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Sample records for based olefinic copolymer

  1. Thermoplastic Adhesives based on polyolefin and olefinic copolymers

    Science.gov (United States)

    Paul, Rituparna

    2014-03-01

    H.B. Fuller has been a leading global industrial adhesive manufacturer for over 125 years. It is a company with a rich history of consistently delivering adhesive innovations for enhancing product performance in the market place. H.B. Fuller technologies/products find application in several markets including packaging, personal hygiene and nonwovens, durable assembly and electronics. In this presentation, H. B. Fuller's technology innovation journey will be shared with emphasis on groundbreaking technologies/products based on polyolefin and olefin copolymers.

  2. Polymer PCF Bragg grating sensors based on poly(methyl methacrylate) and TOPAS cyclic olefin copolymer

    DEFF Research Database (Denmark)

    Johnson, Ian P; Webb, David J; Kalli, Kyriacos

    2011-01-01

    Fibre Bragg grating (FBG) sensors have been fabricated in polymer photonic crystal fibre (PCF). Results are presented using two different types of polymer optical fibre (POF); first multimode PCF with a core diameter of 50μm based on poly(methyl methacrylate) (PMMA) and second, endlessly single...... to no longer than 10cm. However, both have improved attenuation of under 10dB/m in the 800nm spectral region, thus allowing for fibre lengths to be much longer. The focus of current research is to utilise the increased fibre length, widening the range of sensor applications. The Bragg wavelength shift...... the possibility to manufacture multiplexed Bragg sensors in POF using a single phase mask in the UV inscription manufacturing. TOPAS holds certain advantages over PMMA including a much lower affinity for water, this should allow for the elimination of cross-sensitivity to humidity when monitoring temperature...

  3. Olefin-maleic-anhydride copolymer based additives: a novel approach for compatibilizing blends of waste polyethylene and crumb rubber.

    Science.gov (United States)

    Tóth, Balázs; Varga, Csilla; Bartha, László

    2015-04-01

    In our work processing conditions and mechanical properties of waste polyethylene (PE)/crumb rubber (CR) blends have been improved by new types of compatibilizing additives synthesized from experimental olefin-maleic-anhydride copolymers at our laboratory. Compatibilizing additives have been introduced into the PE/CR blends in 0.2 wt% while CR concentration has been varied between 10 and 50 wt%. For comparison of the effects commercially available MA-g-PO type compatibilizing additives have also been applied. Tensile and Charpy impact tests of the compression moulded samples have been carried out. Several experimental additives have enhanced properties of the PE/CR blends either from the point of view of tensile or Charpy impact strength while commercial additives have had improving effects only on one of the abovementioned mechanical properties but not for both of them simultaneously. Since good mechanical properties could be achieved by our experimental compatibilizers good adhesion in the waste PE/CR samples have been considered and was proven by SEM graphs either.

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

    DEFF Research Database (Denmark)

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

    2011-01-01

    A report is presented on the inscription of a fibre Bragg grating into a microstructured polymer optical fibre fabricated from TOPAS cyclic olefin copolymer. This material offers two important advantages over poly (methyl methacrylate), which up to now has formed the basis for polymer fibre Bragg...

  5. 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.

  6. Effects of Process Parameters on Replication Accuracy of Microinjection Molded Cyclic Olefins Copolymers Parts

    Science.gov (United States)

    Lin, Hsuan-Liang; Chen, Chun-Sheng; Lee, Ruey-Tsung; Chen, Shia-Chung; Chien, Rean-Der; Jeng, Ming-Chang; Hwang, Jiun-Ren

    2013-04-01

    In this study, the effects of various processing parameters of microinjection molding on the replication accuracy of the micro featured fluidic platform used for DNA/RNA tests are investigated. LIGA-like processes were utilized to prepare a silicon-based SU-8 photoresist, followed by electroforming to make a Ni-Co-based stamp. A cyclic olefin copolymer (COC) was used as the injection molding material. The molding parameters associated with the replication accuracy of micro channel parts were investigated. It was found that for microinjection molded devices, the replication accuracies of the imprint width and depth increase with increasing of mold temperature, melt temperature, injection velocity, and packing pressure.

  7. Synthesis of a gamma irradiation grafted polytetrafluoroethylene (PTFE) based olefinic copolymer; Estudo da sintese de copolimero olefinico a base de politetrafluoroetileno (PTFE) por meio da enxertia induzida por radiacao gama

    Energy Technology Data Exchange (ETDEWEB)

    Ferreto, Helio Fernando Rodrigues

    2006-07-01

    The extrusion of linear low density polyethylene (LLDPE) is limited by a process related defect known as 'melt fracture' or 'sharkskin', which is a surface defect of the extruded polymer. This defect results in a product with a rough surface that lacks luster and in alterations of specific surface properties. The aim of this study was to obtain a recycled polytetrafluoroethylene polymer with an olefin that could improve the extrudability of the LLDPE. The copolymer was obtained by irradiating recycled PTFE in an inert atmosphere followed by the addition of an olefinic monomer to graft the latter in the polymeric matrix (PTFE). After a certain time of contact, the copolymer was heat treated to permit recombination and elimination of the radicals, both in a reactive and/or inert atmosphere. Three olefinic monomers were used, namely; acetylene, ethylene and 1,3-butadiene. The 1,3-butadiene monomer was found to be more effective with respect to grafting. The specimens were studied using Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA) and differential thermogravimetry (DTG). 0.2-2.0 wt% of the copolymer that was obtained was mixed with LLDPE. The rheological properties of the mixture were determined with a torque rheometer. The results indicated that the process used rendered a copolymer which when added to LLDPE, improved the extrusion process and eliminated the defect 'melt fracture'. (author)

  8. The use of ethylene glycol solution as the running buffer for highly efficient microchip-based electrophoresis in unmodified cyclic olefin copolymer microchips.

    Science.gov (United States)

    Wang, Qin; Zhang, Yuan; Ding, Hui; Wu, Jing; Wang, Lili; Zhou, Lei; Pu, Qiaosheng

    2011-12-30

    An ethylene glycol solution was used as the electrophoretic running buffer in unmodified cyclic olefin copolymer (COC) microchips to minimize the interactions between the analytes and the hydrophobic walls of the plastic microchannels, enhance the resolution of the analytes and eliminate the uncontrollable dispersion caused by uneven liquid levels and non-uniform surfaces of the separation channels. Five amino acids that were labeled with fluorescein isothiocyanate (FITC) were used as model analytes to examine the separation efficiency. The effects of ethylene glycol concentration, pH and sodium tetraborate concentration were systematically investigated. The five FITC-labeled amino acids were effectively resolved using a COC microchip with an effective length of 2.5 cm under optimum conditions, which included using a running buffer of 20 mmol/L sodium tetraborate in ethylene glycol:water (80:20, v/v), pH 6.7. A theoretical plate number of 4.8 × 10(5)/m was obtained for aspartic acid. The system exhibited good repeatability, and the relative standard deviations (n=5) of the peak areas and migration times were no more than 3.4% and 0.7%, respectively. Furthermore, the system was successfully applied to elucidate these five amino acids in human saliva.

  9. Surface functionalization of cyclic olefin copolymer (COC) with evaporated TiO{sub 2} thin film

    Energy Technology Data Exchange (ETDEWEB)

    El Fissi, Lamia, E-mail: lamia.elfissi@uclouvain.be [ICTEAM Institute, Université catholique du Louvain, place de Levant 3, 1348 Louvain-la-Neuve (Belgium); Vandormael, Denis [SIRRIS Liege Science Park, 4102 Seraing (Belgium); Houssiau, Laurent [Research Centre in Physics of Matter and Radiation (PMR), University of Namur, Rue de Bruxelles 61, B-5000 Namur (Belgium); Francis, Laurent A. [ICTEAM Institute, Université catholique du Louvain, place de Levant 3, 1348 Louvain-la-Neuve (Belgium)

    2016-02-15

    Highlights: • TiO{sub 2}/COC (cyclic olefin copolymer) hybrid material for BioMEMS applications. • Thin layer of TiO{sub 2} was deposed on cyclic olefin copolymer using physical vapor deposition (PVD) technique. • The coating possess the highest level of adhesion with an excellent morphology of the hybrid material (TiO{sub 2}/COC). - Abstract: Cyclic olefin copolymer (COC) is a new class of thermoplastic polymers used for a variety of applications ranging from bio-sensing to optics. However, the hydrophobicity of native COC hampers the further development and application of this material [1]. In this work, we report the structural, morphological, and optical properties of the TiO{sub 2}/COC hybrid material, which provides a desirable substrate for optical devices and subsequent surface modifications. The TiO{sub 2} film on COC substrate was deposited by the evaporation method, and it was characterized by X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), profilometry and atomic force microscope (AFM). Using an UV-vis spectrophotometer, we found that the transmittance of the TiO{sub 2}/COC hybrid material in the visible domain reached 80%. The TiO{sub 2}/COC hybrid appeared to be stable in most of the assessed polar solvents and acid/basic solutions. The new TiO{sub 2}/COC hybrid material and the robust fabrication method are expected to enable a variety of BioMEMS applications.

  10. Substantially isotactic, linear, alternating copolymers of carbon monoxide and an olefin

    Science.gov (United States)

    Sen, Ayusman; Jiang, Zhaozhong

    1996-01-01

    The compound, [Pd(Me-DUPHOS)(MeCN).sub.2 ](BF.sub.4).sub.2, [Me-DUPHOS: 1,2-bis(2,5-dimethylphospholano)benzene] is an effective catalyst for the highly enantioselective, alternating copolymerization of olefins, such as aliphatic .alpha.-olefins, with carbon monoxide to form optically active, isotactic polymers which can serve as excellent starting materials for the synthesis of other classes of chiral polymers. For example, the complete reduction of a propylene-carbon monoxide copolymer resulted in the formation of a novel, optically active poly(1,4-alcohol). Also, the previously described catalyst is a catalyst for the novel alternating isomerization cooligomerization of 2-butene with carbon monoxide to form optically active, isotactic poly(1,5-ketone)

  11. Comparison of Topas cyclic olefin copolymers to BK7 glass in night vision goggle objectives

    Science.gov (United States)

    Stevens, James S.

    2004-09-01

    The objective of this study was to determine the suitability of Topas cyclic olefin copolymers (COC) as an optical plastic for use in military-grade night vision goggle (NVG) lens objectives. Test objective lenses that could include either a Topas COC window element or BK7 glass window element were manufactured. The test objectives were evaluated for low light resolution, MTF, off-axis veiling glare, and on-axis stray light. Additionally, the spectral transmittance of the individual windows elements was measured. This paper compares the evaluation results of test objectives containing Topas COC with test objectives containing BK7 glass.

  12. Surface functionalization of cyclic olefin copolymer with aryldiazonium salts: A covalent grafting method

    Energy Technology Data Exchange (ETDEWEB)

    Brisset, Florian, E-mail: florian.brisset@etu.univ-rouen.fr [UMR CNRS 6014 COBRA, FR 3038, Université de Rouen, 55 rue Saint Germain, 27000 Evreux (France); Vieillard, Julien, E-mail: julien.vieillard@univ-rouen.fr [UMR CNRS 6014 COBRA, FR 3038, Université de Rouen, 55 rue Saint Germain, 27000 Evreux (France); Berton, Benjamin, E-mail: benjamin.berton@univ-rouen.fr [EA 3233 SMS, Université de Rouen, 1 rue du 7ème Chasseurs, BP281, 27002 Evreux Cedex (France); Morin-Grognet, Sandrine, E-mail: sandrine.morin@univ-rouen.fr [EA 3829 MERCI, Université de Rouen, 1 rue du 7ème Chasseurs, BP281, 27002 Evreux Cedex (France); Duclairoir-Poc, Cécile, E-mail: cecile.duclairoir@univ-rouen.fr [EA 4312 LMSM, Université de Rouen, 55 rue Saint Germain, 27000 Evreux (France); Le Derf, Franck, E-mail: franck.lederf@univ-rouen.fr [UMR CNRS 6014 COBRA, FR 3038, Université de Rouen, 55 rue Saint Germain, 27000 Evreux (France)

    2015-02-28

    Graphical abstract: - Highlights: • An effective method to modify cyclic olefin copolymer surface. • The surface of COC was modified by covalent grafting of aryl diazonium salts. • The wettability of COC surface was modulated by diazonium salts. • Photoinitiation and chemical reduction have to be combined to graft diazonium salt on COC surface. - Abstract: Covalent immobilization of biomolecules on the surface of cyclic olefin copolymer (COC) is still a tough challenge. We developed a robust method for COC surface grafting through reaction with aryldiazonium. Chemical diazonium reduction generated an aryl radical and the formation of a grafted film layer on the organic surface. We also demonstrated that the chemical reduction of diazonium salt was not sufficient to form a film on the COC surface. UV illumination had to be combined with chemical reduction to graft an aryl layer onto the COC surface. We optimized organic film deposition by using different chemical reducers, different reaction times and reagent proportions. We characterized surface modifications by fluorescence microscopy and contact angle measurements, infrared spectroscopy, X-ray photoemission spectroscopy and Raman spectroscopy, and assessed the topography of the aryl film by atomic force microscopy. This original strategy allowed us to evidence various organic functions to graft biomolecules onto COC surfaces with a fast and efficient technique.

  13. Surface functionalization of cyclic olefin copolymer (COC) with evaporated TiO2 thin film

    Science.gov (United States)

    El Fissi, Lamia; Vandormael, Denis; Houssiau, Laurent; Francis, Laurent A.

    2016-02-01

    Cyclic olefin copolymer (COC) is a new class of thermoplastic polymers used for a variety of applications ranging from bio-sensing to optics. However, the hydrophobicity of native COC hampers the further development and application of this material [1]. In this work, we report the structural, morphological, and optical properties of the TiO2/COC hybrid material, which provides a desirable substrate for optical devices and subsequent surface modifications. The TiO2 film on COC substrate was deposited by the evaporation method, and it was characterized by X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), profilometry and atomic force microscope (AFM). Using an UV-vis spectrophotometer, we found that the transmittance of the TiO2/COC hybrid material in the visible domain reached 80%. The TiO2/COC hybrid appeared to be stable in most of the assessed polar solvents and acid/basic solutions. The new TiO2/COC hybrid material and the robust fabrication method are expected to enable a variety of BioMEMS applications.

  14. High Trans Kinetic Selectivity in Ruthenium-Based Olefin Cross-Metathesis through Stereoretention.

    Science.gov (United States)

    Johns, Adam M; Ahmed, Tonia S; Jackson, Bradford W; Grubbs, Robert H; Pederson, Richard L

    2016-02-19

    The first kinetically controlled, highly trans-selective (>98%) olefin cross-metathesis reaction is demonstrated using Ru-based catalysts. Reactions with either trans or cis olefins afford products with highly trans or cis stereochemistry, respectively. This E-selective olefin cross-metathesis is shown to occur between two trans olefins and between a trans olefin and a terminal olefin. Additionally, new stereoretentive catalysts have been synthesized for improved reactivity.

  15. Characterization of bonding between poly(dimethylsiloxane) and cyclic olefin copolymer using corona discharge induced grafting polymerization.

    Science.gov (United States)

    Liu, Ke; Gu, Pan; Hamaker, Kiri; Fan, Z Hugh

    2012-01-01

    Thermoplastics have been increasingly used for fabricating microfluidic devices because of their low cost, mechanical/biocompatible attributes, and well-established manufacturing processes. However, there is sometimes a need to integrate such a device with components made from other materials such as polydimethylsiloxane (PDMS). Bonding thermoplastics with PDMS to produce hybrid devices is not straightforward. We have reported our method to modify the surface property of a cyclic olefin copolymer (COC) substrate by using corona discharge and grafting polymerization of 3-(trimethoxysilyl)propyl methacrylate; the modified surface enabled strong bonding of COC with PDMS. In this paper, we report our studies on the surface modification mechanism using attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM) and contact angle measurement. Using this bonding method, we fabricated a three-layer (COC/PDMS/COC) hybrid device consisting of elastomer-based valve arrays. The microvalve operation was confirmed through the displacement of a dye solution in a fluidic channel when the elastomer membrane was pneumatically actuated. Valve-enabled microfluidic handling was demonstrated.

  16. Structure-property relationships in multilayered polymeric system and olefinic block copolymers

    Science.gov (United States)

    Khariwala, Devang

    Chapter 1. The effect of tie-layer thickness on delamination behavior of polypropylene/tie-layer/Nylon-6 multilayers is examined in this study. Various maleated polypropylene resins were compared for their effectiveness as tie-layers. Delamination failure occurred cohesively in all the multilayer systems. Two adhesion regimes were defined based on the change in slope of the linear relationship between the delamination toughness and the tie-layer thickness. The measured delamination toughness of the various tie-layers was quantitatively correlated to the damage zone length formed at the crack tip. In addition, the effect of tie-layer thickness on the multilayer tensile properties was correlated with the delamination behavior. The fracture strain of the multilayers decreased with decreasing tie-layer thickness. Examination of the prefracture damage mechanism of stretched multilayers revealed good correlation with the delamination toughness of the tie-layers. In thick tie-layers (>2microm) the delamination toughness of the tie-layers was large enough to prevent delamination of multilayers when they were stretched. In the thin tie-layers (organized lamellar crystals with the orthorhombic unit cell and high melting temperature. The lamellae are organized into space-filling spherulites in all compositions even in copolymers with only 18 wt% hard block. The morphology is consistent with crystallization from a miscible melt. Crystallization of the hard blocks forces segregation of the noncrystallizable soft blocks into the interlamellar regions. Good separation of hard and soft blocks in the solid state is confirmed by distinct and separate beta- and alpha-relaxations in all the block copolymers. Compared to statistical ethylene-octene copolymers, the blocky architecture imparts a substantially higher crystallization temperature, a higher melting temperature and a better organized crystalline morphology, while maintaining a lower glass transition temperature. The

  17. The activation mechanism of Fe-based olefin metathesis catalysts

    Science.gov (United States)

    Poater, Albert; Pump, Eva; Vummaleti, Sai Vikrama Chaitanya; Cavallo, Luigi

    2014-08-01

    Density functional theory calculations have been used to describe the first turnover for olefin metathesis reaction of a homogenous Fe-based catalyst bearing a N-heterocyclic carbene ligand with methoxyethene as a substrate. Equal to conventional Ru-based catalysts, the activation of its Fe congener occurs through a dissociative mechanism, however with a more exothermic reaction energy profile. Predicted upper energy barriers were calculated to be on average ∼2 kcal/mol more beneficial for Fe catalyzed metathesis. Overall, this present computational study emphasises on advantages of Fe-based metathesis and gives a potential recipe for the design of an efficient Fe-based olefin metathesis catalysts.

  18. Atmospheric Solid Analysis Probe-Ion Mobility Mass Spectrometry: An Original Approach to Characterize Grafting on Cyclic Olefin Copolymer Surfaces.

    Science.gov (United States)

    Vieillard, Julien; Hubert-Roux, Marie; Brisset, Florian; Soulignac, Cecile; Fioresi, Flavia; Mofaddel, Nadine; Morin-Grognet, Sandrine; Afonso, Carlos; Le Derf, Franck

    2015-12-01

    A cyclic olefin copolymer (COC) was grafted with aryl layers from aryldiazonium salts, and then we combined infrared spectrometry, atomic force microscopy (AFM), and ion mobility mass spectrometry with atmospheric solid analysis probe ionization (ASAP-IM-MS) to characterize the aryl layers. ASAP is a recent atmospheric ionization method dedicated to the direct analysis of solid samples. We demonstrated that ASAP-IM-MS is complementary to other techniques for characterizing bromine and sulfur derivatives of COC on surfaces. ASAP-IM-MS was useful for optimizing experimental grafting conditions and to elucidate hypotheses around aryl layer formation during the grafting process. Thus, ASAP-IM-MS is a good candidate tool to characterize covalent grafting on COC surfaces.

  19. Synthesis of Ethylene or Propylene/1,3-Butadiene Copolymers Possessing Pendant Vinyl Groups with Virtually No Internal Olefins

    Directory of Open Access Journals (Sweden)

    Kenji Michiue

    2015-11-01

    Full Text Available In general, ethylene/1,3-butadiene copolymerizations provides copolymers possessing both pendant vinyls and vinylenes as olefinic moieties. We, at MCI, studied the substituent effects of C2-symmetric zirconocene complexes, rac-[Me2Si(Indenyl’2]ZrCl2 (Indenyl’ = generic substituted indenyl, after activation on the ratio of the pendant vinyls and vinylenes of the resultant copolymers. Complexes examined in this study were rac-dimethylsilylbis (1-indenylzirconium dichloride (1, rac-dimethylsilyl-bis[1-(2-methyl-4,5-benzoindenyl] zirconium dichloride (2, rac-dimethylsilyl-bis[l-(2-methyl -4-phenylindenyl]zirconium dichloride (3, rac-dimethy1si1y1- bis(2-ethyl-4-phenylindenyl zirconium dichloride (4, rac-dimethylsilyl-bis[l-(2-n-propyl -4-(1-naphthylindenyl]zirconium dichloride (5, rac-dimethylsilyl-[1-(2-ethyl-4-(5-(2,2-dimethyl-2,3-dihydro-1H-cyclopenta [a]naphthalenylindenyl][1-(2-n-propyl-4-(5-(2,2-dimethyl-2,3-dihydro-1H-cyclopenta[a] naphthalenylindenyl]zirconium dichloride (6, rac-dimethylsilyl-bis[1-(2-ethyl-4-(9-phenanthrylindenyl]zirconium dichloride (7, and rac-dimethylsilyl-bis[l-(2-n-propyl-4-(9-phenanthrylindenyl]zirconium dichloride (8. We found that the ratio of the pendant vinyls and vinylenes is strongly affected by the bulkiness of the substituent on the complexes examined. The vinyl content increased linearly in the following order, 8 > 7 > 6 > 5 > 4 > 3 > 2 > 1. Notably, complex 8/DMAO formed ethylene/1,3-butadiene copolymers possessing predominant vinyl groups, which can be crucial precursors for functionalized polyolefins. Likewise, complex 8/DMAO afforded propylene/1,3-butadiene copolymers with predominant vinyl groups.

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

    NARCIS (Netherlands)

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

    2000-01-01

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

  1. IMPACT PROPERTIES OF METALLOCENE-CATALYZED ETHYLENE-α-OLEFIN COPOLYMERS

    Institute of Scientific and Technical Information of China (English)

    Xu-rong Xu; Jun-ting Xua; Lin-xian Feng

    2002-01-01

    The impact properties of two selected metallocene-catalyzed ethylene-butene copolymers and one conventional copolymer were evaluated using Izod impact test. It is found that the metallocene-catalyzed copolymer shows superior impact properties. This result was explained on the basis of the more homogeneous inter-molecular composition distribution and narrower molecular weight distribution, which leads to more homogeneous morphology with fewer defects. Stepwise crystallization improves the impact properties, especially in the crack propagation process, to a large extent. This is due to the decrease of entanglements by stepwise crystallization, which is advantageous for the chain slip and shear. The polymer with heterogeneous intra-molecular composition distribution exhibits a more evident improvement of impact properties under stepwise crystallization.

  2. The activation mechanism of Fe-based olefin metathesis catalysts

    KAUST Repository

    Poater, Albert

    2014-08-01

    Density functional theory calculations have been used to describe the first turnover for olefin metathesis reaction of a homogenous Fe-based catalyst bearing a N-heterocyclic carbene ligand with methoxyethene as a substrate. Equal to conventional Ru-based catalysts, the activation of its Fe congener occurs through a dissociative mechanism, however with a more exothermic reaction energy profile. Predicted upper energy barriers were calculated to be on average ∼2 kcal/mol more beneficial for Fe catalyzed metathesis. Overall, this present computational study emphasises on advantages of Fe-based metathesis and gives a potential recipe for the design of an efficient Fe-based olefin metathesis catalysts. © 2014 Elsevier B.V.

  3. Mechanical behaviour of cyclic olefin copolymer/exfoliated graphite nanoplatelets nanocomposites foamed through supercritical carbon dioxide

    Directory of Open Access Journals (Sweden)

    A. Biani

    2016-12-01

    Full Text Available A cycloolefin copolymer matrix was melt mixed with exfoliated graphite nanoplatelets (xGnP and the resulting nanocomposites were foamed by supercritical carbon dioxide. The density of the obtained foams decreased with the foaming pressure. Moreover, xGnP limited the cell growth during the expansion process thus reducing the cell diameter (from 1.08 to 0.22 mm with an XGnP amount of 10 wt% at 150 bar and increasing the cell density (from 12 to 45 cells/mm2 with a nanofiller content of 10 wt% at 150 bar. Electron microscopy observations of foams evidenced exfoliation and orientation of the nanoplatelets along the cell walls. Quasi-static compressive tests and tensile creep tests on foams clearly indicated that xGnP improved the modulus (up to a factor of 10 for a xGnP content of 10 wt% and the creep stability.

  4. A cyclic-olefin-copolymer microfluidic immobilized-enzyme reactor for rapid digestion of proteins from dried blood spots.

    Science.gov (United States)

    Wouters, Bert; Dapic, Irena; Valkenburg, Thalassa S E; Wouters, Sam; Niezen, Leon; Eeltink, Sebastiaan; Corthals, Garry L; Schoenmakers, Peter J

    2017-03-31

    A critical step in the bottom-up characterization of proteomes is the conversion of proteins to peptides, by means of endoprotease digestion. Nowadays this method typically uses overnight digestion and as such represents a considerable bottleneck for high-throughput analysis. This report describes protein digestion using an immobilized-enzyme reactor (IMER), which enables accelerated digestion times that are completed within seconds to minutes. For rapid digestion to occur, a cyclic-olefin-copolymer microfluidic reactor was constructed containing trypsin immobilized on a polymer monolithic material through a 2-vinyl-4,4-dimethylazlactone linker. The IMER was applied for the rapid offline digestion of both singular protein standards and a complex protein mixture prior to liquid chromatography-electrospray ionisation-tandem mass spectrometry (LC-ESI-MS/MS) analysis. The effects of protein concentration and residence time in the IMER were assessed for protein standards of varying molecular weight between 11 and 240kDa. Compared to traditional in-solution digestion, IMER-facilitated protein digestion at room temperature for 5min yielded similar results in terms of sequence coverage and number of identified peptides. Good repeatability was demonstrated with a relative standard deviation of 6% for protein-sequence coverage. The potential of the IMER was also demonstrated for a complex protein mixture in the analysis of dried blood spots. Compared to a traditional workflow a similar number of proteins could be identified, while reducing the total analysis time from 22.5h to 4h and importantly omitting the sample-pre-treatment steps (denaturation, reduction, and alkylation). The identified proteins from two workflows showed similar distributions in terms of molecular weight and hydrophobic character.

  5. Rapid bonding enhancement by auxiliary ultrasonic actuation for the fabrication of cyclic olefin copolymer (COC) microfluidic devices

    Science.gov (United States)

    Yu, H.; Tor, S. B.; Loh, N. H.

    2014-11-01

    Thermal compression bonding is a straightforward, inexpensive and widely used method for enclosing open microchannels in thermoplastic microfluidic devices. It is advantageous over adhesive, solvent and grafting bonding methods in retaining material homogeneity. However, the trade-off between high bond strength and low microchannel deformation is always a crucial consideration in thermal compression bonding. In this study, an effective method for improving bond strength while retaining the microchannel integrity with negligible distortion is proposed and analyzed. Longitudinal ultrasonic actuation was applied to the preheated cyclic olefin copolymer (COC) substrates to achieve accelerated and enhanced bonding with an ultrasonic welding system. Intimate contact between the bonding surfaces before the ultrasonic actuation was found to be an important prior condition. With improper contact, several bonding defects would occur, such as voids, localized spot melting and edge melting. Under auxiliary ultrasonic vibration, within 10 s, the bond strength developed at the bonding interface could be dramatically improved compared with those achieved without ultrasonic actuation. The enhanced bond strength obtained at a preheating temperature of 20 °C lower than its Tg could be comparable to the strength for pure thermal compression at 5 °C higher than its Tg. It is believed that the ultrasonic energy introduced could elevate the interfacial temperature and facilitate the interdiffusion of molecular chain segments at the interface, consequently resulting in rapidly enhanced bonding. Also, the microchannel distortion after ultrasonic actuation was found to be satisfactory—another important requirement. From dynamic mechanical analysis, the glass transition temperature of COC was found to increase with increasing frequency, and the temperature of the bulk polymer under ultrasonic actuation was still well under Tg; therefore the deformation is minor under ultrasonic

  6. Utilization of α-olefins obtained by pyrolysis of waste high density polyethylene to synthesize α-olefin-succinic-anhydride based cold flow improvers

    Institute of Scientific and Technical Information of China (English)

    Norbert MISKOLCZI; Richard SAGI; László BARTHA; Lívia FORCEK

    2009-01-01

    A new route of utilization of α-olefin rich hydrocarbon fractions obtained by waste polymer pyrolysis was investigated. α-olefin-succinic-anhydride intermediate-based pour point depressant additives for diesel fuel were synthesized, in which reactions needed α-olefins were obtained by pyrolysis of waste high-density polyethylene (HDPE). Fraction of α-olefins was produced by the de-polymerization of plastic waste in a tube reactor at 500℃ in the absence of catalysts and air. C17~22 range of mixtures of olefins and paraffins were separated for synthesis and then, these hydrocarbons were reacted with maleic-anhydride (MA) for formation of α-olefin-succinic-anhydride intermediates. The olefin-rich hydrocarbon fraction contained approximately 60% of olefins, including 90%~95% α-olefins. Other intermediates were produced in the same way by using commercial C20 α-olefin instead of C17~22 olefin mixture. The two different experimental intermediates with number average molecular weights of 1850g/mol and 1760g/mol were reacted with different alcohols: 1-butanol, 1-hexanol, 1-octanol, i-butanol, and c-hexanol to produce their ester derivatives. The synthesized ten experimental pour point depressants were added in different concentrations to conventional diesel fuel, which had no other additive content before. The structure and efficiency of experimental additives were followed by different standardized and non-standardized methods. Results showed that the experimental additives on the basis of the product of waste pyrolysis were able to decrease not only the pour but also the cloud point and cold filter plugging point (CFPP) of diesel fuel, whose effects could be observed even if the concentration of additives was low. Furthermore, all additives had anti-wear and anti-friction effects in diesel fuel.

  7. The Influence of Comonomer on Ethylene/α-Olefin Copolymers Prepared Using [Bis(N-(3-tert butylsalicylideneanilinato] Titanium (IV Dichloride Complex

    Directory of Open Access Journals (Sweden)

    Patcharaporn Kaivalchatchawal

    2011-02-01

    Full Text Available We describe the synthesis of [bis(N-(3-tert-butylsalicylideneanilinato] titanium (IV dichloride (Ti-FI complex and examine the effects of comonomer (feed concentration and type on its catalytic performance and properties of the resulting polymers. Ethylene/1-hexene and ethylene/1-octene copolymers were prepared through copolymerization using Ti-FI catalyst, activated by MAO cocatalyst at 323 K and 50 psi ethylene pressure at various initial comonomer concentrations. The obtained copolymers were characterized by DSC, GPC and 13C-NMR. The results indicate that Ti-FI complex performs as a high potential catalyst, as evidenced by high activity and high molecular weight and uniform molecular weight distribution of its products. Nevertheless, the bulky structure of FI catalyst seems to hinder the insertion of α-olefin comonomer, contributing to the pretty low comonomer incorporation into the polymer chain. The catalytic activity was enhanced with the comonomer feed concentration, but the molecular weight and melting temperature decreased. By comparison both sets of catalytic systems, namely ethylene/1-hexene and ethylene/1-octene copolymerization, the first one afforded better activity by reason of easier insertion of short chain comonomer. Although 1-hexene copolymers also exhibited higher molecular weight than 1-octene, no significant difference in both melting temperature and crystallinity can be noticed between these comonomers.

  8. Glycine/Glycolic acid based copolymers

    NARCIS (Netherlands)

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

    1994-01-01

    Glycine/glycolic acid based biodegradable copolymers have been prepared by ring-opening homopolymerization of morpholine-2,5-dione, and ring-opening copolymerization of morpholine-2,5-dione and glycolide. The homopolymerization of morpholine-2,5-dione was carried out in the melt at 200°C for 3 min u

  9. NONBRIDGED HALF-TITANOCENES CONTAINING ANIONIC ANCILLARY DONOR LIGANDS: PROMISING NEW CATALYSTS FOR PRECISE SYNTHESIS OF CYCLIC OLEFIN COPOLYMERS(COCs)

    Institute of Scientific and Technical Information of China (English)

    Kotohiro Nomura

    2008-01-01

    Precise,efficient copolymerizations of ethylene with cyclic olefins[norbomene(NBE),cyclopentene (CPE) using nonbridged half-titanocenes of type,Cp'TiCI2(L)(Cp'=cyclopentadienyl group,L=aryloxo,ketimide)-MAO catalyst systems have been summarized.CpTiCI2(N=C'Bu2) exhibited both remarkable camlytic activity and efficient NBE incorporation for ethylene/NBE copolymerization:the NBE incorporation by Cp'TiCI2(X)(X=N=C'Bu2,O-2,6-'Pr2C6H3;Cp'=Cp,C5Me5,indenyl) was related to the calculated coordination energy after ethylene insertion.('BuC5H4)TiCI2(N=C'Bu) exhibited significant catalytic activities with efficient CPE incorporations in ethylene/CPE copolymerization in the presence of MAO.The polymerization proceeded with exclusive 1,2-CPE incorporation.affording high molecular weight (altemating)copolymers with uniform distributions.Therefore,the cyclopentadienyl fragment(Cp')plays an essential role in terms of both the activity and the efficient cyclic olefin incorporation.

  10. Living olefin polymerization processes

    Science.gov (United States)

    Schrock, Richard R.; Baumann, Robert

    1999-01-01

    Processes for the living polymerization of olefin monomers with terminal carbon-carbon double bonds are disclosed. The processes employ initiators that include a metal atom and a ligand having two group 15 atoms and a group 16 atom or three group 15 atoms. The ligand is bonded to the metal atom through two anionic or covalent bonds and a dative bond. The initiators are particularly stable under reaction conditions in the absence of olefin monomer. The processes provide polymers having low polydispersities, especially block copolymers having low polydispersities. It is an additional advantage of these processes that, during block copolymer synthesis, a relatively small amount of homopolymer is formed.

  11. Cardanol-Based Materials as Natural Precursors for Olefin Metathesis

    Directory of Open Access Journals (Sweden)

    Giuseppe Vasapollo

    2011-08-01

    Full Text Available Cardanol is a renewable, low cost natural material, widely available as a by-product of the cashew industry. It is a mixture of 3-n-pentadecylphenol, 3-(pentadeca-8-enylphenol, 3-(pentadeca-8,11-dienylphenol and 3-(pentadeca-8,11,14-trienylphenol. Olefin metathesis (OM reaction on cardanol is an important class of reactions that allows for the synthesis of new olefins that are sometime impossible to prepare via other methods. The application of this natural and renewable material to both academic and industrial research will be discussed.

  12. Reactivation of a Ruthenium-Based Olefin Metathesis Catalyst

    Science.gov (United States)

    Tabari, Daniel S.; Tolentino, Daniel R.; Schrodi, Yann

    2013-01-01

    1st Generation Hoveyda-Grubbs olefin metathesis catalyst was purposely decomposed in the presence of ethylene yielding inorganic species that are inactive in the ring-closing metathesis (RCM) of benchmark substrate diethyldiallyl malonate (DEDAM). The decomposed catalyst was treated with 1-(3,5-diisopropoxyphenyl)-1-phenylprop-2-yn-1-ol (3) to generate an olefin metathesis active ruthenium indenylidene-ether complex in 43 % yield. This complex was also prepared independently by reacting RuCl2(p-cymene)(PCy3) with organic precursor 3. The activity of the isolated reactivated catalyst in the RCM of DEDAM is similar to that of the independently prepared complex. PMID:23355756

  13. Reactivation of a Ruthenium-Based Olefin Metathesis Catalyst.

    Science.gov (United States)

    Tabari, Daniel S; Tolentino, Daniel R; Schrodi, Yann

    2013-01-14

    1(st) Generation Hoveyda-Grubbs olefin metathesis catalyst was purposely decomposed in the presence of ethylene yielding inorganic species that are inactive in the ring-closing metathesis (RCM) of benchmark substrate diethyldiallyl malonate (DEDAM). The decomposed catalyst was treated with 1-(3,5-diisopropoxyphenyl)-1-phenylprop-2-yn-1-ol (3) to generate an olefin metathesis active ruthenium indenylidene-ether complex in 43 % yield. This complex was also prepared independently by reacting RuCl(2)(p-cymene)(PCy(3)) with organic precursor 3. The activity of the isolated reactivated catalyst in the RCM of DEDAM is similar to that of the independently prepared complex.

  14. 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

  15. Ruthenium-based four-coordinate olefin metathesis catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Sanford, M.S.; Henling, L.M.; Day, M.W.; Grubbs, R.H. [California Inst. of Tech., Pasadena (United States). Div. of Chemistry and Chemical Engineering

    2000-10-02

    A series of four-coordinate Ru{sup II} alkylidenes has been prepared as analogues of the proposed olefin metathesis intermediate [(PCy{sub 3})Cl{sub 2}Ru=CHPh]. These complexes exhibit unusual trigonal-pyramidal solid-state geometries, and are rendered highly active for ring-closing metathesis by the addition of HCl. (orig.)

  16. Micro pore arrays in free standing cyclic olefin copolymer membranes: fabrication and surface functionalization strategies for in-vitro barrier tissue models

    Science.gov (United States)

    Gel, M.; Kandasamy, S.; Cartledge, K.; Be, C. L.; Haylock, D.

    2013-12-01

    In recent years there has been growing interest in micro engineered in-vitro models of tissues and organs. These models are designed to mimic the in-vivo like physiological conditions with a goal to study human physiology in an organ-specific context or to develop in-vitro disease models. One of the challenges in the development of these models is the formation of barrier tissues in which the permeability is controlled locally by the tissues cultured at the interface. In-vitro models of barrier tissues are typically created by generating a monolayer of cells grown on thin porous membranes. This paper reports a robust preparation method for free standing porous cyclic olefin copolymer (COC) membranes. We also demonstrate that gelatin coated membranes facilitate formation of highly confluent monolayer of HUVECs. Membranes with thickness in the range of 2-3 um incorporating micro pores with diameter approximately 20 um were fabricated and integrated with microfluidic channels. The performance of the device was demonstrated with a model system mimicking the endothelial barrier in bone marrow sinusoids.

  17. Sunflower-based Feedstocks in Nonfood Applications: Perspectives from Olefin Metathesis

    Science.gov (United States)

    Marvey, Bassie B.

    2008-01-01

    Sunflower (Helianthus annuus L.) oil remains under-utilised albeit one of the major seed oils produced world-wide. Moreover, the high oleic sunflower varieties make the oil attractive for applications requiring high temperature processes and those targeting the C=C double bond functionality. Herein an overview of the recent developments in olefin metathesis of sunflower-based feedstocks is presented. The improved performance of olefin metathesis catalysts leading to high turnover numbers, high selectivity and catalyst recyclability, opens new opportunities for tailoring sunflower-based feedstocks into products required for possible new niche market applications. Promising results in biofuel, biopolymers, fragrances and fine chemicals applications have been reported. PMID:19325810

  18. Influência da estrutura de diferentes copolímeros de etileno e a-olefinas na funcionalização com anidrido maleico Influence of structure of ethylene a-olefins copolymers in functionalization with maleic anhydride

    Directory of Open Access Journals (Sweden)

    Carlota H. F. Maurano

    1998-01-01

    Full Text Available A funcionalização de copolímeros de etileno e a-olefinas com anidrido maleico (AM foi realizada em solução de xileno com peróxido de dibenzoíla (DBP como iniciador. Foi estudado o efeito das diferentes estruturas dos copolímeros, como número e comprimento de ramificação, na incorporação do AM. A funcionalização também foi realizada em estado fundido utilizando-se um misturador Rheomix 600 e uma extrusora Rheocord 9000 da Haake. A funcionalidade foi determinada por titulometria de neutralização e os produtos foram caracterizados por espectroscopia na região do infravermelho (FT-IR e por cromatografia de permeação em gel (GPC. A funcionalidade dos copolímeros de etileno com 1-hexeno aumentou com o aumento do teor de comonômero e dos copolímeros com 1-octeno e 1-deceno aumentou com o aumento do teor de a-olefina até um máximo, decrescendo e mantendo-se constante.Chemical modification of ethylene a-olefins copolymers with maleic anhydride was studied by radical reaction in solution, melt mixing and extrusion. The effect of copolymer structure, as the amount and length of the branches, was evaluated on the MA incorporation. The reactions were also achieved in Rheomix 600 (Haake mixer and Rheocord 9000 (Haake extruder. Functionalization was determinated by titration and modified ethylene a-olefins copolymers were characterized by Infrared Spectroscopy and Gel Permeation Chromatography. The maleic anhydride incorporation in the ethylene-hexene copolymers increases with the amount of a-olefin. Functionalization of ethylene-octene and ethylene-decene comonomers increases with increasing peroxide concentration until a maximum and then decreases up to a constant value.

  19. Olefin Metathesis Mediated By: - Schiff Base Ru-Alkylidenes -Ru-Alkylidenes Bearing Unsymmetrical NH Ligands

    Science.gov (United States)

    Monsaert, Stijn; Voort, Pascal Van Der; Ledoux, Nele; Allaert, Bart; Drozdzak, Renata; Verpoort, Francis

    The classic Grubbs second-generation complex 2 was modified through 1. The introduction of a bidentate Schiff base ligand 2. Changes in the amino side groups of the NHC ligand Representative olefin metathesis test reactions show the effects induced by the ligand modifications and demonstrate some interesting new properties of the described catalysts. catalysts.

  20. Synthesis of CO2 Copolymer Based Polyurethane Foams

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    CO2-copolymer based polyurethane foams were synthesized and characterized in this paper. The foams were found to have higher strength and lower heat of combustion than the conventional polyether polyurethane foams. They may find wide applications in many fields.

  1. Design and synthesis of ruthenium indenylidene-based catalysts for olefin metathesis

    OpenAIRE

    Urbina-Blanco, César A

    2013-01-01

    As part of a European wide effort to develop metathesis catalysts for use in fine chemical and pharmaceutical compound synthesis, this study focuses on the design and synthesis of ruthenium based catalysts for olefin metathesis. The aim, of this work was simple: to develop new, more active, more stable, easy to synthesise and commercially viable Ruthenium based catalysts, as well trying to rationalize the effect of structural changes on reactivity. Two different approaches w...

  2. Sunflower-based Feedstocks in Nonfood Applications: Perspectives from Olefin Metathesis

    Directory of Open Access Journals (Sweden)

    Bassie B. Marvey

    2008-08-01

    Full Text Available Sunflower (Helianthus annuus L. oil remains under-utilised albeit one of the major seed oils produced world-wide. Moreover, the high oleic sunflower varieties make the oil attractive for applications requiring high temperature processes and those targeting the C=C double bond functionality. Herein an overview of the recent developments in olefin metathesis of sunflower-based feedstocks is presented. The improved performance of olefin metathesis catalysts leading to high turnover numbers, high selectivity and catalyst recyclability, opens new opportunities for tailoring sunflower-based feedstocks into products required for possible new niche market applications. Promising results in biofuel, biopolymers, fragrances and fine chemicals applications have been reported.

  3. Synthesis and properties of new bolaform and macrocyclic galactose-based surfactants obtained by olefin metathesis.

    Science.gov (United States)

    Satgé, Céline; Granet, Robert; Verneuil, Bernard; Champavier, Yves; Krausz, Pierre

    2004-05-17

    A series of galactose-based surfactants with various structures likely to display new interesting properties were synthesized. Four monocatenary surfactants were elaborated by microwave-assisted galactosylation of undecanol or 10-undecenol. These compounds were slightly soluble in water. Their tensioactive properties were determined at 45 degrees C. Olefin metathesis was used to synthesize the two single-chain bolaforms from undec-10-enyl galactopyranosides; two pseudomacrocyclic bolaforms were prepared by grafting two carbamates at O-4 and O-4' sugar positions of the single-chain bolaforms. These four surfactants are insoluble in water and undergo monolayer compression. Cyclization of these bolaforms by olefin metathesis led to macrocyclic surfactant analogues of archaeobacterial membrane components.

  4. Highly diastereoselective and enantioselective olefin cyclopropanation using engineered myoglobin-based catalysts.

    Science.gov (United States)

    Bordeaux, Melanie; Tyagi, Vikas; Fasan, Rudi

    2015-02-01

    Using rational design, an engineered myoglobin-based catalyst capable of catalyzing the cyclopropanation of aryl-substituted olefins with catalytic proficiency (up to 46,800 turnovers) and excellent diastereo- and enantioselectivity (98-99.9%) was developed. This transformation could be carried out in the presence of up to 20 g L(-1) olefin substrate with no loss in diastereo- and/or enantioselectivity. Mutagenesis and mechanistic studies support a cyclopropanation mechanism mediated by an electrophilic, heme-bound carbene species and a model is provided to rationalize the stereopreference of the protein catalyst. This work shows that myoglobin constitutes a promising and robust scaffold for the development of biocatalysts with carbene-transfer reactivity.

  5. 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

  6. Immobilization of Antibody on a Cyclic Olefin Copolymer Surface with Functionalizable, Non-Biofouling Poly[Oligo(Ethylene Glycol) Methacrylate].

    Science.gov (United States)

    Jeong, Seung Pyo; Kang, Sung Min; Hong, Daewha; Lee, Hee-Yoon; Choi, Insung S; Ko, Sangwon; Lee, Jungkyu K

    2015-02-01

    We report a perfluoroaryl azide-based photoreaction for synthesizing functionalizable and nonbiofouling poly[oligo(ethylene glycol) methacrylate] (pOEGMA) films on a chemically inert COC substrate, and an estimation of a surface coverage of the antibody immobilized onto the surface with the immuno-gold nanoparticles. The processes were confirmed by water contact angle measurement, FT-IR spectroscopy, and FE-SEM. The strategy demonstrated in this work could be applied to functionalizations of other polymeric materials and determination of the binding capacity of analytes in biosensors and microfluidic devices.

  7. Synthesis of Electronically Modified Ru-Based Neutral 16 VE Allenylidene Olefin Metathesis Precatalysts

    Directory of Open Access Journals (Sweden)

    Siegfried Blechert

    2012-05-01

    Full Text Available Electronic modifications within Ru-based olefin metathesis precatalysts have provided a number of new complexes with significant differences in reactivity profiles. So far, this aspect has not been studied for neutral 16 VE allenylidenes. The first synthesis of electronically altered complexes of this type is reported. Following the classical dehydration approach (vide infra modified propargyl alcohols were transformed to the targeted allenylidene systems in the presence of PCy3. The catalytic performance was investigated in RCM reaction (ring closing metathesis of benchmark substrates such as diallyltosylamide (6 and diethyl diallylmalonate (7.

  8. Ruthenium Olefin Metathesis Catalysts Bearing Carbohydrate-Based N-Heterocyclic Carbenes

    Science.gov (United States)

    Keitz, Benjamin K.; Grubbs, Robert H.

    2010-01-01

    Ru-based olefin metathesis catalysts containing carbohydrate-derived NHCs from glucose and galactose were synthesized and characterized by NMR spectroscopy. 2D-NMR spectroscopy revealed the presence of Ru-C (benzylidene) rotamers at RT and the rate of rotation was measured using magnetization transfer and VT-NMR spectroscopy. The catalysts were found to be effective at ring-opening metathesis polymerization (ROMP), ring closing metathesis (RCM), cross metathesis (CM), and asymmetric ring opening cross metathesis (AROCM) and showed surprising selectivity in both CM and AROCM. PMID:21603126

  9. Catalytic Enantioselective Olefin Metathesis in Natural Product Synthesis. Chiral Metal-Based Complexes that Deliver High Enantioselectivity and More

    Science.gov (United States)

    Malcolmson, Steven J.; Meek, Simon J.; Zhugralin, Adil R.

    2012-01-01

    Chiral olefin metathesis catalysts enable chemists to access enantiomerically enriched small molecules with high efficiency; synthesis schemes involving such complexes can be substantially more concise than those that would involve enantiomerically pure substrates and achiral Mo alkylidenes or Ru-based carbenes. The scope of research towards design and development of chiral catalysts is not limited to discovery of complexes that are merely the chiral versions of the related achiral variants. A chiral olefin metathesis catalyst, in addition to furnishing products of high enantiomeric purity, can offer levels of efficiency, product selectivity and/or olefin stereoselectivity that are unavailable through the achiral variants. Such positive attributes of chiral catalysts (whether utilized in racemic or enantiomerically enriched form) should be considered as general, applicable to other classes of transformations. PMID:19967680

  10. A 3 x 1 Integrated Pyroelectric Sensor Based on VDF/TrFE Copolymer

    NARCIS (Netherlands)

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

    1995-01-01

    This paper presents an integrated pyroelectric sensor based on a Vinylidene Fluoride TriFluoroEthylene (VDF/TrFE) copolymer. A silicon substrate that contains FET readout electronics is coated with the VDF/TrFE copolymer film using a spin-coating technique. On-chip poling of the copolymer has been a

  11. A latent ruthenium based olefin metathesis catalyst with a sterically demanding NHC ligand

    KAUST Repository

    Leitgeb, Anita

    2012-01-01

    An olefin metathesis catalyst featuring a SIPr NHC and an ester chelating carbene ligand is introduced. In contrast to its previously published SIMes analogue, only the trans dichloro configurated isomer was obtained. The two counterparts are tested in various olefin metathesis reactions, revealing a striking superiority of the new complex in the cross metathesis of olefins with methyl vinyl ketone allowing for full conversion with only 500 ppm catalyst loading. © 2012 The Royal Society of Chemistry.

  12. Solid-supported biomimetic membranes based on amphiphilic block copolymers

    OpenAIRE

    Kowal, Justyna

    2015-01-01

    Planar artificial membranes based on amphiphilic block copolymers are of high interest due to their potential applications in catalysis, drug screening, sensing, etc. Such polymeric membranes can successfully mimic biological membranes, providing high robustness and stability, which makes them good candidates to be developed in direction of applications. Even though solid-supported polymer membranes have been already investigated to a certain extent, it is still an emerging area. This thesis ...

  13. Beyond ketonization: selective conversion of carboxylic acids to olefins over balanced Lewis acid-base pairs.

    Science.gov (United States)

    Baylon, Rebecca A L; Sun, Junming; Martin, Kevin J; Venkitasubramanian, Padmesh; Wang, Yong

    2016-04-11

    We report the direct conversion of mixed carboxylic acids to C-C olefins with up to 60 mol% carbon yield through cascade (cross) ketonization, (cross) aldolization and self-deoxygenation reactions. Co-feeding hydrogen provides an additional ketone hydrogenation/dehydration pathway to a wider range of olefins.

  14. Consequences of the electronic tuning of latent ruthenium-based olefin metathesis catalysts on their reactivity

    Directory of Open Access Journals (Sweden)

    Karolina Żukowska

    2015-08-01

    Full Text Available Two ruthenium olefin metathesis initiators featuring electronically modified quinoline-based chelating carbene ligands are introduced. Their reactivity in RCM and ROMP reactions was tested and the results were compared to those obtained with the parent unsubstituted compound. The studied complexes are very stable at high temperatures up to 140 °C. The placement of an electron-withdrawing functionality translates into an enhanced activity in RCM. While electronically modified precatalysts, which exist predominantly in the trans-dichloro configuration, gave mostly the RCM and a minor amount of the cycloisomerization product, the unmodified congener, which preferentially exists as its cis-dichloro isomer, shows a switched reactivity. The position of the equilibrium between the cis- and the trans-dichloro species was found to be the crucial factor governing the reactivity of the complexes.

  15. Consequences of the electronic tuning of latent ruthenium-based olefin metathesis catalysts on their reactivity.

    Science.gov (United States)

    Żukowska, Karolina; Pump, Eva; Pazio, Aleksandra E; Woźniak, Krzysztof; Cavallo, Luigi; Slugovc, Christian

    2015-01-01

    Two ruthenium olefin metathesis initiators featuring electronically modified quinoline-based chelating carbene ligands are introduced. Their reactivity in RCM and ROMP reactions was tested and the results were compared to those obtained with the parent unsubstituted compound. The studied complexes are very stable at high temperatures up to 140 °C. The placement of an electron-withdrawing functionality translates into an enhanced activity in RCM. While electronically modified precatalysts, which exist predominantly in the trans-dichloro configuration, gave mostly the RCM and a minor amount of the cycloisomerization product, the unmodified congener, which preferentially exists as its cis-dichloro isomer, shows a switched reactivity. The position of the equilibrium between the cis- and the trans-dichloro species was found to be the crucial factor governing the reactivity of the complexes.

  16. Consequences of the electronic tuning of latent ruthenium-based olefin metathesis catalysts on their reactivity

    Science.gov (United States)

    Pump, Eva; Pazio, Aleksandra E; Woźniak, Krzysztof; Cavallo, Luigi

    2015-01-01

    Summary Two ruthenium olefin metathesis initiators featuring electronically modified quinoline-based chelating carbene ligands are introduced. Their reactivity in RCM and ROMP reactions was tested and the results were compared to those obtained with the parent unsubstituted compound. The studied complexes are very stable at high temperatures up to 140 °C. The placement of an electron-withdrawing functionality translates into an enhanced activity in RCM. While electronically modified precatalysts, which exist predominantly in the trans-dichloro configuration, gave mostly the RCM and a minor amount of the cycloisomerization product, the unmodified congener, which preferentially exists as its cis-dichloro isomer, shows a switched reactivity. The position of the equilibrium between the cis- and the trans-dichloro species was found to be the crucial factor governing the reactivity of the complexes. PMID:26425202

  17. Consequences of the electronic tuning of latent ruthenium-based olefin metathesis catalysts on their reactivity

    KAUST Repository

    Żukowska, Karolina

    2015-08-20

    Two ruthenium olefin metathesis initiators featuring electronically modified quinoline-based chelating carbene ligands are introduced. Their reactivity in RCM and ROMP reactions was tested and the results were compared to those obtained with the parent unsubstituted compound. The studied complexes are very stable at high temperatures up to 140 °C. The placement of an electron-withdrawing functionality translates into an enhanced activity in RCM. While electronically modified precatalysts, which exist predominantly in the trans-dichloro configuration, gave mostly the RCM and a minor amount of the cycloisomerization product, the unmodified congener, which preferentially exists as its cis-dichloro isomer, shows a switched reactivity. The position of the equilibrium between the cis- and the trans-dichloro species was found to be the crucial factor governing the reactivity of the complexes.

  18. Photolithographic olefin metathesis polymerization.

    Science.gov (United States)

    Weitekamp, Raymond A; Atwater, Harry A; Grubbs, Robert H

    2013-11-13

    Patterning functional materials is a central challenge across many fields of science. The ability to lithographically fabricate micro- and nanostructures has been one of the most impactful technological breakthroughs of the last century. In part due to the complexity of the chemical processes in photoresists, there is a limited variety of materials that can currently be patterned by photolithography. We report a negative tone photoresist using a photoactivated olefin metathesis catalyst, which can be quickly prepared in a one-pot synthesis from commercially available starting materials. The resist is based on a ruthenium vinyl ether complex, widely regarded as inactive toward olefin metathesis. The combination of this photoactivated catalyst with the fidelity and functional group tolerance of ruthenium-mediated olefin metathesis enables a host of new possibilities for photopatterned materials.

  19. Simple and highly Z-selective ruthenium-based olefin metathesis catalyst.

    Science.gov (United States)

    Occhipinti, Giovanni; Hansen, Fredrik R; Törnroos, Karl W; Jensen, Vidar R

    2013-03-01

    A one-step substitution of a single chloride anion of the Grubbs-Hoveyda second-generation catalyst with a 2,4,6-triphenylbenzenethiolate ligand resulted in an active olefin metathesis catalyst with remarkable Z selectivity, reaching 96% in metathesis homocoupling of terminal olefins. High turnover numbers (up to 2000 for homocoupling of 1-octene) were obtained along with sustained appreciable Z selectivity (>85%). Apart from the Z selectivity, many properties of the new catalyst, such as robustness toward oxygen and water as well as a tendency to isomerize substrates and react with internal olefin products, resemble those of the parent catalyst.

  20. Enzyme cleavable nanoparticles from peptide based triblock copolymers

    Science.gov (United States)

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

    2013-05-01

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

  1. Electrochemical behavior and conductivity measurements of electropolymerized selenophene-based copolymers

    Directory of Open Access Journals (Sweden)

    Alakhras Fadi

    2015-03-01

    Full Text Available Electrochemical copolymerization of selenophene and thiophene was performed at a constant electrode potential. The obtained homopolymer films and copolymers were studied and characterized with cyclic voltammetry and conductivity measurements, from which conductivity values around 13.35 S · cm-1 were determined. The influence of the applied electropolymerization potential and the monomer feed ratio of selenophene and thiophene on the copolymers properties was investigated. The obtained copolymers showed good stability of the redox activity in an acetonitrile-based electrolyte solution. At higher polymerization potentials and at higher concentrations of thiophene in the feed, more thiophene units were incorporated into the copolymer chain. The conductivities of the copolymers were between those of homopolymers, implying that oxidation of both monomers was possible and the copolymer chains might accordingly be composed of both selenophene and thiophene units.

  2. Footprint, weathering, and persistence of synthetic-base drilling mud olefins in deep-sea sediments following the Deepwater Horizon disaster.

    Science.gov (United States)

    Stout, Scott A; Payne, James R

    2017-03-13

    Olefin-based synthetic-based drilling mud (SBM) was released into the Gulf of Mexico as a result of the Deepwater Horizon (DWH) disaster in 2010. We studied the composition of neat SBM and, using conventional GC-FID, the extent, concentration, and chemical character of SBM-derived olefins in >3600 seafloor sediments collected in 2010/2011 and 2014. SBM-derived (C14-C20) olefins occurred (up to 10cm deep) within a 6.5km(2) "footprint" around the well. The olefin concentration in most sediments decreased an order of magnitude between 2010/2011 and 2014, at least in part due to biodegradation, evidenced by the preferential loss C16 and C18 linear (α- and internal) versus branched olefins. Based on their persistence for 4-years in sediments around the Macondo well, and 13-years near a former unrelated drill site (~62km away), weathered SBM-derived olefins released during the DWH disaster are anticipated to persist in deep-sea sediment for (at least) a comparable duration.

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

    Science.gov (United States)

    Panthani, Tessie Rose

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

  4. In Silico Olefin Metathesis with Ru-Based Catalysts Containing N-Heterocyclic Carbenes Bearing C60 Fullerenes.

    Science.gov (United States)

    Martínez, Juan Pablo; Vummaleti, Sai Vikrama Chaitanya; Falivene, Laura; Nolan, Steven P; Cavallo, Luigi; Solà, Miquel; Poater, Albert

    2016-05-01

    Density functional theory calculations have been used to explore the potential of Ru-based complexes with 1,3-bis(2,4,6-trimethylphenyl)imidazolin-2-ylidene (SIMes) ligand backbone (A) being modified in silico by the insertion of a C60 molecule (B and C), as olefin metathesis catalysts. To this end, we investigated the olefin metathesis reaction catalyzed by complexes A, B, and C using ethylene as the substrate, focusing mainly on the thermodynamic stability of all possible reaction intermediates. Our results suggest that complex B bearing an electron-withdrawing N-heterocyclic carbene improves the performance of unannulated complex A. The efficiency of complex B is only surpassed by complex A when the backbone of the N-heterocyclic carbene of complex A is substituted by two amino groups. The particular performance of complexes B and C has to be attributed to electronic factors, that is, the electronic-donating capacity of modified SIMes ligand rather than steric effects, because the latter are predicted to be almost identical for complexes B and C when compared to those of A. Overall, this study indicates that such Ru-based complexes B and C might have the potential to be effective olefin metathesis catalysts.

  5. In Silico Olefin Metathesis with Ru-Based Catalysts Containing N-Heterocyclic Carbenes Bearing C60Fullerenes

    KAUST Repository

    Martínez, Juan Pablo

    2016-04-10

    Density functional theory calculations have been used to explore the potential of Ru-based complexes with 1,3-bis(2,4,6-trimethylphenyl)imidazolin-2-ylidene (SIMes) ligand backbone (A) being modified in silico by the insertion of a C60 molecule (B and C), as olefin metathesis catalysts. To this end, we investigated the olefin metathesis reaction catalyzed by complexes A, B, and C using ethylene as the substrate, focusing mainly on the thermodynamic stability of all possible reaction intermediates. Our results suggest that complex B bearing an electron-withdrawing N-heterocyclic carbene improves the performance of unannulated complex A. The efficiency of complex B is only surpassed by complex A when the backbone of the N-heterocyclic carbene of complex A is substituted by two amino groups. The particular performance of complexes B and C has to be attributed to electronic factors, that is, the electronic-donating capacity of modified SIMes ligand rather than steric effects, because the latter are predicted to be almost identical for complexes B and C when compared to those of A. Overall, this study indicates that such Ru-based complexes B and C might have the potential to be effective olefin metathesis catalysts. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. A comprehensive study of olefin metathesis catalyzed by Ru-based catalysts.

    Science.gov (United States)

    Poater, Albert; Cavallo, Luigi

    2015-01-01

    During a Ru-catalyzed reaction of an olefin with an alkylidene moiety that leads to a metallacycle intermediate, the cis insertion of the olefin can occur from two different directions, namely side and bottom with respect to the phosphine or N-heterocyclic ligand (NHC), depending on the first or second generation Grubbs catalyst. Here, DFT calculations unravel to which extent the bottom coordination of olefins with respect is favored over the side coordination through screening a wide range of catalysts, including first and second generation Grubbs catalysts as well as the subsequent Hoveyda derivatives. The equilibrium between bottom and side coordination is influenced by sterics, electronics, and polarity of the solvent. The side attack is favored for sterically less demanding NHC and/or alkylidene ligands. Moreover the generation of a 14-electron species is also discussed, with either pyridine or phosphine ligands to dissociate.

  7. A comprehensive study of olefin metathesis catalyzed by Ru-based catalysts

    Science.gov (United States)

    2015-01-01

    Summary During a Ru-catalyzed reaction of an olefin with an alkylidene moiety that leads to a metallacycle intermediate, the cis insertion of the olefin can occur from two different directions, namely side and bottom with respect to the phosphine or N-heterocyclic ligand (NHC), depending on the first or second generation Grubbs catalyst. Here, DFT calculations unravel to which extent the bottom coordination of olefins with respect is favored over the side coordination through screening a wide range of catalysts, including first and second generation Grubbs catalysts as well as the subsequent Hoveyda derivatives. The equilibrium between bottom and side coordination is influenced by sterics, electronics, and polarity of the solvent. The side attack is favored for sterically less demanding NHC and/or alkylidene ligands. Moreover the generation of a 14-electron species is also discussed, with either pyridine or phosphine ligands to dissociate. PMID:26664596

  8. A comprehensive study of olefin metathesis catalyzed by Ru-based catalysts

    KAUST Repository

    Poater, Albert

    2015-09-29

    During a Ru-catalyzed reaction of an olefin with an alkylidene moiety that leads to a metallacycle intermediate, the cis insertion of the olefin can occur from two different directions, namely side and bottom with respect to the phosphine or N-heterocyclic ligand (NHC), depending on the first or second generation Grubbs catalyst. Here, DFT calculations unravel to which extent the bottom coordination of olefins with respect is favored over the side coordination through screening a wide range of catalysts, including first and second generation Grubbs catalysts as well as the subsequent Hoveyda derivatives. The equilibrium between bottom and side coordination is influenced by sterics, electronics, and polarity of the solvent. The side attack is favored for sterically less demanding NHC and/or alkylidene ligands. Moreover the generation of a 14-electron species is also discussed, with either pyridine or phosphine ligands to dissociate.

  9. A comprehensive study of olefin metathesis catalyzed by Ru-based catalysts

    Directory of Open Access Journals (Sweden)

    Albert Poater

    2015-09-01

    Full Text Available During a Ru-catalyzed reaction of an olefin with an alkylidene moiety that leads to a metallacycle intermediate, the cis insertion of the olefin can occur from two different directions, namely side and bottom with respect to the phosphine or N-heterocyclic ligand (NHC, depending on the first or second generation Grubbs catalyst. Here, DFT calculations unravel to which extent the bottom coordination of olefins with respect is favored over the side coordination through screening a wide range of catalysts, including first and second generation Grubbs catalysts as well as the subsequent Hoveyda derivatives. The equilibrium between bottom and side coordination is influenced by sterics, electronics, and polarity of the solvent. The side attack is favored for sterically less demanding NHC and/or alkylidene ligands. Moreover the generation of a 14-electron species is also discussed, with either pyridine or phosphine ligands to dissociate.

  10. A 3x1 integrated pyroelectric sensor based on VDF/TrFE copolymer

    NARCIS (Netherlands)

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

    1996-01-01

    This paper presents an integrated pyroelectric sensor based on a vinylidene fluoride¿trifluoroethylene (VDF/TrFE) copolymer. A silicon substrate that contains field-effect transistor (FET) readout electronics is coated with the VDF/TrFE copolymer film using a spin-coating technique. On-chip poling o

  11. Synthesis and characterization of butadiene-1,3 and octene-1 copolymer prepared by a Ziegler-Natta catalyst based on neodymium

    Directory of Open Access Journals (Sweden)

    Gustavo M. Silva

    2011-01-01

    Full Text Available The aim of this work is to evaluate the influence of octene-1 incorporation in the polybutadiene chain on the polymerization reaction and polymer characteristics. Thus, copolymerization of butadiene-1,3 with octene-1 using a Ziegler-Natta ternary catalyst based on neodymium was performed. The weight ratios of butadiene-1,3/α-olefin 100/0, 99/1, 97/3, 95/5, 90/10, 80/20 and 70/30 were evaluated. The copolymers were characterized by size exclusion chromatography (SEC, infrared spectroscopy (FTIR and thermogravimetric analysis (TG. The results showed that the degradation temperature (Tmax was not affected by the addition of alpha-olefin, while the thermal behavior has undergone significant changes. The polymer microstructure was not influenced by the increasing of octene-1 content. However, a tendency to molecular mass increase was observed with the increasing of octene-1 content. It was also observed a trend in reduction of the polymerization conversion as the octene-1 content increased.

  12. The Right Computational Recipe for Olefin Metathesis with Ru-Based Catalysts: The Whole Mechanism of Ring-Closing Olefin Metathesis.

    Science.gov (United States)

    Poater, Albert; Pump, Eva; Vummaleti, Sai Vikrama Chaitanya; Cavallo, Luigi

    2014-10-14

    The initiation mechanism of ruthenium methylidene complexes was studied detailing mechanistic insights of all involved reaction steps within a classical olefin metathesis pathway. Computational studies reached a good agreement with the rarely available experimental data and even enabled to complement them. As a result, a highly accurate computational and rather cheap recipe is presented; M06/TZVP//BP86/SVP (PCM, P = 1354 atm).

  13. The right computational recipe for olefin metathesis with ru-based catalysts: The whole mechanism of ring-closing olefin metathesis

    KAUST Repository

    Poater, Albert

    2014-10-14

    The initiation mechanism of ruthenium methylidene complexes was studied detailing mechanistic insights of all involved reaction steps within a classical olefin metathesis pathway. Computational studies reached a good agreement with the rarely available experimental data and even enabled to complement them. As a result, a highly accurate computational and rather cheap recipe is presented; M06/TZVP//BP86/SVP (PCM, P = 1354 atm).

  14. Preparation and characterization of lignin based macromonomer and its copolymers with butyl methacrylate.

    Science.gov (United States)

    Liu, Xiaohuan; Wang, Jifu; Yu, Juan; Zhang, Mingming; Wang, Chunpeng; Xu, Yuzhi; Chu, Fuxiang

    2013-09-01

    Copolymerization of butyl methacrylate (BMA) with biobutanol lignin (BBL) was achieved by free-radical polymerization (FRP) using a lignin-based macromonomer. The lignin-based macromonomer containing acrylic groups was prepared by reacting acryloyl chloride with biobutanol lignin using triethylamine (TEA) as absorb acid agentin. From the results of elemental analysis and GPC, the average degree of polymerization (DP) of BBL was estimated to be five. A detailed molecular characterization has been performed, including techniques such as (1)H NMR, (13)C NMR and UV-vis spectroscopies, which provided quantitative information about the composition of the copolymers. The changes in the solubility of lignin-g-poly(BMA) copolymers in ethyl ether were dependent on the length of poly(BMA) side chain. TGA analysis indicated that the lignin-containing poly(BMA) graft copolymers exhibited high thermal stability. The bulky aromatic group of lignin increased the glass-transition temperature of poly(BMA). In order to confirm the main structure of copolymer, (AC-g-BBL)-co-BMA copolymer was also synthesized by atom transfer radical polymerization (ATRP), and the results revealed that the copolymer prepared by ATRP had the same solution behavior as that prepared by FRP, and the lignin-based macromonomer showed no homopolymerizability due to the steric hindrance. In addition, the lignin-co-BMA copolymer had a surprisingly higher molecular weight than poly(BMA) under the same reaction condition, suggesting that a branched lignin based polymer could be formed.

  15. Cycloalkyl-based unsymmetrical unsaturated (U₂)-NHC ligands: flexibility and dissymmetry in ruthenium-catalysed olefin metathesis.

    Science.gov (United States)

    Rouen, Mathieu; Borré, Etienne; Falivene, Laura; Toupet, Loic; Berthod, Mikaël; Cavallo, Luigi; Olivier-Bourbigou, Hélène; Mauduit, Marc

    2014-05-21

    Air-stable Ru-indenylidene and Hoveyda-type complexes bearing new unsymmetrical unsaturated N-heterocyclic carbene (U2-NHC) ligands combining a mesityl unit and a flexible cycloalkyl moiety as N-substituents were synthesised. Structural features, chemical stabilities and catalytic profiles in olefin metathesis of this new library of cycloalkyl-based U2-NHC Ru complexes were studied and compared with their unsymmetrical saturated NHC-Ru homologues as well as a set of commercially available Ru-catalysts bearing either symmetrical SIMes or IMes NHC ligands.

  16. Cycloalkyl-based unsymmetrical unsaturated (U2)-NHC ligands: Flexibility and dissymmetry in ruthenium-catalysed olefin metathesis

    KAUST Repository

    Rouen, Mathieu

    2014-01-01

    Air-stable Ru-indenylidene and Hoveyda-type complexes bearing new unsymmetrical unsaturated N-heterocyclic carbene (U2-NHC) ligands combining a mesityl unit and a flexible cycloalkyl moiety as N-substituents were synthesised. Structural features, chemical stabilities and catalytic profiles in olefin metathesis of this new library of cycloalkyl-based U2-NHC Ru complexes were studied and compared with their unsymmetrical saturated NHC-Ru homologues as well as a set of commercially available Ru-catalysts bearing either symmetrical SIMes or IMes NHC ligands. © 2014 the Partner Organisations.

  17. Modular construction of a porous organometallic network based on rhodium olefin complexation.

    Science.gov (United States)

    Stoeck, Ulrich; Nickerl, Georg; Burkhardt, Ulrich; Senkovska, Irena; Kaskel, Stefan

    2012-10-24

    We describe the rational design and synthesis of the first member of a new class of microporous materials. It is built from rhodium and a polyolefinic ligand featuring a rigid tetraphenylsilane backbone via metal olefin complexation, creating a truly organometallic network. The resulting framework, denoted as DUT-37 (Dresden University of Technology no. 37) exhibits considerable porosity and unprecedented stability under ambient conditions. Furthermore, it is catalytically active in transfer hydrogenation.

  18. Aerobic Epoxidation of Olefins Catalyzed by the Cobalt‐Based Metal–Organic Framework STA‐12(Co)

    DEFF Research Database (Denmark)

    Beier, Matthias Josef; Kleist, Wolfgang; Wharmby, Michael T.

    2012-01-01

    A Co‐based metal–organic framework (MOF) was investigated as a catalytic material in the aerobic epoxidation of olefins in DMF and exhibited, based on catalyst mass, a remarkably high catalytic activity compared with the Co‐doped zeolite catalysts that are typically used in this reaction. The str......A Co‐based metal–organic framework (MOF) was investigated as a catalytic material in the aerobic epoxidation of olefins in DMF and exhibited, based on catalyst mass, a remarkably high catalytic activity compared with the Co‐doped zeolite catalysts that are typically used in this reaction....... The structure of STA‐12(Co) is similar to that of STA‐12(Ni), as shown by XRD Rietveld refinement and is stable up to 270 °C. For the epoxidation reaction, significantly different selectivities were obtained depending on the substrate. Although styrene was epoxidized with low selectivity due to oligomerization......, which was, interestingly, considerably reduced by styrene/stilbene co‐epoxidation. This could be traced back to the formation of benzaldehyde promoting the reaction. Detailed parameter and catalytic studies, including in situ EPR and EXAFS spectroscopy, were performed to obtain an initial insight...

  19. Multiple Olefin Metathesis Polymerization That Combines All Three Olefin Metathesis Transformations: Ring-Opening, Ring-Closing, and Cross Metathesis.

    Science.gov (United States)

    Lee, Ho-Keun; Bang, Ki-Taek; Hess, Andreas; Grubbs, Robert H; Choi, Tae-Lim

    2015-07-29

    We demonstrated tandem ring-opening/ring-closing metathesis (RO/RCM) polymerization of monomers containing two cyclopentene moieties and postmodification via insertion polymerization. In this system, well-defined polymers were efficiently formed by tandem cascade RO/RCM reaction pathway. Furthermore, these polymers could be transformed to new A,B-alternating copolymers via a sequential cross metathesis reaction with a diacrylate. Additionally, we demonstrated the concept of multiple olefin metathesis polymerization in which the dicyclopentene and diacrylate monomers underwent all three olefin metathesis transformations (ring-opening, ring-closing, and cross metathesis) in one shot to produce A,B-alternating copolymer.

  20. Synthesis and characterization of a novel PNIPAAm-based copolymer with hydrolysis-dependent thermosensitivity.

    Science.gov (United States)

    Rosellini, Elisabetta; Cristallini, Caterina; Guerra, Giulio D; Barbani, Niccoletta; Giusti, Paolo

    2010-06-01

    The aim of this work was the synthesis and characterization of a novel poly(N-isopropylacrylamide)-based copolymer, with hydrolysis-dependent thermosensitivity, for bioengineering applications. For this purpose, N-isopropylacrylamide (NIPAAm) and 2-hydroxyethylmethacrylate-6-hydroxyhexanoate (HEMAHex) monomers were chosen. The poly(NIPAAm-co-HEMAHex) copolymer was synthesized by radical polymerization. The physicochemical, mechanical, functional and biological properties of the copolymer were investigated. The physicochemical characterization confirmed that the copolymerization was successfully carried out. In addition, the newly synthesized poly(NIPAAm-co-HEMAHex) copolymer showed temperature sensitivity, with a phase separation temperature under body temperature (at 23 °C). Fourier transform infrared spectroscopy and differential scanning calorimetry results after hydrolysis tests indicated that the incorporation of the HEMAHex ester groups provides the cleavage of the lateral chain, which leads to an increase in the hydrophilicity of the copolymer and, consequently, to an increase in the lower critical solution temperature (LCST) with time. Since the LCST increases above body temperature (up to 40.4 °C), the copolymer becomes soluble again and diffuses away. It was also demonstrated that the hydrolysis occurred on the peripheral ester bond of the lateral chain, with the release of 6-hydroxyhexanoic acid, whose bioresorbibility has been reported in the literature. Therefore, the properties of this copolymer are very interesting and make it particularly attractive for biomedical applications.

  1. SYNTHESIS AND PROPERTIES OF COPOLYMERS CONTAINING CUCURBIT[6]URIL-BASED PSEUDOROTAXANE STRUCTURE

    Institute of Scientific and Technical Information of China (English)

    Qiang Ma; Hui Yang; Kimoon Kim; Ye-bang Tan

    2012-01-01

    Novel copolymers based on acrylamide (AM) and complex pseudorotaxane monomer N'-(3-vinylbenzyl)-l,4-diaminobutane dihydrochloride with cucurbit[6]uril (CB[6]) (3VBCB) were prepared via free-radical polymerization in aqueous solution,and characterized by 1H-NMR,FT-IR,elemental analysis and static light scattering.The compositions of the copolymers (PAM3VBCB) with pseudorotaxane units were determined by 1H-NMR and elemental analysis.Thermal properties of the copolymers were studied by TGA,and the effects of the copolymer concentration and pH on the average hydrodynamic radius (Rh) of the copolymer molecules were studied by dynamic light scattering (DLS).The experiment data show that CB[6] beads are localized on 1,4-diaminobutane units in side chains of the copolymers.TGA results show that thermal stability of the copolymer increases with increasing the content of pseudorotaxane unit because of the enhanced rigidity and the bulky steric hindrance of 3VBCB in side chains of PAM3VBCB.DLS data show that the average hydrodynamic radius of copolymer molecules increases with the increase in the copolymer concentration,and both the pH and electrical conductivity of PAM3VBCB solutions demonstrate an acute change with addition of NaOH because of CB[6]dethreading from the side chains of PAM3VBCB.CB[6] threading and dethreading of PAM3VBCB could be controlled by addition of BaCl2 and Na2SO4.

  2. 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.

  3. 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.

  4. 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.

  5. Syntheses and Surface Properties of Polyacrylonitrile-based Copolymer Membranes Containing Sugar Moieties

    Institute of Scientific and Technical Information of China (English)

    HUANG Xiao-jun; WAN Ling-shu; DAI Zheng-wei; KOU Rui-qiang; XU Zhi-kang

    2005-01-01

    To improve the hydrophilicity of polyacrylonitrile-based membranes, sugar moieties were incorporated into acrylonitrile-based copolymers via the radical copolymerization of α-allyl glucoside(AG) with acrylonitrile(AN) with 2,2'-azobis-iso-butyronitrile(AIBN) as the initiator in dimethyl sulphoxide(DMSO). It was found that the yield increased with the increase of the initiator concentration and reaction time, while it decreased with the increase of the monomer molar ratio of AG to AN. Raising the AG proportion in the monomer mixture resulted in the increase of the AG content in the copolymer. Mv of the copolymers decreased with increasing the AG monomer fraction in feed. The copolymers were fabricated into dense membranes and their surface properties were studied by means of the water contact angle measurement and platelet adhesion tests. It was found that the static water contact angle on the membrane decreased significantly from 70° to 33° with the increase of the AG content. The adhesive number of platelets on the membrane surface also decreased significantly with increasing AG content in the copolymers. These results demonstrate that the hydrophilicity and biocompatibility of the acrylonitrile-based copolymer membranes could be improved efficiently by the copolymerization of acrylonitrile with vinyl carbohydrates.

  6. Diketopyrrolopyrrole-diketopyrrolopyrrole-based conjugated copolymer for high-mobility organic field-effect transistors

    KAUST Repository

    Kanimozhi, Catherine K.

    2012-10-10

    In this communication, we report the synthesis of a novel diketopyrrolopyrrole-diketopyrrolopyrrole (DPP-DPP)-based conjugated copolymer and its application in high-mobility organic field-effect transistors. Copolymerization of DPP with DPP yields a copolymer with exceptional properties such as extended absorption characteristics (up to ∼1100 nm) and field-effect electron mobility values of >1 cm 2 V -1 s -1. The synthesis of this novel DPP-DPP copolymer in combination with the demonstration of transistors with extremely high electron mobility makes this work an important step toward a new family of DPP-DPP copolymers for application in the general area of organic optoelectronics. © 2012 American Chemical Society.

  7. Synthesis and infrared properties of ethylenedioxythiophene and octylthiophene based copolymers

    Science.gov (United States)

    Buvat, P.; Hourquebie, P.

    1998-06-01

    The control of the structural parameters and doping conditions of PATs lead to quasi-metallic materials. We have developed the synthesis of copolymers and PAT to enhance the metallic properties with conservation of the solubility. Le contrôle des paramètres physico-chimiques des PATs et des conditions de dopage conduit à des matériaux quasi-métalliques. Nous nous sommes ici orientés vers des copolymères du PEDOT et des PATs pour augmenter le caractère métallique tout en conservant les propriétés de solubilité.

  8. Light-induced olefin metathesis

    Directory of Open Access Journals (Sweden)

    Yuval Vidavsky

    2010-11-01

    Full Text Available Light activation is a most desirable property for catalysis control. Among the many catalytic processes that may be activated by light, olefin metathesis stands out as both academically motivating and practically useful. Starting from early tungsten heterogeneous photoinitiated metathesis, up to modern ruthenium methods based on complex photoisomerisation or indirect photoactivation, this survey of the relevant literature summarises past and present developments in the use of light to expedite olefin ring-closing, ring-opening polymerisation and cross-metathesis reactions.

  9. Light-induced olefin metathesis

    Science.gov (United States)

    Vidavsky, Yuval

    2010-01-01

    Summary Light activation is a most desirable property for catalysis control. Among the many catalytic processes that may be activated by light, olefin metathesis stands out as both academically motivating and practically useful. Starting from early tungsten heterogeneous photoinitiated metathesis, up to modern ruthenium methods based on complex photoisomerisation or indirect photoactivation, this survey of the relevant literature summarises past and present developments in the use of light to expedite olefin ring-closing, ring-opening polymerisation and cross-metathesis reactions. PMID:21160912

  10. Ruthenium-based olefin metathesis catalysts bearing pH-responsive ligands: External control of catalyst solubility and activity

    Science.gov (United States)

    Balof, Shawna Lynn

    2011-12-01

    Sixteen novel, Ru-based olefin metathesis catalysts bearing pH responsive ligands were synthesized. The pH-responsive groups employed with these catalysts included dimethylamino (NMe2) modified NHC ligands as well as N-donor dimethylaminopyridine (DMAP) and 3-(o-pyridyl)propylidene ligands. These pH-responsive ligands provided the means by which the solubility and/or activity profiles of the catalysts produced could be controlled via acid addition. The main goal of this dissertation was to design catalyst systems capable of performing ring opening metathesis (ROMP) and ring closing metathesis (RCM) reactions in both organic and aqueous media. In an effort to quickly gain access to new catalyst structures, a template synthesis for functionalized NHC ligand precursors was designed, in addition to other strategies, to obtain ligand precursors with ancillary NMe2 groups. Kinetic studies for the catalysts produced from these precursors showed external control of catalyst solubility was afforded via protonation of the NMe2 groups of their NHC ligands. Additionally, this protonation afforded external control of catalyst propagation rates for several catalysts. This is the first known independent external control for the propagation rates of ROMP catalysts. The incorporation of pH-responsive N-donor ligands into catalyst structures also provided the means for the external control of metathesis activity, as the protonation of these ligands resulted in an increased initiation rate based on their fast and irreversible dissociation from the metal center. The enhanced external control makes these catalysts applicable to a wide range of applications, some of which have been explored by us and/or through collaboration. Three of the catalysts designed showed remarkable metathesis activity in aqueous media. These catalysts displayed comparable RCM activity in aqueous media to a class of water-soluble catalysts reported by Grubbs et al., considered to be the most active catalyst for

  11. Moving from Classical Ru-NHC to Neutral or Charged Rh-NHC Based Catalysts in Olefin Metathesis

    Directory of Open Access Journals (Sweden)

    Albert Poater

    2016-01-01

    Full Text Available Considering the versatility of oxidation states of rhodium together with the successful background of ruthenium-N-heterocyclic carbene based catalysts in olefin metathesis, it is envisaged the exchange of the ruthenium of the latter catalysts by rhodium, bearing an open-shell neutral rhodium center, or a +1 charged one. In the framework of in silico experiments, density functional theory (DFT calculations have been used to plot the first catalytic cycle that as a first step includes the release of the phosphine. DFT is, in this case, the tool that allows the discovery of the less endergonic reaction profile from the precatalytic species for the neutral catalyst with respect to the corresponding ruthenium one; increasing the endergonic character when dealing with the charged system.

  12. Moving from Classical Ru-NHC to Neutral or Charged Rh-NHC Based Catalysts in Olefin Metathesis.

    Science.gov (United States)

    Poater, Albert

    2016-01-30

    Considering the versatility of oxidation states of rhodium together with the successful background of ruthenium-N-heterocyclic carbene based catalysts in olefin metathesis, it is envisaged the exchange of the ruthenium of the latter catalysts by rhodium, bearing an open-shell neutral rhodium center, or a +1 charged one. In the framework of in silico experiments, density functional theory (DFT) calculations have been used to plot the first catalytic cycle that as a first step includes the release of the phosphine. DFT is, in this case, the tool that allows the discovery of the less endergonic reaction profile from the precatalytic species for the neutral catalyst with respect to the corresponding ruthenium one; increasing the endergonic character when dealing with the charged system.

  13. Mesoporous Molecular Sieves Based Catalysts for Olefin Metathesis and Metathesis Polymerization

    Science.gov (United States)

    Balcar, Hynek; Čejka, Jiří

    Heterogeneous catalysts for olefin metathesis using different types of (i) siliceous mesoporous molecular sieves, and (ii) organized mesoporous alumina as supports are reported. The catalysts were prepared either by spreading of transition metal oxidic phase on the support surface or by immobilizing transition metal compounds (mostly organometallic) on the support. The activity of these catalysts in various types of metathesis reactions (i.e. alkene and diene metathesis, metathesis of unsaturated esters and ethers, RCM, ROMP and metathesis polymerization of alkynes) was described. The main advantages of these catalysts consist generally in their high activity and selectivity, easy separation of catalysts from reaction products and the preparation of products free of catalyst residue. The examples of pore size influence on the selectivity in metathesis reactions are also given.

  14. The Effects of NHC-Backbone Substitution on Efficiency in Ruthenium-based Olefin Metathesis

    Science.gov (United States)

    Kuhn, Kevin M.; Bourg, Jean-Baptiste; Chung, Cheol K.; Virgil, Scott C.; Grubbs, Robert H.

    2009-01-01

    A series of ruthenium olefin metathesis catalysts bearing N-heterocyclic carbene (NHC) ligands with varying degrees of backbone and N-aryl substitution have been prepared. These complexes show greater resistance to decomposition through C–H activation of the N-aryl group, resulting in increased catalyst lifetimes. This work has utilized robotic technology to examine the activity and stability of each catalyst in metathesis, providing insights into the relationship between ligand architecture and enhanced efficiency. The development of this robotic methodology has also shown that, under optimized conditions, catalyst loadings as low as 25 ppm can lead to 100% conversion in the ring-closing metathesis of diethyl diallylmalonate. PMID:19351207

  15. Nitrogen-based copolymers as wax dispersants for paraffinic gas oils

    Energy Technology Data Exchange (ETDEWEB)

    El-Gamal, I.M.; Khidr, T.T.; Ghuiba, F.M. [Egyptian Petroleum Research Institute, Cairo (Egypt)

    1998-04-01

    n-Alkyl acrylates and n-alkyl methacrylates were prepared by esterification of acrylic and methacrylic acids with two linear long chain alcohol blends NAFOL 1822 and NAFOL 1822C. The four synthesized monomers were characterized and copolymerized with maleic anhydride in 1:1 molar ratio individually. The prepared copolymers were subjected to partial amidation with n-hexadecylamine. The amidated copolymers were purified, characterized, and then evaluated as wax dispersant flow improvers for improving the cold flow properties of a highly paraffinic gas oil G1 through cloud point (CP), cold filter plugging point (CFPP) and pour point (PP) tests. NAFOL 1822C methacrylate-n-hexadecylamine maleamic acid copolymer has achieved the highest CFPP and PP depression. Consequently, NAFOL 1822C methacrylate monomer was selected for further copolymerization with maleic anhydride in a molar ratio 1:4, respectively. The prepared copolymers were then submitted to partial and complete amidation with n-hexadecylamine, ditallowamine, tetraethylenepentamine and morpholine successively. In addition, combined esterification and amidation of the copolymer with NAFOL 1822C and morpholine, respectively, was carried out. Evaluation of the synthesized products as WDFIs in a less paraffinic gas oil G2 revealed that nitrogen and/or oxygen based functional groups of the copolymers are controlling parameters judging their dispersing effect and that NAFOL 1822C methacrylate-n-morpholine amide of NAFOL 1822C maleate copolymer has attained the optimum performance. Results also showed that no correlation is found between gas oil flowability improvements ({Delta}PP) and filterability amelioration ({Delta}CFPP). Stability of performance of the prepared additives as wax dispersants lasted for four weeks while for two weeks only as flow improvers. 18 refs., 8 figs., 9 tabs.

  16. Synthesis of thermoplastic poly(ester-olefin elastomers

    Directory of Open Access Journals (Sweden)

    Tanasijević Branka

    2004-01-01

    Full Text Available A series of thermoplastic poly(ester-olefin elastomers, based on poly(ethylene-stat-butylene, HO-PEB-OH, as the soft segment and poly (butylene terephthalate, PBT, as the hard segment, were synthesized by a catalyzed transesterification reaction in solution. The incorporation of soft hydrogenated poly(butadiene segments into the copolyester backbone was accomplished by the polycondensation of α, ω-dihydroxyl telechelic HO-PEB-OH, (PEB Mn = 3092 g/mol with 1,4-butanediol (BD and dimethyl terephthalate (DMT in the presence of a 50 wt-% high boiling solvent i.e., 1,2,4-trichlorobenzene. The molar ratio of the starting comonomers was selected to result in a constant hard to soft weight ratio of 60:40. The synthesis was optimized in terms of both the concentration of catalyst, tetra-n-butyl-titanate (Ti(OBu4, and stabilizer, N,N'-diphenyl-p-phenylenediamine (DPPD, as well as the reaction time. It was found that the optimal catalyst concentration (Ti(OBu4 for the synthesis of these thermoplastic elastomers was 1.0 mmol/mol ester and the optimal DPPD concentration was 1.0 wt-%. The extent of the reaction was followed by measuring the inherent viscosity of the reaction mixture. The effectiveness of the incorporation of the soft segments into the copolymer chains was proved by Soxhlet extraction with chloroform. The molecular structures, composition and the size of the synthesized poly(ester-butylenes were verified by 1H NMR spectroscopy, viscometry of dilute solutions and the complex dynamic melt viscosity. The thermal properties of poly(ester-olefins were investigated by differential scanning calorimetry (DSC. The degree of crystallinity was also determined by DSC. The thermal and thermo-oxidative stability were investigated by thermogravimetric analysis (TGA. The rheological properties of poly(ester-olefins were investigated by dynamic mechanical spectroscopy in the melt and solid state.

  17. Cellulose-based graft copolymers prepared by simplified electrochemically mediated ATRP

    Directory of Open Access Journals (Sweden)

    P. Chmielarz

    2017-02-01

    Full Text Available Brush-shaped block copolymer with a dual hydrophilic poly(acrylic acid-block-poly(oligo(ethylene glycol acrylate (PAA-b-POEGA arms was synthesized for the first time via a simplified electrochemically mediated ATRP (seATRP under both constant potential electrolysis and constant current electrolysis conditions, utilizing only 30 ppm of catalyst complex. The polymerization conditions were optimized to provide fast reactions while employing low catalyst concentrations and preparation of cellulose-based brush-like copolymers with narrow molecular weight distributions. The results from proton nuclear magnetic resonance (1H NMR spectral studies support the formation of cellulose-based graft (copolymers. It is expected that these new polymer brushes may find application as pH- and thermo-sensitive drug delivery systems.

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

    Science.gov (United States)

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

    2017-03-01

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

  19. PCL-PDMS-PCL copolymer-based microspheres mediate cardiovascular differentiation from embryonic stem cells

    Science.gov (United States)

    Song, Liqing

    Poly-epsilon-caprolactone (PCL) based copolymers have received much attention as drug or growth factor delivery carriers and tissue engineering scaffolds due to their biocompatibility, biodegradability, and tunable biophysical properties. Copolymers of PCL and polydimethylsiloxane (PDMS) also have shape memory behaviors and can be made into thermoresponsive shape memory polymers for various biomedical applications such as smart sutures and vascular stents. However, the influence of biophysical properties of PCL-PDMS-PCL copolymers on stem cell lineage commitment is not well understood. In this study, PDMS was used as soft segments of varying length to tailor the biophysical properties of PCL-based co-polymers. While low elastic modulus (embryonic stem cells, the range of 60-100 MPa PCL-PDMS-PCL showed little influence on the differentiation. Then different size (30-140 mum) of microspheres were fabricated from PCL-PDMS-PCL copolymers and incorporated within embryoid bodies (EBs). Mesoderm differentiation was induced using bone morphogenetic protein (BMP)-4 for cardiovascular differentiation. Differential expressions of mesoderm progenitor marker KDR and vascular markers CD31 and VE-cadherin were observed for the cells differentiated from EBs incorporated with microspheres of different size, while little difference was observed for cardiac marker alpha-actinin expression. Small size of microspheres (30 mum) resulted in higher expression of KDR while medium size of microspheres (94 mum) resulted in higher CD31 and VE-cadherin expression. This study indicated that the biophysical properties of PCL-based copolymers impacted stem cell lineage commitment, which should be considered for drug delivery and tissue engineering applications.

  20. Radiation-chemical synthesis of thermosensitive copolymers based on the vinylbutyl ether and their complexing and emulgating abilities

    Energy Technology Data Exchange (ETDEWEB)

    Zhunuspayev, D.E. [Kazakh National University, Department of Chemical Physics and Macromolecular Chemistry, 95a Karasai Batyr Street, Almaty (Kazakhstan); Mun, G.A. [Kazakh National University, Department of Chemical Physics and Macromolecular Chemistry, 95a Karasai Batyr Street, Almaty (Kazakhstan)], E-mail: gamun@nursat.kz; Dubolazov, A.V.; Nurkeeva, Z.S. [Kazakh National University, Department of Chemical Physics and Macromolecular Chemistry, 95a Karasai Batyr Street, Almaty (Kazakhstan); Gueven, O. [Hacettepe University, Department of Chemistry, 06532 Beytepe, Ankara (Turkey)

    2007-12-15

    Novel water-soluble thermosensitive copolymers of vinyl butyl ether (VBE) with vinyl ether of ethyleneglycol (VEEG) and N-vinylpyrrolidone (NVP) and ternary copolymers based on VBE, 2-hydroxyethylacrylate (HEA) and acrylic acid (AA) were synthesized by {gamma}-induced radiation copolymerization. The composition of copolymers and average molecular weight of copolymers were determined using NMR {sup 13}C-spectroscopy and gel-permeation chromatography. It was shown that aqueous solutions of VBE-VEEG, VBE-NVP, VBE-HEA-AA have lower critical solution temperature (LCST) depending on copolymer composition. The complexation of copolymers with polyacrylic acid (PAA) was studied by turbidimetry method. Critical pH value of complexation (pH{sub crit.}) was used as the criterion of complexing ability. The effect of composition and concentration of copolymers, as well as pH of medium on the formation of IPC was investigated. The effect of VBE-VEEG copolymers of different compositions on the stability of model hexane-water emulsions was studied. It was determined that the regulation of hydrophilic-hydrophobic balance of macrochains and copolymer concentration allows effectively influence on the stability of hexane-water emulsions.

  1. First principles molecular dynamics simulation of a task-specific ionic liquid based on silver-olefin complex: atomistic insight into separation process

    CERN Document Server

    Jiang, De-en

    2008-01-01

    First principles molecular dynamics based on density functional theory is applied to a hypothetical ionic liquid whose cations and anions are silver-ethylene complex [Ag(C2H4)2+] and tetrafluoroborate [BF4-], respectively. This ionic liquid represents a group of task-specific silver complex-based ionic liquids synthesized recently. Molecular dynamics simulations at two temperatures are performed for five picoseconds. Events of association, dissociation, exchange, and recombination of ethylene with silver cation are observed. A mechanism of ethylene transfer similar to the Grotthus type of proton transfer in water is identified, where a silver cation accepts one ethylene molecule and donates another to a neighboring silver cation. This mechanism may contribute to fast transport of olefins through ionic liquid membranes based on silver complexes for olefin/paraffin separation.

  2. First principles molecular dynamics simulation of a task-specific ionic liquid based on silver-olefin complex: atomistic insights into a separation process.

    Science.gov (United States)

    Jiang, De-en; Dai, Sheng

    2008-08-21

    First principles molecular dynamics based on density functional theory is applied to a hypothetical ionic liquid whose cations and anions are silver-ethylene complex [Ag(C2H4)2+] and tetrafluoroborate [BF4-], respectively. This ionic liquid represents a group of task-specific silver complex-based ionic liquids synthesized recently. Molecular dynamics simulations at two temperatures are performed for five picoseconds. Events of association, dissociation, exchange, and recombination of ethylene with silver cation are found. A mechanism of ethylene transfer similar to the Grotthus type of proton transfer in water is identified, where a silver cation accepts one ethylene molecule and donates another to a neighboring silver cation. This mechanism may contribute to fast transport of olefins through ionic liquid membranes based on silver complexes for olefin/paraffin separation.

  3. Blue Light Emitting Diodes based on a partially conjugated Si-containing PPV-copolymer in a multilayer configuration

    NARCIS (Netherlands)

    Garten, F; Hilberer, A; Cacialli, F.; Esselink, F.J; van Dam, Y.; Schlatmann, A.R.; Friend, R.H.; Klapwijk, T.M; Hadziioannou, G

    1997-01-01

    Efficient blue Light Emitting Diodes (LEDs) based on a novel partially conjugated co-polymer (SiPPV) have been realized by a combination of techniques known to enhance the quantum efficiency of organic devices. The copolymer is homogeneously blended in a PVK-matrix to reduce the number of non-radiat

  4. Olefin metathesis and catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Kukes, S. G.; Banks, R. L.

    1985-05-14

    Olefins are converted into other olefins having different numbers of carbon atoms by contact with a catalyst comprising an inorganic refractory oxide support containing at least one of tungsten oxide and molybdenum oxide and a promoting amount of at least one methylating agent under conditions suitable for the methylating agent compounds to promote the activity of tungsten and molybdenum oxides for the disproportionation reaction.

  5. 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.

  6. Multicapillary columns with a porous layer based on the divinylbenzene copolymer

    Science.gov (United States)

    Patrushev, Yu. V.; Nikolaeva, O. A.; Sidelnikov, V. N.

    2010-05-01

    A method for preparing a multicapillary column with a porous layer based on the styrene-divinylbenzene copolymer has been developed. The column makes it possible to quickly separate C1-C4 hydrocarbons and oxygen-containing compounds. The main chromatographic properties of the columns were studied.

  7. PHOTORESPONSIVE BEHAVIOR OF AZOBENZENE-BASED (METH)ACRYLIC (CO)POLYMERS IN THIN-FILMS

    NARCIS (Netherlands)

    HAITJEMA, HJ; VONMORGEN, GL; TAN, YY; CHALLA, G

    1994-01-01

    The reversible photoisomerization and the thermal isomerization of azobenzene-based (Az.b.) groups covalently bound to (meth)acrylic (co)polymers were investigated in thin films. For the amorphous polymers it was found that a broad range of the thermal cis --> trans isomerization rates could be obta

  8. 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 ...

  9. In vitro evaluation of anticancer nanomedicines based on doxorubicin and amphiphilic Y-shaped copolymers

    Directory of Open Access Journals (Sweden)

    Li D

    2012-05-01

    Full Text Available Di Li,1,2,* Jian Xun Ding,1,3,* Zhao Hui Tang,1 Hai Sun,1 Xiu Li Zhuang,1 Jing Zhe Xu,2 Xue Si Chen1 1Key Laboratory of Polymer Ecomaterials, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, 2Department of Chemistry, Yanbian University, Yanji, 3Graduate University of Chinese Academy of Sciences, Beijing, China *These authors contributed equally to this workAbstract: Four monomethoxy poly(ethylene glycol-poly(L-lactide-co-glycolide2 (mPEG-P(LA-co-GA2 copolymers were synthesized by ring-opening polymerization of L-lactide and glycolide with double hydroxyl functionalized mPEG (mPEG-(OH2 as macroinitiator and stannous octoate as catalyst. The copolymers self-assembled into nanoscale micellar/vesicular aggregations in phosphate buffer at pH 7.4. Doxorubicin (DOX, an anthracycline anticancer drug, was loaded into the micellar/vesicular nanoparticles, yielding micellar/vesicular nanomedicines. The in vitro release behaviors could be adjusted by content of hydrophobic polyester and pH of the release medium. In vitro cell experiments showed that the intracellular DOX release could be adjusted by content of P(LA-co-GA, and the nanomedicines displayed effective proliferation inhibition against Henrietta Lacks’s cells with different culture times. Hemolysis tests indicated that the copolymers were hemocompatible, and the presence of copolymers could reduce the hemolysis ratio of DOX significantly. These results suggested that the novel anticancer nanomedicines based on DOX and amphiphilic Y-shaped copolymers were attractive candidates as tumor tissular and intracellular targeting drug delivery systems in vivo, with enhanced stability during circulation and accelerated drug release at the target sites.Keywords: amphiphilic Y-shaped copolymer, anticancer nanomedicine, cellular proliferation inhibition, doxorubicin

  10. Light olefins - challenges from new production routes?

    Energy Technology Data Exchange (ETDEWEB)

    Zimmermann, H. [Linde Engineering, Pullach (Germany)

    2007-07-01

    Light Olefins are the building blocks for many modern plastic products and are produced in large quantities. Driven by high crude oil prices, production is shifted to regions with low cost raw materials. Alternatives to the traditional production from Naphta, AGO and other crude products are becoming attractive. This paper evaluates several methods Ethylene and Pro-pylene production economically and also the regional advantageous routes. The analysis includes Steamcracking, dehydrogenation, dehydration of Ethanol, Methanol based routes and olefin conversion by Metathesis. (orig.)

  11. Microwave assisted synthesis of fluorene-based copolymers with different conjugate degreed quinoxaline segments from reactive polymer

    Energy Technology Data Exchange (ETDEWEB)

    Li, Jixin; Song, Xiaohui; Feng, Ying [School of Petrochemical Engineering, Shenyang University of Technology, 30 Guanghua Street, Liaoyang 111003 (China); Wang, Zhiming, E-mail: wangzm2011@yahoo.com.cn [School of Petrochemical Engineering, Shenyang University of Technology, 30 Guanghua Street, Liaoyang 111003 (China); State Key Laboratory of Supramolecular Structure and Materials, Jilin University, 2699 Qianjin Avenue, Changchun 130012 (China); Zhang, Xiaojuan [School of Petrochemical Engineering, Shenyang University of Technology, 30 Guanghua Street, Liaoyang 111003 (China); Shen, Fangzhong; Lu, Ping [State Key Laboratory of Supramolecular Structure and Materials, Jilin University, 2699 Qianjin Avenue, Changchun 130012 (China)

    2013-10-31

    In this work, we prepared three fluorene-based copolymers with different conjugate degreed quinoxaline segments from one reactive polymer by microwave assisted method. The obtained quinoxaline-based copolymers exhibited different bright color emissions, high photoluminescence quantum, low electron affinity and electron injection barrier. This approach not only simplified the steps of similar-structure polymers, but also avoided the monomer solubility problem. - Highlights: • Quinoxaline-based copolymers were prepared in microwave-assisted synthesis. • Polymer-synthesis containing different acceptors was simplified from reactive polymer. • Multi-functions were tuned by controlling reactive monomer structures.

  12. BODIPY-Based Donor-Acceptor Pi-Conjugated Alternating Copolymers

    Energy Technology Data Exchange (ETDEWEB)

    Popere, Bhooshan C.; Della Pelle, Andrea M.; Thayumanavan, S.

    2011-06-28

    Four novel π-conjugated copolymers incorporating 4,4-difluoro-4-borata-3a-azonia-4a-aza-s-indacene (BODIPY) core as the “donor” and quinoxaline (Qx), 2,1,3-benzothiadiazole (BzT), N,N'-di(2'-ethyl)hexyl-3,4,7,8-naphthalenetetracarboxylic diimide (NDI), and N,N'-di(2'-ethyl)hexyl-3,4,9,10-perylene tetracarboxylic diimide (PDI) as acceptors were designed and synthesized via Sonogashira polymerization. The polymers were characterized by ¹H NMR spectroscopy, gel permeation chromatography (GPC), UV–vis absorption spectroscopy, and cyclic voltammetry. Density functional theory (DFT) calculations were performed on polymer repeat units, and the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) energy levels were estimated from the optimized geometry using B3LYP functional and 6-311g(d,p) basis set. Copolymers with Qx and BzT possessed HOMO and LUMO energy levels comparable to those of BODIPY homopolymer, while PDI stabilized both HOMO and LUMO levels. Semiconductor behavior of these polymers was estimated in organic thin-film transistors (OTFT). While the homopolymer, Qx, and BzT-based copolymers showed only p-type semiconductor behavior, copolymers with PDI and NDI showed only n-type behavior.

  13. A Urea Potentiometric Biosensor Based on a Thiophene Copolymer

    Directory of Open Access Journals (Sweden)

    Cheng-Yuan (Kevin Lai

    2017-03-01

    Full Text Available A potentiometric enzyme biosensor is a convenient detector for quantification of urea concentrations in industrial processes, or for monitoring patients with diabetes, kidney damage or liver malfunction. In this work, poly(3-hexylthiophene-co-3-thiopheneacetic acid (P(3HT-co-3TAA was chemically synthesized, characterized and spin-coated onto conductive indium tin oxide (ITO glass electrodes. Urease (Urs was covalently attached to the smooth surface of this copolymer via carbodiimide coupling. The electrochemical behavior and stability of the modified Urs/P(3HT-co-3TAA/ITO glass electrode were investigated by cyclic voltammetry, and the bound enzyme activity was confirmed by spectrophotometry. Potentiometric response studies indicated that this electrode could determine the concentration of urea in aqueous solutions, with a quasi-Nernstian response up to about 5 mM. No attempt was made to optimize the response speed; full equilibration occurred after 10 min, but the half-time for response was typically <1 min.

  14. Olefin metathesis and catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Kukes, S. G.; Banks, R. L.

    1985-03-12

    Olefins are converted into other olefins having different numbers of carbon atoms by contact with a catalyst comprising an inorganic refractory material containing at least one of tungsten oxide and molybdenum oxide and a promoting amount of at least one treating agent selected from chlorinated silicon compounds, thionyl chloride, and sulfuryl chloride under conditions suitable for the treating agent to promote the activity of tungsten and molybdenum oxides for the disporoportionation reaction.

  15. Production of Natural Rubber Grafted Styrene Copolymer Latex as Water Base Coatings

    Directory of Open Access Journals (Sweden)

    M Utama

    2006-07-01

    Full Text Available Twelve kinds formulation of natural rubber grafted copolymer styrene (NR-g-S prepared by gamma radiation co-polymerization technique has been carried out. The characteristic of NR-g-S and its water base coating such as molecular structure, particle size, and the properties of latex and its film were evaluated. The results showed that the NR-g-S latex as a water base coating has low viscosity, height strength, good grease resistance, good flexibility, good aging and corrosion resistance on concrete cement and metal. The average particle size is between 270-300 nm, and the bonding between poly-isoprene of NRL and styrene molecules were grafted copolymer

  16. Synthesis of Polystyrene-Based Random Copolymers with Balanced Number of Basic or Acidic Functional Groups

    DEFF Research Database (Denmark)

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

    2010-01-01

    Pairs of polystyrene-based random copolymers with balanced number of pendant basic or acidic groups were synthesized utilizing the template strategy. The same poly[(4-hydroxystyrene)-ran-styrene] was used as a template backbone for modification. Two different synthetic approaches for the function......Pairs of polystyrene-based random copolymers with balanced number of pendant basic or acidic groups were synthesized utilizing the template strategy. The same poly[(4-hydroxystyrene)-ran-styrene] was used as a template backbone for modification. Two different synthetic approaches...... by copper-catalyzed 1,3 cycloaddition of aliphatic sulfonate- or amine-contaning azides. Both synthetic approaches proved to be highly efficient as evidenced by H-1-NMR analyses. The thermal properties were evaluated by differential scanning calorimetry and thermal gravimetric analyses and were influenced...

  17. 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.

  18. Factors influencing the biodegradability of biocomposites based on ethylene-octene copolymer (EOC) and vegetable fillers

    Science.gov (United States)

    Zykova, A. K.; Pantyukhov, P. V.; Monakhova, T. V.; Kolesnikova, N. N.; Popov, A. A.; Ramos, C. C.

    2016-11-01

    In this study the role of the content of filler, its nature (particle geometry in particular) and the type of the copolymer matrix were examined. For the study three grades of ethylene-octene copolymer were chosen. Composites were mixed in proportion from 70 to 30 wt % of the polymer matrix content. Water absorption was determined; thermal oxidative degradation was studied; and a biodegradation test on recovered soil was carried out. It was concluded that water absorption and weight loss correlate with the filler content. It was found that biocomposites with oil flax straw are more prone to water absorption and weight loss than the same ones with wood flour. The most stable matrix to oxidation was Lucene 370, then Lucene 670 and Lucene 760. Therefore, biocomposites based on Lucene 760 should be more biodegradable than others.

  19. Synthesis and Characterization of Plant based Polythiophene Copolymers for Light Harvesting Applications

    Science.gov (United States)

    Kodithuwakku, Udari; Malavi Arachchi, Prashantha; Ratnaweera, Dilru

    Polythiophenes became more attractive in diverse applications due to some of their inherent properties including thermal and environmental stability as well as optical and electronic conductive properties. Commonly thiophene monomers are obtained from byproducts of crude oils. The current study discuss for the first time the synthesis and characterization of light harvesting polythiophenes copolymers from thiophene derivatives extracted from Tagetes species. There were mainly two thiophenes derivatives, 5-(3-buten-1-ynyl)-2, 2-bithienyl and 2, 2', 5, 2''-terthienyl (terthiophene), in the roots of the plant. Chemical oxidative radical polymerization was followed during the synthesis of copolymers with various block compositions of plant based terthiophenes and 3-hexyl terthiophenes. Structural characterization of the synthetic products was done using FTIR, NMR, Uv-vis, XRD and DSC techniques. Polythiophene homopolymers obtained from plant based terthiophenes have limited processability of solar cells due to poor solubility in common organic solvents. A significant solubility improvement was observed with copolymers having minor contributions of 3-hexylthiophenes. Research Grants, University of Sri Jayewardenepura, Sri Lanka.

  20. Synthesis and characterization of a novel main chain oxadiazole-based copolymer for n-type solar cell material

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    A novel oxadiazole-based copolymer has been successfully synthesized through the palladium-catalyzed cross-coupling polycondensation method. The copolymer P is soluble in common organic solvents. Its structure has characterized by 1H NMR, 13C NMR, gel permeation chromatagraphy (GPC), UV-vis absorbance (Abs) and photoluniminescence (PL) spectroscopy, and cyclic voltammetry (CV). Investigation of its optical properties revealed that it is yellow emitting material, and the electrochemical analysis showed that P was well suited poly (2,5-dioctyloxy-p-phenylenevinylene) (PDOCPV) for photovoltaic devices, so the copolymer P is able to act as an electron acceptor in combination with PDOCPVas the electron donor to quench photoluminescence of the copolymer in the blend, indicative of the efficient photoinduced electron transfer from the PDOCPV to the P.

  1. Preparation of stable spherical micelles with rigid backbones based on polyaryletherketone copolymers containing lateral pyridyl groups

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Shuling; Liu, Lingzhi; Guo, Yunliang; Jiang, Zhenhua; Wang, Guibin, E-mail: wgb@jlu.edu.cn

    2013-07-15

    A new bisphenol monomer, 3-(3,4-dihydroxyphenylimine) pyridine (PYPH), was synthesized via a deoxidization reaction of an amine. A series of novel polyaryletherketone copolymers containing lateral pyridyl groups (PY-PAEKs) based on PYPH, 2,2-di(4-hydroxyphenyl)propane and 4,4′-difluorobenzophenone were prepared by nucleophilic aromatic substitution polycondensation reactions. Furthermore, spherical micelles with rigid PY-PAEKs as the inner cores and flexible polyacrylic acid (PAA) as the outer shells were obtained in a selective solvent (H{sub 2}O) successfully. The formation of the spherical micelles was confirmed by scanning electron and transmission electron microscopy as well as by surface tension measurements. The formation and size of the spherical micelles depended on the weight ratio of PAA/PY-PAEK, the concentration and pH value of the mixed solution containing the PY-PAEK and PAA, and the number of pyridyl groups in the PY-PAEK. The structure of the spherical micelles could be stabilized by a cross-linking reaction between the pyridyl groups of the PY-PAEKs and 1,4-dibromobutane. The diameter of the spherical micelles decreased because of the removal of the PAA shell from the PY-PAEK core after the cross-linking reaction. The resulting stable spherical micelles with rigid backbones did not dissolve in a number of polar solvents and remained unaffected by changes in the pH values. - Graphical abstract: Display Omitted - Highlights: • Polyaryletherketone copolymers containing lateral pyridyl groups were synthesized. • Spherical micelles were prepared using these copolymers and polyacrylic acid. • The copolymers and polyacrylic acid formed the core and the shell of the micelles, respectively. • The obtained micelles were stabilized by a cross-linking reaction. • The cross-linked micelles had rigid backbones, independent of solvents and pH values.

  2. SYNTHESIS AND CHARACTERIZATION OF NOVEL BIPOLAR PPV-BASED COPOLYMER CONTAINING TRIAZOLE AND CARBAZOLE UNITS

    Institute of Scientific and Technical Information of China (English)

    Ze Liu; Li-xiang Wang; Xia-bin Jing; Fo-song Wang

    2001-01-01

    Two new blue light-emitting PPV-based conjugated copolymers containing both an electron-withdrawing unit (triazole-TAZ) and electron-rich moieties (carbazole-CAR and bicarbazole-BCAR) were prepared by Wittig condensation polymerization between the triazole diphosphonium salt and the corresponding dialdehyde monomers. Their structures and properties were characterized by FT-IR, TGA, DSC, UV-Vis, PL spectroscopy and electrochemical measurements. The resulting copolymers are soluble in common organic solvents and thermally stable with a Ts of 147C for TAZ-CAR-PPV and of 157C for TAZ-BCAR-PPV. The maximum photoluminescence wavelengths of TAZ-CAR-PPV and TAZ-BCAR-PPV film appear at 460 nm and 480 nm, respectively. Cyclic voltammetry measurement demonstrates that TAZ-BCAR-PPV has good electrochemical reversibility, while TAZ-CAR-PPV exhibits the irreversible redox process. The triazole unit was found to be an effective π-conjugation interrupter and can play the rigid spacer role in determining the emission colour of the resulting copolymer.

  3. Binary and Ternary Catalytic Systems for Olefin Metathesis Based on MoCl5/SiO2

    Science.gov (United States)

    Bykov, Victor I.; Belyaev, Boris A.; Butenko, Tamara A.; Finkelshtein, Eugene Sh.

    Kinetics of α-olefin metathesis in the presence of binary (MoCl5/ SiO2-Me4Sn) and ternary catalytic systems (MoCl5/SiO2-Me4Sn-ECl4, E = Si or Ge) was studied. Specifically, kinetics and reactivity of 1-decene, 1-octene, and 1-hexene in the metathesis reaction at 27°C and 50°C in the presence of MoCl5/ SiO2-SnMe4 were examined and evaluated in detail. It was shown that experimental data comply well with the simple kinetic equation for the rate of formation of symmetrical olefins with allowance for the reverse reaction and catalyst deactivation: r = left( {k_1 \\cdot c_α - k_{ - 1} \\cdot c_s } right) \\cdot e^{ - k_d \\cdot tilde n_{tot} } . The coefficients for this equation were determined, and it was shown that these α-olefins had practically the same reactivity. It was found that reactivation in the course of metathesis took place due to the addition of a third component (silicon tetrachloride or germanium tetrachloride in combination with tetramethyltin) to a partially deactivated catalyst. The number of active centers was determined (5-6% of the amount of Mo) and the mechanisms of formation, deactivation, and reactivation were proposed for the binary and ternary catalytic systems. The role of individual components of the catalytic systems was revealed.

  4. Recovery of olefin monomers

    Science.gov (United States)

    Golden, Timothy Christoph; Weist, Jr., Edward Landis; Johnson, Charles Henry

    2004-03-16

    In a process for the production of a polyolefin, an olefin monomer is polymerised said polyolefin and residual monomer is recovered. A gas stream comprising the monomer and nitrogen is subjected to a PSA process in which said monomer is adsorbed on a periodically regenerated silica gel or alumina adsorbent to recover a purified gas stream containing said olefin and a nitrogen rich stream containing no less than 99% nitrogen and containing no less than 50% of the nitrogen content of the gas feed to the PSA process.

  5. MTO Schiff-base complexes: synthesis, structures and catalytic applications in olefin epoxidation.

    Science.gov (United States)

    Zhou, Ming-Dong; Zhao, Jin; Li, Jun; Yue, Shuang; Bao, Chang-Nian; Mink, Janos; Zang, Shu-Liang; Kühn, Fritz E

    2007-01-01

    Several Schiff-base ligands readily form complexes with methyltrioxorhenium(VII) (MTO) by undergoing a hydrogen transfer from a ligand-bound OH group to a ligand N atom. The resulting complexes are stable at room temperature and can be handled and stored in air without problems. Due to the steric demands of the ligands they display distorted trigonal-bipyramidal structures in the solid state, as shown by X-ray crystallography, with the O(-) moiety binding to the Lewis acidic Re atom and the Re-bound methyl group being located either in cis or trans position to the Schiff base. In solution, however, the steric differences seem not to be maintained, as can be deduced from (17)O NMR spectroscopy. Furthermore, the Schiff-base ligands exchange with donor ligands. Nevertheless, the catalytic behaviour is influenced significantly by the Schiff bases coordinated to the MTO moiety, which lead either to high selectivities and good activities or to catalyst decomposition. A large excess of ligand, in contrast to the observations with aromatic N-donor ligands, is detrimental to the catalytic performance as it leads to catalyst decomposition.

  6. Immobilized molybdenum–thiosemicarbazide Schiff base complex on the surface of magnetite nanoparticles as a new nanocatalyst for the epoxidation of olefins

    Energy Technology Data Exchange (ETDEWEB)

    Mohammadikish, M., E-mail: mohammadikish@yahoo.com [Department of Chemistry, Faculty of Sciences, Kermanshah Branch, Islamic Azad University, Kermanshah (Iran, Islamic Republic of); Masteri-Farahani, M.; Mahdavi, S. [Faculty of Chemistry, Kharazmi University, Tehran (Iran, Islamic Republic of)

    2014-03-15

    In this work, a new magnetically recoverable nanocatalyst was developed by immobilization of thiosemicarbazide ligand on the surface of silica coated magnetite nanoparticles (SCMNPs) through Schiff base condensation and followed complexation with MoO{sub 2}(acac){sub 2}. Characterization of the prepared nanocatalyst was performed with different physicochemical methods such as Fourier transform infrared (FT-IR) and atomic absorption spectroscopies, X-ray diffraction (XRD), vibrating sample magnetometry (VSM), thermogravimetric analysis (TGA), field-emission scanning electron microscopy (FE-SEM), and transmission electron microscopy (TEM). The prepared catalyst catalyzed the epoxidation of olefins and allyl alcohols with tert-butyl hydroperoxide (TBHP) and cumene hydroperoxide (CHP) quantitatively with excellent selectivity toward the corresponding epoxides under mild reaction conditions. - Highlights: • Silica coated magnetite nanoparticles were modified with a thiosemicarbazide-Schiff base ligand. • Complexation of the supported ligand with molybdenum resulted in preparation of a new hybrid nanomaterial. • The prepared hybrid nanomaterial acted as an efficient and reusable catalyst in the epoxidation of olefins.

  7. Olefin metathesis in nano-sized systems

    Directory of Open Access Journals (Sweden)

    Denise Méry

    2011-01-01

    Full Text Available The interplay between olefin metathesis and dendrimers and other nano systems is addressed in this mini review mostly based on the authors’ own contributions over the last decade. Two subjects are presented and discussed: (i The catalysis of olefin metathesis by dendritic nano-catalysts via either covalent attachment (ROMP or, more usefully, dendrimer encapsulation – ring closing metathesis (RCM, cross metathesis (CM, enyne metathesis reactions (EYM – for reactions in water without a co-solvent and (ii construction and functionalization of dendrimers by CM reactions.

  8. Olefin metathesis in nano-sized systems

    Science.gov (United States)

    Diallo, Abdou K; Gatard, Sylvain; Liang, Liyuan; Ornelas, Cátia; Martinez, Victor; Méry, Denise; Ruiz, Jaime

    2011-01-01

    Summary The interplay between olefin metathesis and dendrimers and other nano systems is addressed in this mini review mostly based on the authors’ own contributions over the last decade. Two subjects are presented and discussed: (i) The catalysis of olefin metathesis by dendritic nano-catalysts via either covalent attachment (ROMP) or, more usefully, dendrimer encapsulation – ring closing metathesis (RCM), cross metathesis (CM), enyne metathesis reactions (EYM) – for reactions in water without a co-solvent and (ii) construction and functionalization of dendrimers by CM reactions. PMID:21286399

  9. Novel Fluorene-based Conjugated Copolymer Containing Cyclobutenedione Unit for Light Emitting Diodes

    Institute of Scientific and Technical Information of China (English)

    Qiang PENG; Yan HUANG; Zhi Yun LU; Ping ZOU; Ming Gui XIE

    2004-01-01

    A novel fluorene-based conjugated copolymer containing cyclobutenedione unit was synthesized by Suzuki reaction. Its structure and properties were characterized by FTIR,1HNMR,elemental analysis,PL spectroscopy,DSC,TGA and cyclic voltammetry. The resulting polymer shows strong yellow PL emission (561 nm) and good solubility in polar aprotic solvents,I.e.THF, DMF, DMAC, DMSO, etc. DSC and TGA studies reveal that the novel polymer possesses excellent thermal stability with high glass transition temperature of 127℃ and onset decomposition temperature of 411℃.Cyclic voltammetry measurement demonstrated that the polymer has both hole and electron-transporting property.

  10. Optomechanical characterization of freestanding stretchable nanosheet based on polystyrene-polybutadiene-polystyrene copolymer

    Science.gov (United States)

    Kumagai, Hayato; Sato, Nobutaka; Takeoka, Shinji; Sawada, Kazuaki; Fujie, Toshinori; Takahashi, Kazuhiro

    2017-01-01

    In this study, we fabricated a stretchable freestanding ultrathin sheet based on a polystyrene-polybutadiene-polystyrene (SBS) copolymer with entropy-driven elasticity and evaluated its optomechanical properties. The freestanding SBS sheet had a thickness of 675 nm and a size of 10.4 × 10.4 mm2 on a through hole of a poly(dimethylsiloxane) (PDMS) sheet. The measurement of the reflection spectra of the optical interference peaks of the stretched sheets revealed that the SBS nanosheet had a Poisson’s ratio of 0.5-0.68 for a 38% elastic strain, which is one order of magnitude greater than that of parylene.

  11. Synthesis and aqueous solution properties of novel sugar methacrylate-based homopolymers and block copolymers.

    Science.gov (United States)

    Narain, Ravin; Armes, Steven P

    2003-01-01

    We report the facile preparation of a range of novel, well-defined cyclic sugar methacrylate-based polymers without recourse to protecting group chemistry. 2-Gluconamidoethyl methacrylate (GAMA) and 2-lactobionamidoethyl methacrylate (LAMA) were prepared directly by reacting 2-aminoethyl methacrylate with D-gluconolactone and lactobionolactone, respectively. Homopolymerization of GAMA and LAMA by atom transfer radical polymerization (ATRP) gave reasonably low polydispersities as judged by aqueous gel permeation chromatography. A wide range of sugar-based block copolymers were prepared using near-monodisperse macroinitiators based on poly(ethylene oxide) [PEO], poly(propylene oxide) [PPO], or poly(e-caprolactone) [PCL] and/or by sequential monomer addition of other methacrylic monomers such as 2-(diethylamino)ethyl methacrylate [DEA], 2-(diisopropylaminoethyl methacrylate [DPA], or glycerol monomethacrylate [GMA]. The reversible micellar self-assembly of selected sugar-based block copolymers [PEO23-GAMA50-DEA100, PEO23-LAMA30-DEA50, PPO33-GAMA50, and PPO33-LAMA50] was studied in aqueous solution as a function of pH and temperature using dynamic light scattering, transmission electron microscopy, surface tensiometry, and 1H NMR spectroscopy.

  12. Chlorine resistant desalination membranes based on directly sulfonated poly(arylene ether sulfone) copolymers

    Science.gov (United States)

    McGrath, James E.; Park, Ho Bum; Freeman, Benny D.

    2011-10-04

    The present invention provides a membrane, kit, and method of making a hydrophilic-hydrophobic random copolymer membrane. The hydrophilic-hydrophobic random copolymer membrane includes a hydrophilic-hydrophobic random copolymer. The hydrophilic-hydrophobic random copolymer includes one or more hydrophilic monomers having a sulfonated polyarylsulfone monomer and a second monomer and one or more hydrophobic monomers having a non-sulfonated third monomer and a fourth monomer. The sulfonated polyarylsulfone monomer introduces a sulfonate into the hydrophilic-hydrophobic random copolymer prior to polymerization.

  13. Exploitation of in situ generated sugar-based olefin keto-nitrones: synthesis of carbocycles, heterocycles, and nucleoside derivatives.

    Science.gov (United States)

    Das, Soumendra Nath; Chowdhury, Arpan; Tripathi, Neha; Jana, Prithwish K; Mandal, Sukhendu B

    2015-01-16

    Application of intramolecular 1,3-dipolar nitrone cycloaddition reaction on carbohydrate-derived precursors containing an olefin functionality at C-1 or C-3 or C-5 and a nitrone moiety at C-2 or C-3 as appropriate has resulted in the formation of structurally new cycloaddition products containing furanose-fused oxepane, thiepane, azepane, cyclopentane, cycloheptane, tetrahydrofuran, and pyranose-fused tetrahydrofuran rings. The structure and stereochemistry of these products have been characterized by spectral as well as single-crystal X-ray analyses. Two of the compounds have been transformed to the bicyclic nucleoside derivatives applying Vorbrüggen reaction conditions.

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

    Science.gov (United States)

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

    2016-08-01

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

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

    Science.gov (United States)

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

    2016-08-19

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

  16. Bio-based thermosetting copolymers of eugenol and tung oil

    Science.gov (United States)

    Handoko, Harris

    There has been an increasing demand for novel synthetic polymers made of components derived from renewable sources to cope with the depletion of petroleum sources. In fact, monomers derived vegetable oils and plant sources have shown promising results in forming polymers with good properties. The following is a study of two highly viable renewable sources, eugenol and tung oil (TO) to be copolymerized into fully bio-based thermosets. Polymerization of eugenol required initial methacrylate-functionalization through Steglich esterification and the synthesized methacrylated eugenol (ME) was confirmed by 1H-NMR. Rheological studies showed ideal Newtonian behavior in ME and five other blended ME resins containing 10 -- 50 wt% TO. Free-radical copolymerization using 5 mol% of tert-butyl peroxybenzoate (crosslinking catalyst) and curing at elevated temperatures (90 -- 160 °C) formed a series of soft to rigid highly-crosslinked thermosets. Crosslinked material (89 -- 98 %) in the thermosets were determined by Soxhlet extraction to decrease with increase of TO content (0 -- 30%). Thermosets containing 0 -- 30 wt% TO possessed ultimate flexural (3-point bending) strength of 32.2 -- 97.2 MPa and flexural moduli of 0.6 -- 3.5 GPa, with 3.2 -- 8.8 % strain-to-failure ratio. Those containing 10 -- 40 wt% TO exhibited ultimate tensile strength of 3.3 -- 45.0 MPa and tensile moduli of 0.02 GPa to 1.12 GPa, with 8.5 -- 76.7 % strain-to-failure ratio. Glass transition temperatures ranged from 52 -- 152 °C as determined by DMA in 3-point bending. SEM analysis on fractured tensile test specimens detected a small degree of heterogeneity. All the thermosets are thermally stable up to approximately 300 °C based on 5% weight loss.

  17. Complementary study based on DFT to describe the structure and properties relationship of diblock copolymer based on PVK and PPV

    Energy Technology Data Exchange (ETDEWEB)

    Mbarek, M.; Abbassi, F.; Alimi, K., E-mail: kamel.alimi@fsm.rnu.tn

    2016-09-15

    The structure-properties relationships of copolymer involving N-vinylcarbazole (PVK) and poly (p-phenylene-vinylene) (PPV) blocks, denoted PVK–PPV, was investigated by calculations based on density functional theory (DFT) and completed by experimental analyses. Thus, vibrational, optical and emission spectra of model compound have been simulated and compared to the experiments observations published recently. Ionization potentials (IPs), electron affinities (EAs) and energy gaps were determined. Furthermore, quantum yields, radiative and nonradiative exciton lifetime was highlighted.

  18. Assessment of Physical Stability and Antioxidant Activity of Polysiloxane Polyalkyl Polyether Copolymer-Based Creams

    Directory of Open Access Journals (Sweden)

    Atif Ali

    2013-01-01

    Full Text Available The purpose of the present work was to investigate the changes on physical stability (color, creaming, liquefaction, pH, conductivity, centrifugation, viscosity and rheological parameters by non-ionic surfactant polysiloxane polyalkyl polyether copolymer based creams following inclusion of plant extract containing phenolic compounds. The antioxidant activity of the plant extract alone and after addition in the cream was assessed using the stable free radical 1,1-diphenyl-2-picrylhydrazyl (DPPH assay. Physical stability was assessed by submitting the creams to storage at 8°C, 25°C, 40°C, and at 40°C with 70% RH (relative humidity for a period of two months. Physical characteristics of polysiloxane polyalkyl polyether copolymer based creams, that is, color, creaming, liquefaction, centrifugation and pH were noted at various intervals for 2 months. The viscosities and rheological behavior of creams were determined using a rotational rheometer. Data were analyzed by using Brookfield Software Rheocalc version (2.6 with IPC Paste and Power Law (PL math models. Cream with plant extract showed pseudo plastic behaviour with decreasing on viscosity. The Acacia nilotica (AN extract alone and the cream containing this extract showed great antioxidant and free radical scavenging activities. Power Law and IPC analysis were found to fit all the rheograms.

  19. Segmented block copolymers based on poly(butylene terephthalate) and telechelic polyesters and polyamides of dimerized fatty acids

    NARCIS (Netherlands)

    Manuel, H.J.; Gaymans, R.J.

    1993-01-01

    Segmented block copolymers (SBCs) based on poly(butylene terephthalate) (PBT) and telechelics based on dimerized fatty acids have been synthesized in the melt. The dimerized fatty acids were coupled with diols or diamines to synthesize polyesters and polyamides of low molar mass. With these telechel

  20. 长链烯烃的应用%The Application of Long Chain Olefins

    Institute of Scientific and Technical Information of China (English)

    姜秋实; 赵萌; 刘姝

    2013-01-01

    概述了长链烯烃的生产工艺,石蜡裂解和低碳烯烃齐聚.详述了长链烯烃的应用,可生产烯烃共聚体、润滑油、表面活性剂、油田化学品等.通过对它们需求量和生产能力数据进行分析,得出国内外对长链烯烃需求量日益增大,开发生产长链烯烃具有重要意义.%An overview of the production process of long chain olefins, paraffin cracking and low-carbon olefin oligomerization was given. The applications of long chain olefins were detailed, such as producing olefin copolymer, lubricants, surfactants and oil field chemicals, etc. Through the data analysis of demand for long chain olefins and production capacity, it was concluded that the demand for long chain olefins at home and abroad was increasing; the development and production of long chain olefins had a great significance.

  1. Ferroelectric polymer scaffolds based on a copolymer of tetrafluoroethylene with vinylidene fluoride: fabrication and properties.

    Science.gov (United States)

    Bolbasov, E N; Anissimov, Y G; Pustovoytov, A V; Khlusov, I A; Zaitsev, A A; Zaitsev, K V; Lapin, I N; Tverdokhlebov, S I

    2014-07-01

    A solution blow spinning technique is a method developed recently for making nonwoven webs of micro- and nanofibres. The principal advantage of this method compared to a more traditional electrospinning process is its significantly higher production rate. In this work, the solution blow spinning method was further developed to produce nonwoven polymeric scaffolds based on a copolymer of tetrafluoroethylene with vinylidene fluoride solution in acetone. A crucial feature of the proposed method is that high-voltage equipment is not required, which further improves the method's economics. Scanning electron microscopy analysis of the samples demonstrated that the surface morphology of the nonwoven materials is dependent on the polymer concentration in the spinning solution. It was concluded that an optimum morphology of the nonwoven scaffolds for medical applications is achieved by using a 5% solution of the copolymer. It was established that the scaffolds produced from the 5% solution have a fractal structure and anisotropic mechanical properties. X-ray diffraction, infrared spectroscopy, Raman spectroscopy and differential scanning calorimetry demonstrated that the fabricated nonwoven materials have crystal structures that exhibit ferroelectric properties. Gas chromatography has shown that the amount of acetone in the nonwoven material does not exceed the maximum allowable concentration of 0.5%. In vitro analysis, using the culture of motile cells, confirmed that the nonwoven material is non-toxic and does not alter the morpho-functional status of stem cells for short-term cultivation, and therefore can potentially be used in medical applications.

  2. Facile Fabrication of Gradient Surface Based on (meth)acrylate Copolymer Films

    Science.gov (United States)

    Zhang, Y.; Yang, H.; Wen, X.-F.; Cheng, J.; Xiong, J.

    2016-08-01

    This paper describes a simple and economic approach for fabrication of surface wettability gradient on poly(butyl acrylate - methyl methacrylate) [P (BA-MMA)] and poly(butyl acrylate - methyl methacrylate - 2-hydroxyethyl methacrylate) [P (BA-MMA-HEMA)] films. The (meth)acrylate copolymer [including P (BA-MMA) and P (BA-MMA-HEMA)] films are hydrolyzed in an aqueous solution of NaOH and the transformation of surface chemical composition is achieved by hydrolysis in NaOH solution. The gradient wetting properties are generated based on different functional groups on the P (BA-MMA) and P (BA-MMA-HEMA) films. The effects of both the surface chemical and surface topography on wetting of the (meth)acrylate copolymer film are discussed. Surface chemical composition along the materials length is determined by XPS, and surface topography properties of the obtained gradient surfaces are analyzed by FESEM and AFM. Water contact angle system (WCAs) results show that the P (BA-MMA-HEMA) films provide a larger slope of the gradient wetting than P (BA-MMA). Moreover, this work demonstrates that the gradient concentration of chemical composition on the poly(meth) acrylate films is owing to the hydrolysis processes of ester group, and the hydrolysis reactions that have negligible influence on the surface morphology of the poly(meth) acrylate films coated on the glass slide. The gradient wettability surfaces may find broad applications in the field of polymer coating due to the compatibility of (meth) acrylate polymer.

  3. Novel Injectable Pentablock Copolymer Based Thermoresponsive Hydrogels for Sustained Release Vaccines.

    Science.gov (United States)

    Bobbala, Sharan; Tamboli, Viral; McDowell, Arlene; Mitra, Ashim K; Hook, Sarah

    2016-01-01

    The need for multiple vaccinations to enhance the immunogenicity of subunit vaccines may be reduced by delivering the vaccine over an extended period of time. Here, we report two novel injectable pentablock copolymer based thermoresponsive hydrogels made of polyethyleneglycol-polycaprolactone-polylactide-polycaprolactone-polyethyleneglycol (PEG-PCL-PLA-PCL-PEG) with varying ratios of polycaprolactone (PCL) and polylactide (PLA), as single shot sustained release vaccines. Pentablock copolymer hydrogels were loaded with vaccine-encapsulated poly lactic-co-glycolic acid nanoparticles (PLGA-NP) or with the soluble vaccine components. Incorporation of PLGA-NP into the thermoresponsive hydrogels increased the complex viscosity of the gels, lowered the gelation temperature, and minimized the burst release of antigen and adjuvants. The two pentablock hydrogels stimulated both cellular and humoral responses. The addition of PLGA-NP to the hydrogels sustained immune responses for up to 49 days. The polymer with a higher ratio of PCL to PLA formed a more rigid gel, induced stronger immune responses, and stimulated effective anti-tumor responses in a prophylactic melanoma tumor model.

  4. Olefin metathesis in air.

    Science.gov (United States)

    Piola, Lorenzo; Nahra, Fady; Nolan, Steven P

    2015-01-01

    Since the discovery and now widespread use of olefin metathesis, the evolution of metathesis catalysts towards air stability has become an area of significant interest. In this fascinating area of study, beginning with early systems making use of high oxidation state early transition metal centers that required strict exclusion of water and air, advances have been made to render catalysts more stable and yet more functional group tolerant. This review summarizes the major developments concerning catalytic systems directed towards water and air tolerance.

  5. Synthesis and properties of two novel copolymers based on squaraine and fluorene units for solar cell materials

    Institute of Scientific and Technical Information of China (English)

    Zheng Wang; Wei Zhang; Feng Tao; Kai Ge Meng; Long Yi Xi; Ying Li; Qing Jiang

    2011-01-01

    Two novel copolymers based on squaraine and fluorine units have been synthesized through palladium catalyzed Suzuki coupling reaction and Sonogashira coupling reaction, respectively. The structures and properties of the two copolymers were characterized by FT-IR, NMR, UV-vis absorbance (Abs), gel permeation chromatography (GPC), thermal gravimetric analysis (TGA), differential scanning calorimetry (DSC) and cyclic voltammetry (CV). The solution absorption spectrums of P1 and P2 show two distinct absorption bands, one locates at 300-500 nm and the other at 600-800 nm. The absorption spectrums of P1 and P2 in films are broadened obviously and the spectral responses are extended up to 900 nm. Thermal gravimetric analysis demonstrates that the polymers are stable. Cyclic voltammetry experiment shows that the band gaps of the copolymers are 1.65 eV and 1.67 eV, respectively, suggesting their potential for applications as solar cells materials.

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

    Science.gov (United States)

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

    2016-01-07

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

  7. Comparing Ru and Fe-catalyzed olefin metathesis.

    Science.gov (United States)

    Poater, Albert; Chaitanya Vummaleti, Sai Vikrama; Pump, Eva; Cavallo, Luigi

    2014-08-01

    Density functional theory calculations have been used to explore the potential of Fe-based complexes with an N-heterocyclic carbene ligand, as olefin metathesis catalysts. Apart from a less endothermic reaction energy profile, a small reduction in the predicted upper energy barriers (≈ 2 kcal mol(-1)) is calculated in the Fe catalyzed profile with respect to the Ru catalysed profile. Overall, this study indicates that Fe-based catalysts have the potential to be very effective olefin metathesis catalysts.

  8. Immobilized molybdenum-thiosemicarbazide Schiff base complex on the surface of magnetite nanoparticles as a new nanocatalyst for the epoxidation of olefins

    Science.gov (United States)

    Mohammadikish, M.; Masteri-Farahani, M.; Mahdavi, S.

    2014-03-01

    In this work, a new magnetically recoverable nanocatalyst was developed by immobilization of thiosemicarbazide ligand on the surface of silica coated magnetite nanoparticles (SCMNPs) through Schiff base condensation and followed complexation with MoO2(acac)2. Characterization of the prepared nanocatalyst was performed with different physicochemical methods such as Fourier transform infrared (FT-IR) and atomic absorption spectroscopies, X-ray diffraction (XRD), vibrating sample magnetometry (VSM), thermogravimetric analysis (TGA), field-emission scanning electron microscopy (FE-SEM), and transmission electron microscopy (TEM). The prepared catalyst catalyzed the epoxidation of olefins and allyl alcohols with tert-butyl hydroperoxide (TBHP) and cumene hydroperoxide (CHP) quantitatively with excellent selectivity toward the corresponding epoxides under mild reaction conditions.

  9. Production and use of light olefins. Preprints of the conference

    Energy Technology Data Exchange (ETDEWEB)

    Ernst, S.; Buzzoni, R.; Leitner, W.; Lercher, J.A.; Lichtscheidl, J.; Nees, F.; Santacesaria, E. (eds.)

    2009-07-01

    Within the conference of the German Society for Petroleum and Coal Science and Technology e.V. (Hamburg, Federal Republic of Germany) in Berlin (Federal Republic of Germany) at 28th to 30th September, 2009, the following lectures were held: (1) Steamcracking - State of the Art (H. Zimmermann); (2) Diversify Feedstock Options to Olefin Production (Q. Ling et al.); (3) Syngas to lower olefins (E. Schwab et al.); (4) STAR process registered for the on-purpose production of propylene (K. Bueker); (5) The catalytic activity of zinc oxide supported on aerosil for C-H activation of light alkanes (S. Arndt et al.); (6) Novel catalytic approaches for the oxidative dehydrogenation of ethane (D. Hartmann); (7) A comparison of the active sites structures of homogeneous and heterogeneous olefin polymerisation catalysts (A. Zecchina); (8) Catalytic strategies in metathesis (C. Coperet); (9) Multi-technology integrated production and consumption of olefins (J. Popp et al.); (10) Olefin oligomerization for the production of fuels and petrochemicals (H. Olivier-Bourbigou et al.); (11) Dieselization of the world - How to increase diesel yield in a refinery (A. Dueker); (12) Isomerization of butenes: LyondellBasell's Isomplus technology development (T. Zak et al.); (13) Valuable products from butadiene, carbon dioxide and further base chemicals (A. Behr); (14) The partial oxidation of propene to propylene oxide using N{sub 2}O as an oxidant (T. Thoemmes); (15) Alternative feedstocks for olefin production: What role will ethanol play? (B.R. Maughon); (16) Production of light olefins from renewable resources - The effect of deoxygenation degree on yields of light olefins (D. Kubicka et al.); (17) Recovery of low olefins from refinery offgases (M. Bender).

  10. Synthesis of indolo[3,2-b]carbazole-based random copolymers for polymer solar cell applications

    Energy Technology Data Exchange (ETDEWEB)

    Chan, Li-Hsin, E-mail: lhchan@ncnu.edu.tw [Department of Applied Materials and Optoelectronic Engineering, National Chi Nan University, Nantou, Taiwan 54561, ROC (China); Lin, Lu-Chi; Yao, Chi-Han [Department of Applied Materials and Optoelectronic Engineering, National Chi Nan University, Nantou, Taiwan 54561, ROC (China); Liu, You-Ren; Jiang, Zong-Jhih [Department of Applied Chemistry, National Chi Nan University, Nantou, Taiwan 54561, ROC (China); Cho, Ting-Yu [Department of Applied Materials and Optoelectronic Engineering, National Chi Nan University, Nantou, Taiwan 54561, ROC (China)

    2013-10-01

    In addition to preparing two indolocarbazole-based random copolymers (named as r-PICTBT1 and r-PICTBT2), this work investigated their feasibility for bulk heterojunction polymer solar cells (PSCs). These copolymers consisted of commercially available 3,9-dibromo-5,11-dioctyl-5,11-dihydroindole[3,2-b]carbazole, 2,5-bis(trimethylstannyl) thiophene and dibromobenzo[c][1,2,5]thiadiazole by varying the feed in ratios via Stille cross-coupling reactions. The photophysical and electrochemical properties of the resulting copolymers could be fine-modulated easily by adjusting the feed ratios of monomers. Both copolymers in the thin film state exhibited two obvious peaks and a vibronic shoulder in the absorption spectra. Electrochemical experiments indicated that the highest occupied molecular orbital energy levels were − 4.95, − 5.00 eV; meanwhile, the lowest unoccupied molecular orbital energy levels were − 3.38, − 3.54 eV for r-PICTBT1 and r-PICTBT2, respectively. Bulk heterojunction PSCs composed of an electron-donor copolymer blended with an electron acceptor [6,6]-phenyl-C61-butyric acid methyl ester (PC{sub 61}BM) or [6,6]-phenyl-C71-butyric acid methyl ester (PC{sub 71}BM) at a weight ratio of 1:1 or 1:3 were investigated. Moreover, the r-PICTBT2/PC{sub 71}BM-based (w/w = 1:1) PSC performed the best with an open-circuit voltage of 0.54 V, short-circuit current of 6.83 mA/cm{sup 2}, fill factor of 0.44, and power conversion efficiency of 1.63%. - Highlights: • We report two indolocarbazole-based copolymers for photovoltaic applications. • Two copolymers exhibited excellent thermal stability. • Energy levels of copolymers can be modulated by varying the monomers ratios. • Increasing of planar monomer content leads to a relatively smooth morphology. • The optimal device performance reached a power conversion efficiency of 1.63%.

  11. New Enantiomerically Pure Alkylimido Mo-Based Complexes. Synthesis, Characterization, and Activity as Chiral Olefin Metathesis Catalysts

    Science.gov (United States)

    Pilyugina, Tatiana S.; Schrock, Richard R.; Müller, Peter; Hoveyda, Amir H.

    2008-01-01

    Molybdenum olefin metathesis catalysts that contain aliphatic 1-phenylcyclohexylimido (NPhCy) and 2-phenyl-2-adamantylimido (NPhAd) groups and (S)-Biphen or (R)-Trip)(THF) ligands (Biphen = 3,3′-di-tert-butyl-5,5′,6,6′-tetramethyl-1,1′-biphenyl-2,2′-diolate; Trip = 3,3′-bis(2,4,6-triisopropylphenyl)-2,2′-binaphtholate) have been prepared. Their catalytic activity and enantioselectivity in desymmetrization reactions such as ring-closing metathesis of amines and lactams and ring-opening/cross-metathesis of substituted norborneols with styrene were compared to the results obtained with the only known alkylimido catalyst Mo(NAd)(CHCMe2Ph)[(S)-Biphen]. The activities and enantioselectivities provided by these new chiral complexes vary significantly, but in virtually all instances explored were not superior to the adamantylimido analogs. PMID:19079732

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

    Directory of Open Access Journals (Sweden)

    Ahmed Mohamed Alsabagh

    2013-12-01

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

  13. Fouling release nanostructured coatings based on PDMS-polyurea segmented copolymers

    KAUST Repository

    Fang, Jason

    2010-05-01

    The bulk and surface characteristics of a series of coatings based on PDMS-polyurea segmented copolymers were correlated to their fouling release performance. Incorporation of polyurea segments to PDMS backbone gives rise to phase separation with the extensively hydrogen bonded hard domains creating an interconnected network that imparts mechanical rigidity. Increasing the compositional complexity of the system by including fluorinated or POSS-functionalized chain extenders or through nanoclay intercalation, confers further thermomechanical improvements. In analogy to the bulk morphology, the surface topography also reflects the compositional complexity of the materials, displaying a wide range of motifs. Investigations on settlement and subsequent removal of Ulva sporelings on those nanostructured surfaces indicate that the work required to remove the microorganisms is significantly lower compared to coatings based on standard PDMS homopolymer. All in all, the series of materials considered in this study demonstrate advanced fouling release properties, while exhibiting superior mechanical properties and, thus, long term durability. © 2010 Elsevier Ltd.

  14. Plastic solar cells based on fluorenone-containing oligomers and regioregular alternate copolymers

    Energy Technology Data Exchange (ETDEWEB)

    Demadrille, R.; Rannou, P.; Pron, A. [Laboratoire de Physique des Metaux Synthetiques, UMR5819-SPrAM (CEA-CNRS-Univ.Grenoble I), DRFMC CEA-Grenoble, 17 rue des Martyrs F-38054 Grenoble Cedex 9 (France); Firon, M.; Leroy, J. [Laboratoire Cellules et Composants, DRT-LITEN, CEA-Saclay, F-91191 Gif sur Yvette Cedex (France)

    2005-09-01

    Oligomers and regioregular copolymers based on fluorenone subunits are synthesized and used in bulk-heterojunction photovoltaic cells. These are 2,7-bis(5-[(E)-1,2-bis(3-octylthien-2-yl)ethylene])-fluoren-9-one (TVF), the product of its oxidative polymerization, that is, poly[(5,5'-(bis-(E)-1,2-bis(3-octylthien-2-yl)ethylene)-alt-(2,7-fluoren-9-one)]) (PTVF), and an alternate copolymer of fluoren-9-one and di-n-alkylbithiophene, namely poly[(5,5'-(3,3'-di-n-octyl-2,2'-bithiophene))-alt-(2,7-fluoren-9-one)] (PDOBTF). The interpenetrating networks of active layers consisting of these new compounds as electron donors and of methanofullerene [6,6]-phenyl-C{sub 61}-butyric acid methyl ester (PCBM) as an acceptor exhibit an extended absorption band in the visible part of the spectrum with an absorption edge close to 700 nm. The external power conversion efficiencies (EPCEs) and the external quantum efficiency of the various TVF-, PTVF-, and PDOBTF-based photovoltaic cells have been determined. EPCE values of up to 1 % have been achieved, which demonstrate the potential of fluorenone-based materials in solar cells. It has also been demonstrated that fluorenone subunits are efficient photon absorbers for the conversion. Interestingly, some cell parameters such as, for example, the fill factor, have been improved as compared to photovoltaic cells with a ''classical'' poly[2-methoxy-5-(3',7'-dimethyloctyloxy)-1,4-phenylenevinylene]/PCBM active layer, fabricated and studied under the same experimental conditions. (Abstract Copyright [2005], Wiley Periodicals, Inc.)

  15. Consideration of applications of olefin metathesis in synthetic fuel production

    Energy Technology Data Exchange (ETDEWEB)

    Heveling, J.

    1984-07-01

    One of the characteristics of Fischer-Tropsch synthesis and many oligomerization processes, is insufficient selectivity. Efforts have to be made to bring the products obtained in line with the market requirements. The olefin metathesis reaction has the potential to convert less desirable olefins to more useful ones and provides new ways of producing petrochemicals. Based on existing and suggested process technologies, applications of this reaction for the production of synthetic liquid fuels are discussed.

  16. Chelated Ruthenium Catalysts for Z-Selective Olefin Metathesis

    Science.gov (United States)

    Endo, Koji; Grubbs, Robert H.

    2011-01-01

    We report the development of ruthenium-based metathesis catalysts with chelating N-heterocyclic carbene (NHC) ligands which catalyze highly Z-selective olefin metathesis. A very simple and convenient synthetic procedure of such a catalyst has been developed. An intramolecular C-H bond activation of the NHC ligand, which is promoted by anion ligand substitution, forms the appropriate chelate for stereo- controlled olefin metathesis. PMID:21563826

  17. New Flexible Flame Retardant Coatings Based on Siloxane Resin and Ethylene-Vinyl Chloride Copolymer

    Directory of Open Access Journals (Sweden)

    Dorota Wesolek

    2016-12-01

    Full Text Available This work presents the effectiveness of a phosphorus-containing flame retardant based on siloxane resin and ethylene-vinyl chloride copolymer as a back-coating of fabrics. The possibility of improving flame retardant efficiency of this composition by introducing fumed silica, montmorillonite, carbon nanotubes, and graphite was evaluated. The effect of each additive on the efficiency of the composition was examined separately. Flammability tests of flame retardant-coated fabrics (natural and synthetic were carried out using pyrolysis combustion flow calorimetry (PCFC, cone calorimetry, and limiting oxygen index determination. An assessment of the ignitability of upholstered furniture containing flame retardant fabric, resistance to washing, antifungal activity, and some of the utility properties of the final newly-developed flame-retardant coating was conducted.

  18. Nanoporous membrane based on block copolymer thin film for protein drug delivery

    Science.gov (United States)

    Yang, Seung Yun; Yang, Jeong-A.; Kim, Eung-Sam; Jeon, Gumhye; Oh, Eun Ju; Choi, Kwan Yong; Hahn, Sei Kwang; Kim, Jin Kon

    2010-03-01

    We studied long term and controlled release of protein drugs by using nanoporous membranes with various pore sizes. Nanoporous membrane consists of the separation layer prepared by polystyrene-block-poly(methylmethacrylate) copolymer thin film and conventional microfiltration membrane as a support. We demonstrate a long-term constant in vitro release of bovine serum albumin (BSA)and human growth hormone ) (hGH) without their denaturation up to 2 months. A nearly constant serum concentration of hGH was maintained up to 3 weeks in SD rats. The long-term constant delivery based on this membrane for protein drugs within the therapeutic range can be highly appreciated for the patients with hormone- deficiency.

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

    NARCIS (Netherlands)

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

    2016-01-01

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

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

    Directory of Open Access Journals (Sweden)

    Antić Vesna V.

    2011-01-01

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

  1. Ferroelectric polymer scaffolds based on a copolymer of tetrafluoroethylene with vinylidene fluoride: Fabrication and properties

    Energy Technology Data Exchange (ETDEWEB)

    Bolbasov, E.N., E-mail: ebolbasov@gmail.com [Tomsk Polytechnic University, 634050, 30, Lenin Avenue, Tomsk (Russian Federation); Anissimov, Y.G., E-mail: Y.Anissimov@Griffith.edu.au [Griffith University, School of Biomolecular and Physical Sciences, Brisbane, QLD (Australia); Pustovoytov, A.V., E-mail: andrius_222@mail.ru [Tomsk Polytechnic University, 634050, 30, Lenin Avenue, Tomsk (Russian Federation); Khlusov, I.A., E-mail: khlusov63@mail.ru [Tomsk Polytechnic University, 634050, 30, Lenin Avenue, Tomsk (Russian Federation); Tomsk Scientific Research Institute of Balneology and Physiotherapy, Tomsk (Russian Federation); Zaitsev, A.A., E-mail: prim@niikf.tomsk.ru [Tomsk Scientific Research Institute of Balneology and Physiotherapy, Tomsk (Russian Federation); Zaitsev, K.V., E-mail: zaitsev-kv@mail.ru [Tomsk Scientific Research Institute of Balneology and Physiotherapy, Tomsk (Russian Federation); Lapin, I.N., E-mail: 201kiop@mail.ru [Tomsk State University, 634050, 36, Lenin Avenue, Tomsk (Russian Federation); Tverdokhlebov, S.I., E-mail: tverd@tpu.ru [Tomsk Polytechnic University, 634050, 30, Lenin Avenue, Tomsk (Russian Federation)

    2014-07-01

    A solution blow spinning technique is a method developed recently for making nonwoven webs of micro- and nanofibres. The principal advantage of this method compared to a more traditional electrospinning process is its significantly higher production rate. In this work, the solution blow spinning method was further developed to produce nonwoven polymeric scaffolds based on a copolymer of tetrafluoroethylene with vinylidene fluoride solution in acetone. A crucial feature of the proposed method is that high-voltage equipment is not required, which further improves the method's economics. Scanning electron microscopy analysis of the samples demonstrated that the surface morphology of the nonwoven materials is dependent on the polymer concentration in the spinning solution. It was concluded that an optimum morphology of the nonwoven scaffolds for medical applications is achieved by using a 5% solution of the copolymer. It was established that the scaffolds produced from the 5% solution have a fractal structure and anisotropic mechanical properties. X-ray diffraction, infrared spectroscopy, Raman spectroscopy and differential scanning calorimetry demonstrated that the fabricated nonwoven materials have crystal structures that exhibit ferroelectric properties. Gas chromatography has shown that the amount of acetone in the nonwoven material does not exceed the maximum allowable concentration of 0.5%. In vitro analysis, using the culture of motile cells, confirmed that the nonwoven material is non-toxic and does not alter the morpho-functional status of stem cells for short-term cultivation, and therefore can potentially be used in medical applications. - Highlights: • Solution blow spinning was used to fabricate nonwoven material based on VDF-TeFE. • The nonwoven material has complex spatial organization and high porosity. • It was established that the nonwoven material exhibits ferroelectric properties. • In vitro testing demonstrated that the material is non

  2. 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.

  3. Melt-processable hydrophobic acrylonitrile-based copolymer systems with adjustable elastic properties designed for biomedical applications.

    Science.gov (United States)

    Cui, J; Trescher, K; Kratz, K; Jung, F; Hiebl, B; Lendlein, A

    2010-01-01

    Acrylonitrile-based polymer systems (PAN) are comprehensively explored as versatile biomaterials having various potential biomedical applications, such as membranes for extra corporal devices or matrixes for guided skin reconstruction. The surface properties (e.g. hydrophilicity or charges) of such materials can be tailored over a wide range by variation of molecular parameters such as different co-monomers or their sequence structure. Some of these materials show interesting biofunctionalities such as capability for selective cell cultivation. So far, the majority of AN-based copolymers, which were investigated in physiological environments, were processed from the solution (e.g. membranes), as these materials are thermo-sensitive and might degrade when heated. In this work we aimed at the synthesis of hydrophobic, melt-processable AN-based copolymers with adjustable elastic properties for preparation of model scaffolds with controlled pore geometry and size. For this purpose a series of copolymers from acrylonitrile and n-butyl acrylate (nBA) was synthesized via free radical copolymerisation technique. The content of nBA in the copolymer varied from 45 wt% to 70 wt%, which was confirmed by 1H-NMR spectroscopy. The glass transition temperatures (Tg) of the P(AN-co-nBA) copolymers determined by differential scanning calorimetry (DSC) decreased from 58 degrees C to 20 degrees C with increasing nBA-content, which was in excellent agreement with the prediction of the Gordon-Taylor equation based on the Tgs of the homopolymers. The Young's modulus obtained in tensile tests was found to decrease significantly with rising nBA-content from 1062 MPa to 1.2 MPa. All copolymers could be successfully processed from the melt with processing temperatures ranging from 50 degrees C to 170 degrees C, whereby thermally induced decomposition was only observed at temperatures higher than 320 degrees C in thermal gravimetric analysis (TGA). Finally, the melt processed P

  4. Industrial processes of olefin metathesis. Pt. 1

    Energy Technology Data Exchange (ETDEWEB)

    Warwel, S.

    1987-05-01

    Olefin metathesis opens new synthetic routes to typical petrochemicals (ethylene, propylene, n-butenes), special olefins (neohexene, higher molecular linear olefins, , -dienes) and unsaturated polymers (polynorbornene, -cyclooctene, -dicyclopentadiene) in an industrial scale. The 8 metathesis processes used in industry and further possible applications of olefin metathesis are reviewed.

  5. Olefin metathesis in air

    Directory of Open Access Journals (Sweden)

    Lorenzo Piola

    2015-10-01

    Full Text Available Since the discovery and now widespread use of olefin metathesis, the evolution of metathesis catalysts towards air stability has become an area of significant interest. In this fascinating area of study, beginning with early systems making use of high oxidation state early transition metal centers that required strict exclusion of water and air, advances have been made to render catalysts more stable and yet more functional group tolerant. This review summarizes the major developments concerning catalytic systems directed towards water and air tolerance.

  6. Olefin metathesis catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Kukes, S.G.; Banks, R.L.

    1986-05-20

    A process is described for preparing a disproportionation catalyst comprising admixing a catalytically effective amount of a calcined and activated catalyst consisting essentially of at least one metal oxide selected from molybdenum oxide and tungsten oxide and a support containing a major proportion of silica or alumina with a promoting amount of a methylating agent selected from the group consisting of dimethyl sulfate, dimethylsulfoxide, trimethyloxonium tetrafluorborate, methyl iodide, and methyl bromide, and subjecting same to inert atmospheric conditions for the methylating agent to promote the activity of the calcined molybdenum and tungsten oxides for the disproportionation of olefins.

  7. Olefin metathesis in air

    Science.gov (United States)

    Piola, Lorenzo; Nahra, Fady

    2015-01-01

    Summary Since the discovery and now widespread use of olefin metathesis, the evolution of metathesis catalysts towards air stability has become an area of significant interest. In this fascinating area of study, beginning with early systems making use of high oxidation state early transition metal centers that required strict exclusion of water and air, advances have been made to render catalysts more stable and yet more functional group tolerant. This review summarizes the major developments concerning catalytic systems directed towards water and air tolerance. PMID:26664625

  8. Plasmonic nanostructures based on block copolymer templates for efficient organic solar cells

    Science.gov (United States)

    Go, Seung Jae; Lee, Dong-Eun; Lee, Dong Hyun; Chin, Byung Doo

    2016-01-01

    Plasmonic nanostructures fabricated from self-assembled patterns of block copolymers (BCPs) were applied for organic solar cells (OSCs). A thin film of a cylinder-forming polystrene- block-poly(2-vinylpyridine) copolymer (PS- b-P2VP) was spin-coated on the transparent electrode of the OSCs, where nanostructures such as dot, dot with mixed line, and line patterns emerged during different solvent annealing processes. Selective conversion of hydrogen tetrachloroaurate (III) (HAuCl4) in P2VP blocks yielded gold (Au) nanostructures, which were used to trigger the localized surface plasmonic resonance (LSPR) effect at the OSCs. Plasmonic nanostructures with almost similar scales of BCP patterns were formed at the anode/buffer interface at the OSC, showing no-table enhancements of the short circuit current ( J sc) and the power conversion efficiency (3.57% for the reference compared to 4.35% for the optimum LSPR-OSC) as the size and the anisotropy of Au patterns changed from a simple dot through an integrated dot-line pattern to a line pattern. Based on the experimental analyses of the light absorption, photoluminescence, and exciton lifetime of OSC, such an enhancement would be mainly attributed to size-dependent LSPR-induced scattering and absorption at the OSC's active layer, which is not in intimate contact with the Au nanostructures. Up to a 26% increase in the power conversion efficiency could be observed at the plasmonic structures from BCP template, providing an accurately tuning and powerful tailoring of the LSPR-enhancing patterns for the OSCs.

  9. Targeted drug delivery nanosystems based on copolymer poly(lactide)-tocopheryl polyethylene glycol succinate for cancer treatment

    Science.gov (United States)

    Thu Ha, Phuong; Nguyen, Hoai Nam; Doan Do, Hai; Thong Phan, Quoc; Nguyet Tran Thi, Minh; Phuc Nguyen, Xuan; Nhung Hoang Thi, My; Huong Le, Mai; Nguyen, Linh Toan; Quang Bui, Thuc; Hieu Phan, Van

    2016-03-01

    Along with the development of nanotechnology, drug delivery nanosystems (DDNSs) have attracted a great deal of concern among scientists over the world, especially in cancer treatment. DDNSs not only improve water solubility of anticancer drugs but also increase therapeutic efficacy and minimize the side effects of treatment methods through targeting mechanisms including passive and active targeting. Passive targeting is based on the nano-size of drug delivery systems while active targeting is based on the specific bindings between targeting ligands attached on the drug delivery systems and the unique receptors on the cancer cell surface. In this article we present some of our results in the synthesis and testing of DDNSs prepared from copolymer poly(lactide)-tocopheryl polyethylene glycol succinate (PLA-TPGS), which carry anticancer drugs including curcumin, paclitaxel and doxorubicin. In order to increase the targeting effect to cancer cells, active targeting ligand folate was attached to the DDNSs. The results showed copolymer PLA-TPGS to be an excellent carrier for loading hydrophobic drugs (curcumin and paclitaxel). The fabricated DDNSs had a very small size (50-100 nm) and enhanced the cellular uptake and cytotoxicity of drugs. Most notably, folate-decorated paclitaxel-loaded copolymer PLA-TPGS nanoparticles (Fol/PTX/PLA-TPGS NPs) were tested on tumor-bearing nude mice. During the treatment time, Fol/PTX/PLA-TPGS NPs always exhibited the best tumor growth inhibition compared to free paclitaxel and paclitaxel-loaded copolymer PLA-TPGS nanoparticles. All results evidenced the promising potential of copolymer PLA-TPGS in fabricating targeted DDNSs for cancer treatment.

  10. Nanoporous poly(lactide) by olefin metathesis degradation.

    Science.gov (United States)

    Bertrand, Arthur; Hillmyer, Marc A

    2013-07-31

    We describe an approach to ordered nanoporous poly(lactide) that relies on self-assembly of poly(butadiene)-poly(lactide) (PB-PLA) diblock copolymers followed by selective degradation of PB using olefin metathesis. The block copolymers were obtained by a combination of anionic and ring-opening transesterification polymerizations. The molar mass of each block was tailored to target materials with either a lamellar or cylindrical microphase-separated morphology. Orientation of these nanoscale domains was induced in thin films and monolithic samples through solvent annealing and mechanical deformation, respectively. Selective degradation of PB was achieved by immersing the samples in a solution of Grubbs first-generation catalyst in cyclohexane, a nonsolvent for PLA. Successful elimination of PB was confirmed by size-exclusion chromatography and (1)H NMR spectroscopy. Direct imaging of the resulting nanoporous PLA was obtained by scanning electron microscopy.

  11. 基于RAFT聚合策略合成功能化聚烯烃嵌段聚合物的研究进展%Progress of synthesis of functional polyolefin block copolymers via strategy based on RAFT polymerization

    Institute of Scientific and Technical Information of China (English)

    毛国梁; 王欣; 宁英男; 马志

    2012-01-01

    首先介绍了可逆加成-断裂链转移聚合(RAFT)的聚合机理及其常用的RAFT试剂,并与其它两种活性可控自由基聚合[氮氧化合物媒介的自由基聚合(NMP)和原子转移自由基聚合(ATRP)]进行了简单的优缺点对比。其次,介绍了近些年在基于RAFT聚合制备功能化聚烯烃嵌段聚合物研究中取得的进展,重点综述了制备功能化聚烯烃嵌段聚合物时所采用的6种方法,包括①烯烃配位聚合与RAFT聚合相结合;②阴离子聚合与RAFT聚合相结合;③阳离子聚合与RAFT聚合相结合;④Click反应与RAFT聚合相结合;⑤开环聚合与RAFT聚合相结合;⑥叶立德活性聚合与RAFT聚合相结合。最后,对基于RAFT聚合策略设计合成功能化聚烯烃嵌段聚合物的研究前景与实际应用进行了展望。%The paper briefly describes the general polymerization mechanism of reversible addition-fragmentation chain transfer(RAFT) polymerization and some common RAFT agents.The RAFT polymerization is compared with other two kinds of active controlled radical polymerizations [nitrogen oxide mediated free radical polymerization(NMP) and atom transfer radical polymerization(ATRP)].The recent progress of synthesis of functional polyolefin block copolymers on the basis of RAFT polymerization is reviewed.Six kinds of combined methodologies based on RAFT polymerization aiming at the synthesis of functional polyolefin block copolymers are introduced:① Combination of olefin coordination polymerization and RAFT polymerization,②Combination of living anionic polymerization and RAFT polymerization,③Combination of cationic polymerization and RAFT polymerization,④ Combination of Click chemistry and RAFT polymerization,⑤ Combination of ring-opening polymerization and RAFT polymerization,⑥Combination of living polymerization of Ylides and RAFT polymerization.Finally,the prospect of the design and synthesis of functional polyolefin block copolymers via

  12. Novel Blue Light-emitting PPV-based Copolymer Containing Triazole and Carbazole Units

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    A novel alternating conjugated copolymer containing triazole and carbazole units was synthesized by the Wittig reaction. The resulting bipolar conjugated polymer emits a pure light with good thermal stability, which is a promising candidate for polymer light emitting display.

  13. Novel Blue Light—emitting PPV—based Copolymer Containing Trazole and Carbazole Units

    Institute of Scientific and Technical Information of China (English)

    ZeLIU; LiXiangWANG; 等

    2002-01-01

    A novel alternating conjugated copolymer containing triazole and carbazole units was synthesized by the Witting reaction. The resulting bipolar conjugated polymer emits a pure light with good thermal stability, which is a promising candidate for polymer light emitting display.

  14. Synthesis and Characterization of Quinoxaline-Based Low-Bandgap Copolymers for Bulk Heterojunction Solar Cells

    Science.gov (United States)

    Lee, Yoonkyoo; Jo, Won Ho

    2011-03-01

    A series of low-bandgap alternating copolymers consisting of quinoxaline derivatives and electron-donating carbazole or fluorene were synthesized via the Suzuki coupling reaction. For the purpose to improve the molecular packing of polymer chains and to enhance the charge carrier mobility in the packing direction, a new quinoxaline derivative, 5,8-dithien-2-yl-dibenzophenazine which has perfectly planar polycyclic structure, was synthesized and introduced as a new building block for alternating copolymers instead of frequently-used 5,8-dithien-2-yl-2,3-diphenylquinoxaline. The use of planar quinoxaline derivative exhibited better optical, electrochemical, and structural properties of the resulting copolymers as compared to those of polymers with less planar quinoxaline derivatives. Charge transport and photovoltaic properties of these two classes of copolymers are compared and discussed.

  15. Flocculation of chromite ore fines suspension using polysaccharide based graft copolymers

    Indian Academy of Sciences (India)

    N C Karmakar; B S Sastry; R P Singh

    2002-11-01

    Graft copolymers are being experimented at the laboratory scale as flocculants. All the four graft copolymers, viz. starch--polyacrylamide, amylopectin--polyacrylamide, sodium alginate--polyacylamide and carboxymethyl cellulose--polyacrylamide performed well as flocculants on chromite ore fines suspension. Amylopectin--polyacrylamide, in particular, performed superior to the rest of the series from the point of view of settling velocity of flocs which is the most important aspect in solid–liquid separation.

  16. Supramolecular gels of poly-α-cyclodextrin and PEO-based copolymers for controlled drug release.

    Science.gov (United States)

    Simões, Susana M N; Veiga, Francisco; Ribeiro, Ana C F; Figueiras, Ana R; Taboada, Pablo; Concheiro, Angel; Alvarez-Lorenzo, Carmen

    2014-08-01

    The aim of this work was to prepare syringeable supramolecular gels of α-cyclodextrin-polymer (poly-αCD) with various poly(ethylene oxide) (PEO)-based copolymers, which can be suitable to form depots for controlled drug release. A series of water-soluble poly-αCDs was synthesized from αCD by crosslinking with epichlorohydrin in alkaline medium. The chemical composition of the polymers was characterized by NMR (αCD content>53%) and the molecular weight was evaluated using static light scattering (SLS). Supramolecular assemblies occurred by mixing poly-αCD (20-40% w/v) with a PEO-based polymer (i.e., PEG, Pluronic® F127 or Tetronic® 908) (10-15% w/v). Phase separation was observed and the αCD content in each phase was determined by means of the phenol-sulfuric acid colorimetric method. Formation of poly-αCD/PEO-based polymer 3D-supramolecular complexes was confirmed by diffusion-ordered NMR spectroscopy (DOSY) and X-ray diffractometry. The supramolecular assemblies showed good cytocompatibility against SAOS-2 cells and in the HET-CAM test. The supramolecular gels were able to sustain the release of vancomycin for at least 5 days at 37 °C, more efficiently than dispersions of each polymer component in separate. These results open new possibilities in the design of novel controlled delivery systems for the treatment of bone infections.

  17. Mechanistic studies of olefin metathesis

    Energy Technology Data Exchange (ETDEWEB)

    Grubbs, R.H.

    1979-03-01

    A review covers studies of the olefin metathesis mechanism which indicated that the reaction proceeds by a non-pairwise mechanism; detailed mechanistic studies on the homogeneously and heterogeneously catalyzed metathesis; and stereochemical investigations.

  18. A block copolymer based on isobutylene and ethylene oxide as a deemulsifier for oil

    Energy Technology Data Exchange (ETDEWEB)

    Kirpichnikov, P.A.; Akhmadeyev, G.M.; Askarov, R.Z.; Beresnev, V.V.; Gnedenkov, D.A.; Gusev, V.I.; Osipova, T.M.; Petrov, A.G.; Tronov, V.P.; Zaboristov, V.N.

    1983-01-01

    The production of new chemical compounds which have deemulsifying capability and which provide a high degree of dehydration and a high process speed at room temperature with the cited properties is determined by a new chemical structural block copolymer (SPL) based on isobutylene and ethylene oxide, which is expressed by the following formula: H(OCH2CH2)mOC(O)CH2(CMe2CH2)nCHMeC(O)-O(CH2CH2O)pM, where m = p = 5 to 20 and n = 15 to 26. The cited copolymers are produced through oxyethylation of oligoisobutylene with terminal carboxyl groups at 160 to 180 degrees over 8 to 20 hours in the presence of an alkaline catalyst (Kt). Example. Oxyethylation is conducted at atmospheric pressure. Thirty grams (0.03 gram moles) of oligoisobutylene with terminal COOH groups are placed in a flask at n = 15, along with 0.2 grams (0.0035 gram moles) of KOH as a catalyst. The contents of the flask are heated and ethylene oxide is fed in at 160 or 180 degrees with continuous mixing of the reaction mixture. The volume of attached ethylene oxide is determined based on the gain in weight and in this particular case it is 13.58 grams (0.31 gram moles) and equals m = p = 5. A product output of 43.58 grams is 100 percent. The weight of a mole is 1,412. The gross formula is C85Hl68014. The calculated content in percent is 72.2 carbon and 11.9 hydrogen and that found is 72.0 carbon and 12.1 hydrogen. The use of the proposed deemulsifiers makes it possible to speed up the technology in the stage of desalinization of oil since the use of an electrical field leads to an increase in the expense and a complication of the process of oil preparation. Moreover, the increased temperature (65 degrees) leads to a loss in the low boiling point oil fractions which are a valuable petrochemical raw material.

  19. Facile Synthesis of Magnetic Copolymer Microspheres Based on Poly(glycidyl methacrylate-co-N-isopropylacrylamide/Fe3O4 by Suspension Photopolymerization

    Directory of Open Access Journals (Sweden)

    Siti Zulaikha Mazlan

    2014-01-01

    Full Text Available Magnetic copolymer based on poly(glycidyl methacrylate-co-N-isopropylacrylamide microspheres was prepared by 2,2-dimethoxy-2-phenylacetophenone- (DMPP- photo initiated and poly(vinyl alcohol- (PVA- stabilized single step suspension photopolymerization. The effect of chemical interaction, morphology, and thermal properties by adding 0.1% w/v Fe3O4 in the copolymer was investigated. Infrared analysis (FTIR showed that (C=C band disappeared after copolymerization, indicating that the magnetic copolymer microspheres were successfully synthesized and two important bands at 908 cm−1 and 1550 cm−1 appear. These are associated with the epoxy group stretching of GMA and secondary amide (N–H/C–H deformation vibration of NIPAAm in magnetic microspheres. The X-ray diffraction (XRD result proved the incorporation of Fe3O4 nanoparticles with copolymer microspheres as peak of Fe3O4 was observed. Morphology study revealed that magnetic copolymer exhibited uniform spheres and smoother appearance when entrapped with Fe3O4 nanoparticles. The lowest percentage of Fe3O4 nanoparticles leached from the copolymer microspheres was obtained at pH 7. Finally, thermal property of the copolymer microspheres was improved by adding a small amount of Fe3O4 nanoparticles that has been shown from the thermogram.

  20. Fabrication and Characterization of Magnetoresponsive Electrospun Nanocomposite Membranes Based on Methacrylic Random Copolymers and Magnetite Nanoparticles

    Directory of Open Access Journals (Sweden)

    Ioanna Savva

    2012-01-01

    Full Text Available Magnetoresponsive polymer-based fibrous nanocomposites belonging to the broad category of stimuli-responsive materials, is a relatively new class of “soft” composite materials, consisting of magnetic nanoparticles embedded within a polymeric fibrous matrix. The presence of an externally applied magnetic field influences the properties of these materials rendering them useful in numerous technological and biomedical applications including sensing, magnetic separation, catalysis and magnetic drug delivery. This study deals with the fabrication and characterization of magnetoresponsive nanocomposite fibrous membranes consisting of methacrylic random copolymers based on methyl methacrylate (MMA and 2-(acetoacetoxyethyl methacrylate (AEMA (MMA-co-AEMA and oleic acid-coated magnetite (OA·Fe3O4 nanoparticles. The AEMA moieties containing β-ketoester side-chain functionalities were introduced for the first time in this type of materials, because of their inherent ability to bind effectively onto inorganic surfaces providing an improved stabilization. For membrane fabrication the electrospinning technique was employed and a series of nanocomposite membranes was prepared in which the polymer content was kept constant and only the inorganic (OA·Fe3O4 content varied. Further to the characterization of these materials in regards to their morphology, composition and thermal properties, assessment of their magnetic characteristics disclosed tunable superparamagnetic behaviour at ambient temperature.

  1. Molecular architectures based on pi-conjugated block copolymers for global quantum computation

    Energy Technology Data Exchange (ETDEWEB)

    Mujica Martinez, C A; Arce, J C [Universidad del Valle, Departamento de QuImica, A. A. 25360, Cali (Colombia); Reina, J H [Universidad del Valle, Departamento de Fisica, A. A. 25360, Cali (Colombia); Thorwart, M, E-mail: camujica@univalle.edu.c, E-mail: j.reina-estupinan@physics.ox.ac.u, E-mail: jularce@univalle.edu.c [Institut fuer Theoretische Physik IV, Heinrich-Heine-Universitaet Duesseldorf, 40225 Duesseldorf (Germany)

    2009-05-01

    We propose a molecular setup for the physical implementation of a barrier global quantum computation scheme based on the electron-doped pi-conjugated copolymer architecture of nine blocks PPP-PDA-PPP-PA-(CCH-acene)-PA-PPP-PDA-PPP (where each block is an oligomer). The physical carriers of information are electrons coupled through the Coulomb interaction, and the building block of the computing architecture is composed by three adjacent qubit systems in a quasi-linear arrangement, each of them allowing qubit storage, but with the central qubit exhibiting a third accessible state of electronic energy far away from that of the qubits' transition energy. The third state is reached from one of the computational states by means of an on-resonance coherent laser field, and acts as a barrier mechanism for the direct control of qubit entanglement. Initial estimations of the spontaneous emission decay rates associated to the energy level structure allow us to compute a damping rate of order 10{sup -7} s, which suggest a not so strong coupling to the environment. Our results offer an all-optical, scalable, proposal for global quantum computing based on semiconducting pi-conjugated polymers.

  2. Synthesis of Well-Defined Polyethylene-Based 3-Miktoarm Star Copolymers and Terpolymers

    KAUST Repository

    Zhang, Zhen

    2016-03-25

    Novel polyethylene (PE)-based 3-miktoarm star copolymers A2B, (AB)2B and terpolymers (AC)2(BC) [A: PE; B, C: polystyrene (PS) or poly(methyl methacrylate) (PMMA)] were synthesized by combining boron chemistry, polyhomologation, and atom transfer radical polymerization (ATRP). 1,4-Pentadiene-3-yl 2-bromo-2-methylpropanoate was first synthesized followed by hydroboration with thexylborane to afford B-thexylboracyclanes, a multi-heterofunctional initiator with two initiating sites for polyhomologation and one for ATRP. After polyhomologation of dimethylsulfoxonium methylide the α,ω-dihydroxyl polyethylene (PE-OH)2-Br produced served as macroinitiator for the ATRP of styrene to afford (PE-OH)2-(PS-Br). Both (PE-OH)2-Br and (PE-OH)2-(PS-Br) were transformed to two new trifunctional macroinitiators (PE-Br)2-Br and (PE-Br)2-(PS-Br) through esterification reactions and used for the synthesis of (AB)2B and (AC)2(BC) 3-miktoarm star co/terpolymers. All intermediates and final products were characterized by 1H NMR, high temperature gel permeation chromatography (HT-GPC), and differential scanning calorimetry (DSC). The synthetic method is a general one and can be used for the synthesis of complex PE-based architectures by combination with other living/living-controlled polymerization techniques. © 2016 American Chemical Society.

  3. An amphiphilic graft copolymer-based nanoparticle platform for reduction-responsive anticancer and antimalarial drug delivery

    Science.gov (United States)

    Najer, Adrian; Wu, Dalin; Nussbaumer, Martin G.; Schwertz, Geoffrey; Schwab, Anatol; Witschel, Matthias C.; Schäfer, Anja; Diederich, François; Rottmann, Matthias; Palivan, Cornelia G.; Beck, Hans-Peter; Meier, Wolfgang

    2016-08-01

    Medical applications of anticancer and antimalarial drugs often suffer from low aqueous solubility, high systemic toxicity, and metabolic instability. Smart nanocarrier-based drug delivery systems provide means of solving these problems at once. Herein, we present such a smart nanoparticle platform based on self-assembled, reduction-responsive amphiphilic graft copolymers, which were successfully synthesized through thiol-disulfide exchange reaction between thiolated hydrophilic block and pyridyl disulfide functionalized hydrophobic block. These amphiphilic graft copolymers self-assembled into nanoparticles with mean diameters of about 30-50 nm and readily incorporated hydrophobic guest molecules. Fluorescence correlation spectroscopy (FCS) was used to study nanoparticle stability and triggered release of a model compound in detail. Long-term colloidal stability and model compound retention within the nanoparticles was found when analyzed in cell media at body temperature. In contrast, rapid, complete reduction-triggered disassembly and model compound release was achieved within a physiological reducing environment. The synthesized copolymers revealed no intrinsic cellular toxicity up to 1 mg mL-1. Drug-loaded reduction-sensitive nanoparticles delivered a hydrophobic model anticancer drug (doxorubicin, DOX) to cancer cells (HeLa cells) and an experimental, metabolically unstable antimalarial drug (the serine hydroxymethyltransferase (SHMT) inhibitor (+/-)-1) to Plasmodium falciparum-infected red blood cells (iRBCs), with higher efficacy compared to similar, non-sensitive drug-loaded nanoparticles. These responsive copolymer-based nanoparticles represent a promising candidate as smart nanocarrier platform for various drugs to be applied to different diseases, due to the biocompatibility and biodegradability of the hydrophobic block, and the protein-repellent hydrophilic block.Medical applications of anticancer and antimalarial drugs often suffer from low aqueous

  4. Equilibrium and kinetics study on hexavalent chromium adsorption onto diethylene triamine grafted glycidyl methacrylate based copolymers

    Energy Technology Data Exchange (ETDEWEB)

    Maksin, Danijela D., E-mail: dmaksin@vinca.rs [University of Belgrade, Vinca Institute of Nuclear Sciences, P.O. Box 522, Belgrade (Serbia); Nastasovic, Aleksandra B., E-mail: anastaso@chem.bg.ac.rs [University of Belgrade, Institute of Chemistry, Technology and Metallurgy, Njegoseva 12, Belgrade (Serbia); Milutinovic-Nikolic, Aleksandra D., E-mail: snikolic@nanosys.ihtm.bg.ac.rs [University of Belgrade, Institute of Chemistry, Technology and Metallurgy, Njegoseva 12, Belgrade (Serbia); Surucic, Ljiljana T., E-mail: ljilja_m@yahoo.com [University of Belgrade, Faculty of Forestry, Kneza Viseslava 1, Belgrade (Serbia); Sandic, Zvjezdana P., E-mail: zvjezdana.sandic@gmail.com [Faculty of Science, Mladena Stojanovica 2, Banja Luka, Bosnia and Herzegovina (Bosnia and Herzegowina); Hercigonja, Radmila V., E-mail: radah@ffh.bg.ac.rs [University of Belgrade, Faculty of Physical Chemistry, Studentski trg 12-16, 11001 Belgrade (Serbia); Onjia, Antonije E., E-mail: onjia@vinca.rs [University of Belgrade, Vinca Institute of Nuclear Sciences, P.O. Box 522, Belgrade (Serbia)

    2012-03-30

    Highlights: Black-Right-Pointing-Pointer Methacrylate based copolymers grafted with diethylene triamine as Cr(VI) sorbents. Black-Right-Pointing-Pointer Chemisorption and pore diffusion are characteristics of this sorption system. Black-Right-Pointing-Pointer Langmuir isotherm provided best fit and maximum adsorption capacity was 143 mg g{sup -1}. Black-Right-Pointing-Pointer Cr(VI) sorption onto amino-functionalized copolymer was endothermic and spontaneous. Black-Right-Pointing-Pointer A simple, efficient and cost-effective hexavalent chromium removal method. - Abstract: Two porous and one non-porous crosslinked poly(glycidyl methacrylate-co-ethylene glycol dimethacrylate) [abbreviated PGME] were prepared by suspension copolymerization and functionalized with diethylene triamine [abbreviated PGME-deta]. Samples were characterized by elemental analysis, mercury porosimetry, scanning electron microscopy with energy-dispersive X-ray spectroscopy, and transmission electron microscopy. Kinetics of Cr(VI) sorption by PGME-deta were investigated in batch static experiments, in the temperature range 25-70 Degree-Sign C. Sorption was rapid, with the uptake capacity higher than 80% after 30 min. Sorption behavior and rate-controlling mechanisms were analyzed using five kinetic models (pseudo-first order, pseudo-second order, Elovich, intraparticle diffusion and Bangham model). Kinetic studies showed that Cr(VI) adsorption adhered to the pseudo-second-order model, with definite influence of pore diffusion. Equilibrium data was tested with Langmuir, Freundlich and Tempkin adsorption isotherm models. Langmuir model was the most suitable indicating homogeneous distribution of active sites on PGME-deta and monolayer sorption. The maximum adsorption capacity from the Langmuir model, Q{sub max}, at pH 1.8 and 25 Degree-Sign C was 143 mg g{sup -1} for PGME2-deta (sample with the highest amino group concentration) while at 70 Degree-Sign C Q{sub max} reached the high value of 198

  5. Alternative routes to olefins. Chances and challenges

    Energy Technology Data Exchange (ETDEWEB)

    Meiswinkel, A.; Delhomme, C.; Ponceau, M. [Linde AG, Pullach (Germany)

    2013-11-01

    In the future, conventional raw materials which are used for the production of olefins will get shorter and more expensive and alternative raw materials and production routes will gain importance. Natural gas, coal, shale oil or bio-mass are potential sources for the production of olefins, especially ethylene and propylene, as major base chemicals. Several potential production routes were already developed in the past, but cost, energy and environmental considerations might make these unattractive or unfeasible in comparison to traditional processes (e.g. steam cracking). Other processes such as methanol to olefins processes were successfully developed and first commercial units are running. In addition, combination of traditional processes (e.g. coal/biomass gasification, Fischer-Tropsch and steam cracking) might enable new pathways. Besides, dehydration of ethanol is opening direct routes from biomass to 'green' ethylene. However, for these 'bio-routes', feedstock availability and potential land use conflict with food production (sugar cane, wheat,..) still need to be evaluated. finally, new oxidative routes, including processes such as oxidative coupling of methane or oxidative dehydrogenation, are still at an early development stage but present potential for future industrial applications. (orig.) (Published in summary form only)

  6. Perfluorinated carbon-chain copolymers with functional groups and cation exchange membranes based on them: synthesis, structure and properties

    Science.gov (United States)

    Kirsh, Yu E.; Smirnov, S. A.; Popkov, Yu M.; Timashev, Sergei F.

    1990-06-01

    The review is devoted to perfluorinated polymers with sulphonic and carboxylic acid groups and to cation exchange membranes based on them. The synthesis is described of copolymers of tetrafluoroethylene with perfluorovinyl ethers containing functional groups by radical copolymerisation in an organic medium and in aqueous emulsions. Special features of the copolymerisation and approaches to obtaining copolymers with set characteristics are discussed. Data are presented on the structure and physicochemical properties of the polymeric films. Attempts to form membranes from the polymers obtained, the means of strengthening them and methods for chemical modification are described. Data are correlated on the influence of structure and polymer composition and the nature of the functional groups on the electrochemical characteristics of membranes. Special features of the functioning of perfluorinated membranes in the process for making chlorine and alkali by the electrolysis of sodium chloride solution are considered. The bibliography has 104 references.

  7. Photoluminescent nanocomposite materials based on SBMA copolymer and CdS

    Science.gov (United States)

    Iovu, M.; Enachescu, M.; Culeac, I.; Verlan, V.; Robu, S.; Bojin, D.; Nistor, Iu.; Cojocaru, I.

    2015-02-01

    We present experimental results on copolymer-based nanocomposite made of styrene with butyl methacrylate (SBMA) (1:1) and inorganic semiconductor CdS. Thin film composite samples have been characterized by UV-Vis absorption and photoluminescent spectroscopy, as well as by transmission electron microscopy. Transmission electron microscope (TEM) examination confirms a relatively narrow distribution of CdS nanoclusters in the SBMA matrix, which covers the range 2-10 nm. On the other side, the average CdS particles size estimated from the position of first excitonic peak in the UV-Vis absorption spectrum was found to be 2.8 nm and 4.4 nm for two samples with different duration of thermal treatment, which is in good agreement with photoluminescence (PL) experimental data. The PL spectrum for CdS nanocrystals is dominated by near-band-edge emission. The relatively narrow line width (40-45 nm) of the main PL band suggests the nanoparticles having narrow size distribution. On the other side, relatively low PL emission from surface trap states at longer wavelengths were observed in the region 500-750 nm indicating on recombination on defects. Key words: nanocomposite, polymer matrix, photoluminescence,

  8. Efficient photovoltaic cells from low band-gap fluorene-based copolymer

    Institute of Scientific and Technical Information of China (English)

    Tian Ren-Yu; Yang Ren-Qiang; Peng Jun-Biao; Cao Yong

    2005-01-01

    Polymer photovoltaic cells based on low band-gap copolymer, poly [2,7-(9,9-dioctyl) fluorene-co-5,5'-(4,7-diselenophenyl)-2,2'-yl-2,1,3-benzothiadiazole] (PFSeBT) are investigated, focusing on the effects of cathode and blend concentration on device performance. The best device, with active layer from PFSeBT:PCBM=1:2 blend and with LiF/Al as cathode, achieves an open-circuit voltage of 1.00V, a short-circuit current density of 4.42mA/cm2, and energy conversion efficiency of 1.67% under AM1.5 illumination (100mW/cm2).The short-circuit current density indicates the dependence of power law on the incident light intensity with a power index of 0.887. All devices have a spectral response up to 680nm. The results indicate that PFSeBT is a potential polymer functioning as an electron donor in polymer photovoltaic cells.

  9. Olefin cross-metathesis for the synthesis of alkenyl acyclonucleoside phosphonates.

    Science.gov (United States)

    Bessières, Maxime; De Schutter, Coralie; Roy, Vincent; Agofoglio, Luigi A

    2014-12-12

    The detailed synthetic protocol for the straightforward, efficient synthesis of various alkenyl acyclonucleosides, including challenging trisubstituted alkenyl acyclonucleoside phosphonates, is described. The key step of those syntheses is an olefin cross-metathesis reaction between two olefins selected based on their reactivity using well-defined ruthenium alkylidene catalysts.

  10. Effects of Molecular Structure on Intramolecular Charge Carrier Transport in Dithieno [3,2-b: 2,3-d] Pyrrole-Based Conjugated Copolymers

    Directory of Open Access Journals (Sweden)

    Yoshihito Honsho

    2012-01-01

    Full Text Available Intramolecular mobility of positive charge carriers in conjugated polymer films based on dithieno [2,3-b: 2,3-d] pyrrole (DTP is studied by time-resolved microwave conductivity (TRMC. A series of DTP homopolymer and copolymers combined with phenyl, 2,2-biphenyl, thiophene, 2,2-bithiophene, and 9,9-dioctylfluorene were synthesized by Suzuki-Miyaura and Yamamoto coupling reactions. Polymers containing DTP unit are reported to show high value of hole mobility measured by FET method, and this type of polymers is expected to have stable HOMO orbitals which are important for hole transportation. Among these copolymers, DTP coupled with 9,9-dioctylfluorene copolymer showed the highest charge carrier mobility as high as 1.7 cm2/Vs, demonstrating an excellent electrical property on rigid copolymer backbones.

  11. Nanoparticle-based capillary electroseparation of proteins in polymer capillaries under physiological conditions

    DEFF Research Database (Denmark)

    Nilsson, C.; Harwigsson, I.; Becker, K.

    2010-01-01

    Totally porous lipid-based liquid crystalline nanoparticles were used as pseudostationary phase for capillary electroseparation with LIF detection of proteins at physiological conditions using unmodified cyclic olefin copolymer capillaries (Topas (R), 6.7 cm effective length). In the absence of n...... at protein friendly conditions. The developed capillary-based method facilitates future electrochromatography of proteins on polymer-based microchips under physiological conditions and enables the initial optimization of separation conditions in parallel to the chip development....

  12. Preparation and characterization of polyethylene based graft copolymers. Applications in the immobilization of enzymes

    Science.gov (United States)

    Ferreira, L. M.; Rocha, J. M. S.; Andrade, M. E.; Gil, M. H.

    1998-06-01

    In the last few years new copolymeric supports for the immobilization of biological compounds have been developed. The graft copolymer polyethylene-g.co-hydroxyethyl methacrylate, partially hydrolyzed, has shown to be a very promising support for this purpose. The more recent work in the preparation and characterization of this copolymer, as well as the immobilization of a lipase, is reported in this paper. Branches of poly(hydroxyethyl methacrylate) were grafted onto low density polyethylene by using gamma radiation. The influence of the presence and absence of air, as well as the monomer concentration on the yield of grafting were evaluated. The obtained copolymers were characterized by DSC and FTIR. The influence of the support properties on the synthesis biocatalytic activity was detected.

  13. Biomimetic potential of some methacrylate-based copolymers: a comparative study.

    Science.gov (United States)

    Zecheru, Teodora; Filmon, Robert; Rusen, Edina; Mărculescu, Bogdan; Zerroukhi, Amar; Cincu, Corneliu; Chappard, Daniel

    2009-11-01

    Preparation of new biocompatible materials for bone recovery has consistently gained interest in the last few decades. Special attention was given to polymers that contain negatively charged groups, such as phosphate, carboxyl, and sulfonic groups toward calcification. This present paper work demonstrates that other functional groups present also potential application in bone pathology. New copolymers of 2-hydroxyethyl methacrylate with diallyldimethylammonium chloride (DADMAC), glycidyl methacrylate (GlyMA), methacrylic acid (MAA), 2-methacryloyloxymethyl acetoacetate (MOEAA), 2-methacryloyloxyethyltriethylammonium chloride (MOETAC), and tetrahydrofurfuryl methacrylate (THFMA) were obtained. The copolymers were characterized by FTIR, swelling potential, and they were submitted to in vitro tests for calcification and cytotoxicity evaluation. GlyMA and MOETAC-containing copolymers show promising results for further in vivo mineralization tests, as a potential alternative to the classical bone grafts, in bone tissue engineering.

  14. Stereospecific olefin polymerization catalysts

    Science.gov (United States)

    Bercaw, John E.; Herzog, Timothy A.

    1998-01-01

    A metallocene catalyst system for the polymerization of .alpha.-olefins to yield stereospecific polymers including syndiotactic, and isotactic polymers. The catalyst system includes a metal and a ligand of the formula ##STR1## wherein: R.sup.1, R.sup.2, and R.sup.3 are independently selected from the group consisting of hydrogen, C.sub.1 to C.sub.10 alkyl, 5 to 7 membered cycloalkyl, which in turn may have from 1 to 3 C.sub.1 to C.sub.10 alkyls as a substituent, C.sub.6 to C.sub.15 aryl or arylalkyl in which two adjacent radicals may together stand for cyclic groups having 4 to 15 carbon atoms which in turn may be substituted, or Si(R.sup.8).sub.3 where R.sup.8 is selected from the group consisting of C.sub.1 to C.sub.10 alkyl, C.sub.6 to C.sub.15 aryl or C.sub.3 to C.sub.10 cycloalkyl; R.sup.4 and R.sup.6 are substituents both having van der Waals radii larger than the van der Waals radii of groups R.sup.1 and R.sup.3 ; R.sup.5 is a substituent having a van der Waals radius less than about the van der Waals radius of a methyl group; E.sup.1, E.sup.2 are independently selected from the group consisting of Si(R.sup.9).sub.2, Si(R.sup.9).sub.2 --Si(R.sup.9).sub.2, Ge(R.sup.9).sub.2, Sn(R.sup.9).sub.2, C(R.sup.9).sub.2, C(R.sup.9).sub.2 --C(R.sup.9).sub.2, where R.sup.9 is C.sub.1 to C.sub.10 alkyl, C.sub.6 to C.sub.15 aryl or C.sub.3 to C.sub.10 cycloalkyl; and the ligand may have C.sub.S or C.sub.1 -symmetry. Preferred metals are selected from the group consisting of group III, group IV, group V or lanthanide group elements. The catalysts are used to prepare stereoregular polymers including polypropylene from .alpha.-olefin monomers.

  15. Hydride Olefin complexes of tantalum and niobium

    NARCIS (Netherlands)

    Klazinga, Aan Hendrik

    1979-01-01

    This thesis describes investigations on low-valent tantalum and niobium hydride and alkyl complexes, particularly the dicyclopentadienyl tantalum hydride olefin complexes Cp2Ta(H)L (L=olefin). ... Zie: Summary

  16. Observation of Different Catalytic Activity of Various 1-Olefins during Ethylene/1-Olefin Copolymerization with Homogeneous Metallocene Catalysts

    Directory of Open Access Journals (Sweden)

    Mingkwan Wannaborworn

    2011-01-01

    Full Text Available This research aimed to investigate the copolymerization of ethylene and various 1-olefins. The comonomer lengths were varied from 1-hexene (1-C6 up to 1-octadecene (1-C18 in order to study the effect of comonomer chain length on the activity and properties of the polymer in the metallocene/MAO catalyst system. The results indicated that two distinct cases can be described for the effect of 1-olefin chain length on the activity. Considering the short chain length comonomers, such as 1-hexene, 1-octene and 1-decene, it is obvious that the polymerization activity decreased when the length of comonomer was higher, which is probably due to increased steric hindrance at the catalytic center hindering the insertion of ethylene monomer to the active sites, hence, the polymerization rate decreased. On the contrary, for the longer chain 1-olefins, namely 1-dodecene, 1-tetradecene and 1-octadecene, an increase in the comonomer chain length resulted in better activity due to the opening of the gap aperture between Cp(centroid-M-Cp-(centroid, which forced the coordination site to open more. This effect facilitated the polymerization of the ethylene monomer at the catalytic sites, and thus, the activity increased. The copolymers obtained were further characterized using thermal analysis, X-ray diffraction spectroscopy and 13C-NMR techniques. It could be seen that the melting temperature and comonomer distribution were not affected by the 1-olefin chain length. The polymer crystallinity decreased slightly with increasing comonomer chain length. Moreover, all the synthesized polymers were typical LLDPE having random comonomer distribution.

  17. SYNTHESIS AND CHARACTERIZATION OF POLY(p-ARYLENE SULFIDE KETONE/SCHIFF BASE) COPOLYMERS

    Institute of Scientific and Technical Information of China (English)

    Yan-lun Wang; Gang Zhang; Mei-lin Zhang; Yu Fan; Bao-ying Liu; Jie Yang

    2012-01-01

    Poly(p-arylene sulfide ketone/Schiffbase) copolymers (PASK/SB) were prepared by solution polycondensation of 4,4'-diflurobenzophenone (DFBP) and N-phenyl(4,4'-diflurodiphenyl) ketimine (DFBI) with sodium sulfide in the presence of sodium hydroxide under normal pressure.Elemental analyses,FT-IR,NMR,DSC,TGA and XRD were used to characterize the resultant copolymers.It was found that the copolymers had good thermal properties with glass transition temperature (Tg) of 155.0-172.0°C,melting temperature (Tm) of 298-344°C,5% weight loss temperatures (Td) of 471.0-501.5℃.These copolymers were almost amorphous with the content of DFBI beyond 30%.The polymer with 100%DFBI had excellent solubility,and it could dissolve in some solvents such as tetrahydrofuran (THF) and N-methy1-2-pyrrolidone (NMP).The processability of polymers was improved.Meantime the viscosity of PASK made from hydrolysis of PASK/SB (H-PASK/SB) was greatly improved from 0.135 dL/g to 0.605 dL/g.

  18. Hybrid titanium dioxide/PS-b-PEO block copolymer nanocomposites based on sol-gel synthesis

    Energy Technology Data Exchange (ETDEWEB)

    Gutierrez, J; Tercjak, A; Garcia, I; Peponi, L; Mondragon, I [' Materials-Technologies' Group, Departamento Ingenieria Quimica y Medio Ambiente, Escuela Politecnica, Universidad PaIs Vasco/Euskal Herriko Unibertsitatea, Plaza Europa 1, E-20018 Donostia-San Sebastian (Spain)], E-mail: inaki.mondragon@ehu.es

    2008-04-16

    The poly(styrene)-b-poly(ethylene oxide) (SEO) amphiphilic block copolymer, with two different molecular weights, has been used as a structure directing agent for generating nanocomposites of TiO{sub 2}/SEO via the sol-gel process. SEO amphiphilic block copolymers are designed with a hydrophilic PEO-block which can interact with inorganic molecules, as well as a hydrophobic PS-block which builds the matrix. The addition of different amounts of sol-gel provokes strong variations in the self-assembled morphology of TiO{sub 2}/SEO nanocomposites with respect to the neat block copolymer. As confirmed by atomic force microscopy (AFM), TiO{sub 2}/PEO-block micelles get closer, forming well-ordered spherical domains, in which TiO{sub 2} nanoparticles constitute the core surrounded by a corona of PEO-blocks. Moreover, for 20 vol% sol-gel the generated morphology changes to a hexagonally ordered structure for both block copolymers. The cylindrical structure of these nanocomposites has been confirmed by the two-dimensional Fourier transform power spectrum of the corresponding AFM height images. Affinity between titanium dioxide precursor and PEO-block of SEO allows us to generate hybrid inorganic/organic nanocomposites, which retain the optical properties of TiO{sub 2}, as evaluated by UV-vis spectroscopy.

  19. Polyether-amide segmented copolymers based on ethylene terephthalamide units of uniform length

    NARCIS (Netherlands)

    Bouma, Krista; Wester, Geertje A.; Gaymans, Reinoud J.

    2001-01-01

    Segmented copolymers were synthesized using the crystallizable bisesterdiamide segment (N,N-bis(p-carbomethoxybenzoyl)ethanediamine) T2T-dimethyl (a one-and-a-half repeating unit of nylon 2,T) and poly(tetramethyleneoxide) segments. Poly(tetramethyleneoxide) (PTMO) is amorphous and has a low Tg. The

  20. Comparing Ru and Fe-catalyzed olefin metathesis

    KAUST Repository

    Poater, Albert

    2014-01-01

    Density functional theory calculations have been used to explore the potential of Fe-based complexes with an N-heterocyclic carbene ligand, as olefin metathesis catalysts. Apart from a less endothermic reaction energy profile, a small reduction in the predicted upper energy barriers (≈ 2 kcal mol -1) is calculated in the Fe catalyzed profile with respect to the Ru catalysed profile. Overall, this study indicates that Fe-based catalysts have the potential to be very effective olefin metathesis catalysts. This journal is © the Partner Organisations 2014.

  1. 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.

  2. Application of olefin metathesis in petrochemistry

    Energy Technology Data Exchange (ETDEWEB)

    Warwel, S.

    1979-01-01

    A survey covers the catalysts used in olefin metathesis; olefin types which undergo metathesis, e.g., ring-opening metathetic polymerization of cycloolefins; equilibria and side reactions; the Phillips Triolefin process for 2-butene production; the Shell Higher Olefin Process (SHOP) for the production of C/sub 11/-C/sub 14/ ..cap alpha..-olefins; the Phillips Petroleum 225 ton/yr process for the conversion of trimethylpentane to neohexene, which is used in gasoline and pharmaceutical manufacture; the production of isoprene precursors; and various other metathesis reactions used in synthesizing specific olefins.

  3. Catalytic Transformation of Bio-oil to Olefins with Molecular Sieve Catalysts

    Science.gov (United States)

    Huang, Wei-wei; Gong, Fei-yan; Zhai, Qi; Li, Quan-xin

    2012-08-01

    Catalytic conversion of bio-oil into light olefins was performed by a series of molecular sieve catalysts, including HZSM-5, MCM-41, SAPO-34 and Y-zeolite. Based on the light olefins yield and its carbon selectivity, the production of light olefins decreased in the following order: HZSM-5>SAPO-34>MCM-41> Y-zeolite. The highest olefins yield from bio-oil using HZSM-5 catalyst reached 0.22 kg/kgbio-oil with carbon selectivity of 50.7% and a nearly complete bio-oil conversion. The reaction conditions and catalyst characterization were investigated in detail to reveal the relationship between the catalyst structure and the production of olefins. The comparison between the pyrolysis and catalytic pyrolysis of bio-oil was also performed.

  4. Review of Directly Producing Light Olefins via CO Hydrogenation

    Institute of Scientific and Technical Information of China (English)

    Chong Wang; Longya Xu; Qingxia Wang

    2003-01-01

    Directly making light olefins via CO hydrogenation is a promising process to obtain a non-petroleum based supply of alkenes. Limited by the ASF distribution function of Fischer-Tropsch synthesis,the yield of light olefins (C2-C4) can not reach the desired levels, which is a great challenge to overcome.Beginning with a brief introduction of F-T synthesis, this paper provides a review of current research,including thermodynamic analysis, the ASF distribution function, the reaction performance of CO hydro-genation and slurry reactor studies. The problems currently faced by this research area are presented atthe end of the article.

  5. Enhanced Olefin Cross Metathesis Reactions: The Copper Iodide Effect

    Science.gov (United States)

    Voigtritter, Karl; Ghorai, Subir

    2011-01-01

    Copper iodide has been shown to be an effective co-catalyst for the olefin cross metathesis reaction. In particular, it has both a catalyst stabilizing effect due to iodide ion, as well as copper(I)-based phosphine-scavenging properties that apply to use of the Grubbs-2 catalyst. A variety of Michael acceptors and olefinic partners can be cross-coupled under mild conditions in refluxing diethyl ether that avoid chlorinated solvents. This effect has also been applied to chemistry in water at room temperature using the new surfactant TPGS-750-M. PMID:21528868

  6. Application of olefin metathesis in the synthesis of steroids.

    Science.gov (United States)

    Morzycki, Jacek W

    2011-01-01

    Over the past decade, ruthenium-mediated metathesis transformations, including cross-metathesis, ring-closing metathesis, enyne metathesis, ring-opening metathesis polymerization, and also tandem processes, belong to the most intensively studied reactions. Many applications of olefin metathesis in the synthesis of natural products have been recently described. Also in the field of steroid chemistry new methods of total synthesis and hemisynthesis based on metathesis reactions have been elaborated. Various biologically active compounds, e.g. vitamin D and hormone analogues, steroid dimers and macrocycles, etc. have been prepared using a variety of olefin-metathesis protocols.

  7. Novel fluorene-carzazole-based conjugated copolymers containing pyrazoline and benzothiazole segments for blue light-emitting materials

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    A series of novel fluorene-carbazole-based copolymers with pyrazoline and benzothiazole units were synthesized successfully through Suzuki coupling reactions. The molecular structures and thermal properties of these polymers were characterized by FT-IR,1H NMR, DSC and TGA. GPC results indicated that the weight-average molecular weight (Mw) and polydispersity of these polymers were in range (12,000-14,000) and (1.8-2.0), respectively. The two resulting polymers have high photoluminescence quantum efficiency implying that they may be promising candidates for polymer light-emitting diodes (PLEDs).

  8. Electrical characterization of fluorinated benzothiadiazole based conjugated copolymer – a promising material for high-performance solar cells

    Energy Technology Data Exchange (ETDEWEB)

    Toušek, J., E-mail: jiri.tousek@mff.cuni.cz; Toušková, J.; Chomutová, R. [Charles University in Prague, Faculty of Mathematics and Physics, V Holešovičkách 2, 182 00 Prague 8 (Czech Republic); Remeš, Z.; Čermák, J. [Institute of Physics of the Academy of Sciences, Cukrovarnická 10, 162 53 Prague 6 (Czech Republic); Helgesen, M.; Carlé, J. E.; Krebs, F. C. [Department of Energy Conversion and Storage, Technical University of Denmark, Frederiksborgvej 399, DK-4000 Roskilde (Denmark)

    2015-12-15

    Measurements of electrical conductivity, electron work function, carrier mobility of holes and the diffusion length of excitons were performed on samples of conjugated polymers relevant to polymer solar cells. A state of the art fluorinated benzothiadiazole based conjugated copolymer (PBDT{sub THD} − DTBTff) was studied and benchmarked against the reference polymer poly-3-hexylthiophene (P3HT). We employed, respectively, four electrode conductivity measurements, Kelvin probe work function measurements, carrier mobility using charge extraction by linearly increasing voltage (CELIV) measurements and diffusion length determinaton using surface photovoltage measurements.

  9. Electrical characterization of fluorinated benzothiadiazole based conjugated copolymer – a promising material for high-performance solar cells

    Directory of Open Access Journals (Sweden)

    J. Toušek

    2015-12-01

    Full Text Available Measurements of electrical conductivity, electron work function, carrier mobility of holes and the diffusion length of excitons were performed on samples of conjugated polymers relevant to polymer solar cells. A state of the art fluorinated benzothiadiazole based conjugated copolymer (PBDTTHD − DTBTff was studied and benchmarked against the reference polymer poly-3-hexylthiophene (P3HT. We employed, respectively, four electrode conductivity measurements, Kelvin probe work function measurements, carrier mobility using charge extraction by linearly increasing voltage (CELIV measurements and diffusion length determinaton using surface photovoltage measurements.

  10. Synthesis and self-assembly behavior of a biodegradable and sustainable soybean oil-based copolymer nanomicelle

    Science.gov (United States)

    Bao, Lixia; Bian, Longchun; Zhao, Mimi; Lei, Jingxin; Wang, Jiliang

    2014-08-01

    Herein, we report a novel amphiphilic biodegradable and sustainable soybean oil-based copolymer (SBC) prepared by grafting hydrophilic and biocompatible hydroxyethyl acrylate (HEA) polymeric segments onto the natural hydrophobic soybean oil chains. FTIR, H1-NMR, and GPC measurements have been used to investigate the molecular structure of the obtained SBC macromolecules. Self-assembly behaviors of the prepared SBC in aqueous solution have also been extensively evaluated by fluorescence spectroscopy and transmission electron microscopy. The prepared SBC nanocarrier with the size range of 40 to 80 nm has a potential application in the biomedical field.

  11. Tuning the chromaticity of the emission color of the copolymers containing Eu(III), Tb(III), Be(II) ions based on colorimetric principle

    Science.gov (United States)

    Zhang, Aiqin; Yang, Yamin; Zhai, Guangmei; Jia, Husheng; Xu, Bingshe

    2016-02-01

    In this work, a method of tuning the chromaticity of the emission color of the copolymers containing Eu(III), Tb(III), Be(II) ions based on colorimetric principle was proposed. The technological route from coordination to copolymerization was employed to obtain the white light macromolecular phosphor. The three primary color monomers have been synthesized and their Commission Internationale de L'Eclairage (CIE) coordinates are respectively (0.540, 0.314), (0.231, 0.463), and (0.161, 0.054). The molar feed ratios of the three primary color monomers were calculated from the CIE coordinates based on colorimetric principle. Serial copolymers have been synthesized by free radical copolymerization of the three primary color monomers and methyl methacrylate. The quantum efficiency of the copolymers was higher than that of the complex monomers. The complexes were directly boned to the polymer chain, in which the energy transfer was reduced significantly compared to the doped-polymers. The experimental values of copolymers' CIE coordinates were located in the white light region in good agreement with theoretical values. The results indicate that the chromaticity of the emission color of the copolymers containing Eu(III), Tb(III), Be(II) ions could be tuned by theoretical calculation based on colorimetric principle.

  12. Radiation-induced synthesis of vinyl copolymer based nanocomposites filled with reactive organic montmorillonite clay

    Science.gov (United States)

    Kim, Sang-Kyum; Kwen, Hai-Doo; Choi, Seong-Ho

    2012-05-01

    Vinyl copolymer-clay nanocomposites were prepared by γ-irradiation-initiated radical polymerization using a mixture of styrene (St) and divinyl benzene (DVB) in the presence of reactive organic montmorillonite clay (OMMT) in methanol at room temperature. Reactive OMMT was synthesized by a cation exchange reaction of Na+-MMT and 1-[(4-ethylphenyl)methyl]-3-butyl-imidazolium chloride as a reactive organic modifier in an aqueous solution. The microstructures of the nanocomposites were confirmed by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The thermal stability was examined by thermo gravimetric analysis (TGA). As a result, the reactive OMMT was a good additive material for preparing vinyl copolymer-clay nanocomposites.

  13. Quinone diazides for olefin functionalization.

    Science.gov (United States)

    Dao, Hai T; Baran, Phil S

    2014-12-22

    The utility of quinone diazides in materials science is vast and well-documented, yet this potentially useful motif has languished in the annals of organic synthesis. Herein we show that modern tools of catalysis can be employed with free or suitably masked quinone diazides to unleash the power of these classic diazo compounds in the context of both inter- and intramolecular olefin cyclopropanation.

  14. Copolymers based on N-acryloyl-L-leucine and urea methacrylate with pyridine moieties

    Directory of Open Access Journals (Sweden)

    Buruiana Emil C.

    2016-01-01

    Full Text Available By using free radical polymerization of (N-methacryloyloxyethyl-N′-4-picolyl-urea (MAcPU and N-acryloyl-L-leucine (AcLeu, an optically active copolymer, poly[(N-methacryloyloxyethyl-N′-4-picolyl-urea-co-N-acryloyl-L-leucine], MAcPU-co-AcLeu (1.86:1 molar ratio was prepared and subsequently functionalized at the pyridine-N with (1R/S-(−/+-10-camphorsulfonic acid (R/S-CSA and at carboxyl group with (R-(+-α-ethylbenzylamine (R-EBA or trans-4-stilbene methanol (t-StM. The structures, chemical composition and chiroptical activity of the monomers and the copolymers were characterized by spectral analysis (FTIR, 1H (13C-NMR, 1H,1H-COSY, UV/vis, thermal methods (TGA, DSC, fluorescence spectroscopy, gel permeation chromatography and specific rotation measurements. Influence of the optical activity of monomer and modifier on modified copolymers suggested a good correlation between the experimental data obtained (23[α]589=+12.5° for AcLeu and MAcPU-co-AcLeu, 23[α]589=0°+27.5° for (MAcPU-co-AcLeu-R/S-CSA, 23[α]589=+25° for (MAcPU-co-AcLeu-R-EBA, and 23[α]589 = 0° for (MAcPU-co-AcLeu-St. In addition, the photobehavior of the stilbene copolymer (MAcPU-co-AcLeu-St in film was investigated by UV-vis spectroscopy. The fluorescence quenching of the stilbene species in the presence of aliphatic/aromatic amine in DMF solution was evaluated, more efficiently being 4,4′−dipyridyl (detection limit: 7.2 x 10-6 mol/L.

  15. Enhanced infarct myocardium repair mediated by thermosensitive copolymer hydrogel-based stem cell transplantation

    OpenAIRE

    Xia, Yu; Zhu, Kai; Lai, Hao; Lang, Meidong; Xiao, Yan; Lian, Sheng; Guo, Changfa; Wang, Chunsheng

    2015-01-01

    Mesenchymal stem cell (MSC) transplantation by intramyocardial injection has been proposed as a promising therapy strategy for cardiac repair after myocardium infarction. However, low retention and survival of grafted MSCs hinder its further application. In this study, copolymer with N-isopropylacrylamide/acrylic acid/2-hydroxylethyl methacrylate-poly(ɛ-caprolactone) ratio of 88:9.6:2.4 was bioconjugated with type I collagen to construct a novel injectable thermosensitive hydrogel. The inject...

  16. NEW MATERIALS BY POLYMERIZATION OF OLEFINS AND STYRENE BY METALLOCENE/MAO CATALYSTS

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    Metallocenes and other transition metal compounds comprise a newgeneration of single site catalysts for the production of precisely designed polyolefins and engineering plastics. The discovery of metallocene methylalumoxane (MAO) catalysts has opened a frontier in the area of polymer synthesis and processing. A great number of symmetric and chiral zirconocenes have been synthesized to give isotactic,syndiotactic,isoblock,or stereoblock polymers with increased impact strength and toughness,better melt characteristics or elasticity,and improved clarity in films. Cycloolefin copolymers (COC) and syndiotactic polystyrene can be produced by metallocene catalysts. These are new types of polymers with special properties and a high potential as engineering plastics. Norbornene-ethene copolymers are most interesting for technical uses because of the easily available monomers. Due to different incorporation values of the cyclic olefin in the copolymer,the glass transition temperature can vary over a wide range and reaches 180 ℃.

  17. Solar cells based on block copolymer semiconductor nanowires: effects of nanowire aspect ratio.

    Science.gov (United States)

    Ren, Guoqiang; Wu, Pei-Tzu; Jenekhe, Samson A

    2011-01-25

    The solution-phase self-assembly of nanowires (NWs) from diblock copolymer semiconductors, poly(3-butylthiophene)-block-poly(3-octylthiophene), of different block compositions gave crystalline NWs of similar width (13-16 nm) but a tunable average aspect ratio (length/width) of 50-260. The power conversion efficiency of bulk heterojunction solar cells comprising the diblock copolythiophene NWs and PC(71)BM was found to increase with increasing aspect ratio, reaching 3.4% at the highest average aspect ratio of 260. The space charge limited current mobility of holes in neat films of the copolymer NWs and in copolymer NWs/PC(71)BM films (∼1.0 × 10(-4) cm(2)/(V s)) was invariant with aspect ratio, reflecting the parallel orientation of the NWs to the substrate. The enhancement of photovoltaic efficiency with increasing aspect ratio of NWs was explained in terms of increased exciton and charge photogeneration and collection in the bulk heterojunction solar cells.

  18. Separation of parent homopolymers from polystyrene and poly(ethylene oxide) based block copolymers by liquid chromatography under limiting conditions of desorption-3. Study of barrier efficiency according to block copolymers' chemical composition.

    Science.gov (United States)

    Rollet, Marion; Pelletier, Bérengère; Berek, Dušan; Maria, Sébastien; Phan, Trang N T; Gigmes, Didier

    2016-09-02

    Liquid Chromatography under Limiting Conditions of Desorption (LC LCD) is a powerful separation tool for multicomponent polymer systems. This technique is based on a barrier effect of an appropriate solvent, which is injected in front of the sample, and which decelerates the elution of selected macromolecules. In this study, the barrier effects have been evaluated for triblock copolymers polystyrene-b-poly(ethylene oxide)-b-polystyrene (PS-b-PEO-b-PS) according to the content of polystyrene (wt% PS) and PEO-block molar mass. PS-b-PEO-b-PS samples were prepared by Atom Transfer Radical Polymerization (ATRP). The presence of respective parent homopolymers was investigated by applying optimized LC LCD conditions. It was found that the barrier composition largely affects the efficiency of separation and it ought to be adjusted for particular composition range of block copolymers.

  19. Nanoscaled copper metal-organic framework (MOF) based on carboxylate ligands as an efficient heterogeneous catalyst for aerobic epoxidation of olefins and oxidation of benzylic and allylic alcohols.

    Science.gov (United States)

    Qi, Yue; Luan, Yi; Yu, Jie; Peng, Xiong; Wang, Ge

    2015-01-19

    Aerobic epoxidation of olefins at a mild reaction temperature has been carried out by using nanomorphology of [Cu3(BTC)2] (BTC = 1,3,5-benzenetricarboxylate) as a high-performance catalyst through a simple synthetic strategy. An aromatic carboxylate ligand was employed to furnish a heterogeneous copper catalyst and also serves as the ligand for enhanced catalytic activities in the catalytic reaction. The utilization of a copper metal-organic framework catalyst was further extended to the aerobic oxidation of aromatic alcohols. The shape and size selectivity of the catalyst in olefin epoxidation and alcohol oxidation was investigated. Furthermore, the as-synthesized copper catalyst can be easily recovered and reused several times without leaching of active species or significant loss of activity.

  20. 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.

  1. Synthesis of the EF-ring of ciguatoxin 3C based on the [2,3]-Wittig rearrangement and ring-closing olefin metathesis.

    Science.gov (United States)

    Goto, Akiyoshi; Fujiwara, Kenshu; Kawai, Ayako; Kawai, Hidetoshi; Suzuki, Takanori

    2007-12-20

    The EF-ring segment of ciguatoxin 3C, a causative toxin of ciguatera fish poisoning, was synthesized in three major steps: 1,4-addition for the C20O-C27 bond connection, chirality transferring anti selective [2,3]-Wittig rearrangement for the construction of the anti-2-hydroxyalkyl ether part, and ring-closing olefin metathesis for the F-ring formation.

  2. Novel docetaxel-loaded nanoparticles based on PCL-Tween 80 copolymer for cancer treatment

    Directory of Open Access Journals (Sweden)

    Mei L

    2011-11-01

    Full Text Available Yuandong Ma1,2*, Yi Zheng1,2*, Xiaowei Zeng1-3*, Liqin Jiang4, Hongbo Chen1,2, Ranyi Liu5, Laiqiang Huang1,2, Lin Mei1,21School of Life Sciences, Tsinghua University, Beijing, 2Division of Life and Health Sciences, Graduate School at Shenzhen, Tsinghua University, Shenzhen, Guangdong, 3Materials and Environment Experimental Center, Department of Materials Science and Engineering, Qinhuangdao Branch, Northeastern University, Qinhuangdao, 4Insitute of Biomedical Engineering, Peking Union Medical College, Chinese Academy of Medical Sciences, Tianjin, 5State Key Laboratory of Oncology in South China, Sun Yat-sen University Cancer Center, Guangzhou, People’s Republic of China *These authors contributed equally to this workBackground: The formulation of docetaxel available for clinical use (Taxotere® contains a high concentration of polysorbate 80 (Tween 80. After incorporation of Tween 80 into poly-ε-caprolactone (PCL-Tween 80 copolymer, the relative amount of Tween 80 should be decreased and the advantages of PCL and Tween 80 should be combined.Methods: A novel PCL-Tween 80 copolymer was synthesized from ε-caprolactone and Tween 80 in the presence of stannous octoate as a catalyst via ring opening polymerization. Two types of nanoparticle formulation were made from commercial PCL and a self-synthesized PCL-Tween 80 copolymer using a modified solvent extraction/evaporation method.Results: The nanoparticles were found by field emission scanning electron microscopy to have a spherical shape and be 200 nm in diameter. The copolymers could encapsulate 10% of the drug in the nanoparticles and release 34.9% of the encapsulated drug over 28 days. PCL-Tween 80 nanoparticles could be internalized into the cells and had higher cellular uptake than the PCL nanoparticles. The drug-loaded PCL-Tween 80 nanoparticles showed better in vitro cytotoxicity towards C6 cancer cells than commercial Taxotere at the same drug concentration.Conclusion: Nanoparticles

  3. Poly(vinylidene fluoride)-based, co-polymer separator electrolyte membranes for lithium-ion battery systems

    Science.gov (United States)

    Costa, C. M.; Gomez Ribelles, J. L.; Lanceros-Méndez, S.; Appetecchi, G. B.; Scrosati, B.

    2014-01-01

    In the present paper we report and discuss the physicochemical properties of novel electrolyte membranes, based on poly(vinylidenefluoride-co-trifluoroethylene), PVdF-TrFE, and poly(vinylidenefluoride-co-hexafluoropropylene), PVdF-HFP, co-polymer hosts and the PVdF-TrFE/poly(ethylene oxide (PEO) blend as separators for lithium battery systems. The results have shown that the examined separator membranes, particularly those based on the PVdF co-polymers, are able to uptake large liquid amounts leading to high ionic conductivity values. Tests performed on Li/LiFePO4 and Li/Sn-C cells have revealed very good cycling performance even at high current rates and 100% of DOD, approaching the results achieved in liquid electrolytes. A capacity fading lower than 0.002% per cycle was observed. Particularly, the Li/LiFePO4 cathode cells have exhibited excellent rate capability, being still able to deliver at 2C above 89% of the capacity discharged at 0.1C. These results, in conjunction with the about 100% coulombic efficiency, suggest very good electrolyte/electrode compatibility, which results from the high purity and stability of the electrolyte and electrode materials and the cell manufacturing.

  4. GRAFTED STYRENE-DIVINYLBENZENE COPOLYMERS CONTAINING BENZALDEHYDES AND THEIR WITTIG REACTIONS WITH VARIOUS PHOSPHONIUM SALTS

    Institute of Scientific and Technical Information of China (English)

    Adriana Popa; Gheorghe Ilia; Aurelia Pascariu; Smaranda Iliescu; Nicoleta Plesu

    2005-01-01

    A chloromethylated styrene-divinylbenzene copolymer support system functionalized with 4-benzaldehyde and 2-benzaldehyde was prepared. The degree of functionalization with aldehyde groups is well suited for the subsequent use of the products as Wittig reagents. The polymer bound aldehyde was reacted with Wittig reagents to give olefin groups grafted on styrene-divinylbenzene copolymers. The reactions were carried out in phase transfer catalysis conditions. A simple procedure for the calculation of the degree of functionalization and the statistical modeling of the structural repetitive unit of the copolymer are reported.

  5. 希夫碱类金属配合物催化剂催化氧化烯烃研究进展%Progress in research of Schiff base metal complexes catalytic using for olefins catalytic oxidation

    Institute of Scientific and Technical Information of China (English)

    冯辉霞; 李汉峰; 王利杰

    2011-01-01

    The structure of metal complexes characteristic of Schiff base was analyzed and catalytic oxidation olefins was studied on current situation systematically.And it expressed the classification application of Schiff base which used in type of homogeneous catalysis oxidization and metal complexes of solid catalyst.By analyzing the defects of small molecules metal complexes catalysis-oxidization olefins,the conclusion indicated that the heterogeneous load type of metal complexes of Schiff base in category catalyst is the main development direction in present.%分析了希夫碱金属配合物的结构特点及其催化氧化烯烃的研究现状,阐述了用于均相催化氧化的希夫碱、固载型希夫碱金属配合物催化剂的分类及其在氧化烯烃领域的应用研究.通过分析希夫碱类小分子金属配合物催化氧化烯烃的缺陷,得出非均相的负载型希夫碱类金属配合物催化剂是目前主要发展方向的结论.

  6. Study on the oxidative stability of poly a-olefin aviation lubricating base oil using PDSC method

    Science.gov (United States)

    Wu, N.; Fei, Y. W.; Yang, H. W.; Wang, Y. M.; Zong, Z. M.

    2016-08-01

    The oxidation stability of the domestic and import PAO aviation lubricating base oil was studied by the method of pressurized differential scanning calorimetry testing the initial oxidation temperature. The effects of anti-oxidants were investigated, and the best ratio of antioxidants was determined.

  7. Separation of Olefin/Paraffin Mixtures with Carrier Facilitated Membrane Final Report

    Energy Technology Data Exchange (ETDEWEB)

    Merkel, T.C.; Blanc, R.; Zeid, J.; Suwarlim, A.; Firat, B.; Wijmans, H.; Asaro, M. (SRI); Greene, M.(Lummus)

    2007-03-12

    This document describes the results of a DOE funded joint effort of Membrane Technology and Research Inc. (MTR), SRI International (SRI), and ABB Lummus (ABB) to develop facilitated transport membranes for olefin/paraffin separations. Currently, olefin/paraffin separation is done by distillation—an extremely energy-intensive process because of the low relative volatilities of olefins and paraffins. If facilitated transport membranes could be successfully commercialized, the potential energy savings achievable with this membrane technology are estimated to be 48 trillion Btu per year by the year 2020. We discovered in this work that silver salt-based facilitated transport membranes are not stable even in the presence of ideal olefin/paraffin mixtures. This decline in membrane performance appears to be caused by a previously unrecognized phenomenon that we have named olefin conditioning. As the name implies, this mechanism of performance degradation becomes operative once a membrane starts permeating olefins. This project is the first study to identify olefin conditioning as a significant factor impacting the performance of facilitated olefin transport membranes. To date, we have not identified an effective strategy to mitigate the impact of olefin conditioning. other than running at low temperatures or with low olefin feed pressures. In our opinion, this issue must be addressed before further development of facilitated olefin transport membranes can proceed. In addition to olefin conditioning, traditional carrier poisoning challenges must also be overcome. Light, hydrogen, hydrogen sulfide, and acetylene exposure adversely affect membrane performance through unwanted reaction with silver ions. Harsh poisoning tests with these species showed useful membrane lifetimes of only one week. These tests demonstrate a need to improve the stability of the olefin complexing agent to develop membranes with lifetimes satisfactory for commercial application. A successful effort

  8. Fe-Catalyzed C–C Bond Construction from Olefins via Radicals

    Science.gov (United States)

    2017-01-01

    This Article details the development of the iron-catalyzed conversion of olefins to radicals and their subsequent use in the construction of C–C bonds. Optimization of a reductive diene cyclization led to the development of an intermolecular cross-coupling of electronically-differentiated donor and acceptor olefins. Although the substitution on the donor olefins was initially limited to alkyl and aryl groups, additional efforts culminated in the expansion of the scope of the substitution to various heteroatom-based functionalities, providing a unified olefin reactivity. A vinyl sulfone acceptor olefin was developed, which allowed for the efficient synthesis of sulfone adducts that could be used as branch points for further diversification. Moreover, this reactivity was extended into an olefin-based Minisci reaction to functionalize heterocyclic scaffolds. Finally, mechanistic studies resulted in a more thorough understanding of the reaction, giving rise to the development of a more efficient second-generation set of olefin cross-coupling conditions. PMID:28094980

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

    Science.gov (United States)

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

    2015-03-01

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

  10. A multiscale modeling study of loss processes in block-copolymer-based solar cell nanodevices

    Science.gov (United States)

    Donets, Sergii; Pershin, Anton; Christlmaier, Martin J. A.; Baeurle, Stephan A.

    2013-03-01

    Flexible photovoltaic devices possess promising perspectives in opto-electronic technologies, where high mobility and/or large-scale applicability are important. However, their usefulness in such applications is currently still limited due to the low level of optimization of their performance and durability. For the improvement of these properties, a better understanding and control of small-scale annihilation phenomena involved in the photovoltaic process, such as exciton loss and charge carrier loss, is necessary, which typically implicates multiple length- and time-scales. Here, we study the causes for their occurrence on the example of nanostructured diblock- and triblock-copolymer systems by making use of a novel solar-cell simulation algorithm and explore new routes to optimize their photovoltaic properties. A particular focus is set on the investigation of exciton and charge carrier loss phenomena and their dependence on the inter-monomeric interaction strength, chain architecture, and external mechanical loading. Our simulation results reveal that in the regime from low up to intermediate χ-parameters an increasing number of continuous percolation paths is created. In this parameter range, the internal quantum efficiency (IQE) increases up to a maximum, characterized by a minimum in the number of charge losses due to charge recombination. In the regime of high χ-parameters both block-copolymer systems form nanostructures with a large number of bottlenecks and dead ends. These lead to a large number of charge losses due to charge recombination, charge trapping, and a deteriorated exciton dissociation, resulting in a significant drop in the IQE. Moreover, we find that the photovoltaic performance of the triblock-copolymer material decreases with increasing mechanical loading, caused by a growing number of charge losses due to charge recombination and charge accumulation. Finally, we demonstrate that the process of charge trapping in defects can be reversed

  11. Cationic nanoparticles with quaternary ammonium-functionalized PLGA–PEG-based copolymers for potent gene transfection

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Yan-Hsung [Kaohsiung Medical University, School of Dentistry, College of Dental Medicine (China); Fu, Yin-Chih [Kaohsiung Medical University, Graduate Institute of Medicine, College of Medicine (China); Chiu, Hui-Chi [Kaohsiung Medical University, Department of Medicinal and Applied Chemistry, College of Life Science (China); Wang, Chau-Zen [Kaohsiung Medical University, Department of Physiology, College of Medicine (China); Lo, Shao-Ping [Kaohsiung Medical University, Department of Medicinal and Applied Chemistry, College of Life Science (China); Ho, Mei-Ling [Kaohsiung Medical University, Department of Physiology, College of Medicine (China); Liu, Po-Len [Kaohsiung Medical University, Department of Respiratory Therapy, College of Medicine (China); Wang, Chih-Kuang, E-mail: ckwang@kmu.edu.tw [Kaohsiung Medical University, Department of Medicinal and Applied Chemistry, College of Life Science (China)

    2013-11-15

    The objective of the present work was to develop new cationic nanoparticles (cNPs) with amphiphilic cationic copolymers for the delivery of plasmid DNA (pDNA). Cationic copolymers were built on the synthesis of quaternary ammonium salt compounds from diethylenetriamine (DETA) to include the positively charged head group and amphiphilic multi-grafts. PLGA-phe-PEG-qDETA (PPD), phe-PEG-qDETA-PLGA (PDP), and PLGA-phe-PEG-qDETA-PLGA (PPDP) cationic copolymers were created by this moiety of DETA quaternary ammonium, heterobifunctional polyethylene glycol (COOH-PEG-NH{sub 2}), phenylalanine (phe), and poly(lactic-co-glycolic acid) (PLGA). These new cNPs were prepared by the water miscible solvent displacement method. They exhibit good pDNA binding ability, as shown in a retardation assay that occurred at a particle size of ∼217 nm. The zeta potential was approximately +21 mV when the cNP concentration was 25 mg/ml. The new cNPs also have a better buffering capacity than PLGA NPs. However, the pDNA binding ability was demonstrated starting at a weight ratio of approximately 6.25 cNPs/pDNA. Gene transfection results showed that these cNPs had transfection effects similar to those of Lipofectamine 2000 in 293T cells. Furthermore, cNPs can also transfect human adipose-derived stem cells. The results indicate that the newly developed cNP is a promising candidate for a novel gene delivery vehicle.

  12. Synthesis of β-cyclodextrin-Based Star Block Copolymers with Thermo-Responsive Behavior

    Directory of Open Access Journals (Sweden)

    Agnes Wycisk

    2015-05-01

    Full Text Available Star polymers are one example of three-dimensional macromolecules containing several arms with similar molecular weight connected to a central core. Due to their compact structure and their enhanced segment density in comparison to linear polymers of the same molecular weight, they have attracted significant attention during recent years. The preparation of block-arm star copolymers with a permanently hydrophilic block and an “environmentally” sensitive block, which can change its nature from hydrophilic to hydrophobic, leads to nanometer-sized responsive materials with unique properties. These polymers are able to undergo a conformational change or phase transition as a reply to an external stimulus resulting in the formation of core–shell nanoparticles, which further tend to aggregate. Star-shaped copolymers with different cores were synthesized via atom transfer radical polymerization (ATRP. The core-first method chosen as synthetic strategy allows good control over the polymer architecture. First of all the multifunctional initiators were prepared by esterification reaction of the hydroxyl groups with 2-chloropropionyl chloride. Using β-cyclodextrin as core molecules, which possess a well-defined number of functional groups up to 21, allows defining the number of arms per star polymer. In order to prepare stimuli-responsive multi-arm copolymers, containing a stimuli-responsive (poly(N-isopropylacrylamide (PNIPAAm and a non-responsive block (poly(N,N-dimethylacrylamide (PDMAAm, consecutive ATRP was carried out. The polymers were characterized intensively using NMR spectroscopy and size exclusion chromatography (SEC, whereas the temperature-depending aggregation behavior in aqueous solution was determined via turbidimetry and differential scanning calorimetry (DSC.

  13. Printed thin film transistors and CMOS inverters based on semiconducting carbon nanotube ink purified by a nonlinear conjugated copolymer.

    Science.gov (United States)

    Xu, Wenya; Dou, Junyan; Zhao, Jianwen; Tan, Hongwei; Ye, Jun; Tange, Masayoshi; Gao, Wei; Xu, Weiwei; Zhang, Xiang; Guo, Wenrui; Ma, Changqi; Okazaki, Toshiya; Zhang, Kai; Cui, Zheng

    2016-02-28

    Two innovative research studies are reported in this paper. One is the sorting of semiconducting carbon nanotubes and ink formulation by a novel semiconductor copolymer and second is the development of CMOS inverters using not the p-type and n-type transistors but a printed p-type transistor and a printed ambipolar transistor. A new semiconducting copolymer (named P-DPPb5T) was designed and synthesized with a special nonlinear structure and more condensed conjugation surfaces, which can separate large diameter semiconducting single-walled carbon nanotubes (sc-SWCNTs) from arc discharge SWCNTs according to their chiralities with high selectivity. With the sorted sc-SWCNTs ink, thin film transistors (TFTs) have been fabricated by aerosol jet printing. The TFTs displayed good uniformity, low operating voltage (±2 V) and subthreshold swing (SS) (122-161 mV dec(-1)), high effective mobility (up to 17.6-37.7 cm(2) V(-1) s(-1)) and high on/off ratio (10(4)-10(7)). With the printed TFTs, a CMOS inverter was constructed, which is based on the p-type TFT and ambipolar TFT instead of the conventional p-type and n-type TFTs. Compared with other recently reported inverters fabricated by printing, the printed CMOS inverters demonstrated a better noise margin (74% 1/2 Vdd) and was hysteresis free. The inverter has a voltage gain of up to 16 at an applied voltage of only 1 V and low static power consumption.

  14. Vegetable-Oil-Based Hyperbranched Polyester-Styrene Copolymer Containing Silver Nanoparticle as Antimicrobial and Corrosion-Resistant Coating Materials

    Directory of Open Access Journals (Sweden)

    Manawwer Alam

    2013-01-01

    Full Text Available Pongamia oil (PO was converted to Pongamia oil hydroxyl (POH via epoxidation process. The esterification of POH with linolenic acid was carried out to form hyperbranched polyester (HBPE, and further styrenation was performed at the conjugated double bond in the chain of linolenic acid. After styrenation, silver nanoparticle was added in different weight percentages (0.1–0.4 wt%. The structural elucidation of POH, HBPE, and HBPE-St was carried out by FT-IR, 1H-NMR, and 13C-NMR spectroscopic techniques. Physicochemical and physicomechanical analyses were performed by standard method. Thermal behavior of the HBPE-St was analyzed by using thermogravimetric analysis (TGA and differential scanning calorimetry (DSC. The coatings of HBPE-St were prepared on mild steel strips. The anticorrosive behavior of HBPE-St resin-based coatings in acid, saline, and tap water was evaluated, and the molecular weight of HBPE-St was determined by gel permeation chromatography (GPC. The antibacterial activities of the HBPE-St copolymers were tested in vitro against bacteria and fungi by disc diffusion method. The HBPE-St copolymers exhibited good antibacterial activities and can be used as antimicrobial and corrosion-resistant coating materials.

  15. Liquid crystal alignment in electro-responsive nanostructured thermosetting materials based on block copolymer dispersed liquid crystal

    Energy Technology Data Exchange (ETDEWEB)

    Tercjak, A; Garcia, I; Mondragon, I [Materials-Technologies Group, Departamento IngenierIa Quimica y M Ambiente, Escuela Politecnica, Universidad PaIs Vasco/Euskal Herriko Unibertsitatea, Plaza Europa 1, E-20018 Donostia-San Sebastian (Spain)], E-mail: scptesza@sc.ehu.es, E-mail: inaki.mondragon@ehu.es

    2008-07-09

    Novel well-defined nanostructured thermosetting systems were prepared by modification of a diglicydylether of bisphenol-A epoxy resin (DGEBA) with 10 or 15 wt% amphiphilic poly(styrene-b-ethylene oxide) block copolymer (PSEO) and 30 or 40 wt% low molecular weight liquid crystal 4'-(hexyl)-4-biphenyl-carbonitrile (HBC) using m-xylylenediamine (MXDA) as a curing agent. The competition between well-defined nanostructured materials and the ability for alignment of the liquid crystal phase in the materials obtained has been studied by atomic and electrostatic force microscopy, AFM and EFM, respectively. Based on our knowledge, this is the first time that addition of an adequate amount (10 wt%) of a block copolymer to 40 wt% HBC-(DGEBA/MXDA) leads to a well-organized nanostructured thermosetting system (between a hexagonal and worm-like ordered structure), which is also electro-responsive with high rate contrast. This behavior was confirmed using electrostatic force microscopy (EFM), by means of the response of the HBC liquid crystal phase to the voltage applied to the EFM tip. In contrast, though materials containing 15 wt% PSEO and 30 wt% HBC also form a well-defined nanostructured thermosetting system, they do not show such a high contrast between the uncharged and charged surface.

  16. Liquid crystal alignment in electro-responsive nanostructured thermosetting materials based on block copolymer dispersed liquid crystal

    Science.gov (United States)

    Tercjak, A.; Garcia, I.; Mondragon, I.

    2008-07-01

    Novel well-defined nanostructured thermosetting systems were prepared by modification of a diglicydylether of bisphenol-A epoxy resin (DGEBA) with 10 or 15 wt% amphiphilic poly(styrene-b-ethylene oxide) block copolymer (PSEO) and 30 or 40 wt% low molecular weight liquid crystal 4'-(hexyl)-4-biphenyl-carbonitrile (HBC) using m-xylylenediamine (MXDA) as a curing agent. The competition between well-defined nanostructured materials and the ability for alignment of the liquid crystal phase in the materials obtained has been studied by atomic and electrostatic force microscopy, AFM and EFM, respectively. Based on our knowledge, this is the first time that addition of an adequate amount (10 wt%) of a block copolymer to 40 wt% HBC-(DGEBA/MXDA) leads to a well-organized nanostructured thermosetting system (between a hexagonal and worm-like ordered structure), which is also electro-responsive with high rate contrast. This behavior was confirmed using electrostatic force microscopy (EFM), by means of the response of the HBC liquid crystal phase to the voltage applied to the EFM tip. In contrast, though materials containing 15 wt% PSEO and 30 wt% HBC also form a well-defined nanostructured thermosetting system, they do not show such a high contrast between the uncharged and charged surface.

  17. Tunable Mesoporous Bragg Reflectors Based on Block-Copolymer Self-Assembly

    KAUST Repository

    Guldin, Stefan

    2011-07-06

    Mesoporous Bragg reflectors are a promising materials platform for photovoltaics, light emission, and sensing. A fast and versatile fabrication route that relies on the self-assembly of the block copolymer poly(isoprene-b-ethylene oxide) in combination with simple sol-gel chemistry is reported. The method allows extended control over porosity and pore size in the resulting inorganic material and results in high-quality optical elements. © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Design of 3D scaffolds for tissue engineering testing a tough polylactide-based graft copolymer

    Energy Technology Data Exchange (ETDEWEB)

    Dorati, R., E-mail: rossella.dorati@unipv.it [Department of Drug Sciences, University of Pavia, V.le Taramelli 12, 27100 Pavia (Italy); Center for Tissue Engineering (CIT), University of Pavia, Via Ferrata 1, 27100 Pavia (Italy); Colonna, C. [Department of Drug Sciences, University of Pavia, V.le Taramelli 12, 27100 Pavia (Italy); Center for Tissue Engineering (CIT), University of Pavia, Via Ferrata 1, 27100 Pavia (Italy); Tomasi, C. [C.S.G.I., Department of Chemistry, Division of Physical Chemistry, University of Pavia, V.le Taramelli 16 I, 27100 Pavia (Italy); Genta, I. [Department of Drug Sciences, University of Pavia, V.le Taramelli 12, 27100 Pavia (Italy); Center for Tissue Engineering (CIT), University of Pavia, Via Ferrata 1, 27100 Pavia (Italy); Bruni, G. [C.S.G.I., Department of Chemistry, Division of Physical Chemistry, University of Pavia, V.le Taramelli 16 I, 27100 Pavia (Italy); Conti, B. [Department of Drug Sciences, University of Pavia, V.le Taramelli 12, 27100 Pavia (Italy); Center for Tissue Engineering (CIT), University of Pavia, Via Ferrata 1, 27100 Pavia (Italy)

    2014-01-01

    The aim of this research was to investigate a tough polymer to develop 3D scaffolds and 2D films for tissue engineering applications, in particular to repair urethral strictures or defects. The polymer tested was a graft copolymer of polylactic acid (PLA) synthesized with the rationale to improve the toughness of the related PLA homopolymer. The LMP-3055 graft copolymer (in bulk) demonstrated to have negligible cytotoxicity (bioavailability > 85%, MTT test). Moreover, the LMP-3055 sterilized through gamma rays resulted to be cytocompatible and non-toxic, and it has a positive effect on cell biofunctionality, promoting the cell growth. 3D scaffolds and 2D film were prepared using different LMP-3055 polymer concentrations (7.5, 10, 12.5 and 15%, w/v), and the effect of polymer concentration on pore size, porosity and interconnectivity of the 3D scaffolds and 2D film was investigated. 3D scaffolds got better results for fulfilling structural and biofunctional requirements: porosity, pore size and interconnectivity, cell attachment and proliferation. 3D scaffolds obtained with 10 and 12.5% polymer solutions (3D-2 and 3D-3, respectively) were identified as the most suitable construct for the cell attachment and proliferation presenting pore size ranged between 100 and 400 μm, high porosity (77–78%) and well interconnected pores. In vitro cell studies demonstrated that all the selected scaffolds were able to support the cell proliferation, the cell attachment and growth resulting to their dependency on the polymer concentration and structural features. The degradation test revealed that the degradation of polymer matrix (ΔMw) and water uptake of 3D scaffolds exceed those of 2D film and raw polymer (used as control reference), while the mass loss of samples (3D scaffold and 2D film) resulted to be controlled, they showed good stability and capacity to maintain the physical integrity during the incubation time. - Highlights: • Tough PLA graft copolymer was proposed

  19. Synthesis and Characterization of Novel Polymethylene-Based 3-Miktoarm Star Copolymers by Combining Polyhomologation with Other Living Polymerizations

    KAUST Repository

    Altaher, Maryam

    2015-05-01

    Polyethylene (PE) is produced in a huge scale globally and has plenty of desirable properties. It is used in coating, packaging, and artificial joint replacements. The growing need for high performance polyethylene led to the development of new catalysts, monomers and polymerizations. The synthesis of polymethylene (equivalent to polyethylene) by living polyhomologation opened the way to well-defined polymethylenes-based polymeric materials with controlled structure, molecular weight and narrow polydispersity. Such model polymers are substantial to study the structure-properties relationships. This research presents a new strategy based on the in situ formation of B-thexyl-silaboracyclic serving as initiating sites for the polyhomologation of dimethylsulfoxonium methylide. Combination with metal-free ring-opening polymerization (ROP) of ɛ-caprolactone (CL) and atom transfer radical polymerization (ATRP) of styrene led to three polymethylene-based 3-miktoarm stars copolymers PCL(PM-OH)2, Br-PCL(PM-OH)2 and PS(PM-OH)2.

  20. A Novel Co-polymer Based on Hydroxypropyl α-Cyclodextrin Conjugated to Low Molecular Weight Polyethylenimine as an in Vitro Gene Delivery Vector

    Directory of Open Access Journals (Sweden)

    Hai Yu

    2008-11-01

    Full Text Available A novel co-polymer based on 2-hydroxypropyl-α-cyclodextrin cross-linked by low molecular weight polyethylenimine was synthesized as a gene delivery vector. The copolymer could bind and condense DNA tightly. It showed lower cytotoxicity than PEI 25kDa in SK-BR-3 cells. Transfection efficiency was increased over 5.5-fold higher than PEI 25 kDa in SK-BR-3 cells in complete serum medium. It is a potential candidate vector for gene therapy.

  1. 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.

  2. Effect of Olefins on Formation of Sulfur Compounds in FCC Gasoline

    Institute of Scientific and Technical Information of China (English)

    Tang Jinlian; Xu Youhao; Gong Jianhong; Wang Xieqing

    2008-01-01

    The effect of olefins on formation of sulfur compounds in FCC gasoline was studied in a small-scale fixed fluidized bed (FFB) unit at temperatures ranging from 400℃ to 500℃, a weight hourly space velocity (WHSV) of 10 h-1, and a catalyst/oil ratio of 6. The results showed that C4-C6 olefins contained in the FCC gasoline could react with H2S to form predominantly thiophenes, alkyl-thiophenes as well as a fractional amount of thiols, while large molecular olefins such as heptene could react with hydrogen sulfide to form benzothiophenes. The amount of sulfur compounds formed at different tem-peratures over different catalysts were in proportion to the mass fractions of olefins in the feedstock,with the amount of sulfur compounds formed over REUSY catalyst exceeding those formed over the shape selective zeolite catalyst owing to the effect of catalyst performance and the impact of catalyst on the degree of olefin conversion. The amount of sulfur compounds generated and their increase reached a maximum at 450℃ and a minimum at 400℃ because of the influence of temperature on the thermody-namic and kinetic constants for formation of sulfur compound as well as on the olefin conversion degree.Based on the above-mentioned study, a reaction network and a model for prediction of sulfur com-pounds generated upon reaction of olefins in FCC gasoline with H2S were established.

  3. Microwave-Assisted Olefin Metathesis

    Science.gov (United States)

    Nicks, François; Borguet, Yannick; Sauvage, Xavier; Bicchielli, Dario; Delfosse, Sébastien; Delaude, Lionel; Demonceau, Albert

    Since the first reports on the use of microwave irradiation to accelerate organic chemical transformations, a plethora of papers have been published in this field. In most examples, microwave heating has been shown to dramatically reduce reaction times, increase product yields, and enhance product purity by reducing unwanted side reactions compared to conventional heating methods. The present contribution aims at illustrating the advantages of this technology in olefin metathesis and, when data are available, at comparing microwave-heated and conventionally heated experiments

  4. THE AMPHIPHILIC MULTIARM COPOLYMERS BASED ON HYPERBRANCHED POLYESTER AND LYSINE: SYNTHESIS AND SELF-ASSEMBLY

    Institute of Scientific and Technical Information of China (English)

    Jing Wang; Yuan Yao; Bing Ji; Wei Huang; Yong-feng Zhou; De-yue Yan

    2011-01-01

    The amphiphilic multiarm copolymers were synthesized through the modification of commercially available hyperbranched polyesters (Boltom H40) with N-ε-carbobenzoxy-L-Lysine N-carboxyanhydride (ZLys-NCA). After being condensed with N-Boc-phenylalanine (Boc-NPhe) and deprotected the Boc-groups in trifluoroacetic acid (TFA), the original terminal hydroxyl groups were transformed into the amino groups and then initiated the ring-opening polymerization of ZLys-NCA. The hydrophilic poly(L-lysine) was grafted to the surface of Boltorn H40 successfully after the protecting benzyl groups were removed by the HBr solution in glacial acetic acid (33 wt%). The resulting multiarm copolymers were characterized by the 1H-NMR, GPC and FTIR. The arm length calculated by NMR and GPC analysis was about 3 and 13 lysine-units for H40-Phe-PLysl and H40-Phe-PLys2 respectively. Due to the amphiphilic molecular structure, they displayed ability to self-assemble into spherical micelles in aqueous solution with the average diameter in the range from 70 nm to 250 nm. The CMC of H40-Phe-PLysl and H40-Phe-PLys2 was 0.013 mg/mL and 0.028 mg/mL, respectively,indicating that H40-Phe-PLysl with shorter arm length is easier to self-assemble than H40-Phe-PLys2 with longer arm length.

  5. Hydroquinone based sulfonated poly (arylene ether sulfone copolymer as proton exchange membrane for fuel cell applications

    Directory of Open Access Journals (Sweden)

    V. Kiran

    2015-12-01

    Full Text Available Synthesis of sulfonated poly (arylene ether sulfone copolymer by direct copolymerization of 4,4'-bis(4-hydroxyphenyl valeric acid, benzene 1,4-diol and synthesized sulfonated 4,4'-difluorodiphenylsulfone and its characterization by using FTIR (Fourier Transform Infrared and NMR (Nuclear Magnetic Resonance spectroscopic techniques have been performed. The copolymer was subsequently cross-linked with 4, 4!(hexafluoroisopropylidenediphenol epoxy resin by thermal curing reaction to synthesize crosslinked membranes. The evaluation of properties showed reduction in water and methanol uptake, ion exchange capacity, proton conductivity with simultaneous enhancement in oxidative stability of the crosslinked membranes as compared to pristine membrane. The performance of the membranes has also been evaluated in terms of thermal stability, morphology, mechanical strength and methanol permeability by using Thermo gravimetric analyzer, Differential scanning calorimetery, Atomic force microscopy, XPERT-PRO diffractometer, universal testing machine and diffusion cell, respectively. The results demonstrated that the crosslinked membranes exhibited high thermal stability with phase separation, restrained crystallinity, acceptable mechanical properties and methanol permeability. Therefore, these can serve as promising proton exchange membranes for fuel cell applications.

  6. Stimuli-Responsive Block Copolymer-Based Assemblies for Cargo Delivery and Theranostic Applications

    Directory of Open Access Journals (Sweden)

    Jun Yin

    2016-07-01

    Full Text Available Although a number of tactics towards the fabrication and biomedical exploration of stimuli-responsive polymeric assemblies being responsive and adaptive to various factors have appeared, the controlled preparation of assemblies with well-defined physicochemical properties and tailor-made functions are still challenges. These responsive polymeric assemblies, which are triggered by stimuli, always exhibited reversible or irreversible changes in chemical structures and physical properties. However, simple drug/polymer nanocomplexes cannot deliver or release drugs into the diseased sites and cells on-demand due to the inevitable biological barriers. Hence, utilizing therapeutic or imaging agents-loaded stimuli-responsive block copolymer assemblies that are responsive to tumor internal microenvironments (pH, redox, enzyme, and temperature, etc. or external stimuli (light and electromagnetic field, etc. have emerged to be an important solution to improve therapeutic efficacy and imaging sensitivity through rationally designing as well as self-assembling approaches. In this review, we summarize a portion of recent progress in tumor and intracellular microenvironment responsive block copolymer assemblies and their applications in anticancer drug delivery and triggered release and enhanced imaging sensitivity. The outlook on future developments is also discussed. We hope that this review can stimulate more revolutionary ideas and novel concepts and meet the significant interest to diverse readers.

  7. Preparation of amorphous aluminum oxide-hydroxide nanoparticles in amphiphilic silicone-based copolymer microemulsions.

    Science.gov (United States)

    Berkovich, Yana; Aserin, Abraham; Wachtel, Ellen; Garti, Nissim

    2002-01-01

    Organo-inorgano nanocomposites with colloidal dimensions have interesting optical, catalytic, and mechanical properties, particularly when such hybrids are reinforced with transition metal oxide nanoparticles. Nanoparticles with a mean size of 1.0-2.4 nm are obtained through hydrolysis of aluminum isopropoxide in the L(2) phase of amphiphilic (PDMS-POE) polydimethylsiloxane-polyoxyethylene Silwet L-7607-octanol/acetylacetone-water mixtures. The particle sizes are related weakly to the microemulsion composition: 0.8-1.2 nm for 20 wt% Silwet L-7607 and 2.0-2.4 nm for 50 wt% Silwet L-7607. Protection of the particles against aggregation is ensured through their confinement in the intraaggregate colloidal domains. Factors affecting the hydrolysis-condensation process of acetylacetone-complexed aluminum isopropoxide in copolymer-poor and copolymer-rich regions of PDMS-POE W/O microemulsions are studied by Fourier transform infrared spectroscopy, small angle X-ray scattering, and transmission electron microscopy. Prepared nanoparticulate dispersions possess long-term stability and form clear mixtures in different organic polar and nonpolar solvents.

  8. Lithium battery with solid polymer electrolyte based on comb-like copolymers

    Science.gov (United States)

    Daigle, Jean-Christophe; Vijh, Ashok; Hovington, Pierre; Gagnon, Catherine; Hamel-Pâquet, Julie; Verreault, Serge; Turcotte, Nancy; Clément, Daniel; Guerfi, Abdelbast; Zaghib, Karim

    2015-04-01

    In this paper we report on the synthesis of comb-like copolymers as solid polymer electrolytes (SPE). The synthesis involved anionic polymerization of styrene (St) and 4-vinylanisole (VA) as the followed by grafting of poly(ethylene glycol) monomethyl ether methacrylate (PEGMA) by Atom Transfer Radical Polymerization (ATRP). The comb-like copolymer's structure was analyzed by Fourier transform infrared (FTIR) spectroscopy, nuclear magnetic resonance (NMR) and gel permeation chromatography (GPC). The membranes were made by solvent casting and the morphologies were analyzed by atomic forces microscopy (AFM) and scanning electron microscopy (SEM). We observed that a nano and micro phase separation occurs which improves ionic conductivity. The ionic conductivities were determined by AC Impedance, which showed that the SPEs have good conductivities (10-5 Scm-1) at room temperature owing to the negligible values (<10 kJ mol-1) of the activation energies for conductivity. The batteries with these polymers exhibit a capacity of 146 mAh g-1 at C/24, and no evidence of degradation after intense cycling was observed. However, poor cycle life was observed at C/6 and C/3, which is a consequence of several factors. We partially explain that behavior by arguing that whereas PEO lightly "solvates" Li+ thus slowing Li-ion mobility, and PEGMA chains "solvate" Li ions too strongly, trapping and inhibiting their mobility.

  9. Studies on gel electrolyte based on nitrile-butadiene copolymers. Final report, 1 November 1991-30 November 1992

    Energy Technology Data Exchange (ETDEWEB)

    Sircar, A.K.; Kumar, B.; Linden, S.M.; Weissman, P.T.

    1993-06-01

    This study is concerned with the preparation of a hybrid electrolyte, suitable for solid-polymer batteries. Based on the study of ionic conductivity in the presence of LiBF4 of a number of nitrile-butadiene copolymers (NBR), hydrogenated NBR (HNBR) was selected as the host polymer. DC conductivity studies with three different lithium salts in different plasticizers showed the highest conductivity for LiBF4. Conductivity of LiBF4 in different plasticizers decreases in the order DMF > DMAC > Gamma butyrolactone > NMP > PC=gamma-valerolactone > glymes. NMP was chosen as the plasticizer for hybrid films based on its moderate conductivity, low vapor pressure, and low freezing point. Polymer electrolytes, Gel electrolytes, Ionic conductivity.

  10. Synthesis, characterizations and biocompatibility of novel biodegradable star block copolymers based on poly[(R)-3-hydroxybutyrate] and poly(epsilon-caprolactone)

    DEFF Research Database (Denmark)

    Wang, Liang; Wang, Xiaojuan; Xu, Kaitian;

    2010-01-01

    Star block copolymers based on poly[(R)-3-hydroxybutyrate] (PHB) and poly(epsilon-caprolactone) (PCL), termed SPHBCL, were successfully synthesized with structural variation on arm numbers and lengths via coupling reactions and ring opening polymerizations. Arm numbers 3, 4 and 6 of SPHBCL were...

  11. Impacts of Repeat Unit Structure and Copolymer Architecture on Thermal and Solution Properties in Homopolymers, Copolymers, and Copolymer Blends

    Science.gov (United States)

    Marrou, Stephen Raye

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

  12. Volatile organic compound detection using nanostructured copolymers.

    Science.gov (United States)

    Li, Bo; Sauvé, Genevieve; Iovu, Mihaela C; Jeffries-El, Malika; Zhang, Rui; Cooper, Jessica; Santhanam, Suresh; Schultz, Lawrence; Revelli, Joseph C; Kusne, Aaron G; Kowalewski, Tomasz; Snyder, Jay L; Weiss, Lee E; Fedder, Gary K; McCullough, Richard D; Lambeth, David N

    2006-08-01

    Regioregular polythiophene-based conductive copolymers with highly crystalline nanostructures are shown to hold considerable promise as the active layer in volatile organic compound (VOC) chemresistor sensors. While the regioregular polythiophene polymer chain provides a charge conduction path, its chemical sensing selectivity and sensitivity can be altered either by incorporating a second polymer to form a block copolymer or by making a random copolymer of polythiophene with different alkyl side chains. The copolymers were exposed to a variety of VOC vapors, and the electrical conductivity of these copolymers increased or decreased depending upon the polymer composition and the specific analytes. Measurements were made at room temperature, and the responses were found to be fast and appeared to be completely reversible. Using various copolymers of polythiophene in a sensor array can provide much better discrimination to various analytes than existing solid state sensors. Our data strongly indicate that several sensing mechanisms are at play simultaneously, and we briefly discuss some of them.

  13. Modification of ethylene-norbornene copolymer by Gamma irradiation

    Directory of Open Access Journals (Sweden)

    Kačarević-Popović Zorica M.

    2006-01-01

    Full Text Available The possibility of modifying polyethylene and many other polymers with high energy radiation has led to many useful applications. Due to their new combination of properties and the shortage of experimental data, the radiolysis of a new class of materials, cyclo-olefin copolymers (COC, polymerised from norbornene and ethylene using metallocene catalysts, is of great interest to the study of radiation chemistry and the physics of polymeric systems. Ethylenenorbornene copolymer, pristine and containing an antioxidant were subjected to gamma irradiation in the presence of air and in water. The irradiated copolymer was studied using IR and UV-vis spectrophotometric analysis. The radiation-induced changes in the molecular structure were correlated to changes in the glass transition temperature measured by the DSC method.

  14. Rapid Identification and Quantification of Linear Olefin Isomers by Online Ozonolysis-Single Photon Ionization Time-of-Flight Mass Spectrometry.

    Science.gov (United States)

    Xie, Yuanyuan; Chen, Ping; Hua, Lei; Hou, Keyong; Wang, Yongchao; Wang, Haiyan; Li, Haiyang

    2016-01-01

    The specific locations of the double bonds in linear olefins can facilitate olefin catalytic synthetic reactions to improve the quality of target olefin products. We developed a simple and efficient approach based on single photon ionization time-of-flight mass spectrometry (SPI-TOFMS) combined with online ozonolysis to identify and quantify the linear olefin double bond positional isomers. The online ozonolysis cleaved the olefins at the double bond positions that led to formation of corresponding characteristic aldehydes. The aldehydes were then detected by SPI-TOFMS to achieve unique spectrometric "fingerprints" for each linear olefin to successfully identify the isomeric ones. To accurately quantify the isomeric components in olefin mixtures, an algorithm was proposed to quantify three isomeric olefin mixtures based on characteristic ion intensities and their equivalent ionization coefficients. The relative concentration errors for the olefin components were lower than 2.5% while the total analysis time was less than 2 min. These results demonstrate that the online ozonolysis SPI-TOFMS has the potential for real-time monitoring of catalytic olefin synthetic reactions.

  15. Performance of an in situ formed bioactive hydrogel dressing from a PEG-based hyperbranched multifunctional copolymer.

    Science.gov (United States)

    Dong, Yixiao; Hassan, Waqar U; Kennedy, Robert; Greiser, Udo; Pandit, Abhay; Garcia, Yolanda; Wang, Wenxin

    2014-05-01

    Hydrogel dressings have been widely used for wound management due to their ability to maintain a hydrated wound environment, restore the skin's physical barrier and facilitate regular dressing replacement. However, the therapeutic functions of standard hydrogel dressings are restricted. In this study, an injectable hybrid hydrogel dressing system was prepared from a polyethylene glycol (PEG)-based thermoresponsive hyperbranched multiacrylate functional copolymer and thiol-modified hyaluronic acid in combination with adipose-derived stem cells (ADSCs). The cell viability, proliferation and metabolic activity of the encapsulated ADSCs were studied in vitro, and a rat dorsal full-thickness wound model was used to evaluate this bioactive hydrogel dressing in vivo. It was found that long-term cell viability could be achieved for both in vitro (21days) and in vivo (14days) studies. With ADSCs, this hydrogel system prevented wound contraction and enhanced angiogenesis, showing the potential of this system as a bioactive hydrogel dressing for wound healing.

  16. From blood dialysis to desalination: A one-size fits all block copolymer based membrane system

    Science.gov (United States)

    Sanna Kotrappanavar, Nataraj; Zavala-Rivera, Paul; Chonnon, Kevin; Almuhtaseb, Shaheen S. A.; Sivaniah, Easan; University of Cambridge Team; Qatar University Collaboration

    2011-03-01

    Asymmetric membrane with ultrahigh selective self-assembled nanoporous block copolymer layer were developed successfully on polyimide (PI) support, which demonstrated excellent thermal, chemical and mechanical stability. Membranes with specific nano- structural architectures and optimized cascades of block assemblies on the top selective skin have been used largely for separation of colour from aqueous streams, wastewater treatment, desalination, blood filtration and gas separation with dense layer transformation. A consistent and reliable method of membrane preparation and measuring separation performance has been adopted. A homologous series of ethylene oxide oligomers covering a large range was used to characterise MWCO of Membrane and were able to provide many points to give a comprehensive description of the membrane performance in the nanofiltration range.

  17. Thermoelectric Properties of Carbon Nanotube and Nanofiber Based Ethylene-Octene Copolymer Composites for Thermoelectric Devices

    Directory of Open Access Journals (Sweden)

    P. Slobodian

    2013-01-01

    Full Text Available Polymer composites have been created from multiwalled carbon nanotubes or carbon nanofibers and ethylene-octene copolymer. The composites have thermoelectric properties and exhibit thermoelectric effect, that is, the conversion of temperature differences into electricity. The thermoelectric efficiency of created composites with nanotube or nanofiber concentration of 30 wt% evaluated by a thermoelectric power at room temperature is 13.3 μV/K and 14.2 μV/K, respectively. The flexible thermoelectric device (thermopile was constructed with three different composite legs to produce electric current and the output voltage was measured in the range of temperature difference from −15 to 25°C.

  18. Enhanced infarct myocardium repair mediated by thermosensitive copolymer hydrogel-based stem cell transplantation

    Science.gov (United States)

    Xia, Yu; Zhu, Kai; Lai, Hao; Lang, Meidong; Xiao, Yan; Lian, Sheng

    2015-01-01

    Mesenchymal stem cell (MSC) transplantation by intramyocardial injection has been proposed as a promising therapy strategy for cardiac repair after myocardium infarction. However, low retention and survival of grafted MSCs hinder its further application. In this study, copolymer with N-isopropylacrylamide/acrylic acid/2-hydroxylethyl methacrylate-poly(ɛ-caprolactone) ratio of 88:9.6:2.4 was bioconjugated with type I collagen to construct a novel injectable thermosensitive hydrogel. The injectable and biocompatible hydrogel-mediated MSC transplantation could enhance the grafted cell survival in the myocardium, which contributed to the increased neovascularization, decreased interstitial fibrosis, and ultimately improved heart function to a significantly greater degree than regular MSC transplantation. We suggest that this novel hydrogel has the potential for future stem cell transplantation. PMID:25432986

  19. Polyhydroxyalkanoate-based natural synthetic hybrid copolymer films: A small-angle neutron scattering study

    Science.gov (United States)

    Foster, L. John R.; Knott, Robert; Sanguanchaipaiwong, Vorapat; Holden, Peter J.

    2006-11-01

    Polyhydroxyalkanoates have attracted attention as biodegradable alternatives to conventional thermoplastics and as biomaterials. Through modification of their biosynthesis using Pseudomonas oleovorans, we have manipulated the material properties of these biopolyesters and produced a natural-synthetic hybrid copolymer of polyhydroxyoctanoate- block-diethylene glycol (PHO- b-DEG). A mixture of PHO and PHO-DEG were solvent cast from analytical grade chloroform and analysed using small-angle neutron scattering. A scattering pattern, easily distinguished above the background, was displayed by the films with a diffraction ring at q∼0.12 Å -1. This narrow ring of intensity is suggestive of a highly ordered system. Analysis of the diffraction pattern supported this concept and showed a d-spacing of approximately 50 Å. In addition, conformation of the hybrid polymer chains can be manipulated to support their self-assembly into ordered microporous films.

  20. Enhanced infarct myocardium repair mediated by thermosensitive copolymer hydrogel-based stem cell transplantation.

    Science.gov (United States)

    Xia, Yu; Zhu, Kai; Lai, Hao; Lang, Meidong; Xiao, Yan; Lian, Sheng; Guo, Changfa; Wang, Chunsheng

    2015-05-01

    Mesenchymal stem cell (MSC) transplantation by intramyocardial injection has been proposed as a promising therapy strategy for cardiac repair after myocardium infarction. However, low retention and survival of grafted MSCs hinder its further application. In this study, copolymer with N-isopropylacrylamide/acrylic acid/2-hydroxylethyl methacrylate-poly(ɛ-caprolactone) ratio of 88:9.6:2.4 was bioconjugated with type I collagen to construct a novel injectable thermosensitive hydrogel. The injectable and biocompatible hydrogel-mediated MSC transplantation could enhance the grafted cell survival in the myocardium, which contributed to the increased neovascularization, decreased interstitial fibrosis, and ultimately improved heart function to a significantly greater degree than regular MSC transplantation. We suggest that this novel hydrogel has the potential for future stem cell transplantation.

  1. SYNTHESIS AND CHARACTERIZATION OF PHENOTHIAZINE-BASED PPV-TYPE COPOLYMERS CONTAINING FLUORENE AND THIOPHENE MOIETIES

    Institute of Scientific and Technical Information of China (English)

    2005-01-01

    Copolymers of fluorene-co-phenothiazine (P1) and thiophene-co-phenothiazine (P2) were prepared respectively by Wittig reaction. The synthesis, photo-physical and electroluminescent properties of the resulting polymers were analyzed by FT-IR, GPC, 1H-NMR, UV-Vis, Photoluminescence (PL), Electroluminescence (EL) and Cyclic Voltammetry (CV). Their single layer devices with configuration of ITO/polymers/Ca/Al were studied. GPC results revealed the weight-average molecular weight (Mw) was 3.0×103 and 5.4×103, respectively. The device with a single layer structure of ITO/P1/Ca/Al emits green light with the maximum peak at 552nm. However,the device with a single layer structure of ITO/P2/Ca/Al emit red light with the maximum peak at 616nm.

  2. Applications of Tris(4-(thiophen-2-ylphenylamine- and Dithienylpyrrole-based Conjugated Copolymers in High-Contrast Electrochromic Devices

    Directory of Open Access Journals (Sweden)

    Tzi-Yi Wu

    2016-05-01

    Full Text Available Tris(4-(thiophen-2-ylphenylamine- and dithienylpyrrole-based copolymers (P(TTPA-co-DIT and P(TTPA-co-BDTA were electropolymerized on ITO electrode by applying constant potentials of 1.0, 1.1, and 1.2 V. Spectroelectrochemical investigations revealed that P(TTPA-co-DIT film displayed more color changes than P(TTPA-co-BDTA film. The P(TTPA-co-DIT film is yellow in the neutral state, yellowish-green and green in the intermediate state, and blue (1.2 V in highly oxidized state. The ∆Tmax of the P(TTPA-co-DIT and P(TTPA-co-BDTA films were measured as 60.3% at 1042 nm and 47.1% at 1096 nm, respectively, and the maximum coloration efficiency (η of P(TTPA-co-DIT and P(TTPA-co-BDTA films were calculated to be 181.9 cm2·C−1 at 1042 nm and 217.8 cm2·C−1 at 1096 nm, respectively, in an ionic liquid solution. Dual type electrochromic devices (ECDs consisting of P(TTPA-co-DIT (or P(TTPA-co-BDTA anodic copolymer, ionic liquid-based electrolyte, and poly(3,4-(2,2-diethylpropylenedioxythiophene (PProDOT-Et2 cathodic polymer were constructed. P(TTPA-co-BDTA/PProDOT-Et2 ECD showed high ΔTmax (48.1% and high coloration efficiency (649.4 cm2·C−1 at 588 nm. Moreover, P(TTPA-co-DIT/PProDOT-Et2 and P(TTPA-co-BDTA/PProDOT-Et2 ECDs displayed satisfactory optical memory and long term switching stability.

  3. Fluorene-based narrow-band-gap copolymers for red light- emitting diodes and bulk heterojunction photovoltaic cells

    Institute of Scientific and Technical Information of China (English)

    Mingliang SUN; Li WANG; Yangjun XIA; Bin DU; Ransheng LIU; Yong CAO

    2008-01-01

    A series of narrow band-gap conjugated copo-lymers (PFO-DDQ) derived from 9,9-dioctylfluorene (DOF) and 2,3-dimethyl-5,8-dithien-2-yl-quinoxalines (DDQ) is prepaid by the palladium-catalyzed Suzuki coupling reaction with the molar feed ratio of DDQ at around 1%,5%,15%,30% and 50%,respectively.The obtained polymers are readily soluble in common organic solvents.The solutions and the thin solid films of the copolymers absorb light from 300-590 nm with two absorbance.peaks at around 380 and 490 nm.The intens-ity of 490 nm peak increases with the increasing DDQ content in the polymers.Efficient energy transfer due to exciton trapping on narrow-band-gap DDQ sites has been observed.The PL emission consists exclusively of DDQ unit emission at around 591 643 nm depending on the DDQ content in solid film.The EL emission peaks are red-shifted from 580 nm for PFO-DDQ1 to 635 nm for PFO-DDQ50.The highest external quantum efficiency achieved with the device configuration ITO/PEDOT/ PVK/PFO-DDQt5/Ba/A1 is 1.33% with a luminous effi-ciency 1.54 cd/A.Bulk heterojunction photovoltaic cells fabricated from composite films of PFO-DDQ30 copoly-mer and [6,6]-phenyl C61 butyric acid methyl ester (PCBM) as electron donor and electron acceptor,respect-ively in device configuration:ITO/PEDOT:PSS/PFO-DDQ30:PCBM/PFPNBr/Al shows power conversion effi-ciencies of 1.18% with open-circuit voltage (Voc) of 0.90 V and short-circuit current density (Jsc) of 2.66 mA/cm2 under an AM1.5 solar simulator (100 mW/cm2).The photocurrent response wavelengths of the PVCs based on PFO-DDQ30/PCBM blends covers 300-700 nm.This indicates that these kinds of low band-gap polymers are promising candidates for polymeric solar cells and red light-emitting diodes.

  4. Mechanochemical ruthenium-catalyzed olefin metathesis.

    Science.gov (United States)

    Do, Jean-Louis; Mottillo, Cristina; Tan, Davin; Štrukil, Vjekoslav; Friščić, Tomislav

    2015-02-25

    We describe the development of a mechanochemical approach for Ru-catalyzed olefin metathesis, including cross-metathesis and ring-closing metathesis. The method uses commercially available catalysts to achieve high-yielding, rapid, room-temperature metathesis of solid or liquid olefins on a multigram scale using either no or only a catalytic amount of a liquid.

  5. Synthesis of Dialkyl-substituted Terminal Olefin

    Institute of Scientific and Technical Information of China (English)

    2005-01-01

    Dialkyl-substituted terminal olefins were synthesized from the coupling reaction of αt-olefins which were catalyzed by zirconocene dichloride/methylalumoxane (MAO) catalyst system under mild condition. High yield was gained and no other oligmer was detected. It was found that the ratio of Al/Zr is responsible for the selectivity of product.

  6. Polyisobutylene chain end transformations: Block copolymer synthesis and click chemistry functionalizations

    Science.gov (United States)

    Magenau, Andrew Jackson David

    The primary objectives of this research were twofold: (1) development of synthetic procedures for combining quasiliving carbocationic polymerization (QLCCP) of isobutylene (IB) and reversible addition fragmentation chain transfer (RAFT) polymerization for block copolymer synthesis; (2) utilization of efficient, robust, and modular chemistries for facile functionalization of polyisobutylene (PIB). In the first study block copolymers consisting of PIB, and either PMMA or PS block segments, were synthesized by a site transformation approach combining living cationic and reversible addition-fragmentation chain transfer (RAFT) polymerizations. The initial PIB block was synthesized via quasiliving cationic polymerization using the TMPCl/TiCl4 initiation system and was subsequently converted into a hydroxylterminated PIB. Site transformation of the hydroxyl-terminated PIB into a macro chain transfer agent (PIB-CTA) was accomplished by N,N'-dicyclohexylcarbodiimide/dimethylaminopyridine-catalyzed esterification with 4-cyano-4-(dodecylsulfanylthiocarbonylsulfanyl)pentanoic acid. In the second study another site transformation approach was developed to synthesize a novel block copolymer, composed of PIB and PNIPAM segments. The PIB block was prepared via quasiliving cationic polymerization and end functionalized by in-situ quenching to yield telechelic halogen-terminated PIB. Azido functionality was obtained by displacement of the terminal halogen through nucleophilic substitution, which was confirmed by both 1H and 13C NMR. Coupling of an alkyne-functional chain transfer agent (CTA) to azido PIB was successfully accomplished through a copper catalyzed click reaction. Structure of the resulting PIB-based macro-CTA was verified with 1H NMR, FTIR, and GPC; whereas coupling reaction kinetics were monitored by real time variable temperature (VT) 1H NMR. In a third study, a click chemistry functionalization procedure was developed based upon the azide-alkyne 1,3-dipolar

  7. Catalytic Enantioselective Allylic Amination of Olefins for the Synthesis of ent-Sitagliptin.

    Science.gov (United States)

    Bao, Hongli; Bayeh, Liela; Tambar, Uttam K

    2013-11-01

    The presence of nitrogen atoms in most chiral pharmaceutical drugs has motivated the development of numerous strategies for the synthesis of enantioenriched amines. Current methods are based on the multi-step transformation of pre-functionalized allylic electrophiles into chiral allylic amines. The enantioselective allylic amination of unactivated olefins represents a more direct and attractive strategy. We report the enantioselective synthesis of ent-sitagliptin via an allylic amination of an unactivated terminal olefin.

  8. Supramolecular micellar nanoaggregates based on a novel chitosan/vitamin E succinate copolymer for paclitaxel selective delivery

    Directory of Open Access Journals (Sweden)

    Lian H

    2011-12-01

    experiments, conducted by confocal laser scanning microscopy, showed an enhanced cellular uptake efficiency of the CS-VES micelles in MCF-7 cells compared with Taxol. The PTX-micelles exhibited a comparable but delayed cytotoxic effect compared with Taxol against MCF-7 cells, due to the sustained-release characteristics of the nanomicelles. More interestingly, blank nanomicelles based on CS-VES copolymer demonstrated significant cytotoxicity against MCF-7 cells.Conclusion: The supramolecular micellar aggregates based on CS-VES copolymer is a promising nanocarrier and efficacy enhancer when used as an anticancer drug-delivery system.Keywords: nanomicelles, cellular uptake, cytotoxicity

  9. Poly(L-histidine) based copolymers: Effect of the chemically substituted L-histidine on the physio-chemical properties of the micelles and in vivo biodistribution.

    Science.gov (United States)

    Zhang, Xiaojun; Chen, Dawei; Ba, Shuang; Chang, Jing; Zhou, Jiaying; Zhao, Haixia; Zhu, Jia; Zhao, Xiuli; Hu, Haiyang; Qiao, Mingxi

    2016-04-01

    Even though the Poly(l-histidine) (PHis) based copolymers have been well studied, the effect of the chemically substituted l-histidine on the physio-chemical and biological properties of the micelles has never been elucidated to date. To address this issue, triblock copolymer of poly(ethylene glycol)-poly(D,L-lactide)-poly(2,4-dinitrophenol-L-histidine)(mPEG-b-PLA-b-DNP-PHis) with DNP group substituted to the saturated nitrogen of l-histidine were synthesized. The pH sensitive properties of the copolymer micelles were characterized using an acid-base titration method, fluorescene probe technique, DLS observation, in vitro drug release and cytotoxicity against MCF-7 cells under different pH conditions, respectively. The results suggest that mPEG-b-PLA-b-DNP-PHis copolymers showed similar micellar stability for DOX loaded micelles, increased particle size, and similar pH responsive properties with mPEG-b-PLA-b-PHis copolymers. The subcellular distribution observation demonstrated that mPEG-b-PLA-b-DNP-PHis micelles showed a slightly compromised endo-lysosmal escape of doxorubicin as compared to mPEG-b-PLA-b-PHis micelles. The mPEG-b-PLA-b-DNP-PHis micelles showed higher cellular uptake by MCF-7 cells than mPEG-b-PLA-b-PHis micelles due to the different uptake pathways. Effect of DNP substitution on the in vivo distribution of the copolymer micelles was studied using non-invasive near-infrared fluorescence (NIRF) imaging with mPEG-b-PLA-b-PHis micelles as control. The results indicate that the mPEG-b-PLA-b-DNP-PHis micelles showed a reduced passive targeting to the tumor due to the larger particle size. These results suggest that saturated nitrogen of PHis may serve as a valuable site for chemical modification of the PHis based copolymers because of the little effect on the pH responsive properties. However, selection of the substitution group needs to be considered due to the possible increase of micellar particle size of the micelles, leading to compromised passive

  10. Team for Research on Methanol-to-Olefins Technology

    Institute of Scientific and Technical Information of China (English)

    2012-01-01

    Olefins, traditionally derived from oil, are important basic materials for the modern chemical industry. To make olefins from coal rather than oil has been a dream and also a big challenge for scientists all over the world. The step from methanol to olefins is vital in the transformation from coal or natural gas to olefins,

  11. Drug targeting to tumors using HPMA copolymers

    NARCIS (Netherlands)

    Lammers, T.G.G.M.

    2009-01-01

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

  12. 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 ...

  13. Ionic liquid-polymer gel electrolytes based on morpholinium salt and PVdF(HFP) copolymer

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Ki-Sub; Park, Seung-Yeob; Choi, Sukjeong; Lee, Huen [Department of Chemical and Biomolecular Engineering, Korea Advanced Institute of Science and Technology, 373-1 Guseong-dong, Yuseong-gu, Daejeon 305-701 (Korea, Republic of)

    2006-04-21

    New ionic liquid-polymer gel electrolytes (IPGEs) are prepared from N-ethyl-N-methylmorpholinium bis(trifluoromethanesulfonyl)imide (Mor{sub 1,2}TFSI) and poly(vinylidene fluoride)-hexafluoropropylene copolymer (PVdF(HFP)). To investigate the effect of propylene carbonate (PC) on the ionic conductivity of the IPGEs, the preparation methods are roughly divided into two groups according to the presence or absence of PC. The ionic conductivity for each IPGE is measured with increasing temperature and changing weight ratio of Mor{sub 1,2}TFSI. The results show that the ionic conductivity increases as the temperature and weight ratio of the Mor{sub 1,2}TFSI increase, and that the added PC improves the ionic conductivity of the IPGEs. In addition, thermogravimetric analysis and the data from infrared spectroscopy demonstrate the thermal stability of each IPGE and the presence of PC in the polymer network. Although the IPGEs that contain PC display high conductivity ({approx}1.1x10{sup -2}Scm{sup -1}) at 60{sup o}C, they are thermally unstable. (author)

  14. Electrospun functionalized polyaniline copolymer-based nanofibers with potential application in tissue engineering.

    Science.gov (United States)

    Gizdavic-Nikolaidis, Marija; Ray, Sudip; Bennett, Jared R; Easteal, Allan J; Cooney, Ralph P

    2010-12-08

    Nanofibrous blends of HCl-doped poly(aniline-co-3-aminobenzoic acid) (3ABAPANI) copolymer and poly(lactic acid) (PLA) were fabricated by electrospinning solutions of the polymers, in varying relative proportions, in dimethyl sulfoxide/tetrahydrofuran mixture. The morphology, mechanical and electrical properties of the nanofibers were characterized and an assessment of their bioactivity performed. To assess cell morphology and biocompatibility, pure PLA and 3ABAPANI-PLA nanofibrous mats were deposited in the form of three-dimensional networks with a high degree of connectivity, on glass substrates, and their ability to promote proliferation of COS-1 fibroblast cells was determined. The nanofibrous electrospun 3ABAPANI-PLA blends gave enhanced cell growth, potent antimicrobial capability against Staphylococcus aureus and electrical conductivity. This new class of nanofibrous blends can potentially be employed as tissue engineering scaffolds, and in particular have showed promise as the basis of a new generation of functional wound dressings that may eliminate deficiencies of currently available antimicrobial dressings.

  15. [INVITED] Hyperbolic-by-design self-assembled metamaterial based on block copolymers lamellar phases

    Science.gov (United States)

    Wang, Xuan; Ehrhardt, Kevin; Tallet, Clémence; Warenghem, Marc; Baron, Alexandre; Aradian, Ashod; Kildemo, Morten; Ponsinet, Virginie

    2017-02-01

    Hyperbolic metamaterials use the concept of controlling the propagative modes through the engineering of the dispersion relation, and are considered highly promising to reach different meta-properties. Here we propose a novel bottom-up fabrication technique for uniaxial anisotropic metamaterials presenting a strongly anisotropic dispersion relation in the visible wavelength range, using self-assembled nanostructured block copolymers hybridized with gold nanoparticles. The materials consist in periodic lamellar stacks of period 28 nm, of alternating layers of pure polymer (dielectric) and layers of composite of polymer loaded with a high density of 7 nm gold nanoparticles. The spectral variation of their anisotropic effective dielectric permittivity is determined by variable-angle spectroscopic ellipsometry using appropriate effective medium models, as a function of the density of plasmonic nanoparticles. For large gold loading and close to the plasmon resonance of the nanoparticles, the lamellar stack presents ordinary and extraordinary components of the dielectric function of opposite signs. We therefore demonstrate for the first time the possibility of using a self-assembly methodology for the fabrication of bulk hyperbolic metamaterial.

  16. Flexible supercapacitor based on electrochemically synthesized pyrrole formyl pyrrole copolymer coated on carbon microfibers

    Science.gov (United States)

    Gholami, Mehrdad; Moozarm Nia, Pooria; Narimani, Leila; Sokhakian, Mehran; Alias, Yatimah

    2016-08-01

    The main objective of this work is to prepare a flexible supercapacitor using electrochemically synthesized pyrrole formyl pyrrole copolymer P(Py-co-FPy) coated on the carbon microfibers. Due to difficulties of working with carbon microfibers, glassy carbon was used to find out optimized conditions by varying mole ratio of pyrrole and formyl pyrrole monomers on the capacitance value. The prepared electrodes were characterized using Fourier transform infrared spectroscopy (FT-IR), field emission scanning electron microscope (FESEM), Brunauer-Emmett-Teller (BET) analysis, cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). Then the X-ray photoelectron spectroscopy (XPS) was used to characterize the optimized electrode. The specific capacitance is calculated using cyclic voltammetry, charge/discharge method, and impedance spectroscopy. The charge/discharge study reveals that the best specific capacitance is estimated to be 220.3 mF cm-2 for equal mole fraction of pyrrole and formyl pyrrole Py (0.1)-FP (0.1) at discharge current of 3 × 10-4 A. This optimized electrode keeps about 92% of its capacitance value in high current of discharging. The specific capacitances calculated by all the mentioned methods are in agreement with each other. Finally, the found optimized conditions were successfully applied to produce a flexible supercapacitor on the surface of carbon microfibers.

  17. 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.

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

    Science.gov (United States)

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

    2016-01-27

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

  19. Electrical characterization of fluorinated benzothiadiazole based conjugated copolymer – a promising material for high-performance solar cells

    DEFF Research Database (Denmark)

    Toušek, J.; Toušková, J.; Remeš, Z.;

    2015-01-01

    Measurements of electrical conductivity, electron work function, carrier mobility ofholes and the diffusion length of excitons were performed on samples of conjugatedpolymers relevant to polymer solar cells. A state of the art fluorinated benzothiadiazolebased conjugated copolymer (PBDTTHD − DTBTff...

  20. Organic Solar Cells with Controlled Nanostructures Based on Microphase Separation of Fullerene-Attached Thiophene-Selenophene Heteroblock Copolymers.

    Science.gov (United States)

    Chen, Peihong; Nakano, Kyohei; Suzuki, Kaori; Hashimoto, Kazuhito; Kikitsu, Tomoka; Hashizume, Daisuke; Koganezawa, Tomoyuki; Tajima, Keisuke

    2017-02-08

    Heteroblock copolymers consisting of poly(3-hexylthiophene) and fullerene-attached poly(3-alkylselenophene) (T-b-Se-PCBP) were synthesized for organic photovoltaic applications by quasi-living catalyst transfer polycondensation and subsequent conversion reactions. Characterization of the polymers confirmed the formation of well-defined diblock structures with high loading of the fullerene at the side chain (∼40 wt %). Heteroblock copolymer cast as a thin film showed a clear microphase-separated nanostructure approximately 30 nm in repeating unit after thermal annealing, which is identical to the microphase-separated nanostructure of diblock copolymer consisting of poly(3-hexylthiophene) and fullerene-attached poly(3-alkylthiophene) (T-b-T-PCBP). These heteroblock copolymers provide an ideal platform for investigating the effects of nanostructures and interfacial energetics on the performance of organic photovoltaic devices.

  1. Synthesis and characterization of polyester copolymers based on poly(butylene succinate) and poly(ethylene glycol)

    Energy Technology Data Exchange (ETDEWEB)

    Zhou, Xiao-Ming, E-mail: xiaomingzhou@tust.edu.cn

    2012-12-01

    A series of polyester copolymers was synthesized from 1,4-succinic acid with 1,4-butanediol and poly(ethylene glycol) through a two-step process of esterification and polycondensation in this article. The composition and physical properties of copolyesters were investigated via GPC, {sup 1}HNMR, DSC and PLM. The copolymer composition was in good agreement with that expected from the feed composition of the reactants. The melting temperature (T{sub m}), crystallization temperature (T{sub c}), and crystallinity (X{sub c}) of these copolyesters decreased gradually as the content of PEG unit increased. Otherwise, experimental results also showed that the contents of PEG in copolymers had an effect on the molecular weight, distribution, thermal properties, hydrolysis degradation properties, and crystalline morphology of polyester copolymers. - Graphical abstract: The composition of polyester copolymer was determined from the {sup 1}H NMR spectra using the relative intensities of the proton peaks. As a sample, the {sup 1}H NMR spectrum of polyester copolymer with 10 mol% of PEG is shown in Fig. 2: CO-(CH{sub 2}){sub 2}-CO; O-CH{sub 2}- and C-(CH{sub 2}){sub 2}-C from the SA and BD unit at {delta}2.59; {delta} 4.08 and {delta}1.67; O-(CH{sub 2}CH{sub 2}){sub n}-O from the PEG unit at {delta} 3.61. The molar composition of polyester copolymer was measured as the area ratio of {delta}3.61/({delta}4.08 + {delta}1.67) peak. The PEG unit is incorporated into the copolymers in an amount of about 9.12mol% less than that of the feed proportion. These results showed that the composition of the copolymers is in good agreement with that expected from the feed proportion. Highlights: Black-Right-Pointing-Pointer The introduction of PEG unit changed the flexibility of PBS main chain. Black-Right-Pointing-Pointer PEG unit did not alter the crystal form of PBS in copolymers. Black-Right-Pointing-Pointer PEG unit hindered the formation of ring-banded spherulite morphology in copolymers

  2. Flexible supercapacitor based on electrochemically synthesized pyrrole formyl pyrrole copolymer coated on carbon microfibers

    Energy Technology Data Exchange (ETDEWEB)

    Gholami, Mehrdad, E-mail: mehrdad897@um.edu.my [University of Malaya center for ionic liquids, Department of Chemistry, Faculty of Science, University of Malaya, 50603 Kuala Lumpur (Malaysia); Department of Chemistry, Faculty of Science, University of Malaya, 50603 Kuala Lumpur (Malaysia); Department of Chemistry, Marvdasht Branch, Islamic Azad University, P.O. Box 465, Marvdasht (Iran, Islamic Republic of); Moozarm Nia, Pooria, E-mail: pooriamn@yahoo.com [University of Malaya center for ionic liquids, Department of Chemistry, Faculty of Science, University of Malaya, 50603 Kuala Lumpur (Malaysia); Narimani, Leila, E-mail: Narimani.leila@gmail.com [University of Malaya center for ionic liquids, Department of Chemistry, Faculty of Science, University of Malaya, 50603 Kuala Lumpur (Malaysia); Sokhakian, Mehran, E-mail: m.sokhakian@gmail.com [University of Malaya center for ionic liquids, Department of Chemistry, Faculty of Science, University of Malaya, 50603 Kuala Lumpur (Malaysia); Alias, Yatimah, E-mail: yatimah70@um.edu.my [University of Malaya center for ionic liquids, Department of Chemistry, Faculty of Science, University of Malaya, 50603 Kuala Lumpur (Malaysia); Department of Chemistry, Faculty of Science, University of Malaya, 50603 Kuala Lumpur (Malaysia)

    2016-08-15

    Highlights: • A Flexible supercapacitor prepared by carbon microfibers coated with P(Py-co-FPy). • The variation of capacitance with different mole ratio of monomers is investigated. • The capacitance measured by different electrochemical methods. • This flexible supercapacitor can be discharged in higher currents for longer time. - Abstract: The main objective of this work is to prepare a flexible supercapacitor using electrochemically synthesized pyrrole formyl pyrrole copolymer P(Py-co-FPy) coated on the carbon microfibers. Due to difficulties of working with carbon microfibers, glassy carbon was used to find out optimized conditions by varying mole ratio of pyrrole and formyl pyrrole monomers on the capacitance value. The prepared electrodes were characterized using Fourier transform infrared spectroscopy (FT-IR), field emission scanning electron microscope (FESEM), Brunauer–Emmett–Teller (BET) analysis, cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). Then the X-ray photoelectron spectroscopy (XPS) was used to characterize the optimized electrode. The specific capacitance is calculated using cyclic voltammetry, charge/discharge method, and impedance spectroscopy. The charge/discharge study reveals that the best specific capacitance is estimated to be 220.3 mF cm{sup −2} for equal mole fraction of pyrrole and formyl pyrrole Py (0.1)-FP (0.1) at discharge current of 3 × 10{sup −4} A. This optimized electrode keeps about 92% of its capacitance value in high current of discharging. The specific capacitances calculated by all the mentioned methods are in agreement with each other. Finally, the found optimized conditions were successfully applied to produce a flexible supercapacitor on the surface of carbon microfibers.

  3. Structures and photoelectric properties of five benzotrithiophene isomers-based donor-acceptor copolymers

    Science.gov (United States)

    Cheng, Na; Ma, Yuchen; Liu, Yongjun; Zhang, Changqiao; Liu, Chengbu

    2016-04-01

    In this paper, we have investigated the structures, electronic and optical properties of five conjugated copolymers (BTT1-BTz, BTT2-BTz, BTT3-BTz, BTT4-BTz and BTT5-BTz) featuring benzotrithiophene (BTT) isomers as donor units and benzothiadiazole (BTz) as acceptor units, linked through thiophene spacers, employing many-body perturbation theory (MBPT). We have explored the isomer effects by configuration of the sulfur atoms in BTT units, aimed to get insight into how the structural modifications to the conjugated backbone can influence the molecular structures and electronic properties of conjugated polymers. Using the trimer as the computational model, the calculated low and high energy absorption bands (660 and 413 nm) for BTT1-BTz agree well with the experimental ones (645 and 430 nm) with a small offset of ~ 15 nm. On the basis of our calculations, it is found that the backbones of these polymers display different coplanarities, with the dihedral angles between the two neighboring rings varying from 12.3° to 79.0°. Importantly, both BTT1-BTz and BTT2-BTz exhibit intense adsorption around 660 and 623 nm, indicating their promising application in solar cells, whereas BTT3-BTz and BTT4-BTz display the intense adsorption at 569 and 551 nm, which are also usable in the tandem solar cells. BTT5-BTz has narrow and weak adsorption in the visible and infrared region, implying it is not conducive to the sunlight absorption. The blue shift of about 150 nm from BTT1-BTz to BTT5-BTz is suggested to be originated from the shorter effective conjugation lengths.

  4. Single-layer electroluminescent devices based on fluorene-1H-pyrazolo[3,4-b]quinoxaline co-polymers

    Science.gov (United States)

    Pokladko-Kowar, Monika; Danel, Andrzej; Chacaga, Łukasz

    2013-11-01

    A fluorene based copolymer was synthesized for electroluminescent application. To the main chain of polymer the nitrogen heterocyclic, 1H-pyrazolo[3,4-b]quinoxaline, unit was introduced. The incorporation of this derivative tuned the emission from the blue to yellow-green one. A simple, single layered device was fabricated with the configuration ITO/PEDOT/co-poly-FLU-PQX/Ca/Mg.

  5. Thermally reactive Thiazolo[5,4-d]thiazole based copolymers for high photochemical stability in polymer solar cells

    DEFF Research Database (Denmark)

    Helgesen, Martin; Vesterager Madsen, Morten; Andreasen, Birgitta

    2011-01-01

    New thermally reactive copolymers based on dithienylthiazolo[5,4-d]thiazole (DTZ) and silolodithiophene (SDT) have been synthesized and explored in bulk heterojunction solar cells as mixtures with [6,6]-phenyl-C61-butyric acid methyl ester (PCBM). In thin films the polymers had optical band gaps...... in the range of 1.64-1.80 eV. For solubility the polymers have incorporated alkyl groups on the SDT unit and thermally removable ester groups on the DTZ unit that can be eliminated around 200 °C for improved photochemical stability in thin films. The bulkiness of the alkyl chains on the SDT unit proved...... to be very significant in terms of photovoltaic performance of the polymer:PCBM solar cells. Polymers based on 4,4-dihexyl-4H-silolo[3,2-b:4,5-b′]dithiophene reached power conversion efficiencies (PCEs) up to 1.45% but changing the alkyl groups to more bulky ethylhexyl chains reduced the PCE to 1.17%. More...

  6. EFFICIENT WHITE EMITTING COPOLYMERS BASED ON BIPOLAR FLUORENE-co-DIBENZOTHIOPHENE-S,S-DIOXIDE-co-CARBAZOLE BACKBONE

    Institute of Scientific and Technical Information of China (English)

    Lei Ying; Yan-hu Li; Cai-hong Wei; Min-quan Wang; Wei Yang; Hong-bin Wu; Yong Cao

    2013-01-01

    Efficient white light emitting polymers were synthesized based on poly(9,9-dioctylfluorene-co-dibenzothiopheneS,S-dioxide) as blue emitter and a bisphenylamine functionalized 2,1,3-benzothiadiazole (DPABT) as red emitter.It was found that the incorporation of hole-transporting carbazole moiety into polymer main chain could effectively reduce the hole injection barriers,which can lead to distinctly improved charge balance in the emissive layer.Additionally,the holetransporting carbazole units may form efficient bipolar host with electron-transporting dibenzothiophene-S,S-dioxide units.The white light emitting diodes based on single polymer PFSOCzDPABT showed the maximum luminous efficiency of 3.3 cd/A with the maximum luminance of 10282 cd/m2,and the luminous efficiency showed only 24% roll off at current density of 400 mA/cm2.These Commission Intemationale d'Enclairage (CIE) coordinates of the devices changed slightly with the driving voltages increasing from 8 V to 12 V,and were very close to National Television System Committee (NTSC) standard white light emission of (0.33,0.33).The results indicated that the incorporating bipolar host and low band gap DPABT unit was a promising way to achieve efficient single white light emitting copolymers.

  7. The allylic chalcogen effect in olefin metathesis

    Directory of Open Access Journals (Sweden)

    Yuya A. Lin

    2010-12-01

    Full Text Available Olefin metathesis has emerged as a powerful tool in organic synthesis. The activating effect of an allylic hydroxy group in metathesis has been known for more than 10 years, and many organic chemists have taken advantage of this positive influence for efficient synthesis of natural products. Recently, the discovery of the rate enhancement by allyl sulfides in aqueous cross-metathesis has allowed the first examples of such a reaction on proteins. This led to a new benchmark in substrate complexity for cross-metathesis and expanded the potential of olefin metathesis for other applications in chemical biology. The enhanced reactivity of allyl sulfide, along with earlier reports of a similar effect by allylic hydroxy groups, suggests that allyl chalcogens generally play an important role in modulating the rate of olefin metathesis. In this review, we discuss the effect of allylic chalcogens in olefin metathesis and highlight its most recent applications in synthetic chemistry and protein modifications.

  8. Tandem Catalysis Utilizing Olefin Metathesis Reactions.

    Science.gov (United States)

    Zieliński, Grzegorz K; Grela, Karol

    2016-07-01

    Since olefin metathesis transformation has become a favored synthetic tool in organic synthesis, more and more distinct non-metathetical reactions of alkylidene ruthenium complexes have been developed. Depending on the conditions applied, the same olefin metathesis catalysts can efficiently promote isomerization reactions, hydrogenation of C=C double bonds, oxidation reactions, and many others. Importantly, these transformations can be carried out in tandem with olefin metathesis reactions. Through addition of one portion of a catalyst, a tandem process provides structurally advanced products from relatively simple substrates without the need for isolation of the intermediates. These aspects not only make tandem catalysis very attractive from a practical point of view, but also open new avenues in (retro)synthetic planning. However, in the literature, the term "tandem process" is sometimes used improperly to describe other types of multi-reaction sequences. In this Concept, a number of examples of tandem catalysis involving olefin metathesis are discussed with an emphasis on their synthetic value.

  9. The allylic chalcogen effect in olefin metathesis

    Science.gov (United States)

    Lin, Yuya A

    2010-01-01

    Summary Olefin metathesis has emerged as a powerful tool in organic synthesis. The activating effect of an allylic hydroxy group in metathesis has been known for more than 10 years, and many organic chemists have taken advantage of this positive influence for efficient synthesis of natural products. Recently, the discovery of the rate enhancement by allyl sulfides in aqueous cross-metathesis has allowed the first examples of such a reaction on proteins. This led to a new benchmark in substrate complexity for cross-metathesis and expanded the potential of olefin metathesis for other applications in chemical biology. The enhanced reactivity of allyl sulfide, along with earlier reports of a similar effect by allylic hydroxy groups, suggests that allyl chalcogens generally play an important role in modulating the rate of olefin metathesis. In this review, we discuss the effect of allylic chalcogens in olefin metathesis and highlight its most recent applications in synthetic chemistry and protein modifications. PMID:21283554

  10. Drug governs the morphology of polyalkylated block copolymer aggregates.

    Science.gov (United States)

    Le Dévédec, F; Her, S; Vogtt, K; Won, A; Li, X; Beaucage, G; Yip, C; Allen, C

    2017-02-16

    Polyalkylated copolymers based on mPEG-b-(AGE-C6,12 or 18)25 have been used to formulate clinically relevant concentrations of doxorubicin (DOX) and the impact of drug incorporation on copolymer aggregation behaviour was examined. The copolymer aggregates were analyzed by various microscopy techniques (TEM, cryo-TEM and AFM) and scattering methods (SANS, DLS). In the absence of the drug, the copolymers formed largely non-spherical aggregates (i.e. cylinders, vesicles). Drug incorporation during copolymer aggregate formation directed the formation of only spherical aggregates. As well, the nature of the core-forming block was found to influence drug release and cytotoxicity of the formulations.

  11. Olefin Metathesis for Chemical Biology

    Science.gov (United States)

    Binder, Joseph B; Raines, Ronald T

    2009-01-01

    Summary Chemical biology relies on effective synthetic chemistry for building molecules to probe and modulate biological function. Olefin metathesis in organic solvents is a valuable addition to this armamentarium, and developments during the previous decade are enabling metathesis in aqueous solvents for the manipulation of biomolecules. Functional group-tolerant ruthenium metathesis catalysts modified with charged moieties or hydrophilic polymers are soluble and active in water, enabling ring-opening metathesis polymerization, cross metathesis, and ring-closing metathesis. Alternatively, conventional hydrophobic ruthenium complexes catalyze a similar array of metathesis reactions in mixtures of water and organic solvents. This strategy has enabled cross metathesis on the surface of a protein. Continuing developments in catalyst design and methodology will popularize the bioorthogonal reactivity of metathesis. PMID:18935975

  12. MANUFACTURING BIODEGRADABLE COMPOSITE MATERIALS BASED ON POLYETHYLENE AND FUNCTIONALIZED BY ALCOHOLYSIS OF ETHYLENE-VINYL ACETATE COPOLYMER

    Directory of Open Access Journals (Sweden)

    Aleksandr A. Shabarin

    2016-06-01

    Full Text Available Introduction. The continuous growth of production and consumption of plastic packaging creates a serious problem of disposal of package. This problem has ecological character, because the contents of the landfills decompose for decades, emit toxic com¬pounds and pollute the environment. The work is devoted to obtaining and investigation mechanical and rheological properties of biodegradable composite materials based on polyethylene and starch. Materials and Methods. In this work the author used polyethylene grade HDPE 273- 83 (GOST 16338-85, Sevilen brand 12206-007 (TU 6-05-1636-97 and potato starch (GOST 53876-2010 as a filler. Functionalization of sevilen was carried in the 30 % ethanol solution KOH at a temperature 80 °C during 3 hours. Compounding components was carried out at the laboratory of the two rotary mixer HAAKE PolyLab Rheomix 600 OS with rotors Banbury. Formation of plates for elastic strength and rheological studies were carried out on a hydraulic press Gibitre. Elastic and strength tests were carried out on the tensile machine the UAI-7000 M. Rheology tests were carried out on the rheometer Haake MARS III. The humidity filler (starch authors determined by the thermogravimetric method on the analyzer of moisture “Evlas-2M”. Results. It is shown, that the filler should not contain more than 7% moisture. Functionalization of ethylene with vinyl acetate copolymer (sevilen has performed by the method of alkaline alcoholysis. By the method of IC – spectroscopy the authors confirmed the presence of hydroxyl groups in the polymer. Using as a compatibilizer functionalized by the method of alcoholises has greatly ( significantly improved physical, mechanical and rheological properties of composite materials. Optimal content of sevilen (F in the compound according to the results of experiments amount 10 %. Discussion and Conclusions. Using of functionalized by the method of alcoholysis ethy-lene-vinyl acetate copolymer as a

  13. A new method for preparation of α-olefin olefin metathesis%烯烃歧化制备α-烯烃新方法研究

    Institute of Scientific and Technical Information of China (English)

    王如文; 郑来昌; 杨小辉; 杨克

    2012-01-01

    制备了一种负载型Re基催化剂Re2O7/γ-Al2O3,用于直链内烯烃与乙烯歧化制备α-烯烃.结果表明,以C11~C12直链内烯烃为原料,反应温度60 ℃,反应体积空速1 h-1,反应压力3 MPa的条件下,C11~C12烯烃的单程转化率达到90.0%,歧化选择性达到85.98%.%Preparation of supported Re based catalysts modified Re2O7/λ-Al2O3 ,used in the preparation of a-olefin metathesis of olefins with ethylene in the straight chain internal olefins process. The results showed that to C11,to C12,a straight chain internal olefin as raw material, the reaction temperature of 60 ℃ ,the reaction volume airspeed 1 h-1, C11~C12 ,olefin-way conversion rate of 90.0% under the conditions of the reaction pressure 3 MPa,metathesis selectivity 85.98%.

  14. (Z)-Selective Takai olefination of salicylaldehydes

    Science.gov (United States)

    Galloway, Warren R J D; Sore, Hannah F; Goodman, Jonathan M

    2017-01-01

    The Takai olefination (or Takai reaction) is a method for the conversion of aldehydes to vinyl iodides, and has seen widespread implementation in organic synthesis. The reaction is usually noted for its high (E)-selectivity; however, herein we report the highly (Z)-selective Takai olefination of salicylaldehyde derivatives. Systematic screening of related substrates led to the identification of key factors responsible for this surprising inversion of selectivity, and enabled the development of a modified mechanistic model to rationalise these observations.

  15. Cyclopentadienyl-containing low-valent early transition metal olefin polymerization catalysts

    Science.gov (United States)

    Marks, Tobin J.; Luo, Lubin; Yoon, Sung Cheol

    2003-12-30

    A catalyst system useful to polymerize and co-polymerize polar and non-polar olefin monomers is formed by in situ reduction with a reducing agent of a catalyst precursor comprising wherein Cp* is a cyclopentadienyl or substituted cyclopentadienyl moiety; M is an early transition metal; R is a C.sub.1 -C.sub.20 hydrocarbyl; R' are independently selected from hydride, C.sub.1 -C.sub.20 hydrocarbyl, SiR".sub.3, NR".sub.2, OR", SR", GeR".sub.3, SnR".sub.3, and C.dbd.C containing groups (R".dbd.C.sub.1 -C.sub.10 hydrocarbyl); n is an integer selected to balance the oxidation state of M; and A is a suitable non-coordinating anionic cocatalyst or precursor. This catalyst system may form stereoregular olefin polymers including syndiotactic polymers of styrene and methylmethacrylate and isotactic copolymers of polar and nonpolar olefin monomers such as methylmethacrylate and styrene.

  16. Synthesis and Photophysical Studies of Thiadiazole[3,4-c]pyridine Copolymer Based Organic Field-Effect Transistors.

    Science.gov (United States)

    Bathula, Chinna; Lee, Sang Kyu; Kalode, Pranav; Badgujar, Sachin; Belavagi, Ningaraddi S; Khazi, Imtiyaz Ahmed M; Kang, Youngjong

    2016-05-01

    A novel thiadiazolo[3,4-c]pyridine] based donor-acceptor (D-A) copolymer, poly[4,8-bis(triisopropylsilylethynyl)benzo[1,2-b:4,5-b']dithiophene-2,6-diyl-alt-[4,7-bis(4-(2-ethylhexyl)thiophen-2-yl)-[1,2,5]thiadiazolo[3,4-c]pyridine] (PTBDTPT), containing triisopropylsilylethynyl(TIPS)benzo[1,2-b:4,5-b']dithiophene as a donor is synthesized by Stille polymerization reaction. All the important photo physical prerequisites for organic field-effect transistor (OFET) application such as strong and broad optical absorption, thermal stability, and compatible HOMO-LUMO levels can be accomplished and combined on one macromolecule. Optical band gap of the polymer was found to be 1.61 eV as calculated from its film onset absorption edge. The hole mobility of bottom gate OFET using the synthesized polymer as an active channel is found to be 1.92 X 10(-2) cm V(-1) s(-1) with the On/Off ratio of 25. The photophysical study suggests that PTBDTPT is promising candidate for future large area organic electronic applications.

  17. SIMULTANEOUS SAXS/WAXS/DSC STUDIES ON MICROSTRUCTURE OF CONVENTIONAL AND METALLOCENE-BASED ETHYLENE-BUTENE COPOLYMERS

    Institute of Scientific and Technical Information of China (English)

    Jun-ting Xu; Bo-tao Li; Zhi-qiang Fan; Anthony J. Ryan

    2004-01-01

    The fractions of one metallocene-based (mPE) and one conventional (znPE) ethylene-butene copolymer eluted at 80-82℃ from temperature rising elution fractionation were selected for DSC and time-resolved small angle X-ray scattering (SAXS) and wide angle X-ray scattering (WAXS) characterization. The DSC and WAXS results show that two crystal structures exist in both mPE and znPE: structure A with higher melting temperature and structure B with lower melting temperature. It was found that original znPE (s-znPE) contains more highly ordered structure A than original mPE (s-mPE)in spite of the higher comonomer content of znPE. Another structure C is also identified because of higher crystallinity measured by WAXS than by DSC and is attributed to the interfacial region. The SAXS data were analyzed with correlation function and two maxima were observed in s-mPE and s-znPE, in agreement with the conclusion of two crystal populations drawn from DSC and WAXS results. These two crystal populations have close long periods in s-mPE, but very different long periods in s-znPE. In contrast, freshly crystallized mPE and znPE (f-mPE and f-znPE) contain only a single crystal population with a broader distribution of long period.

  18. Preparation and properties of BSA-loaded microspheres based on multi-(amino acid) copolymer for protein delivery.

    Science.gov (United States)

    Chen, Xingtao; Lv, Guoyu; Zhang, Jue; Tang, Songchao; Yan, Yonggang; Wu, Zhaoying; Su, Jiacan; Wei, Jie

    2014-01-01

    A multi-(amino acid) copolymer (MAC) based on ω-aminocaproic acid, γ-aminobutyric acid, L-alanine, L-lysine, L-glutamate, and hydroxyproline was synthetized, and MAC microspheres encapsulating bovine serum albumin (BSA) were prepared by a double-emulsion solvent extraction method. The experimental results show that various preparation parameters including surfactant ratio of Tween 80 to Span 80, surfactant concentration, benzyl alcohol in the external water phase, and polymer concentration had obvious effects on the particle size, morphology, and encapsulation efficiency of the BSA-loaded microspheres. The sizes of BSA-loaded microspheres ranged from 60.2 μm to 79.7 μm, showing different degrees of porous structure. The encapsulation efficiency of BSA-loaded microspheres also ranged from 38.8% to 50.8%. BSA release from microspheres showed the classic biphasic profile, which was governed by diffusion and polymer erosion. The initial burst release of BSA from microspheres at the first week followed by constant slow release for the next 7 weeks were observed. BSA-loaded microspheres could degrade gradually in phosphate buffered saline buffer with pH value maintained at around 7.1 during 8 weeks incubation, suggesting that microsphere degradation did not cause a dramatic pH drop in phosphate buffered saline buffer because no acidic degradation products were released from the microspheres. Therefore, the MAC microspheres might have great potential as carriers for protein delivery.

  19. Synthesis of Bio-Based Poly(lactic acid-co-10-hydroxy decanoate Copolymers with High Thermal Stability and Ductility

    Directory of Open Access Journals (Sweden)

    Dongjian Shi

    2015-03-01

    Full Text Available Novel bio-based aliphatic copolyesters, poly(lactic acid-co-10-hydroxy decanoate (P(LA-co-HDA, PLH, were successfully synthesized from lactic acid (LA and 10-hydroxycapric acid (HDA by a thermal polycondensation process, in the presence of p-toluenesulfonic acid (p-TSA and SnCl2·2H2O as co-catalyst. The copolymer structure was characterized by Fourier transform infrared (FTIR and proton nuclear magnetic resonance (1H NMR. The weight average molecular weights (Mw of PLH, from gel permeation chromatography (GPC measurements, were controlled from 18,500 to 37,900 by changing the molar ratios of LA and HDA. Thermogravimetric analysis (TGA results showed that PLH had excellent thermal stability, and the decomposition temperature at the maximum rate was above 280 °C. The glass transition temperature (Tg and melting temperature (Tm of PLH decreased continuously with increasing the HDA composition by differential scanning calorimetry (DSC measurements. PLH showed high ductility, and the breaking elongation increased significantly by the increment of the HDA composition. Moreover, the PLH copolymer could degrade in buffer solution. The cell adhesion results showed that PLH had good biocompatibility with NIH/3T3 cells. The bio-based PLH copolymers have potential applications as thermoplastics, elastomers or impact modifiers in the biomedical, industrial and agricultural fields.

  20. Imidazolium-based Block Copolymers as Solid-State Separators for Alkaline Fuel Cells and Lithium Ion Batteries

    Science.gov (United States)

    Nykaza, Jacob Richard

    In this study, polymerized ionic liquid (PIL) diblock copolymers were explored as solid-state polymer separators as an anion exchange membrane (AEM) for alkaline fuel cells AFCs and as a solid polymer electrolyte (SPE) for lithium-ion batteries. Polymerized ionic liquid (PIL) block copolymers are a distinct set of block copolymers that combine the properties of both ionic liquids (e.g., high conductivity, high electrochemical stability) and block copolymers (e.g., self-assembly into various nanostructures), which provides the opportunity to design highly conductive robust solid-state electrolytes that can be tuned for various applications including AFCs and lithium-ion batteries via simple anion exchange. A series of bromide conducting PIL diblock copolymers with an undecyl alkyl side chain between the polymer backbone and the imidazolium moiety were first synthesized at various compositions comprising of a PIL component and a non-ionic component. Synthesis was achieved by post-functionalization from its non-ionic precursor PIL diblock copolymer, which was synthesized via the reverse addition fragmentation chain transfer (RAFT) technique. This PIL diblock copolymer with long alkyl side chains resulted in flexible, transparent films with high mechanical strength and high bromide ion conductivity. The conductivity of the PIL diblock copolymer was three times higher than its analogous PIL homopolymer and an order of magnitude higher than a similar PIL diblock copolymer with shorter alkyl side chain length, which was due to the microphase separated morphology, more specifically, water/ion clusters within the PIL microdomains in the hydrated state. Due to the high conductivity and mechanical robustness of this novel PIL block copolymer, its application as both the ionomer and AEM in an AFC was investigated via anion exchange to hydroxide (OH-), where a maximum power density of 29.3 mW cm-1 (60 °C with H2/O2 at 25 psig (172 kPa) backpressure) was achieved. Rotating disk

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

    Science.gov (United States)

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

    2014-01-01

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

  2. Retrofit with membrane the Paraffin/Olefin separation

    Energy Technology Data Exchange (ETDEWEB)

    Motelica, A.; Bruinsma, O.S.L.; Kreiter, R.; Den Exter, M.J.; Vente, J.F. [ECN Biomass and Energy Efficiency, Petten (Netherlands)

    2012-10-15

    Olefins, such as ethylene, propylene, and butadiene, are among the most produced intermediates in petrochemical industry. They are produced from a wide range of hydrocarbon feedstocks (ethane, propane, butane, naphtha, gas oil) via a cracking process. The last step in this process is the separation of olefins from other hydrocarbons, which is traditionally performed with distillation. As the physicochemical properties, such as volatility and boiling point, of the compounds are very similar, the purification becomes capital and energy intensive. For example, the top of an ethylene/ethane distillation column needs to be chilled to -30C and this requires large amount of electric energy consumption. The separation of butadiene from the C4-fraction is performed with the aid of an additional solvent. This solvent has to be regenerated at the cost of additional high temperature steam. To overcome these separation disadvantages of olefin/paraffin separation, different separation methods have been investigated and proposed in recent years. Suggested options are based on better heat integration of the overall process, or on novel separation systems such as Heat Integrated Distillation Columns, membrane separation, adsorption-desorption systems or on hybrid separation methods, for example, distillation combined with membrane separation.

  3. Supramolecular hydrogels based on self-assembly between PEO-PPO-PEO triblock copolymers and alpha-cyclodextrin.

    Science.gov (United States)

    Ni, Xiping; Cheng, Alan; Li, Jun

    2009-03-15

    This article reports a detailed study on the hydrogel formation of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) triblock copolymers with alpha-cyclodextrin (alpha-CD) in aqueous solutions. The gelation kinetics and the gel rheological properties were studied using viscometry. The sol-gel phase transitions were studied using phase diagrams, while the gelation mechanism was studied using differential scanning calorimetric analysis. It was concluded that the gelation was induced by the complex formation between the PEO segments of the PEO-PPO-PEO triblock copolymer and alpha-CD, and the further self-assembly of the partially formed inclusion complexes. The addition of alpha-CD largely reduced the concentration of the copolymer needed for gel formation. The gels were thixotropic and reversible, and potentially suitable for use as an injectable drug-delivery system.

  4. Theoretical Investigation of Donor-Acceptor Copolymers Based on C-, Si-, and Ge-Bridged Thieno[3,2- b]dithiophene for Organic Solar Cell Applications

    Science.gov (United States)

    Liu, Xiaorui; Huang, Chengzhi; Shen, Wei; He, Rongxing; Li, Ming

    2016-10-01

    The aim of this work is to modify the electron-donating block in donor-acceptor (D-A) copolymers to improve their electronic and photophysical properties for organic solar cell (OSC) applications. Based on the reported polymer PCPDTTTTz (Pa1), which includes electron-rich cyclopenta[2,1- b:3,4- b']dithiophene (CPDT), electron-withdrawing tetrazine, and bridge thiophene, we substituted CPDT with electron-rich dithienocyclopentadithiophene, dithienosiloledithiophene, and dithienogermolodithiophene to design three D-A copolymers (Pa2 to Pa4). The calculation results indicate that Pa3 and Pa4 show lower highest occupied molecular orbital (HOMO)/lowest unoccupied molecular orbital (LUMO) energy levels and larger open-circuit voltage ( V oc) than Pa1. Polymers Pa2 to Pa4 exhibit better performance with stronger and wider optical absorption and good hole transport properties in comparison with Pa1. The predicted power conversion efficiencies for the designed polymers Pa2 to Pa4 in OSC applications are ˜5.7%, ˜5.9%, and 6.0%, respectively. These results clearly indicate that modifying the electron-donating block in D-A copolymers can effectively improve their electronic and photophysical properties and OSC performance. The designed polymers Pa2 to Pa4 may be promising donor candidates for OSC applications.

  5. Improving the Performances of Random Copolymer Based Organic Solar Cells by Adjusting the Film Features of Active Layers Using Mixed Solvents

    Directory of Open Access Journals (Sweden)

    Xiangwei Zhu

    2015-12-01

    Full Text Available A novel random copolymer based on donor–acceptor type polymers containing benzodithiophene and dithienosilole as donors and benzothiazole and diketopyrrolopyrrole as acceptors was designed and synthesized by Stille copolymerization, and their optical, electrochemical, charge transport, and photovoltaic properties were investigated. This copolymer with high molecular weight exhibited broad and strong absorption covering the spectra range from 500 to 800 nm with absorption maxima at around 750 nm, which would be very conducive to obtaining large short-circuits current densities. Unlike the general approach using single solvent to prepare the active layer film, mixed solvents were introduced to change the film feature and improve the morphology of the active layer, which lead to a significant improvement of the power conversion efficiency. These results indicate that constructing random copolymer with multiple donor and acceptor monomers and choosing proper mixed solvents to change the characteristics of the film is a very promising way for manufacturing organic solar cells with large current density and high power conversion efficiency.

  6. Olefins-selective asymmetric carbon molecular sieve hollow fiber membranes for hybrid membrane-distillation processes for olefin/paraffin separations

    KAUST Repository

    Xu, Liren

    2012-12-01

    In this paper, the development of asymmetric carbon molecular sieve (CMS) hollow fiber membranes and advanced processes for olefin/paraffin separations based on the CMS membranes are reported. Membrane-based olefin/paraffin separations have been pursued extensively over the past decades. CMS membranes are promising to exceed the performance upper bound of polymer materials and have demonstrated excellent stability for gas separations. Previously, a substructure collapse phenomenon was found in Matrimid ® precursor derived CMS fiber. To overcome the permeance loss due to the increased separation layer thickness, 6FDA-DAM and 6FDA/BPDA-DAM precursors were selected as potential new precursors for carbon membrane formation. Defect-free asymmetric 6FDA-DAM and 6FDA/BPDA-DAM hollow fibers were successfully fabricated from a dry-jet/wet-quench spinning process. Polymer rigidity, glass-rubber transition and asymmetric morphology were correlated. CMS hollow fiber membranes produced from 6FDA-polymer precursors showed significant improvement in permeance for ethylene/ethane and propylene/propane separations. Further studies revealed that the CMS membranes are olefins-selective, which means the membranes are able to effectively separate olefins (ethylene and propylene) from paraffins (ethane and propane). This unique feature of CMS materials enables advanced hybrid membrane-distillation process designs. By using the olefins-selective membranes, these new processes may provide advantages over previously proposed retrofitting concepts. Further applications of the membranes are explored for hydrocarbons processes. Significant energy savings and even reduced footprint may be achieved in olefins production units. © 2012 Elsevier B.V.

  7. Study of cross-linking process in grafted polyethylene and ethylene based copolymer using a phase resolved photoacoustic method

    Science.gov (United States)

    Dias, D. T.; Medina, A. N.; Baesso, M. L.; Bento, A. C.; Porto, M. F.; Muniz, E. C.; Rubira, A. F.

    2003-01-01

    In this work, the phase resolved photoacoustic method has been employed to monitor water saturated vapor cross linking in both copolymer and grafted polyethylene. The overtone bands and stretching frequencies combinations of the -Si-OH, =CH2, -CH3, and -CH2-CH3 were monitored and analyzed accordingly to a 32 factorial design with nine samples. The results showed that the cross-linking processes were more efficient when the samples were prepared at 80 °C with the catalyst in the concentration range between 3% and 5% for grafted PE, while 70 °C was the best temperature to obtain copolymer.

  8. Cobalt carbide nanoprisms for direct production of lower olefins from syngas.

    Science.gov (United States)

    Zhong, Liangshu; Yu, Fei; An, Yunlei; Zhao, Yonghui; Sun, Yuhan; Li, Zhengjia; Lin, Tiejun; Lin, Yanjun; Qi, Xingzhen; Dai, Yuanyuan; Gu, Lin; Hu, Jinsong; Jin, Shifeng; Shen, Qun; Wang, Hui

    2016-10-06

    Lower olefins-generally referring to ethylene, propylene and butylene-are basic carbon-based building blocks that are widely used in the chemical industry, and are traditionally produced through thermal or catalytic cracking of a range of hydrocarbon feedstocks, such as naphtha, gas oil, condensates and light alkanes. With the rapid depletion of the limited petroleum reserves that serve as the source of these hydrocarbons, there is an urgent need for processes that can produce lower olefins from alternative feedstocks. The 'Fischer-Tropsch to olefins' (FTO) process has long offered a way of producing lower olefins directly from syngas-a mixture of hydrogen and carbon monoxide that is readily derived from coal, biomass and natural gas. But the hydrocarbons obtained with the FTO process typically follow the so-called Anderson-Schulz-Flory distribution, which is characterized by a maximum C2-C4 hydrocarbon fraction of about 56.7 per cent and an undesired methane fraction of about 29.2 per cent (refs 1, 10, 11, 12). Here we show that, under mild reaction conditions, cobalt carbide quadrangular nanoprisms catalyse the FTO conversion of syngas with high selectivity for the production of lower olefins (constituting around 60.8 per cent of the carbon products), while generating little methane (about 5.0 per cent), with the ratio of desired unsaturated hydrocarbons to less valuable saturated hydrocarbons amongst the C2-C4 products being as high as 30. Detailed catalyst characterization during the initial reaction stage and theoretical calculations indicate that preferentially exposed {101} and {020} facets play a pivotal role during syngas conversion, in that they favour olefin production and inhibit methane formation, and thereby render cobalt carbide nanoprisms a promising new catalyst system for directly converting syngas into lower olefins.

  9. Mechanism Analysis on Viscosity Degradation of Poly α-Olefin Aviation Lubricating Base Oil%聚α-烯烃航空润滑油基础油黏度衰变机理分析

    Institute of Scientific and Technical Information of China (English)

    费逸伟; 郭峰; 姚婷; 杨宏伟; 郭青鹏

    2015-01-01

    以聚α-烯烃(PAO)基础油、2,6-二叔丁基对甲酚(T501)和 p,p’-二异辛基二苯胺(Tz516)混合油样为研究对象,运用高温高压反应釜装置,模拟航空发动机工作环境,测定不同温度反应后的运动黏度,借助 GC/MS 现代检测手段,根据检测到的产物分布,从分子水平推测 PAO 基础油的黏度衰变机理。结果表明,高温环境中,基础油主要发生了热裂解和热氧化等反应,其中分子链的断裂是最主要的反应,产生链长较短的正构烷烃、异构烷烃和烯烃,使分子间作用力减弱,进而降低油样的运动黏度。抗氧剂 T501和 Tz516的加入能够极大地延缓了基础油的黏度降解。%Under stimulated aeroengine working condition in high temperature and high pressure reaction kettle, the kinematic viscosity of poly-α-olefin (PAO) aviation lubricating base oil with 2,6 ditbutyl-p-cresol (T501) and p,p'-diisooctyl diphenylamine (Tz516) after the reaction at different temperature was determined. Meanwhile, the composition and structure of reacted samples were detected by gas chromatography/mass spectrometry (GC/MS) to investigate the mechanism of viscosity degradation. The results show that, under high temperature, pyrolysis and thermal oxidation of the aviation lubricating base oil can happen, the breakage of molecular chain can produce n-alkanes, iso-paraffins and olefins, which will cause intermolecular force reduce to decrease the kinematic viscosity. In addition, adding T501 and Tz516 can prevent the thermal oxidation of PAO significantly.

  10. Medium area, flexible single and tandem junction solar cells based on roll coated semi-random copolymers

    DEFF Research Database (Denmark)

    Andersen, Thomas Rieks; Dam, Henrik Friis; Burkhart, Beate;

    2014-01-01

    We report on medium area (1 cm2) slot-die coated organic photovoltaic devices (OPVs) of a recently developed semi-random copolymer of poly-3-hexylthiophene and diketopyrrolopyrrole (P3HTT–DPP- 10%) mixed with phenyl-C61-butyric acid methyl ester ([60]PCBM). The devices were prepared using a compa...

  11. Unusual Emission of Polystyrene-Based Alternating Copolymers Incorporating Aminobutyl Maleimide Fluorophore-Containing Polyhedral Oligomeric Silsesquioxane Nanoparticles

    Directory of Open Access Journals (Sweden)

    Mohamed Gamal Mohamed

    2017-03-01

    Full Text Available In this study, we synthesized an unusual 2-aminobutyl maleimide isobutyl polyhedral oligomeric silsesquioxane (MIPOSS-NHBu monomer lacking conventional fluorescent groups. We then prepared poly(styrene-alt-2-aminobutyl maleimide isobutyl POSS [poly(S-alt-MIPOSS-NHBu] and poly(4-acetoxystyrene-alt-2-aminobutyl maleimide isobutyl POSS [poly(AS-alt-MIPOSS-NHBu] copolymers through facile free radical copolymerizations using azobisisobutyronitrile as the initiator and tetrahydrofuran as the solvent. A poly(4-hydroxystyrene-alt-2-aminobutyl maleimide isobutyl POSS [poly(HS-alt-MIPOSS-NHBu] copolymer was prepared through acetoxyl hydrazinolysis of poly(AS-alt-MIPOSS-NHBu. We employed 1H, 13C, and 29Si nuclear magnetic resonance spectroscopy; Fourier transform infrared spectroscopy; differential scanning calorimetry; and photoluminescence spectroscopy to investigate the structures and the thermal and optical properties of the monomers and novel POSS-containing alternating copolymers. Intramolecular hydrogen bonding between the amino and dihydrofuran-2,5-dione group and clustering of the locked C=O groups from the POSS nanoparticles in the MIPOSS-NHBu units restricted the intramolecular motion of the polymer chain, causing it to exhibit strong light emission. As a result, the MIPOSS-NHBu monomer and the poly(AS-alt-MIPOSS-NHBu copolymer both have potential applicability in the detection of metal ions with good selectivity.

  12. The Structure of Water in PEO-Based Segmented Block Copolymers and its Effect on Transition Temperatures

    NARCIS (Netherlands)

    Husken, Debby; Gaymans, Reinoud J.

    2008-01-01

    The effect of water on block copolymers that contain hydrophilic PEO flexible segments is studied. The polyether phase consisted of either PEO or mixtures of PEO and hydrophobic PTMO, monodisperse crystallisable T6T6T was used as hard segments. Water absorption as a function of relative humidity and

  13. Olefin metathesis : tapping into breakthrough chemical technology

    Energy Technology Data Exchange (ETDEWEB)

    Granson, E.

    2010-06-15

    Olefin metathesis is a catalyst technology where 2 double bond-containing molecules or olefins are split in order to exchange atoms and result in the formation of 2 new molecules or substances. Earlier researchers used a variety of materials to convert propylene into a mixture of butenes and ethylenes. A method developed by Shell researchers produces linear olefins used as detergent feedstocks. In 1971, scientists used a metal-carbene catalyst to react with the olefins to produce both a new olefin and a new metal carbene in order to perpetuate the process. In 2002, a new metathesis technology was developed using renewable natural oils as a feedstock. The catalyst is introduced as a solid into the oil, and then agitated by stirring. The modified oil is then reacted with hydrogen to remove the double bonds and filter off the catalyst. The method is offered on a contract basis by Elevance Renewable Sciences in a variety of application. The process was designed to take place at lower temperatures with the release of fewer greenhouse gases (GHGs). New metathesis technologies are also being developed to reduce the molecular weight of polymers in order to reduce viscosity and increase flow. 3 figs.

  14. Thermally Stable, Latent Olefin Metathesis Catalysts

    Science.gov (United States)

    Thomas, Renee M.; Fedorov, Alexey; Keitz, Benjamin K.

    2011-01-01

    Highly thermally stable N-aryl,N-alkyl N-heterocyclic carbene (NHC) ruthenium catalysts were designed and synthesized for latent olefin metathesis. These catalysts showed excellent latent behavior toward metathesis reactions, whereby the complexes were inactive at ambient temperature and initiated at elevated temperatures, a challenging property to achieve with second generation catalysts. A sterically hindered N-tert-butyl substituent on the NHC ligand of the ruthenium complex was found to induce latent behavior toward cross-metathesis reactions, and exchange of the chloride ligands for iodide ligands was necessary to attain latent behavior during ring-opening metathesis polymerization (ROMP). Iodide-based catalysts showed no reactivity toward ROMP of norbornene-derived monomers at 25 °C, and upon heating to 85 °C gave complete conversion of monomer to polymer in less than 2 hours. All of the complexes were very stable to air, moisture, and elevated temperatures up to at least 90 °C, and exhibited a long catalyst lifetime in solution at elevated temperatures. PMID:22282652

  15. Synthesis of Z-alkenes from Rh(I)-catalyzed olefin isomerization of β,γ-unsaturated ketones.

    Science.gov (United States)

    Zhuo, Lian-Gang; Yao, Zhong-Ke; Yu, Zhi-Xiang

    2013-09-20

    Developing olefin isomerization reactions to reach kinetically controlled Z-alkenes is challenging because formation of trans-alkenes is thermodynamically favored under the traditional catalytic conditions using acids, bases, or transition metals as the catalysts. A new synthesis of Z-alkenes from Rh(I)-catalyzed olefin isomerization of β,γ-unsaturated ketones to α,β-unsaturated ketones was developed, providing an easy and efficient way to access various Z-enones.

  16. Thermally stable drilling fluid additive comprised of a copolymer of catechol-based monomer

    Energy Technology Data Exchange (ETDEWEB)

    Patel, A.D.

    1986-06-17

    A water soluble polymer is described having thermal stability and exhibiting utility as an aqueous drilling fluid additive comprising: (a) a major portion of a catechol based monomer; (b) a minor portion of a dicarboxylic acid monomer.

  17. Drug targeting to tumors using HPMA copolymers

    OpenAIRE

    Lammers, T.G.G.M.

    2009-01-01

    Copolymers based on N-(2-hydroxypropyl)methacrylamide (HPMA) are prototypic and well-characterized polymeric drug carriers that have been broadly implemented in the delivery of anticancer agents. HPMA copolymers circulate for prolonged periods of time, and by means of the Enhance Permeability and Retention (EPR) effect, they localize to tumors both effectively and selectively. As a consequence, the concentrations of attached active agents in tumors can be increased, and their accumulation in ...

  18. Simulation and optimization of the performance of organic photovoltaic cells based on capped copolymers for bulk heterojunctions

    Science.gov (United States)

    Mhamdi, A.; Boukhili, W.; Raissi, M.; Mahdouani, M.; Vignau, L.; Bourguiga, R.

    2016-08-01

    Recently many investigations have been done to improve the performance of solar cells photovoltaic. One of this devices developed is the Bulk Heterojunction (BHJ) solar cells based on poly (3-hexylthiophene) (P3HT)/[6, 6]-phenyl C61-butyric acid methyl ester (PCBM) blend which have been fabricated by spin-coating. It is known that the nanostructure of the active layer of this device has an important impact on the photovoltaic performances. In this work, we analyze the results obtained on solar cells using a copolymer P3HT-b-PS based on poly (3-hexylthiophene) (P3HT) as a donor block and polystyrene (PS) as a soft block, their compatibility with the blend of P3HT/PCBM at various weight percentages (0%-5%). The addition of this weight percentage is in order to improve the performance of polymer solar cells. It has been demonstrated that the addition of a small amount of P3HT-b-PS (from 0.5%-1.5%) led to an increase in photovoltaic efficiency compared to devices made from P3HT/PCBM only. To study the impact of the added amount of the P3HT-b-PS on the performances of the fabricated organic cells, we used an equivalent circuit model based on single diode model with five photovoltaic parameters. Then, we extracted these physical parameters of the organic photovoltaic cells such as the saturation current density, the series and shunt resistances, the ideality factor and the photogenerated current density from the experimental characteristics (J-V) in the dark and under illumination. We proposed and developed the used procedure based on this model and we resolved the analytic equations of the density-current using the Lambert W-function. A good agreement between the theoretical model and the experimental data of electrical characteristics is obtained illustrating the enhancement of the addition of a small amount of P3HT-b-PS (≤1.5%) in the P3HT/PCBM blend on the characteristics of BHJ organic photovoltaic cells.

  19. Tandem Olefin Metathesis/Oxidative Cyclization: Synthesis of Tetrahydrofuran Diols from Simple Olefins.

    Science.gov (United States)

    Dornan, Peter K; Lee, Daniel; Grubbs, Robert H

    2016-05-25

    A tandem olefin metathesis/oxidative cyclization has been developed to synthesize 2,5-disubstituted tetrahydrofuran (THF) diols in a stereocontrolled fashion from simple olefin precursors. The ruthenium metathesis catalyst is converted into an oxidation catalyst in the second step and is thus responsible for both catalytic steps. The stereochemistry of the 1,5-diene intermediate can be controlled through the choice of catalyst and the type of metathesis conducted. This olefin stereochemistry then controls the THF diol stereochemistry through a highly stereospecific oxidative cyclization.

  20. The Olefin Metathesis Reactions in Dendrimers

    Science.gov (United States)

    Astruc, Didier

    Dendrimers containing terminal olefins or ruthenium-benzylidene terminal groups undergo olefin metathesis reactions (RCM and ROMP types), and essentially results from our group are reviewed here. Dendrimers have been loaded at their periphery with ruthenium-chelating bis-phosphines, which leads to the formation of dendrimer-cored stars by ring-opening-metathesis polymerization (ROMP). CpFe+-induced perallylation of polymethylaromatics (Cp = η5-C5H5) followed by ring-closing metathesis (RCM) and/or cross metathesis (CM) leads to poly-ring, cage, oligomeric and polymeric architectures. In the presence of acrylic acid or metha-crylate, stereospecific CM inhibits oligomerization, and dendritic olefins yield polyacid dendrimers. Finally, cros-metahesis reactions with dendronic acrylate allow dendritic construction and growth.

  1. A Comparison of the Performance of the Semiempirical PM6 Method Versus DFT Methods in Ru-Catalyzed Olefin Metathesis

    Science.gov (United States)

    Correa, Andrea; Poater, Albert; Ragone, Francesco; Cavallo, Luigi

    In this work we compare the performance of the semiempirical PM6 method with a more accurate DFT method when applied to Ru-catalyzed olefin metathesis. We demonstrate that the PM6 method reproduces with interesting accuracy the geometries located with a DFT approach. As for the energetics, the relative DFT stability of the metallacycle with respect to the coordination intermediate is reproduced with reasonable accuracy by the PM6 method, whereas the olefin coordination energy and the energy barrier of the metathesis step are overestimated. Further, for the same system we performed a PM6-based meta-dynamics study of the olefin metathesis reaction, which indicated a reasonable good behavior of the system also under dynamic conditions. In conclusion, the obtained results validate the use of the semiempirical PM6 method for preliminary and computationally fast screening on new ligands/substrates in Ru catalyzed olefin metathesis.

  2. The solubilization of fatty acids in systems based on block copolymers and nonionic surfactants

    Science.gov (United States)

    Mirgorodskaya, A. B.; Yatskevich, E. I.; Zakharova, L. Ya.

    2010-12-01

    The solubilizing action of micellar, microemulsion, and polymer-colloid systems formed on the basis of biologically compatible amphiphilic polymers and nonionic surfactants on capric, lauric, palmitic, and stearic acids was characterized quantitatively. Systems based on micelle forming oxyethyl compounds increased the solubility of fatty acids by more than an order of magnitude. Acid molecules incorporated into micelles increased their size and caused structural changes. Solubilization was accompanied by complete or partial destruction of intrinsic acid associates and an increase in their p K a by 1.5-2 units compared with water.

  3. Synthesis and Properties of 1,8-Carbazole-Based Conjugated Copolymers

    Directory of Open Access Journals (Sweden)

    Tsuyoshi Michinobu

    2010-07-01

    Full Text Available A new series of conjugated carbazole polymers based on the 1,8-carbazolylene unit was synthesized by the Pd-catalyzed polycondensation between the 1,8-diiodocarbazole derivative and various bifunctional counter comonomers. An alkyne spacer was found to be a key to increasing the molecular weight of the resulting polymers. All the obtained polymers showed good solubilities in the common organic solvents, and they were fully characterized by Gel permeation chromatography (GPC, and 1H NMR and infrared (IR spectroscopies. The UV-vis absorption and fluorescence spectra revealed the relationship between the chemical structure and effective conjugation length. The efficiency order of the carbazole connectivity was 2,7-carbazolylene > 1,8-carbazolylene > 3,6-carbazolylene. The electrochemical properties of these polymers suggested the relatively facile oxidation at ca. +0.5–0.7 V vs. Fc/Fc+ or a high potential as p-type semiconductors. The combination of the electrochemical oxidation potentials and the optical band gaps allowed us to estimate the HOMO and LUMO levels of the polymers. It was shown that the energy levels of the 1,8-carbazole-based conjugated polymers can be tunable by selecting the appropriate comonomer structures.

  4. Analysis of degradation mechanisms in donor-acceptor copolymer based organic photovoltaic devices using impedance spectroscopy

    Science.gov (United States)

    Srivastava, S. B.; Sonar, P.; Singh, S. P.

    2016-09-01

    The stability of organic photovoltaic (OPV) devices in ambient conditions has been a serious issue which needs to be addressed and resolved timely. In order to probe the degradation mechanism in a donor-acceptor polymer PDPP-TNT: PC71BM bulk heterojunction based OPV devices, we have studied current density-voltage (J-V) behavior and impedance spectroscopy of fresh and aged devices. The current-voltage characteristic of optimized fresh devices exhibit a short circuit current density (J sc) of 8.9 mA cm-2, open circuit voltage (V oc) of 0.79 V, fill factor (FF) of 54.6%, and power conversion efficiency (PCE) of 3.8%. For aged devices, J sc, V oc, FF, and PCE were reduced to 57.3%, 89.8%, 44.3% and 23.7% of its initial value, respectively. The impedance spectra measured under illumination for these devices were successfully fitted using a CPE-based circuit model. For aged devices, the low-frequency response in impedance spectra suggests an accumulation of the photo-generated charge carriers at the interfaces which leads to a significant lowering in fill factor. Such degradation in device performance is attributed to the incorporation of oxygen and water molecules in devices. An increase in the recombination resistance indicates a deterioration of free charge carrier generation and conduction in devices.

  5. Metathesis process for preparing an alpha, omega-functionalized olefin

    Energy Technology Data Exchange (ETDEWEB)

    Burdett, Kenneth A. (Midland, MI); Mokhtarzadeh, Morteza (Charleston, WV); Timmers, Francis J. (Midland, MI)

    2010-10-12

    A cross-metathesis process for preparing an .alpha.,.omega.-functionalized olefin, such as methyl 9-decenoate, and an .alpha.-olefin having three or more carbon atoms, such as 1-decene. The process involves contacting in a first reaction zone an .alpha.-functionalized internal olefin, such as methyl oleate, and an .alpha.-olefinic monomer having three or more carbon atoms, such as 1-decene, with a first metathesis catalyst to prepare an effluent stream containing the .alpha.,.omega.-functionalized olefin, such as methyl 9-decenoate, an unfunctionalized internal olefin, such as 9-octadecene, unconverted reactant olefins, and optionally, an .alpha.,.omega.-difunctionalized internal olefinic dimer, such as dimethyl 9-octadecen-1,18-dioate; separating said effluent streams; then contacting in a second reaction zone the unfunctionalized internal olefin with ethylene in the presence of a second metathesis catalyst to obtain a second product effluent containing the .alpha.-olefinic monomer having three or more carbon atoms; and cycling a portion of the .alpha.-olefinic monomer stream(s) to the first zone.

  6. Carbon nanotubes and carbon onions for modification of styrene-acrylate copolymer based nanocomposites

    Energy Technology Data Exchange (ETDEWEB)

    Merijs-Meri, Remo; Zicans, Janis; Ivanova, Tatjana; Bitenieks, Juris [Institute of Polymer Materials, Riga Technical University, Azenes street 14/24, LV-1048, Riga (Latvia); Kuzhir, Polina; Maksimenko, Sergey [Institute of Nuclear Problems, Belarus State University, Bobruiskaya str. 11, 220030, Minsk (Belarus); Kuznetsov, Vladimir; Moseenkov, Sergey [Boreskov Institute of Catalyst Siberian branch of RAS, pr. Lavrentieva 5, 630090, Novosibirsk (Russian Federation)

    2014-05-15

    Styrene acrylate polymer (SAC) nanocomposites with various carbon nanofillers (multiwalled carbon nanotubes MWCNTs and onion like carbon OLC) are manufactured by means of latex based routes. Concentration of the carbon nanofillers is changed in a broad interval starting from 0.01 up to 10 wt. %. Elastic, dielectric and electromagnetic properties of SAC nanocomposites are investigated. Elastic modulus, electrical conductivity and electromagnetic radiation absorption of the investigated SAC nanocomposites increase along with rising nanofiller content. The effect of the addition of anisometric MWCNTs on the elastic properties of the composite is higher than in the case of the addition of OLC. Higher electrical conductivity of the OLC containing nanocomposites is explained with the fact that reasonable agglomeration of the nanofiller can promote the development of electrically conductive network. Efficiency of the absorption of electromagnetic radiation depends on the development of conductive network within the SAC matrix.

  7. Linear-g-hyperbranched and cyclodextrin-based amphiphilic block copolymer as a multifunctional nanocarrier

    Directory of Open Access Journals (Sweden)

    Yamei Zhao

    2014-11-01

    Full Text Available In this paper, a novel, multifunctional polymer nanocarrier was designed to provide adequate volume for high drug loading, to afford a multiregion encapsulation ability, and to achieve controlled drug release. An amphiphilic, triblock polymer (ABC with hyperbranched polycarbonsilane (HBPCSi and β-cyclodextrin (β-CD moieties were first synthesized by the combination of a two-step reversible addition-fragmentation transfer polymerization into a pseudo-one-step hydrosilylation and quaternization reaction. The ABC then self-assembled into stable micelles with a core–shell structure in aqueous solution. These resulting micelles are multifunctional nanocarriers which possess higher drug loading capability due to the introduction of HBPCSi segments and β-CD moieties, and exhibit controlled drug release based on the diffusion release mechanism. The novel multifunctional nanocarrier may be applicable to produce highly efficient and specialized delivery systems for drugs, genes, and diagnostic agents.

  8. Desymmetrization of 7-azabicycloalkenes by tandem olefin metathesis for the preparation of natural product scaffolds

    Directory of Open Access Journals (Sweden)

    Deppermann Nina

    2007-12-01

    Full Text Available Abstract Background Tandem olefin metathesis sequences are known to be versatile for the generation of natural product scaffolds and have also been used for ring opening of strained carbo- and heterocycles. In this paper we demonstrate the potential of these reactions for the desymmetrization of 7-azabicycloalkenes. Results We have established efficient protocols for the desymmetrization of different 7-azabicycloalkenes by intra- and intermolecular tandem metathesis sequences with ruthenium based catalysts. Conclusion Desymmetrization of 7-azabicycloalkenes by olefin metathesis is an efficient process for the preparation of common natural product scaffolds such as pyrrolidines, indolizidines and isoindoles.

  9. Desymmetrization of 7-azabicycloalkenes by tandem olefin metathesis for the preparation of natural product scaffolds

    Science.gov (United States)

    Maison, Wolfgang; Büchert, Marina; Deppermann, Nina

    2007-01-01

    Background Tandem olefin metathesis sequences are known to be versatile for the generation of natural product scaffolds and have also been used for ring opening of strained carbo- and heterocycles. In this paper we demonstrate the potential of these reactions for the desymmetrization of 7-azabicycloalkenes. Results We have established efficient protocols for the desymmetrization of different 7-azabicycloalkenes by intra- and intermolecular tandem metathesis sequences with ruthenium based catalysts. Conclusion Desymmetrization of 7-azabicycloalkenes by olefin metathesis is an efficient process for the preparation of common natural product scaffolds such as pyrrolidines, indolizidines and isoindoles. PMID:18088413

  10. Cis/trans Coordination in olefin metathesis by static and molecular dynamic DFT calculations

    KAUST Repository

    Poater, Albert

    2014-05-25

    In regard to [(N-heterocyclic carbene)Ru]-based catalysts, it is still a matter of debate if the substrate binding is preferentially cis or trans to the N-heterocyclic carbene ligand. By means of static and molecular dynamic DFT calculations, a simple olefin, like ethylene, is shown to be prone to the trans binding. Bearing in mind the higher reactivity of trans isomers in olefin metathesis, this insight helps to construct small alkene substrates with increased reactivity. © 2014 Springer Science+Business Media New York.

  11. Sunitinib microspheres based on [PDLLA-PEG-PDLLA]-b-PLLA multi-block copolymers for ocular drug delivery.

    Science.gov (United States)

    Ramazani, F; Hiemstra, C; Steendam, R; Kazazi-Hyseni, F; Van Nostrum, C F; Storm, G; Kiessling, F; Lammers, T; Hennink, W E; Kok, R J

    2015-09-01

    Sunitinib is a multi-targeted receptor tyrosine kinase (RTK) inhibitor that blocks several angiogenesis related pathways. The aim of this study was to develop sunitinib-loaded polymeric microspheres that can be used as intravitreal formulation for the treatment of ocular diseases. A series of novel multi-block copolymers composed of amorphous blocks of poly-(D,L-lactide) (PDLLA) and polyethylene glycol (PEG) and of semi-crystalline poly-(L-lactide) (PLLA) blocks were synthesized. Sunitinib-loaded microspheres were prepared by a single emulsion method using dichloromethane as volatile solvent and DMSO as co-solvent. SEM images showed that the prepared microspheres (∼ 30 μm) were spherical with a non-porous surface. Sunitinib-loaded microspheres were studied for their degradation and in-vitro release behavior. It was found that increasing the percentage of amorphous soft blocks from 10% to 30% accelerated the degradation of the multi-block copolymers. Sunitinib microspheres released their cargo for a period of at least 210 days by a combination of diffusion and polymer erosion. The initial burst (release in 24h) and release rate could be tailored by controlling the PEG-content of the multi-block copolymers. Sunitinib-loaded microspheres suppressed angiogenesis in a chicken chorioallantoic membrane (CAM) assay. These microspheres therefore hold promise for long-term suppression of ocular neovascularization.

  12. Amphiphilic graft copolymer based on poly(styrene-co-maleic anhydride with low molecular weight polyethylenimine for efficient gene delivery

    Directory of Open Access Journals (Sweden)

    Duan XP

    2012-09-01

    Full Text Available Xiaopin Duan,1,2 Jisheng Xiao,2 Qi Yin,2 Zhiwen Zhang,2 Shirui Mao,1 Yaping Li21School of Pharmacy, Shenyang Pharmaceutical University, Shenyang, 2Center of Pharmaceutics, Shanghai Institute of Materia Medica, Chinese Academy of Sciences, Shanghai, ChinaBackground and methods: A new amphiphilic comb-shaped copolymer (SP was synthesized by conjugating poly(styrene-co-maleic anhydride with low molecular weight polyethyleneimine for gene delivery. Fourier transform infrared spectrum, 1H nuclear magnetic resonance, and gel permeation chromatography were used to characterize the graft copolymer.Results: The buffering capability of SP was similar to that of polyethyleneimine within the endosomal pH range. The copolymer could condense DNA effectively to form complexes with a positive charge (13–30 mV and a small particle size (130–200 nm at N/P ratios between 5 and 20, and protect DNA from degradation by DNase I. In addition, SP showed much lower cytotoxicity than polyethyleneimine 25,000. Importantly, the gene transfection activity and cellular uptake of SP-DNA complexes were all markedly higher than that of complexes of polyethyleneimine 25,000 and DNA in MCF-7 and MCF-7/ADR cell lines.Conclusion: This work highlights the promise of SP as a safe and efficient synthetic vector for DNA delivery.Keywords: poly(styrene-co-maleic anhydride, polyethylenimine, DNA, gene delivery

  13. Impact of structural changes on dielectric and thermal properties of vinylidene fluoride-trifluoroethylene-based terpolymer/copolymer blends

    Science.gov (United States)

    Casar, G.; Li, X.; Malič, B.; Zhang, Q. M.; Bobnar, V.

    2015-03-01

    We report dielectric and thermal properties of the poly(vinylidene fluoride-trifluoroethylene-chlorofluoroethylene) terpolymer [P(VDF-TrFE-CFE), a member of the relaxor polymer family that exhibits fast response speeds, giant electrostriction, high electric energy density, and large electrocaloric effect] blended with the ferroelectric poly(vinylidene fluoride-trifluoroethylene) copolymer, P(VDF-TrFE). Although the differential scanning calorimetry (DSC) clearly reveals that both components form separate crystalline phases, at low copolymer content blends entirely exhibit a relaxorlike linear dielectric response, since the interfacial couplings to the bulky defects in the terpolymer convert the normal ferroelectric copolymer into a relaxor. On the other hand, dielectric experiments evidence that in blends with 20-50 wt% of P(VDF-TrFE) the ferroelectric and relaxor states coexist. This coexistence is confirmed by DSC results, which further reveal the influence of blending on the terpolymer crystallinity and melting point. At last, the crystallinity data appropriately explain the variation of the dielectric constant in P(VDF-TrFE-CFE)/P(VDF-TrFE) blends.

  14. Impact of structural changes on dielectric and thermal properties of vinylidene fluoride–trifluoroethylene-based terpolymer/copolymer blends

    Energy Technology Data Exchange (ETDEWEB)

    Casar, G. [Jožef Stefan Institute and Jožef Stefan International Postgraduate School, Jamova 39, SI-1000 Ljubljana (Slovenia); Li, X. [Department of Electrical Engineering and Materials Research Institute, The Pennsylvania State University, University Park, PA 16802 (United States); Malič, B. [Jožef Stefan Institute and Jožef Stefan International Postgraduate School, Jamova 39, SI-1000 Ljubljana (Slovenia); Zhang, Q.M. [Department of Electrical Engineering and Materials Research Institute, The Pennsylvania State University, University Park, PA 16802 (United States); Bobnar, V., E-mail: vid.bobnar@ijs.si [Jožef Stefan Institute and Jožef Stefan International Postgraduate School, Jamova 39, SI-1000 Ljubljana (Slovenia)

    2015-03-15

    We report dielectric and thermal properties of the poly(vinylidene fluoride–trifluoroethylene–chlorofluoroethylene) terpolymer [P(VDF–TrFE–CFE), a member of the relaxor polymer family that exhibits fast response speeds, giant electrostriction, high electric energy density, and large electrocaloric effect] blended with the ferroelectric poly(vinylidene fluoride–trifluoroethylene) copolymer, P(VDF–TrFE). Although the differential scanning calorimetry (DSC) clearly reveals that both components form separate crystalline phases, at low copolymer content blends entirely exhibit a relaxorlike linear dielectric response, since the interfacial couplings to the bulky defects in the terpolymer convert the normal ferroelectric copolymer into a relaxor. On the other hand, dielectric experiments evidence that in blends with 20–50 wt% of P(VDF–TrFE) the ferroelectric and relaxor states coexist. This coexistence is confirmed by DSC results, which further reveal the influence of blending on the terpolymer crystallinity and melting point. At last, the crystallinity data appropriately explain the variation of the dielectric constant in P(VDF–TrFE–CFE)/P(VDF–TrFE) blends.

  15. Biomineralization behavior of a vinylphosphonic acid-based copolymer added with polymerization accelerator in simulated body fluid

    Directory of Open Access Journals (Sweden)

    Ryo Hamai

    2015-12-01

    Full Text Available Apatite-polymer composites have been evaluated in terms of its potential application as bone substitutes. Biomimetic processes using simulated body fluid (SBF are well-known methods for preparation of such composites. They are reliant on specific functional groups to induce the heterogeneous apatite nucleation and phosphate groups possess good apatite-forming ability in SBF. Improving the degree of polymerization is important for obtaining phosphate-containing polymers, because the release of significant quantities of monomer or low molecular weight polymers can lead to suppression of the apatite formation. To date, there have been very few studies pertaining to the effect of adding a polymerization accelerator to the polymerization reaction involved in the formation of these composite materials under physiological conditions. In this study, we have prepared a copolymer from triethylene glycol dimethacrylate and vinylphosphonic acid (VPA in the presence of different amounts of sodium p-toluenesulfinate (p-TSS as a polymerization accelerator. The effects of p-TSS on the chemical durability and apatite formation of the copolymers were investigated in SBF. The addition of 0.1–1.0 wt% of p-TSS was effective for suppressing the dissolution of the copolymers in SBF, whereas larger amount had a detrimental effect. A calcium polyvinylphosphate instead of the apatite was precipitated in SBF.

  16. Effective removal of toxic metal ions from aqueous solutions: 2-Bifunctional magnetic nanocomposite base on novel reactive PGMA-MAn copolymer@Fe3O4 nanoparticles.

    Science.gov (United States)

    Hasanzadeh, Reza; Moghadam, Peyman Najafi; Bahri-Laleh, Naeimeh; Sillanpää, Mika

    2017-03-15

    In this study, effective novel magnetic nanocomposite particles (MNCPs) were prepared based on iminodiacetic acid grafted poly (glycidylmethacrylate-maleicanhydride) (PGMA-MAn) copolymer. For this purpose, firstly Fe3O4 nanoparticles reacted with 3-aminopropyl triethoxysilane for the production of magnetite nanoparticles containing amine groups (MNPs-NH2). Then iminodiacetic acid reacted with PGMA-MAn copolymer to produce iminodiacetic acid grafted PGMA-MAn copolymer (ID-g-PGMA-MAn). Finally, the MNPs-NH2 reacted with the ID-g-PGMA-MAn and the reaction was completed by propylenediamine (PDA) to produce MNCPs. Structure, magnetic property, size, and porosity of the prepared magnetic nanocomposite were investigated by FT-IR, XRD, VSM, EDX, SEM and BET analyses. The ability of these MNCPs for removing Pb(II) and Cd(II) from water and wastewater was studied, and the effects of different parameters (pH, adsorbent dosage, metal ion concentration, contact time and agitation) on the adsorption process were investigated. The isotherm models were used to describe adsorption equilibrium. The results showed that the best fit was achieved with the Langmuir isotherm equation, yielding maximum adsorption capacities of 53.33 and 48.53mg/g for Pb(II) and Cd(II), respectively. The kinetics equations were used for modeling of adsorption data and it was shown that pseudo-second-order kinetic equation could best describe the adsorption kinetics. Furthermore, phenol pollutant can be removed effectively by metal ions of the nanocomposite-metal complex; therefore, the synthesized adsorbent was useful not only in recovering toxic metal ions but also in the treating phenol pollutants in wastewater.

  17. On the impact of olefins and aromatics in the methanol-to-hydrocarbon conversion over H-ZSM-5 catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Sun, X.; Mueller, S.; Veen, A.C. van; Lercher, J.A. [Technische Univ. Muenchen, Garching (Germany). Dept. of Chemistry

    2012-07-01

    Methanol-to-hydrocarbons processes using HZSM-5 archetype acidic zeolites or zeotype SAPO-34 catalysts are regarded as a vital suite of conversion technologies to bypass petroleum-based routes for the production of specific fuels and petrochemical commodities. Special significance of the methanol chemistry originates from its versatility enabling selective transformations towards various products. Industry demonstrated successfully implementations of Methanol-To-Gasoline, Methanol-To-Olefin, and Methanol-To-Propylene processes, although the typical single-pass selectivity remained limited and recycling is necessary. Considerable fundamental research efforts both from experimental and computational sides contributed to unravel the underlying complex reaction mechanism. The indirect hydrocarbon pool mechanism, in which Broensted acid sites combined with adsorbed light olefins or lower methylbenzenes act as active centers, is generally accepted to explain the formation of light olefins. As olefin and aromatics populated catalytic sites show different reactivity in terms of activity and selectivity to ethylene or propylene, one could envision optimizing the product distribution by suitable co-feeding of specific hydrocarbons. The present work addresses three questions with an experimental study conducted under realistic MTP operation conditions: (1) How are ethylene and propylene formed at molecular level? (2) Which reaction pathway leads to the formation of undesired hydrogen transfer products? (3) Does olefin or aromatics co-feeding change the selectivity to ethylene or propylene? Xylenes and various olefins were co-fed with methanol to achieve a detailed understanding of the reaction mechanism over acidic HZSM-5 zeolites. Results suggest, that an olefin homologation/cracking route (olefin cycle) accounts for the autocatalytic (-like) nature and the majority of methanol consumption rather than the route involving aromatic intermediates (aromatics cycle). Co

  18. 基于聚-α烯烃油的锂基润滑脂流变性%Rheological of Lithium Lubricating Grease Based on Poly-αOlefins Oil

    Institute of Scientific and Technical Information of China (English)

    周维贵; 郭小川; 蒋明俊; 郭婉晴

    2014-01-01

    为系统研究锂基润滑脂的流变性能,以12-羟基硬脂酸锂皂为稠化剂和聚-α烯烃(PAO)油为基础油制备了锂基润滑脂。考察了稠化剂含量、基础油黏度和温度对锂基润滑脂的触变性、储存模量、损耗模量、表观黏度和应变幅度等流变参数的影响,并对其影响机理进行了探讨。实验表明:锂基润滑脂是屈服性假塑性流体,在很小应变范围内以可恢复的弹性变形为主导,达到其屈服应力后,具有明显的剪切变稀现象;达到其流动点后,表现出黏性流体性质。%In order to study the rheological properties of lithium base grease in a systematic way, lithium lubricating grease is prepared with 12-hydroxy stearic acid lithium soap as the thickener and poly-αolefins(PAO)synthetic oil as base oil. The influ-ence factors such as the content of the thickener, base oil viscosity and temperature on the rheological parameters concerning thixot-ropy, storage modulus, loss modulus, apparent viscosity and strain amplitude are studied and the mechanism is also discussed. Ex-perimental results show that the lithium lubricating grease is yield pseudoplastic fluid, which is highly elastic and can restore elastic deformation at very small strain range, has obvious shear thinning phenomenon after reaching the yield stress, and is highly viscous when it reached its yield point.

  19. Rhodium olefin complexes of diiminate type ligands

    NARCIS (Netherlands)

    Willems, Sander Theodorus Hermanus

    2003-01-01

    The mono-anionic beta-diiminate ligand (ArNC(CH3)CHC(CH3)NAr) on several previous occasions proved useful in stabilising low coordination numbers for both early and late transition metals. In this thesis the reactivity of the rhodium olefin complexes of one of these beta-diiminate ligands (Ar = 2,6-

  20. Olefin Recovery from Chemical Industry Waste Streams

    Energy Technology Data Exchange (ETDEWEB)

    A.R. Da Costa; R. Daniels; A. Jariwala; Z. He; A. Morisato; I. Pinnau; J.G. Wijmans

    2003-11-21

    The objective of this project was to develop a membrane process to separate olefins from paraffins in waste gas streams as an alternative to flaring or distillation. Flaring these streams wastes their chemical feedstock value; distillation is energy and capital cost intensive, particularly for small waste streams.

  1. Synthesis of pterostilbene by Julie Olefination

    Science.gov (United States)

    A simple, stereoselective route for the synthesis of the biologically active compounds trans-pterostilbene and tetramethoxy stilbene from the readily available starting materials 3,5-dimethoxy benzyl alcohol and 4-hydroxy benzaldehyde was developed using Julia olefination as a key reaction....

  2. The progress of SINOPEC methanol-to-olefins (S-MTO) technology

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Hongxing; Xie, Zaiku; Zhao, Guoliang [SINOPEC Shanghai Research Institute of Petrochemical Technology (China)

    2013-11-01

    It is widely recognized that naphtha steam crackers and FCC units are the main current sources of ethylene and propylene. On the condition of high oil price, olefin producers are striving to develop new economical routes to produce ethylene and propylene with low-cost feedstocks. Methanol to olefins (MTO) has aroused great attention in recent years, and SINOPEC has developed a new kind of MTO process named S-MTO which features high olefins selectivity, high methanol conversion and low catalyst consumption. Puyang Zhongyuan 200 KTA S-MTO has been in steady operation for more than 17 months. The catalyst used in the process is based on a silicoaluminophosphate, SAPO-34, which has very high carbon selectivity to low carbon olefins. Results from the commercial plant show that S-MTO process converts methanol to ethylene and propylene at about 81% carbon selectivity. The carbon selectivity approaches 92% if butenes are also accounted for as part of the product. Typically, the ratio of propylene to ethylene can range from 0.6 to 1.3. When combined with OCC (Olefin Catalytic Cracking) process to convert the heavier olefins, the overall yield of ethylene and propylene can increase to 85% {proportional_to} 87% and propylene-ethylene ratios of more than 1.5 are achievable. Other co-products include very small amounts of C1-C4 paraffins, hydrogen, CO and CO{sub 2}, as well as heavier oxygenates only with ppm level. Because of the quick deactivation of MTO catalyst, a kind of high efficiency fast fluidized bed reactor is adopted. The activity of deactivated catalyst is recovered by burning the coke in the regenerator. This paper gives an updated introduction of S-MTO technology developed by SINOPEC SRIPT. (orig.)

  3. Efficient White Light Emission Using a Single Copolymer with Red and Green Chromophores on a Conjugated Polyfluorene Backbone Hybridized with InGaN-Based Light-Emitting Diodes

    Institute of Scientific and Technical Information of China (English)

    ZHANG Yong; HOU Qiong; NIU Qiao-Li; ZHENG Shu-Wen; LI Shu-Ti; HE Miao; FAN Guang-Han

    2009-01-01

    We report an efficient white-light emission based on a single copolymer/InGaN hybrid light-emitting diode.The single copolymer consists of a conjugated polyfluorene backbone by incorporating 2,1,3-benzothiadiazole (BT) and 4, 7-bis(2-thienyl)-2,1,3-benzothiadiazole (DBT) as green and red light-emitting units, respectively. For the single eopolymer/lnGaN hybrid device, the Commission Internationale de l'Eclairage (CIE) coordinates,color temperature Tc and color rendering index Ra at 20mA are (0.323,0.329), 5960K and 86, respectively.In comparison with the performance of red copolymer PFO-DBT15 (DOF:DBT=85:15 with DOF being 9'9-dioctylfluorene) and green copolymer PFO-BT35 (DOF:BT=65:35) blend/InGaN hybrid white devices, it is concluded that the chemically doped copolymer hybridized device shows a higher emission intensity and spectral stability at a high driving current than the polymer blend.

  4. Monodentate phosphoramidites : A breakthrough in rhodium-catalysed asymmetric hydrogenation of olefins

    NARCIS (Netherlands)

    Berg, Michel van den; Minnaard, Adriaan J.; Haak, Robert M.; Leeman, Michel; Schudde, Ebe P.; Meetsma, Auke; de Vries, Andre H.M.; Maljaars, C. Elizabeth P.; Willans, Charlotte E.; Hyett, David; Boogers, Jeroen A.F.; Henderickx, Hubertus; Feringa, Ben L.

    2003-01-01

    Monodentate phosphoramidites based on BINOL or substituted BINOL are excellent ligands for the rhodium-catalysed asymmetric hydrogenation of olefins. Very high enantioselectivities were obtained with MonoPhos (7a) the simplest member of this class, a ligand that is prepared in a single step from BIN

  5. 温度及pH双敏感性的新型接枝共聚物%Synthesis and Characterization of Novel Temperature and pH Responsive Hydroxylpropyl Cellulose-based Graft Copolymers

    Institute of Scientific and Technical Information of China (English)

    李小军; 尹明辉; 张国亮; 张风宝

    2009-01-01

    In this study, double-hydrophilic hydroxylpropyl cellulose (HPC) based copolymers with poly(Nisopropylaerylamide) (PNIPAM) and poly(acrylic acid) (PAA) as graft chains were synthesized and characterized. The release behavior of drug-loaded micelles was studied. The results show that the hydrophilicity of copolymers improves as the pH increases, whereas the hydrophobicity of copolymers enhances as the temperature increases, and all the phase behaviors are reversible. The diameter of micelles decreases and then increases with pH increase. It shows different micellizing behavior under acidic and basic conditions according to the temperature increase. In vitro release experiments, which used theophylline as a model drug, show that the micelles enhance pH sensitivity in the release process.

  6. Synthesis of Graft Copolymers Based on Poly(2‐Methoxyethyl Acrylate) and Investigation of the Associated Water Structure

    DEFF Research Database (Denmark)

    Javakhishvili, Irakli; Tanaka, Masaru; Ogura, Keiko;

    2012-01-01

    Graft copolymers composed of poly(2‐methoxyethyl acrylate) are prepared employing controlled radical polymerization techniques. Linear backbones bearing atom transfer radical polymerization (ATRP) initiating sites are obtained by reversible addition–fragmentation chain transfer copolymerization...... of 2‐methoxyethyl acrylate (MEA) and 2‐(bromoisobutyryloxy)ethyl methacrylate (BriBuEMA) as well as 2‐hydroxyethyl methacrylate and BriBuEMA in a controlled manner . MEA is then grafted from the linear macroinitiators by Cu (I)‐mediated ATRP. Fairly high molecular weights (>120 000 Da) and low...

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

    NARCIS (Netherlands)

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

    1995-01-01

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

  8. Rechargeable lithium battery employing a new ambient temperature hybrid polymer electrolyte based on PVK+PVdF-HFP (copolymer)

    Science.gov (United States)

    Michael, M. S.; Prabaharan, S. R. S.

    We describe here for the first time, our recent success in developing an ambient temperature Li + conducting solid polymer electrolyte (SPE) using the concept of polymer alloying upon blending two thermoplastic polymers such as poly(vinylidene) fluoride-hexafluoropropylene (PVdF-HFP-copolymer) and poly( N-vinylcarbazole), PVK and achieved the room temperature electrolytic conductivity ( σi) of 0.7×10 -3 S/cm for a typical composition of PVdF-HFP copolymer/PVK blend mixed with EC/LiBF 4 molar composition. The ionic transference number of 0.49 was deduced from combined ac-impedance and dc polarization method. High-resolution optical microscopic examination revealed the disappearance of characteristic highly porous surface structure of PVdF-HFP matrix upon blending with PVK leading to the formation of resultant PVdF-HFP/PVK blend polymer alloy. The electrochemical stability of the polymer electrolyte membrane thus obtained was found to be stable up to ˜4.7 V versus Li/Li +. The new hybrid alloy polymer electrolyte membrane was found to exhibit good interfacial properties against lithium metal and thus, it was found to aid the room temperature operation as electrolytic membrane cum separator in all-solid state rechargeable lithium polymer test cell, LiCo 0.8Ni 0.2O 2/SPE/Li.

  9. Tunable Nanocarrier Morphologies from Glycopolypeptide-based Amphiphilic Biocompatible Star Copolymers and Their Carbohydrate Specific Intracellular Delivery

    KAUST Repository

    Pati, Debasis

    2015-12-21

    Nano-carriers with carbohydrates on the surface represent a very interesting class of drug delivery vehicles since carbohydrates are involved in bio-molecular recognition events in vivo. We have synthesized biocompatible miktoarm star copolymers comprising glycopolypeptide and poly(ε-caprolactone) chains, using ring opening polymerization and ‘click chemistry’. The amphiphilic copolymers were self-assembled in water into morphologies such as nanorods, polymersomes and micelles with carbohydrates displayed on the surface. We demonstrate that, the formation of nanostructure could be tuned by chain length of the blocks and was not affected by the type of sugar residue. These nanostructures were characterized in detail using a variety of techniques such as TEM, AFM, cryogenic electron microscopy, spectrally resolved fluorescence imaging and dye encapsulation techniques. We show that it is possible to sequester both hydrophobic as well as hydrophilic dyes within the nanostructures. Finally, we show that these non-cytotoxic manno-sylated rods and polymersomes were selectively and efficiently taken up by MDA-MB-231 breast cancer cells demonstrating their potential as nanocarriers for drug delivery.

  10. Alkene Chemoselectivity in Ruthenium-Catalyzed Z-Selective Olefin Metathesis

    Science.gov (United States)

    Cannon, Jeffrey S.

    2013-01-01

    Chelated ruthenium catalysts have achieved highly chemoselective olefin metathesis reactions. Terminal and internal Z olefins were selectively reacted in the presence of internal E olefins. Products were produced in good yield and high stereoselectivity for formation of a new Z olefin. No products of metathesis with the internal E olefin were observed. Chemoselectivity for terminal olefins was also observed over both sterically hindered and electronically deactivated alkenes. PMID:23832646

  11. Olefin hydroformylation catalysis with RuCl2(DMSO4.

    Directory of Open Access Journals (Sweden)

    Marisela Reyes*

    2008-05-01

    Full Text Available The RuCl2(DMSO4 complex was used as catalytic precursor in olefin hydroformylation reactions, giving good percent yield and better selectivity for linear aldehydes. The reactions were tested in homogeneous medium and biphasic organic solvent/ water systems. The substrates tried were 1-hexene, cyclohexene, 2-methyl-2-pentene, 2,3-dimethyl-2-butene; binary mixtures and synthetic naphtha and real naphtha. The activity is better for linear olefins compared with substituted olefins.

  12. Integrated process and dual-function catalyst for olefin epoxidation

    Science.gov (United States)

    Zhou, Bing; Rueter, Michael

    2003-01-01

    The invention discloses a dual-functional catalyst composition and an integrated process for production of olefin epoxides including propylene oxide by catalytic reaction of hydrogen peroxide from hydrogen and oxygen with olefin feeds such as propylene. The epoxides and hydrogen peroxide are preferably produced simultaneously in situ. The dual-functional catalyst comprises noble metal crystallites with dimensions on the nanometer scale (on the order of olefin oxides such as propylene oxide without formation of undesired co-products.

  13. A chameleon catalyst for nonheme iron-promoted olefin oxidation.

    Science.gov (United States)

    Iyer, Shyam R; Javadi, Maedeh Moshref; Feng, Yan; Hyun, Min Young; Oloo, Williamson N; Kim, Cheal; Que, Lawrence

    2014-11-18

    We report the chameleonic reactivity of two nonheme iron catalysts for olefin oxidation with H2O2 that switch from nearly exclusive cis-dihydroxylation of electron-poor olefins to the exclusive epoxidation of electron-rich olefins upon addition of acetic acid. This switching suggests a common precursor to the nucleophilic oxidant proposed to Fe(III)-η(2)-OOH and electrophilic oxidant proposed to Fe(V)(O)(OAc), and reversible coordination of acetic acid as a switching pathway.

  14. Structural color-tunable mesoporous bragg stack layers based on graft copolymer self-assembly for high-efficiency solid-state dye-sensitized solar cells

    Science.gov (United States)

    Lee, Chang Soo; Park, Jung Tae; Kim, Jong Hak

    2016-08-01

    We present a facile fabrication route for structural color-tunable mesoporous Bragg stack (BS) layers based on the self-assembly of a cost-effective graft copolymer. The mesoporous BS layers are prepared through the alternating deposition of organized mesoporous-TiO2 (OM-TiO2) and -SiO2 (OM-SiO2) films on the non-conducting side of the counter electrode in dye-sensitized solar cells (DSSCs). The OM layers with controlled porosity, pore size, and refractive index are templated with amphiphilic graft copolymers consisting of poly(vinyl chloride) backbones and poly(oxyethylene methacrylate) side chains, i.e., PVC-g-POEM. The morphology and properties of the structural color-tunable mesoporous BS-functionalized electrodes are characterized using energy filtered transmission electron microscopy (EF-TEM), field emission-scanning electron microscopy (FE-SEM), spectroscopic ellipsometry, and reflectance spectroscopy. The solid-state DSSCs (ssDSSCs) based on a structural color-tunable mesoporous BS counter electrode with a single-component solid electrolyte show an energy conversion efficiency (η) of 7.1%, which is much greater than that of conventional nanocrystalline TiO2-based cells and one of the highest values for N719 dye-based ssDSSCs. The enhancement of η is due to the enhancement of current density (Jsc), attributed to the improved light harvesting properties without considerable decrease in fill factor (FF) or open-circuit voltage (Voc), as confirmed by incident photon-to-electron conversion efficiency (IPCE) and electrochemical impedance spectroscopy (EIS).

  15. Organic chemistry. Practical olefin hydroamination with nitroarenes.

    Science.gov (United States)

    Gui, Jinghan; Pan, Chung-Mao; Jin, Ying; Qin, Tian; Lo, Julian C; Lee, Bryan J; Spergel, Steven H; Mertzman, Michael E; Pitts, William J; La Cruz, Thomas E; Schmidt, Michael A; Darvatkar, Nitin; Natarajan, Swaminathan R; Baran, Phil S

    2015-05-22

    The synthesis and functionalization of amines are fundamentally important in a vast range of chemical contexts. We present an amine synthesis that repurposes two simple feedstock building blocks: olefins and nitro(hetero)arenes. Using readily available reactants in an operationally simple procedure, the protocol smoothly yields secondary amines in a formal olefin hydroamination. Because of the presumed radical nature of the process, hindered amines can easily be accessed in a highly chemoselective transformation. A screen of more than 100 substrate combinations showcases tolerance of numerous unprotected functional groups such as alcohols, amines, and even boronic acids. This process is orthogonal to other aryl amine syntheses, such as the Buchwald-Hartwig, Ullmann, and classical amine-carbonyl reductive aminations, as it tolerates aryl halides and carbonyl compounds.

  16. Organic synthesis with olefin metathesis catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Grubbs, R.H. [California Institute of Technology, Pasadena, CA (United States)

    1995-12-31

    Over the past nine years, early transition metal catalysts for the ring opening metathesis polymerization of cyclic olefins have been developed. These catalysts are simple organometallic complexes containing metal carbon multiple bonds that in most cases polymerize olefins by a living process. These catalysts have been used to prepare a family of near monodispersed and structurally homogeneous polymers. A series of group VII ROMP catalysts that allow a wide range of functionality to be incorporated into the polymer side chains have been prepared. The most important member of this family of complexes are the bisphosphinedihalo-ruthenium carbene complexes. These polymerization catalysts can also be used in the synthesis of fine chemicals by ring closing (RCM) and vinyl coupling reactions. The availability of the group VII catalysts allow metathesis to be carried out on highly functionalized substrates such as polypeptides and in unusual environments such as in aqueous emulsions.

  17. Homogeneous catalysts for stereoregular olefin polymerization

    Science.gov (United States)

    Marks, Tobin J.; Eisen, Moris S.; Giardello, Michael A.

    1994-01-01

    The synthesis, and use as precatalysts of chiral organozirconium complexes for olefin polymerization are disclosed, having the structure (C.sub.5 R'.sub.4-x R*.sub.x) A (C.sub.5 R".sub.4-y R'".sub.y) M Q.sub.p, where x and y represent the number of unsubstituted locations on the cyclopentadienyl ring; R', R", R'", and R* represent substituted and unsubstituted alkyl groups having 1-30 carbon atoms and R* is a chiral ligand; A is a fragment containing a Group 13, 14, 15, or 16 element of the Periodic Table; M is a Group 3, 4, or 5 metal of the Periodic Table; and Q is a hydrocarbyl radical, or halogen radical, with 3.ltoreq.p.ltoreq.o. Related complexes may be prepared by alkylation of the corresponding dichorides. In the presence of methylalumoxane or triarylborane cocatalysts, these complexes form "cation-like" species which are highly active for olefin polymerization. In combination with a Lewis acid cocatalyst, propylene or other .alpha.-olefin polymerization can be effected with very high efficiency and isospecificity.

  18. Self-aggregated nanoparticles based on amphiphilic poly(lactic acid-grafted-chitosan copolymer for ocular delivery of amphotericin B

    Directory of Open Access Journals (Sweden)

    Zhou WJ

    2013-09-01

    Full Text Available Wenjun Zhou,1 Yuanyuan Wang,2 Jiuying Jian,2 Shengfang Song1 1Department of Ophthalmology, Yongchuan Hospital, Chongqing Medical University, Chongqing, People’s Republic of China; 2College of Life Science, Chongqing Medical University, Chongqing, People’s Republic of China Background: The purpose of this study was to develop a self-aggregated nanoparticulate vehicle using an amphiphilic poly(lactic acid-grafted-chitosan (PLA-g-CS copolymer and to evaluate its potential for ocular delivery of amphotericin B. Methods: A PLA-g-CS copolymer was synthesized via a “protection-graft-deprotection” procedure and its structure was confirmed by Fourier transform infrared spectroscopy, 1H nuclear magnetic resonance, and X-ray diffraction spectra. Amphotericin B-loaded nanoparticles based on PLA-g-CS (AmB/PLA-g-CS were prepared by the dialysis method and characterized for particle size, zeta potential, and encapsulation efficiency. Studies of these AmB/PLA-g-CS nanoparticles, including their mucoadhesive strength, drug release properties, antifungal activity, ocular irritation, ocular pharmacokinetics, and corneal penetration were performed in vitro and in vivo. Results: Fourier transform infrared spectroscopy, 1H nuclear magnetic resonance, and X-ray diffraction spectra showed that the PLA chains were successfully grafted onto chitosan molecules and that crystallization of chitosan was suppressed. The self-aggregated PLA-g-CS nanoparticles had a core-shell structure with an average particle size of approximately 200 nm and zeta potentials higher than 30 mV. Amphotericin B was incorporated into the hydrophobic core of the nanoparticles with high encapsulation efficiency. Sustained drug release from the nanoparticles was observed in vitro. The ocular irritation study showed no sign of irritation after instillation of the PLA-g-CS nanoparticles into rabbit eyes. The minimal inhibitory concentration of the AmB/PLA-g-CS nanoparticles showed antifungal

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

    Science.gov (United States)

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

    2012-03-12

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

  20. Continuous reaction performances of benzene alkylation with long chain olefins catalyzed by ionic liquid

    Institute of Scientific and Technical Information of China (English)

    Congzhen QIAO; Chengyue LI

    2008-01-01

    Based on a compulsive mixing-reacting-sepa-rating-recycling small experimental setup,the continuous reaction performances of benzene alkylation with long chain olefins catalyzed by [BMIM]Cl-AlCl3 ionic liquid were investigated. Three different situations including normal continuous operation mode (reagent materials), sidetrack feeding from different axial positions along the static mixing reactor (reagent materials) and normal con-tinuous alkylation using industrial paraffin and olefins materials were examined. Even under the relatively hype-critical reaction conditions, the single pass conversion of pure 1-dodecene could reach to nearly 100.0%, and the selectivity of 2-phenyl isomer was higher than 37.7%. Although the positions along the reactor for sidetrack feeding were different, the 100.0% single pass conversion of 1-dodecene was also attained before the outlet of the reactor. The refined industrial olefins as raw material could meet with the requirements of continuous alkyla-tion. The influences of impurities such as di-olefins and non-benzene aromatics on the catalytic activity and stability should be studied further.

  1. NATO Advanced Study Institute on Ring-opening Metathesis Polymerization of Olefins and Polymerization of Alkynes

    CERN Document Server

    1998-01-01

    The first NATO Advanced Study Institute on Olefin Metathesis and Polymerization Catalysts was held on September 10-22, 1989 in Akcay, Turkey. Based on the fundamental research of RRSchrock, RGrubbs and K.B.Wagener in the field of ring opening metathesis polymerization (ROMP), acyclic diene metathesis (ADMET) and alkyne polymerization, these areas gained growing interest within the last years. Therefore the second NATO-ASI held on metathesis reactions was on Ring Opening Metathesis Po­ lymerization of Olefins and Polymerization of Alkynes on September 3-16, 1995 in Akcay, Turkey. The course joined inorganic, organic and polymer chemists to exchange their knowledge in this field. This volume contains the main and short lectures held in Akcay. To include ADMET reactions better into the title of this volume we changed it into: Metathesis Polymerization of Olefins and Alkyne Polymerization. This volume is addressed to research scientists, but also to those who start to work in the area of olefin metathesis and al...

  2. Proton conducting membranes based on benzimidazole sulfonic acid doped sulfonated poly(oxadiazole-triazole) copolymer for low humidity operation

    Energy Technology Data Exchange (ETDEWEB)

    Boaventura, M.; Mendes, A.; Madeira, L.M. [LEPAE - Laboratorio de Engenharia de Processos Ambiente e Energia, Faculdade de Engenharia da Universidade do Porto, Rua Dr. Roberto Frias s/n, 4200-465 Porto (Portugal); Gomes, D.; Nunes, S.P. [GKSS Research Centre Geesthacht GmbH, Max Planck Str. 1, D-21502, Geesthacht (Germany); Ponce, M.L.

    2008-07-15

    This work reports for the first time the preparation of sulphonated poly(oxadiazole-triazole) copolymer membranes doped with amphoteric molecule, 1H-benzimidazole-2-sulphonic acid and their characterisation as proton conductors at 120 C and low humidity. The membranes had not only high proton conductivities, up to 4 x 10{sup -3} S cm{sup -1} at 120 C and low relative humidity (5 and 10%), but also had good mechanical properties with a storage modulus of about 3 GPa at 300 C and high thermal stability with T{sub g} up to around 420 C. Because of their superior ion conducting and mechanical properties they have potential as a proton conducting membrane for fuel cell applications, in particular at high temperature and extremely low-humidity conditions. (Abstract Copyright [2008], Wiley Periodicals, Inc.)

  3. Synthesis of Acenaphthyl and Phenanthrene Based Fused-Aromatic Thienopyrazine Co-Polymers for Photovoltaic and Thin Film Transistor Applications

    KAUST Repository

    Mondal, Rajib

    2009-08-11

    Dithiophene and fluorene co-polymers containing fused aromatic thieno[3,4-b]pyrazine moieties were synthesized for organic thin film transistor (OTFT) and organic photovoltaic (OPV) applications. Suzuki and Stille polycondensation reactions were used for the polymerization. The band gap (Eg) of the polymers was tuned in the range of 1.15-1.6 eV to match the solar spectrum. Density functional theory calculations were carried out to rationalize the low band gaps. These polymers showed field effect mobility (μ) as high as 0.2 cm2/(V.s) with an on/off ratio as high as 106 in OTFT devices. Interestingly, one polymer in this class also showed ambipolar charge transport. Power conversion efficiency (PCE) up to 1.3% was achieved in bulk heterojunction solar cells, indicating that these materials are promising for OPV applications. © 2009 American Chemical Society.

  4. LITHIUM ION CONDUCTING POLYMER ELECTROLYTES BASED ON ALTERNATING MALEIC ANHYDRIDE COPOLYMER WITH OLIGO-OXYETHYLENE SIDE CHAINS

    Institute of Scientific and Technical Information of China (English)

    DING Liming

    1996-01-01

    A comb polymer with oligo-oxyethylene side chains of the type -(CH2CH2O)12CH3 was prepared from methyl vinyl ether/maleic anhydride copolymer and poly (ethylene glycol) methyl ether. The polymer can dissolve LiClO4 salt to form homogeneous amorphous polymer electrolyte. The ac ion conduction was measured using the complex impedance method, and conductivities were investigated as functions of temperatures and salt concentration. The complexes were first found to have two classes of glass transition which increase with increasing salt content. The optimum conductivity attained at 25℃ is in the order of 5.50 × 10-6Scm-1. IR spectroscopy was used to study the cation-polymer interaction.

  5. Stereocomplexation in Copolymer Networks Incorporating Enantiomeric Glycerol-Based 3-Armed Lactide Oligomers and a 2-Armed ɛ-Caprolactone Oligomer

    Directory of Open Access Journals (Sweden)

    Ayaka Shibita

    2016-07-01

    Full Text Available The reactions of enantiomeric glycerol-based 3-armed lactide oligomers (H3DLAO and H3LLAO and a diethylene glycol-based 2-armed ɛ-caprolactone oligomer (H2CLO with hexamethylene diisocyanate (HDI produced polyesterurethane copolymer networks (PEU-3scLAO/2CLOs 100/0, 75/25, 50/50, 25/75 and 0/100 with different feed ratios of stereocomplex (sc lactide oligomer (H3scLAO = H3DLAO + H3LLAO, H3DLAO/H3LLAO = 1/1 and H2CLO. Thermal and mechanical properties of the copolymer networks were compared with those of a simple homochiral (hc network (PEU-3DLAO produced by the reaction of H3DLAO and HDI. X-ray diffraction and differential scanning calorimetric analyses revealed that sc crystallites are formed without any hc crystallization for PEU-3scLAO/2CLOs, and that PEU-3DLAO is amorphous. The melting temperatures of sc crystallites for PEU-3scLAO/2CLOs were much higher than that of hc crystallites of H3DLAO. The polarized optical microscopic analysis revealed that the nucleation efficiency is enhanced with increasing feed of H3scLAO fraction, whereas the spherulite growth rate is accelerated with increasing feed H2CLO fraction over 100/0-50/50 networks. PEU-3scLAO/2CLO 100/0 (i.e., PEU-3scLAO exhibited a higher tensile strength and modulus than PEU-3DLAO. The elongation at break and tensile toughness for PEU-3scLAO/2CLOs increased with an increasing feed amount of H2CLO.

  6. Thermoreversible copolymer gels for extracellular matrix.

    Science.gov (United States)

    Vernon, B; Kim, S W; Bae, Y H

    2000-07-01

    To improve the properties of a reversible synthetic extracellular matrix based on a thermally reversible polymer, copolymers of N-isopropylacrylamide and acrylic acid were prepared in benzene with varying contents of acrylic acid (0 to 3%) and the thermal properties were evaluated. The poly(N-isopropylacrylamide) and copolymers made with acrylic acid had molecular weights from 0.8 to 1.7 x10(6) D. Differential scanning calorimetry (DSC) showed the high-molecular-weight acrylic acid copolymers had similar onset temperatures to the homopolymers, but the peak width was considerably increased with increasing acrylic acid content. DSC and cloud point measurements showed that polymers with 0 to 3% acrylic acid exhibit a lower critical solution temperature (LCST) transition between 30 degrees and 37 degrees C. In swelling studies, the homopolymer showed significant syneresis at temperatures above 31 degrees C. Copolymers with 1 and 1.5% showed syneresis beginning at 32 degrees and 37 degrees C, respectively. At 37 degrees C the copolymers with 1.5-3% acrylic acid showed little or no syneresis. Due to the high water content and a transition near physiologic conditions (below 37 degrees C), the polymers with 1.5-2.0% acrylic acid exhibited properties that would be useful in the development of a refillable synthetic extracellular matrix. Such a matrix could be applied to several cell types, including islets of Langerhans, for a biohybrid artificial pancreas.

  7. 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.

  8. Syntheses of Some New Group 4 non-Cp Complexes Bearing Schiff-base,Thiophene Diamide Ligands Respectively and Their Catalytic Activities for α-Olefin Polymerization

    Institute of Scientific and Technical Information of China (English)

    HUANG, Ji-Ling(黄吉玲); LIAN, Bing(廉兵); YONG, Li(雍莉); QIAN, Yan-Long(钱延龙)

    2004-01-01

    Totally sixteen new titanium and zirconium non-Cp complexes supported by Schiff-base, or thiophene diamide ligands have been synthesized. The complexes are obtained by the reaction of M(OPr-i)4 (M=Ti, Zr) with the corresponding Schiff-base ligand in 1 :1 molar ratio in good yield. The thiophene diamide titanium complex has been prepared from trimethylsilyl amine [N,S,N] ligand and TiCl4 in toluene at 120 ℃. All complexes are well characterized by 1H NMR, IR, MS and elemental analysis. When activated by excess methylaluminoxane (MAO), complexes show moderate catalytic activity for ethylene polymerization, and complex 1f (R1 =CH3, R2=Br) exhibits the highest activity for ethylene and styrene polymerization. When the complexes were preactivated by triethylaluminum (TEA), both polymerization activities and syndiotacticity of the polymers were greatly improved.

  9. Ring-Opening Metathesis Activity of Ruthenium-Based Olefin Metathesis Catalyst Coordinated with 1,3-Bis(2,6-Diisopropylphenyl)-4,5-Dihydroimidazoline

    Science.gov (United States)

    Karabulut, Solmaz; Verpoort, Francis

    A 1,3-bis-(2,6-diisopropylphenyl)-4,5-dihydroimidazol-2-ylidene substituted ruthenium (Ru)-based complex (4) has been prepared starting from (PCy3)2(Cl)2Ru=CHPh (2). The catalytic performance of catalyst (4) is checked on ring-opening metathesis polymerization (ROMP) of the low strain monomer, cycloocta-1,5-diene (COD), and also compared with catalyst (2) and (3).

  10. Probing the Mechanism of the Double C—H (De)Activation Route of a Ru-Based Olefin Metathesis Catalyst

    Science.gov (United States)

    Poater, Albert; Cavallo, Luigi

    A theoretical study of a double C—H activation mechanism that deactivates a family of second generation Ru-based catalysts is presented. DFT calculations are used to rationalize the complex mechanistic pathway from the starting precatalyst to the experimentally characterized decomposition products. In particular, we show that all the intermediates proposed by Grubbs and coworkers are indeed possible intermediates in the deactivation pathway, although the sequence of steps is somewhat different

  11. Catalytic Olefin Hydroamidation Enabled by Proton-Coupled Electron Transfer.

    Science.gov (United States)

    Miller, David C; Choi, Gilbert J; Orbe, Hudson S; Knowles, Robert R

    2015-10-28

    Here we report a ternary catalyst system for the intramolecular hydroamidation of unactivated olefins using simple N-aryl amide derivatives. Amide activation in these reactions occurs via concerted proton-coupled electron transfer (PCET) mediated by an excited state iridium complex and weak phosphate base to furnish a reactive amidyl radical that readily adds to pendant alkenes. A series of H-atom, electron, and proton transfer events with a thiophenol cocatalyst furnish the product and regenerate the active forms of the photocatalyst and base. Mechanistic studies indicate that the amide substrate can be selectively homolyzed via PCET in the presence of the thiophenol, despite a large difference in bond dissociation free energies between these functional groups.

  12. Cobalt carbide nanoprisms for direct production of lower olefins from syngas

    Science.gov (United States)

    Zhong, Liangshu; Yu, Fei; An, Yunlei; Zhao, Yonghui; Sun, Yuhan; Li, Zhengjia; Lin, Tiejun; Lin, Yanjun; Qi, Xingzhen; Dai, Yuanyuan; Gu, Lin; Hu, Jinsong; Jin, Shifeng; Shen, Qun; Wang, Hui

    2016-10-01

    Lower olefins—generally referring to ethylene, propylene and butylene—are basic carbon-based building blocks that are widely used in the chemical industry, and are traditionally produced through thermal or catalytic cracking of a range of hydrocarbon feedstocks, such as naphtha, gas oil, condensates and light alkanes. With the rapid depletion of the limited petroleum reserves that serve as the source of these hydrocarbons, there is an urgent need for processes that can produce lower olefins from alternative feedstocks. The ‘Fischer-Tropsch to olefins’ (FTO) process has long offered a way of producing lower olefins directly from syngas—a mixture of hydrogen and carbon monoxide that is readily derived from coal, biomass and natural gas. But the hydrocarbons obtained with the FTO process typically follow the so-called Anderson-Schulz-Flory distribution, which is characterized by a maximum C2-C4 hydrocarbon fraction of about 56.7 per cent and an undesired methane fraction of about 29.2 per cent (refs 1, 10, 11, 12). Here we show that, under mild reaction conditions, cobalt carbide quadrangular nanoprisms catalyse the FTO conversion of syngas with high selectivity for the production of lower olefins (constituting around 60.8 per cent of the carbon products), while generating little methane (about 5.0 per cent), with the ratio of desired unsaturated hydrocarbons to less valuable saturated hydrocarbons amongst the C2-C4 products being as high as 30. Detailed catalyst characterization during the initial reaction stage and theoretical calculations indicate that preferentially exposed {101} and {020} facets play a pivotal role during syngas conversion, in that they favour olefin production and inhibit methane formation, and thereby render cobalt carbide nanoprisms a promising new catalyst system for directly converting syngas into lower olefins.

  13. Separation of parent homopolymers from poly(ethylene oxide) and polystyrene-based block copolymers by liquid chromatography under limiting conditions of desorption--1. Determination of the suitable molar mass range and optimization of chromatographic conditions.

    Science.gov (United States)

    Rollet, Marion; Pelletier, Bérengère; Altounian, Anaïs; Berek, Dusan; Maria, Sébastien; Phan, Trang N T; Gigmes, Didier

    2015-05-01

    We studied molar mass limits for the LC LCD separation of parent polystyrene (PS) and poly(ethylene oxide) (PEO) homopolymers from PEO/PS based block copolymers and we identified optimized chromatographic conditions. Time delays between barriers and sample injections were 0-2-3'10. Eluent was composed of dimethylformamide (DMF) 40 wt.% and 1-chlorobutane (CLB) 60 wt.%; Barrier 1 (B1), which retained block copolymer, was composed of 100 wt.% CLB and Barrier 2 (B2), which retained PEO, was a mixture of DMF and CLB, which proportions were adjusted to studied block copolymers. With B2 composed of DMF 23 wt.% and CLB 77 wt.%, we obtained successful separation of PS23K-b-PEO35K-b-PS23K (56.5 wt.% of PS, the subscripts indicate the molar mass in kg mol(-1) of each polymer part in the block copolymer) from its parent homopolymers. With B2 adjusted to DMF 30 wt.% and CLB 70 wt.%, PS2.3K-b-PEO3.1K (42.6 wt.% of PS) was also efficiently separated from its parent homopolymers.

  14. NHC Backbone Configuration in Ruthenium-Catalyzed Olefin Metathesis

    Directory of Open Access Journals (Sweden)

    Veronica Paradiso

    2016-01-01

    Full Text Available The catalytic properties of olefin metathesis ruthenium complexes bearing N-heterocyclic carbene ligands with stereogenic centers on the backbone are described. Differences in catalytic behavior depending on the backbone configurations of symmetrical and unsymmetrical NHCs are discussed. In addition, an overview on asymmetric olefin metathesis promoted by chiral catalysts bearing C2-symmetric and C1-symmetric NHCs is provided.

  15. Total Synthesis of Mycalolides A and B through Olefin Metathesis.

    Science.gov (United States)

    Kita, Masaki; Oka, Hirotaka; Usui, Akihiro; Ishitsuka, Tomoya; Mogi, Yuzo; Watanabe, Hidekazu; Tsunoda, Masaki; Kigoshi, Hideo

    2015-11-16

    An asymmetric total synthesis of the trisoxazole marine macrolides mycalolides A and B is described. This synthesis involves the convergent assembly of highly functionalized C1-C19 trisoxazole and C20-C35 side-chain segments through the use of olefin metathesis and esterification as well as Julia-Kocienski olefination and enamide formation as key steps.

  16. NHC Backbone Configuration in Ruthenium-Catalyzed Olefin Metathesis.

    Science.gov (United States)

    Paradiso, Veronica; Costabile, Chiara; Grisi, Fabia

    2016-01-20

    The catalytic properties of olefin metathesis ruthenium complexes bearing N-heterocyclic carbene ligands with stereogenic centers on the backbone are described. Differences in catalytic behavior depending on the backbone configurations of symmetrical and unsymmetrical NHCs are discussed. In addition, an overview on asymmetric olefin metathesis promoted by chiral catalysts bearing C₂-symmetric and C₁-symmetric NHCs is provided.

  17. Supported organometallic catalysts for hydrogenation and Olefin Polymerization

    Science.gov (United States)

    Marks, Tobin J.; Ahn, Hongsang

    2001-01-01

    Novel heterogeneous catalysts for the which hydrogenation of olefins and arenes with high conversion rates under ambient conditions and the polymerization of olefins have been developed. The catalysts are synthesized from Ziegler-type precatalysts by supporting them on sulfate-modified zirconia.

  18. Cobalt carbonyl catalyzed olefin hydroformylation in supercritical carbon dioxide

    Science.gov (United States)

    Rathke, Jerome W.; Klingler, Robert J.

    1993-01-01

    A method of olefin hydroformylation is provided wherein an olefin reacts with a carbonyl catalyst and with reaction gases such as hydrogen and carbon monoxide in the presence of a supercritical reaction solvent, such as carbon dioxide. The invention provides higher yields of n-isomer product without the gas-liquid mixing rate limitation seen in conventional Oxo processes using liquid media.

  19. Analysis of Factors Affecting Olefin Content in FCC Gasoline

    Institute of Scientific and Technical Information of China (English)

    Wang Tao

    2005-01-01

    In order to meet the urgent need for reducing olefin content in cracked naphtha, the influence of feedstock characteristics on the olefin content was discussed. The different types and performance of catalysts developed by RIPP were introduced. Moreover, some effective operation approaches in commercial units were presented to serve as a reference to the refiners for catalyst selection.

  20. High Temperature, Low Relative Humidity, Polymer-type Membranes Based on Disulfonated Poly(arylene ether) Block and Random Copolymers Optionally Incorporating Protonic Conducting Layered Water insoluble Zirconium Fillers

    Energy Technology Data Exchange (ETDEWEB)

    McGrath, James E.; Baird, Donald G.

    2010-06-03

    Our research group has been engaged in the past few years in the synthesis of biphenol based partially disulfonated poly(arylene ether sulfone) random copolymers as potential PEMs. This series of polymers are named as BPSH-xx, where BP stands for biphenol, S stands for sulfonated, H stands for acidified and xx represents the degree of disulfonation. All of these sulfonated copolymers phase separate to form nano scale hydrophilic and hydrophobic morphological domains. The hydrophilic phase containing the sulfonic acid moieties causes the copolymer to absorb water. Water confined in hydrophilic pores in concert with the sulfonic acid groups serve the critical function of proton (ion) conduction and water transport in these systems. Both Nafion and BPSH show high proton conductivity at fully hydrated conditions. However proton transport is especially limited at low hydration level for the BPSH random copolymer. It has been observed that the diffusion coefficients of both water and protons change with the water content of the pore. This change in proton and water transport mechanisms with hydration level has been attributed to the solvation of the acid groups and the amount of bound and bulk-like water within a pore. At low hydration levels most of the water is tightly associated with sulfonic groups and has a low diffusion coefficient. This tends to encourage isolated domain morphology. Thus, although there may be significant concentrations of protons, the transport is limited by the discontinuous morphological structure. Hence the challenge lies in how to modify the chemistry of the polymers to obtain significant protonic conductivity at low hydration levels. This may be possible if one can alter the chemical structure to synthesize nanophase separated ion containing block copolymers. Unlike the BPSH copolymers, where the sulfonic acid groups are randomly distributed along the chain, the multiblock copolymers will feature an ordered sequence of hydrophilic and

  1. Maximizing light olefins production in fluid catalytic cracking (FCC) units; Maximizacao de olefinas leves em unidades de craqueamento catalitico fluido

    Energy Technology Data Exchange (ETDEWEB)

    Pimenta, Ricardo D.M.; Pinho, Andrea de Rezende [PETROBRAS, Rio de Janeiro, RJ (Brazil)

    2004-07-01

    The Fluid Catalytic Cracking (FCC) process is widely spread over the ten PETROBRAS refineries in its thirteen industrial units. The importance of the FCC process resides on its high gasoline output, being the main supplier of this important product to the system. Additionally, FCC process is the main source of light hydrocarbons in the LPG range, including light olefins. The increasing demand for ethylene, propylene and butylenes was encouraging to concentrate the research efforts on studies about alternatives for the traditional FCC process. In the present work, the proposals from main licensors (UOP, KBR, Stone and Webster) for a light-olefins-driven FCC process (Petrochemical FCC) will be compared. Furthermore, the catalytic route for light olefins production in FCC units is also described. An additive based on ZSM- 5 zeolite, which is produced following a PETROBRAS proprietary technology, is being largely applied into the catalyst inventories of all FCC units. An analysis of different scenarios was performed to estimate the maximum potential of light olefins production from the highest possible ZSM-5 additive usage. More specifically for the case of ethylene, which production is also boosted by the same type of additive, studies are being conducted with the objective of recovering it from a C2 stream using specific units to do the splitting (UPGR). The search for increasing light olefins production in the refining processes is in line with PETROBRAS strategic plan which targeted for the company a more intense activity in the Brazilian petrochemical market (author)

  2. Carbonyl-Olefin Exchange Reaction: Present State and Outlook

    Science.gov (United States)

    Kalinova, Radostina; Jossifov, Christo

    The carbonyl-olefin exchange reaction (COER) is a new reaction between carbonyl group and olefin double bond, which has a formal similarity with the olefin metathesis (OM) - one carbon atom in the latter is replaced with an oxygen atom. Till now the new reaction is performed successfully only when the two functional groups (carbonyl group and olefin double bond) are in one molecule and are conjugated. The α, β-unsaturated carbonyl compounds (substituted propenones) are the compounds with such a structure. They polymerize giving substituted polyacetylenes. The chain propagation step of this polymerization is in fact the COER. The question arises: is it possible the COER to take place when the two functional groups are not in one molecule and are not conjugated, and could this reaction became an alternative of the existing carbonyl olefination reactions?

  3. Variation of the Sterical Properties of the N-Heterocyclic Carbene Coligand in Thermally Triggerable Ruthenium-Based Olefin Metathesis Precatalysts/Initiators

    KAUST Repository

    Pump, Eva

    2015-11-09

    A series of ruthenium complexes based on the κ(C,N)-(2-(benzo[h]quinolin-10-yl)methylidene ruthenium dichloride fragment featuring different neutral coligands L (L = 1,3-bis(2,6-diisopropylphenyl)-4,5-dihydroimidazol-2-ylidene (SIPr), 1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene (SIMes), 1,3-bis(2,4-dimethylphenyl)-4,5-dihydroimidazol-2-ylidene (SIXyl), and 1,3-bis(2-methylphenyl)-4,5-dihydroimidazol-2-ylidene (SITol)) was prepared, characterized, and tested in the thermally induced ring-opening metathesis polymerization of dicyclopentadiene. In addition, the corresponding tricyclohexylphosphine derivative was investigated for comparison. All compounds were isolated as their trans-dichloro isomers. NMR spectroscopic features as well as structural features are, particularly within the NHC-bearing complexes, very similar, but their polymerization activity at elevated temperatures is distinctly different. While the SIMes derivative shows the desired properties, i.e., latency at room temperature and pronounced polymerization activity at elevated temperature, all other preinitiators do not. The preinitiator featuring the SIPr coligand is the most latent one, needing temperatures > 140 °C to show moderate activity in the polymerization of dicyclopentadiene. Compounds bearing the smaller N-heterocyclic carbene congeners are stable and latent at room temperature, but decompose upon heating, diminishing the polymerization activity at elevated temperatures. Density functional calculations show that the SIMes derivative is the easiest to activate and yields the most stable 14-electron intermediate. Finally calculations reveal a distinct influence of the nature of the N-heterocyclic carbene ligand on the position of the equilibrium of cis- and trans-dichloro isomers of the complexes. While the SIPr and the SIMes derivatives prefer the cis-configuration, all other derivatives favor, at least in solvents with low dielectric constants, the trans

  4. Excited-state dynamics in diketopyrrolopyrrole-based copolymer for organic photovoltaics investigated by transient optical spectroscopy

    Science.gov (United States)

    Matsuzaki, Hiroyuki; Furube, Akihiro; Katoh, Ryuzi; Pratap Singh, Samarendra; Sonar, Prashant; Williams, Evan Laurence; Vijila, Chellappan; Sandhya Subramanian, Gomathy; Gorelik, Sergey; Hobley, Jonathan

    2014-01-01

    We investigate the photoexcited state dynamics in a donor-acceptor copolymer, poly{3,6-dithiophene-2-yl-2,5-di(2-octyldodecyl)-pyrrolo[3,4-c]pyrrole-1,4-dione-alt-naphthalene} (pDPP-TNT), by picosecond fluorescence and femtosecond transient absorption spectroscopies. Time-resolved fluorescence lifetime measurements of pDPP-TNT thin films reveal that the lifetime of the singlet excited state is 185 ± 5 ps and that singlet-singlet annihilation occurs at excitation photon densities above 6 × 1017 photons/cm3. From the results of singlet-singlet annihilation analysis, we estimate that the single-singlet annihilation rate constant is (6.0 ± 0.2) × 10-9 cm3 s-1 and the singlet diffusion length is ~7 nm. From the comparison of femtosecond transient absorption measurements and picosecond fluorescence measurements, it is found that the time profile of the photobleaching signal in the charge-transfer (CT) absorption band coincides with that of the fluorescence intensity and there is no indication of long-lived species, which clearly suggests that charged species, such as polaron pairs and triplet excitons, are not effectively photogenerated in the neat pDPP-TNT polymer.

  5. Thermoplastic biodegradable elastomers based on ε-caprolactone and L-lactide block co-polymers: a new synthetic approach.

    Science.gov (United States)

    Lipik, Vitali T; Kong, Jen Fong; Chattopadhyay, Sujay; Widjaja, Leonardus K; Liow, Sing S; Venkatraman, Subbu S; Abadie, Marc J M

    2010-11-01

    Although biodegradable polymers have found extensive application in medical devices, there are very few commercially available elastomeric biodegradable polymers. In this work, starting with the well-known monomers L-lactide and ε-caprolactone, we developed elastomers using a multiblock co-polymer approach. This ensures that the degradation products of such elastomers are also acceptable from a cytotoxicity standpoint. A series of polymers with various structures was synthesized utilizing a design of experiment approach. The basic structure is that of a diblock, with each block being modified by the addition of co-monomer. The synthesized polymers exhibited a range of mechanical properties from a typical thermoplastic polymer to that approaching a good thermoplastic elastomer. 13C nuclear magnetic resonance analysis, size exclusion chromatography and differential scanning calorimetry measurements have been utilized to relate the observed range of mechanical properties to the structure. In addition, the elastomeric nature has been established with the use of creep and recovery measurements. Such elastomers may find a variety of biomedical applications, ranging from stent coatings to atrial septal defect occluders.

  6. New Polytetrahydrofuran Graft Copolymers.

    Science.gov (United States)

    1979-03-15

    chioroprene) , chiorobutyl - ~~~~~ rubber , bromobutyl rubber , chlorinated EPDM , chlorinated poly(buta— diene) and chlorinated butadiene styrene copolymer...for initial detailed studies (3 ,4 , 6 , 7 — 9 ) . Many soluble metal salts with cations capable of stabilizing an on].um ion polymerization (SO3CF 3

  7. 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.

  8. 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.

  9. Kinetically controlled E-selective catalytic olefin metathesis.

    Science.gov (United States)

    Nguyen, Thach T; Koh, Ming Joo; Shen, Xiao; Romiti, Filippo; Schrock, Richard R; Hoveyda, Amir H

    2016-04-29

    A major shortcoming in olefin metathesis, a chemical process that is central to research in several branches of chemistry, is the lack of efficient methods that kinetically favor E isomers in the product distribution. Here we show that kinetically E-selective cross-metathesis reactions may be designed to generate thermodynamically disfavored alkenyl chlorides and fluorides in high yield and with exceptional stereoselectivity. With 1.0 to 5.0 mole % of a molybdenum-based catalyst, which may be delivered in the form of air- and moisture-stable paraffin pellets, reactions typically proceed to completion within 4 hours at ambient temperature. Many isomerically pure E-alkenyl chlorides, applicable to catalytic cross-coupling transformations and found in biologically active entities, thus become easily and directly accessible. Similarly, E-alkenyl fluorides can be synthesized from simpler compounds or more complex molecules.

  10. Olefin Epoxidation in Aqueous Phase Using Ionic-Liquid Catalysts.

    Science.gov (United States)

    Cokoja, Mirza; Reich, Robert M; Wilhelm, Michael E; Kaposi, Marlene; Schäffer, Johannes; Morris, Danny S; Münchmeyer, Christian J; Anthofer, Michael H; Markovits, Iulius I E; Kühn, Fritz E; Herrmann, Wolfgang A; Jess, Andreas; Love, Jason B

    2016-07-21

    Hydrophobic imidazolium-based ionic liquids (IL) act as catalysts for the epoxidation of unfunctionalized olefins in water using hydrogen peroxide as oxidant. Although the catalysts are insoluble in both the substrate and in water, surprisingly, they are very well soluble in aqueous H2 O2 solution, owing to perrhenate-H2 O2 interactions. Even more remarkably, the presence of the catalyst also boosts the solubility of substrate in water. This effect is crucially dependent on the cation design. Hence, the imidazolium perrhenates enable both the transfer of hydrophobic substrate into the aqueous phase, and serve as actual catalysts, which is unprecedented. At the end of the reaction and in absence of H2 O2 the IL catalyst forms a third phase next to the lipophilic product and water and can easily be recycled.

  11. Molybdenum chloride catalysts for Z-selective olefin metathesis reactions

    Science.gov (United States)

    Koh, Ming Joo; Nguyen, Thach T.; Lam, Jonathan K.; Torker, Sebastian; Hyvl, Jakub; Schrock, Richard R.; Hoveyda, Amir H.

    2017-01-01

    The development of catalyst-controlled stereoselective olefin metathesis processes has been a pivotal recent advance in chemistry. The incorporation of appropriate ligands within complexes based on molybdenum, tungsten and ruthenium has led to reactivity and selectivity levels that were previously inaccessible. Here we show that molybdenum monoaryloxide chloride complexes furnish higher-energy (Z) isomers of trifluoromethyl-substituted alkenes through cross-metathesis reactions with the commercially available, inexpensive and typically inert Z-1,1,1,4,4,4-hexafluoro-2-butene. Furthermore, otherwise inefficient and non-stereoselective transformations with Z-1,2-dichloroethene and 1,2-dibromoethene can be effected with substantially improved efficiency and Z selectivity. The use of such molybdenum monoaryloxide chloride complexes enables the synthesis of representative biologically active molecules and trifluoromethyl analogues of medicinally relevant compounds. The origins of the activity and selectivity levels observed, which contradict previously proposed principles, are elucidated with the aid of density functional theory calculations.

  12. Olefin metathesis over UV-irradiated silica

    Science.gov (United States)

    Tanaka, Tsunehiro; Matsuo, Shigehiro; Maeda, Takashi; Yoshida, Hisao; Funabiki, Takuzo; Yoshida, Satohiro

    1997-11-01

    Photoirradiated silica evacuated at temperatures higher than 800 K was found to be active for olefin metathesis reactions. The analysis of products shows that the metalacyclobutane intermediate is likely. The instantaneous response of the reaction to the irradiation and the activity change with various UV filter showed that the reaction is induced by UV-excitation of silica. The correlation between the evacuation temperature and the activity showed that the surface free from water molecules plays a role in the reaction and the removal of isolated OH groups strongly relates to the generation of active sites.

  13. Ruthenium-Aryloxide Catalysts for Olefin Metathesis

    Science.gov (United States)

    Monfette, Sebastien; Blacquiere, Johanna M.; Conrad, Jay C.; Beach, Nicholas J.; Fogg, Deryn E.

    : Advances in design of ruthenium aryloxide catalysts for olefin metathesis are described. The target complexes are accessible on reaction of RuCl2(NHC)(py)2 (CHPh) (NHC - N-heterocyclic carbene) with electron-deficient, monodentate aryl- oxides, or aryloxides that yield small, rigid chelate rings. The best of these catalysts offer activity comparable to or greater than that of the parent chloride (Grubbs) systems in ring-closing metathesis (RCM). Preliminary studies of the electronic nature of the Ru-X bond suggest that the metal center is more electropositive in the aryloxide complexes than in the Grubbs systems.

  14. Methyltrioxorhenium as catalyst for olefin metathesis

    Energy Technology Data Exchange (ETDEWEB)

    Herrmann, W.A. (Technische Univ. Muenchen, Garching (Germany). Anorganisch-Chemisches Inst.); Wagner, W. (Consortium fuer Elektrochemische Industrie GmbH, Muenchen (Germany)); Flessner, U.N.; Volkhardt, U.; Komber, H. (Institut fuer Technologie der Polymere, Dresden (Germany))

    1991-12-01

    No cocatalysts are needed as additives when methyltrioxorhenium (MTO) supported on acidic carriers is employed to catalyze the metathesis of functionalized olefins. A typical system is MTO/Al{sub 2}O{sub 3}-SiO{sub 2}, which is active, for instance, in the metathesis of allyl halides, allylsilanes, unsaturated carboxylates, and nitriles. MTO in combination with R{sub n}AlCl{sub 3-n} is a homogeneous catalyst in ring-opening polymerizations (R = CH{sub 3}, C{sub 2}H{sub 5}; n = 1,2). (orig.).

  15. Characterization of thermal destruction behavior of hybrid composites based on polyoxymethylene, ethylene-octene copolymer impact modifier and ZnO nanofiller

    Science.gov (United States)

    Meri, Remo Merijs; Zicans, Janis; Abele, Agnese; Ivanova, Tatjana; Kalnins, Martins

    2016-05-01

    Hybrid polymer nanocomposites, composed of polyoxymethylene (POM), ethylene octene copolymer (EOC) and plasma synthesized tetrapod shaped zinc oxide (ZnO), were prepared by using melt compounding. The content of EOC in the POM based composites was varied between 10 and 50 mass %, while the content of ZnO was constant (2 mass %). Thermal behaviour of POM based systems was studied by using thermogravimetric analysis coupled with Fourier transform infrared spectroscopy. The influence of the elastomer content and/or ZnO addition on the thermal stability of POM based systems was evaluated. The influence of the α-octene content in the elastomer on the thermal decomposition behaviour of POM and its nanocomposites with ZnO was also evaluated. Results of thermogravimetric analysis showed that, by rising either the elastomer or ZnO content, thermal stability of the investigated POM composites was increased. The modifying effect of EOC17 in respect of thermal resistance was somewhat larger than that of EOC38 because of the smaller amount of tertiary carbon atoms in the macromolecular structure of the former elastomer. Improved thermal resistance of ZnO containing POM based composites was because of impermeable structure the inorganic nanofiller allowing decrease gas exchange rate and facilitating non-combustible gases, such as CO2, stay in the zone of burning. Addition of ZnO have a potential to influence structure of the polymer blend matrix itself by improving its barrier characteristics.

  16. Palladium(II-catalyzed Heck reaction of aryl halides and arylboronic acids with olefins under mild conditions

    Directory of Open Access Journals (Sweden)

    Tanveer Mahamadali Shaikh

    2013-08-01

    Full Text Available A series of general and selective Pd(II-catalyzed Heck reactions were investigated under mild reaction conditions. The first protocol has been developed employing an imidazole-based secondary phosphine oxide (SPO ligated palladium complex (6 as a precatalyst. The catalytic coupling of aryl halides and olefins led to the formation of the corresponding coupled products in excellent yields. A variety of substrates, both electron-rich and electron-poor olefins, were converted smoothly to the targeted products in high yields. Compared with the existing approaches employing SPO–Pd complexes in a Heck reaction, the current strategy features mild reaction conditions and broad substrate scope. Furthermore, we described the coupling of arylboronic acids with olefins, which were catalyzed by Pd(OAc2 and employed N-bromosuccinimide as an additive under ambient conditions. The resulted biaryls have been obtained in moderate to good yields.

  17. Synthesis of High Performance Cyclic Olefin Polymers (COPs with Ester Group via Ring-Opening Metathesis Polymerization

    Directory of Open Access Journals (Sweden)

    Jing Cui

    2015-08-01

    Full Text Available Novel ester group functionalized cyclic olefin polymers (COPs with high glass transition temperature, high transparency, good mechanical performance and excellent film forming ability have been achieved in this work via efficient ring-opening metathesis copolymerization of exo-1,4,4a,9,9a,10-hexahydro-9,10(1′,2′-benzeno-l,4-methanoanthracene (HBM and comonomers (5-norbornene-2-yl methylacetate (NMA, 5-norbornene-2-yl methyl 2-ethylhexanoate (NME or 5-norbornene-2-yl methyldodecanoate (NMD utilizing the Grubbs first generation catalyst, Ru(CHPh(Cl2(PCy32 (Cy = cyclohexyl, G1, followed by hydrogenation of double bonds in the main chain. The fully hydrogenated copolymers were characterized by nuclear magnetic resonance, FT-IR spectroscopy analysis, gel permeation chromatography, and thermo gravimetric analysis. Differential scanning calorimetry curves showed that the glass transition temperatures (Tg linearly decreased with the increasing of comonomers content, which was easily controlled by changing feed ratios of HBM and comonomers. Static water contact angles tests indicate that hydrophilicity of copolymers can also be modulated by changing the comonomers incorporation. Additionally, the mechanical performances of copolymers were also investigated.

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

    Science.gov (United States)

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

    2014-10-01

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

  19. Simple, chemoselective, catalytic olefin isomerization.

    Science.gov (United States)

    Crossley, Steven W M; Barabé, Francis; Shenvi, Ryan A

    2014-12-01

    Catalytic amounts of Co(Sal(tBu,tBu))Cl and organosilane irreversibly isomerize terminal alkenes by one position. The same catalysts effect cycloisomerization of dienes and retrocycloisomerization of strained rings. Strong Lewis bases like amines and imidazoles, and labile functionalities like epoxides, are tolerated.

  20. Exploring new generations of ruthenium olefin metathesis catalysts: The reactivity of a bis-ylidene ruthenium complex by DFT

    KAUST Repository

    Poater, Albert

    2013-01-01

    Density functional theory calculations were used to predict the behaviour of a potential novel architecture of olefin metathesis catalysts, in which one of the neutral ligands of classical Ru-based catalysts, e.g. a phosphine or an N-heterocyclic carbene, is replaced by an alkylidene group. Introduction of a second alkylidene ligand favors dissociation of the remaining phosphine and the overall energy profile for the metathesis using ethylene as the probe substrate reveals that the proposed bis-alkylidene complexes might match the requirements of a good performing olefin metathesis catalyst. © 2013 The Royal Society of Chemistry.

  1. Surface self-assembled PEGylation of fluoro-based PVDF membranes via hydrophobic-driven copolymer anchoring for ultra-stable biofouling resistance.

    Science.gov (United States)

    Lin, Nien-Jung; Yang, Hui-Shan; Chang, Yung; Tung, Kuo-Lun; Chen, Wei-Hao; Cheng, Hui-Wen; Hsiao, Sheng-Wen; Aimar, Pierre; Yamamoto, Kazuo; Lai, Juin-Yih

    2013-08-13

    Stable biofouling resistance is significant for general filtration requirements, especially for the improvement of membrane lifetime. A systematic group of hyper-brush PEGylated diblock copolymers containing poly(ethylene glycol) methacrylate (PEGMA) and polystyrene (PS) was synthesized using an atom transfer radical polymerization (ATRP) method and varying PEGMA lengths. This study demonstrates the antibiofouling membrane surfaces by self-assembled anchoring PEGylated diblock copolymers of PS-b-PEGMA on the microporous poly(vinylidene fluoride) (PVDF) membrane. Two types of copolymers are used to modify the PVDF surface, one with different PS/PEGMA molar ratios in a range from 0.3 to 2.7 but the same PS molecular weights (MWs, ∼5.7 kDa), the other with different copolymer MWs (∼11.4, 19.9, and 34.1 kDa) but the similar PS/PEGMA ratio (∼1.7 ± 0.2). It was found that the adsorption capacities of diblock copolymers on PVDF membranes decreased as molar mass ratios of PS/PEGMA ratio reduced or molecular weights of PS-b-PEGMA increased because of steric hindrance. The increase in styrene content in copolymer enhanced the stability of polymer anchoring on the membrane, and the increase in PEGMA content enhanced the protein resistance of membranes. The optimum PS/PEGMA ratio was found to be in the range between 1.5 and 2.0 with copolymer MWs above 20.0 kDa for the ultrastable resistance of protein adsorption on the PEGylated PVDF membranes. The PVDF membrane coated with such a diblock copolymer owned excellent biofouling resistance to proteins of BSA and lysozyme as well as bacterium of Escherichia coli and Staphylococcus epidermidis and high stable microfiltration operated with domestic wastewater solution in a membrane bioreactor.

  2. Development of new antioxidant active packaging films based on ethylene vinyl alcohol copolymer (EVOH) and green tea extract.

    Science.gov (United States)

    Lopez de Dicastillo, Carol; Nerin, Cristina; Alfaro, Pilar; Catala, Ramon; Gavara, Rafael; Hernandez-Munoz, Pilar

    2011-07-27

    Ethylene vinyl alcohol copolymer (EVOH) films containing green tea extract were successfully produced by extrusion. The films were brown and translucent, and the addition of the extract increased the water and oxygen barrier at low relative humidity but increased the water sensitivity, the glass transition temperature, and the crystallinity of the films and improved their thermal resistance. An analysis by HPLC revealed that the antioxidant components of the extract suffered partial degradation during extrusion, reducing the content of catechin gallates and increasing the concentration of free gallic acid. Exposure of the films to various food simulants showed that the liquid simulants increased their capacity to reduce DPPH(•) and ABTS(•+) radicals. The release of green tea extract components into the simulant monitored by HPLC showed that all compounds present in the green tea extract were partially released, although the extent and kinetics of release were dependent on the type of food. In aqueous food simulants, gallic acid was the main antioxidant component released with partition coefficient values ca. 200. In 95% ethanol (fatty food simulant) the K value for gallic acid decreased to 8 and there was a substantial contribution of catechins (K in the 1000 range) to a greatly increased antioxidant efficiency. Kinetically, gallic acid was released more quickly than catechins, owing to its faster diffusivity in the polymer matrix as a consequence of its smaller molecular size, although the most relevant effect is the plasticization of the matrix by alcohol, increasing the diffusion coefficient >10-fold. Therefore, the materials here developed with the combination of antioxidant substances that constitute the green tea extract could be used in the design of antioxidant active packaging for all type of foods, from aqueous to fatty products, the compounds responsible for the protection being those with the higher compatibility with the packaged product.

  3. Synthesis of interlocked molecules by olefin metathesis

    Science.gov (United States)

    Clark, Paul Gregory

    A large body of work in the Grubbs group has focused on the development of functional-group tolerant ruthenium alkylidene catalysts that perform a number of olefin metathesis reactions. These catalysts have seen application in a wide range of fields, including classic total synthesis as well as polymer and materials chemistry. One particular family of compounds, interlocked molecules, has benefitted greatly from these advances in catalyst stability and activity. This thesis describes several elusive and challenging interlocked architectures whose syntheses have been realized through the utilization of different types of ruthenium-catalyzed olefin metathesis reactions. Ring-closing olefin metathesis has enabled the synthesis of a [c2]daisy-chain dimer with the ammonium binding site near the cap of the dimer. A deprotonated DCD possessing such a structural attribute will more forcefully seek to restore coordinating interactions upon reprotonation, enhancing its utility as a synthetic molecular actuator. Dimer functionalization facilitated incorporation into linear polymers, with a 48% size increase of an unbound, extended analogue of the polymer demonstrating slippage of the dimer units. Ongoing work is directed at further materials studies, in particular, exploring the synthesis of macroscopic networks containing the DCD units and analyzing the correlation between molecular-scale extension-contraction manipulations and resulting macro-scale changes. A "clipping" approach to a polycatenated cyclic polymer, a structure that resembles a molecular "charm bracelet", has been described. The use of ring-opening metathesis polymerization of a carbamate monomer in the presence of a chain transfer agent allowed for the synthesis of a linear polymer that was subsequently functionalized and cyclized to the corresponding cyclic analogue. This cyclic polymer was characterized through a variety of techniques, and subjected to further functionalization reactions, affording a cyclic

  4. Synthesis and characterization of new magnetically recoverable molybdenum nanocatalyst for epoxidation of olefins

    Energy Technology Data Exchange (ETDEWEB)

    Masteri-Farahani, M., E-mail: mfarahany@yahoo.com [Faculty of Chemistry, University of Tarbiat Moallem, Tehran (Iran, Islamic Republic of); Kashef, Z. [Faculty of Chemistry, University of Tarbiat Moallem, Tehran (Iran, Islamic Republic of)

    2012-04-15

    New heterogeneous molybdenum catalyst was prepared through covalent attachment of a Schiff base ligand on the surface of silica coated magnetite nanoparticles via aminopropyl spacer and subsequent complexation with MoO{sub 2}(acac){sub 2}. The prepared nanocatalyst was characterized with Fourier transform infrared spectroscopy, X-ray diffraction, scanning and transmission electron microscopies and vibrating sample magnetometry. Catalytic epoxidation of some olefins and allylic alcohols by prepared nanocatalyst using tert-butyl hydroperoxide and cumene hydroperoxide as oxidants was achieved with good activities and selectivities. - Highlights: Black-Right-Pointing-Pointer Silica coated magnetite nanoparticles were modified with a Schiff base ligand. Black-Right-Pointing-Pointer Next reaction with MoO{sub 2}(acac){sub 2} afforded magnetically recoverable nanocatalyst. Black-Right-Pointing-Pointer The prepared nanocatalyst catalyzed the epoxidation of olefins with TBHP.

  5. Self-assembled antimicrobial and biocompatible copolymer films on titanium.

    Science.gov (United States)

    Pfaffenroth, Cornelia; Winkel, Andreas; Dempwolf, Wibke; Gamble, Lara J; Castner, David G; Stiesch, Meike; Menzel, Henning

    2011-11-10

    Copolymers of 4-vinyl-N-hexylpyridinium bromide and dimethyl(2-methacryloyloxyethyl) phosphonate self-assemble to form ultrathin layers on titanium surfaces that show antimicrobial activity, and biocompatibility. The copolymer layers are characterized by contact angle measurements, ellipsometry and XPS. Antibacterial activity is assessed by investigation of adherence of S. mutans. Biocompatibility is rated based on human gingival fibroblast adhesion and proliferation. By balancing the opposing effects of the chemical composition on biocompatibility and antimicrobial activity, copolymer coatings are fabricated that are able to inhibit the growth of S. mutans on the surface but still show attachment of gingival fibroblasts, and therefore might prevent biofilm formation on implants.

  6. Ruthenium indenylidene “1st generation” olefin metathesis catalysts containing triisopropyl phosphite

    Directory of Open Access Journals (Sweden)

    Stefano Guidone

    2015-09-01

    Full Text Available The reaction of triisopropyl phosphite with phosphine-based indenylidene pre-catalysts affords “1st generation” cis-complexes. These have been used in olefin metathesis reactions. The cis-Ru species exhibit noticeable differences with the trans-Ru parent complexes in terms of structure, thermal stability and reactivity. Experimental data underline the importance of synergistic effects between phosphites and L-type ligands.

  7. Ruthenium indenylidene "1(st) generation" olefin metathesis catalysts containing triisopropyl phosphite.

    Science.gov (United States)

    Guidone, Stefano; Nahra, Fady; Slawin, Alexandra M Z; Cazin, Catherine S J

    2015-01-01

    The reaction of triisopropyl phosphite with phosphine-based indenylidene pre-catalysts affords "1(st) generation" cis-complexes. These have been used in olefin metathesis reactions. The cis-Ru species exhibit noticeable differences with the trans-Ru parent complexes in terms of structure, thermal stability and reactivity. Experimental data underline the importance of synergistic effects between phosphites and L-type ligands.

  8. Ruthenium indenylidene “1st generation” olefin metathesis catalysts containing triisopropyl phosphite

    Science.gov (United States)

    Guidone, Stefano; Nahra, Fady; Slawin, Alexandra M Z

    2015-01-01

    Summary The reaction of triisopropyl phosphite with phosphine-based indenylidene pre-catalysts affords “1st generation” cis-complexes. These have been used in olefin metathesis reactions. The cis-Ru species exhibit noticeable differences with the trans-Ru parent complexes in terms of structure, thermal stability and reactivity. Experimental data underline the importance of synergistic effects between phosphites and L-type ligands. PMID:26425210

  9. STUDY ON PET-PA66 COPOLYMER

    Institute of Scientific and Technical Information of China (English)

    WU Rongrui; SHI Weitong

    1992-01-01

    In this work the PET-PA66 copolymers are obtained. The characterization of chemical structure of copolymer chain by NMR method is also given . It is shown that when the 66 Nylon salt is added in the copolycondensation, the adipic acid and hexamethylenediamine reacted mainly by itself and the obtained copolymer is a random copolymer, and when the Nylon 66 oligomer is added, the obtained copolymer is a block copolymer. The result of NMR analysis is demonstrated by properties investigation.

  10. Block copolymer battery separator

    Science.gov (United States)

    Wong, David; Balsara, Nitash Pervez

    2016-04-26

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

  11. Helical Ordering in Chiral Block Copolymers

    Science.gov (United States)

    Zhao, Wei; Hong, Sung Woo; Chen, Dian; Grason, Gregory; Russell, Thomas

    2012-02-01

    Introducing molecular chirality into the segments of block copolymers can influence the nature of the resultant morphology. Such an effect was found for poly(styrene-b-L-lactide) (PS-b-PLLA) diblock copolymers where hexagonally packed PLLA helical microdomains (H* phase) form in a PS matrix. However, molecular ordering of PLLA within the helical microdomains and the transfer of chirality from the segmental level to the mesoscale is still not well understood. We developed a field theoretic model to describe the interactions between segments of chiral blocks, which have the tendency to form a ``cholesteric'' texture. Based on the model, we calculated the bulk morphologies of chiral AB diblock copolymers using self-consistent field theory (SCFT). Experiments show that the H* phase only forms when microphase separation between PS and PLLA block happens first and crystallization of PLLA block is suppressed or happens within confined microdomain. Hence, crystalline ordering is not necessary for H* phase formation. The SCFT offers the chance to explore the range of thermodynamic stability of helical structures in the phase diagram of chiral block copolymer melts, by tuning parameters not only like the block segregation strength and composition, but also new parameters such as the ratio between preferred helical pitch to the radius of gyration and the Frank elastic constant for inter-segment distortions.

  12. The activation mechanism of Ru-indenylidene complexes in olefin metathesis.

    Science.gov (United States)

    Urbina-Blanco, César A; Poater, Albert; Lebl, Tomas; Manzini, Simone; Slawin, Alexandra M Z; Cavallo, Luigi; Nolan, Steven P

    2013-05-01

    Olefin metathesis is a powerful tool for the formation of carbon-carbon double bonds. Several families of well-defined ruthenium (Ru) catalysts have been developed during the past 20 years; however, the reaction mechanism for all such complexes was assumed to be the same. In the present study, the initiation mechanism of Ru-indenylidene complexes was examined and compared with that of benzylidene counterparts. It was discovered that not all indenylidene complexes followed the same mechanism, highlighting the importance of steric and electronic properties of so-called spectator ligands, and that there is no single mechanism for the Ru-based olefin metathesis reaction. The experimental findings are supported quantitatively by DFT calculations.

  13. The activation mechanism of Ru-indenylidene complexes in olefin metathesis

    KAUST Repository

    Urbina-Blanco, César A.

    2013-05-08

    Olefin metathesis is a powerful tool for the formation of carbon-carbon double bonds. Several families of well-defined ruthenium (Ru) catalysts have been developed during the past 20 years; however, the reaction mechanism for all such complexes was assumed to be the same. In the present study, the initiation mechanism of Ru-indenylidene complexes was examined and compared with that of benzylidene counterparts. It was discovered that not all indenylidene complexes followed the same mechanism, highlighting the importance of steric and electronic properties of so-called spectator ligands, and that there is no single mechanism for the Ru-based olefin metathesis reaction. The experimental findings are supported quantitatively by DFT calculations. © 2013 American Chemical Society.

  14. Ligand-Enabled γ-C–H Olefination and Carbonylation: Construction of β-Quaternary Carbon Centers

    OpenAIRE

    Li, Suhua; Chen, Gang; Feng, Chen-Guo; Gong, Wei; Yu, Jin-Quan

    2014-01-01

    Monoselective γ-C–H olefination and carbonylation of aliphatic acids has been accomplished by using a combination of a quinoline-based ligand and a weakly coordinating amide directing group. The reaction provides a new route for constructing richly functionalized all-carbon quaternary carbon centers at the β-position of aliphatic acids.

  15. Ligand-enabled γ-C-H olefination and carbonylation: construction of β-quaternary carbon centers.

    Science.gov (United States)

    Li, Suhua; Chen, Gang; Feng, Chen-Guo; Gong, Wei; Yu, Jin-Quan

    2014-04-09

    Monoselective γ-C-H olefination and carbonylation of aliphatic acids has been accomplished by using a combination of a quinoline-based ligand and a weakly coordinating amide directing group. The reaction provides a new route for constructing richly functionalized all-carbon quaternary carbon centers at the β-position of aliphatic acids.

  16. Photoorganocatalysed and visible light photoredox catalysed trifluoromethylation of olefins and (hetero)aromatics in batch and continuous flow.

    Science.gov (United States)

    Lefebvre, Quentin; Hoffmann, Norbert; Rueping, Magnus

    2016-02-11

    Trifluoromethylation of olefins and (hetero)aromatics with sodium triflinate as CF3 source and readily accessible benzophenone derivatives as photosensitisers has been developed in batch and flow. The use of an iridium-based photocatalyst enables the trifluoromethylation to proceed under visible light irradiation.

  17. An Approach to Solid-State Electrical Double Layer Capacitors Fabricated with Graphene Oxide-Doped, Ionic Liquid-Based Solid Copolymer Electrolytes

    Directory of Open Access Journals (Sweden)

    N. F. A. Fattah

    2016-06-01

    Full Text Available Solid polymer electrolyte (SPE composed of semi-crystalline poly (vinylidene fluoride-hexafluoropropylene [P(VdF-HFP] copolymer, 1-ethyl-3-methylimidazolium bis (trifluoromethyl sulphonyl imide [EMI-BTI] and graphene oxide (GO was prepared and its performance evaluated. The effects of GO nano-filler were investigated in terms of enhancement in ionic conductivity along with the electrochemical properties of its electrical double layer capacitors (EDLC. The GO-doped SPE shows improvement in ionic conductivity compared to the P(VdF-HFP-[EMI-BTI] SPE system due to the existence of the abundant oxygen-containing functional group in GO that assists in the improvement of the ion mobility in the polymer matrix. The complexation of the materials in the SPE is confirmed in X-ray diffraction (XRD and thermogravimetric analysis (TGA studies. The electrochemical performance of EDLC fabricated with GO-doped SPE is examined using cyclic voltammetry and charge–discharge techniques. The maximum specific capacitance obtained is 29.6 F∙g−1, which is observed at a scan rate of 3 mV/s in 6 wt % GO-doped, SPE-based EDLC. It also has excellent cyclic retention as it is able keep the performance of the EDLC at 94% even after 3000 cycles. These results suggest GO doped SPE plays a significant role in energy storage application.

  18. A novel pulsatile drug delivery system based on the physiochemical reaction between acrylic copolymer and organic acid: in vitro and in vivo evaluation.

    Science.gov (United States)

    Zhang, Ziwei; Qi, Xiaole; Li, Xiangbo; Xing, Jiayu; Zhu, Xuehua; Wu, Zhenghong

    2014-02-28

    Multilayer-coating technology is the traditional method to achieve pulsatile drug release with the drawbacks of time consuming, more materials demanding and lack of efficiency. The purpose of this study was to design a novel pulsatile drug delivery system based on the physiochemical interaction between acrylic copolymer and organic acid with relatively simpler formulation and manufacturing process. The Enalapril Maleate (EM) pulsatile release pellets were prepared using extruding granulation, spheronization and fluid-bed coating technology. The ion-exchange experiment, hydration study and determination of glass transition temperature were conducted to explore the related drug release mechanism. Bioavailability experiment was carried out by administering the pulsatile release pellets to rats compared with marketed rapid release tablets Yisu. An obvious 4h lag time period and rapid drug release was observed from in vitro dissolution profiles. The release mechanism was a combination of both disassociated and undisassociated forms of succinic acid physiochemically interacting with Eudragit RS. The AUC0-τ of the EM pulsatile pellets and the market tablets was 702.384 ± 96.89 1 hn g/mL and 810.817 ± 67.712 h ng/mL, while the relative bioavailability was 86.62%. These studies demonstrate this novel pulsatile release concept may be a promising strategy for oral pulsatile delivery system.

  19. Charge transport studies in donor-acceptor block copolymer PDPP-TNT and PC71BM based inverted organic photovoltaic devices processed in room conditions

    Energy Technology Data Exchange (ETDEWEB)

    Srivastava, Shashi B.; Singh, Samarendra P., E-mail: samarendra.singh@snu.edu.in [Department of Physics, Shiv Nadar University, Gautam Buddha Nagar, Uttar Pradesh, India-201307 (India); Sonar, Prashant [School of Chemistry, Physics and Mechanical Engineering, Queensland University of Technology, Brisbane, Australia-4001 (Australia)

    2015-07-15

    Diketopyrrolopyrole-naphthalene polymer (PDPP-TNT), a donor-acceptor co-polymer, has shown versatile behavior demonstrating high performances in organic field-effect transistors (OFETs) and organic photovoltaic (OPV) devices. In this paper we report investigation of charge carrier dynamics in PDPP-TNT, and [6,6]-phenyl C{sub 71} butyric acid methyl ester (PC71BM) bulk-heterojunction based inverted OPV devices using current density-voltage (J-V) characteristics, space charge limited current (SCLC) measurements, capacitance-voltage (C-V) characteristics, and impedance spectroscopy (IS). OPV devices in inverted architecture, ITO/ZnO/PDPP-TNT:PC71BM/MoO{sub 3}/Ag, are processed and characterized at room conditions. The power conversion efficiency (PCE) of these devices are measured ∼3.8%, with reasonably good fill-factor 54.6%. The analysis of impedance spectra exhibits electron’s mobility ∼2 × 10{sup −3} cm{sup 2}V{sup −1}s{sup −1}, and lifetime in the range of 0.03-0.23 ms. SCLC measurements give hole mobility of 1.12 × 10{sup −5} cm{sup 2}V{sup −1}s{sup −1}, and electron mobility of 8.7 × 10{sup −4} cm{sup 2}V{sup −1}s{sup −1}.

  20. Thermo-Responsive Polyurethane Hydrogels Based on Poly(ε-caprolactone Diol and Amphiphilic Polylactide-Poly(Ethylene Glycol Block Copolymers

    Directory of Open Access Journals (Sweden)

    Shan-hui Hsu

    2016-07-01

    Full Text Available Waterborne polyurethane (PU based on poly(ε-caprolactone (PCL diol and an amphiphilic polylactide-poly(ethylene glycol (PLA-PEG diblock copolymer was synthesized. The molar ratio of PCL/PLA-PEG was 9:1 with different PLA chain lengths. The PU nanoparticles were characterized by dynamic light scattering (DLS, small angle X-ray scattering (SAXS and rheological analysis. The water contact angle measurement, infrared spectroscopy, wide angle X-ray scattering (WAXS, thermal and mechanical analyses were conducted on PU films. Significant changes in physio-chemical properties were observed for PUs containing 10 mol % of amphiphilic blocks. The water contact angle was reduced to 12°–13°, and the degree of crystallinity was 5%–10%. The PU dispersions underwent sol-gel transition upon the temperature rise to 37 °C. The gelation time increased as the PLA chain length increased. In addition, the fractal dimension of each gel was close to that of a percolation cluster. Moreover, PU4 with a solid content of 26% could support the proliferation of human mesenchymal stem cells (hMSCs. Therefore, thermo-responsive hydrogels with tunable properties are promising injectable materials for cell or drug delivery.

  1. A novel intrinsically microporous ladder polymer and copolymers derived from 1,1′,2,2′-tetrahydroxy-tetraphenylethylene for membrane-based gas separation

    KAUST Repository

    Ma, Xiaohua

    2015-12-09

    A novel intrinsically microporous polymer was synthesized by polycondensation reaction of 1,1′,2,2′,-tetrahydroxy-tetraphenylethylene (TPE) and 2,3,5,6-tetrafluoroterephthalonitrile (TFTPN). In addition, a series of copolymers was prepared from TPE, 5,5′,6,6′-tetrahydroxy-3,3,3′,3′-tetramethylspirobisindane (TTSBI) and TFTPN. All TPE-derived polymers exhibited high molecular weight, good solubility in common organic solvents, high thermal stability and high surface area (550 to 660 m2 g−1). The CO2 permeability of a methanol-treated and 120 °C vacuum-dried TPE-TFTPN film was 862 Barrer with a moderate CO2/N2 selectivity of 26. The selectivity of the TPE-TTSBI-PIMs decreased with increasing TTSBI content coupled with a sharp increase in permeability. Molecular simulations indicated that the introduction of the tetraphenylethylene unit resulted in an increased rotational freedom of dihedral angles in the polymer main chain relative to those of the spirobisindane-based PIM-1.

  2. Fast quantifying collision strength index of ethylene-vinyl acetate copolymer coverings on the fields based on near infrared hyperspectral imaging techniques

    Science.gov (United States)

    Chen, Y. M.; Lin, P.; He, Y.; He, J. Q.; Zhang, J.; Li, X. L.

    2016-02-01

    A novel strategy based on the near infrared hyperspectral imaging techniques and chemometrics were explored for fast quantifying the collision strength index of ethylene-vinyl acetate copolymer (EVAC) coverings on the fields. The reflectance spectral data of EVAC coverings was obtained by using the near infrared hyperspectral meter. The collision analysis equipment was employed to measure the collision intensity of EVAC materials. The preprocessing algorithms were firstly performed before the calibration. The algorithms of random frog and successive projection (SP) were applied to extracting the fingerprint wavebands. A correlation model between the significant spectral curves which reflected the cross-linking attributions of the inner organic molecules and the degree of collision strength was set up by taking advantage of the support vector machine regression (SVMR) approach. The SP-SVMR model attained the residual predictive deviation of 3.074, the square of percentage of correlation coefficient of 93.48% and 93.05% and the root mean square error of 1.963 and 2.091 for the calibration and validation sets, respectively, which exhibited the best forecast performance. The results indicated that the approaches of integrating the near infrared hyperspectral imaging techniques with the chemometrics could be utilized to rapidly determine the degree of collision strength of EVAC.

  3. Amphiphilic Cellulose Ethers Designed for Amorphous Solid Dispersion via Olefin Cross-Metathesis.

    Science.gov (United States)

    Dong, Yifan; Mosquera-Giraldo, Laura I; Taylor, Lynne S; Edgar, Kevin J

    2016-02-01

    The design of cellulose ether-based amphiphiles has been difficult and limited because of the harsh conditions typically required for appending ether moieties to cellulose. Olefin cross-metathesis recently has been shown to be a valuable approach for appending a variety of functional groups to cellulose ethers and esters, provided that an olefin handle for metathesis can be attached. This synthetic pathway gives access to these functional derivatives under very mild conditions and at high efficiency. Modification of ethyl cellulose by metathesis to prepare useful derivatives, for example, for solubility and bioavailability enhancement of drugs by amorphous solid dispersion (ASD), has been limited by the low DS(OH) of commercial ethyl cellulose derivatives. This is problematic because ethyl cellulose is otherwise a very attractive substrate for synthesis of amphiphilic derivatives by olefin metathesis. Herein we explore two methods for opening up this design space for ether-based amphiphiles, for example, permitting synthesis of more hydrophilic derivatives. One approach is to start with the more hydrophilic commercial methyl cellulose, which contains much higher DS(OH) and therefore is better suited for introduction of high DS of olefin metathesis "handles". In another approach, we explored a homogeneous one-pot synthesis methodology from cellulose, where controlled DS of ethyl groups was introduced at the same time as the ω-unsaturated alkyl groups, thereby permitting complete control of DS(OH), DS(Et), and ultimately DS of the functional group added by metathesis. We describe the functionalized derivatives available by these successful approaches. In addition, we explore new methods for reduction of the unsaturation in initial metathesis products to provide robust methods for enhancing product stability against further radical-catalyzed reactions. We demonstrate initial evidence that the products show strong promise as amphiphilic matrix polymers for amorphous

  4. Selective Oxidation and Ammoxidation of Olefins by Heterogeneous Catalysis.

    Science.gov (United States)

    Grasselli, Robert K.

    1986-01-01

    Shows how the ammoxidation of olefins can be understood in terms of free radicals and surface bound organometallic intermediates. Also illustrates the close intellectual relationships between heterogeneous catalysis and organometallic chemistry. (JN)

  5. Cobalt catalyzed hydroesterification of a wide range of olefins

    Energy Technology Data Exchange (ETDEWEB)

    Van Rensburg, H.; Hanton, M.; Tooze, R.P.; Foster, D.F. [Sasol Technology UK, St Andrews (United Kingdom)

    2011-07-01

    Petrochemical raw materials are an essential raw material for the production of detergents with a substantial portion of synthetic fatty alcohols being produced via hydroformylation of oil or coal derived olefins. Carbonylation processes other than hydroformylation have to date not been commercially employed for the production of fatty esters or alcohols. In this document we highlight the opportunities of converting olefins to esters using cobalt catalyzed alkoxycarbonylation. This process is highly versatile and applicable to a wide range of olefins, linear or branched, alpha or internal in combination with virtually any chain length primary or secondary alcohol allowing the synthesis of a diverse array of compounds such as ester ethoxylated surfactants, methyl branched detergents, lubricants and alkyl propanoates. Furthermore, alkoxycarbonylation of a broad olefin/paraffin hydrocarbon range could be used to produce the corresponding broad cut detergent alcohols. (orig.)

  6. Rapid prototyping tools and methods for all-Topas (R) cyclic olefin copolymer fluidic microsystems

    DEFF Research Database (Denmark)

    Bundgaard, Frederik; Perozziello, Gerardo; Geschke, Oliver

    2006-01-01

    , good machinability, and good optical properties. A number of different processes for rapid and low-cost prototyping of all-Topas microfluidic systems, made with desktop machinery, are presented. Among the processes are micromilling of fluidic structures with a width down to 25 p,m and sealing...

  7. Prototyping of Microfluidic Systems with Integrated Waveguides in Cyclin Olefin Copolymer

    DEFF Research Database (Denmark)

    Bundgaard, Frederik

    2007-01-01

    for rapid prototyping of this polymer is now available. These tools include: • Micro milling of fluidic channels and optical waveguides with dimensions down to 25 μm. • Spin coating of polymer layers on polymer substrates with a thickness from 100 nm to 20 μm. The spin coat layers act as a glue for joining...... handling and measurement on a single chip, and both optical and electronical components can be embedded. For polymer microsystems, integration of optical waveguides can be achieved by structuring polymers with different refractive indices. This thesis treats aspects of prototyping and fabrication...... properties makes it suited for integrated optics in microfluidic systems. Also, the engineerable glass transition temperature is an advantage, when making single-polymer systems. During the project existing fabrication methods have been adapted or improved for use with Topas, so that a number of tools...

  8. Enantioselective olefin metathesis with cyclometalated ruthenium complexes.

    Science.gov (United States)

    Hartung, John; Dornan, Peter K; Grubbs, Robert H

    2014-09-17

    The success of enantioselective olefin metathesis relies on the design of enantioenriched alkylidene complexes capable of transferring stereochemical information from the catalyst structure to the reactants. Cyclometalation of the NHC ligand has proven to be a successful strategy to incorporate stereogenic atoms into the catalyst structure. Enantioenriched complexes incorporating this design element catalyze highly Z- and enantioselective asymmetric ring opening/cross metathesis (AROCM) of norbornenes and cyclobutenes, and the difference in ring strain between these two substrates leads to different propagating species in the catalytic cycle. Asymmetric ring closing metathesis (ARCM) of a challenging class of prochiral trienes has also been achieved. The extent of reversibility and effect of reaction setup was also explored. Finally, promising levels of enantioselectivity in an unprecedented Z-selective asymmetric cross metathesis (ACM) of a prochiral 1,4-diene was demonstrated.

  9. Theoretical investigations of olefin metathesis catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Cundari, T.R.; Gordon, M.S. [North Dakota State Univ., Fargo, ND (United States)

    1992-01-01

    An ab initio analysis of the electronic structure of high-valent, transition-metal alkylidenes as models for olefin metathesis catalysts is presented. The catalyst models studied fall into three categories: {open_quotes}new{close_quotes} metathesis catalyst models-tetrahedral M(OH){sup 2}(XH)(CH{sub 2}) complexes; {open_quotes}old{close_quotes} metathesis catalyst models-tetrahedral MCl{sub 2}(Y)(CH{sub 2}) complexes and alkylidene-substituted Mo metathesis catalysts, Mo(OH){sub 2}(NH)(=C(H)Z). The effect on the bonding caused by modification of either the metal, ligands, or alkylidene substitutents is considered. 21 refs., 2 figs., 5 tabs.

  10. Enantioselective Olefin Metathesis with Cyclometalated Ruthenium Complexes

    Science.gov (United States)

    2015-01-01

    The success of enantioselective olefin metathesis relies on the design of enantioenriched alkylidene complexes capable of transferring stereochemical information from the catalyst structure to the reactants. Cyclometalation of the NHC ligand has proven to be a successful strategy to incorporate stereogenic atoms into the catalyst structure. Enantioenriched complexes incorporating this design element catalyze highly Z- and enantioselective asymmetric ring opening/cross metathesis (AROCM) of norbornenes and cyclobutenes, and the difference in ring strain between these two substrates leads to different propagating species in the catalytic cycle. Asymmetric ring closing metathesis (ARCM) of a challenging class of prochiral trienes has also been achieved. The extent of reversibility and effect of reaction setup was also explored. Finally, promising levels of enantioselectivity in an unprecedented Z-selective asymmetric cross metathesis (ACM) of a prochiral 1,4-diene was demonstrated. PMID:25137310

  11. Olefins and chemical regulation in Europe: REACH.

    Science.gov (United States)

    Penman, Mike; Banton, Marcy; Erler, Steffen; Moore, Nigel; Semmler, Klaus

    2015-11-05

    REACH (Registration, Evaluation, Authorisation and Restriction of Chemicals) is the European Union's chemical regulation for the management of risk to human health and the environment (European Chemicals Agency, 2006). This regulation entered into force in June 2007 and required manufacturers and importers to register substances produced in annual quantities of 1000 tonnes or more by December 2010, with further deadlines for lower tonnages in 2013 and 2018. Depending on the type of registration, required information included the substance's identification, the hazards of the substance, the potential exposure arising from the manufacture or import, the identified uses of the substance, and the operational conditions and risk management measures applied or recommended to downstream users. Among the content developed to support this information were Derived No-Effect Levels or Derived Minimal Effect Levels (DNELs/DMELs) for human health hazard assessment, Predicted No Effect Concentrations (PNECs) for environmental hazard assessment, and exposure scenarios for exposure and risk assessment. Once registered, substances may undergo evaluation by the European Chemicals Agency (ECHA) or Member State authorities and be subject to requests for additional information or testing as well as additional risk reduction measures. To manage the REACH registration and related activities for the European olefins and aromatics industry, the Lower Olefins and Aromatics REACH Consortium was formed in 2008 with administrative and technical support provided by Penman Consulting. A total of 135 substances are managed by this group including 26 individual chemical registrations (e.g. benzene, 1,3-butadiene) and 13 categories consisting of 5-26 substances. This presentation will describe the content of selected registrations prepared for 2010 in addition to the significant post-2010 activities. Beyond REACH, content of the registrations may also be relevant to other European activities, for

  12. Analysis of olefinic hydrocarbons in cracked petroleum stocks: a review

    Energy Technology Data Exchange (ETDEWEB)

    Badoni, R.P.; Bhagat, S.D.; Joshi, G.C. (Indian Institute of Petroleum, Dehradun (India))

    1992-05-01

    The present review surveys the existing methods of analysis, both chemical and instrumental techniques applicable for the determination of olefinic unsaturation in petroleum products ranging from gases to high molecular weight complex residues. The scope and limitation of each method in relation to its applicability to specific petroleum products is critically discussed. Standardized methods of olefin analysis covered by ASTM, IP and UOP test procedures have also been compiled. 123 refs., 1 tab.

  13. Carbonyl-Olefin Exchange Reaction and Related Chemistry

    Science.gov (United States)

    Jossifov, Christo; Kalinova, Radostina

    A new carbon—carbon double bond forming reaction (carbonyl olefin exchange reaction) mediated by transition metal catalytic systems has been discovered. The catalytic systems used (transition metal halides or oxohalides alone or in combination with Lewis acids) are active only in the case when the two reacting groups are in one molecules and are conjugated. In addition these systems accelerate other reactions which run simultaneously with the carbonyl olefin metathesis rendering a detailed investigation of the process very complicated.

  14. Methods for suppressing isomerization of olefin metathesis products

    Energy Technology Data Exchange (ETDEWEB)

    Firth, Bruce E.; Kirk, Sharon E.

    2015-10-27

    A method for suppressing isomerization of an olefin metathesis product produced in a metathesis reaction includes adding an isomerization suppression agent that includes nitric acid to a mixture that includes the olefin metathesis product and residual metathesis catalyst from the metathesis reaction under conditions that are sufficient to passivate at least a portion of the residual metathesis catalyst. Methods of refining a natural oil are described.

  15. Methods for suppressing isomerization of olefin metathesis products

    Energy Technology Data Exchange (ETDEWEB)

    Firth, Bruce E.; Kirk, Sharon E.; Gavaskar, Vasudeo S.

    2015-09-22

    A method for suppressing isomerization of an olefin metathesis product produced in a metathesis reaction includes adding an isomerization suppression agent to a mixture that includes the olefin metathesis product and residual metathesis catalyst from the metathesis reaction under conditions that are sufficient to passivate at least a portion of the residual metathesis catalyst. The isomerization suppression agent is phosphorous acid, a phosphorous acid ester, phosphinic acid, a phosphinic acid ester or combinations thereof. Methods of refining natural oils are described.

  16. Zwitterionic Group VIII transition metal initiators supported by olefin ligands

    Science.gov (United States)

    Bazan, Guillermo C.; Chen, Yaofeng

    2011-10-25

    A zwitterionic Group VIII transition metal complex containing the simple and relatively small 3-(arylimino)-but-1-en-2-olato ligand that catalyzes the formation of polypropylene and high molecular weight polyethylene. A novel feature of this catalyst is that the active species is stabilized by a chelated olefin adduct. The present invention also provides methods of polymerizing olefin monomers using zwitterionic catalysts, particularly polypropylene and high molecular weight polyethylene.

  17. Coordinatively unsaturated metal organic frameworks for olefin separations

    OpenAIRE

    Renouf, Catherine Louise

    2013-01-01

    The research presented in this thesis aims to assess the capacity of metal organic frameworks with open metal sites for the separation of olefin mixtures. Chapter 1 provides a background to the field, including industrial separation techniques, metal organic frameworks and their applications and the current state-of-the- art for olefin separation. Chapter 3 describes the experimental techniques used in this research. Ethylene and propylene adsorption and desorption isotherms...

  18. Iron(III)-catalysed carbonyl-olefin metathesis.

    Science.gov (United States)

    Ludwig, Jacob R; Zimmerman, Paul M; Gianino, Joseph B; Schindler, Corinna S

    2016-04-27

    The olefin metathesis reaction of two unsaturated substrates is one of the most powerful carbon-carbon-bond-forming reactions in organic chemistry. Specifically, the catalytic olefin metathesis reaction has led to profound developments in the synthesis of molecules relevant to the petroleum, materials, agricultural and pharmaceutical industries. These reactions are characterized by their use of discrete metal alkylidene catalysts that operate via a well-established mechanism. While the corresponding carbonyl-olefin metathesis reaction can also be used to construct carbon-carbon bonds, currently available methods are scarce and severely hampered by either harsh reaction conditions or the required use of stoichiometric transition metals as reagents. To date, no general protocol for catalytic carbonyl-olefin metathesis has been reported. Here we demonstrate a catalytic carbonyl-olefin ring-closing metathesis reaction that uses iron, an Earth-abundant and environmentally benign transition metal, as a catalyst. This transformation accommodates a variety of substrates and is distinguished by its operational simplicity, mild reaction conditions, high functional-group tolerance, and amenability to gram-scale synthesis. We anticipate that these characteristics, coupled with the efficiency of this reaction, will allow for further advances in areas that have historically been enhanced by olefin metathesis.

  19. Iron(III)-catalysed carbonyl-olefin metathesis

    Science.gov (United States)

    Ludwig, Jacob R.; Zimmerman, Paul M.; Gianino, Joseph B.; Schindler, Corinna S.

    2016-05-01

    The olefin metathesis reaction of two unsaturated substrates is one of the most powerful carbon-carbon-bond-forming reactions in organic chemistry. Specifically, the catalytic olefin metathesis reaction has led to profound developments in the synthesis of molecules relevant to the petroleum, materials, agricultural and pharmaceutical industries. These reactions are characterized by their use of discrete metal alkylidene catalysts that operate via a well-established mechanism. While the corresponding carbonyl-olefin metathesis reaction can also be used to construct carbon-carbon bonds, currently available methods are scarce and severely hampered by either harsh reaction conditions or the required use of stoichiometric transition metals as reagents. To date, no general protocol for catalytic carbonyl-olefin metathesis has been reported. Here we demonstrate a catalytic carbonyl-olefin ring-closing metathesis reaction that uses iron, an Earth-abundant and environmentally benign transition metal, as a catalyst. This transformation accommodates a variety of substrates and is distinguished by its operational simplicity, mild reaction conditions, high functional-group tolerance, and amenability to gram-scale synthesis. We anticipate that these characteristics, coupled with the efficiency of this reaction, will allow for further advances in areas that have historically been enhanced by olefin metathesis.

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

    Science.gov (United States)

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

    2015-01-01

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

  1. Preparation of dual-sensitive graft copolymer hydrogel based on N-maleoyl-chitosan and poly(N-isopropylacrylamide) by electron beam radiation

    Indian Academy of Sciences (India)

    Jinchen Fan; Jie Chen; Liming Yang; Han Lin; Fangqi Cao

    2009-10-01

    Organic solvent-soluble N-maleoyl-chitosan (NMCS) was synthesized by reaction of chitosan with maleic anhydride (MAH) in N,N-dimethylformamide (DMF). N-maleoyl-chitosan-graft-poly(N-isopropylacrylamide) (NMCS-g-PNIPAAm) copolymer hydrogel was prepared via free radical polymerization by electron beam (EB) irradiation. The copolymer obtained was analysed by FT–IR, XRD and thermal gravimetric analysis (TGA). It was found that the grafting yield and grafting efficiency increased with increasing radiation absorbed dose and monomer amount, and then decreased. The swelling ratio of the copolymer hydrogel was low at pH 4–5, and LCST of the hydrogel was around 32°C.

  2. Polyether/Polyester Graft Copolymers

    Science.gov (United States)

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

    1986-01-01

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

  3. Thermal analytical study of polyamide copolymer/Surlyn Ionomers Blends

    Energy Technology Data Exchange (ETDEWEB)

    Qin, C.; Ding, Y.P. [Baxter Healthcare Corp., Round Lake, IL (United States)

    1993-12-31

    Thermal analytical technique was used as a screening method to study polyamide(Nylon)/ethylene-co-methacrylic acid copolymer-based ionomer(Surlyn)blends. The retardation of crystallization process from molten state of Nylon-12 by the existence of the ionomer was observed, but the crystallization of Nylon-12 can not be thwarted even at high concentration of ionomers. Zinc ionomers shows stronger effect than sodium ionomers. A Nylon copolymer, polyamide-6,6-co-polyamide-6,10, was used to blend with different ionomers and the crystallization process from molten state of Nylon copolymer could be thwarted at high concentration of zinc ionomer even at very cooling rate. Interesting cold crystallization behavior of polyamide copolymer was observed during second DSC heating cycle in the temperature range of the melting process of ionomer.

  4. Thermal Stability of Poly (acrylonitrile-methyl acrylate) Copolymers

    Institute of Scientific and Technical Information of China (English)

    HAN Na; ZHANG Xing-xiang; WANG Xue-chen

    2008-01-01

    Poly (acrylonitrile-methyl acrylate) copolymer was synthesized by water depositing polymerization and has a typical feed ratio of 85/15. And then 1 - 3 wt% lauryl alcohol maleic anhydride (LAM) was adopted as stabilizer to mix with the acrylonitrile based copolymer. The mixtures were characterized by using Fourier Transform Infrared Spectroscopy (FTIR), Nuclear Magnetic Resonance (1H NMR ), Gel Permeation Chromatography ( GPC ), Differential Scanning Calorimetry (DSC), optic microscope and Ubbelohde viscosimetryr etc. The melting point (Tm) and glass transition temperature (Tg) of the 85/15 AN/MA copolymer mixed with LAM all decrease with the increase of stabilizer content. The lowest Tg and Tm were 116.1 ℃ and 209. 1℃ respectively at the heating rate of 100℃/min when the content of LAM is 2 wt%. The 85°/15 AN/MA copolymer mixed with 1 - 3 w t% LAM possess good thermal stability up to 30 min at 220 ℃.

  5. "Click" and Olefin Metathesis Chemistry in Water at Room Temperature Enabled by Biodegradable Micelles.

    Science.gov (United States)

    Lipshutz, Bruce H; Bošković, Zarko; Crowe, Christopher S; Davis, Victoria K; Whittemore, Hannah C; Vosburg, David A; Wenzel, Anna G

    2013-11-12

    The two laboratory reactions focus on teaching several concepts associated with green chemistry. Each uses a commercial, nontoxic, and biodegradable surfactant, TPGS-750-M, to promote organic reactions within the lipophilic cores of nanoscale micelles in water. These experiments are based on work by K. Barry Sharpless (an azide-alkyne "click" reaction) and Robert Grubbs (an olefin cross-metathesis reaction); both are suitable for an undergraduate organic laboratory. The copper-catalyzed azide-alkyne [3+2] cycloaddition of benzyl azide and 4-tolylacetylene is very rapid: the triazole product is readily isolated by filtration and is characterized by thin-layer chromatography and melting point analysis. The ruthenium-catalyzed olefin cross-metathesis reaction of benzyl acrylate with 1-hexene is readily monitored by thin-layer chromatography and gas chromatography. The metathesis experiment comparatively evaluates the efficacy of a TPGS-750-M/water medium relative to a traditional reaction performed in dichloromethane (a common solvent used for olefin metathesis).

  6. “Click” and Olefin Metathesis Chemistry in Water at Room Temperature Enabled by Biodegradable Micelles

    Science.gov (United States)

    Lipshutz, Bruce H.; Bošković, Zarko; Crowe, Christopher S.; Davis, Victoria K.; Whittemore, Hannah C.; Vosburg, David A.; Wenzel, Anna G.

    2013-01-01

    The two laboratory reactions focus on teaching several concepts associated with green chemistry. Each uses a commercial, nontoxic, and biodegradable surfactant, TPGS-750-M, to promote organic reactions within the lipophilic cores of nanoscale micelles in water. These experiments are based on work by K. Barry Sharpless (an azide–alkyne “click” reaction) and Robert Grubbs (an olefin cross-metathesis reaction); both are suitable for an undergraduate organic laboratory. The copper-catalyzed azide–alkyne [3+2] cycloaddition of benzyl azide and 4-tolylacetylene is very rapid: the triazole product is readily isolated by filtration and is characterized by thin-layer chromatography and melting point analysis. The ruthenium-catalyzed olefin cross-metathesis reaction of benzyl acrylate with 1-hexene is readily monitored by thin-layer chromatography and gas chromatography. The metathesis experiment comparatively evaluates the efficacy of a TPGS-750-M/water medium relative to a traditional reaction performed in dichloromethane (a common solvent used for olefin metathesis). PMID:24324282

  7. Wood-derived olefins by steam cracking of hydrodeoxygenated tall oils.

    Science.gov (United States)

    Pyl, Steven P; Dijkmans, Thomas; Antonykutty, Jinto M; Reyniers, Marie-Françoise; Harlin, Ali; Van Geem, Kevin M; Marin, Guy B

    2012-12-01

    Tall oil fractions obtained from Norwegian spruce pulping were hydrodeoxygenated (HDO) at pilot scale using a commercial NiMo hydrotreating catalyst. Comprehensive two dimensional gas chromatography (GC×GC) showed that HDO of both tall oil fatty acids (TOFA) and distilled tall oil (DTO) produced highly paraffinic hydrocarbon liquids. The hydrotreated fractions also contained fatty acid methyl esters and norabietane and norabietatriene isomers. Steam cracking of HDO-TOFA in a pilot plant revealed that high light olefin yields can be obtained, with 35.4 wt.% of ethene and 18.2 wt.% of propene at a coil outlet pressure (COP) of 1.7 bara, a dilution of 0.45 kg(steam)/kg(HDO-TOFA) and a coil outlet temperature (COT) of 820 °C. A pilot plant coking experiment indicated that cracking of HDO-TOFA at a COT of 850 °C results in limited fouling in the reactor. Co-cracking of HDO tall oil fractions with a typical fossil-based naphtha showed improved selectivity to desired light olefins, further demonstrating the potential of large scale olefin production from hydrotreated tall oil fractions in conventional crackers.

  8. Electron transfer-induced four-membered cyclic intermediate formation: Olefin cross-coupling vs. olefin cross-metathesis

    Energy Technology Data Exchange (ETDEWEB)

    Okada, Yohei [Department of Applied Life Science, Tokyo University of Agriculture and Technology, 3-5-8 Saiwai-cho, Fuchu, Tokyo 183-8509 (Japan); Chiba, Kazuhiro, E-mail: chiba@cc.tuat.ac.j [Department of Applied Life Science, Tokyo University of Agriculture and Technology, 3-5-8 Saiwai-cho, Fuchu, Tokyo 183-8509 (Japan)

    2011-01-01

    An electron transfer-induced four-membered cyclic intermediate, formed between a radical cation of an enol ether and an unactivated olefin, played a key role in the pathway toward either cross-coupling or cross-metathesis. The presence of an alkoxy group on the phenyl ring of the olefin entirely determined the synthetic outcome of the reaction, which mirrored the efficiency of the intramolecular electron transfer.

  9. Evaluation of a new biocompatible poly(N-(morpholino ethyl methacrylate)-based copolymer for the delivery of ruthenium oligonucleotides, targeting HPV16 E6 oncogene.

    Science.gov (United States)

    Reschner, Anca; Shim, Yong Ho; Dubois, Philippe; Delvenne, Philippe; Evrard, Brigitte; Marcélis, Lionel; Moucheron, Cécile; Kirsch-De Mesmaeker, Andrée; Defrancq, Eric; Raes, Martine; Piette, Jacques; Collard, Laurence; Piel, Géraldine

    2013-08-01

    This study investigates the use of a new biocompatible block copolymer poly(2-(dimethylamino)ethyl methacrylate-N-(morpholino)ethyl methacrylate (PDMAEMA-b-PMEMA) for the delivery of a particular antisense oligonucleotide targeting E6 gene from human papilloma virus. This antisense oligonucleotide was derivatized with a polyazaaromatic Ru(II) complex which, under visible illumination, is able to produce an irreversible crosslink with the complementary targeted sequence. The purpose of this study is to determine whether by the use of a suitable transfection agent, it is possible to increase the efficiency of the antisense oligonucleotide targeting E6 gene, named Ru-P-4. In a recent study, we showed that Oligofectamine transfected Ru-P-4 antisense oligonucleotide failed to inhibit efficiently the growth of cervical cancer cell line SiHa, contrarily to the Ru-P-6 antisense oligonucleotide, another sequence also targeting the E6 gene. The ability of PDMAEMA-b-PMEMA to form polyplexes with optimal physicochemical characteristics was investigated first. Then the ability of the PDMAEMA-b-PMEMA/Ru-P-4 antisense oligonucleotide polyplexes to transfect two keratinocyte cell lines (SiHa and HaCat) and the capacity of polyplexes to inhibit HPV16+ cervical cancer cell growth was evaluated. PDMAEMA-b-PMEMA base polyplexes at the optimal molar ratio of polymer nitrogen atoms to DNA phosphates (N/P), were able to deliver Ru-P-4 antisense oligonucleotide and to induce a higher growth inhibition in human cervical cancer SiHa cells, compared to other formulations based on Oligofectamine.

  10. Multi-input and -output logic circuits based on bioelectrocatalysis with horseradish peroxidase and glucose oxidase immobilized in multi-responsive copolymer films on electrodes.

    Science.gov (United States)

    Yu, Xue; Lian, Wenjing; Zhang, Jiannan; Liu, Hongyun

    2016-06-15

    Herein, poly(N-isopropylacrylamide-co-N,N'-dimethylaminoethylmethacrylate) copolymer films were polymerized on electrode surface with a simple one-step method, and the enzyme horseradish peroxidase (HRP) was embedded in the films simultaneously, which were designated as P(NiPAAm-co-DMEM)-HRP. The films exhibited a reversible structure change with the external stimuli, such as pH, CO2, temperature and SO4(2-), causing the cyclic voltammetric (CV) response of electroactive K3Fe(CN)6 at the film electrodes to display the corresponding multi-stimuli sensitive ON-OFF behavior. Based on the switchable CV property of the system and the electrochemical reduction of H2O2 catalyzed by HRP in the films and mediated by Fe(CN)6(3-) in solution, a 5-input/3-output logic gate was established. To further increase the complexity of the logic system, another enzyme glucose oxidase (GOD) was added into the films, designated as P(NiPAAm-co-DMEM)-HRP-GOD. In the presence of oxygen, the oxidation of glucose in the solution was catalyzed by GOD in the films, and the produced H2O2 in situ was recognized and electrocatalytically reduced by HRP and mediated by Fe(CN)6(3-). Based on the bienzyme films, a cascaded or concatenated 4-input/3-output logic gate system was proposed. The present work combined the multi-responsive interface with bioelectrocatalysis to construct cascaded logic circuits, which might open a new avenue to develop biocomputing elements with more sophisticated functions and design novel glucose biosensors.

  11. In situ gelling stimuli-sensitive block copolymer hydrogels for drug delivery.

    Science.gov (United States)

    He, Chaoliang; Kim, Sung Wan; Lee, Doo Sung

    2008-05-08

    Stimuli-sensitive block copolymer hydrogels, which are reversible polymer networks formed by physical interactions and exhibit a sol-gel phase-transition in response to external stimuli, have great potential in biomedical and pharmaceutical applications, especially in site-specific controlled drug-delivery systems. The drug may be mixed with a polymer solution in vitro and the drug-loaded hydrogel can form in situ after the in vivo administration, such as injection; therefore, stimuli-sensitive block copolymer hydrogels have many advantages, such as simple drug formulation and administration procedures, no organic solvent, site-specificity, a sustained drug release behavior, less systemic toxicity and ability to deliver both hydrophilic and hydrophobic drugs. Among the stimuli in the biomedical applications, temperature and pH are the most popular physical and chemical stimuli, respectively. The temperature- and/or pH-sensitive block copolymer hydrogels for biomedical applications have been extensively developed in the past decade. This review focuses on recent development of the preparation and application for drug delivery of the block copolymer hydrogels that respond to temperature, pH or both stimuli, including poly(N-substituted acrylamide)-based block copolymers, poloxamers and their derivatives, poly(ethylene glycol)-polyester block copolymers, polyelectrolyte-based block copolymers and the polyelectrolyte-modified thermo-sensitive block copolymers. In addition, the hydrogels based on other stimuli-sensitive block copolymers are discussed.

  12. Synthesis and Characterization of a Systematic Series of All-Conjugated Diblock Copolymers

    Science.gov (United States)

    Smith, Kendall; Verduzco, Rafael

    2012-02-01

    All-conjugated block copolymers can potentially self-assemble into nanoscale structures beneficial for charge separation and transport, but due to synthetic challenges a comprehensive investigation of all-conjugated block copolymers has not been carried out . Here we detail a novel synthetic approach to all-conjugated block copolymers and characterize the structure of a systematic series of materials. The materials are prepared via copper-catalyzed azide-alkyne click chemistry followed by selective solvent removal of homopolymer impurities. This allows us to readily vary the molecular weight and type of each block in order to systematically study the properties of a family of block copolymers. As a system relevant to organic photovoltatics, we investigate a series of diblock copolymers based on poly(9,9-dioctyl-fluorene) and poly(3-alkylthiophene). This series of block copolymers is characterized with respect to phase behavior, including micro-phase segregation and crystallinity, optical properties, and charge mobilities.

  13. Nanoparticle carriers based on copolymers of poly( l-aspartic acid co- l-lactide)-1,2-dipalmitoyl-sn-glycero-3-phosphoethanolamine for drug delivery

    Science.gov (United States)

    Han, Siyuan; Wang, Huan; Liang, Xingjie; Hu, Liming; Li, Min; Wu, Yan

    2011-09-01

    A novel poly( l-aspartic) derivative (PAL-DPPE) containing polylactide and 1,2-dipalmitoyl-sn-glycero-3-phosphoethanolamine (DPPE) segments has been successfully synthesized. The chemical structures of the copolymers were confirmed by Fourier-transform infrared spectroscopy (FTIR), NMR (1H NMR, 13C NMR, 31P NMR), and thermogravimetric analysis (TGA). Fluorescence spectroscopy, dynamic light scattering (DLS), and transmission electron microscopy (TEM) confirmed the formation of micelles of the PAL-DPPE copolymers. In order to estimate the feasibility as novel drug carriers, an anti-tumor model drug doxorubicin (DOX) was incorporated into polymeric micelles by double emulsion and nanoprecipitation method. The DOX-loaded micelle size, size distribution, and encapsulation efficiency (EE) were influenced by the feed weight ratio of the copolymer to DOX. In addition, in vitro release experiments of the DOX-loaded PAL-DPPE micelles exhibited that faster release in pH 5.0 than their release in pH 7.4 buffer. The poly( l-aspartic) derivative copolymer was proved to be an available carrier for the preparation of micelles for anti-tumor drug delivery.

  14. Amphiphilic star block copolymers as gene carrier Part I: Synthesis via ATRP using calix[4]resorcinarene-based initiators and characterization

    Energy Technology Data Exchange (ETDEWEB)

    Zheng, Anna; Xue, Yan; Wei, Dafu [Shanghai Key Laboratory of Advanced Polymeric Materials, Key Laboratory for Ultrafine Materials of Ministry of Education, School of Materials Science and Engineering, East China University of Science and Technology, Shanghai 200237 (China); Guan, Yong, E-mail: yguan@ecust.edu.cn [Shanghai Key Laboratory of Advanced Polymeric Materials, Key Laboratory for Ultrafine Materials of Ministry of Education, School of Materials Science and Engineering, East China University of Science and Technology, Shanghai 200237 (China); Xiao, Huining [Department of Chemical Engineering, University of New Brunswick, Fredericton, New Brunswick, Canada E3B 5A3 (Canada)

    2013-01-01

    In this work, a cationic star polymer [poly(2-dimethylamino)ethyl methacrylate (PDMAEMA)] was prepared via atom transfer radical polymerization (ATRP), using brominated calix[4]resorcinarene as an initiator. Hydrophobic moieties, methyl methacrylate (MMA) and butyl acrylate (BA), were further incorporated via 'one-pot' method. Well-defined eight-armed star block copolymers bearing hydrophilic blocks inside and hydrophobic blocks outside were synthesized. The molecular weight, particle size, electrophoretic mobility and apparent charge density were determined by gel permeation chromatography (GPC), dynamic light scattering (DLS), phase analysis light scattering (PALS) and colloidal titration, respectively. The zeta potentials and apparent charge densities of the products exhibited the characteristics of polyelectrolyte. The incorporation of hydrophobic moieties generated electrostatic screening effect. The as-synthesized amphiphilic star copolymer is promising as a thermo-sensitive gene carrier for gene therapy. Highlights: Black-Right-Pointing-Pointer Amphiphilic cationic star block copolymers with well-controlled structures were prepared via ATRP. Black-Right-Pointing-Pointer The molecular structures and properties of the initiator and copolymers were systematically characterized. Black-Right-Pointing-Pointer The products exhibited the positive charged character, and hydrophobic moieties generated electrostatic screening effect.

  15. Nanoparticle carriers based on copolymers of poly(l-aspartic acid co-l-lactide)-1,2-dipalmitoyl-sn-glycero-3-phosphoethanolamine for drug delivery

    Energy Technology Data Exchange (ETDEWEB)

    Han Siyuan; Wang Huan; Liang Xingjie [National Center for Nanoscience and Technology, Laboratory of Nanobiomedicine and Nanosafety, Division of Nanomedicine and Nanobiology (China); Hu Liming, E-mail: huliming@bjut.edu.cn [Beijing University of Technology, College of Life Science and Bioengineering (China); Li Min; Wu Yan, E-mail: wuy@nanoctr.cn [National Center for Nanoscience and Technology, Laboratory of Nanobiomedicine and Nanosafety, Division of Nanomedicine and Nanobiology (China)

    2011-09-15

    A novel poly(l-aspartic) derivative (PAL-DPPE) containing polylactide and 1,2-dipalmitoyl-sn-glycero-3-phosphoethanolamine (DPPE) segments has been successfully synthesized. The chemical structures of the copolymers were confirmed by Fourier-transform infrared spectroscopy (FTIR), NMR ({sup 1}H NMR, {sup 13}C NMR, {sup 31}P NMR), and thermogravimetric analysis (TGA). Fluorescence spectroscopy, dynamic light scattering (DLS), and transmission electron microscopy (TEM) confirmed the formation of micelles of the PAL-DPPE copolymers. In order to estimate the feasibility as novel drug carriers, an anti-tumor model drug doxorubicin (DOX) was incorporated into polymeric micelles by double emulsion and nanoprecipitation method. The DOX-loaded micelle size, size distribution, and encapsulation efficiency (EE) were influenced by the feed weight ratio of the copolymer to DOX. In addition, in vitro release experiments of the DOX-loaded PAL-DPPE micelles exhibited that faster release in pH 5.0 than their release in pH 7.4 buffer. The poly(l-aspartic) derivative copolymer was proved to be an available carrier for the preparation of micelles for anti-tumor drug delivery.

  16. Injectable biodegradable hybrid hydrogels based on thiolated collagen and oligo(acryloyl carbonate)-poly(ethylene glycol)-oligo(acryloyl carbonate) copolymer for functional cardiac regeneration.

    Science.gov (United States)

    Xu, Guohui; Wang, Xiaolin; Deng, Chao; Teng, Xiaomei; Suuronen, Erik J; Shen, Zhenya; Zhong, Zhiyuan

    2015-03-01

    Injectable biodegradable hybrid hydrogels were designed and developed based on thiolated collagen (Col-SH) and multiple acrylate containing oligo(acryloyl carbonate)-b-poly(ethylene glycol)-b-oligo(acryloyl carbonate) (OAC-PEG-OAC) copolymers for functional cardiac regeneration. Hydrogels were readily formed under physiological conditions (37°C and pH 7.4) from Col-SH and OAC-PEG-OAC via a Michael-type addition reaction, with gelation times ranging from 0.4 to 8.1 min and storage moduli from 11.4 to 55.6 kPa, depending on the polymer concentrations, solution pH and degrees of substitution of Col-SH. The collagen component in the hybrid hydrogels retained its enzymatic degradability against collagenase, and the degradation time of the hydrogels increased with increasing polymer concentration. In vitro studies showed that bone marrow mesenchymal stem cells (BMSCs) exhibited rapid cell spreading and extensive cellular network formation on these hybrid hydrogels. In a rat infarction model, the infarcted left ventricle was injected with PBS, hybrid hydrogels, BMSCs or BMSC-encapsulating hybrid hydrogels. Echocardiography demonstrated that the hybrid hydrogels and BMSC-encapsulating hydrogels could increase the ejection fraction at 28 days compared to the PBS control group, resulting in improved cardiac function. Histology revealed that the injected hybrid hydrogels significantly reduced the infarct size and increased the wall thickness, and these were further improved with the BMSC-encapsulating hybrid hydrogel treatment, probably related to the enhanced engraftment and persistence of the BMSCs when delivered within the hybrid hydrogel. Thus, these injectable hybrid hydrogels combining intrinsic bioactivity of collagen, controlled mechanical properties and enhanced stability provide a versatile platform for functional cardiac regeneration.

  17. High-Yield Process for Selectively Converting CO2 to Aromatics and Olefins Project

    Data.gov (United States)

    National Aeronautics and Space Administration — This proposed Phase I addresses the selective conversion of CO2 to hydrocarbons via integrated CO2-to-methanol, methanol-to-olefins, and olefins-to-aromatics...

  18. 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.

  19. Performance impact of dynamic surface coatings on polymeric insulator-based dielectrophoretic particle separators.

    Science.gov (United States)

    Davalos, Rafael V; McGraw, Gregory J; Wallow, Thomas I; Morales, Alfredo M; Krafcik, Karen L; Fintschenko, Yolanda; Cummings, Eric B; Simmons, Blake A

    2008-02-01

    Efficient and robust particle separation and enrichment techniques are critical for a diverse range of lab-on-a-chip analytical devices including pathogen detection, sample preparation, high-throughput particle sorting, and biomedical diagnostics. Previously, using insulator-based dielectrophoresis (iDEP) in microfluidic glass devices, we demonstrated simultaneous particle separation and concentration of various biological organisms, polymer microbeads, and viruses. As an alternative to glass, we evaluate the performance of similar iDEP structures produced in polymer-based microfluidic devices. There are numerous processing and operational advantages that motivate our transition to polymers such as the availability of numerous innate chemical compositions for tailoring performance, mechanical robustness, economy of scale, and ease of thermoforming and mass manufacturing. The polymer chips we have evaluated are fabricated through an injection molding process of the commercially available cyclic olefin copolymer Zeonor 1060R. This publication is the first to demonstrate insulator-based dielectrophoretic biological particle differentiation in a polymeric device injection molded from a silicon master. The results demonstrate that the polymer devices achieve the same performance metrics as glass devices. We also demonstrate an effective means of enhancing performance of these microsystems in terms of system power demand through the use of a dynamic surface coating. We demonstrate that the commercially available nonionic block copolymer surfactant, Pluronic F127, has a strong interaction with the cyclic olefin copolymer at very low concentrations, positively impacting performance by decreasing the electric field necessary to achieve particle trapping by an order of magnitude. The presence of this dynamic surface coating, therefore, lowers the power required to operate such devices and minimizes Joule heating. The results of this study demonstrate that iDEP polymeric

  20. CHARACTERISTICS OF STRUCTURE OF IMPACT COPOLYMERS OF POLYPROPYLENE WITH LOW ETHYLENE CONTENTS

    Institute of Scientific and Technical Information of China (English)

    MA Dezhu; LI Xiqiang; ZHANG Ruiyun; HONG Kunlun; LUO Xiaolie

    1994-01-01

    In the present work, the structure and impact properties of copolymers of polypropylene with low ethylene contents have been investigated. Based on the results of 13C-NMR, FTIR,WAXD, DSC, PLM and SEM, the relationship between impact properties and morphology of the copolymers has been discussed. The high impact properties of copolymer ICP2 may attribute to the relatively higher ethylene content and homogeneous ethylene unit distribution. The size and its distribution of spherulite in the copolymers and cycloid cavities dispersed in polypropylene continue phase may also be two important factors which affect the impact properties of these materials.

  1. Formation of Anisotropic Block Copolymer Gels

    Science.gov (United States)

    Liaw, Chya Yan; Shull, Kenneth; Henderson, Kevin; Joester, Derk

    2011-03-01

    Anisotropic, fibrillar gels are important in a variety of processes. Biomineralization is one example, where the mineralization process often occurs within a matrix of collagen or chitin fibers that trap the mineral precursors and direct the mineralization process. We wish to replicate this type of behavior within block copolymer gels. Particularly, we are interested in employing gels composed of cylindrical micelles, which are anisotropic and closely mimic biological fibers. Micelle geometry is controlled in our system by manipulating the ratio of molecular weights of the two blocks and by controlling the detailed thermal processing history of the copolymer solutions. Small-Angle X-ray Scattering and Dynamic Light Scattering are used to determine the temperature dependence of the gel formation process. Initial experiments are based on a thermally-reversible alcohol-soluble system, that can be subsequently converted to a water soluble system by hydrolysis of a poly(t-butyl methacrylate) block to a poly (methacrylic acid) block. MRSEC.

  2. Functional Nanoporous Polymers from Block Copolymer Precursors

    DEFF Research Database (Denmark)

    Guo, Fengxiao

    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...... functional nanoporous polymers based on nanoporous 1,2- polybuatdiene 1,2-PB, which is derived from a 1,2-PB-b-PDMS diblock copolymer precursor. As a result, nanoporous 1,2-PB with pores decorated of polyacrylates, sulfonated polymers and poly(ethylene glycol) are created. A method of vapor phase deposition...... has also been generated to obtain nanoporous polymers with functional coatings on pore walls. Vapor phase polymerization of pyrrole is performed to incorporate an ultra thin film of polypyrrole into nanoporous 1,2-PB. The preliminary test shows that nanoporous 1,2-PB gains conductivity. Generally...

  3. The intriguing modeling of cis–trans selectivity in ruthenium-catalyzed olefin metathesis

    Directory of Open Access Journals (Sweden)

    Luigi Cavallo

    2011-01-01

    Full Text Available In this study we have investigated computationally the origin of the cis–trans selectivity in the Ru-catalyzed cross metathesis (CM of a prototype monosubstituted olefin, i.e., propene. Our calculations suggest that the origin of the preferential formation of trans-olefins is in the product release step, which prevents the initially formed cis-olefin from escaping the metal, and returns it to the reaction pool until the trans-olefin is formed.

  4. The intriguing modeling of cis–trans selectivity in ruthenium-catalyzed olefin metathesis

    Science.gov (United States)

    Bahri-Laleh, Naeimeh; Credendino, Raffaele

    2011-01-01

    Summary In this study we have investigated computationally the origin of the cis–trans selectivity in the Ru-catalyzed cross metathesis (CM) of a prototype monosubstituted olefin, i.e., propene. Our calculations suggest that the origin of the preferential formation of trans-olefins is in the product release step, which prevents the initially formed cis-olefin from escaping the metal, and returns it to the reaction pool until the trans-olefin is formed. PMID:21286393

  5. High performance cyclo olefin polymer ZEONEX

    Science.gov (United States)

    Konishi, Yuichiro; Sawaguchi, Taichi; Kubomura, Kyoichi; Minami, Koji

    2005-09-01

    Zeon Corporation developed quite new optical plastic Cyclo Olefin Polymer; COP(ZEONEX) with own technology in 1990 then started sales for ZEONEX for optical application with its very unique properties such as low birefringence, low water absorption, high glass-transition temperature 136 °C and high light transmission etc. Currently, ZEONEX is well known in optical market and used widely as optical plastic for pick up lens and other many kinds of optical parts for laser beam printer and digital camera. Addition to those ZEONEX grades, in last year, Zeon Corporation developed a new ZEONEX grade called ZEONEX340R, which was designed for blue laser devices requiring more severe specification. ZEONEX340R has high transmission at 405nm which is used laser wavelength for Blu-ray Disk / HD-DVD as well as enough durability under exposure of 405nm laser, addition to those new properties, keeps other optical properties such as low birefringence and very low water absorption.

  6. A bis-calixarene from olefin metathesis

    Directory of Open Access Journals (Sweden)

    Shimelis T. Hailu

    2012-06-01

    Full Text Available A ring-closing olefin metathesis reaction of tetrakis(allyloxycalix[4]arene gave the bis calixarene, (15E,40E,60E-65,74-bis(prop-2-en-1-yloxy-13,18,38,43,58,63-hexaoxadodecacyclo[28.26.8.720,36.111,45.151,55.05,57.07,12.019,24.026,64.032,37.044,49.168,72]tetraheptaconta-1,3,5(57,7,9,11,15,19(24,20,22,26,28,30(64,32,34,36,40,44(49,45,47,51,53,55(65,60,68,70,72(74-heptacosaene, C74H68O8. It is a cage formed from two calix[4]arene units joined by butenyl groups at three of the O atoms on the narrow rim. The fourth O atom on each calixarene unit is joined with an allyl group. Each of the calix[4]arene units has a flattened cone conformation in which the allyloxy-substituted aryl group and the opposite aryl group are close together and almost parallel [dihedral angle between planes = 1.09 (11°], and the other two aryl groups are splayed outward [dihedral angle between planes = 79.53 (11°]. No guest molecule (e.g. solvent was observed within the cage. The alkene C atoms of one of the links between the calixarene moieties are disordered over two orientations with occupancies of 0.533 (9 and 0.467 (9.

  7. A well-defined rhenium(VII) olefin metathesis catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Toreki, R.; Schrock, R.R. (Massachusetts Institute of Technology, Cambridge (USA))

    1990-03-14

    Molybdenum tungsten, and rhenium are the three most active metals in classical olefin metathesis systems. Molybdenum (VI){sup 2} and tungsten(VI){sup 3} alkylidene complexes of the type M-(CHR{prime})(NAr)(OR){sub 2} (Ar = 2,6-C{sub 6}H{sub 3}-i-Pr{sub 2}) have been shown to be well-behaved olefin metathesis catalysts with an activity that can be controlled through the choice of OR. Although several rhenium alkylidene complexes have been reported, none has shown any confirmable metathesis activity, even toward strained cyclic olefins such as norbornene. Since Re{triple bond}CR{double prime} and M{double bond}NR{double prime} (M = Mo or W) can be regarded as isoelectronic units, plausible candidates as olefin metathesis catalysts are complexes of the type Re(CHR{prime})(CR{double prime})(OR){sub 2}. The authors report here that such a complex in which OR = OCMe(CF{sub 3}){sub 2} is a well-behaved olefin metathesis catalyst.

  8. Low severity coal liquefaction promoted by cyclic olefins

    Energy Technology Data Exchange (ETDEWEB)

    Curtis, C.W.

    1992-01-01

    Low severity coal liquefaction promoted by cyclic olefins offers a means of liquefying coal at low severity conditions. Lower temperature, 350[degrees]C, and lower hydrogen pressure, 500 psi, have been used to perform liquefaction reactions. The presence of the cyclic olefin, hexahydroanthracene, made a substantial difference in the conversion of Illinois No. 6 coal at these low severity conditions. The Researchperformed this quarter was a parametric evaluation of the effect of different parameters on the coal conversion and product distribution from coal. The effect of the parameters on product distribution from hexahydroanthracene was also determined. The work planned for next quarter includes combining the most effective parametric conditions for the low severity reactions and determining their effect. The second part ofthe research performed this quarter involved performing Fourier transform infrared (FTIR) spectroscopy using cyclic olefins. The objective of this study was to determine the feasibility of using FTIR and a heated cell to determine the reaction pathway that occurs in the hydrogen donation reactions from cyclic olefins. The progress made to date includes evaluating the FTIR spectra of cyclic olefins and their expected reaction products. This work is included in this progress report.

  9. Effect of poly (isopropylacrylamide)-based copolymer structure on protein adsorption resistance%聚(N-异丙基丙烯酰胺)基共聚物结构对抗蛋白吸附性能的影响

    Institute of Scientific and Technical Information of China (English)

    刘娜; 鹿浩; 吴丙照; 裴爱达; 魏小飞; 陈晓农

    2009-01-01

    BACKGROUND: Non-specific protein adsorption resistance is the most important factor for biocompatibility; pre-adsorption of hydrophilic polymer on artificial material surface is one of the effective methods to inhibit protein adsorption. OBJECTIVE: To study pre-adsorption and protein adsorption resistance of poly (isopropylacrylamide) (PNIPAM)-based amphiphilic comb-block copolymers on polystyrene (PS) surface, and to understand the effect of the copolymer structure, i.e. the chain length and the number of hydrophilic polyvinylpyrrolidone (PVP) or polyethylene oxide (PEO) comb-branches, on protein adsorption resistance. DESIGN, TIME AND SETTING: An observational study was performed at College of Materials Science and Engineering, Beijing University of Chemical Technology from November 2007 to November 2008. MATERIALS: Monodisperse PS microsphere was employed to simulate surface of hydrophobic materials, and lysozyme was used as protein model. METHODS:① Qualitative analysis: Aqueous suspension of PS microspheres (0.1 g/L) was treated with PNIPAM-based copolymer (0.1 g/L) at room temperature for 24 hours to allow pre-adsorption of the copolymer on PS surface to build up a hydrophilic layer. Lysozyme (0.1 g/L) was mixed with the PS suspension at 37 ℃ and the mixture was kept for 24 hours. Apparent particle size and turbidity of the suspension were measured at 37 C to observe coagulation or flocculation of PS microspheres, which related to the extent of protein adsorption on PS surface. ②Quantitative analysis of protein adsorption: The PS suspension containing lysozyme was subjected to ultracentrifuge (15 000 r/min) to collect clear aqueous solution. The lysozyme concentration in the clear solution was measured by spectrophotometry at 280 nm. The amount of protein adsorbed on PS surface was calculated based on the decrease in the protein concentration in the supernatant solution. MAIN OUTCOME MEASURES: Apparent particle diameter, turbidity, mass concentration of

  10. 40 CFR 721.5425 - α-Olefin sulfonate, potassium salts.

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false α-Olefin sulfonate, potassium salts... Substances § 721.5425 α-Olefin sulfonate, potassium salts. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as an α-olefin sulfonate, potassium salt...

  11. 40 CFR 721.5450 - α-Olefin sulfonate, sodium salt.

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false α-Olefin sulfonate, sodium salt. 721... Substances § 721.5450 α-Olefin sulfonate, sodium salt. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as α-olefin sulfonate, sodium...

  12. Polyhydroxyalkanoate copolymers from forest biomass.

    Science.gov (United States)

    Keenan, Thomas M; Nakas, James P; Tanenbaum, Stuart W

    2006-07-01

    The potential for the use of woody biomass in poly-beta-hydroxyalkanoate (PHA) biosynthesis is reviewed. Based on previously cited work indicating incorporation of xylose or levulinic acid (LA) into PHAs by several bacterial strains, we have initiated a study for exploring bioconversion of forest resources to technically relevant copolymers. Initially, PHA was synthesized in shake-flask cultures of Burkholderia cepacia grown on 2.2% (w/v) xylose, periodically amended with varying concentrations of levulinic acid [0.07-0.67% (w/v)]. Yields of poly(beta-hydroxybutyrate-co-beta-hydroxyvalerate) [P(3HB-co-3HV)] from 1.3 to 4.2 g/l were obtained and could be modulated to contain from 1.0 to 61 mol% 3-hydroxyvalerate (3HV), as determined by 1H and 13C NMR analyses. No evidence for either the 3HB or 4HV monomers was found. Characterization of these P(3HB-co-3HV) samples, which ranged in molecular mass (viscometric, Mv) from 511-919 kDa, by differential scanning calorimetry and thermogravimetric analyses (TGA) provided data which were in agreement for previously reported P(3HB-co-3HV) copolymers. For these samples, it was noted that melting temperature (Tm) and glass transition temperature (Tg) decreased as a function of 3HVcontent, with Tm demonstrating a pseudoeutectic profile as a function of mol% 3HV content. In order to extend these findings to the use of hemicellulosic process streams as an inexpensive carbon source, a detoxification procedure involving sequential overliming and activated charcoal treatments was developed. Two such detoxified process hydrolysates (NREL CF: aspen and CESF: maple) were each fermented with appropriate LA supplementation. For the NREL CF hydrolysate-based cultures amended with 0.25-0.5% LA, P(3HB-co-3HV) yields, PHA contents (PHA as percent of dry biomass), and mol% 3HV compositions of 2.0 g/l, 40% (w/w), and 16-52 mol% were obtained, respectively. Similarly, the CESF hydrolysate-based shake-flask cultures yielded 1.6 g/l PHA, 39% (w

  13. Multinuclear group 4 catalysis: olefin polymerization pathways modified by strong metal-metal cooperative effects.

    Science.gov (United States)

    McInnis, Jennifer P; Delferro, Massimiliano; Marks, Tobin J

    2014-08-19

    Polyolefins are produced today catalytically on a vast scale, and the manufactured polymers find use in everything from artificial limbs and food/medical packaging to automotive and electrical components and lubricants. Although polyolefin monomers are typically cheap (e.g., ethylene, propylene, α-olefins), the resulting polymer properties can be dramatically tuned by the particular polymerization catalyst employed, and reflect a rich interplay of macromolecular chemistry, materials science, and physics. For example, linear low-density polyethylene (LLDPE), produced by copolymerization of ethylene with linear α-olefin comonomers such as 1-butene, 1-hexene, or 1-octene, has small but significant levels of short alkyl branches (C2, C4, C6) along the polyethylene backbone, and is an important technology material due to outstanding rheological and mechanical properties. In 2013, the total world polyolefin production was approximately 211 million metric tons, of which about 11% was LLDPE. Historically, polyolefins were produced using ill-defined but highly active heterogeneous catalysts composed of supported groups 4 or 6 species (usually halides) activated by aluminum alkyls. In 1963, Karl Ziegler and Giulio Natta received the Nobel Prize for these discoveries. Beginning in the late 1980s, a new generation of group 4 molecule-based homogeneous olefin polymerization catalysts emerged from discoveries by Walter Kaminsky, a team led by James Stevens at The Dow Chemical Company, this Laboratory at Northwestern University, and a host of talented groups in Germany, Italy, Japan, the United Kingdom, and the United States. These new "single-site" catalysts and their activating cocatalysts were far better defined and more rationally tunable in terms of structure, mechanism, thermodynamics, and catalyst activity and selectivity than ever before possible. An explosion of research advances led to new catalysts, cocatalysts, deeper mechanistic understanding of both the

  14. SYNTHESES AND OPTOELECTRONIC PROPERTIES OF A HEXA-ARMED FLUORENE-BENZENE COPOLYMER BASED ON 2,4,6,8,10,12-HEXABENZYL 2,4,6,8,10,12-HEXAAZAISOWURTZITANECAGED-CORE

    Institute of Scientific and Technical Information of China (English)

    Qian-jin Zhao; Wen-hui Wu; Qiao-li Niu; Jun-biao Peng; Yiu-wing Mai

    2009-01-01

    A novel kind of hexa-armed fluorene-benzene copolymer based on a hexaazaisowurtzitane core was synthesized through Suzuki coupling polycondensation.The introduction of this bulky caged-core could not only enhance the photoluminescence quantum efficiency,but also improve the electroluminescence properties,especially suppress the common green-color emission of polyfluorenes(PFs)material during device operation.These features can be attributed to the successful suppression of PF's chain aggregation which profits from the introduction of the bulky hexaazaisowurtzitane core and the design of multi-armed architecture.

  15. Large-area photovoltaics based on low band gap copolymers of thiophene and benzothiadiazole or benzo-bis(thiadiazole)

    DEFF Research Database (Denmark)

    Bundgaard, Eva; Krebs, Frederik C

    2007-01-01

    Large-area solar cells (active area = 3 and 10cm(2)) were prepared with low band gap polymers based on thiophene and benzothiadiazole (1) or thiophene and benzo-bis(thiadiazole) (2). The band gaps of the polymers were 1.65 and 0.67 eV, respectively. The best photovoltaic performance was obtained...... for the device ITO/PEDOT/1:PCBM (1:2)/Al with an active area of 3 cm(2). The efficiency of the device was 0.62%. This is a high efficiency for a low band gap polymer in a large-area organic solar cell and thus polymer I is a very promising material for organic solar cells. The devices based on 2 were found...

  16. Ionic liquids for separation of olefin-paraffin mixtures

    Energy Technology Data Exchange (ETDEWEB)

    Dai, Sheng; Luo, Huimin; Huang, Jing-Fang

    2014-07-15

    The invention is directed to an ionic liquid comprising (i) a cationic portion containing a complex of a silver (I) ion and one or more neutral ligands selected from organoamides, organoamines, olefins, and organonitriles, and (ii) an anionic portion having the chemical formula ##STR00001## wherein m and n are independently 0 or an integer of 1 or above, and p is 0 or 1, provided that when p is 0, the group --N--SO.sub.2--(CF.sub.2).sub.nCF.sub.3 subtended by p is replaced with an oxide atom connected to the shown sulfur atom. The invention is also directed to a method for separating an olefin from an olefin-paraffin mixture by passing the mixture through a layer of the ionic liquid described above.

  17. Low Severity Coal Liquefaction Promoted by Cyclic Olefins

    Energy Technology Data Exchange (ETDEWEB)

    Christine W. Curtis

    1998-04-09

    The development of the donor solvent technology for coal liquefaction has drawn a good deal of attention over the last three decades. The search for better hydrogen donors led investigators to a class of compounds known as cyclic olefins. Cyclic olefins are analogues of the conventional hydroaromatic donor species but do not contain aromatic rings. The cyclic olefins are highly reactive compounds which readily release their hydrogen at temperatures of 200 C or higher. Considerable effort has been o expended toward understanding the process of hydrogen donation. Most of this work was conducted in bomb reactors, with product analysis being carried out after the reaction was complete. Efforts directed towards fundamental studies of these reactions in situ are rare. The current work employs a high temperature and high pressure infrared cell to monitor in situ the concentrations of reactants and products during hydrogen release from hydrogen donor compounds.

  18. [The study of quality characteristics of the hydrogel ointments and films based on copolymers divinyl esters of diethylene glycol].

    Science.gov (United States)

    Bakirova, R E; Tazhbaeva, E M; Muravleva, L E; Fazylov, S D; Akhmetova, S B

    2014-12-01

    The possibility of using a hydrogel based on divinyl ether co- and terpolymer of diethylene glycol as the backbone polymer for incorporating water-soluble medicinal substances was examined. The character of the influence of emulsifiers, plasticizers, high-boiling liquids and bioactive substances is defined within the changes of physical-chemical properties of obtained hydrogels. The obtained polyelectrolyte hydrogels by their homogeneity, dehydration and rheological characteristics may be of concern in function of matrices to create external prolonged-action dosage forms.

  19. Mechanical Characterization of Hybrid Vesicles Based on Linear Poly(Dimethylsiloxane-b-Ethylene Oxide) and Poly(Butadiene-b-Ethylene Oxide) Block Copolymers

    OpenAIRE

    2016-01-01

    Poly(dimethylsiloxane-ethylene oxide) (PDMS-PEO) and poly(butadiene-b-ethylene oxide) (PBd-PEO) are two block copolymers which separately form vesicles with disparate membrane permeabilities and fluidities. Thus, hybrid vesicles formed from both PDMS-PEO and PBd-PEO may ultimately allow for systematic, application-specific tuning of vesicle membrane fluidity and permeability. However, given the relatively low strength previously noted for comb-type PDMS-PEO vesicles, the mechanical robustness...

  20. Dynamic pyroelectric response of composite based on ferroelectric copolymer of poly(vinylidene fluoride-trifluoroethylene) and ferroelectric ceramics of barium lead zirconate titanate

    Energy Technology Data Exchange (ETDEWEB)

    Solnyshkin, A.V. [Tver State University, Department of Condensed Matter Physics, Tver (Russian Federation); National Research University ' ' MIET' ' , Department of Intellectual Technical Systems, Zelenograd, Moscow (Russian Federation); Morsakov, I.M.; Bogomolov, A.A. [Tver State University, Department of Condensed Matter Physics, Tver (Russian Federation); Belov, A.N.; Vorobiev, M.I.; Shevyakov, V.I.; Silibin, M.V. [National Research University ' ' MIET' ' , Department of Intellectual Technical Systems, Zelenograd, Moscow (Russian Federation); Shvartsman, V.V. [University of Duisburg-Essen, Institute for Materials Science, Essen (Germany)

    2015-10-15

    In this work, pyroelectric properties of composite films on the basis of poly(vinylidene fluoride-trifluoroethylene) copolymer with a various level of ferroelectric ceramics inclusions of barium lead zirconate titanate solid solution were investigated by the dynamic method. The composite films were prepared by the solvent cast method. The unusual spike-like dynamic response with a quasi-stationary component was observed. It is supposed that composite films may be effectively used for pyroelectric applications. (orig.)

  1. 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.

  2. Polymethylene-based copolymers by polyhomologation or by its combination with controlled/living and living polymerizations

    KAUST Repository

    Zhang, Hefeng

    2014-01-20

    Polyhomologation, recently developed by Shea, is a borane-initiated living polymerization of ylides leading to linear polymethylenes (C1 polymerization) with controlled molecular weight, low polydispersity, and well-defined structures. In this Review, the copolyhomologation of different ylides as well as the combination of polyhomologation with controlled/living (nitroxide-mediated, atom transfer radical, reversible addition-fragmentation chain-transfer) and living (ring opening, anionic) polymerizations is discussed. Polyhomologation of ylides, in combination with living and controlled/living polymerizations, leads to a plethora novel well-defined polymethylene (polyethylene)-based polymeric materials, which are very important for understanding/improving the behavior of industrial polyethylenes. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Block copolymer route towards poly(vinylidene fluoride)/poly(methacrylic acid)/nickel nanocomposites

    NARCIS (Netherlands)

    Voet, V.S.D.; Hermida-Merino, D.; Brinke, G. ten; Loos, K.

    2013-01-01

    PVDF-based block copolymers have been employed as precursors for the construction of PVDF/PMAA/Ni nanocomposites. New poly(tert-butyl methacrylate)-block-poly(vinylidene fluoride)-block-poly(tert-butyl methacrylate) (PtBMA-b-PVDF-b-PtBMA) triblock copolymers were synthesized via atom transfer radica

  4. Structure–property relations of segmented block copolymers with liquid–liquid demixed morphologies

    NARCIS (Netherlands)

    Schuur, van der Martijn; Heide, van der Evert; Feijen, Jan; Gaymans, Reinoud J.

    2005-01-01

    Poly(propylene oxide) based polyether(ester-amide)s (PEEA) with non-crystallisable amide segments were synthesized and their structure–property relations studied. These model segmented block copolymers were used to gain insight in the structure–property relations of block copolymers with liquid–liqu

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

    DEFF Research Database (Denmark)

    Jankova, Katja; Hvilsted, Søren

    2005-01-01

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

  6. The heat-chill method for preparation of self-assembled amphiphilic poly(ε-caprolactone)-poly(ethylene glycol) block copolymer based micellar nanoparticles for drug delivery.

    Science.gov (United States)

    Payyappilly, Sanal Sebastian; Dhara, Santanu; Chattopadhyay, Santanu

    2014-04-07

    A new method is developed for preparation of amphiphilic block copolymer micellar nanoparticles and investigated as a delivery system for celecoxib, a hydrophobic model drug. Biodegradable block copolymers of poly(ethylene glycol) (PEG) and poly(ε-caprolactone) (PCL) were synthesized by ring opening copolymerization and characterized thoroughly using FTIR, (1)H NMR and GPC. The block copolymer was dispersed in distilled water at 60 °C and then it was chilled in an ice bath for the preparation of the micellar nanoparticles. Polymers self-assembled to form micellar nanoparticles (HR-TEM, DLS and DSC. The cytotoxicity of the polymer micellar nanoparticles was investigated against HaCaT cell lines. The study of celecoxib release from the micellar nanoparticles was carried out to assess their suitability as a drug delivery vehicle. Addition of the drug to the system at low temperature is an added advantage of this method compared to the other temperature assisted nanoparticle preparation techniques. In a nutshell, polymer micellar nanoparticles prepared using the heat-chill method are believed to be promising for the controlled drug release system of labile drugs, which degrade in toxic organic solvents and at higher temperatures.

  7. A bis-calixarene from olefin metathesis

    Science.gov (United States)

    Hailu, Shimelis T.; Butcher, Ray J.; Hudrlik, Paul F.; Hudrlik, Anne M.

    2012-01-01

    A ring-closing olefin metathesis reaction of tetra­kis­(all­yl­oxy)calix[4]arene gave the bis­ calixarene, (15E,40E,60E)-65,74-bis­(prop-2-en-1-yl­oxy)-13,18,38,43,58,63-hexa­oxado­deca­cyclo­[28.26.8.720,36.111,45.151,55.05,57.07,12.019,24.026,64.032,37.044,49.168,72]tetra­hepta­conta-1,3,5(57),7,9,11,15,19(24),20,22,26,28,30(64),32,34,36,40,44(49),45,47,51,53,55(65),60,68,70,72(74)-hepta­cosa­ene, C74H68O8. It is a cage formed from two calix[4]arene units joined by butenyl groups at three of the O atoms on the narrow rim. The fourth O atom on each calixarene unit is joined with an allyl group. Each of the calix[4]arene units has a flattened cone conformation in which the all­yloxy-substituted aryl group and the opposite aryl group are close together and almost parallel [dihedral angle between planes = 1.09 (11)°], and the other two aryl groups are splayed outward [dihedral angle between planes = 79.53 (11)°]. No guest mol­ecule (e.g. solvent) was observed within the cage. The alkene C atoms of one of the links between the calixarene moieties are disordered over two orientations with occupancies of 0.533 (9) and 0.467 (9). PMID:22719604

  8. A bis-calixarene from olefin metathesis.

    Science.gov (United States)

    Hailu, Shimelis T; Butcher, Ray J; Hudrlik, Paul F; Hudrlik, Anne M

    2012-06-01

    A ring-closing olefin metathesis reaction of tetra-kis-(all-yl-oxy)calix[4]arene gave the bis- calixarene, (15E,40E,60E)-65,74-bis-(prop-2-en-1-yl-oxy)-13,18,38,43,58,63-hexa-oxado-deca-cyclo-[28.26.8.7(20,36).1(11,45).1(51,55).0(5,57).0(7,12).0(19,24).0(26,64).0(32,37).0(44,49).1(68,72)]tetra-hepta-conta-1,3,5(57),7,9,11,15,19(24),20,22,26,28,30(64),32,34,36,40,44(49),45,47,51,53,55(65),60,68,70,72(74)-hepta-cosa-ene, C(74)H(68)O(8). It is a cage formed from two calix[4]arene units joined by butenyl groups at three of the O atoms on the narrow rim. The fourth O atom on each calixarene unit is joined with an allyl group. Each of the calix[4]arene units has a flattened cone conformation in which the all-yloxy-substituted aryl group and the opposite aryl group are close together and almost parallel [dihedral angle between planes = 1.09 (11)°], and the other two aryl groups are splayed outward [dihedral angle between planes = 79.53 (11)°]. No guest mol-ecule (e.g. solvent) was observed within the cage. The alkene C atoms of one of the links between the calixarene moieties are disordered over two orientations with occupancies of 0.533 (9) and 0.467 (9).

  9. Ethylene copolymerization: the influence of catalyst type on the copolymer formation; Copolimerizacao de etileno: influencia do tipo de catalisador no copolimero formado

    Energy Technology Data Exchange (ETDEWEB)

    Miranda, Marcia S. Lacerda; Dupont, Jairton; Galland, Griselda B. [Rio Grande do Sul Univ., Porto Alegre, RS (Brazil). Inst. de Quimica; Quijada, Raul [Chile Univ., Santiago (Chile). Dept. de Ingenieria Quimica

    1996-01-01

    The behaviour of catalytic systems based on zirconium compounds as Me{sub 2} Si Cp{sub 2} Zr C L{sub 2} (1) and cp{sub 2} Zr Cl{sub 2} (2) (C{sub p} ={eta}{sup 5}-cyclopentadienyl), in the copolymerization of ethylene with 1-hexene and 1-hexene and 1-octane have been investigated. It has been observed that the presence of the bridge between the cyclopentadienyl ligands has no effect on the catalytic activity for the ethylene-1-hexene copolymerization {sup 13} C NMR analysis showed that the copolymers obtained with the bridged catalyst presented higher incorporation of comonomer. Thermal analysis data and viscosity measurements proved the effect of the comonomer concentration on the structure and molecular weight of the polymer formed. Infrared results show that a possible termination reaction is the {beta}-elimination. reactivity ratio values calculated by Fineman-Ross and {sup 13} C NMR methods showed a close relation between them. values of r{sub 1} and r{sub 2} show that the metallocene and the alpha-olefin have a strong effect on the structure of the polymer. (author) 9 refs., 4 figs., 4 tabs.

  10. Quasi-solid state dye-sensitized solar cells based on pyridine or imidazole containing copolymer chemically crosslinked gel electrolytes

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    Quasi-solid state dye-sensitized solar cells based on chemically crosslinking with backbone polymers of poly(vinylpyridine-co-acrylonitrile) (P(VP-co-AN)) or poly(vinylimidazole-co-acrylonitrile) (P(VIM-co- AN)) and diiodide compounds of I(CH2)6I or I(CH2CH2O)nCH2CH2I solidified EC/PC/KI/I2 gel electrolytes have been fabricated. The ionic conductivities and apparent diffusion coefficients of I3-Of the electrolytes and cell performances have been investigated. Providing chemically crosslinking points, pyridine or imidazole from the backbone polymers benefited the open circuit voltage and fill factor of the cells. Consequently, the overall energy conversion efficiencies of the quasi-solid DSSCs improved over 10% even near 20% from that of the liquid electrolyte before solidification. Besides, the employing of crosslinker I(CH2CH2O)nCH2CH2I showed higher electrolytic and cell characters than that of I(CH2)6I.

  11. Photocurable biodegradable liquid copolymers: synthesis of acrylate-end-capped trimethylene carbonate-based prepolymers, photocuring, and hydrolysis.

    Science.gov (United States)

    Matsuda, Takehisa; Kwon, Il Keun; Kidoaki, Satoru

    2004-01-01

    Various photocurable liquid biodegradable trimethylene carbonate (TMC)-based (co)oligomers were prepared by ring-opening (co)polymerization of TMC with or without L-lactide (LL) using low molecular weight poly(ethylene glycol) (PEG) (mol wt 200, 600, or 1000) or trimethylolpropane (TMP) as an initiator. Resultant (co)oligomers were pastes, viscous liquids, or liquids at room temperature, depending on the monomer composition and monomer/initiator ratio. Liquid (co)oligomers were subsequently end-capped with acrylate groups. Upon visible-light irradiation in the presence of camphorquinone as a radical generator, rapid liquid-to-solid transformation occurred to produce photocured solid. The photocuring yield increased with photoirradiation time, photointensity, and camphorquinone concentration. The photocured polymers derived from low molecular weight PEG (PEG200) and TMP exhibited much reduced hydrolysis potential compared with PEG1000-derived polymers in terms of weight loss, water uptake, and swelling depth. Force-distance curve measurements by nanoindentation using atomic force microscopy clearly showed that Young's moduli of the photocured polymer films decreased with increasing hydrolysis time. Their potential biomedical applications are discussed.

  12. IMPROVING THE PROPERTIES OF HDPE BASED SEPARATORS FOR LITHIUM ION BATTERIES BY BLENDING BLOCK WITH COPOLYMER PE-b-PEG

    Institute of Scientific and Technical Information of China (English)

    Jun-li Shi; Hao Li; Li-feng Fang; Zhi-ying Liang; Bao-ku Zhu

    2013-01-01

    To improve the performances of HDPE-based separators,polyether chains were incorporated into HDPE membranes by blending with poly(ethylene-block-ethylene glycol) (PE-b-PEG) via thermally induced phase separation (TIPS) process.By measuring the composition,morphology,crystallinity,ion conductivity,etc,the influence of PE-b-PEG on structures and properties of the blend separator were investigated.It was found that the incorporated PEG chains yielded higher surface energy for HDPE separator and improved affinity to liquid electrolyte.Thus,the stability of liquid electrolyte trapped in separator was increased while the interfacial resistance between separator and electrode was reduced effectively.The ionic conductivity of liquid electrolyte soaked separator could reach 1.28 × 10-3 S.cm-1 at 25℃,and the electrochemical stability window was up to 4.5 V (versus Li+/Li).These results revealed that blending PE-b-PEG into porous HDPE membranes could efficiently improve the performances of PE separators for lithium batteries.

  13. Preparation and Characterization of Facilitated Transport Membranes Composed of Chitosan-Styrene and Chitosan-Acrylonitrile Copolymers Modified by Methylimidazolium Based Ionic Liquids for CO₂ Separation from CH₄ and N₂.

    Science.gov (United States)

    Otvagina, Ksenia V; Mochalova, Alla E; Sazanova, Tatyana S; Petukhov, Anton N; Moskvichev, Alexandr A; Vorotyntsev, Andrey V; Afonso, Carlos A M; Vorotyntsev, Ilya V

    2016-06-09

    CO₂ separation was found to be facilitated by transport membranes based on novel chitosan (CS)-poly(styrene) (PS) and chitosan (CS)-poly(acrylonitrile) (PAN) copolymer matrices doped with methylimidazolium based ionic liquids: [bmim][BF₄], [bmim][PF₆], and [bmim][Tf₂N] (IL). CS plays the role of biodegradable film former and selectivity promoter. Copolymers were prepared implementing the latest achievements in radical copolymerization with chosen monomers, which enabled the achievement of outstanding mechanical strength values for the CS-based membranes (75-104 MPa for CS-PAN and 69-75 MPa for CS-PS). Ionic liquid (IL) doping affected the surface and mechanical properties of the membranes as well as the gas separation properties. The highest CO₂ permeability 400 Barrers belongs to CS-b-PS/[bmim][BF₄]. The highest selectivity α (CO₂/N₂) = 15.5 was achieved for CS-b-PAN/[bmim][BF₄]. The operational temperature of the membranes is under 220 °C.

  14. Preparation and Characterization of Facilitated Transport Membranes Composed of Chitosan-Styrene and Chitosan-Acrylonitrile Copolymers Modified by Methylimidazolium Based Ionic Liquids for CO2 Separation from CH4 and N2

    Directory of Open Access Journals (Sweden)

    Ksenia V. Otvagina

    2016-06-01

    Full Text Available CO2 separation was found to be facilitated by transport membranes based on novel chitosan (CS–poly(styrene (PS and chitosan (CS–poly(acrylonitrile (PAN copolymer matrices doped with methylimidazolium based ionic liquids: [bmim][BF4], [bmim][PF6], and [bmim][Tf2N] (IL. CS plays the role of biodegradable film former and selectivity promoter. Copolymers were prepared implementing the latest achievements in radical copolymerization with chosen monomers, which enabled the achievement of outstanding mechanical strength values for the CS-based membranes (75–104 MPa for CS-PAN and 69–75 MPa for CS-PS. Ionic liquid (IL doping affected the surface and mechanical properties of the membranes as well as the gas separation properties. The highest CO2 permeability 400 Barrers belongs to CS-b-PS/[bmim][BF4]. The highest selectivity α (CO2/N2 = 15.5 was achieved for CS-b-PAN/[bmim][BF4]. The operational temperature of the membranes is under 220 °C.

  15. Electrochemistry for biofuel generation: transformation of fatty acids and triglycerides to diesel-like olefin/ether mixtures and olefins.

    Science.gov (United States)

    dos Santos, Tatiane R; Harnisch, Falk; Nilges, Peter; Schröder, Uwe

    2015-03-01

    Electroorganic synthesis can be exploited for the production of biofuels from fatty acids and triglycerides. With Coulomb efficiencies (CE) of up to 50 %, the electrochemical decarboxylation of fatty acids in methanolic and ethanolic solutions leads to the formation of diesel-like olefin/ether mixtures. Triglycerides can be directly converted in aqueous solutions by using sonoelectrochemistry, with olefins as the main products (with a CE of more than 20 %). The latter reaction, however, is terminated at around 50 % substrate conversion by the produced side-product glycerol. An energy analysis shows that the electrochemical olefin synthesis can be an energetically competitive, sustainable, and--in comparison with established processes--economically feasible alternative for the exploitation of fats and oils for biofuel production.

  16. Biodegradable block poly(ester-urethane)s based on poly(3-hydroxybutyrate-co-4-hydroxybutyrate) copolymers.

    Science.gov (United States)

    Ou, Wenfeng; Qiu, Handi; Chen, Zhifei; Xu, Kaitian

    2011-04-01

    A series of block poly(ester-urethane)s (abbreviated as PU3/4HB) based on biodegradable poly(3-hydroxybutyrate-co-4-hydroxybutyrate) (P3/4HB) segments were synthesized by a facile way of melting polymerization using 1,6-hexamethylene diisocyanate (HDI) as the coupling agent and stannous octanoate (Sn(Oct)(2)) as catalyst, with different 4HB contents and segment lengths. The chemical structure, molecular weight and distribution were systematically characterized by (1)H nuclear magnetic resonance spectrum (NMR), Fourier transform infrared spectroscopy (FTIR) and gel permeation chromatography (GPC). The thermal property was studied by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The hydrophilicity was investigated by static contact angle of deionized water and CH(2)I(2). DSC curves revealed that the PU3/4HB polyurethanes have their T(g) from -25.6 °C to -4.3 °C, and crystallinity from 2.5% to 25.3%, being almost amorphous to semi-crystalline. The obtained PU3/4HBs are hydrophobic (water contact angle 77.4°-95.9°), and their surface free energy (SFE) were studied. The morphology of platelets adhered on the polyurethane film observed by scanning electron microscope (SEM) showed that platelets were activated on the PU3/4HB films which would lead to blood coagulation. The lactate dehydrogenase (LDH) assay revealed that the PU3/4HBs displayed higher platelet adhesion property than raw materials and biodegradable polymer polylactic acid (PLA) and would be potential hemostatic materials. Crystallinity degree, hydrophobicity, surface free energy and urethane linkage content play important roles in affecting the LDH activity and hence the platelet adhesion. CCK-8 assay showed that the PU3/4HB is non-toxic and well for cell growth and proliferation of mouse fibroblast L929. It showed that the hydrophobicity is an important factor for cell growth while 3HB content of the PU3/4HB is important for the cell proliferation. Through changing the

  17. Modification of TiO2 Nanoparticles with Oleyl Phosphate via Phase Transfer in the Toluene-Water System and Application of Modified Nanoparticles to Cyclo-Olefin-Polymer-Based Organic-Inorganic Hybrid Films Exhibiting High Refractive Indices.

    Science.gov (United States)

    Takahashi, Shiori; Hotta, Shuhei; Watanabe, Akira; Idota, Naokazu; Matsukawa, Kimihiro; Sugahara, Yoshiyuki

    2017-01-18

    Oleyl-phosphate-modified TiO2 nanoparticles (OP_TiO2) were prepared via phase transfer from an aqueous phase containing dispersed TiO2 nanoparticles to a toluene phase containing oleyl phosphate (OP, a mixture of monoester and diester), and employed for the preparation of OP_TiO2/cyclo-olefin polymer (COP) hybrid films with high-refractive indices. The modification of TiO2 by OP was essentially completed by reaction at room temperature for 8 h, and essentially all the TiO2 nanoparticles in the aqueous phase were transferred to the toluene phase. The infrared and solid-state (13)C cross-polarization and magic-angle spinning (CP/MAS) NMR spectrum of OP_TiO2 showed the presence of oleyl groups originating from oleyl phosphate. The solid-state (31)P MAS NMR spectrum of OP_TiO2 exhibited new signals at -1.4, 2.1, and 4.8 ppm, indicating the formation of Ti-O-P bonds. CHN and inductively coupled plasma analyses revealed that the major species bound to the TiO2 surface was tridentate CH3(CH2)7CH═CH(CH2)8P(OTi)3. These results clearly indicate that the surfaces of the TiO2 nanoparticles were modified by OP moieties via phase transfer. OP_TiO2/COP hybrid films exhibited excellent optical transparency up to 19.1 vol % TiO2 loading, and the light transmittance of the hybrid films with 19.1 vol % TiO2 loading was 99.8% at 633 nm. The refractive index of these hybrid films rose to 1.83.

  18. Biopolymer-supported ionic-liquid-phase ruthenium catalysts for olefin metathesis.

    Science.gov (United States)

    Clousier, Nathalie; Filippi, Alexandra; Borré, Etienne; Guibal, Eric; Crévisy, Christophe; Caijo, Fréderic; Mauduit, Marc; Dez, Isabelle; Gaumont, Annie-Claude

    2014-04-01

    Original ruthenium supported ionic liquid phase (SILP) catalysts based on alginates as supports were developed for olefin metathesis reactions. The marine biopolymer, which fulfills most of the requisite properties for a support such as widespread abundance, insolubility in the majority of organic solvents, a high affinity for ionic liquids, high chemical stability, biodegradability, low cost, and easy processing, was impregnated by [bmim][PF6 ] containing an ionically tagged ruthenium catalyst. These biosourced catalysts show promising performances in ring-closing metathesis (RCM) and cross-metathesis (CM) reactions, with a high level of recyclability and reusability combined with a good reactivity.

  19. Bulky N-Phosphino-Functionalized N-Heterocyclic Carbene Ligands: Synthesis, Ruthenium Coordination Chemistry, and Ruthenium Alkylidene Complexes for Olefin Metathesis.

    Science.gov (United States)

    Brown, Christopher C; Rominger, Frank; Limbach, Michael; Hofmann, Peter

    2015-11-01

    Ruthenium chemistry and applications in catalytic olefin metathesis based on N-phosphino-functionalized N-heterocyclic carbene ligands (NHCPs) are presented. Alkyl NHCP Ru coordination chemistry is described, and access to several potential synthetic precursors for ruthenium alkylidene complexes is outlined, incorporating both trimethylsilyl and phenyl alkylidenes. The Ru alkylidene complexes are evaluated as potential olefin metathesis catalysts and were shown to behave in a latent fashion. They displayed catalytic activity at elevated temperatures for both ring closing metathesis and ring opening metathesis polymerization.

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

    DEFF Research Database (Denmark)

    Noguer, Albert Camós; Olsen, Stefan Møller

    in the worsening of the fouling-inhibition properties of these complex systems, specially focusing on the behaviour and fate of the block copolymers used as additives. The development of various methods to visualize and quantify processes involving these copolymers are presented. Chapter 1 provides an overview......-release coatings. A coating based on a PDMS binder has been employed as model system in the thesis. The effect of the addition of various PEG-based surfactants and copolymers (i.e. amphiphiles) was investigated by a novel method developed in this project, and the diffusion coefficient and biofouling...... coatings. Images obtained by confocal microscopy proved that the copolymer molecules assemble in spherical domains inside the PDMS coating. The domains are smaller close to the surface and larger in the bulk of the film (with domains as large as 7 µm in diameter). The diffusion of copolymer from the bulk...