The transformation is completely reversible. With the rather slow kinetics in the transformation of copolymer systems, it is possible in detail to follow the complex transformation process, where we find transient ordered

  19. Segmented block copolymers with polyesteramide blocks of uniform length: synthesis

    NARCIS (Netherlands)

    Gaymans, R.J.; Haan, de J.L.

    1993-01-01

    Segmented copolymers were synthesized from poly(tetramethylene oxide) with hydroxy end-groups or aliphatic diols and a short-chain diester diamide with a uniform length. The diester diamide (N,N'-bis(p-carbomethoxybenzoyl)butanediamine) (Tm = 257°C) used is made from butanediamine and an excess of d

  20. Low molecular weight block copolymers as plasticizers for polystyrene

    DEFF Research Database (Denmark)

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

    2005-01-01

    Polystyrene-b-alkyl, polystyrene-b-polybutadiene-b-polystyrene, and polystyrene-b-poly(propylene glycol)monotridecyl ether were synthesized using macro initiators and atom transfer radical polymerization or by esterifications of homopolymers. The aim was a maximum molecular weight of 4 kg....../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...

  1. Solubilization of docetaxel in poly(ethylene oxide)-block-poly(butylene/styrene oxide) micelles.

    Science.gov (United States)

    Elsabahy, Mahmoud; Perron, Marie-Eve; Bertrand, Nicolas; Yu, Ga-Er; Leroux, Jean-Christophe

    2007-07-01

    Poly(ethylene oxide)-block-poly(styrene oxide) (PEO-b-PSO) and PEO-b-poly(butylene oxide) (PEO-b-PBO) of different chain lengths were synthesized and characterized for their self-assembling properties in water by dynamic/static light scattering, spectrofluorimetry, and transmission electron microscopy. The resulting polymeric micelles were evaluated for their ability to solubilize and protect the anticancer drug docetaxel (DCTX) from degradation. The drug release kinetics as well as the cytotoxicity of the loaded micelles were assessed in vitro. All polymers formed micelles with a highly viscous core at low critical association concentrations (<10 mg/L). Micelle morphology depended on the nature of the hydrophobic block, with PBO- and PSO-based micelles yielding monodisperse spherical and cylindrical nanosized aggregates, respectively. The maximum solubilization capacity for DCTX ranged from 0.7 to 4.2% and was the highest for PSO micelles exhibiting the longest hydrophobic segment. Despite their high affinity for DCTX, PEO-b-PSO micelles were not able to efficiently protect DCTX against hydrolysis under accelerated stability testing conditions. Only PEO-b-PBO bearing 24 BO units afforded significant protection against degradation. In vitro, DCTX was released slower from the latter micelles, but all formulations possessed a similar cytotoxic effect against PC-3 prostate cancer cells. These data suggest that PEO-b-P(SO/BO) micelles could be used as alternatives to conventional surfactants for the solubilization of taxanes. PMID:17579476

  2. Reversible Tuning of a Block Copolymer Nanostructure via Electric Fields

    Energy Technology Data Exchange (ETDEWEB)

    Schmidt, K. [Universitat Bayreuth; Schoberth, Heiko [University of Bayreuth; Ruppel, Markus A. [Universitat Bayreuth; Zettl, H [University of Bayreuth; Weiss, Thomas [European Synchrotron Radiation Facility (ESRF); Urban, Volker S [ORNL; Krausch, G [University of Bayreuth; Boker, A. [Universitat Bayreuth

    2007-01-01

    Block copolymers consisting of incompatible components self-assemble into microphase-separated domains yielding highly regular structures with characteristic length scales of the order of several tens of nanometres. Therefore, in the past decades, block copolymers have gained considerable potential for nanotechnological applications, such as in nanostructured networks and membranes, nanoparticle templates and high-density data storage media. However, the characteristic size of the resulting structures is usually determined by molecular parameters of the constituent polymer molecules and cannot easily be adjusted on demand. Here, we show that electric d.c. fields can be used to tune the characteristic spacing of a block-copolymer nanostructure with high accuracy by as much as 6% in a fully reversible way on a timescale in the range of several milliseconds. We discuss the influence of various physical parameters on the tuning process and study the time response of the nanostructure to the applied field. A tentative explanation of the observed effect is given on the basis of anisotropic polarizabilities and permanent dipole moments of the monomeric constituents. This electric-field-induced effect further enhances the high technological potential of block-copolymer-based soft-lithography applications.

  3. Complexes of block copolymers in solution: tree approximation

    NARCIS (Netherlands)

    Geurts, Bernard J.; Damme, van Ruud

    1989-01-01

    We determine the statistical properties of block copolymer complexes in solution. These complexes are assumed to have the topological structure of (i) a tree or of (ii) a line-dressed tree. In case the structure is that of a tree, the system is shown to undergo a gelation transition at sufficiently

  4. 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.

  5. Novel multiarm star block copolymer ionomers as proton conductive membranes

    OpenAIRE

    Demirel, Adem Levent; Erdoğan, Tuba; Bilir, Çiğdem; Ünveren, Elif; Tunca, Ümit

    2014-01-01

    A series of well-defined novel multiarm star block copolymer ionomers with an average of 6, 11 and 15 arms, sulfonated polystyrene-block-poly(2,2,3,3,3-pentafluoropropyl methacrylate) (SPS-b-PFPMA), were prepared via a combination of atom transfer radical polymerization (ATRP), Diels–Alder click reaction and postsulfonation reaction. First, multiarm star polymer with anthracene functionality as reactive periphery groups was prepared by a cross-linking reaction of divinyl benzene using ?-anthr...

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

    DEFF Research Database (Denmark)

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

    With the aim of creating tough nanocomposits (NC) [1] based on polypropylene (PP) and nanoclay (NCl) in the framework of the 7th EU program NANOTOUGH we have designed amphiphilic block copolymers utilizing Atom Transfer Radical Polymerization (ATRP) [2]. They consist of a hydrophobic block...... 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....

  7. Interaction between Albumin and Pluronic F127 Block Copolymer Revealed by Global and Local Physicochemical Profiling.

    Science.gov (United States)

    Neacsu, Maria Victoria; Matei, Iulia; Micutz, Marin; Staicu, Teodora; Precupas, Aurica; Popa, Vlad Tudor; Salifoglou, Athanasios; Ionita, Gabriela

    2016-05-12

    The interaction of human serum albumin (HSA) with amphiphilic block copolymer Pluronic F127 has been investigated by several physical methods. Interest in studying this system stems from a broad range of bioactivities involving both macromolecules. Serum albumins constitute a significant class of proteins in the circulatory system, acting as carriers for a wide spectrum of compounds or assemblies. Pluronic block copolymers have revealed their capacity to ferry a variety of biologically active compounds. Circular dichroism, rheological measurements, and differential scanning microcalorimetry (μDSC) were employed to get insight into the interaction betweeen the two macromolecules. The results reveal that Pluronic F127 induces conformational changes to albumin if it is organized in a micellar form, while albumin influences the self-assembly of Pluronic F127 into micelles or gels. F127 micelles, however, induce smaller conformational changes compared to ionic surfactants. The μDSC thermograms obtained for HSA and/or F127 show that HSA shifts the critical micellar temperature (cmt) to lower values, while concurrently the HSA denaturation behavior is influenced by F127, depending on its concentration. Rheological measurements on solutions of F127 17% have shown that a sol-to-gel transition occurs at higher temperatures in the presence of HSA and the resulting gel is weaker. The global profile on HSA/F127 systems was complemented by local information provided by EPR measurements. A series of X-band EPR experiments was performed with spin probes 4-(N,N'-dimethyl-N-hexadecyl)ammonium-2,2',6,6'-tetramethylpiperidine-1-oxyl iodide (CAT16) and 5-doxyl stearic acid (5-DSA). These spin probes bind to albumin sites and are sensitive to phase transformations in Pluronic block copolymer solutions. For a given F127 concentration, the spin probe binds only to HSA below cmt and migrates to the F127 micelles above cmt. The collective data suggest soft interactions between the

  8. Nanostructured Amphiphilic Star-Hyperbranched Block Copolymers for Drug Delivery.

    Science.gov (United States)

    Seleci, Muharrem; Seleci, Didem Ag; Ciftci, Mustafa; Demirkol, Dilek Odaci; Stahl, Frank; Timur, Suna; Scheper, Thomas; Yagci, Yusuf

    2015-04-21

    A robust drug delivery system based on nanosized amphiphilic star-hyperbranched block copolymer, namely, poly(methyl methacrylate-block-poly(hydroxylethyl methacrylate) (PMMA-b-PHEMA) is described. PMMA-b-PHEMA was prepared by sequential visible light induced self-condensing vinyl polymerization (SCVP) and conventional vinyl polymerization. All of the synthesis and characterization details of the conjugates are reported. To accomplish tumor cell targeting property, initially cell-targeting (arginylglycylaspactic acid; RGD) and penetrating peptides (Cys-TAT) were binding to each other via the well-known EDC/NHS chemistry. Then, the resulting peptide was further incorporated to the surface of the amphiphilic hyperbranched copolymer via a coupling reaction between the thiol (-SH) group of the peptide and the hydroxyl group of copolymer by using N-(p-maleinimidophenyl) isocyanate as a heterolinker. The drug release property and targeting effect of the anticancer drug (doxorobucin; DOX) loaded nanostructures to two different cell lines were evaluated in vitro. U87 and MCF-7 were chosen as integrin αvβ3 receptor positive and negative cells for the comparison of the targeting efficiency, respectively. The data showed that drug-loaded copolymers exhibited enhanced cell inhibition toward U87 cells in compared to MCF-7 cells because targeting increased the cytotoxicity of drug-loaded copolymers against integrin αvβ3 receptor expressing tumor cells. PMID:25816726

  9. 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.

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

    Science.gov (United States)

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

    2016-05-18

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

  11. A shear stabilized biaxial texture in a lamellar block copolymer

    Energy Technology Data Exchange (ETDEWEB)

    Polis, D.L.; Pinheiro, B.S.; Winey, K.I.; Lakis, R.E. [Univ. of Pennsylvania, Philadelphia, PA (United States)

    1996-12-31

    Block copolymers spontaneously self-assemble into a variety of morphologies. Recent studies have produced a biaxial texture in poly(styrene-b-ethylene propylene), SEP, diblock copolymers by applying oscillatory shear. This biaxial texture consists of {open_quotes}parallel{close_quotes} lamellae (normal to lamellae aligned perpendicular to shearing surfaces) and {open_quotes}transverse{close_quotes} lamellae (normal to lamellae aligned parallel to shearing direction) according to small-angle X-ray scattering, SAXS. The present study has determined how these two populations of lamellae are arranged and how they relax upon quiescent annealing by examining the superstructure via FE-SEM.

  12. Stereo block copolymers of L- and D-lactides

    OpenAIRE

    Yui, Nobuhiko; Pieter J. Dijkstra; Feijen, Jan

    1990-01-01

    Sequential diblock copolymers composed of L- and D-lactic acid residues were synthesized through a living ring-opening polymerization of L- and D-lactide initiated by aluminium tris(2-propanolate). The composition of the block copolymers was varied by changing the reaction conditions and monomer over initiator ratio and confirmed by 1H NMR analysis, molecular weight determination and optical rotation measurements. Molecular weights ranged from 1,3 to 2,0 · 104 with 1,2 < Mw/Mn < 1,4. Stereoco...

  13. Block copolymer-nanoparticle hybrid self-assembly

    KAUST Repository

    Hoheisel, Tobias N.

    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.

  14. PEG-b-PCL copolymer micelles with the ability of pH-controlled negative-to-positive charge reversal for intracellular delivery of doxorubicin.

    Science.gov (United States)

    Deng, Hongzhang; Liu, Jinjian; Zhao, Xuefei; Zhang, Yuming; Liu, Jianfeng; Xu, Shuxin; Deng, Liandong; Dong, Anjie; Zhang, Jianhua

    2014-11-10

    The application of PEG-b-PCL micelles was dampened by their inherent low drug-loading capability and relatively poor cell uptake efficiency. In this study, a series of novel PEG-b-PCL copolymers methoxy poly(ethylene glycol)-b-poly(ε-caprolactone-co-γ-dimethyl maleamidic acid -ε-caprolactone) (mPEG-b-P(CL-co-DCL)) bearing different amounts of acid-labile β-carboxylic amides on the polyester moiety were synthesized. The chain structure and chemical composition of copolymers were characterized by (1)H NMR, Fourier transform infrared spectroscopy (FT-IR), and gel permeation chromatography (GPC). mPEG-b-P(CL-co-DCL) with critical micellar concentrations (CMCs) of 3.2-6.3 μg/mL could self-assemble into stable micelles in water with diameters of 100 to 150 nm. Doxorubicin (DOX), a cationic hydrophobic drug, was successfully encapsulated into the polymer micelles, achieving a very high loading content due to electrostatic interaction. Then the stability, charge-conversional behavior, loading and release profiles, cellular uptake and in vitro cytotoxicity of free drug and drug-loaded micelles were evaluated. The β-carboxylic amides functionalized polymer micelles are negatively charged and stable in neutral solution but quickly become positively charged at pH 6.0, due to the hydrolysis of β-carboxylic amides in acidic conditions. The pH-triggered negative-to-positive charge reversal not only resulted in a very fast drug release in acidic conditions, but also effectively enhanced the cellular uptake by electrostatic absorptive endocytosis. The MTT assay demonstrated that mPEG-b-P(CL-co-DCL) micelles were biocompatible to HepG2 cells while DOX-loaded micelles showed significant cytotoxicity. In sum, the introduction of acid-labile β-carboxylic amides on the polyester block in mPEG-b-P(CL-co-DCL) exhibited great potentials for the modifications in the stability in blood circulation, drug solubilization, and release properties, as well as cell internalization and

  15. Methotrexate-Loaded Four-Arm Star Amphiphilic Block Copolymer Elicits CD8+ T Cell Response against a Highly Aggressive and Metastatic Experimental Lymphoma.

    Science.gov (United States)

    Hira, Sumit Kumar; Ramesh, Kalyan; Gupta, Uttam; Mitra, Kheyanath; Misra, Nira; Ray, Biswajit; Manna, Partha Pratim

    2015-09-16

    We have synthesized a well-defined four-arm star amphiphilic block copolymer [poly(DLLA)-b-poly(NVP)]4 [star-(PDLLA-b-PNVP)4] that consists of D,L-lactide (DLLA) and N-vinylpyrrolidone (NVP) via the combination of ring-opening polymerization (ROP) and xanthate-mediated reversible addition-fragmentation chain transfer (RAFT) polymerization. Synthesis of the polymer was verified by 1H NMR spectroscopy and gel permeation chromatography (GPC). The amphiphilic four-arm star block copolymer forms spherical micelles in water as demonstrated by transmission electron microscopy (TEM) and 1H NMR spectroscopy. Pyrene acts as a probe to ascertain the critical micellar concentration (cmc) by using fluorescence spectroscopy. Methotrexate (MTX)-loaded polymeric micelles of star-(PDLLA15-b-PNVP10)4 amphiphilic block copolymer were prepared and characterized by fluorescence and TEM studies. Star-(PDLLA15-b-PNVP10)4 copolymer was found to be significantly effective with respect to inhibition of proliferation and lysis of human and murine lymphoma cells. The amphiphilic block copolymer causes cell death in parental and MTX-resistant Dalton lymphoma (DL) and Raji cells. The formulation does not cause hemolysis in red blood cells and is tolerant to lymphocytes compared to free MTX. Therapy with MTX-loaded star-(PDLLA15-b-PNVP10)4 amphiphilic block copolymer micelles prolongs the life span of animals with neoplasia by reducing the tumor load, preventing metastasis and augmenting CD8+ T cell-mediated adaptive immune responses. PMID:26323031

  16. Design and Application of Nanoscale Actuators Using Block-Copolymers

    Directory of Open Access Journals (Sweden)

    Paul D. Topham

    2010-10-01

    Full Text Available Block copolymers are versatile designer macromolecules where a “bottom-up” approach can be used to create tailored materials with unique properties. These simple building blocks allow us to create actuators that convert energy from a variety of sources (such as chemical, electrical and heat into mechanical energy. In this review we will discuss the advantages and potential pitfalls of using block copolymers to create actuators, putting emphasis on the ways in which these materials can be synthesised and processed. Particular attention will be given to the theoretical background of microphase separation and how the phase diagram can be used during the design process of actuators. Different types of actuation will be discussed throughout.

  17. Gas Permeation through Polystyrene-Poly(ethylene oxide) Block Copolymers

    Science.gov (United States)

    Hallinan, Daniel, Jr.; Minelli, Matteo; Giacinti-Baschetti, Marco; Balsara, Nitash

    2013-03-01

    Lithium air batteries are a potential technology for affordable energy storage. They consist of a lithium metal anode and a porous air cathode separated by a solid polymer electrolyte membrane, such as PEO/LiTFSI (PEO = poly(ethylene oxide), LiTFSI = lithium bis-trifluoromethane sulfonimide). For extended operation of such a battery, the polymer electrolyte must conduct lithium ions while blocking electrons and gases present in air. In order to maintain a pressure difference the membrane must be mechanically robust, which can be achieved by incorporating the PEO into a block copolymer with a glassy block such as PS (PS = polystyrene). To protect the lithium electrode, the membrane must have low permeability to gases in air such as CO2, N2, and O2. We have therefore studied the permeation of pure gases through a PS-PEO block copolymer. A high molecular weight, symmetric block copolymer with a lamellar morphology was used to cast free-standing membranes. Gas permeability was measured through these membranes with a standard, pressure-based technique. A model was developed to account for transport through the polymer membrane consisting of semi-crystalline PEO lamellae and amorphous PS lamellae. PEO crystallinity was extracted from the permeation model and compares well with values from differential scanning calorimetry measurements.

  18. The micellization and dissociation transitions of thermo-, pH- and sugar-sensitive block copolymer investigated by laser light scattering

    Directory of Open Access Journals (Sweden)

    Y. C. Tang

    2012-08-01

    Full Text Available A triple-stimuli responsive polymer, poly(3-acrylamidophenylboronic acid-b-poly(N-isopropylacrylamide (PAAPBA-b-PNIPAM, has been synthesized by reversible addition-fragmentation chain transfer polymerization. Temperature, pH, and fructose induced micellization and dissociation transition of block copolymer was investigated by a combination of static and dynamic laser light scattering. PAAPBA-b-PNIPAM copolymer self-assembles into micelles with PAAPBA block as core and PNIPAM as shell in lower pH aqueous solution at room temperature. Increasing the temperature causes the micelle to shrink due to the dehydration of PNIPAM segments at pH 6.2. After the elevation of solution pH from 6.2 to 10.0, the increase in the hydrophilicity of PAAPBA block leads to an expulsion of unimers from micelles. In addition, the fructose addition further enhances the dissociation of micelles. Our experiments demonstrate that the micelle to unimer transition process proceeds via the step-by-step sequential expulsion of individual chains.

  19. Thermal Analysis, Structural Studies and Morphology of Spider Silk-like Block Copolymers

    Science.gov (United States)

    Huang, Wenwen

    both the bound water removal induced conformational change and the hydrophobicity of the protein sequences, while the high temperature glass transition, Tg( 2), above 130 °C is the now dry protein glass transition. Real-time Fourier transform infrared spectroscopy (FTIR) confirmed that conformational change occurred during the two glass transition, with a random coils to beta turns transition during Tg(1) and alpha helices to beta turns transition during Tg( 2). Due to the hydrophobic and hydrophilic nature of the blocks, the spider silk block copolymers tend to self-assemble into various microstructures. To study the morphological features, the spider silk-like block copolymers were treated with hexafluoroisopropanol or methanol, or subjected to thermal treatment. Using scanning electron microscopies, micelles were observed in thermally treated films. Fibrillar networks and hollow vesicles were observed in methanol-cast samples, while no micro-structures were formed in HFIP-cast films, indicating that morphology and crystallinity can be tuned by thermal treatments. Results indicate when we increase the number of repeating unit of A-block in the protein, sample films crystallize more easily and are more thermally stable. Moreover, when samples crystallize, the secondary structure of A-block and B-block become different, thus it will be easier to form bilayer structures which could fold into vesicles or tube structures during drying.

  20. Synthesis and interactions with blood of polyetherurethaneurea/polypeptide block copolymers.

    Science.gov (United States)

    Ito, Y; Miyashita, K; Kashiwagi, T; Imanishi, Y

    1993-01-01

    Polyurethane/polypeptide block copolymers were synthesized. Infrared spectroscopy and differential scanning calorimetry revealed that in the block copolymers both segments undergo phase-mixing, while in polyurethane/polypeptide blend both components undergo phase-separation. Contact angle measurement showed that in the block copolymers polyurethane segments tended to appear on the membrane surface, whereas in polyurethane/polypeptide blend polypeptide components appeared on the membrane surface. In vitro nonthrombogenicity of the block copolymers was similar to that of homopolymers or polymer blends, though adhesion and deformation of platelets were suppressed on the block copolymer membranes. PMID:8260582

  1. Block copolymer hollow fiber membranes with catalytic activity and pH-response

    KAUST Repository

    Hilke, Roland

    2013-08-14

    We fabricated block copolymer hollow fiber membranes with self-assembled, shell-side, uniform pore structures. The fibers in these membranes combined pores able to respond to pH and acting as chemical gates that opened above pH 4, and catalytic activity, achieved by the incorporation of gold nanoparticles. We used a dry/wet spinning process to produce the asymmetric hollow fibers and determined the conditions under which the hollow fibers were optimized to create the desired pore morphology and the necessary mechanical stability. To induce ordered micelle assembly in the doped solution, we identified an ideal solvent mixture as confirmed by small-angle X-ray scattering. We then reduced p-nitrophenol with a gold-loaded fiber to confirm the catalytic performance of the membranes. © 2013 American Chemical Society.

  2. Biomimetic block copolymer particles with gated nanopores and ultrahigh protein sorption capacity

    KAUST Repository

    Yu, Haizhou

    2014-06-17

    The design of micro-or nanoparticles that can encapsulate sensitive molecules such as drugs, hormones, proteins or peptides is of increasing importance for applications in biotechnology and medicine. Examples are micelles, liposomes and vesicles. 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 particles have monodispersed nanopores that can act as pH-responsive gates. They contain a highly porous internal structure, which is analogous to the Schwarz P structure. The internal porosity of the particles contributes to their high sorption capacity and sustained release behaviour. We successfully separated similarly sized proteins using these particles. The ease of particle fabrication by macrophase separation and self-assembly, and the robustness of the particles makes them ideal for sorption, separation, transport and sustained delivery of pharmaceutical substances. © 2014 Macmillan Publishers Limited.

  3. Crystallization induced block copolymer assembly at curved liquid-liquid interface

    Science.gov (United States)

    Qi, Hao; Zhou, Tian; Zhou, Hao; Li, Christopher; Soft Materials Lab Team

    In a selected solvent, amphiphilic block copolymers can self-assemble into various micelle structures which find widespread applications in nanomedicine. Herein we report a directed assembly of poly (l-lactide acid)-b-poly (ethylene glycol) (PLLA-b-PEG) at curved oil/water interfaces. Oil droplets were dispersed in water phase upon sonication with amphiphilic PLLA-b-PEG as the surfactant. Subsequent crystallization of PLLA segments resulted in the formation of lamellasomes consisting of crystalline PLLA shell and densely-grafted (approx.1chain/nm2) PEG layer. The structure, morphology, and mechanical properties of these unique polymer ensembles were investigated using transmission electron microscopy and atomic force microscopy. Detailed formation mechanism will be discussed in detail.

  4. Adsorption of polyelectrolytes and charged block copolymers on oxides. Consequences for colloidal stability.

    OpenAIRE

    Hoogeveen, N.G.

    1996-01-01

    The aim of the study described in this thesis was to examine the adsorption properties of polyelectrolytes and charged block copolymers on oxides, and the effect of these polymers on the colloidal stability of oxidic dispersions. For this purpose the interaction of some well-characterised polyelectrolytes and block copolymers with oxidic substrates has been systematically studied. A set of block copolymers with one charged block and one neutral water-soluble block had to be synthesised becaus...

  5. Dissipative Particle Dynamics Study on Aggregation of MPEG- PAE-PLA Block Polymer Micelles Loading Doxorubicine

    Institute of Scientific and Technical Information of China (English)

    杨楚芬; 孙尧; 章莉娟; 朱国典; 张灿阳; 钱宇

    2012-01-01

    To guide the molecular design of the pH-sensitive triblock amphiphilic polymer MPEG-PAE-PLA and the for- mula design of its doxorubicine (DOX)-loaded micelles, dissipative particle dynamics (DPD) simulations are em- ployed to investigate the aggregation behaviors of the DOX-loaded micelles. The simulation results showed that the aggregate morphologies of micelles and DOX distribution are influenced by degree of polymerization of blocks, and the proposed structure of polymer is MPEG44-PAE3-PLA4. With different contents of polymer or DOX, differ- ent aggregate morphologies of the micelles, like microsphere, spindle/column, reticulation or lamella are observed. To prepare the micro-spherical DOX-loaded micelles, the polymer content is proposed as 10%--15%, and the DOX content less than 10%.

  6. Synthesis and self-assembly behavior of amphiphilic diblock copolymer dextran-block-poly(ε-caprolactone (DEX-b-PCL in aqueous media

    Directory of Open Access Journals (Sweden)

    2010-10-01

    Full Text Available An amphiphilic diblock copolymer, dextran-block-poly(ε-caprolactone (DEX-b-PCL, with a series of welldefined chain lengths of each block was prepared by conjugating a dextran chain with a PCL block via aza-Michael addition reaction under mild conditions. For the dextran block, samples with relatively uniform molecular weight, 3.5 and 6.0 kDa, were used, and the PCL blocks were prepared via ring-opening polymerization at defined ratios of ε-caprolactone to initiator in order to give copolymers with mass fraction of dextran (fDEX ranging from 0.16 to 0.45. When these copolymers were allowed to self-assemble in aqueous solution, the morphology of assembled aggregates varied as a function of fDEX when characterized by transmission electron microscope (TEM, fluorescence microscope (FM and dynamic laser scattering (DLS. As fDEX decreases gradually from 0.45 to 0.16, the morphology of the copolymer assembly changes from spherical micelles to worm-like micelles and eventually to polymersomes, together with an increase in particle sizes.

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

    International Nuclear Information System (INIS)

    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.

  8. Aqueous Self-Assembly of Non-Ionic Bottlebrush Block Copolymer Surfactants with Tunable Molecular Shapes

    Science.gov (United States)

    Rzayev, Javid

    2015-03-01

    Polymer amphiphiles provide a robust and versatile platform for the fabrication of nanostructured soft matter. In this research, we explore a new class of polymer surfactants based on comb-like bottlebrush architecture as highly tunable molecular building blocks for aqueous self-assembly. Excluded volume interactions between densely grafted polymer side chains in the bottlebrush architecture are alleviated by backbone stretching, which leads to the formation of shape-persistent cylindrical macromolecules whose molecular dimensions can be precisely tailored during chemical synthesis. Amphiphilic bottlebrush block copolymers containing hydrophobic polylactide (PLA) and hydrophilic poly(oligoethylene oxide methacrylate) (PEO) side chains of various lengths were synthesized by a combination of controlled radical and ring-opening polymerizations. In dilute aqueous solutions, bottlebrush surfactants rapidly assembled into spherical, cylindrical and bilayer aggregates, as visualized by cryogenic transmission electron microscopy (cryo-TEM). Depending on the compositional side chain asymmetry, the formation of spherical micelles with different sizes and dispersities was observed. The molecular shape-dependent assembly was analyzed with help of a packing parameter (p) computed from the molecular composition data akin to small molecule surfactants, with most uniform spherical aggregates observed for bottlebrush amphiphiles with p close to 0.3. The formation of highly uniform micelles and the presence of a rich morphological diagram with relatively narrow compositional windows were attributed to the lack of conformational freedom in bottlebrush surfactants. Similarly, the unusual formation of cylindrical micelles with long aspect ratios for such high molecular weight amphiphiles was attributed to their inability to stabilize morphological defects, such as Y-junctions, with large deviations from mean curvature. Financial support for this work was provided by the National

  9. Conformation and structural changes of diblock copolymers with octopus-like micelle formation in the presence of external stimuli

    Science.gov (United States)

    Dammertz, K.; Saier, A. M.; Marti, O.; Amirkhani, M.

    2014-04-01

    External stimuli such as vapours and electric fields can be used to manipulate the formation of AB-diblock copolymers on surfaces. We study the conformational variation of PS-b-PMMA (polystyrene-block-poly(methyl methacrylate)), PS and PMMA adsorbed on mica and their response to saturated water or chloroform atmospheres. Using specimens with only partial polymer coverage, new unanticipated effects were observed. Water vapour, a non-solvent for all three polymers, was found to cause high surface mobility. In contrast, chloroform vapour (a solvent for all three polymers) proved to be less efficient. Furthermore, the influence of an additional applied electric field was investigated. A dc field oriented parallel to the sample surface induces the formation of polymer islands which assemble into wormlike chains. Moreover, PS-b-PMMA forms octopus-like micelles (OLMs) on mica. Under the external stimuli mentioned above, the wormlike formations of OLMs are able to align in the direction of the external electric field. In the absence of an electric field, the OLMs disaggregate and exhibit phase separated structures under chloroform vapour.

  10. Beyond Orientation: The Impact of Electric Fields on Block Copolymers

    Energy Technology Data Exchange (ETDEWEB)

    Liedel, Clemens [RWTH Aachen University; Boker, A. [Universitat Bayreuth; Pester, Christian [RWTH Aachen University; Ruppel, Markus A [ORNL; Urban, Volker S [ORNL

    2012-01-01

    Since the first report on electric field-induced alignment of block copolymers (BCPs) in 1991, electric fields have been shown not only to direct the orientation of BCP nanostructures in bulk, solution, and thin films, but also to reversibly induce order-order transitions, affect the order-disorder transition temperature, and control morphologies' dimensions with nanometer precision. Theoretical and experimental results of the past years in this very interesting field of research are summarized and future perspectives are outlined.

  11. Transient instability upon temperature quench in weakly ordered block copolymers

    OpenAIRE

    Qi, Shuyan; Wang, Zhen-Gang

    1999-01-01

    We report a novel transient instability upon temperature quench in weakly ordered block copolymer microphases possessing a soft direction or directions, such as the lamellar and hexagonal cylinder (HEX) phases. We show that reequilibration of the order parameter is accompanied by transient long wavelength undulation of the layers or cylinders—with an initial wavelength that depends on the depth of the temperature quench—that eventually disappears as the structure reaches its equilibrium at th...

  12. Host-Guest Self-assembly in Block Copolymer Blends

    OpenAIRE

    Woon Ik Park; YongJoo Kim; Jae Won Jeong; Kyungho Kim; Jung-Keun Yoo; Yoon Hyung Hur; Jong Min Kim; Thomas, Edwin L.; Alfredo Alexander-Katz; Yeon Sik Jung

    2013-01-01

    Ultrafine, uniform nanostructures with excellent functionalities can be formed by self-assembly of block copolymer (BCP) thin films. However, extension of their geometric variability is not straightforward due to their limited thin film morphologies. Here, we report that unusual and spontaneous positioning between host and guest BCP microdomains, even in the absence of H-bond linkages, can create hybridized morphologies that cannot be formed from a neat BCP. Our self-consistent field theory (...

  13. Grafted block complex coacervate core micelles and their effect on protein adsorption on silica and polystyrene.

    Science.gov (United States)

    Brzozowska, Agata M; de Keizer, Arie; Norde, Willem; Detrembleur, Christophe; Cohen Stuart, Martien A

    2010-07-01

    We have studied the formation and the stability of grafted block complex coacervate core micelles (C3Ms) in solution and the influence of grafted block C3M coatings on the adsorption of the proteins beta-lactoglobulin, bovine serum albumin, and lysozyme. The C3Ms consist of a grafted block copolymer PAA(21)-b-PAPEO(14) (poly(acrylic acid)-b-poly(acrylate methoxy poly(ethylene oxide)), with a negatively charged PAA block and a neutral PAPEO block and a positively charged homopolymer P2MVPI (poly(N-methyl 2-vinyl pyridinium iodide). In solution, these C3Ms partly disintegrate at salt concentrations between 50 and 100 mM NaCl. Adsorption of C3Ms and proteins has been studied with fixed-angle optical reflectometry, at salt concentrations ranging from 1 to 100 mM NaCl. In comparison with the adsorption of PAA(21)-b-PAPEO(14) alone adsorption of C3Ms significantly increases the amount of PAA(21)-b-PAPEO(14) on the surface. This results in a higher surface density of PEO chains. The stability of the C3M coatings and their influence on protein adsorption are determined by the composition and the stability of the C3Ms in solution. A C3M-PAPEO(14)/P2MVPI(43) coating strongly suppresses the adsorption of all proteins on silica and polystyrene. The reduction of protein adsorption is the highest at 100 mM NaCl (>90%). The adsorbed C3M-PAPEO(14)/P2MVPI(43) layer is partly removed from the surface upon exposure to an excess of beta-lactoglobulin solution, due to formation of soluble aggregates consisting of beta-lactoglobulin and P2MVPI(43). In contrast, C3M-PAPEO(14)/P2MVPI(228) which has a fivefold longer cationic block enhances adsorption of the negatively charged proteins on both surfaces at salt concentrations above 1 mM NaCl. A single PAA(21)-b-PAPEO(14) layer causes only a moderate reduction of protein adsorption.

  14. 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.

  15. Electrically Tunable Soft-Solid Block Copolymer Structural Color.

    Science.gov (United States)

    Park, Tae Joon; Hwang, Sun Kak; Park, Sungmin; Cho, Sung Hwan; Park, Tae Hyun; Jeong, Beomjin; Kang, Han Sol; Ryu, Du Yeol; Huh, June; Thomas, Edwin L; Park, Cheolmin

    2015-12-22

    One-dimensional photonic crystals based on the periodic stacking of two different dielectric layers have been widely studied, but the fabrication of mechanically flexible polymer structural color (SC) films, with electro-active color switching, remains challenging. Here, we demonstrate free-standing electric field tunable ionic liquid (IL) swollen block copolymer (BCP) films. Placement of a polymer/ionic liquid film-reservoir adjacent to a self-assembled poly(styrene-block-quaternized 2-vinylpyridine) (PS-b-QP2VP) copolymer SC film allowed the development of red (R), green (G), and blue (B) full-color SC block copolymer films by swelling of the QP2VP domains by the ionic liquid associated with water molecules. The IL-polymer/BCP SC film is mechanically flexible with excellent color stability over several days at ambient conditions. The selective swelling of the QP2VP domains could be controlled by both the ratio of the IL to a polymer in the gel-like IL reservoir layer and by an applied voltage in the range of -3 to +6 V using a metal/IL reservoir/SC film/IL reservoir/metal capacitor type device. PMID:26505787

  16. 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.

  17. The self-assembly of copolymers with one hydrophobic and one polyelectrolyte block in aqueous media: a dissipative particle dynamics study.

    Science.gov (United States)

    Lísal, Martin; Limpouchová, Zuzana; Procházka, Karel

    2016-06-28

    The reversible self-assembly of symmetrical block copolymers consisting of one hydrophobic block and one ionizable polyelectrolyte block of the same length has been studied in aqueous solutions by dissipative particle dynamics simulations. In addition to three standard dissipative particle dynamics forces (conservative soft repulsion, dissipative and stochastic forces), explicit interaction between smeared charges on ions and on ionized polymer beads described by the electrostatic potential with appropriately localized charges was taken into account. The self-assembly and properties of formed core-shell micelles were investigated as functions of the degree of ionization for systems differing in the hydrophobicity of the non-ionized polyelectrolyte block and in the compatibility of the polymer blocks. This study shows that micelles undergo massive dissociation with increasing degree of ionization. The simulation data compare well with the predictions of scaling theories for systems with soluble polyelectrolytes on a semi-quantitative level and broaden the knowledge of systems in poor solvents. PMID:27254381

  18. Metal Nanoparticle/Block Copolymer Composite Assembly and Disassembly

    OpenAIRE

    Li, Zihui; Sai, Hiroaki; Warren, Scott C.; Kamperman, Marleen; Arora, Hitesh; Gruner, Sol M.; Wiesner, Ulrich

    2009-01-01

    Ligand-stabilized platinum nanoparticles (Pt NPs) were self-assembled with poly(isoprene-block-dimethylaminoethyl methacrylate) (PI-b-PDMAEMA) block copolymers to generate organic-inorganic hybrid materials. High loadings of NPs in hybrids were achieved through usage of N,N-di-(2-(allyloxy)ethyl)-N-3-mercaptopropyl-N-3-methylammonium chloride as the ligand, which provided high solubility of NPs in various solvents as well as high affinity to PDMAEMA. From NP synthesis, existence of sub-1 nm P...

  19. 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.

  20. 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.

  1. 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. PMID:25393374

  2. Tacticity-induced changes in the micellization and degradation properties of poly(lactic acid)-block-poly(ethylene glycol) copolymers.

    Science.gov (United States)

    Agatemor, Christian; Shaver, Michael P

    2013-03-11

    Poly(lactic acid)-block-poly(ethylene glycol) copolymers (PLA-b-PEG) featuring varying tacticities (atactic, heterotactic, isotactic) in the PLA block were synthesized and investigated for their micellar stability, degradation, and thermal properties. Utilizing tin(II) bis(2-ethylhexanoate), aluminum salan, and aluminum salen catalysts, the copolymers were synthesized through the ring-opening polymerization of d-, l-, rac-, or a blend of l- and rac-lactide using monomethoxy-poly(ethylene glycol) as a macroinitiator. The critical micelle concentration, which reflects the micellar stability, was probed using a fluorescence spectroscopic method with pyrene as the probe. The copolymers were degraded in a methanolic solution of 1,5,7-triaza-bicyclo[4.4.0]dec-5-ene and the degradation was measured by (1)H NMR spectroscopic and gel permeation chromatographic analyses. Differential scanning calorimetry and thermogravimetric analysis provided information on the thermal properties of the copolymers. Atactic and heterotactic microstructures in the PLA block resulted in lower micellar stability, as well as faster degradation and shorter erosion time compared to polymers with high isotactic enchainment (Pm). By modification of the Pm, micellar stability, degradation, and erosion rates of the copolymers can be tuned to specific biomedical applications. Interestingly, while tin(II) bis(2-ethylhexanoate) and aluminum salan-catalyzed PLA-b-PEG copolymers exhibited similar micellization behavior, the aluminum salen-catalyzed PLA-b-PEG exhibited unique behavior at high micelle concentration in the presence of the pyrene probe. This unique behavior can be attributed to the disintegration of the micelles through the interactions of long isotactic stereoblock segments. PMID:23402292

  3. Block copolymers for alkaline fuel cell membrane materials

    Science.gov (United States)

    Li, Yifan

    Alkaline fuel cells (AFCs) using anion exchange membranes (AEMs) as electrolyte have recently received considerable attention. AFCs offer some advantages over proton exchange membrane fuel cells, including the potential of non-noble metal (e.g. nickel, silver) catalyst on the cathode, which can dramatically lower the fuel cell cost. The main drawback of traditional AFCs is the use of liquid electrolyte (e.g. aqueous potassium hydroxide), which can result in the formation of carbonate precipitates by reaction with carbon dioxide. AEMs with tethered cations can overcome the precipitates formed in traditional AFCs. Our current research focuses on developing different polymer systems (blend, block, grafted, and crosslinked polymers) in order to understand alkaline fuel cell membrane in many aspects and design optimized anion exchange membranes with better alkaline stability, mechanical integrity and ionic conductivity. A number of distinct materials have been produced and characterized. A polymer blend system comprised of poly(vinylbenzyl chloride)-b-polystyrene (PVBC-b-PS) diblock copolymer, prepared by nitroxide mediated polymerization (NMP), with poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) or brominated PPO was studied for conversion into a blend membrane for AEM. The formation of a miscible blend matrix improved mechanical properties while maintaining high ionic conductivity through formation of phase separated ionic domains. Using anionic polymerization, a polyethylene based block copolymer was designed where the polyethylene-based block copolymer formed bicontinuous morphological structures to enhance the hydroxide conductivity (up to 94 mS/cm at 80 °C) while excellent mechanical properties (strain up to 205%) of the polyethylene block copolymer membrane was observed. A polymer system was designed and characterized with monomethoxy polyethylene glycol (mPEG) as a hydrophilic polymer grafted through substitution of pendent benzyl chloride groups of a PVBC

  4. Biodegradable PELA block copolymers: in vitro degradation and tissue reaction.

    Science.gov (United States)

    Younes, H; Nataf, P R; Cohn, D; Appelbaum, Y J; Pizov, G; Uretzky, G

    1988-01-01

    Degradation of, and tissue reaction elicited by a series of polyethylene oxide (PEO)/polylactic acid (PLA) PELA block copolymers were studied in vitro and in vivo. In particular, the effect of pH, temperature and enzymatic activity was addressed. The mass loss was faster, the more basic the media, while, expectedly, PELA copolymers degraded faster with the higher temperature. The addition of an enzyme (carboxylic ester hydrolase) had no effect. The degradation process strongly affected the mechanical properties of the materials under investigation, the elongation at break dropping drastically after two days of degradation. After seven days, only gross observation of the extensively degraded samples was possible. The in vivo studies compared the tissue reaction elicited by various PELA copolymers to that evoked by PLA. Evaluation of tissue reaction observed with a PELA sample after sterilization with gamma radiation showed acute inflammation with considerable dispersion of the material, 12 days after implantation. The granulomatous reaction observed with PELA copolymers after ethylene oxide sterilization was identical to the reaction observed with PLA. PMID:3064826

  5. Design and characterization of multicompartment micelles in aqueous solution

    OpenAIRE

    Kubowicz, Stephan

    2005-01-01

    Self-assembly of polymeric building blocks is a powerful tool for the design of novel materials and structures that combine different properties and may respond to external stimuli. In the past decades, most studies were focused on the self-assembly of amphiphilic diblock copolymers in solution. The dissolution of these block copolymers in a solvent selective for one block results mostly in the formation of micelles. The micellar structure of diblock copolymers is inherently limited to a homo...

  6. NaCl-triggered self-assembly of hydrophilic poloxamine block copolymers.

    Science.gov (United States)

    Bahadur, Anita; Cabana-Montenegro, Sonia; Aswal, Vinod Kumar; Lage, Emilio V; Sandez-Macho, Isabel; Concheiro, Angel; Alvarez-Lorenzo, Carmen; Bahadur, Pratap

    2015-10-15

    Tetronic 1307 (T1307) is a hydrophilic poloxamine (HLB>24) with a high molecular mass owing to its long PEO and PPO blocks. In spite of good biocompatibility, its use as a component of drug delivery systems is limited by its high critical micelle concentration (CMC) and temperature (CMT). The aim of this work was to elucidate whether the addition of NaCl or the combination of salts and temperature may bring T1307 micellization and gelling features into more practically useful values. Increasing NaCl concentration in the 0.154 M (isotonic) to 2M (hypertonic) range made the copolymer more hydrophobic and more prone to self-assemble into unimodal micelles, as observed by means of π-A isotherms, (1)H NMR, dynamic light scattering (DLS), small-angle neutron scattering (SANS), and pyrene fluorescence. The decrease in CMC and CMT observed for T1307 in 0.5 M NaCl medium (tolerable hypertonic solution), compared to water, notably favored the solubility of hydrophobic drugs such as curcumin and quercetin. Moreover, phase diagram, intrinsic viscosity and sol-to-gel transition were markedly affected by NaCl concentration. Overall, the strong dependence of T1307 self-assembly features on NaCl opens interesting possibilities for tuning the performance of T1307 as a component of nanocarriers and in situ gelling systems. PMID:26315124

  7. Terminal groups control self-assembly of amphiphilic block copolymers in solution

    Science.gov (United States)

    Grzelakowski, M.; Kita-Tokarczyk, K.

    2016-03-01

    The terminal groups of amphiphilic block copolymers are shown to control macromolecular self-assembly in aqueous solutions, in the micellar/lamellar region of the phase diagram. At the same concentration and using the same self-assembly conditions, dramatic differences are observed in polymer hydration and the resulting nano-/microstructure for two series of polymers with identical block chemistry and hydrophilic-lipophilic balance (HLB). This suggests a strong contribution from end groups to the hydration as the initial step of the self-assembly process, and could be conveniently used to guide the particle morphology and size. Additionally, for polymers with those head groups which drive vesicular structures, differences in membrane organization affect their physical properties, such as permeability.The terminal groups of amphiphilic block copolymers are shown to control macromolecular self-assembly in aqueous solutions, in the micellar/lamellar region of the phase diagram. At the same concentration and using the same self-assembly conditions, dramatic differences are observed in polymer hydration and the resulting nano-/microstructure for two series of polymers with identical block chemistry and hydrophilic-lipophilic balance (HLB). This suggests a strong contribution from end groups to the hydration as the initial step of the self-assembly process, and could be conveniently used to guide the particle morphology and size. Additionally, for polymers with those head groups which drive vesicular structures, differences in membrane organization affect their physical properties, such as permeability. Electronic supplementary information (ESI) available: Fig. S1: Particle diameters for hydrated NH2-ABA-NH2 polymers with different degrees of functionalization; Fig. S2: TEM characterization of compound micelles from BA-OH polymer after extrusion; Fig. S3: Cryo-TEM and stopped flow characterization of lipid vesicles; Fig. S4 and S5: NMR spectra for ABA and BA polymers

  8. Morphology and Proton Transport in Humidified Phosphonated Peptoid Block Copolymers

    Science.gov (United States)

    2016-01-01

    Polymers that conduct protons in the hydrated state are of crucial importance in a wide variety of clean energy applications such as hydrogen fuel cells and artificial photosynthesis. Phosphonated and sulfonated polymers are known to conduct protons at low water content. In this paper, we report on the synthesis phosphonated peptoid diblock copolymers, poly-N-(2-ethyl)hexylglycine-block-poly-N-phosphonomethylglycine (pNeh-b-pNpm), with volume fractions of pNpm (ϕNpm) values ranging from 0.13 to 0.44 and dispersity (Đ) ≤ 1.0003. The morphologies of the dry block copolypeptoids were determined by transmission electron microscopy and in both the dry and hydrated states by synchrotron small-angle X-ray scattering. Dry samples with ϕNpm > 0.13 exhibited a lamellar morphology. Upon hydration, the lowest molecular weight sample transitioned to a hexagonally packed cylinder morphology, while the others maintained their dry morphologies. Water uptake of all of the ordered samples was 8.1 ± 1.1 water molecules per phosphonate group. In spite of this, the proton conductivity of the ordered pNeh-b-pNpm copolymers ranged from 0.002 to 0.008 S/cm. We demonstrate that proton conductivity is maximized in high molecular weight, symmetric pNeh-b-pNpm copolymers. PMID:27134312

  9. Metal Nanoparticle/Block Copolymer Composite Assembly and Disassembly.

    Science.gov (United States)

    Li, Zihui; Sai, Hiroaki; Warren, Scott C; Kamperman, Marleen; Arora, Hitesh; Gruner, Sol M; Wiesner, Ulrich

    2009-01-01

    Ligand-stabilized platinum nanoparticles (Pt NPs) were self-assembled with poly(isoprene-block-dimethylaminoethyl methacrylate) (PI-b-PDMAEMA) block copolymers to generate organic-inorganic hybrid materials. High loadings of NPs in hybrids were achieved through usage of N,N-di-(2-(allyloxy)ethyl)-N-3-mercaptopropyl-N-3-methylammonium chloride as the ligand, which provided high solubility of NPs in various solvents as well as high affinity to PDMAEMA. From NP synthesis, existence of sub-1 nm Pt NPs was confirmed by high-angle annular dark field scanning transmission electron microscopy (HAADF-STEM) images. Estimations of the Pt NP ligand head group density based on HAADF-STEM images and thermogravimetric analysis (TGA) data yielded results comparable to what has been found for alkanethiol self-assembled monolayers (SAMs) on flat Pt {111} surfaces. Changing the volume fraction of Pt NPs in block copolymer-NP composites yielded hybrids with spherical micellar, wormlike micellar, lamellar and inverse hexagonal morphologies. Disassembly of hybrids with spherical, wormlike micellar, and lamellar morphologies generated isolated metal-NP based nano-spheres, cylinders and sheets, respectively. Results suggest the existence of powerful design criteria for the formation of metal-based nanostructures from designer blocked macromolecules.

  10. Metal Nanoparticle/Block Copolymer Composite Assembly and Disassembly.

    Science.gov (United States)

    Li, Zihui; Sai, Hiroaki; Warren, Scott C; Kamperman, Marleen; Arora, Hitesh; Gruner, Sol M; Wiesner, Ulrich

    2009-01-01

    Ligand-stabilized platinum nanoparticles (Pt NPs) were self-assembled with poly(isoprene-block-dimethylaminoethyl methacrylate) (PI-b-PDMAEMA) block copolymers to generate organic-inorganic hybrid materials. High loadings of NPs in hybrids were achieved through usage of N,N-di-(2-(allyloxy)ethyl)-N-3-mercaptopropyl-N-3-methylammonium chloride as the ligand, which provided high solubility of NPs in various solvents as well as high affinity to PDMAEMA. From NP synthesis, existence of sub-1 nm Pt NPs was confirmed by high-angle annular dark field scanning transmission electron microscopy (HAADF-STEM) images. Estimations of the Pt NP ligand head group density based on HAADF-STEM images and thermogravimetric analysis (TGA) data yielded results comparable to what has been found for alkanethiol self-assembled monolayers (SAMs) on flat Pt {111} surfaces. Changing the volume fraction of Pt NPs in block copolymer-NP composites yielded hybrids with spherical micellar, wormlike micellar, lamellar and inverse hexagonal morphologies. Disassembly of hybrids with spherical, wormlike micellar, and lamellar morphologies generated isolated metal-NP based nano-spheres, cylinders and sheets, respectively. Results suggest the existence of powerful design criteria for the formation of metal-based nanostructures from designer blocked macromolecules. PMID:21103025

  11. The effect of PEO block lengths on the size and stability of complex coacervate core micelles.

    Science.gov (United States)

    Adams, Dave J; Rogers, Sue H; Schuetz, Peter

    2008-06-15

    We report on a series of polyion complexes from mixtures of poly(ethylene oxide)-block-poly(N,N-diethylaminoethylmethacrylate) (PEO-PDEAMA) and poly(ethylene oxide)-block-poly(aspartic acid) (PEO-PAsp). As expected, the micelle size, polydispersity and stability are dependant on the relative and absolute lengths of the polyelectrolyte chains. However, we also demonstrate that whilst the length of the charged polyelectrolyte blocks is important, the length of the PEO chains is an equally relevant variable in determining both the size and stability of the final micelles as well as the degree of charge neutralisation at which micellisation occurs. We also show that the kinetics of formation can result in very different stability of the final micelles.

  12. Complex self-assembly of reverse poly(butylene oxide)-poly(ethylene oxide)-poly(butylene oxide) triblock copolymers with long hydrophobic and extremely lengthy hydrophilic blocks.

    Science.gov (United States)

    Cambón, Adriana; Figueroa-Ochoa, Edgar; Juárez, Josué; Villar-Álvarez, Eva; Pardo, Alberto; Barbosa, Silvia; Soltero, J F Armando; Taboada, Pablo; Mosquera, Víctor

    2014-05-15

    Amphiphilic block copolymers have emerged during last years as a fascinating substrate material to develop micellar nanocontainers able to solubilize, protect, transport, and release under external or internal stimuli different classes of cargos to diseased cells or tissues. However, this class of materials can also induce biologically relevant actions, which complement the therapeutic activity of their cargo molecules through their mutual interactions with biologically relevant entities (cellular membranes, proteins, organelles...); these interactions at the same time, are regulated by the nature, conformation, and state of the copolymeric chains. For these reasons, in this paper we investigated the self-assembly process and physico-chemcial properties of two reverse triblock poly(butylene oxide)-poly(ethylene oxide)-poly(butylene oxide) block copolymers, BO14EO378BO14 and BO21EO385BO21, which have been recently found to be very useful as drug delivery nanovehicles and biological response modifiers under certain conditions (A. Cambón et al. Int. J. Pharm. 2013, 445, 47-57) in order to obtain a clear picture of the solution behavior of this class or block copolymers and to understand their biological activity. These block copolymers are characterized by possessing long BO blocks and extremely lengthy central EO ones, which provide them with a rich rheological behavior characterized by the formation of flowerlike micelles with sizes ranging from 20 to 40 nm in aqueous solution and the presence of intermicellar bridging even at low copolymers concentrations as denoted by atomic force microscopy. Bridging is also clearly observed by analyzing the rheological response of these block copolymers both storage and loss moduli upon changes on time, temperature, and or concentration. Strikingly, the relatively wide Poisson distribution of the polymeric chains make the present copolymers behave rather distinctly to conventional associative thickeners. The observed rich

  13. Synthesis of segmented PB(SMA-block-PB)(n) block copolymers through a polymeric iniferter technique

    NARCIS (Netherlands)

    Kroeze, E; ten Brinke, G.; Hadziioannou, G

    1997-01-01

    A technique is described for the synthesis of segmented block copolymers of polybutadiene and poly(styrene-co-maleic anhydride) through a polymeric therma iniferter based on polybutadiene, which was used as an initiator for the thermal copolymerization of styrene and maleic anhydride. The polymeric

  14. Synthesis of polyacrylonitrile-block-polydimethylsiloxane-block-polyacrylonitrile triblock copolymers via RAFT polymerization

    Institute of Scientific and Technical Information of China (English)

    Zheng Yue; Deng Xu Wang; Jing Quan Liu; Jie Zhang; Sheng Yu Feng

    2012-01-01

    A new A-B-A type of block copolymers,polyacrylonitrile-block-polydimethylsiloxane-block-polyacrylonitrile (PAN-b-PDMS-b-PAN),which comprises two polymer blocks of different polarities and compatibilities,were synthesized for the first time via reversible addition-fragmentation chain transfer polymerization.Reaction kinetics was investigated.PAN-b-PDMS-b-PAN films were prepared by spin-coating on glass chips.Significant order on the film surface morphologies was observed.(C) 2012 Jie Zhang.Published by Elsevier B.V.on behalf of Chinese Chemical Society.All rights reserved.

  15. Hybrid - block copolymer nanocomposites. characterization of nanostructure by small-angle X-ray scattering (SAXS)

    OpenAIRE

    A. Romo-Uribe

    2007-01-01

    The nanoscopic order of a series of block copolymer-inorganic nanocomposites was characterized using small-angle X-ray scattering (SAXS). The nanostructures were obtained via a diblock copolymer directed sol-gel synthesis. The copolymer consists of blocks of poly(isoprene) -PI- and blocks of poly(ethylene oxide) -PEO. The inorganic material consists of a crosslinked sol of 3-glycidoxypropyltrimethoxysilane and aluminum-tri-sec-butoxide in a 4:1 mole ratio, to generate an aluminosilicate ceram...

  16. Pharmacokinetics and antitumor efficacy of micelles assembled from multiarmed amphiphilic copolymers with drug conjugates in comparison with drug-encapsulated micelles.

    Science.gov (United States)

    Luo, Xiaoming; Chen, Maohua; Zhang, Yun; Chen, Zhoujiang; Li, Xiaohong

    2016-01-01

    The premature drug release and structural dissociation before reaching pathological sites have posed major challenges for self-assembled micelles. To address these challenges, star-shaped amphiphilic copolymers derived from 4-armed poly(ethylene glycol) (PEG) were proposed for chemical conjugation of chemotherapeutic drugs and assembly into drug-conjugated micelles (DCM) with reductive sensitivity. The current study aimed to elucidate the in vitro and in vivo performance of DCM and a comparison with conventional drug-encapsulated micelles (DEM) was initially launched. DEM carriers were constructed with a similar structure to DCM from 4-armed PEG, and disulfide linkages were located between the hydrophilic and hydrophobic segments. Both DCM and DEM had an average size of around 130 nm, camptothecin (CPT) loadings of around 7.7% and critical micelle concentrations of around 0.95 μg/ml. Compared with DEM, DCM showed a lower initial drug release, a lower sensitivity of drug release to glutathione, and a higher structural stability after incubation with human serum albumin (HSA). The CPT derivatives (CPT-SH) released from DCM indicated cytotoxicities similar to CPT and remained a higher lactone stability than CPT in the presence of HSA. DCM showed slightly higher cytotoxicities to 4T1 cells and significantly lower cytotoxicities to normal cells than DEM. Pharmacokinetic analyses after intravenous administration of DCM indicated around 2.65 folds higher AUC0-∞, 2.66 folds lower clearance, and 1.87 folds higher tumor accumulation than those of DEM. In addition to a less disturbance to hematological and biochemical parameters and a lower acute toxicity to small intestines, DCM showed more significant tumor suppression efficacy and less tumor metastasis to lungs than DEM. It is suggested that DCM could overcome the limitation of conventional micelles by alleviating the premature drug release during blood circulation, relieving the systemic toxicity and promoting the

  17. Perfluorocyclobutyl-containing Amphiphilic Block Copolymers Synthesized by RAFT Polymerization

    Institute of Scientific and Technical Information of China (English)

    LI, Yongjun; ZHANG, Sen; FENG, Chun; ZHANG, Yaqin; LI, Qingnuan; LI, Wenxin; HUANG, Xiaoyu

    2009-01-01

    Amphiphilic block copolymers containing hydrophobic perfluorocyclobutyl-based (PFCB) polyacrylate and hydrophilic poly(ethylene glycol) (PEG) segments were prepared via reversible addition-fragmentation chain transfer (RAP-T) polymerization. The PFCB-containing acrylate monomer, p-(2-(p-tolyloxy)perfluorocyclobutoxy)phenyl acrylate, was first synthesized from commercially available compounds in good yields, and this kind of acrylate monomer can be homopolymerized by free radical polymerization or RAFT polymerization. Kinetic study showed the 2,2'-azobis(isobutyronitrile) (AIBN) initiated and cumyl dithiobenzoate (CDB) mediated RAFT polymerization was in a living fashion, as suggested by the fact that the number-average molecular weights (M_n) increased linearly with the conversions of the monomer, while the polydispersity indices kept less than 1.10. The block polymers with narrow molecular weight distributions (M_w/M_n≤1.21) were prepared through RAFT polymerization using PEG monomethyl ether capped with 4-cyanopentanoic acid dithiobenzoate end group as the macro chain transfer agent (mPEG-CTA). The length of the hydrophobic segment can be tuned by the feed ratio of the PFCB-based acrylate monomer and the extending of the polymerization time. The micellization behavior of the block copolymers in aqueous media was investigated by the fluorescence probe technique.

  18. 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.

  19. Shear induced order in SEP diblock copolymer micelles: multiple BCC slip systems

    Science.gov (United States)

    Torija, Maria A.; Choi, Soohyung; Bates, Frank S.; Lodge, Timothy P.

    2010-03-01

    Poly(styrene-b-ethylene-alt-propylene) (SEP) diblock copolymers are solvated by squalane leading to glassy poly(styrene) domains dispersed in a viscoelastic medium. For diblocks containing less than about 50% by weight poly(styrene) and at SEP concentrations greater than 6 w. % these mixtures self-assemble into glassy spherical microdomains that order on a body centered cubic (BCC) lattice. We have investigated how polycrystalline configurations respond to large amplitude oscillatory shear as a function of shear rate, strain amplitude and block copolymer composition. Structure was characterized by small-angle X-ray scattering measurements while simultaneously deforming the mixtures with an in-situ rheometer. All three slip systems associated with plastic deformation in BCC metals110,211,321, were identified with the x-ray beam oriented perpendicular to the shear plane. Higher shear rates and larger strain amplitudes produced more slip within the 211 system. These results represent one of the most comprehensive assessments of BCC structure in solvated copolymers and will be discussed within the context of the associated linear viscoelastic behavior.

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

    Science.gov (United States)

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

    2015-05-21

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

  1. Self-assembly of block copolymers on topographically patterned polymeric substrates

    Energy Technology Data Exchange (ETDEWEB)

    Russell, Thomas P.; Park, Soojin; Lee, Dong Hyun; Xu, Ting

    2016-05-10

    Highly-ordered block copolymer films are prepared by a method that includes forming a polymeric replica of a topographically patterned crystalline surface, forming a block copolymer film on the topographically patterned surface of the polymeric replica, and annealing the block copolymer film. The resulting structures can be used in a variety of different applications, including the fabrication of high density data storage media. The ability to use flexible polymers to form the polymeric replica facilitates industrial-scale processes utilizing the highly-ordered block copolymer films.

  2. Gamma radiation induced degradation in PE-PP block copolymer

    Energy Technology Data Exchange (ETDEWEB)

    Ravi, H. R.; Sreepad, H. R.; Ahmed, Khaleel; Govindaiah, T. N. [P.G. Department of Physics, Government College (Autonomous), Mandya - 571401, Karnataka State (India)

    2012-06-05

    In the present investigation, effect of gamma irradiation on the PP-PE block copolymer has been studied. The polymer has been subjected to gamma irradiation from 100 to 500 Mrad dosages. Characterization of the polymer using XRD and FTIR was done both before irradiation and after irradiation in each step. Effect of irradiation on the electrical properties of the material has also been studied. FTIR study shows that the sample loses C - C stretching mode of vibration but gains C=C stretching mode of vibration after irradiation. Present investigation clearly indicates that though the electrical conductivity increases in the material, it undergoes degradation and shows brittleness due to irradiation.

  3. Self-assembly in casting solutions of block copolymer membranes

    KAUST Repository

    Marques, Debora S.

    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. Perspective: Evolutionary design of granular media and block copolymer patterns

    Science.gov (United States)

    Jaeger, Heinrich M.; de Pablo, Juan J.

    2016-05-01

    The creation of new materials "by design" is a process that starts from desired materials properties and proceeds to identify requirements for the constituent components. Such process is challenging because it inverts the typical modeling approach, which starts from given micro-level components to predict macro-level properties. We describe how to tackle this inverse problem using concepts from evolutionary computation. These concepts have widespread applicability and open up new opportunities for design as well as discovery. Here we apply them to design tasks involving two very different classes of soft materials, shape-optimized granular media and nanopatterned block copolymer thin films.

  5. PEG-PLA diblock copolymer micelle-like nanoparticles as all-trans-retinoic acid carrier: in vitro and in vivo characterizations

    Science.gov (United States)

    Li, Yuan; Qi, Xian Rong; Maitani, Yoshie; Nagai, Tsuneji

    2009-02-01

    The purpose of this study was to characterize the properties in vitro, i.e. release, degradation, hemolytic potential and anticancer activity, and in vivo disposition of all-trans-retinoic acid (ATRA) in rats after administration of ATRA-loaded micelle-like nanoparticles. The amphiphilic block copolymers consisted of a micellar shell-forming mPEG block and a core-forming PLA block. The mPEG-PLA nanoparticles prepared by an acetone volatilization dialysis procedure were identified as having core-shell structure by 1H NMR spectroscopy. Critical association concentration, drug contents, loading efficiency, particle size and ξ potential were evaluated. The release of ATRA from the nanoparticles and the degradation of PLA were found to be mostly associated with the compositions of the nanoparticles. ATRA release was faster at smaller molecular weight of copolymer and lower drug contents. In vitro, the incorporation of ATRA in mPEG-PLA nanoparticles reduced the hemolytic potential of ATRA. Furthermore, anticancer activity of ATRA against HepG2 cell was increased by encapsulation, which showed an enhancement of tumor treatment of ATRA. In vivo, after intravenous injection to rats, the levels of ATRA in the blood stream and the bioavailability were higher for ATRA-loaded mPEG-PLA nanoparticles than those for ATRA solution. In conclusion, the structure of the mPEG-PLA diblock copolymer could be modulated to fit the demand of in vitro and in vivo characterizations of nanoparticles. The mPEG-PLA nanoparticles' loading ATRA have a promising future for injection administration.

  6. Tough Block Copolymer Organogels and Elastomers as Short Fiber Composites

    Science.gov (United States)

    Kramer, Edward J.

    2012-02-01

    The origins of the exceptional toughness and elastomeric properties of gels and elastomers from block copolymers with semicrystalline syndiotactic polypropylene blocks will be discussed. Using synchrotron X-radiation small angle (SAXS) and wide angle X-ray scattering (WAXS) experiments were simultaneously performed during step cycle tensile deformation of these elastomers and gels. From these results the toughness can be attributed to the formation, orientation and elongation of the crystalline fibrils along the tensile direction. The true stress and true strain ɛH during each cycle were recorded, including the true strain at zero load ɛH,p after each cycle that resulted from the plastic deformation of the sPP crystals in the gel or elastomer. The initial Young's modulus Einit and maximum tangent modulus Emax in each cycle undergo dramatic changes as a function of ɛH,p, with Einit decreasing for ɛH,p 100 to 1000 at the highest maximum (nominal) strain. Based on SAXS patterns from the deformed and relaxed gels, as well as on previous results on deformation of semicrystalline random copolymers by Strobl and coworkers, we propose that the initial decrease in Einit and increase in Emax with ɛH,p are due to a breakup of the network of the original sPP crystal lamellae and the conversion of the sPP lamellae into fibrils whose aspect ratio increases with further plastic deformation, respectively. The gel elastic properties can be understood quantitatively as those of a short fiber composite with a highly deformable matrix. At zero stress the random copolymer midblock chains that connect the fibrils cause these to make all angles to the tensile axis (low Einit), while at the maximum strain the stiff, crystalline sPP fibrils align with the tensile axis producing a strong, relatively stiff gel. The evolution of the crystalline structure during deformation is confirmed by WAXS and FTIR measurements.

  7. Effects of X-shaped reduction-sensitive amphiphilic block copolymer on drug delivery

    Directory of Open Access Journals (Sweden)

    Xiao H

    2015-08-01

    Full Text Available Haijun Xiao, Lu WangState Key Laboratory of Quality Research in Chinese Medicine, Institute of Chinese Medical Sciences, University of Macau, Macau, People’s Republic of ChinaAbstract: To study the effects of X-shaped amphiphilic block copolymers on delivery of docetaxel (DTX and the reduction-sensitive property on drug release, a novel reduction-sensitive amphiphilic copolymer, (PLGA2-SS-4-arm-PEG2000 with a Gemini-like X-shape, was successfully synthesized. The formation of nanomicelles was proved with respect to the blue shift of the emission fluorescence as well as the fluorescent intensity increase of coumarin 6-loaded particles. The X-shaped polymers exhibited a smaller critical micelle concentration value and possessed higher micellar stability in comparison with those of linear ones. The size of X-shaped (PLGA2-SS-4-arm-PEG2000 polymer nanomicelles (XNMs was much smaller than that of nanomicelles prepared with linear polymers. The reduction sensitivity of polymers was confirmed by the increase of micellar sizes as well as the in vitro drug release profile of DTX-loaded XNMs (DTX/XNMs. Cytotoxicity assays in vitro revealed that the blank XNMs were nontoxic against A2780 cells up to a concentration of 50 µg/mL, displaying good biocompatibility. DTX/XNMs were more toxic against A2780 cells than other formulations in both dose- and time-dependent manners. Cellular uptake assay displayed a higher intracellular drug delivery efficiency of XNMs than that of nanomicelles prepared with linear polymers. Besides, the promotion of tubulin polymerization induced by DTX was visualized by immunofluorescence analysis, and the acceleration of apoptotic process against A2780 cells was also imaged using a fluorescent staining method. Therefore, this X-shaped reduction-sensitive (PLGA2-SS-4-arm-PEG2000 copolymer could effectively improve the micellar stability and significantly enhance the therapeutic efficacy of DTX by increasing the cellular uptake and

  8. Characterizing the interfaces of block copolymers with high χ

    Science.gov (United States)

    Sunday, Daniel; Maher, Michael; Blachut, Gregory; Asano, Yusuke; Tein, Summer; Willson, C. Grant; Ellison, Christopher; Kline, R. Joseph

    In order for block copolymer (BCP) directed self-assembly (DSA) to be able to pattern features below 10 nm there must be materials which can spontaneously assembly at the required length scales. For the smallest features this will require phase separation where the total chain lengths are under 50 monomer units, demanding very large interaction parameters (χ) to have an order-disorder transition. One of the key parameters for DSA will be the interfacial width between the blocks, which is expected to be correlated to the interaction parameter and will help determine the line edge roughness (LER). We have used resonant soft X-ray reflectivity to investigate a series of high χ BCPs with different compositions and molecular weights to determine the interfacial width and degree of phase separation. We use these results to estimate the value of χ and determine relationships between χ and the interfacial mixing.

  9. 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.

  10. 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.

  11. Water distributions in polystyrene-block-poly[styrene-g-poly(ethylene oxide)] block grafted copolymer system in aqueous solutions revealed by contrast variation small angle neutron scattering study

    Science.gov (United States)

    Li, Xin; Hong, Kunlun; Liu, Yun; Shew, Chwen-Yang; Liu, Emily; Herwig, Kenneth W.; Smith, Gregory S.; Zhao, Junpeng; Zhang, Guangzhao; Pispas, Stergios; Chen, Wei-Ren

    2010-10-01

    We develop an experimental approach to analyze the water distribution around a core-shell micelle formed by polystyrene-block-poly[styrene-g-poly(ethylene oxide (PEO)] block copolymers in aqueous media at a fixed polymeric concentration of 10 mg/ml through contrast variation small angle neutron scattering (SANS) study. Through varying the D2O/H2O ratio, the scattering contributions from the water molecules and the micellar constituent components can be determined. Based on the commonly used core-shell model, a theoretical coherent scattering cross section incorporating the effect of water penetration is developed and used to analyze the SANS I(Q ). We have successfully quantified the intramicellar water distribution and found that the overall micellar hydration level increases with the increase in the molecular weight of hydrophilic PEO side chains. Our work presents a practical experimental means for evaluating the intramacromolecular solvent distributions of general soft matter systems.

  12. Structure and stability of complex coacervate core micelles with lysozyme

    NARCIS (Netherlands)

    Lindhoud, Saskia; de Vries, Renko; Norde, Willem; Cohen Stuart, Martien A.

    2007-01-01

    Encapsulation of enzymes by polymers is a promising method to influence their activity and stability. Here, we explore the use of complex coacervate core micelles for encapsulation of enzymes. The core of the micelles consists of negatively charged blocks of the diblock copolymer PAA(42)PAAm(417) an

  13. Structure and Stability of Complex Coacervate Core Micelles with Lysozyme

    NARCIS (Netherlands)

    Lindhoud, Saskia; Vries, de Renko; Norde, Willem; Cohen Stuart, Martien A.

    2007-01-01

    Encapsulation of enzymes by polymers is a promising method to influence their activity and stability. Here, we explore the use of complex coacervate core micelles for encapsulation of enzymes. The core of the micelles consists of negatively charged blocks of the diblock copolymer PAA42PAAm417 and th

  14. Structure and stability of complex coacervate core micelles with lysozyme

    NARCIS (Netherlands)

    Lindhoud, S.; Vries, de R.J.; Norde, W.; Cohen Stuart, M.A.

    2007-01-01

    Encapsulation of enzymes by polymers is a promising method to influence their activity and stability. Here, we explore the use of complex coacervate core micelles for encapsulation of enzymes. The core of the micelles consists of negatively charged blocks of the diblock copolymer PAA42PAAm417 and th

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

    KAUST Repository

    Moreno, 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.

  16. Synthesis and self-assembly of temperature and anion double responsive ionic liquid block copolymers

    Science.gov (United States)

    Liang, Ju; Wu, Wenlan; Li, Junbo; Han, Chen; Zhang, Shijie; Guo, Jinwu; Zhou, Huiyun

    2015-09-01

    In this paper, double hydrophilic ionic liquid block copolymers (ILBCs), poly(N-isopropylacrylamide)-block-poly[1-methyl-3-(2-methacryloyloxy propylimidazolium bromine)] (PNIPAM- b-PMMPImB), were polymerized by two-step reversible addition-fragmentation chain transfer (RAFT) process. The composition and molecular weight distributions of ILBCs were characterized using 1HNMR and gel permeation chromatography (GPC). The self-assembly and temperature- and anion-responsive behaviors of ILBCs were investigated by UV-Vis spectroscopy, TEM and dynamic light scattering (DLS). With increasing the concentration of (CF3SO2)2N-, the micellization of self-assembling PNIPAM- b-PMMPImB was induced to form a core—shell structure containing the core with hydrophilic PMMPIm-(CF3SO2)2N- surrounded by the shell of PNIPAM via the anion-responsive properties of ILBCs. However, upon temperature increasing, PNIPAM- b-PMMPImB formed the micelles composing of PNIPAM core and PMMPImB shell. The ionic liquid segment with strong hydrophilic property enhanced the hydrogen bonding interaction which expanded the temperature range of phase transition and increased the lower critical solution temperature (LCST) of the system. These results indicate that ILBCs prepared in this paper have excellent temperature and anion double responsive properties, and may be applied as a kind of potential environmental responsive polymer nanoparticles.

  17. RAFT polymerization kinetics and polymer characterization of P3HT rod-coil block copolymers and their uses to prepare hybrid nanocomposites

    Science.gov (United States)

    Kern, Melissa Robin

    group reactions result in P3HT homopolymer in the final sample. Therefore accurate characterization requires molecular weight determination of the block copolymer and quantification of the sample composition. Also presented in this work is the synthesis of amphiphilic rod-coil block copolymers of P3HT with poly(4-vinyl pyridine) (4VP) and poly(acrylic acid) (AA). Here, P3HT-b-PAA is prepared by the direct synthesis of acrylic acid with the macroRAFT agent using a binary solvent system of trichlorobenzene and dioxane to maintain polymer solubility throughout the polymerization. The micelle formation of the resulting block copolymer is detailed as the transparent micelle solution of P3HT-b-PAA exhibits the optical behavior of solid-state P3HT. Finally, the preparation of various nanocomposites from the synthesized P3HT homopolymer and block copolymers is presented. In the first method, the RAFT end group of the P3HT macroRAFT agent and the P3HT block copolymers is reduced to a thiol to allow for attachment to Au nanoparticles. While Au nanoparticles are not useful for photovoltaic applications, the surface modification demonstrates the utility of the P3HT macroRAFT agent, which is used to modify the surface with P3HT homopolymer and P3HT block copolymers. The second method to prepare P3HT hybrid nanocomposites is in-situ growth of CdS in P3HT-b-P4VP. With analysis by dynamic light scattering (DLS), Fourier-transform infrared (FT-IR) spectroscopy and transmission electron microscopy (TEM), it is concluded that a majority of the CdS growth in the P3HT-b-P4VP was confined to the P4VP block.

  18. PRECISE SYNTHESIS OF OLEFIN BLOCK COPOLYMERS USING A SYNDIOSPECIFIC LIVING POLYMERIZATION SYSTEM

    Institute of Scientific and Technical Information of China (English)

    Zheng-guo Cai; Hai-hui Su; Takeshi Shiono

    2013-01-01

    This feature article summarizes the synthesis of novel olefin block copolymers using fast syndiospecific living homo-and copolymerization of propylene,higher 1-alkene,and norbomene with ansa-fluorenylamidodimethyltitaniumbased catalyst according to the authors' recent results.The catalytic synthesis of monodisperse polyolefin and olefin block copolymer was also described using this living system.

  19. Block copolymer self-assembly : homopolymer additives and multiple length scales

    NARCIS (Netherlands)

    Klymko, Tetyana Romanivna

    2008-01-01

    This thesis is devoted to a theoretical study of self-assembly in specific block-copolymer systems. The ability of block copolymer-based systems to organize at the nanoscale level depends on several parameters, such as volume fraction of the different components, their molar masses and the strength

  20. Dilute gels with exceptional rigidity from self-assembling silk-collagen-like block copolymers

    NARCIS (Netherlands)

    Martens, A.A.; Gucht, van der J.; Eggink, G.; Wolf, de F.A.; Cohen Stuart, M.A.

    2009-01-01

    Rheological data on monodisperse block copolymer hydrogels are rare because the amounts produced with various methods usually are not sufficient for materials testing. By biotechnological means, expression of a block copolymer encoding gene in the yeast Pichia pastoris, we produced enough protein bl

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

    Science.gov (United States)

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

  2. Morphological study of biodegradable PEO/PLA block copolymers.

    Science.gov (United States)

    Younes, H; Cohn, D

    1987-11-01

    A series of PEO/PLA copolymers, covering a wide range of compositions and segmental lengths, was synthesized, and their morphology was investigated by means of DSC and IR studies. For matrices comprising PEO chains with molecular weights below 3400, no soft-segment crystallinity was detected. When long hard segments were present, essentially monophasic, semicrystalline polymers were obtained, with PLA blocks melting around 130 degrees C. Polymers containing longer soft segments (PEO 6000) exhibited a two-phase matrix, with both components being able to crystallize. The relative degree of crystallinity of PEO and PLA blocks was also determined. The thermal history of the sample strongly affected the morphology of the matrix, especially when both blocks were long enough to crystallize. To further explore these polymers, solvent cast films were prepared and their morphology assessed. Casting from acetone, which is an excellent solvent for PLA, resulted in hard blocks exhibiting lower degrees of crystallinity, while methanol had a similar effect on PEO soft segments. PMID:3680315

  3. 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 homopol

  4. Understanding the ordering mechanisms of self-assembled nanostructures of block copolymers during zone annealing.

    Science.gov (United States)

    Cong, Zhinan; Zhang, Liangshun; Wang, Liquan; Lin, Jiaping

    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. PMID:27004895

  5. Phase behavior of multi-arm star-shaped polystyrene-block-poly(methyl methacrylate) copolymer

    Science.gov (United States)

    Jang, Sangshin; Moon, Hong Chul; Bae, Dusik; Kwak, Jonghen; Kim, Jin Kon

    2013-03-01

    We synthesized star-shaped polystyrene-block-poly(methyl methacrylate) copolymer (PS- b-PMMA) by utilizing α-cyclodextrin (α-CD) as a core of the star-shaped block copolymer. Eighteen hydroxyl groups on α-CD were transformed to bromine by the reaction with α-bromoisobutyryl bromide. We found that the number of bromine substituted arms per one α-CD was higher than 16, which was determined by nuclear magnetic resonance and Matrix-assisted laser desorption/ionization. We could control molecular weight of block copolymers by changing polymerization times. The block copolymers were characterized by gel permeation chromatography and nuclear magnetic resonance. Phase behaviors of these star-shaped block copolymers were investigated by small angle X-ray scattering and transmission electron microscopy.

  6. 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......-linked phase are sliced with microtome and pattern is transfered from flakes to substrate by plasma etching. Experimental Section. Group of Self-organized Nanoporous Materials in Technical University of Denmark has developed series of block copolymers of Polybutadiene-b-Polydimethylsiloxane (PB...... 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...

  7. Nanowire polarizers by guided self-assembly of block copolymers

    Science.gov (United States)

    Roberts, Philip M. S.; Baum, Alexandra; Karamath, James; Evans, Allan; Shibata, Satoshi; Walton, Harry

    2014-01-01

    Wire-grid polarizers (WGPs) are currently limited by their wafer-scale manufacturing methods to sizes of approximately 12 to 18 in. For large-size displays, a new method for the production of large-area WGPs is required. Large-area WGPs were simulated using the finite-difference-time-domain method, and a scaleable method for their production based on a block copolymer (BCP)-nanostructured template was implemented. The nanostructured template is globally aligned through the use of a cylinder-forming liquid crystal (LC) diblock copolymer, which is first aligned on a rubbed polyimide substrate. A surface-relief template is produced using the differential dry etch rates of the cylinder-forming component and LC polymer matrix component of the BCP. The template is metalized to produce a WGP. Polarizers of arbitrary size with polarization efficiency up to 0.6 have been made in close agreement with calculated values for idealized structures. The choice of the cylinder-forming polymer is critical to the degree of alignment of the template, and the thermal stability of the LC polymer matrix is critical to the stability of the template during etching.

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

    Science.gov (United States)

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

    2009-04-01

    Fibers with long-range ordered internal structures have applications in various areas such as photonic band gap fibers, optical waveguides, wearable power, sensors, and sustained drug release. Up to now, such fibers have been formed by melt extrusion or drawing from a macroscopic preformed rod and were typically limited to diameters >10 microm with internal features >1 microm (Abouraddy, A. F.; et al. Nat. Mater. 2007, 6, 336). We describe a new class of continuous fibers and fibrous membranes with long-range ordered concentric lamellar structure that have fiber diameters and feature sizes 2-3 orders of magnitude smaller than those made by conventional methods. These fibers are created through confined self-assembly of block copolymers within core-shell electrospun filaments. In contrast to the copolymer in bulk or thin films, the domains of the concentric lamellar structure are shown here to vary quantitatively with (radial) position and to exhibit a novel dislocation that accommodates variations in fiber diameter robustly, permitting for the first time the realization of long-range order in technologically meaningful, continuous fibers with approximately 300 nm diameter and 50 nm radial period. PMID:19351195

  9. Novel fluorescent amphiphilic block copolymers: photophysics behavior and interactions with DNA

    Directory of Open Access Journals (Sweden)

    2007-06-01

    Full Text Available In this study, novel amphiphilic fluorescent copolymers poly(N-vinylpyrrolidone-b-poly(N-methacryloyl-N'-(α-naphthylthiourea (PVP-b-PNT were synthesized via ATRP with poly(N-vinylpyrrolidone-Cl as macroinitiator and N-methacryloyl-N'-α-naphthylthiourea (NT as hydrophobic segment. PVP-b-PNT copolymers were characterized by 1H NMR, GPC-MALLS and fluorescence measurements. The aggregation behavior of PVP-b-PNT in water was investigated by transmission electron microscope (TEM and dynamic light scattering (DLS measurement. The photophysics behavior of PVP-b-PNT showed that block copolymer formed strong excimer. The interaction of DNA with the block copolymer made the excimer of block copolymer quench. The cytotoxicity result of PVP-b-PNT in cell culture in vitro indicated that this copolymer PVP-b-PNT had good biocompatibility.

  10. Synthesis and Surface Tension Properties of Polyethyleneimine—Polyethylene Oxide Block Copolymers

    Institute of Scientific and Technical Information of China (English)

    张剑; LONNIE,Bryant

    2003-01-01

    This peper describes the synthesis,surface tension and dispersancy properties of block copolymer nonionic surfactants comprised of polyethyleneimine(PEI) and polyethlene oxide(PEO) blocks of selected lengths.These block copolymers were prepared by a threestep synthetic sequence.Firstly,PEO glycol was converted to its dimethanesulphonylester (dimesyl) derivative by reacting with methanesulphonyl chloride.Then a tri-block polymer was preparaed by the ring-opening polymerization of 2-methly-2-oxazoline(MeOZO)with the dimesyl PEO derivative.Lastly,linear PEI blocks were obtained by subsequent hydrolysis and purification.1H NMR spectra confirmed the structures of the intermediate,final products and their purities(>99%).The utility of these block copolymers is described in terms of their surface tension and clay dispersancy measurements as a function of copolymer chain and block length.

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

    Science.gov (United States)

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

    2016-08-10

    The ability to fabricate nanostructured films by exploiting the phenomenon of microphase separation has made block copolymers an invaluable tool for a wide array of coating applications. Standard approaches to engineering nanodomains commonly involve the application of organic solvents, either through dissolution or annealing protocols, resulting in the release of volatile organic compounds (VOCs). In this paper, an aqueous-based method of fabricating low-VOC nanostructured block copolymer films is presented. The reported procedure allows for the phase transfer of water insoluble triblock copolymer, poly(styrene-block-2 vinylpyridine-block-ethylene oxide) (PS-b-P2VP-b-PEO), from a water immiscible phase to an aqueous environment with the assistance of a diblock copolymeric phase transfer agent, poly(styrene-block-ethylene oxide) (PS-b-PEO). Phase transfer into the aqueous phase results in self-assembly of PS-b-P2VP-b-PEO into core-shell-corona micelles, which are characterized by dynamic light scattering techniques. The films that result from coating the micellar solution onto Si/SiO2 surfaces exhibit nanoscale features that disrupt the ability of a model foulant, a zoospore of Ulva linza, to settle. The multilayered architecture consists of a pH-responsive P2VP-"shell" which can be stimulated to control the size of these features. The ability of these nanostructured thin films to resist protein adsorption and serve as potential marine antifouling coatings is supported through atomic force microscopy (AFM) and analysis of the settlement of Ulva linza zoospore. Field trials of the surfaces in a natural environment show the inhibition of macrofoulants for 1 month. PMID:27388921

  12. Correlative infrared nanospectroscopic and nanomechanical imaging of block copolymer microdomains.

    Science.gov (United States)

    Pollard, Benjamin; Raschke, Markus B

    2016-01-01

    Intermolecular interactions and nanoscale phase separation govern the properties of many molecular soft-matter systems. Here, we combine infrared vibrational scattering scanning near-field optical microscopy (IR s-SNOM) with force-distance spectroscopy for simultaneous characterization of both nanoscale optical and nanomechanical molecular properties through hybrid imaging. The resulting multichannel images and correlative analysis of chemical composition, spectral IR line shape, modulus, adhesion, deformation, and dissipation acquired for a thin film of a nanophase separated block copolymer (PS-b-PMMA) reveal complex structural variations, in particular at domain interfaces, not resolved in any individual signal channel alone. These variations suggest that regions of multicomponent chemical composition, such as the interfacial mixing regions between microdomains, are correlated with high spatial heterogeneity in nanoscale material properties. PMID:27335750

  13. Aligned nanowires and nanodots by directed block copolymer assembly

    Energy Technology Data Exchange (ETDEWEB)

    Xiao Shuaigang; Yang Xiaomin; Lee, Kim Y; Ver der Veerdonk, Rene J M; Kuo, David [Seagate Technology, 47010 Kato Road, Fremont, CA 94538 (United States); Russell, Thomas P, E-mail: shuaigang.xiao@seagate.com [Department of Polymer Science and Engineering, University of Massachusetts, 120 Governors Drive, Amherst, MA 01003 (United States)

    2011-07-29

    The directed self-assembly of block copolymers (BCPs) is a promising route to generate highly ordered arrays of sub-10 nm features. Ultradense arrays of a monolayer of spherical microdomains or cylindrical microdomains oriented parallel to the surface have been produced where the lateral ordering is guided by surface patterning and the lattice defined by the patterning can be commensurate or incommensurate with the natural period of the BCP. Commensurability between the two can be used to elegantly manipulate the lateral ordering and orientation of the BCP microdomains so as to form well-aligned arrays of 1D nanowires or 2D addressable nanodots. No modification of the substrate surface, aside from the patterning, was used, making the influence of lattice mismatch and pattern amplification on the size, shape and pitch of the BCP microdomains more transparent. A skew angle between incommensurate lattices, defining a stretching or compression of the BCP chains to compensate for the lattice mismatch, is presented.

  14. Microstructural organization of polydimethylsiloxane based polyurethane block copolymers

    Science.gov (United States)

    Hernandez, Rebeca; Weksler, Jadwiga; Padsalgikar, Ajay; Runt, James

    2007-03-01

    Microphase separation was investigated for polyurethane block copolymers synthesized from MDI and 1,4 butanediol as the hard segments, and poly(hexamethyleneoxide) (MW ˜ 700) and bis(6-hydroxyethoxypropyl) poly(dimethylsiloxane) as soft segments (MW ˜ 1000). The neat PDMS-based diol presents two segmental relaxations corresponding to the principle siloxane repeat unit and to the hydroxyethoxypropyl end group segments, respectively. When incorporated in the polyurethane, the siloxane units form a phase without intermixing with hard segments and the polyether end group segments are mixed with the second macrodiol and some short hard segment sequences. The microdomain morphology was characterized by atomic force microscopy and small-angle X-ray scattering, and the scattering data were analyzed using an approach based on a modified core-shell model. The model includes core hard segment particles (MDI-BDO), surrounded by a mixed polyether shell (PHMO and hydroxyethoxypropyl end group segments), and a matrix composed of the siloxane units.

  15. pH-sensitive poly(histidine)-PEG/DSPE-PEG co-polymer micelles for cytosolic drug delivery.

    Science.gov (United States)

    Wu, Hong; Zhu, Lin; Torchilin, Vladimir P

    2013-01-01

    To introduce pH sensitivity into the DSPE-PEG-based micellar system and achieve the quick intracellular drug release in response to the acidity in endosomes, a mixed polymeric micelle was developed based on three grafted copolymers, including 1,2-distearoyl-sn-glycero-3-phosphoethanolamine-polyethylene glycol-2000(DSPE-PEG(2000)), antinucleosome antibody (mAb 2C5)-modified DSPE-PEG(3400) (DSPE-PEG(3400)-2C5), and poly(ethylene glycol)-coupled poly(L-histidine) (PHIS-PEG(2000)). The structure of PHIS-PEG(2000) was confirmed by (1)H NMR spectroscopy. The mixed micelles with the diameter ranging from 110 to 135 nm were prepared using a dialysis method against pH 7.6 PBS. Paclitaxel (PCT) was used as a model drug, the encapsulation efficiency and loading content of PCT were 88% and 5%, respectively. The mixed micelles composed with 50 wt% of PHIS-PEG(2000) showed the desired pH-dependent drug release property with much faster drug release than micelles without PHIS-PEG(2000). At pH around 5.5, about 75-95% of the loaded drug was released within 2 h. The MTT assay showed PCT-loaded mixed micelles had higher cytotoxicity at pH 5.8 than that at pH 7.4. Further modification of the mixed micelles with anti-cancer nucleosome-specific monoclonal antibody 2C5 significantly increased their cellular uptake efficiency and cytotoxicity. Thus, the low pH in endosomes could trigger the PCT release from the pH-sensitive mixed micelles after 2C5-mediated endocytosis. The results of this study suggest that the mixed micelles (DSPE-PEG(2000)/DSPE-PEG(3400)-2C5/PHIS-PEG(2000)) could enhance the tumor cell-specific internalization and trigger the quick drug release, resulting in the improved anti-cancer efficacy. PMID:23102622

  16. Directed Nanorod Assembly Using Block Copolymer-Based Supramolecules

    Science.gov (United States)

    Thorkelsson, Kari; Mastroianni, Alexander; Ercius, Peter; Xu, Ting

    2013-03-01

    Nanorods display many unique electrical, mechanical, and optical properties unavailable in traditional bulk materials, and are attractive building blocks toward functional materials. The collective properties of anisotropic building blocks often depend strongly on their spatial arrangements, interparticle ordering, and macroscopic alignment. We have systematically investigated the phase behavior of nanocomposites composed of nanorods and block copolymer (BCP)-based supramolecules forming spherical, cylindrical and lamellar morphologies. Initial exploration showed that the nanorods can be readily dispersed in polymeric matrix and the overall morphology of nanorod-containing supramolecular nanocomposite depends on the nanorod-polymer interactions, inter-rod interactions and entropy associated with polymer chain deformation. The energetic contributions from the components of the system can be tailored to disperse nanorods with control over inter-rod ordering and the alignment of nanorods within BCP microdomains. By varying the supramolecular morphology and composition, arrays, sheets, and interconnected networks of nanorods are demonstrated that may prove useful for fabrication of optically and electrically active nanodevices.

  17. Fluorinated polyphenylenevinylene (PPV) block co-polymers for nanophotonics

    Science.gov (United States)

    Sun, Sam-Shajing; Nguyen, Thuong; Brooks, Jaleesa

    2013-09-01

    Polymer based optoelectronic materials and thin film devices exhibit great potential in future space applications due to their flexibility, light weight, large light absorption coefficient, and promising radiation tolerance in space environment as compared to their inorganic semiconductor counterparts. Since carbon-fluorine (C-F) chemical bonds are much stronger than the carbon-hydrogen (C-H) bonds, fluorinated polymer films offer great potential for space applications due their expected resistance to oxidation, thermal stability, excellent wear properties, and low coefficients of friction. Their use in a space environment is extremely attractive since they are expected to retain their lubricating characteristics in vacuum, unlike many solid lubricants. Current existing polymer photovoltaic materials and devices suffer low photoelectric power conversion efficiencies due to a number factors including poor morphologies at nano scale that hinder the charge separation and transport. This paper reports our recent work on a fluorinated DBfA type block copolymer system where the donor (D) block contains a donor substituted and hydrocarbon based polyphenylenevinylene (PPV), acceptor (fA) block contains a fluorinated and a sulfone acceptor substituted polyphenylenevinylene (f-PPV), and B is a non-conjugated and flexible bridge unit. Preliminary studies reveal DBfA exhibits better nano phase morphologies and over 100 times more efficient optoelectronic conversion efficiencies as compared to D/fA blend.

  18. Using click chemistry to modify block copolymers and their morphologies

    Science.gov (United States)

    Wollbold, Johannes

    Microphase separated block copolymers (BCPs) are emerging as promising templates and scaffolds for the fabrication of nanostructured materials. To achieve the desired nanostructures, it is necessary to establish convenient approaches to control the morphology of BCPs. It remains challenging to induce morphological transitions of BCPs via external fields. Click chemistry, especially alkyne/azide click chemistry, has been widely used to synthesize novel functionalized materials. Here, we demonstrate that alkyne/azide click chemistry can be used as an efficient approach to chemically modify BCPs and therefore induce morphological transitions. Alkyne-functionalized diblock copolymers (di-BCPs) poly(ethylene oxide)- block-poly(n-butyl methacrylate-random-propargyl methacrylate) (PEO-b-P(nBMA-r-PgMA)) have been successfully synthesized. When the di-BCP is blended with an azide additive Rhodamine B azide and annealed at elevated temperatures, click reaction occurs between the two components. With the Rhodamine B structure attached to the polymer backbone, the di-BCP shows dramatic change in the interactions between the two blocks and the volume fraction of each block. As a result, morphological transitions, such as disorder-to-order transitions (DOTs) and order-to-order transitions (OOTs), are observed. The reaction kinetics and morphology evolution during the click chemistry induced DOTs have been investigated by in-situ and ex-situ characterizations, and fast kinetics properties are observed. Microphase separated morphologies after the DOTs or OOTs are dictated by the composition of neat di-BCPs and the mole ratio between the alkyne and azide groups. The DOTs of PEO-b-P(nBMA-r-PgMA) di-BCPs induced by alkyne/azide click chemistry have also been achieved in thin film geometries, with comparable kinetics to bulk samples. The orientation of the microdomains is dependent on the grafting density of Rhodamine B structure as well as film thickness. At higher grafting densities

  19. Amine-containing block copolymers: long-term adhesion promoters and corrosion resistant coatings

    Energy Technology Data Exchange (ETDEWEB)

    Small, J.H.; Saunders, R.S.; Kent, M.S.

    1996-07-01

    Arylamine-containing diblock copolymers were prepared via ring- opening metathesis polymerization (ROMP) to afford well-defined phase- separated materials. Alteration of the functionaity in a block, as well as the size of the blocks, allowed for the synthesis of self- assembled monolayers on a copper surface. The arylamine-containing block exhibited a strong binding affinity for the copper surface as seen by neutron reflectivity experiments. In addition, neutron reflectivity data verifies the self-assembly of block copolymer monolayers normal to the copper surface. Block copolymers prepared in this manner allow for the preparation of a wide range of adhesives and corrosion resistant materials. The use of ring-opening metathesis polymerization is important because it permits the synthesis of a variety of functionalized block copolymers.

  20. 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.

  1. Study of matrix micro-cracking in nano clay and acrylic tri-block-copolymer modified epoxy/basalt fiber-reinforced pressure-retaining structures

    Directory of Open Access Journals (Sweden)

    2011-10-01

    Full Text Available In fiber-reinforced polymer pressure-retaining structures, such as pipes and vessels, micro-level failure commonly causes fluid permeation due to matrix cracking. This study explores the effect of nano-reinforcements on matrix cracking in filament-wound basalt fiber/epoxy composite structures. The microstructure and mechanical properties of bulk epoxy nanocomposites and hybrid fiber-reinforced composite pipes modified with acrylic tri-block-copolymer and organophilic layered silicate clay were investigated. In cured epoxy, the tri-block-copolymer phase separated into disordered spherical micelle inclusions; an exfoliated and intercalated structure was observed for the nano-clay. Block-copolymer addition significantly enhanced epoxy fracture toughness by a mechanism of particle cavitation and matrix shear yielding, whereas toughness remained unchanged in nano-clay filled nanocomposites due to the occurrence of lower energy resistance phenomena such as crack deflection and branching.Tensile stiffness increased with nano-clay content, while it decreased slightly for block-copolymer modified epoxy. Composite pipes modified with either the organic and inorganic nanoparticles exhibited moderate improvements in leakage failure strain (i.e. matrix cracking strain; however, reductions in functional and structural failure strength were observed.

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

    Directory of Open Access Journals (Sweden)

    Alok Chaurasia

    2015-01-01

    Full Text Available We report a supramolecular process for the synthesis of well-defined fullerene (C60/polymer colloid nanocomposites in an aqueous solution via complex formation. A biocompatible triblock poly(4-vinylpyridine-b-polyethylene-b-poly(4-vinylpyridine, P4VP8-b-PEO105-b-P4VP8, was synthesized by atom transfer radical polymerization. The block copolymer formed complexes with C60 in toluene and resulted in fullerene assembly in cluster form. Nanocomposite dispersion in an aqueous solution could be obtained using an aged solution of the polymer/C60/toluene solution by a solvent evaporation technique. The UV-Vis and FTIR spectroscopy confirmed the complex formation of fullerene with the polymer which plays a significant role in controlling the PDI and size of polymer/C60 micelles in the toluene solution. The particle size and morphology of P4VP8-b-PEO105-b-P4VP8 and P4VP8-b-PEO105-b-P4VP8/C60 mixture were studied by dynamic light scattering (DLS and transmission electron microscopy (TEM. In a cytotoxicity test, both pure polymer and the resulting polymer/C60 composite in water showed more than 90% cell viability at 1 mg/mL concentration.

  3. Research on Influence Factors of Surfactivity of Polyester Polyether Block Copolymer

    Institute of Scientific and Technical Information of China (English)

    WU Ming-hua; LIN He-ming

    2008-01-01

    Polyester polyether block copolymer (PPBC) was synthesized by ester-exchange and polycodensation reactions using dimethyl terephthalate (DMT), ethylene glycol (EG) and polyethylene glycol (PEG) as monomer. The effects of PEG molecular weight, mol ratio of DMT to PEG (nDMT/nPEG), temperature and time of polycondensation reaction and vacuum degree in the reaction system on the surface tension and critical micelle concentration (CMC) of PPBC aqueous solution were studied. It was found that both the molecular weight and the concentration of PEG can affect PPBC'S surface activity obviously, and the optimum synthesis condition of PPBC used as surfactant is as follows: PEG molecular weight is 1500, mol ratio of DMT to PEG is 3, temperature and time of polycondensation reaction is 260°C×1h, vacuum degree of condensation reaction is 0.03-0.05 MPa. It was proved by surface tension measurement of PPBC aqueous solution that the PPBC synthesized in this condition is a good surfactant with excellent surfactivity.

  4. Compatibilization of low-density polyethylene/polystyrene blends by segmented EB(PS-block-EB)(n) block copolymers

    NARCIS (Netherlands)

    Kroeze, E; ten Brinke, G.; Hadziioannou, G

    1997-01-01

    Hydrogenated segmented poly[butadiene-block-(styrene-block-butadiene)(n)] block copolymers, which were developed by use of a polymeric iniferter technique, were tested on their compatibilizing effectiveness for (10/90) LDPE/PS blends. They were found to be effective compatibilizers for this mixture,

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

    CERN Document Server

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

    2002-01-01

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

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

    Directory of Open Access Journals (Sweden)

    Omotunde Olubi

    2014-08-01

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

  7. Bicontinuous ceramics with high surface area from block copolymer templates.

    Science.gov (United States)

    Hsueh, Han-Yu; Ho, Rong-Ming

    2012-06-01

    Mesoporous polymers with gyroid nanochannels can be fabricated from the self-assembly of degradable block copolymer, polystyrene-b-poly(L-lactide) (PS-PLLA), followed by hydrolysis of PLLA block. Well-defined polymer/ceramic nanohybrid materials with inorganic gyroid nanostructures in a PS matrix can be obtained by using the mesoporous PS as a template for sol-gel reaction. Titanium tetraisopropoxide (TTIP) is used as a precursor to give a model system for the fabrication of metal oxide nanostructures from reactive transition metal alkoxides. By controlling the rates of capillary-driven pore filling and sol-gel reaction, the templated synthesis can be well-developed. Also, by taking advantage of calcination, bicontinuous TiO(2) with controlled crystalline phase (i.e., anatase phase) can be fabricated after removal of the PS template and crystallization of TiO(2) by calcination leading to high photocatalytic efficiency. This new approach provides an easy way to fabricate high-surface-area and high-porosity ceramics with self-supporting structure and controlled crystalline phase for practical applications. As a result, a platform technology to fabricate precisely controlled polymer/ceramic nanohybrids and mesoporous ceramic materials can be established. PMID:22530553

  8. 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

  9. Self-associating poly(ethylene oxide)-b-poly(alpha-cholesteryl carboxylate-epsilon-caprolactone) block copolymer for the solubilization of STAT-3 inhibitor cucurbitacin I.

    Science.gov (United States)

    Mahmud, Abdullah; Patel, Sarthak; Molavi, Ommoleila; Choi, Phillip; Samuel, John; Lavasanifar, Afsaneh

    2009-03-01

    An increase in the degree of chemical compatibility between drug and polymeric structure in the core has been shown to raise the encapsulation efficiency and lower the rate of drug release from polymeric micelles. In this study, to achieve an optimized polymeric micellar delivery system for the solubilization and controlled delivery of cucurbitacin I (CuI), the Flory-Huggins interaction parameter (chi(sc)) between CuI and poly(epsilon-caprolactone) (PCL), poly(alpha-benzylcarboxylate-epsilon-caprolactone) (PBCL) and poly(alpha-cholesteryl carboxylate-epsilon-caprolactone) (PChCL) structures was calculated by group contribution method (GCM) as an indication for the degree of chemical compatibility between different micellar core structures and CuI. The results pointed to a better compatibility between CuI and PChCL core rationalizing the synthesis of self-associating methoxy poly(ethylene oxide)-b-poly(alpha-cholesteryl carboxylate-epsilon-caprolactone) block copolymer (MePEO-b-PChCL). Novel block copolymer of MePEO-b-PChCL was synthesized through, first, preparation of substituted monomer, that is, alpha-cholesteryl carboxylate-epsilon-caprolactone, and further ring opening polymerization of this monomer by methoxy PEO (5000 g mol(-1)) using stannous octoate as catalyst. Synthesized block copolymers were characterized for their molecular weight and polydispersity by (1)H NMR and gel permeation chromatography. Self-assembled MePEO-b-PChCL micelles were characterized for their size, morphology, critical micellar concentration (CMC), capacity for the physical encapsulation of CuI, and mode of CuI release in comparison to MePEO-b-PCL and MePEO-b-PBCL micelles. Overall, the experimental order for the level of CuI encapsulation in different polymeric micellar formulations was consistent with what was predicted by the Flory-Huggins interaction parameter. Although MePEO-b-PChCL micelles exhibited the highest level of CuI loading, this structure did not show any significant

  10. Electric-Field-Induced Alignment of Block Copolymer/Nanoparticle Blends

    Energy Technology Data Exchange (ETDEWEB)

    Liedel, Clemens [RWTH Aachen University; Schindler, Kerstin [RWTH Aachen University; Pavan, Mariela J. [Hebrew University of Jerusalem; Lewin, Christian [RWTH Aachen University; Pester, Christian W [ORNL; Ruppel, Markus A [ORNL; Urban, Volker S [ORNL; Shenhar, Roy [Hebrew University of Jerusalem; Boker, Alexander [RWTH Aachen University

    2013-01-01

    External electric fi elds readily align birefringent block-copolymer mesophases. In this study the effect of gold nanoparticles on the electric-fi eld-induced alignment of a lamellae-forming polystyrene- block -poly(2-vinylpyridine) copolymer is assessed. Nanoparticles are homogeneously dispersed in the styrenic phase and promote the quantitative alignment of lamellar domains by substantially lowering the critical field strength above which alignment proceeds. The results suggest that the electric-fi eldassisted alignment of nanostructured block copolymer/nanoparticle composites may offer a simple way to greatly mitigate structural and orientational defects of such fi lms under benign experimental conditions.

  11. Anti-Biofouling Effect of PEG-Grafted Block Copolymer Synthesized by RAFT Polymerization.

    Science.gov (United States)

    Kim, Seon-Mi; Han, Sang Suk; Kim, A Young; Choi, Beom-Jin; Paik, Hyun-Jong; Lee, Inwon; Park, Hyun; Chun, Ho Hwan; Cho, Youngjin; Hwang, Do-Hoon

    2015-10-01

    Poly(glycidyl methadrylate-block-styrene) (PGMA-b-PS), a block copolymer consisting of glycidyl methacrylate and styrene, was synthesized via reversible addition-fragmentation chain transfer living polymerization. The synthesized PGMA-b-PS was then grafted with low-molecular-weight polyethylene glycol (PEG) via epoxy ring opening to give PGMA-g-PEG-b-PS, which was evaluated as an anti-biofouling coating material. As a preliminary test for the anti-biofouling effect, a protein adsorption experiment was performed on the synthesized block copolymer surface. The block copolymers were spin-coated onto silicon wafers, and protein adsorption experiments were carried out using fluorescein isothiocyanate conjugate-labeled bovine serum albumin. The fluorescence intensity of the protein adsorbed on the block copolymer surface was compared with that of a polystyrene film as a reference. The synthesized PGMA-g-PEG-b-PS film showed much lower fluorescence intensity than that of the PS film.

  12. Micellar Structures of Hydrophilic/Lipophilic and Hydrophilic/Fluorophilic Poly(2-oxazoline) Diblock Copolymers in Water

    DEFF Research Database (Denmark)

    Ivanova, Ruzha; Komenda, Thomas; Bonné, Tune B.;

    2008-01-01

    cationic polymerization. The polymer amphiphiles form core/shell micelles in aqueous solution as evidenced using small-angle neutron scattering (SANS). Whereas the diblock copolymer micelles with a hydrophobic NOxn block are spherical, the micelles with the fluorophilic FOxn are slightly elongated...

  13. Thermosensitive tribrachia star-shaped s-P(NIPAM-co-DMAM) random copolymer micelle aggregates: Preparation, characterization, and drug release applications.

    Science.gov (United States)

    Luo, Yan-Ling; Wang, Yuan; Wang, Xuan; Xu, Feng; Chen, Ya-Shao

    2016-01-01

    Tribrachia star-shaped random copolymers with tunable thermosensitive phase transition temperature were designed and synthesized via a simple one-pot ammonolysis reaction approach with trimesic acid as cores. The self-assembly micellization behavior of the copolymers in aqueous solution was examined by surface tension, UV-vis transmittance, transmission electron microscope, and dynamic light scattering measurements, etc. The results indicated that the resultant copolymers formed thermosensitive micelle aggregates through hydrophobic interactions among the isopropyl groups of poly(N-isopropylacrylamide) PNIPAM chains and inter-star association at a polymer concentration above critical aggregation concentrations from 4.06 to 6.55 mg L(-1), with a cloud point range from 36.6℃ to 52.1℃, and homogeneously distributed micelle size below 200 nm. The arm length and the compositional ratios of the two comonomers had effect on physicochemical properties of the polymer micelle aggregates. Particularly, the cloud point values were enhanced as the (N,N-dimethylacrylamide) DMAM monomer was introduced and reached to 36.6℃ and 41.0℃-44.7℃ when the mass ratio of NIPAM to DMAM was 90:10 and 80:20, respectively. The thermo-triggered drug release and cytotoxicity were evaluated to confirm the applicability of the random copolymer micelle aggregates as novel drug targeted release carriers. PMID:25926671

  14. Fluorosilicone multi-block copolymers tethering quaternary ammonium salt groups for antimicrobial purpose

    Science.gov (United States)

    Zhou, Fang; Qin, Xiaoshuai; Li, Yancai; Ren, Lixia; Zhao, Yunhui; Yuan, Xiaoyan

    2015-08-01

    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.

  15. STUDY ON STYRENE-BUTADIENE BLOCK COPOLYMER FOR THE MODIFICATION OF TIRE TREAD

    Institute of Scientific and Technical Information of China (English)

    WANG Yan; CHEN Weijie; MU Ruifeng; WANG Yongwei; YU Fengnian; LIU Qing

    1996-01-01

    This paper mainly deals with the design and synthesis of a novel styrene-butadiene block copolymer. When this copolymer is used in the tread portion of tyres, it can improve wet skid resistance and reduce rolling resistance without sacrificing its general physicalmechanical properties. The visco-elastic curve of tire tread using the novel copolymer as its rubber portion was showed. Reactivity ratios for two monomers in the polymerizing system were calculated. The diagrams of differential, integral and finite difference calculi throughout the whole molecular chain were presented. The influence of the micro- and macro-structure of the copolymer chain on wet skid resistance and rolling resistance was discussed.

  16. Synthesis and Characterization of ABBA Block Copolymer of Glycolide and ε-Caprolactone

    Institute of Scientific and Technical Information of China (English)

    CHEN Li; CHEN Xue-si; DENG Ming-xiao; JING Xia-bin

    2005-01-01

    A biodegradable ABBA block copolymer was synthesized via the ring-opening co-polymerization of ε-caprolactone(CL, B) and glycolide(A) by means of step polymerization in the presence of ethylene glycol as an initiator and stannous octanoate as a catalyst at 110 ℃ for 48 h. The molecular length of the PCL pre-polymer(BB) could be adjusted by controlling the molar ratio of the ethylene glycol initiator to ε-caprolactone monomer. The structure and the composition of the block copolymer were determined by the weight ratio of the monomer glycolide(A) to PCL pre-polymer(BB). The block copolymers were characterized by 1H NMR, GPC, DSC and X-ray. The results confirm the successful synthesis of an ABBA block copolymer.

  17. Phase Behavior of Star-shaped polystyrene-block-poly(methyl methacrylate) Copolymers

    Science.gov (United States)

    Jang, Sangshin; Moon, Hongchul; Lee, Youngmin; Kim, Jin Kon

    2012-02-01

    Star-shaped polystyrene-block-poly(methyl methacrylate) copolymer (PS-b-PMMA) was synthesized by utilizing α-cyclodextrin (α-CD) as a junction point of the star-shaped block copolymer. Eighteen hydroxyl groups on α-CD were substituted with bromine by the reaction with α-bromoisobutyryl bromide for atom transfer radical polymerization. We found that the number of bromine substituted arms per one α-CD was higher than 16 measured by nuclear magnetic resonance and Matrix-assisted laser desorption/ionization. We could control molecular weight of this unusual kind of block copolymer depending on polymerization times. Those polymers were characterized by gel permeation chromatography and nuclear magnetic resonance. Phase behavior of these star-shaped block copolymers were investigated.

  18. Direct Nanorod Assembly Using Block Copolymer-Based Supramolecules

    Science.gov (United States)

    Thorkelsson, Kari; Mastroianni, Alexander; Ercius, Peter; Xu, Ting

    2012-02-01

    One-dimensional nanomaterials with high aspect ratios, such as nanorods, exhibit unique and useful anisotropic optical, magnetic, and electrical properties. The collective properties of 1-D nanomaterials depend on their spatial arrangements, interparticle ordering, and macroscopic alignment. Developing routes to control their organization with high precision is critical to generate functional materials. We have investigated the co-assemblies of nanorods and block copolymer (BCP)-based supramolecules that self-assemble into spherical, lamellar and cylindrical morphologies. By varying energetic contributions from the rod-rod interactions and the deformation of the supramolecule, a wide library of nanorod assemblies including highly aligned arrays, continuous networks, and clusters can be readily accessed. Since macroscopic alignment of BCP microdomains can be obtained by application of external fields, present studies open up a new route to manipulate macroscopic alignments of nanorods. Fundamentally, these studies have demonstrated that in these blends, the energetic contributions from the polymer chain deformation and rod-rod interactions are comparable and can be tailored to disperse nanorods with control over inter-rod ordering and their relative alignment.

  19. Silicon crystallization in nanodot arrays organized by block copolymer lithography

    Energy Technology Data Exchange (ETDEWEB)

    Perego, Michele, E-mail: michele.perego@mdm.imm.cnr.it; Andreozzi, Andrea; Seguini, Gabriele [IMM-CNR, Laboratorio MDM (Italy); Schamm-Chardon, Sylvie; Castro, Celia; BenAssayag, Gerard [Université de Toulouse, nMat Group, CEMES-CNRS (France)

    2014-12-15

    Asymmetric polystyrene-b-polymethylmethacrylate (PS-b-PMMA) block copolymers are used to fabricate nanoporous PS templates with different pore diameter depending on the specific substrate neutralization protocol. The resulting polymeric templates are used as masks for the subsequent deposition of a thin (h = 5 nm) amorphous Si layer by electron beam evaporation. After removal of the polymeric film and of the silicon excess, well-defined hexagonally packed amorphous Si nanodots are formed on the substrate. Their average diameter (d < 20 nm), density (1.2 × 10{sup 11} cm{sup −2}), and lateral distribution closely mimic the original nanoporous template. Upon capping with SiO{sub 2} and high temperature annealing (1050 °C, N{sub 2}), each amorphous Si nanodot rearranges in agglomerates of Si nanocrystals (d < 4 nm). The average diameter and shape of these Si nanocrystals strongly depend on the size of the initial Si nanodot.

  20. Host-guest self-assembly in block copolymer blends.

    Science.gov (United States)

    Park, Woon Ik; Kim, Yongjoo; Jeong, Jae Won; Kim, Kyungho; Yoo, Jung-Keun; Hur, Yoon Hyung; Kim, Jong Min; Thomas, Edwin L; Alexander-Katz, Alfredo; Jung, Yeon Sik

    2013-01-01

    Ultrafine, uniform nanostructures with excellent functionalities can be formed by self-assembly of block copolymer (BCP) thin films. However, extension of their geometric variability is not straightforward due to their limited thin film morphologies. Here, we report that unusual and spontaneous positioning between host and guest BCP microdomains, even in the absence of H-bond linkages, can create hybridized morphologies that cannot be formed from a neat BCP. Our self-consistent field theory (SCFT) simulation results theoretically support that the precise registration of a spherical BCP microdomain (guest, B-b-C) at the center of a perforated lamellar BCP nanostructure (host, A-b-B) can energetically stabilize the blended morphology. As an exemplary application of the hybrid nanotemplate, a nanoring-type Ge2Sb2Te5 (GST) phase-change memory device with an extremely low switching current is demonstrated. These results suggest the possibility of a new pathway to construct more diverse and complex nanostructures using controlled blending of various BCPs. PMID:24217036

  1. Synthesis and self-assembly of multiple thermoresponsive amphiphilic block copolymers

    OpenAIRE

    Weiß, Jan

    2011-01-01

    In the present thesis, the self-assembly of multi thermoresponsive block copolymers in dilute aqueous solution was investigated by a combination of turbidimetry, dynamic light scattering, TEM measurements, NMR as well as fluorescence spectroscopy. The successive conversion of such block copolymers from a hydrophilic into a hydrophobic state includes intermediate amphiphilic states with a variable hydrophilic-to-lipophilic balance. As a result, the self-organization is not following an all-or-...

  2. Ionic Liquids As Self-Assembly Guide for the Formation of Nanostructured Block Copolymer Membranes

    KAUST Repository

    Madhavan, Poornima

    2015-04-30

    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-b-PV4P) diblock as membrane copolymer matrix and imidazolium and pyridinium based ILs. The effect of IL concentration and chemical composition was evident with particular interaction with P4VP blocks. The order of block copolymer/ILs solutions previous to the membrane casting was confirmed by cryo scanning electron microscopy and the morphologies of the manufactured nanostructured membranes were characterized by transmission and scanning electron microscopy. Non-protic ionic liquids facilitate the formation of hexagonal nanoporous block copolymer structure, while protic ILs led to a lamella-structured membrane. The rheology of the IL/block copolymer solutions was investigated, evaluating the storage and loss moduli. Most membranes prepared with ionic liquid had higher water flux than pure block copolymer membranes without additives.

  3. 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.

  4. Polymeric micelles as carriers of diagnostic agents.

    Science.gov (United States)

    Trubetskoy

    1999-04-01

    This review deals with diagnostic applications of polymeric micelles composed of amphiphilic block-copolymers. In aqueous solutions these polymers spontaneously form particles with diameter 20-100 nm. A variety of diagnostic moieties can be incorporated covalently or non-covalently into the particulates with high loads. Resulting particles can be used as particulate agents for diagnostic imaging using three major imaging modalities: gamma-scintigraphy, magnetic resonance imaging and computed tomography. The use of polyethyleneoxide-diacyllipid micelles loaded with chelated (111)In/Gd(3+) as well as iodine-containing amphiphilic copolymer in percutaneous lymphography and blood pool/liver imaging are discussed as specific examples.

  5. Ionic Interactions for Aqueous Templating of Biofunctional Molecules in Block Copolymer Nanostructures

    Science.gov (United States)

    Olsen, Bradley; Kim, Bokyung; Lam, Christopher; Stewart-Sloan, Charlotte; Gkikas, Emmanouil

    2013-03-01

    The use of ionic interactions to direct both biomolecular templating and block copolymer self-assembly into nanopatterned films with only aqueous processing conditions is demonstrated using block copolymers containing both thermally responsive and pH responsive blocks. Reversible addition-fragmentation chain transfer (RAFT) polymerization is employed to synthesize diblock copolymers with one neutral thermoresponsive and one polycationic block and the pH-dependnent complexation between model proteins or biomimetic J-aggregating chromophores and the polycationic block is demonstrated. Spin casting is used to prepare nanostructured films from the protein-block copolymer and chromophore-block copolymer coacervates. After film formation, the lower critical solution temperature (LCST) of the thermoresponsive block allows the nanomaterial to be effectively immobilized in aqueous environments at physiological temperatures, enabling use of the materials for biomolecule immobilization and controlled release. In the case of protein nanotemplating, the ionic environment in which the protein is confined enables the majority of the protein (80%) to retain its activity, even after having been dehydrated in vacuum and confined in the thin film.

  6. Synthesis of an amphiphilic dendrimer-like block copolymer and its application on drug delivery

    KAUST Repository

    Wang, Shuaipeng

    2014-10-27

    Dendrimer-like amphiphilic copolymer is a kind of three-dimensional spherical structure polymer. An amphiphilic dendrimer-like diblock copolymer, PEEGE-G2-b-PEO(OH)12, constituted of a hydrophobic poly(ethoxyethyl glycidol ether) inner core and a hydrophilic poly(ethylene oxide) outer layer, has been successfully synthesized by the living anionic ring-opening polymerization method. The intermediates and targeted products were characterized with 1H NMR spectroscopy and gel permeation chromatography. The application on drug delivery of dendrimer-like diblock copolymer PEEGE-G2-b-PEO(OH)12 using DOX as a model drug was also studied. The drug loading content and encapsulation efficiency were found at 13.07% and 45.75%, respectively. In vitro release experiment results indicated that the drug-loaded micelles exhibited a sustained release behavior under acidic media.

  7. Spontaneous symmetry breaking: formation of Janus micelles

    NARCIS (Netherlands)

    Voets, I.K.; Fokkink, R.G.; Hellweg, T.; King, S.M.; Waard, de P.; Keizer, de A.; Cohen Stuart, M.A.

    2009-01-01

    We describe the preparation and solution properties of Janus micelles, i.e., non-centrosymmetric nanoparticles with compartmentalized shells, via co-assembly of two fully water-soluble block copolymers. They consist of a mixed core of poly(N-methyl-2-vinyl pyridinium iodide) (P2MVP) and poly(acrylic

  8. Synthesis of carboxylic block copolymers via reversible addition fragmentation transfer polymerization for tooth erosion prevention.

    Science.gov (United States)

    Lei, Y; Wang, T; Mitchell, J W; Qiu, J; Kilpatrick-Liverman, L

    2014-12-01

    Dental professionals are seeing a growing population of patients with visible signs of dental erosion. The approach currently being used to address the problem typically leverages the enamel protection benefits of fluoride. In this report, an alternative new block copolymer with a hydrophilic polyacrylic acid (PAA) block and a hydrophobic poly(methyl methacrylate) (PMMA) block was developed to similarly reduce the mineral loss from enamel under acidic conditions. This series of PMMA-b-PAA block copolymers was synthesized by reversible addition fragmentation transfer (RAFT) polymerization. Their structures were characterized by gel permeation chromatography (GPC) and (1)H nuclear magnetic resonance (NMR) spectra. The molar fractions of acrylic acid (AA) in the final block copolymer were finely controlled from 0.25 to 0.94, and the molecular weight (Mn) of PMMA-b-PAA was controlled from 10 kDa to 90 kDa. The binding capability of the block copolymer with hydroxyapatite (HAP) was investigated by ultraviolet-visible spectroscopy (UV-Vis) and Fourier transform infrared (FTIR) spectroscopy. FTIR spectra confirmed that the PMMA-b-PAA block copolymer could bind to HAP via bridging bidentate bonds. Both UV-Vis and FTIR spectra additionally indicated that a high polymer concentration and low solution pH favored the polymer binding to HAP. The erosion-preventing efficacy of the PMMA-b-PAA block copolymer in inhibiting HAP mineral loss was quantitatively evaluated by atomic absorption spectroscopy (AAS). Based on the results, polymer treatment reduced the amount of calcium released by 27% to 30% in comparison with the unprotected samples. Scanning electron microscope (SEM) observations indicated that PMMA-b-PAA polymer treatment protected enamel from acid erosion. This new amphiphilic block copolymer has significant potential to be integrated into dentifrices or mouthrinses as an alternative non-fluoride ingredient to reduce tooth erosion. PMID:25248611

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

    Directory of Open Access Journals (Sweden)

    2011-02-01

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

  10. A soft and conductive PDMS-PEG block copolymer as a compliant electrode for dielectric elastomers

    DEFF Research Database (Denmark)

    A Razak, Aliff Hisyam; Szabo, Peter; Skov, Anne Ladegaard

    conductivity. The combination of soft chainextended PDMS-PEG block copolymers and conductive MWCNTs results in a soft and conductive block copolymer composite which potentially can be used as a compliant and highly stretchable electrode for dielectric elastomers. The addition of MWCNTs into the PDMS-PEG matrix......Conductive PDMS-PEG block copolymers (Mn = 3 – 5 kg/mol) were chain-extended (Mn = 30 – 45 kg/mol) using hydrosilylation reaction as presented in figure 1. Subsequently, the extended copolymers were added to a conductive nano-filler (multi-walled carbon nanotubes – MWCNTs) in order to enhance...... not only increases the conductivity, but also increases mechanical strength by reinforcing the network1. However, incorporating MWCNTs into the PDMS-PEG matrix is challenging due to strong van der Waals forces between the MWCNTs2. In the present study, MWCNTs were dispersed in organic solvent (N...

  11. Surface affinity role in graphoepitaxy of lamellar block copolymers

    Science.gov (United States)

    Claveau, G.; Quemere, P.; Argoud, M.; Hazart, J.; Pimenta Barros, P.; Sarrazin, A.; Posseme, N.; Tiron, R.; Chevalier, X.; Nicolet, C.; Navarro, C.

    2016-03-01

    Overcoming the optical limitations of 193nm immersion lithography can be achieved using Directed Self Assembly (DSA) of block-copolymers (BCPs) as a low-cost and versatile complementary technique. The goal of this paper is to investigate the potential of DSA to address line and space (L/S) high resolution patterning by performing the density multiplication of lines with the graphoepitaxy approach. As surface affinity is a key parameter in self-assembly, three variations, or "flavors", of DSA template affinity are investigated regarding several success criteria such as morphology control or defectivity. More precisely, both the methodology to register DSA defects and the impact of process parameters on defectivity are detailed. Using the 300mm pilot line available in LETI and Arkema's advanced materials, we investigate process optimization of DSA line/space patterning of a 38nm period lamellar PS-b-PMMA BCP (L38). For this study, our integration scheme, depicted in figure 2-1, is based on BCP self-assembly inside organic hard mask guiding patterns obtained using 193i nm lithography. Defect analysis coupled with the fine tuning of process parameters (annealing, brush material) provided the optimum conditions for the L38 self-assembly. Using such conditions, DSA using the three affinity flavors is investigated by means of SEM top-view and cross-section review. Lithographic performances of one selected flavor are then evaluated with the comparison of Process Windows (PWs) function of either commensurability, morphology or LWR. This work is a first step in finding the best process for an industrial graphoepitaxy approach.

  12. Preparation of Pickering double emulsions using block copolymer worms.

    Science.gov (United States)

    Thompson, Kate L; Mable, Charlotte J; Lane, Jacob A; Derry, Mathew J; Fielding, Lee A; Armes, Steven P

    2015-04-14

    The rational formulation of Pickering double emulsions is described using a judicious combination of hydrophilic and hydrophobic block copolymer worms as highly anisotropic emulsifiers. More specifically, RAFT dispersion polymerization was utilized to prepare poly(lauryl methacrylate)-poly(benzyl methacrylate) worms at 20% w/w solids in n-dodecane and poly(glycerol monomethacrylate)-poly(2-hydroxypropyl methacrylate)-poly(benzyl methacrylate) worms at 13% w/w solids in water by polymerization-induced self-assembly (PISA). Water-in-oil-in-water (w/o/w) double emulsions can be readily prepared with mean droplet diameters ranging from 30 to 80 μm using a two-stage approach. First, a w/o precursor emulsion comprising 25 μm aqueous droplets is prepared using the hydrophobic worms, followed by encapsulation within oil droplets stabilized by the hydrophilic worms. The double emulsion droplet diameter and number of encapsulated water droplets can be readily varied by adjusting the stirring rate employed during the second stage. For each stage, the droplet volume fraction is relatively high at 0.50. The double emulsion nature of the final formulation was confirmed by optical and fluorescence microscopy studies. Such double emulsions are highly stable to coalescence, with little or no change in droplet diameter being detected over storage at 20 °C for 10 weeks as judged by laser diffraction. Preliminary experiments indicate that the complementary o/w/o emulsions can also be prepared using the same pair of worms by changing the order of homogenization, although somewhat lower droplet volume fractions were required in this case. Finally, we demonstrate that triple and even quadruple emulsions can be formulated using these new highly anisotropic Pickering emulsifiers.

  13. Interactions between plasma and block copolymers used in directed self-assembly patterning

    Science.gov (United States)

    Sirard, Stephen; Azarnouche, Laurent; Gurer, Emir; Durand, William; Maher, Michael; Mori, Kazunori; Blachut, Gregory; Janes, Dustin; Asano, Yusuke; Someya, Yasunobu; Hymes, Diane; Graves, David; Ellison, Christopher J.; Willson, C. Grant

    2016-03-01

    The directed self-assembly (DSA) of block copolymers offers a promising route for scaling feature sizes below 20 nm. At these small dimensions, plasmas are often used to define the initial patterns. It is imperative to understand how plasmas interact with each block in order to design processes with sufficient etch contrast and pattern fidelity. Symmetric lamella forming block copolymers including, polystyrene-b-poly(methyl methacrylate) and several high-χ silicon-containing and tin-containing block copolymers were synthesized, along with homopolymers of each block, and exposed to various oxidizing, reducing, and fluorine-based plasma processes. Etch rate kinetics were measured, and plasma modifications of the materials were characterized using XPS, AES, and FTIR. Mechanisms for achieving etch contrast were elucidated and were highly dependent on the block copolymer architecture. For several of the polymers, plasma photoemissions were observed to play an important role in modifying the materials and forming etch-resistant protective layers. Furthermore, it was observed for the silicon- and tin-containing polymers that an initial transient state exists, where the polymers exhibit an enhanced etch rate, prior to the formation of the etch-resistant protective layer. Plasma developed patterns were demonstrated for the differing block copolymer materials with feature sizes ranging from 20 nm down to approximately 5 nm.

  14. Thermosensitive Polymer Nanocontainers Prepared by Self-Assembly of Block Copolymers

    Institute of Scientific and Technical Information of China (English)

    Chen Xiangrong; Ding Xiaobing; Zheng Zhaohui; Peng Yuxing

    2004-01-01

    In recent years, considerable effort has been devoted to the preparation of polymer nanocontainers because of their unique advantages. Compared to polymer microspheres or micelles,polymer nanocontainers are hollow-sphere structures and can encapsulate large quantities of guest molecules or large-sized guests within the "empty" core domain. Compared to polymer vesicles,polymer nanocontainers have enough mechanical stability to prevent them from structure changes due to covalent or ionic interactions responsible for their formation. Therefore, polymer nanocontainers have many potential applications such as confined reaction vesicles, drug carriers,protective shells for cells or enzymes, artificial cells and so on. However, most of polymer nanocontainers reported by now, load and release guest molecules from their interior only through diffuse mechanism. It is rather difficult to control intelligently the process based on demands. In order to solve this problem, one promising strategy is to design intelligent polymer nanocontainers.They can undergo reversible structural transitions from a closed to an open state with the help of external stimuli.In this paper, we report on our preliminary study of the thermosensitive polymer nanocontainers formed by self-assembly of the block copolymers PCEMA-b-PNIPAM and sequent photo-crosslinking of PCEMA shells.Block copolymers PCEMA-b-PNIPAM were prepared by reacting PHEMA-b-PNIPAM with excess cinnamoyl chloride in pyridine at room temperature, where PHEMA-b-PNIPAM was prepared by reacting succinimidyl ester of PHEMA-COOH with PNIPAAm-NH2, similar to the method of the literature. The block copolymers were characterized by FTIR and 1H-NMR and GPC.To obtain polymer vesicles, deionized water, as a precipitant, was added at a rate of 0.3wt%/10s with vigorous stirring to the PCEMA-b-PNIPAM solution in THE After the formation of polymer vesicles, more water was added until the water content reached ca.50wt%. The hollow structure of the

  15. COMPARISON OF DRUG DELIVERY PROPERTIES OF PEG-b-PDHPC MICELLES WITH DIFFERENT COMPOSITIONS

    Institute of Scientific and Technical Information of China (English)

    Chun-yan Long; Ming-ming Sheng; Bin He; Yao Wu; Gang Wang; Zhong-wei Gu

    2012-01-01

    An anti-tumor drug doxombicin was encapsulated in micelles of poly(ethylene glycol)-b-poly(2,2-dihydroxyl-methyl propylene carbonate) (PEG-b-PDHPC) diblock copolymers.The morphology of both blank micelles and drug loaded micelles was characterized by TEM.The in vitro drug release profiles of micelles were investigated.The cytotoxicity of the micelles was evaluated by incubating with Hela tumor cells and 3T3 fibroblasts.The drug loaded micelles were co-cultured with HepG2 cells to evaluate the in vitro anti-tumor efficacies.The results showed that the mean sizes of both micelles with different copolymer compositions increased after being loaded with drugs.The drug release rate of PEG45-b-PDHPC34 micelles was faster than that of rnPEG114-b-PDHPC26 micelles.Both of the two block copolymers were non-toxic.The confocal laser scanning microscopy and flow cytometry results showed that both the drug loaded micelles could be internalized efficiently in HepG2 cells.The PEG45-b-PDHPC34 micelles exhibited higher anti-tumor activity comparing to mPEG114-b-PDHPC26 micelles.

  16. 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 polymerizati

  17. Influence of polydispersity on the phase behavior of statistical multiblock copolymers with Schultz-Zimm block molecular weight distributions

    NARCIS (Netherlands)

    Angerman, H.J.; Brinke, G. ten; Slot, J.J.M.

    1999-01-01

    In this paper we investigate in a systematic way the influence of polydispersity in the block lengths on the phase behavior of AB-multiblock copolymer melts. As model system we take a polydisperse multiblock copolymer for which both the A-blocks and the B-blocks satisfy a Schultz-Zimm distribution.

  18. Paclitaxel-incorporated nanoparticles using block copolymers composed of poly(ethylene glycol)/poly(3-hydroxyoctanoate)

    OpenAIRE

    Kim, Hyun Yul; Ryu, Je Ho; Chu, Chong Woo; Son, Gyung Mo; Jeong, Young-IL; Kwak, Tae-Won; Kim, Do Hyung; Chung, Chung-Wook; Rhee, Young Ha; Kang, Dae Hwan; Kim, Hyung Wook

    2014-01-01

    Block copolymers composed of poly(3-hydroxyoctanoate) (PHO) and methoxy poly(ethylene glycol) (PEG) were synthesized to prepare paclitaxel-incorporated nanoparticle for antitumor drug delivery. In a 1H-NMR study, chemical structures of PHO/PEG block copolymers were confirmed and their molecular weight (M.W.) was analyzed with gel permeation chromatography (GPC). Paclitaxel as a model anticancer drug was incorporated into the nanoparticles of PHO/PEG block copolymer. They have spherical shapes...

  19. Self-Assembly of Oligosaccharide-b-PMMA Block Copolymer Systems: Glyco-Nanoparticles and Their Degradation under UV Exposure.

    Science.gov (United States)

    Zepon, Karine M; Otsuka, Issei; Bouilhac, Cécile; Muniz, Edvani C; Soldi, Valdir; Borsali, Redouane

    2016-05-10

    This paper discusses the self-assembly of oligosaccharide-containing block copolymer and the use of ultraviolet (UV) to obtain nanoporous glyco-nanoparticles by photodegradation of the synthetic polymer block. Those glyco-nanoparticles consisting of oligosaccharide-based shell and a photodegradable core domain were obtained from the self-assembly of maltoheptaose-block-poly(methyl methacrylate) (MH-b-PMMA48) using the nanoprecipitation protocol. MH-b-PMMA48 self-assembled into well-defined spherical micelles (major compound) with a hydrodynamic radius (Rh) of ca. 10 nm and also into large compound micellar aggregates (minor compound) with an Rh of ca. 65 nm. The oligosaccharide shells of these glyco-nanoparticles were cross-linked through the Michael-type addition of divinyl sulfone under dilute conditions to minimize the intermicellar cross-linking. The core domain photodegradation of the cross-linked glyco-nanoparticles was induced under exposure to 254 nm UV radiation, resulting in porous glyco-nanoparticles with an Rh of ca. 44 nm. The morphology of the cross-linked shell and the core photodegradation of these glyco-nanoparticles were characterized using static light scattering, dynamic light scattering, Fourier transform infrared spectroscopy, proton nuclear magnetic resonance, field-emission gun-scanning electron microscopy, and transmission electron microscopy. The innovative aspect of this approach concerns the fact that after removing the PMMA domains the porous nanoparticles are mostly composed of biocompatible and nontoxic oligosaccharides. PMID:27054350

  20. Synthesis of Cobalt Containing Block Copolymers Via Ring Opening Metathesis Polymerizastion (ROMP)

    Institute of Scientific and Technical Information of China (English)

    Bongjin Moon; Minhyuk Kang

    2004-01-01

    In order to realize a metal containing nano-structure, a block-copolymer containing alkynyl groups in one block was designed and synthesized by living ring opening metathesis polymerization (ROMP) technique. The newly developed bis-3-bromopyridine complex of Grubbs catalyst was employed in the series of polymerization and it yielded the desired polymers with great molecular weight control and narrow polydispersities. The characteristics of the block copolymers were investigated by gel permeation chromatography, H- and 13H- NMR spectroscopy. Complexation of the alkynyl group containing block copolymers by treatment with dicobalt octacarbonyl occurred smoothly in 5 min at room temperature. GPC analysis before and after cobalt complexation indicated a significant increase of the hydrodynamic volume. AFM images of the films before and after the complexation also showed a noticeable change in its morphology where grain sizes become smaller and more regular upon complexation.

  1. Analytic Structure of the SCFT Energy Functional of Multicomponent Block Copolymers

    CERN Document Server

    Jiang, Kai; Zhang, Pingwen

    2013-01-01

    This paper concerns the analytic structure of the self-consistent field theory (SCFT) energy functional of multicomponent block copolymer systems which contain more than two chemically distinct blocks. The SCFT has enjoyed considered success and wide usage in investigation of the complex phase behavior of block copolymers. It is well-known that the physical solutions of the SCFT equations are saddle points, however, the analytic structure of the SCFT energy functional has received little attention over the years. A recent work by Fredrickson and collaborators [see the monograph by Fredrickson, The Equilibrium Theory of Inhomogeneous Polymers, (2006), pp. 203-209] has analysed the mathematical structure of the field energy functional for polymeric systems, and clarified the index-1 saddle point nature of the problem produced by the incompressibility constraint. In this paper, our goals are to draw further attention to multicomponent block copolymers utilizing the Hubbard-Stratonovich transformation used by Fre...

  2. Sub-15nm Silicon Lines Fabrication via PS-b-PDMS Block Copolymer Lithography

    DEFF Research Database (Denmark)

    Rasappa, Sozaraj; Schulte, Lars; Borah, Dipu;

    2013-01-01

    This paper describes the fabrication of nanodimensioned silicon structures on silicon wafers from thin films of a poly(styrene)-block-poly(dimethylsiloxane) (PS-b-PDMS) block copolymer (BCP) precursor self-assembling into cylindrical morphology in the bulk. The structure alignment of the PS-b-PDM...

  3. Synthesis and properties of lyotropic poly(amide-block-aramid) copolymers

    NARCIS (Netherlands)

    De Ruijter, C.

    2006-01-01

    This thesis describes the synthesis and properties of liquid crystalline block copolymers comprised of alternating rigid and flexible blocks for the preparation of self-reinforcing materials. The incentive for this work was the expectation that the rigid segments would phase separate on a microscopi

  4. Multi-block sulfonated poly(phenylene) copolymer proton exchange membranes

    Science.gov (United States)

    Fujimoto, Cy H.; Hibbs, Michael; Ambrosini, Andrea

    2012-02-07

    Improved multi-block sulfonated poly(phenylene) copolymer compositions, methods of making the same, and their use as proton exchange membranes (PEM) in hydrogen fuel cells, direct methanol fuel cells, in electrode casting solutions and electrodes. The multi-block architecture has defined, controllable hydrophobic and hydrophilic segments. These improved membranes have better ion transport (proton conductivity) and water swelling properties.

  5. Photocatalytic Nanostructuring of Graphene Guided by Block Copolymer Self-Assembly

    DEFF Research Database (Denmark)

    Wang, Zhongli; Li, Tao; Schulte, Lars;

    2016-01-01

    graphene nanomesh was fabricated by photocatalysis of single-layer graphene suspended on top of TiO2-covered nanopillars, which were produced by combining block copolymer nanolithography with atomic layer deposition. Graphene nanoribbons were also prepared by the same method applied to a line-forming block...

  6. Block-copolymer of polyethylene glycol and polylysine as a carrier of organic iodine: design of long-circulating particulate contrast medium for X-ray computed tomography.

    Science.gov (United States)

    Trubetskoy, V S; Gazelle, G S; Wolf, G L; Torchilin, V P

    1997-01-01

    In order to obtain small, polymer-stabilized particulate carriers for organic iodine to serve as a contrast agent for X-ray computed tomography (CT) an attempt was made to design a carrier based on polymeric micelles. Here we describe the synthesis of an iodine-containing amphiphilic block-copolymer which can micellize in aqueous solutions. The two blocks of the copolymer consisted of methoxypoly(ethyleneglycol) and poly[epsilon,N-(triiodobenzoyl)-L-lysine]. Upon dispersion in water, the block copolymer formed particles with average diameter 80 nm and iodine content up to 44.7%. The particles start to dissociate to the individual polymeric chains in the concentration range of 0.05-0.5 microM in water at 23 degrees C. Upon intravenous injection at 250 mg of iodine/kg (570 mg of the agent/kg) in rabbits the medium demonstrated exceptional 24 hr half-life in the blood substantiating corona/core structure of the particles with PEG chains protecting the iodine-containing core. The possible use of these particulates as contrast medium for X-ray computed tomography is discussed.

  7. DETERMINATION OF THE CRYSTALLINITY IN DIFFERENT TYPE POLY (OXYETHYLENE -STYRENE )BLOCK COPOLYMERS BY X- RAY DIFFRACTION METHOD

    Institute of Scientific and Technical Information of China (English)

    YAO Ning

    1989-01-01

    By means of the intensity theory of X- ray scattering and the two - phase concept of high polymer, the basic formula of the crystallinity in block copolymers has been proposed after the corrections of atomic, temperature, absorption, Lorentz and polarization factor. Application of this method to different type poly (oxyethylene - styrene) block copolymers and the same type block copolymers with different EO contents indicates that the crystallinity in poly (oxyethylene - styrene) block copolymers increases with the increase of the EO content and decreases in the order: PEO - PS - PEO > PEO - PS > PS - PEO - PS.

  8. First observation of an ordered microphase in melts of poly(oxyethylene)-poly(oxypropylene) block copolymers

    DEFF Research Database (Denmark)

    Patrick, J.; Fairclough, J.P.A.; Yu, G.E.;

    2000-01-01

    The first observation of ordered microphase structures in poly(oxyethylene)-poly(oxypropylene) diblock copolymers melts is reported. Two diblock copolymers were synthesised by anionic polymerisation, i.e. E130P58 and E107P69 where E represents an oxyethylene unit, OCH2CH2, and P an oxypropylene...... triblock copolymer with perdeuterated P blocks, E(33)dP(42)E(33), was synthesised and studied in the melt phase by small-angle neutron scattering. This allowed determination of the temperature dependence of the Flory-Huggins interaction parameter for the poly(oxyethylene)-poly(oxypropylene) system, i...

  9. Epitaxial relationships for hexagonal-to-cubic phase transition in a block copolymer mixture

    DEFF Research Database (Denmark)

    Schulz, M.F.; Bates, F.S.; Almdal, K.;

    1994-01-01

    Small-angle neutron scattering experiments have revealed an epitaxial relationship between the hexagonal cylinder phase, and a bicontinuous cubic phase with Ia3dBAR space group symmetry, in a poly(styrene)-poly(2-vinylpyridine) diblock copolymer mixture. Proximity to the order-disorder transition...... and an inelastic low frequency rheological response suggest that the cubic phase is stabilized by fluctuations. These results identify block copolymers as model compounds for investigating the thermodynamics and dynamics of complex ''soft'' condensed matter....

  10. An Observation on the Microphase Separation of Poly(methyl methacrylate)-block-Polystyrene Copolymer

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    The phase behavior of a well-defined poly(methyl methacrylate)-b-polystyrene block copolymer was studied by transmission electron microscope.The results show that a microphase transition may have occurred in the copolymer film.A kind of lamellae and an ordered bicontinuous double-diamond morphology are observed clearly.The lamellar morphology reveals a larger period of about 400 nm.

  11. Synthesis of manganese oxide supported on mesoporous titanium oxide: Influence of the block copolymer

    Energy Technology Data Exchange (ETDEWEB)

    Schmit, F. [Laboratoire des Multimatériaux et Interfaces, UMR CNRS 5615, Bât. Berthollet, Université Claude Bernard—Lyon 1, 43 Bd 11 novembre 1918, 69622 Villeurbanne (France); IRCELYON, Institut de recherches sur la catalyse et l’environnement de Lyon (UMR 5256 CNRS/Université Lyon 1), Lyon (France); Bois, L., E-mail: laurence.bois@univ-lyon1.fr [Laboratoire des Multimatériaux et Interfaces, UMR CNRS 5615, Bât. Berthollet, Université Claude Bernard—Lyon 1, 43 Bd 11 novembre 1918, 69622 Villeurbanne (France); Chiriac, R.; Toche, F.; Chassagneux, F. [Laboratoire des Multimatériaux et Interfaces, UMR CNRS 5615, Bât. Berthollet, Université Claude Bernard—Lyon 1, 43 Bd 11 novembre 1918, 69622 Villeurbanne (France); Besson, M.; Descorme, C. [IRCELYON, Institut de recherches sur la catalyse et l’environnement de Lyon (UMR 5256 CNRS/Université Lyon 1), Lyon (France); Khrouz, L. [ENS LYON Laboratoire de Chimie (LR6, site Monod), 46, allée d’Italie, 69364 Lyon Cedex 07 (France)

    2015-01-15

    Manganese oxides supported on mesoporous titanium oxides were synthesized via a sol–gel route using block copolymer self-assembly. The oxides were characterized by X-ray diffraction, infrared spectroscopy, thermal analyses, nitrogen adsorption/desorption, electron microscopy and electronic paramagnetic resonance. A mesoporous anatase containing amorphous manganese oxide particles could be obtained with a 0.2 Mn:Ti molar ratio. At higher manganese loading (0.5 Mn:Ti molar ratio), segregation of crystalline manganese oxide occurred. The influence of block copolymer and manganese salt on the oxide structure was discussed. The evolution of the textural and structural characteristics of the materials upon hydrothermal treatment was also investigated. - Graphical abstract: One-pot amorphous MnO{sub 2} supported on mesoporous anataseTiO{sub 2}. - Highlights: • Mesoporous manganese titanium oxides were synthesized using block copolymer. • Block copolymers form complexes with Mn{sup 2+} from MnCl{sub 2}. • With block copolymer, manganese oxide can be dispersed around the titania crystallites. • With Mn(acac){sub 2}, manganese is dispersed inside titania. • MnOOH crystallizes outside mesoporous titania during hydrothermal treatment.

  12. Controlled specific placement of nanoparticles into microdomains of block copolymer thin films

    Energy Technology Data Exchange (ETDEWEB)

    Bae, Joonwon, E-mail: joonwonbae@gmail.com [Department of Applied Chemistry, Dongduk Women' s University, Seoul 136-714 (Korea, Republic of); Kim, Jungwook [Department of Chemical and Biomolecular Engineering, Sogang University, Seoul 121-742 (Korea, Republic of); Park, Jongnam, E-mail: jnpark@unist.ac.kr [Interdisciplinary School of Green Energy, Ulsan National Institute of Science and Technology (UNIST), Ulsan 689-798 (Korea, Republic of)

    2014-07-01

    Conceptually attractive hybrid materials composed of nanoparticles and elegant block copolymers have become important for diverse applications. In this work, controlled specific placement of nanoparticles such as gold (Au) and titania (TiO{sub 2}) into microphase separated domains in poly(styrene)-b-poly(2-vinylpyridine) (PS-b-P2VP) block copolymer thin films was demonstrated. The effect of nanoparticle surface functionality on the spatial location of particles inside polymer film was observed by transmission electron microscopy. It was revealed that the location of nanoparticles was highly dependent on the surface ligand property of nanoparticle. In addition, the microphase separation behavior of thin block copolymer film was also affected by the nanoparticle surface functional groups. This study might provide a way to understand the properties and behaviors of numerous block copolymer/nanoparticle hybrid systems. - Highlights: • Controlled location of nanoparticles in the block copolymer matrix • Tailoring surface functionality of metal nanocrystals • Fabrication of homogeneous nanocomposites using organic inorganic components • Possibility for the preparation of nanohybrids.

  13. New Strategies for Constructing Polymeric Micelles and Hollow Spheres Via Self-Assembly

    Institute of Scientific and Technical Information of China (English)

    Ming Jiang

    2005-01-01

    @@ 1Introduction In recent years, self-assembly of block copolymers leading to micelles in selective solvents, which dissolve only one of the blocks, has developed rapidly because the micelles are very strong candidates for potential applications in advanced technologies. The micelles usually have core-shell structure which are connected by covalent bonds. Based on our long-term research on interpolymer complexation due to hydrogen bonding, where we noticed that the complexation often led to the formation of irregular aggregates, we succeeded recently in developing a series of new approaches to polymeric micelles and hollow spheres via specific intermolecular interactions. As in these approaches, a variety of polymers with interacting groups i.e. homopolymers, random copolymers, graft copolymers as well as low mass compounds (LMC), can be used as building blocks, our research strategies have substantially extended the field of self-assembly.

  14. Polydimethylsiloxane-polymethacrylate block copolymers tethering quaternary ammonium salt groups for antimicrobial coating

    Energy Technology Data Exchange (ETDEWEB)

    Qin, Xiaoshuai; Li, Yancai; Zhou, Fang; Ren, Lixia; Zhao, Yunhui, E-mail: zhaoyunhui@tju.edu.cn; Yuan, Xiaoyan

    2015-02-15

    Highlights: • A series of PDMS-b-QPDMAEMA block copolymers were synthesized via RAFT polymerization. • The composition and morphology of the copolymer films strongly depended on the content of QPDMAEMA. • Migration of QPDMAEMA blocks toward surface was promoted when contacting with water. • Heterogeneous film surfaces with higher N{sup +} content exhibited more obvious antimicrobial activity. - Abstract: Block copolymers PDMS-b-PDMAEMA were synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization involving N,N-dimethylaminoethyl methacrylate (DMAEMA) by using poly(dimethylsiloxane) (PDMS) macro-chain transfer agent. And, the tertiary amino groups in PDMAEMA were quaternized with n-octyliodide to provide quaternary ammonium salts (QPDMAEMA). The well-defined copolymers generated composition variation and morphology evolvement on film surfaces, which were characterized by X-ray photoelectron spectroscopy, atomic force microscopy, and contact angle measurements. The results indicated that the enrichment of QPDMAEMA brought about lower elemental ratios of Si/N on the film surfaces. The surface morphologies evolved with the variations of QPDMAEMA content, and the variation trend of film roughness was exactly opposite to that of water contact angle hysteresis. With regard to structure-antimicrobial relationships, the copolymer films had more evident antimicrobial activity against Gram-positive, Bacillus subtilis, and the surfaces with heterogeneous morphology and higher N{sup +} content presented better antimicrobial activity. The functionalized copolymers based PDMS and quaternary ammonium salts materials have the potential applications as antimicrobial coatings.

  15. Structure and ionic conductivity of block copolymer electrolytes over a wide salt concentration range

    Science.gov (United States)

    Chintapalli, Mahati; Le, Thao; Venkatesan, Naveen; Thelen, Jacob; Rojas, Adriana; Balsara, Nitash

    Block copolymer electrolytes are promising materials for safe, long-lasting lithium batteries because of their favorable mechanical and ion transport properties. The morphology, phase behavior, and ionic conductivity of a block copolymer electrolyte, SEO mixed with LiTFSI was studied over a wide, previously unexplored salt concentration range using small angle X-ray scattering, differential scanning calorimetry and ac impedance spectroscopy, respectively. SEO exhibits a maximum in ionic conductivity at twice the salt concentration that PEO, the homopolymer analog of the ion-containing block, does. This finding is contrary to prior studies that examined a more limited range of salt concentrations. In SEO, the phase behavior of the PEO block and LiTFSI closely resembles the phase behavior of homopolymer PEO and LiTFSI. The grain size of the block copolymer morphology was found to decrease with increasing salt concentration, and the ionic conductivity of SEO correlates with decreasing grain size. Structural effects impact the ionic conductivity-salt concentration relationship in block copolymer electrolytes. SEO: polystyrene-block-poly(ethylene oxide); also PS-PEO LiTFSI: lithium bis(trifluoromethanesulfonyl imide

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

    NARCIS (Netherlands)

    Martens, A.A.

    2008-01-01

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

  17. In-situ formation of biodegradable hydrogels by stereocomplexation of PEG-(PLLA)8 and PEG-(PDLA)8 star block copolymers.

    Science.gov (United States)

    Hiemstra, Christine; Zhong, Zhiyuan; Li, Liangbin; Dijkstra, Pieter J; Feijen, Jan

    2006-10-01

    Eight-arm poly(ethylene glycol)-poly(L-lactide), PEG-(PLLA)(8), and poly(ethylene glycol)-poly(D-lactide), PEG-(PDLA)(8), star block copolymers were synthesized by ring-opening polymerization of either L-lactide or D-lactide at room temperature in the presence of a single-site ethylzinc complex and 8-arm PEG (M(n) = 21.8 x 10(3) or 43.5 x 10(3)) as a catalyst and initiator, respectively. High lactide conversions (>95%) and well-defined copolymers with PLLA or PDLA blocks of the desired molecular weights were obtained. Star block copolymers were water-soluble when the number of lactyl units per poly(lactide) (PLA) block did not exceed 14 and 17 for PEG21800-(PLA)(8) and PEG43500-(PLA)(8), respectively. PEG-(PLA)(8) stereocomplexed hydrogels were prepared by mixing aqueous solutions with equimolar amounts of PEG-(PLLA)(8) and PEG-(PDLA)(8) in a polymer concentration range of 5-25 w/v % for PEG21800-(PLA)(8) star block copolymers and of 6-8 w/v % for PEG43500-(PLA)(8) star block copolymers. The gelation is driven by stereocomplexation of the PLLA and PDLA blocks, as confirmed by wide-angle X-ray scattering experiments. The stereocomplexed hydrogels were stable in a range from 10 to 70 degrees C, depending on their aqueous concentration and the PLA block length. Stereocomplexed hydrogels at 10 w/v % polymer concentration showed larger hydrophilic and hydrophobic domains as compared to 10 w/v % single enantiomer solutions, as determined by cryo-TEM. Correspondingly, dynamic light scattering showed that 1 w/v % solutions containing both PEG-(PLLA)(8) and PEG-(PDLA)(8) have larger "micelles" as compared to 1 w/v % single enantiomer solutions. With increasing polymer concentration and PLLA and PDLA block length, the storage modulus of the stereocomplexed hydrogels increases and the gelation time decreases. Stereocomplexed hydrogels with high storage moduli (up to 14 kPa) could be obtained at 37 degrees C in PBS. These stereocomplexed hydrogels are promising for use in

  18. Synthesis of Carboxylic Block Copolymers via Reversible Addition Fragmentation Transfer Polymerization for Tooth Erosion Prevention

    OpenAIRE

    Lei, Y.; Wang, T.; Mitchell, J. W.; Qiu, J.; Kilpatrick-Liverman, L.

    2014-01-01

    Dental professionals are seeing a growing population of patients with visible signs of dental erosion. The approach currently being used to address the problem typically leverages the enamel protection benefits of fluoride. In this report, an alternative new block copolymer with a hydrophilic polyacrylic acid (PAA) block and a hydrophobic poly(methyl methacrylate) (PMMA) block was developed to similarly reduce the mineral loss from enamel under acidic conditions. This series of PMMA-b-PAA blo...

  19. A functionalizable reverse thermal gel based on a polyurethane/PEG block copolymer

    OpenAIRE

    Park, Daewon; Wu, Wei; Wang, Yadong

    2011-01-01

    Injectable reverse thermal gels have great potentials as biomaterials for tissue engineering and drug delivery. However, most existing gels lack functional groups that can be modified with biomolecules that can guide cell/material interactions. We created an amine-functionalized ABA block copolymer, poly(ethylene glycol)-poly(serinol hexamethylene urethane), or ESHU. This reverse thermal gel consists of a hydrophobic block (B): poly(serinol hexamethylene urethane) and a hydrophilic block (A):...

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

    Science.gov (United States)

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

    2001-03-01

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

  1. Amphiphilic block copolymers in oil-water-surfactant mixtures: efficiency boosting, structure, phase behaviour and mechanism

    Science.gov (United States)

    Gompper, G.; Richter, D.; Strey, R.

    2001-10-01

    The effect of amphiphilic block copolymers on the phase behaviour and structure of ternary microemulsions in water, oil and non-ionic surfactant mixtures is reviewed. Recent experiments have revealed that the addition of small amounts of polyethylenepropylene-polyethyleneoxide block copolymer to the ternary systems leads to a dramatic increase in the volumes of oil and water solubilized into a bicontinuous microemulsion for a given surfactant volume fraction. While phase diagrams directly show the power of the amphiphilic block copolymers as efficiency boosters, the theoretical analysis in terms of bending energy discloses the mechanism for the efficiency boosting as due to the variation of the surfactant film curvature elasticity by tethered polymers in the form of mushrooms at the interface. Neutron scattering experiments employing a high-precision two-dimensional contrast variation technique confirm this picture and demonstrate that the polymer molecules uniformly decorate the surfactant film.

  2. Selective directed self-assembly of coexisting morphologies using block copolymer blends

    Science.gov (United States)

    Stein, A.; Wright, G.; Yager, K. G.; Doerk, G. S.; Black, C. T.

    2016-08-01

    Directed self-assembly (DSA) of block copolymers is an emergent technique for nano-lithography, but is limited in the range of structures possible in a single fabrication step. Here we expand on traditional DSA chemical patterning. A blend of lamellar- and cylinder-forming block copolymers assembles on specially designed surface chemical line gratings, leading to the simultaneous formation of coexisting ordered morphologies in separate areas of the substrate. The competing energetics of polymer chain distortions and chemical mismatch with the substrate grating bias the system towards either line/space or dot array patterns, depending on the pitch and linewidth of the prepattern. This is in contrast to the typical DSA, wherein assembly of a single-component block copolymer on chemical templates generates patterns of either lines/spaces (lamellar) or hexagonal dot arrays (cylinders). In our approach, the chemical template encodes desired local spatial arrangements of coexisting design motifs, self-assembled from a single, sophisticated resist.

  3. Three-dimensional inverse design of nanopatterns with block copolymers and homopolymers

    Science.gov (United States)

    Xu, Dan; Liu, Hong; Zhu, You-Liang; Lu, Zhong-Yuan

    2016-02-01

    We propose a facile inverse design strategy to generate three-dimensional (3D) nanopatterns by using either block copolymers or a binary homopolymer blend via dissipative particle dynamics simulations. We find that the composition window of block copolymers to form a specific 3D morphology can be expanded when the self-assembly of block copolymers is directed by templates. We also find that a binary homopolymer blend can serve as a better candidate in the inverse templating design, since they have similar performances on recovering the target pattern, with much lower cost. This strategy is proved efficient for fabricating templates with desired topographical configuration, and the inverse design idea sheds lights on better control and design of materials with complex nanopatterns.

  4. Three-dimensional inverse design of nanopatterns with block copolymers and homopolymers.

    Science.gov (United States)

    Xu, Dan; Liu, Hong; Zhu, You-Liang; Lu, Zhong-Yuan

    2016-03-01

    We propose a facile inverse design strategy to generate three-dimensional (3D) nanopatterns by using either block copolymers or a binary homopolymer blend via dissipative particle dynamics simulations. We find that the composition window of block copolymers to form a specific 3D morphology can be expanded when the self-assembly of block copolymers is directed by templates. We also find that a binary homopolymer blend can serve as a better candidate in the inverse templating design, since they have similar performances on recovering the target pattern, with much lower cost. This strategy is proved efficient for fabricating templates with desired topographical configuration, and the inverse design idea sheds lights on better control and design of materials with complex nanopatterns. PMID:26880143

  5. AMPHIPHILIC STAR-BLOCK COPOLYMERS BY IODIDE-MEDIATED RADICAL POLYMERIZATION

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    Amphiphilic star-block copolymers composed of polystyrene and poly(acrylic acid) were synthesized by iodidemediated radical polymerization. Firstly, free radical polymerization of styrene was carried out with AIBN as initiator and 1,1,1-trimethyolpropane tri(2-iodoisobutyrate) as chain transfer agent, giving iodine atom ended star-shaped polystyrene with three arm chains, R(polystyrene)3. Secondly, tert-butyl acrylate was polymerization using polystyrene obtained as macro-chain transfer agent, and star-block copolymer, R(polystyrene-b-poly(tert-butyl acrylate))3 with controlled molecular weight was obtained. Finally, amphiphilic star-block copolymer, R(polystyrene-b-poly(acrylic acid))3 was obtained by hydrolysis of R(polystyrene-b-poly(tert-butyl acrylate))3 under acidic condition.

  6. Synthesis of Dumbbell-shaped Hyperbranched Amphiphilic Block Copolymer by Controlled Atom Transfer Radical Polymerization

    Energy Technology Data Exchange (ETDEWEB)

    Kim, In Kyoung; An, Sung Guk; Cho, Chang Gi [Center for Advanced Functional Polymers, Department of Fiber and Polymer Science, Hanyang University, Seoul (Korea); Noh, Si Tae [Department of Chemical Engineering, Hanyang University, Ansan (Korea)

    2001-04-01

    Amphiphilic block copolymers containing hydrophilic ethylene glycol core and hyperbranched polystyrene (PS) arm were synthesized by atom transfer radical polymerization using hydrophilic macroinitiator and p-chloromethyl styrene (CMS) as AB type monomer. Hydrophilic poly(ethylene glycol)(PEG) macroinitiators with difuntional groups were synthesized by reacting PEG and 2-bromopropionyl bromide. The chemical structure, molecular weight, and polydispersity index of the amphiphilic block copolymer were characterized by {sup 1}H-NMR spectroscopy and GPC analysis. The molecular weight increased as the reaction time increased. Polydispersity index of the obtained polymer was relatively narrow (below 1.39). To control chain density of the hyperbranched PS, styrene and CMS were copolymerized. It was found that amphiphilic block copolymer molecule underwent conformational change in different solvents based on the result for {sup 1}H-NMR spectroscopic analysis. 29 refs., 8 figs., 2 tabs.

  7. Efficient Synthesis of Cyclic Block Copolymers by Rotaxane Protocol by Linear/Cyclic Topology Transformation.

    Science.gov (United States)

    Valentina, Stephanie; Ogawa, Takahiro; Nakazono, Kazuko; Aoki, Daisuke; Takata, Toshikazu

    2016-06-20

    High-yielding synthesis of cyclic block copolymer (CBC) using the rotaxane protocol by linear-cyclic polymer topology transformation was first demonstrated. Initial complexation of OH-terminated sec-ammonium salt and a crown ether was followed by the successive living ring-opening polymerizations of two lactones to a linear block copolymer having a rotaxane structure by the final capping of the propagation end. CBC was obtained in a high yield by an exploitation of the mechanical linkage through the translational movement of the rotaxane component to transform polymer structure from linear to cyclic. Furthermore, the change of the polymer topology was translated into a macroscopic change in crystallinity of the block copolymer.

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

    KAUST Repository

    Madhavan, Poornima

    2016-06-01

    Isoporous membranes are attractive for the regulation and detection of transport at the molecular level. A well-defined asymmetric membranes from diblock copolymers with an ordered nanoporous membrane morphologies were fabricated by the combination of block copolymer self-assembly and non-solvent-induced phase separation (NIPS) technique. This is a straightforward and fast one step procedure to develop integrally anisotropic (“asymmetric”) membranes having isoporous top selective layer. Membranes prepared via this method exhibit an anisotropic cross section with a thin separation layer supported from underneath a macroporous support. These membrane poses cylindrical pore structure with ordered nanopores across the entire membrane surfaces with pore size in the range from 20 to 40 nm. Tuning the pore morphology of the block copolymer membranes before and after fabrication are of great interest. In this thesis, we first investigated the pore morphology tuning of asymmetric block copolymer membrane by complexing with small organic molecules. We found that the occurrence of hydrogen-bond formation between PS-b-P4VP block copolymer and –OH/ –COOH functionalized organic molecules significantly tunes the pore morphology of asymmetric nanoporous membranes. In addition, we studied the complexation behavior of ionic liquids with PS-b-P4VP block copolymer in solutions and investigated their effect on final membrane morphology during the non-solvent induced phase separation process. We found that non-protic ionic liquids facilitate the formation of hexagonal nanoporous block copolymer structure, while protic ionic liquids led to a lamella-structured membrane. Secondly, we demonstrated the catalytic activity of the gold nanoparticle-enhanced hollow fiber membranes by the reduction of nitrophenol. Also, we systematically investigated the pore morphology of isoporous PS-b-P4VP using 3D imaging technique. Thirdly, we developed well-distributed silver nanoparticles on the

  9. Self-assembly of pluronic block copolymers in aqueous dispersions of single-wall carbon nanotubes as observed by spin probe EPR.

    Science.gov (United States)

    Florent, Marc; Shvartzman-Cohen, Rina; Goldfarb, Daniella; Yerushalmi-Rozen, Rachel

    2008-04-15

    The self-assembly of Pluronic block copolymers in dispersions of single-wall carbon nanotubes (SWNT) was investigated by spin probe electron paramagnetic resonance (EPR) spectroscopy. Nitroxide spin labeled block copolymers derived from Pluronic L62 and P123 were introduced in minute amounts into the dispersions. X-band EPR spectra of the SWNT dispersions and of native polymer solutions were measured as a function of temperature. All spectra, below and above the critical micelle temperature (CMT), were characteristic of the fast limit motional regime. The temperature dependence of the 14N isotropic hyperfine coupling, aiso, and the rotational correlation time, tauc, were determined. It was observed that, below the CMT, EPR does not distinguish between chains adsorbed on SWNT and free chains. Above CMT, substantial differences were observed: in the native solution, the Pluronics spin labels experience only one environment, Sm, assigned to spin labels in the corona of the Pluronic micelle, whereas in the SWNT dispersions, in addition to Sm, a second population of nonaggregated, individual chains, Si, is observed. The relative amounts of Sm and Si were found to depend on the relative concentrations of the Pluronic and SWNT. Furthermore, the aggregates formed in the SWNT dispersions do not show the typical increase in chain-end mobility as a function of temperature, observed in the post-CMT regime of the native Pluronic solutions. This suggests a larger dynamical coupling among aggregated chains in the presence of the SWNT as compared to the native micelles. The overall findings are consistent with the formation of a new type of aggregates, composed of a SWNT-polymer hybrid. PMID:18331068

  10. Data on macrophage mediated muscle transfection upon delivery of naked plasmid DNA with block copolymers.

    Science.gov (United States)

    Mahajan, Vivek; Gaymalov, Zagit; Alakhova, Daria; Gupta, Richa; Zucker, Irving H; Kabanov, Alexander V

    2016-06-01

    The data contains 14 figures supporting the research article "Horizontal gene transfer from macrophages to ischemic muscles upon delivery of naked DNA with Pluronic block copolymers" [1]. The data explains the surgical procedure and histological characterization of Murine Hind Limb Ischemia. The data also shows the kinetics of luciferase gene expression, spread of GFP expression through muscle and the colocalization of GFP with cellular markers in ischemic muscles injected with pDNA alone or pDNA/Pluronic. Finally the data shows the effect of Pluronic Block Copolymer to enhance total gene expression (cmv-promoter driven luciferase gene) in coculture of DNA transfected MØs with muscle cells. PMID:27222845

  11. Synthesis of Dextran/Methoxy Poly(ethylene glycol) Block Copolymer

    OpenAIRE

    Young-Il Jeong; Dong-Gon Kim; Dae-Hwan Kang

    2013-01-01

    We synthesized a block copolymer composed of dextran and methoxy poly(ethylene glycol) (mPEG). To accomplish this, the end group of dextran was modified by reductive amination. The aminated dextran (Dextran-NH2) showed the intrinsic peaks of both dextran at 3~5.5 ppm and hexamethylene diamine at 1~2.6 ppm at 1H nuclear magnetic resonance (NMR) spectrum. The amino end group of dextran was conjugated with mPEG to make the block copolymer consisting of dextran/mPEG (abbre...

  12. Enhancing relative permittivity by incorporating PDMS-PEG multi block copolymers in binary polymer blends

    DEFF Research Database (Denmark)

    A Razak, Aliff Hisyam; Szabo, Peter; Skov, Anne Ladegaard

    Polydimethylsiloxanes (PDMS) are well-known to actuate with relatively large strains due to low modulus, but they possess lowpermittivity. Contrary, polyethyleneglycols (PEG) are not stretchable but possess high permittivity. Combination of the two polymers in a block copolymer depicts a possibil......Polydimethylsiloxanes (PDMS) are well-known to actuate with relatively large strains due to low modulus, but they possess lowpermittivity. Contrary, polyethyleneglycols (PEG) are not stretchable but possess high permittivity. Combination of the two polymers in a block copolymer depicts a...

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

    Science.gov (United States)

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

    2016-07-01

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

  14. 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).

  15. Synthesis And Properties Of Functional Ultra-High Molecular Weight Transparent Styrene-Butadiene Block Copolymer

    Institute of Scientific and Technical Information of China (English)

    GONG Guang-bi; ZHAO Xu-tao; WANG Gui-lun

    2004-01-01

    Functional ultra-high molecular weight transparent styrene-butadiene block copolymer possesses both high transparency and impact resistance and has excellent comprehensive properties prior to other transparent resins. In this paper we not only use anionic polymerization process which includes 1 time addition of initiator and 3 time addition of monomers, but also introduce functional coupling agent for the fist time to prepare mentioned functional block copolymer.The typical preparation process is described as the following: (a) Adding cyclohexane, styrene and initiator to the polymerizer, the polymerization is carried out at 50~75℃; (b) adding a mixture of styrene, butadiene and cyclohexane, the polymerization is carried out at 50~70℃ ;(c) adding a mixture of butadiene and cyclohexane, the polymerization is finished at 60~70℃ ;(d) adding coupling agent which is a substituted trimethoxysilane being expressed as N-silane, O-silane and being converted into a functional group (-NH, -OH) of mentioned block copolymer, coupling at 75~90℃ for 1 hr; (e) The amounts of coupling agent are about one sixth to one third of the initiator; (f) treating the prepared copolymer solution with some water and Carbon dioxide at 50~70℃ for 15 min.The copolymer is from three-arm to six-arm mono-modal radial block copolymer having 75~90%styrene, 10~25% butadiene and functional group of-NH or-OH. of the copolymer, Mw is from 30×104 to 120×104, Mw/Mn from 2.0 to 2.5, Izod notched impact strength 50~65 J/m,light transmission not less 87.5%, tensile strength not less 45 Mpa.The exploratory research shows that the mole ratio and feed rate of the random copolymerized styrene-butadiene, as well as the total ratio of styrene-butadiene have greater influence on the properties of the copolymer. The following model is established:Y=bo +∑3j=1 bjxj+∑3j=1bkjxkxj+∑3j=1bjjx2j (k<j)Where: Y is the light transmission, tensile strength, elongation, Izod notched impact

  16. High quality sub-10 nm graphene nanoribbons by on-chip PS-b-PDMS block copolymer lithography

    DEFF Research Database (Denmark)

    Rasappa, Sozaraj; Caridad, Jose; Schulte, Lars;

    2015-01-01

    Block copolymer self-assembly holds great promise as a rapid, cheap and scalable approach to nanolithography. We present a straightforward method for fabrication of sub-10 nm line patterns from a lamellar polystyrene-b-polydimethylsiloxane (SD) block copolymer with total average molecular weight ...

  17. Nanoporous materials from stable and metastable structures of 1,2-PB-b-PDMS block copolymers

    DEFF Research Database (Denmark)

    Schulte, Lars; Grydgaard, Anne; Jakobsen, Mathilde R.;

    2011-01-01

    Experimental procedures used at the preparation and characterization stages of nanoporous materials (NPM) from 1,2-polybutadiene-b-polydimethylsiloxane (1,2-PB-b-PDMS) block copolymers are presented. The NPM were obtained from self-assembled block copolymers after firstly cross-linking 1,2-PB (the...

  18. Self-assembled structures of amphiphilic ionic block copolymers: Theory, self-consistent field modeling and experiment

    NARCIS (Netherlands)

    Borisov, O.V.; Zhulina, E.B.; Leermakers, F.A.M.; Muller, A.H.E.

    2011-01-01

    We present an overview of statistical thermodynamic theories that describe the self-assembly of amphiphilic ionic/hydrophobic diblock copolymers in dilute solution. Block copolymers with both strongly and weakly dissociating (pH-sensitive) ionic blocks are considered. We focus mostly on structural a

  19. Dissipative Particle Dynamics Simulation of Onion Phase in Star-block Copolymer

    Institute of Scientific and Technical Information of China (English)

    WU Shao-gui; DU Ting-ting

    2013-01-01

    A dissipative particle dynamics simulation technique was used to investigate the effect of molecular architecture of star-block copolymer on the patterned structure in a nanodroplet.With increasing the ratio of solvophilic to block length to solvophobic block length(RH/T),solvophobic sphere,ordered hexagonal phase,onion phase,perforated onion phase and flocculent phase are formed,respectively.Since onion phase has potential application in controlled drug release,it has received wide attention experimentally and theoretically.Our simulation indicates onion phase forms at a certain RH/T(close to but less than 1).A star-block copolymer molecule has two conformations in onion phase:either fully located in a shell or shared by two neighboring shells.Central structure affects onion's final shape.The molecular number of the copolymer in each shell is a quadratic function of the shell's radius.The arm number of star-block copolymer has little influence on onion's structure,but slightly affects the solvent content.Additionally,we studied the influence of arm length on onion's structure.

  20. Effect of Macromolecular Architecture on the Morphology of Polystyrene Polyisoprene Block Copolymers

    Energy Technology Data Exchange (ETDEWEB)

    Kumar, Rajeev [ORNL; Goswami, Monojoy [ORNL; Mays, Jimmy [ORNL; Sides, Scott [ORNL; Sumpter, Bobby G [ORNL; Dadmun, Mark D [ORNL; Dyer, Caleb W [ORNL; Driva, Paraskevi [ORNL; Chen, Jihua [ORNL

    2013-01-01

    The impact of block connectivity on the morphologies of four block copolymers of varying architecture containing polystyrene (PS) and polyisoprene (PI) has been studied. The volume fraction of PS and molecular weight are held constant while varying the architecture from a linear PS-PI diblock copolymer to three different miktoarm star architectures: PS2PI, PSPI2, and PS2PI2. Morphologies of the PS2PI and PSPI2 miktoarm stars are different from those observed for the linear copolymer and dependent on the connectivity of the copolymer blocks. The change in morphology with connectivity indicates that combining two chains at a junction point leads to chain crowding, where subsequent excluded volume effects drive the change in morphology for each sample. The PS2PI2 miktoarm star exhibits the same morphology as the linear diblock but with a reduction in the size of the domains. The extent of the decrease in domain size indicates that chain stretching impacts the formation of this morphology. Experimentally observed morphologies for different chain architectures are generally consistent with three-dimensional self-consistent field theory simulations, taking into account conformational asymmetry and experimental uncertainty in the copolymer composition. Furthermore, these results generally agree with analytical theory predictions that account for architectural and conformational asymmetry.

  1. Block copolymer modified surfaces for conjugation of biomacromolecules with control of quantity and activity.

    Science.gov (United States)

    Li, Xin; Wang, Mengmeng; Wang, Lei; Shi, Xiujuan; Xu, Yajun; Song, Bo; Chen, Hong

    2013-01-29

    Polymer brush layers based on block copolymers of poly(oligo(ethylene glycol) methacrylate) (POEGMA) and poly(glycidyl methacrylate) (PGMA) were formed on silicon wafers by activators generated by electron transfer atom transfer radical polymerization (AGET ATRP). Different types of biomolecule can be conjugated to these brush layers by reaction of PGMA epoxide groups with amino groups in the biomolecule, while POEGMA, which resists nonspecific protein adsorption, provides an antifouling environment. Surfaces were characterized by water contact angle, ellipsometry, and Fourier transform infrared spectroscopy (FTIR) to confirm the modification reactions. Phase segregation of the copolymer blocks in the layers was observed by AFM. The effect of surface properties on protein conjugation was investigated using radiolabeling methods. It was shown that surfaces with POEGMA layers were protein resistant, while the quantity of protein conjugated to the diblock copolymer modified surfaces increased with increasing PGMA layer thickness. The activity of lysozyme conjugated on the surface could also be controlled by varying the thickness of the copolymer layer. When biotin was conjugated to the block copolymer grafts, the surface remained resistant to nonspecific protein adsorption but showed specific binding of avidin. These properties, that is, well-controlled quantity and activity of conjugated biomolecules and specificity of interaction with target biomolecules may be exploited for the improvement of signal-to-noise ratio in sensor applications. More generally, such surfaces may be useful as biological recognition elements of high specificity for functional biomaterials. PMID:23265296

  2. Effects of copolymer composition, film thickness, and solvent vapor annealing time on dewetting of ultrathin block copolymer films.

    Science.gov (United States)

    Huang, Changchun; Wen, Gangyao; Li, Jingdan; Wu, Tao; Wang, Lina; Xue, Feifei; Li, Hongfei; Shi, Tongfei

    2016-09-15

    Effects of copolymer composition, film thickness, and solvent vapor annealing time on dewetting of spin-coated polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) films (annealed for different times were performed using X-ray photoelectron spectroscopy and contact angle measurement. With the annealing of acetone vapor, dewetting of the films with different thicknesses occur via the spinodal dewetting and the nucleation and growth mechanisms, respectively. The PS-b-PMMA films rupture into droplets which first coalesce into large ones to reduce the surface free energy. Then the large droplets rupture into small ones to increase the contact area between PMMA blocks and acetone molecules resulting from ultimate migration of PMMA blocks to droplet surface, which is a novel dewetting process observed in spin-coated films for the first time. PMID:27309943

  3. Self-Assembled Asymmetric Block Copolymer Membranes: Bridging the Gap from Ultra- to Nanofiltration.

    Science.gov (United States)

    Yu, Haizhou; Qiu, Xiaoyan; Moreno, Nicolas; Ma, Zengwei; Calo, Victor Manuel; Nunes, Suzana P; Peinemann, Klaus-Viktor

    2015-11-16

    The self-assembly of block copolymers is an emerging strategy to produce isoporous ultrafiltration membranes. However, thus far, it has not been possible to bridge the gap from ultra- to nanofiltration and decrease the pore size of self-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 containing an ultraporous, 60 nm thin separation layer can fully reject solutes with molecular weights of 600 g mol(-1) in aqueous solutions with a water flux that is more than one order of magnitude higher than the permeance of commercial nanofiltration membranes. Simulations of the membrane formation process by dissipative particle dynamics (DPD) were used to explain the dramatic observed pore size reduction combined with an increase in water flux. PMID:26388216

  4. Self-Assembled Asymmetric Block Copolymer Membranes: Bridging the Gap from Ultra- to Nanofiltration

    KAUST Repository

    Yu, Haizhou

    2015-09-21

    The self-assembly of block copolymers is an emerging strategy to produce isoporous ultrafiltration membranes. However, thus far, it has not been possible to bridge the gap from ultra- to nanofiltration and decrease the pore size of self-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 containing an ultraporous, 60 nm thin separation layer can fully reject solutes with molecular weights of 600 g mol−1 in aqueous solutions with a water flux that is more than one order of magnitude higher than the permeance of commercial nanofiltration membranes. Simulations of the membrane formation process by dissipative particle dynamics (DPD) were used to explain the dramatic observed pore size reduction combined with an increase in water flux.

  5. Block Copolymer Electrolytes: Thermodynamics, Ion Transport, and Use in Solid- State Lithium/Sulfur Cells

    Science.gov (United States)

    Teran, Alexander Andrew

    Nanostructured block copolymer electrolytes containing an ion-conducting block and a modulus-strengthening block are of interest for applications in solid-state lithium metal batteries. These materials can self-assemble into well-defined microstructures, creating conducting channels that facilitate ion transport. The overall objective of this dissertation is to gain a better understanding of the behavior of salt-containing block copolymers, and evaluate their potential for use in solid-state lithium/sulfur batteries. Anionically synthesized polystyrene-b-poly(ethylene oxide) (SEO) copolymers doped with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt were used as a model system. This thesis investigates the model system on several levels: from fundamental thermodynamic studies to bulk characterization and finally device assembly and testing. First, the thermodynamics of neat and salt-containing block copolymers was studied. The addition of salt to these materials is necessary to make them conductive, however even small amounts of salt can have significant effects on their phase behavior, and consequently their iontransport and mechanical properties. As a result, the effect of salt addition on block copolymer thermodynamics has been the subject of significant interest over the last decade. A comprehensive study of the thermodynamics of block copolymer/salt mixtures over a wide range of molecular weights, compositions, salt concentrations and temperatures was conducted. Next, the effect of molecular weight on ion transport in both homopolymer and copolymer electrolytes were studied over a wide range of chain lengths. Homopolymer electrolytes show an inverse relationship between conductivity and chain length, with a plateau in the infinite molecular weight limit. This is due to the presence of two mechanisms of ion conduction in homopolymers; the first mechanism is a result of the segmental motion of the chains surrounding the salt ions, 2 creating a liquid

  6. SYNTHESIS AND CHARACTERIZATION OF NOVEL CHIRAL SMECTIC C(Sc*) PHASE SHISH-KEBAB TYPE LIQUID CRYSTALLINE BLOCK COPOLYMERS

    Institute of Scientific and Technical Information of China (English)

    Shi-jun Zheng; Zi-fa Li; Shu-yuan Zhang; Shao-kui Cao; Ming-sheng Tang; Qiu-jun Fen; Qi-feng Zhou

    1999-01-01

    A new series of chiral shish-kebab type liquid crystal block copolymers that form the smectic C(Sc*) phase was synthesized by solution polycondensation. The copolymers were characterized by GPC,DSC, TG, POM, X-ray diffraction and polarimeter. The copolymers 7 entered into liquid crystal phase when they were heated to their melting temperatures (Tm) and the copolymers 8 were in liquid crystal phase at room temperature with low viscosities. The smectic sanded texture or focal-conic texture were observed on POM.All the chiral block copolymers showed high optical activity. No racemization has happened. Temperaturevariable X-ray diffraction study together with POM and polarimetric analysis realized that they are chiral smectic C(Sc*) phase. Thus we offer in this report the first example of shish-kebab type liquid crystal block copolymers that form a chiral smectic C(Sc*) phase. The variation of melting and isotropization temperatures with molecular structure was also discussed.

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

    Directory of Open Access Journals (Sweden)

    2008-08-01

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

  8. Study of the interface solid/solutions containing PEO-PPO block copolymers and asphaltenes by FTIR/ATR; Estudo de solucoes de copolimeros em bloco de PEO-PPO contendo asfaltenos por FTIR/DTA

    Energy Technology Data Exchange (ETDEWEB)

    Aguiar, Janaina I.S.; Neto, Jessica S.G.; Mansur, Claudia R.E. [Universidade Federal do Rio de Janeiro, Instituto de Macromoleculas, Laboratorio de Macromoleculas e Coloides na Industria de Petroleo, Rio de Janeiro, RJ (Brazil)], E-mails: janaina_333@hotmail.com, kinha_dac_dm@hotmail.com; celias@ima.ufrj.br

    2011-07-01

    The formation of water/oil emulsions can cause problems in various stages of production, processing and refining of petroleum. In this study, the technique of Fourier transform infrared spectroscopy (FTIR) using the method of attenuated total reflectance (ATR) was applied to study the solid-solutions of block copolymers based on poly(ethylene oxide)-poly(propylene oxide) (PEO-PPO) interface and its interaction in this interface with asphaltenic fractions of petroleum. The solid is the crystal of the ATR. Initially, we determined the critical micelle concentration values of the copolymers, which were consistent those obtained by a tensiometer. Bottle Test was also performed to correlate the efficiency of PEO-PPO copolymers in the breaking of water/oil emulsions with its adsorption at the interfaces solutions. (author)

  9. Quasi-Block Copolymers Based on a General Polymeric Chain Stopper.

    Science.gov (United States)

    Sanguramath, Rajashekharayya A; Nealey, Paul F; Shenhar, Roy

    2016-07-11

    Quasi-block copolymers (q-BCPs) are block copolymers consisting of conventional and supramolecular blocks, in which the conventional block is end-terminated by a functionality that interacts with the supramolecular monomer (a "chain stopper" functionality). A new design of q-BCPs based on a general polymeric chain stopper, which consists of polystyrene end-terminated with a sulfonate group (PS-SO3 Li), is described. Through viscosity measurements and a detailed diffusion-ordered NMR spectroscopy study, it is shown that PS-SO3 Li can effectively cap two types of model supramolecular monomers to form q-BCPs in solution. Furthermore, differential scanning calorimetry data and structural characterization of thin films by scanning force microscopy suggests the existence of the q-BCP architecture in the melt. The new design considerably simplifies the synthesis of polymeric chain stoppers; thus promoting the utilization of q-BCPs as smart, nanostructured materials.

  10. Stability of the fcc structure in block copolymer systems.

    Science.gov (United States)

    Nonomura, Makiko

    2008-11-19

    The stability of the face-centered cubic (fcc) structure in microphase separated copolymers is investigated by a coarse-grained approach. Direct simulations of the equation for the microphase separation in three dimensions indicate that there is a narrow area above a certain degree of segregation in the phase diagram, where the fcc structure is the most stable structure. By employing the mode expansion, we have confirmed that the fcc structure can form as a metastable structure even in the weak segregation regime.

  11. Self-assembled Block Copolymers with Various Architectures Designed by ATRP

    DEFF Research Database (Denmark)

    Jankova Atanasova, Katja

    networks and demonstrate good Li+ complexation and conductivity. These make the materials a potential for solid electrolyte applications in Li+ ion batteries (4, 6). iii. Amphiphilic water soluble star block copolymers with a polyacrylic acid core form hydrogels at room temperature above concentration 22g...

  12. Lamellar Microdomains of Block-Copolymer-Based Ionic Supramolecules Exhibiting a Hierarchical Self-Assembly

    DEFF Research Database (Denmark)

    Ayoubi, Mehran Asad; Almdal, Kristoffer; Zhu, Kaizheng;

    2014-01-01

    Based on a parent diblock copolymer of poly(styrene)-b-poly(methacrylic acid), PS-b-PMAA, linear-b-amphiphilic comb (L-b-AC) ionic supramolecules [Soft Matter 2013, 9, 1540-1555] are synthesized in which the poly(methacrylate) backbone of the ionic supramolecular AC-block is neutralized by alkyl ...

  13. Anionic polymerization and polyhomologation: An ideal combination to synthesize polyethylene-based block copolymers

    KAUST Repository

    Zhang, H.

    2013-08-07

    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 with the "bridge" molecule to afford a 3-arm star (trimacromolecular borane) which serves as an initiator for the polyhomologation. 2013 The Royal Society of Chemistry.

  14. Gas plasma etching of PEO/PBT segmented block copolymer films

    NARCIS (Netherlands)

    Olde Riekerink, M.B.; Claase, M.B.; Engbers, G.H.M.; Grijpma, D.W.; Feijen, J.

    2003-01-01

    A series of poly(ethylene oxide)/poly(butylene terephthalate) (PEO/PBT) segmented block copolymer films was treated with a radio-frequency carbon dioxide (CO2) or with argon (Ar) plasma. The effects of (preferential) etching on surface structure, topography, chemistry, and wettability were studied b

  15. 78 FR 20032 - Styrene-Ethylene-Propylene Block Copolymer; Tolerance Exemption

    Science.gov (United States)

    2013-04-03

    .... No. 108388-87-0) when used as an inert ingredient in a pesticide formulation. AgroFresh Inc... permissible level for residues of styrene-ethylene-propylene block copolymer on food or feed commodities... code 111). Animal production (NAICS code 112). Food manufacturing (NAICS code 311)....

  16. Water vapor and gas transport through a poly (butylene terephthalate) poly (ethylene oxide) block copolymer

    NARCIS (Netherlands)

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

    2002-01-01

    In this paper the transport behavior of water vapor and nitrogen in a poly(butylene terephthalate) poly (ethylene oxide) block copolymer is discussed. This polymer has a high solubility for water (300 cm3 (STP)/cm3 polymer at activity 0.9). A new permeation set up has been built to determine the wat

  17. Adsorption of polyelectrolytes and charged block copolymers on oxides. Consequences for colloidal stability.

    NARCIS (Netherlands)

    Hoogeveen, N.G.

    1996-01-01

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

  18. DYNAMIC DENSITY-FUNCTIONAL THEORY FOR MICROPHASE SEPARATION KINETICS OF BLOCK-COPOLYMER MELTS

    NARCIS (Netherlands)

    FRAAIJE, JGEM

    1993-01-01

    In this paper, we describe a numerical method for the calculation of collective diffusion relaxation mechanisms in quenched block copolymer melts. The method entails the repeated calculation of two opposing fields-an external potential field U, conjugate to the density field rho, and an energetic in

  19. LEO resistant PI-B-PDMS block copolymer films for solar array applications

    NARCIS (Netherlands)

    Lonkhuyzen, H. van; Bongers, E.; Fischer, H.R.; Dingemans, T.J.; Semprimoschnig, C.

    2013-01-01

    Due to their low atomic oxygen erosion yields PI-b-PDMS block copolymer films have considerable potential for application onto space exposed surfaces of satellites in low earth orbit. On solar arrays these materials might be used as electrical electrical insulation film, flexprint outer layer, elect

  20. Composition and solution properties of fluorinated block copolymers and their surface structures in the solid state

    Institute of Scientific and Technical Information of China (English)

    NI HuaGang; XUE DongWu; WANG XiaoFang; ZHANG Wei; WANG XinPing; SHEN ZhiQuan

    2009-01-01

    A series of diblock copolymers composed of methyl methacrylate and 2-perfluorooctylethyl methacry-late (PMMA144-b-PFMAn) with various PFMA block lengths were prepared by atom transfer radical po-lymerization (ATRP). The surface structures and properties of these polymers in the solid state and in solution were investigated using contact angle measurement, X-ray photoelectron spectroscopy (XPS), sum frequency generation (SFG) vibrational spectroscopy, surface tension and dynamic laser light scattering (DLS). It was found that with increasing PFMA block length, water and oil repellency de-creased, the ratio of F/C increased with increasing film depth, and the degree of ordered packing of the perfluoroalkyl side chains at the surface decreased. When the number of PFMA block units reached 10, PMMA segments were detected at the copolymer surface, which was attributed to the PFMA block length affecting molecular aggregation structure of the copolymer in the solution and the interfacial structure at the air/liquid interface, which in turn affects surface structure formation during solution solidification. The results suggest that copolymer solution properties play an important role in struc-ture formation on the solid surface.

  1. Complexes of block copolymers in solution: a graph-theoretical approach

    NARCIS (Netherlands)

    Damme, van Ruud; Geurts, Bernard J.

    1989-01-01

    We determine the statistical properties of block copolymers in solution. These complexes are assumed to have the topological structure of connected graphs with “nonnested” loops and cycles. The generating function method is used to determine the number of topologically different complexes containing

  2. Thin block copolymer films : film formation and corrugation under the AFM tip

    NARCIS (Netherlands)

    Maas, J.H.; Cohen Stuart, M.A.; Fleer, G.J.

    2000-01-01

    The tip of an atomic force microscope was used to induce nanoscale ordering in thin films of polystyrene-poly(4-vinyl pyridine) block copolymers under low force. The AFM tip produces rims on a mesoscopic scale oriented perpendicularly to the scanning direction. A wide range of molecular weights of b

  3. Self-assembled block copolymer membranes: From basic research to large-scale manufacturing

    KAUST Repository

    Nunes, Suzana Pereira

    2013-09-24

    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 of conventional membrane production technology.

  4. Synthesis of Dendritic-Linear Block Copolymers by Atom Transfer Radical Polymerization

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    The dendritic polyarylether 2-bromoisobutyrate as the macromolecular initiator for the controlled free radical polymerization of styrene was investigated. The polymerization was carried out with CuBr/2,2′-bipyridine catalyst at 110℃. It is found that the hybrid dendritic-linear block copolymers possess well-defined molecular weights and low polydispersities.

  5. Poly(dimethylsiloxane)-poly(ethyleneoxide)-heparin block copolymers. I. Synthesis and characterization

    NARCIS (Netherlands)

    Grainger, D.W.; Kim, S.W.; Feijen, J.

    1988-01-01

    Amphiphilic block copolymers containing poly(dimethylsiloxane), poly(ethylene oxide), and heparin (PDMS-PEO-Hep) have been prepared via a series of coupling reactions using functionalized prepolymers, diisocyanates, and derivatized heparins. All intermediate steps of the synthesis yield quantifiable

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

    KAUST Repository

    Mugemana, Clement

    2014-01-01

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

  7. Water vapor transmission of poly(ethylene oxide)-based segmented block copolymers

    NARCIS (Netherlands)

    Husken, D.; Gaymans, R.J.

    2009-01-01

    This article discusses the rate of water vapor transmission (WVT) through monolithic films of segmented block copolymers based on poly(ethylene oxide) (PEO) and monodisperse crystallisable tetra-amide segments. The polyether phase consisted of hydrophilic PEO or mixtures of PEO and hydrophobic poly(

  8. Surface properties of poly(ethylene oxide)-based segmented block copolymers with monodisperse hard segments

    NARCIS (Netherlands)

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

    2009-01-01

    The surface properties of segmented block copolymers based on poly(ethylene oxide) (PEO) segments and monodisperse crystallizable tetra-amide segments were studied. The monodisperse crystallizable segments (T6T6T) were based on terephthalate (T) and hexamethylenediamine (6). Due to the crystallinity

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

    NARCIS (Netherlands)

    Husken, Debby; Feijen, Jan; Gaymans, Reinoud J.

    2007-01-01

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

  10. Wafer-Scale Nanopillars Derived from Block Copolymer Lithography for Surface-Enhanced Raman Spectroscopy

    DEFF Research Database (Denmark)

    Li, Tao; Wu, Kaiyu; Rindzevicius, Tomas;

    2016-01-01

    ). Direct silicon etching with high aspect ratio templated by the block copolymer mask is realized without any intermediate layer or external precursors. Uniquely, an atomic layer deposition (ALD)-assisted method is introduced to allow reversing of the morphology relative to the initial pattern. As a result...

  11. Ligand switch in photoinduced copper-mediated polymerization: synthesis of methacrylate-acrylate block copolymers

    OpenAIRE

    CHUANG, Ya-Mi; Wenn, Benjamin; Gielen, Sam; Ethirajan, Anitha; Junkers, Thomas

    2015-01-01

    The use of photo-induced copper-mediated radical polymerization (photoCMP) to synthesize mixed acrylate/methacrylate (methyl acrylate, MA and methyl methacrylate, MMA) block copolymers is investigated. Reactions in which only one type of ligand (Me6TREN) is used lead to unsuccessful outcomes of polymerization due to a mismatch in reactivity of the two monomers. A ligand exchange to PMDETA for methacrylate is required to obtain good block structures. Due to insufficient re-initiation of polyac...

  12. Bioinspired amphiphilic phosphate block copolymers as non-fluoride materials to prevent dental erosion

    OpenAIRE

    Lei, Yanda; Wang, Tongxin; Mitchell, James W; Zaidel, Lynette; Qiu, Jianhong; Kilpatrick-Liverman, LaTonya

    2014-01-01

    Inspired by the fact that certain natural proteins, e.g. casein phosphopeptide or amelogenin, are able to prevent tooth erosion (mineral loss) and to enhance tooth remineralization, a synthetic amphiphilic diblock copolymer, containing a hydrophilic methacryloyloxyethyl phosphate block (MOEP) and a hydrophobic methyl methacrylate block (MMA), was designed as a novel non-fluoride agent to prevent tooth erosion under acidic conditions. The structure of the polymer, synthesized by reversible add...

  13. Thermally sensitive block copolymer hydrogels in bulk and with decreased dimensions

    OpenAIRE

    Nykänen, Antti

    2013-01-01

    The research on stimuli-responsive polymers has increased rapidly during the last two decades. Poly(N-isopropylacrylamide) (PNIPAM) is one of the most studied thermally responsive polymer because its lower critical solution temperature (LCST) 32 ℃ is close to the ambient conditions. Below 32 ℃, PNIPAM is water soluble, but at temperatures above 32 ℃ the polymer phase separates from water. In this thesis, amphiphilic triblock copolymer polystyrene-block-poly(N-isopropylacrylamide)-block-polys...

  14. Phase behavior of ABC-type triple-hydrophilic block copolymers in aqueous solutions.

    Science.gov (United States)

    Zheng, Lingfei; Wu, Jianqi; Wang, Zheng; Yin, Yuhua; Jiang, Run; Li, Baohui

    2016-07-01

    The phase behavior of symmetric ABC triple-hydrophilic triblock copolymers in concentrated aqueous solutions is investigated using a simulated annealing technique. Two typical cases, in which the hydrophilicity of the middle B-block is either stronger or weaker than that of the end A- and C-blocks, are studied. In these two cases, a variety of phase diagrams are constructed as a function of the volume fraction of the B-block and the copolymer concentration ([Formula: see text] for both non-frustrated and frustrated copolymers. Structures, such as two-color alternatingly packed cylinders or gyroid, and lamellae-in-lamellae etc. that do not occur in the melt system, are obtained in solutions. Rich phase transition sequences, especially re-entrant phase transitions involving complex continuous networks of alternating gyroid and alternating diamond are observed for a given copolymer with decreasing [Formula: see text] . The difference in hydrophilicity among different blocks can result in inhomogeneous distribution of solvent molecules in the morphology, and with the decrease of [Formula: see text] , the distribution of solvent molecules presents a non-monotonic variation. This results in a non-monotonic variation of the effective volume fraction of each domain with the decrease of [Formula: see text] , which induces the re-entrant phase transitions. The presence of a good solvent for all the blocks can cause changes in the effective segregation strengths between different blocks and also in chain conformations, hence can alter the bulk phases and results in the occurrence of new structures and phase transitions. Especially, structures having A-C interfaces or A-C mixed domains can be obtained even in the non-frustrated copolymer systems, and structures obtained in the frustrated systems may be similar to those obtained in the non-frustrated systems. The window of the alternating gyroid structures may occupy a large part of the phase diagram for non

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

    Science.gov (United States)

    Mulhearn, William; Register, Richard

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

  16. Surface Modification for Controlling the Orientation of Block Copolymers in thin film and in Cylindrical Nanopores

    Science.gov (United States)

    Lin, Xin-Guan; Lin, Feng-Cheng; Tung, Shih-Huang

    2012-02-01

    A series of benzocyclobutene-functionalized random copolymers of styrene and 4-vinylpyridine were synthesized by nitroxide-mediated controlled radical polymerization with BPO and TEMPO. Our research was to use these random copolymers of P(S-r-BCB-r-4VP) to control the orientation of microdomains in block copolymers(BCPs) of poly(styrene-b-4-vinylpyridine)(PS-b-P4VP) thin films and in cylindrical nanopores of anodized aluminum oxide (AAO) membranes. On P(S-r-BCB-r-4VP)-modified substrate,we found that in some particular compositions of random copolymer ,the parallel orientation of the microdomains is switched to be perpendicular in PS-b-P4VP thin film. We also introduced P(S-r-BCB-r-4VP) solution into the nanopores of the AAO and nanotubes formed after solvent evaporation and pyrolysis. And then BCPs of PS-b-P4VP were drawn into the P(S-r-BCB-r-4VP)-modified nanopores in the melt via capillary action to form P(S-r-BCB-r-4VP) coated nanorods of PS-b-P4VP.Similarly,in some particular compositions of random copolymer, we observed that the interactions of the blocks with the walls are not strong or if the interactions are balanced, then the orientation of the microdomains will change from being parallel to being perpendicular to the confining walls.

  17. Interfacial behaviors of PMMA-PEO block copolymers at the air/water interface

    Institute of Scientific and Technical Information of China (English)

    CHENG Caixia; JIAO Tifeng; TANG Rupei; LIU Minghua; XI Fu

    2005-01-01

    Diblock copolymer of PMMA291-b-PEO114 and triblock copolymer of PMMA120-b- PEO227-b-PMMA120 were synthesized and their interfacial properties at the air-water interface were investigated, where both blocks of polyethylene oxide (PEO) and poly(methyl methacrylate) (PMMA) are surface active but the former is soluble in water while the latter is not. Both the block copolymers could form monolayers with two obvious transition regions. The first transition point is around 10 mN/m, which could be assigned to the pancake-brush change of the PEO chains. The other is around 18 mN/m, which could be ascribed to the condensed packing of PMMA. The surface morphological changes during the compression of the Langmuir monolayers are investigated by using the AFM and SEM methods for the films deposited at different surface pressure or molecular areas. At a lower surface pressure, a typical morphology of PEO-con- taining lipopolymers is observed. Upon compression, sphere-dominant morphologies were observed. While the diblock copolymer is easy to folding, the triblock copolymer is in favor of formation of circular domains through vesiculation.

  18. Compatibilization of blends of low density polyethylene and poly(vinyl chloride) by segmented EB(SAN-block-EB)(n) block copolymers

    NARCIS (Netherlands)

    Kroeze, E; ten Brinke, G.; Hadziioannou, G

    1997-01-01

    Hydrogenated segmented poly[butadiene-block-((styrene-co-acrylonitrile)-block-butadiene)(n)] block copolymers, which were developed by use of the polymeric iniferter technique, were tested for their compatibilizing capacities for (10/90) LDPE/PVC blends. The acrylonitrile content of the SAN blocks o

  19. Synthesis of Inorganic Nanocomposites by Selective Introduction of Metal Complexes into a Self-Assembled Block Copolymer Template

    Directory of Open Access Journals (Sweden)

    Hiroaki Wakayama

    2015-01-01

    Full Text Available Inorganic nanocomposites have characteristic structures that feature expanded interfaces, quantum effects, and resistance to crack propagation. These structures are promising for the improvement of many materials including thermoelectric materials, photocatalysts, and structural materials. Precise control of the inorganic nanocomposites’ morphology, size, and chemical composition is very important for these applications. Here, we present a novel fabrication method to control the structures of inorganic nanocomposites by means of a self-assembled block copolymer template. Different metal complexes were selectively introduced into specific polymer blocks of the block copolymer, and subsequent removal of the block copolymer template by oxygen plasma treatment produced hexagonally packed porous structures. In contrast, calcination removal of the block copolymer template yielded nanocomposites consisting of metallic spheres in a matrix of a metal oxide. These results demonstrate that different nanostructures can be created by selective use of processes to remove the block copolymer templates. The simple process of first mixing block copolymers and magnetic nanomaterial precursors and then subsequently removing the block copolymer template enables structural control of magnetic nanomaterials, which will facilitate their applicability in patterned media, including next-generation perpendicular magnetic recording media.

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

    Science.gov (United States)

    Fei, Pengzhan; Cavicchi, Kevin

    2011-03-01

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

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

    OpenAIRE

    Martens, A.A.

    2008-01-01

    The research described in this thesis concerns the design, biotechnological production, and physiochemical study of large water-soluble (monodisperse) protein triblock-copolymers with sequential blocks, some of which are positively or negatively charged and self-assemble in response to a change in pH or co-assemble in response to oppositely charged polyelectrolytes (including each other). Such molecules displaying controlled self-assembly may lead to new biocompatible nano-structured material...

  2. Antibacterial modification of an injectable, biodegradable, non-cytotoxic block copolymer-based physical gel with body temperature-stimulated sol-gel transition and controlled drug release.

    Science.gov (United States)

    Wang, Xiaowen; Hu, Huawen; Wang, Wenyi; Lee, Ka I; Gao, Chang; He, Liang; Wang, Yuanfeng; Lai, Chuilin; Fei, Bin; Xin, John H

    2016-07-01

    Biomaterials are being extensively used in various biomedical fields; however, they are readily infected with microorganisms, thus posing a serious threat to the public health care. We herein presented a facile route to the antibacterial modification of an important A-B-A type biomaterial using poly (ethylene glycol) methyl ether (mPEG)- poly(ε-caprolactone) (PCL)-mPEG as a typical model. Inexpensive, commercial bis(2-hydroxyethyl) methylammonium chloride (DMA) was adopted as an antibacterial unit. The effective synthesis of the antibacterial copolymer mPEG-PCL-∼∼∼-PCL-mPEG (where ∼∼∼ denotes the segment with DMA units) was well confirmed by FTIR and (1)H NMR spectra. At an appropriate modification extent, the DMA unit could render the copolymer mPEG-PCL-∼∼∼-PCL-mPEG highly antibacterial, but did not largely alter its fascinating intrinsic properties including the thermosensitivity (e.g., the body temperature-induced sol-gel transition), non-cytotoxicity, and controlled drug release. A detailed study on the sol-gel-sol transition behavior of different copolymers showed that an appropriate extent of modification with DMA retained a sol-gel-sol transition, despite the fact that a too high extent caused a loss of sol-gel-sol transition. The hydrophilic and hydrophobic balance between mPEG and PCL was most likely broken upon a high extent of quaternization due to a large disturbance effect of DMA units at a large quantity (as evidenced by the heavily depressed PCL segment crystallinity), and thus the micelle aggregation mechanism for the gel formation could not work anymore, along with the loss of the thermosensitivity. The work presented here is highly expected to be generalized for synthesis of various block copolymers with immunity to microorganisms. Light may also be shed on understanding the phase transition behavior of various multiblock copolymers.

  3. Antibacterial modification of an injectable, biodegradable, non-cytotoxic block copolymer-based physical gel with body temperature-stimulated sol-gel transition and controlled drug release.

    Science.gov (United States)

    Wang, Xiaowen; Hu, Huawen; Wang, Wenyi; Lee, Ka I; Gao, Chang; He, Liang; Wang, Yuanfeng; Lai, Chuilin; Fei, Bin; Xin, John H

    2016-07-01

    Biomaterials are being extensively used in various biomedical fields; however, they are readily infected with microorganisms, thus posing a serious threat to the public health care. We herein presented a facile route to the antibacterial modification of an important A-B-A type biomaterial using poly (ethylene glycol) methyl ether (mPEG)- poly(ε-caprolactone) (PCL)-mPEG as a typical model. Inexpensive, commercial bis(2-hydroxyethyl) methylammonium chloride (DMA) was adopted as an antibacterial unit. The effective synthesis of the antibacterial copolymer mPEG-PCL-∼∼∼-PCL-mPEG (where ∼∼∼ denotes the segment with DMA units) was well confirmed by FTIR and (1)H NMR spectra. At an appropriate modification extent, the DMA unit could render the copolymer mPEG-PCL-∼∼∼-PCL-mPEG highly antibacterial, but did not largely alter its fascinating intrinsic properties including the thermosensitivity (e.g., the body temperature-induced sol-gel transition), non-cytotoxicity, and controlled drug release. A detailed study on the sol-gel-sol transition behavior of different copolymers showed that an appropriate extent of modification with DMA retained a sol-gel-sol transition, despite the fact that a too high extent caused a loss of sol-gel-sol transition. The hydrophilic and hydrophobic balance between mPEG and PCL was most likely broken upon a high extent of quaternization due to a large disturbance effect of DMA units at a large quantity (as evidenced by the heavily depressed PCL segment crystallinity), and thus the micelle aggregation mechanism for the gel formation could not work anymore, along with the loss of the thermosensitivity. The work presented here is highly expected to be generalized for synthesis of various block copolymers with immunity to microorganisms. Light may also be shed on understanding the phase transition behavior of various multiblock copolymers. PMID:27022875

  4. Mechanical contrast in block copolymers manifested as kink band defects

    Science.gov (United States)

    Winey, Karen I.; Polis, Daniel L.

    1998-03-01

    Kink bands are an established defect structure found in materials with a preferential slip plane, such as select crystalline solids and foliated rocks. Kink bands are induced by steady shear in a predominately parallel-oriented, lamellar poly(styrene-b-ethylene propylene) diblock copolymer. Steady shear induces kink bands which have their boundaries oriented at 45^o relative to the shearing direction. The lamellar orientations inside and outside the kink bands are asymmetric with respect to the kink band boundaries. This asymmetry is due to a lamellar dilation inside the kink band relative to lamellae outside the kink band. A comparison of the zero shear viscosities of homopolystyrene and homopoly(ethylene-propylene) suggest that the PS microdomains deform preferentially. The presence of a preferential slip plane is consistent with the formation of kink bands. Furthermore, estimates of the number of entanglements in the interpenetration zone between opposing brushes suggest an even larger disparity between PS and PEP relaxation times.

  5. Multiple ordered phases in a block copolymer melt

    DEFF Research Database (Denmark)

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

    1992-01-01

    -order based on discontinuities in the SANS pattern symmetries and intensities and dynamic elastic moduli. At the lowest experimental temperatures the material exhibits a (rippled) lamellar phase. At intermediate temperatures two new ordered phases appear. Above the order-disorder transition temperature a......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...... temperatures and a disordered phase at elevated temperatures. Evaluation of the ordered phases was facilitated by the introduction of long-range order using a shear-orientation technique. SANS data were acquired as a function of temperature for three specimen orientations corresponding to the principle...

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

    DEFF Research Database (Denmark)

    Jankova, Katja; Hvilsted, Søren

    2005-01-01

    , or segmented fluorinated star-shaped block copolymers are further designed by use of different multifunctional initiators. The composition of the novel materials with PFS is determined by combination of SEC and I H NMR. Glass transition temperatures and thermal stabilities of the hydrophobic star-shaped PFSs......,4-dibromoxylene as initiators for ATRP. Diverse bromo(ester) (macro)initiators were also devised and involved in the formulation of fluorinated pentablock as well as amphiphilic triblock copolymers with a central polyether segment. Amphiphilic star-shaped fluoropolymers, hydrophobic fluorinated nanoparticles...

  7. Controlling kink band morphology in block copolymers: Threshold criteria and stability

    Science.gov (United States)

    Polis, Daniel L.; Winey, Karen I.

    1998-03-01

    Controlling defects in block copolymers is crucial in optimizing optical, mechanical and transport properties. Forward kink bands can be induced in an aligned lamellar poly(styrene-b-ethylene propylene) diblock copolymer by steady shear if the strain exceeds a critical value. However, these forward kink bands are unstable relative to reverse steady shear, i.e. they can be "erased." The critical strain and the ability to erase kink bands can be extended to large-amplitude oscillatory shear (LAOS) alignment, giving additional control over microdomain orientation. Using strain ramping, a parallel-transverse biaxial orientation can be avoided and LAOS can induce a parallel orientation.

  8. Nature of Viscoelasticity in Lamellar Block Copolymers: Contraction Correlated to Strain Localization

    Science.gov (United States)

    Polis, D. L.; Winey, K. I.; Ryan, A. J.; Smith, S. D.

    1999-10-01

    We determined the local strain profile in sheared lamellar block copolymers. A trilayer model, based on elastic brushes separated by viscous interpenetration zones, captures the rheological response of these materials and provides a measure of the relative contributions of elastic versus viscous strain. The elastic chain distortions were evident from a reversible lamellar contraction, as measured from in situ small-angle x-ray scattering. The contraction was directly correlated to the elastic strain from our trilayer model; three distinct diblock copolymers conform to the predicted relationship, thus suggesting universal behavior.

  9. SYNTHESIS OF POLY(ETHYLENE TEREPHTHALATE)-POLYCAPROLACTONE BLOCK COPOLYMER BY DIRECT COPOLYMERIZATION

    Institute of Scientific and Technical Information of China (English)

    Shen-guo Wang; Kai Tang

    1999-01-01

    Poly(ethylene terephthalate)-polycaprolactone block copolymer (PCL-b-PET) is a polyester with improved biodegradability. In the present paper, a new direct copolymerization method of ε-caprolactone (ε-CL) and bishydroxyethylene terephthalate (BHET) in the presence of Ti(OBu)4 was proposed for the synthesis of PCL-b-PET. The PCL-b-PET copolymer was characterized by IR, GPC and 1H-NMR techniques, and the effects of synthesis conditions, such as temperature, reaction time and concentration of catalyst on the copolymerization were discussed.

  10. Synthesis and Characterization of Smart Block Copolymers for Biomineralization and Biomedical Applications

    Energy Technology Data Exchange (ETDEWEB)

    Mathumai Kanapathipillai

    2008-08-18

    Self-assembly is a powerful tool in forming structures with nanoscale dimensions. Self-assembly of macromolecules provides an efficient and rapid pathway for the formation of structures from the nanometer to micrometer range that are difficult, if not impossible to obtain by conventional lithographic techniques [1]. Depending on the morphologies obtained (size, shape, periodicity, etc.) these self-assembled systems have already been applied or shown to be useful for a number of applications in nanotechnology [2], biomineralization [3, 4], drug delivery [5, 6] and gene therapy [7]. In this respect, amphiphilic block copolymers that self-organize in solution have been found to be very versatile [1]. In recent years, polymer-micellar systems have been designed that are adaptable to their environment and able to respond in a controlled manner to external stimuli. In short, synthesis of 'nanoscale objects' that exhibit 'stimulus-responsive' properties is a topic gathering momentum, because their behavior is reminiscent of that exhibited by proteins [8]. By integrating environmentally sensitive homopolymers into amphiphilic block copolymers, smart block copolymers with self assembled supramolecular structures that exhibit stimuli or environmentally responsive properties can be obtained [1]. Several synthetic polymers are known to have environmentally responsive properties. Changes in the physical, chemical or biochemical environment of these polymers results in modulation of the solubility or chain conformation of the polymer [9]. There are many common schemes of engineering stimuli responsive properties into materials [8, 9]. Polymers exhibiting lower critical solution temperature (LCST) are soluble in solvent below a specific temperature and phase separate from solvent above that temperature while polymers exhibiting upper critical solution temperatures (UCST) phase separate below a certain temperature. The solubility of polymers with ionizable

  11. Synthesis and Characterization of Smart Block Copolymers for Biomineralization and Biomedical Applications

    Energy Technology Data Exchange (ETDEWEB)

    Kanapathipillai, Mathumai [Iowa State Univ., Ames, IA (United States)

    2008-01-01

    Self-assembly is a powerful tool in forming structures with nanoscale dimensions. Self-assembly of macromolecules provides an efficient and rapid pathway for the formation of structures from the nanometer to micrometer range that are difficult, if not impossible to obtain by conventional lithographic techniques [1]. Depending on the morphologies obtained (size, shape, periodicity, etc.) these self-assembled systems have already been applied or shown to be useful for a number of applications in nanotechnology [2], biomineralization [3, 4], drug delivery [5, 6] and gene therapy [7]. In this respect, amphiphilic block copolymers that self-organize in solution have been found to be very versatile [1]. In recent years, polymer-micellar systems have been designed that are adaptable to their environment and able to respond in a controlled manner to external stimuli. In short, synthesis of 'nanoscale objects' that exhibit 'stimulus-responsive' properties is a topic gathering momentum, because their behavior is reminiscent of that exhibited by proteins [8]. By integrating environmentally sensitive homopolymers into amphiphilic block copolymers, smart block copolymers with self assembled supramolecular structures that exhibit stimuli or environmentally responsive properties can be obtained [1]. Several synthetic polymers are known to have environmentally responsive properties. Changes in the physical, chemical or biochemical environment of these polymers results in modulation of the solubility or chain conformation of the polymer [9]. There are many common schemes of engineering stimuli responsive properties into materials [8, 9]. Polymers exhibiting lower critical solution temperature (LCST) are soluble in solvent below a specific temperature and phase separate from solvent above that temperature while polymers exhibiting upper critical solution temperatures (UCST) phase separate below a certain temperature. The solubility of polymers with ionizable

  12. Effective co-delivery of doxorubicin and curcumin using a glycyrrhetinic acid-modified chitosan-cystamine-poly(ε-caprolactone) copolymer micelle for combination cancer chemotherapy.

    Science.gov (United States)

    Yan, Tingsheng; Li, Dalong; Li, Jiwei; Cheng, Feng; Cheng, Jinju; Huang, Yudong; He, Jinmei

    2016-09-01

    A glycyrrhetinic acid-modified chitosan-cystamine-poly(ε-caprolactone) copolymer (PCL-SS-CTS-GA) micelle was developed for the co-delivery of doxorubicin (DOX) and curcumin (CCM) to hepatoma cells. Glycyrrhetinic acid (GA) was used as a targeting unit to ensure specific delivery. Co-encapsulation of DOX and CCM was facilitated by the incorporation of poly(ε-caprolactone) (PCL) groups. The highest drug loading content was 19.8% and 8.9% (w/w) for DOX and CCM, respectively. The PCL-SS-CTS-GA micelle presented a spherical or ellipsoidal geometry with a mean diameter of approximately 110nm. The surface charge of the micelle changed from negative to positive, when the pH value of the solution decreased from 7.4 to 6.8. Meanwhile, it also exhibited a character of redox-responsive drug release and GA/pH-mediated endocytosis in vitro. In simulated body fluid with 10mM glutathione, the release rate in 12h was 80.6% and 67.2% for DOX and CCM, respectively. The cell uptake of micelles was significantly higher at pH 6.8 than pH 7.4. The combined administration of DOX and CCM was facilitated by PCL-SS-CTS-GA micelle. Results showed that there was strong synergic effect between the two drugs. The PCL-SS-CTS-GA micelle might turn into a promising and effective carrier for improved combination chemotherapy. PMID:27281238

  13. Novel lift-off technique for Transmission Electron Microscopy imaging of block copolymer films

    Energy Technology Data Exchange (ETDEWEB)

    Roache, Fergus J.M. [MacDiarmid Institute for Advanced Materials and Nanotechnology (New Zealand); Radjainia, Mazdak [School of Biological Sciences, University of Auckland (New Zealand); Williams, David E. [School of Chemical Sciences, University of Auckland (New Zealand); MacDiarmid Institute for Advanced Materials and Nanotechnology (New Zealand); Gerrard, Juliet A. [School of Chemical Sciences, University of Auckland (New Zealand); MacDiarmid Institute for Advanced Materials and Nanotechnology (New Zealand); School of Biological Sciences, University of Auckland (New Zealand); Travas-Sejdic, Jadranka [School of Chemical Sciences, University of Auckland (New Zealand); MacDiarmid Institute for Advanced Materials and Nanotechnology (New Zealand); Malmström, Jenny, E-mail: j.malmstrom@auckland.ac.nz [School of Chemical Sciences, University of Auckland (New Zealand); MacDiarmid Institute for Advanced Materials and Nanotechnology (New Zealand)

    2015-03-15

    We have developed a simple technique to allow for the lift-off and subsequent transfer of poly(styrene-block-ethylene glycol) films to Transmission Electron Microscopy (TEM) grids. The block copolymer is spin coated onto carbon coated mica and annealed. After the thin film is produced it can easily be floated onto water and picked up by a TEM grid. This method offers better control over film processing than dip coating the TEM grid and is also a significant improvement over methods using etchants such as hydrofluoric acid. - Highlights: • We have developed a simple method to lift block copolymer films to TEM grids. • Polymer films prepared on carbon coated mica are easily floated on water. • The new method circumvents the use of harsh chemicals.

  14. Highly ordered palladium nanodots and nanowires from switchable block copolymer thin films

    Energy Technology Data Exchange (ETDEWEB)

    Bhoje Gowd, E; Nandan, Bhanu; Vyas, Mukesh Kumar; Stamm, Manfred [Leibniz Institute of Polymer Research Dresden, Hohe Strasse 6, 01069, Dresden (Germany); Bigall, Nadja C; Eychmueller, Alexander [Physical Chemistry and Electrochemistry, TU Dresden, Bergstrasse 66b, 01062, Dresden (Germany); Schloerb, Heike, E-mail: gowd@ipfdd.d, E-mail: nandan@ipfdd.d [Leibniz Institute for Solid State and Materials Research Dresden, PO Box 27 00 16, D-01171, Dresden (Germany)

    2009-10-14

    We demonstrate a new approach to fabricate highly ordered arrays of nanoscopic palladium dots and wires using switchable block copolymer thin films. The surface-reconstructed block copolymer templates were directly deposited with palladium nanoparticles from a simple aqueous solution. The preferential interaction of the nanoparticles with one of the blocks is mainly responsible for the lateral arrangement of the nanoparticles inside the pores of the templates in addition to the capillary forces. A subsequent stabilization by UV-irradiation followed by pyrolysis in air at 450 {sup 0}C removes the polymer to produce highly ordered metallic nanostructures. We extended this approach to micellar films to obtain metallic nanostructures. This method is highly versatile as the procedure used here is simple, eco-friendly and provides a simple approach to fabricate a broad range of nanoscaled architectures with tunable lateral spacing, and can be extended to systems with even smaller dimensions.

  15. Molecular transport into and out of ionic-liquid filled block copolymer vesicles in water

    Science.gov (United States)

    Lodge, Timothy; Yao, Letitia; So, Soonyong

    We have developed a method to prepare stable, size-controlled block copolymer vesicles that contain ionic liquid in the interior, but that are dispersed in water. Such nanoemulsions are of interest as nanoreactors, because the mass transfer and cost limitations of ionic liquids are circumvented. However, a crucial question is whether target molecules (e . g ., reagents and products) can enter and leave the vesicles, respectively, on a useful time scale (i . e ., seconds or shorter). In this talk we will briefly describe methods to prepare such vesicles with narrow size distributions, using poly(styrene)-block-poly(ethylene oxide) and poly(butadiene)-block-poly(ethylene oxide) copolymers of various compositions. We will then present results of pulsed-field gradient NMR measurements of probe diffusion that yield independent measurements of the entry and escape rates for selected small molecules, as a function of membrane thickness and temperature.

  16. Novel lift-off technique for Transmission Electron Microscopy imaging of block copolymer films

    International Nuclear Information System (INIS)

    We have developed a simple technique to allow for the lift-off and subsequent transfer of poly(styrene-block-ethylene glycol) films to Transmission Electron Microscopy (TEM) grids. The block copolymer is spin coated onto carbon coated mica and annealed. After the thin film is produced it can easily be floated onto water and picked up by a TEM grid. This method offers better control over film processing than dip coating the TEM grid and is also a significant improvement over methods using etchants such as hydrofluoric acid. - Highlights: • We have developed a simple method to lift block copolymer films to TEM grids. • Polymer films prepared on carbon coated mica are easily floated on water. • The new method circumvents the use of harsh chemicals

  17. PVP-b-PEO block copolymers for stable aqueous and ethanolic graphene dispersions.

    Science.gov (United States)

    Perumal, Suguna; Park, Kyung Tae; Lee, Hyang Moo; Cheong, In Woo

    2016-02-15

    The ability to disperse pristine (unfunctionalized) graphene is important for various applications, coating, nanocomposites, and energy related systems. Herein we report that amphiphilic copolymers of poly(4-vinyl pyridine)-block-poly(ethylene oxide) (PVP-b-PEO) are able to disperse graphene with high concentrations about 2.6mg/mL via sonication and centrifugation. Ethanolic and aqueous highly-ordered pyrolytic graphite (HOPG) dispersions with block copolymers were prepared and they were compared with the dispersions stabilized by P-123 Pluronic® (P123) and poly(styrene)-block-poly(ethylene oxide) (PS-b-PEO) synthesized. Transmission electron microscopy, scanning electron microscopy, atomic force microscopy, X-ray diffraction, Raman and UV-visible spectroscopic studies confirmed that PVP-b-PEO block copolymers are better stabilizers for HOPG graphene than P123 and PS-b-PEO. X-ray photoelectron spectroscopy and force-distance (F-d) curve analyses revealed that the nitrogen of vinyl pyridine plays a vital role in better attractive interaction with surface of graphene sheet. Thermogravimetric analysis showed that larger amount of PVP-b-PEO was adsorbed onto graphene with longer poly(4-vinyl pyridine) (PVP) block length and in aqueous medium, respectively, and which was consistent with electrical conductivity decreases. This study presents the dispersion efficiency of graphene using PVP-b-PEO varies substantially depending on the lengths of their hydrophobic (PVP) domains. PMID:26606378

  18. Bioinspired amphiphilic phosphate block copolymers as non-fluoride materials to prevent dental erosion.

    Science.gov (United States)

    Lei, Yanda; Wang, Tongxin; Mitchell, James W; Zaidel, Lynette; Qiu, Jianhong; Kilpatrick-Liverman, LaTonya

    2014-01-01

    Inspired by the fact that certain natural proteins, e.g. casein phosphopeptide or amelogenin, are able to prevent tooth erosion (mineral loss) and to enhance tooth remineralization, a synthetic amphiphilic diblock copolymer, containing a hydrophilic methacryloyloxyethyl phosphate block (MOEP) and a hydrophobic methyl methacrylate block (MMA), was designed as a novel non-fluoride agent to prevent tooth erosion under acidic conditions. The structure of the polymer, synthesized by reversible addition-fragment transfer (RAFT) polymerization, was confirmed by gel permeation chromatography (GPC), Fourier transform infrared spectroscopy (FTIR), and nuclear magnetic resonance spectroscopy (NMR). While the hydrophilic PMOEP block within the amphiphilic block copolymer strongly binds to the enamel surface, the PMMA block forms a hydrophobic shell to prevent acid attack on tooth enamel, thus preventing/reducing acid erosion. The polymer treatment not only effectively decreased the mineral loss of hydroxyapatite (HAP) by 36-46% compared to the untreated control, but also protected the surface morphology of the enamel specimen following exposure to acid. Additionally, experimental results confirmed that low pH values and high polymer concentrations facilitate polymer binding. Thus, the preliminary data suggests that this new amphiphilic diblock copolymer has the potential to be used as a non-fluoride ingredient for mouth-rinse or toothpaste to prevent/reduce tooth erosion. PMID:25419457

  19. Morphology And Local Mechanical Properties Of A Block Copolymer Cell Substrate

    Science.gov (United States)

    Wall, Craig; Yermolenko, Ivan; Krishnan, G. Rajesh; Sarkar, Debanjan; Alexander, John

    2014-03-01

    Atomic force microscopy (AFM) was applied for the characterization of morphology and mechanical properties of a block copolymer coating designed for biomaterials applications. The material is a block-copolymer with poly(ethylene glycol) as one block and a peptide as second block, which are connected through urethane bonds. The AFM images obtained in amplitude modulation mode revealed the morphology is characterized by micron-scale sheaf-like structures embedded in a more homogeneous and, presumably, amorphous matrix. The self-assembly of the peptide segments is responsible for the formation of the ordered sheaf structures and this phenomenon was common for different variations of the components. Maps of elastic modulus and work of adhesion of the block copolymer, which also differentiate the matrix and ordered regions, were obtained with Hybrid mode at different tip-force levels. The quantitative estimates show that elastic modulus varies in the MPa range and work of adhesion in the hundreds of mJ/m2 range. These data are compared with AFM-based nanoindentation that was performed at higher tip-force level. The results indicate that material surface is more complicated and they suggest in-depth morphology variations. A tentative model of the structural organization is proposed.

  20. Effect of Surfactants on Association Characteristics of Di- and Triblock Copolymers of Oxyethylene and Oxybutylene in Aqueous Solutions: Dilute Solution Phase Diagrams, SANS, and Viscosity Measurements at Different Temperatures

    Directory of Open Access Journals (Sweden)

    Sanjay H. Punjabi

    2011-01-01

    Full Text Available The interactions in poly(oxyethylene (E – poly(oxybutylene (B of EB or EBE type block copolymers-sodium dodoecyl sulfate (SDS or dodecyltrimethylammonium bromide (DTAB and/or t-octylphenoxy polyethoxyethanol, (TX-100 have been monitored as a function of surfactant concentration and temperature. The addition of ionic surfactants to copolymer micellar solutions in general induced not only shape transition from spherical to prolate ellipsoids at 30∘C in the copolymer micelles but also destabilize them and even suppress the micelle formation at high surfactant loading. DTAB destabilizes the copolymer micelles more than SDS. TX-100, being nonionic, however, forms stable mixed micelles. The block copolymer-surfactant complexes are hydrophilic in nature and are characterized by high turbid and cloud points. Triblock copolymer micelles got easily destabilized than the diblock copolymer ones, indicating the importance of the interaction between the hydrophilic E chains and surfactants. The effects of destabilization of the copolymer micelles are more dominating than the micellar growth at elevated temperatures, which is otherwise predominant in case of copolymer micelles alone.

  1. Shear-induced kink bands, lamellar rotation, and lamellar contraction observed in block copolymers

    Science.gov (United States)

    Polis, Daniel L.

    The discovery of flow-induced alignment in block copolymers was made in 1970. Since then researchers have focused on the final alignment as a function of processing conditions, which has provided a good "road map" for detailed explorations into shear-induced alignment. In this dissertation, we have explored a portion of the "road map" in detail. Specifically, we have studied shear-induced alignment of lamellar diblock copolymers, in which the time scale of the deformation is faster than molecular diffusion. When unmatched block copolymers are deformed rapidly a puzzling parallel-transverse orientation results. We developed a novel FE-SEM technique to accurately characterize the microstructure (35 nm) and superstructure (10 000 nm) of this parallel-transverse morphology. This demonstrated that the parallel-transverse morphology, induced by large-amplitude oscillatory shear, was an intriguing defect structure, namely conjugate kink bands. A systematic investigation of kink band defects provided insight that promotes the control of morphology through processing design. We induced an aligned "starting state," and investigated subtle changes in the morphology, due to a subsequent steadyshear deformation, using FE-SEM. This study uncovered a number of critical kink band characteristics. Based on these discoveries, we designed a strain ramping procedure using oscillatory shear that led to a well-aligned parallel morphology in these unmatched block copolymers. Finally, we used in-situ small-angle x-ray scattering to follow subtle changes in orientation of lamellae and lamellar period during steady shear. We were able to accurately model the changes in lamellar orientation during shear by assuming that all lamellae rotate toward the parallel orientation and the rate of rotation varies with orientation. This experiment provided the first conclusive evidence for lamellar rotation in diblock copolymers. Furthermore, we constructed a trilayer model based on the spatially

  2. Tailor-made polyfluoroacrylate and its block copolymer by RAFT polymerization in miniemulsion; improved hydrophobicity in the core-shell block copolymer.

    Science.gov (United States)

    Chakrabarty, Arindam; Singha, Nikhil K

    2013-10-15

    Controlled/living radical polymerization (CRP) of a fluoroacrylate was successfully carried out in miniemulsion by Reversible Addition Fragmentation chain Transfer (RAFT) process. In this case, 2,2,3,3,4,4,4-heptafluorobutyl acrylate (HFBA) was polymerized using 2-cyanopropyl dodecyl trithiocarbonate (CPDTC) as RAFT agent, Triton X-405 and sodium dodecyl sulfonate (SDS) as surfactant, and potassium persulphate (KPS) or 2,2'-azobis isobutyronitrile (AIBN) as initiator. Being compatible with hydrophobic fluoroacrylate, this RAFT agent offered very high conversion and good control over the molecular weight of the polymer. The miniemulsion was stable without any costabilizer. The long chain dodecyl group (-C12H25) (Z-group in the RAFT agent) had beneficial effect in stabilizing the miniemulsion. When 2-cyano 2-propyl benzodithioate (CPBD) (Z=-C6H5) was used as RAFT agent, the conversion was less and particle size distribution was very broad. Block copolymerization with butyl acrylate (BA) using PHFBA as macro-RAFT agent showed core-shell morphology with the aggregation of PHFBA segment in the shell. GPC as well as DSC analysis confirmed the formation of block copolymer. The core-shell morphology was confirmed by TEM analysis. The block copolymers (PHFBA-b-PBA) showed significantly higher water contact angle (WCA) showing much better hydrophobicity compared to PHFBA alone. PMID:23953650

  3. Tailor-made polyfluoroacrylate and its block copolymer by RAFT polymerization in miniemulsion; improved hydrophobicity in the core-shell block copolymer.

    Science.gov (United States)

    Chakrabarty, Arindam; Singha, Nikhil K

    2013-10-15

    Controlled/living radical polymerization (CRP) of a fluoroacrylate was successfully carried out in miniemulsion by Reversible Addition Fragmentation chain Transfer (RAFT) process. In this case, 2,2,3,3,4,4,4-heptafluorobutyl acrylate (HFBA) was polymerized using 2-cyanopropyl dodecyl trithiocarbonate (CPDTC) as RAFT agent, Triton X-405 and sodium dodecyl sulfonate (SDS) as surfactant, and potassium persulphate (KPS) or 2,2'-azobis isobutyronitrile (AIBN) as initiator. Being compatible with hydrophobic fluoroacrylate, this RAFT agent offered very high conversion and good control over the molecular weight of the polymer. The miniemulsion was stable without any costabilizer. The long chain dodecyl group (-C12H25) (Z-group in the RAFT agent) had beneficial effect in stabilizing the miniemulsion. When 2-cyano 2-propyl benzodithioate (CPBD) (Z=-C6H5) was used as RAFT agent, the conversion was less and particle size distribution was very broad. Block copolymerization with butyl acrylate (BA) using PHFBA as macro-RAFT agent showed core-shell morphology with the aggregation of PHFBA segment in the shell. GPC as well as DSC analysis confirmed the formation of block copolymer. The core-shell morphology was confirmed by TEM analysis. The block copolymers (PHFBA-b-PBA) showed significantly higher water contact angle (WCA) showing much better hydrophobicity compared to PHFBA alone.

  4. Modular synthesis of a block copolymer with a cleavable linkage via “click” chemistry

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    A diblock copolymer poly(ethylene glycol)-block-polystyrene or PEG-b-PS with an olefinic double bond at the PEG and PS junction has been prepared by modular synthesis via"click"chemistry.This involved the synthesis of PS by atom transfer radical polymerization and the nucleophilic substitution of the terminal bromide group with azide to yield azide-terminated PS. PEG with an alkynyl terminal group was prepared from reacting carboxyl-end-functionalized PEG with 4-hydroxybut-2-enyl prop-2-ynyl succinate,which contained an alkynyl group as well as an olefin group.The PS and PEG polymers were linked via the 1,3-dipolar cycloaddition of the end azide and alkyne groups.The obtained copolymer was characterized by 1H NMR spectroscopy and size exclusion chromatography(SEC).SEC analysis indicated that the diblock copolymer produced could be readily cleaved by ozonolysis to regenerate the constituent homopolymers.

  5. 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) appear...... the copolymers in which azobenzene units segregate to nano spheres and the lowest (and less stable) Delta n(N) values, appear in disordered systems not showing any defined microstructure. Besides, higher Delta n(N) is obtained in the copolymers with larger molecular weight of the poly (methyl......) and light power (from 100 to 500 mW/cm(2)) also influence the photoinduced response. Photoinduced Delta n(N) growth rate is faster when both temperature and irradiation power increase. Furthermore, birefringence is only induced at temperatures up to 90 degrees C, the maximum value being obtained at...

  6. Application of Block Copolymer in Three-Liquid-Phase Extraction System

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    A novel three-liquid-phase extraction system (TES) composed of butyl acetate, block copolymer polyethylene oxide-polypropylene oxide-polyethylene oxide and ammonium sulphate aqueous solution [(NH4)2SO4] as top, middle, and bottom phase, respectively, has been developed. The copolymer recycling and partitioning behavior of penicillin V has been studied in this system. Results show that the copolymer could be purified and recycled and penicillin V of the filtrated ferment broth could be partitioned unevenly among the phases and purified in the top phase of this TES. About 90 wt.% of penicillin V could be distributed into the top phase around pH 2.5 and only less than 0.1 wt.% left in the bottom phase.

  7. Environment-induced self-assembly in phase separated block copolymer systems: A SANS investigation

    International Nuclear Information System (INIS)

    In this research, we examine the effect of non-selective solvent on the large-scale mesoscopic ordering in asymmetric block copolymers, poly(styrene-block-ethylene/butylene-block-styrene) (SEBS) using small angle neutron scattering technique (SANS). SANS measurements were carried out over a wide range of concentrations and temperatures. Evolution of the self-assembled phase morphology in such polymer with the thermodynamic selectivity of solvent, temperature and concentration has been discussed. Correlation between morphology and thermorheological behavior of the gels has also been established

  8. Morphological Studies on Sn-O Coordination Driving Self-assembly of Well-defined Organotin-containing Block Copolymers

    Institute of Scientific and Technical Information of China (English)

    Jian Jiang; Wei Yan; Ling-yan Liu; Wei-xing Chang; Jing Li

    2014-01-01

    A tin-oxygen coordination driving self-assembly was developed in the block copolymers containing organotin,which were prepared by the radical addition-fraction transfer (RAFT) method and characterized by the gel-permeation chromatography (GPC) and 1H-NMR.And the self-assemblies of these block copolymers with various chain length ratios in the different concenaations in CHCl3 were stable according to the results of DLS and TEM.Additionally,it was also given an insight investigation on the regulation of self-assembly of the block copolymers by adding dibutyltin dichloride and a possible mechanism was proposed.

  9. Electrospinning of a functional perfluorinated block copolymer as a powerful route for imparting superhydrophobicity and corrosion resistance to aluminum substrates.

    Science.gov (United States)

    Grignard, Bruno; Vaillant, Alexandre; de Coninck, Joel; Piens, Marcel; Jonas, Alain M; Detrembleur, Christophe; Jerome, Christine

    2011-01-01

    Superhydrophobic aluminum surfaces with excellent corrosion resistance were successfully prepared by electrospinning of a novel fluorinated diblock copolymer solution. Micro- and nanostructuration of the diblock copolymer coating was obtained by electrospinning which proved to be an easy and cheap electrospinning technology to fabricate superhydrophobic coating. The diblock copolymer is made of poly(heptadecafluorodecylacrylate-co-acrylic acid) (PFDA-co-AA) random copolymer as the first block and polyacrylonitrile (PAN) as the second one. The fluorinated block promotes hydrophobicity to the surface by reducing the surface tension, while its carboxylic acid functions anchor the polymer film onto the aluminum surface after annealing at 130 °C. The PAN block of this copolymer insures the stability of the structuration of the surface during annealing, thanks to the infusible character of PAN. It is also demonstrated that the so-formed superhydrophobic coating shows good adhesion to aluminum surfaces, resulting in excellent corrosion resistance. PMID:21141949

  10. Preparation, Stability, and Bio-Compatability of Block Copolymer Vesicles

    Science.gov (United States)

    Discher, Dennis; Lee, James C.-M.; Bermudez, Harry; Bates, Frank; Discher, Bohdana

    2001-03-01

    Vesicles made completely from diblock copolymers polymersomes can be stably prepared by a wide range of techniques common to liposomes. Processes such as film rehydration, sonication, and extrusion can generate many micron giants as well as monodisperse, 100 nm vesicles of PEO-PEE (polyethyleneoxide polyethylethylene) or PEO PBD (polyethyleneoxide polybutadiene). These thick-walled vesicles of polymer can encapsulate macromolecules just as liposomes can, but, unlike many pure liposome systems, these polymersomes exhibit no in-surface thermal transitions and a sub-population even survive autoclaving. Suspension in blood plasma has no immediate ill-effect on vesicle stability, and neither adhesion nor stimulation of phagocytes are apparent when giant polymersomes are held in direct, protracted contact. Proliferating cells, in addition, are unaffected when cultured for an extended time with an excess of polymersomes, and several injections of 10 mg doses into rats show no ill-effect. The results are consistent with the steric stabilization that PEG-lipid can impart to liposomes, but the present single-component polymersomes are far more stable mechanically and are not limited by PEG driven micellization.

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

    Science.gov (United States)

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

    2016-01-14

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

  12. Fluctuations, conformational asymmetry and block copolymer phase behaviour

    DEFF Research Database (Denmark)

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

    1994-01-01

    parameter and degree of polymerization, respectively. epsilon accounts for differences in the conformational and volume-filling characteristics of each block. Conformational asymmetry, epsilon not equal 1, produces an asymmetric phase diagram around f = 1/2. The importance of fluctuation effects...

  13. Water vapor and gas transport through PEO PBT block copolymers

    NARCIS (Netherlands)

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

    2002-01-01

    Introduction At the bore well natural gas is saturated with water. Downstream the presence of water may cause: formation of methane hydrates (blocking eventually the pipeline), condensation of water in the pipeline and corrosion effects. A process used for the dehydration of natural gas is glycol ab

  14. Block Copolymers of Ethylene Oxide and Styrene Oxide:New Copolymer Surfactants(Ⅰ)

    Institute of Scientific and Technical Information of China (English)

    Zhuo Yang; David Attwood; Colin Booth

    2003-01-01

    @@ 1 Introduction The range and application, actual and potential, of water-soluble block-copoly (oxyalkylene)s have beenextensively reviewed in recent compilations by edited by Nace[1] and by Alexandridis and Lindman[2].

  15. Thin Isoporous Block Copolymer Membranes: It Is All about the Process.

    Science.gov (United States)

    Hahn, Janina; Clodt, Juliana I; Abetz, Clarissa; Filiz, Volkan; Abetz, Volker

    2015-09-30

    The combination of the self-assembly of amphiphilic block copolymers and the nonsolvent induced phase inversion process offers an efficient way to isoporous integral-asymmetric membranes. In this context we report fast, easily upscalable and material reducing ways to thin self-assembled membranes. Therefore, we succeeded to implement a spray or dip coating step into the membrane formation process of different diblock copolymers like polystyrene-block-poly(4-vinylpyridine), poly(α-methylstyrene)-bock-poly(4-vinylpyridine), and polystyrene-block-poly(iso-propylglycidyl methacrylate). The formation of hexagonal pore structures was possible using a highly diluted one solvent system allowing the reduction of diblock copolymer consumption and therefore the production costs are minimized compared to conventional blade casting approaches. The broad applicability of the process was proven by using different flat and hollow fiber support materials. Furthermore, the membranes made by this new method showed a more than 6-fold increase in water flux compared to conventional polystyrene-block-poly(4-vinylpyridine) membranes with similar pore sizes prepared by blade casting. The membranes could be proven to be stable at transmembrane pressures of 2 bar and showed a pH responsive flux behavior over several cycles. PMID:26349610

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

    Science.gov (United States)

    Lecocq, Eva; Nony, Fabien; Tcharkhtchi, Abbas; Gérard, Jean-François

    2011-05-01

    Poly(styrene-butadiene-methylmethacrylate) (SBM) and poly(methylmethacrylate-butyle-acrylate-methylmethacrylate) (MAM) triblock copolymers have been dissolved in liquid DGEBA epoxy resin which is subsequently polymerized by meta-xylene diamine (MXDA) or Jeffamine EDR-148. A chemorheology study of these formulations by plate-plate rheology and by thermal analysis has allowed to conclude that the addition of these copolymer blocks improve the reactive rotational moulding processability without affecting the processing time. Indeed, it prevents the pooling of the formulation at the bottom of the mould and a too rapid build up of resin viscosity of these thermosetting systems. The morphology of the cured blends examined by scanning electron microscopy (SEM) shows an increase of fracture surface area and thereby a potential increase of the toughness with the modification of epoxy system. Dynamic mechanical spectroscopy (DMA) and opalescence of final material show that the block PMMA, initially miscible, is likely to induce phase separation from the epoxy-amine matrix. Thereby, the poor compatibilisation between the toughener and the matrix has a detrimental effect on the tensile mechanical properties. The compatibilisation has to be increased to improve in synergy the processability and the final properties of these block copolymer modified formulations. First attempts could be by adapting the length and ratio of each block.

  17. Ionic Conductivity and Gas Permeability of Polymerized Ionic Liquid Block Copolymer Membranes

    Science.gov (United States)

    Evans, Christopher; Sanoja, Gabriel; Schneider, Yanika; Modestino, Miguel; Segalman, Rachel; Joint CenterArtificial Photosynthesis Team

    2014-03-01

    Polymer membranes for many energy applications, such as solar-to-hydrogen fuel production, require ionic conductivity while acting as gas diffusion barriers. We have synthesized a diblock copolymer consisting of poly(styrene-block-(4-(2-methacrylamidoethyl)-imidazolium trifluoroacetate) by treating poly(styrene-block-histamine methacrylamide) (PS- b-PHMA) with trifluoroacetic acid. The PS block serves as the structural support while the imidazolium derivative is an ion conducting polymerized ionic liquid (PIL). Small angle X-ray scattering and transmission electron microscopy demonstrate that the block copolymer self-assembles into well-ordered nanostructures, with lamellae and hexagonally packed cylindrical morphologies. The ionic conductivities of the PS-b-PHMA materials were as high as 2 x 10-4 S/cm while an order of magnitude increase in conductivity was observed upon conversion to PS-b-PIL. The ionic conductivity of the PS-b-PIL increased by a factor of ~ 4 up to 1.2 x 10-3 S/cm as the PIL domain size increased from 20 to 40 nm. These insights allow for the rational design of high performance ion conducting membranes with even greater conductivities via precise morphological control. Additionally, the role of thermal annealing on the ionic conductivity and gas permeability of copolymer membranes was investigated.

  18. Poly(dimethylsiloxane)-poly(ethylene oxide)-heparin block copolymers II: Surface characterization and in vitro assessments

    NARCIS (Netherlands)

    Grainger, D.W.; Knutson, K.; Kim, S.W.; Feijen, J.

    1990-01-01

    Amphiphilic block copolymers containing poly(dimethylsiloxane), poly(ethylene oxide), as well as heparin-coated glass beads and tubes were evaluated for the amounts and activities of surface-immobilized heparin. Because the amphiphilic copolymer system is thermodynanmcally predicted to demonstrate l

  19. Unconventional Routes for the Enhancement of the Efficiency of Dye-Sensitized Solar Cells (DSSCs) Based on Self-Assembled Block Copolymer Nanotemplates

    Science.gov (United States)

    Jang, Yoonhee; Kim, Dongha

    2013-03-01

    We introduce distinctly different and creative two strategies for improving the efficiency of TiO2-based DSSCs by incorporation of tailored hybrid nanostrcutures prepared from self-assembled block copolymer nanotemplates. Firstly, carbonized TiO2 thin layer was incorporated into at the interface either between the transparent electrode and TiO2 NP layers or between the electrolyte and TiO2 NP layers. Massively-ordered arrays of TiO2 dots embedded in carbon matrix were fabricated via direct carbonization of UV-stabilized PS- b-P4VP block copolymer films containing TiO2 sol-gel precursors. DSSCs containing carbon/TiO2 thin layers exhibited remarkably enhanced overall power conversion efficiency compared with DSSCs based on neat TiO2 NPs. Secondly, we introduce a new class of organic/inorganic 1D photonic crystals exhibiting stop bands in the specific wavelength range, which was created by stepwise layer-by-layer deposition of UV-crosslinked BCP reverse micelle layers. The simple yet novel 1D layered BCP films have been introduced into the back-side of the counter electrodes as light reflector in DSSCs system to increase the light harvesting of dye.

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

    Science.gov (United States)

    Wei, Ling; van Winkle, David H.

    2015-03-01

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

  1. Computational Investigation of Block Copolymer Surfactants for Stabilizing Fluctuation-Induced Polymeric Microemulsions

    Science.gov (United States)

    Delaney, Kris; Fredrickson, Glenn

    2013-03-01

    High molecular weight diblock copolymers introduced into a blend of immiscible homopolymers can act as a surfactant to suppress macroscopic two-fluid phase separation. With variation of block copolymer composition, the crossover between low-temperature ordering into microphase or macrophase separated states is marked by a mean-field isotropic Lifshitz multi-critical point. Strong fluctuations close to the Lifshitz point are observed to suppress the low-temperature ordering; a microemulsion state emerges, with large, co-continuous domains of segregated fluid lacking any long-range order. We study this phenomenon with fully fluctuating field-theoretic simulations based on complex Langevin sampling, and we attempt to design new block polymer surfactants that can produce the microemulsion state with a wider composition tolerance.

  2. Iron Oxide Arrays Prepared from Ferrocene- and Silsesquioxane-Containing Block Copolymers

    Directory of Open Access Journals (Sweden)

    Raita Goseki

    2012-01-01

    Full Text Available Arrays of iron oxides as precursors of iron clusters were prepared by oxygen plasma treatment of block copolymer microphase-separated nanostructures in thin films. Block copolymers composed of ferrocene-containing and silsesquioxane-containing polymethacrylate (PMAPOSS-b-PMAHFC were successfully prepared, with different molecular weights and compositions and narrow molecular weight distributions, by living anionic polymerization. The formed microphase-separated nanostructures in the bulk were characterized by wide- and small-angle X-ray scattering (WAXS and SAXS, scanning electron microscopy (SEM, and transmission electron microscopy (TEM. Thin films were prepared from a solution of PMAPOSS-b-PMAHFC in tetrahydrofuran by spin coating onto silicon wafers. Fingerprint-type line nanostructures were formed in the PMAPOSS-b-PMAHFCs thin films after solvent annealing with carbon disulfide. Oxygen plasma treatment provided the final line arrays of iron oxides based on the formed nanostructural patterns.

  3. Filtration on block copolymer solution used in directed self assembly lithography

    Science.gov (United States)

    Umeda, Toru; Takakura, Tomoyuki; Tsuzuki, Shuichi

    2016-03-01

    In this paper, we presented the filtration effects on block copolymers (BCP) that are commonly used in directed self-assembly lithographic (DSAL) imaging schemes. Specifically we focused on filtration effects on micro-contaminants such as metal ions and metal induced gels. Gel removal efficiency studies carried out with HDPE, Nylon and PTFE filters pointed out that Nylon 6,6 membrane is the most effective in removing gels in block copolymer (BCP) solutions. Metal removal efficiency studies were conducted using multistep filtrations such as repetitive filtration of single membrane material and combination of different type of membranes. Results showed that a combination of Nylon-6,6 and ion-exchange filters is highly effective in reducing metals such as Li, Mg and Al to > 99.99% efficiency. The mechanism of metal removal efficiency is discussed in detail.

  4. Synthesis of manganese oxide supported on mesoporous titanium oxide: Influence of the block copolymer

    Science.gov (United States)

    Schmit, F.; Bois, L.; Chiriac, R.; Toche, F.; Chassagneux, F.; Besson, M.; Descorme, C.; Khrouz, L.

    2015-01-01

    Manganese oxides supported on mesoporous titanium oxides were synthesized via a sol-gel route using block copolymer self-assembly. The oxides were characterized by X-ray diffraction, infrared spectroscopy, thermal analyses, nitrogen adsorption/desorption, electron microscopy and electronic paramagnetic resonance. A mesoporous anatase containing amorphous manganese oxide particles could be obtained with a 0.2 Mn:Ti molar ratio. At higher manganese loading (0.5 Mn:Ti molar ratio), segregation of crystalline manganese oxide occurred. The influence of block copolymer and manganese salt on the oxide structure was discussed. The evolution of the textural and structural characteristics of the materials upon hydrothermal treatment was also investigated.

  5. Preparation and properties of proton conducting blending polymers with fluorous block copolymers as compatibilizers

    Energy Technology Data Exchange (ETDEWEB)

    Shi, K. [National Research Council of Canada, Vancouver, BC (Canada). Inst. for Fuel Cell Innovation; Murphy, J.; Sieb, N.; Holdcroft, S. [Simon Fraser Univ., Burnaby, BC (Canada). Dept. of Chemistry]|[National Research Council of Canada, Vancouver, BC (Canada). Inst. for Fuel Cell Innovation

    2005-07-01

    This paper presented the results of an experiment in which 3 series of membranes were prepared by blending polyvinylidene difluoride (PVDF) or poly(vinylidene difluoride-co-hexafluoropropylene) (P(VDF/HFP)) with sulfonated poly(ether ether ketone) (S-PEEK), sulfonated polysulfone (SPU), or sulfonated polystyrene in order to develop novel Proton Exchange Membranes (PEMs) suitable for melt processing. The incorporation of fluorine-containing block copolymer into the blended system resulted in the preparation of acceptable proton conductivity and low water containing PEM materials. The effect of sulfonated poly([vinylidene difluoride-co-hexafluoropropylene]-b-styrene block copolymers as compatibilizers was also investigated. It was observed that conductivity was enhanced for S-PEEK/fluoropolymer blends. Microstructures for the blends were examined by transmission electron microscope and scanning electron microscope.

  6. Laser Writing Block Copolymer Self-Assembly on Graphene Light-Absorbing Layer.

    Science.gov (United States)

    Jin, Hyeong Min; Lee, Seung Hyun; Kim, Ju Young; Son, Seung-Woo; Kim, Bong Hoon; Lee, Hwan Keon; Mun, Jeong Ho; Cha, Seung Keun; Kim, Jun Soo; Nealey, Paul F; Lee, Keon Jae; Kim, Sang Ouk

    2016-03-22

    Recent advance of high-power laser processing allows for rapid, continuous, area-selective material fabrication, typically represented by laser crystallization of silicon or oxides for display applications. Two-dimensional materials such as graphene exhibit remarkable physical properties and are under intensive development for the manufacture of flexible devices. Here we demonstrate an area-selective ultrafast nanofabrication method using low intensity infrared or visible laser irradiation to direct the self-assembly of block copolymer films into highly ordered manufacturing-relevant architectures at the scale below 12 nm. The fundamental principles underlying this light-induced nanofabrication mechanism include the self-assembly of block copolymers to proceed across the disorder-order transition under large thermal gradients, and the use of chemically modified graphene films as a flexible and conformal light-absorbing layers for transparent, nonplanar, and mechanically flexible surfaces.

  7. Block copolymer with simultaneous electric and ionic conduction for use in lithium ion batteries

    Energy Technology Data Exchange (ETDEWEB)

    Javier, Anna Esmeralda K; Balsara, Nitash Pervez; Patel, Shrayesh Naran; Hallinan, Jr., Daniel T

    2013-10-08

    Redox reactions that occur at the electrodes of batteries require transport of both ions and electrons to the active centers. Reported is the synthesis of a block copolymer that exhibits simultaneous electronic and ionic conduction. A combination of Grignard metathesis polymerization and click reaction was used successively to synthesize the block copolymer containing regioregular poly(3-hexylthiophene) (P3HT) and poly(ethylene oxide) (PEO) segments. The P3HT-PEO/LiTFSI mixture was then used to make a lithium battery cathode with LiFePO.sub.4 as the only other component. All-solid lithium batteries of the cathode described above, a solid electrolyte and a lithium foil as the anode showed capacities within experimental error of the theoretical capacity of the battery. The ability of P3HT-PEO to serve all of the transport and binding functions required in a lithium battery electrode is thus demonstrated.

  8. Laser Writing Block Copolymer Self-Assembly on Graphene Light-Absorbing Layer.

    Science.gov (United States)

    Jin, Hyeong Min; Lee, Seung Hyun; Kim, Ju Young; Son, Seung-Woo; Kim, Bong Hoon; Lee, Hwan Keon; Mun, Jeong Ho; Cha, Seung Keun; Kim, Jun Soo; Nealey, Paul F; Lee, Keon Jae; Kim, Sang Ouk

    2016-03-22

    Recent advance of high-power laser processing allows for rapid, continuous, area-selective material fabrication, typically represented by laser crystallization of silicon or oxides for display applications. Two-dimensional materials such as graphene exhibit remarkable physical properties and are under intensive development for the manufacture of flexible devices. Here we demonstrate an area-selective ultrafast nanofabrication method using low intensity infrared or visible laser irradiation to direct the self-assembly of block copolymer films into highly ordered manufacturing-relevant architectures at the scale below 12 nm. The fundamental principles underlying this light-induced nanofabrication mechanism include the self-assembly of block copolymers to proceed across the disorder-order transition under large thermal gradients, and the use of chemically modified graphene films as a flexible and conformal light-absorbing layers for transparent, nonplanar, and mechanically flexible surfaces. PMID:26871736

  9. Thermally induced structural evolution and performance of mesoporous block copolymer-directed alumina perovskite solar cells.

    KAUST Repository

    Tan, Kwan Wee

    2014-04-11

    Structure control in solution-processed hybrid perovskites is crucial to design and fabricate highly efficient solar cells. Here, we utilize in situ grazing incidence wide-angle X-ray scattering and scanning electron microscopy to investigate the structural evolution and film morphologies of methylammonium lead tri-iodide/chloride (CH3NH3PbI(3-x)Cl(x)) in mesoporous block copolymer derived alumina superstructures during thermal annealing. We show the CH3NH3PbI(3-x)Cl(x) material evolution to be characterized by three distinct structures: a crystalline precursor structure not described previously, a 3D perovskite structure, and a mixture of compounds resulting from degradation. Finally, we demonstrate how understanding the processing parameters provides the foundation needed for optimal perovskite film morphology and coverage, leading to enhanced block copolymer-directed perovskite solar cell performance.

  10. Amphiphilic block copolymers as efficiency boosters in microemulsions a SANS investigation of the role of polymers

    CERN Document Server

    Endo, H; Mihailescu, M; Monkenbusch, M; Gompper, G; Richter, D; Jakobs, B; Sottmann, T; Strey, R

    2002-01-01

    The effect of amphiphilic block copolymers on ternary microemulsions (water, oil and non-ionic surfactant) is investigated. Small amounts of PEP-PEO block copolymer lead to a dramatic expansion of the one-phase region where water and oil can be solubilized by the mediation of surfactant molecules. Small-angle neutron-scattering experiments employing a high-precision two-dimensional contrast-variation technique demonstrate that the polymer is distributed uniformly on the surfactant membrane, where it modifies the membrane curvature elasticity. Furthermore, a new approach to determine the bending rigidity of an amphiphilic membrane is proposed, which is precise enough to measure the logarithmic scale dependence of the bending rigidity and its universal prefactor in bicontinuous microemulsions. (orig.)

  11. Block copolymer mixtures as antimicrobial hydrogels for biofilm eradication.

    Science.gov (United States)

    Lee, Ashlynn L Z; Ng, Victor W L; Wang, Weixin; Hedrick, James L; Yang, Yi Yan

    2013-12-01

    Current antimicrobial strategies have mostly been developed to manage infections due to planktonic cells. However, microbes in their nature state will tend to exist by attaching to and growing on living and inanimate surfaces that result in the formation of biofilms. Conventional therapies for treating biofilm-related infections are likely to be insufficient due to the lower susceptibility of microbes that are embedded in the biofilm matrix. In this study, we report the development of biodegradable hydrogels from vitamin E-functionalized polycarbonates for antimicrobial applications. These hydrogels were formed by incorporating positively-charged polycarbonates containing propyl and benzyl side chains with vitamin E moiety into physically cross-linked networks of "ABA"-type polycarbonate and poly(ethylene glycol) triblock copolymers. Investigations of the mechanical properties of the hydrogels showed that the G' values ranged from 1400 to 1600 Pa and the presence of cationic polycarbonate did not affect the stiffness of the hydrogels. Shear-thinning behavior was observed as the hydrogels displayed high viscosity at low shear rates that dramatically decreased as the shear rate increased. In vitro antimicrobial studies revealed that the more hydrophobic VE/BnCl(1:30)-loaded hydrogels generally exhibited better antimicrobial/antifungal effects compared to the VE/PrBr(1:30) counterpart as lower minimum biocidal concentrations (MBC) were observed in Staphylococcus aureus (Gram-positive), Escherichia coli (Gram-negative) and Candida albicans (fungus) (156.2, 312.5, 312.5 mg/L for VE/BnCl(1:30) and 312.5, 2500 and 625 mg/L for VE/PrBr(1:30) respectively). Similar trends were observed for the treatment of biofilms where VE/BnCl(1:30)-loaded hydrogels displayed better efficiency with regards to eradication of biomass and reduction of microbe viability of the biofilms. Furthermore, a high degree of synergistic antimicrobial effects was also observed through the co

  12. Electrochemical and bioelectrocatalytical properties of novel block-copolymers containing interacting ferrocenyl units

    OpenAIRE

    Garcia Armada, Maria del Pilar; Losada del Barrio, Jose; Lopez Villanueva, F.J.; H. Frey; Alonso Garrido, Beatriz; Casado Santana, Carmen M.

    2008-01-01

    The electrochemical characterization of three different polystyrene-b-polybutadiene block copolymers functionalized with ferrocenyl units electronically communicated, PSm-PBn(HSiMeFc2)p where m=615, n=53, p=39 (1), m=375, n=92, p=76 (2) and m=455, n=204, p=170 (3), has been carried out both in solution and electrochemically deposited onto platinum electrodes. The bioelectrocatalytical properties of electrodes modified with the polymers in the nicotinamide dinucleotide (NADH) and glucose oxida...

  13. Poly(dimethylsiloxane)-poly(ethyleneoxide)-heparin block copolymers. I. Synthesis and characterization

    OpenAIRE

    D.W. Grainger; S. W. Kim; Feijen, J.

    1988-01-01

    Amphiphilic block copolymers containing poly(dimethylsiloxane), poly(ethylene oxide), and heparin (PDMS-PEO-Hep) have been prepared via a series of coupling reactions using functionalized prepolymers, diisocyanates, and derivatized heparins. All intermediate steps of the synthesis yield quantifiable products with reactive end-groups, while the final products demonstrate bioactive, covalently bound heparin moieties. Due to the solvent systems required, commercial sodium heparin was converted t...

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

    OpenAIRE

    von der Heydt, Alice; Zippelius, Annette

    2014-01-01

    We study analytically the intricate phase behavior of cross-linked $AB$ diblock copolymer melts, which can undergo two main phase transitions due to quenched random constraints: Gelation, i.e., spatially random localization of polymers forming a system-spanning cluster, is driven by increasing the number parameter $\\mu$ of irreversible, type-selective cross-links between random pairs of $A$ blocks. Self-assembly into a periodic pattern of $A$/$B$-rich microdomains (microphase separation) is c...

  15. Tunable Mesoporous Bragg Reflectors Based on Block-Copolymer Self-Assembly

    OpenAIRE

    Guldin, S.; Kolle, M.; Stefik, M.; Langford, R; Eder, D.; Wiesner, U.; Steiner, U.

    2011-01-01

    Mesoporous Bragg reflectors are a promising materials platform for photovoltaics, light emission, and sensing. A fast and versatile fabrication route that relies on the self-assembly of the block copolymer poly(isoprene-b-ethylene oxide) in combination with simple sol-gel chemistry is reported. The method allows extended control over porosity and pore size in the resulting inorganic material and results in high-quality optical elements.

  16. Aggregate of Amphiphilic Block Copolymer as a Pseudo-Stationary Phase in Capillary Electrophoresis

    OpenAIRE

    Nakamura, Tohru; OHKI, Akira; Mishiro, Masaki; Tsuyashima, Osamu; Maeda, Shigeru; ナカムラ, トオル; オオキ, アキラ; ミシロ, マサキ; ツヤシマ, オサム; マエダ, シゲル; 中村, 透; 大木, 章; 艶島, 修; 前田, 滋

    1999-01-01

    The use of an aggregate of amphiphilic block copolymer 1, which consists of poly[(N-acetylimino)ethylene] and poly[(N-pentanoylimino)ethylene], for a pseudo-stationary phase in capillary electrophoresis has been examined. From gel-filtration chromatography, the aggregate from 1 (1-AG) was found to incorporate phenol. When the running solution contains 1-AG and sodium dodecyl sulfate (SDS), the electrophoretic mobility becomes nearly zero. Thus, it is found that when 1-AG and SDS are added to ...

  17. Precise Control over the Rheological Behavior of Associating Stimuli-Responsive Block Copolymer Gels

    OpenAIRE

    Jérémy Brassinne; Flanco Zhuge; Charles-André Fustin; Jean-François Gohy

    2015-01-01

    “Smart” materials have considerably evolved over the last few years for specific applications. They rely on intelligent macromolecules or (supra-)molecular motifs to adapt their structure and properties in response to external triggers. Here, a supramolecular stimuli-responsive polymer gel is constructed from heterotelechelic double hydrophilic block copolymers that incorporate thermo-responsive sequences. These macromolecular building units are synthesized via a three-step controlled radical...

  18. Holographic Gratings and Data Storage in Azobenzene-Containing Block Copolymers and Molecular Glasses

    Science.gov (United States)

    Audorff, Hubert; Kreger, Klaus; Walker, Roland; Haarer, Dietrich; Kador, Lothar; Schmidt, Hans-Werner

    This review covers synthesis, materials development, and photophysics of azobenzene-containing block copolymers as potential media for reversible volume holographic data storage. For high-density holographic data storage, volume gratings must be inscribed in millimeter-thick samples to achieve efficient angle multiplexing. It is demonstrated that block copolymers with azobenzene side-groups in the minority block develop no detrimental surface relief structures and exhibit superior performance regarding volume gratings, compared to homopolymers and statistical copolymers. Several material concepts for optimizing the refractive index modulation and the stability of volume gratings are presented. Stabilities of more than 2 years were achieved. Most important is the development of polymer blends comprising the azobenzene-containing block copolymer and an optically transparent homopolymer. This enables the preparation of millimeter-thick samples with the required optical density of ˜ 0. 7 at the writing wavelength by conventional injection molding techniques. The inscription of up to 200 holograms at the same lateral position was demonstrated. In addition, more than 1,000 write/erase cycles can be performed. This is the first time that the inscription and erasure of the long-term stable angle-multiplexed volume gratings in a rewritable polymeric medium have been achieved by purely optical means. A second important application for azobenzene-containing materials is the controlled preparation of surface relief structures. It is demonstrated that azobenzene-containing molecular glasses are an ideal class for efficient formation of surface relief gratings (SRGs) with amplitude heights of more than 600 nm. Clear relationships can be established between the chemical structure of the molecules and the behavior of SRG formation. All results are in agreement with the gradient force model by Kumar et al. The surface patterns are stable enough to be transferred to a polymer

  19. Vertically oriented hexagonal mesoporous zirconia thin films by block copolymer templating

    OpenAIRE

    Miko, Annamaria ; Demirel, A. Levent ; Somer, Mehmet

    2012-01-01

    We report the synthesis of vertically oriented, long-range ordered hexagonal mesoporous zirconia thin ?lms. The orientation of hexagonally ordered cylindrical mesopores in thin ?lms was effectively controlled by taking advantage of the temperature dependent hydrophobicity of the templating block copolymer PEO–PPO–PEO. Vertical orientation was obtained when temperature was 30 C or above throughout the process. Dehydration and enhanced chemical incompatibility between the PEO and PPO b...

  20. Synthetic routes toward functional block copolymers and bioconjugates via RAFT polymerization

    OpenAIRE

    Wiss, Kerstin T.

    2010-01-01

    Synthetic Routes toward Functional Block Copolymers and Bioconjugates via RAFT PolymerizationrnSynthesewege für funktionelle Blockcopolymere und Biohybride über RAFT PolymerisationrnDissertation von Dipl.-Chem. Kerstin T. WissrnIm Rahmen dieser Arbeit wurden effiziente Methoden für die Funktionalisierung beider Polymerkettenenden für Polymer- und Bioanbindung von Polymeren entwickelt, die mittels „Reversible Addition-Fragmentation Chain Transfer“ (RAFT) Polymerisation hergestellt wurden. Zu d...

  1. Single-molecule protein arrays enabled by scanning probe block copolymer lithography

    OpenAIRE

    Chai, Jinan; Wong, Lu Shin; Giam, Louise; Mirkin, Chad A.

    2011-01-01

    The ability to control the placement of individual protein molecules on surfaces could enable advances in a wide range of areas, from the development of nanoscale biomolecular devices to fundamental studies in cell biology. Such control, however, remains a challenge in nanobiotechnology due to the limitations of current lithographic techniques. Herein we report an approach that combines scanning probe block copolymer lithography with site-selective immobilization strategies to create arrays o...

  2. Self-assembled block copolymer-nanoparticle hybrids: interplay between enthalpy and entropy.

    Science.gov (United States)

    Sarkar, Biswajit; Alexandridis, Paschalis

    2012-11-13

    The dispersion of nanoparticles in ordered block copolymer nanostructures can provide control over particle location and orientation, and pave the way for engineered nanomaterials that have enhanced mechanical, electrical, or optical properties. Fundamental questions pertaining to the role of enthalpic and entropic particle-polymer interactions remain open and motivate the present work. We consider here a system of 10.6 nm silica nanoparticles (NPs) dispersed in ordered cylinders formed by hydrated poly(ethylene oxide)-poly(propylene oxide) block copolymers (Pluronic P105: EO(37)PO(56)EO(37)). Protonation of silica was used to vary the NP-polymer enthalpic interactions, while polar organic solvents (glycerol, DMSO, ethanol, and DMF) were used to modulate the NP-polymer entropic interactions. The introduction of deprotonated NPs in the place of an equal mass of water did not affect the lattice parameter of the PEO-PPO-PEO block copolymer hexagonal lyotropic liquid crystalline structures. However, the dispersion of protonated NPs led to an increase in the lattice parameter, which was attributed to stronger NP-polymer hydrogen bonding (enthalpic) interactions. Dispersion of protonated NPs into cylindrical structures formed by Pluronic P105 in 80/20 water/organic solvents does not influence the lattice parameter, different from the case of protonated NP in plain water. Organic solvents appear to screen the NP-polymer hydrogen bonding interactions.

  3. Triazene UV-triggered photogeneration of silver/gold nanoparticles in block copolymer templates

    Energy Technology Data Exchange (ETDEWEB)

    Melinte, Violeta; Chibac, Andreea; Buruiana, Tinca; Hitruc, Gabriela; Buruiana, Emil C., E-mail: emilbur@icmpp.ro [Petru Poni Institute of Macromolecular Chemistry, Polyaddition and Photochemistry Department (Romania)

    2015-10-15

    This article describes an attractive way to in situ create noble metal nanoparticles in block copolymer matrixes through the UV-triggered photodecomposition of the photolabile triazene units without the use of any conventional reducing agent. The poly(isodecyl methacrylate-co-triazene urethane methacrylate) random copolymer containing pendent photocleavable triazene junctions (COP-1) was synthesized under RAFT conditions and subsequently employed as macroinitiator to obtain a block copolymer, namely poly(isodecyl methacrylate-co-triazene urethane methacrylate)-block-poly(acrylic acid) (COP-2). The photogeneration of silver/gold metal nanoparticles (NPs) from noble metal precursors (1 wt% AgNO{sub 3} or AuBr{sub 3} metal salts) induced through the UV decomposition of triazene units with the formation of some radical active species was monitored in solution and thin films. The in situ growth of Ag/Au nanostructures into polymer matrixes for which the light is a key element has been confirmed by UV spectroscopy and TEM analysis. The TEM images allowed the visualization of the silver NPs (sizes of 4–16 nm in COP-1 and of 2–6 nm in COP-2) as well as of the gold NPs (sizes between 10 and 20 nm in COP-1 and from 15 to 25 nm in COP-2), which are mainly spherical in shape, even though there is some triangular or hexagonal gold nanoparticles.

  4. Gel formation in a mixture of a block copolymer and a nematic liquid crystal.

    Science.gov (United States)

    Khazimullin, Maxim; Müller, Thomas; Messlinger, Stephan; Rehberg, Ingo; Schöpf, Wolfgang; Krekhov, Alexei; Pettau, Robin; Kreger, Klaus; Schmidt, Hans-Werner

    2011-08-01

    The viscoelastic properties of a binary mixture of a mesogenic side-chain block copolymer in a low molecular weight nematic liquid crystal are studied for mass concentrations ranging from the diluted regime up to a liquid crystalline gel state at about 3%. In the gel state, the system does not flow, exhibits a polydomain structure on a microscopic level, and strongly scatters light. Below the gelation point, the system is homogeneous and behaves like a usual nematic, so the continuum theory of liquid crystals can be applied for interpreting the experimental data. Using the dynamic Fréedericksz transition technique, the dependence of the splay elastic constant and the rotational viscosity on the polymer concentration have been obtained. Comparing the dynamic behavior of block copolymer solutions with the respective homopolymer solutions reveals that, above a mass concentration of 1%, self-assembling of the block copolymer chain segments in clusters occurred, resulting in a gel state at higher concentrations. The effective cluster size is estimated as a function of the concentration, and a scaling-law behavior near the sol-gel transition is confirmed. This technique may serve as an alternative method for determining the gelation point. PMID:21929007

  5. Gel formation in a mixture of a block copolymer and a nematic liquid crystal

    Science.gov (United States)

    Khazimullin, Maxim; Müller, Thomas; Messlinger, Stephan; Rehberg, Ingo; Schöpf, Wolfgang; Krekhov, Alexei; Pettau, Robin; Kreger, Klaus; Schmidt, Hans-Werner

    2011-08-01

    The viscoelastic properties of a binary mixture of a mesogenic side-chain block copolymer in a low molecular weight nematic liquid crystal are studied for mass concentrations ranging from the diluted regime up to a liquid crystalline gel state at about 3%. In the gel state, the system does not flow, exhibits a polydomain structure on a microscopic level, and strongly scatters light. Below the gelation point, the system is homogeneous and behaves like a usual nematic, so the continuum theory of liquid crystals can be applied for interpreting the experimental data. Using the dynamic Fréedericksz transition technique, the dependence of the splay elastic constant and the rotational viscosity on the polymer concentration have been obtained. Comparing the dynamic behavior of block copolymer solutions with the respective homopolymer solutions reveals that, above a mass concentration of 1%, self-assembling of the block copolymer chain segments in clusters occurred, resulting in a gel state at higher concentrations. The effective cluster size is estimated as a function of the concentration, and a scaling-law behavior near the sol-gel transition is confirmed. This technique may serve as an alternative method for determining the gelation point.

  6. Selective directed self-assembly of coexisting morphologies using block copolymer blends

    Science.gov (United States)

    Stein, A.; Wright, G.; Yager, K. G.; Doerk, G. S.; Black, C. T.

    2016-01-01

    Directed self-assembly (DSA) of block copolymers is an emergent technique for nano-lithography, but is limited in the range of structures possible in a single fabrication step. Here we expand on traditional DSA chemical patterning. A blend of lamellar- and cylinder-forming block copolymers assembles on specially designed surface chemical line gratings, leading to the simultaneous formation of coexisting ordered morphologies in separate areas of the substrate. The competing energetics of polymer chain distortions and chemical mismatch with the substrate grating bias the system towards either line/space or dot array patterns, depending on the pitch and linewidth of the prepattern. This is in contrast to the typical DSA, wherein assembly of a single-component block copolymer on chemical templates generates patterns of either lines/spaces (lamellar) or hexagonal dot arrays (cylinders). In our approach, the chemical template encodes desired local spatial arrangements of coexisting design motifs, self-assembled from a single, sophisticated resist. PMID:27480327

  7. Amphiphilic Spider Silk-Like Block Copolymers with Tunable Physical Properties and Morphology for Biomedical Applications

    Science.gov (United States)

    Huang, Wenwen; Krishnaji, Sreevidhya; Kaplan, David; Cebe, Peggy

    2013-03-01

    Silk-based materials are important candidates for biomedical applications because of their excellent biocompatibility and biodegradability. To generate silk amphiphilic biopolymers with potential use in guided tissue repair and drug delivery, a novel family of spider silk-like block copolymers was synthesized by recombinant DNA technology. Block copolymer thermal properties, structural conformations, protein-water interactions, and self-assembly morphologies were studied with respect to well controlled protein amino acid sequences. A theoretical model was used to predict the heat capacity of the protein and protein-water complex. Using thermal analysis, two glass transitions were observed: Tg1 is related to conformational changes caused by bound water removal, while Tg2 (>Tg1) is the glass transition of dry protein. Real-time infrared spectroscopy and X-ray diffraction confirmed that different secondary structural changes occur during the two Tg relaxations. Using scanning electron microscopy, fibrillar networks and hollow vesicles are observed, depending on protein block copolymer sequence. This study provides a deeper understanding of the relationship between protein physical properties and amino acid sequence, with implications for design of other protein-based materials. Support was provided from the NSF CBET-0828028 and the MRI Program under DMR-0520655 for thermal analysis instrumentation.

  8. Triazene UV-triggered photogeneration of silver/gold nanoparticles in block copolymer templates

    International Nuclear Information System (INIS)

    This article describes an attractive way to in situ create noble metal nanoparticles in block copolymer matrixes through the UV-triggered photodecomposition of the photolabile triazene units without the use of any conventional reducing agent. The poly(isodecyl methacrylate-co-triazene urethane methacrylate) random copolymer containing pendent photocleavable triazene junctions (COP-1) was synthesized under RAFT conditions and subsequently employed as macroinitiator to obtain a block copolymer, namely poly(isodecyl methacrylate-co-triazene urethane methacrylate)-block-poly(acrylic acid) (COP-2). The photogeneration of silver/gold metal nanoparticles (NPs) from noble metal precursors (1 wt% AgNO3 or AuBr3 metal salts) induced through the UV decomposition of triazene units with the formation of some radical active species was monitored in solution and thin films. The in situ growth of Ag/Au nanostructures into polymer matrixes for which the light is a key element has been confirmed by UV spectroscopy and TEM analysis. The TEM images allowed the visualization of the silver NPs (sizes of 4–16 nm in COP-1 and of 2–6 nm in COP-2) as well as of the gold NPs (sizes between 10 and 20 nm in COP-1 and from 15 to 25 nm in COP-2), which are mainly spherical in shape, even though there is some triangular or hexagonal gold nanoparticles

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

    Science.gov (United States)

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

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

  10. Biosynthesis and characterization of diblock copolymer of p(3-hydroxypropionate)-block-p(4-hydroxybutyrate) from recombinant Escherichia coli

    DEFF Research Database (Denmark)

    Tripathi, Lakshmi; Wu, Linping; Meng, Dechuan;

    2013-01-01

    Poly(4-hydroxybutyrate) (P4HB) is a highly elastic polymer, whereas poly(3-hydroxypropionate) (P3HP) is a polymer with enormous tensile strength. This study aimed to biosynthesize a block copolymer consisting of soft P4HB block with a strong P3HP block to gain unique and excellent material proper...

  11. Quantitative Control of Pore Size of Mesoporous Carbon Nanospheres through the Self-Assembly of Diblock Copolymer Micelles in Solution.

    Science.gov (United States)

    Tian, Hao; Lin, Zhixing; Xu, Fugui; Zheng, Jingxu; Zhuang, Xiaodong; Mai, Yiyong; Feng, Xinliang

    2016-06-01

    This paper reports facile synthesis of nitrogen-doped mesoporous carbon nanospheres (MCNSs) with average diameters of around 300 nm and well-controlled pore sizes ranging from 8 to 38 nm, by employing polystyrene-b-poly(ethylene oxide) (PS-b-PEO) diblocks with different PS block lengths as the soft templates and dopamine as the carbon-rich precursor. For the first time, a linear equation is achieved for the quantitative control of the average pore size of MCNSs by simply adjusting a block length of diblock copolymer. The resultant MCNSs possess high surface areas of up to 450 m(2) g(-1) and nitrogen doping contents of up to ≈3 wt%. As electrode materials of supercapacitors, the MCNSs exhibit excellent electrochemical performance with high specific capacitances of up to 350 F g(-1) at 0.1 A g(-1) , superior rate capability, and cycling stability. Interestingly, the specific capacitance of the MCNSs reduces linearly with increasing pore size, whereas the normalized capacitance by specific surface area remains invariable. This represents a new spectrum of the relationship between electrochemical capacitance and pore size (>5 nm) for porous carbons, which makes a complement to the existing spectra focusing on pore diameters of <5 nm. PMID:27120340

  12. Progress in Self-assembly of the Block Copolymers%嵌段共聚物自组装的研究进展

    Institute of Scientific and Technical Information of China (English)

    唐林; 宋颖; 李冬梅; 马晓燕

    2011-01-01

    Self-Assembly is the process by which a system of molecules relied on non-covalent interaction spontaneously assemble into a structure-determinated and stable molecular aggregates or supramolecular structures which possess specific functions or performances in the mean time. Block copolymer systems exhibit well-known ability to self-assemble into a wide variety of morphologies either in bulk (lamellas, gyriods, cylinders, spheres, etc. ) or in solution (spherical micelles, vesicles,cylinders, etc. ). In this paper, the main factors which may influence the self-assembled morphology of the block copolymers in solution, including the length of the building blocks, the property of the selective solvents, the concentration of the block copolymers and the pH value of the solutions, are reviewed. Moreover, various methods of the computer simulation for the self-assembly of the block copolymers, such as self-consistent field theory, simulation of Monte Carlo, dissipative particle dynamics and simulated annealing, are introduced.%自组装是分子间通过非共价键相互作用自发组合形成的一类结构明确、稳定,同时具有某种特定功能或性能的分子聚集体或超分子结构的现象.嵌段共聚物不仅可以在本体中自组装,还能在溶液中自组装.本文综述了嵌段共聚物在溶液中自组装的规律及其主要影响因素,包括嵌段共聚物链段长度、选择性溶剂的性质、嵌段共聚物的浓度、溶液的pH值等;并介绍了计算机模拟中模拟退火(simulated annealing)、自洽场理论(self-consistent field theory,SCFT)、蒙特卡洛(Monte Carlo,MC)模拟、耗散粒子动力学(dissipative particle dynamics,DPD)等方法在该领域的应用.

  13. Flash NanoPrecipitation of organic actives via confined micromixing and block copolymer stabilization

    Science.gov (United States)

    Johnson, Brian K.

    This dissertation provides a method and the understanding required to produce nanoparticles of organic actives using Flash NanoPrecipitation . The process comprises mixing a solvent phase containing molecularly dissolved amphiphilic block copolymer and an organic active with an anti-solvent. One block of the copolymer precipitates to alter the nucleation and growth of the organic active while the other remains in solution for particle stabilization. A custom built confined impinging jets (CIJ) mixer provides optimum micromixing at the laboratory or full scale within milliseconds. Comparison to other reactor designs is provided. The resulting nanoparticles have functional surfaces tailored to meet the needs of pharmaceutical or specialty chemical formulations. Example beta-carotene nanoparticles with a polyethylene oxide surface are produced at high concentration, high yield, low stabilizer content, and a size suitable for sterile filtration or larger. The technical challenges in nanoparticle production are explained via the characteristic times for mixing, copolymer aggregation, and organic active particle formation. The time for Flash NanoPrecipitation is shown to depend strongly on the time for copolymer aggregation, and control of the organic nucleation versus growth is critical to achieve nanoparticles. Mixing operating lines explain the impact of solubility differences between the colloidal stabilizer and the organic active as function of mixing rate. Techniques to measure the solubility of the copolymer and DeltaG° , DeltaH°, and DeltaS° of micellization are demonstrated. An analytical CIJ mixer is developed by quantifying the characteristic time and physical mechanism of mixing. The methodology described to find an absolute mixing lifetime is also applied to a vortex mixer at a spectrum of flow ratios away from one. Dimensional analysis using the process Damkohler number, defined as the ratio of the mixing to the process time, is applied to precipitation

  14. Polymeric micelles of amphiphilic graft copolymer of α-tocopherol succinate-g-carboxymethyl chitosan for tamoxifen delivery: Synthesis, characterization and in vivo pharmacokinetic study.

    Science.gov (United States)

    Jena, Sunil K; Sangamwar, Abhay T

    2016-10-20

    Novel amphiphilic graft copolymers were prepared from low molecular weight carboxymethyl chitosan (LMW Cmc) and α-tocopherol succinate (TS) via an amidation reaction and confirmed by (1)H NMR and IR spectroscopy. These graft copolymers are self-assembled to nanosized core-shell-structural micelles in an aqueous milieu. The critical micelle concentration (CMC) decreased with an increasing substitution of TS on LMW Cmc, which ranged from 7.94×10(-8) to 1.58×10(-6)g/mL. Cmc-TS4.5 (Cmc-TS with a charged molar ratio of TS to glucosamine units of Cmc∼4.5) was shown maximum TMX loading up to 8.08±0.98%. Both blank and TMX-loaded PM's of Cmc-TS4.5 exhibit spherical shape with particle size below 200nm. An in vitro release study in simulated gastric and intestinal fluid demonstrated that TMX release from TMX-PM4.5 (TMX-PMs prepared with amphiphilic polymer Cmc-TS4.5, and the weight ratio of Cmc-TS4.5 to TMX was 8:1) was slow and pH dependent. In vivo oral absorption study revealed Cmc-TS4.5 based PM's permeated the epithelial barrier via the paracellular route without causing any intestinal damage. In vivo toxicity study demonstrated the safety of PM's after oral administration. Compared to tamoxifen control, TMX-PM4.5 dosed to fasted female Sprague Dawley rats showed a 1.9 fold increase in AUC0-72h. Thus, the results suggested that Cmc-TS micelles are a promising carrier for TMX delivery. PMID:27474667

  15. Highly protein-resistant coatings and suspension cell culture thereon from amphiphilic block copolymers prepared by RAFT polymerization.

    Science.gov (United States)

    Haraguchi, Kazutoshi; Kubota, Kazuomi; Takada, Tetsuo; Mahara, Saori

    2014-06-01

    Novel amphiphilic block copolymers composed of hydrophobic (poly(2-methoxyethyl acrylate): M) and hydrophilic (poly(N,N-dimethylacrylamide): D) segments were synthesized by living radical polymerization: a reversible addition-fragmentation chain-transfer polymerization. Two types of amphiphilic block copolymers, triblock (MDM) and 4-arm block ((MD)4) copolymers with specific compositions (D/M = (750-1500)/250), were prepared by a versatile one-pot synthesis. These copolymers show good adhesion to various types of substrates (e.g., polystyrene, polycarbonate, polypropylene, Ti, and glass), and the surface coating showed high protein repellency and a low contact angle for water, regardless of the substrate. The two opposing characteristics of high protein repellency and good substrate adhesion were achieved by the combined effects of the molecular architecture of the block copolymers, the high molecular weight, and the characteristics of each segment, that is, low protein adsorption capability of both segments and low glass transition temperature of the hydrophobic segment. Further, a polystyrene dish coated with the MDM block copolymer could be sterilized by γ-ray irradiation and used as a good substrate for a suspension cell culture that exhibits low cell adhesion and good cell growth.

  16. Highly protein-resistant coatings and suspension cell culture thereon from amphiphilic block copolymers prepared by RAFT polymerization.

    Science.gov (United States)

    Haraguchi, Kazutoshi; Kubota, Kazuomi; Takada, Tetsuo; Mahara, Saori

    2014-06-01

    Novel amphiphilic block copolymers composed of hydrophobic (poly(2-methoxyethyl acrylate): M) and hydrophilic (poly(N,N-dimethylacrylamide): D) segments were synthesized by living radical polymerization: a reversible addition-fragmentation chain-transfer polymerization. Two types of amphiphilic block copolymers, triblock (MDM) and 4-arm block ((MD)4) copolymers with specific compositions (D/M = (750-1500)/250), were prepared by a versatile one-pot synthesis. These copolymers show good adhesion to various types of substrates (e.g., polystyrene, polycarbonate, polypropylene, Ti, and glass), and the surface coating showed high protein repellency and a low contact angle for water, regardless of the substrate. The two opposing characteristics of high protein repellency and good substrate adhesion were achieved by the combined effects of the molecular architecture of the block copolymers, the high molecular weight, and the characteristics of each segment, that is, low protein adsorption capability of both segments and low glass transition temperature of the hydrophobic segment. Further, a polystyrene dish coated with the MDM block copolymer could be sterilized by γ-ray irradiation and used as a good substrate for a suspension cell culture that exhibits low cell adhesion and good cell growth. PMID:24773089

  17. Nanostructured Double Hydrophobic Poly(Styrene-b-Methyl Methacrylate) Block Copolymer Membrane Manufactured Via Phase Inversion Technique

    KAUST Repository

    Karunakaran, Madhavan

    2016-03-11

    In this paper, we demonstrate the formation of nanostructured double hydrophobic poly(styrene-b-methyl methacrylate) (PS-b-PMMA) block copolymer membranes via state-of-the-art phase inversion technique. The nanostructured membrane morphologies are tuned by different solvent and block copolymer compositions. The membrane morphology has been investigated using FESEM, AFM and TEM. Morphological investigation shows the formation of both cylindrical and lamellar structures on the top surface of the block copolymer membranes. The PS-b-PMMA having an equal block length (PS160K-b-PMMA160K) exhibits both cylindrical and lamellar structures on the top layer of the asymmetric membrane. All membranes fabricated from PS160K-b-PMMA160K shows an incomplete pore formation in both cylindrical and lamellar morphologies during the phase inversion process. However, PS-b-PMMA (PS135K-b-PMMA19.5K) block copolymer having a short PMMA block allowed us to produce open pore structures with ordered hexagonal cylindrical pores during the phase inversion process. The resulting PS-b-PMMA nanostructured block copolymer membranes have pure water flux from 105-820 l/m2.h.bar and 95% retention of PEG50K

  18. Effects of Sequence Distribution and Physical Aging on Physical Properties of PES/PEES Random, Block, and Alternative Copolymers

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    The random, block, and alternative copolymers of poly ether sulfone(PES) and poly ether ether sulfone(PEES) were synthesized via three kinds of methods. The chemical structures of the three kinds of copolymers were characterized by 13 C NMR. Three kinds of PES/PEES copolymers(Tg=215 ℃), which were almost identical in composition but different in sequence distribution, were used. Their physical aging process was studied by differential scanning calorimetry(DSC) at three aging temperatures ranging between Tg-15 ℃ and Tg-25 ℃. The experimental results reveal that the alternative copolymer shows a lower enthalpy relaxation timeand apparent activation energy when compared with the random and block copolymers. The result of the electron-microscopy investigation of the three copolymers that were treated at 200 ℃ for 96 h indicates that the molecular aggregation of the copolymers changed from a randomly coiled amorphous phase to an ordered phase, and the ordered structure of the alternative copolymer was more distinct than that of the random phase. The experimental results of this study suggest that the motion of the segments is affected by the different molecular-chain sequence distribution.

  19. Nanopatterning by large block copolymers for application in photonic devices (Conference Presentation)

    Science.gov (United States)

    Mokarian-Tabari, Parvaneh; Senthamaraikannan, Ramsankar; Collins, Timothy W.; Glynn, Colm; O'Dwyer, Colm; Morris, Michael

    2016-04-01

    The extensive benefits of the new generation of nanostructured surfaces is very promising for enhancing light absorption efficiency in photonic devices. However, the low throughput and the high cost of available technologies such as lithography for fabrication of nanostructures has proved to be a difficult technological hurdle for advanced manufacturing. In this research we present a solution based process based on high molecular weight block copolymer (BCP) nanolithography for fabrication of periodic structures on large areas of optical surfaces. Block copolymer self- assembly technique is a solution based process that offers an alternative route to produce highly ordered photonic crystal structures. BCPs forms nanodomains (5-10 nm) due to microphase separation of incompatible constitute blocks. The size and shape of the nanostructure can be customised by the molecular weight and volume fraction of the polymer blocks. However, the major challenge is BCPs do not phase separate into their signature ordered pattern above 100 nm, whereas for nanofeatures to be used as photonic gratings, they must be greater than 100 nm (typically ¼ wavelength). This is due to significant kinetic penalty arising from higher entanglement in high molecular weight polymers. In this work we present the results of exploiting commercially available block copolymers to phase separate into periodic domains greater than 100 nm. The process do not include any blending with homopolymers, or adding colloidal particles, and to our best knowledge, has not been yet achieved or reported in the literatures. We have pattern transferred the BCP mask to silicon substrate by reactive ion etch (ICP-RIE). The final product is black silicon, consists of hexagonally packed conic Si nanofeatures with diameter above 100nm and periodicity of 200 nm. The height of the Si nanopillars varies from 100 nm to 1 micron. We have characterized the angle dependent optical reflectance properties of the black silicon. The

  20. Intracellular trafficking of polyamidoamine-poly(ethylene glycol) block copolymers in DNA delivery.

    Science.gov (United States)

    Bonner, Daniel K; Leung, Cheuk; Chen-Liang, Jane; Chingozha, Loice; Langer, Robert; Hammond, Paula T

    2011-08-17

    The delivery of nucleic acids has the potential to revolutionize medicine by allowing previously untreatable diseases to be clinically addressed. Viral delivery systems have shown immunogenicity and toxicity dangers, but synthetic vectors have lagged in transfection efficiency. Previously, we developed a modular, linear-dendritic block copolymer architecture with high gene transfection efficiency compared to commercial standards. This rationally designed system makes use of a cationic dendritic block to condense the anionic DNA and forms complexes with favorable endosomal escape properties. The linear block provides biocompatibility and protection from serum proteins, and can be functionalized with a targeting ligand. In this work, we quantitate performance of this system with respect to intracellular barriers to gene delivery using both high-throughput and traditional approaches. An image-based, high-throughput assay for endosomal escape is described and applied to the block copolymer system. Nuclear entry is demonstrated to be the most significant barrier to more efficient delivery and will be addressed in future versions of the system.