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Sample records for catalyzed silica polymerization

  1. Metal-catalyzed living radical polymerization and radical polyaddition for precision polymer synthesis

    Energy Technology Data Exchange (ETDEWEB)

    Mizutani, M; Satoh, K [Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8603 (Japan); Kamigaito, M, E-mail: kamigait@apchem.nagoya-u.ac.j

    2009-08-01

    The metal-catalyzed radical addition reaction can be evolved into two different polymerization mechanisms, i.e.; chain- and step-growth polymerizations, while both the polymerizations are based on the same metal-catalyzed radical formation reaction. The former is a widely employed metal-catalyzed living radical polymerization or atom transfer radical polymerization of common vinyl monomers, and the latter is a novel metal-catalyzed radical polyaddition of designed monomer with an unconjugated C=C double bond and a reactive C-Cl bond in one molecule. The simultaneous ruthenium-catalyzed living radical polymerization of methyl acrylate and radical polyaddition of 3-butenyl 2-chloropropionate was achieved with Ru(Cp*)Cl(PPh{sub 3}){sub 2} to afford the controlled polymers, in which the homopolymer segments with the controlled chain length were connected by the ester linkage.

  2. Modification of silica surface by gamma ray induced Ad micellar Polymerization

    International Nuclear Information System (INIS)

    Buathong, Salukjit; Pongprayoon, Thirawudh; Suwanmala, Phiriyatorn

    2005-10-01

    Precipitated silica is often added to natural rubber compounds in order to improve performance in commercial application. A problem with using silica as filler is the poor compatibility between silica and natural rubber. In this research, polyisoprene was coated on silica surface by gamma ray induced ad micellar polymerization in order to achieve the better compatibility between silica and natural rubber. The modified silica was characterized by FT-IR, and SEM. The results show that polyisoprene was successfully coated on silica surface via gamma ray induced ad micellar polymerization

  3. In situ polymerization of L-Lactide in the presence of fumed silica

    International Nuclear Information System (INIS)

    Prebe, A.; Alcouffe, P.; Cassagnau, Ph.; Gerard, J.F.

    2010-01-01

    Chemiorheology, i.e. rheological changes during the polymerization, of a biosourced monomer, i.e. L-Lactide, containing fumed silica have been studied. For that purpose, the reaction was proceeded in situ between the plates of a dynamic rheometer. The polymerization kinetics was followed from the variation of the complex shear modulus versus reaction time. Moreover, at temperatures lower than the crystallization temperature, it was possible to follow the crystallization process while the polymerization takes place. Adding fumed silica particles into the monomer leads to the formation of a physical (percolated) network from particle-particle interactions, i.e. silica, in the L-Lactide probably hydrophilic interactions. The gel-like structure was kept while the polymerization as long as the strain remains low indicating that the silica particle network remains weak. Furthermore, the mechanism of the break down of the gel structure under large deformation as well as the recovery was discussed. It seems that the non-linearity effect of the nanocomposites stems in the silica inter-particle interactions. It was found that silica particles do not have any effect on the temperature of crystallization - molar mass relation but could act as nucleating agent. In situ polymerization of L-Lactide in the presence of 5 wt.% of modified fumed silica was carried out in a reactor. It was found that fumed hydrophilic silica leaded to a microcomposite with highly dense agglomerates in the polymer matrix whereas with a less hydrophilic silica it was possible to decrease the size of the agglomerates increasing the dispersion. The finest dispersion state was achieved with the 'initiating' functionalized silica leading to a 'grafting from' polymerization of the L-Lactide. Such functionalized silica leads to a nanoscale dispersion in a one-step bulk polymerization with only a few small agglomerates.

  4. In situ polymerization of L-Lactide in the presence of fumed silica

    Energy Technology Data Exchange (ETDEWEB)

    Prebe, A. [Universite de Lyon, F-69361, Lyon (France); CNRS, UMR 5223, Ingenierie des Materiaux Polymeres, F-69622, Villeurbanne (France); Universite Claude Bernard Lyon 1, F-69622, Villeurbanne (France); INSA Lyon, F-69621, Villeurbanne (France); Alcouffe, P. [Universite de Lyon, F-69361, Lyon (France); CNRS, UMR 5223, Ingenierie des Materiaux Polymeres, F-69622, Villeurbanne (France); Universite Claude Bernard Lyon 1, F-69622, Villeurbanne (France); Cassagnau, Ph., E-mail: philippe.cassagnau@univ-lyon1.fr [Universite de Lyon, F-69361, Lyon (France); CNRS, UMR 5223, Ingenierie des Materiaux Polymeres, F-69622, Villeurbanne (France); Universite Claude Bernard Lyon 1, F-69622, Villeurbanne (France); Gerard, J.F. [Universite de Lyon, F-69361, Lyon (France); CNRS, UMR 5223, Ingenierie des Materiaux Polymeres, F-69622, Villeurbanne (France); INSA Lyon, F-69621, Villeurbanne (France)

    2010-11-01

    Chemiorheology, i.e. rheological changes during the polymerization, of a biosourced monomer, i.e. L-Lactide, containing fumed silica have been studied. For that purpose, the reaction was proceeded in situ between the plates of a dynamic rheometer. The polymerization kinetics was followed from the variation of the complex shear modulus versus reaction time. Moreover, at temperatures lower than the crystallization temperature, it was possible to follow the crystallization process while the polymerization takes place. Adding fumed silica particles into the monomer leads to the formation of a physical (percolated) network from particle-particle interactions, i.e. silica, in the L-Lactide probably hydrophilic interactions. The gel-like structure was kept while the polymerization as long as the strain remains low indicating that the silica particle network remains weak. Furthermore, the mechanism of the break down of the gel structure under large deformation as well as the recovery was discussed. It seems that the non-linearity effect of the nanocomposites stems in the silica inter-particle interactions. It was found that silica particles do not have any effect on the temperature of crystallization - molar mass relation but could act as nucleating agent. In situ polymerization of L-Lactide in the presence of 5 wt.% of modified fumed silica was carried out in a reactor. It was found that fumed hydrophilic silica leaded to a microcomposite with highly dense agglomerates in the polymer matrix whereas with a less hydrophilic silica it was possible to decrease the size of the agglomerates increasing the dispersion. The finest dispersion state was achieved with the 'initiating' functionalized silica leading to a 'grafting from' polymerization of the L-Lactide. Such functionalized silica leads to a nanoscale dispersion in a one-step bulk polymerization with only a few small agglomerates.

  5. Silica-Polystyrene Nanocomposite Particles Synthesized by Nitroxide-Mediated Polymerization and Their Encapsulation through Miniemulsion Polymerization

    Directory of Open Access Journals (Sweden)

    Bérangère Bailly

    2006-01-01

    Full Text Available Polystyrene (PS chains with molecular weights comprised between 8000 and 64000 g⋅mol-1 and narrow polydispersities were grown from the surface of silica nanoparticles (Aerosil A200 fumed silica and Stöber silica, resp. through nitroxide-mediated polymerization (NMP. Alkoxyamine initiators based on N-tert-butyl-1-diethylphosphono-2,2-dimethylpropyl nitroxide (DEPN and carrying a terminal functional group have been synthesized in situ and grafted to the silica surface. The resulting grafted alkoxyamines have been employed to initiate the growth of polystyrene chains from the inorganic surface. The maximum grafting density of the surface-tethered PS chains was estimated and seemed to be limited by initiator confinement at the interface. Then, the PS-grafted Stöber silica nanoparticles were entrapped inside latex particles via miniemulsion polymerization. Transmission electron microscopy indicated the successful formation of silica-polystyrene core-shell particles.

  6. Metal-ion catalyzed polymerization in the eutectic phase in water-ice

    DEFF Research Database (Denmark)

    Monnard, Pierre-Alain; Szostak, Jack W.

    2008-01-01

    The emergence of an RNA world requires among other processes the non-enzymatic, template-directed replication of genetic polymers such as RNA or related nucleic acids, possibly catalyzed by metal ions. The absence of uridilate derivative polymerization on adenine containing templates has been...... the main issue preventing an efficient template-directed RNA polymerization. We report here the investigation of template-directed RNA polymerization in the eutectic phase in water-ice. In particular, it was found that activated Uridilate monomers in the presence of metal-ion catalysts could efficiently......-pairing opportunities. These results suggest that a template-directed RNA polymerization catalyzed by metal-ions could be carried out under eutectic phase in water-ice conditions....

  7. Polymeric bionanocomposite cast thin films with in situ laccase-catalyzed polymerization of dopamine for biosensing and biofuel cell applications.

    Science.gov (United States)

    Tan, Yueming; Deng, Wenfang; Li, Yunyong; Huang, Zhao; Meng, Yue; Xie, Qingji; Ma, Ming; Yao, Shouzhuo

    2010-04-22

    We report here on the facile preparation of polymer-enzyme-multiwalled carbon nanotubes (MWCNTs) cast films accompanying in situ laccase (Lac)-catalyzed polymerization for electrochemical biosensing and biofuel cell applications. Lac-catalyzed polymerization of dopamine (DA) as a new substrate was examined in detail by UV-vis spectroscopy, cyclic voltammetry, quartz crystal microbalance, and scanning electron microscopy. Casting the aqueous mixture of DA, Lac and MWCNTs on a glassy carbon electrode (GCE) yielded a robust polydopamine (PDA)-Lac-MWCNTs/GCE that can sense hydroquinone with 643 microA mM(-1) cm(-2) sensitivity and 20-nM detection limit (S/N = 3). The DA substrate yielded the best biosensing performance, as compared with aniline, o-phenylenediamine, or o-aminophenol as the substrate for similar Lac-catalyzed polymerization. Casting the aqueous mixture of DA, glucose oxidase (GOx), Lac, and MWCNTs on a Pt electrode yielded a robust PDA-GOx-Lac-MWCNTs/Pt electrode that exhibits glucose-detection sensitivity of 68.6 microA mM(-1) cm(-2). In addition, 2,2'-azinobis (3-ethylbenzothiazoline-6-sulfonate) diammonium salt (ABTS) was also coimmobilized to yield a PDA-Lac-MWCNTs-ABTS/GCE that can effectively catalyze the reduction of O(2), and it was successfully used as the biocathode of a membraneless glucose/O(2) biofuel cell (BFC) in pH 5.0 Britton-Robinson buffer. The proposed biomacromolecule-immobilization platform based on enzyme-catalyzed polymerization may be useful for preparing many other multifunctional polymeric bionanocomposites for wide applications.

  8. Comparison between rice husk ash and commercial silica as filler in polymeric composites

    International Nuclear Information System (INIS)

    Fernandes, I.J.; Calheiro, D.; Santos, E.C.A. dos; Oliveira, R.; Rocha, T.L.A.C.; Moraes, C.A.M.

    2014-01-01

    The use of rice husk ash (RHA) as filler in polymeric materials has been studied in different polymers. Research reported that RHA may successfully replace silica. The silica production process using ore demands high energy input and produces considerable amounts of waste. Therefore, the replacement of silica by RHA may be economically and environmentally advantageous, reducing environmental impact and adding value to a waste material. In this context, this study characterizes and compares RHA of different sources (travelling grate reactor and fluidized bed reactor) with commercially available silicas to assess performance as filler in polymeric materials. Samples were characterized by X-ray fluorescence, loss on ignition, X-ray diffraction, grain size, specific surface area and specific weight. The results show that RHA may be used as a filler in several polymeric materials.(author)

  9. Polymerization of Methyl Methacrylate with Samarocene Complex Supported on Mesoporous Silica

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    Samarocene complex was supported on a series of mesoporous silica with various pore sizes. Polymerization of methyl methacrylate (MMA) by these catalysts provide highly syndiotactic PMMAs with higher molecular weights compared with those obtained by solution polymerization with homogeneous catalyst system.

  10. Surface modification of silica nanoparticles by UV-induced graft polymerization of methyl methacrylate.

    Science.gov (United States)

    Kim, Sooyeon; Kim, Eunhye; Kim, Sungsoo; Kim, Woosik

    2005-12-01

    In this study we modified the surface of silica nanoparticles with methyl methacrylate by UV-induced graft polymerization. It is a surface-initiated polymerization reaction induced by ultraviolet irradiation. The resulting organic-inorganic nanocomposites were near-monodisperse and fabricated without homopolymerization of the monomer. Substantial increase in mean particle size was observed by SEM image analysis after UV-induced grafting of methyl methacrylate onto pure silica particles. FT-Raman spectroscopy and X-ray photoelectron spectroscopy studies of these materials revealed the successful grafting of methyl methacrylate onto the silica surface. The formation of a covalent bond between the grafted PMMA chains and silica surface was indicated by FT-Raman spectra. Thermogravimetric analysis of the PMMA-grafted silica particles indicated the polymer contents in good agreement with SEM photographs.

  11. Enzymatically-Catalyzed Polymerization (ECP)- Derived Polymer Electrolyte for Rechargeable Li-Ion Batteries

    National Research Council Canada - National Science Library

    Chua, David

    1998-01-01

    Report developed under SBIR contract covers the syntheses and electrochemical characterizations of novel polymer electrolytes derived from compounds synthesized via enzyme-catalyzed polymerization(ECP) techniques...

  12. Architecture of Amylose Supramolecules in Form of Inclusion Complexes by Phosphorylase-Catalyzed Enzymatic Polymerization

    Directory of Open Access Journals (Sweden)

    Jun-ichi Kadokawa

    2013-07-01

    Full Text Available This paper reviews the architecture of amylose supramolecules in form of inclusion complexes with synthetic polymers by phosphorylase-catalyzed enzymatic polymerization. Amylose is known to be synthesized by enzymatic polymerization using α-d-glucose 1-phosphate as a monomer, by phosphorylase catalysis. When the phosphorylase-catalyzed enzymatic polymerization was conducted in the presence of various hydrophobic polymers, such as polyethers, polyesters, poly(ester-ether, and polycarbonates as a guest polymer, such inclusion supramolecules were formed by the hydrophobic interaction in the progress of polymerization. Because the representation of propagation in the polymerization is similar to the way that a vine of a plant grows, twining around a rod, this polymerization method for the formation of amylose-polymer inclusion complexes was proposed to be named “vine-twining polymerization”. To yield an inclusion complex from a strongly hydrophobic polyester, the parallel enzymatic polymerization system was extensively developed. The author found that amylose selectively included one side of the guest polymer from a mixture of two resemblant guest polymers, as well as a specific range in molecular weights of the guest polymers poly(tetrahydrofuran (PTHF in the vine-twining polymerization. Selective inclusion behavior of amylose toward stereoisomers of chiral polyesters, poly(lactides, also appeared in the vine-twining polymerization.

  13. Plasma Polymerization of Acetylene onto silica: and Approach to control the distribution of silica in single elastomers and immiscible blends

    NARCIS (Netherlands)

    Tiwari, M.; Noordermeer, Jacobus W.M.; Ooij, W.J.; Dierkes, Wilma K.

    2008-01-01

    Surface modification of silica by acetylene plasma polymerization is applied in order to improve the dispersion in and compatibility with single rubbers and their blends. Silica, used as a reinforcing filler for elastomers, is coated with a polyacetylene (PA) film under vacuum conditions. Water

  14. Lipase-catalyzed ring-opening polymerization of lactones to polyesters and its mechanistic aspects.

    Science.gov (United States)

    Namekawa, S; Suda, S; Uyama, H; Kobayashi, S

    1999-01-01

    Lipase catalysis induced a ring-opening polymerization of lactones with different ring-sizes. Small-size (four-membered) and medium-size lactones (six- and seven-membered) as well as macrolides (12-, 13-, 16-, and 17-membered) were subjected to lipase-catalyzed polymerization. The polymerization behaviors depended primarily on the lipase origin and the monomer structure. The macrolides showing much lower anionic polymerizability were enzymatically polymerized faster than epsilon-caprolactone. The granular immobilized lipase derived from Candida antartica showed extremely efficient catalysis in the polymerization of epsilon-caprolactone. Single-step terminal functionalization of the polyester was achieved by initiator and terminator methods. The enzymatic polymerizability of lactones was quantitatively evaluated by Michaelis-Menten kinetics.

  15. Study of Catalyst, Aging Time and Surfactant Effects on Silica Inorganic Polymer Characteristics

    Directory of Open Access Journals (Sweden)

    M. Pakizeh

    2007-06-01

    Full Text Available In the present study the sol-gel method is used for synthesis of amorphous nanostructure silica polymer using tetraethoxysilane (TEOS as silicon source. This polymer can be used in manufacturing of nanoporous asymmetricmembranes. The effect of catalyst on silica particle size has been studied under acidic and basic conditions.زAcid-catalyzed reaction leads to the formation of fine particles while the base-catalyzed reaction produceslarger particles. The presence of cationic template surfactant namely cetyl pyridinium bromide (CPBزdirects the structural formation of the polymer by preventing the highly branched polymeric clusters. This will increase the effective area of the produced silica membrane. Nitrogen physisorption tests by Brunaver- Emmett-Teller (BET and Barrett-Joyner-Halenda (BJH methods revealed that the surface area of the membrane increases significantly around 5-folds when acid-catalyzed reaction is used. 29Si-NMR test is also used to study the aging time effect on the level of silica polymer branching. The results show that in acidic condition, aging time up to three weeks can still affect branching. The calcinations process in which the organic materials and CPB (surfactant are burned and released from the silica particles, is studied on template free silica materials as well as templated silica materials using TGA and DTA techniques.

  16. Comparison between rice husk ash and commercial silica as filler in polymeric composites; Comparacao de cinza de casca de arroz e silica comercial como carga em compositos polimericos

    Energy Technology Data Exchange (ETDEWEB)

    Fernandes, I.J.; Calheiro, D.; Santos, E.C.A. dos; Oliveira, R.; Rocha, T.L.A.C.; Moraes, C.A.M., E-mail: ijk.fernandes@gmail.com [Universidade do Vale do Rio dos Sinos (UNISINOS), Sao Leopoldo, RS (Brazil). Pos-Graduacao em Engenharia Civil

    2014-07-01

    The use of rice husk ash (RHA) as filler in polymeric materials has been studied in different polymers. Research reported that RHA may successfully replace silica. The silica production process using ore demands high energy input and produces considerable amounts of waste. Therefore, the replacement of silica by RHA may be economically and environmentally advantageous, reducing environmental impact and adding value to a waste material. In this context, this study characterizes and compares RHA of different sources (travelling grate reactor and fluidized bed reactor) with commercially available silicas to assess performance as filler in polymeric materials. Samples were characterized by X-ray fluorescence, loss on ignition, X-ray diffraction, grain size, specific surface area and specific weight. The results show that RHA may be used as a filler in several polymeric materials.(author)

  17. Silica metal-oxide vesicles catalyze comprehensive prebiotic chemistry.

    Science.gov (United States)

    Bizzarri, Bruno Mattia; Botta, Lorenzo; Pérez-Valverde, Maritza Iveth; Saladino, Raffaele; Di Mauro, Ernesto; Garcia Ruiz, Juan Manuel

    2018-03-30

    It has recently been demonstrated that mineral self-assembled structures catalyzing prebiotic chemical reactions may form in natural waters derived from serpentinization, a geological process widespread in the early stages of Earth-like planets. We have synthesized self-assembled membranes by mixing microdrops of metal solutions with alkaline silicate solutions in the presence of formamide (NH2CHO), a single carbon molecule, at 80ºC. We found that these bilayer membranes, made of amorphous silica and metal oxide-hydroxide nanocrystals, catalyze the condensation of formamide, yielding the four nucleobases of RNA, three aminoacids and several carboxylic acids in a single pot experiment. Besides manganese, iron and magnesium, two abundant elements in the earliest Earth crust that are key in serpentinization reactions, are enough to produce all these biochemical compounds. These results suggest that the transition from inorganic geochemistry to prebiotic organic chemistry is common on a universal scale and, most probably, earlier than ever thought for our planet. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Constrained Geometry Organotitanium Catalysts Supported on Nanosized Silica for Ethylene (co)Polymerization.

    Science.gov (United States)

    Li, Kuo-Tseng; Wu, Ling-Huey

    2017-05-05

    Supported olefin polymerization catalysts can prevent reactor-fouling problems and produce uniform polymer particles. Constrained geometry complexes (CGCs) have less sterically hindered active sites than bis-cyclopentadienyl metallocene catalysts. In the literature, micrometer-sized silica particles were used for supporting CGC catalysts, which might have strong mass transfer limitations. This study aims to improve the activity of supported CGC catalysts by using nanometer-sized silica. Ti[(C₅Me₄)SiMe₂(N t Bu)]Cl₂, a "constrained-geometry" titanium catalyst, was supported on MAO-treated silicas (nano-sized and micro-sized) by an impregnation method. Ethylene homo-polymerization and co-polymerization with 1-octene were carried out in a temperature range of 80-120 °C using toluene as the solvent. Catalysts prepared and polymers produced were characterized. For both catalysts and for both reactions, the maximum activities occurred at 100 °C, which is significantly higher than that (60 °C) reported before for supported bis-cyclopentadienyl metallocene catalysts containing zirconium, and is lower than that (≥140 °C) used for unsupported Ti[(C₅Me₄)SiMe₂(N t Bu)]Me₂ catalyst. Activities of nano-sized catalyst were 2.6 and 1.6 times those of micro-sized catalyst for homopolymerization and copolymerization, respectively. The former produced polymers with higher crystallinity and melting point than the latter. In addition, copolymer produced with nanosized catalyst contained more 1-octene than that produced with microsized catalyst.

  19. Self-catalyzed photo-initiated RAFT polymerization for fabrication of fluorescent polymeric nanoparticles with aggregation-induced emission feature.

    Science.gov (United States)

    Zeng, Guangjian; Liu, Meiying; Jiang, Ruming; Huang, Qiang; Huang, Long; Wan, Qing; Dai, Yanfeng; Wen, Yuanqing; Zhang, Xiaoyong; Wei, Yen

    2018-02-01

    In recent years, the fluorescent polymeric nanoparticles (FPNs) with aggregation-induced emission (AIE) feature have been extensively exploited in various biomedical fields owing to their advantages, such as low toxicity, biodegradation, excellent biocompatibility, good designability and optical properties. Therefore, development of a facile, efficient and well designable strategy should be of great importance for the biomedical applications of these AIE-active FPNs. In this work, a novel method for the fabrication of AIE-active FPNs has been developed through the self-catalyzed photo-initiated reversible addition fragmentation chain transfer (RAFT) polymerization using an AIE dye containing chain transfer agent (CTA), which could initiate the RAFT polymerization under light irradiation. The results suggested that the final AIE-active FPNs (named as TPE-poly(St-PEGMA)) showed great potential for biomedical applications owing to their optical and biological properties. More importantly, the method described in the work is rather simple and effective and can be further extended to prepare many other different AIE-active FPNs owing to the good monomer adoptability of RAFT polymerization. Copyright © 2017 Elsevier B.V. All rights reserved.

  20. Metal-silica sol-gel materials

    Science.gov (United States)

    Stiegman, Albert E. (Inventor)

    2002-01-01

    The present invention relates to a single phase metal-silica sol-gel glass formed by the co-condensation of a transition metal with silicon atoms where the metal atoms are uniformly distributed within the sol-gel glass as individual metal centers. Any transition metal may be used in the sol-gel glasses. The present invention also relates to sensor materials where the sensor material is formed using the single phase metal-silica sol-gel glasses. The sensor materials may be in the form of a thin film or may be attached to an optical fiber. The present invention also relates to a method of sensing chemicals using the chemical sensors by monitoring the chromatic change of the metal-silica sol-gel glass when the chemical binds to the sensor. The present invention also relates to oxidation catalysts where a metal-silica sol-gel glass catalyzes the reaction. The present invention also relates to a method of performing oxidation reactions using the metal-silica sol-gel glasses. The present invention also relates to organopolymer metal-silica sol-gel composites where the pores of the metal-silica sol-gel glasses are filled with an organic polymer polymerized by the sol-gel glass.

  1. Grafting of polymer onto silica surface in the presence of γ-ray irradiated silica

    International Nuclear Information System (INIS)

    Tsuchida, A.; Yokoyama, R.; Takami, M.; Chen, J.; Ohta, M.; Tsubokawa, N.

    2002-01-01

    Complete text of publication follows. We have reported the graft polymerization of vinyl monomers initiated by surface radicals formed by the decomposition of azo and peroxide groups previously introduced onto the surface. In addition, the grafting of polymers onto carbon black has been reported by the reaction of polymer radicals with the surface. On the other hand, it is well known that the relatively stable radicals are generated on the surface by the γ-ray irradiation. In this paper, the grafting of polystyrene onto silica surface during the thermal polymerization of styrene in the presence of γ-ray irradiated silica, grafting mechanism and thermal stability of grafted polymer will be discussed. The grafting of polymers onto silica surface by irradiation of polymer-adsorbed silica was also investigated. Silica obtained from Mitsubishi Chemical Co., Japan was used after pulverization: the particle size was 0.037-0.088 mm. Irradiation was performed in Cs-137 source at room temperature. The silica was irradiated at 50 Gy with dose rate of 3.463 Gy/min. Into a polymerization tube, styrene and irradiated silica was charged and the polymerization was carried out under argon under stirring. The percentage of polystyrene grafting was determined from weight loss when polystyrene-grafted silica was heated at 600 deg C by a thermal analyzer. Untreated silica did not affect the thermal polymerization of styrene. On the contrary, the thermal polymerization of styrene was remarkably retarded in the presence of the irradiated silica at 60 deg C. Similar tendency was reported during the polymerization of vinyl monomers in the presence of carbon black. In the initial stage of the polymerization in the presence of the irradiated silica below 50 deg C, the polymerization was accelerated. During the polymerization in the presence of irradiated silica, polystyrene was grafted onto the surface: the percentage of grafting was 5-11%. The amount of polystyrene grafted onto silica

  2. Preparation and Applications of Amylose Supramolecules by Means of Phosphorylase-Catalyzed Enzymatic Polymerization

    Directory of Open Access Journals (Sweden)

    Jun-ichi Kadokawa

    2012-01-01

    Full Text Available This paper reviews preparation and applications of amylose supramolecules by means of phosphorylase-catalyzed enzymatic polymerization. When the enzymatic polymerization of α-d-glucose 1-phosphate (G-1-P as a monomer was carried out in the presence of poly(tetrahydrofuran (PTHF of a hydrophobic polyether as a guest polymer, the supramolecule, i.e., an amylose-PTHF inclusion complex, was formed in the process of polymerization. Because the representation of propagation in the polymerization is similar to the way that vines of plants grow twining around rods, this polymerization method for the preparation of amylose-polymer inclusion complexes was proposed to be named “vine-twining polymerization”. Various hydrophobic polyethers, polyesters, poly(ester-ether, and polycarbonates were also employed as the guest polymer in the vine-twining polymerization to produce the corresponding inclusion complexes. To obtain the inclusion complex from a strongly hydrophobic guest polymer, the parallel enzymatic polymerization system was developed as an advanced extension of the vine-twining polymerization. In addition, it was found that amylose selectively includes one side of the guest polymer from a mixture of two resemblant guest polymers, as well as a specific range in molecular weights of the guest PTHF. Amylose also exhibited selective inclusion behavior toward stereoisomers of poly(lactides. Moreover, the preparation of hydrogels through the formation of inclusion complexes of amylose in vine-twining polymerization was achieved.

  3. Effect of polyvinylpyrrolidone on mesoporous silica morphology and esterification of lauric acid with 1-butanol catalyzed by immobilized enzyme

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Jinyu; Zhou, Guowei, E-mail: guoweizhou@hotmail.com; Jiang, Bin; Zhao, Minnan; Zhang, Yan

    2014-05-01

    Mesoporous silica materials with a range of morphology evolution, i.e., from curved rod-shaped mesoporous silica to straight rod-shaped mesoporous silica, were successfully prepared using polyvinylpyrrolidone (PVP) and triblock copolymer as dual template. The effects of PVP molecular weight and concentration on mesoporous silica structure parameters were studied. Results showed that surface area and pore volume continuously decreased with increased PVP molecular weight. Mesoporous silica prepared with PVP K30 also possessed larger pore diameter, interplanar spacing (d{sub 100}), and cell parameter (a{sub 0}) than that prepared with PVP K15 and PVP K90. In addition, with increased PVP concentration, d{sub 100} and a{sub 0} continuously decreased. The mechanism of morphology evolution caused by the change in PVP concentration was investigated. The conversion rate of lauric acid with 1-butanol catalyzed by immobilized Porcine pancreatic lipase (PPL) was also evaluated. Results showed that PPL immobilized on amino-functionalized straight rod-shaped mesoporous silica maintained 50% of its esterification conversion rate even after five cycles of use with a maximum conversion rate was about 90.15%. - Graphical abstract: Curved rod-shaped mesoporous silica can be obtained at low and the highest PVP concentration, while straight rod-shaped mesoporous silica can be obtained at higher PVP concentration. - Highlights: • Mesoporous silica with morphology evolution from CRMS to SRMS were prepared. • Effects of PVP molecular weight and concentration on silica morphology were studied. • A possible mechanism for the formation of morphology evolution SiO{sub 2} was proposed. • Esterification of lauric acid with 1-butanol catalyzed by immobilized PPL.

  4. Preparation and thermal properties of mesoporous silica/phenolic resin nanocomposites via in situ polymerization

    Directory of Open Access Journals (Sweden)

    J. Lv

    2012-10-01

    Full Text Available In order to enhance the adhesion between inorganic particles and polymer matrix, in this paper, the mesoporous silica SBA-15 material was synthesized by the sol-gel method. The surface of SBA-15 was modified using γ-glycidyloxypropyltrimethoxysilane (GOTMS as a coupling agent, and then mesoporous silica/phenolic resin (SBA-15/PF nanocomposites were prepared via in situ polymerization. The structural parameters and physical properties of SBA-15, SBA-15-GOTMS (SBA-15 surface treated using GOTMS as coupling agents and E-SBA-15/PF (SBA-15/PF nanocomposites extracted using ethanol as solvent were characterized by X-ray diffraction (XRD, N2 adsorption-desorption, Fourier transform infrared spectroscopy (FTIR, scanning electron microscopy (SEM, transmission electron microscopy (TEM and thermogravimetric analysis (TGA. The thermal properties of the nanocomposites were studied by differential scanning calorimetry (DSC and thermogravimetric analysis (TGA. The results demonstrated that the GOTMS were successfully grafted onto the surface of SBA-15, and chemical bonds between PF and SBA-15-GOTMS were formed after in situ polymerization. In addition, it is found that the in situ polymerization method has great effects on the textural parameters of SBA-15. The results also showed that the glass transition temperatures and thermal stability of the PF nanocomposites were obviously enhanced as compared with the pure PF at silica contents between 1–3 wt%, due to the uniform dispersion of the modified SBA-15 in the matrix.

  5. Obtainment of silica nanofiber and its preliminary investigation and its effects as reinforcement in polymeric matrix

    International Nuclear Information System (INIS)

    Teixeira, R.S.; Oliveira, G.L.; Silva, F.D.C.; Teofilo, E. T.; Farias, R.C.; Menezes, R.R.

    2016-01-01

    Silica is widely used as fillers in polymers, and may confer flame retardant characteristics and improve mechanical properties. their use usually occurs as spherical nanoparticles or short fibers of. Studies using this reinforce in the form of nanofibers are promising. This analysis proposes to obtain silica nanofibers by blowspinning method in solution (SBS), and investigate its application in polymeric matrix. To synthesize the silica nanofibers it was used a precursor solution that has been subjected to SBS process and calcined for forming the silica layer. The DR-X indicated the obtainment of amorphous silica phase and SEM showed the the fibers are at the nanometer scale. Silica nanofibers were incorporated into filmogenic solution Polyamide 6. Preliminary results showed no improvement in mechanical properties. Future stages propose to verify that the surface chemical modification of silica nanofibers enables interaction charge / matrix. (author)

  6. Morphology and properties of silica/novolac hybrid xerogels synthesized using sol–gel polymerization at solvent vapor-saturated atmosphere

    International Nuclear Information System (INIS)

    Seraji, Mohamad Mehdi; Seifi, Azadeh; Bahramian, Ahmad Reza

    2015-01-01

    Highlights: • Sol–gel polymerization in vapor of solvent saturated atmosphere is developed. • Highly porous novolac–silica hybrid xerogels are successfully synthesized. • Novolac–silica hybrid gel was dried in ambient condition with low shrinkage. • Required time for preparation of gel reduced from 5 days to about 5 h. • By incorporation of silica into the novolac xerogel structure, the pore size decreases. - Abstract: Highly porous novolac–silica hybrid xerogels were successfully synthesized via the novel method of sol–gel polymerization in solvent vapor-saturated atmosphere. This method removes the need for supercritical drying and yields the hybrid xerogels with reduced shrinkage in comparison with conventional sol–gel process. Tetraethoxysilane (TEOS) was used as the precursor of silica-based inorganic phase. The chemical and structural characterization of the prepared hybrid xerogels were performed by Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM) analysis, respectively. Thermal and mechanical properties of the hybrid samples were investigated by differential scanning calorimetry (DSC), and compressive strength analysis. The resultant hybrid xerogels show a nanostructured colloidal hybrid network with high porosity (above 80%) and low density (below 0.25 g cm −3 ). Si mapping images shows the good distribution of silica phase throughout the hybrid structure

  7. Highly porous flame-retardant and sustainable biofoams based on wheat gluten and in situ polymerized silica

    DEFF Research Database (Denmark)

    Wu, Qiong; Andersson, Richard L.; Holgate, Tim

    2014-01-01

    This article presents a novel type of flame-retardant biohybrid foam with good insulation properties based on wheat gluten and silica, the latter polymerized in situ from hydrolysed tetraethyl orthosilicate (TEOS). This led to the formation of intimately mixed wheat gluten and silica phases, wher...... with a vacuum treatment to remove the largest air bubbles. X-ray photoelectron and infrared spectroscopy showed that silicon was present mainly as SiO2....

  8. Synthesis of polystyrene with high melting temperature through BDE/CuCl catalyzed polymerization

    Institute of Scientific and Technical Information of China (English)

    WAN; Xiaolong

    2001-01-01

    Lecomte, P., Drapier, I., Dubios, P. et al., Controlled radical polymerization of methyl methacrylate in the presence of palladium acetate, triphenyl phosphine, and carbon tetrachloride, Macromolecules, 1997, 30: 7631.[12]Kotani, Y., Kamigaito, Y., Sawamoto, M., Re(V)-mediated living radical polymerization of styrene: ReO2I(PPh3)2/RI initiating system, Macromolecules, 1999, 32: 2420.[13]Makino, T., Tokunaga, E., Hogen-Esch, T. E., Controlled atom transfer radical polymerizations of methyl methacrylate under micellar conditions, Polym. Prep., 1998, 39(1): 288.[14]Gaynor, S. G., Qiu, J., Matyjaszewski, K., Controlled/"living" radical polymerization applied to water-borne system, Macromolecule, 1998, 31: 5951.[15]Qiu, J., Gaynor, S. G., Matyjaszewski, K., Controlled/"living" radical polymerization of n-butyl methacrylate by reverse atom transfer radical polymerization, Macromolecules, 1999, 32: 2872.[16]Shipp, D. A., McMurtry, G. P., Gaynor, S. G. et al., Water-borne block copolymer synthesis and a simple and effective one-pot synthesis of acrylate-methacrylate block copolymers by atom transfer radical polymerization, Polym. Prep., 1999, 40(2): 448.[17]Nishikawa, T., Kamigaito, M., Sawamoto, M., Living radical polymerization in water and alcohols: suspension polymerization of methyl methacrylate with RuCl2(PPh3)3 complex, Macromolecules, 1999, 32: 2204.[18]Wan, X. L., Ying, S. K., "Living" radical emulsion polymerization of styrene under Cu0/Bpy/CCl4 and CuCl2/Bpy/AIBN system, Chinese J. Polym. Sci., 2000, (1): 27.[19]Wan, X. L., Ying, S. K., Controlled radical polymerization catalyzed by Cu/BDE complex in water medium, 1. Polymerization of styrene and synthesis of poly(St-b-MMA), J. Appl. Polym. Sci., 2000, 75(1): 802.[20]Wan, X. L., Ying, S. K., Synthesis of block copolymers by emulsion "living"/controlled radical polymerization of vinyl monomers in sequence, Polym. Prep., 1999, 40: 1055.[21]Keller, R. N., Wycoff, H. D., The synthesis

  9. Superhydrophobic Surfaces with Very Low Hysteresis Prepared by Aggregation of Silica Nanoparticles During In Situ Urea-Formaldehyde Polymerization.

    Science.gov (United States)

    Diwan, Anubhav; Jensen, David S; Gupta, Vipul; Johnson, Brian I; Evans, Delwyn; Telford, Clive; Linford, Matthew R

    2015-12-01

    We present a new method for the preparation of superhydrophobic materials by in situ aggregation of silica nanoparticles on a surface during a urea-formaldehyde (UF) polymerization. This is a one-step process in which a two-tier topography is obtained. The polymerization is carried out for 30, 60, 120, 180, and 240 min on silicon shards. Silicon surfaces are sintered to remove the polymer. SEM and AFM show both an increase in the area covered by the nanoparticles and their aggregation with increasing polymerization time. Chemical vapor deposition of a fluorinated silane in the presence of a basic catalyst gives these surfaces hydrophobicity. Deposition of this low surface energy silane is confirmed by the F 1s signal in XPS. The surfaces show advancing water contact angles in excess of 160 degrees with very low hysteresis (polymerization times for 7 nm and 14 nm silica, respectively. Depositions are successfully demonstrated on glass substrates after they are primed with a UF polymer layer. Superhydrophobic surfaces can also be prepared on unsintered substrates.

  10. Lipase catalyzed HEMA initiated ring-opening polymerization: In situ formation of mixed polyester methacrylates by transesterification

    NARCIS (Netherlands)

    Takwa, M.; Xiao, Y.; Simpson, N.; Malmstrom, E.; Hult, K.; Koning, C.E.; Heise, A.; Martinelle, M.

    2008-01-01

    2-Hydroxyethyl methacrylate (HEMA) was used as initiator for the enzymatic ring-opening polymerization (ROP) of ¿-pentadecalactone (PDL) and e-caprolactone (CL). The lipase B from Candida antarctica was found to catalyze the cleavage of the ester bond in the HEMA end group of the formed polyesters,

  11. Thermal and Mechanical Properties of Novolac-Silica Hybrid Aerogels Prepared by Sol-Gel Polymerization in Solvent-Saturated Vapor Atmosphere

    Directory of Open Access Journals (Sweden)

    Mohamad Mehdi Seraji1, Seraji

    2015-05-01

    Full Text Available Nowadays organic–inorganic hybrid aerogel materials have attracted increasing interests due to improved thermal and mechanical properties. In the present research, initially, novolac type phenolic resin-silica hybrid gels with different solid concentrations were synthesized using sol-gel polymerization in solvent-saturatedvapor atmosphere. The hybrid gels were dried at air atmosphere through ambient drying process. This method removed the need for costly and risky supercritical drying process. The yields of the obtained hybrid aerogels increased with less shrinkage in comparison with conventional sol-gel process. The precursor of silica phase in this study was tetraethoxysilane and inexpensive novolac resin was used as a reinforcing phase. The results of FTIR analysis confirmed the simultaneous formation of silica and novolac gels in the hybrid systems. The resultant hybrid aerogels showed a nanostructure hybrid network with high porosity (above 80% and low density (below 0.25 g/cm3. Nonetheless, higher content of silica resulted in more shrinkage in the hybrid aerogel structure due to the tendency of the silica network to shrink more during gelation and drying process. The SEM images of samples exhibited a continuous network of interconnected colloidal particles formed during sol-gel polymerization with mean particle size of less than 100 nanometers. Si mapping analysis showed good distribution of silica phase throughout the hybrid structure. The results demonstrated improvements in insulation properties and thermal stability of novolac-silica aerogel with increasing the silica content. The results of compressive strength showed that the mechanical properties of samples declined with increasing the silica content.

  12. Activators generated by electron transfer for atom transfer radical polymerization of styrene in the presence of mesoporous silica nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Khezri, Khezrollah, E-mail: kh.khezri@ut.ac.ir [School of Chemistry, University College of Science, University of Tehran, PO Box 14155-6455, Tehran (Iran, Islamic Republic of); Roghani-Mamaqani, Hossein [Department of Polymer Engineering, Sahand University of Technology, PO Box 51335-1996, Tabriz (Iran, Islamic Republic of)

    2014-11-15

    Graphical abstract: Effect of mesoporous silica nanoparticles (MCM-41) on the activator generated by electron transfer for atom transfer radical polymerization (AGET ATRP) is investigated. Decrement of conversion and number average molecular weight and also increment of polydispersity index (PDI) values are three main results of addition of MCM-41 nanoparticles. Incorporation of MCM-41 nanoparticles in the polystyrene matrix can clearly increase thermal stability and decrease glass transition temperature of the nanocomposites. - Highlights: • Spherical morphology, hexagonal structure, and high surface area with regular pore diameters of the synthesized MCM-41 nanoparticles are examined. • AGET ATRP of styrene in the presence of MCM-41 nanoparticles is performed. • Effect of MCM-41 nanoparticles addition on the polymerization rate, conversion and molecular weights of the products are discussed. • Improvement in thermal stability of the nanocomposites and decreasing T{sub g} values was also observed by incorporation of MCM-41 nanoparticles. - Abstract: Activator generated by electron transfer for atom transfer radical polymerization was employed to synthesize well-defined mesoporous silica nanoparticles/polystyrene composites. Inherent features of spherical mesoporous silica nanoparticles were evaluated by nitrogen adsorption/desorption isotherm, X-ray diffraction and scanning electron microscopy analysis techniques. Conversion and molecular weight evaluations were carried out using gas and size exclusion chromatography respectively. By the addition of only 3 wt% mesoporous silica nanoparticles, conversion decreases from 81 to 58%. Similarly, number average molecular weight decreases from 17,116 to 12,798 g mol{sup −1}. However, polydispersity index (PDI) values increases from 1.24 to 1.58. A peak around 4.1–4.2 ppm at proton nuclear magnetic resonance spectroscopy results clearly confirms the living nature of the polymerization. Thermogravimetric

  13. Polymerization of 5-alkyl δ-lactones catalyzed by diphenyl phosphate and their sequential organocatalytic polymerization with monosubstituted epoxides

    KAUST Repository

    Zhao, Junpeng

    2015-02-04

    Organocatalytic ring-opening polymerization (ROP) reactions of three renewable 5-alkyl δ-lactones, namely δ-hexalactone (HL), δ-nonalactone (NL) and δ-decalactone (DL), using diphenyl phosphate (DPP) were investigated. Room temperature, together with a relatively high monomer concentration (≥3 M), was demonstrated to be suitable for achieving a living ROP behavior, a high conversion of the lactone, a controlled molecular weight and a low dispersity of the polyester. HL, containing a 5-methyl substituent, showed a much higher reactivity (polymerization rate) and a slightly higher equilibrium conversion than the compounds with longer alkyl substituents (NL and DL). The effectiveness of DPP-catalyzed ROP of 5-alkyl δ-lactones facilitated the one-pot performance following the t-BuP4-promoted ROP of monosubstituted epoxides. It has been shown in an earlier study that substituted polyethers acted as "slow initiators" for non-substituted lactones. However, efficient initiations were observed in the present study as substituted lactones were polymerized from the substituted polyethers. Therefore, this reinforces the previously developed "catalyst switch" strategy, making it a more versatile tool for the synthesis of well-defined polyether-polyester block copolymers from a large variety of epoxide and lactone monomers. © The Royal Society of Chemistry 2015.

  14. Synthesis of nanocrystalline LaF3 doped silica glasses by hydrofluoric acid catalyzed sol–gel process

    International Nuclear Information System (INIS)

    Nagayama, Shuhei; Kajihara, Koichi; Kanamura, Kiyoshi

    2012-01-01

    Highlights: ► Silica glasses doped by LaF 3 nanocrystals are obtained by HF-catalyzed sol–gel method. ► The processing time (∼1 week) is much shorter than that of previous studies. ► The uptake of SiF groups in the glass matrix greatly reduces the SiOH concentration. ► Effects of sintering conditions and properties of Er 3+ -doped samples are presented. - Abstract: Silica glasses doped with LaF 3 nanocrystals were prepared by HF-catalyzed sol–gel method. HF was used both as fluorine source and as catalyst of the sol–gel reaction, making it possible to shorten the processing time with reducing the concentration of SiOH groups to ∼10 18 cm −3 . The resultant glasses are transparent at visible spectral range, and the optical loss at the ultraviolet absorption edge is dominated by the Rayleigh scattering from LaF 3 crystallites. The size of LaF 3 crystallites increases with an increase in the sintering temperature and time, and is smaller than ∼40 nm in samples showing good visible transparency. Green upconversion photoluminescence is observed in an Er 3+ -doped sample under excitation at 980 nm.

  15. Structural evolution of silica sols modified with formamide

    Directory of Open Access Journals (Sweden)

    Lenza R.F.S.

    2001-01-01

    Full Text Available In this work we investigated the influence of formamide on the acid-catalyzed sol-gel process by Fourier transform infrared spectroscopy (FTIR. Three silica sols were studied: Sol catalyzed with nitric acid without formamide, sol catalyzed with nitric acid containing formamide and sol catalyzed with a mixture of nitric acid and hydrofluoric acid and modified with formamide. Following the time evolution of both the Si-(OH stretching vibration at around 950 cm-1 and the Si-O-(Si vibration between 1040 cm-1 and 1200 cm-1 we were able to describe the structural evolution of each sol. The curve of evolution of Si-(OH stretching vibration corresponding to sol A has a simple asymptotic evolution. In the case of formamide containing sol, we observed a two-step structural evolution indicating that for the system containing formamide the polymerization goes through a temporary stabilization of oligomers, which can explain the non-variation of the Si-O(H bond wavenumber for a certain time. Gelation times were of several days for gels without formamide and few hours for gels containing additive. The presence of additive resulted in a highly interconnected gel.

  16. Polymeric-silica-based sols for membrane modification applications: sol-gel synthesis and characterization with SAXS

    NARCIS (Netherlands)

    de Lange, Rob; de Lange, R.S.A.; Hekkink, J.H.A.; Hekkink, J.H.A.; Keizer, Klaas; Burggraaf, Anthonie; Burggraaf, A.J.

    1995-01-01

    Polymeric SiO2 and binary SiO2/TiO2, SiO2/ZrO2 and SiO2/Al2O3 sols, for ceramic membrane modification applications, have been prepared by acid-catalyzed hydrolysis and condensation of alkoxides in alcohol. The sols were characterized with small angle X-ray scattering, using synchrotron radiation.

  17. Coating of calcia-doped ceria with amorphous silica shell by seeded polymerization technique

    International Nuclear Information System (INIS)

    El-Toni, Ahmed Mohamed; Yin, Shu; Yabe, Shinryo; Sato, Tsugio

    2005-01-01

    Calcia-doped ceria is of potential interest as an ultraviolet (UV) radiation blocking material in personal care products. However, its high catalytic ability for oxidation of organic materials makes it difficult to use as a sunscreen material. Therefore, calcia-doped ceria was coated with amorphous silica by means of seeded polymerization technique in order to depress its oxidation catalytic ability. The catalytic ability as well as UV-shielding ability was investigated for coated particles

  18. Atom Transfer Radical Polymerization of Styrene in Presence of Mesoporous Silica Nanoparticles: Application of Reverse, Simultaneous Reverse and Normal Initiation Techniques

    Directory of Open Access Journals (Sweden)

    Khezrollah Khezri

    2014-04-01

    Full Text Available Atom transfer radical polymerization (ATRP of styrene in presence of mesoporous silica nanoparticles was carried out at 110 °C. Reverse atom transfer radical polymerization (RATRP and simultaneous reverse and normal initiation for atom transfer radical polymerization (SR&NI ATRP techniques were used as two appropriate introduced techniques for circumventing oxidation problems. Usage of metal catalyst in its higher oxidation state was the main feature of these initiation techniques in which deficiencies of normal ATRP were circumvented. Structure, surface area and pore diameter of synthesized mesoporous silica nanoparticles were evaluated using X–ray diffraction and nitrogen adsorption/desorption isotherm analysis. Average particle size was estimated around 600 nm by electron microscopy images. In addition, according to these images, nanoparticles revealed an appropriate size distribution. Particles size and their distribution were examined using scanning. Final monomer conversion was determined by using gas chromatography. The number and weight average molecular weights (Mn and Mw and polydispersity indexes (PDI were also evaluated by gel permeation chromatography. According to the results obtained, addition of mesoporous silica nanoparticles in both RATRP and SR&NI ATRP systems revealed similar effects: decrement of conversion and Mn and also increment of PDI values observed by increasing of mesoporous silica nanoparticles content. Improvement in thermal stability of the nanocomposites in comparison with neat polystyrene was demonstrated by thermogravimetric analysis (TGA. Moreover, in case of nanocomposites, thermal stability was obtained by higher loading of nanoparticles. A decrease in glass transition temperature by higher content of mesoporous silica nanoparticles has been demonstrated by differential scanning calorimetry analysis.

  19. Preparation of Mesoporous Carbons from Acrylonitrile-methyl Methacrylate Copolymer/Silica Nanocomposites Synthesized by in-situ Emulsion Polymerization

    Institute of Scientific and Technical Information of China (English)

    BAO Yongzhong; ZHAO Wenting; HUANG Zhiming

    2013-01-01

    Acrylonitrile-methyl methacrylate (AN-MMA) copolymer/silica nanocomposites were synthesized by in-situ emulsion polymerization initiated by 2,2′-azobis(2-amidinopropane) dihydrochloride absorbed onto colloidal silica particles,and the mesoporous carbon materials were prepared through carbonization of the obtained AN-MMA copolymer/silica nanocomposites,followed by HF etching.Thermogravimetric analysis of AN-MMA copolymer/silica nanocomposites showed that the carbon yield of copolymer was slightly decreased as silica particle incorporated.N2 adsorption-desorption,scan electron microscopy (SEM) and transmission electron microscopy (TEM) were used to characterize the structure and morphology of the mesoporous carbon materials.Both SEM and TEM results showed that disordered mesopores were formed in the obtained carbon material mainly through templating effect of silica nanoparticles.The diameter of mesopores was mainly distributed in the range from 5 nm to 15 nm.The mean pore diameter and total pore volume of the material increased as the mass fraction of silica in the nanocomposites increased from 0 to 24.93%.The significant increase of the mean pore diameter and the decrease of surface area for the carbon material prepared from the nanocomposite with 24.93% silica were caused by partial aggregation of silica nanoparticles in the polymer matrix.

  20. Study of radiation-induced polymerization of vinyl monomers adsorbed on inorganic substances. VIII. Polymerization of styrene and methyl methacrylate adsorbed on aerosil

    International Nuclear Information System (INIS)

    Fukano, K.; Kageyama, E.

    1976-01-01

    Aerosol is silica having a purity which is very high compared with that of silica gel and having, unlike silica gel, no micropores. To investigate the effects of impurities and micropores on the radiation-induced polymerization of styrene and methyl methacrylate adsorbed on silica gel, the radiation-induced polymerization of styrene and methyl methacrylate adsorbed on Aerosil was carried out. The results of both the styrene--Aerosil 300 system and the methyl methacrylate--Aerosil 300 system were similar to those of the styrene-silica gel and methyl methacrylate-silica gel systems, respectively. This suggests that in the radiation-induced polymerization of both styrene--silica gel and methyl methacrylate--silica gel systems the impurities and the presence of micropores have almost no effect on the reaction mechanism. The effect of aluminum as an impurity was investigated on the styrene--Aerosil MOX 170 system. It was found that aluminum accelerated the cationic polymerization

  1. A comprehensive study of soft magnetic materials based on FeSi spheres and polymeric resin modified by silica nanorods

    International Nuclear Information System (INIS)

    Strečková, M.; Füzer, J.; Kobera, L.; Brus, J.; Fáberová, M.; Bureš, R.; Kollár, P.; Lauda, M.; Medvecký, Ĺ.; Girman, V.; Hadraba, H.; Bat'ková, M.; Bat'ko, I.

    2014-01-01

    A novel soft magnetic composite (SMC) based on spherical FeSi particles precisely covered by hybrid phenolic resin was designed. The hybrid resin including silica nano-rods chemically incorporated into the phenolic polymer matrix was prepared by the modified sol–gel method. A chemical bridge connecting silica nano-rods with the base polymeric net was verified by FTIR, 13 C and 29 Si NMR spectroscopy, whereas the shape and size of silica nano-rods were determined by TEM. It is shown that the modification of polymeric resin by silica nano-rods generally leads to the improved thermal and mechanical properties of the final samples. The hybrid resin serves as a perfect insulating coating deposited on FeSi particles and the core–shell particles can be further compacted by standard powder metallurgy methods in order to prepare final samples for mechanical, electric and magnetic testing. SEM images evidence negligible porosity, uniform distribution of the hybrid resin around FeSi particles, as well as, dimensional shape stability of the final samples after thermal treatment. The hardness, flexural strength and density of the final samples are comparable to the sintered SMCs, but they simultaneously exhibit much higher specific resistivity along with only slightly lower coercivity and permeability. - Highlights: • Soft magnetic composites are designed for electrotechnical applications. • Electroinsulating layer consists of phenolic resin modified with silica nano-rods. • NMR, FTIR and DSC analysis is used to characterize hybrid resin. • Spherical Fe–Si particles covered by hybrid resin form a core–shell composite. • Mechanical, electrical and magnetic properties are described in detail

  2. In vitro reconstitution of sortase-catalyzed pilus polymerization reveals structural elements involved in pilin cross-linking.

    Science.gov (United States)

    Chang, Chungyu; Amer, Brendan R; Osipiuk, Jerzy; McConnell, Scott A; Huang, I-Hsiu; Hsieh, Van; Fu, Janine; Nguyen, Hong H; Muroski, John; Flores, Erika; Ogorzalek Loo, Rachel R; Loo, Joseph A; Putkey, John A; Joachimiak, Andrzej; Das, Asis; Clubb, Robert T; Ton-That, Hung

    2018-06-12

    Covalently cross-linked pilus polymers displayed on the cell surface of Gram-positive bacteria are assembled by class C sortase enzymes. These pilus-specific transpeptidases located on the bacterial membrane catalyze a two-step protein ligation reaction, first cleaving the LPXTG motif of one pilin protomer to form an acyl-enzyme intermediate and then joining the terminal Thr to the nucleophilic Lys residue residing within the pilin motif of another pilin protomer. To date, the determinants of class C enzymes that uniquely enable them to construct pili remain unknown. Here, informed by high-resolution crystal structures of corynebacterial pilus-specific sortase (SrtA) and utilizing a structural variant of the enzyme (SrtA 2M ), whose catalytic pocket has been unmasked by activating mutations, we successfully reconstituted in vitro polymerization of the cognate major pilin (SpaA). Mass spectrometry, electron microscopy, and biochemical experiments authenticated that SrtA 2M synthesizes pilus fibers with correct Lys-Thr isopeptide bonds linking individual pilins via a thioacyl intermediate. Structural modeling of the SpaA-SrtA-SpaA polymerization intermediate depicts SrtA 2M sandwiched between the N- and C-terminal domains of SpaA harboring the reactive pilin and LPXTG motifs, respectively. Remarkably, the model uncovered a conserved TP(Y/L)XIN(S/T)H signature sequence following the catalytic Cys, in which the alanine substitutions abrogated cross-linking activity but not cleavage of LPXTG. These insights and our evidence that SrtA 2M can terminate pilus polymerization by joining the terminal pilin SpaB to SpaA and catalyze ligation of isolated SpaA domains in vitro provide a facile and versatile platform for protein engineering and bio-conjugation that has major implications for biotechnology.

  3. Synthesis and characterisation of polymeric nanofibers poly (vinyl alcohol) and poly (vinyl alcohol)/silica using indigenous electrospinning set up

    International Nuclear Information System (INIS)

    Sasipriya, K.; Suriyaprabha, R.; Prabu, P.; Rajendran, V.

    2013-01-01

    Indigenous design and fabrication horizontal of electrospinning set up was developed to facilitate with double drum conveyor belt system to make ease in harvesting nanofibers rapidly. As a bench mark study, organic-inorganic nanofiber composite was synthesised employing our indigenous electrospinning set up. The aqueous solution of poly (vinyl alcohol) and poly (vinyl alcohol)/silica sol were employed to produce nanofiber mats in order to vary the experimental parameters such as voltage, solvent effect and the effect of catalyst. The synthesised pure electro spun poly (vinyl alcohol) and poly (vinyl alcohol)/silica sol fibers were characterized by Scanning electron microscopy (SEM), Atomic force microscopy (AFM) and Fourier transform infra red spectroscopy (FTIR). According to the results, the fine polymeric nanofibers were achieved in the size range of 100-500 nm for pure poly (vinyl alcohol) fiber and 100-700 nm for polyvinyl alcohol/silica and the constitution of silica in rendering better fiber mats with this double drum set up. (author)

  4. Synthesis and characterisation of polymeric nanofibers poly (vinyl alcohol) and poly (vinyl alcohol)/silica using indigenous electrospinning set up

    Energy Technology Data Exchange (ETDEWEB)

    Sasipriya, K.; Suriyaprabha, R.; Prabu, P.; Rajendran, V., E-mail: veerajendran@gmail.com [Centre for Nanoscience and Technology, K. S. Rangasamy College of Technology, Tamil Nadu (India)

    2013-11-01

    Indigenous design and fabrication horizontal of electrospinning set up was developed to facilitate with double drum conveyor belt system to make ease in harvesting nanofibers rapidly. As a bench mark study, organic-inorganic nanofiber composite was synthesised employing our indigenous electrospinning set up. The aqueous solution of poly (vinyl alcohol) and poly (vinyl alcohol)/silica sol were employed to produce nanofiber mats in order to vary the experimental parameters such as voltage, solvent effect and the effect of catalyst. The synthesised pure electro spun poly (vinyl alcohol) and poly (vinyl alcohol)/silica sol fibers were characterized by Scanning electron microscopy (SEM), Atomic force microscopy (AFM) and Fourier transform infra red spectroscopy (FTIR). According to the results, the fine polymeric nanofibers were achieved in the size range of 100-500 nm for pure poly (vinyl alcohol) fiber and 100-700 nm for polyvinyl alcohol/silica and the constitution of silica in rendering better fiber mats with this double drum set up. (author)

  5. Synthesis and characterisation of polymeric nanofibers poly (vinyl alcohol and poly (vinyl alcohol/silica using indigenous electrospinning set up

    Directory of Open Access Journals (Sweden)

    K. Sasipriya

    2013-01-01

    Full Text Available Indigenous design and fabrication horizontal of electrospinning set up was developed to facilitate with double drum conveyor belt system to make ease in harvesting nanofibers rapidly. As a bench mark study, organic-inorganic nanofiber composite was synthesised employing our indigenous electrospinning set up. The aqueous solution of poly (vinyl alcohol and poly (vinyl alcohol/silica sol were employed to produce nanofiber mats in order to vary the experimental parameters such as voltage, solvent effect and the effect of catalyst. The synthesised pure electro spun poly (vinyl alcohol and poly (vinyl alcohol/silica sol fibers were characterized by Scanning electron microscopy (SEM, Atomic force microscopy (AFM and Fourier transform infra red spectroscopy (FTIR. According to the results, the fine polymeric nanofibers were achieved in the size range of 100-500 nm for pure poly (vinyl alcohol fiber and 100-700 nm for polyvinyl alcohol/silica and the constitution of silica in rendering better fiber mats with this double drum set up.

  6. Polymeric carbon nitride/mesoporous silica composites as catalyst support for Au and Pt nanoparticles.

    Science.gov (United States)

    Xiao, Ping; Zhao, Yanxi; Wang, Tao; Zhan, Yingying; Wang, Huihu; Li, Jinlin; Thomas, Arne; Zhu, Junjiang

    2014-03-03

    Small and homogeneously dispersed Au and Pt nanoparticles (NPs) were prepared on polymeric carbon nitride (CNx )/mesoporous silica (SBA-15) composites, which were synthesized by thermal polycondensation of dicyandiamide-impregnated preformed SBA-15. By changing the condensation temperature, the degree of condensation and the loading of CNx can be controlled to give adjustable particle sizes of the Pt and Au NPs subsequently formed on the composites. In contrast to the pure SBA-15 support, coating of SBA-15 with polymeric CNx resulted in much smaller and better-dispersed metal NPs. Furthermore, under catalytic conditions the CNx coating helps to stabilize the metal NPs. However, metal NPs on CNx /SBA-15 can show very different catalytic behaviors in, for example, the CO oxidation reaction. Whereas the Pt NPs already show full CO conversion at 160 °C, the catalytic activity of Au NPs seems to be inhibited by the CNx support. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Synthesis and silica coating of calcia-doped ceria/plate-like titanate (K0.8Li0.27Ti1.73O4) nanocomposite by seeded polymerization technique

    International Nuclear Information System (INIS)

    El-Toni, Ahmed Mohamed; Yin, Shu; Sato, Tsugio

    2007-01-01

    Calcia-doped ceria is of potential interest as an ultraviolet (UV) radiation blocking material in personal care products because of the excellent UV light absorption property and low catalytic ability for the oxidation of organic materials superior to undoped ceria. In order to reduce the oxidation catalytic activity further, calcia-doped ceria was coated with amorphous silica by means of seeded polymerization technique. Generally, nanoparticles of inorganic materials do not provide a good coverage for human skin because of the agglomeration of the particles. The plate-like particles are required to enhance the coverage ability of inorganic materials. This can be accomplished by synthesis of calcia-doped ceria/plate-like potassium lithium titanate (K 0.8 Li 0.27 Ti 1.73 O 4 ) nanocomposite with subsequent silica coating to control catalytic activity of calcia-doped ceria. Calcia-doped ceria/plate-like potassium lithium titanate nanocomposite was prepared by soft chemical method followed by silica coating via seeded polymerization technique. Silica coated calcia-doped ceria/plate-like potassium lithium titanate nanocomposite was characterized by X-ray diffraction, SEM, TEM, XPS and FT-IR

  8. Application of mercapto-silica polymerized high internal phase emulsions for the solid-phase extraction and preconcentration of trace lead(II).

    Science.gov (United States)

    Su, Rihui; Ruan, Guihua; Chen, Zhengyi; Du, Fuyou; Li, Jianping

    2015-12-01

    A new class of solid-phase extraction column prepared with grafted mercapto-silica polymerized high internal phase emulsion particles was used for the preconcentration of trace lead. First, mercapto-silica polymerized high internal phase emulsion particles were synthesized by using high internal phase emulsion polymerization and carefully assembled in a polyethylene syringe column. The influences of various parameters including adsorption pH value, adsorption and desorption solvents, flow rate of the adsorption and desorption procedure were optimized, respectively, and the suitable uploading sample volumes, adsorption capacity, and reusability of solid phase extraction column were also investigated. Under the optimum conditions, Pb(2+) could be preconcentrated quantitatively over a wide pH range (2.0-5.0). In the presence of foreign ions, such as Na(+) , K(+) , Ca(2+) , Zn(2+) , Mg(2+) , Cu(2+) , Fe(2+) , Cd(2+) , Cl(-) and NO3 (-) , Pb(2+) could be recovered successfully. The prepared solid-phase extraction column performed with high stability and desirable durability, which allowed more than 100 replicate extractions without measurable changes of performance. The feasibility of the developed method was further validated by the extraction of Pb(2+) in rice samples. At three spiked levels of 40.0, 200 and 800 μg/kg, the average recoveries for Pb(2+) in rice samples ranged from 87.3 to 105.2%. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Fabrication of high-capacity polyelectrolyte brush-grafted porous AAO-silica composite membrane via RAFT polymerization.

    Science.gov (United States)

    Song, Cunfeng; Wang, Meijie; Liu, Xin; Wang, He; Chen, Xiaoling; Dai, Lizong

    2017-09-01

    Surface-initiated reversible addition-fragmentation chain transfer (RAFT) polymerization has been utilized to fabricate high-capacity strong anion-exchange (AEX) membrane for the separation of protein. By means of RAFT polymerization, quaternized poly(3-(methacrylamidomethyl)-pyridine) brushes formed 3-dimensional nanolayers on the surface of porous anodic aluminum oxide (AAO)-silica composite membrane. The surface properties of the membranes were analyzed by SEM, water contact angle, ATR-FTIR, XPS and TGA. To investigate the adsorption performance, the new AEX membranes were applied to recover a model protein, ovalbumin (OVA). High adsorption capacities of 95.8mg/g membranes (static) and 65.3mg/g membranes (dynamic) were obtained at ambient temperature. In the further studies, up to 90% of the adsorbed OVA was efficiently eluted by using phosphate buffer-1M NaCl as elution medium. The successful separation of OVA with high purity from a mixture protein solution was also achieved by using the AEX membranes. The present study demonstrated that under mild reaction condition, RAFT polymerization can be used to fabricate ion-exchange membrane which has many remarkable features, such as high capacity and selectivity, easy elution and so on. Copyright © 2017. Published by Elsevier B.V.

  10. Precision Synthesis of Functional Polysaccharide Materials by Phosphorylase-Catalyzed Enzymatic Reactions

    Directory of Open Access Journals (Sweden)

    Jun-ichi Kadokawa

    2016-04-01

    Full Text Available In this review article, the precise synthesis of functional polysaccharide materials using phosphorylase-catalyzed enzymatic reactions is presented. This particular enzymatic approach has been identified as a powerful tool in preparing well-defined polysaccharide materials. Phosphorylase is an enzyme that has been employed in the synthesis of pure amylose with a precisely controlled structure. Similarly, using a phosphorylase-catalyzed enzymatic polymerization, the chemoenzymatic synthesis of amylose-grafted heteropolysaccharides containing different main-chain polysaccharide structures (e.g., chitin/chitosan, cellulose, alginate, xanthan gum, and carboxymethyl cellulose was achieved. Amylose-based block, star, and branched polymeric materials have also been prepared using this enzymatic polymerization. Since phosphorylase shows a loose specificity for the recognition of substrates, different sugar residues have been introduced to the non-reducing ends of maltooligosaccharides by phosphorylase-catalyzed glycosylations using analog substrates such as α-d-glucuronic acid and α-d-glucosamine 1-phosphates. By means of such reactions, an amphoteric glycogen and its corresponding hydrogel were successfully prepared. Thermostable phosphorylase was able to tolerate a greater variance in the substrate structures with respect to recognition than potato phosphorylase, and as a result, the enzymatic polymerization of α-d-glucosamine 1-phosphate to produce a chitosan stereoisomer was carried out using this enzyme catalyst, which was then subsequently converted to the chitin stereoisomer by N-acetylation. Amylose supramolecular inclusion complexes with polymeric guests were obtained when the phosphorylase-catalyzed enzymatic polymerization was conducted in the presence of the guest polymers. Since the structure of this polymeric system is similar to the way that a plant vine twines around a rod, this polymerization system has been named

  11. Nucleation of polystyrene latex particles in the presence of gamma-methacryloxypropyltrimethoxysilane: functionalized silica particles.

    Science.gov (United States)

    Bourgeat-Lami, Elodie; Insulaire, Mickaelle; Reculusa, Stéphane; Perro, Adeline; Ravaine, Serge; Duguet, Etienne

    2006-02-01

    Silica/polystyrene nanocomposite particles with different morphologies were synthesized through emulsion polymerization of styrene in the presence of silica particles previously modified by gamma-methacryloxypropyltrimethoxysilane (MPS). Grafting of the silane molecule was performed by direct addition of MPS to the aqueous silica suspension in the presence of an anionic surfactant under basic conditions. The MPS grafting density on the silica surface was determined using the depletion method and plotted against the initial MPS concentration. The influence of the MPS grafting density, the silica particles size and concentration and the nature of the surfactant on the polymerization kinetics and the particles morphology was investigated. When the polymerization was performed in the presence of an anionic surfactant, transmission electron microscopy images showed the formation of polymer spheres around silica for MPS grafting densities lower than typically 1 micromole x m(-2) while the conversion versus time curves indicated a strong acceleration effect under such conditions. In contrast, polymerizations performed in the presence of a larger amount of MPS moieties or in the presence of a non ionic emulsifier resulted in the formation of "excentered" core-shell morphologies and lower polymerization rates. The paper identifies the parameters that allow to control particles morphology and polymerization kinetics and describes the mechanism of formation of the nanocomposite colloids.

  12. Polymerization Using Phosphazene Bases

    KAUST Repository

    Zhao, Junpeng

    2015-09-01

    In the recent rise of metal-free polymerization techniques, organic phosphazene superbases have shown their remarkable strength as promoter/catalyst for the anionic polymerization of various types of monomers. Generally, the complexation of phosphazene base with the counterion (proton or lithium cation) significantly improves the nucleophilicity of the initiator/chain end resulting in highly enhanced polymerization rates, as compared with conventional metalbased initiating systems. In this chapter, the general features of phosphazenepromoted/catalyzed polymerizations and the applications in macromolecular engineering (synthesis of functionalized polymers, block copolymers, and macromolecular architectures) are discussed with challenges and perspectives being pointed out.

  13. Polymerization Using Phosphazene Bases

    KAUST Repository

    Zhao, Junpeng; Hadjichristidis, Nikolaos; Schlaad, Helmut

    2015-01-01

    . In this chapter, the general features of phosphazenepromoted/catalyzed polymerizations and the applications in macromolecular engineering (synthesis of functionalized polymers, block copolymers, and macromolecular architectures) are discussed with challenges

  14. The One-Step Pickering Emulsion Polymerization Route for Synthesizing Organic-Inorganic Nanocomposite Particles

    Directory of Open Access Journals (Sweden)

    Kaushal Rege

    2010-02-01

    Full Text Available Polystyrene-silica core-shell nanocomposite particles are successfully prepared via one-step Pickering emulsion polymerization. Possible mechanisms of Pickering emulsion polymerization are addressed in the synthesis of polystyrene-silica nanocomposite particles using 2,2-azobis(2-methyl-N-(2-hydroxyethylpropionamide (VA-086 and potassium persulfate (KPS as the initiator. Motivated by potential applications of “smart” composite particles in controlled drug delivery, the one-step Pickering emulsion polymerization route is further applied to synthesize polystyrene/poly(N-isopropylacrylamide (PNIPAAm-silica core-shell nanoparticles with N-isopropylacrylamide incorporated into the core as a co-monomer. The polystyrene/PNIPAAm-silica composite nanoparticles are temperature sensitive and can be taken up by human prostate cancer (PC3-PSMA cells.

  15. Thiolated Chitosan Masked Polymeric Microspheres with Incorporated Mesocellular Silica Foam (MCF for Intranasal Delivery of Paliperidone

    Directory of Open Access Journals (Sweden)

    Stavroula Nanaki

    2017-11-01

    Full Text Available In this study, mesocellular silica foam (MCF was used to encapsulate paliperidone, an antipsychotic drug used in patients suffering from bipolar disorder. MCF with the drug adsorbed was further encapsulated into poly(lactic acid (PLA and poly(lactide-co-glycolide (PLGA 75/25 w/w microspheres and these have been coated with thiolated chitosan. As found by TEM analysis, thiolated chitosan formed a thin layer on the polymeric microspheres’ surface and was used in order to enhance their mucoadhesiveness. These microspheres aimed at the intranasal delivery of paliperidone. The DSC and XRD studies showed that paliperidone was encapsulated in amorphous form inside the MCF silica and for this reason its dissolution profile was enhanced compared to the neat drug. In coated microspheres, thiolated chitosan reduced the initial burst effect of the paliperidone dissolution profile and in all cases sustained release formulations have been prepared. The release mechanism was also theoretically studied and three kinetic models were proposed and successfully fitted for a dissolution profile of prepared formulations to be found.

  16. Unraveling the role of entropy in tuning unimolecular vs . bimolecular reaction rates: The case of olefin polymerization catalyzed by transition metals

    KAUST Repository

    Falivene, Laura

    2018-04-24

    Olefin polymerization catalyzed by Group 4 transition metals is studied here as test case to reveal the entropy effects when bimolecular and unimolecular reactions are computed for processes occurring in solution. Catalytic systems characterized by different ligand frameworks, metal, and growing polymeric chain for which experimental data are available have been selected in order to validate the main approaches to entropy calculation. Applying the “standard” protocol results in a strong disagreement with the experimental results and the methods introducing a direct correction of the translational entropy term based on a single experimental parameter emerge as the most reliable. The general and powerful computational tool achieved in this study can represent a further step towards the “catalyst design” to control and predict the molecular mass of the resulting polymers.

  17. Synthesis of PANi-SiO2 Nanocomposite with In-Situ Polymerization Method: Nanoparticle Silica (NPS) Amorphous and Crystalline Phase

    Science.gov (United States)

    Munasir; Luvita, N. R. D.; Kusumawati, D. H.; Putri, N. P.; Triwikantoro; Supardi, Z. A. I.

    2018-03-01

    Silica which is synthesized from natural materials such as Bancar Tuban’s sand composited with Polyaniline (PANi), where the silica used are silica has an amorphous phase and cristobalite phase. In this research, the composite method used is in- situ polymerization, which is silica entered during the fabrication of PANi, then automatically silica will be substitute into the chain bonding of PANi. The aim of this research is to find out the results of a composite process using in-situ methods as well as differences in the morphology of PANi/a- SiO2 and PANi/c-SiO2. For the characterization of samples tested in the form of FTIR to determine the functional groups of the composite and SEM to determine the morphology of the sample. From the test results of FTIR are known composite possibility has occurred because there are several functional groups belonging to silica also functional groups belonging polyaniline, functional group that’s happened in wave numbers were almost identical between PANi/a-SiO2 and PANi/c-SiO2, but there are little differences were seen in the form of a graph generated from the peak and intensity that occurred charts for PANi/c-SiO2 has peak more pointed or sharp compared to PANi/a-SiO2 because that bond of crystal is strong, stiff and has a larger particle size than the amorphous composite. Then from the data of SEM seen clearly their morphological differences between PANi/a-SiO2 and PANi/c-SiO2 where polyaniline is composited with amorphous silica will have a fault that is not uniform or irregular different from PANi/c -SiO2 has a regular fault and this is corresponding with the nature of the typical structure of amorphous and crystalline.

  18. RNA-Catalyzed Polymerization and Replication of RNA

    Science.gov (United States)

    Horning, D. P.; Samantha, B.; Tjhung, K. F.; Joyce, G. F.

    2017-07-01

    In an effort to reconstruct RNA-based life, in vitro evolution was used to obtain an RNA polymerase ribozyme that can synthesize a variety of complex functional RNAs and can catalyze the exponential amplification of short RNAs.

  19. Silyl Ketene Acetals/B(C6F53 Lewis Pair-Catalyzed Living Group Transfer Polymerization of Renewable Cyclic Acrylic Monomers

    Directory of Open Access Journals (Sweden)

    Lu Hu

    2018-03-01

    Full Text Available This work reveals the silyl ketene acetal (SKA/B(C6F53 Lewis pair-catalyzed room-temperature group transfer polymerization (GTP of polar acrylic monomers, including methyl linear methacrylate (MMA, and the biorenewable cyclic monomers γ-methyl-α-methylene-γ-butyrolactone (MMBL and α-methylene-γ-butyrolactone (MBL as well. The in situ NMR monitored reaction of SKA with B(C6F53 indicated the formation of Frustrated Lewis Pairs (FLPs, although it is sluggish for MMA polymerization, such a FLP system exhibits highly activity and living GTP of MMBL and MBL. Detailed investigations, including the characterization of key reaction intermediates, polymerization kinetics and polymer structures have led to a polymerization mechanism, in which the polymerization is initiated with an intermolecular Michael addition of the ester enolate group of SKA to the vinyl group of B(C6F53-activated monomer, while the silyl group is transferred to the carbonyl group of the B(C6F53-activated monomer to generate the single-monomer-addition species or the active propagating species; the coordinated B(C6F53 is released to the incoming monomer, followed by repeated intermolecular Michael additions in the subsequent propagation cycle. Such neutral SKA analogues are the real active species for the polymerization and are retained in the whole process as confirmed by experimental data and the chain-end analysis by matrix-assisted laser desorption/ionization time of flight mass spectroscopy (MALDI-TOF MS. Moreover, using this method, we have successfully synthesized well-defined PMMBL-b-PMBL, PMMBL-b-PMBL-b-PMMBL and random copolymers with the predicated molecular weights (Mn and narrow molecular weight distribution (MWD.

  20. Interphases, gelation, vitrification, porous glasses and the generalized Cauchy relation: epoxy/silica nanocomposites

    Energy Technology Data Exchange (ETDEWEB)

    Philipp, M; Mueller, U; Jimenez Rioboo, R J; Baller, J; Sanctuary, R; Krueger, J K [Laboratoire de Physique des Materiaux, University of Luxembourg, 162A avenue de la Faiencerie, L-1511 Luxembourg (Luxembourg); Possart, W [Fachbereich Werkstoffwissenschaften, Universitaet des Saarlandes, D-66123 Saarbruecken (Germany)], E-mail: martine.philipp@uni.lu

    2009-02-15

    The generalized Cauchy relation (gCR) of epoxy/silica nano-composites does not show either the chemically induced sol-gel transition or the chemically induced glass transition in the course of polymerization. Astonishingly, by varying the silica nanoparticles' concentration between 0 and 25 vol% in the composites, the Cauchy parameter A of the gCR remains universal and can be determined from the pure epoxy's elastic moduli. Air-filled porous silica glasses are considered as models for percolated silica particles. A longitudinal modulus versus density representation evidences the aforementioned transition phenomena during polymerization of the epoxy/silica nanocomposites. The existence of optically and mechanically relevant interphases is discussed.

  1. Interphases, gelation, vitrification, porous glasses and the generalized Cauchy relation: epoxy/silica nanocomposites

    International Nuclear Information System (INIS)

    Philipp, M; Mueller, U; Jimenez Rioboo, R J; Baller, J; Sanctuary, R; Krueger, J K; Possart, W

    2009-01-01

    The generalized Cauchy relation (gCR) of epoxy/silica nano-composites does not show either the chemically induced sol-gel transition or the chemically induced glass transition in the course of polymerization. Astonishingly, by varying the silica nanoparticles' concentration between 0 and 25 vol% in the composites, the Cauchy parameter A of the gCR remains universal and can be determined from the pure epoxy's elastic moduli. Air-filled porous silica glasses are considered as models for percolated silica particles. A longitudinal modulus versus density representation evidences the aforementioned transition phenomena during polymerization of the epoxy/silica nanocomposites. The existence of optically and mechanically relevant interphases is discussed.

  2. Preparation of Biocolorant and Eco-Dyeing Derived from Polyphenols Based on Laccase-Catalyzed Oxidative Polymerization

    Directory of Open Access Journals (Sweden)

    Fubang Wang

    2018-02-01

    Full Text Available Natural products have been believed to be a promising source to obtain ecological dyes and pigments. Plant polyphenol is a kind of significant natural compound, and tea provides a rich source of polyphenols. In this study, biocolorant derived from phenolic compounds was generated based on laccase-catalyzed oxidative polymerization, and eco-dyeing of silk and wool fabrics with pigments derived from tea was investigated under the influence of pH variation. This work demonstrated that the dyeing property was better under acidic conditions compared to alkalinity, and fixation rate was the best when pH value was 3. Furthermore, breaking strength of dyed fabrics sharply reduced under the condition of pH 11. Eventually, the dyeing method was an eco-friendly process, which was based on bioconversion, and no mordant was added during the process of dyeing.

  3. Single-Site Tetracoordinated Aluminum Hydride Supported on Mesoporous Silica. From Dream to Reality!

    KAUST Repository

    Werghi, Baraa; Bendjeriou-Sedjerari, Anissa; Jedidi, Abdesslem; Abou-Hamad, Edy; Cavallo, Luigi; Basset, Jean-Marie

    2016-01-01

    The reaction of mesoporous silica (SBA15) dehydroxylated at 700 °C with diisobutylaluminum hydride, i-Bu2AlH, gives after thermal treatment a single-site tetrahedral aluminum hydride with high selectivity. The starting aluminum isobutyl and the final aluminum hydride have been fully characterized by FT-IR, advanced SS NMR spectroscopy (1H, 13C, multiple quanta (MQ) 2D 1H-1H, and 27Al), and elemental analysis, while DFT calculations provide a rationalization of the occurring reactivity. Trimeric i-Bu2AlH reacts selectively with surface silanols without affecting the siloxane bridges. Its analogous hydride catalyzes ethylene polymerization. Indeed, catalytic tests show that this single aluminum hydride site is active in the production of a high-density polyethylene (HDPE). © 2016 American Chemical Society.

  4. Single-Site Tetracoordinated Aluminum Hydride Supported on Mesoporous Silica. From Dream to Reality!

    KAUST Repository

    Werghi, Baraa

    2016-09-26

    The reaction of mesoporous silica (SBA15) dehydroxylated at 700 °C with diisobutylaluminum hydride, i-Bu2AlH, gives after thermal treatment a single-site tetrahedral aluminum hydride with high selectivity. The starting aluminum isobutyl and the final aluminum hydride have been fully characterized by FT-IR, advanced SS NMR spectroscopy (1H, 13C, multiple quanta (MQ) 2D 1H-1H, and 27Al), and elemental analysis, while DFT calculations provide a rationalization of the occurring reactivity. Trimeric i-Bu2AlH reacts selectively with surface silanols without affecting the siloxane bridges. Its analogous hydride catalyzes ethylene polymerization. Indeed, catalytic tests show that this single aluminum hydride site is active in the production of a high-density polyethylene (HDPE). © 2016 American Chemical Society.

  5. Photooxidation of ethylene over Cu-modified and unmodified silica

    OpenAIRE

    Ichihashi, Yuichi; Matsumura, Yasuyuki

    2003-01-01

    Silica catalyzes photooxidation of ethylene to carbon dioxide and modification of copper on silica results in the lower reaction rate and partial production of ethylene oxide. The reaction does not proceed by the light irradiation through a color filter (λ>280 nm). ESR measurement indicates that radical oxygen species assignable T-shape Si − O3− can be produced on silica by UV irradiation at 77 K. The same species are also found on silica modified with copper by UV irradiation whi...

  6. CuX2络合物催化甲基丙烯酸甲酯的氧化聚合%CuX2 COMPLEX-CATALYZED OXIDATIVE POLYMERIZATIONS OF METHYL METHACRYLATE

    Institute of Scientific and Technical Information of China (English)

    孙燕; 孙晋; 宋瑾; 黄文艳; 蒋必彪; 翟光群

    2011-01-01

    Oxidative polymerizations of methyl methacrylate ( MMA) catalyzed by complexes of transition metal halides in high oxidation states were investigated. First, CuBr2/2, 2'-bipyridine ( bPy)-catalyzed oxidative polymerizations of MMA in the presence of poly (2-( N, iV-dimethylamino) ethyl methacrylate) were performed in different solvents. When cyclohexanone was used as a solvent, only poly ( methyl methacrylate) ( PMMA) was obtained, suggesting redox initiation between CuBr2/bPy and tertiary amines in cyclohexanone is negligible. Second, oxidative polymerizations of MMA catalyzed by different complexes were carried out. Complexes of CuCl2 ,CuBr2 or FeCl3 with bPy,N,N,/V',N",/V"-pentamethyldiethylenetriamine or N,N,N',N'-tetramethylethylenediamine can catalyze oxidative polymerizations of MMA, and polymerization rates increased with the increase of the catalyst concentration. Molecular weight of PMMA increases with monomer conversions initially and maintains constant later. Last,atom transfer radical polymerization ( ATRP) chain extension using PMMA from the oxidative polymerizations at different conversions was performed. The results show the C-X functionality of PMMA chains at low conversion was also 100% ,and it decreased sharply with conversions. Two different mechanisms were conceived to contribute to the oxidative polymerization of MMA: (1) the complexes form ATRP initiators and catalysts with MMA via monomer addition, and then ATRP proceeds to give rise to PMMA chains with C-X terminal groups; (2) the complexes catalyze/initiate conventional free radical polymerizations of MMA.%研究了高氧化态过渡金属卤化物络合物催化甲基丙烯酸甲酯(MMA)的氧化聚合.首先在叔胺类聚合物存在条件下以CuBr2/2,2′-联吡啶(bPy)络合物催化MMA在不同溶剂中的氧化聚合,结果在环己酮中得到PMMA均聚物,CuBr2/b

  7. Pyrolytic carbon membranes containing silica: morphological approach on gas transport behavior

    Science.gov (United States)

    Park, Ho Bum; Lee, Sun Yong; Lee, Young Moo

    2005-04-01

    Pyrolytic carbon membrane containing silica (C-SiO 2) is a new-class material for gas separation, and in the present work we will deal with it in view of the morphological changes arising from the difference in the molecular structure of the polymeric precursors. The silica embedded carbon membranes were fabricated by a predetermined pyrolysis step using imide-siloxane copolymers (PISs) that was synthesized from benzophenone tetracarboxylic dianhydrides (BTDA), 4,4'-oxydianiline (ODA), and amine-terminated polydimethylsiloxane (PDMS). To induce different morphologies at the same chemical composition, the copolymers were prepared using one-step (preferentially a random segmented copolymer) sand two-step polymerization (a block segmented copolymer) methods. The polymeric precursors and their pyrolytic C-SiO 2 membranes were analyzed using thermal analysis, atomic force microscopy, and transmission electron microscopy, etc. It was found that the C-SiO 2 membrane derived from the random PIS copolymer showed a micro-structure containing small well-dispersed silica domains, whereas the C-SiO 2 membrane from the block PIS copolymer exhibited a micro-structure containing large silica domains in the continuous carbon matrix. Eventually, the gas transport through these C-SiO 2 membranes was significantly affected by the morphological changes of the polymeric precursors.

  8. Carboxyl-Functionalized Polymeric Microspheres Prepared by One-Stage Photoinitiated RAFT Dispersion Polymerization

    Directory of Open Access Journals (Sweden)

    Jianbo Tan

    2017-12-01

    Full Text Available Herein, we report a photoinitiated reversible addition-fragmentation chain transfer (RAFT dispersion copolymerization of methyl methacrylate (MMA and methyl methacrylic (MAA for the preparation of highly monodisperse carboxyl-functionalized polymeric microspheres. High rates of polymerization were observed, with more than 90% particle yields being achieved within 3 h of UV irradiation. Effects of reaction parameters (e.g., MAA concentration, RAFT agent concentration, photoinitiator concentration, and solvent composition were studied in detail, and highly monodisperse polymeric microspheres were obtained in most cases. Finally, silver (Ag composite microspheres were prepared by in situ reduction of AgNO3 using the carboxyl-functionalized polymeric microspheres as the template. The obtained Ag composite microspheres were able to catalyze the reduction of methylene blue (MB with NaBH4 as a reductant.

  9. Mechanistic Studies of Hafnium-Pyridyl Amido-Catalyzed 1-Octene Polymerization and Chain Transfer Using Quench-Labeling Methods.

    Science.gov (United States)

    Cueny, Eric S; Johnson, Heather C; Anding, Bernie J; Landis, Clark R

    2017-08-30

    Chromophore quench-labeling applied to 1-octene polymerization as catalyzed by hafnium-pyridyl amido precursors enables quantification of the amount of active catalyst and observation of the molecular weight distribution (MWD) of Hf-bound polymers via UV-GPC analysis. Comparison of the UV-detected MWD with the MWD of the "bulk" (all polymers, from RI-GPC analysis) provides important mechanistic information. The time evolution of the dual-detection GPC data, concentration of active catalyst, and monomer consumption suggests optimal activation conditions for the Hf pre-catalyst in the presence of the activator [Ph 3 C][B(C 6 F 5 ) 4 ]. The chromophore quench-labeling agents do not react with the chain-transfer agent ZnEt 2 under the reaction conditions. Thus, Hf-bound polymeryls are selectively labeled in the presence of zinc-polymeryls. Quench-labeling studies in the presence of ZnEt 2 reveal that ZnEt 2 does not influence the rate of propagation at the Hf center, and chain transfer of Hf-bound polymers to ZnEt 2 is fast and quasi-irreversible. The quench-label techniques represent a means to study commercial polymerization catalysts that operate with high efficiency at low catalyst concentrations without the need for specialized equipment.

  10. Characterization of silica particles prepared via urease-catalyzed urea hydrolysis and activity of urease in sol–gel silica matrix

    International Nuclear Information System (INIS)

    Kato, Katsuya; Nishida, Masakazu; Ito, Kimiyasu; Tomita, Masahiro

    2012-01-01

    Highlights: ► Silica precipitation occurred via urease-catalytic reactions. ► Higher urease activity for silica synthesis enables mesostructure of silica–urease composites. ► Urease encapsulating in silica matrix retained high activity. - Abstract: Urease templated precipitation of silica synthesized by sol–gel chemistry produces a composite material allowing high urease activity. This study investigates the structural properties of the composite material that allow for the retention of the urease hydrolysis activity. Scanning (SEM) and transmission (TEM) electron microscopy reveal that the composite has a mesoporous structure composed of closely packed spherical structures ∼20–50 nm in diameter. Brunauer–Emmett–Teller (BET) analysis revealed that the surface area and pore volume of the composite prepared under the conditions of 50 mM urea and 25 °C is relatively high (324 m 2 /g and 1.0 cm 3 /g). These values are equivalent to those of usual mesoporous silica materials synthesized from the self-assembly of triblock copolymers as organic templates. In addition, after encapsulating in a sol–gel silica matrix, urease retained high activity (∼90% of the activity compared with native urease). Our results suggest a new method for synthesizing mesoporous silica materials with highly tunable pore sizes and shapes under mild conditions.

  11. Oxidative polymerization of lignins by laccase in water-acetone mixture.

    Science.gov (United States)

    Fiţigău, Ionița Firuța; Peter, Francisc; Boeriu, Carmen Gabriela

    2013-01-01

    The enzymatic oxidative polymerization of five technical lignins with different molecular properties, i.e. Soda Grass/Wheat straw Lignin, Organosolv Hardwood Lignin, Soda Wheat straw Lignin, Alkali pretreated Wheat straw Lignin, and Kraft Softwood was studied. All lignins were previously fractionated by acetone/water 50:50 (v/v) and the laccase-catalyzed polymerization of the low molecular weight fractions (Mw Reactivity of lignin substrates in laccase-catalyzed reactions was determined by monitoring the oxygen consumption. The oxidation reactions in 50% acetone in water mixture proceed with high rate for all tested lignins. Polymerization products were analyzed by size exclusion chromatography, FT-IR, and (31)P-NMR and evidence of important lignin modifications after incubation with laccase. Lignin polymers with higher molecular weight (Mw up to 17500 g/mol) were obtained. The obtained polymers have potential for applications in bioplastics, adhesives and as polymeric dispersants.

  12. Designer silica layers for advanced applications: Processing and properties

    Science.gov (United States)

    Anderson, Adam

    Recently, as scientists have investigated the application of conventional MEMS devices to biological systems, the exciting fields of bio-MEMS and microfluidics have emerged. Due to their small size, bio-MEMS and microfluidics devices offer the advantage of requiring only small sample and reagent volumes, in a potentially low-cost, integrated package. Such devices have the potential to significantly advance point-of-care diagnostics devices and improve overall patient care. However, due to the extremely small feature size, the large surface area-to-volume ratio in these devices makes controlling surface interactions of critical importance. Recently, there has been a shift to polymeric materials for fabrication of microfluidics devices due to their lower cost, ease of device fabrication by various processes, varied and favorable material properties, and, in some cases, pre-existing regulatory agency approvals. As a result, various surface modification strategies for polymeric surfaces have been proposed, but with only limited success. The proven success of organosilicon-based precursors in a wide variety of surface modification strategies has been demonstrated, with a body of knowledge on the general subject dating back nearly fifty years. However, these proven methodologies cannot be transferred to many important polymeric materials due to a lack of sufficient reactive groups on the surface. If any polymer surface could be made reactive by some intermediate treatment, the wide body of knowledge of organosilicon-based surface modification chemistries could be leveraged to advance the state-of-the-art in surface modification for microfluidics applications, where polymeric substrates are commonly encountered. This thesis reports on the processing properties and chemical properties of a vapor deposited silica layer, which is formed from the vapor phase hydrolysis of silicon tetrachloride. This layer can be deposited at low temperatures to a wide variety of substrates

  13. Trapping of intermediates with substrate analog HBOCoA in the polymerizations catalyzed by class III polyhydroxybutyrate (PHB) synthase from Allochromatium vinosum.

    Science.gov (United States)

    Chen, Chao; Cao, Ruikai; Shrestha, Ruben; Ward, Christina; Katz, Benjamin B; Fischer, Christopher J; Tomich, John M; Li, Ping

    2015-05-15

    Polyhydroxybutyrate (PHB) synthases (PhaCs) catalyze the formation of biodegradable PHB polymers that are considered as an ideal alternative to petroleum-based plastics. To provide strong evidence for the preferred mechanistic model involving covalent and noncovalent intermediates, a substrate analog HBOCoA was synthesized chemoenzymatically. Substitution of sulfur in the native substrate HBCoA with an oxygen in HBOCoA enabled detection of (HB)nOCoA (n = 2-6) intermediates when the polymerization was catalyzed by wild-type (wt-)PhaECAv at 5.84 h(-1). This extremely slow rate is due to thermodynamically unfavorable steps that involve the formation of enzyme-bound PHB species (thioesters) from corresponding CoA oxoesters. Synthesized standards (HB)nOCoA (n = 2-3) were found to undergo both reacylation and hydrolysis catalyzed by the synthase. Distribution of the hydrolysis products highlights the importance of the penultimate ester group as previously suggested. Importantly, the reaction between primed synthase [(3)H]-sT-PhaECAv and HBOCoA yielded [(3)H]-sTet-O-CoA at a rate constant faster than 17.4 s(-1), which represents the first example that a substrate analog undergoes PHB chain elongation at a rate close to that of the native substrate (65.0 s(-1)). Therefore, for the first time with a wt-synthase, strong evidence was obtained to support our favored PHB chain elongation model.

  14. Polymerization of MMA catalyzed by different novel mixed ligand lanthanocene { ( Cp ) ( Cl ) LnSchiff-base (THF) }, ( COT ) Ln(methoxyethylindenyl) (THF)/Al (i-Bu) 3 systems

    Institute of Scientific and Technical Information of China (English)

    YOUSAF, Muhammad; QIAN, Yan-Long; FENG, Zuo-Feng; HUANG, Ji-Ling; SUN, Jun-Quan; PAN, Zhi-Da

    2000-01-01

    This article deals that the rare earth metal complexes along with Al (i-Bu)3 can catalyze the polymerization of methyl methacrylate (MMA) into high molecular weight poly(MMA) along with narrow molecular weight distributions (MWD). A typical example wan mentioned in the case of {Cp(Cl)Sm Schiff-base(THF)} which expresses maximum (conv.%= 55.46 and Mn=354×103) efficiency along with narrow MWD(Mw/Mn<2) at 60°C. The resulting polymer was partially syndiotactic (>60%). The effect of the catalyst, temperature, catalyst/MMA molar ratio, catalyst/Al(i-Bu)3 molar ratio on the polymerization of MMA at 60°C were also investigated.

  15. Glycine Polymerization on Oxide Minerals

    Science.gov (United States)

    Kitadai, Norio; Oonishi, Hiroyuki; Umemoto, Koichiro; Usui, Tomohiro; Fukushi, Keisuke; Nakashima, Satoru

    2017-06-01

    It has long been suggested that mineral surfaces played an important role in peptide bond formation on the primitive Earth. However, it remains unclear which mineral species was key to the prebiotic processes. This is because great discrepancies exist among the reported catalytic efficiencies of minerals for amino acid polymerizations, owing to mutually different experimental conditions. This study examined polymerization of glycine (Gly) on nine oxide minerals (amorphous silica, quartz, α-alumina and γ-alumina, anatase, rutile, hematite, magnetite, and forsterite) using identical preparation, heating, and analytical procedures. Results showed that a rutile surface is the most effective site for Gly polymerization in terms of both amounts and lengths of Gly polymers synthesized. The catalytic efficiency decreased as rutile > anatase > γ-alumina > forsterite > α- alumina > magnetite > hematite > quartz > amorphous silica. Based on reported molecular-level information for adsorption of Gly on these minerals, polymerization activation was inferred to have arisen from deprotonation of the NH3 + group of adsorbed Gly to the nucleophilic NH2 group, and from withdrawal of electron density from the carboxyl carbon to the surface metal ions. The orientation of adsorbed Gly on minerals is also a factor influencing the Gly reactivity. The examination of Gly-mineral interactions under identical experimental conditions has enabled the direct comparison of various minerals' catalytic efficiencies and has made discussion of polymerization mechanisms and their relative influences possible Further systematic investigations using the approach reported herein (which are expected to be fruitful) combined with future microscopic surface analyses will elucidate the role of minerals in the process of abiotic peptide bond formation.

  16. Glycine Polymerization on Oxide Minerals.

    Science.gov (United States)

    Kitadai, Norio; Oonishi, Hiroyuki; Umemoto, Koichiro; Usui, Tomohiro; Fukushi, Keisuke; Nakashima, Satoru

    2017-06-01

    It has long been suggested that mineral surfaces played an important role in peptide bond formation on the primitive Earth. However, it remains unclear which mineral species was key to the prebiotic processes. This is because great discrepancies exist among the reported catalytic efficiencies of minerals for amino acid polymerizations, owing to mutually different experimental conditions. This study examined polymerization of glycine (Gly) on nine oxide minerals (amorphous silica, quartz, α-alumina and γ-alumina, anatase, rutile, hematite, magnetite, and forsterite) using identical preparation, heating, and analytical procedures. Results showed that a rutile surface is the most effective site for Gly polymerization in terms of both amounts and lengths of Gly polymers synthesized. The catalytic efficiency decreased as rutile > anatase > γ-alumina > forsterite > α- alumina > magnetite > hematite > quartz > amorphous silica. Based on reported molecular-level information for adsorption of Gly on these minerals, polymerization activation was inferred to have arisen from deprotonation of the NH 3 + group of adsorbed Gly to the nucleophilic NH 2 group, and from withdrawal of electron density from the carboxyl carbon to the surface metal ions. The orientation of adsorbed Gly on minerals is also a factor influencing the Gly reactivity. The examination of Gly-mineral interactions under identical experimental conditions has enabled the direct comparison of various minerals' catalytic efficiencies and has made discussion of polymerization mechanisms and their relative influences possible Further systematic investigations using the approach reported herein (which are expected to be fruitful) combined with future microscopic surface analyses will elucidate the role of minerals in the process of abiotic peptide bond formation.

  17. Modeling of lipase catalyzed ring-opening polymerization of epsilon-caprolactone.

    Science.gov (United States)

    Sivalingam, G; Madras, Giridhar

    2004-01-01

    Enzymatic ring-opening polymerization of epsilon-caprolactone by various lipases was investigated in toluene at various temperatures. The determination of molecular weight and structural identification was carried out with gel permeation chromatography and proton NMR, respectively. Among the various lipases employed, an immobilized lipase from Candida antartica B (Novozym 435) showed the highest catalytic activity. The polymerization of epsilon-caprolactone by Novozym 435 showed an optimal temperature of 65 degrees C and an optimum toluene content of 50/50 v/v of toluene and epsilon-caprolactone. As lipases can degrade polyesters, a maximum in the molecular weight with time was obtained due to the competition of ring opening polymerization and degradation by specific chain end scission. The optimum temperature, toluene content, and the variation of molecular weight with time are consistent with earlier observations. A comprehensive model based on continuous distribution kinetics was developed to model these phenomena. The model accounts for simultaneous polymerization, degradation and enzyme deactivation and provides a technique to determine the rate coefficients for these processes. The dependence of these rate coefficients with temperature and monomer concentration is also discussed.

  18. Atom transfer radical polymerization of n-butyl acrylate catalyzed by atom transfer radical polymerization of n-butyl acrylate catalyzed by

    NARCIS (Netherlands)

    Zhang, H.; Linde, van der R.

    2002-01-01

    The homogeneous atom transfer radical polymerization (ATRP) of n-butyl acrylate with CuBr/N-(n-hexyl)-2-pyridylmethanimine as a catalyst and ethyl 2-bromoisobutyrate as an initiator was investigated. The kinetic plots of ln([M]0/[M]) versus the reaction time for the ATRP systems in different

  19. Cascade synthesis of chiral block copolymers combining lipase catalyzed ring opening polymerization and atom transfer radical polymerization

    NARCIS (Netherlands)

    Peeters, J.W.; Palmans, A.R.A.; Veld, M.A.J.; Scheijen, F.J.E.; Heise, A.; Meijer, E.W.

    2004-01-01

    The enantioselective polymerization of methyl-substituted -caprolactones using Novozym 435 as the catalyst was investigated. All substituted monomers could be polymerized except 6-methyl--caprolactone (6-MeCL), which failed to propagate after ring opening. Interestingly, an odd-even effect in the

  20. Dispersion of nano-silica in monomer casting nylon6 and its effect on the structure and properties of composites

    Directory of Open Access Journals (Sweden)

    2010-07-01

    Full Text Available To promote dispersion of nano-silica in monomer casting nylon6 (MC nylon6, nano-silica was dispersed in melted caprolactam with the assistance of ultrasound, anionic polymerization was then initiated to form silica/MC nylon6 in-situ nanocomposites. It was found that hydrogen bonds were formed between nano-silica and caprolactam, in the meantime, ultrasound helped to break the nanoparticles aggregations into smaller ones or even mono-dispersing particles. Therefore, the agglomerated nanoparticles were pulled apart and stabilized by caprolactam. Additionally, the rapid anionic polymerization of caprolactam also contributed to the avoidance of re-agglomeration and deposition of nanoparticles during the polymerization process, leading to the uniform distribution of nanoparticles in the polymer matrix. Mechanical tests indicated that the silica/MC nylon6 in-situ nanocomposites prepared according to the above strategy were simultaneously toughened, strengthened and stiffened. Thermogravimetric analysis (TGA results showed that thermal stability of nanocomposites was notably improved compared to neat MC nylon6.

  1. Amylase catalyzed synthesis of glycosyl acrylates and their polymerization

    NARCIS (Netherlands)

    Kloosterman, Wouter M.J.; Jovanovic, Danijela; Brouwer, Sander; Loos, Katja

    2014-01-01

    The enzymatic synthesis of novel (di)saccharide acrylates from starch and 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate and 4-hydroxybutyl acrylate (2-HEA, 2-HEMA and 4-HBA) catalyzed by various commercially available amylase preparations is demonstrated. Both liquefaction and

  2. Investigation of emulsified, acid and acid-alkali catalyzed mesoporous bioactive glass microspheres for bone regeneration and drug delivery

    Energy Technology Data Exchange (ETDEWEB)

    Miao, Guohou [School of Materials Science and Engineering, South China University of Technology, Guangzhou 510641 China (China); National Engineering Research Center for Tissue Restoration and Reconstruction, Guangzhou 510006 China (China); Guangdong Province Key Laboratory of Biomedical Engineering, South China University of Technology, Guangzhou 510006 China (China); Chen, Xiaofeng, E-mail: chenxf@scut.edu.cn [School of Materials Science and Engineering, South China University of Technology, Guangzhou 510641 China (China); National Engineering Research Center for Tissue Restoration and Reconstruction, Guangzhou 510006 China (China); Guangdong Province Key Laboratory of Biomedical Engineering, South China University of Technology, Guangzhou 510006 China (China); Dong, Hua [National Engineering Research Center for Tissue Restoration and Reconstruction, Guangzhou 510006 China (China); Guangdong Province Key Laboratory of Biomedical Engineering, South China University of Technology, Guangzhou 510006 China (China); School of Biological Science and Engineering, South China University of Technology, Guangzhou 510006 (China); Fang, Liming; Mao, Cong; Li, Yuli; Li, Zhengmao; Hu, Qing [School of Materials Science and Engineering, South China University of Technology, Guangzhou 510641 China (China); National Engineering Research Center for Tissue Restoration and Reconstruction, Guangzhou 510006 China (China); Guangdong Province Key Laboratory of Biomedical Engineering, South China University of Technology, Guangzhou 510006 China (China)

    2013-10-15

    Acid-catalyzed mesoporous bioactive glass microspheres (MBGMs-A) and acid-alkali co-catalyzed mesoporous bioactive glass microspheres (MBGMs-B) were successfully synthesized via combination of sol-gel and water-in-oil (W/O) micro-emulsion methods. The structural, morphological and textural properties of mesoporous bioactive glass microspheres (MBGMs) were characterized by various techniques. Results show that both MBGMs-A and MBGMs-B exhibit regularly spherical shape but with different internal porous structures, i.e., a dense microstructure for MBGMs-A and internally porous structure for MBGMs-B. {sup 29}Si NMR data reveal that MGBMs have low polymerization degree of silica network. The in vitro bioactivity tests indicate that the apatite formation rate of MBGMs-B was faster than that of MBGMs-A after soaking in simulated body fluid (SBF) solution. Furthermore, the two kinds of MBGMs have similar storage capacity of alendronate (AL), and the release behaviors of AL could be controlled due to their unique porous structure. In conclusion, the microspheres are shown to be promising candidates as bone-related drug carriers and filling materials of composite scaffold for bone repair. - Graphical abstract: The morphologies and microstructures of acid-catalyzed mesoporous bioactive glass microspheres (MBGMs-A) and acid-alkali co-catalyzed mesoporous bioactive glass microspheres (MBGMs-B) were observed by scanning electron microscope and transmission electron microscope. MBGMs-A exhibits a dense structure and a porous can be observed in MBGMs-B. The microspheres have a quick inducing-apatite formation ability and show a sustained release of alendronate (AL). Highlights: • A rapid method was reported to prepare mesoporous bioactive glass microspheres. • The addition of ammonia significantly shortens the preparation time. • Acid and acid-alkali co-catalyzed microspheres were studied for the first time. • The materials exhibited excellent in vitro bioactivity and

  3. Biocompatible Polymeric Materials Intended for Drug Delivery and Therapeutic Applications

    DEFF Research Database (Denmark)

    Hvilsted, Søren; Javakhishvili, Irakli; Bednarek, Melania

    2007-01-01

    of polymer blocks by “click chemistry”. An all polymerization strategy would imply preparing polymers by living/controlled techniques in such a manner that one block after polymerization can be converted to a macroinitiator enabling the second block to polymerize. The coupling strategy invariably inserts...... a linking unit, 1,4-triazol, resulting from the catalyzed, irreversible 1,3-dipolar cycloaddition reaction between an alkyne and an azide. Thus, this strategy necessitates the proper end functionalization of the polymeric building blocks. Fortunately the 1,4-triazol unit is FDA approved already existing...

  4. Neutral hydrophilic coatings for capillary electrophoresis prepared by controlled radical polymerization

    Energy Technology Data Exchange (ETDEWEB)

    Navarro, Fabián H.; Gómez, Jorge E.; Espinal, José H.; Sandoval, Junior E., E-mail: junior.sandoval@correounivalle.edu.co

    2016-12-15

    In the present study, porous silica particles as well as impervious fused-silica wafers and capillary tubes were modified with hydrophilic polymers (hydroxylated polyacrylamides and polyacrylates), using a surface-confined grafting procedure based on atom transfer radical polymerization (ATRP) which was also surface-initiated from α-bromoisobutyryl groups. Initiator immobilization was achieved by hydrosilylation of allyl alcohol on hydride silica followed by esterification of the resulting propanol-bonded surface with α-bromoisobutyryl bromide. Elemental analysis, IR and NMR spectroscopies on silica micro-particles, atomic force microscopy, ellipsometry and profilometry on fused-silica wafers, as well as CE on fused-silica tubes were used to characterize the chemically modified silica substrate at different stages. We studied the effect of monomer concentration as well as cross-linker on the ability of the polymer film to reduce electroosmosis and to prevent protein adsorption (i. e., its non-fouling capabilities) and found that the former was rather insensitive to both parameters. Surface deactivation towards adsorption was somewhat more susceptible to monomer concentration and appeared also to be favored by a low concentration of the cross-linker. The results show that hydrophilic polyacrylamide and polyacrylate coatings of controlled thickness can be prepared by ATRP under very mild polymerization conditions (aqueous solvent, room temperature and short reaction times) and that the coated capillary tubes exhibit high efficiencies for protein separations (0.3–0.6 million theoretical plates per meter) as well as long-term hydrolytic stability under the inherently harsh conditions of capillary isoelectric focusing. Additionally, there was no adsorption of lysozyme on the coated surface as indicated by a complete recovery of the basic enzyme. Furthermore, since polymerization is confined to the inner capillary surface, simple precautions (e.g., solution

  5. Kinetics and mechanics of photo-polymerized triazole-containing thermosetting composites via the copper(I)-catalyzed azide-alkyne cycloaddition.

    Science.gov (United States)

    Song, Han Byul; Wang, Xiance; Patton, James R; Stansbury, Jeffrey W; Bowman, Christopher N

    2017-06-01

    Several features necessary for polymer composite materials in practical applications such as dental restorative materials were investigated in photo-curable CuAAC (copper(I)-catalyzed azide-alkyne cycloaddition) thermosetting resin-based composites with varying filler loadings and compared to a conventional BisGMA/TEGDMA based composite. Tri-functional alkyne and di-functional azide monomers were synthesized for CuAAC resins and incorporated with alkyne-functionalized glass microfillers for CuAAC composites. Polymerization kinetics, in situ temperature change, and shrinkage stress were monitored simultaneously with a tensometer coupled with FTIR spectroscopy and a data-logging thermocouple. The glass transition temperature was analyzed by dynamic mechanical analysis. Flexural modulus/strength and flexural toughness were characterized in three-point bending on a universal testing machine. The photo-CuAAC polymerization of composites containing between 0 and 60wt% microfiller achieved ∼99% conversion with a dramatic reduction in the maximum heat of reaction (∼20°C decrease) for the 60wt% filled CuAAC composites as compared with the unfilled CuAAC resin. CuAAC composites with 60wt% microfiller generated more than twice lower shrinkage stress of 0.43±0.01MPa, equivalent flexural modulus of 6.1±0.7GPa, equivalent flexural strength of 107±9MPa, and more than 10 times higher energy absorption of 10±1MJm -3 when strained to 11% relative to BisGMA-based composites at equivalent filler loadings. Mechanically robust and highly tough, photo-polymerized CuAAC composites with reduced shrinkage stress and a modest reaction exotherm were generated and resulted in essentially complete conversion. Copyright © 2017 The Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

  6. Fluoropolymer materials and architectures prepared by controlled radical polymerizations

    DEFF Research Database (Denmark)

    Hansen, Natanya Majbritt Louie; Jankova Atanasova, Katja; Hvilsted, Søren

    2007-01-01

    This review initially summarizes the mechanisms, merits and limitations of the three controlled radical polymerizations: nitroxide mediated polymerization (NMP), atom transfer radical polymerization (ATRP) or metal catalyzed living radical polymerization, and reversible addition–fragmentation chain...... transfer (RAFT) polymerization. This is followed by two parts, one dealing with homo- and copolymerizations of fluorinated methacrylates and acrylates, and a second where fluorinated styrenes, alone or in combination with other monomers, are the main issues. In these parts, initiators (including...... properties and functionalities that can be obtained from these novel fluorinated materials and architectures are especially emphasized. Thus, various amphiphilic, biocompatible or low energy materials, fluorinated nanoparticles and nanoporous films/membranes as well as materials for submicron and nanolevel...

  7. Design of water-repellant coating using dual scale size of hybrid silica nanoparticles on polymer surface

    Science.gov (United States)

    Conti, J.; De Coninck, J.; Ghazzal, M. N.

    2018-04-01

    The dual-scale size of the silica nanoparticles is commonly aimed at producing dual-scale roughness, also called hierarchical roughness (Lotus effect). In this study, we describe a method to build a stable water-repellant coating with controlled roughness. Hybrid silica nanoparticles are self-assembled over a polymeric surface by alternating consecutive layers. Each one uses homogenously distributed silica nanoparticles of a particular size. The effect of the nanoparticle size of the first layer on the final roughness of the coating is studied. The first layer enables to adjust the distance between the silica nanoparticles of the upper layer, leading to a tuneable and controlled final roughness. An optimal size nanoparticle has been found for higher water-repellency. Furthermore, the stability of the coating on polymeric surface (Polycarbonate substrate) is ensured by photopolymerization of hybridized silica nanoparticles using Vinyl functional groups.

  8. Poly(ethyleneimine) infused and functionalized Torlon®-silica hollow fiber sorbents for post-combustion CO2 capture

    KAUST Repository

    Li, Fuyue Stephanie

    2014-03-01

    Organic-inorganic hybrid materials functionalized with amine-containing reagents are emerging as an important class of materials for capturing carbon dioxide from flue gas. Polymeric silica hollow fiber sorbents are fabricated through the proven dry-jet/wet-quench spinning process. In our study, a new technique for functionalizing polymeric silica hollow fiber sorbents with poly(ethyleneimine), followed by a post-spinning infusion step was studied. This two step process introduces a sufficient amount of poly(ethyleneimine) to the polymeric silica hybrid material support to improve the CO2 sorption capacity due to the added amine groups. The poly(ethyleneimine) infused and functionalized hollow fiber sorbents are also characterized by a thermal gravimetric analyzer (TGA) to assess their CO2 sorption capacities. © 2014 Elsevier Ltd. All rights reserved.

  9. Deposition kinetics of extracellular polymeric substances (EPS) on silica in monovalent and divalent salts.

    Science.gov (United States)

    Zhu, Pingting; Long, Guoyu; Ni, Jinren; Tong, Meiping

    2009-08-01

    The deposition kinetics of extracellular polymeric substances (EPS) on silica surfaces were examined in both monovalent and divalent solutions under a variety of environmentally relevant ionic strength and pH conditions by employing a quartz crystal microbalance with dissipation (DCM-D). Soluble EPS (SEPS) and bound EPS (BEPS) were extracted from four bacterial strains with different characteristics. Maximum favorable deposition rates (k(fa)) were observed for all EPS at low ionic strengths in both NaCl and CaCl2 solutions. With the increase of ionic strength, k(fa) decreased due to the simultaneous occurrence of EPS aggregation in solutions. Deposition efficiency (alpha; the ratio of deposition rates obtained under unfavorable versus corresponding favorable conditions) for all EPS increased with increasing ionic strength in both NaCl and CaCl2 solutions, which agreed with the trends of zeta potentials and was consistent with the classic Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. Comparison of alpha for SEPS and BEPS extracted from the same strain showed that the trends of alpha did not totally agree with trends of zeta potentials, indicating the deposition kinetics of EPS on silica surfaces were not only controlled by DLVO interactions, but also non-DLVO forces. Close comparison of alpha for EPS extracted from different sources showed alpha increased with increasing proteins to polysaccharides ratio. Subsequent experiments for EPS extracted from the same strain but with different proteins to polysaccharides ratios and from activated sludge also showed that alpha were largest for EPS with greatest proteins to polysaccharides ratio. Additional experiments for pure protein and solutions with different pure proteins to pure saccharides ratios further corroborated that larger proteins to polysaccharides ratio resulted in greater EPS deposition.

  10. Study on radiation-induced polymerization of vinyl monomers adsorbed on inorganic substances. II. Radiation-induced polymerization of methyl methacrylate adsorbed on several inorganic substances

    International Nuclear Information System (INIS)

    Fukano, K.; Kageyama, E.

    1975-01-01

    The radiation-induced polymerization of methyl methacrylate (MMA) adsorbed on such inorganic substances as silica gel, white carbon, silicic acid anhydride, zeolite, and activated alumina was carried out to compare with the case of styrene. The rate of radiation-induced polymerization adsorbed on inorganic substances was high compared with that of radiation-induced bulk state polymerization, as was the case with styrene. Inorganic substrates which contain aluminum as a component element are more likely to be grafted than those which consist of SiO 2 alone, as with styrene. The molecular weight distribution of unextractable polymer and extractable polymer differs, depending on the type of inorganic substance. Experiments by a preirradiation method were carried out in case of silica gel, white carbon, and silicic acid anhydride. GPC spectra of the polymer obtained were different from those of polymer formed by the simultaneous irradiation method. It appears that all the unextractable polymer is grafted to the inorganic surface with chemical bond

  11. Direct Synthesis of Telechelic Polyethylene by Selective Insertion Polymerization

    KAUST Repository

    Jian, Zhongbao; Falivene, Laura; Boffa, Giusi; Sá nchez, Sheila Ortega; Caporaso, Lucia; Grassi, Alfonso; Mecking, Stefan

    2016-01-01

    A single-step route to telechelic polyethylene (PE) is enabled by selective insertion polymerization. PdII-catalyzed copolymerization of ethylene and 2-vinylfuran (VF) generates α,ω-di-furan telechelic polyethylene. Orthogonally reactive exclusively

  12. Enhanced removal of aqueous acetaminophen by a laccase-catalyzed oxidative coupling reaction under a dual-pH optimization strategy.

    Science.gov (United States)

    Wang, Kaidong; Huang, Ke; Jiang, Guoqiang

    2018-03-01

    Acetaminophen is one kind of pharmaceutical contaminant that has been detected in municipal water and is hard to digest. A laccase-catalyzed oxidative coupling reaction is a potential method of removing acetaminophen from water. In the present study, the kinetics of radical polymerization combined with precipitation was studied, and the dual-pH optimization strategy (the enzyme solution at pH7.4 being added to the substrate solution at pH4.2) was proposed to enhance the removal efficiency of acetaminophen. The reaction kinetics that consisted of the laccase-catalyzed oxidation, radical polymerization and precipitation were studied by UV in situ, LC-MS and DLS (dynamic light scattering) in situ. The results showed that the laccase-catalyzed oxidation is the rate-limiting step in the whole process. The higher rate of enzyme-catalyzed oxidation under a dual-pH optimization strategy led to much faster formation of the dimer, trimer and tetramer. Similarly, the formation of polymerized products that could precipitate naturally from water was faster. Under the dual-pH optimization strategy, the initial laccase activity was increased approximately 2.9-fold, and the activity remained higher for >250s, during which approximately 63.7% of the total acetaminophen was transformed into biologically inactive polymerized products, and part of these polymerized products precipitated from the water. Laccase belongs to the family of multi-copper oxidases, and the present study provides a universal method to improve the activity of multi-copper oxidases for the high-performance removal of phenol and its derivatives. Copyright © 2017 Elsevier B.V. All rights reserved.

  13. Preparation and Characterization of Hybrid Nanocomposite of Polyacrylamide/Silica-Nanoparticles

    Directory of Open Access Journals (Sweden)

    Ahmad Rabiee

    2013-01-01

    Full Text Available Polyacrylamides are water soluble macromolecules. These polymers are widely used for flocculation, separation and treatment of solid-liquid phase materials. In this research, organic-inorganic hybrid of polyacrylamide/silica nanoparticle is prepared via radical polymerization. First, the silica nanoparticle surfaces were modified by 3-methacryloxypropyltrimethoxysilane as coupling agent using a sol-gel technique in aqueous media in acidic condition. Afterwards, the modified nanoparticles are copolymerized by acrylamide monomer in presence of a peroxide initiator during a free radical polymerization. The chemical structure of the prepared modified nano-silica as well as polyacrylamide nanocomposite was studied and confirmed by FTIR spectroscopy technique. The morphology of nanocomposite was investigated by scanning electron microscopy. The SEM micrograph showed that the surface of the composite did not display any phase separation. Nanoparticles distribution was investigated by SEM-EDX technique. The results showed a uniform distribution of particles throughout the polymer bulk. TEM analysis showed the presence of silica nanoparticles in bulk of polymer which is an indicative of suitable dispersion of nanoparticles. The thermal stability of hybrid nanocomosite with that of polyacrylamide was compared by TGA technique. The higher thermal stability of hybrid nanocomposite with respect to homopolymer is indicative of a reaction between the modified nanoparticles and polyacrylamide chain. The presence of silica particles in copolymer was also confirmed with EDX analysis in ash content of hybrid nanocomposite.

  14. Catalytic olefin polymerization with early transition metal compounds

    NARCIS (Netherlands)

    Eshuis, Johan Jan Willem

    1991-01-01

    The catalysis of organic reactions by soluble metal complexes has become a major tool in synthesis, both in the laboratory and in the chemical industry. Processes catalyzed by transition metal complexes include carbonylation, olefin polymerization, olefin addition, olefin oxidation and alkane and

  15. Surface PEGylation of mesoporous silica materials via surface-initiated chain transfer free radical polymerization: Characterization and controlled drug release.

    Science.gov (United States)

    Huang, Long; Liu, Meiying; Mao, Liucheng; Huang, Qiang; Huang, Hongye; Wan, Qing; Tian, Jianwen; Wen, Yuanqing; Zhang, Xiaoyong; Wei, Yen

    2017-12-01

    As a new type of mesoporous silica materials with large pore diameter (pore size between 2 and 50nm) and high specific surface areas, SBA-15 has been widely explored for different applications especially in the biomedical fields. The surface modification of SBA-15 with functional polymers has demonstrated to be an effective way for improving its properties and performance. In this work, we reported the preparation of PEGylated SBA-15 polymer composites through surface-initiated chain transfer free radical polymerization for the first time. The thiol group was first introduced on SBA-15 via co-condensation with γ-mercaptopropyltrimethoxysilane (MPTS), that were utilized to initiate the chain transfer free radical polymerization using poly(ethylene glycol) methyl ether methacrylate (PEGMA) and itaconic acid (IA) as the monomers. The successful modification of SBA-15 with poly(PEGMA-co-IA) copolymers was evidenced by a series of characterization techniques, including 1 H NMR, FT-IR, TGA and XPS. The final SBA-15-SH- poly(PEGMA-co-IA) composites display well water dispersity and high loading capability towards cisplatin (CDDP) owing to the introduction of hydrophilic PEGMA and carboxyl groups. Furthermore, the CDDP could be released from SBA-15-SH-poly(PEGMA-co-IA)-CDDP complexes in a pH dependent behavior, suggesting the potential controlled drug delivery of SBA-15-SH-poly(PEGMA-co-IA). More importantly, the strategy should be also useful for fabrication of many other functional materials for biomedical applications owing to the advantages of SBA-15 and well monomer adoptability of chain transfer free radical polymerization. Copyright © 2017 Elsevier B.V. All rights reserved.

  16. Solid-State Polymerization of Acetylene under Pressure: {ital Ab Initio} Simulation

    Energy Technology Data Exchange (ETDEWEB)

    Bernasconi, M.; Parrinello, M. [Max-Planck-Institut fuer Festkoerperforschung, Heisenbergstr.1, D-70569 Stuttgart (Germany); Bernasconi, M. [Istituto Nazionale Fisica della Materia and Dipartimento di Fisica, Universita di Milano, Via Celoria 16, 20133 Milano (Italy); Chiarotti, G.; Focher, P.; Tosatti, E. [Istituto Nazionale Fisica della Materia and International School for Advanced Studies, Via Beirut 4, I-34014 Trieste (Italy); Tosatti, E. [International Centre for Theoretical Physics (ICTP), P.O.Box 586, I-34014 Trieste (Italy)

    1997-03-01

    We have simulated by {ital ab initio} constant pressure molecular dynamics the solid-state polymerization of acetylene recently observed experimentally in the pressure range 3.5{endash}14 GPa. We have found a massive polymerization only at much higher pressure (25 GPa). However, we have also found that a triplet exciton self-trapped on a single, {ital cis}-bent molecule in crystalline acetylene is a very effective polymerization seed at lower pressure ({lt}9GPa), much closer to the experimental threshold. Therefore, we propose that the polymerization observed experimentally is possibly catalyzed by a similar seed. We predict that injection of triplet excitons would greatly enhance the polymerization rate. {copyright} {ital 1997} {ital The American Physical Society}

  17. Targeting of porous hybrid silica nanoparticles to cancer cells

    NARCIS (Netherlands)

    Rosenholm, J.M.; Meinander, A.; Peuhu, E.; Niemi, R.; Eriksson, J.E.; Sahlgren, C.; Lindén, M.

    2009-01-01

    Mesoporous silica nanoparticles functionalized by surface hyperbranching polymerization of polyethylene imine), PEI, were further modified by introducing both fluorescent and targeting moieties, with the aim of specifically targeting cancer cells. Owing to the high abundance of folate receptors in

  18. Low-temperature specific heat and thermal conductivity of silica aerogels

    DEFF Research Database (Denmark)

    Sleator, T.; Bernasconi, A.; Posselt, D.

    1991-01-01

    Specific-heat and thermal-conductivity measurements were made on a series of base-catalyzed silica aerogels at temperatures between 0.05 and 20 K. Evidence for a crossover between regimes of characteristically different excitations was observed. The data analysis indicates a "bump" in the density...

  19. Ring-opening polymerization of ω-pentadecalactone catalyzed by phosphazene superbases

    KAUST Repository

    Ladelta, Viko

    2016-12-12

    A fast and living ring-opening polymerization (ROP) of ω-pentadecalactone (PDL), a representative monomer of macrolactones, was achieved using a primary alcohol as the initiator and t-BuP or t-octP as the catalyst. The use of t-BuP instead of the t-BuP superbase slows down the polymerization rate. The ROP of PDL proceeds to high conversion not only at 80 °C in bulk but also at room temperature and in dilute solution. The synthesized PDL homopolymers and block copolymers with poly(ethylene glycol) were characterized by high-temperature GPC (HT-GPC), H NMR and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS). Melting temperatures, determined by differential scanning calorimetry, are also reported.

  20. Ring-opening polymerization of ω-pentadecalactone catalyzed by phosphazene superbases

    KAUST Repository

    Ladelta, Viko; Bilalis, Panayiotis; Gnanou, Yves; Hadjichristidis, Nikolaos

    2016-01-01

    A fast and living ring-opening polymerization (ROP) of ω-pentadecalactone (PDL), a representative monomer of macrolactones, was achieved using a primary alcohol as the initiator and t-BuP or t-octP as the catalyst. The use of t-BuP instead of the t-BuP superbase slows down the polymerization rate. The ROP of PDL proceeds to high conversion not only at 80 °C in bulk but also at room temperature and in dilute solution. The synthesized PDL homopolymers and block copolymers with poly(ethylene glycol) were characterized by high-temperature GPC (HT-GPC), H NMR and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS). Melting temperatures, determined by differential scanning calorimetry, are also reported.

  1. Unsaturated Fatty Acid Esters Metathesis Catalyzed by Silica Supported WMe5

    KAUST Repository

    Riache, Nassima; Callens, Emmanuel; Talbi, Karima; Basset, Jean-Marie

    2015-01-01

    Metathesis of unsaturated fatty acid esters (FAEs) by silica supported multifunctional W-based catalyst is disclosed. This transformation represents a novel route towards unsaturated di-esters. Especially, the self-metathesis of ethyl undecylenate

  2. Poly(BODIPY)s : A New Class of Tunable Polymeric Dyes

    NARCIS (Netherlands)

    Alemdaroglu, Fikri E.; Alexander, Seth C.; Ji, Dongmei; Prusty, Deepak K.; Boersch, Michael; Herrmann, Andreas

    2009-01-01

    We present a new class of polymeric dyes bearing the difluoroboraindacene (BODIPY) chromophore within the main chain. Starting from a diiodinated BODIPY monomer, homo- and copolymers with a fully conjugated backbone were efliciently synthesized by transition-metal-catalyzed polycondensation

  3. Elastic Modulus at High Frequency of Polymerically Stabilized Suspensions

    NARCIS (Netherlands)

    Nommensen, P.A.; Duits, Michael H.G.; van den Ende, Henricus T.M.; Mellema, J.

    2000-01-01

    The elastic moduli of polymerically stabilized suspensions consisting of colloidal silica particles coated with endgrafted PDMS (Mn = 80 000) in heptane, were measured as a function of concentration. And the elastic modulus at high frequency G'.. was quantitatively described by model calculations

  4. Phosphazene-catalyzed ring-opening polymerization of ε-caprolactone: Influence of solvents and initiators

    KAUST Repository

    Alamri, Haleema; Zhao, Junpeng; Pahovnik, David; Hadjichristidis, Nikolaos

    2014-01-01

    Phosphazene base (t-BuP2) catalysed metal-free ring-opening polymerization of ε-caprolactone (ε-CL) at room temperature with various protic initiators in different solvents was investigated. The polymerization proceeded, in most cases, in a controlled manner to afford poly(ε-caprolactone) with low dispersities and expected molecular weights. Kinetic studies showed that when a primary alcohol was used as an initiator the polymerization rate in different solvents followed the order of dichloromethane ≫ toluene > 1,4-dioxane ≈ tetrahydrofuran. Extremely fast polymerization of l-lactide (LLA), which was added as a second monomer, was observed in different solvents giving rise to poly(ε-caprolactone)-b- poly(l-lactide) diblock copolymers with neat PLLA blocks despite incomplete conversion of ε-CL. The dependence of polymerization rate on the concentrations of ε-CL and t-BuP2 was also revealed. In addition to primary alcohol, the feasibility of using other protic initiators, such as secondary alcohol (either on a small molecule or a polymer chain-end), (aliphatic/aromatic) amide, carboxylic acid, phenol and thiophenol, was also investigated. These studies provided important information for designing a metal-free route towards polyester-based (bio)materials. © 2014 the Partner Organisations.

  5. Low-temperature specific-heat and thermal-conductivity of silica aerogels

    DEFF Research Database (Denmark)

    Bernasconi, A.; Sleator, T.; Posselt, D.

    1992-01-01

    Specific heat, C(p), and thermal conductivity, lambda, have been measured on a series of base-catalyzed silica aerogels at temperatures between 0.05 and 20 K. Results for both C(p)(T) and lambda(T) confirm that the different length-scale regions observed in the aerogel structure are reflected...

  6. Isolation and Characterization of Silaffin that Catalyze Biosilica Formation from Marine Diatom Chaetoceros gracilis

    Directory of Open Access Journals (Sweden)

    AGNES IMELDA MANURUNG

    2007-09-01

    Full Text Available The method of making silica in industries requires extreme conditions. The finding of proteins involved in the formation of biosilica from diatoms, has opened up an alternative way of production. Chaetoceros gracilis is one of the diatoms, which is potential in producing silaffin protein. This study aimed to isolate and to characterize the protein. We also analyzed the protein activity toward tetraethoxyorthosilicate (TEOS substrate in in vitro reaction. Diatom biomass was harvested and further kept in 2% SDS/100 mM EDTA solution. Protein isolation was conducted by dissolving the silica and separating the protein by soaking in 2 M HF/8 M NH4F. Protein concentration was analyzed using Bradford method and the molecular weight was estimated through SDS-PAGE. Protein activity was observed by reacting it with TEOS substrate to form silica polymer and measured by colorimetric molibdate assay. Protein concentration was 1.20 mg/ml and appeared filamentous. The apparent molecular weights consisted of 12, 23, 42, 44 kDa. These protein was able to polymerize the silica at room temperature within 10 min. As much as 85.65 μmol TEOS was polymerized per 1.4 × 106 silaffin protein per min. SEM analysis showed the formation of spherical, aggregate biosilica.

  7. Isolation and Characterization of Silaffin that Catalyze Biosilica Formation from Marine Diatom Chaetoceros gracilis

    Directory of Open Access Journals (Sweden)

    AGNES IMELDA MANURUNG

    2007-09-01

    Full Text Available The method of making silica in industries requires extreme conditions. The finding of proteins involved in the formation of biosilica from diatoms, has opened up an alternative way of production. Chaetoceros gracilis is one of the diatoms, which is potential in producing silaffin protein. This study aimed to isolate and to characterize the protein. We also analyzed the protein activity toward tetraethoxyorthosilicate (TEOS substrate in in vitro reaction. Diatom biomass was harvested and further kept in 2% SDS/100 mM EDTA solution. Protein isolation was conducted by dissolving the silica and separating the protein by soaking in 2 M HF/8 M NH4F. Protein concentration was analyzed using Bradford method and the molecular weight was estimated through SDS-PAGE. Protein activity was observed by reacting it with TEOS substrate to form silica polymer and measured by colorimetric molibdate assay. Protein concentration was 1.20 mg/ml and appeared filamentous. The apparent molecular weights consisted of 12, 23, 42, 44 kDa. These protein was able to polymerize the silica at room temperature within 10 min. As much as 85.65 mol TEOS was polymerized per 1.4 x 106 silaffin protein per min. SEM analysis showed the formation of spherical, aggregate biosilica.

  8. Could Mineral Surfaces have Oriented Amino Acid Polymerization Towards Useful Products?

    Science.gov (United States)

    Lambert, J. F.; Sakhno, Y.; Battistella, A.; Ribetto, B.; Mezzetti, A.; Georgelin, T.; Jaber, M.; Michot, L.

    2017-07-01

    We investigated selective amino acid polymerization on the surface of silicic minerals. Specific amino acid couples were deposited on silica or clays, thermally activated, and the oligomers formed were analyzed. Very different behaviors were observed.

  9. Preparation of EVA/silica nano composites characterized with solid state nuclear magnetic resonance; Obtencao de nanocomposito de EVA/SILICA e caracterizacao por ressonancia magnetica nuclear no estado solido

    Energy Technology Data Exchange (ETDEWEB)

    Passos, Adriano A; Tavares, Maria I.B.; Neto, Roberto C.P.; Moreira, Leonardo A; Ferreira, Antonio G., E-mail: mibt@ima.ufrj.br [Centro de Tecnologia, Instituto de Macromoleculas Professora Eloisa Mano, Universidade Federal do Rio de Janeiro, Rio de Janeiro, RJ (Brazil)

    2011-07-01

    Nano composites of poly(ethylene-co-vinyl acetate)/silica (SiO{sub 2}) with dimensions of ca. 40 nm were prepared via solution intercalation employing chloroform as a solvent. They were mainly characterized with nuclear magnetic resonance spectroscopy (NMR) employing carbon-13 (polymeric matrix), silicon-29 (nanoparticles) and through the determination of the proton spin-lattice relaxation time in the rotating frame (T{sub 1{rho}H}) (polymer matrix). From the NMR results it was inferred that up to 5% of silica in mass a well dispersed nano composite was obtained, owing to a strong interaction between silica and the EVA matrix. (author)

  10. Synthesis and Gas Transport Properties of Hyperbranched Polyimide–Silica Hybrid/Composite Membranes

    Directory of Open Access Journals (Sweden)

    Masako Miki

    2013-12-01

    Full Text Available Hyperbranched polyimide–silica hybrids (HBPI–silica HBDs and hyperbranched polyimide–silica composites (HBPI–silica CPTs were prepared, and their general and gas transport properties were investigated to clarify the effect of silica sources and preparation methods. HBPI–silica HBDs and HBPI–silica CPTs were synthesized by two-step polymerization of A2 + B3 monomer system via polyamic acid as precursor, followed by hybridizing or blending silica sources. Silica components were incorporated by the sol-gel reaction with tetramethoxysilane (TMOS or the addition of colloidal silica. In HBPI-silica HBDs, the aggregation of silica components is controlled because of the high affinity of HBPI and silica caused by the formation of covalent bonds between HBPI and silica. Consequently, HBPI-silica HBDs had good film formability, transparency, and mechanical properties compared with HBPI-silica CPTs. HBPI-silica HBD and CPT membranes prepared via the sol-gel reaction with TMOS showed specific gas permeabilities and permselectivities for CO2/CH4 separation, that is, both CO2 permeability and CO2/CH4 selectivity increased with increasing silica content. This result suggests that gas transport can occur through a molecular sieving effect of the porous silica network derived from the sol-gel reaction and/or through the narrow interfacial region between the silica networks and the organic matrix.

  11. Differently-catalyzed silica-based precursors as functional additives for the epoxy-based hybrid materials

    Czech Academy of Sciences Publication Activity Database

    Perchacz, Magdalena; Beneš, Hynek; Zhigunov, Alexander; Serkis, Magdalena; Pavlova, Ewa

    2016-01-01

    Roč. 99, 2 September (2016), s. 434-446 ISSN 0032-3861 R&D Projects: GA ČR(CZ) GA14-05146S; GA MŠk(CZ) LO1507 Institutional support: RVO:61389013 Keywords : epoxy-silica hybrid material * solvent-free sol-gel process * silica-based precursor Subject RIV: CD - Macromolecular Chemistry Impact factor: 3.684, year: 2016

  12. Poly(2-aminothiazole)-silica nanocomposite particles: Synthesis and morphology control

    Science.gov (United States)

    Zou, Hua; Wu, Di; Sun, Hao; Chen, Suwu; Wang, Xia

    2018-04-01

    Synthesis of conducting polymer-silica colloidal nanocomposites has been recognized as an effective method to overcome the poor processability of heterocyclic conducting polymers prepared by chemical oxidative method. However, the morphology control of such conducting polymer-silica nanocomposites was seldomly reported in the literature. Novel poly(2-aminothiazole)(PAT)-silica nanocomposite particles can be conveniently prepared by chemical oxidative polymerization of 2-aminothiazole using CuCl2 oxidant in the presence of ∼20 nm silica nanoparticles. The effects of varying the oxidant/monomer ratio and silica sol concentration on the morphology and size of the resulting PAT-silica nanocmposites have been studied. Optimization of the oxidant/monomer molar ratio and initial silica sol concentration allows relatively round spherical particles of 150-350 nm in diameter to be achieved. The nanocomposite particles have a well-defined raspberry-like morphology with a silica-rich surface, but a significant fraction of PAT component still exists on the surface and, which is beneficial for its applications. Furthermore, the surface compositions of the colloidal nanocomposites could be regulated to some extent. Based on the above results, a possible formation mechanism of the spherical nanocomposite particles is proposed.

  13. Non-isothermal crystallization kinetic of poly(ethylene terephthalate)/fumed silica (PET/SiO2) prepared by in situ polymerization

    International Nuclear Information System (INIS)

    Antoniadis, G.; Paraskevopoulos, K.M.; Bikiaris, D.; Chrissafis, K.

    2010-01-01

    A number of poly(ethylene terephthalate) (PET) nanocomposites were prepared by in situ polymerization using different amounts (0.5, 1, 2, 3 and 4 wt%) of fumed silica (SiO 2 ). The polymerization of PET was carried out by the two-stage melt polycondensation method. From DSC studies it was found that the melting point of the nanocomposites was shifted slightly to higher temperatures by the addition of SiO 2 till 3 wt% while for PET-4 wt% SiO 2 nanocomposite the melting point was reduced. As the amount of SiO 2 was increased the crystallization became faster, and there was, also, a shifting of the temperature of the crystallization peak to higher values, this being evidence that SiO 2 can act as nucleating agent. At higher content (3 and 4 wt%) the temperature of the crystallization peak is lower than that of PET-2 wt% SiO 2 due to the formation of crosslinked macromolecules. The activation energy is calculated with the Friedman's method. PET/SiO 2 samples present lower activation energy compared to that of neat PET, except those of PET-4% SiO 2 , in which the activation energy have a maximum value for α = 0.8 probably due to the second crystallization peak. Extensive crystallization studies by using Avrami, Ozawa and Malek methods verified that PET and its nanocomposites must be crystallized by two mechanisms with different activation energies taking place in different degrees of crystallization.

  14. Surface modification of nano-silica on the ligament advanced reinforcement system for accelerated bone formation: primary human osteoblasts testing in vitro and animal testing in vivo.

    Science.gov (United States)

    Li, Mengmeng; Wang, Shiwen; Jiang, Jia; Sun, Jiashu; Li, Yuzhuo; Huang, Deyong; Long, Yun-Ze; Zheng, Wenfu; Chen, Shiyi; Jiang, Xingyu

    2015-05-07

    The Ligament Advanced Reinforcement System (LARS) has been considered as a promising graft for ligament reconstruction. To improve its biocompatibility and effectiveness on new bone formation, we modified the surface of a polyethylene terephthalate (PET) ligament with nanoscale silica using atom transfer radical polymerization (ATRP) and silica polymerization. The modified ligament is tested by both in vitro and in vivo experiments. Human osteoblast testing in vitro exhibits an ∼21% higher value in cell viability for silica-modified grafts compared with original grafts. Animal testing in vivo shows that there is new formed bone in the case of a nanoscale silica-coated ligament. These results demonstrate that our approach for nanoscale silica surface modification on LARS could be potentially applied for ligament reconstruction.

  15. Interferences of Silica Nanoparticles in Green Fluorescent Protein Folding Processes.

    Science.gov (United States)

    Klein, Géraldine; Devineau, Stéphanie; Aude, Jean Christophe; Boulard, Yves; Pasquier, Hélène; Labarre, Jean; Pin, Serge; Renault, Jean Philippe

    2016-01-12

    We investigated the relationship between unfolded proteins, silica nanoparticles and chaperonin to determine whether unfolded proteins could stick to silica surfaces and how this process could impair heat shock protein activity. The HSP60 catalyzed green fluorescent protein (GFP) folding was used as a model system. The adsorption isotherms and adsorption kinetics of denatured GFP were measured, showing that denaturation increases GFP affinity for silica surfaces. This affinity is maintained even if the surfaces are covered by a protein corona and allows silica NPs to interfere directly with GFP folding by trapping it in its unstructured state. We determined also the adsorption isotherms of HSP60 and its chaperonin activity once adsorbed, showing that SiO2 NP can interfere also indirectly with protein folding through chaperonin trapping and inhibition. This inhibition is specifically efficient when NPs are covered first with a layer of unfolded proteins. These results highlight for the first time the antichaperonin activity of silica NPs and ask new questions about the toxicity of such misfolded proteins/nanoparticles assembly toward cells.

  16. Modular in situ-Functionalization Strategy: Multicomponent Polymerization via Palladium/Norbornene Cooperative Catalysis.

    Science.gov (United States)

    Yoon, Ki-Young; Dong, Guangbin

    2018-05-23

    Herein, we report the palladium/norbornene cooperatively catalyzed polymerization, which simplifies synthesis of functional aromatic polymers, including conjugated polymers. Specifically, an A2B2C-type multicomponent polymerization is developed using ortho-amination/ipso-alkynylation reaction for preparing various amine-functionalized arylacetylene-containing polymers. Within a single catalytic cycle, the amine side-chains are site-selectively installed in situ via C-H activation during the polymerization process, which represents a major difference from conventional cross-coupling polymerizations. This in situ-functionalization strategy enables modular incorporation of functional side-chains from simple monomers, thereby conveniently affording a diverse range of functional polymers. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. On the enhancement of pervaporation properties of plasma-deposited hybrid silica membranes

    Energy Technology Data Exchange (ETDEWEB)

    Ngamou, P.H.T.; Creatore, M. [Department of Applied Physics, Eindhoven University of Technology, 5600 MB Eindhoven (Netherlands); Overbeek, J.P.; Kreiter, R.; Van Veen, H.M.; Vente, J.F. [ECN, Energy research Centre of the Netherlands, Petten (Netherlands); Cuperus, P.F. [SolSep BV, Apeldoorn (Netherlands)

    2013-06-24

    The separation performance of a polymeric-supported hybrid silica membrane in the dehydration process of a butanol-water mixture at 95C has been enhanced by applying a bias to the substrate during the plasma deposition.

  18. An effective approach to synthesis of poly(methyl methacrylate)/silica nanocomposites

    International Nuclear Information System (INIS)

    Ding Xuefeng; Wang Zichen; Han Dongxue; Zhang Yuanjian; Shen Yanfei; Wang Zhijuan; Niu Li

    2006-01-01

    A novel synthetic route for nearly monodispersed poly(methyl methacrylate)/SiO 2 composite particles (PMSCP) is reported. Silica nanoparticles modified with oleic acid were used as 'seeds'. Methyl methacrylate (MMA) monomer was copolymerized with oleic acid via in situ emulsion polymerization, in the presence of an initiator; it resulted finally in the formation of composites with core-shell morphology. The composite particles were examined by transmission electron microscopy (TEM), scanning electron microscopy (SEM), x-ray photoelectron spectroscopy (XPS) and thermogravimetric analysis (TGA). The number of silica particles inside the composite particles increases with an increase in the silica concentration. The effect of grafted silica concentration on the morphology of PMSCP is also reported in detail. It was found by thermogravimetric analysis that PMSCP show a potential application for fire retardance

  19. Silicoaluminates as “Support Activator” Systems in Olefin Polymerization Processes

    Science.gov (United States)

    Tabernero, Vanessa; Camejo, Claudimar; Terreros, Pilar; Alba, María Dolores; Cuenca, Tomás

    2010-01-01

    In this work we report the polymerization behaviour of natural clays (montmorillonites, MMT) as activating supports. These materials have been modified by treatment with different aluminium compounds in order to obtain enriched aluminium clays and to modify the global Brönsted/Lewis acidity. As a consequence, the intrinsic structural properties of the starting materials have been changed. These changes were studied and these new materials used for ethylene polymerization using a zirconocene complex as catalyst. All the systems were shown to be active in ethylene polymerization. The catalyst activity and the dependence on acid strength and textural properties have been also studied. The behaviour of an artificial silica (SBA 15) modified with an aluminium compound to obtain a silicoaluminate has been studied, but no ethylene polymerization activity has been found yet.

  20. Treatment of oil sands mature fine tailings with silica

    Energy Technology Data Exchange (ETDEWEB)

    Moffett, R.H. [DuPont Canada Inc., Mississauga, ON (Canada)

    2010-07-01

    This PowerPoint presentation discussed a method of treating mature fine tailings (MFT) with silica. Rheology modifications with silica treatments were examined. Experimental studies demonstrated a significant slump at 30 minutes after mixing. Flow properties were studied at a 2 degree angle. The MFT thin lift evaporative drying procedure was used to determine the effects of the silica treatments. Methods of using pressure to dewater MFTs were reviewed. The results of a field test conducted to determine the flow behaviour of MFTs treated with low dose silica were presented. Drying characteristics and strength gains were also evaluated. Results of the study showed that the MFTs had a tendency to channel at discharge points. After a 15 day period that included a freeze-thaw the MFTs had cracks that continued to enlarge, full depth cracking, and fine cracking. The field tests demonstrated that in-situ polymerization of silica within the water phase of fluid fine tails provides significant modifications to rheological properties, and that the onset of rheological modification can be controlled over a range of conditions and times. tabs., figs.

  1. Variability of biological effects of silicas: Different degrees of activation of the fifth component of complement by amorphous silicas

    International Nuclear Information System (INIS)

    Governa, Mario; Amati, Monica; Fenoglio, Ivana; Valentino, Matteo; Coloccini, Sabrina; Bolognini, Lucia; Carlo Botta, Gian; Emanuelli, Monica; Pierella, Francesca; Volpe, Anna Rita; Astolfi, Paola; Carmignani, Marco; Fubini, Bice

    2005-01-01

    A biogenic and a pyrogenic amorphous silica were incubated in normal human plasma and compared on a per unit surface basis for their ability to split C5 molecules and yield small C5a peptides. Since C5a peptides induce selective chemotactic attraction of polymorphonuclear leukocytes (PMN), measurement of PMN-induced chemotaxis was used as an index of C5 activation. Though to a lesser extent than the crystalline forms, amorphous silicas can promote the cleavage of C5 protein and generation of C5a-like fragment. The biogenic silica, which differs from the pyrogenic variety in particle shape, level of contaminants, and degree of surface hydrophilicity, besides specific surface, induced a greater response. Both silicas activated C5 through a process which seems to involve multiple events similar to those induced by crystalline silica. C5 molecules are adsorbed and hydroxyl radicals are generated through Haber Weiss cycles catalyzed by the redox-active iron present at the particle surface either as trace impurities or chelated from plasma by silanol groups. In turn, these radicals convert native C5 to an oxidized C5-like form C5(H 2 O 2 ). Finally, C5(H 2 O 2 ) is cleaved by protease enzymatic action of plasma kallikrein activated by the same silica dusts, yielding a product, C5a(H 2 O 2 ), having the same functional characteristic as C5a

  2. Characterization of transparent silica films deposited on polymeric materials

    International Nuclear Information System (INIS)

    Teshima, K.; Sugimura, H.; Inoue, Y.; Takai, O.

    2002-01-01

    Silica films were synthesized by capacitively coupled RF PECVD using mixtures of organo-silane and oxygen as a source. The chemical bonding states and compositions of the films deposited were evaluated with FTIR and XPS. Film surfaces and cross-sections were observed by SEM. Oxygen transmission rates (OTR) of the films coated on polyethylene terephthalate (PET) substrates were measured by an isopiestic method. (Authors)

  3. Tailoring Silica Surface Properties by Plasma Polymerization for Elastomer Applications

    NARCIS (Netherlands)

    Tiwari, M.; Dierkes, Wilma K.; Datta, Rabin; Talma, Auke; Noordermeer, Jacobus W.M.; van Ooij, W.J.

    2009-01-01

    The surface properties of reinforcing fillers are a crucial factor for dispersion and filler–polymer interaction in rubber compounds, as they strongly influence the final vulcanized properties of the rubber article. Silica is gaining more and more importance as reinforcing filler for rubbers, as it

  4. Tailoring Silica Surface Properties by Plasma Polymerization for Elastomer Applications

    NARCIS (Netherlands)

    Tiwari, M.; Dierkes, W.K.; Datta, R.N.; Talma, A.G.; Noordermeer, J.W.M.; van Ooij, W.J.

    2011-01-01

    The surface properties of reinforcing fillers are a crucial factor for dispersion and filler–polymer interaction in rubber compounds, as they strongly influence the final vulcanized properties of the rubber article. Silica is gaining more and more importance as reinforcing filler for rubbers, as it

  5. Sequential polymerization of ethylene oxide, ε-caprolactone and l-lactide: A one-pot metal-free route to tri- and pentablock terpolymers

    KAUST Repository

    Zhao, Junpeng; Pahovnik, David; Gnanou, Yves; Hadjichristidis, Nikolaos

    2014-01-01

    Metal-free polymerization of ethylene oxide (EO) catalyzed by a relatively mild phosphazene base (t-BuP2) was proven feasible, which enabled the one-pot sequential polymerization of EO, ε-caprolactone, and l-lactide. Using either 3-phenyl-1-propanol

  6. Kinetics of enzyme-catalyzed cross-linking of feruloylated arabinan from sugar beet

    DEFF Research Database (Denmark)

    Abang Zaidel, Dayang Norulfairuz; Arnous, Anis; Holck, Jesper

    2011-01-01

    the kinetics of HRP catalyzed cross-linking of FA esterified to α-(1,5)-linked arabinans are affected by the length of the arabinan chains carrying the feruloyl substitutions. The kinetics of the HRP-catalyzed cross-linking of four sets of arabinan samples from sugar beet pulp, having different molecular...... weights and hence different degrees of polymerization, were monitored by the disappearance of FA absorbance at 316 nm. MALDI-TOF/TOF-MS analysis confirmed that the sugar beet arabinans were feruloyl-substituted, and HPLC analysis verified that the amounts of diFAs increased when FA levels decreased...

  7. Radiation hardening in sol-gel derived Er3+-doped silica glasses

    International Nuclear Information System (INIS)

    Hari Babu, B.; León Pichel, Mónica; Ollier, Nadège; El Hamzaoui, Hicham; Bigot, Laurent; Savelii, Inna; Bouazaoui, Mohamed; Poumellec, Bertrand; Lancry, Matthieu; Ibarra, Angel

    2015-01-01

    The aim of the present paper is to report the effect of radiation on the Er 3+ -doped sol-gel silica glasses. A possible application of these sol-gel glasses could be their use in harsh radiation environments. The sol-gel glasses are fabricated by densification of erbium salt-soaked nanoporous silica xerogels through polymeric sol-gel technique. The radiation-induced attenuation of Er 3+ -doped sol-gel silica is found to increase with erbium content. Electron paramagnetic resonance studies reveal the presence of E′ δ point defects. This happens in the sol-gel aluminum-silica glass after an exposure to γ-rays (kGy) and in sol-gel silica glass after an exposure to electrons (MGy). The concentration levels of these point defects are much lower in γ-ray irradiated sol-gel silica glasses. When the samples are co-doped with Al, the exposure to γ-ray radiation causes a possible reduction of the erbium valence from Er 3+ to Er 2+ ions. This process occurs in association with the formation of aluminum oxygen hole centers and different intrinsic point defects

  8. Coupling Reagent for UV/vis Absorbing Azobenzene-Based Quantitative Analysis of the Extent of Functional Group Immobilization on Silica.

    Science.gov (United States)

    Choi, Ra-Young; Lee, Chang-Hee; Jun, Chul-Ho

    2018-05-18

    A methallylsilane coupling reagent, containing both a N-hydroxysuccinimidyl(NHS)-ester group and a UV/vis absorbing azobenzene linker undergoes acid-catalyzed immobilization on silica. Analysis of the UV/vis absorption band associated with the azobenzene group in the adduct enables facile quantitative determination of the extent of loading of the NHS groups. Reaction of NHS-groups on the silica surface with amine groups of GOx and rhodamine can be employed to generate enzyme or dye-immobilized silica for quantitative analysis.

  9. Incorporation of Znq2 complexes into mesoporous silica and their transparent polymer luminescent nanocomposites

    International Nuclear Information System (INIS)

    Du Yaying; Fu Yuqin; Shi Yongli; Lue Xiaodan; Lue Changli; Su Zhongmin

    2009-01-01

    Znq 2 -functionalized colloidal mesoporous silicas (Znq 2 -CMS)/polymer transparent nanocomposites were prepared by in situ bulk polymerization. CMS nanoparticles or nanorods with hydroxyl-, mercapto- and sulfonic-functionalized interiors were obtained by different synthetic routes in the nanosize dimensions between 50 and 500 nm. The luminescent Znq 2 complex was successfully introduced in the pores of different mesoporous silicas by chemical adsorption as the driving force. The different internal circumstances of mesoporous silicas had an obvious effect on the luminescence and lifetime of Znq 2 complex. The transparent fluorescent nanocomposites were fabricated from different Znq 2 -CMS and suitable monomers. The Znq 2 -CMS were uniformly dispersed in the polymer matrix without evident aggregation. The photoluminescence properties of Znq 2 -CMS in the transparent matrix exhibited a dependence on the inner surrounding of CMS due to the interaction between Znq 2 -CMS and polymers. The maximum emission peak of the nanocomposites had a red-shift of 28 nm as compared to pure Znq 2 -CMS. - Graphical abstract: Znq 2 -functionalized colloidal mesoporous silicas (Znq 2 -CMS)/polymer transparent fluorescent nanocomposites were prepared by in situ bulk polymerization. The figure shows the synthetic scheme for the Znq 2 -CMS and their transparent bulk nanocomposites.

  10. Polysiloxanes derived from the controlled hydrolysis of tetraethoxysilane as precursors to silica for use in ceramic processing

    Science.gov (United States)

    Philipp, Warren H.

    1990-01-01

    Synthesis, properties, and potential applications in ceramic processing for two polysiloxane silica precursors derived from the controlled hydrolysis of tetraethoxysilane (TEOS) are presented. The higher molecular weight TEOS-A is a thick adhesive liquid of viscosity 8000 to 12,000 c.p. having a SiO2 char yield of about 55 percent. The lower molecular weight TEOS-B is a more fluid liquid of viscosity 150 to 200 c.p. having a SiO2 char yield of about 52 percent. The acid catalyzed hydrolysis of TEOS to hydrated silica gel goes through a series of polysiloxane intermediates. The rate of this transition increases with the quantity of water added to the TEOS; thus, for ease of polymer isolation, the amount of water added must be carefully determined so as to produce the desired polymer in a reasonable time. The water to TEOS mole ratio falls in the narrow range of 1.05 for TEOS-A and 0.99 for TEOS-B. Further polymerization or gelation is prevented by storing at -5 C in a freezer. Both polysiloxanes thermoset to a glassy solid at 115 C. The liquid polymers are organic in nature in that they are miscible with toluene and ethanol, slightly souble in heptane, but immiscible with water. For both polymers, results on viscosity versus time are given at several temperatures and water additions. Based on these results, some examples of practical utilization of the precursors for ceramic fabrication are given.

  11. Radiation effect on polystyrene deposited and grafted on silica gel

    International Nuclear Information System (INIS)

    Kusama, Y.; Udagawa, A.; Takehisa, M.

    1978-01-01

    The effect of radiation on polystyrene was studied in the presence and absence of silica gel by molecular weight measurement with gel permeation chromatography (GPC). Polystyrene crosslinked under vacuum in the absence of silica gel, but it either crosslinked or degraded by radiation, depending on the molecular weight of the polymer in the presence of silica gel. part of the deposited polymer bonded to silica gel by radiation; the G value for graft-chain formation is in the range of 0.01 to 0.1. Irradiation of polystyrene grafted on silica gel resulted in degradation of the graft chain because of the transfer of energy from silica gel. The G value for main chain scission was about 2 when graft polymer was irradiated in the absence of homopolymer. The degradation of graft polymer was suppressed when the polymer was irradiated in the presence of homopolymer, and the amount of unextractable polymer from silica gel increased with increasing irradiation. This adds evidence to the estimation that an increase in grafting percent coupled with a slight decrease in molecular weight at a later stage of radiation-induced polymerization of styrene adsorbed on slica gel is due to a secondary effect of radiation on the polymer

  12. Polymer-silica hybrids for separation of CO2 and catalysis of organic reactions

    Science.gov (United States)

    Silva Mojica, Ernesto

    Porous materials comprising polymeric and inorganic segments have attracted interest from the scientific community due to their unique properties and functionalities. The physical and chemical characteristics of these materials can be effectively exploited for adsorption applications. This dissertation covers the experimental techniques for fabrication of poly(vinyl alcohol) (PVA) and silica (SiO2) porous supports, and their functionalization with polyamines for developing adsorbents with potential applications in separation of CO2 and catalysis of organic reactions. The supports were synthesized by processes involving (i) covalent cross-linking of PVA, (ii) hydrolysis and poly-condensation of silica precursors (i,e,. sol-gel synthesis), and formation of porous structures via (iii) direct templating and (iv) phase inversion techniques. Their physical structure was controlled by the proper combination of the preparation procedures, which resulted in micro-structured porous materials in the form of micro-particles, membranes, and pellets. Their adsorption characteristics were tailored by functionalization with polyethyleneimine (PEI), and their physicochemical properties were characterized by vibrational spectroscopy (FTIR, UV-vis), microscopy (SEM), calorimetry (TGA, DSC), and adsorption techniques (BET, step-switch adsorption). Spectroscopic investigations of the interfacial cross-linking reactions of PEI and PVA with glutaraldehyde (GA) revealed that PEI catalyzes the cross-linking reactions of PVA in absence of external acid catalysts. In-situ IR spectroscopy coupled with a focal plane array (FPA) image detector allowed the characterization of a gradient interface on a PEI/PVA composite membrane and the investigation of the cross-linking reactions as a function of time and position. The results served as a basis to postulate possible intermediates, and propose the reaction mechanisms. The formulation of amine-functionalized CO2 capture sorbents was based on the

  13. Formation of Silica-Lysozyme Composites Through Co-Precipitation and Adsorption

    Science.gov (United States)

    van den Heuvel, Daniela B.; Stawski, Tomasz M.; Tobler, Dominique J.; Wirth, Richard; Peacock, Caroline L.; Benning, Liane G.

    2018-04-01

    Interactions between silica and proteins are crucial for the formation of biosilica and the production of novel functional hybrid materials for a range of industrial applications. The proteins control both precipitation pathway and the properties of the resulting silica-organic composites. Here we present data on the formation of silica-lysozyme composites through two different synthesis approaches (co-precipitation vs. adsorption) and show that the chemical and structural properties of these composites, when analyzed using a combination of synchrotron-based scattering (total scattering and SAXS), spectroscopic, electron microscopy and potentiometric methods vary dramatically. We document that while lysozyme was not incorporated into nor did its presence alter the molecular structure of silica, it strongly enhanced the aggregation of silica particles due to electrostatic and potentially hydrophobic interactions, leading to the formation of composites with characteristics differing from pure silica. The differences increased with increasing lysozyme content for both synthesis approaches. Yet, the absolute changes differ substantially between the two sets of composites, as lysozyme did not just affect aggregation during co-precipitation but also particle growth and likely polymerization during co-precipitation. Our results improve the fundamental understanding of how organic macromolecules interact with dissolved and nanoparticulate silica and how these interactions control the formation pathway of silica-organic composites from sodium silicate solutions, a widely available and cheap starting material.

  14. Enzymatic polymerization of bio-based monomers for applications in hydrogels and coatings

    DEFF Research Database (Denmark)

    Hoffmann, Christian; Nguyen, Hiep Dinh; Storgaard, Thomas

    of the enzymatic catalysts that can provide control over polymer structure in functional polymers. Lipase catalyzed polymerizations (specifically CALB) has been applied to prepare functional polyesters and to evaluate the possibilities of using less stable bio-based monomers such as itaconic acid or its...

  15. Silica-gel Catalyzed Facile Synthesis of 3,4-Dihydropyrimidinones

    International Nuclear Information System (INIS)

    Agarwal, Sameer; Aware, Umesh; Patil, Amit; Rohera, Vinita; Jain, Mukul; Patel, Pankaj; Ghate, Manjunath

    2012-01-01

    We have developed a mild and highly effective procedure for the one-pot synthesis of substituted dihydropyrimidinones in high yields using silica gel as a green, highly efficient and recyclable heterogeneous catalyst. Our approach can be applied to the preparation of a wide range of synthetic analogues for structure-activity studies. Investigations in this direction are ongoing. The pyrimidinone ring is a basic substructure of numerous biologically active alkaloids and pharmaceutical products. These cores are regarded as one of the most important groups of drug-like scaffolds. 3,4-dihydropyrimidinones above are known to exhibit variety of pharmacological activity such as calcium channel modulation, mitotic kinesin Eg5 inhibition, antiviral, anti-inflammatory, antibacterial activity, etc

  16. Silica-gel Catalyzed Facile Synthesis of 3,4-Dihydropyrimidinones

    Energy Technology Data Exchange (ETDEWEB)

    Agarwal, Sameer; Aware, Umesh; Patil, Amit; Rohera, Vinita; Jain, Mukul; Patel, Pankaj [Zydus Research Centre, Sarkhej-Bavla N.H., Ahmedabad (India); Ghate, Manjunath [Nirma University, Ahmedabad (India)

    2012-02-15

    We have developed a mild and highly effective procedure for the one-pot synthesis of substituted dihydropyrimidinones in high yields using silica gel as a green, highly efficient and recyclable heterogeneous catalyst. Our approach can be applied to the preparation of a wide range of synthetic analogues for structure-activity studies. Investigations in this direction are ongoing. The pyrimidinone ring is a basic substructure of numerous biologically active alkaloids and pharmaceutical products. These cores are regarded as one of the most important groups of drug-like scaffolds. 3,4-dihydropyrimidinones above are known to exhibit variety of pharmacological activity such as calcium channel modulation, mitotic kinesin Eg5 inhibition, antiviral, anti-inflammatory, antibacterial activity, etc.

  17. Rapid Precipitation of Amorphous Silica in Experimental Systems with Nontronite (NAu-1) and Shewanella oneidensis MR-1

    National Research Council Canada - National Science Library

    Furukawa, Yoko; O'Reilly, S. E

    2007-01-01

    ...) silica globule formation was confirmed in the immediate vicinity of bacterial cells and extracellular polymeric substances in all experimental systems that contained bacteria, whether the bacteria...

  18. Synthesis of polymeric fluorinated sol–gel precursor for fabrication of superhydrophobic coating

    International Nuclear Information System (INIS)

    Li, Qianqian; Yan, Yuheng; Yu, Miao; Song, Botao; Shi, Suqing; Gong, Yongkuan

    2016-01-01

    Graphical abstract: - Highlights: • A polymeric fluorinated sol–gel precursor PFT is designed to fabricate superhydrophobic coatings. • The superhydrophobicity could be governed by the concentration of PFT. • Bio-mimicking self-cleaning property similar to lotus leaves could also be achieved. - Abstract: A fluorinated polymeric sol–gel precursor (PFT) is synthesized by copolymerization of 2,3,4,5,5,5-hexafluoro-2,4-bis(trifluorinated methyl)pentyl methacrylate (FMA) and 3-methacryloxypropyltrimethoxysilane (TSMA) to replace the expensive long chain fluorinated alkylsilanes. The fluorinated silica sol is prepared by introducing PFT as co-precursor of tetraethyl orthosilicate (TEOS) in the sol–gel process with ammonium hydroxide as catalyst, which is then used to fabricate superhydrophobic coating on glass substrate through a simple dip-coating method. The effects of PFT concentrations on the chemical structure of the formed fluorinated silica, the surface chemical composition, surface morphology, wetting and self-cleaning properties of the resultant fluorinated silica coatings were studied by using X-ray powder diffraction (XRD), Fourier transform infrared spectrometer (FTIR), X-ray photoelectron spectrophotometer (XPS), scanning electron microscopy (SEM) and water contact angle measurements (WCA). The results show that the fluorinated silica sols are successfully obtained. The size and size distribution of the fluorinated silica particles are found greatly dependent on the concentration of PFT, which play a crucial role in the surface morphology of the corresponding fluorinated silica coatings. The suitable PFT concentration added in the sol–gel stage, i.e. for F-sol-1 and F-sol-2, is helpful to achieve both the low surface energy and multi-scaled microstructures, leading to the formation of the superhydrophobic coatings with bio-mimicking self-cleaning property similar to lotus leaves.

  19. Mechanistic aspects of the metal catalyzed alternating copolymerization of epoxides and carbon monoxide.

    Science.gov (United States)

    Allmendinger, Markus; Molnar, Ferenc; Zintl, Manuela; Luinstra, Gerrit A; Preishuber-Pflügl, Peter; Rieger, Bernhard

    2005-09-05

    The cobalt-catalyzed alternating copolymerization of epoxides and CO is a novel, direct approach to aliphatic polyesters, such as poly(hydroxybutyrate) (PHB). This reaction was found to be catalyzed by Ph3Si[Co(CO)4] (4) and pyridine affording in a first step the stable mono-insertion product Ph3Si-O-CH(CH3)-CH2-CO-Co(CO)4 (5). However, a profound mechanistic understanding, especially of the role of pyridine as the key component for the polymerization reaction was missing. ATR-IR online monitoring under catalytic conditions and DFT calculations were used to show that an acylpyridinium cation is formed by cleavage of the cobalt-acyl bond of 5 in the presence of pyridine. The Lewis acid thus generated activates the next incoming epoxide monomer for ring opening through [Co(CO)4]-. The catalytic cycle is completed by a subsequent CO insertion in the new cobalt-alkyl bond. The calculations are used to explore the energetic hypersurface of the polymerization reaction and are complemented by extended experimental investigations that also support the mechanistic hypotheses.

  20. Room temperature synthesis of Si-MCM-41 using polymeric version of ethyl silicate as a source of silica

    International Nuclear Information System (INIS)

    Gaydhankar, T.R.; Samuel, V.; Jha, R.K.; Kumar, R.; Joshi, P.N.

    2007-01-01

    Synthesis of mesoporous MCM-41 materials at room temperature using less expensive polymeric version of ethyl silicate (40 wt% SiO 2 ) as a source of silica was established. The influence of crucial synthesis parameters such as molar ratios of H 2 O/NH 4 OH, NH 4 OH/SiO 2 and CTMABr/SiO 2 in gel on the quality of the phase formed was investigated. Powder X-ray diffraction (XRD), scanning electron microscopy (SEM) and low temperature N 2 adsorption-desorption isotherms have been employed to characterize the products. The magnitude of orderness, textural properties and thermal stability of the Si-MCM-41 samples prepared under identical judiciously pre-controlled synthesis conditions using ethyl silicate and conventional tetraethyl orthosilicate (TEOS) were assessed. Even though, ethyl silicate has proved to be suitable source for the preparation of MCM-41 at room temperature, there exists an optimum value of H 2 O/NH 4 OH for different NH 4 OH/SiO 2 molar ratios in the gel. Changes in the morphology were observed when NH 4 OH/SiO 2 , H 2 O/NH 4 OH molar ratios in the gels were changed

  1. Catalytic olefin polymerization with early transition metal compounds

    OpenAIRE

    Eshuis, Johan Jan Willem

    1991-01-01

    The catalysis of organic reactions by soluble metal complexes has become a major tool in synthesis, both in the laboratory and in the chemical industry. Processes catalyzed by transition metal complexes include carbonylation, olefin polymerization, olefin addition, olefin oxidation and alkane and arene oxidation. Traditionally, heterogeneous catalysts have been used for the production of large-scale commodity chemicals such as methanol and ammonia and in the production of high octane gasoline...

  2. Preparation and controlled drug delivery applications of mesoporous silica polymer nanocomposites through the visible light induced surface-initiated ATRP

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Long; Liu, Meiying; Mao, Liucheng; Xu, Dazhuang; Wan, Qing; Zeng, Guangjian; Shi, Yingge [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Wen, Yuanqing, E-mail: m18600788382@163.com [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Zhang, Xiaoyong, E-mail: xiaoyongzhang1980@gmail.com [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Wei, Yen, E-mail: weiyen@tsinghua.edu.cn [Department of Chemistry and The Tsinghua Center for Frontier Polymer Research, Tsinghua University, Beijing, 100084 (China)

    2017-08-01

    Graphical abstract: A novel strategy for surface PEGylation of mesoporous silica nanoparticles was developed based on the light induced surface-initiated atom transfer radical polymerization. - Highlights: • Surface modification of silica nanoparticles through light induced surface-initiated ATRP. • MSNs-NH{sub 2}-poly(IA-co-PEGMA) nanocomposites show high water dispersity. • MSNs-NH{sub 2}-poly(IA-co-PEGMA) nanocomposites are promising for biomedical applications. • The light induced ATRP possesses many advantages as compared with traditional ATRP. - Abstract: The mesoporous materials with large pore size, high specific surface area and high thermal stability have been widely utilized in a variety of fields ranging from environmental remediation to separation and biomedicine. However, surface modification of these silica nanomaterials is required to endow novel properties and achieve better performance for most of these applications. In this work, a new method has been established for surface modification of mesoporous silica nanoparticles (MSNs) that relied on the visible light induced atom transfer radical polymerization (ATRP). In the procedure, the copolymers composited with itaconic acid (IA) and poly(ethylene glycol)methyl acrylate (PEGMA) were grafted from MSNs using IA and PEGMA as the monomers and 10-Phenylphenothiazine(PTH) as the organic catalyst. The successful preparation of final polymer nanocomposites (named as MSNs-NH{sub 2}-poly(IA-co-PEGMA)) were evidenced by a series of characterization techniques. More importantly, the anticancer agent cisplatin can be effectively loaded on MSNs-NH{sub 2}-poly(IA-co-PEGMA) and controlled release it from the drug-loading composites with pH responsive behavior. As compared with conventional ATRP, the light induced surface-initiated ATRP could also be utilized for preparation of various silica polymer nanocomposites under rather benign conditions (e.g. absent of transition metal ions, low polymerization

  3. Synthesis of Donor-Acceptor Conjugated Polymers by "CLICK" Polymerization for OPV applications

    DEFF Research Database (Denmark)

    Brandt, Rasmus Guldbæk; Yu, Donghong

    The intent of this study was to utilize the Copper(I)-catalyzed Azide Alkyne Cycloaddition (CuAAC) as a polymerization technique (“Click” Polymerization) for synthesizing novel π-conjugated low band gap polymers for organic photovoltaic applications (OPV). The chosen approach was to synthesize...... an alternating electron donating (donor, D) and electron withdrawing (acceptor, A) co-polymer. The chosen monomers were well known units, and the novelty lies in using the monomer units with the click methodology. An insoluble alternating copolymer consisting of 2,7-diazido-9,9-dioctyl-9Hflourene and 1...

  4. Triconstituent co-assembly to ordered mesostructured polymer-silica and carbon-silica nanocomposites and large-pore mesoporous carbons with high surface areas.

    Science.gov (United States)

    Liu, Ruili; Shi, Yifeng; Wan, Ying; Meng, Yan; Zhang, Fuqiang; Gu, Dong; Chen, Zhenxia; Tu, Bo; Zhao, Dongyuan

    2006-09-06

    Highly ordered mesoporous polymer-silica and carbon-silica nanocomposites with interpenetrating networks have been successfully synthesized by the evaporation-induced triconstituent co-assembly method, wherein soluble resol polymer is used as an organic precursor, prehydrolyzed TEOS is used as an inorganic precursor, and triblock copolymer F127 is used as a template. It is proposed for the first time that ordered mesoporous nanocomposites have "reinforced concrete"-structured frameworks. By adjusting the initial mass ratios of TEOS to resol, we determined the obtained nanocomposites possess continuous composition with the ratios ranging from zero to infinity for the two constituents that are "homogeneously" dispersed inside the pore walls. The presence of silicates in nanocomposites dramatically inhibits framework shrinkage during the calcination, resulting in highly ordered large-pore mesoporous carbon-silica nanocomposites. Combustion in air or etching in HF solution can remove carbon or silica from the carbon-silica nanocomposites and yield ordered mesoporous pure silica or carbon frameworks. The process generates plenty of small pores in carbon or/and silica pore walls. Ordered mesoporous carbons can then be obtained with large pore sizes of approximately 6.7 nm, pore volumes of approximately 2.0 cm(3)/g, and high surface areas of approximately 2470 m(2)/g. The pore structures and textures can be controlled by varying the sizes and polymerization degrees of two constituent precursors. Accordingly, by simply tuning the aging time of TEOS, ordered mesoporous carbons with evident bimodal pores at 2.6 and 5.8 nm can be synthesized.

  5. Polymerization of Alkylsilanes on ZIF-8 to Hierarchical Siloxane Microspheres and Microflowers

    Directory of Open Access Journals (Sweden)

    Lin Yang

    2017-03-01

    Full Text Available The use of metal-organic frameworks (MOFs in the polymerization field remains comparatively rare up to now, let alone studies on the fabrication of polymer microstructures through a MOFs-catalyzed assembly process. Zeolitic imidazolate framework-8 (ZIF-8, a well-known MOF for its chemical and thermal stabilities, was used to induce a polymerization reaction of saturated alkylsilanes for the first time. The reaction temperature was found to be critical for morphology control of the polymerized ZIF-siloxane composites. The polymerization of alkylsilanes by ZIF-8 at room temperature resulted in siloxane microspheres while rose petal-like microstructures were obtained at higher temperature. The effects of the reaction time on the structures of the polymerization products were also investigated and the polymerization reaction process was proposed. This work expands the field of MOFs’ applications and develops a reasonable method for the multidimensional assembly of MOFs building blocks into required structures or platforms for designing new kinds of hierarchical morphologies, which to our knowledge has not been previously investigated.

  6. Immobilization of Styrene-acrylamide Co-polymer on Either Silica Particles or Inner Surface of Silica Capillary for the Separation of D-Glucose Anomers

    International Nuclear Information System (INIS)

    Ali, Faiz; Kim, Yune Sung; Cheong, Won Jo

    2014-01-01

    Styrene-acrylamide co-polymer was immobilized on porous partially sub-2 μm silica monolith particles and inner surface of fused silica capillary (50 μm ID and 28 cm length) to result in μLC and CEC stationary phases, respectively, for separation of anomeric D-glucose derivatives. Reversed addition-fragmentation transfer (RAFT) polymerization was incorporated to induce surface polymerization. Acrylamide was employed to incorporate amide-functionality in the stationary phase. The resultant μLC and CEC stationary phases were able to separate isomers of D-glucose derivatives with high selectivity and efficiency. The mobile phase of 75/ 25 (v/v) acetonitrile (ACN)/water with 0.1% TFA, was used for HPLC with a packed column (1 mm ID, 300 mm length). The effects of pH and ACN composition on anomeric separation of D-glucose in CEC have been examined. A mobile phase of 85/15 (v/v) ACN/30 mM sodium acetate pH 6.7 was found the optimized mobile phase for CEC. The CEC stationary phase also gave good separation of other saccharides such as maltotriose and Dextran 1500 (MW∼1500) with good separation efficiency (number of theoretical plates ∼300,000/m)

  7. Immobilization of Styrene-acrylamide Co-polymer on Either Silica Particles or Inner Surface of Silica Capillary for the Separation of D-Glucose Anomers

    Energy Technology Data Exchange (ETDEWEB)

    Ali, Faiz; Kim, Yune Sung; Cheong, Won Jo [Inha Univ., Incheon (Korea, Republic of)

    2014-02-15

    Styrene-acrylamide co-polymer was immobilized on porous partially sub-2 μm silica monolith particles and inner surface of fused silica capillary (50 μm ID and 28 cm length) to result in μLC and CEC stationary phases, respectively, for separation of anomeric D-glucose derivatives. Reversed addition-fragmentation transfer (RAFT) polymerization was incorporated to induce surface polymerization. Acrylamide was employed to incorporate amide-functionality in the stationary phase. The resultant μLC and CEC stationary phases were able to separate isomers of D-glucose derivatives with high selectivity and efficiency. The mobile phase of 75/ 25 (v/v) acetonitrile (ACN)/water with 0.1% TFA, was used for HPLC with a packed column (1 mm ID, 300 mm length). The effects of pH and ACN composition on anomeric separation of D-glucose in CEC have been examined. A mobile phase of 85/15 (v/v) ACN/30 mM sodium acetate pH 6.7 was found the optimized mobile phase for CEC. The CEC stationary phase also gave good separation of other saccharides such as maltotriose and Dextran 1500 (MW∼1500) with good separation efficiency (number of theoretical plates ∼300,000/m)

  8. A comparative study of three different synthesis routes for hydrophilic fluorophore-doped silica nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Shahabi, Shakiba [University of Bremen, Advanced Ceramics (Germany); Treccani, Laura, E-mail: treccani@petroceramics.com [Petroceramics S.p.A., Kilometro Rosso Science Park (Italy); Rezwan, Kurosch [University of Bremen, Advanced Ceramics (Germany)

    2016-01-15

    The synthesis of fluorophore-doped silica nanoparticles (FDS NPs) with two conventional approaches, Stöber and microemulsion, as well as a novel amino acid-catalyzed seeds regrowth technique (ACSRT) is presented. The efficiency of each applied synthesis route toward incorporation of selected hydrophilic fluorophores, including rhodamine B isothiocyanate and fluorescein isothiocyanate, without and with an amine-containing crosslinker, into silica matrix was systematically studied. Our results clearly highlight the advantages of ACSRT to obtain FDS NPs with a remarkable encapsulation efficiency, high quantum yield, and enhanced stability against bleaching and dye leaking due to efficient embedding of the dyes inside silica network even without the amine-containing silane reagent. Moreover, evaluation of photostability of FDNPs internalized in human bone cells demonstrates the merits of ACSRT.

  9. Application of Super-Amphiphilic Silica-Nanogel Composites for Fast Removal of Water Pollutants

    Directory of Open Access Journals (Sweden)

    Ayman M. Atta

    2016-10-01

    Full Text Available This work first reports the preparation of super-amphiphilic silica-nanogel composites to reduce the contact angle of water to increase the diffusion of pollutant into adsorbents. In this respect, the silica nanoparticles were encapsulated into nanogels based on ionic and nonionic polyacrylamides by dispersion polymerization technique. The morphologies and the dispersion stability of nanogel composites were investigated to clarify the ability of silica-nanogel composites to adsorb at different interfaces. The feasibility of silica polyacrylamide nanogel composites to act as a high-performance adsorbent for removal of methylene blue (MB dye and heavy metals (Co2+ and Ni2+ from aqueous solution was investigated. The surface tension, contact angle, average pore size, and zeta potential of the silica-nanogel composites have been evaluated. The MB dye and heavy metal adsorption capacity achieved Qmax = 438–387 mg/g which is considerably high. The adsorption capacity results are explained from the changes in the morphology of the silica surfaces as recorded from scanning electron microscopy (SEM.

  10. Simultaneous measurement of polymerization stress and curing kinetics for photo-polymerized composites with high filler contents.

    Science.gov (United States)

    Wang, Zhengzhi; Landis, Forrest A; Giuseppetti, Anthony A M; Lin-Gibson, Sheng; Chiang, Martin Y M

    2014-12-01

    Photopolymerized composites are used in a broad range of applications with their performance largely directed by reaction kinetics and contraction accompanying polymerization. The present study was to demonstrate an instrument capable of simultaneously collecting multiple kinetics parameters for a wide range of photopolymerizable systems: degree of conversion (DC), reaction exotherm, and polymerization stress (PS). Our system consisted of a cantilever beam-based instrument (tensometer) that has been optimized to capture a large range of stress generated by lightly-filled to highly-filled composites. The sample configuration allows the tensometer to be coupled to a fast near infrared (NIR) spectrometer collecting spectra in transmission mode. Using our instrument design, simultaneous measurements of PS and DC are performed, for the first time, on a commercial composite with ≈80% (by mass) silica particle fillers. The in situ NIR spectrometer collects more than 10 spectra per second, allowing for thorough characterization of reaction kinetics. With increased instrument sensitivity coupled with the ability to collect real time reaction kinetics information, we show that the external constraint imposed by the cantilever beam during polymerization could affect the rate of cure and final degree of polymerization. The present simultaneous measurement technique is expected to provide new insights into kinetics and property relationships for photopolymerized composites with high filler content such as dental restorative composites. Published by Elsevier Ltd.

  11. Cellobiose Dehydrogenase Inhibition of Polymerization of Phenolic Compounds and Enhancing Lignin Degradation by Lignina.

    Science.gov (United States)

    Fang, Jing; Liu, Wen; Gao, Pei-Ji

    1999-01-01

    The kinetic behavior of cellobiose dehydrogenase (CDH) was investigated by steady-state initial velocity studies. Variation in the concentration of one substrate led to changes in K(m) and V(max) of the other substrate. The results were consistent with a ping-pong mechanism. In the presence of cellobiose, CDH could reduce many oxidized products catalyzed by soybean hull peroxidase (SHP). The oxidation product of 1-hydroxybenzotriazole (HBT) catalyzed by SHP inactivated the enzyme itself however, CDH could prevent SHP from inactivation by reducing the oxidation product of HBT. CDH could also inhibit the polymerization of phenolic compounds catalyzed by SHP. It was found that the addition of CDH could enhance kraft pulp lignin degradation by ligninases.

  12. Faraday rotation measurements in maghemite-silica aerogels

    International Nuclear Information System (INIS)

    Taboada, E.; Real, R.P. del; Gich, M.; Roig, A.; Molins, E.

    2006-01-01

    Faraday rotation measurements have been performed on γ-Fe 2 O 3 /SiO 2 nanocomposite aerogels which are light, porous and transparent magnetic materials. The materials have been prepared by sol-gel polymerization of a silicon alkoxide, impregnation of the intermediate silica gel with a ferrous salt and supercritical drying of the gels. During supercritical evacuation of the solvent, spherical nanoparticles of iron oxide, with a mean particle diameter of 8.1±2.0 nm, are formed and are found to be homogenously distributed within the silica matrix. The specific Faraday rotation of the composite was measured at 0.6 T using polarized light of 810 nm, being 29.6 deg./cm. The changes in the plane of polarization of the transmitted light and the magnetization of the material present similar magnetic field dependencies and are characteristic of a superparamagnetic system

  13. Synthesis of click-reactive HPMA copolymers using RAFT polymerization for drug delivery applications

    DEFF Research Database (Denmark)

    Ebbesen, Morten F; Schaffert, D.H.; Crowley, Michael L

    2013-01-01

    This study describes a versatile strategy combining reversible addition fragmentation transfer (RAFT) polymerization and click chemistry to synthesize well-defined, reactive copolymers of N-(2-hydroxypropyl)methacrylamide (HPMA) for drug delivery applications. A novel azide containing monomer N-(3......-azidopropyl)methacrylamide (AzMA) was synthesized and copolymerized with HPMA using RAFT polymerization to provide p(HPMA-co-AzMA) copolymers with high control of molecular weight (∼10–54 kDa) and polydispersity (≤1.06). The utility of the side-chain azide functionality by Cu(I)-catalyzed azide...

  14. Development of new microporous silica membranes for gas separation

    International Nuclear Information System (INIS)

    Camelia Barboiu; Alejandro Mourgues; Beatrice Sala; Serge de Perthuis; Camelia Barboiu; Alejandro Mourgues; Beatrice Sala; Anne Julbe; Jose Sanchez

    2006-01-01

    This paper presents the synthesis and the application of molecular sieving ceramic membranes to purify hydrogen or helium from various gas mixtures. The membranes prepared in this work consist of an ultra-microporous silica-based separative layer produced via a sol-gel process. Ultra microporous silica containing boron is synthesized by the acid catalyzed hydrolysis and condensation of tetra-ethyl-ortho-silicate in ethanol. The layer is deposited inside a tubular asymmetric alumina support with a meso-porous y alumina inner layer. The thickness of the silica layers after treatment is about 200 nm, estimated from their cross-section SEM micrographs. Ultra-microporous membranes (with pore sizes less than 0.7 nm) are thus required to get high selectivity. Such membranes enable to carry out gas separation up to 500 deg C under a transmembrane pressure lower than 8 bars. He and H 2 permeance values close to 10 -7 mol.m -2 s -1 Pa -1 are obtained, associated with ideal selectivities α(He/CO 2 ) and α(H 2 /CO 2 ) between 10 and 20 at 300 deg C. (authors)

  15. Improvement of thermal stability of UV curable pressure sensitive adhesive by surface modified silica nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Pang, Beili; Ryu, Chong-Min; Kim, Hyung-Il, E-mail: hikim@cnu.ac.kr

    2013-11-01

    Highlights: • Silica nanoparticles were modified to carry the vinyl groups for photo-crosslinking. • Acrylic copolymer was modified to have the vinyl groups for photo-crosslinking. • Strong and extensive interfacial bondings were formed between polymer and silica. • Thermal stability of PSA was improved by forming nanocomposite with modified silica. -- Abstract: Pressure sensitive adhesives (PSAs) with higher thermal stability were successfully prepared by forming composite with the silica nanoparticles modified via reaction with 3-methacryloxypropyltrimethoxysilane. The acrylic copolymer was synthesized as a base resin for PSAs by solution polymerization of 2-EHA, EA, and AA with AIBN as an initiator. The acrylic copolymer was further modified with GMA to have the vinyl groups available for UV curing. The peel strength decreased with the increase of gel content which was dependent on both silica content and UV dose. Thermal stability of the composite PSAs was improved noticeably with increasing silica content and UV dose mainly due to the strong and extensive interfacial bonding between the organic polymer matrix and silica.

  16. Modeling intraparticle transports during propylene polymerizations using supported metallocene and dual function metallocene as catalysts: Single particle model

    Directory of Open Access Journals (Sweden)

    Li Hua-Rong

    2014-01-01

    Full Text Available Two improved multigrain models (MGMs for preparing homopolypropylene and long chain branched polypropylene via propylene polymerization using silica-supported metallocene or dual function metallocene as catalysts are presented in this paper. The presented models are used to predict the intraparticle flow fields involved in the polymerizations. The simulation results show that the flow field distributions involve dare basically identical. The results also show that both the two polymerization processes have an initiation stage and the controlling step for them is reaction-diffusion-reaction with the polymerization proceeding. Furthermore, the simulation results show that the intra particle mass transfer resistance has significant effect on the polymerization but the heat transfer resistance can be ignored.

  17. Silica particles encapsulated poly(styrene-divinylbenzene) monolithic stationary phases for micro-high performance liquid chromatography.

    Science.gov (United States)

    Bakry, R; Stöggl, W M; Hochleitner, E O; Stecher, G; Huck, C W; Bonn, G K

    2006-11-03

    In the paper we demonstrate a new approach for the preparation and application of continuous silica bed columns that involve encapsulation (entrapment) of functionalized silica microparticles, which can be used as packing material in micro high performance liquid chromatography (micro-HPLC) and capillary electrochromatography (CEC). Like traditional packed columns, these capillaries possess characterized silica particles that offer high phase ratio and narrow pore size distribution leading to high retention and separation efficiency, respectively. More importantly, immobilization of the microparticles stabilizes the separation bed and eliminates the need for retaining frits. The developed capillary columns were fabricated in exactly the same way as a packed capillary column (slurry packing) but with an additional entrapment step. This immobilization of the packed bed was achieved by in situ polymerization of styrene and divinylbenzene in presence of decanol as a porogen and azobisisobutyronitrile as thermal initiator. Silica particles with different particle sizes and pore sizes ranging from 60 to 4000 A were studied. In addition different modified silica was used, including C-18 reversed phase, anion exchange and chiral stationary phases. Efficient separation of polyphenolic compounds, peptides, proteins and even DNA mutation were achieved using the developed technique depending on the properties of the silica particles used (particles pore size). For example, using 3 microm ProntoSIL C-18 particles with 300 A pore size, separation efficiencies in the range of 120,000-200,000 plates/m were obtained for protein separation, in a 6 cm x 200 microm i.d. capillary column. Using encapsulated silica C-18 with 1000 A pore size, separation of DNA homo and hetero duplexes were achieved under denaturing HPLC conditions for mutation detection. In addition, nucleotides were separated using anion exchange material encapsulated with poly(styrene-divinylbenzene) (PS/DVB), which

  18. Comparative Theoretical Study of the Ring-Opening Polymerization of Caprolactam vs Caprolactone Using QM/MM Methods

    Energy Technology Data Exchange (ETDEWEB)

    Elsasser, Brigitta M.; Schoenen, Iris; Fels, Gregor

    2013-06-07

    Candida antarctica lipase B (CALB) efficiently catalyzes the ring-opening polymerization of lactones to high molecular weight products in good yield. In contrast, an efficient enzymatic synthesis of polyamides has so far not been described in the literature. This obvious difference in enzyme catalysis is the subject of our comparative study of the initial steps of a CALB catalyzed ring-opening polymerization of ε- caprolactone and ε-caprolactam. We have applied docking tools to generate the reactant state complex and performed quantum mechanical/molecular mechanical (QM/MM) calculations at the density functional theory (DFT) PBE0 level of theory to simulate the acylation of Ser105 by the lactone and the lactam, respectively, via the corresponding first tetrahedral intermediates. We could identify a decisive difference in the accessibility of the two substrates in the ring-opening to the respective acyl enzyme complex as the attack of ε-caprolactam is hindered because of an energetically disfavored proton transfer during this part of the catalytic reaction while ε-caprolactone is perfectly processed along the widely accepted pathway using the catalytic triade of Ser105, His224, and Asp187. Since the generation of an acylated Ser105 species is the crucial step of the polymerization procedure, our results give an explanation for the unsatisfactory enzymatic polyamide formation and opens up new possibilities for targeted rational catalyst redesign in hope of an experimentally useful CALB catalyzed polyamide synthesis.

  19. Highly Branched Bio-Based Unsaturated Polyesters by Enzymatic Polymerization

    DEFF Research Database (Denmark)

    Nguyen, Hiep Dinh; Löf, David; Hvilsted, Søren

    2016-01-01

    A one-pot, enzyme-catalyzed bulk polymerization method for direct production of highly branched polyesters has been developed as an alternative to currently used industrial procedures. Bio-based feed components in the form of glycerol, pentaerythritol, azelaic acid, and tall oil fatty acid (TOFA)...... stability, very high water contact angles of up to 141° and a glass transition temperature that could be controlled through the feed composition....

  20. Synthesis of N-halamine-functionalized silica-polymer core-shell nanoparticles and their enhanced antibacterial activity

    International Nuclear Information System (INIS)

    Dong, Alideertu; Wang Tao; Xiao Linghan; Wang Weiwei; Zhao Tianyi; Zheng Xin; Liu Fengqi; Gao Ge; Huang Jinfeng; Chen Yuxin; Lan Shi

    2011-01-01

    N-halamine-functionalized silica-polymer core-shell nanoparticles with enhanced antibacterial activity were synthesized through the encapsulation of silica nanoparticles as support with polymeric N-halamine. The as-synthesized nanoparticles were characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), energy-dispersive x-ray spectrometry (EDX), dynamic light scattering (DLS), thermogravimetric analysis (TGA), and Fourier transform infrared (FTIR). These N-halamine-functionalized silica-polymer core-shell nanoparticles displayed powerful antibacterial performance against both Gram-positive bacteria and Gram-negative bacteria, and their antibacterial activities have been greatly improved compared with their bulk counterparts. Therefore, these N-halamine-functionalized silica-polymer core-shell nanoparticles have the potential for various significant applications such as in medical devices, healthcare products, water purification systems, hospitals, dental office equipment, food packaging, food storage, household sanitation, etc.

  1. Synthesis of N-halamine-functionalized silica-polymer core-shell nanoparticles and their enhanced antibacterial activity

    Energy Technology Data Exchange (ETDEWEB)

    Dong, Alideertu; Wang Tao; Xiao Linghan; Wang Weiwei; Zhao Tianyi; Zheng Xin; Liu Fengqi; Gao Ge [College of Chemistry, Jilin University and MacDiarmid Laboratory, Changchun 130021 (China); Huang Jinfeng; Chen Yuxin [Key Laboratory for Molecular Enzymology and Engineering of the Ministry of Education, Jilin University, Changchun 130012 (China); Lan Shi, E-mail: gaoge@jlu.edu.cn [College of Chemistry and Chemical Engineering, Inner Mongolia University for the Nationalities, Tongliao 028000 (China)

    2011-07-22

    N-halamine-functionalized silica-polymer core-shell nanoparticles with enhanced antibacterial activity were synthesized through the encapsulation of silica nanoparticles as support with polymeric N-halamine. The as-synthesized nanoparticles were characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), energy-dispersive x-ray spectrometry (EDX), dynamic light scattering (DLS), thermogravimetric analysis (TGA), and Fourier transform infrared (FTIR). These N-halamine-functionalized silica-polymer core-shell nanoparticles displayed powerful antibacterial performance against both Gram-positive bacteria and Gram-negative bacteria, and their antibacterial activities have been greatly improved compared with their bulk counterparts. Therefore, these N-halamine-functionalized silica-polymer core-shell nanoparticles have the potential for various significant applications such as in medical devices, healthcare products, water purification systems, hospitals, dental office equipment, food packaging, food storage, household sanitation, etc.

  2. Poly I-lactide-layered double hydroxide nanocomposites via in situ polymerization of I-lactide

    DEFF Research Database (Denmark)

    Katiyar, Vimal; Gerds, N.; Koch, C.B.

    2010-01-01

    The use of clay nanofillers offers a potential route to improved barrier properties in polylactide films. Magnesium–aluminium layered double hydroxides (LDHs) are interesting in this respect and we therefore explored synthesis of PLA-LDH nanocomposites by ring-opening polymerization. This method ...... weight was significantly reduced when in-situ polymerization was conducted in the presence of the LDHs and we suggest that chain termination via LDH surface hydroxyl groups and/or metal-catalyzed degradation could be responsible.......The use of clay nanofillers offers a potential route to improved barrier properties in polylactide films. Magnesium–aluminium layered double hydroxides (LDHs) are interesting in this respect and we therefore explored synthesis of PLA-LDH nanocomposites by ring-opening polymerization. This method...

  3. Synthesis of highly fluorescent silica nanoparticles in a reverse microemulsion through double-layered doping of organic fluorophores

    International Nuclear Information System (INIS)

    Yoo, Hyojong; Pak, Joonsung

    2013-01-01

    Water-soluble, highly fluorescent double-layered silica nanoparticles (FL-DLSN) have been successfully synthesized through a reverse (water-in-oil) microemulsion method. The microemulsion was prepared by mixing a surfactant (Brij35), co-surfactant, organic solvent, water, and fluorescein as an organic fluorophore. The sizes of the silica nanoparticles were successfully controlled in the reverse microemulsion using Brij35 by changing the water-to-Brij35 ratio and by adding HCl. Initially, tetraethylorthosilicate was hydrolyzed by adding NH 4 OH as a catalyst and then polymerized to generate core fluorescent silica nanoparticles with fluorescein. 3-(Aminopropyl)triethoxysilane (APTS) was sequentially added into the reaction mixture, and reacted on the surface of pre-generated core silica nanoparticles to form the second layer in the form of a shell. The second silica layer that was derived from the condensation of APTS effectively protected the fluorescein dye within the silica matrix. This is a novel and simple synthetic approach to generate highly fluorescent, monodispersed silica nanoparticles by doping organic molecules into a silica matrix.Graphical Abstract

  4. Synthesis of highly fluorescent silica nanoparticles in a reverse microemulsion through double-layered doping of organic fluorophores

    Energy Technology Data Exchange (ETDEWEB)

    Yoo, Hyojong, E-mail: hyojong@hallym.ac.kr; Pak, Joonsung [Hallym University, Department of Chemistry (Korea, Republic of)

    2013-05-15

    Water-soluble, highly fluorescent double-layered silica nanoparticles (FL-DLSN) have been successfully synthesized through a reverse (water-in-oil) microemulsion method. The microemulsion was prepared by mixing a surfactant (Brij35), co-surfactant, organic solvent, water, and fluorescein as an organic fluorophore. The sizes of the silica nanoparticles were successfully controlled in the reverse microemulsion using Brij35 by changing the water-to-Brij35 ratio and by adding HCl. Initially, tetraethylorthosilicate was hydrolyzed by adding NH{sub 4}OH as a catalyst and then polymerized to generate core fluorescent silica nanoparticles with fluorescein. 3-(Aminopropyl)triethoxysilane (APTS) was sequentially added into the reaction mixture, and reacted on the surface of pre-generated core silica nanoparticles to form the second layer in the form of a shell. The second silica layer that was derived from the condensation of APTS effectively protected the fluorescein dye within the silica matrix. This is a novel and simple synthetic approach to generate highly fluorescent, monodispersed silica nanoparticles by doping organic molecules into a silica matrix.Graphical Abstract.

  5. Candida antartica lipase B catalyzed polycaprolactone synthesis: effects of organic media and temperature.

    Science.gov (United States)

    Kumar, A; Gross, R A

    2000-01-01

    Engineering of the reaction medium and study of an expanded range of reaction temperatures were carried out in an effort to positively influence the outcome of Novozyme-435 (immobilized Lipase B from Candida antarctica) catalyzed epsilon-CL polymerizations. A series of solvents including acetonitrile, dioxane, tetrahydrofuran, chloroform, butyl ether, isopropyl ether, isooctane, and toluene (log P from -1.1 to 4.5) were evaluated at 70 degrees C. Statistically (ANOVA), two significant regions were observed. Solvents having log P values from -1.1 to 0.49 showed low propagation rates (< or = 30% epsilon-CL conversion in 4 h) and gave products of short chain length (Mn < or = 5200 g/mol). In contrast, solvents with log P values from 1.9 to 4.5 showed enhanced propagation rates and afforded polymers of higher molecular weight (Mn = 11,500-17,000 g/mol). Toluene, a preferred solvent for this work, was studied at epsilon-CL to toluene (wt/vol) ratios from 1:1 to 10:1. The ratio 1:2 was selected since, for polymerizations at 70 degrees C, 0.3 mL of epsilon-CL and 4 h, gave high monomer conversions and Mn values (approximately 85% and approximately 17,000 g/mol, respectively). Increasing the scale of the reaction from 0.3 to 10 mL of CL resulted in a similar isolated product yield, but the Mn increased from 17,200 to 44,800 g/mol. Toluene appeared to help stabilize Novozyme-435 so that lipase-catalyzed polymerizations could be conducted effectively at 90 degrees C. For example, within only 2 h at 90 degrees C (toluene-d8 to epsilon-CL, 5:1, approximately 1% protein), the % monomer conversion reached approximately 90%. Also, the controlled character of these polymerizations as a function of reaction temperature was evaluated.

  6. Omega-3 PUFA concentration by a novel PVDF nano-composite membrane filled with nano-porous silica particles.

    Science.gov (United States)

    Ghasemian, Samaneh; Sahari, Mohammad Ali; Barzegar, Mohsen; Ahmadi Gavlighi, Hasan

    2017-09-01

    In this study, polyvinylidene fluoride (PVDF) and nano-porous silica particle were used to fabricate an asymmetric nano-composite membrane. Silica particles enhanced the thermal stability of PVDF/SiO 2 membranes; increasing the decomposition temperature from 371°C to 408°C. Cross sectional morphology showed that silica particles were dispersed in polymer matrix uniformly. However, particle agglomeration was found at higher loading of silica (i.e., 20 by weight%). The separation performance of nano-composite membranes was also evaluated using the omega-3 polyunsaturated fatty acids (PUFA) concentration at a temperature and pressure of 30°C and 4bar, respectively. Silica particle increased the omega-3PUFA concentration from 34.8 by weight% in neat PVDF to 53.9 by weight% in PVDF with 15 by weight% of silica. Moreover, PVDF/SiO 2 nano-composite membranes exhibited enhanced anti-fouling property compared to neat PVDF membrane. Fouling mechanism analysis revealed that complete pore blocking was the predominant mechanism occurring in oil filtration. The concentration of omega-3 polyunsaturated fatty acids (PUFA) is important in the oil industries. While the current methods demand high energy consumptions in concentrating the omega-3, membrane separation technology offers noticeable advantages in producing pure omega-3 PUFA. Moreover, concentrating omega-3 via membrane separation produces products in the triacylglycerol form which possess better oxidative stability. In this work, the detailed mechanisms of fouling which limits the performance of membrane separation were investigated. Incorporating silica particles to polymeric membrane resulted in the formation of mixed matrix membrane with improved anti-fouling behaviour compared to the neat polymeric membrane. Hence, the industrial potential of membrane processing to concentrate omega-3 fatty acids is enhanced. Copyright © 2017. Published by Elsevier Ltd.

  7. Immobilized Candida antarctica lipase B on ZnO nanowires/macroporous silica composites for catalyzing chiral resolution of (R,S)-2-octanol.

    Science.gov (United States)

    Shang, Chuan-Yang; Li, Wei-Xun; Zhang, Rui-Feng

    2014-01-01

    ZnO nanowires were successfully introduced into a macroporous SiO2 by in situ hydrothermal growth in 3D pores. The obtained composites were characterized by SEM and XRD, and used as supports to immobilize Candida antarctica lipase B (CALB) through adsorption. The high specific surface area (233 m(2)/g) and strong electrostatic interaction resulted that the average loading amount of the composite supports (196.8 mg/g) was 3-4 times of that of macroporous SiO2 and approximate to that of a silica-based mesoporous material. Both adsorption capacity and the activity of the CALB immobilized on the composite supports almost kept unchanged as the samples were soaked in buffer solution for 48 h. The chiral resolution of 2-octanol was catalyzed by immobilized CALB. A maximum molar conversion of 49.1% was achieved with 99% enantiomeric excess of (R)-2-octanol acetate under the optimal condition: a reaction using 1.0 mol/L (R,S)-2-octanol, 2.0 mol/L vinyl acetate and 4.0 wt.% water content at 60°C for 8h. After fifteen recycles the immobilized lipase could retain 96.9% of relative activity and 93.8% of relative enantioselectivity. Copyright © 2014 Elsevier Inc. All rights reserved.

  8. Wood-polymer composites from Philippine tree plantation species by radiation polymerization I. Uptake and irradiation parameters

    International Nuclear Information System (INIS)

    Dela Rosa, A.M.; Castaneda, S.S.; Real, M.P.N.; Sta Ana, L.P.; Mosteiro, A.P.; Bauza, E.; Carandang, J.P.

    1993-01-01

    Radiation catalyzed polymerization of methyl methacrylate (MMA) in various Philippine tree plantation species were investigated. Wood samples measuring 1x6cm were impregnated with monomer at reduced pressure and gamma irradiated for various doses at a dose rate of 0.53 kGy/h. The parameters used to assess the polymerization reaction were the uptake of monomer by the wood samples, monomer conversion, and polymer loading in the irradiated samples. The uptake and polymerization data indicate that coconut wood, rubber wood, bagras, and Moluccan sau could be potential raw materials for the production of wood-polymer composites (WPC). (author). 6 refs.; 2 figs.; 1 tab

  9. Sequential polymerization of ethylene oxide, ε-caprolactone and l-lactide: A one-pot metal-free route to tri- and pentablock terpolymers

    KAUST Repository

    Zhao, Junpeng

    2014-01-01

    Metal-free polymerization of ethylene oxide (EO) catalyzed by a relatively mild phosphazene base (t-BuP2) was proven feasible, which enabled the one-pot sequential polymerization of EO, ε-caprolactone, and l-lactide. Using either 3-phenyl-1-propanol or water as an initiator, the corresponding triblock or pentablock terpolymers were easily prepared. © 2014 the Partner Organisations.

  10. Vapor phase reactions in polymerization plasma for divinylsiloxane-bis-benzocyclobutene film deposition

    International Nuclear Information System (INIS)

    Kinoshita, Keizo; Nakano, Akinori; Kawahara, Jun; Kunimi, Nobutaka; Hayashi, Yoshihiro; Kiso, Osamu; Saito, Naoaki; Nakamura, Keiji; Kikkawa, Takamaro

    2006-01-01

    Vapor phase reactions in plasma polymerization of divinylsiloxane-bis-benzocyclobutene (DVS-BCB) low-k film depositions on 300 mm wafers were studied using mass spectrometry, in situ Fourier transform infrared, and a surface wave probe. Polymerization via Diels-Alder cycloaddition reaction was identified by the detection of the benzocyclohexene group. Hydrogen addition and methyl group desorption were also detected in DVS-BCB monomer and related large molecules. The dielectric constant k of plasma polymerized DVS-BCB with a plasma source power range up to 250 W was close to ∼2.7 of thermally polymerized DVS-BCB, and increased gradually over 250 W. The electron density at 250 W was about 1.5x10 10 cm -3 . The increase of the k value at higher power was explained by the decrease of both large molecular species via multistep dissociation and incorporation of silica components into the polymer. It was found that the reduction of electron density as well as precursor residence time is important for the plasma polymerization process to prevent the excess dissociation of the precursor

  11. Peptide bond formation of alanine on silica and alumina surfaces as a catalyst

    Science.gov (United States)

    Sánchez Arenillas, M.; Mateo-Martí, E.

    2012-09-01

    Polymerization of amino acids has been important for the origin of life because the peptides may have been the first self-replicating systems. The amino acid concentrations in the oceans may have been too diluted in the early phases of the Earth. The formation of the biopolymers could have been due to the catalytic action of various minerals (such as silica or alumina). Our work is based on the comparison between alumina and silica minerals with and without prior activation of their silanol groups for the formation of peptide bonds using alanina like amino acid which it is the simplest quiral amino acid.

  12. Homogeneity characterization of ethylene-co-vinyl acetate copolymer (EVA) and hydrophobic silica nanocomposite by low field NMR

    International Nuclear Information System (INIS)

    Stael, Giovanni Chaves; Tavares, Maria I.B.

    2005-01-01

    This project proposes the characterization of a polymeric matrix composite material using nanometric scale hydrophobic silica as charge element, with the ethylene-vinyl acetate (EVA), by using the spin-lattice relaxation time measurement applying the low field NMR

  13. Innovative Route to Prepare of Au/C Catalysts by Replication of Gold-containing Mesoporous Silicas

    KAUST Repository

    Kerdi, Fatmé

    2011-12-23

    Gold-catalyzed aerobic epoxidations in the liquid phase are generally performed in low-polarity solvents, in which conventional oxide-supported catalysts are poorly dispersed. To improve the wettability of the catalytic powder and, thus, the efficiency of the catalyst, gold nanoparticles (NPs) have been dispersed on meso-structured carbons. Gold is first introduced in functionalized mesostructured silica and particles are formed inside the porosity. Silica pores are then impregnated with a carbon precursor and the composite material is heated at 900 °C under vacuum or nitrogen. Silica is then removed by acid leaching, leading to partially encapsulated gold particles in mesoporous carbon. Carbon prevents aggregation of gold particles at high temperature, both the mean size and distribution being similar to those observed in silica. However, while Au@SiO2 exhibit significant catalytic activity in the aerobic oxidation of trans-stilbene in the liquid phase, its Au@C mesostructured replica is quite inactive.

  14. The Effect of Microporous Polymeric Support Modification on Surface and Gas Transport Properties of Supported Ionic Liquid Membranes.

    Science.gov (United States)

    Akhmetshina, Alsu A; Davletbaeva, Ilsiya M; Grebenschikova, Ekaterina S; Sazanova, Tatyana S; Petukhov, Anton N; Atlaskin, Artem A; Razov, Evgeny N; Zaripov, Ilnaz I; Martins, Carla F; Neves, Luísa A; Vorotyntsev, Ilya V

    2015-12-30

    Microporous polymers based on anionic macroinitiator and toluene 2,4-diisocyanate were used as a support for 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF₆]) and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([emim][Tf₂N]) immobilization. The polymeric support was modified by using silica particles associated in oligomeric media, and the influence of the modifier used on the polymeric structure was studied. The supported ionic liquid membranes (SILMs) were tested for He, N₂, NH₃, H₂S, and CO₂ gas separation and ideal selectivities were calculated. The high values of ideal selectivity for ammonia-based systems with permanent gases were observed on polymer matrixes immobilized with [bmim][PF₆] and [emim][Tf₂N]. The modification of SILMs by nanosize silica particles leads to an increase of NH₃ separation relatively to CO₂ or H₂S.

  15. Vibrational mode frequencies of silica species in SiO2-H2O liquids and glasses from ab initio molecular dynamics.

    Science.gov (United States)

    Spiekermann, Georg; Steele-MacInnis, Matthew; Schmidt, Christian; Jahn, Sandro

    2012-04-21

    Vibrational spectroscopy techniques are commonly used to probe the atomic-scale structure of silica species in aqueous solution and hydrous silica glasses. However, unequivocal assignment of individual spectroscopic features to specific vibrational modes is challenging. In this contribution, we establish a connection between experimentally observed vibrational bands and ab initio molecular dynamics (MD) of silica species in solution and in hydrous silica glass. Using the mode-projection approach, we decompose the vibrations of silica species into subspectra resulting from several fundamental structural subunits: The SiO(4) tetrahedron of symmetry T(d), the bridging oxygen (BO) Si-O-Si of symmetry C(2v), the geminal oxygen O-Si-O of symmetry C(2v), the individual Si-OH stretching, and the specific ethane-like symmetric stretching contribution of the H(6)Si(2)O(7) dimer. This allows us to study relevant vibrations of these subunits in any degree of polymerization, from the Q(0) monomer up to the fully polymerized Q(4) tetrahedra. Demonstrating the potential of this approach for supplementing the interpretation of experimental spectra, we compare the calculated frequencies to those extracted from experimental Raman spectra of hydrous silica glasses and silica species in aqueous solution. We discuss observed features such as the double-peaked contribution of the Q(2) tetrahedral symmetric stretch, the individual Si-OH stretching vibrations, the origin of the experimentally observed band at 970 cm(-1) and the ethane-like vibrational contribution of the H(6)Si(2)O(7) dimer at 870 cm(-1).

  16. Protection of Wood from Microorganisms by Laccase-Catalyzed Iodination

    Science.gov (United States)

    Engel, J.; Thöny-Meyer, L.; Schwarze, F. W. M. R.; Ihssen, J.

    2012-01-01

    In the present work, Norway spruce wood (Picea abies L.) was reacted with a commercial Trametes versicolor laccase in the presence of potassium iodide salt or the phenolic compounds thymol and isoeugenol to impart an antimicrobial property to the wood surface. In order to assess the efficacy of the wood treatment, a leaching of the iodinated and polymerized wood and two biotests including bacteria, a yeast, blue stain fungi, and wood decay fungi were performed. After laccase-catalyzed oxidation of the phenols, the antimicrobial effect was significantly reduced. In contrast, the enzymatic oxidation of iodide (I−) to iodine (I2) in the presence of wood led to an enhanced resistance of the wood surface against all microorganisms, even after exposure to leaching. The efficiency of the enzymatic wood iodination was comparable to that of a chemical wood preservative, VP 7/260a. The modification of the lignocellulose by the laccase-catalyzed iodination was assessed by the Fourier transform infrared spectroscopy-attenuated total reflectance (FTIR-ATR) technique. The intensities of the selected lignin-associated bands and carbohydrate reference bands were analyzed, and the results indicated a structural change in the lignin matrix. The results suggest that the laccase-catalyzed iodination of the wood surface presents an efficient and ecofriendly method for wood protection. PMID:22865075

  17. Diastereoisomeric diversity dictates reactivity of epoxy groups in limonene dioxide polymerization

    Directory of Open Access Journals (Sweden)

    M. Soto

    2018-06-01

    Full Text Available Limonene dioxide (LDO has the potential to find a wide application as a bio-based epoxy resin. Its polymerizations by catalyzed ring-opening, and by polyaddition with diamines were compared with the polymerizations of the commercial epoxy resins bisphenol-A diglycidyl ether (BADGE, and 3,4-epoxycyclohexylmethyl-3′,4′-epoxycyclohexane carboxylate (ECC. Differential scanning calorimetry (DSC studies showed that LDO polymerizations suffer in all cases studied from incomplete conversions. Nuclear magnetic resonance (NMR studies revealed that in cis-isomers of LDO the internal epoxide rings were not reacting. The low reactivity of this epoxide group was explained by mechanistic considerations making use of the Fürst-Plattner rule, or trans-diaxial effect. Due to diastereomeric diversity approximately one-fourth of epoxide groups present in LDO could not react. Therefore, a diastereoselective epoxidation of limonene could provide a fully reactive bio-based epoxy resin.

  18. Homogeneity characterization of ethylene-co-vinyl acetate copolymer (EVA) and hydrophobic silica nanocomposite by low field NMR; Caracterizacao da homogeneidade de nanocomposito do copolimero etileno acetato de vinila (EVA) e silica hidrofobica atraves de ressonancia magnetica nuclear de baixo campo

    Energy Technology Data Exchange (ETDEWEB)

    Stael, Giovanni Chaves [Observatorio Nacional, Rio de Janeiro, RJ (Brazil). Dept. de Geofisica (DGE); Tavares, Maria I.B. [Universidade Federal do Rio de Janeiro, RJ (Brazil). Inst. de Macromoleculas

    2005-07-01

    This project proposes the characterization of a polymeric matrix composite material using nanometric scale hydrophobic silica as charge element, with the ethylene-vinyl acetate (EVA), by using the spin-lattice relaxation time measurement applying the low field NMR.

  19. Reinforcement of Natural Rubber with Core-Shell Structure Silica-Poly(Methyl Methacrylate Nanoparticles

    Directory of Open Access Journals (Sweden)

    Qinghuang Wang

    2012-01-01

    Full Text Available A highly performing natural rubber/silica (NR/SiO2 nanocomposite with a SiO2 loading of 2 wt% was prepared by combining similar dissolve mutually theory with latex compounding techniques. Before polymerization, double bonds were introduced onto the surface of the SiO2 particles with the silane-coupling agent. The core-shell structure silica-poly(methyl methacrylate, SiO2-PMMA, nanoparticles were formed by grafting polymerization of MMA on the surface of the modified SiO2 particles via in situ emulsion, and then NR/SiO2 nanocomposite was prepared by blending SiO2-PMMA and PMMA-modified NR (NR-PMMA. The Fourier transform infrared spectroscopy results show that PMMA has been successfully introduced onto the surface of SiO2, which can be well dispersed in NR matrix and present good interfacial adhesion with NR phase. Compared with those of pure NR, the thermal resistance and tensile properties of NR/SiO2 nanocomposite are significantly improved.

  20. Production of margarine fats by enzymatic interesterification with silica-granulated Thermomyces lanuginosa lipase in a large-scale study

    DEFF Research Database (Denmark)

    Zhang, Hong; Xu, Xuebing; Nilsson, Jörgen

    2001-01-01

    Interesterification of a blend of palm stearin and coconut oil (75:25, w/w), catalyzed by an immobilized Thermomyces lanuginosa lipase by silica granulation, Lipozyme TL IM, was studied for production of margarine fats in a 1- or 300-kg pilot-scale batch-stirred tank reactor. Parameters...

  1. Poly(ethyleneimine) infused and functionalized Torlon®-silica hollow fiber sorbents for post-combustion CO2 capture

    KAUST Repository

    Li, Fuyue Stephanie; Labreche, Ying; Lively, Ryan P.; Lee, Jong Suk; Jones, Christopher W.; Koros, William J.

    2014-01-01

    -jet/wet-quench spinning process. In our study, a new technique for functionalizing polymeric silica hollow fiber sorbents with poly(ethyleneimine), followed by a post-spinning infusion step was studied. This two step process introduces a sufficient amount of poly

  2. Synthesis of Cross-Linked Polymeric Micelle pH Nanosensors

    DEFF Research Database (Denmark)

    Ek, Pramod Kumar; Jølck, Rasmus Irming; Andresen, Thomas Lars

    2015-01-01

    The design flexibility that polymeric micelles offer in the fabrication of optical nanosensors for ratiometric pH measurements is investigated. pH nanosensors based on polymeric micelles are synthesized either by a mixed-micellization approach or by a postmicelle modification strategy. In the mixed......-micellization approach, self-assembly of functionalized unimers followed by shell cross-linking by copper-catalyzed azide-alkyne cycloaddition (CuAAC) results in stabilized cRGD-functionalized micelle pH nanosensors. In the postmicelle modification strategy, simultaneous cross-linking and fluorophore conjugation...... at the micelle shell using CuAAC results in a stabilized micelle pH nanosensor. Compared to the postmicelle modification strategy, the mixed-micellization approach increases the control of the overall composition of the nanosensors.Both approaches provide stable nanosensors with similar pKa profiles and thereby...

  3. Metallocene-catalyzed ethylene−α-olefin isomeric copolymerization: A perspective from hydrodynamic boundary layer mass transfer and design of MAO anion

    KAUST Repository

    Adamu, Sagir; Atiqullah, Muhammad; Malaibari, Zuhair O.; Al-Harthi, Mamdouh A.; Emwas, Abdul-Hamid M.; Ul-Hamid, Anwar

    2015-01-01

    -catalyzed ethylene polymerization. This approach was illustrated by conducting homo- and isomeric copolymerization of ethylene with 1-hexene and 4-methyl-1-pentene in the presence of bis(n-butylcyclopentadienyl) zirconium dichloride (nBuCp)2ZrCl2, using (i) MAO anion

  4. The Effect of Microporous Polymeric Support Modification on Surface and Gas Transport Properties of Supported Ionic Liquid Membranes

    OpenAIRE

    Akhmetshina, Alsu A.; Davletbaeva, Ilsiya M.; Grebenschikova, Ekaterina S.; Sazanova, Tatyana S.; Petukhov, Anton N.; Atlaskin, Artem A.; Razov, Evgeny N.; Zaripov, Ilnaz I.; Martins, Carla F.; Neves, Lu?sa A.; Vorotyntsev, Ilya V.

    2015-01-01

    Microporous polymers based on anionic macroinitiator and toluene 2,4-diisocyanate were used as a support for 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF6]) and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([emim][Tf2N]) immobilization. The polymeric support was modified by using silica particles associated in oligomeric media, and the influence of the modifier used on the polymeric structure was studied. The supported ionic liquid membranes (SILMs) were tested ...

  5. Comparison of optical properties of Eu3+ ions in the silica gel glasses obtained by different preparation techniques

    International Nuclear Information System (INIS)

    Legendziewicz, J.; Sokolnicki, J.; Keller, B.; Borzechowska, M.; Strek, W.

    1996-01-01

    Silica-gel glasses doped with Eu 3+ ions were obtained by different preparation techniques. The absorption, emission and excitation spectra of the obtained glasses were measured in the range of 77-300 K. The energy levels diagrams of Eu 3+ ions were derived. An intensity analysis of f-f transitions was performed. In particular, polymeric structure behaviour of europium compounds entrapped in silica gel glasses was temperature controlled during the preparation of glasses. Their optical properties were investigated. (author)

  6. Synthesis of poly(ethylene oxide)-silica hybrids

    International Nuclear Information System (INIS)

    Ishak Manaf

    2002-01-01

    A hybrid material incorporating silica networks in poly (ethylene oxide) was produced using the sol-gel process from solution mixtures of poly (ethylene oxide) dissolved in water and partially polymerized tetraethylorthosilicate (TEOS) with and without compatibilisation agent. These mixtures were converted into films by solvent evaporation and drying them in an air-circulating oven at 60 degree C. Depending on the alkoxysilane solution composition and several mixing parameters, different morphologies were obtained, varying from semi-interpenetrating networks of PEO within highly cross linked silica chains, to finely dispersed heterogeneous system exhibiting either co-continuous or particulate microstructure. The influence of pH, type of solvents, mixing temperatures and time, as well as the nature of compatibiliser was found to be extremely important in controlling the morphology and properties of the fine hybrid films. It was found that compatibilisation of PEO-SiO 2 hybrid system is achieved exclusively with the use of γ-glycidyloxypropyltrimethoxysilane (GOTMS) coupling agent. (Author)

  7. Formation of Silica-Lysozyme Composites Through Co-Precipitation and Adsorption

    Directory of Open Access Journals (Sweden)

    Daniela B. van den Heuvel

    2018-04-01

    Full Text Available Interactions between silica and proteins are crucial for the formation of biosilica and the production of novel functional hybrid materials for a range of industrial applications. The proteins control both precipitation pathway and the properties of the resulting silica–organic composites. Here, we present data on the formation of silica–lysozyme composites through two different synthesis approaches (co-precipitation vs. adsorption and show that the chemical and structural properties of these composites, when analyzed using a combination of synchrotron-based scattering (total scattering and small-angle X-ray scattering, spectroscopic, electron microscopy, and potentiometric methods vary dramatically. We document that while lysozyme was not incorporated into nor did its presence alter the molecular structure of silica, it strongly enhanced the aggregation of silica particles due to electrostatic and potentially hydrophobic interactions, leading to the formation of composites with characteristics differing from pure silica. The differences increased with increasing lysozyme content for both synthesis approaches. Yet, the absolute changes differ substantially between the two sets of composites, as lysozyme did not just affect aggregation during co-precipitation but also particle growth and likely polymerization during co-precipitation. Our results improve the fundamental understanding of how organic macromolecules interact with dissolved and nanoparticulate silica and how these interactions control the formation pathway of silica–organic composites from sodium silicate solutions, a widely available and cheap starting material.

  8. Synthesis of encapsulated pigments based on Fe, Co and Si by route of polymeric precursors

    International Nuclear Information System (INIS)

    Macedo, D.S.S.M.; Macedo Neto, O.C.; Paskocimas, C.A.; Varela, M.L.N.

    2012-01-01

    The objective is to apply the polymeric precursor method to obtain encapsulated pigments, the basis of oxides of iron and cobalt deposited on silica. The method has advantages such as reduction of time and reproducibility in the conventional methods, and also improves optical properties, thermal stability and morphology. The synthesis was based on the dissolution of the citric acid (complexing agent), addition of oxides of iron and cobalt (ions chromophores) polymerization of ethylene glycol and silica coating. The mixture was pre-calcined to form the precursor powder was analyzed by TG and DTA. Was then split, and calcined at different temperatures (700 ° C - 900 ° C) and analyzed by BET, DRX, MEV and UV-Visible. The pigments were stable thermally, with surface area ranging between 3,09 and 7,65 m² / g, formation of crystalline phases of cobalt ferrite (CoFe 2 O 4 ) and Cristobalite (SiO 2 ) and agglomerates of particles slightly rounded. (author)

  9. Unsaturated Fatty Acid Esters Metathesis Catalyzed by Silica Supported WMe5

    KAUST Repository

    Riache, Nassima

    2015-11-14

    Metathesis of unsaturated fatty acid esters (FAEs) by silica supported multifunctional W-based catalyst is disclosed. This transformation represents a novel route towards unsaturated di-esters. Especially, the self-metathesis of ethyl undecylenate results almost exclusively on the homo-coupling product whereas with such catalyst, 1-decene gives ISOMET (isomerization and metathesis olefin) products. The olefin metathesis in the presence of esters is very selective without any secondary cross-metathesis products demonstrating that a high selective olefin metathesis could operate at 150 °C. Additionally, a cross-metathesis of unsaturated FAEs and α-olefins allowed the synthesis of the corresponding ester with longer hydrocarbon skeleton without isomerisation.

  10. Effect of Synthesis Time on Morphology of Hollow Porous Silica Microspheres

    Directory of Open Access Journals (Sweden)

    Qian CHEN

    2012-03-01

    Full Text Available Hollow porous silica microspheres may be applicable as containers for the controlled release in drug delivery systems (DDS, foods, cosmetics, agrochemical, textile industry, and in other technological encapsulation use. In order to control the surface morphological properties of the silica microspheres, the effect of synthesis time on their formation was studied by a method of water-in-oil (W/O emulsion mediated sol-gel techniques. An aqueous phase of water, ammonium hydroxide and a surfactant Tween 20 was emulsified in an oil phase of 1-octanol with a stabilizer, hydroxypropyl cellulose (HPC, and a surfactant, sorbitan monooleate (Span 80 with low hydrophile-lipophile balance (HLB value. Tetraethyl orthosilicate (TEOS as a silica precursor was added to the emulsion. The resulting silica particles at different synthesis time 24, 48, and 72 hours were air-dried at room temperature and calcinated at 773 K for 3 hours. The morphology of the particles was characterized by scanning electron microscopy and the particle size distribution was measured by laser diffraction. The specific surface areas were studied by 1-point BET method, and pore sizes were measured by Image Tool Software. Both dense and porous silica microspheres were observed after all three syntheses. Hollow porous silica microspheres were formed at 24 and 48 hours synthesis time. Under base catalyzed sol-gel solution, the size of silica particles was in the range of 5.4 μm to 8.2 μm, and the particles had surface area of 111 m2/g – 380 m2/g. The longer synthesis time produced denser silica spheres with decreased pore sizes.DOI: http://dx.doi.org/10.5755/j01.ms.18.1.1344

  11. Radiation hardening of sol gel-derived silica fiber preforms through fictive temperature reduction.

    Science.gov (United States)

    Hari Babu, B; Lancry, Matthieu; Ollier, Nadege; El Hamzaoui, Hicham; Bouazaoui, Mohamed; Poumellec, Bertrand

    2016-09-20

    The impact of fictive temperature (Tf) on the evolution of point defects and optical attenuation in non-doped and Er3+-doped sol-gel silica glasses was studied and compared to Suprasil F300 and Infrasil 301 glasses before and after γ-irradiation. To this aim, sol-gel optical fiber preforms have been fabricated by the densification of erbium salt-soaked nanoporous silica xerogels through the polymeric sol-gel technique. These γ-irradiated fiber preforms have been characterized by FTIR, UV-vis-NIR absorption spectroscopy, electron paramagnetic resonance, and photoluminescence measurements. We showed that a decrease in the glass fictive temperature leads to a decrease in the glass disorder and strained bonds. This mainly results in a lower defect generation rate and thus less radiation-induced attenuation in the UV-vis range. Furthermore, it was found that γ-radiation "hardness" is higher in Er3+-doped sol-gel silica compared to un-doped sol-gel silica and standard synthetic silica glasses. The present work demonstrates an effective strategy to improve the radiation resistance of optical fiber preforms and glasses through glass fictive temperature reduction.

  12. Dual soft-template system based on colloidal chemistry for the synthesis of hollow mesoporous silica nanoparticles.

    Science.gov (United States)

    Li, Yunqi; Bastakoti, Bishnu Prasad; Imura, Masataka; Tang, Jing; Aldalbahi, Ali; Torad, Nagy L; Yamauchi, Yusuke

    2015-04-20

    A new dual soft-template system comprising the asymmetric triblock copolymer poly(styrene-b-2-vinyl pyridine-b-ethylene oxide) (PS-b-P2VP-b-PEO) and the cationic surfactant cetyltrimethylammonium bromide (CTAB) is used to synthesize hollow mesoporous silica (HMS) nanoparticles with a center void of around 17 nm. The stable PS-b-P2VP-b-PEO polymeric micelle serves as a template to form the hollow interior, while the CTAB surfactant serves as a template to form mesopores in the shells. The P2VP blocks on the polymeric micelles can interact with positively charged CTA(+) ions via negatively charged hydrolyzed silica species. Thus, dual soft-templates clearly have different roles for the preparation of the HMS nanoparticles. Interestingly, the thicknesses of the mesoporous shell are tunable by varying the amounts of TEOS and CTAB. This study provides new insight on the preparation of mesoporous materials based on colloidal chemistry. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Preparation and controlled drug delivery applications of mesoporous silica polymer nanocomposites through the visible light induced surface-initiated ATRP

    Science.gov (United States)

    Huang, Long; Liu, Meiying; Mao, Liucheng; Xu, Dazhuang; Wan, Qing; Zeng, Guangjian; Shi, Yingge; Wen, Yuanqing; Zhang, Xiaoyong; Wei, Yen

    2017-08-01

    The mesoporous materials with large pore size, high specific surface area and high thermal stability have been widely utilized in a variety of fields ranging from environmental remediation to separation and biomedicine. However, surface modification of these silica nanomaterials is required to endow novel properties and achieve better performance for most of these applications. In this work, a new method has been established for surface modification of mesoporous silica nanoparticles (MSNs) that relied on the visible light induced atom transfer radical polymerization (ATRP). In the procedure, the copolymers composited with itaconic acid (IA) and poly(ethylene glycol)methyl acrylate (PEGMA) were grafted from MSNs using IA and PEGMA as the monomers and 10-Phenylphenothiazine(PTH) as the organic catalyst. The successful preparation of final polymer nanocomposites (named as MSNs-NH2-poly(IA-co-PEGMA)) were evidenced by a series of characterization techniques. More importantly, the anticancer agent cisplatin can be effectively loaded on MSNs-NH2-poly(IA-co-PEGMA) and controlled release it from the drug-loading composites with pH responsive behavior. As compared with conventional ATRP, the light induced surface-initiated ATRP could also be utilized for preparation of various silica polymer nanocomposites under rather benign conditions (e.g. absent of transition metal ions, low polymerization temperature and short polymerization time). Taken together, we have developed a rather promising strategy method for fabrication of multifunctional MSNs-NH2-poly(IA-co-PEGMA) with great potential for biomedical applications.

  14. Effect of concentrated epoxidised natural rubber and silica masterbatch for tyre application

    Energy Technology Data Exchange (ETDEWEB)

    Azira, A. A., E-mail: azira@lgm.gov.my; Kamal, M. M., E-mail: mazlina@lgm.gov.my [High Value Added Rubber Products and Nanostructured Materials, Stesen Penyelidikan RRIM, LGM 47000 Sungai Buloh, Selangor (Malaysia); Verasamy, D., E-mail: devaraj@lgm.gov.my [Environmental Technology & Sustainability, Technology & Engineering Division, Malaysian Rubber Board, Stesen Penyelidikan RRIM, LGM 47000 Sungai Buloh, Selangor (Malaysia)

    2016-07-06

    The availability of concentrated epoxidised natural rubber (ENR-LC) has provided a better opportunity for using epoxidised natural rubber (ENR) with silica to reinforce natural rubber for tyre application. ENR-LC mixed directly with silica to rubber by high speed stirrer without using any coupling agent. Some rubber compounds were prepared by mixing a large amount of precipitated amorphous white silica with natural rubber. The silica was prepared in aqueous dispersion and the filler was perfectly dispersed in the ENR-LC. The performance of the composites was evaluated in this work for the viability of ENR-LC/Si in tyre compounding. Compounding was carried out on a two roll mill, where the additives and curing agents was later mixed. Characterization of these composites was performed by Field Emission Scanning Electron Microscopy (FESEM) and Transmission Electron Microscopy (TEM) for dispersion as well as mechanical testing. C-ENR/Si showed efficient as primary reinforcing filler in ENR with regard to modulus and tensile strength, resulting on an increase in the stiffness of the rubbers compared to ENR latex. Overall improvement in the mechanical properties for the ENR-LC over the control crosslinked rubber sample was probably due to synergisms of silica reinforcement and crosslinking of the polymeric matrix phase.

  15. Effect of concentrated epoxidised natural rubber and silica masterbatch for tyre application

    International Nuclear Information System (INIS)

    Azira, A. A.; Kamal, M. M.; Verasamy, D.

    2016-01-01

    The availability of concentrated epoxidised natural rubber (ENR-LC) has provided a better opportunity for using epoxidised natural rubber (ENR) with silica to reinforce natural rubber for tyre application. ENR-LC mixed directly with silica to rubber by high speed stirrer without using any coupling agent. Some rubber compounds were prepared by mixing a large amount of precipitated amorphous white silica with natural rubber. The silica was prepared in aqueous dispersion and the filler was perfectly dispersed in the ENR-LC. The performance of the composites was evaluated in this work for the viability of ENR-LC/Si in tyre compounding. Compounding was carried out on a two roll mill, where the additives and curing agents was later mixed. Characterization of these composites was performed by Field Emission Scanning Electron Microscopy (FESEM) and Transmission Electron Microscopy (TEM) for dispersion as well as mechanical testing. C-ENR/Si showed efficient as primary reinforcing filler in ENR with regard to modulus and tensile strength, resulting on an increase in the stiffness of the rubbers compared to ENR latex. Overall improvement in the mechanical properties for the ENR-LC over the control crosslinked rubber sample was probably due to synergisms of silica reinforcement and crosslinking of the polymeric matrix phase.

  16. Influence of pH, Temperature and Sample Size on Natural and Enforced Syneresis of Precipitated Silica

    Directory of Open Access Journals (Sweden)

    Sebastian Wilhelm

    2015-12-01

    Full Text Available The production of silica is performed by mixing an inorganic, silicate-based precursor and an acid. Monomeric silicic acid forms and polymerizes to amorphous silica particles. Both further polymerization and agglomeration of the particles lead to a gel network. Since polymerization continues after gelation, the gel network consolidates. This rather slow process is known as “natural syneresis” and strongly influences the product properties (e.g., agglomerate size, porosity or internal surface. “Enforced syneresis” is the superposition of natural syneresis with a mechanical, external force. Enforced syneresis may be used either for analytical or preparative purposes. Hereby, two open key aspects are of particular interest. On the one hand, the question arises whether natural and enforced syneresis are analogous processes with respect to their dependence on the process parameters: pH, temperature and sample size. On the other hand, a method is desirable that allows for correlating natural and enforced syneresis behavior. We can show that the pH-, temperature- and sample size-dependency of natural and enforced syneresis are indeed analogous. It is possible to predict natural syneresis using a correlative model. We found that our model predicts maximum volume shrinkages between 19% and 30% in comparison to measured values of 20% for natural syneresis.

  17. Recent Advances in Recoverable Systems for the Copper-Catalyzed Azide-Alkyne Cycloaddition Reaction (CuAAC

    Directory of Open Access Journals (Sweden)

    Alessandro Mandoli

    2016-09-01

    Full Text Available The explosively-growing applications of the Cu-catalyzed Huisgen 1,3-dipolar cycloaddition reaction between organic azides and alkynes (CuAAC have stimulated an impressive number of reports, in the last years, focusing on recoverable variants of the homogeneous or quasi-homogeneous catalysts. Recent advances in the field are reviewed, with particular emphasis on systems immobilized onto polymeric organic or inorganic supports.

  18. Carbon dots based dual-emission silica nanoparticles as ratiometric fluorescent probe for nitrite determination in food samples.

    Science.gov (United States)

    Xiang, Guoqiang; Wang, Yule; Zhang, Heng; Fan, Huanhuan; Fan, Lu; He, Lijun; Jiang, Xiuming; Zhao, Wenjie

    2018-09-15

    In this work, a simple and effective strategy for designing a ratiometric fluorescent nanosensor was described. A carbon dots (CDs) based dual-emission nanosensor for nitrite was prepared by coating the CDs on to dye-doped silica nanoparticles. Dual-emission silica nanoparticles fluorescence was quenched in sulfuric acid using potassium bromate (KBrO 3 ). The nitrite present catalyzed the KBrO 3 oxidation, resulting in ratiometric fluorescence response of the dual-emission silica nanoparticles. Several important parameters affecting the performance of the nanosensor were investigated. Under optimized conditions, the limit of detection was 1.0 ng mL -1 and the linear range 10-160 ng mL -1 . Furthermore, the sensor was suitable for nitrite determination in different food samples. Copyright © 2018 Elsevier Ltd. All rights reserved.

  19. Vapour-phase method in the synthesis of polymer-ibuprofen sodium-silica gel composites.

    Science.gov (United States)

    Kierys, Agnieszka; Krasucka, Patrycja; Grochowicz, Marta

    2017-11-01

    The study discusses the synthesis of polymer-silica composites comprising water soluble drug (ibuprofen sodium, IBS). The polymers selected for this study were poly(TRIM) and poly(HEMA- co -TRIM) produced in the form of permanently porous beads via the suspension-emulsion polymerization method. The acid and base set ternary composites were prepared by the saturation of the solid dispersions of drug (poly(TRIM)-IBS and/or poly(HEMA- co -TRIM)-IBS) with TEOS, and followed by their exposition to the vapour mixture of water and ammonia, or water and hydrochloric acid, at autogenous pressure. The conducted analyses reveal that the internal structure and total porosity of the resulting composites strongly depend on the catalyst which was used for silica precursor gelation. The parameters characterizing the porosity of both of the acid set composites are much lower than the parameters of the base set composites. Moreover, the basic catalyst supplied in the vapour phase does not affect the ibuprofen sodium molecules, whereas the acid one causes transformation of the ibuprofen sodium into the sodium chloride and a derivative of propanoic acid, which is poorly water soluble. The release profiles of ibuprofen sodium from composites demonstrate that there are differences in the rate and efficiency of drug desorption from them. They are mainly affected by the chemical character of the polymeric carrier but are also associated with the restricted swelling of the composites in the buffer solution after precipitation of silica gel.

  20. Vapour-phase method in the synthesis of polymer-ibuprofen sodium-silica gel composites

    Directory of Open Access Journals (Sweden)

    Agnieszka Kierys

    2017-11-01

    Full Text Available The study discusses the synthesis of polymer-silica composites comprising water soluble drug (ibuprofen sodium, IBS. The polymers selected for this study were poly(TRIM and poly(HEMA-co-TRIM produced in the form of permanently porous beads via the suspension-emulsion polymerization method. The acid and base set ternary composites were prepared by the saturation of the solid dispersions of drug (poly(TRIM-IBS and/or poly(HEMA-co-TRIM-IBS with TEOS, and followed by their exposition to the vapour mixture of water and ammonia, or water and hydrochloric acid, at autogenous pressure. The conducted analyses reveal that the internal structure and total porosity of the resulting composites strongly depend on the catalyst which was used for silica precursor gelation. The parameters characterizing the porosity of both of the acid set composites are much lower than the parameters of the base set composites. Moreover, the basic catalyst supplied in the vapour phase does not affect the ibuprofen sodium molecules, whereas the acid one causes transformation of the ibuprofen sodium into the sodium chloride and a derivative of propanoic acid, which is poorly water soluble. The release profiles of ibuprofen sodium from composites demonstrate that there are differences in the rate and efficiency of drug desorption from them. They are mainly affected by the chemical character of the polymeric carrier but are also associated with the restricted swelling of the composites in the buffer solution after precipitation of silica gel.

  1. Stereoselectivity in metallocene-catalyzed coordination polymerization of renewable methylene butyrolactones: From stereo-random to stereo-perfect polymers

    KAUST Repository

    Chen, Xia; Caporaso, Lucia; Cavallo, Luigi; Chen, Eugene You Xian

    2012-01-01

    Coordination polymerization of renewable α-methylene-γ-(methyl) butyrolactones by chiral C 2-symmetric zirconocene catalysts produces stereo-random, highly stereo-regular, or perfectly stereo-regular polymers, depending on the monomer and catalyst structures. Computational studies yield a fundamental understanding of the stereocontrol mechanism governing these new polymerization reactions mediated by chiral metallocenium catalysts. © 2012 American Chemical Society.

  2. Stereoselectivity in metallocene-catalyzed coordination polymerization of renewable methylene butyrolactones: From stereo-random to stereo-perfect polymers

    KAUST Repository

    Chen, Xia

    2012-05-02

    Coordination polymerization of renewable α-methylene-γ-(methyl) butyrolactones by chiral C 2-symmetric zirconocene catalysts produces stereo-random, highly stereo-regular, or perfectly stereo-regular polymers, depending on the monomer and catalyst structures. Computational studies yield a fundamental understanding of the stereocontrol mechanism governing these new polymerization reactions mediated by chiral metallocenium catalysts. © 2012 American Chemical Society.

  3. Synthesis of mesoporous hollow silica nanospheres using polymeric micelles as template and their application as a drug-delivery carrier.

    Science.gov (United States)

    Sasidharan, Manickam; Zenibana, Haruna; Nandi, Mahasweta; Bhaumik, Asim; Nakashima, Kenichi

    2013-10-07

    Mesoporous hollow silica nanospheres with uniform particle sizes of 31-33 nm have been successfully synthesized by cocondensation of tetramethoxysilane (TMOS) and alkyltrimethoxysilanes [RSi(OR)3], where the latter also acts as a porogen. ABC triblock copolymer micelles of poly(styrene-b-2-vinyl pyridine-b-ethylene oxide) (PS-PVP-PEO) with a core-shell-corona architecture have been employed as a soft template at pH 4. The cationic shell block with 2-vinyl pyridine groups facilitates the condensation of silica precursors under the sol-gel reaction conditions. Phenyltrimethoxysilane, octyltriethoxysilane, and octadecyltriethoxysilanes were used as porogens for generating mesopores in the shell matrix of hollow silica and the octadecyl precursor produced the largest mesopore among the different porogens, of dimension ca. 4.1 nm. The mesoporous hollow particles were thoroughly characterized by small-angle X-ray diffraction (SXRD), thermal (TG/DTA) and nitrogen sorption analyses, infra-red (FTIR) and nuclear magnetic resonance ((13)C-CP MAS NMR and (29)Si MAS NMR) spectroscopies, and transmission electron microscopy (TEM). The mesoporous hollow silica nanospheres have been investigated for drug-delivery application by an in vitro method using ibuprofen as a model drug. The hollow silica nanospheres exhibited higher storage capacity than the well-known mesoporous silica MCM-41. Propylamine functionalized hollow particles show a more sustained release pattern than their unfunctionalized counterparts, suggesting a huge potential of hollow silica nanospheres in the controlled delivery of small drug molecules.

  4. Chain-growth cycloaddition polymerization via a catalytic alkyne [2 + 2 + 2] cyclotrimerization reaction and its application to one-shot spontaneous block copolymerization.

    Science.gov (United States)

    Sugiyama, Yu-ki; Kato, Rei; Sakurada, Tetsuya; Okamoto, Sentaro

    2011-06-29

    A cobalt-catalyzed alkyne [2 + 2 + 2] cycloaddition reaction has been applied to polymerizations yielding linear polymers via selective cross-cyclotrimerization of yne-diyne monomers, which occurs in a chain-growth manner. Additionally, through control of the alkyne reactivity of the two monomers, this method was efficiently applied to the spontaneous block copolymerization of their mixture. Here we present the proposed mechanism of the catalyst transfer process of this cycloaddition polymerization.

  5. Myoglobin-biomimetic electroactive materials made by surface molecular imprinting on silica beads and their use as ionophores in polymeric membranes for potentiometric transduction.

    Science.gov (United States)

    Moreira, Felismina T C; Dutra, Rosa A F; Noronha, Joao P C; Sales, M Goreti F

    2011-08-15

    Myoglobin (Mb) is among the cardiac biomarkers playing a major role in urgent diagnosis of cardiovascular diseases. Its monitoring in point-of-care is therefore fundamental. Pursuing this goal, a novel biomimetic ionophore for the potentiometric transduction of Mb is presented. It was synthesized by surface molecular imprinting (SMI) with the purpose of developing highly efficient sensor layers for near-stereochemical recognition of Mb. The template (Mb) was imprinted on a silane surface that was covalently attached to silica beads by means of self-assembled monolayers. First the silica was modified with an external layer of aldehyde groups. Then, Mb was attached by reaction with its amine groups (on the external surface) and subsequent formation of imine bonds. The vacant places surrounding Mb were filled by polymerization of the silane monomers 3-aminopropyltrimethoxysilane (APTMS) and propyltrimethoxysilane (PTMS). Finally, the template was removed by imine cleavage after treatment with oxalic acid. The results materials were finely dispersed in plasticized PVC selective membranes and used as ionophores in potentiometric transduction. The best analytical features were found in HEPES buffer of pH 4. Under this condition, the limits of detection were of 1.3 × 10(-6)mol/L for a linear response after 8.0 × 10(-7) mol/L with an anionic slope of -65.9 mV/decade. The imprinting effect was tested by preparing non-imprinted (NI) particles and employing these materials as ionophores. The resulting membranes showed no ability to detect Mb. Good selectivity was observed towards creatinine, sacarose, fructose, galactose, sodium glutamate, and alanine. The analytical application was conducted successfully and showed accurate and precise results. Copyright © 2011 Elsevier B.V. All rights reserved.

  6. In-Situ Immobilization of Ni Complex on Amine-Grafted SiO₂ for Ethylene Polymerization.

    Science.gov (United States)

    Lee, Sang Yun; Ko, Young Soo

    2018-02-01

    The results on the In-Situ synthesis of Ni complex on amine-grafted SiO2 and its ethylene polymerization were explained. SiO2/2NS/(DME)NiBr2 and SiO2/3NS/(DME)NiBr2(Ni(II) bromide ethylene glycol dimethyl ether) catalysts were active for ethylene polymerization. The highest activity was shown at the polymerization temperature of 25 °C, and SiO2/2NS/(DME)NiBr2 exhibited higher activity than SiO2/3NS/(DME)NiBr2. The PDI values of SiO2/2NS/(DME)NiBr2 were in the range of 8~18. The aminosilane compounds and Ni were evenly grafted and distributed in the silica. It was proposed that DME ligand was mostly removed during the supporting process, and only NiBr2 was complexed with the amine group of 2NS based on the results of FT-IR and ethylene polymerization.

  7. On the problem of silica solubility at high pH

    International Nuclear Information System (INIS)

    Eikenberg, J.

    1990-07-01

    The aqueous system Na 2 O-H 2 O-SiO 2 is considered to play an important role when strong alkaline pore waters of a cement based intermediate level radioactive waste repository intrude into the rock formations surrounding the near field. Under such conditions unknown quantities of silica may dissolve. Therefore the pH-dependence of the solubility of amorphous silica and quartz is investigated by a parameter variation study using the geochemical speciation code MINEQL/EIR. Published silica solubility data obtained in sodium hydroxide solutions at 25 and 90 o C are compared with the results of four models which use different proposed values of the rather uncertain equilibrium constants. Of main interest is the question of whether, in a high pH region, the silica solubility can be explained with different monomeric species only, or to what extent additional polymeric silica species have to be considered as well. The solubility of amorphous silica at 25 o C is well understood up to a pH of about 10.5, where it is determined by the solubility product and the first dissociation constant of monomeric silic acid. The most probable cause of the increased solubility of amorphous silica in the region between pH 10.5 and 11.3 is the formation of dimers, trimers and tetramers. Below a total silica concentration of 0.001 M and pH ≤ 10.0, however, polymerisation proves to be insignificant. Besides low temperature studies using amorphous silica, the solubility of quartz has also been measured in NaOH solutions at 90 o C. As is the case at lower temperatures, the reported values for the second dissociation constant at 90 o C scatter widely. It can be shown that in a NaOH medium up to 0.1 M only mononuclear silica species are stable. Therefore it is concluded that the trend of monomers to form polymers decreases strongly with temperature. In strong NaOH solutions at elevated temperatures, silica-sodium ion pairing seems to gain importance. (author) 12 figs., 9 tabs., 65 refs

  8. The Effect of Microporous Polymeric Support Modification on Surface and Gas Transport Properties of Supported Ionic Liquid Membranes

    Directory of Open Access Journals (Sweden)

    Alsu A. Akhmetshina

    2015-12-01

    Full Text Available Microporous polymers based on anionic macroinitiator and toluene 2,4-diisocyanate were used as a support for 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF6] and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonylimide ([emim][Tf2N] immobilization. The polymeric support was modified by using silica particles associated in oligomeric media, and the influence of the modifier used on the polymeric structure was studied. The supported ionic liquid membranes (SILMs were tested for He, N2, NH3, H2S, and CO2 gas separation and ideal selectivities were calculated. The high values of ideal selectivity for ammonia-based systems with permanent gases were observed on polymer matrixes immobilized with [bmim][PF6] and [emim][Tf2N]. The modification of SILMs by nanosize silica particles leads to an increase of NH3 separation relatively to CO2 or H2S.

  9. Kinetic modelling of slurry polymerization of ethylene with a polymer supported Ziegler-Natta catalyst (hydrogen)

    Energy Technology Data Exchange (ETDEWEB)

    Shariati, A.

    1996-12-31

    The kinetics of polymerization of ethylene catalyzed by a polymer supported Ziegler-Natta catalyst were investigated in a semi-batch reactor system. The influences of six polymerization variables were investigated using a central composite design. The variables were monomer partial pressure, catalyst loading, co-catalyst loading, catalyst particle size and hydrogen to monomer ratio. The influence of temperature on rate and polymer properties were investigated. Empirical models were fitted to the experimental data to quantify the effects of the polymerization variables on the rate characteristics and polymer properties. The rate of polymerization exhibited a first order dependency with respect to monomer partial pressure, but a nonlinear relationship with respect to catalyst loading. In the absence of hydrogen, the polymerization rate showed a non-decaying profile at the centre point conditions for the other variables. Catalyst loading and catalyst particle size had a negligible effect on weight-and-number-average molecular weights, while increasing co-catalysts loading lowered the molecular weights, as did increased temperature and hydrogen concentration. refs., figs.

  10. Heterogeneously Catalyzed Oxidation Reactions Using Molecular Oxygen

    DEFF Research Database (Denmark)

    Beier, Matthias Josef

    Heterogeneously catalyzed selective oxidation reactions have attracted a lot of attention in recent time. The first part of the present thesis provides an overview over heterogeneous copper and silver catalysts for selective oxidations in the liquid phase and compared the performance and catalytic...... that both copper and silver can function as complementary catalyst materials to gold showing different catalytic properties and being more suitable for hydrocarbon oxidation reactions. Potential opportunities for future research were outlined. In an experimental study, the potential of silver as a catalyst...... revealed that all catalysts were more active in combination with ceria nanoparticles and that under the tested reaction conditions silver was equally or even more efficient than the gold catalysts. Calcination at 900 °C of silver on silica prepared by impregnation afforded a catalyst which was used...

  11. Functionalization of Silica Nanoparticles for Polypropylene Nanocomposite Applications

    Directory of Open Access Journals (Sweden)

    Diego Bracho

    2012-01-01

    Full Text Available Synthetic silica nanospheres of 20 and 100 nm diameter were produced via the sol-gel method to be used as filler in polypropylene (PP composites. Modification of the silica surface was further performed by reaction with organic chlorosilanes in order to improve the particles interaction with the hydrophobic polyolefin matrix. These nanoparticles were characterized using transmission electronic microscopy (TEM, elemental analysis, thermogravimetric analysis (TGA, and solid-state nuclear magnetic resonance (NMR spectroscopy. For unmodified silica, it was found that the 20 nm particles have a greater effect on both mechanical and barrier properties of the polymeric composite. In particular, at 30 wt%, Young's modulus increases by 70%, whereas water vapor permeability (WVP increases by a factor of 6. Surface modification of the 100 nm particles doubles the value of the composite breaking strain compared to unmodified particles without affecting Young's modulus, while 20 nm modified particles presented a slight increase on both Young's modulus and breaking strain. Modified 100 nm particles showed a higher WVP compared to the unmodified particles, probably due to interparticle condensation during the modification step. Our results show that the addition of nanoparticles on the composite properties depends on both particle size and surface modifications.

  12. Fabrication of superhydrophobic fluorinated silica nanoparticles for multifunctional liquid marbles

    Science.gov (United States)

    Shang, Qianqian; Hu, Lihong; Hu, Yun; Liu, Chengguo; Zhou, Yonghong

    2018-01-01

    A facile one-pot method for the fabrication of superhydrophobic fluorinated silica nanoparticles is reported. Fluorinated aggregated silica (A-SiO2/FAS) nanoparticles were synthesized by controlling the nanoparticles assembly, in situ fixation and overgrowth of particle seeds with the assist of tetraethoxysilane (TEOS) in ethanol/water solution and then modification with fluoroalkylsilane (FAS) molecules. Such kind of A-SiO2/FAS nanoparticles showed superhydrophobicity and was not wetted by water, thus it could be served as the encapsulating shells to manipulate liquid droplets. Liquid marbles fabricated from A-SiO2/FAS nanoparticles were used for ammonia gas sensing or emitting by taking advantage of the porosity and superhydrophobicity of the liquid marble shells. In addition, the posibility of A-SiO2/FAS-based liquid marbles as microreactor for dopamine polymerization also was explored.

  13. Iron halide mediated atom transfer radical polymerization of methyl methacrylate with N-Alkyl-2-pyridylmethanimine as the ligand

    NARCIS (Netherlands)

    Zhang, H.; Schubert, U.S.

    2004-01-01

    The controlled atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) catalyzed by iron halide/N-(n-hexyl)-2-pyridylmethanimine (NHPMI) is described. The ethyl 2-bromoisobutyrate (EBIB)-initiated ATRP with [MMA]0/[EBIB]0/[iron halide]0/[NHPMI]0 = 150/1/1/2 was better controlled in

  14. Composite hydrogel based on surface modified mesoporous silica and poly[(2-acryloyloxy)ethyl trimethylammonium chloride

    International Nuclear Information System (INIS)

    Torres, Cecilia C.; Urbano, Bruno F.; Campos, Cristian H.; Rivas, Bernabé L.; Reyes, Patricio

    2015-01-01

    This work focused on the synthesis, characterization and water absorbency of a composite hydrogel based on poly[(2-acryloyloxy)ethyl trimethylammonium chloride] and mesoporous silica, MCM-41. The MCM-41 was synthesized and later surface functionalized with triethoxyvinylsilane (VTES) and 3-trimethoxysilylpropylmethacrylate (TMSPM) by a post-grafting procedure. The composite hydrogels were obtained by in-situ polymerization using a mixture of monomer, crosslinker and initiator in the presence of functionalized MCM-41. Diverse characterization techniques were used at the different stages of synthesis, namely, FT-IR, TEM, SEM, DRX, 29 Si and 13 C solid state NMR, and N 2 adsorption isotherms at 77 K. Finally, the water uptake performance of the composites was tested as a function of time, mesoporous silica loading and coupling agent used at the functionalization. The composites using non-functionalized MCM-41 reached the highest water uptake, whereas those composite with MCM-41 TMSPM exhibited the lowest sorption. - Highlights: • Hydrophilic crosslinked polymer-mesoporous silica was obtained. • Mesoporous silica MCM-41 was synthesized and functionalized with organosilane. • Functionalization of MCM-41 affects the water uptake of composite. • Mesoporous silica is covalently bound to the polymer acting as crosslinked point

  15. Investigation of Optimum Polymerization Conditions for Synthesis of Cross-Linked Polyacrylamide-Amphoteric Surfmer Nanocomposites for Polymer Flooding in Sandstone Reservoirs

    Directory of Open Access Journals (Sweden)

    A. N. El-hoshoudy

    2015-01-01

    Full Text Available Currently enhanced oil recovery (EOR technology is getting more attention by many countries since energy crises are getting worse and frightening. Polymer flooding by hydrophobically associated polyacrylamides (HAPAM and its modified silica nanocomposite are a widely implemented technique through enhanced oil recovery (EOR technology. This polymers class can be synthesized by copolymerization of acrylamide (AM, reactive surfmer, functionalized silica nanoparticles, and a hydrophobic cross-linker moiety in the presence of water soluble initiator via heterogeneous emulsion polymerization technique, to form latexes that can be applied during polymer flooding. Chemical structure of the prepared copolymers was proven through different techniques such as Fourier transform infrared spectroscopy (FTIR, and nuclear magnetic spectroscopy (1H&13C-NMR, and molecular weight was measured by gel permeation chromatography. Study of the effects of monomer, surfmer, cross-linker, silica, and initiator concentrations as well as reaction temperature was investigated to determine optimum polymerization conditions through single factor and orthogonal experiments. Evaluation of the prepared copolymers for enhancing recovered oil amount was evaluated by carrying out flooding experiments on one-dimensional sandstone model to determine recovery factor.

  16. Characterization of changes in floc morphology, extracellular polymeric substances and heavy metals speciation of anaerobically digested biosolid under treatment with a novel chelated-Fe2+ catalyzed Fenton process.

    Science.gov (United States)

    He, Juanjuan; Yang, Peng; Zhang, Weijun; Cao, Bingdi; Xia, Hua; Luo, Xi; Wang, Dongsheng

    2017-11-01

    A novel chelated-Fe 2+ catalyzed Fenton process (CCFP) was developed to enhance dewatering performance of anaerobically digested biosolid, and changes in floc morphology, extracellular polymeric substances (EPS) and heavy metals speciation were also investigated. The results showed that addition of chelating agents caused EPS solubilization by binding multivalent cations. Like traditional Fenton, CCFP performed well in improving anaerobically digested sludge dewatering property. The highly active radicals (OH, O 2 - ) produced in classical Fenton and CCFP were responsible for sludge flocs destruction and consequently degradation of biopolymers into small molecules. Furthermore, more plentiful pores and channels were presented in cake after Fenton treatment, which was conducive to water drainage under mechanical compression. Additionally, a portion of active heavy metals in the form of oxidizable and reducible states were dissolved under CCFP. Therefore, CCFP could greatly simplify the operating procedure of Fenton conditioning and improve its process adaptability for harmless treatment of biological sludge. Copyright © 2017 Elsevier Ltd. All rights reserved.

  17. Amorphous Silica-Promoted Lysine Dimerization: a Thermodynamic Prediction

    Science.gov (United States)

    Kitadai, Norio; Nishiuchi, Kumiko; Nishii, Akari; Fukushi, Keisuke

    2018-03-01

    It has long been suggested that mineral surfaces played a crucial role in the abiotic polymerization of amino acids that preceded the origin of life. Nevertheless, it remains unclear where the prebiotic process took place on the primitive Earth, because the amino acid-mineral interaction and its dependence on environmental conditions have yet to be understood adequately. Here we examined experimentally the adsorption of L-lysine (Lys) and its dimer (LysLys) on amorphous silica over a wide range of pH, ionic strength, adsorbate concentration, and the solid/water ratio, and determined the reaction stoichiometries and the equilibrium constants based on the extended triple-layer model (ETLM). The retrieved ETLM parameters were then used, in combination with the equilibrium constant for the peptide bond formation in bulk water, to calculate the Lys-LysLys equilibrium in the presence of amorphous silica under various aqueous conditions. Results showed that the silica surface favors Lys dimerization, and the influence varies greatly with changing environmental parameters. At slightly alkaline pH (pH 9) in the presence of a dilute NaCl (1 mM), the thermodynamically attainable LysLys from 0.1 mM Lys reached a concentration around 50 times larger than that calculated without silica. Because of the versatility of the ETLM, which has been applied to describe a wide variety of biomolecule-mineral interactions, future experiments with the reported methodology are expected to provide a significant constraint on the plausible geological settings for the condensation of monomers to polymers, and the subsequent chemical evolution of life.

  18. Mechanism of isotactic styrene polymerization with a C 6F 5-substituted bis(phenoxyimine) titanium system

    KAUST Repository

    Caporaso, Lucia; Loria, Marianna; Mazzeo, Mina; Michiue, Kenji; Nakano, Takashi; Fujita, Terunori; Cavallo, Luigi

    2012-01-01

    We report a combined, experimental and theoretical, study of styrene polymerization to clarify the regio- and stereocontrol mechanism operating with a C 6F 5-substituted bis(phenoxyimine) titanium dichloride complex. Styrene homopolymerization, styrene-propene and styrene-ethene-propene copolymerizations have been carried out to this aim. A combination of 13C NMR analysis of the chain-end groups and of the microstructure of the homopolymers and copolymers reveals that styrene polymerization is highly regioselective and occurs prevalently through 2,1-monomer insertion. DFT calculations evidenced that steric interaction between the growing chain and the monomer in the transition state insertion stage is at the origin of this selectivity. The formation of isotactic polystyrene with a chain-end like microstructure is rationalized on the base of a mechanism similar to that proposed for the syndiospecific propene polymerization catalyzed by bis(phenoxyimine) titanium dichloride complexes. Finally, a general stereocontrol mechanism operative in olefin polymerization with this class of complexes is proposed. © 2012 American Chemical Society.

  19. Mechanism of isotactic styrene polymerization with a C 6F 5-substituted bis(phenoxyimine) titanium system

    KAUST Repository

    Caporaso, Lucia

    2012-11-13

    We report a combined, experimental and theoretical, study of styrene polymerization to clarify the regio- and stereocontrol mechanism operating with a C 6F 5-substituted bis(phenoxyimine) titanium dichloride complex. Styrene homopolymerization, styrene-propene and styrene-ethene-propene copolymerizations have been carried out to this aim. A combination of 13C NMR analysis of the chain-end groups and of the microstructure of the homopolymers and copolymers reveals that styrene polymerization is highly regioselective and occurs prevalently through 2,1-monomer insertion. DFT calculations evidenced that steric interaction between the growing chain and the monomer in the transition state insertion stage is at the origin of this selectivity. The formation of isotactic polystyrene with a chain-end like microstructure is rationalized on the base of a mechanism similar to that proposed for the syndiospecific propene polymerization catalyzed by bis(phenoxyimine) titanium dichloride complexes. Finally, a general stereocontrol mechanism operative in olefin polymerization with this class of complexes is proposed. © 2012 American Chemical Society.

  20. All-polymeric sensing platform based on packaged self-assembled bottle microresonator (Conference Presentation)

    Science.gov (United States)

    Bernini, Romeo; Grimaldi, Immacolata A.; Persichetti, Gianluca; Testa, Genni

    2017-02-01

    In recent years, microbottle resonators that support non-degenerate whispering gallery modes (WGMs), propagating by successive total internal reflections close to the resonator surface and all along its axis, have been widely investigated due to their potential applications in optical sensing, microlasers and nonlinear optics. To overcome some drawbacks of the standard silica microbottle resonators, we focused our attention on polymers such as SU-8 resist and NOA resins. A drop of polymeric material is dispensed onto a fiber stem, providing a mechanical support for the bottle resonator, and is photo-polymerized by an UV lamp. The interrogation system, usually constituted by a tapered silica fiber evanescently coupled with the microresonator, is substituted by a more stable planar waveguide realized in SU-8 by means of standard photolithography technique. Moreover, for guarantying the stability to surrounding disturbance of the coupling between the microbottle resonator and the planar waveguide, the fiber stem is glued to substrate. Two drilled holes in the substrate allow the rise of the glue at the ends of the fiber stem and the fixing of sensor on PMMA substrate. In the present work, we presented an integrated full polymeric platform with self-assembled bottle microresonators packaged in a stable structure. SU-8 and NOA based microbottles are realized and morphologically characterized. The low autofluorescence emission and long term stability make the NOA based bottles suitable to be employed in a great variety of conditions. Bulk sensing measurements are performed by using water:ethanol solutions and a bulk sensitivity of 120 nm/RIU is estimated.

  1. Highly Branched Bio-Based Unsaturated Polyesters by Enzymatic Polymerization

    Directory of Open Access Journals (Sweden)

    Hiep Dinh Nguyen

    2016-10-01

    Full Text Available A one-pot, enzyme-catalyzed bulk polymerization method for direct production of highly branched polyesters has been developed as an alternative to currently used industrial procedures. Bio-based feed components in the form of glycerol, pentaerythritol, azelaic acid, and tall oil fatty acid (TOFA were polymerized using an immobilized Candida antarctica lipase B (CALB and the potential for an enzymatic synthesis of alkyds was investigated. The developed method enables the use of both glycerol and also pentaerythritol (for the first time as the alcohol source and was found to be very robust. This allows simple variations in the molar mass and structure of the polyester without premature gelation, thus enabling easy tailoring of the branched polyester structure. The postpolymerization crosslinking of the polyesters illustrates their potential as binders in alkyds. The formed films had good UV stability, very high water contact angles of up to 141° and a glass transition temperature that could be controlled through the feed composition.

  2. Preparation of polymeric silica composites through polydopamine-mediated surface initiated ATRP for highly efficient removal of environmental pollutants

    International Nuclear Information System (INIS)

    Huang, Qiang; Liu, Meiying; Wan, Qing; Jiang, Ruming; Mao, Liucheng; Zeng, Guangjian; Huang, Hongye; Deng, Fengjie; Zhang, Xiaoyong; Wei, Yen

    2017-01-01

    anionic dyes from aqueous solution. - Graphical abstract: Cationic polymers functionalized silica nanocomposites have been fabricated through the combination of mussel inspired surface initiated atom transfer radical polymerization and utilized for removal of Congo red. - Highlights: • Surface grafting of SiO_2 nanoparticles. • Synthesis of SiO_2 based polymer nanocomposites through polydopamine-mediated SI-ATRP. • This surface modification strategy is rather facile and universal. • SiO_2 nanocomposites showed enhanced adsorption capability.

  3. Nano-structured silica coated mesoporous carbon micro-granules for potential application in water filtration

    Science.gov (United States)

    Das, Avik; Sen, D.; Mazumder, S.; Ghosh, A. K.

    2017-05-01

    A novel nano-composite spherical micro-granule has been synthesized using a facile technique of solvent evaporation induced assembly of nanoparticles for potential application in water filtration. The spherical micro-granule is comprised of nano-structured shell of hydrophilic silica encapsulating a hydrophobic mesoporous carbon at the core. Hierarchical structure of such core-shell micro-granules has been rigorously characterized using small-angle neutron and X-ray scattering techniques and complemented with scanning electron microscopy. The hydrophilic silica envelope around the carbon core helps in incorporation of such granules into the hydrophilic polymeric ultra-filtration membrane. The interstitial micro-pores present in the silica shell can serve as water transport channels and the mesoporus carbon core enhances the separation performance due its well adsorption characteristics. It has been found that the incorporation of such granules inside the ultra-filtration membrane indeed enhances the water permeability as well as the separation performance in a significant way.

  4. High-temperature synthesis of highly hydrothermal stable mesoporous silica and Fe-SiO2 using ionic liquid as a template

    International Nuclear Information System (INIS)

    Liu, Hong; Wang, Mengyang; Hu, Hongjiu; Liang, Yuguang; Wang, Yong; Cao, Weiran; Wang, Xiaohong

    2011-01-01

    Mesoporous silicas and Fe-SiO 2 with worm-like structures have been synthesized using a room temperature ionic liquid, 1-hexadecane-3-methylimidazolium bromide, as a template at a high aging temperature (150-190 o C) with the assistance of NaF. The hydrothermal stability of mesoporous silica was effectively improved by increasing the aging temperature and adding NaF to the synthesis gel. High hydrothermally stable mesoporous silica was obtained after being aged at 190 o C in the presence of NaF, which endured the hydrothermal treatment in boiling water at least for 10 d or steam treatment at 600 o C for 6 h. The ultra hydrothermal stability could be attributed to its high degree of polymerization of silicate. Furthermore, highly hydrothermal stable mesoporous Fe-SiO 2 has been synthesized, which still remained its mesostructure after being hydrothermally treated at 100 o C for 12 d or steam-treated at 600 o C for 6 h. -- Graphical abstract: Worm-like mesoporous silica and Fe-SiO 2 with high hydrothermal stability have been synthesized using ionic liquid 1-hexadecane-3-methylimidazolium bromide as a template under the assistance of NaF at high temperature. Display Omitted Research highlights: → Increasing aging temperature improved the hydrothermal stability of materials. →Addition of NaF enhanced the polymerization degree of silicates. → Mesoporous SiO 2 and Fe-SiO 2 obtained have remarkable hydrothermal stability.

  5. Silica-bound copper(II)triazacyclononane as a phosphate esterase: effect of linker length and surface hydrophobicity.

    Science.gov (United States)

    Bodsgard, Brett R; Clark, Robert W; Ehrbar, Anthony W; Burstyn, Judith N

    2009-04-07

    A series of silica-bound Cu(ii) triazacyclononane materials was prepared to study the effect of linker length and surface hydrophobicity on the hydrolysis of phosphate esters. The general synthetic approach for these heterogeneous reagents was rhodium-catalyzed hydrosilation between an alkenyl-modified triazacyclononane and hydride-modified silica followed by metallation with a Cu(ii) salt. Elemental analysis confirmed that organic functionalization of the silica gel was successful and provided an estimate of the surface concentration of triazacyclononane. EPR spectra were consistent with square pyramidal Cu(ii), indicating that Cu(ii) ions were bound to the immobilized macrocycles. The hydrolytic efficacies of these heterogeneous reagents were tested with bis(p-nitrophenyl)phosphate (BNPP) and diethyl 4-nitrophenyl phosphate (paraoxon). The agent that performed best was an octyl-linked, propanol-blocked material. This material had the most hydrophilic surface and the most accessible active site, achieving a rate maximum on par with the other materials, but in fewer cycles and without an induction period.

  6. Hydrothermal stability of silica, hybrid silica and Zr-doped hybrid silica membranes

    NARCIS (Netherlands)

    ten Hove, Marcel; Luiten-Olieman, Mieke W.J.; Huiskes, Cindy; Nijmeijer, Arian; Winnubst, Louis

    2017-01-01

    Hybrid silica membranes have demonstrated to possess a remarkable hydrothermal stability in pervaporation and gas separation processes allowing them to be used in industrial applications. In several publications the hydrothermal stability of pure silica or that of hybrid silica membranes are

  7. Fumed silica. Fumed silica

    Energy Technology Data Exchange (ETDEWEB)

    Sukawa, T.; Shirono, H. (Nippon Aerosil Co. Ltd., Tokyo (Japan))

    1991-10-18

    The fumed silica is explained in particulate superfineness, high purity, high dispersiveness and other remarkable characteristics, and wide application. The fumed silica, being presently produced, is 7 to 40nm in average primary particulate diameter and 50 to 380m{sup 2}/g in specific surface area. On the surface, there coexist hydrophilic silanol group (Si-OH) and hydrophobic siloxane group (Si-O-Si). There are many characteristics, mutually different between the fumed silica, made hydrophobic by the surface treatment, and untreated hydrophilic silica. The treated silica, if added to the liquid product, serves as agent to heighten the viscosity, prevent the sedimentation and disperse the particles. The highest effect is given to heighten the viscosity in a region of 4 to 9 in pH in water and alcohol. As filling agent to strengthen the elastomer and polymer, and powder product, it gives an effect to prevent the consolidation and improve the fluidity. As for its other applications, utilization is made of particulate superfineness, high purity, thermal insulation properties and adsorption characteristics. 2 to 3 patents are published for it as raw material of quartz glass. 38 refs., 16 figs., 4 tabs.

  8. Immobilization of isolated FI catalyst on polyhedral oligomeric silsesquioxane-functionalized silica for the synthesis of weakly entangled polyethylene.

    Science.gov (United States)

    Li, Wei; Yang, Huaqin; Zhang, Jingjing; Mu, Jingshan; Gong, Dirong; Wang, Xiaodong

    2016-09-25

    Polyhedral oligomeric silsesquioxanes (POSSs) were adsorbed on methylaluminoxane-activated silica for the immobilization of fluorinated bis(phenoxyimine)Ti complexes (FI catalyst). These POSSs have been characterized as horizontal spacers isolating the active sites and hindering the chain overlap in polymerization. The heterogeneous catalyst exhibits considerable activity in the synthesis of weakly entangled polyethylene.

  9. Fabrication of BCP/Silica Scaffolds with Dual-Pore by Combining Fused Deposition Modeling and the Particle Leaching Method

    International Nuclear Information System (INIS)

    Sa, Min-Woo; Kim, Jong Young

    2016-01-01

    In recent years, traditional scaffold fabrication techniques such as gas foaming, salt leaching, sponge replica, and freeze casting in tissue engineering have significantly limited sufficient mechanical property and cell interaction effect due to only random pores. Fused deposition modeling is the most apposite technology for fabricating the 3D scaffolds using the polymeric materials in tissue engineering application. In this study, 3D slurry mould was fabricated with a blended biphasic calcium phosphate (BCP)/Silica/Alginic acid sodium salt slurry in PCL mould and heated for two hours at 100 .deg. C to harden the blended slurry. 3D dual-pore BCP/Silica scaffold, composed of macro pores interconnected with micro pores, was successfully fabricated by sintering at furnace of 1100 .deg. C. Surface morphology and 3D shape of dual-pore BCP/Silica scaffold from scanning electron microscopy were observed. Also, the mechanical properties of 3D BCP/Silica scaffold, according to blending ratio of alginic acid sodium salt, were evaluated through compression test

  10. Fabrication of BCP/Silica Scaffolds with Dual-Pore by Combining Fused Deposition Modeling and the Particle Leaching Method

    Energy Technology Data Exchange (ETDEWEB)

    Sa, Min-Woo; Kim, Jong Young [Andong National Univ., Andong (Korea, Republic of)

    2016-10-15

    In recent years, traditional scaffold fabrication techniques such as gas foaming, salt leaching, sponge replica, and freeze casting in tissue engineering have significantly limited sufficient mechanical property and cell interaction effect due to only random pores. Fused deposition modeling is the most apposite technology for fabricating the 3D scaffolds using the polymeric materials in tissue engineering application. In this study, 3D slurry mould was fabricated with a blended biphasic calcium phosphate (BCP)/Silica/Alginic acid sodium salt slurry in PCL mould and heated for two hours at 100 .deg. C to harden the blended slurry. 3D dual-pore BCP/Silica scaffold, composed of macro pores interconnected with micro pores, was successfully fabricated by sintering at furnace of 1100 .deg. C. Surface morphology and 3D shape of dual-pore BCP/Silica scaffold from scanning electron microscopy were observed. Also, the mechanical properties of 3D BCP/Silica scaffold, according to blending ratio of alginic acid sodium salt, were evaluated through compression test.

  11. Conjugation of diisocyanate side chains to dimethacrylate reduces polymerization shrinkage and increases the hardness of composite resins.

    Science.gov (United States)

    Jan, Yih-Dean; Lee, Bor-Shiunn; Lin, Chun-Pin; Tseng, Wan-Yu

    2014-04-01

    Polymerization shrinkage is one of the main causes of dental restoration failure. This study tried to conjugate two diisocyanate side chains to dimethacrylate resins in order to reduce polymerization shrinkage and increase the hardness of composite resins. Diisocyanate, 2-hydroxyethyl methacrylate, and bisphenol A dimethacrylate were reacted in different ratios to form urethane-modified new resin matrices, and then mixed with 50 wt.% silica fillers. The viscosities of matrices, polymerization shrinkage, surface hardness, and degrees of conversion of experimental composite resins were then evaluated and compared with a non-modified control group. The viscosities of resin matrices increased with increasing diisocyanate side chain density. Polymerization shrinkage and degree of conversion, however, decreased with increasing diisocyanate side chain density. The surface hardness of all diisocyanate-modified groups was equal to or significantly higher than that of the control group. Conjugation of diisocyanate side chains to dimethacrylate represents an effective means of reducing polymerization shrinkage and increasing the surface hardness of dental composite resins. Copyright © 2012. Published by Elsevier B.V.

  12. Entrapment of Enzymes and Carbon Nanotubes in Biologically Synthesized Silica: Glucose Oxidase-catalyzed Direct Electron Transfer, Preprint

    National Research Council Canada - National Science Library

    Invitski, Dmitri; Artyuskova, Kateryna; Rincon, Rosalba A; Atanassov, Plamen; Luckarift, Heather R; Johnson, Glenn R

    2007-01-01

    This work demonstrates a new approach for building bio-inorganic interfaces by integrating biomimetically-derived silica with single-walled carbon nanotubes to create a conductive matrix for immobilization of enzymes...

  13. Composite hydrogel based on surface modified mesoporous silica and poly[(2-acryloyloxy)ethyl trimethylammonium chloride

    Energy Technology Data Exchange (ETDEWEB)

    Torres, Cecilia C. [Department of Organic Chemistry, Faculty of Chemical Science, University of Concepción (Chile); Urbano, Bruno F., E-mail: burbano@udec.cl [Department of Polymer Chemistry, Faculty of Chemical Science, University of Concepción (Chile); Campos, Cristian H. [Department of Organic Chemistry, Faculty of Chemical Science, University of Concepción (Chile); Rivas, Bernabé L. [Department of Polymer Chemistry, Faculty of Chemical Science, University of Concepción (Chile); Reyes, Patricio [Department of Physical Chemistry, Faculty of Chemical Science, University of Concepción (Chile)

    2015-02-15

    This work focused on the synthesis, characterization and water absorbency of a composite hydrogel based on poly[(2-acryloyloxy)ethyl trimethylammonium chloride] and mesoporous silica, MCM-41. The MCM-41 was synthesized and later surface functionalized with triethoxyvinylsilane (VTES) and 3-trimethoxysilylpropylmethacrylate (TMSPM) by a post-grafting procedure. The composite hydrogels were obtained by in-situ polymerization using a mixture of monomer, crosslinker and initiator in the presence of functionalized MCM-41. Diverse characterization techniques were used at the different stages of synthesis, namely, FT-IR, TEM, SEM, DRX, {sup 29}Si and {sup 13}C solid state NMR, and N{sub 2} adsorption isotherms at 77 K. Finally, the water uptake performance of the composites was tested as a function of time, mesoporous silica loading and coupling agent used at the functionalization. The composites using non-functionalized MCM-41 reached the highest water uptake, whereas those composite with MCM-41 TMSPM exhibited the lowest sorption. - Highlights: • Hydrophilic crosslinked polymer-mesoporous silica was obtained. • Mesoporous silica MCM-41 was synthesized and functionalized with organosilane. • Functionalization of MCM-41 affects the water uptake of composite. • Mesoporous silica is covalently bound to the polymer acting as crosslinked point.

  14. Design and synthesis of structurally well-defined functional polypropylenes via transition metal-mediated olefin polymerization chemistry

    Institute of Scientific and Technical Information of China (English)

    Dong Jinyong

    2006-01-01

    Functionalization of polyolefins is an industrially important yet scientifically challenging research subject.This paper summarizes our recent effort to access structurally well-defined functional polypropylenes via transition metal-mediated olefin polymerization.In one approach,polypropylenes containing side chain functional groups of controlled concentrations were obtained by Ziegler-Natta-catalyzed copolymerization of propylene in combination with either living anionic or controlled radical polymerization of polar monomers.The copolymerization of propylene with 1,4-divinylbenzene using an isospecific MgC12-supported TIC14 catalyst yielded potypropylenes containing pendant styrene moieties.Both metalation reaction with n-butyllithium and hydrochlorination reaction with dry hydrogen chloride selectively and quantitatively occurred at the pendant reactive sites,generating polymeric benzyllithium and 1-chloroethylbenzene species.These species initiated living anionic polymerization of styrene(S)and atom transfer radical polymerization(in the presence of CuC1 and pentamethyldiethylenetriamine) of methyl methacrylate(MMA),respectively,resulting in functional polypropylene graft copolymers(PP-g-PS and PP-g-PMMA)with controllable graft lengths.In another approach,chain end-functionalized polypropylenes containing a terminal OH-group with controlled molecular weights were directly prepared by propylene polymerization with a metaUocene catalyst through a selective aluminum chain transfer reaction.Both approaches proved to be desirable polyolefin functionalization routes in terms of efficiency and polymer structure controllability.

  15. Modification of oligo-Ricinoleic Acid and Its Derivatives with 10-Undecenoic Acid via Lipase-Catalyzed Esterification

    Directory of Open Access Journals (Sweden)

    M. Claudia Montiel

    2012-04-01

    Full Text Available Lipases were employed under solvent-free conditions to conjugate oligo-ricinoleic acid derivatives with 10-undecenoic acid, to incorporate a reactive terminal double bond into the resultant product. First, undecenoic acid was covalently attached to oligo-ricinoleic acid using immobilized Candida antarctica lipase (CAL at a 30% yield. Thirty percent conversion also occurred for CAL-catalyzed esterification between undecenoic acid and biocatalytically-prepared polyglycerol polyricinoleate (PGPR, with attachment of undecenoic acid occurring primarily at free hydroxyls of the polyglycerol moiety. The synthesis of oligo-ricinoleyl-, undecenoyl- structured triacylglycerols comprised two steps. The first step, the 1,3-selective lipase-catalyzed interesterification of castor oil with undecenoic acid, occurred successfully. The second step, the CAL-catalyzed reaction between ricinoleyl-, undecenoyl structured TAG and ricinoleic acid, yielded approximately 10% of the desired structured triacylglycerols (TAG; however, a significant portion of the ricinoleic acid underwent self-polymerization as a side-reaction. The employment of gel permeation chromatography, normal phase HPLC, NMR, and acid value measurements was effective for characterizing the reaction pathways and products that formed.

  16. Tailored Cyclic and Linear Polycarbosilazanes by Barium-Catalyzed N-H/H-Si Dehydrocoupling Reactions.

    Science.gov (United States)

    Bellini, Clément; Orione, Clément; Carpentier, Jean-François; Sarazin, Yann

    2016-03-07

    Ba[CH(SiMe3 )2 ]2 (THF)3 catalyzes the fast and controlled dehydrogenative polymerization of Ph2 SiH2 and p-xylylenediamine to afford polycarbosilazanes. The structure (cyclic versus linear; end-groups) and molecular weight of the macromolecules can be tuned by adjusting the Ph2 SiH2 /diamine feed ratio. A detailed analysis of the resulting materials (mol. wt up to ca. 10 000 g mol(-1) ) is provided. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Carbon-dot-based dual-emission silica nanoparticles as a ratiometric fluorescent probe for vanadium(V) detection in mineral water samples

    Science.gov (United States)

    He, Lijun; Zhang, Heng; Fan, Huanhuan; Jiang, Xiuming; Zhao, Wenjie; Xiang, Guo Qiang

    2018-01-01

    Herein, we propose a simple and effective strategy for designing a ratiometric fluorescent nanosensor. We designed and developed a carbon dots (CDs) based dual-emission nanosensor for vanadium(V) by coating the surface of dye-doped silica nanoparticles with CDs. The fluorescence of dual-emission silica nanoparticles was quenched in acetic acid through potassium bromate (KBrO3) oxidation. V(V) could catalyze KBrO3 oxidation reaction process, resulting in the ratiometric fluorescence quenching of dual-emission silica nanoparticles. We investigated several important parameters affecting the performance of the nanosensor. Under the optimized conditions, the detection limit of this nanosensor reached 1.1 ng mL- 1 and the linear range from 10 to 800 ng mL- 1. Furthermore, we found that the sensor was suitable for determination of V(V) in different mineral water samples with satisfactory results.

  18. Sol-gel derived flexible silica aerogel as selective adsorbent for water decontamination from crude oil.

    Science.gov (United States)

    Abolghasemi Mahani, A; Motahari, S; Mohebbi, A

    2018-04-01

    Oil spills are the most important threat to the sea ecosystem. The present study is an attempt to investigate the effects of sol-gel parameters on seawater decontamination from crude oil by use of flexible silica aerogel. To this goal, methyltrimethoxysilane (MTMS) based silica aerogels were prepared by two-step acid-base catalyzed sol-gel process, involving ambient pressure drying (APD) method. To investigate the effects of sol-gel parameters, the aerogels were prepared under two different acidic and basic pH values (i.e. 4 and 8) and varied ethanol/MTMS molar ratios from 5 to 15. The adsorption capacity of the prepared aerogels was evaluated for two heavy and light commercial crude oils under multiple adsorption-desorption cycles. To reduce process time, desorption cycles were carried out by using roll milling for the first time. At optimum condition, silica aerogels are able to uptake heavy and light crude oils with the order of 16.7 and 13.7, respectively. Copyright © 2017 Elsevier Ltd. All rights reserved.

  19. Studies of Immobilized Homogeneous Metal Catalysts on Silica Supports

    Energy Technology Data Exchange (ETDEWEB)

    Stanger, Keith James [Iowa State Univ., Ames, IA (United States)

    2003-01-01

    The tethered, chiral, chelating diphosphine rhodium complex, which catalyzes the enantioselective hydrogenation of methyl-α-acetamidocinnamate (MAC), has the illustrated structure as established by 31P NMR and IR studies. Spectral and catalytic investigations also suggest that the mechanism of action of the tethered complex is the same as that of the untethered complex in solution. The rhodium complexes, [Rh(COD)H]4, [Rh(COD)2]+BF4-, [Rh(COD)Cl]2, and RhCl3• 3H2O, adsorbed on SiO2 are optimally activated for toluene hydrogenation by pretreatment with H2 at 200 C. The same complexes on Pd-SiO2 are equally active without pretreatments. The active species in all cases is rhodium metal. The catalysts were characterized by XPS, TEM, DRIFTS, and mercury poisoning experiments. Rhodium on silica catalyzes the hydrogenation of fluorobenzene to produce predominantly fluorocyclohexane in heptane and 1,2-dichloroethane solvents. In heptane/methanol and heptane/water solvents, hydrodefluorination to benzene and subsequent hydrogenation to cyclohexane occurs exclusively. Benzene inhibits the hydrodefluorination of fluorobenzene. In DCE or heptane solvents, fluorocyclohexane reacts with hydrogen fluoride to form cyclohexene. Reaction conditions can be chosen to selectively yield fluorocyclohexane, cyclohexene, benzene, or cyclohexane. The oxorhenium(V) dithiolate catalyst [-S(CH2)3s-]Re(O)(Me)(PPh3) was modified by linking it to a tether that could be attached to a silica support. Spectroscopic investigation and catalytic oxidation reactivity showed the heterogenized catalyst's structure and reactivity to be similar to its homogeneous analog. However, the immobilized catalyst offered additional advantages of recyclability, extended stability, and increased resistance to deactivation.

  20. The influence of the matrix structure on the oxidation of aniline in a silica sol-gel composite

    International Nuclear Information System (INIS)

    Widera, J.; Kijak, A.M.; Ca, D.V.; Pacey, G.E.; Taylor, R.T.; Perfect, H.; Cox, J.A.

    2005-01-01

    Mesoporous and microporous silica matrices were formed on indium tin oxide electrodes for liquid-phase voltammetry and as monoliths for solid-state voltammetry of aniline. The pore structure, which was verified by scanning probe microscopy and by surface area measurement, was directed by either control of pH during sol-gel processing or by inclusion of a templating agent. Whether aniline was included as a dopant in the sol-gel or as a component of the contacting liquid, the pore size influenced the coupling of the product of its electrochemical oxidation. With microporous silica, the dominant products were dimers and related short-chain products whereas with mesoporous silica, polymerization was suggested. As a step toward the formation of polyaniline (PANI) that is covalently anchored to the sol-gel, the electrochemistry of aniline was investigated using composites prepared from sols comprising tetraethyl orthosilicate (TEOS), 3-aminophenyl-[3-triethoxylsilyl)-propyl] urea (ormosil), and aniline in various ratios. Combinatorial chemistry identified that the optimum combination of silica precursors in terms of obtaining PANI was a 1:12 mole ratio of ormosil:TEOS

  1. Polymeric ionic liquid modified graphene oxide-grafted silica for solid-phase extraction to analyze the excretion-dynamics of flavonoids in urine by Box-Behnken statistical design.

    Science.gov (United States)

    Hou, Xiudan; Liu, Shujuan; Zhou, Panpan; Li, Jin; Liu, Xia; Wang, Licheng; Guo, Yong

    2016-07-22

    A solid-phase extraction method for the efficient analysis of the excretion-dynamics of flavonoids in urine was established and described. In this work, in situ surface radical chain-transfer polymerization and in situ anion exchange were utilized to tune the extraction performance of poly(1-vinyl-3-hexylimidazolium bromide)-graphene oxide-grafted silica (poly(VHIm(+)Br(-))@GO@Sil). Graphene oxide (GO) was first coated onto the silica using a layer-by-layer fabrication method, and then the anion of poly(VHIm(+)Br(-))@GO@Sil was changed into hexafluorophosphate (PF6(-)) by in situ anion exchange. The interaction energies between two PILs and four flavonoids were calculated with the Gaussian09 suite of programs. A Box-Behnken design was used for the optimization of four greatly influential parameters after single-factor experiments to obtain more accurate and precise results. Coupled to high performance liquid chromatography, the poly(VHIm(+)PF6(-))@GO@Sil method showed acceptable extraction recoveries for the four flavonoids, with limits of detection in the range of 0.1-0.5μgL(-1), and wide linear ranges with correlation coefficients (R) ranging from 0.9935 to 0.9987. Under the optimum conditions, the proposed method was applied to analyze the urines collected from a healthy volunteer. The excretion amount-time profiles revealed that 4-15h was the main excretion time for the detected flavonoids. The results indicated that the newly developed method offered the advantages of being feasible, green and cost-effective, and could be successfully applied to the extraction and enrichment of flavonoids in human body systems allowing the study of the metabolic kinetics. Copyright © 2016. Published by Elsevier B.V.

  2. Advanced treatment technique for swine wastewater using two agents: Thermally polymerized amorphous silica and hydrated lime for color and phosphorus removal and sulfur for nitrogen removal.

    Science.gov (United States)

    Hasegawa, Teruaki; Kurose, Yohei; Tanaka, Yasuo

    2017-10-01

    The efficacy of advanced treatment of swine wastewater using thermally polymerized, modified amorphous silica and hydrated lime (M-CSH-lime) for color and phosphorus removal and sulfur for nitrogen removal was examined with a demonstration-scale treatment plant. The color removal rate was approximately 78% at M-CSH-lime addition rates of > 0.055 wt/v%. The PO43--P removal rate exceeded 99.9% with > 0.023 wt/v%. pH of the effluent from the M-CSH-lime reactor increased with the addition rate till a maximum value of 12.7, which was effective in disinfection. The recovered M-CSH-lime would be suitable as a phosphorus fertilizer because the total P 2 O 5 content was approximately 10%. The nitrogen oxide (NOx-N) removal rate by sulfur denitrification increased to approximately 80% when the NOx-N loading rate was around 0.1 kg-N/ton-S/day. It was suggested that the combination of the two processes would be effective in the advanced treatment of swine wastewater. © 2017 Japanese Society of Animal Science.

  3. Magnetic silica hybrids modified with guanidine containing co-polymers for drug delivery applications

    Energy Technology Data Exchange (ETDEWEB)

    Timin, Alexander S., E-mail: a_timin@mail.ru [Inorganic Chemistry Department, Ivanovo State University of Chemistry and Technology (ISUCT), 7, Sheremetevsky prosp., 153000 Ivanovo (Russian Federation); RASA Center in Tomsk, Tomsk Polytechnic University, 30, Lenin Avenue, 634500 Tomsk (Russian Federation); Khashirova, Svetlana Yu. [Kabardino-Balkar State University, ul. Chernyshevskogo 173, Nal' chik, 360004 Kabardino-Balkaria (Russian Federation); Rumyantsev, Evgeniy V.; Goncharenko, Alexander A. [Inorganic Chemistry Department, Ivanovo State University of Chemistry and Technology (ISUCT), 7, Sheremetevsky prosp., 153000 Ivanovo (Russian Federation)

    2016-07-01

    Guanidine containing co-polymers grafted onto silica nanoparticles to form core-shell structure were prepared by sol-gel method in the presence of γ-Fe{sub 2}O{sub 3} nanoparticles. The morphological features for uncoated and coated silica particles have been characterized with scanning electron microscopy. The results show that the polymer coated silicas exhibit spherical morphology with rough polymeric surface covered by γ-Fe{sub 2}O{sub 3} nanoparticles. The grafting amount of guanidine containing co-polymers evaluated by thermogravimetric analysis was in the range from 17 to 30%. Then, the drug loading properties and cumulative release of silica hybrids modified with guanidine containing co-polymers were evaluated using molsidomine as a model drug. It was shown that after polymer grafting the loading content of molsidomine could reach up to 3.42 ± 0.21 and 2.34 ± 0.14 mg/g respectively. The maximum drug release of molsidomine is achieved at pH 1.6 (approximately 71–75% release at 37 °C), whereas at pH 7.4 drug release is lower (50.4–59.6% release at 37 °C). These results have an important implication that our magneto-controlled silica hybrids modified with guanidine containing co-polymers are promising as drug carriers with controlled behaviour under influence of magnetic field. - Highlights: • Polymer coated silica hybrids containing γ-Fe{sub 2}O{sub 3} were prepared via sol–gel method. • Polymer grafting influences pH-response and surface properties of final products. • Molsidomine as a model drug was effectively loaded into polymer coated silicas. • The drug loading depends on the nature of grafted polymer and its content.

  4. Nanostructural control of the release of macromolecules from silica sol–gels

    Science.gov (United States)

    Radin, Shula; Bhattacharyya, Sanjib; Ducheyne, Paul

    2013-01-01

    The therapeutic use of biological molecules such as growth factors and monoclonal antibodies is challenging in view of their limited half-life in vivo. This has elicited the interest in delivery materials that can protect these molecules until released over extended periods of time. Although previous studies have shown controlled release of biologically functional BMP-2 and TGF-β from silica sol–gels, more versatile release conditions are desirable. This study focuses on the relationship between room temperature processed silica sol–gel synthesis conditions and the nanopore size and size distribution of the sol–gels. Furthermore, the effect on release of large molecules with a size up to 70 kDa is determined. Dextran, a hydrophilic polysaccharide, was selected as a large model molecule at molecular sizes of 10, 40 and 70 kDa, as it enabled us to determine a size effect uniquely without possible confounding chemical effects arising from the various molecules used. Previously, acid catalysis was performed at a pH value of 1.8 below the isoelectric point of silica. Herein the silica synthesis was pursued using acid catalysis at either pH 1.8 or 3.05 first, followed by catalysis at higher values by adding base. This results in a mesoporous structure with an abundance of pores around 3.5 nm. The data show that all molecular sizes can be released in a controlled manner. The data also reveal a unique in vivo approach to enable release of large biological molecules: the use more labile sol–gel structures by acid catalyzing above the pH value of the isoelectric point of silica; upon immersion in a physiological fluid the pores expand to reach an average size of 3.5 nm, thereby facilitating molecular out-diffusion. PMID:23643607

  5. Stable Poly(methacrylic acid Brush Decorated Silica Nano-Particles by ARGET ATRP for Bioconjugation

    Directory of Open Access Journals (Sweden)

    Marcello Iacono

    2015-08-01

    Full Text Available The synthesis of polymer brush decorated silica nano-particles is demonstrated by activator regeneration by electron transfer atom transfer radical polymerization (ARGET ATRP grafting of poly(tert-butyl methacrylate. ATRP initiator decorated silica nano-particles were obtained using a novel trimethylsiloxane derivatised ATRP initiator obtained by click chemistry. Comparison of de-grafted polymers with polymer obtained from a sacrificial initiator demonstrated good agreement up to 55% monomer conversion. Subsequent mild deprotection of the tert-butyl ester groups using phosphoric acid yielded highly colloidal and pH stable hydrophilic nano-particles comprising approximately 50% methacrylic acid groups. The successful bio-conjugation was achieved by immobilization of Horseradish Peroxidase to the polymer brush decorated nano-particles and the enzyme activity demonstrated in a conversion of o-phenylene diamine dihydrochloride assay.

  6. Rheological behavior of alkali-activated metakaolin during geo-polymerization

    International Nuclear Information System (INIS)

    Poulesquen, A.; Frizon, F.; Lambertin, D.

    2011-01-01

    The dynamic rheological behavior of geo-polymers, inorganic materials synthesized by activation of an aluminosilicate source by an alkaline solution, is described. The pastes studied were mixtures of an activation solution (alkali + silica) and metakaolin. The influence of the activation solution (NaOH vs. KOH), the silica (Aerosil vs. Tixosil), and the temperature on the evolution of the elastic modulus (G') and viscous modulus (G') over time were studied in the linear viscoelastic range. The results show that the nature of the silica has little influence on the viscous and elastic moduli when the geo-polymer is activated by KOH, and that the setting time is faster with sodium hydroxide and at higher temperatures regardless of the geo-polymer. In addition, during geo-polymerization the stepwise variation of the modulus values indicates that the formation of the 3D network occurs in several steps. Moreover, geo-polymers activated by potassium hydroxide exhibit slower kinetics but the interactions between constituents are stronger, as the loss tangent (tanδ = G''/G') is lower. Finally, the maximum loss tangent, tanδ, was also used as a criterion to determine the temperature dependence of the geo-polymers synthesized. This criterion is a precursor of the transition to the glassy state. The activation energies could thus be determined for the geo-polymers synthesized with potassium hydroxide or sodium hydroxide. (authors)

  7. Preparation of polymeric silica composites through polydopamine-mediated surface initiated ATRP for highly efficient removal of environmental pollutants

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Qiang; Liu, Meiying; Wan, Qing; Jiang, Ruming; Mao, Liucheng; Zeng, Guangjian; Huang, Hongye; Deng, Fengjie [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Zhang, Xiaoyong, E-mail: xiaoyongzhang1980@gmail.com [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Wei, Yen [Department of Chemistry and the Tsinghua Center for Frontier Polymer Research, Tsinghua University, Beijing 100084 (China)

    2017-06-01

    developed as a new adsorbent for the removal of anionic dyes from aqueous solution. - Graphical abstract: Cationic polymers functionalized silica nanocomposites have been fabricated through the combination of mussel inspired surface initiated atom transfer radical polymerization and utilized for removal of Congo red. - Highlights: • Surface grafting of SiO{sub 2} nanoparticles. • Synthesis of SiO{sub 2} based polymer nanocomposites through polydopamine-mediated SI-ATRP. • This surface modification strategy is rather facile and universal. • SiO{sub 2} nanocomposites showed enhanced adsorption capability.

  8. Hydroformylation of dihydrofurans catalyzed by rhodium complex encapsulated hexagonal mesoporous silica

    KAUST Repository

    Khokhar, Munir; Shukla, Ram S.; Jasra, Raksh Vir

    2015-01-01

    HRh(CO)(PPh3)3 encapsulated hexagonal mesoporous silica (HMS) is found to be an efficient heterogeneous catalyst for the selective hydroformylation of 2,3-dihydrofuran (2,3DHF) and 2,5-dihydrofuran (2,5DHF). The Rh-complex encapsulated in situ in the organic phase of template inside the pores of HMS was found to act as nano phase reactors. Conversion of 2,3-DHF and 2,5-DHF and selectivity of the corresponding aldehydes were thoroughly investigated by studying the reaction parameters: catalyst amount, substrate concentration, partial as well as total pressure of CO and H2, and temperature. The selectivity for the formation of tetrahydrofuran-2-carbaldehyde (THF-2-carbaldehyde) from the hydroformylation of 2,3-DHF was found to be more than the selectivity of the formation of tetrahydrofuran-3-carbaldehyde (THF-3-carbaldehyde) from 2,5-DHF. The reaction paths are suggested and discussed for the selective formation of the corresponding aldehydes. The catalyst was elegantly separated and effectively recycled for six times.

  9. Hydroformylation of dihydrofurans catalyzed by rhodium complex encapsulated hexagonal mesoporous silica

    KAUST Repository

    Khokhar, Munir

    2015-05-01

    HRh(CO)(PPh3)3 encapsulated hexagonal mesoporous silica (HMS) is found to be an efficient heterogeneous catalyst for the selective hydroformylation of 2,3-dihydrofuran (2,3DHF) and 2,5-dihydrofuran (2,5DHF). The Rh-complex encapsulated in situ in the organic phase of template inside the pores of HMS was found to act as nano phase reactors. Conversion of 2,3-DHF and 2,5-DHF and selectivity of the corresponding aldehydes were thoroughly investigated by studying the reaction parameters: catalyst amount, substrate concentration, partial as well as total pressure of CO and H2, and temperature. The selectivity for the formation of tetrahydrofuran-2-carbaldehyde (THF-2-carbaldehyde) from the hydroformylation of 2,3-DHF was found to be more than the selectivity of the formation of tetrahydrofuran-3-carbaldehyde (THF-3-carbaldehyde) from 2,5-DHF. The reaction paths are suggested and discussed for the selective formation of the corresponding aldehydes. The catalyst was elegantly separated and effectively recycled for six times.

  10. Hydrosilane-B(C6F5)3 adducts as activators in zirconocene catalyzed ethylene polymerization

    Czech Academy of Sciences Publication Activity Database

    Varga, Vojtěch; Lamač, Martin; Horáček, Michal; Gyepes, Robert; Pinkas, Jiří

    2016-01-01

    Roč. 45, MAY 2016 (2016), s. 10146-10150 ISSN 1477-9226 R&D Projects: GA ČR(CZ) GAP207/12/2368; GA ČR(CZ) GA14-08531S Institutional support: RVO:61388955 Keywords : ethylene * zirconium compounds * polymerization Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 4.029, year: 2016

  11. A Thin Film Nanocomposite Membrane with MCM-41 Silica Nanoparticles for Brackish Water Purification

    Directory of Open Access Journals (Sweden)

    Mohammed Kadhom

    2016-12-01

    Full Text Available Thin film nanocomposite (TFN membranes containing MCM-41 silica nanoparticles (NPs were synthesized by the interfacial polymerization (IP process. An m-phenylenediamine (MPD aqueous solution and an organic phase with trimesoyl chloride (TMC dissolved in isooctane were used in the IP reaction, occurring on a nanoporous polysulfone (PSU support layer. Isooctane was introduced as the organic solvent for TMC in this work due to its intermediate boiling point. MCM-41 silica NPs were loaded in MPD and TMC solutions in separate experiments, in a concentration range from 0 to 0.04 wt %, and the membrane performance was assessed and compared based on salt rejection and water flux. The prepared membranes were characterized via scanning electron microscopy (SEM, transmission electron microscopy (TEM, contact angle measurement, and attenuated total reflection Fourier transform infrared (ATR FT-IR analysis. The results show that adding MCM-41 silica NPs into an MPD solution yields slightly improved and more stable results than adding them to a TMC solution. With 0.02% MCM-41 silica NPs in the MPD solution, the water flux was increased from 44.0 to 64.1 L/m2·h, while the rejection virtually remained the same at 95% (2000 ppm NaCl saline solution, 25 °C, 2068 kPa (300 psi.

  12. A Thin Film Nanocomposite Membrane with MCM-41 Silica Nanoparticles for Brackish Water Purification.

    Science.gov (United States)

    Kadhom, Mohammed; Yin, Jun; Deng, Baolin

    2016-12-06

    Thin film nanocomposite (TFN) membranes containing MCM-41 silica nanoparticles (NPs) were synthesized by the interfacial polymerization (IP) process. An m -phenylenediamine (MPD) aqueous solution and an organic phase with trimesoyl chloride (TMC) dissolved in isooctane were used in the IP reaction, occurring on a nanoporous polysulfone (PSU) support layer. Isooctane was introduced as the organic solvent for TMC in this work due to its intermediate boiling point. MCM-41 silica NPs were loaded in MPD and TMC solutions in separate experiments, in a concentration range from 0 to 0.04 wt %, and the membrane performance was assessed and compared based on salt rejection and water flux. The prepared membranes were characterized via scanning electron microscopy (SEM), transmission electron microscopy (TEM), contact angle measurement, and attenuated total reflection Fourier transform infrared (ATR FT-IR) analysis. The results show that adding MCM-41 silica NPs into an MPD solution yields slightly improved and more stable results than adding them to a TMC solution. With 0.02% MCM-41 silica NPs in the MPD solution, the water flux was increased from 44.0 to 64.1 L/m²·h, while the rejection virtually remained the same at 95% (2000 ppm NaCl saline solution, 25 °C, 2068 kPa (300 psi)).

  13. Direct Synthesis of Telechelic Polyethylene by Selective Insertion Polymerization

    KAUST Repository

    Jian, Zhongbao

    2016-10-14

    A single-step route to telechelic polyethylene (PE) is enabled by selective insertion polymerization. PdII-catalyzed copolymerization of ethylene and 2-vinylfuran (VF) generates α,ω-di-furan telechelic polyethylene. Orthogonally reactive exclusively in-chain anhydride groups are formed by terpolymerization with carbic anhydride. Combined experimental and theoretical DFT studies reveal the key for this direct approach to telechelics to be a match of the comonomers’ different electronics and bulk. Identified essential features of the comonomer are that it is an electron-rich olefin that forms an insertion product stabilized by an additional interaction, namely a π–η3 interaction for the case of VF.

  14. Novel polyoxometalate silica nano-sized spheres: efficient catalysts for olefin oxidation and the deep desulfurization process.

    Science.gov (United States)

    Nogueira, Lucie S; Ribeiro, Susana; Granadeiro, Carlos M; Pereira, Eulália; Feio, Gabriel; Cunha-Silva, Luís; Balula, Salete S

    2014-07-07

    A novel method to prepare silica nano-sized particles incorporating polyoxometalates was developed leading to a new efficient heterogeneous oxidative catalyst. Zinc-substituted polyoxotungstate [PW11Zn(H2O)O39](5-) (PW11Zn) was encapsulated into silica nanoparticles using a cross-linked organic-inorganic core, performed through successive spontaneous reactions in water. The potassium salt of PW11Zn and the composite formed, PW11Zn-APTES@SiO2, were characterized by a myriad of solid-state methods such as FT-IR, FT-Raman, (31)P and (13)C CP/MAS solid-state NMR, elemental analysis and SEM-EDS, confirming the integrity of the PW11Zn structure immobilized in the silica nanoparticles. The new composite has shown to be a versatile catalyst for the oxidation of olefins and also to catalyze the desulfurization of a model oil using H2O2 as the oxidant and acetonitrile as the solvent. The novel composite material was capable of being recycled without significant loss of activity and maintaining its structural stability for consecutive desulfurization and olefin oxidative cycles.

  15. Polymeric supported sorbents for decreasing hazardous metal ions content in wet process phosphoric acid

    International Nuclear Information System (INIS)

    El-Zahhar, A.A.; El-Naggar, H.A.; Ahmed, M.

    2005-01-01

    Procedure for preparation of polymeric supported silica, and their usage for decreasing hazardous metal ion content in wet process phosphoric acid was developed. The procedure is based firstly on extraction silica from rice straw by alkaline treatment , secondly supporting the produced silica on binding polyacrylonitrile (PAN). The produced polymer based sorbent was used for decreasing hazardous metal ions (especially iron) present as inorganic impurities in crud Egyptian phosphoric acid (green acid). Different factors affecting the sorption equilibrium ( contact time, temperature , sorbent mass and batch factor ) were studied. Studying the sorption isotherm revealed that the adsorption data could favorably fit the Langmuir adsorption isotherm. In the dynamic study , the sorption capacity at (Cξ/Cο = 50%) was found to be 28.5 mg/g and the loaded column could be regenerated using 50ml of 0.15 M HNO 3 . The regenerated column could undergo sorption regeneration cycles up to four cycles without significant decrease in the sorption capacity , weight loss or change in the physical properties of the sorbent

  16. Melting and crystallization of in-situ polymerized cyclic butylene terephthalates with and without organoclay: a modulated DSC study

    Directory of Open Access Journals (Sweden)

    2007-02-01

    Full Text Available The polymerization of cyclic butylene terephthalate oligomers (CBT were studied in presence (in 5 wt.% and absence of an organoclay (Cloisite® 30B by modulated DSC (MDSC. The organoclay containing samples were produced by dry and melt blending, respectively. The first heating, causing the polymerization of the CBT catalyzed by an organotin compound, was followed by cooling prior to the second heating. The MDSC scans covered the temperature interval between 0 and 260°C. The aim of this protocol was to study the crystallization and melting behavior of the resulting polybutylene terephthalate (pCBT and its organoclay modified nanocomposites. It was found that the thermal behaviors of the polymerizing and polymerized CBT (pCBT were strongly affected by the sample preparation. The organoclay suppressed the crystallization of the pCBT produced during the first heating. However, results from the second heating suggest that more perfect crystallites were formed in the organoclay modified pCBT variants. The organoclay also affected the conversion and mean molecular mass of the resulting pCBT which were slightly lower than those of the plain pCBT polymerized under identical conditions.

  17. A new nanocomposite polymer electrolyte based on poly(vinyl alcohol) incorporating hypergrafted nano-silica

    KAUST Repository

    Hu, Xian-Lei

    2012-01-01

    Solid-state nanocomposite polymer electrolytes based on poly(vinyl alcohol)(PVA) incorporating hyperbranched poly(amine-ester) (HBPAE) grafted nano-silica (denoted as SiO2-g-HBPAE) have been prepared and investigated. Through surface pretreatment of nanoparticles, followed by Michael-addition and a self-condensation process, hyperbranched poly(amine-ester) was directly polymerized from the surface of nano-silica. Then the hypergrafted nanoparticles were added to PVA matrix, and blended with lithium perchlorate via mold casting method to fabricate nanocomposite polymer electrolytes. By introducing hypergrafted nanoparticles, ionic conductivity of solid composite is improved significantly at the testing temperature. Hypergrafted nano-silica may act as solid plasticizer, promoting lithium salt dissociation in the matrix as well as improving segmental motion of matrix. In addition, tensile testing shows that such materials are soft and tough even at room temperature. From the dielectric spectra of nanocomposite polymer electrolyte as the function of temperature, it can be deduced that Arrhenius behavior appears depending on the content of hypergrafted nano-silica and concentration of lithium perchlorate. At a loading of 15 wt% hypergrafted nano-silica and 54 wt% lithium perchlorate, promising ionic conductivities of PVA nanocomposite polymer electrolyte are achieved, about 1.51 × 10 -4 S cm-1 at 25 °C and 1.36 × 10-3 S cm-1 at 100 °C. © The Royal Society of Chemistry.

  18. Phosphasalen indium complexes showing high rates and isoselectivities in rac-lactide polymerizations

    Energy Technology Data Exchange (ETDEWEB)

    Myers, Dominic; White, Andrew J.P. [Department of Chemistry, Imperial College London (United Kingdom); Forsyth, Craig M. [School of Chemistry, Monash University, Clayton, VIC (Australia); Bown, Mark [CSIRO Manufacturing, Bayview Avenue, Clayton, VIC (Australia); Williams, Charlotte K. [Department of Chemistry, Oxford University (United Kingdom)

    2017-05-02

    Polylactide (PLA) is the leading bioderived polymer produced commercially by the metal-catalyzed ring-opening polymerization of lactide. Control over tacticity to produce stereoblock PLA, from rac-lactide improves thermal properties but is an outstanding challenge. Here, phosphasalen indium catalysts feature high rates (30±3 m{sup -1} min{sup -1}, THF, 298 K), high control, low loadings (0.2 mol %), and isoselectivity (P{sub i}=0.92, THF, 258 K). Furthermore, the phosphasalen indium catalysts do not require any chiral additives. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  19. Surface Modification of Silica Nanoparticles with Titanium Tetraisopropoxide and Evaluation of their Photocatalytic Activity

    Directory of Open Access Journals (Sweden)

    Leila Mazaheri

    2012-12-01

    Full Text Available Silica nanoparticles were modified with titanium tetraisopropoxide (TTIP via atwo-step sol-gel route. The modified silica nanoparticles were characterized using FTIR spectroscopy, thermal gravimetric analysis (TGA and EDAX elemental analysis. Photocatalytic activity of the modified nanocomposites was evaluated by photo-activated degradation of Rhodamine B (Rh.B dyestuff, as a colorant model, in distilled water. Reduction in Rh.B concentration in aqueous solution was evaluated by UV-visible spectroscopy and with the aid of visual observations. The FTIR spectroscopy results confirmed the formation of Ti-O-Si chemical bond on the surfaceof silica nanoparticles. TGA test results showed that the weight loss of the modified sample is due to deterioration of the alkoxy groups of the SiO2 surface. According to the results of EDAX elemental analysis, the presence of carbon and titanium in the structure of the modified samples and also reduction in oxygen levels are attributed to the chemical interactions due to surface chemical modification. Carbon detection in the composition can be attributed to the presence of isopropoxide in titanium tetraisopropoxide compound. The results also revealed that, with TiO2 grafting on the silica nanoparticles surface, absorption in UV region is increased and that the silica nanoparticles modified with titanate compound show photocatalytic characteristics and degradation ability of Rh.B dyestuff under UV light irradiation. It became also evident that the photocatalytic activity of the modified nanoparticles is less than TiO2 nanoparticles. However, by inclusion of modified silica nanoparticles into the polymeric coating, the photocatalytic properties of the coating can be established. Although modified silica nanoparticles have less photocatalytic activity compared to TiO2 nanoparticles, but they cause less damage to the polymer matrix.

  20. Cerasomes and Bicelles: Hybrid Bilayered Nanostructures with Silica-like Surface in Cancer Theranostics

    Science.gov (United States)

    Hameed, Sadaf; Bhattarai, Pravin; Dai, Zhifei

    2018-04-01

    Over years, theranostic nanoplatforms have provided a new avenue for the diagnosis and treatment of various cancer types. To this end, a myriad of nanocarriers such as polymeric micelles, liposomes, and inorganic nanoparticles (NPs) with distinct physiochemical and biological properties are routinely investigated for preclinical and clinical studies. So far, liposomes have received great attention for various biomedical applications, however, it still suffers from insufficient morphological stability. On the other hand, inorganic NPs depicting excellent therapeutic ability have failed to address biocompatibility issues. This has raised a serious concern about the clinical approval of multifunctional organic or inorganic-based theranostic agents. Recently, partially silica coated nanohybrids such as cerasomes and bicelles demonstrating both diagnostic and therapeutic ability in a single system, have drawn profound attention as a fascinating novel drug delivery system. Compared with traditional liposomal or inorganic-based nanoformulations, this new and highly stable nanocarriers integrates the functional attributes of biomimetic liposomes and silica NPs, therefore, synergize strengths and functions, or even surpass weaknesses of individual components. This review at its best enlightens the emerging concept of such partially silica coated nanohybrids, fabrication strategies, and theranostic opportunities to combat cancer and related diseases.

  1. "Hydro-metathesis" of olefins: A catalytic reaction using a bifunctional single-site tantalum hydride catalyst supported on fibrous silica (KCC-1) nanospheres

    KAUST Repository

    Polshettiwar, Vivek

    2011-02-18

    Tantalizing hydrocarbons: Tantalum hydride supported on fibrous silica nanospheres (KCC-1) catalyzes, in the presence of hydrogen, the direct conversion of olefins into alkanes that have higher and lower numbers of carbon atoms (see scheme). This catalyst shows remarkable catalytic activity and stability, with excellent potential of regeneration. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. "Hydro-metathesis" of olefins: A catalytic reaction using a bifunctional single-site tantalum hydride catalyst supported on fibrous silica (KCC-1) nanospheres

    KAUST Repository

    Polshettiwar, Vivek; Thivolle-Cazat, Jean; Taoufik, Mostafa; Stoffelbach, Franç ois; Norsic, Sé bastien; Basset, Jean-Marie

    2011-01-01

    Tantalizing hydrocarbons: Tantalum hydride supported on fibrous silica nanospheres (KCC-1) catalyzes, in the presence of hydrogen, the direct conversion of olefins into alkanes that have higher and lower numbers of carbon atoms (see scheme). This catalyst shows remarkable catalytic activity and stability, with excellent potential of regeneration. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Gold-catalyzed aerobic epoxidation of trans-stilbene in methylcyclohexane. Part I: Design of a reference catalyst

    KAUST Repository

    Guillois, Kevin

    2012-02-01

    The kinetics of the heterogeneous gold-catalyzed aerobic epoxidation of stilbene in the liquid phase has been shown to be hindered by diffusion limitations, due to the use of supports which are unsuitable to apolar reaction media. The choice of these supports is generally dictated by the ability of standard methods of preparation to stabilize highly dispersed gold nanoparticles on them. Hence, new methods need to be designed in order to produce catalytically active gold nanoparticles on hydrophobic supports in general and on passivated silicas in particular. By investigating Tsukuda\\'s method to produce colloidal solutions of gold nanoparticles upon reduction of the triphenylphosphine gold chloride complex in solution, we found that direct reduction of AuPPh3Cl in the presence of a commercially available silica support functionalized with dimethylsiloxane, Aerosil R972, leads, in a highly reproducible and potentially scalable way, to the best catalyst ever reported for this reaction. (C) 2011 Elsevier BM. All rights reserved.

  4. Gold-catalyzed aerobic epoxidation of trans-stilbene in methylcyclohexane. Part I: Design of a reference catalyst

    KAUST Repository

    Guillois, Kevin; Burel, Laurence; Tuel, Alain; Caps, Valerie

    2012-01-01

    The kinetics of the heterogeneous gold-catalyzed aerobic epoxidation of stilbene in the liquid phase has been shown to be hindered by diffusion limitations, due to the use of supports which are unsuitable to apolar reaction media. The choice of these supports is generally dictated by the ability of standard methods of preparation to stabilize highly dispersed gold nanoparticles on them. Hence, new methods need to be designed in order to produce catalytically active gold nanoparticles on hydrophobic supports in general and on passivated silicas in particular. By investigating Tsukuda's method to produce colloidal solutions of gold nanoparticles upon reduction of the triphenylphosphine gold chloride complex in solution, we found that direct reduction of AuPPh3Cl in the presence of a commercially available silica support functionalized with dimethylsiloxane, Aerosil R972, leads, in a highly reproducible and potentially scalable way, to the best catalyst ever reported for this reaction. (C) 2011 Elsevier BM. All rights reserved.

  5. Highly luminescent and photostable quantum dot-silica monolith and its application to light-emitting diodes.

    Science.gov (United States)

    Jun, Shinae; Lee, Junho; Jang, Eunjoo

    2013-02-26

    A highly luminescent and photostable quantum dot-silica monolith (QD-SM) substance was prepared by preliminary surface exchange of the QDs and base-catalyzed sol-gel condensation of silica. The SM was heavily doped with 6-mercaptohexanol exchanged QDs up to 12 vol % (26 wt %) without particle aggregation. Propylamine catalyst was important in maintaining the original luminescence of the QDs in the SM during sol-gel condensation. The silica layer was a good barrier against oxygen and moisture, so that the QD-SM maintained its initial luminescence after high-power UV radiation (∼1 W) for 200 h and through the 150 °C LED encapsulant curing process. Green and red light-emitting QD-SMs were applied as color-converting layers on blue LEDs, and the external quantum efficiency reached up to 89% for the green QD-SM and 63% for the red one. A white LED made with a mixture of green and red QDs in the SM, in which the color coordinate was adjusted at (0.23, 0.21) in CIE1931 color space for a backlight application, showed an efficacy of 47 lm/W, the highest value yet reported.

  6. Silica Nephropathy

    Directory of Open Access Journals (Sweden)

    N Ghahramani

    2010-06-01

    Full Text Available Occupational exposure to heavy metals, organic solvents and silica is associated with a variety of renal manifestations. Improved understanding of occupational renal disease provides insight into environmental renal disease, improving knowledge of disease pathogenesis. Silica (SiO2 is an abundant mineral found in sand, rock, and soil. Workers exposed to silica include sandblasters, miners, quarry workers, masons, ceramic workers and glass manufacturers. New cases of silicosis per year have been estimated in the US to be 3600–7300. Exposure to silica has been associated with tubulointerstitial disease, immune-mediated multisystem disease, chronic kidney disease and end-stage renal disease. A rare syndrome of painful, nodular skin lesions has been described in dialysis patients with excessive levels of silicon. Balkan endemic nephropathy is postulated to be due to chronic intoxication with drinking water polluted by silicates released during soil erosion. The mechanism of silica nephrotoxicity is thought to be through direct nephrotoxicity, as well as silica-induced autoimmune diseases such as scleroderma and systemic lupus erythematosus. The renal histopathology varies from focal to crescentic and necrotizing glomerulonephritis with aneurysm formation suggestive of polyarteritis nodosa. The treatment for silica nephrotoxicity is non-specific and depends on the mechanism and stage of the disease. It is quite clear that further research is needed, particularly to elucidate the pathogenesis of silica nephropathy. Considering the importance of diagnosing exposure-related renal disease at early stages, it is imperative to obtain a thorough occupational history in all patients with renal disease, with particular emphasis on exposure to silica, heavy metals, and solvents.

  7. In situ immobilization on the silica gel surface and adsorption capacity of polymer-based azobenzene on toxic metal ions

    Science.gov (United States)

    Savchenko, Irina; Yanovska, Elina; Sternik, Dariusz; Kychkyruk, Olga; Ol'khovik, Lidiya; Polonska, Yana

    2018-03-01

    In situ immobilization of poly[(4-methacryloyloxy-(4'-carboxy)azobenzene] on silica gel surface has been performed by radical polymerization of monomer. The fact of polymer immobilization is confirmed by IR spectroscopy. TG and DSC-MS analysis showed that the mass of the immobilized polymer was 10.61%. The SEM-microphotograph-synthesized composite analysis showed that the immobilized polymer on the silica gel surface is placed in the form of fibers. It has been found that the synthesized composite exhibits the sorption ability in terms of microquantities of Cu(II), Cd(II), Pb(II), Mn(II) and Fe(III) ions in a neutral aqueous medium. The quantitative sorption of microquantities of Pb(II) and Fe(III) ions has been recorded. It has been found that immobilization of the silica gel surface leads to an increase in its sorption capacitance for Fe(III), Cu(II) and Pb(II) ions by half.

  8. Zn(OAc2-Catalyzing Ring-Opening Polymerization of N-Carboxyanhydrides for the Synthesis of Well-Defined Polypeptides

    Directory of Open Access Journals (Sweden)

    Yanzhao Nie

    2018-03-01

    Full Text Available Despite notable progress, the fabrication of well-defined polypeptides via controlled ring-opening polymerization (ROP of α-amino acid N-carboxyanhydrides (NCAs using convenient catalysts under mild conditions in a relatively short polymerization time is still challenging. Herein, an easily obtained catalyst system composed of zinc acetate and aniline was explored to mediate the fast ROP of γ-benzyl-l-glutamate-N-carboxyanhydride (BLG-NCA monomer, to produce poly(γ-benzyl-l-glutamates (PBLGs with controllable molecular weights and narrow dispersity. Considering the excellent cooperative action of zinc acetate and a broad scope of aniline derivatives with different functional groups to control ROP of BLG-NCA, this method may offer a useful platform enabling the rapid generation of end-functionalized PBLG and block copolymers for numerous biomedical applications.

  9. Preparation of thermally stable microcapsules with a chitosan-silica hybrid.

    Science.gov (United States)

    Kang, Hong-Yi; Chen, Hui-Huang

    2014-09-01

    Addition of microcapsules with a high dielectric constant and low specific heat capacity to a battered layer was designed to create a higher temperature in the crust than in the prefried fish nuggets to prevent the water vapor in the fish nuggets from migrating to the crust during microwave heating. Therefore, chitosan-silica hybrids and soybean oil were utilized to prepare the shell and core of the thermally stable microcapsules (MC(CS)), respectively. The MC(CS) were prepared by sol-gel coacervation from an oil-in-water emulsion. The sodium silicate was hydrolyzed and coacervated through polymerization for 24 h at pH 5. The zeta potential analysis indicated that chitosan with a positive charge and silica with a negative charge interacted through electrostatic attraction to form a hybrid shell. The volume mean particle size and encapsulation efficiency of the MC(CS) were 9.6 ± 0.2 μm and 75.6% ± 1.3%, respectively, when oil/chitosan = 0.2 and chitosan/silica = 0.5 (w/w). In addition to H-bonding and electrostatic attraction, Si-O-N bonds were formed between chitosan and silica. Dehydration of the bound water in the MC(CS) was observed in the range of 25 to 250 °C in the differential scanning calorimetry thermal analysis, with the lack of apparent thermal peaks indicating its high thermal stability. The decrease of force to cut the crust observed by texture analysis as well as the increase of hedonic score by consumer acceptance test revealed the addition of 1% MC(CS) significantly improved the crispness of the crust in the microwave-reheated nuggets. © 2014 Institute of Food Technologists®

  10. Analysis of the polymerization initiation and activity of Pasteurella multocida heparosan synthase PmHS2, an enzyme with glycosyltransferase and UDP-sugar hydrolase activity

    NARCIS (Netherlands)

    Chavaroche, A.A.E.; Broek, van den L.A.M.; Springer, J.; Boeriu, C.; Eggink, G.

    2011-01-01

    Heparosan synthase catalyzes the polymerization of heparosan [-4GlcUAß1-4GlcNAca1-]n by transferring alternatively the monosaccharide units from UDP-GlcUA and UDP-GlcNAc to an acceptor molecule. Details on the heparosan chain initiation by Pasteurella multocida heparosan synthase PmHS2 and its

  11. HDO of Methyl Palmitate over Silica-Supported Ni Phosphides: Insight into Ni/P Effect

    Directory of Open Access Journals (Sweden)

    Irina V. Deliy

    2017-10-01

    Full Text Available Two sets of silica-supported nickel phosphide catalysts with a nickel content of about 2.5 and 10 wt % and Ni/P molar ratio 2/1, 1/1 and 1/2 in each set, were prepared by way of a temperature-programmed reduction method using (Ni(CH3COO2 and ((NH42HPO4 as a precursor. The NixPy/SiO2 catalysts were characterized using chemical analysis N2 physisorption, XRD, TEM, 31P MAS NMR. Methyl palmitate hydrodeoxygenation (HDO was performed in a trickle-bed reactor at 3 MPa and 290 °C with LHSV ranging from 0.3 to 16 h−1. The Ni/P ratio was found to affect the nickel phosphide phase composition, POx groups content and catalytic properties in methyl palmitate HDO with the TOF increased along with a decline of Ni/P ratio and a growth of POx groups’ content. Taking into account the possible routes of methyl palmitate conversion (metal-catalyzed hydrogenolysis or acid-catalyzed hydrolysis, we proposed that the enhancement of acid POx groups’ content with the Ni/P ratio decrease provides an enhancement of the rate of methyl palmitate conversion through the acceleration of acid-catalyzed hydrolysis.

  12. Kinetics of aggregation growth with competition between catalyzed birth and catalyzed death

    International Nuclear Information System (INIS)

    Wang Haifeng; Gao Yan; Lin Zhenquan

    2008-01-01

    An aggregation growth model of three species A, B and C with the competition between catalyzed birth and catalyzed death is proposed. Irreversible aggregation occurs between any two aggregates of the like species with the constant rate kernels I n (n = 1,2,3). Meanwhile, a monomer birth of an A species aggregate of size k occurs under the catalysis of a B species aggregate of size j with the catalyzed birth rate kernel K(k,j) = Kkj v and a monomer death of an A species aggregate of size k occurs under the catalysis of a C species aggregate of size j with the catalyzed death rate kernel L(k,j)=Lkj v , where v is a parameter reflecting the dependence of the catalysis reaction rates of birth and death on the size of catalyst aggregate. The kinetic evolution behaviours of the three species are investigated by the rate equation approach based on the mean-field theory. The form of the aggregate size distribution of A species a k (t) is found to be dependent crucially on the competition between the catalyzed birth and death of A species, as well as the irreversible aggregation processes of the three species: (1) In the v k (t) satisfies the conventional scaling form; (2) In the v ≥ 0 case, the competition between the catalyzed birth and death dominates the process. When the catalyzed birth controls the process, a k (t) takes the conventional or generalized scaling form. While the catalyzed death controls the process, the scaling description of the aggregate size distribution breaks down completely

  13. Plasma polymer-functionalized silica particles for heavy metals removal.

    Science.gov (United States)

    Akhavan, Behnam; Jarvis, Karyn; Majewski, Peter

    2015-02-25

    Highly negatively charged particles were fabricated via an innovative plasma-assisted approach for the removal of heavy metal ions. Thiophene plasma polymerization was used to deposit sulfur-rich films onto silica particles followed by the introduction of oxidized sulfur functionalities, such as sulfonate and sulfonic acid, via water-plasma treatments. Surface chemistry analyses were conducted by X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectroscopy. Electrokinetic measurements quantified the zeta potentials and isoelectric points (IEPs) of modified particles and indicated significant decreases of zeta potentials and IEPs upon plasma modification of particles. Plasma polymerized thiophene-coated particles treated with water plasma for 10 min exhibited an IEP of less than 3.5. The effectiveness of developed surfaces in the adsorption of heavy metal ions was demonstrated through copper (Cu) and zinc (Zn) removal experiments. The removal of metal ions was examined through changing initial pH of solution, removal time, and mass of particles. Increasing the water plasma treatment time to 20 min significantly increased the metal removal efficiency (MRE) of modified particles, whereas further increasing the plasma treatment time reduced the MRE due to the influence of an ablation mechanism. The developed particulate surfaces were capable of removing more than 96.7% of both Cu and Zn ions in 1 h. The combination of plasma polymerization and oxidative plasma treatment is an effective method for the fabrication of new adsorbents for the removal of heavy metals.

  14. Modification of a Phenolic Resin with Epoxy- and Methacrylate-Functionalized Silica Sols to Improve the Ablation Resistance of Their Glass Fiber-Reinforced Composites

    Directory of Open Access Journals (Sweden)

    Yu Hu

    2014-01-01

    Full Text Available Functionalized silica sols were obtained by the hydrolytic condensation of (γ-methacryloxypropyltrimethoxysilane (MPMS, (γ-glycidyloxypropyltrimethoxysilane (GPMS and tetraethoxysilane (TEOS. Three different sols were obtained: MPS (derived from MPMS and TEOS, GPS-MPS (derived from GPMS, MPMS and TEOS, and GPSD (derived from GPMS, TEOS and diglycidyl ether of bisphenol A, DGEBA. These silica sols were mixed with a phenolic resin (PR. Ethylenediamine was used as a hardener for epoxy-functionalized sols and benzoyl peroxide was used as an initiator of the free-radical polymerization of methacrylate-functionalized silica sols. Glass fiber-reinforced composites were obtained from the neat PR and MPS-PR, GPS-MPS-PR and GPSD-PR. The resulting composites were evaluated as ablation resistant materials in an acetylene-oxygen flame. A large increase in the ablation resistance was observed when the PR was modified by the functionalized silica sols. The ablation resistance of the composites decreased as follows: GPSD-PR > MPS-PR > GPS-MPS-PR > PR.

  15. Some Durability Characteristics of Micro Silica and Nano Silica Contained Concrete

    Directory of Open Access Journals (Sweden)

    Mohammed Salah Nasr

    2016-12-01

    Full Text Available This paper aims to investigate the influence of replacement of cement with nano and micro silica admixtures on some durability properties of concrete such as water absorption, chloride content and pH tests. Three replacement ratios (5%,10%,15% of micro silica and four replacement proportions (0.5%,1.5%,3%,5% for nano silica were used in this study. Two exposure conditions were considered for chloride content test: wetting-drying and full immersing exposure in 6% of chloride ions solution, NaCl type. Results showed that mixes of %5 micro silica and 5% nano silica had lower content of chloride (about 0.19% and 0.18% for wetting-drying and full immersing exposure respectively. For water absorption test, all mixes incorporated micro and nano silica, except for %5 micro silica mix, showed lower absorption than control mixes. For pH test, results indicated that the adding of nano and micro silica didn’t affect adversely the alkalinity of concrete.

  16. Effects of 3D microlens transfer into fused silica substrate by CF{sub 4}/O{sub 2} dry etching

    Energy Technology Data Exchange (ETDEWEB)

    Grigaliūnas, Viktoras, E-mail: Viktoras.Grigaliunas@ktu.lt [Institute of Materials Science, Kaunas University of Technology, Barsausko 59, LT-51423 Kaunas (Lithuania); Jucius, Dalius; Lazauskas, Algirdas; Andrulevičius, Mindaugas; Sakaliūnienė, Jolita; Abakevičienė, Brigita; Kopustinskas, Vitoldas [Institute of Materials Science, Kaunas University of Technology, Barsausko 59, LT-51423 Kaunas (Lithuania); Smetona, Saulius [Qorvo, 7628 Thorndike Road Greensboro, NC 27409 United States (United States); Tamulevičius, Sigitas [Institute of Materials Science, Kaunas University of Technology, Barsausko 59, LT-51423 Kaunas (Lithuania)

    2017-01-30

    Highlights: • The etching rate of PMMA is dependent on the plasma etching time. • The etching rate ratio between PMMA and fused silica vary during plasma treatment. • The etching rate ratio variation must be assessed during the microlens design phase. - Abstract: Nowadays, 3D microoptical elements find a variety of applications from light emitting diodes and household appliances to precise medical endoscopes. Such elements, fabricated in a fused silica substrate by combining 3D e-beam patterning and dry etching, can be used as a mold for the high throughput replication in polymeric materials by UV nanoimprint technique. Flexible and precise control of 3D shape in the resist layer can be achieved by e-beam patterning, but it is also very important to know peculiarities of 3D pattern transfer from resist layer into the fused silica substrate. This paper reports on the effects of PMMA 3D microlens pattern transfer into fused silica substrate by CF{sub 4}/O{sub 2} dry etching. It is demonstrated that etching rate ratio between PMMA and fused silica changes during plasma treatment. Thus, the resulting shape of transferred 3D profile is different from the shape in PMMA and this variation must be assessed during the design phase.

  17. Investigation of dielectric breakdown in silica-epoxy nanocomposites using designed interfaces.

    Science.gov (United States)

    Bell, Michael; Krentz, Timothy; Keith Nelson, J; Schadler, Linda; Wu, Ke; Breneman, Curt; Zhao, Su; Hillborg, Henrik; Benicewicz, Brian

    2017-06-01

    Adding nano-sized fillers to epoxy has proven to be an effective method for improving dielectric breakdown strength (DBS). Evidence suggests that dispersion state, as well as chemistry at the filler-matrix interface can play a crucial role in property enhancement. Herein we investigate the contribution of both filler dispersion and surface chemistry on the AC dielectric breakdown strength of silica-epoxy nanocomposites. Ligand engineering was used to synthesize bimodal ligands onto 15nm silica nanoparticles consisting of long epoxy compatible, poly(glycidyl methacrylate) (PGMA) chains, and short, π-conjugated, electroactive surface ligands. Surface initiated RAFT polymerization was used to synthesize multiple graft densities of PGMA chains, ultimately controlling the dispersion of the filler. Thiophene, anthracene, and terthiophene were employed as π-conjugated surface ligands that act as electron traps to mitigate avalanche breakdown. Investigation of the synthesized multifunctional nanoparticles was effective in defining the maximum particle spacing or free space length (L f ) that still leads to property enhancement, as well as giving insight into the effects of varying the electronic nature of the molecules at the interface on breakdown strength. Optimization of the investigated variables was shown to increase the AC dielectric breakdown strength of epoxy composites as much as 34% with only 2wt% silica loading. Copyright © 2017 Elsevier Inc. All rights reserved.

  18. Click polymerization for the synthesis of reduction-responsive polymeric prodrug

    Science.gov (United States)

    Zhang, Xiaojin; Wang, Hongquan; Dai, Yu

    2018-05-01

    Click polymerization is a powerful polymerization technique for the construction of new macromolecules with well-defined structures and multifaceted functionalities. Here, we synthesize reduction-responsive polymeric prodrug PEG- b-(PSS- g-MTX)- b-PEG containing disulfide bonds and pendant methotrexate (MTX) via two-step click polymerization followed by conjugating MTX to pendant hydroxyl. MTX content in polymeric prodrug is 13.5%. Polymeric prodrug is able to form polymeric micelles by self-assembly in aqueous solution. Polymeric micelles are spherical nanoparticles with tens of nanometers in size. Of note, polymeric micelles are reduction-responsive due to disulfide bonds in the backbone of PEG- b-(PSS- g-MTX)- b-PEG and could release pendant drugs in the presence of the reducing agents such as dl-dithiothreitol (DTT).

  19. Pulsed-laser polymerization in compartmentalized liquids. 1. Polymerization in vesicles

    NARCIS (Netherlands)

    Jung, M.; Casteren, van I.A.; Monteiro, M.J.; Herk, van A.M.; German, A.L.

    2000-01-01

    Polymerization in vesicles is a novel type of polymerization in heterogeneous media, leading to parachute-like vesicle-polymer hybrid morphologies. To explore the kinetics of vesicle polymerizations and to learn more about the actual locus of polymerization we applied the pulsed-laser polymerization

  20. The effect of impeller type on silica sol formation in laboratory scale agitated tank

    Science.gov (United States)

    Nurtono, Tantular; Suprana, Yayang Ade; Latif, Abdul; Dewa, Restu Mulya; Machmudah, Siti; Widiyastuti, Winardi, Sugeng

    2016-02-01

    The multiphase polymerization reaction of the silica sol formation produced from silicic acid and potassium hydroxide solutions in laboratory scale agitated tank was studied. The reactor is equipped with four segmental baffle and top entering impeller. The inside diameter of reactor is 9 cm, the baffle width is 0.9 cm, and the impeller position is 3 cm from tank bottom. The diameter of standard six blades Rushton and three blades marine propeller impellers are 5 cm. The silicic acid solution was made from 0.2 volume fraction of water glass (sodium silicate) solution in which the sodium ion was exchanged by hydrogen ion from cation resin. The reactor initially filled with 286 ml silicic acid solution was operated in semi batch mode and the temperature was kept constant in 60 °C. The 3 ml/minute of 1 M potassium hydroxide solution was added into stirred tank and the solution was stirred. The impeller rotational speed was varied from 100 until 700 rpm. This titration was stopped if the solution in stirred tank had reached the pH of 10-The morphology of the silica particles in the silica sol product was analyzed by Scanning Electron Microscope (SEM). The size of silica particles in silica sol was measured based on the SEM image. The silica particle obtained in this research was amorphous particle and the shape was roughly cylinder. The flow field generated by different impeller gave significant effect on particle size and shape. The smallest geometric mean of length and diameter of particle (4.92 µm and 2.42 µm, respectively) was generated in reactor with marine propeller at 600 rpm. The reactor with Rushton impeller produced particle which the geometric mean of length and diameter of particle was 4.85 µm and 2.36 µm, respectively, at 150 rpm.

  1. A 2H nuclear magnetic resonance study of the state of water in neat silica and zwitterionic stationary phases and its influence on the chromatographic retention characteristics in hydrophilic interaction high-performance liquid chromatography.

    Science.gov (United States)

    Wikberg, Erika; Sparrman, Tobias; Viklund, Camilla; Jonsson, Tobias; Irgum, Knut

    2011-09-23

    2H NMR has been used as a tool for probing the state of water in hydrophilic stationary phases for liquid chromatography at temperatures between -80 and +4 °C. The fraction of water that remained unfrozen in four different neat silicas with nominal pore sizes between 60 and 300 Å, and in silicas with polymeric sulfobetaine zwitterionic functionalities prepared in different ways, could be determined by measurements of the line widths and temperature-corrected integrals of the 2H signals. The phase transitions detected during thawing made it possible to estimate the amount of non-freezable water in each phase. A distinct difference was seen between the neat and modified silicas tested. For the neat silicas, the relationship between the freezing point depression and their pore size followed the expected Gibbs-Thomson relationship. The polymeric stationary phases were found to contain considerably higher amounts of non-freezable water compared to the neat silica, which is attributed to the structural effect that the sulfobetaine polymers have on the water layer close to the stationary phase surface. The sulfobetaine stationary phases were used alongside the 100 Å silica to separate a number of polar compounds in hydrophilic interaction (HILIC) mode, and the retention characteristics could be explained in terms of the surface water structure, as well as by the porous properties of the stationary phases. This provides solid evidence supporting a partitioning mechanism, or at least of the existence of an immobilized layer of water into which partitioning could be occurring. Copyright © 2011 Elsevier B.V. All rights reserved.

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

    Science.gov (United States)

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

    2015-04-14

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

  3. Microporous silica membranes

    DEFF Research Database (Denmark)

    Boffa, Vittorio; Yue, Yuanzheng

    2012-01-01

    Hydrothermal stability is a crucial factor for the application of microporous silica-based membranes in industrial processes. Indeed, it is well established that steam exposure may cause densification and defect formation in microporous silica membranes, which are detrimental to both membrane...... permeability and selectivity. Numerous previous studies show that microporous transition metal doped-silica membranes are hydrothermally more stable than pure silica membranes, but less permeable. Here we present a quantitative study on the impact of type and concentration of transition metal ions...... on the microporous structure, stability and permeability of amorphous silica-based membranes, providing information on how to design chemical compositions and synthetic paths for the fabrication of silica-based membranes with a well accessible and highly stabile microporous structure....

  4. Multi input single output model predictive control of non-linear bio-polymerization process

    Energy Technology Data Exchange (ETDEWEB)

    Arumugasamy, Senthil Kumar; Ahmad, Z. [School of Chemical Engineering, Univerisiti Sains Malaysia, Engineering Campus, Seri Ampangan,14300 Nibong Tebal, Seberang Perai Selatan, Pulau Pinang (Malaysia)

    2015-05-15

    This paper focuses on Multi Input Single Output (MISO) Model Predictive Control of bio-polymerization process in which mechanistic model is developed and linked with the feedforward neural network model to obtain a hybrid model (Mechanistic-FANN) of lipase-catalyzed ring-opening polymerization of ε-caprolactone (ε-CL) for Poly (ε-caprolactone) production. In this research, state space model was used, in which the input to the model were the reactor temperatures and reactor impeller speeds and the output were the molecular weight of polymer (M{sub n}) and polymer polydispersity index. State space model for MISO created using System identification tool box of Matlab™. This state space model is used in MISO MPC. Model predictive control (MPC) has been applied to predict the molecular weight of the biopolymer and consequently control the molecular weight of biopolymer. The result shows that MPC is able to track reference trajectory and give optimum movement of manipulated variable.

  5. Synthesis of silica nanoparticles for the manufacture of porous carbon membrane and particle size analysis by sedimentation field-flow fractionation

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Seung Ho; Eum, Chul; Hun; Choi, Seong Ho; Kim, Woon Jung [Dept. of Chemistry, Hannam University, Daejeon (Korea, Republic of)

    2016-11-15

    Silica nanoparticles were synthesized by emulsion polymerization by mixing ethanol, ammonium hydroxide, water, and tetraethyl orthosilicate. An apparatus was designed and assembled for a large-scale synthesis of silica nanospheres, which was aimed for uniform mixing of the reactants. Then sedimentation field-flow fractionation (SdFFF) was used to determine the size distribution of the silica nanoparticles. SdFFF provided mass-based separation where the retention time increased with the particle size, thus the size distribution of silica nanoparticles obtained from SdFFF appeared more accurate than that from dynamic light scattering, particularly for those having broad and multimodal size distributions. A disk-shaped porous carbon membrane (PCM) was manufactured for application as an adsorbent by pressurizing the silica particles, followed by calcination. Results showed that PCM manufactured in this study has relatively high surface area and temperature stability. The PCM surface was modified by attaching a carboxyl group (PCM-COOH) and then by incorporating silver (PCM-COOH-Ag). The amount of COOH group on PCM was measured electrochemically by cyclic voltammetry, and the surface area, pore size, pore volume of PCM-COOH-Ag by Brunauer–Emmet–Teller measurement. The surface area was 40.65 and reduced to 13.02 after loading a COOH group then increased up to 30.37 after incorporating Ag.

  6. Mechanism of papain-catalyzed synthesis of oligo-tyrosine peptides.

    Science.gov (United States)

    Mitsuhashi, Jun; Nakayama, Tsutomu; Narai-Kanayama, Asako

    2015-01-01

    Di-, tri-, and tetra-tyrosine peptides with angiotensin I-converting enzyme inhibitory activity were synthesized by papain-catalyzed polymerization of L-tyrosine ethyl ester in aqueous media at 30 °C. Varying the reaction pH from 6.0 to 7.5 and the initial concentration of the ester substrate from 25 to 100 mM, the highest yield of oligo-tyrosine peptides (79% on a substrate basis) was produced at pH 6.5 and 75 mM, respectively. In the reaction initiated with 100 mM of the substrate, approx. 50% yield of insoluble, highly polymerized peptides accumulated. At less than 15 mM, the reaction proceeded poorly; however, from 30 mM to 120 mM a dose-dependent increase in the consumption rate of the substrate was observed with a sigmoidal curve. Meanwhile, each of the tri- and tetra-tyrosine peptides, even at approx. 5mM, was consumed effectively by papain but was not elongated to insoluble polymers. For deacylation of the acyl-papain intermediate through which a new peptide bond is made, L-tyrosine ethyl ester, even at 5mM, showed higher nucleophilic activity than di- and tri-tyrosine. These results indicate that the mechanism through which papain polymerizes L-tyrosine ethyl ester is as follows: the first interaction between papain and the ester substrate is a rate-limiting step; oligo-tyrosine peptides produced early in the reaction period are preferentially used as acyl donors, while the initial ester substrate strongly contributes as a nucleophile to the elongation of the peptide product; and the balance between hydrolytic fragmentation and further elongation of oligo-tyrosine peptides is dependent on the surrounding concentration of the ester substrate. Copyright © 2015 Elsevier Inc. All rights reserved.

  7. Self-Propagating Frontal Polymerization in Water at Ambient Pressure

    Science.gov (United States)

    Olten, Nesrin; Kraigsley, Alison; Ronney, Paul D.

    2003-01-01

    boiling point solutions are needed because in order to produce a propagating front, a high front temperature is needed to produce sufficiently rapid decomposition of the free radical initiator and subsequent free radical polymerization and heat release at a rate faster than heat losses remove thermal energy from the system. (While the conduction heat loss rate increases linearly with temperature, the free radical initiator decomposition is a high activation energy process whose rate increases much more rapidly than linearly with temperature, thus as the temperature decreases, the ratio of heat loss to heat generation increases, eventually leading to extinction of the front if the temperature is too low.) In order to obtain atmospheric pressure frontal polymerization in water, it is necessary to identify a monomer/initiator combination that is water soluble and will not extinguish even when the peak temperature (T*) is less than 100 C. In this work acrylic acid (AA) was chosen as the monomer because is it one of the most reactive monomers and can polymerize readily at low temperatures even without initiators. Ammonium persulfate (AP) was chosen as the initiator because it decomposes readily at low temperatures, produces relatively few bubbles and is commercially available. The propagation rates and extinction conditions of the fronts are studied for a range of AA and AP concentrations. Small amounts of fumed silica powder (Cab-o-sil, Cabot Corporation) were added to the solutions to inhibit buoyancy induced convection in the solutions; future studies will investigate the effects of buoyant convection within the solutions.

  8. Elimination of ketone vapors by adsorption on spherical MCM-41 and MCM-48 silicas decorated with thermally activated poly(furfuryl alcohol)

    Energy Technology Data Exchange (ETDEWEB)

    Machowski, Kamil [Faculty of Chemistry, Jagiellonian University, Ingardena 3, 30-060 Kraków (Poland); Kuśtrowski, Piotr, E-mail: kustrows@chemia.uj.edu.pl [Faculty of Chemistry, Jagiellonian University, Ingardena 3, 30-060 Kraków (Poland); Dudek, Barbara [Faculty of Chemistry, Jagiellonian University, Ingardena 3, 30-060 Kraków (Poland); Michalik, Marek [Institute of Geological Sciences, Jagiellonian University, Oleandry 2a, 30-063 Kraków (Poland)

    2015-09-01

    Spherical MCM-41 and MCM-48 silicas with different arrangements of mesopores were synthesized in a water–alcohol solution of surfactant by the hard-templating method. The pore structure and morphology of the obtained materials were confirmed by powder X-ray diffraction (XRD), low-temperature adsorption of nitrogen and scanning electron microscopy (SEM). The surface of mesoporous silicas was decorated with small amounts of poly(furfuryl alcohol) (PFA), which was introduced by the precipitation polymerization and subsequently thermally activated at 523 K to form stable C=O surface species detected by FTIR spectroscopy. The adsorption capacity of the PFA/silica composites in the elimination of various ketone (acetone, methyl-ethyl ketone and methyl-isobutyl ketone) vapors was compared to the effectiveness of pristine silicas. It was found that the modification of silicas by thermally degraded PFA enhanced their adsorption capacity. This effect was attributed to the appearance of another type of surface centers (namely carbonyl groups), which beside silanols interact with ketone molecules via hydrogen bonds. DRIFT spectra showed that a ketone molecule is bonded on silanol species in its keto form, whereas on carbonyl functionalities in enol one. - Highlights: • Surface of spherical MCM-type silicas was decorated with poly(furfuryl alcohol). • Thermal degradation of deposited polymer resulted in formation of C=O species. • Carbonyl groups enhanced adsorption capacity of MCM-41 and MCM-48 silicas. • Adsorption of ketones in enol or keto forms was revealed by DRIFT measurements.

  9. Elimination of ketone vapors by adsorption on spherical MCM-41 and MCM-48 silicas decorated with thermally activated poly(furfuryl alcohol)

    International Nuclear Information System (INIS)

    Machowski, Kamil; Kuśtrowski, Piotr; Dudek, Barbara; Michalik, Marek

    2015-01-01

    Spherical MCM-41 and MCM-48 silicas with different arrangements of mesopores were synthesized in a water–alcohol solution of surfactant by the hard-templating method. The pore structure and morphology of the obtained materials were confirmed by powder X-ray diffraction (XRD), low-temperature adsorption of nitrogen and scanning electron microscopy (SEM). The surface of mesoporous silicas was decorated with small amounts of poly(furfuryl alcohol) (PFA), which was introduced by the precipitation polymerization and subsequently thermally activated at 523 K to form stable C=O surface species detected by FTIR spectroscopy. The adsorption capacity of the PFA/silica composites in the elimination of various ketone (acetone, methyl-ethyl ketone and methyl-isobutyl ketone) vapors was compared to the effectiveness of pristine silicas. It was found that the modification of silicas by thermally degraded PFA enhanced their adsorption capacity. This effect was attributed to the appearance of another type of surface centers (namely carbonyl groups), which beside silanols interact with ketone molecules via hydrogen bonds. DRIFT spectra showed that a ketone molecule is bonded on silanol species in its keto form, whereas on carbonyl functionalities in enol one. - Highlights: • Surface of spherical MCM-type silicas was decorated with poly(furfuryl alcohol). • Thermal degradation of deposited polymer resulted in formation of C=O species. • Carbonyl groups enhanced adsorption capacity of MCM-41 and MCM-48 silicas. • Adsorption of ketones in enol or keto forms was revealed by DRIFT measurements.

  10. FINAL TECHNICAL REPORT Synthetic, Structural and Mechanistic Investigations of Olefin Polymerization Catalyzed by Early Transition Metal Compounds

    Energy Technology Data Exchange (ETDEWEB)

    Bercaw, John E. [California Institute of Technology

    2014-05-23

    The goal of this project is to develop new catalysts and provide understanding of ligand effects on catalyst composition in order to guide development of superior catalyst systems for polymerization of olefins. Our group is designing and synthesizing new “LX2”,“pincer” type ligands and complexing early transition metals to afford precatalysts. In a collaboration with Hans Brintzinger from the University of Konstanz, we are also examining the structures of the components of catalyst systems obtained from reaction of zirconocene dichlorides with aluminum alkyls and aluminum hydrides. Such systems are currently used commercially to produce polyolefins, but the nature of the active and dormant species as well as the mechanisms of their interconversions are not understood. New information on catalyst design and performance may lead to new types of polymers and/or new chemical transformations between hydrocarbons and transition metal centers, ultimately contributing to the development of catalytic reactions for the production of fuels, commodity and polymeric materials.

  11. Crystalline Silica Primer

    Science.gov (United States)

    ,

    1992-01-01

    Crystalline silica is the scientific name for a group of minerals composed of silicon and oxygen. The term crystalline refers to the fact that the oxygen and silicon atoms are arranged in a threedimensional repeating pattern. This group of minerals has shaped human history since the beginning of civilization. From the sand used for making glass to the piezoelectric quartz crystals used in advanced communication systems, crystalline silica has been a part of our technological development. Crystalline silica's pervasiveness in our technology is matched only by its abundance in nature. It's found in samples from every geologic era and from every location around the globe. Scientists have known for decades that prolonged and excessive exposure to crystalline silica dust in mining environments can cause silicosis, a noncancerous lung disease. During the 1980's, studies were conducted that suggested that crystalline silica also was a carcinogen. As a result of these findings, crystalline silica has been regulated under the Occupational Safety and Health Administration's (OSHA) Hazard Communication Standard (HCS). Under HCS, OSHAregulated businesses that use materials containing 0.1% or more crystalline silica must follow Federal guidelines concerning hazard communication and worker training. Although the HCS does not require that samples be analyzed for crystalline silica, mineral suppliers or OSHAregulated

  12. On the Relation between Natural and Enforced Syneresis of Acidic Precipitated Silica

    Directory of Open Access Journals (Sweden)

    Sebastian Wilhelm

    2014-11-01

    Full Text Available Silica in industrial production processes is precipitated by mixing an acid and an inorganic precursor. In this aqueous solution, silica particles form due to a polymerization reaction and agglomeration and, finally, build a gel. Thereafter, the reaction continues, and the gel network shrinks with the expulsion of the enclosed pore liquid. This slow process is known as “natural syneresis” and strongly affects the product properties, such as the agglomerate size, specific surface or porosity of the silica produced. In order to investigate the influence of process parameters, such as temperature, pH or ionic strength, on the shrinkage in shorter time-scales, we propose an acceleration of this process and define it as “enforced syneresis”. The acceleration is performed by applying a mechanical external force to the gel by means of a plunger and measuring the shrinkage behavior under these conditions. Thereby, the conceptual idea is the prediction of the shrinkage due to natural syneresis based on the results of enforced syneresis. We are now able to predict the natural syneresis behavior from enforced syneresis data by the development of a correlative model. Using this prediction model, we can show the influence of temperature on the maximum shrinkage and on its rate in a significantly shorter time of about 12 h instead of several days.

  13. Polycyclopentene-Crystal-Decorated Carbon Nanotubes by Convenient Large-Scale In Situ Polymerization and their Lotus-Leaf-Like Superhydrophobic Films.

    Science.gov (United States)

    Xu, Lixin; Huang, Lingqi; Ye, Zhibin; Meng, Nan; Shu, Yang; Gu, Zhiyong

    2017-02-01

    In situ Pd-catalyzed cyclopentene polymerization in the presence of multi-walled carbon nanotubes (MWCNTs) is demonstrated to effectively render, on a large scale, polycyclopentene-crystal-decorated MWCNTs. Controlling the catalyst loading and/or time in the polymerization offers a convenient tuning of the polymer content and the morphology of the decorated MWCNTs. Appealingly, films made of the decorated carbon nanotubes through simple vacuum filtration show the characteristic lotus-leaf-like superhydrophobicity with high water contact angle (>150°), low contact angle hysteresis (<10°), and low water adhesion, while being electrically conductive. This is the first demonstration of the direct fabrication of lotus-leaf-like superhydrophobic films with solution-grown polymer-crystal-decorated carbon nanotubes. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. ADMET Polymerization Activities of Electrochemically Reduced W-Based Active Species for Ge- and Sn-Containing Dienes

    Science.gov (United States)

    Imamoglu, Yavuz; Aydogdu, Cemil; Karabulut, Solmaz; Düz, Bülent

    In the last 20 years metal atom-containing polymers have become important classes of polymers [1]. Properties like high thermic stability, electric, and photo conductometry make them very interesting for producing films, fibers, and coating [2]. Many of these compounds can be synthesized by conventional methods [3]. For producing metal-containing polymers anionic, cationic, and radicalic polymerizations were used [4-6]. Metal-containing polymers were also synthesized via acyclic diene metathesis (ADMET) polymerization that is facilitated by Schrock’s molybdenum alkylidene, or Grubbs’ ruthenium carbene catalyst [7-9]. In 1979, Gilet and coworkers succeeded in synthesizing metathetically active species from electrochemical reduction of WCl6 and MoCl5 [10,11]. In the light of these works, we have showed that electrochemically generated tungsten-based active species (WCl6-e--Al-CH2Cl2) catalyzes various metathesis-related reactions [12-16].

  15. Superhydrophobic silica wool—a facile route to separating oil and hydrophobic solvents from water

    Science.gov (United States)

    Crick, Colin R.; Bhachu, Davinder S.; Parkin, Ivan P.

    2014-12-01

    Silica microfiber wool was systematically functionalized in order to provide an extremely water repellent and oleophilic material. This was carried out using a two-step functionalization that was shown to be a highly effective method for generating an intense water repulsion and attraction for oil. A demonstration of the silica wools application is shown through the highly efficient separation of oils and hydrophobic solvents from water. Water is confined to the extremities of the material, while oil is absorbed into the voids within the wool. The effect of surface functionalization is monitored though observing the interaction of the material with both oils and water, in addition to scanning electron microscope images, x-ray photoelectron spectroscopy and energy dispersive x-ray analysis. The material can be readily utilized in many applications, including the cleaning of oil spills and filtering during industrial processes, as well as further water purification tasks—while not suffering the losses of efficiency observed in current leading polymeric materials.

  16. Guanidine-based polymer brushes grafted onto silica nanoparticles as efficient artificial phosphodiesterases.

    Science.gov (United States)

    Savelli, Claudia; Salvio, Riccardo

    2015-04-07

    Polymer brushes grafted to the surface of silica nanoparticles were fabricated by atom-transfer radical polymerization (ATRP) and investigated as catalysts in the cleavage of phosphodiesters. The surfaces of silica nanoparticles were functionalized with an ATRP initiator. Surface-initiated ATRP reactions, in varying proportions, of a methacrylate moiety functionalized with a phenylguanidine moiety and an inert hydrophilic methacrylate species afforded hybrid nanoparticles that were characterized with potentiometric titrations, thermogravimetric analysis, and SEM. The activity of the hybrid nanoparticles was tested in the transesterification of the RNA model compound 2-hydroxypropyl para-nitrophenylphosphate (HPNP) and diribonucleoside monophosphates. A high catalytic efficiency and a remarkable effective molarity, thus overcoming the effective molarities previously observed for comparable systems, indicate the existence of an effective cooperation of the guanidine/guanidinium units and a high level of preorganization in the nanostructure. The investigated system also exhibits a marked and unprecedented selectivity for the diribonucleoside sequence CpA. The results presented open up the way for a novel and straightforward strategy for the preparation of supramolecular catalysts. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Metallocene-catalyzed ethylene−α-olefin isomeric copolymerization: A perspective from hydrodynamic boundary layer mass transfer and design of MAO anion

    KAUST Repository

    Adamu, Sagir

    2015-11-28

    This study reports a novel conceptual framework that can be easily experimented to evaluate the effects of hydrodynamic boundary layer mass transfer, methylaluminoxane (MAO) anion design, and comonomer steric hindrance on metallocene-catalyzed ethylene polymerization. This approach was illustrated by conducting homo- and isomeric copolymerization of ethylene with 1-hexene and 4-methyl-1-pentene in the presence of bis(n-butylcyclopentadienyl) zirconium dichloride (nBuCp)2ZrCl2, using (i) MAO anion 1 (unsupported [MAOCl2]−) and pseudo-homogeneous reference polymerization, and (ii) MAO anion 2 (supported Si−O−[MAOCl2]−) and in-situ heterogeneous polymerization. The measured polymer morphology, catalyst productivity, molecular weight distribution, and inter-chain composition distribution were related to the locus of polymerization, comonomer effect, in-situ chain transfer process, and micromixing effect, respectively. The peak melting and crystallization temperatures and %crystallinity were mathematically correlated to the parameters of microstructural composition distributions, melt fractionation temperatures, and average lamellar thickness. These relations showed to be insightful. The comonomer-induced enchainment defects and the eventual partial disruption of the crystal lattice were successfully modeled using Flory and Gibbs–Thompson equations. The present methodology can also be applied to study ethylene−α-olefin copolymerization, performed using MAO-activated non-metallocene precatalysts.

  18. Copper-catalyzed azide alkyne cycloaddition polymer networks

    Science.gov (United States)

    Alzahrani, Abeer Ahmed

    -CuAAC reaction and a chain-growth acrylate homopolymerization were demonstrated and used to form branched polymer structures. A bulk, organic soluble initiation system consisting of a Cu(II) salt and a primary amine was also examined in both model reactions and in bulk polymerizations. The system was shown to be highly efficient, leading to nearly complete CuAAC polymerization at ambient temperature. Increasing the ratio of amine to copper from 1 to 4 increases the CuAAC reaction rate significantly from 4 mM/min for 1:1 ratio of Cu(II):hexyalmine to 14mM/min for 1:4 ratio. The concentration dependence of the amine on the reaction rate enables the polymerization rate to be controlled simply by manipulating the hexylamine concentration. Sequential thiol--acrylate and photo-CuAAC click reactions were utilized to form two-stage reactive polymer networks capable of generating wrinkles in a facile manner. The click thiol-Michael addition reaction was utilized to form a cross-linked polymer with residual, reactive alkyne sites that remained tethered throughout the network. The latent, unreacted alkyne sites are subsequently reacted with diazide monomers via a photoinduced Cu(I)-catalyzed alkyne-azide cycloaddition (CuAAC) reaction to increase the cross-link density. Increased cross-linking raised the modulus and glass transition temperature from 1.6 MPa and 2 °C after the thiol-acrylate reaction to 4.4 MPa and 22 °C after the CuAAC reaction, respectively. The double click reaction approach led to micro-wrinkles with well-controlled wavelength and amplitude of 8.50 +/- 1.6 and 1.4 μm, respectively, for a polymer with a 1280 μm total film thickness. Additionally, this approach further enables spatial selectivity of wrinkle formation by photo-patterning. The CuAAC-based polymerization was also used to design smart, responsive porous materials from well-defined CuAAC networks, which possesses a high glass transition temperature (Tg= 115°C) due to the formation of the triazole linkages

  19. Dynamic properties of silica aerogels as deduced from specific-heat and thermal-conductivity measurements

    DEFF Research Database (Denmark)

    Bernasconi, A.; Sleator, T.; Posselt, D.

    1992-01-01

    The specific heat C(p) and the thermal conductivity lambda of a series of base-catalyzed silica aerogels have been measured at temperatures between 0.05 and 20 K. The results confirm that the different length-scale regions observed in the aerogel structure are reflected in the dynamic behavior of...... SiO2 are most likely not due to fractal behavior....... the possibility of two spectral dimensions characterizing the fracton modes. Our data imply important differences between the physical mechanisms dominating the low-temperature behavior of aerogels and dense glasses, respectively. From our analysis we also conclude that the low-temperature properties of amorphous...

  20. A New Route for Preparation of Hydrophobic Silica Nanoparticles Using a Mixture of Poly(dimethylsiloxane and Diethyl Carbonate

    Directory of Open Access Journals (Sweden)

    Iryna Protsak

    2018-01-01

    uniform dispersity and an average particle size of 15–17 nm. The fumed silica nanoparticles chemically modified with mixtures of PDMS-x/DEC have potential applications such as nanofillers of various polymeric systems, thickeners in dispersing media, and additives in coatings.

  1. Silica coated ionic liquid templated mesoporous silica nanoparticles ...

    African Journals Online (AJOL)

    A series of long chain pyridinium based ionic liquids 1-tetradecylpyridinium bromide, 1-hexadecylpyridinium bromide and 1-1-octadecylpyridinium bromide were used as templates to prepare silica coated mesoporous silica nanoparticles via condensation method under basic condition. The effects of alkyl chain length on ...

  2. Synthesis and comparison of mechanical behavior of fly ash-epoxy and silica fumes-epoxy composite

    Science.gov (United States)

    Sangamesh; Ravishankar, K. S.; Kulkarni, S. M.

    2017-08-01

    Present day innovation requires materials with a typical combination of properties that are not possible by conventional metal, alloys, ceramics and polymeric materials. Particulate reinforcements for polymers are selected with the dual objective of improving composite properties and save on the total cost of the system. The point of this study is to utilize and compare the mechanical properties of filler (fly ash and silica fumes) reinforced epoxy composites. The composites of different proportions by percentage of matrix (100%), fillers (5%, 10% and 15%) volume are developed using hand lay-up process are tested for tensile and compression, according to ASTM Standards. From these mechanical properties, the flexural analysis of these composites is simulated. And which are characterized by Scanning electron microscopy for the fracture surface study, which reveals the brittle fracture, this also conforms from the Finite element analysis (FEA). And the overall mechanical properties of the fly ash reinforced polymer composites were found to have better than silica fumes reinforced composites.

  3. A pure silica ytterbium-doped sol–gel-based fiber laser

    International Nuclear Information System (INIS)

    Baz, Assaad; El Hamzaoui, Hicham; Fsaifes, Ihsan; Bouwmans, Géraud; Bouazaoui, Mohamed; Bigot, Laurent

    2013-01-01

    In this letter it is demonstrated that the sol–gel route combined with fiber fabrication by the stack and draw method can be used to realize efficient fiber lasers. More precisely, a pure silica ytterbium-doped photonic crystal fiber with a core obtained by the sol–gel polymeric technique is studied, and a laser efficiency of more than 73% is achieved for a laser emission around 1034 nm. The optical and spectroscopic properties of the monolith and fiber are investigated, together with the sensitivity of the fiber to photodarkening. The dimensions of the ytterbium-doped monolith combined with the uniform doping and refractive index that are reported make this technique particularly interesting for the realization of large-mode area fibers. (letter)

  4. Biochemical evolution. I. Polymerization on internal, organophilic silica surfaces of dealuminated zeolites and feldspars

    Science.gov (United States)

    Smith, Joseph V.

    1998-01-01

    Catalysis at mineral surfaces might generate replicating biopolymers from simple chemicals supplied by meteorites, volcanic gases, and photochemical gas reactions. Many ideas are implausible in detail because the proposed mineral surfaces strongly prefer water and other ionic species to organic ones. The molecular sieve silicalite (Union Carbide; = Al-free Mobil ZSM-5 zeolite) has a three-dimensional, 10-ring channel system whose electrically neutral Si-O surface strongly adsorbs organic species over water. Three -O-Si tetrahedral bonds lie in the surface, and the fourth Si-O points inwards. In contrast, the outward Si-OH of simple quartz and feldspar crystals generates their ionic organophobicity. The ZSM-5-type zeolite mutinaite occurs in Antarctica with boggsite and tschernichite (Al-analog of Mobil Beta). Archean mutinaite might have become de-aluminated toward silicalite during hot/cold/wet/dry cycles. Catalytic activity of silicalite increases linearly with Al-OH substitution for Si, and Al atoms tend to avoid each other. Adjacent organophilic and catalytic Al-OH regions in nanometer channels might have scavenged organic species for catalytic assembly into specific polymers protected from prompt photochemical destruction. Polymer migration along weathered silicic surfaces of micrometer-wide channels of feldspars might have led to assembly of replicating catalytic biomolecules and perhaps primitive cellular organisms. Silica-rich volcanic glasses should have been abundant on the early Earth, ready for crystallization into zeolites and feldspars, as in present continental basins. Abundant chert from weakly metamorphosed Archaean rocks might retain microscopic clues to the proposed mineral adsorbent/catalysts. Other framework silicas are possible, including ones with laevo/dextro one-dimensional channels. Organic molecules, transition-metal ions, and P occur inside modern feldspars. PMID:9520372

  5. Highly hydrophilic and nonionic poly(2-vinyloxazoline)-grafted silica: a novel organic phase for high-selectivity hydrophilic interaction chromatography.

    Science.gov (United States)

    Mallik, Abul K; Cheah, Wee Keat; Shingo, Kaori; Ejzaki, Aika; Takafuji, Makoto; Ihara, Hirotaka

    2014-07-01

    A new hydrophilic and nonionic poly(2-vinyloxazoline)-grafted silica (Sil-VOX(n)) phase was synthesized and applied for the separation of nucleosides and nucleobases in hydrophilic interaction chromatography (HILIC). Polymerization and immobilization onto silica were confirmed by using characterization techniques including (1)H NMR spectroscopy, elemental analysis, and diffuse reflectance infrared Fourier transform spectroscopy. The hydrophilicity or wettability of Sil-VOX(n) was observed by measuring the contact angle (59.9°). The chromatographic results were compared with those obtained with a conventional HILIC silica column. The Sil-VOX(n) phase showed much better separation of polar test analytes than the silica column, and the elution order was different. Differences in selectivity between these two columns indicate that the stationary phase cannot function merely as an inert support for a water layer into which the solutes are partitioned from the bulk mobile phase. To elucidate the interaction mechanism, the separation of dihydroxybenzene isomers was performed on both columns in normal-phase liquid chromatography. Sil-VOX(n) was very sensitive to the dipole moments of the positional isomers of polycyclic aromatic compounds in normal-phase liquid chromatography. The interaction mechanism for Sil-VOX(n) in HILIC separation is also described.

  6. pH dependent polymeric micelle adsorption

    Energy Technology Data Exchange (ETDEWEB)

    McLean, S C; Gee, M L [The University of Melbourne, VIC (Australia). School of Chemistry

    2003-07-01

    Full text: Poly(2-vinylpyridine)-poly(ethylene oxide) (P2VP-PEO) shows potential as a possible drug delivery system for anti-tumour drugs since it forms pH dependent polymeric micelles. Hence to better understand the adsorption behaviour of this polymer we have studied the interaction forces between layers of P2VP-PEO adsorbed onto silica as a function of solution pH using an Atomic Force Microscope (AFM). When P2VP-PEO is initially adsorbed above the pKa of the P2VP block, P2VP-PEO adsorbs from solution as micelles that exist as either partially collapsed- or a hemi-micelles at the silica surface. Below the pKa of P2VP, the P2VP-PEO adsorbs as unimers, forming a compact layer with little looping and tailing into solution. When initial adsorption of P2VP-PEO is in the form of unimers, any driving force to self-assembly of the now charge neutral polymer is kinetically hindered. Hence, after initial adsorption at pH 3.6, a subsequent increase in pH to 6.6 results in a slow surface restructuring towards self-assembly and equilibrium. When the pH is increased from pH 6.6 to 9.7 there is a continuation of the evolution of the system to its equilibrium position during which the adsorbed P2VP-PEO unimers continue to 'unravel' from the surface, extending away from it, towards eventual complete surface self-assembly.

  7. The effect of impeller type on silica sol formation in laboratory scale agitated tank

    Energy Technology Data Exchange (ETDEWEB)

    Nurtono, Tantular; Suprana, Yayang Ade; Latif, Abdul; Dewa, Restu Mulya; Machmudah, Siti; Widiyastuti,, E-mail: widi@chem-eng.its.ac.id; Winardi, Sugeng [Chemical Engineering Department, Institute of Technology Sepuluh Nopember, Surabaya 60111 (Indonesia)

    2016-02-08

    The multiphase polymerization reaction of the silica sol formation produced from silicic acid and potassium hydroxide solutions in laboratory scale agitated tank was studied. The reactor is equipped with four segmental baffle and top entering impeller. The inside diameter of reactor is 9 cm, the baffle width is 0.9 cm, and the impeller position is 3 cm from tank bottom. The diameter of standard six blades Rushton and three blades marine propeller impellers are 5 cm. The silicic acid solution was made from 0.2 volume fraction of water glass (sodium silicate) solution in which the sodium ion was exchanged by hydrogen ion from cation resin. The reactor initially filled with 286 ml silicic acid solution was operated in semi batch mode and the temperature was kept constant in 60 °C. The 3 ml/minute of 1 M potassium hydroxide solution was added into stirred tank and the solution was stirred. The impeller rotational speed was varied from 100 until 700 rpm. This titration was stopped if the solution in stirred tank had reached the pH of 10-The morphology of the silica particles in the silica sol product was analyzed by Scanning Electron Microscope (SEM). The size of silica particles in silica sol was measured based on the SEM image. The silica particle obtained in this research was amorphous particle and the shape was roughly cylinder. The flow field generated by different impeller gave significant effect on particle size and shape. The smallest geometric mean of length and diameter of particle (4.92 µm and 2.42 µm, respectively) was generated in reactor with marine propeller at 600 rpm. The reactor with Rushton impeller produced particle which the geometric mean of length and diameter of particle was 4.85 µm and 2.36 µm, respectively, at 150 rpm.

  8. Polypropylene Nanocomposites Obtained by In Situ Polymerization Using Metallocene Catalyst: Influence of the Nanoparticles on the Final Polymer Morphology

    Directory of Open Access Journals (Sweden)

    Paula Zapata

    2012-01-01

    Full Text Available Polypropylene nanocomposites containing silica nanospheres based on the sol-gel methods were produced via in situ polymerization using a rac-Et(Ind2ZrCl2/methylaluminoxane (MAO system. Two different routes were used depending on the interaction between the silica nanoparticles with the catalytic system. In route 1 the nanoparticles were added together with the catalytic system (rac-Et(Ind2ZrCl2/(MAO directly into the reactor, and in route 2 the metallocene rac-Et(Ind2ZrCl2 was supported on silica nanospheres pretreated with (MAO. SEM images show that when the nanospheres were added by both routes, they were replicated in the final polymer particle morphology; this phenomenon was more pronounced for PP obtained by route 2. The polypropylene (PP nanocomposites obtained by both routes had a slightly higher percent crystallinities and crystallinity temperatures than pure PP. Transmission electron microscopy (TEM images show that the nanospheres were well dispersed into the polypropylene matrix, particularly in the nanocomposites obtained by the support system (route 2.

  9. Self-propelled micromotors based on Au-mesoporous silica nanorods

    Science.gov (United States)

    Wang, Ying-Shuai; Xia, Hong; Lv, Chao; Wang, Lei; Dong, Wen-Fei; Feng, Jing; Sun, Hong-Bo

    2015-07-01

    Here, a chemical powered micromotor from the assembly of Au-SiO2 nanorods is presented. This new micromotor can be propelled efficiently by hydrogen bubbles generated from a hydrolysis reaction of aqueous NaBH4 and KBH4 and by oxygen bubbles produced by decomposition of H2O2. The monodisperse Au nanoparticles in mesoporous silica particles could catalyze the decomposition of two different kinds of fuels and produce bubbles. High speeds of 80 μm s-1 and recycles of more than 30 times are achieved in both NaBH4 and H2O2 media. Locomotion and rolling forms of movement were found. The locomotion forms can be obtained in a larger proportion by patterning the Au-SiO2 nanorods and a PDMS membrane. These micromotors that use multiple fuel sources to power them offer a broader scope of preparation and show considerable promise for diverse applications of nanomotors in different chemical environments.Here, a chemical powered micromotor from the assembly of Au-SiO2 nanorods is presented. This new micromotor can be propelled efficiently by hydrogen bubbles generated from a hydrolysis reaction of aqueous NaBH4 and KBH4 and by oxygen bubbles produced by decomposition of H2O2. The monodisperse Au nanoparticles in mesoporous silica particles could catalyze the decomposition of two different kinds of fuels and produce bubbles. High speeds of 80 μm s-1 and recycles of more than 30 times are achieved in both NaBH4 and H2O2 media. Locomotion and rolling forms of movement were found. The locomotion forms can be obtained in a larger proportion by patterning the Au-SiO2 nanorods and a PDMS membrane. These micromotors that use multiple fuel sources to power them offer a broader scope of preparation and show considerable promise for diverse applications of nanomotors in different chemical environments. Electronic supplementary information (ESI) available: More electronic microscopy graphs, UV-Vis spectra and N2 adsorption isotherms. See DOI: 10.1039/c5nr02545a

  10. ABTS-Modified Silica Nanoparticles as Laccase Mediators for Decolorization of Indigo Carmine Dye

    Directory of Open Access Journals (Sweden)

    Youxun Liu

    2015-01-01

    Full Text Available Efficient reuse and regeneration of spent mediators are highly desired for many of the laccases’ biotechnology applications. This investigation demonstrates that a redox mediator 2,2′-azino-bis-(3-ethylbenzothiazoline-6-sulfonic acid (ABTS covalently attached to silica nanoparticles (SNPs effectively mediated dye decolorization catalyzed by laccase. Characteristics of ABTS-modified silica nanoparticles (ABTS-SNPs were researched by scanning electron microscopy and Fourier-transformed infrared spectroscopy. When ABTS and ABTS-SNPs were used as laccase mediators, the decolorization yields of 96 and 95% were, respectively, obtained for indigo carmine dye. The results suggest that ABTS immobilized on SNPs can be used as laccase mediators as they retain almost the same efficiency as the free ABTS. The oxidized ABTS-SNPs were regenerated by their reduction reaction with ascorbic acid. Decolorization efficiency of regenerated ABTS-SNPs and their initial forms were found to be almost equivalent. Six reuse cycles for spent ABTS-SNPs were run for the treatment of indigo carmine, providing decolorization yields of 96–77%. Compared with free mediator, the immobilized mediators have the advantage of being easily recovered, regenerated, and reused making the whole process environmentally friendly.

  11. Polymerization of Polar Monomers from a Theoretical Perspective

    KAUST Repository

    Alghamdi, Miasser

    2016-10-11

    Density functional theory calculations have been used to investigate catalytic mechanism of polymer formation containing polar groups, from the synthesis of the monomer to the synthesis of the macromolecule. In the spirit of a sustainable and green chemistry, we initially focused attention on the coupling of CO2 as economically convenient and recyclable C1 source with C2H4 to form acrylate and/or butirro-lactone, two important polar monomers. In this process formation of a mettallolactone via oxidative coupling of CO2 and C2H4 is an important intermediate. Given this background, we explored in detail (chapter-3) several Ni based catalysts for CO2 coupling with C2H4 to form acrylate. In this thesis we report on the competitive reaction mechanisms (inner vs outer sphere) for the oxidative coupling of CO2 and ethylene for a set of 11 Ni-based complexes containing bisphosphine ligands. In another effort, considering incorporation of a C=C bond into a metal-oxygen-Functional-Group moiety is a challenging step in several polymerization reactions, we explored the details of this reaction (chapter4) using two different catalysts that are capable to perform this reaction in the synthesis of heterocycles. Specifically, the [Rh]-catalyzed intramolecular alkoxyacylation ([Rh] = [RhI(dppp)+] (dppp, 1,3-Bis-diphenylphosphino-propane), and the [Pd]/BPh3 intramolecular alkoxyfunctionalizations. Rest of the thesis we worked on understanding the details of the polymerization of polar monomers using organocatalysts based on N-heterocyclic carbenes (NHC) or N-heterocyclic olefins (NHO). In particular (chapter-5) we studied the polymerization of N-methyl N-carboxy- anhydrides, towards cyclic poly(N-substituted glycine)s, promoted by NHC catalysts. In good agreement with the experimental findings, we demonstrated that NHC promoted ring opening polymerization of N-Me N-Carboxyanhydrides may proceed via two different catalytic pathways. In a similar effort we studied polymerization of

  12. Incorporation of Nanohybrid Films of Silica into Recycled Polystyrene Matrix

    Directory of Open Access Journals (Sweden)

    Genoveva Hernández-Padrón

    2015-01-01

    Full Text Available An alternative for the reutilization of polystyrene waste containers consisting in creating a hybrid material made of SiO2 nanoparticles embedded in a matrix of recycled polystyrene (PSR has been developed. Recycled polystyrene functionalized (PSRF was used to influence the morphological and antifog properties by the sol-gel synthesis of nanohybrid silica. To this end, silica nanoparticles were produced from alkoxide precursors in the presence of recycled polystyrene. The functionalization of this polymeric matrix was with the purpose of uniting in situ carboxyl and silanol groups during the sol-gel process. In this way, opaque or transparent solid substrates can be obtained, with each of these endowed with optical conditions that depend on the amount of reactants employed to prepare each nanohybrid specimen. The nanohybrids were labelled as SiO2/PSR (HPSR and SiO2/PSRF (HPSRF and their properties were then compared to those of commercial polystyrene (PS. All the prepared samples were used for coating glass substrates. The hydrophobicity of the resultant coatings was determined through contact angle measurement. The nanohybrid materials were characterized by FT-IR and 1H-NMR techniques. Additionally, TGA and SEM were employed to determine their thermal and textural properties.

  13. Radical-Mediated Enzymatic Polymerizations

    Science.gov (United States)

    Zavada, Scott R.; Battsengel, Tsatsral; Scott, Timothy F.

    2016-01-01

    Polymerization reactions are commonly effected by exposing monomer formulations to some initiation stimulus such as elevated temperature, light, or a chemical reactant. Increasingly, these polymerization reactions are mediated by enzymes―catalytic proteins―owing to their reaction efficiency under mild conditions as well as their environmental friendliness. The utilization of enzymes, particularly oxidases and peroxidases, for generating radicals via reduction-oxidation mechanisms is especially common for initiating radical-mediated polymerization reactions, including vinyl chain-growth polymerization, atom transfer radical polymerization, thiol–ene step-growth polymerization, and polymerization via oxidative coupling. While enzyme-mediated polymerization is useful for the production of materials intended for subsequent use, it is especially well-suited for in situ polymerizations, where the polymer is formed in the place where it will be utilized. Such polymerizations are especially useful for biomedical adhesives and for sensing applications. PMID:26848652

  14. Silica-Immobilized Enzyme Reactors

    Science.gov (United States)

    2007-08-01

    Silica-IMERs 14 implicated in neurological disorders such as Schizophrenia and Parkinson’s disease.[86] Drug discovery for targets that can alter the...primarily the activation of prodrugs and proantibiotics for cancer treatments or antibiotic therapy , respectively.[87] Nitrobenzene nitroreductase was...BuChE) Monolith disks* Packed Silica Biosilica Epoxide- Silica Silica-gel Enzyme Human AChE Human AChE Human AChE Equine BuChE Human

  15. MASS BALANCE OF SILICA IN STRAW FROM THE PERSPECTIVE OF SILICA REDUCTION IN STRAW PULP

    Directory of Open Access Journals (Sweden)

    Celil Atik,

    2012-06-01

    Full Text Available The high silica content of wheat straw is an important limiting factor for straw pulping. High silica content complicates processing and black liquor recovery, wears out factory installations, and lowers paper quality. Each section of wheat straw has different cells and chemical compositions and thus different silica content. In this work, the silica content of balled straw samples were examined according to their physical components, including internodes, nodes, leaves (sheath and blade, rachis, grain, other plant bodies, and other plant spikes. Mass distribution of silica was determined by a dry ashing method. Half (50.90% of the silica comes from leaves, and its mechanical separation will reduce the silica content in wheat straw pulp significantly. Destroying silica bodies by sonication will increase the strength properties of straw pulp.

  16. Liquid Phase Deposition of Silica on the Hexagonally Close-Packed Monolayer of Silica Spheres

    Directory of Open Access Journals (Sweden)

    Seo Young Yoon

    2013-01-01

    Full Text Available Liquid phase deposition is a method used for the nonelectrochemical production of polycrystalline ceramic films at low temperatures, most commonly silicon dioxide films. Herein, we report that silica spheres are organized in a hexagonal close-packed array using a patterned substrate. On this monolayer of silica spheres, we could fabricate new nanostructures in which deposition and etching compete through a modified LPD reaction. In the early stage, silica spheres began to undergo etching, and then, silica bridges between the silica spheres appeared by the local deposition reaction. Finally, the silica spheres and bridges disappeared completely. We propose the mechanism for the formation of nanostructure.

  17. Ambient pressure dried tetrapropoxysilane-based silica aerogels with high specific surface area

    Science.gov (United States)

    Parale, Vinayak G.; Han, Wooje; Jung, Hae-Noo-Ree; Lee, Kyu-Yeon; Park, Hyung-Ho

    2018-01-01

    In the present paper, we report the synthesis of tetrapropoxysilane (TPOS)-based silica aerogels with high surface area and large pore volume. The silica aerogels were prepared by a two-step sol-gel process followed by surface modification via a simple ambient pressure drying approach. In order to minimize drying shrinkage and obtain hydrophobic aerogels, the surface of the alcogels was modified using trichloromethylsilane as a silylating agent. The effect of the sol-gel compositional parameters on the polymerization of aerogels prepared by TPOS, one of the precursors belonging to the Si(OR)4 family, was reported for the first time. The oxalic acid and NH4OH concentrations were adjusted to achieve good-quality aerogels with high surface area, low density, and high transparency. Controlling the hydrolysis and condensation reactions of the TPOS precursor turned out to be the most important factor to determine the pore characteristics of the aerogel. Highly transparent aerogels with high specific surface area (938 m2/g) and low density (0.047 g/cm3) could be obtained using an optimized TPOS/MeOH molar ratio with appropriate concentrations of oxalic acid and NH4OH.

  18. Thermodynamics of Silica Dissolution From In-situ Raman +Spectroscopy

    Science.gov (United States)

    Davis, M. K.; Fumagalli, P.; Stixrude, L. P.

    2001-12-01

    Solubilities of cations, such as silicon, in water strongly effect both the physical and thermodynamical properties of supercritical metamorphic fluids. Modeling the thermodynamics of fluid-rock interactions requires therefore a profound understanding of cation dissolution and aqueous speciation. In-situ Raman experiments of the silica-water system were performed in an externally heated Bassett-type diamond-anvil cell at the Department of Geological Sciences, University of Michigan. Natural quartz samples (from Owl Creek Mountains, Wyoming) were loaded in the sample chamber with de-ionized or spectrographic water. All experiments used doubly polished rhenium gaskets with a thickness of 200 μ m, diameter of 1.0 mm, and a 500 μ m drillhole for the sample chamber. Temperature was measured using K-type thermocouples wrapped around both the upper and lower diamond anvils. Pressures are obtained on the basis of the shift of the 464 cm-1 Raman mode of quartz. In-situ Raman spectra were collected from 250-1200 cm-1, focusing on the vibrational modes of aqueous silica species at temperatures up to 700 ° C and pressures up to 14 kbar. We observed Si-O stretching modes attributable to dimer (H6Si2O7, 965 cm-1) and monomer (H4SiO4, 771 cm-1) aqueous silica species. The relative intensities of these two bands as a function of isochoric heating place constraints on the energetics of the polymerization reaction, if we assume that the intensity ratio is linearly related to concentration ratio. We have been able to perform experiments along two different isochores (0.9 and 0.75 g/cm3, respectively) from which we are able to derive the enthalpy of reaction.

  19. Carbon Isotope Systematics in Mineral-Catalyzed Hydrothermal Organic Synthesis Processes at High Temperature and Pressures

    Science.gov (United States)

    Fu, Qi; Socki, R. A.; Niles, Paul B.

    2011-01-01

    Observation of methane in the Martian atmosphere has been reported by different detection techniques. Reduction of CO2 and/or CO during serpentization by mineral surface catalyzed Fischer-Tropsch Type (FTT) synthesis may be one possible process responsible for methane generation on Mars. With the evidence a recent study has discovered for serpentinization in deeply buried carbon rich sediments, and more showing extensive water-rock interaction in Martian history, it seems likely that abiotic methane generation via serpentinization reactions may have been common on Mars. Experiments involving mineral-catalyzed hydrothermal organic synthesis processes were conducted at 750 C and 5.5 Kbars. Alkanes, alcohols and carboxylic acids were identified as organic compounds. No "isotopic reversal" of delta C-13 values was observed for alkanes or carboxylic acids, suggesting a different reaction pathway than polymerization. Alcohols were proposed as intermediaries formed on mineral surfaces at experimental conditions. Carbon isotope data were used in this study to unravel the reaction pathways of abiotic formation of organic compounds in hydrothermal systems at high temperatures and pressures. They are instrumental in constraining the origin and evolution history of organic compounds on Mars and other planets.

  20. Polypropylene Nano composites Obtained by In Situ Polymerization Using Metallocenes Catalyst: Influence of the Nanoparticles on the Final Polymer Morphology

    International Nuclear Information System (INIS)

    Zapata, P.; Quijada, R.

    2012-01-01

    Polypropylene nano composites containing silica nanospheres based on the sol-gel methods were produced via in situ polymerization using a rac-Et(Ind) 2 ZrCl 2 /methylaluminoxane (MAO) system. Two different routes were used depending on the interaction between the silica nanoparticles with the catalytic system. In route 1 the nanoparticles were added together with the catalytic system (rac-Et(Ind) 2 ZrCl 2 )/(MAO) directly into the reactor, and in route 2 the metallocenes rac-Et(Ind) 2 ZrCl 2 was supported on silica nanospheres pretreated with (MAO). SEM images show that when the nanospheres were added by both routes, they were replicated in the final polymer particle morphology; this phenomenon was more pronounced for PP obtained by route 2. The polypropylene (PP) nano composites obtained by both routes had a slightly higher percent crystallinity and crystallinity temperatures than pure PP. Transmission electron microscopy (TEM) images show that the nanospheres were well dispersed into the polypropylene matrix, particularly in the nano composites obtained by the support system (route 2).

  1. Effects of silica coating and silane surface conditioning on the bond strength of rebonded metal and ceramic brackets

    Directory of Open Access Journals (Sweden)

    Saadet Atsü

    2011-06-01

    Full Text Available OBJECTIVE: The aim of this study was to evaluate the effects of tribochemical silica coating and silane surface conditioning on the bond strength of rebonded metal and ceramic brackets. MATERIAL AND METHODS: Twenty debonded metal and 20 debonded ceramic brackets were randomly assigned to receive one of the following surface treatments (n=10 for each group: (1 sandblasting (control; (2 tribochemical silica coating combined with silane. Brackets were rebonded to the enamel surface on the labial and lingual sides of premolars with a light-polymerized resin composite. All specimens were stored in distilled water for 1 week and then thermocycled (5,000 cycles between 5-55ºC. Shear bond strength values were measured using a universal testing machine. Student's t-test was used to compare the data (α=0.05. Failure mode was assessed using a stereomicroscope, and the treated and non-treated bracket surfaces were observed by scanning electron microscopy. RESULTS: Rebonded ceramic brackets treated with silica coating followed by silanization had significantly greater bond strength values (17.7±4.4 MPa than the sandblasting group (2.4±0.8 MPa, P<0.001. No significant difference was observed between the rebonded metal brackets treated with silica coating with silanization (15±3.9 MPa and the sandblasted brackets (13.6±3.9 MPa. Treated rebonded ceramic specimens primarily exhibited cohesive failure in resin and adhesive failure at the enamel-adhesive interface. CONCLUSIONS: In comparison to sandblasting, silica coating with aluminum trioxide particles followed by silanization resulted in higher bond strengths of rebonded ceramic brackets.

  2. Effect of the size of silica nanoparticles on wettability and surface chemistry of sol–gel superhydrophobic and oleophobic nanocomposite coatings

    Energy Technology Data Exchange (ETDEWEB)

    Lakshmi, R.V., E-mail: lakshmi_rv@nal.res.in; Bera, Parthasarathi; Anandan, C.; Basu, Bharathibai J.

    2014-11-30

    Highlights: • Superhydrophobic coatings from Cab-O-Sil EH5 and M5 particles in MTEOS sol. • Particle size of Cab-O-Sil influenced its optimum concentration in coating. • FAS-13 modification improved the oleophobicity of the coating. • Coating surface exhibited porous structure with nanovoids and microscale bumps. • Coatings with Cab-O-Sil EH5 retained water repelling property for a long time. - Abstract: Superhydrophobic sol–gel nanocomposite coatings have been fabricated by incorporating silica nanoparticles with different particle sizes separately in an acid-catalyzed sol of methyltriethoxysilane (MTEOS). Water contact angle (WCA) of the coatings increased with increase in the concentration of silica nanoparticles in both the cases. The coatings became superhydrophobic at an optimum silica concentration. The water repellency was further improved by the addition of fluoroalkylsilane (FAS). The optimum silica concentration was found to depend on the size of silica nanoparticles and FAS content and the coatings exhibited WCA of about 160° and water sliding angle (WSA) of <2°. FAS addition also improved the oleophobicity of the coatings. The coatings exhibited oil-repellency with a lubricant oil contact angle of 126° and ethylene glycol contact angle of 153.3°. Surface morphology of the coatings analyzed using field emission scanning electron microscopy (FESEM) showed a rough surface with microscale bumps and nanoscale pores. XPS was used to study the surface composition of the coatings. The superhydrophobic property of the coatings was due to the synergistic effect of surface chemistry and surface microstructure and can be explained using Cassie-Baxter model.

  3. Elektroaktive polymerer

    DEFF Research Database (Denmark)

    West, K.

    Traditionelt tænker vi på polymerer (plastik) som elektrisk isolerende materialer - det som er udenpå ledningerne. I dag kender vi imidlertid også polymerer med intrinsisk elektrisk ledningsevne, og plast er på vej ind i anvendelser, der tidligereudelukkende var baseret på metaller og uorganiske...... halvledere. Hertil kommer, at en del af de ledende polymerer kan stimuleres til at skifte mellem en ledende og en halvledende tilstand, hvorved de ændret både form og farve. I foredraget gives der enrække eksempler på anvendelse af polymerer som elektriske komponenter - rækkende fra polymer elektronik over...

  4. Hydrothermal stability of microporous silica and niobia-silica membranes

    NARCIS (Netherlands)

    Boffa, V.; Blank, David H.A.; ten Elshof, Johan E.

    2008-01-01

    The hydrothermal stability of microporous niobia–silica membranes was investigated and compared with silica membranes. The membranes were exposed to hydrothermal conditions at 150 and 200 °C for 70 h. The change of pore structure before and after exposure to steam was probed by single-gas permeation

  5. Serpentinization processes: Influence of silica

    Science.gov (United States)

    Huang, R.; Sun, W.; Ding, X.; Song, M.; Zhan, W.

    2016-12-01

    Serpentinization systems are highly enriched in molecular hydrogen (H2) and hydrocarbons (e.g. methane, ethane and propane). The production of hydrocarbons results from reactions between H2 and oxidized carbon (carbon dioxide and carbon monoxide), which possibly contribute to climate changes during early history of the Earth. However, the influence of silica on the production of H2 and hydrocarbons was poorly constrained. We performed experiments at 311-500 °C and 3.0 kbar using mechanical mixtures of silica and olivine in ratios ranging from 0 to 40%. Molecular hydrogen (H2), methane, ethane and propane were formed, which were analyzed by gas chromatography. It was found that silica largely decreased H2 production. Without any silica, olivine serpentinization produced 94.5 mmol/kg H2 after 20 days of reaction time. By contrast, with the presence of 20% silica, H2 concentrations decreased largely, 8.5 mmol/kg. However, the influence of silica on the production of hydrocarbons is negligible. Moreover, with the addition of 20%-40% silica, the major hydrous minerals are talc, which was quantified according to an established standard curve calibrated by infrared spectroscopy analyses. It shows that silica greatly enhances olivine hydration, especially at 500 °C. Without any addition of silica, reaction extents were serpentinization at 500 °C and 3.0 kbar. By contrast, with the presence of 50% silica, olivine was completely transformed to talc within 9 days. This study indicates that silica impedes the oxidation of ferrous iron into ferric iron, and that rates of olivine hydration in natural geological settings are much faster with silica supply.

  6. Interfacial interaction between the epoxidized natural rubber and silica in natural rubber/silica composites

    Science.gov (United States)

    Xu, Tiwen; Jia, Zhixin; Luo, Yuanfang; Jia, Demin; Peng, Zheng

    2015-02-01

    The epoxidized natural rubber (ENR) as an interfacial modifier was used to improve the mechanical and dynamical mechanical properties of NR/silica composites. In order to reveal the interaction mechanism between ENR and silica, the ENR/Silica model compound was prepared by using an open mill and the interfacial interaction of ENR with silica was investigated by Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), X-ray diffraction (XRD) and stress-strain testing. The results indicated that the ring-opening reaction occurs between the epoxy groups of ENR chains and Si-OH groups on the silica surfaces and the covalent bonds are formed between two phases, which can improve the dispersion of silica in the rubber matrix and enhance the interfacial combination between rubber and silica. The ring-opening reaction occurs not only in vulcanization process but also in mixing process, meanwhile, the latter seems to be more important due to the simultaneous effects of mechanical force and temperature.

  7. Interference lithography for optical devices and coatings

    Science.gov (United States)

    Juhl, Abigail Therese

    Interference lithography can create large-area, defect-free nanostructures with unique optical properties. In this thesis, interference lithography will be utilized to create photonic crystals for functional devices or coatings. For instance, typical lithographic processing techniques were used to create 1, 2 and 3 dimensional photonic crystals in SU8 photoresist. These structures were in-filled with birefringent liquid crystal to make active devices, and the orientation of the liquid crystal directors within the SU8 matrix was studied. Most of this thesis will be focused on utilizing polymerization induced phase separation as a single-step method for fabrication by interference lithography. For example, layered polymer/nanoparticle composites have been created through the one-step two-beam interference lithographic exposure of a dispersion of 25 and 50 nm silica particles within a photopolymerizable mixture at a wavelength of 532 nm. In the areas of constructive interference, the monomer begins to polymerize via a free-radical process and concurrently the nanoparticles move into the regions of destructive interference. The holographic exposure of the particles within the monomer resin offers a single-step method to anisotropically structure the nanoconstituents within a composite. A one-step holographic exposure was also used to fabricate self-healing coatings that use water from the environment to catalyze polymerization. Polymerization induced phase separation was used to sequester an isocyanate monomer within an acrylate matrix. Due to the periodic modulation of the index of refraction between the monomer and polymer, the coating can reflect a desired wavelength, allowing for tunable coloration. When the coating is scratched, polymerization of the liquid isocyanate is catalyzed by moisture in air; if the indices of the two polymers are matched, the coatings turn transparent after healing. Interference lithography offers a method of creating multifunctional self

  8. Fumed Silica Nanoparticles Incorporated in Quaternized Poly(Vinyl Alcohol Nanocomposite Membrane for Enhanced Power Densities in Direct Alcohol Alkaline Fuel Cells

    Directory of Open Access Journals (Sweden)

    Selvaraj Rajesh Kumar

    2015-12-01

    Full Text Available A nanocomposite polymer membrane based on quaternized poly(vinyl alcohol/fumed silica (QPVA/FS was prepared via a quaternization process and solution casting method. The physico-chemical properties of the QPVA/FS membrane were investigated. Its high ionic conductivity was found to depend greatly on the concentration of fumed silica in the QPVA matrix. A maximum conductivity of 3.50 × 10−2 S/cm was obtained for QPVA/5%FS at 60 °C when it was doped with 6 M KOH. The permeabilities of methanol and ethanol were reduced with increasing fumed silica content. Cell voltage and peak power density were analyzed as functions of fumed silica concentration, temperature, methanol and ethanol concentrations. A maximum power density of 96.8 mW/cm2 was achieved with QPVA/5%FS electrolyte using 2 M methanol + 6 M KOH as fuel at 80 °C. A peak power density of 79 mW/cm2 was obtained using the QPVA/5%FS electrolyte with 3 M ethanol + 5 M KOH as fuel. The resulting peak power densities are higher than the majority of published reports. The results confirm that QPVA/FS exhibits promise as a future polymeric electrolyte for use in direct alkaline alcoholic fuel cells.

  9. Bioinspired thermo- and pH-responsive polymeric amines: multimolecular aggregates in aqueous media and matrices for silica/polymer nanocomposites.

    Science.gov (United States)

    Danilovtseva, Elena N; Aseyev, Vladimir; Belozerova, Olga Yu; Zelinskiy, Stanislav N; Annenkov, Vadim V

    2015-05-15

    Polymeric amines have been intensively studied for application in smart systems and as matrices for the design of composite materials, including bioinspired substances. A new thermo- and pH-responsive polymer was obtained by radical polymerization of N-(3-(diethylamino)propyl)-N-methylacrylamide. Upon heating, the polymer precipitated from aqueous solutions above pH 9; the observed cloud point was dependent on the polymer concentration and decreased from 95°C at pH 9 to 40°C at pH 11. The basicity of the polymer decreased at elevated temperatures owing to an increase in the hydrophobicity-driven compaction of the macromolecules. Dynamic light scattering analysis demonstrated that the formation of large multimolecular associates with radius 1000-2000 nm was initiated from 1 to 2°C below the cloud point. The new polymer is demonstrated to be an effective matrix for various siliceous composite structures, including 200-300 nm solid spherical raspberry-like particles and hollow hemispherical particles of more than 1000 nm diameter. Condensation of silicic acid in the presence of polymeric amines is a model reaction in biosilicification studies, and the obtained data are also discussed from the perspective of the matrix hypothesis for biosilica formation. Copyright © 2015 Elsevier Inc. All rights reserved.

  10. Interfacial interaction between the epoxidized natural rubber and silica in natural rubber/silica composites

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Tiwen [College of Materials Science and Engineering, South China University of Technology, Guangzhou 510640 (China); Jia, Zhixin, E-mail: zxjia@scut.edu.cn [College of Materials Science and Engineering, South China University of Technology, Guangzhou 510640 (China); Luo, Yuanfang; Jia, Demin [College of Materials Science and Engineering, South China University of Technology, Guangzhou 510640 (China); Peng, Zheng [Agricultural Product Processing Research Institute, Chinese Academy of Tropical Agriculture Sciences, Zhanjiang 524001 (China)

    2015-02-15

    Highlights: • Substantiate the ring open reaction between Si-OH of silica and epoxy groups of ENR. • ENR can act as a bridge between NR and silica to enhance the interfacial interaction. • As a modifier, ENR gets the potential to be used in the tread of green tire for improving the wet skid resistance apparently. - Abstract: The epoxidized natural rubber (ENR) as an interfacial modifier was used to improve the mechanical and dynamical mechanical properties of NR/silica composites. In order to reveal the interaction mechanism between ENR and silica, the ENR/Silica model compound was prepared by using an open mill and the interfacial interaction of ENR with silica was investigated by Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), X-ray diffraction (XRD) and stress–strain testing. The results indicated that the ring-opening reaction occurs between the epoxy groups of ENR chains and Si-OH groups on the silica surfaces and the covalent bonds are formed between two phases, which can improve the dispersion of silica in the rubber matrix and enhance the interfacial combination between rubber and silica. The ring-opening reaction occurs not only in vulcanization process but also in mixing process, meanwhile, the latter seems to be more important due to the simultaneous effects of mechanical force and temperature.

  11. Application of a Burkholderia cepacia lipase-immobilized silica monolith to batch and continuous biodiesel production with a stoichiometric mixture of methanol and crude Jatropha oil

    Directory of Open Access Journals (Sweden)

    Takahashi Ryo

    2011-10-01

    Full Text Available Abstract Background The enzymatic production of biodiesel through alcoholysis of triglycerides has become more attractive because it shows potential in overcoming the drawbacks of chemical processes. In this study, we investigate the production of biodiesel from crude, non-edible Jatropha oil and methanol to characterize Burkholderia cepacia lipase immobilized in an n-butyl-substituted hydrophobic silica monolith. We also evaluate the performance of a lipase-immobilized silica monolith bioreactor in the continuous production of biodiesel. Results The Jatropha oil used contained 18% free fatty acids, which is problematic in a base-catalyzed process. In the lipase-catalyzed reaction, the presence of free fatty acids made the reaction mixture homogeneous and allowed bioconversion to proceed to 90% biodiesel yield after a 12 hour reaction time. The optimal molar ratio of methanol to oil was 3.3 to 3.5 parts methanol to one part oil, with water content of 0.6% (w/w. Further experiments revealed that B. cepacia lipase immobilized in hydrophobic silicates was sufficiently tolerant to methanol, and glycerol adsorbed on the support disturbed the reaction to some extent in the present reaction system. The continuous production of biodiesel was performed at steady state using a lipase-immobilized silica monolith bioreactor loaded with 1.67 g of lipase. The yield of 95% was reached at a flow rate of 0.6 mL/h, although the performance of the continuous bioreactor was somewhat below that predicted from the batch reactor. The bioreactor was operated successfully for almost 50 days with 80% retention of the initial yield. Conclusions The presence of free fatty acids originally contained in Jatropha oil improved the reaction efficiency of the biodiesel production. A combination of B. cepacia lipase and its immobilization support, n-butyl-substituted silica monolith, was effective in the production of biodiesel. This procedure is easily applicable to the design

  12. Cyclooctane metathesis catalyzed by silica-supported tungsten pentamethyl [(ΞSiO)W(Me)5]: Distribution of macrocyclic alkanes

    KAUST Repository

    Riache, Nassima

    2014-10-03

    Metathesis of cyclic alkanes catalyzed by the new surface complex [(ΞSiO)W(Me)5] affords a wide distribution of cyclic and macrocyclic alkanes. The major products with the formula CnH2n are the result of either a ring contraction or ring expansion of cyclooctane leading to lower unsubstituted cyclic alkanes (5≤n≤7) and to an unprecedented distribution of unsubstituted macrocyclic alkanes (12≤n≤40), respectively, identified by GC/MS and by NMR spectroscopies.

  13. Ordered mesoporous polymer-silica hybrid nanoparticles as vehicles for the intracellular controlled release of macromolecules.

    Science.gov (United States)

    Kim, Tae-Wan; Slowing, Igor I; Chung, Po-Wen; Lin, Victor Shang-Yi

    2011-01-25

    A two-dimensional hexagonal ordered mesoporous polymer-silica hybrid nanoparticle (PSN) material was synthesized by polymerization of acrylate monomers on the surface of SBA-15 mesoporous silica nanoparticles. The structure of the PSN material was analyzed using a series of different techniques, including transmission electron microscopy, powder X-ray diffraction, and N(2) sorption analysis. These structurally ordered mesoporous polymer-silica hybrid nanoparticles were used for the controlled release of membrane-impermeable macromolecules inside eukaryotic cells. The cellular uptake efficiency and biocompatibility of PSN with human cervical cancer cells (HeLa) were investigated. Our results show that the inhibitory concentration (IC(50)) of PSN is very high (>100 μg/mL per million cells), while the median effective concentration for the uptake (EC(50)) of PSN is low (EC(50) = 4.4 μg/mL), indicating that PSNs are fairly biocompatible and easily up-taken in vitro. A membrane-impermeable macromolecule, 40 kDa FITC-Dextran, was loaded into the mesopores of PSNs at low pH. We demonstrated that the PSN material could indeed serve as a transmembrane carrier for the controlled release of FITC-Dextran at the pH level inside live HeLa cells. We believe that further developments of this PSN material will lead to a new generation of nanodevices for intracellular controlled delivery applications.

  14. A Comparative Study on Graphene Oxide and Carbon Nanotube Reinforcement of PMMA-Siloxane-Silica Anticorrosive Coatings.

    Science.gov (United States)

    Harb, Samarah V; Pulcinelli, Sandra H; Santilli, Celso V; Knowles, Kevin M; Hammer, Peter

    2016-06-29

    Carbon nanotubes (CNTs) and graphene oxide (GO) have been used to reinforce PMMA-siloxane-silica nanocomposites considered to be promising candidates for environmentally compliant anticorrosive coatings. The organic-inorganic hybrids were prepared by benzoyl peroxide (BPO)-induced polymerization of methyl methacrylate (MMA) covalently bonded through 3-(trimethoxysilyl)propyl methacrylate (MPTS) to silica domains formed by hydrolytic condensation of tetraethoxysilane (TEOS). Single-walled carbon nanotubes and graphene oxide nanosheets were dispersed by surfactant addition and in a water/ethanol solution, respectively. These were added to PMMA-siloxane-silica hybrids at a carbon (CNT or GO) to silicon (TEOS and MPTS) molar ratio of 0.05% in two different matrices, both prepared at BPO/MMA molar ratios of 0.01 and 0.05. Atomic force microscopy and scanning electron microscopy showed very smooth, homogeneous, and defect-free surfaces of approximately 3-7 μm thick coatings deposited onto A1020 carbon steel by dip coating. Mechanical testing and thermogravimetric analysis confirmed that both additives CNT and GO improved the scratch resistance, adhesion, wear resistance, and thermal stability of PMMA-siloxane-silica coatings. Results of electrochemical impedance spectroscopy in 3.5% NaCl solution, discussed in terms of equivalent circuits, showed that the reinforced hybrid coatings act as a very efficient anticorrosive barrier with an impedance modulus up to 1 GΩ cm(2), approximately 5 orders of magnitude higher than that of bare carbon steel. In the case of GO addition, the high corrosion resistance was maintained for more than 6 months in saline medium. These results suggest that both carbon nanostructures can be used as structural reinforcement agents, improving the thermal and mechanical resistance of high performance anticorrosive PMMA-siloxane-silica coatings and thus extending their application range to abrasive environments.

  15. Gas Separation through Bilayer Silica, the Thinnest Possible Silica Membrane.

    Science.gov (United States)

    Yao, Bowen; Mandrà, Salvatore; Curry, John O; Shaikhutdinov, Shamil; Freund, Hans-Joachim; Schrier, Joshua

    2017-12-13

    Membrane-based gas separation processes can address key challenges in energy and environment, but for many applications the permeance and selectivity of bulk membranes is insufficient for economical use. Theory and experiment indicate that permeance and selectivity can be increased by using two-dimensional materials with subnanometer pores as membranes. Motivated by experiments showing selective permeation of H 2 /CO mixtures through amorphous silica bilayers, here we perform a theoretical study of gas separation through silica bilayers. Using density functional theory calculations, we obtain geometries of crystalline free-standing silica bilayers (comprised of six-membered rings), as well as the seven-, eight-, and nine-membered rings that are observed in glassy silica bilayers, which arise due to Stone-Wales defects and vacancies. We then compute the potential energy barriers for gas passage through these various pore types for He, Ne, Ar, Kr, H 2 , N 2 , CO, and CO 2 gases, and use the data to assess their capability for selective gas separation. Our calculations indicate that crystalline bilayer silica, which is less than a nanometer thick, can be a high-selectivity and high-permeance membrane material for 3 He/ 4 He, He/natural gas, and H 2 /CO separations.

  16. Synthesis of uniform carbon at silica nanocables and luminescent silica nanotubes with well controlled inner diameters

    International Nuclear Information System (INIS)

    Qian Haisheng; Yu Shuhong; Ren Lei; Yang Yipeng; Zhang Wei

    2006-01-01

    Uniform carbon at silica nanocables and silica nanotubes with well-controlled inner diameters can be synthesized in an easy way by a sacrificial templating method. This was performed using carbon nanofibres as hard templates that were synthesized previously by a hydrothermal carbonization process. Silica nanotubes with well-controlled inner diameters were synthesized from carbon at silica core-shell nanostructures by removal of the core carbon component. The inner diameters of the as-prepared silica nanotubes can be well controlled from several nanometres to hundreds of nanometres by adjusting the diameters of the carbon nanofibres. The silica nanotubes synthesized by this method display strong photoluminescence in ultraviolet at room temperature. Such uniform silica nanotubes might find potential applications in many fields such as encapsulation, catalysis, chemical/biological separation, and sensing

  17. Silica/Perfluoropolymer nanocomposites fabricated by direct melt-compounding: a novel method without surface modification on nano-silica.

    Science.gov (United States)

    Tanahashi, Mitsuru; Hirose, Masaki; Watanabe, Yusuke; Lee, Jeong-Chang; Takeda, Kunihiko

    2007-07-01

    A novel method for the fabrication of silica/perfluoropolymer nanocomposites was investigated, whereby nano-sized silica particles without surface modification were dispersed uniformly through mechanical breakdown of loosely packed agglomerates of silica nanoparticles with low fracture strength in a polymer melt during direct melt-compounding. The method consists of two stages. The first stage involves preparation of the loose silica agglomerate, and the second stage involves melt-compounding of a completely hydrophobic perfluoropolymer, poly(tetrafluoroethyleneco-perfluoropropylvinylether), with the loose silica agglomerates prepared in the first stage. In the first stage, the packing structure and the fracture strength of the silica agglomerate were controlled by destabilizing an aqueous colloidal silica solution with a mean primary diameter of 190 nm via pH control and salt addition. In the next stage, the silica/perfluoropolymer nanocomposite was fabricated by breaking down the prepared loose silica agglomerates with low fracture strength by means of a shear force inside the polymer melt during melt-compounding.

  18. On the mechanism of activation of copper-catalyzed atom transfer radical polymerization

    International Nuclear Information System (INIS)

    Isse, Abdirisak Ahmed; Bortolamei, Nicola; De Paoli, Patrizia; Gennaro, Armando

    2013-01-01

    The mechanism of activation of atom transfer radical polymerization (ATRP) has been analyzed by investigating the kinetics of dissociative electron transfer (ET) to alkyl halides (RX) in acetonitrile. Using a series of alkyl halides, including both bromides and chlorides, the rate constants of ET (k ET ) to RX by electrogenerated aromatic radical anions (A· − ) acting as outer-sphere donors have been measured and analyzed according to the current theories of dissociative ET. This has shown that the kinetic data fit very well the “sticky” dissociative ET model with the formation of a weak adduct held together by electrostatic interactions. The rate constants of activation, k act , of some alkyl halides, namely chloroacetonitrile, methyl 2-bromopropionate and ethyl chloroacetate, by [Cu I L] + (L = tris(2-dimethylaminoethyl)amine, tris(2-pyridylmethyl)amine, 1,1,4,7,7-pentamethyldiethylenetriamine) have also been measured in the same experimental conditions. Comparisons of the measured k act values with those predicted assuming an outer-sphere ET for the complexes have shown that activation by Cu(I) is 7–10 orders of magnitude faster than required by outer-sphere ET. Therefore, the mechanism of RX activation by Cu(I) complexes used as catalysts in ATRP occurs by an inner-sphere ET or more appropriately by a halogen atom abstraction

  19. Oligomerization of glycine and alanine catalyzed by iron oxides: implications for prebiotic chemistry.

    Science.gov (United States)

    Shanker, Uma; Bhushan, Brij; Bhattacharjee, G; Kamaluddin

    2012-02-01

    Iron oxide minerals are probable constituents of the sediments present in geothermal regions of the primitive earth. They might have adsorbed different organic monomers (amino acids, nucleotides etc.) and catalyzed polymerization processes leading to the formation of the first living cell. In the present work we tested the catalytic activity of three forms of iron oxides (Goethite, Akaganeite and Hematite) in the intermolecular condensation of each of the amino acids glycine and L-alanine. The effect of zinc oxide and titanium dioxide on the oligomerization has also been studied. Oligomerization studies were performed for 35 days at three different temperatures 50, 90 and 120°C without applying drying/wetting cycling. The products formed were characterized by HPLC and ESI-MS techniques. All three forms of iron oxides catalyzed peptide bond formation (23.2% of gly2 and 10.65% of ala2). The reaction was monitored every 7 days. Formation of peptides was observed to start after 7 days at 50°C. Maximum yield of peptides was found after 35 days at 90°C. Reaction at 120°C favors formation of diketopiperazine derivatives. It is also important to note that after 35 days of reaction, goethite produced dimer and trimer with the highest yield among the oxides tested. We suggest that the activity of goethite could probably be due to its high surface area and surface acidity.

  20. Preparation and Application of Hollow Silica/magnetic Nanocomposite Particle

    Science.gov (United States)

    Wang, Cheng-Chien; Lin, Jing-Mo; Lin, Chun-Rong; Wang, Sheng-Chang

    The hollow silica/cobalt ferrite (CoFe2O4) magnetic microsphere with amino-groups were successfully prepared via several steps, including preparing the chelating copolymer microparticles as template by soap-free emulsion polymerization, manufacturing the hollow cobalt ferrite magnetic microsphere by in-situ chemical co-precipitation following calcinations, and surface modifying of the hollow magnetic microsphere by 3-aminopropyltrime- thoxysilane via the sol-gel method. The average diameter of polymer microspheres was ca. 200 nm from transmission electron microscope (TEM) measurement. The structure of the hollow magnetic microsphere was characterized by using TEM and scanning electron microscope (SEM). The spinel-type lattice of CoFe2O4 shell layer was identified by using XRD measurement. The diameter of CoFe2O4 crystalline grains ranged from 54.1 nm to 8.5 nm which was estimated by Scherrer's equation. Additionally, the hollow silica/cobalt ferrite microsphere possesses superparamagnetic property after VSM measurement. The result of BET measurement reveals the hollow magnetic microsphere which has large surface areas (123.4m2/g). After glutaraldehyde modified, the maximum value of BSA immobilization capacity of the hollow magnetic microsphere was 33.8 mg/g at pH 5.0 buffer solution. For microwave absorption, when the hollow magnetic microsphere was compounded within epoxy resin, the maximum reflection loss of epoxy resins could reach -35dB at 5.4 GHz with 1.9 mm thickness.

  1. Fabrication, Light Emission, and Magnetism of Silica Nanoparticles Hybridized with AIE Luminogens and Inorganic Nanostructures

    Science.gov (United States)

    Faisal, Mahtab

    . Sol-gel reaction in the presence of (3-aminopropyl)triethoxysilane has generated MFSNP-NH2 with numerous amino functionalities decorated on the surfaces, enabling them to immobilize bovine serum albumin efficiently. FSNPs with strong light emissions are facilely fabricated by thio-click chemistry, Cu(I)-catalyzed 1,3-dipolar cycloaddition, and sol-gel reaction. The FSNPs are characterized by SEM, TEM, IR, PL, and zeta potential analyses. They are uniformly sized with smooth surfaces. Upon photoexcitation, the FSNPs emit strong visible lights with fluorescence quantum yields up to 25.5%. Sugar-functionalized fluorescent silica nanoparticles are facilely fabricated by click reaction of azide-modified FSNPs with sugar- containing phenylacetylene catalyzed by Cu(PPh3)3Br in THF. The nanoparticles are uniformly sized and emit efficient light upon photoexcitation. They can function as fluorescent visualizers for intracellular imaging and can target specific cancer cells. Folic acid-functionalized fluorescent silica nanoparticles are facilely fabricated by surface functionalization of FSNPs with folic acid. The nanoparticles are spherical in shape. They possess high zeta potentials and hence exhibit excellent colloidal stability. UV irradiation of suspensions of the nanoparticles in ethanol gives strong blue and green emissions at 465 and 490 nm with absolute fluorescence quantum yields up to 47%. Carboxylic acid and thiol-functionalized fluorescent silica nanoparticles (FSNP-COOH and FSNP-SH) with uniform particle sizes, narrow size distributions, and smooth surface morphologies are fabricated. The nanoparticles possess high surface charges and exhibit strong light emissions upon photoexcitation. They can adsorb lysozyme strongly on their surfaces and for 5 mg of FSNP-COOH and FSNP-SH, they can take 209 and 86 mug of lysozyme. Thus, they are potential carriers for protein and fluorescent probes or biosensors for an array of biological applications.

  2. The Effect of Photon Source on Heterogeneous Photocatalytic Oxidation of Ethanol by a Silica-Titania Composite

    Science.gov (United States)

    Coutts, Janelle L.; Levine, Lanfang H.; Richards, Jeffrey T.; Mazyck, David W.

    2011-01-01

    The objective of this study was to distinguish the effect of photon flux (i.e., photons per unit time reaching a surface) from that of photon energy (i.e., wavelength) of a photon source on the silica-titania composite (STC)-catalyzed degradation of ethanol in the gas phase. Experiments were conducted in a bench-scale annular reactor packed with STC pellets and irradiated with either a UV-A fluorescent black light blue lamp ((gamma)max=365 nm) at its maximum light intensity or a UV-C germicidal lamp ((gamma)max=254 nm) at three levels of light intensity. The STC-catalyzed oxidation of ethanol was found to follow zero-order kinetics with respect to CO2 production, regardless of the photon source. Increased photon flux led to increased EtOH removal, mineralization, and oxidation rate accompanied by lower intermediate concentration in the effluent. The oxidation rate was higher in the reactor irradiated by UV-C than by UV-A (38.4 vs. 31.9 nM/s) at the same photon flux, with similar trends for mineralization (53.9 vs. 43.4%) and reaction quantum efficiency (i.e., photonic efficiency, 63.3 vs. 50.1 nmol CO2 (mu)mol/photons). UV-C irradiation also led to decreased intermediate concentration in the effluent . compared to UV-A irradiation. These results demonstrated that STC-catalyzed oxidation is enhanced by both increased photon flux and photon energy.

  3. Spray-drying nanocapsules in presence of colloidal silica as drying auxiliary agent: formulation and process variables optimization using experimental designs.

    Science.gov (United States)

    Tewa-Tagne, Patrice; Degobert, Ghania; Briançon, Stéphanie; Bordes, Claire; Gauvrit, Jean-Yves; Lanteri, Pierre; Fessi, Hatem

    2007-04-01

    Spray-drying process was used for the development of dried polymeric nanocapsules. The purpose of this research was to investigate the effects of formulation and process variables on the resulting powder characteristics in order to optimize them. Experimental designs were used in order to estimate the influence of formulation parameters (nanocapsules and silica concentrations) and process variables (inlet temperature, spray-flow air, feed flow rate and drying air flow rate) on spray-dried nanocapsules when using silica as drying auxiliary agent. The interactions among the formulation parameters and process variables were also studied. Responses analyzed for computing these effects and interactions were outlet temperature, moisture content, operation yield, particles size, and particulate density. Additional qualitative responses (particles morphology, powder behavior) were also considered. Nanocapsules and silica concentrations were the main factors influencing the yield, particulate density and particle size. In addition, they were concerned for the only significant interactions occurring among two different variables. None of the studied variables had major effect on the moisture content while the interaction between nanocapsules and silica in the feed was of first interest and determinant for both the qualitative and quantitative responses. The particles morphology depended on the feed formulation but was unaffected by the process conditions. This study demonstrated that drying nanocapsules using silica as auxiliary agent by spray drying process enables the obtaining of dried micronic particle size. The optimization of the process and the formulation variables resulted in a considerable improvement of product yield while minimizing the moisture content.

  4. Sonochemical coating of magnetite nanoparticles with silica.

    Science.gov (United States)

    Dang, Feng; Enomoto, Naoya; Hojo, Junichi; Enpuku, Keiji

    2010-01-01

    Magnetite nanoparticles were coated with silica through the hydrolysis and condensation of tetraethyl orthosilicate (TEOS) under ultrasonic irradiation. The ultrasonic irradiation was used to prevent the agglomeration of the magnetite particles and accelerate the hydrolysis and condensation of TEOS. TEM, DLS, XRF, VSM, TG and sedimentation test were used to characterize the silica-coated magnetite particles. The dispersibility of silica-coated magnetite particles in aqueous solution was improved significantly and the agglomerate particle size was decreased to 110 nm. It was found that the agglomerate particle size of silica-coated magnetite particles was mainly decided by the coating temperature and the pH value in the silica-coating process. The weight ratio of silica in silica-coated magnetite particles was mainly decided by the pH value in the silica-coating process. The dispersibility of silica-coated magnetite particles was mainly decided by the agglomerate particle size of the suspension. The oxidation of magnetite particles in air was limited through the coated silica. The magnetism of silica-coated magnetite particles decreased slightly after silica-coating.

  5. [(≢SiO)TaVCl2Me2]: A well-defined silica-supported tantalum(V) surface complex as catalyst precursor for the selective cocatalyst-free trimerization of ethylene

    KAUST Repository

    Chen, Yin; Callens, Emmanuel; Abou-Hamad, Edy; Merle, Nicolas; White, Andrew J P; Taoufik, Mostafa; Copé ret, Christophe; Le Roux, Erwan; Basset, Jean-Marie

    2012-01-01

    On the surface of it: In the absence of co-catalyst, a well-defined silica-supported surface organometallic complex [(≢SiO)Ta VCl2Me2] selectively catalyzes the oligomerization of ethylene. The use of surface organometallic species allows three different pathways to be determined for the reduction of TaV to TaIII species under pressure of ethylene. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. [(≢SiO)TaVCl2Me2]: A well-defined silica-supported tantalum(V) surface complex as catalyst precursor for the selective cocatalyst-free trimerization of ethylene

    KAUST Repository

    Chen, Yin

    2012-10-22

    On the surface of it: In the absence of co-catalyst, a well-defined silica-supported surface organometallic complex [(≢SiO)Ta VCl2Me2] selectively catalyzes the oligomerization of ethylene. The use of surface organometallic species allows three different pathways to be determined for the reduction of TaV to TaIII species under pressure of ethylene. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Selective Oxidation of Cyclohexene, Toluene and Ethyl Benzene Catalyzed by Bis-(L-tyrosinatocopper(II, Immersed in a Magnetite-Infused Silica Matrix

    Directory of Open Access Journals (Sweden)

    Massomeh Ghorbanloo

    2016-01-01

    Full Text Available Bis-(L-tyrosinatocopper(II was reacted with 3-(chloropropyl-trimethoxysilane functionalized silica that has infused magnetite to yield a magnetically separable catalyst in which the copper carboxylate is covalently linked to the silica matrix through the silane linkage. The immobilized catalyst has been characterized by spectroscopic studies (such as FT-IR, EPR, Magnetic Measurement, SEM and chemical analyses. The immobilized catalytic system functions as an efficient heterogeneous catalyst for oxidation of cyclohexene, toluene and ethyl benzene in the presence of hydrogen peroxide (as an oxidant and sodium bicarbonate (a co-catalyst. The reaction conditions have been optimized for solvent, temperature and amount of oxidant and catalyst. Comparison of the encapsulated catalyst with the corresponding homogeneous catalyst showed that the heterogeneous catalyst had higher activity and selectivity than the homogeneous catalyst. The immobilized catalyst could be readily recovered from the reaction mixture by using a simple magnet, and  reused up to five times without any loss of activity.

  8. Facile Synthesis of Well-Defined MDMO-PPV Containing (TriBlock—Copolymers via Controlled Radical Polymerization and CuAAC Conjugation

    Directory of Open Access Journals (Sweden)

    Neomy Zaquen

    2015-02-01

    Full Text Available A systematic investigation into the chain transfer polymerization of the so-called radical precursor polymerization of poly(p-phenylene vinylene (PPV materials is presented. Polymerizations are characterized by systematic variation of chain transfer agent (CTA concentration and reaction temperature. For the chain transfer constant, a negative activation energy of −12.8 kJ·mol−1 was deduced. Good control over molecular weight is achieved for both the sulfinyl and the dithiocarbamate route (DTC. PPVs with molecular weights ranging from thousands to ten thousands g·mol−1 were obtained. To allow for a meaningful analysis of the CTA influence, Mark–Houwink–Kuhn–Sakurada (MHKS parameters were determined for conjugated MDMO-PPV ([2-methoxy-5-(3',7'-dimethyloctyloxy]-1,4-phenylenevinylene to α = 0.809 and k = 0.00002 mL·g−1. Further, high-endgroup fidelity of the CBr4-derived PPVs was proven via chain extension experiments. MDMO-PPV-Br was successfully used as macroinitiator in atom transfer radical polymerization (ATRP with acrylates and styrene. A more polar PPV counterpart was chain extended by an acrylate in single-electron transfer living radical polymerization (SET-LRP. In a last step, copper-catalyzed azide alkyne cycloaddition (CuAAC was used to synthesize block copolymer structures. Direct azidation followed by macromolecular conjugation showed only partial success, while the successive chain extension via ATRP followed by CuAAC afforded triblock copolymers of the poly(p-phenylene vinylene-block-poly(tert-butyl acrylate-block-poly(ethylene glycol (PPV-b-PtBuA-b-PEG.

  9. Direct Production of Silicones From Sand

    Energy Technology Data Exchange (ETDEWEB)

    Larry N. Lewis; F.J. Schattenmann: J.P. Lemmon

    2001-09-30

    Silicon, in the form of silica and silicates, is the second most abundant element in the earth's crust. However the synthesis of silicones (scheme 1) and almost all organosilicon chemistry is only accessible through elemental silicon. Silicon dioxide (sand or quartz) is converted to chemical-grade elemental silicon in an energy intensive reduction process, a result of the exceptional thermodynamic stability of silica. Then, the silicon is reacted with methyl chloride to give a mixture of methylchlorosilanes catalyzed by cooper containing a variety of tract metals such as tin, zinc etc. The so-called direct process was first discovered at GE in 1940. The methylchlorosilanes are distilled to purify and separate the major reaction components, the most important of which is dimethyldichlorosilane. Polymerization of dimethyldichlorosilane by controlled hydrolysis results in the formation of silicone polymers. Worldwide, the silicones industry produces about 1.3 billion pounds of the basic silicon polymer, polydimethylsiloxane.

  10. Radiation chemistry of polymeric system

    International Nuclear Information System (INIS)

    Machi, Sueo; Ishigaki, Isao

    1978-01-01

    Among wide application of radiation in the field of polymer chemistry, practices of polymerization, graft polymerization, bridging, etc. are introduced hereinafter. As for the radiation sources of radiation polymerization, in addition to the 60 Co-γ ray with long permeation distance which has been usually applied, electron beam accelerators with high energy, large current and high reliability have come to be produced, and the liquid phase polymerization by electron beam has attracted attention industrially. Concerning polymerizing reactions, explanations were given to electron beam polymerization under high dose rate, the polymerization in supercooling state or under high pressure, and emulsifying polymerization. As for radiation bridging, radiation is applied for the bridging of hydrogel, acceleration of bridging and improvement of radiation resistance. It is also utilized for reforming membranes by graft polymerization, and synthesis of polymers for medical use. Application of fixed enzymes in the medical field has been investigated by fixing various enzymes by low temperature γ-ray polymerization with glassy monomers such as HEMA. (Kobatake, H.)

  11. Polyacrolein/mesoporous silica nanocomposite: Synthesis, thermal stability and covalent lipase immobilization

    Energy Technology Data Exchange (ETDEWEB)

    Motevalizadeh, Seyed Farshad; Khoobi, Mehdi; Shabanian, Meisam [Department of Medicinal Chemistry, Faculty of Pharmacy and Pharmaceutical Sciences Research Center, Tehran University of Medical Sciences, Tehran 14176 (Iran, Islamic Republic of); Asadgol, Zahra; Faramarzi, Mohammad Ali [Department of Pharmaceutical Biotechnology, Faculty of Pharmacy and Biotechnology Research Center, Tehran University of Medical Sciences, P.O. Box 14155-6451, Tehran 14176 (Iran, Islamic Republic of); Shafiee, Abbas, E-mail: ashafiee@ams.ac.ir [Department of Medicinal Chemistry, Faculty of Pharmacy and Pharmaceutical Sciences Research Center, Tehran University of Medical Sciences, Tehran 14176 (Iran, Islamic Republic of); Center of Excellence in Biothermodynamics, University of Tehran, Tehran (Iran, Islamic Republic of)

    2013-12-16

    In this work, new polyacrolein/MCM-41 nanocomposites with good phase mixing behavior were prepared through an emulsion polymerization technique. Mesoporous silica was synthesized by in situ assembly of tetraethyl orthosilicate (TEOS) and cetyl trimethyl ammonium bromide (CTAB). The structure and properties of polyacrolein containing nanosized MCM-41 particle (5 and 10 wt%), were investigated by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction, Dynamic light scattering (DLS), scanning electron microscopy (SEM), transmission electron microscopy (TEM), N{sub 2} adsorption techniques, and thermogravimetric (TGA) analyses. The SEM images from the final powder have revealed good dispersion of the MCM-41 nanoparticles throughout polymeric matrix with no distinct voids between two phases. The results indicated that the thermal properties of the nanocomposite were enhanced by addition of MCM-41. Thermomyces lanuginosa lipase (TLL) was used as a model biocatalyst and successfully immobilized with polyacrolein and the nanocomposite via covalent bonds with the aldehyde groups. The activity between free enzyme, polyacrolein, and MCM-41 nanocomposite (10 wt%)-immobilized TLL was compared. The immobilized lipase with the nanocomposite shows better operational stability such as pH tolerance, thermal and storage stability. In addition, the immobilized lipase with the nanocomposite can be easily recovered and retained at 74% of its initial activity after 15 time reuses. - Graphical abstract: The influence of incorporation of mesoporous MCM-41 nanoparticle with polyacrolein on the thermal properties and enzyme immobilization was investigated. - Highlights: • Polyacrolein/MCM-41 nanocomposites were prepared by emulsion polymerization method. • Thermal stability and char residues in nanocomposites were improved. • Nanocomposites significant effects on immobilization of lipase.

  12. Synthesis and characterization of branched polymers from lipase-catalyzed trimethylolpropane copolymerizations.

    Science.gov (United States)

    Kulshrestha, Ankur S; Gao, Wei; Fu, Hongyong; Gross, Richard A

    2007-06-01

    Lipase-catalyzed terpolymerizations were performed with the monomers trimethylolpropane (B3), 1,8-octanediol (B2), and adipic acid (A2). Polymerizations were performed in bulk, at 70 degrees C, for 42 h, using immobilized lipase B from Candida antartica (Novozyme-435) as a catalyst. To determine the substitution pattern of trimethylolpropane (TMP) in copolymers, model compounds with variable degrees of acetylation were synthesized. Inverse-gated 13C NMR spectra were recorded to first determine the chemical shift positions for mono-, di-, and trisubstituted TMP units and, subsequently, to determine substitution of TMP units along chains. Variation of TMP in the monomer feed gave copolymers with degrees of branching (DB) from 20% to 67%. In one example, a hyperbranched copolyester with 53 mol % TMP adipate units was formed in 80% yield, with Mw 14 100 (relative to polystyrene standards), Mw/Mn 5.3, and DB 36%. Thermal and crystalline properties of the copolyesters were studied by thermogravimetric analysis and differential scanning calorimetry.

  13. Microrheology of polymeric solutions using x-ray photon correlation spectroscopy

    International Nuclear Information System (INIS)

    Papagiannopoulos, A; Waigh, T A; Fluerasu, A; Fernyhough, C; Madsen, A

    2005-01-01

    We demonstrate the technique of XPCS microrheology on opaque polymeric solutions (1-20% w/w) using colloidal silica probes. The short time decay of the intensity correlation function provides the mean square displacement (MSD) of the colloidal probes. The MSDs of the probes are subsequently transformed using the generalized Stokes-Einstein equation, allowing the linear viscoelastic spectra of a biopolymer (gellan) and a synthetic polyelectrolyte (polystyrene sulfonate, PSS) to be calculated over two decades of frequency. MSDs can be measured that are two orders of magnitude smaller than those possible with video particle tracking microrheology, with a sensitivity of ∼10 nm s -1 for displacements of ∼nms. The XPCS data for water, glycerol and PSS combs are in agreement with video particle tracking microrheology experiments performed at lower polymer concentrations. (letter to the editor)

  14. Silica reinforced triblock copolymer gels

    DEFF Research Database (Denmark)

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

    2004-01-01

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

  15. Effect of silica concentration on electrical conductivity of epoxy resin-carbon black-silica nanocomposites

    International Nuclear Information System (INIS)

    Zhang Wei; Blackburn, Richard S.; Dehghani-Sanij, Abbas A.

    2007-01-01

    Electrical properties of nanocomposites are determined by the conductive paths of carbon black and influenced by a 'network' of silica. With increasing content of silica, carbon black (CB) particles are optimally dispersed, contributing to the generation of a conductive network between CB particles via direct particle contact and a tunneling effect; maximum conductivity for the epoxy resin-CB-silica nanocomposite described herein occurs at a ratio of 0.6:1.0 (SiO 2 :CB). As a non-conductive component, excessive silica will prevent electron flow, giving rise to low conductivity

  16. Thermodynamics of Enzyme-Catalyzed Reactions Database

    Science.gov (United States)

    SRD 74 Thermodynamics of Enzyme-Catalyzed Reactions Database (Web, free access)   The Thermodynamics of Enzyme-Catalyzed Reactions Database contains thermodynamic data on enzyme-catalyzed reactions that have been recently published in the Journal of Physical and Chemical Reference Data (JPCRD). For each reaction the following information is provided: the reference for the data, the reaction studied, the name of the enzyme used and its Enzyme Commission number, the method of measurement, the data and an evaluation thereof.

  17. Silica particles and method of preparation thereof

    NARCIS (Netherlands)

    2015-01-01

    The invention is in the field of silica products. More in particular, the invention is in the field of amorphous silica particles. The invention is directed to amorphous silica particles and related products including clusters of said silica particles, a suspension of said silica particles, and an

  18. Evidence for an RNA polymerization activity in axolotl and Xenopus egg extracts.

    Directory of Open Access Journals (Sweden)

    Hélène Pelczar

    2010-12-01

    Full Text Available We have previously reported a post-transcriptional RNA amplification observed in vivo following injection of in vitro synthesized transcripts into axolotl oocytes, unfertilized (UFE or fertilized eggs. To further characterize this phenomenon, low speed extracts (LSE from axolotl and Xenopus UFE were prepared and tested in an RNA polymerization assay. The major conclusions are: i the amphibian extracts catalyze the incorporation of radioactive ribonucleotide in RNase but not DNase sensitive products showing that these products correspond to RNA; ii the phenomenon is resistant to α-amanitin, an inhibitor of RNA polymerases II and III and to cordycepin (3'dAMP, but sensitive to cordycepin 5'-triphosphate, an RNA elongation inhibitor, which supports the existence of an RNA polymerase activity different from polymerases II and III; the detection of radiolabelled RNA comigrating at the same length as the exogenous transcript added to the extracts allowed us to show that iii the RNA polymerization is not a 3' end labelling and that iv the radiolabelled RNA is single rather than double stranded. In vitro cell-free systems derived from amphibian UFE therefore validate our previous in vivo results hypothesizing the existence of an evolutionary conserved enzymatic activity with the properties of an RNA dependent RNA polymerase (RdRp.

  19. Up-converter nanophosphor Y2O2S:Er,Yb aminofunctionalized containing or not spherical silica conjugated with BSA

    International Nuclear Information System (INIS)

    Gelamos, Joao Paulo; Laranja, Marlon Larry; Alvino, Karla Cristina Lombardi; Camacho, Sabrina Alessio; Pires, Ana Maria

    2009-01-01

    This work reports on the study of the nanophosphor Y 2 O 2 S:Er(2%),Yb(1%) obtained from polymeric resin to be evaluated as fluorescent label with suitable features to conjugate with bio-molecules for bioassay up-converting phosphor technology (UPT) application. A conjugation protocol between bovine serum albumin (BSA) and the aminofunctionalized nanophosphor containing or not spherical silica was established. UV-vis results indicated an effective conjugation between nanophosphor particles and the protein. Up-conversion measurements under 980 nm excitation performed for samples before and after aminofunctionalization showed that nanophosphor particles luminescence features keep unchanged in all cases. All results suggest that the adapted protocol is feasible to provide a nanoparticle-protein effective conjugation preserving nanophosphor optical features. The presence of spherical silica can be considered advantageous to increase conjugation efficiency. Therefore, the developed procedure is applicable for future conjugations between the chosen nanophosphor and the streptavidin protein that takes part in the well known self-recognition system avidin-biotin.

  20. Solid phase extraction of penicillins from milk by using sacrificial silica beads as a support for a molecular imprint

    International Nuclear Information System (INIS)

    Giovannoli, Cristina; Anfossi, Laura; Biagioli, Flavia; Passini, Cinzia; Baggiani, Claudio

    2013-01-01

    We have prepared molecularly imprinted beads with molecular recognition capability for target molecules containing the penicillanic acid substructure. They were prepared by (a) grafting mesoporous silica beads with 6-aminopenicillanic acid as the mimic template, (b) filling the pores with a polymerized mixture of methacrylic acid and trimethylolpropane trimethacrylate, and (c) removing the silica support with ammonium fluoride. The resulting imprinted beads showed good molecular recognition capability for various penicillanic species, while antibiotics such as cephalosporins or chloramphenicol were poorly recognized. The imprinted beads were used to extract penicillin V, nafcillin, oxacillin, cloxacillin and dicloxacillin from skimmed and deproteinized milk in the concentration range of 5–100 μg·L −1 . The extracts were then analyzed by micellar electrokinetic chromatography by applying reverse polarity staking as an in-capillary preconcentration step, and this resulted in a fast and affordable method within the MRL levels, characterized by minimal pretreatment steps and recoveries of 64–90 %. (author)

  1. Thermo-stabilized, porous polyimide microspheres prepared from nanosized SiO2 templating via in situ polymerization

    Directory of Open Access Journals (Sweden)

    M. Q. Liu

    2015-01-01

    Full Text Available In this article, we addressed a feasible and versatile method of the fabrication of porous polyimide microspheres presenting excellent heat resistance. The preparation process consisted of two steps. Firstly, a novel polyimide/nano-silica composite microsphere was prepared via the self-assembly structures of poly(amic acid (PAA, precursor of PI/nanosized SiO2 blends after in situ polymerization, following the two-steps imidization. Subsequently, the encapsulated nanoparticles were etched away by hydrofluoric acid treatment, giving rise to the pores. It is found the composite structure of PI/SiO2 is a precondition of the formation of nanoporous structures, furthermore, the morphology of the resultant pore could be relatively tuned by changing the content and initial morphology of silica nano-particles trapped into PI matrix. The thermal properties of the synthesized PI porous spheres were studied, indicating that the introduction of nanopores could not effectively influence the thermal stabilities of PI microspheres. Moreover, the fabrication technique described here may be extended to other porous polymer systems.

  2. Enhancing the muon-catalyzed fusion yield

    International Nuclear Information System (INIS)

    Jones, S.E.

    1987-01-01

    Much has been learned about muon-catalyzed fusion since the last conference on emerging nuclear energy systems. Here the authors consider what they have learned about enhancing the muon-catalyzed fusion energy yield

  3. Twin screw extruders as polymerization reactors for a free radical homo polymerization

    NARCIS (Netherlands)

    Ganzeveld, K.J.; Janssen, L.P.B.M.

    The bulk polymerization of n-butylmethacrylate was investigated in a counter-rotating twin screw extruder. It appeared that the gel effect, occurring with bulk polymerizations, affected the polymerization progress very strongly. Due to this effect the conversion of the reaction is independent of the

  4. COOH-functionalisation of silica particles

    Energy Technology Data Exchange (ETDEWEB)

    Majewski, Peter, E-mail: peter.majewski@unisa.edu.au [School of Advanced Manufacturing and Mechanical Engineering, Mawson Institute, University of South Australia, Adelaide (Australia); Albrecht, Trent [Ian Wark Research Institute, University of South Australia, Adelaide (Australia); Weber, Siegfried [Department of Biotechnology, University of Applied Sciences, Mannheim (Germany)

    2011-09-01

    In this study COOH-functionalised silica is synthesised using phosphonateN-(phosphonomethyl)iminodiacetic acid (PMIDA) in an aqueous solution. The presence of PMIDA on the silica particles was verified using Fourier Transform Infrared Spectroscopy, X-ray Photoelectron Spectroscopy and titration. Experimentally, surface concentrations of COOH functional groups of up to about 3 mmol/g{sub silica} were achieved, whereas theoretical calculation of the maximum COOH functional group concentration gave about 1 mmol/g{sub silica}. The discrepancy may be caused by PMIDA multilayer formation on the particle.

  5. Mechanocatalytic polymerization and cross-linking in a polymeric matrix

    NARCIS (Netherlands)

    Jakobs, R.T.M.; Ma, Shuang; Sijbesma, R.P.

    2013-01-01

    A latent olefin metathesis catalyst, bearing two polymeric NHC ligands, was embedded in a semicrystalline polymer matrix containing cyclic olefins. The catalyst was activated by straining the solid material under compression, resulting in polymerization and cross-linking reactions of the monomers in

  6. A kinetic mechanistic study of acid-catalyzed alkylation of isobutane with C4-olefins at low temperatures

    Energy Technology Data Exchange (ETDEWEB)

    Doshi, B.M.

    1978-01-01

    A kinetic and mechanistic study of sulfuric acid-catalyzed alkylation of isobutane with C/sub 4/-Olefins at Low Temperatures(-20/sup 0/ to 0/sup 0/C) was based on a new two-step reaction sequence in which the desired first-step reactions are between acid and olefin to form sulfates and the desired second-step reactions are between sulfates and isobutane to form mostly trimethylpentanes. Linear butenes formed stable sulfates that formed alkylates of exceptionally high quality, up to 100 Research octane, whereas isobutylene and trimethylpentene mainly polymerized during the first step, and the alkylate produced had only 90 Research octane. Trimethylpentanes and dimethylhexanes, when contacted with concentrated sulfuric acid at -10/sup 0/ to +25/sup 0/C, degraded and isomerized to form C/sub 4/-C/sub 9/ and higher isoparaffins and acid-soluble hydrocarbons (conjunct polymers). For the two-step process and the degradation and isomerization reactions, kinetic models based on reaction at the interface were developed; but for isoolefins, a polymerization-cracking sequence (via C/sub 12/- and even C/sub 16/-olefins) is the preferred route. Commercial applications of the results are proposed.

  7. Characterization of alkali silica reaction gels using Raman spectroscopy

    International Nuclear Information System (INIS)

    Balachandran, C.; Muñoz, J.F.; Arnold, T.

    2017-01-01

    The ability of Raman spectroscopy to characterize amorphous materials makes this technique ideal to study alkali silica reaction (ASR) gels. The structure of several synthetic ASR gels was thoroughly characterized using Raman Spectroscopy. The results were validated with additional techniques such as Fourier transmission infrared spectroscopy, X-ray powder diffraction and thermogravimetric analysis. The Raman spectra were found to have two broad bands in the 800 to 1200 cm −1 range and the 400 to 700 cm −1 range indicating the amorphous nature of the gel. Important information regarding the silicate polymerization was deduced from both of these spectral regions. An increase in alkali content of the gels caused a depolymerization in the silicate framework which manifested in the Raman spectra as a gradual shift of predominant peaks in both regions. The trends in silicate depolymerization were in agreement with results from a NMR spectroscopy study on similar synthetic ASR gels.

  8. Unraveling the role of entropy in tuning unimolecular vs . bimolecular reaction rates: The case of olefin polymerization catalyzed by transition metals

    KAUST Repository

    Falivene, Laura; Barone, Vincenzo; Talarico, Giovanni

    2018-01-01

    by different ligand frameworks, metal, and growing polymeric chain for which experimental data are available have been selected in order to validate the main approaches to entropy calculation. Applying the “standard” protocol results in a strong disagreement

  9. Additional Nucleophile-Free FeCl3-Catalyzed Green Deprotection of 2,4-Dimethoxyphenylmethyl-Protected Alcohols and Carboxylic Acids.

    Science.gov (United States)

    Sawama, Yoshinari; Masuda, Masahiro; Honda, Akie; Yokoyama, Hiroki; Park, Kwihwan; Yasukawa, Naoki; Monguchi, Yasunari; Sajiki, Hironao

    2016-01-01

    The deprotection of the methoxyphenylmethyl (MPM) ether and ester derivatives can be generally achieved by the combinatorial use of a catalytic Lewis acid and stoichiometric nucleophile. The deprotections of 2,4-dimethoxyphenylmethyl (DMPM)-protected alcohols and carboxylic acids were found to be effectively catalyzed by iron(III) chloride without any additional nucleophile to form the deprotected mother alcohols and carboxylic acids in excellent yields. Since the present deprotection proceeds via the self-assembling mechanism of the 2,4-DMPM protective group itself to give the hardly-soluble resorcinarene derivative as a precipitate, the rigorous purification process by silica-gel column chromatography was unnecessary and the sufficiently-pure alcohols and carboxylic acids were easily obtained in satisfactory yields after simple filtration.

  10. Chelating polymeric membranes

    KAUST Repository

    Peinemann, Klaus-Viktor; Villalobos Vazquez de la Parra, Luis Francisco; Hilke, Roland

    2015-01-01

    microporous chelating polymeric membrane. Embodiments include, but are not limited to, microporous chelating polymeric membranes, device comprising the membranes, and methods of using and making the same.

  11. Silica aerogel Cerenkov counter

    International Nuclear Information System (INIS)

    Yasumi, S.; Masaike, A.; Yamamoto, A.; Yoshimura, Y.; Kawai, H.

    1984-03-01

    In order to obtain silica aerogel radiators of good quality, the prescription used by Saclay group has been developed. We have done several experiments using beams from KEK.PS to test the performance of a Cerenkov counter with aerogel modules produced in KEK. It turned out that these modules had excellent quality. The production rate of silica aerogel in KEK is 15 -- 20 litres a week. Silica aerogel modules of 20 x 10 x 3 cm 3 having the refractive index of 1.058 are successfully being used by Kyoto University group in the KEK experiment E92 (Σ). Methodes to produce silica aerogel with higher refractive index than 1.06 has been investigated both by heating an module with the refractive index of 1.06 and by hydrolyzing tetraethyl silicate. (author)

  12. Melt flow and mechanical properties of silica/perfluoropolymer nanocomposites Fabricated by direct melt-compounding without surface modification on nano-silica.

    Science.gov (United States)

    Tanahashi, Mitsuru; Watanabe, Yusuke; Lee, Jeong-Chang; Takeda, Kunihiko; Fujisawa, Toshiharu

    2009-01-01

    The authors have previously developed a novel method for the fabrication of silica/perfluoropolymer nanocomposites, wherein nano-sized silica particles without surface modification were dispersed uniformly through breakdown of loosely packed agglomerates of silica nanoparticles with low fracture strength in a polymer melt during direct melt-compounding. The method consists of two stages; the first stage involves preparation of the loose silica agglomerate, and the second stage involves melt-compounding of a completely hydrophobic perfluoropolymer, PFA (poly(tetrafluoroethylene-co-perfluoropropylvinylether)), with the loose silica agglomerates. By using this simple method without any lipophilic treatment of the silica surfaces, silica nanoparticles with a primary diameter of 190 nm could be dispersed uniformly into the PFA matrix. The main purpose of the present study is to evaluate the melt flow and tensile properties of silica/PFA nanocomposites fabricated by the above method. In order to elucidate the effects of the size of the dispersed silica in the PFA matrix on the properties of the composites, silica/PFA composite samples exhibiting the dispersion of larger-sized silica particle-clusters were fabricated as negative controls of the silica dispersion state. The results obtained under the present experimental conditions showed that the size of the dispersed silica in the PFA matrix exerts a strong influence on the ultimate tensile properties, such as tensile strength and elongation at break, and the melt flow rate (MFR) of the composite materials. The MFR of the silica/PFA nanocomposite became higher than that of the pure PFA without silica addition, although the MFR of the PFA composites containing larger silica particle-clusters became much lower than that of the pure PFA. Furthermore, uniform dispersion of isolated silica nanoparticles was found to improve not only the Young's modulus but also the ultimate tensile properties of the composite.

  13. Olefin polymerization from single site catalysts confined within porous media

    Science.gov (United States)

    Kasi, Rajeswari M.

    Single Site Catalysts (SSCs) have been utilized for olefin polymerization. Altering the metal-ligand architecture in the SSCs, polyolefin properties can be enhanced in a rational manner. This influence of the ligands in the SSC on the property of polyolefins prepared can be referred to as the primary ligand influence. Extending this understanding and subsequent control of the metal-ligand framework to the interaction of SSCs within organic and inorganic supports is vital for the synthesis of polyolefins with tailored properties. The motivation behind this thesis was to explore the support influence on the reactivity of the SSC tethered to a support matrix during ethylene homo and copolymerization. In order to address this question of the support influence on the final polyolefin properties, synthetic routes to covalently bind SSCs on different matrices have been explored. Two distinct supported SSCs have been used to prepare branched polyethylenes. Branched polyethylenes can be prepared by either copolymerization (ethylene and alpha-olefin) or oligomerization/copolymerization processes (ethylene and in situ generated alpha-olefin). Synthetic routes to prepare precursor catalysts to Constrained Geometry Catalysts (CGCs) by silyl elimination chemistry have been developed (Chapter 2). Efficient synthetic protocols to assemble CGCs on aminomethylpolysytrene matrices (Chapter 3) and amine-functionalized mesoporous silica (Chapter 4) are also reported. These supported catalysts, with appropriate cocatalysts have been used to prepare ethylene homo and copolymers, the polymer thermal properties and microstructures were analyzed by various analytical techniques. Branched polyethylenes (LLDPE) can be prepared by copolymerization chemistry. It has been observed is that the influence of the support is seen in the production of lower crystalline forms of high density polyethylene (HDPE, 20--50% crystalline), while homogeneous polymerization of analogous soluble CGCs afford HDPE

  14. Multifunctional nanomedicine with silica: Role of silica in nanoparticles for theranostic, imaging, and drug monitoring.

    Science.gov (United States)

    Chen, Fang; Hableel, Ghanim; Zhao, Eric Ruike; Jokerst, Jesse V

    2018-07-01

    The idea of multifunctional nanomedicine that enters the human body to diagnose and treat disease without major surgery is a long-standing dream of nanomaterials scientists. Nanomaterials show incredible properties that are not found in bulk materials, but achieving multi-functionality on a single material remains challenging. Integrating several types of materials at the nano-scale is critical to the success of multifunctional nanomedicine device. Here, we describe the advantages of silica nanoparticles as a tool for multifunctional nano-devices. Silica nanoparticles have been intensively studied in drug delivery due to their biocompatibility, degradability, tunable morphology, and ease of modification. Moreover, silica nanoparticles can be integrated with other materials to obtain more features and achieve theranostic capabilities and multimodality for imaging applications. In this review, we will first compare the properties of silica nanoparticles with other well-known nanomaterials for bio-applications and describe typical routes to synthesize and integrate silica nanoparticles. We will then highlight theranostic and multimodal imaging application that use silica-based nanoparticles with a particular interest in real-time monitoring of therapeutic molecules. Finally, we will present the challenges and perspective on future work with silica-based nanoparticles in medicine. Copyright © 2018 Elsevier Inc. All rights reserved.

  15. Rh-catalyzed linear hydroformylation of styrene

    NARCIS (Netherlands)

    Boymans, E.H.; Janssen, M.C.C.; Mueller, C.; Lutz, M.; Vogt, D.

    2012-01-01

    Usually the Rh-catalyzed hydroformylation of styrene predominantly yields the branched, chiral aldehyde. An inversion of regioselectivity can be achieved using strong p-acceptor ligands. Binaphthol-based diphosphite and bis(dipyrrolyl-phosphorodiamidite) ligands were applied in the Rh-catalyzed

  16. Synthesis and Characterization of Poly (styrene-co-butyl acrylate)/Silica Aerogel Nanocomposites by in situ AGET ATRP: Investigating Thermal Properties

    Science.gov (United States)

    Khezri, Khezrollah; Fazli, Yousef

    2017-10-01

    Hydrophilic silica aerogel nanoparticles surface was modified with hexamethyldisilazane. Then, the resultant modified nanoparticles were used in random copolymerization of styrene and butyl acrylate via activators generated by electron transfer for atom transfer radical polymerization. Conversion and molecular weight determinations were performed using gas and size exclusion chromatography respectively. Addition of modified nanoparticles by 3 wt% results in a decrease of conversion from 68 to 46 %. Molecular weight of copolymer chains decreases from 12,500 to 7,500 g.mol-1 by addition of 3 wt% modified nanoparticles; however, PDI values increase from 1.1 to 1.4. Proton nuclear magnetic resonance spectroscopy results indicate that the molar ratio of each monomer in the copolymer chains is approximately similar to the initial selected mole ratio of them. Increasing thermal stability of the nanocomposites is demonstrated by thermal gravimetric analysis. Differential scanning calorimetry also shows a decrease in glass transition temperature by increasing modified silica aerogel nanoparticles.

  17. Effect of the Polymeric Stabilizer in the Aqueous Phase Fischer-Tropsch Synthesis Catalyzed by Colloidal Cobalt Nanocatalysts

    Directory of Open Access Journals (Sweden)

    Jorge A. Delgado

    2017-03-01

    Full Text Available A series of small and well defined cobalt nanoparticles were synthesized by the chemical reduction of cobalt salts in water using NaBH4 as a reducing agent and using various polymeric stabilizers. The obtained nanocatalysts of similar mean diameters (ca. 2.6 nm were fully characterized and tested in the aqueous phase Fischer-Tropsch Synthesis (AFTS. Interestingly, the nature and structure of the stabilizers used during the synthesis of the CoNPs affected the reduction degree of cobalt and the B-doping of these NPs and consequently, influenced the performance of these nanocatalysts in AFTS.

  18. Study of the pluronic-silica interaction in synthesis of mesoporous silica under mild acidic conditions.

    Science.gov (United States)

    Sundblom, Andreas; Palmqvist, Anders E C; Holmberg, Krister

    2010-02-02

    The interaction between silica and poly(ethylene oxide) (PEO) in water may appear trivial and it is generally stated that hydrogen bonding is responsible for the attraction. However, a literature search shows that there is not a consensus with respect to the mechanism behind the attractive interaction. Several papers claim that only hydrogen bonding is not sufficient to explain the binding. The silica-PEO interaction is interesting from an academic perspective and it is also exploited in the preparation of mesoporous silica, a material of considerable current interest. This study concerns the very early stage of synthesis of mesoporous silica under mild acidic conditions, pH 2-5, and the aim is to shed light on the interaction between silica and the PEO-containing structure directing agent. The synthesis comprises two steps. An organic silica source, tetraethylorthosilicate (TEOS), is first hydrolyzed and Pluronic P123, a poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) block copolymer, is subsequently added at different time periods following the hydrolysis of TEOS. It is shown that the interaction between the silica and the Pluronic is dependent both on the temperature and on the time between onset of TEOS hydrolysis and addition of the copolymer. The results show that the interaction is mainly driven by entropy. The effect of the synthesis temperature and of the time between hydrolysis and addition of the copolymer on the final material is also studied. The material with the highest degree of mesoorder was obtained when the reaction was performed at 20 degrees C and the copolymer was added 40 h after the start of TEOS hydrolysis. It is claimed that the reason for the good ordering of the silica is that whereas particle formation under these conditions is fast, the rate of silica condensation is relatively low.

  19. Silica coatings on clarithromycin.

    Science.gov (United States)

    Bele, Marjan; Dmitrasinovic, Dorde; Planinsek, Odon; Salobir, Mateja; Srcic, Stane; Gaberscek, Miran; Jamnik, Janko

    2005-03-03

    Pre-crystallized clarithromycin (6-O-methylerythromycin A) particles were coated with silica from the tetraethyl orthosilicate (TEOS)-ethanol-aqueous ammonia system. The coatings had a typical thickness of 100-150 nm and presented about 15 wt.% of the silica-drug composite material. The properties of the coatings depended on reactant concentration, temperature and mixing rate and, in particular, on the presence of a cationic surfactant (cetylpyridinium chloride). In the presence of cetylpyridinium chloride the silica coatings slightly decreased the rate of pure clarithromycin dissolution.

  20. Oxygen configurations in silica

    International Nuclear Information System (INIS)

    Chelikowsky, James R.; Chadi, D. J.; Binggeli, N.

    2000-01-01

    We propose a transition state for oxygen in silica. This state is produced by the insertion of an oxygen molecule into the Si-O-Si bond, i.e., it consists of producing a Si-O-O-O-Si bond. This state allows molecular oxygen diffusion in silica without breaking the molecular O 2 bond and it is energetically more stable than a peroxy configuration. This configuration may allow for exchange of molecular oxygen with the oxygen in the silica framework. (c) 2000 The American Physical Society

  1. A facile FeBr3 based photoATRP for surface modification of mesoporous silica nanoparticles for controlled delivery cisplatin

    Science.gov (United States)

    Huang, Long; Liu, Meiying; Mao, Liucheng; Huang, Qiang; Huang, Hongye; Zeng, Guangjian; Tian, Jianwen; Wen, Yuanqing; Zhang, Xiaoyong; Wei, Yen

    2018-03-01

    Mesoporous silica nanoparticles (MSNs) should be one of the most important materials for biomedical application owing to their high specific surface area, regular porous structure, adjustable pore size and chemical inert. However, the biomedical applications of unmodified MSNs are largely impeded for their poor hydrophilicity and lack of functional groups. In this work, a novel photo-initiated atom transfer radical polymerization (ATRP) strategy has been reported for modified mesoporous silica nanoparticles (MSNs) with hydrophilicility copolymers using FeBr3 as the novel photocatalyst and itaconic acid (IA) and 2-methacryloyloxyethyl phosphorylcholine (MPC) as monomers. Because of the hydrophilicity and anticancer agent cis-dichlorodiamineplatinum(II) (CDDP) loading capacity of poly(MPC-co-IA), the controlled drug delivery applications MSNs-NH2-poly(MPC-co-IA) composites toward CDDP were further investigated. A series of characterization results demonstrated that MSNs-NH2-poly(MPC-co-IA) composites can be successfully fabricated through the novel photo-initiated ATRP. MSNs-NH2-poly(MPC-co-IA) composites showed obvious enhancement of water dispersibility, desirable biocompatibility, high drug loading capability, making them great potential for controlled drug delivery of CDDP. Moreover, as compared with the traditional ATRP, that using the transition metal ions and organic ligands as the catalysis systems in elevated temperature, our method provides a more facile, benign and cost-effective route for fabrication of multifunctional MSNs with great potential for biomedical applications. Finally, this FeBr3 based photoATRP strategy should be further extended for the fabrication of many other polymeric composites owing to its good monomer adoptability.

  2. The Effect of Various Acids to the Gelation Process to the Silica Gel Characteristic Using Organic Silica

    Science.gov (United States)

    Rahman, NA; Widiyastuti, W.; Sigit, D.; Ajiza, M.; Sujana, W.

    2018-01-01

    Bagasse ash is solid waste of cane sugar industry which contain of silica more than 51%. Some previous study of silica gel from bagasse ash have been conducted often and been applied. This study concerns about the effect of various acid used in the process of gelation to the characteristic of silica gel produced. Then, this silica gel will be used as adsorbent. As that, the silica gel must fulfill the requirements of adsorbent, as have good pores characteristics, fit in mesoporous size so that adsorbent diffusion process is not disturbed. A fitted pores size of silica gel can be prepared by managing acid concentration used. The effect of acid, organic acid (tartaric acid) and inorganic acid (hydrochloric acid), is investigated in detail. The acid is added into sodium silicate solution in that the gel is formed, the pores structures can be investigated with BET, the crystal form is analyzed with XRD and the pore structure is analyzed visually with SEM. By managing the acid concentration added, it gets the effect of acid to the pore structure of silica gel. The bigger concentration is, the bigger the pore’s size of silica gel produced.

  3. Size-dependent cytotoxicity and inflammatory responses of PEGylated silica-iron oxide nanocomposite size series

    Science.gov (United States)

    Injumpa, Wishulada; Ritprajak, Patcharee; Insin, Numpon

    2017-04-01

    Iron oxides nanoparticles have been utilized in biological systems and biomedical applications for many years because they are relatively safe and stable comparing to other magnetic nanomaterials. In some applications, iron oxide nanoparticles were modified with silica in order to be more stable in biological systems and able to be functionalized with various functional groups. Moreover, poly(ethylene glycol) (PEG) was one on the most used polymer to graft onto the nanoparticles in order to increase their biocompatibility, dispersibility and stability in aqueous solutions. Therefore, the nanocomposites comprising iron oxide nanoparticles, silica, and PEG could become multifunctional carriers combining superparamagnetic character, multi-functionality and high stability in biological environments. Herein, we reported the preparation of the nanocomposites and effects of their sizes on cytotoxicity and inflammatory responses. The PEGylated silica-iron oxide nanocomposites were prepared by coating of poly(poly(ethylene glycol) monomethyl ether methacrylate) (PPEGMA) on magnetic nanoparticle-silica nanocomposites via Atom Transfer Radical Polymerization (ATRP). The iron oxide nanoparticles were synthesized using a thermal decomposition method. The silica shells were then coated on iron oxides nanoparticles using reverse microemulsion and sol-gel methods. The size series of the nanocomposites with the diameter of 24.86±4.38, 45.24±5.00, 98.10±8.88 and 202.22±6.70 nm as measured using TEM were obtained. Thermogravimetric analysis (TGA) was used for the determination of % weight of PPEGMA on the nanocomposites showing the weight loss of ranging from 65% for smallest particles to 30% for largest particles. The various sizes (20, 40, 100, 200 nm) and concentrations (10, 100, 1000 μg/mL) of the nanocomposites were tested for their cytotoxicity in fibroblast and macrophage cell lines using MTT assay. The different sizes did not affect cell viability of fibroblast, albeit

  4. Living catalyzed-chain-growth polymerization and block copolymerization of isoprene by rare-earth metal allyl precursors bearing a constrained-geometry-conformation ligand.

    Science.gov (United States)

    Jian, Zhongbao; Cui, Dongmei; Hou, Zhaomin; Li, Xiaofang

    2010-05-07

    Aminophenyl functionalized cyclopentadienyl ligated rare-earth metal allyl mediated cationic systems display high cis-1,4 selectivity for the polymerization of isoprene, and living reversible and rapid chain transfer to aluminium additives.

  5. Preparation and characterization of hybrid Nafion/silica and Nafion/silica/PTA membranes for redox flow batteries

    Energy Technology Data Exchange (ETDEWEB)

    Glibin, V.; Pupkevich, V.; Svirko, L.; Karamanev, D. [Western Ontario Univ., London, ON (Canada). Dept. of Biochemical and Chemical Engineering

    2008-07-01

    Redox flow batteries are both efficient and cost-effective. However, the long-term stability of most ion-exchange membranes is limited as a result of the high oxidation rates of ions with high redox potentials. A method of synthesizing multi-component Nafion-silica and Nafion-silica-PTA membranes was presented in this study, which also investigated the electrochemical and ion transport properties of the membranes. Membranes were cast from dimethylformamide (DMFA) solution. The iron ion diffusion kinetics of the Nafion-silica and Nafion-silica PTA membranes were studied by dialysis. Results of the investigation demonstrated that the introduction of silica and phosphotungstic acid (PTA) into the Nafion membrane composition resulted in a significant decrease of ion transfer through the membrane. The addition of PTA also increased membrane permeability to ferric ions. The low iron diffusion coefficient and high ionic conductivity of the Nafion-silica membrane makes it a promising material for use in redox flow batteries. 4 refs., 1 tab., 1 fig.

  6. Silica-Coated Liposomes for Insulin Delivery

    Directory of Open Access Journals (Sweden)

    Neelam Dwivedi

    2010-01-01

    Full Text Available Liposomes coated with silica were explored as protein delivery vehicles for their enhanced stability and improved encapsulation efficiency. Insulin was encapsulated within the fluidic phosphatidylcholine lipid vesicles by thin film hydration at pH 2.5, and layer of silica was formed above lipid bilayer by acid catalysis. The presence of silica coating and encapsulated insulin was identified using confocal and electron microscopy. The native state of insulin present in the formulation was evident from Confocal Micro-Raman spectroscopy. Silica coat enhances the stability of insulin-loaded delivery vehicles. In vivo study shows that these silica coated formulations were biologically active in reducing glucose levels.

  7. Silica artificial opal incorporated with silver nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Li Wenjiang, E-mail: wjli@zju.edu.cn [Center for Optical and Electromagnetic Research, State Key Laboratory for Modern Optical Instrumentation, Zhejiang University, Joint Research Center of Photonics of the Royal Institute of Technology and Zhejiang University, Zijingang Campus, Room 210, East Building 5, Hangzhou 310058 (China); Sun Tan [Center for Optical and Electromagnetic Research, State Key Laboratory for Modern Optical Instrumentation, Zhejiang University, Joint Research Center of Photonics of the Royal Institute of Technology and Zhejiang University, Zijingang Campus, Room 210, East Building 5, Hangzhou 310058 (China)

    2009-07-15

    The silica artificial opal with a three-dimensional (3D) periodic structure was prepared using highly monodispersed silica microspheres by a force packing method in ITO glass cell. The silica artificial opal incorporated with silver nanoparticles was fabricated by the electroplating technique. The optical microscope images of the synthetic sample and the corresponding optical properties were measured after each treatment of electroplating-washing-drying circle. The transmission and reflection spectra presented a red shift, showing that the effective refractive index of the complex silver/silica opal increased after each electroplating. Combining the SEM images, it was seen that the silver nanoparticles could be directly deposited on the surface of silica spheres in the opaline structure. The silver/silica complex opal film could provide a simple way to tune the opal properties by controlling silver nanoparticles in the silica opal. The silver/silica opal crystal structures could be used for nano-photonic circuits, white-light LEDs or as photocatalysts.

  8. Silica artificial opal incorporated with silver nanoparticles

    International Nuclear Information System (INIS)

    Li Wenjiang; Sun Tan

    2009-01-01

    The silica artificial opal with a three-dimensional (3D) periodic structure was prepared using highly monodispersed silica microspheres by a force packing method in ITO glass cell. The silica artificial opal incorporated with silver nanoparticles was fabricated by the electroplating technique. The optical microscope images of the synthetic sample and the corresponding optical properties were measured after each treatment of electroplating-washing-drying circle. The transmission and reflection spectra presented a red shift, showing that the effective refractive index of the complex silver/silica opal increased after each electroplating. Combining the SEM images, it was seen that the silver nanoparticles could be directly deposited on the surface of silica spheres in the opaline structure. The silver/silica complex opal film could provide a simple way to tune the opal properties by controlling silver nanoparticles in the silica opal. The silver/silica opal crystal structures could be used for nano-photonic circuits, white-light LEDs or as photocatalysts.

  9. Silica nanoparticle stability in biological media revisited.

    Science.gov (United States)

    Yang, Seon-Ah; Choi, Sungmoon; Jeon, Seon Mi; Yu, Junhua

    2018-01-09

    The stability of silica nanostructure in the core-silica shell nanomaterials is critical to understanding the activity of these nanomaterials since the exposure of core materials due to the poor stability of silica may cause misinterpretation of experiments, but unfortunately reports on the stability of silica have been inconsistent. Here, we show that luminescent silver nanodots (AgNDs) can be used to monitor the stability of silica nanostructures. Though relatively stable in water and phosphate buffered saline, silica nanoparticles are eroded by biological media, leading to the exposure of AgNDs from AgND@SiO 2 nanoparticles and the quenching of nanodot luminescence. Our results reveal that a synergistic effect of organic compounds, particularly the amino groups, accelerates the erosion. Our work indicates that silica nanostructures are vulnerable to cellular medium and it may be possible to tune the release of drug molecules from silica-based drug delivery vehicles through controlled erosion.

  10. Thermally stable silica-coated hydrophobic gold nanoparticles.

    Science.gov (United States)

    Kanehara, Masayuki; Watanabe, Yuka; Teranishi, Toshiharu

    2009-01-01

    We have successfully developed a method for silica coating on hydrophobic dodecanethiol-protected Au nanoparticles with coating thickness ranging from 10 to 40 nm. The formation of silica-coated Au nanoparticles could be accomplished via the preparation of hydrophilic Au nanoparticle micelles by cationic surfactant encapsulation in aqueous phase, followed by hydrolysis of tetraethylorthosilicate on the hydrophilic surface of gold nanoparticle micelles. Silica-coated Au nanoparticles exhibited quite high thermal stability, that is, no agglomeration of the Au cores could be observed after annealing at 600 degrees C for 30 min. Silica-coated Au nanoparticles could serve as a template to derive hollow nanoparticles. An addition of NaCN solution to silica-coated Au nanoparticles led the formation of hollow silica nanoparticles, which were redispersible in deionized water. The formation of the hollow silica nanoparticles results from the mesoporous structures of the silica shell and such a mesoporous structure is applicable to both catalyst support and drug delivery.

  11. Double-Layer Surface Modification of Polyamide Denture Base Material by Functionalized Sol-Gel Based Silica for Adhesion Improvement.

    Science.gov (United States)

    Hafezeqoran, Ali; Koodaryan, Roodabeh

    2017-09-21

    Limited surface treatments have been proposed to improve the bond strength between autopolymerizing resin and polyamide denture base materials. Still, the bond strength of autopolymerizing resins to nylon polymer is not strong enough to repair the fractured denture effectively. This study aimed to introduce a novel method to improve the adhesion of autopolymerizing resin to polyamide polymer by a double layer deposition of sol-gel silica and N-2-(aminoethyl)-3-aminopropyltrimethoxysilane (AE-APTMS). The silica sol was synthesized by acid-catalyzed hydrolysis of tetraethylorthosilicate (TEOS) as silica precursors. Polyamide specimens were dipped in TEOS-derived sol (TS group, n = 28), and exposed to ultraviolet (UV) light under O 2 flow for 30 minutes. UV-treated specimens were immersed in AE-APTMS solution and left for 24 hours at room temperature. The other specimens were either immersed in AE-APTMS solution (AP group, n = 28) or left untreated (NT group, n = 28). Surface characterization was investigated by fourier transform infrared spectroscopy (FTIR) and atomic force microscopy (AFM). Two autopolymerizing resins (subgroups G and T, n = 14) were bonded to the specimens, thermocycled, and then tested for shear bond strength with a universal testing machine. Data were analyzed with one-way ANOVA followed by Tukey's HSD (α = 0.05). FTIR spectra of treated surfaces confirmed the chemical modification and appearance of functional groups on the polymer. One-way ANOVA revealed significant differences in shear bond strength among the study groups. Tukey's HSD showed that TS T and TS G groups had significantly higher shear bond strength than control groups (p = 0.001 and p < 0.001, respectively). Moreover, bond strength values of AP T were statistically significant compared to controls (p = 0.017). Amino functionalized TEOS-derived silica coating is a simple and cost-effective method for improving the bond strength between the autopolymerizing resin and polyamide

  12. Chitosan-silica complex membranes from sulfonic acid functionalized silica nanoparticles for pervaporation dehydration of ethanol-water solutions.

    Science.gov (United States)

    Liu, Ying-Ling; Hsu, Chih-Yuan; Su, Yu-Huei; Lai, Juin-Yih

    2005-01-01

    Nanosized silica particles with sulfonic acid groups (ST-GPE-S) were utilized as a cross-linker for chitosan to form a chitosan-silica complex membranes, which were applied to pervaporation dehydration of ethanol-water solutions. ST-GPE-S was obtained from reacting nanoscale silica particles with glycidyl phenyl ether, and subsequent sulfonation onto the attached phenyl groups. The chemical structure of the functionalized silica was characterized with FTIR, (1)H NMR, and energy-dispersive X-ray. Homogeneous dispersion of the silica particles in chitosan was observed with electronic microscopies, and the membranes obtained were considered as nanocomposites. The silica nanoparticles in the membranes served as spacers for polymer chains to provide extra space for water permeation, so as to bring high permeation rates to the complex membranes. With addition of 5 parts per hundred of functionalized silica into chitosan, the resulting membrane exhibited a separation factor of 919 and permeation flux of 410 g/(m(2) h) in pervaporation dehydration of 90 wt % ethanol aqueous solution at 70 degrees C.

  13. Muon catalyzed fusion under compressive conditions

    International Nuclear Information System (INIS)

    Cripps, G.; Goel, B.; Harms, A.A.

    1991-01-01

    The viability of a symbiotic combination of Muon Catalyzed Fusion (μCF) and high density generation processes has been investigated. The muon catalyzed fusion reaction rates are formulated in the temperature and density range found under moderate compressive conditions. Simplified energy gain and power balance calculations indicate that significant energy gain occurs only if standard type deuterium-tritium (dt) fusion is ignited. A computer simulation of the hydrodynamics and fusion kinetics of a spherical deuterium-tritium pellet implosion including muons is performed. Using the muon catalyzed fusion reaction rates formulated and under ideal conditions, the pellet ignites (and thus has a significant energy gain) only if the initial muon concentration is approximately 10 17 cm -3 . The muons need to be delivered to the pellet within a very short-time (≅ 1 ns). The muon pulse required in order to make the high density and temperature muon catalyzed fusion scheme viable is beyond the present technology for muon production. (orig.) [de

  14. Silica-filled elastomers polymer chain and filler characterization by a SANS-SAXS approach

    CERN Document Server

    Botti, A; Richter, D; Urban, V; Ipns, A 6 4; Kohlbrecher, J; Straube, E

    2002-01-01

    A study of composites based upon commercially available silica fillers and networks of blends of protonated and deuterated anionically prepared polyisoprene is presented. The extraction of the single chain structure factor for SANS in the polymeric soft phase in isotropic and deformed state has been performed for the first time. The quasi three-component system could not be compositionally matched due to the internal structures of the activated fillers. For this, a parallel SAXS investigation provided the neccessary information on the filler structure which was lacking in the SANS analysis. Whereas mechanically clear reinforcement at low strains and filler-networking can be observed, the microscopic characterization of the chain deformation in the framework of the network tube model agrees with the estimates for hydrodynamic reinforcement of fractal fillers. (orig.)

  15. Silica-filled elastomers: polymer chain and filler characterization by a SANS-SAXS approach

    International Nuclear Information System (INIS)

    Botti, A.; Pyckhout-Hintzen, W.; Richter, D.; Urban, V.; Kohlbrecher, J.; Straube, E.

    2002-01-01

    A study of composites based upon commercially available silica fillers and networks of blends of protonated and deuterated anionically prepared polyisoprene is presented. The extraction of the single chain structure factor for SANS in the polymeric soft phase in isotropic and deformed state has been performed for the first time. The quasi three-component system could not be compositionally matched due to the internal structures of the activated fillers. For this, a parallel SAXS investigation provided the neccessary information on the filler structure which was lacking in the SANS analysis. Whereas mechanically clear reinforcement at low strains and filler-networking can be observed, the microscopic characterization of the chain deformation in the framework of the network tube model agrees with the estimates for hydrodynamic reinforcement of fractal fillers. (orig.)

  16. Amorphous silica from rice husk at various temperatures

    International Nuclear Information System (INIS)

    Javed, S.J.; Feroze, N.; Tajwar, S.

    2008-01-01

    Rice husk is being used as a source of energy in many heat generating system because of its high calorific value and its availability in many rice producing areas. Rice husk contains approximately 20% silica which is presented in hydrated form. This hydrated silica can be retrieved as amorphous silica under controlled thermal conditions. Uncontrolled burning of rice husk produces crystalline silica which is not reactive silica but can be used as filler in many applications. Amorphous silica is reactive silica which has better market value due to its reactive nature in process industry. The present study deals with the production of amorphous silica at various temperatures from rice husk. Various ashes were prepared in tube furnace by changing the burning temperatures for fixed time intervals and analyzed by XRD. It has been observed that for two hours calculation's of rice husk renders mostly amorphous silica at 650 degree C where as at higher temperatures crystalline silica was obtained. (author)

  17. Cellular membrane trafficking of mesoporous silica nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Fang, I-Ju [Iowa State Univ., Ames, IA (United States)

    2012-01-01

    This dissertation mainly focuses on the investigation of the cellular membrane trafficking of mesoporous silica nanoparticles. We are interested in the study of endocytosis and exocytosis behaviors of mesoporous silica nanoparticles with desired surface functionality. The relationship between mesoporous silica nanoparticles and membrane trafficking of cells, either cancerous cells or normal cells was examined. Since mesoporous silica nanoparticles were applied in many drug delivery cases, the endocytotic efficiency of mesoporous silica nanoparticles needs to be investigated in more details in order to design the cellular drug delivery system in the controlled way. It is well known that cells can engulf some molecules outside of the cells through a receptor-ligand associated endocytosis. We are interested to determine if those biomolecules binding to cell surface receptors can be utilized on mesoporous silica nanoparticle materials to improve the uptake efficiency or govern the mechanism of endocytosis of mesoporous silica nanoparticles. Arginine-glycine-aspartate (RGD) is a small peptide recognized by cell integrin receptors and it was reported that avidin internalization was highly promoted by tumor lectin. Both RGD and avidin were linked to the surface of mesoporous silica nanoparticle materials to investigate the effect of receptor-associated biomolecule on cellular endocytosis efficiency. The effect of ligand types, ligand conformation and ligand density were discussed in Chapter 2 and 3. Furthermore, the exocytosis of mesoporous silica nanoparticles is very attractive for biological applications. The cellular protein sequestration study of mesoporous silica nanoparticles was examined for further information of the intracellular pathway of endocytosed mesoporous silica nanoparticle materials. The surface functionality of mesoporous silica nanoparticle materials demonstrated selectivity among the materials and cancer and normal cell lines. We aimed to determine

  18. Synthesis of Various Silica Nanoparticles for Foam Stability

    International Nuclear Information System (INIS)

    Yoon, Suk Bon; Yoon, Inho; Jung, Chonghun; Kim, Chorong; Choi, Wangkyu; Moon, Jeikwon

    2013-01-01

    The synthesis of the non-porous silica nanoparticles with uniform sizes has been reported through the Sto ber method, the synthesis of meso porous silica nanoparticles with a specific morphology such as core-shell, rod-like, and hexagonal shapes is not so common. As a synthetic strategy for controlling the particle size, shape, and porosity, the synthesis of core-shell silicas with meso porous shells formed on silica particle cores through the self-assembly of silica precursor and organic templates or spherical meso porous silicas using modified Sto ber method was also reported. Recently, in an effort to reduce the amount of radioactive waste and enhance the decontamination efficiency during the decontamination process of nuclear facilities contaminated with radionuclides, a few research for the preparation of the decontamination foam containing solid nanoparticles has been reported. In this work, the silica nanoparticles with various sizes, shapes, and structures were synthesized based on the previous literatures. The resulting silica nanoparticles were used to investigate the effect of the nanoparticles on the foam stability. In a study on the foam stability using various silica nanoparticles, the results showed that the foam volume and liquid volume in foam was enhanced when using a smaller size and lower density of the silica nanoparticles. Silica nanoparticles with various sizes, shapes, and structures such as a non-porous, meso porous core-shell, and meso porous silica were synthesized to investigate the effect of the foam stability. The sizes and structural properties of the silica nanoparticles were easily controlled by varying the amount of silica precursor, surfactant, and ammonia solution as a basic catalyst. The foam prepared using various silica nanoparticles showed that foam the volume and liquid volume in the foam were enhanced when using a smaller size and lower density of the silica nanoparticles

  19. Silica removal in industrial effluents with high silica content and low hardness.

    Science.gov (United States)

    Latour, Isabel; Miranda, Ruben; Blanco, Angeles

    2014-01-01

    High silica content of de-inked paper mill effluents is limiting their regeneration and reuse after membrane treatments such as reverse osmosis (RO). Silica removal during softening processes is a common treatment; however, the effluent from the paper mill studied has a low hardness content, which makes the addition of magnesium compounds necessary to increase silica removal. Two soluble magnesium compounds (MgCl₂∙6H₂O and MgSO₄∙7H₂O) were tested at five dosages (250-1,500 mg/L) and different initial pH values. High removal rates (80-90%) were obtained with both products at the highest pH tested (11.5). With these removal efficiencies, it is possible to work at high RO recoveries (75-85%) without silica scaling. Although pH regulation significantly increased the conductivity of the waters (at pH 11.5 from 2.1 to 3.7-4.0 mS/cm), this could be partially solved by using Ca(OH)₂ instead of NaOH as pH regulator (final conductivity around 3.0 mS/cm). Maximum chemical oxygen demand (COD) removal obtained with caustic soda was lower than with lime (15 vs. 30%). Additionally, the combined use of a polyaluminum coagulant during the softening process was studied; the coagulant, however, did not significantly improve silica removal, obtaining a maximum increase of only 10%.

  20. Catalyzed deuterium fueled tokamak reactors

    International Nuclear Information System (INIS)

    Southworth, F.H.

    1977-01-01

    Catalyzed deuterium fuel presents several advantages relative to D-T. These are, freedom from tritium breeding, high charged particle power fraction and lowered neutron energy deposition in the blanket. Higher temperature operation, lower power densities and increased confinement are simultaneously required. However, the present study has developed designs which have capitalized upon the advantages of catalyzed deuterium to overcome the difficulties associated with the fuel while obtaining high efficiency

  1. Sonolytic and Silent Polymerization of Methacrlyic Acid Butyl Ester Catalyzed by a New Onium Salt with bis-Active Sites in a Biphasic System — A Comparative Investigation

    Directory of Open Access Journals (Sweden)

    Perumberkandgai A. Vivekanand

    2013-02-01

    Full Text Available Currently, ingenious new analytical and process experimental techniques which are environmentally benign techniques, viz., ultrasound irradiation, have become immensely popular in promoting various reactions. In this work, a novel soluble multi-site phase transfer catalyst (PTC viz., 1,4-bis-(propylmethyleneammounium chloridebenzene (BPMACB was synthesized and its catalytic efficiency was assessed by observing the kinetics of sonolytic polymerization of methacrylic acid butyl ester (MABE using potassium persulphate (PPS as an initiator. The ultrasound–multi-site phase transfer catalysis (US-MPTC-assisted polymerization reaction was compared with the silent (non-ultrasonic polymerization reaction. The effects of the catalyst and various reaction parameters on the catalytic performance were in detail investigated by following the kinetics of polymerization of MABE in an ethyl acetate-water biphasic system. From the detailed kinetic investigation we propose a plausible mechanism. Further the kinetic results demonstrate clearly that ultrasound-assisted phase-transfer catalysis significantly increased the reaction rate when compared to silent reactions. Notably, this environmentally benign and cost-effective process has great potential to be applied in various polymer industries.

  2. Polymeric micelles for drug targeting.

    Science.gov (United States)

    Mahmud, Abdullah; Xiong, Xiao-Bing; Aliabadi, Hamidreza Montazeri; Lavasanifar, Afsaneh

    2007-11-01

    Polymeric micelles are nano-delivery systems formed through self-assembly of amphiphilic block copolymers in an aqueous environment. The nanoscopic dimension, stealth properties induced by the hydrophilic polymeric brush on the micellar surface, capacity for stabilized encapsulation of hydrophobic drugs offered by the hydrophobic and rigid micellar core, and finally a possibility for the chemical manipulation of the core/shell structure have made polymeric micelles one of the most promising carriers for drug targeting. To date, three generations of polymeric micellar delivery systems, i.e. polymeric micelles for passive, active and multifunctional drug targeting, have arisen from research efforts, with each subsequent generation displaying greater specificity for the diseased tissue and/or targeting efficiency. The present manuscript aims to review the research efforts made for the development of each generation and provide an assessment on the overall success of polymeric micellar delivery system in drug targeting. The emphasis is placed on the design and development of ligand modified, stimuli responsive and multifunctional polymeric micelles for drug targeting.

  3. Phosphazene-promoted anionic polymerization

    KAUST Repository

    Zhao, Junpeng

    2014-01-01

    In the recent surge of metal-free polymerization techniques, phosphazene bases have shown their remarkable potential as organic promoters/catalysts for the anionic polymerization of various types of monomers. By complexation with the counterion (e.g. proton or lithium cation), phosphazene base significantly improve the nucleophilicity of the initiator/chain-end resulting in rapid and usually controlled anionic/quasi-anionic polymerization. In this review, we will introduce the general mechanism, i.e. in situ activation (of initiating sites) and polymerization, and summarize the applications of such a mechanism on macromolecular engineering toward functionalized polymers, block copolymers and complex macromolecular architectures.

  4. Conducting Polymeric Materials

    DEFF Research Database (Denmark)

    Hvilsted, Søren

    2016-01-01

    The overall objective of this collection is to provide the most recent developments within the various areas of conducting polymeric materials. The conductivity of polymeric materials is caused by electrically charged particles, ions, protons and electrons. Materials in which electrons...

  5. The Pozzolanic reaction of silica fume

    DEFF Research Database (Denmark)

    Jensen, Ole Mejlhede

    2012-01-01

    Silica fume is a very important supplementary cementitious binder in High-Performance and Ultra High-Performance Concretes. Through its pozzolanic reaction the silica fume densifies the concrete micro-structure, in particular it strengthens the paste-aggregate interfacial transition zone. In the ......Silica fume is a very important supplementary cementitious binder in High-Performance and Ultra High-Performance Concretes. Through its pozzolanic reaction the silica fume densifies the concrete micro-structure, in particular it strengthens the paste-aggregate interfacial transition zone....... In the present paper different aspects of the pozzolanic reaction of silica fume are investigated. These include chemical shrinkage, isothermal heat development and strength development. Key data for these are given and compared with theoretical calculations, and based on presented measurements the energy...

  6. Cyclodextrin-functionalized mesostructured silica nanoparticles for removal of polycyclic aromatic hydrocarbons.

    Science.gov (United States)

    Topuz, Fuat; Uyar, Tamer

    2017-07-01

    Polycyclic aromatic hydrocarbons (PAHs) are the byproducts of the incomplete combustion of carbon-based fuels, and have high affinity towards DNA strands, ultimately exerting their carcinogenic effects. They are ubiquitousenvironmental contaminants,and can accumulate on tissues due to their lipophilic nature. In this article, we describe a novel concept for PAH removal from aqueous solutions using cyclodextrin-functionalized mesostructured silica nanoparticles (CDMSNs) and pristine mesostructured silica nanoparticles (MSNs). The adsorption applications of MSNs are greatly restricted due to the absence of surface functional groups on such particles. In this regard, cyclodextrins can serve as ideal functional molecules with their toroidal, cone-type structure, capable of inclusion-complex formation with many hydrophobic molecules, including genotoxic PAHs. The CDMSNs were synthesized by the surfactant-templated, NaOH-catalyzed condensation reactions of tetraethyl orthosilicate (TEOS) in the presence of two different types of cyclodextrin (i.e. hydroxypropyl-β-cyclodextrin (HP-β-CD) and native β-cyclodextrin (β-CD)). The physical incorporation of CD moieties was supported by XPS, FT-IR, NMR, TGA and solid-state 13 C NMR. The CDMSNs were treated with aqueous solutions of five different PAHs (e.g. pyrene, anthracene, phenanthrene, fluorene and fluoranthene). The functionalization of MSNs with cyclodextrin moieties significantly boosted the sorption capacity (q) of the MSNs up to ∼2-fold, and the q ranged between 0.3 and 1.65mg per gram CDMSNs, of which the performance was comparable to that of the activated carbon. Copyright © 2017 Elsevier Inc. All rights reserved.

  7. Mesoporous Silica Nanomaterials for Applications in Catalysis, Sensing, Drug Delivery and Gene Transfection

    Energy Technology Data Exchange (ETDEWEB)

    Radu, Daniela Rodica [Iowa State Univ., Ames, IA (United States)

    2004-01-01

    The central theme of this dissertation is represented by the versatility of mesoporous silica nanomaterials in various applications such as catalysis and bio-applications, with main focus on biological applications of Mesoporous Silica Nanospheres (MSN). The metamorphosis that we impose to these materials from catalysis to sensing and to drug and gene delivery is detailed in this dissertation. First, we developed a synthetic method that can fine tune the amount of chemically accessible organic functional groups on the pores surface of MSN by exploiting electrostatic and size matching between the cationic alkylammonium head group of the cetyltrimethylammonium bromide (CTAB) surfactant and various anionic organoalkoxysilane precursors at the micelle-water interface in a base-catalyzed condensation reaction of silicate. Aiming nature imitation, we demonstrated the catalytic abilities of the MSNs, We utilized an ethylenediamine functional group for chelating Cu2+ as a catalytic functional group anchored inside the mesopores. Thus, a polyalkynylene-based conducting polymer (molecular wire) was synthesized within the Cu-functionalized MSNs silica catalyst. For sensing applications, we have synthesized a poly(lactic acid) coated mesoporous silica nanosphere (PLA-MSN) material that serves as a fluorescence sensor system for detection of amino-containing neurotransmitters in neutral aqueous buffer. We exploited the mesoporosity of MSNs for encapsulating pharmaceutical drugs. We examined bio-friendly capping molecules such as polyamidoamine dendrimers of generations G2 to G4, to prevent the drug leaching. Next, the drug delivery system employed MSNs loaded with Doxorubicin, an anticancer drug. The results demonstrated that these nano-Trojan horses have ability to deliver Doxorubicin to cancer cells and induce their death. Finally, to demonstrate the potential of MSN as an universal cellular transmembrane nanovehicle, we anchored positively charged dendrimers on

  8. Simple addition of silica to an alkane solution of Wilkinson WMe6 or Schrock W alkylidyne complex give active complex for saturated and unsaturated hydrocarbons metathesis

    KAUST Repository

    Callens, Emmanuel

    2015-08-24

    Addition of PDA silica to a solution of the Wilkinson WMe6 as well as the Schrock W neopentilidyne tris neopentyl complex catalyzes linear or cyclic alkanes to produce respectively a distribution of linear alkanes from methane up to triacontane or a mixture of cyclic and macrocyclic hydrocarbons. This single catalytic system transforms also linear α-olefins into higher and lower homologues via isomerization/metathesis mechanism (ISOMET). This complex is also efficient towards functionalized olefins. Unsaturated fatty acid esters (FAEs) are converted into diesters corresponding to self-metathesis products.

  9. 21 CFR 584.700 - Hydrophobic silicas.

    Science.gov (United States)

    2010-04-01

    ...) Product. Amorphous fumed hydrophobic silica or precipitated hydrophobic silica (CAS Reg. No. 68611-0944... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Hydrophobic silicas. 584.700 Section 584.700 Food... DRUGS, FEEDS, AND RELATED PRODUCTS FOOD SUBSTANCES AFFIRMED AS GENERALLY RECOGNIZED AS SAFE IN FEED AND...

  10. Biomimetic silica encapsultation of living cells

    Science.gov (United States)

    Jaroch, David Benjamin

    Living cells perform complex chemical processes on size and time scales that artificial systems cannot match. Cells respond dynamically to their environment, acting as biological sensors, factories, and drug delivery devices. To facilitate the use of living systems in engineered constructs, we have developed several new approaches to create stable protective microenvironments by forming bioinspired cell-membrane-specific silica-based encapsulants. These include vapor phase deposition of silica gels, use of endogenous membrane proteins and polysaccharides as a site for silica nucleation and polycondensation in a saturated environment, and protein templated ordered silica shell formation. We demonstrate silica layer formation at the surface of pluripotent stem-like cells, bacterial biofilms, and primary murine and human pancreatic islets. Materials are characterized by AFM, SEM and EDS. Viability assays confirm cell survival, and metabolite flux measurements demonstrate normal function and no major diffusion limitations. Real time PCR mRNA analysis indicates encapsulated islets express normal levels of genetic markers for β-cells and insulin production. The silica glass encapsulant produces a secondary bone like calcium phosphate mineral layer upon exposure to media. Such bioactive materials can improve device integration with surrounding tissue upon implantation. Given the favorable insulin response, bioactivity, and long-term viability observed in silica-coated islets, we are currently testing the encapsulant's ability to prevent immune system recognition of foreign transplants for the treatment of diabetes. Such hybrid silica-cellular constructs have a wide range of industrial, environmental, and medical applications.

  11. Synthesis of titania modified silica-pillared clay (SPC) with highly ordered interlayered mesoporous structure for removing toxic metal ion Cr(VI) from aqueous state

    International Nuclear Information System (INIS)

    Mao, Huihui; Zhu, Kongnan; Li, Baoshan; Yao, Chao; Kong, Yong

    2014-01-01

    Titanium-functionalized silica-pillared clays synthesized through post synthetic route was utilized as adsorbers for the removal of Cr(VI) ions from aqueous solutions under different temperatures and initial concentrations. The starting mesostructured silica-pillared clay is assembled by intragallery ammonia-catalyzed hydrolysis of tetraethoxysilane using cationic surfactant as gallery template, and subsequently, the formed interlayered pore walls were decorated with nano-sized TiO 2 particle through organic titanium functionalization process. The kind of structural transformation has been confirmed by X-ray diffraction (XRD), nitrogen adsorption–desorption isotherms, Fourier transform infrared (FT-IR) analysis, UV–vis diffuse reflectance spectroscopy (DRS), elemental analysis (XRF), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Such results indicate that most of the grafted titanium species was combined with Si–OH on the surface of gallery pores. By changing the concentration of organic titanium source during synthesis, the porous structure system is effected. Under suitable conditions, these materials exhibit high adsorption capacity and efficiency. Qualitative estimates of the thermodynamic parameters showed that the overall adsorption process is spontaneous (ΔG° 0). The adsorption isotherms of Cr(VI) on titanium-functionalized silica-pillared clay were best fitted by Redlich–Peterson models. Detail results of thermodynamics and kinetics are also presented.

  12. Synthesis of titania modified silica-pillared clay (SPC) with highly ordered interlayered mesoporous structure for removing toxic metal ion Cr(VI) from aqueous state

    Energy Technology Data Exchange (ETDEWEB)

    Mao, Huihui, E-mail: maohuihui_beijing@126.com [State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029 (China); Jiangsu Key Laboratory of Advanced Catalytic Materials and Technology, Changzhou University, Changzhou, Jiangsu Province 213164 (China); Zhu, Kongnan [Jiangsu Key Laboratory of Advanced Catalytic Materials and Technology, Changzhou University, Changzhou, Jiangsu Province 213164 (China); Li, Baoshan, E-mail: bsli@mail.buct.edu.cn [State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029 (China); Yao, Chao; Kong, Yong [Jiangsu Key Laboratory of Advanced Catalytic Materials and Technology, Changzhou University, Changzhou, Jiangsu Province 213164 (China)

    2014-02-15

    Titanium-functionalized silica-pillared clays synthesized through post synthetic route was utilized as adsorbers for the removal of Cr(VI) ions from aqueous solutions under different temperatures and initial concentrations. The starting mesostructured silica-pillared clay is assembled by intragallery ammonia-catalyzed hydrolysis of tetraethoxysilane using cationic surfactant as gallery template, and subsequently, the formed interlayered pore walls were decorated with nano-sized TiO{sub 2} particle through organic titanium functionalization process. The kind of structural transformation has been confirmed by X-ray diffraction (XRD), nitrogen adsorption–desorption isotherms, Fourier transform infrared (FT-IR) analysis, UV–vis diffuse reflectance spectroscopy (DRS), elemental analysis (XRF), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Such results indicate that most of the grafted titanium species was combined with Si–OH on the surface of gallery pores. By changing the concentration of organic titanium source during synthesis, the porous structure system is effected. Under suitable conditions, these materials exhibit high adsorption capacity and efficiency. Qualitative estimates of the thermodynamic parameters showed that the overall adsorption process is spontaneous (ΔG° < 0) and endothermic (ΔH° > 0). The adsorption isotherms of Cr(VI) on titanium-functionalized silica-pillared clay were best fitted by Redlich–Peterson models. Detail results of thermodynamics and kinetics are also presented.

  13. A new parameter-free soft-core potential for silica and its application to simulation of silica anomalies

    Energy Technology Data Exchange (ETDEWEB)

    Izvekov, Sergei, E-mail: sergiy.izvyekov.civ@mail.mil; Rice, Betsy M. [Weapons and Materials Research Directorate, U.S. Army Research Laboratory, Aberdeen Proving Ground, Maryland 21005 (United States)

    2015-12-28

    A core-softening of the effective interaction between oxygen atoms in water and silica systems and its role in developing anomalous thermodynamic, transport, and structural properties have been extensively debated. For silica, the progress with addressing these issues has been hampered by a lack of effective interaction models with explicit core-softening. In this work, we present an extension of a two-body soft-core interatomic force field for silica recently reported by us [S. Izvekov and B. M. Rice, J. Chem. Phys. 136(13), 134508 (2012)] to include three-body forces. Similar to two-body interaction terms, the three-body terms are derived using parameter-free force-matching of the interactions from ab initio MD simulations of liquid silica. The derived shape of the O–Si–O three-body potential term affirms the existence of repulsion softening between oxygen atoms at short separations. The new model shows a good performance in simulating liquid, amorphous, and crystalline silica. By comparing the soft-core model and a similar model with the soft-core suppressed, we demonstrate that the topology reorganization within the local tetrahedral network and the O–O core-softening are two competitive mechanisms responsible for anomalous thermodynamic and kinetic behaviors observed in liquid and amorphous silica. The studied anomalies include the temperature of density maximum locus and anomalous diffusivity in liquid silica, and irreversible densification of amorphous silica. We show that the O–O core-softened interaction enhances the observed anomalies primarily through two mechanisms: facilitating the defect driven structural rearrangements of the silica tetrahedral network and modifying the tetrahedral ordering induced interactions toward multiple characteristic scales, the feature which underlies the thermodynamic anomalies.

  14. Synthesis of heterocycles via transition-metal-catalyzed hydroarylation of alkynes.

    Science.gov (United States)

    Yamamoto, Yoshihiko

    2014-03-07

    Transition-metal (TM)-catalyzed hydroarylation reactions of alkynes have received much attention, because they enable the net insertion of alkyne C-C triple bonds into C-H bonds of aromatic precursors, resulting in regio- and stereo-selective formation of synthetically useful arylalkenes. Taking advantage of this feature, TM-catalyzed alkyne hydroarylations have been successfully used for the synthesis of heterocycles. TM-catalyzed alkyne hydroarylations can be classified into three major categories depending on the type of reaction and precursors involved: (1) palladium-catalyzed reductive Heck reactions of alkynes with aryl halides, (2) TM-catalyzed conjugate arylation reactions of activated alkynes with arylboronic acids, and (3) TM-catalyzed aromatic C-H alkenylations with alkynes. This review surveys heterocycle synthesis via TM-catalyzed hydroarylation of alkynes according to the above classification, with an emphasis on the scope and limitations, as well as the underlying mechanisms.

  15. Organocatalytic conjugate-addition polymerization of linear and cyclic acrylic monomers by N-heterocyclic carbenes: Mechanisms of chain initiation, propagation, and termination

    KAUST Repository

    Zhang, Yuetao

    2013-11-27

    This contribution presents a full account of experimental and theoretical/computational investigations into the mechanisms of chain initiation, propagation, and termination of the recently discovered N-heterocyclic carbene (NHC)-mediated organocatalytic conjugate-addition polymerization of acrylic monomers. The current study specifically focuses on three commonly used NHCs of vastly different nucleophilicity, 1,3-di-tert-butylimidazolin-2-ylidene (ItBu), 1,3- dimesitylimidazolin-2-ylidene (IMes), and 1,3,4-triphenyl-4,5-dihydro-1H-1,2,4- triazol-5-ylidene (TPT), and two representative acrylic monomers, the linear methyl methacrylate (MMA) and its cyclic analog, biomass-derived renewable γ-methyl-α-methylene-γ-butyrolactone (MMBL). For MMA, there exhibits an exquisite selectivity of the NHC structure for the three types of reactions it promotes: enamine formation (single-monomer addition) by IMes, dimerization (tail-to-tail) by TPT, and polymerization by ItBu. For MMBL, all three NHCs promote no dimerization but polymerization, with the polymerization activity being highly sensitive to the NHC structure and the solvent polarity. Thus, ItBu is the most active catalyst of the series and converts quantitatively 1000-3000 equiv of MMBL in 1 min or 10 000 equiv in 5 min at room temperature to MMBL-based bioplastics with a narrow range of molecular weights of Mn = 70-85 kg/mol, regardless of the [MMBL]/[ItBu] ratio employed. The ItBu-catalyzed MMBL polymerization reaches an exceptionally high turnover frequency up to 122 s -1 and a high initiator efficiency value up to 1600%. Unique chain-termination mechanisms have been revealed, accounting for the production of relative high-molecular-weight linear polymers and the catalytic nature of this NHC-mediated conjugate-addition polymerization. Computational studies have provided mechanistic insights into reactivity and selectivity between two competing pathways for each NHC-monomer zwitterionic adduct, namely enamine

  16. Organocatalytic conjugate-addition polymerization of linear and cyclic acrylic monomers by N-heterocyclic carbenes: Mechanisms of chain initiation, propagation, and termination

    KAUST Repository

    Zhang, Yuetao; Schmitt, Meghan L.; Falivene, Laura; Caporaso, Lucia; Cavallo, Luigi; Chen, Eugene You Xian

    2013-01-01

    This contribution presents a full account of experimental and theoretical/computational investigations into the mechanisms of chain initiation, propagation, and termination of the recently discovered N-heterocyclic carbene (NHC)-mediated organocatalytic conjugate-addition polymerization of acrylic monomers. The current study specifically focuses on three commonly used NHCs of vastly different nucleophilicity, 1,3-di-tert-butylimidazolin-2-ylidene (ItBu), 1,3- dimesitylimidazolin-2-ylidene (IMes), and 1,3,4-triphenyl-4,5-dihydro-1H-1,2,4- triazol-5-ylidene (TPT), and two representative acrylic monomers, the linear methyl methacrylate (MMA) and its cyclic analog, biomass-derived renewable γ-methyl-α-methylene-γ-butyrolactone (MMBL). For MMA, there exhibits an exquisite selectivity of the NHC structure for the three types of reactions it promotes: enamine formation (single-monomer addition) by IMes, dimerization (tail-to-tail) by TPT, and polymerization by ItBu. For MMBL, all three NHCs promote no dimerization but polymerization, with the polymerization activity being highly sensitive to the NHC structure and the solvent polarity. Thus, ItBu is the most active catalyst of the series and converts quantitatively 1000-3000 equiv of MMBL in 1 min or 10 000 equiv in 5 min at room temperature to MMBL-based bioplastics with a narrow range of molecular weights of Mn = 70-85 kg/mol, regardless of the [MMBL]/[ItBu] ratio employed. The ItBu-catalyzed MMBL polymerization reaches an exceptionally high turnover frequency up to 122 s -1 and a high initiator efficiency value up to 1600%. Unique chain-termination mechanisms have been revealed, accounting for the production of relative high-molecular-weight linear polymers and the catalytic nature of this NHC-mediated conjugate-addition polymerization. Computational studies have provided mechanistic insights into reactivity and selectivity between two competing pathways for each NHC-monomer zwitterionic adduct, namely enamine

  17. Ultra-sensitive EUV resists based on acid-catalyzed polymer backbone breaking

    Science.gov (United States)

    Manouras, Theodoros; Kazazis, Dimitrios; Koufakis, Eleftherios; Ekinci, Yasin; Vamvakaki, Maria; Argitis, Panagiotis

    2018-03-01

    The main target of the current work was to develop new sensitive polymeric materials for lithographic applications, focusing in particular to EUV lithography, the main chain of which is cleaved under the influence of photogenerated acid. Resist materials based on the cleavage of polymer main chain are in principle capable to create very small structures, to the dimensions of the monomers that they consist of. Nevertheless, in the case of the commonly used nonchemically amplified materials of this type issues like sensitivity and poor etch resistance limit their areas of application, whereas inadequate etch resistance and non- satisfactory process reliability are the usual problems encountered in acid catalysed materials based on main chain scission. In our material design the acid catalyzed chain cleavable polymers contain very sensitive moieties in their backbone while they remain intact in alkaline ambient. These newly synthesized polymers bear in addition suitable functional groups for the achievement of desirable lithographic characteristics (thermal stability, acceptable glass transition temperature, etch resistance, proper dissolution behavior, adhesion to the substrate). Our approach for achieving acceptable etch resistance, a main drawback in other main chain cleavable resists, is based on the introduction of polyaromatic hydrocarbons in the polymeric backbone, whereas the incorporation of an inorganic component further enhances the etch resistance. Single component systems can also be designed following the proposed approach by the incorporation of suitable PAGs and base quencher molecules in the main chain. Resist formulations based on a random copolymer designed according to the described rules evaluated in EUV exhibit ultrahigh sensitivity, capability for high resolution patterning and overall processing characteristics that make them strong candidates for industrial use upon further optimization.

  18. Microporous Silica Based Membranes for Desalination

    Directory of Open Access Journals (Sweden)

    João C. Diniz da Costa

    2012-09-01

    Full Text Available This review provides a global overview of microporous silica based membranes for desalination via pervaporation with a focus on membrane synthesis and processing, transport mechanisms and current state of the art membrane performance. Most importantly, the recent development and novel concepts for improving the hydro-stability and separating performance of silica membranes for desalination are critically examined. Research into silica based membranes for desalination has focussed on three primary methods for improving the hydro-stability. These include incorporating carbon templates into the microporous silica both as surfactants and hybrid organic-inorganic structures and incorporation of metal oxide nanoparticles into the silica matrix. The literature examined identified that only metal oxide silica membranes have demonstrated high salt rejections under a variety of feed concentrations, reasonable fluxes and unaltered performance over long-term operation. As this is an embryonic field of research several target areas for researchers were discussed including further improvement of the membrane materials, but also regarding the necessity of integrating waste or solar heat sources into the final process design to ensure cost competitiveness with conventional reverse osmosis processes.

  19. Size-dependent cytotoxicity and inflammatory responses of PEGylated silica-iron oxide nanocomposite size series

    Energy Technology Data Exchange (ETDEWEB)

    Injumpa, Wishulada [Department of Chemistry, Faculty of Science, Chulalongkorn University, Bangkok 10330 (Thailand); Ritprajak, Patcharee [Department of Microbiology, and RU in Oral Microbiology and Immunology, Faculty of Dentistry, Chulalongkorn University, Bangkok 10330 (Thailand); Insin, Numpon, E-mail: Numpon.I@chula.ac.th [Department of Chemistry, Faculty of Science, Chulalongkorn University, Bangkok 10330 (Thailand)

    2017-04-01

    Iron oxides nanoparticles have been utilized in biological systems and biomedical applications for many years because they are relatively safe and stable comparing to other magnetic nanomaterials. In some applications, iron oxide nanoparticles were modified with silica in order to be more stable in biological systems and able to be functionalized with various functional groups. Moreover, poly(ethylene glycol) (PEG) was one on the most used polymer to graft onto the nanoparticles in order to increase their biocompatibility, dispersibility and stability in aqueous solutions. Therefore, the nanocomposites comprising iron oxide nanoparticles, silica, and PEG could become multifunctional carriers combining superparamagnetic character, multi-functionality and high stability in biological environments. Herein, we reported the preparation of the nanocomposites and effects of their sizes on cytotoxicity and inflammatory responses. The PEGylated silica-iron oxide nanocomposites were prepared by coating of poly(poly(ethylene glycol) monomethyl ether methacrylate) (PPEGMA) on magnetic nanoparticle-silica nanocomposites via Atom Transfer Radical Polymerization (ATRP). The iron oxide nanoparticles were synthesized using a thermal decomposition method. The silica shells were then coated on iron oxides nanoparticles using reverse microemulsion and sol-gel methods. The size series of the nanocomposites with the diameter of 24.86±4.38, 45.24±5.00, 98.10±8.88 and 202.22±6.70 nm as measured using TEM were obtained. Thermogravimetric analysis (TGA) was used for the determination of % weight of PPEGMA on the nanocomposites showing the weight loss of ranging from 65% for smallest particles to 30% for largest particles. The various sizes (20, 40, 100, 200 nm) and concentrations (10, 100, 1000 μg/mL) of the nanocomposites were tested for their cytotoxicity in fibroblast and macrophage cell lines using MTT assay. The different sizes did not affect cell viability of fibroblast, albeit

  20. Can laccases catalyze bond cleavage in lignin?

    DEFF Research Database (Denmark)

    Munk, Line; Sitarz, Anna Katarzyna; Kalyani, Dayanand

    2015-01-01

    illustrations of the putative laccase catalyzed reactions, including the possible reactions of the reactive radical intermediates taking place after the initial oxidation of the phenol-hydroxyl groups, we show that i) Laccase activity is able to catalyze bond cleavage in low molecular weight phenolic lignin......-substituted phenols, benzenethiols, polyphenols, and polyamines, which may be oxidized. In addition, the currently available analytical methods that can be used to detect enzyme catalyzed changes in lignin are summarized, and an improved nomenclature for unequivocal interpretation of the action of laccases on lignin...

  1. Applied bioactive polymeric materials

    CERN Document Server

    Carraher, Charles; Foster, Van

    1988-01-01

    The biological and biomedical applications of polymeric materials have increased greatly in the past few years. This book will detail some, but not all, of these recent developments. There would not be enough space in this book to cover, even lightly, all of the major advances that have occurred. Some earlier books and summaries are available by two of this book's Editors (Gebelein & Carraher) and these should be consul ted for additional information. The books are: "Bioactive Polymeric Systems" (Plenum, 1985); "Polymeric Materials In Medication" (Plenum, 1985); "Biological Acti vi ties of Polymers" (American Chemical Society, 1982). Of these three, "Bioacti ve Polymeric Systems" should be the most useful to a person who is new to this field because it only contains review articles written at an introductory level. The present book primarily consists of recent research results and applications, with only a few review or summary articles. Bioactive polymeric materials have existed from the creation of life...

  2. Radiation induced emulsion polymerization

    International Nuclear Information System (INIS)

    Stannett, V.T.; Stahel, E.P.

    1990-01-01

    High energy radiation is particularly favored for the initiation of emulsion polymerization. The yield of free radicals, for example, from the radiolysis of the aqueous phase, is high; G(radical) values of 5-7. In addition, the rather special kinetics associated with emulsion polymerization lead, in general, to very large kinetic chain lengths, even with 'non-ideal' monomers such as vinyl acetate. Together, high polymerization rates at low doses become possible. There are some important advantages of radiation polymerization compared with chemical initiators, such as potassium persulfate. Perhaps the most important among them is the temperature independence of the initiation step. This makes low temperature polymerization very accessible. With monomers such as vinyl acetate, where chain termination to monomer is predominant, low temperatures lead to often highly desirable higher molecular weights. With styrene, the classical ideally behaved monomer, there are the advantages such as, for example, the feasibility of using cationic monomers. These and some attendant disadvantages are discussed in detail, including pilot plant studies

  3. UV-cured methacrylic-silica hybrids: Effect of oxygen inhibition on photo-curing kinetics

    International Nuclear Information System (INIS)

    Corcione, C. Esposito; Striani, R.; Frigione, M.

    2014-01-01

    Highlights: • The kinetic behavior of novel photopolymerizable organic–inorganic hybrid system was studied as a function of the composition and of the atmosphere for reactions. • The UV-curing reaction of the hybrid mixture was found fast and complete. • The combined presence of thiol monomer and nanostructured silica allows to reduce the effect of inhibition of oxygen towards the radical photopolymerization. - Abstract: The kinetic behavior of innovative photopolymerizable UV-cured methacrylic–silica hybrid formulations, previously developed, was studied and compared to that of a reference control system. The organic–inorganic (O–I) hybrids proposed in this study are obtained from organic precursors with a high siloxane content mixed with tetraethoxysilane (TEOS) in such a way to produce co-continuous silica nano-domains dispersed within a cross-linked organic phase, as a result of the hydrolysis and condensation reactions. The kinetics of the radical photopolymerization mechanism induced by UV-radiations, in presence of a suitable photoinitiator, was studied by calorimetric, FTIR and Raman spectroscopic analyses, by varying the composition of the mixtures and the atmosphere for reactions. The well known effect of oxygen on the kinetic mechanism of the free radical photopolymerization of the methacrylic–siloxane based monomers was found to be strongly reduced in the hybrid system, especially when a proper thiol was used. The experimental calorimetric data were fitted using a simple kinetic model for radical photopolymerization reactions, obtaining a good agreement between the experimental data and the theoretical model. From the comparison of the kinetic constants calculated for control and hybrid systems, it was possible to assess the effect of the composition, as well as of the atmosphere used during the photo-polymerization process, on the kinetic of photopolymerization reaction

  4. Synthesis and application of silica gel modified with alkoxyalcohols. Alkoxyalcohol shushoku silica gel no gosei to riyo

    Energy Technology Data Exchange (ETDEWEB)

    Moriguchi, T.; Ishiguro, H.; Matsubara, Y.; Yoshihara, M.; Maeshima, T.; Ito, S. (Kinki University, Osaka (Japan). Faculty of Science and Engineering)

    1991-08-20

    Several kinds of silica gel modified by alkoxyalcohols were synthesized by refluxing and dehyration and the organic reactions were studied when these silica gels were used as the catalyst. It could be confirmed by FT-IR spectra, DTA and elementary analysis that alkoxylalcohols adhere to the surface of silica gels without any decomposition. The acetate was produced by using alkyl halides. It was found that the modified silica gels had clearly the catalytic action for the reaction with n-hexyl bromide and dibromoethane although unmodified silica gels did not show the catalytic action. The reducing reaction of carbonyl compounds was carried out. The reaction proceeded at 25 centigrade for acetophenone, cyclohexanone, 1-indanone and 2-octanone to produce the corresponding reduction products. 11 refs., 5 figs., 4 tabs.

  5. Solvent cleanup using base-treated silica gel solid adsorbent

    International Nuclear Information System (INIS)

    Tallent, O.K.; Mailen, J.C.; Pannell, K.D.

    1984-06-01

    A solvent cleanup method using silica gel columns treated with either sodium hydroxide (NaOH) or lithium hydroxide (LiOH) has been investigated. Its effectiveness compares favorably with that of traditional wash methods. After treatment with NaOH solution, the gels adsorb HNO 3 , dibutyl phosphate (DBP), UO 2 2+ , Pu 4+ , various metal-ion fission products, and other species from the solvent. Adsorption mechanisms include neutralization, hydrolysis, polymerization, and precipitation, depending on the species adsorbed. Sodium dibutyl phosphate, which partially distributes to the solvent from the gels, can be stripped with water; the stripping coefficient ranges from 280 to 540. Adsorption rates are diffusion controlled such that temperature effects are relatively small. Recycle of the gels is achieved either by an aqueous elution and recycle sequence or by a thermal treatment method, which may be preferable. Potential advantages of this solvent cleanup method are that (1) some operational problems are avoided and (2) the amount of NaNO 3 waste generated per metric ton of nuclear fuel reprocessed would be reduced significantly. 19 references, 6 figures, 12 tables

  6. Dynamics Research on the Gelling Course of Silica Sol

    Institute of Scientific and Technical Information of China (English)

    LUYi-chun; LIZai-geng

    1995-01-01

    Dreipping electrolytes into silica sol ,gelling reaction will occur,The research indicates:this is a complicated physicemistry course,which consists of a pre-reaction and a polymerizaion,The former controls the whole course,and in which electronic layers of the sol's particles be-come more and more thiner,but with incresing of the sol concentration,its control force will be diminished ,till the fast-coagulation ,the gelling couse becomes o-controlled,The latter is an in-finite polymeric chani-reaction.The result of gelatination is to produce a very big plymeric molecule-gel,which involves in all space,includes all water ,and its molecular weight is in-definite big.The researh also indicates:the dy-namic course of the gelling could be described quantitaively by an experience formula:lgt=-nlgc+B,All of the characteristic values have definite physical meaning,Electronic value of the contrary-inos is the biggest influential factor ,the natures of the contrary-ions and the natures of the same-electronic-inos have a few influential forces on the characteristic values,The temperature increasing makes the gelling reaction fast.

  7. Nanoengineered mesoporous silica nanoparticles for smart delivery of doxorubicin

    Science.gov (United States)

    Mishra, Akhilesh Kumar; Pandey, Himanshu; Agarwal, Vishnu; Ramteke, Pramod W.; Pandey, Avinash C.

    2014-08-01

    The motive of the at hand exploration was to contrive a proficient innovative pH-responsive nanocarrier designed for an anti-neoplastic agent that not only owns competent loading capacity but also talented to liberate the drug at the specific site. pH sensitive hollow mesoporous silica nanoparticles ( MSN) have been synthesized by sequence of chemical reconstruction with an average particle size of 120 nm. MSN reveal noteworthy biocompatibility and efficient drug loading magnitude. Active molecules such as Doxorubicin (DOX) can be stocked and set free from the pore vacuities of MSN by tuning the pH of the medium. The loading extent of MSN was found up to 81.4 wt% at pH 7.8. At mild acidic pH, DOX is steadily released from the pores of MSN. Both, the nitrogen adsorption-desorption isotherms and X-ray diffraction patterns reflects that this system holds remarkable stable mesostructure. Additionally, the outcomes of cytotoxicity assessment further establish the potential of MSN as a relevant drug transporter which can be thought over an appealing choice to a polymeric delivery system.

  8. SCC modification by use of amorphous nano-silica

    NARCIS (Netherlands)

    Quercia Bianchi, G.; Spiesz, P.R.; Hüsken, G.; Brouwers, H.J.H.

    2014-01-01

    In this study two different types of nano-silica (nS) were applied in self-compacting concrete (SCC), both having similar particle size distributions (PSD), but produced through two different processes: fumed powder silica and precipitated silica in colloidal suspension. The influence of nano-silica

  9. Agmatine attenuates silica-induced pulmonary fibrosis.

    Science.gov (United States)

    El-Agamy, D S; Sharawy, M H; Ammar, E M

    2014-06-01

    There is a large body of evidence that nitric oxide (NO) formation is implicated in mediating silica-induced pulmonary fibrosis. As a reactive free radical, NO may not only contribute to lung parenchymal tissue injury but also has the ability to combine with superoxide and form a highly reactive toxic species peroxynitrite that can induce extensive cellular toxicity in the lung tissues. This study aimed to explore the effect of agmatine, a known NO synthase inhibitor, on silica-induced pulmonary fibrosis in rats. Male Sprague Dawley rats were treated with agmatine for 60 days following a single intranasal instillation of silica suspension (50 mg in 0.1 ml saline/rat). The results revealed that agmatine attenuated silica-induced lung inflammation as it decreased the lung wet/dry weight ratio, protein concentration, and the accumulation of the inflammatory cells in the bronchoalveolar lavage fluid. Agmatine showed antifibrotic activity as it decreased total hydroxyproline content of the lung and reduced silica-mediated lung inflammation and fibrosis in lung histopathological specimen. In addition, agmatine significantly increased superoxide dismutase (p Agmatine also reduced silica-induced overproduction of pulmonary nitrite/nitrate as well as tumor necrosis factor α. Collectively, these results demonstrate the protective effects of agmatine against the silica-induced lung fibrosis that may be attributed to its ability to counteract the NO production, lipid peroxidation, and regulate cytokine effects. © The Author(s) 2014.

  10. "Click" i polymerer 2

    DEFF Research Database (Denmark)

    Hvilsted, Søren

    2012-01-01

    "Click"-reaktioner til fremstilling af ledende polymerer med funktionelle håndtag og bipolymermaterialer......"Click"-reaktioner til fremstilling af ledende polymerer med funktionelle håndtag og bipolymermaterialer...

  11. Boron-Catalyzed C3-Polymerization of ω-2-Methyl Allylarsonium Ylide and Its C3/C1 Copolymers with Dimethylsulfoxonium Methylide

    KAUST Repository

    Wang, De

    2016-03-01

    A novel arsonium ylide, ω-2-methylallylarsonium ylide, was synthesized and used as monomer for polyhomologation with triethyborane as initiator. It was found that the terminal methyl group leads to C3 polymerization. Furthermore, the copolyhomologation of arsonium ylide with dimethylsulfoxonium methylide is reported for the first time. (Chemical Equation Presented). © 2016 American Chemical Society.

  12. All-silica nanofluidic devices for DNA-analysis fabricated by imprint of sol-gel silica with silicon stamp

    DEFF Research Database (Denmark)

    Mikkelsen, Morten Bo Lindholm; Letailleur, Alban A; Søndergård, Elin

    2011-01-01

    We present a simple and cheap method for fabrication of silica nanofluidic devices for single-molecule studies. By imprinting sol-gel materials with a multi-level stamp comprising micro- and nanofeatures, channels of different depth are produced in a single process step. Calcination of the imprin......We present a simple and cheap method for fabrication of silica nanofluidic devices for single-molecule studies. By imprinting sol-gel materials with a multi-level stamp comprising micro- and nanofeatures, channels of different depth are produced in a single process step. Calcination...... of the imprinted hybrid sol-gel material produces purely inorganic silica, which has very low autofluorescence and can be fusion bonded to a glass lid. Compared to top-down processing of fused silica or silicon substrates, imprint of sol-gel silica enables fabrication of high-quality nanofluidic devices without...

  13. Degradability and Clearance of Silicon, Organosilica, Silsesquioxane, Silica Mixed Oxide, and Mesoporous Silica Nanoparticles

    KAUST Repository

    Croissant, Jonas G.

    2017-01-13

    The biorelated degradability and clearance of siliceous nanomaterials have been questioned worldwide, since they are crucial prerequisites for the successful translation in clinics. Typically, the degradability and biocompatibility of mesoporous silica nanoparticles (MSNs) have been an ongoing discussion in research circles. The reason for such a concern is that approved pharmaceutical products must not accumulate in the human body, to prevent severe and unpredictable side-effects. Here, the biorelated degradability and clearance of silicon and silica nanoparticles (NPs) are comprehensively summarized. The influence of the size, morphology, surface area, pore size, and surface functional groups, to name a few, on the degradability of silicon and silica NPs is described. The noncovalent organic doping of silica and the covalent incorporation of either hydrolytically stable or redox- and enzymatically cleavable silsesquioxanes is then described for organosilica, bridged silsesquioxane (BS), and periodic mesoporous organosilica (PMO) NPs. Inorganically doped silica particles such as calcium-, iron-, manganese-, and zirconium-doped NPs, also have radically different hydrolytic stabilities. To conclude, the degradability and clearance timelines of various siliceous nanomaterials are compared and it is highlighted that researchers can select a specific nanomaterial in this large family according to the targeted applications and the required clearance kinetics.

  14. Survey and research on precision polymerization polymeric materials; Seimitsu jugo kobunshi zairyo ni kansuru chosa kenkyu

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1996-03-01

    Survey and research on the precision control of primary structure of polymeric materials and the precision evaluation technology have been conducted to develop advanced polymeric materials. It is proposed that the three basic processes of polymer synthesis, i.e., addition, condensation, and biomimesis, in forming the precision polymerization skeleton are to be covered through a centralized joint research effort with participation of industry, academia, and the government institute and under the leadership of researchers from academic institutions as the team leaders. For the study of technology trends, international conferences held in UK, Germany, and Hawaii are introduced, and domestic meetings, i.e., Annual Polymer Congress and Polymer Conference, are summarized. In addition, Precision Polymerization Forum and International Workshop on Precision Polymerization were held. The basic studies include a quantum-chemical elucidation of the elementary process in polymerization reaction, time-resolved analysis of polymerization process and polymer properties, synthesis of polymers with controlled microstructures by coordination polymerization using metal complexes, synthesis of polymer with controlled microstructures by precision polycondensation, molecular recognition in catalyst-reaction site, and synthesis of imprinting polymers. 246 refs., 117 figs., 14 tabs.

  15. Functionalization of silica nanoparticles for polypropylene nanocomposites applications

    International Nuclear Information System (INIS)

    Bracho, Diego; Palza, Humberto; Quijada, Raul; Dougnac, Vivianne

    2011-01-01

    Synthetic silica nanospheres of different diameters produced via the sol-gel method were used in order to enhance the barrier properties of the polypropylene-silica nanocomposites. Modification of the silica surface by reaction with organic chlorosilanes was performed in order to improve the particles interaction with the polypropylene matrix and its dispersion. Unmodified and modified silica nanoparticles were characterized using electronic microscopy (TEM), elemental analysis, thermo gravimetric analysis (TGA), and solid state nuclear magnetic resonance (NMR) spectroscopy. Preliminary permeability tests of the polymer-silica nanocomposite films showed no significant change at low particles load (3 wt%) regardless its size or surface functionality, mainly because of the low aspect ratio of the silica nanospheres. However, it is expected that at a higher concentration of silica particles differences will be observed. (author)

  16. Toughening Mechanisms in Silica-Filled Epoxy Nanocomposites

    Science.gov (United States)

    Patel, Binay S.

    Epoxies are widely used as underfill resins throughout the microelectronics industry to mechanically couple and protect various components of flip-chip assemblies. Generally rigid materials largely surround underfill resins. Improving the mechanical and thermal properties of epoxy resins to better match those of their rigid counterparts can help extend the service lifetime of flip-chip assemblies. Recently, researchers have demonstrated that silica nanoparticles are effective toughening agents for lightly-crosslinked epoxies. Improvements in the fracture toughness of silica-filled epoxy nanocomposites have primarily been attributed to two toughening mechanisms: particle debonding with subsequent void growth and matrix shear banding. Various attempts have been made to model the contribution of these toughening mechanisms to the overall fracture energy observed in silica-filled epoxy nanocomposites. However, disparities still exist between experimental and modeled fracture energy results. In this dissertation, the thermal, rheological and mechanical behavior of eight different types of silica-filled epoxy nanocomposites was investigated. Each nanocomposite consisted of up to 10 vol% of silica nanoparticles with particle sizes ranging from 20 nm to 200 nm, with a variety of surface treatments and particle structures. Fractographical analysis was conducted with new experimental approaches in order to accurately identify morphological evidence for each proposed toughening mechanism. Overall, three major insights into the fracture behavior of real world silica-filled epoxy nanocomposites were established. First, microcracking was observed as an essential toughening mechanism in silica-filled epoxy nanocomposites. Microcracking was observed on the surface and subsurface of fractured samples in each type of silica-filled epoxy nanocomposite. The additional toughening contribution of microcracking to overall fracture energy yielded excellent agreement between experimental

  17. Biodiesel production by enzyme-catalyzed transesterification

    Directory of Open Access Journals (Sweden)

    Stamenković Olivera S.

    2005-01-01

    Full Text Available The principles and kinetics of biodiesel production from vegetable oils using lipase-catalyzed transesterification are reviewed. The most important operating factors affecting the reaction and the yield of alkyl esters, such as: the type and form of lipase, the type of alcohol, the presence of organic solvents, the content of water in the oil, temperature and the presence of glycerol are discussed. In order to estimate the prospects of lipase-catalyzed transesterification for industrial application, the factors which influence the kinetics of chemically-catalysed transesterification are also considered. The advantages of lipase-catalyzed transesterification compared to the chemically-catalysed reaction, are pointed out. The cost of down-processing and ecological problems are significantly reduced by applying lipases. It was also emphasized that lipase-catalysed transesterification should be greatly improved in order to make it commercially applicable. The further optimization of lipase-catalyzed transesterification should include studies on the development of new reactor systems with immobilized biocatalysts and the addition of alcohol in several portions, and the use of extra cellular lipases tolerant to organic solvents, intracellular lipases (i.e. whole microbial cells and genetically-modified microorganisms ("intelligent" yeasts.

  18. Polyacrolein with microspherical structure obtained by radiation-Initiation and base catalysis

    International Nuclear Information System (INIS)

    Usanmaz, A.; Dogan, R.D.

    1990-01-01

    Acrolein was polymerized by radiation and base catalyzed condensation. Radiation polymerization was carried in bulk form under vacuum and air atmosphere at several temperatures. The conversion reached close to 100 %, and polymers were free flowing white powders up to 5 % conversion at -15degC, up to 80 % at higher temperatures and up to 10 % in air atmosphere polymerization. Radiation polymerization from aqueous solutions of various pH and from acetone solutions gave white powder polymers with limiting conversions ranging from 10 to 18 % depending on the solution type or pH. The conversion at pH between 1, 5 to 8 gave minimum pH of 5 to 6. The base catalyzed polymerization at pH of 9 to 12 gave white powdered polymers changing to a yellowish colour with increase of pH. The limiting conversion was about 14 %. The nature of repeating units in the polymer chains was studied by IR and thermogravimetry. The polymers contained different repeating units randomly, and the aldehyde content was higher for radiation polymerization than base catalyzed polymerization. A scanning electron microscope investigation showed the powder polymers to have microspherical structures of various size depending on polymerization conditions. (author)

  19. Synthesis of magnetic polymeric microspheres

    Energy Technology Data Exchange (ETDEWEB)

    Gervald, A Yu; Gritskova, Inessa A; Prokopov, Nikolai I [M.V. Lomonosov Moscow State Academy of Fine Chemical Technology, Moscow (Russian Federation)

    2010-05-13

    The key types of magnetic polymeric microspheres are considered. Methods of synthesis of different types of magnetic nanoparticles and of preparation of stable magnetic fluids on their basis are outlined. The overview of the methods for the manufacture of magnetic polymeric microspheres is presented. The effect of the synthesis conditions on the characteristics of magnetic polymeric microspheres such as the diameter and the particle size distribution and the content of magnetic material is discussed by particular examples. The application fields of magnetic polymeric microspheres are briefly surveyed.

  20. Synthesis of magnetic polymeric microspheres

    International Nuclear Information System (INIS)

    Gervald, A Yu; Gritskova, Inessa A; Prokopov, Nikolai I

    2010-01-01

    The key types of magnetic polymeric microspheres are considered. Methods of synthesis of different types of magnetic nanoparticles and of preparation of stable magnetic fluids on their basis are outlined. The overview of the methods for the manufacture of magnetic polymeric microspheres is presented. The effect of the synthesis conditions on the characteristics of magnetic polymeric microspheres such as the diameter and the particle size distribution and the content of magnetic material is discussed by particular examples. The application fields of magnetic polymeric microspheres are briefly surveyed.

  1. Polar silica-based stationary phases. Part II- Neutral silica stationary phases with surface bound maltose and sorbitol for hydrophilic interaction liquid chromatography.

    Science.gov (United States)

    Rathnasekara, Renuka; El Rassi, Ziad

    2017-07-28

    Two neutral polyhydroxylated silica bonded stationary phases, namely maltose-silica (MALT-silica) and sorbitol-silica (SOR-silica), have been introduced and chromatographically characterized in hydrophilic interaction liquid chromatography (HILIC) for a wide range of polar compounds. The bonding of the maltose and sorbitol to the silica surface was brought about by first converting bare silica to an epoxy-activated silica surface via reaction with γ-glycidoxypropyltrimethoxysilane (GPTMS) followed by attaching maltose and sorbitol to the epoxy surface in the presence of the Lewis acid catalyst BF 3 .ethereate. Both silica based columns offered the expected retention characteristics usually encountered for neutral polar surface. The retention mechanism is majorly based on solute' differential partitioning between an organic rich hydro-organic mobile phase (e.g., ACN rich mobile phase) and an adsorbed water layer on the surface of the stationary phase although additional hydrogen bonding was also responsible in some cases for solute retention. The MALT-silica column proved to be more hydrophilic and offered higher retention, separation efficiency and resolution than the SOR-silica column among the tested polar solutes such as derivatized mono- and oligosaccharides, weak phenolic acids, cyclic nucleotide monophosphate and nucleotide-5'-monophosphates, and weak bases, e.g., nucleobases and nucleosides. Copyright © 2017 Elsevier B.V. All rights reserved.

  2. 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...

  3. Magnetic core-shell silica particles

    NARCIS (Netherlands)

    Claesson, E.M.

    2007-01-01

    This thesis deals with magnetic silica core-shell colloids and related functionalized silica structures. Synthesis routes have been developed and optimized. The physical properties of these colloids have been investigated, such as the magnetic dipole moment, dipolar structure formation and

  4. Impact of nanoclay dispersed phenol formaldehyde/fumed silica nanocomposites on physico-mechanical and thermal properties

    Science.gov (United States)

    Lai, Josephine Chang Hui; Rahman, Md. Rezaur; Hamdan, Sinin

    2017-12-01

    In this study, the physical, mechanical and thermal properties of phenol formaldehyde/fumed silica/nanoclay (PF/FS/clay) nanocomposites were investigated. PF/FS/clay nanocomposites were prepared via condensation polymerization method and the effect of different clays as compatibilizers were subsequently investigated. The properties of nanocomposites were characterized through Fourier Transform Infrared Spectroscopy (FT-IR), Scanning Electron Microscopy (SEM), Thermogravimetric Analysis (TGA) and tensile test. FT-IR results confirmed the condensation polymerization and the formation of nanocomposites. SEM result revealed that the surface-modified clay (1.34TCN) had better compatibility with PF/FS matrix compared to surface-modified clay (1.28E), clay (1.30E) and clay (1.31PS). Besides, clay (1.34TCN)-loaded nanocomposites showed better surface morphology among all the nanocomposites. Furthermore, PF/FS/clay (1.34TCN) nanocomposite exhibited better tensile strength and modulus up to 68% due to the strong interfacial bonding between the polymer matrix and fillers. Thermal stability of PF/FS/clay (1.34TCN) nanocomposite showed the highest weight percent loss at the final degradation stage with higher activation energy. Overall, this study proved that clay (1.34TCN) was the most suitable to be introduced in PF/FS matrix.

  5. Rhodium Catalyzed Decarbonylation

    DEFF Research Database (Denmark)

    Garcia Suárez, Eduardo José; Kahr, Klara; Riisager, Anders

    2017-01-01

    Rhodium catalyzed decarbonylation has developed significantly over the last 50 years and resulted in a wide range of reported catalyst systems and reaction protocols. Besides experimental data, literature also includes mechanistic studies incorporating Hammett methods, analysis of kinetic isotope...

  6. Clay catalyzed RNA synthesis under Martian conditions: Application for Mars return samples.

    Science.gov (United States)

    Joshi, Prakash C; Dubey, Krishna; Aldersley, Michael F; Sausville, Meaghen

    2015-06-26

    Catalysis by montmorillonites clay minerals is regarded as a feasible mechanism for the abiotic production and polymerization of key biomolecules on early Earth. We have investigated a montmorillonite-catalyzed reaction of the 5'-phosphorimidazolide of nucleosides as a model to probe prebiotic synthesis of RNA-type oligomers. Here we show that this model is specific for the generation of RNA oligomers despite deoxy-mononucleotides adsorbing equally well onto the montmorillonite catalytic surfaces. Optimum catalytic activity was observed over a range of pH (6-9) and salinity (1 ± 0.2 M NaCl). When the weathering steps of early Earth that generated catalytic montmorillonite were modified to meet Martian soil conditions, the catalytic activity remained intact without altering the surface layer charge. Additionally, the formation of oligomers up to tetramer was detected using as little as 0.1 mg of Na⁺-montmorillonite, suggesting that the catalytic activity of a Martian clay return sample can be investigated with sub-milligram scale samples. Copyright © 2015 Elsevier Inc. All rights reserved.

  7. Investigation of Supramolecular Coordination Self-Assembly and Polymerization Confined on Metal Surfaces Using Scanning Tunneling Microscopy

    Science.gov (United States)

    Lin, Tao

    derivatives. Firstly, we investigated the coordination self-assembly of a series of peripheral bromo-phenyl and pyridyl substituted porphyrins with Fe. The self-assembly of the porphyrin derivatives in which phenyl groups are substituted by bromo-phenyl results in coordination networks exhibiting identical structures to that of the parent compounds, but contained nanopores that are functionalized by bromine substitutes. Secondly, we studied a two-dimensional coordination networks formed by 5,10,15,20-tetra(4-pyridyl)porphyrin and Fe. We discovered a novel coordination motif in which a pair of vertically aligned Fe atoms is ligated by four equatorial pyridyl groups. Lateral manipulation, vertical manipulation and tunneling spectroscopy were employed to characterize the networks. These novel coordination networks decorated with Br or vertically aligned Fe atoms may provide potential functions as nano-receptor, molecular magnetism or catalyst. Part III addresses the mechanism of on-surface Ullmann coupling reaction. We studied Pd- and Cu-catalyzed Ullmann coupling reactions between phenyl bromide functionalized porphyrin derivatives. We discovered that the reactions catalyzed by Pd or Cu can be described as a two-phase process that involves an initial activation followed by C-C bond formation. Analysis of rate constants of the Pd-catalyzed reactions allowed us to determine its activation energy as (0.41 +/- 0.03) eV. These results provide a quantitative understanding of on-surface Ullmann coupling reaction. Part IV addresses the on-surface self-assembly driven by a combination of coordination bonds and covalent bonds. Firstly, we utilized metal-directed template to control the on-surface polymerization process. Taking advantage of efficient topochemical enhancement owing to the conformation flexibility of the Cu-pyridyl bonds, macromolecular porphyrin structures that exhibit a narrow size distribution were synthesized. The results reveal that the polymerization process profited

  8. Aza‐Michael addition reaction: Post‐polymerization modification and preparation of PEI/PEG‐based polyester hydrogels from enzymatically synthesized reactive polymers

    DEFF Research Database (Denmark)

    Hoffmann, Christian; Stuparu, Mihaiela C.; Daugaard, Anders Egede

    2015-01-01

    The utility of aza‐Michael addition chemistry for post‐polymerization functionalization of enzymatically prepared polyesters is established. For this, itaconate ester and oligoethylene glycol are selected as monomers. A Candida Antarctica lipase B catalyzed polycondensation reaction between the two...... monomers provides the polyesters, which carry an activated carbon‐carbon double bond in the polymer backbone. These electron deficient alkenes represent suitable aza‐Michael acceptors and can be engaged in a nucleophilic addition reaction with small molecular mono‐amines (aza‐Michael donors) to yield...... functionalized linear polyesters. Employing a poly‐amine as the aza‐Michael donor, on the other hand, results in the formation of hydrophilic polymer networks....

  9. Highly Active and Isospecific Styrene Polymerization Catalyzed by Zirconium Complexes Bearing Aryl-substituted [OSSO]-Type Bis(phenolate Ligands

    Directory of Open Access Journals (Sweden)

    Norio Nakata

    2016-01-01

    Full Text Available [OSSO]-type dibenzyl zirconium(IV complexes 9 and 10 possessing aryl substituents ortho to the phenoxide moieties (ortho substituents, phenyl and 2,6-dimethylphenyl (Dmp were synthesized and characterized. Upon activation with dMAO (dried methylaluminoxane, complex 9 was found to promote highly isospecific styrene polymerizations ([mm] = 97.5%–99% with high molecular weights Mw up to 181,000 g·mmol−1. When the Dmp-substituted pre-catalyst 10/dMAO system was used, the highest activity, over 7700 g·mmol(10−1·h−1, was recorded involving the formation of precisely isospecific polystyrenes of [mm] more than 99%.

  10. Unexpectedly Facile Rh(I) Catalyzed Polymerization of Ethynylbenzaldehyde Type Monomers: Synthesis of Polyacetylenes Bearing Reactive and Easy Transformable Pendant Carbaldehyde Groups

    Czech Academy of Sciences Publication Activity Database

    Sedláček, J.; Havelková, L.; Zedník, J.; Coufal, R.; Faukner, T.; Balcar, Hynek; Brus, Jiří

    2017-01-01

    Roč. 38, č. 8 (2017), č. článku 1600792. ISSN 1022-1336 R&D Projects: GA ČR(CZ) GA15-09637S Institutional support: RVO:61388955 ; RVO:61389013 Keywords : Ethynylbenzaldehydes * Inhibition of polymerization * Polyacetylenes Subject RIV: CF - Physical ; Theoretical Chemistry; CD - Macromolecular Chemistry (UMCH-V) OBOR OECD: Physical chemistry; Polymer science (UMCH-V) Impact factor: 4.265, year: 2016

  11. Anomalous enthalpy relaxation in vitreous silica

    DEFF Research Database (Denmark)

    Yue, Yuanzheng

    2015-01-01

    scans. It is known that the liquid fragility (i.e., the speed of the viscous slow-down of a supercooled liquid at its Tg during cooling) has impact on enthalpy relaxation in glass. Here, we find that vitreous silica (as a strong system) exhibits striking anomalies in both glass transition and enthalpy...... relaxation compared to fragile oxide systems. The anomalous enthalpy relaxation of vitreous silica is discovered by performing the hyperquenching-annealing-calorimetry experiments. We argue that the strong systems like vitreous silica and vitreous Germania relax in a structurally cooperative manner, whereas...... the fragile ones do in a structurally independent fashion. We discuss the origin of the anomalous enthalpy relaxation in the HQ vitreous silica....

  12. Solvent-Free Lipase-Catalyzed Synthesis of Diacylgycerols as Low-Calorie Food Ingredients.

    Science.gov (United States)

    Vázquez, Luis; González, Noemí; Reglero, Guillermo; Torres, Carlos

    2016-01-01

    Problems derived from obesity and overweight have recently promoted the development of fat substitutes and other low-calorie foods. On the one hand, fats with short- and medium-chain fatty acids are a source of quick energy, easily hydrolyzable and hardly stored as fat. Furthermore, 1,3-diacylglycerols are not hydrolyzed to 2-monoacylglycerols in the gastrointestinal tract, reducing the formation of chylomicron and lowers the serum level of triacylglycerols by decreasing its resynthesis in the enterocyte. In this work, these two effects were combined to synthesize short- and medium-chain 1,3-diacylglycerols, leading to a product with great potential as for their low-calorie properties. Lipase-catalyzed transesterification reactions were performed between short- and medium-chain fatty acid ethyl esters and glycerol. Different variables were investigated, such as the type of biocatalyst, the molar ratio FAEE:glycerol, the adsorption of glycerol on silica gel, or the addition of lecithin. Best reaction conditions were evaluated considering the percentage of 1,3-DAG produced and the reaction rate. Except Novozym 435 (Candida antarctica), other lipases required the adsorption of glycerol on silica gel to form acylglycerols. Lipases that gave the best results with adsorption were Novozym 435 and Lipozyme RM IM (Rhizomucor miehei) with 52 and 60.7% DAG at 32 h, respectively. Because of its specificity for sn-1 and sn-3 positions, lipases leading to a higher proportion of 1,3-DAG vs. 1,2-DAG were Lipozyme RM IM (39.8 and 20.9%, respectively) and Lipase PLG (Alcaligenes sp.) (35.9 and 19.3%, respectively). By adding 1% (w/w) of lecithin to the reaction with Novozym 435 and raw glycerol, the reaction rate was considerably increased from 41.7 to 52.8% DAG at 24 h.

  13. Chromatographic separation of metal cations on silica gel chemically modified with a polymeric derivative of diaza-18-crown-6

    International Nuclear Information System (INIS)

    Basyuk, V.A.

    1991-01-01

    Sorbent on the basis of γ-aminopropyl silica gel, containing chemically grafted polymer derivatives of diaza-18-crown-6, has been synthesized. Retaining of certain metal cations when acid mobile phases are used is studied. Acetate buffer solution, 0.005% aqueous solution of acetic acid and 10 mM aqueous solution of oxalic acid were used as mobile phases. Rare earth cations (including Sr 2+ ones) are weakly retained when any mobile phase is used. Retention of VO 2+ cations is the strongest one

  14. Mesoporous Silica from Rice Husk Ash

    Directory of Open Access Journals (Sweden)

    S.A. Mandavgane

    2010-12-01

    Full Text Available Mesoporous silica is used as a raw material in several areas: in preparation of catalysts, in inks, as aconcrete hardening accelerator, as a component of detergents and soaps, as a refractory constituent etc.Sodium silicate is produced by reacting rice hull ash (RHA with aqueous NaOH and silica is precipitatedfrom the sodium silicate by acidification. In the present work, conversion of about 90% of silica containedin RHA into sodium silicate was achieved in an open system at temperatures of about 100 °C. The resultsshowed that silica obtained from RHA is mesoporous, has a large surface area and small particle size.Rice Husk is usually mixed with coal and this mixture is used for firing boilers. The RHA therefore, usuallycontains carbon particles. Activated carbon embedded on silica has been prepared using the carbon alreadypresent in RHA. This carbon shows good adsorption capacity. ©2010 BCREC UNDIP. All rights reserved(Received: 25th April 2010, Revised: 17th June 2010, Accepted: 24th June 2010[How to Cite: V.R. Shelke, S.S. Bhagade, S.A. Mandavgane. (2010. Mesoporous Silica from Rice Husk Ash. Bulletin of Chemical Reaction Engineering and Catalysis, 5 (2: 63-67. doi:10.9767/bcrec.5.2.793.63-67

  15. Practical Hydrogen Loading of Air Silica Fibres

    DEFF Research Database (Denmark)

    Sørensen, Henrik Rokkjær; Jensen, Jesper Bevensee; Jensen, Jesper Bo Damm

    2005-01-01

    A method for hydrogen-loading air-silica optical fibres has been developed allowing out-diffusion times comparable to standard step-index fibres. Examples of the first grating written in Ge-doped air-silica fibres using a 266nm UV-laser are shown.......A method for hydrogen-loading air-silica optical fibres has been developed allowing out-diffusion times comparable to standard step-index fibres. Examples of the first grating written in Ge-doped air-silica fibres using a 266nm UV-laser are shown....

  16. RAFT polymerization mediated bioconjugation strategies

    OpenAIRE

    Bulmuş, Volga

    2011-01-01

    This review aims to highlight the use of RAFT polymerization in the synthesis of polymer bioconjugates. It covers two main bioconjugation strategies using the RAFT process: (i) post-polymerization bioconjugations using pre-synthesized reactive polymers, and (ii) bioconjugations via in situ polymerization using biomolecule-modified monomers or chain transfer agents. © 2011 The Royal Society of Chemistry.

  17. Effect of support on hydro-metathesis of propene: A comparative study of W(CH 3 ) 6 anchored to silica vs. silica-alumina

    KAUST Repository

    Tretiakov, Mykyta; Samantaray, Manoja; Saidi, Aya; Basset, Jean-Marie

    2018-01-01

    Hydro-metathesis of propene was carried out by using well-defined W(CH3)6 supported on silica and silica-alumina. It was observed that W(CH3)6 supported silica-alumina catalyst is much better (TON 4577) than the silica supported catalyst (TON 2104

  18. Altering the concentration of silica tunes the functional properties of collagen-silica composite scaffolds to suit various clinical requirements.

    Science.gov (United States)

    Perumal, Sathiamurthi; Ramadass, Satiesh Kumar; Gopinath, Arun; Madhan, Balaraman; Shanmugam, Ganesh; Rajadas, Jayakumar; Mandal, Asit Baran

    2015-12-01

    The success of a tissue engineering scaffold depends on a fine balance being achieved between the physicochemical and biological properties. This study attempts to understand the influence of silica concentration on the functional properties of collagen-silica (CS) composite scaffolds for soft tissue engineering applications. Increasing the ratio of silica to collagen (0.25, 0.5, 0.75, 1.0, 1.25, 1.5 and 2.0 w/w) gave a marked advantage in terms of improving the water uptake and compressive modulus of the CS scaffolds, while also enhancing the biological stability and the turnover time. With increase in silica concentration the water uptake and compressive modulus increased concurrently, whereas it was not so for surface porous architecture and biocompatibility which are crucial for cell adhesion and infiltration. Silica:collagen ratio of ≤1 exhibits favourable surface biocompatibility, and any further increase in silica concentration has a detrimental effect. Copyright © 2015 Elsevier Ltd. All rights reserved.

  19. Packaging based on polymeric materials

    Directory of Open Access Journals (Sweden)

    Jovanović Slobodan M.

    2005-01-01

    Full Text Available In the past two years the consumption of common in the developed countries world wide (high tonnage polymers for packaging has approached a value of 50 wt.%. In the same period more than 50% of the packaging units on the world market were made of polymeric materials despite the fact that polymeric materials present 17 wt.% of all packaging materials. The basic properties of polymeric materials and their environmental and economical advantages, providing them such a position among packaging materials, are presented in this article. Recycling methods, as well as the development trends of polymeric packaging materials are also presented.

  20. Silica-Coated Liposomes for Insulin Delivery

    OpenAIRE

    Neelam Dwivedi; M. A. Arunagirinathan; Somesh Sharma; Jayesh Bellare

    2010-01-01

    Liposomes coated with silica were explored as protein delivery vehicles for their enhanced stability and improved encapsulation efficiency. Insulin was encapsulated within the fluidic phosphatidylcholine lipid vesicles by thin film hydration at pH 2.5, and layer of silica was formed above lipid bilayer by acid catalysis. The presence of silica coating and encapsulated insulin was identified using confocal and electron microscopy. The native state of insulin present in the formulation was evid...

  1. Synthesis of Isotactic-block-Syndiotactic Poly(methyl Methacrylate via Stereospecific Living Anionic Polymerizations in Combination with Metal-Halogen Exchange, Halogenation, and Click Reactions

    Directory of Open Access Journals (Sweden)

    Naoya Usuki

    2017-12-01

    Full Text Available Isotactic (it- and syndiotactic (st- poly(methyl methacrylates (PMMAs form unique crystalline stereocomplexes, which are attractive from both fundamental and application viewpoints. This study is directed at the efficient synthesis of it- and st-stereoblock (it-b-st- PMMAs via stereospecific living anionic polymerizations in combination with metal-halogen exchange, halogenation, and click reactions. The azide-capped it-PMMA was prepared by living anionic polymerization of MMA, which was initiated with t-BuMgBr in toluene at –78 °C, and was followed by termination using CCl4 as the halogenating agent in the presence of a strong Lewis base and subsequent azidation with NaN3. The alkyne-capped st-PMMA was obtained by living anionic polymerization of MMA, which was initiated via an in situ metal-halogen exchange reaction between 1,1-diphenylhexyl lithium and an α-bromoester bearing a pendent silyl-protected alkyne group. Finally, copper-catalyzed alkyne-azide cycloaddition (CuAAC between these complimentary pairs of polymers resulted in a high yield of it-b-st-PMMAs, with controlled molecular weights and narrow molecular weight distributions. The stereocomplexation was evaluated in CH3CN and was affected by the block lengths and ratios.

  2. Synthesis of New Silicon-linked Lanthanocene Complexes and Their High Catalytic Activity for Methyl Methacrylate Polymerization with Nanometric Sodium Hydride as Co-catalyst

    Institute of Scientific and Technical Information of China (English)

    谢小敏; 黄吉玲

    2005-01-01

    The synthesis and characterization of four new silicon-linked lanthanocene complexes with pendant phenyl groups on cyclopentadiene were reported. Based on the data of elemental analyses, MS and IR, the complexes were presumed to be unsolvated and dimeric complexes [Me2Si(C5H3CMe2C6H5)2LnC1]2 [Ln=Er (1), Gd (2), Sm (3), Dy (4)]. In conjunction with AlEt3 or sodium hydride as the co-catalyst, these complexes could efficiently catalyze the polymerization of methyl methacrylate (MMA). When the nanometric sodium hydride was used as a co-catalyst, the complexes were highly effective for the polymerization of MMA. At low temperature and in short time, in [MeESi(C5H3CMe2C6H5)2LnC1]2/NaH (nanometric) system, the polymer was obtained in more than 80% yield and the molecular weight was greater than 105. The activity reached that of organolanthanide hydride as a single-component catalyst. In ]MeESi(C5H3CMe2C6H5)2ErC1]2/Nail (nanometric) system, the effects of the molar ratio of MMA/catalyst and catalyst/co-catalyst, and the temperature on polymerization were studied.

  3. Kinetics of silica-phase transitions

    International Nuclear Information System (INIS)

    Duffy, C.J.

    1993-07-01

    In addition to the stable silica polymorph quartz, several metastable silica phases are present in Yucca Mountain. The conversion of these phases to quartz is accompanied by volume reduction and a decrease in the aqueous silica activity, which may destabilize clinoptilolite and mordenite. The primary reaction sequence for the silica phases is from opal or glass to disordered opal-CT, followed by ordering of the opal-CT and finally by the crystallization of quartz. The ordering of opal-CT takes place in the solid state, whereas the conversion of opal-CT takes place through dissolution-reprecipitation involving the aqueous phase. It is proposed that the rate of conversion of opal-CT to quartz is controlled by diffusion of defects out of a disordered surface layer formed on the crystallizing quartz. The reaction rates are observed to be dependent on temperature, pressure, degree of supersaturation, and pH. Rate equations selected from the literature appear to be consistent with observations at Yucca Mountain

  4. Iodine-catalyzed diazo activation to access radical reactivity.

    Science.gov (United States)

    Li, Pan; Zhao, Jingjing; Shi, Lijun; Wang, Jin; Shi, Xiaodong; Li, Fuwei

    2018-05-17

    Transition-metal-catalyzed diazo activation is a classical way to generate metal carbene, which are valuable intermediates in synthetic organic chemistry. An alternative iodine-catalyzed diazo activation is disclosed herein under either photo-initiated or thermal-initiated conditions, which represents an approach to enable carbene radical reactivity. This metal-free diazo activation strategy were successfully applied into olefin cyclopropanation and epoxidation, and applying this method to pyrrole synthesis under thermal-initiated conditions further demonstrates the unique reactivity using this method over typical metal-catalyzed conditions.

  5. Silica-Gentamicin Nanohybrids: Synthesis and Antimicrobial Action

    Directory of Open Access Journals (Sweden)

    Dina Ahmed Mosselhy

    2016-03-01

    Full Text Available Orthopedic applications commonly require the administration of systemic antibiotics. Gentamicin is one of the most commonly used aminoglycosides in the treatment and prophylaxis of infections associated with orthopedic applications, but gentamicin has a short half-life. However, silica nanoparticles (SiO2 NPs can be used as elegant carriers for antibiotics to prolong their release. Our goal is the preparation and characterization of SiO2-gentamicin nanohybrids for their potential antimicrobial administration in orthopedic applications. In vitro gentamicin release profile from the nanohybrids (gentamicin-conjugated SiO2 NPs prepared by the base-catalyzed precipitation exhibited fast release (21.4% during the first 24 h and further extension with 43.9% release during the five-day experiment. Antimicrobial studies of the SiO2-gentamicin nanohybrids versus native SiO2 NPs and free gentamicin were performed against Bacillus subtilis (B. subtilis, Pseudomonas fluorescens (P. fluorescens and Escherichia coli (E. coli. SiO2-gentamicin nanohybrids were most effective against B. subtilis. SiO2 NPs play no antimicrobial role. Parallel antimicrobial studies for the filter-sterilized gentamicin were performed to assess the effect of ultraviolet (UV-irradiation on gentamicin. In summary, the initial fast gentamicin release fits the need for high concentration of antibiotics after orthopedic surgical interventions. Moreover, the extended release justifies the promising antimicrobial administration of the nanohybrids in bone applications.

  6. Health hazards due to the inhalation of amorphous silica

    Energy Technology Data Exchange (ETDEWEB)

    Merget, R.; Bruening, T. [Research Institute for Occupational Medicine (BGFA), Bochum (Germany); Bauer, T. [Bergmannsheil, University Hospital, Department of Internal Medicine, Division of Pneumonology, Allergology and Sleep Medicine, Bochum (Germany); Kuepper, H.U.; Breitstadt, R. [Degussa-Huels Corp., Wesseling (Germany); Philippou, S. [Department of Pathology, Augusta Krankenanstalten, Bochum (Germany); Bauer, H.D. [Research Institute for Hazardous Substances (IGF), Bochum (Germany)

    2002-01-01

    Occupational exposure to crystalline silica dust is associated with an increased risk for pulmonary diseases such as silicosis, tuberculosis, chronic bronchitis, chronic obstructive pulmonary disease (COPD) and lung cancer. This review summarizes the current knowledge about the health effects of amorphous (non-crystalline) forms of silica. The major problem in the assessment of health effects of amorphous silica is its contamination with crystalline silica. This applies particularly to well-documented pneumoconiosis among diatomaceous earth workers. Intentionally manufactured synthetic amorphous silicas are without contamination of crystalline silica. These synthetic forms may be classified as (1) wet process silica, (2) pyrogenic (''thermal'' or ''fumed'') silica, and (3) chemically or physically modified silica. According to the different physico-chemical properties, the major classes of synthetic amorphous silica are used in a variety of products, e.g. as fillers in the rubber industry, in tyre compounds, as free-flow and anti-caking agents in powder materials, and as liquid carriers, particularly in the manufacture of animal feed and agrochemicals; other uses are found in toothpaste additives, paints, silicon rubber, insulation material, liquid systems in coatings, adhesives, printing inks, plastisol car undercoats, and cosmetics. Animal inhalation studies with intentionally manufactured synthetic amorphous silica showed at least partially reversible inflammation, granuloma formation and emphysema, but no progressive fibrosis of the lungs. Epidemiological studies do not support the hypothesis that amorphous silicas have any relevant potential to induce fibrosis in workers with high occupational exposure to these substances, although one study disclosed four cases with silicosis among subjects exposed to apparently non-contaminated amorphous silica. Since the data have been limited, a risk of chronic bronchitis, COPD or

  7. Health hazards due to the inhalation of amorphous silica

    International Nuclear Information System (INIS)

    Merget, R.; Bruening, T.; Bauer, T.; Kuepper, H.U.; Breitstadt, R.; Philippou, S.; Bauer, H.D.

    2002-01-01

    Occupational exposure to crystalline silica dust is associated with an increased risk for pulmonary diseases such as silicosis, tuberculosis, chronic bronchitis, chronic obstructive pulmonary disease (COPD) and lung cancer. This review summarizes the current knowledge about the health effects of amorphous (non-crystalline) forms of silica. The major problem in the assessment of health effects of amorphous silica is its contamination with crystalline silica. This applies particularly to well-documented pneumoconiosis among diatomaceous earth workers. Intentionally manufactured synthetic amorphous silicas are without contamination of crystalline silica. These synthetic forms may be classified as (1) wet process silica, (2) pyrogenic (''thermal'' or ''fumed'') silica, and (3) chemically or physically modified silica. According to the different physico-chemical properties, the major classes of synthetic amorphous silica are used in a variety of products, e.g. as fillers in the rubber industry, in tyre compounds, as free-flow and anti-caking agents in powder materials, and as liquid carriers, particularly in the manufacture of animal feed and agrochemicals; other uses are found in toothpaste additives, paints, silicon rubber, insulation material, liquid systems in coatings, adhesives, printing inks, plastisol car undercoats, and cosmetics. Animal inhalation studies with intentionally manufactured synthetic amorphous silica showed at least partially reversible inflammation, granuloma formation and emphysema, but no progressive fibrosis of the lungs. Epidemiological studies do not support the hypothesis that amorphous silicas have any relevant potential to induce fibrosis in workers with high occupational exposure to these substances, although one study disclosed four cases with silicosis among subjects exposed to apparently non-contaminated amorphous silica. Since the data have been limited, a risk of chronic bronchitis, COPD or emphysema cannot be excluded. There is no

  8. Mesoporous silica/polyacrylamide composite: Preparation by UV-graft photopolymerization, characterization and use as Hg(II) adsorbent

    Energy Technology Data Exchange (ETDEWEB)

    Saad, Ali, E-mail: ali.saad8803@gmail.com [Laboratory of Materials, Molecules and Applications, IPEST, University of Carthage, Sidi Bou Said road, B.P. 51, 2070 La Marsa (Tunisia); Faculté des Sciences de Tunis, Université El Manar, PO Box 248, El Manar II, 2092 Tunis (Tunisia); Univ Paris Diderot, Sorbonne Paris Cité, ITODYS, UMR 7086, CNRS, F-75013 Paris (France); Bakas, Idriss [Univ Paris Diderot, Sorbonne Paris Cité, ITODYS, UMR 7086, CNRS, F-75013 Paris (France); Laboratoire AQUAMAR, Equipe Matériaux Photocatalyse et Environnement, Faculté des Sciences, Université Ibn Zohr, B.P. 8106, Cité Dakhla, Agadir (Morocco); Piquemal, Jean-Yves; Nowak, Sophie [Univ Paris Diderot, Sorbonne Paris Cité, ITODYS, UMR 7086, CNRS, F-75013 Paris (France); Abderrabba, Manef, E-mail: abderrabbamanef@gmail.com [Laboratory of Materials, Molecules and Applications, IPEST, University of Carthage, Sidi Bou Said road, B.P. 51, 2070 La Marsa (Tunisia); Chehimi, Mohamed M., E-mail: chehimi@icmpe.cnrs.fr [Univ Paris Diderot, Sorbonne Paris Cité, ITODYS, UMR 7086, CNRS, F-75013 Paris (France); Université Paris Est, ICMPE (UMR7182), CNRS, UPEC, F-94320 Thiais (France)

    2016-03-30

    Graphical abstract: - Highlights: • Mesoporous silica/polyacrylamide nanocomposite adsorbent was prepared by UV-graft polymerization. • Polyacrylamide was successfully grafted onto the silanized mesoporous silica. • The Hg(II) adsorption capacity of the nanocomposite was as high as 177 mg g{sup −1} after 1 h at RT. • Adsorption process was found to fit pseudo second order kinetics and exothermic. - Abstract: MCM-41 ordered mesoporous silica was prepared, aminosilanized and grafted with polyacrylamide (PAAM) through in situ radical photopolymerization process. The resulting composite, denoted PAAM-NH{sub 2}-MCM-41, the calcined and silanized reference MCM-41s were characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), scanning electron microscopy (SEM) and N{sub 2} physisorption at 77 K. These complementary techniques brought strong supporting evidence for the silanization process followed by PAAM grafting. The surface composition was found to be PAAM-rich as judged by XPS. The composite was then employed for the uptake of Hg(II) from aqueous solutions. Adsorption was monitored versus pH, time, and temperature. The maximum adsorption capacity at 25 °C and pH 5.2 was 177 mg g{sup −1}. Kinetically, the equilibrium was reached within 60 min for a 100 mg L{sup −1} mercury solution. The adsorption of Hg(II) on PAAM-NH{sub 2}-MCM-41 composites followed second order kinetics. Thermodynamic parameters suggested that the favorable adsorption process is exothermic in nature and the adsorption is ascribed to a decrease in the degree of freedom of adsorbed ions which results in the entropy change. This work conclusively shows that mesoporous silica–polymer hybrid metal ion adsorbents (with robust silica–polymer interface) can be prepared in a simple way by in situ radical photopolymerization in the presence of

  9. Cooperative effect by monopodal silica-supported niobium com-plexes pairs enhancing catalytic cyclic carbonate production

    KAUST Repository

    D'Elia, Valerio

    2015-05-07

    Recent discoveries highlighted the activity and the intriguing mechanistic features of NbCl5 as a molecular catalyst for the cycloaddition of CO2 and epoxides under ambient conditions. This has inspired the preparation of novel silica supported Nb-species by reacting a molecular niobium precursor [NbCl5•OEt2] with silica dehydroxylated at 700 °C (SiO2-700) or at 200 oC (SiO2-200) to generate diverse surface complexes. The product of the reaction between SiO2-700 and [NbCl5•OEt2] was identified as a monopodal supported surface species [≡SiONbCl4•OEt2] (1a). The reactions of SiO2-200 with the niobium precursor, according to two different protocols, generated surface complexes 2a and 3a presenting significant, but different, populations of the monopodal surface complex along with bipodal [(≡SiO)2NbCl3•OEt2]. 93Nb SSNMR spectra of 1a-3a and 31P SSNMR on their PMe3 derivatives (1b-3b) led to the unambiguous assignment of 1a as a single site, monopodal Nb-species while 2a and 3a were found to present two distinct surface-supported components, with 2a being mostly monopodal [≡SiONbCl4•OEt2] and 3a being mostly bipodal [≡S ONbCl3•OEt2]. Double-quantum/single-quantum 31P NMR correlation experiment carried out on 2b supported the existence of vicinal Nb centers on the silica surface for this species. 1a-3a were active heterogeneous catalysts for the synthesis of propylene carbonate from CO2 and propylene oxide under mild catalytic conditions; the performance of 2a was found to significantly surpass that of 1a and 3a. With the support of a systematic DFT study carried out on model silica surfaces, the observed differences in catalytic efficiency were correlated with an unprece-dented cooperative effect between two neighboring Nb centers on the surface of 2a. This is in an excellent agreement with our previous discoveries regarding the mechanism of the NbCl5 catalyzed cycloaddition in the homogeneous phase.

  10. Cooperative effect by monopodal silica-supported niobium com-plexes pairs enhancing catalytic cyclic carbonate production

    KAUST Repository

    D'Elia, Valerio; Dong, Hailin; Rossini, Aaron J; Widdifield, Cory M.; Vummaleti, Sai V. C.; Minenkov, Yury; Poater, Albert; Abou-Hamad, Edy; Pelletier, Jeremie D. A.; Cavallo, Luigi; Emsley, Lyndon; Basset, Jean-Marie

    2015-01-01

    Recent discoveries highlighted the activity and the intriguing mechanistic features of NbCl5 as a molecular catalyst for the cycloaddition of CO2 and epoxides under ambient conditions. This has inspired the preparation of novel silica supported Nb-species by reacting a molecular niobium precursor [NbCl5•OEt2] with silica dehydroxylated at 700 °C (SiO2-700) or at 200 oC (SiO2-200) to generate diverse surface complexes. The product of the reaction between SiO2-700 and [NbCl5•OEt2] was identified as a monopodal supported surface species [≡SiONbCl4•OEt2] (1a). The reactions of SiO2-200 with the niobium precursor, according to two different protocols, generated surface complexes 2a and 3a presenting significant, but different, populations of the monopodal surface complex along with bipodal [(≡SiO)2NbCl3•OEt2]. 93Nb SSNMR spectra of 1a-3a and 31P SSNMR on their PMe3 derivatives (1b-3b) led to the unambiguous assignment of 1a as a single site, monopodal Nb-species while 2a and 3a were found to present two distinct surface-supported components, with 2a being mostly monopodal [≡SiONbCl4•OEt2] and 3a being mostly bipodal [≡S ONbCl3•OEt2]. Double-quantum/single-quantum 31P NMR correlation experiment carried out on 2b supported the existence of vicinal Nb centers on the silica surface for this species. 1a-3a were active heterogeneous catalysts for the synthesis of propylene carbonate from CO2 and propylene oxide under mild catalytic conditions; the performance of 2a was found to significantly surpass that of 1a and 3a. With the support of a systematic DFT study carried out on model silica surfaces, the observed differences in catalytic efficiency were correlated with an unprece-dented cooperative effect between two neighboring Nb centers on the surface of 2a. This is in an excellent agreement with our previous discoveries regarding the mechanism of the NbCl5 catalyzed cycloaddition in the homogeneous phase.

  11. Grassy Silica Nanoribbons and Strong Blue Luminescence

    Science.gov (United States)

    Wang, Shengping; Xie, Shuang; Huang, Guowei; Guo, Hongxuan; Cho, Yujin; Chen, Jun; Fujita, Daisuke; Xu, Mingsheng

    2016-09-01

    Silicon dioxide (SiO2) is one of the key materials in many modern technological applications such as in metal oxide semiconductor transistors, photovoltaic solar cells, pollution removal, and biomedicine. We report the accidental discovery of free-standing grassy silica nanoribbons directly grown on SiO2/Si platform which is commonly used for field-effect transistors fabrication without other precursor. We investigate the formation mechanism of this novel silica nanostructure that has not been previously documented. The silica nanoribbons are flexible and can be manipulated by electron-beam. The silica nanoribbons exhibit strong blue emission at about 467 nm, together with UV and red emissions as investigated by cathodoluminescence technique. The origins of the luminescence are attributed to various defects in the silica nanoribbons; and the intensity change of the blue emission and green emission at about 550 nm is discussed in the frame of the defect density. Our study may lead to rational design of the new silica-based materials for a wide range of applications.

  12. Bleeding evaluation of the stationary phase from a few novel macroporous silica-substrate polymeric materials used for radionuclide partitioning from HLLW in MAREC process

    International Nuclear Information System (INIS)

    Zhang, A.; Wei, Y.; Kumagai, M.

    2005-01-01

    To separate minor actinides from HLLW by extraction chromatography, a few novel silica-based di(2-ethylhexyl)phosphoric acid (HDEHP), 4,4',(5')-di(tert-butylcyclohexano)-18-crown-6 (DtBuCH18C6), octyl(phenyl)-N,N-diisobutylcarbamoylmethylphosphine oxide (CMPO), and N,N,N',N'-tetraoctyl-3-oxapentane-1,5-diamide (TODGA) polymeric adsorption materials (HDEHP/SiO 2 -P, DtBuCH18C6/SiO 2 -P, CMPO/SiO 2 -P, and TODGA/SiO 2 -P) were synthesized by impregnating HDEHP, DtBuCH18C6, CMPO, and TODGA into the pores of porous SiO 2 -P particles, which were the new kind of inorganic/organic composites consisted of macroporous SiO 2 and copolymer. The bleeding behavior of these composites was investigated by examining the effect of contact time and HNO 3 concentration. It was found that in the tested HNO 3 concentration range, a noticeable quantity of DtBuCH18C6, at least 600 ppm, leaked out from DtBuCH18C6/SiO 2 -P because of the protonation of DtBuCH18C6 with hydrogen ion, while the others were lower and basically equivalent to the solubility of HDEHP, CMPO, or TODGA in corresponding acidities solutions. Based on the batch experiment, the bleeding of CMPO/SiO 2 -P and TODGA/SiO 2 -P, the main adsorbents used in MAREC process for HLLW partitioning, was evaluated by column operation in 0.01M HNO 3 and 3M HNO 3 . The quantity of CMPO leaked was ∼48 ppm in 0.01M HNO 3 and ∼37 ppm in 3.0M HNO 3 . The bleeding of TODGA decreased from 23.2 ppm to 7.27 ppm at the initial stage and then basically kept constant. An actual bleeding of TODGA was evaluated by the separation of Sr(II) from a 2.0M HNO 3 solution containing 5.0 x 10 -3 M of 6 typically simulated elements. (author)

  13. Winter climate change and fine root biogenic silica in sugar maple trees (Acer saccharum): Implications for silica in the Anthropocene

    Science.gov (United States)

    Maguire, Timothy J.; Templer, Pamela H.; Battles, John J.; Fulweiler, Robinson W.

    2017-03-01

    Winter temperatures are projected to increase over the next century, leading to reductions in winter snowpack and increased frequency of soil freezing in many northern forest ecosystems. Here we examine biogenic silica (BSi) concentrations in sugar maple (Acer saccharum) fine roots collected from a snow manipulation experiment at Hubbard Brook Experimental Forest (New Hampshire, USA). Increased soil freezing significantly lowered the BSi content of sugar maple fine roots potentially decreasing their capacity to take up water and dissolved nutrients. The reduced silica uptake (8 ± 1 kmol silica km-2) by sugar maple fine roots is comparable to silica export from temperate forest watersheds. We estimate that fine roots account for 29% of sugar maple BSi, despite accounting for only 4% of their biomass. These results suggest that increased frequency of soil freezing will reduce silica uptake by temperate tree roots, thereby changing silica availability in downstream receiving waters.

  14. Chelating polymeric membranes

    KAUST Repository

    Peinemann, Klaus-Viktor

    2015-01-22

    The present application offers a solution to the current problems associated with recovery and recycling of precious metals from scrap material, discard articles, and other items comprising one or more precious metals. The solution is premised on a microporous chelating polymeric membrane. Embodiments include, but are not limited to, microporous chelating polymeric membranes, device comprising the membranes, and methods of using and making the same.

  15. Mesoporous Silica from Rice Husk Ash

    Directory of Open Access Journals (Sweden)

    V.R. Shelke

    2011-01-01

    Full Text Available Mesoporous silica is used as a raw material in several areas: in preparation of catalysts, in inks, as a concrete hardening accelerator, as a component of detergents and soaps, as a refractory constituent etc. Sodium silicate is produced by reacting rice hull ash (RHA with aqueous NaOH and silica is precipitated from the sodium silicate by acidification. In the present work, conversion of about 90% of silica contained in RHA into sodium silicate was achieved in an open system at temperatures of about 100 °C. The results showed that silica obtained from RHA is mesoporous, has a large surface area and small particle size. Rice Husk is usually mixed with coal and this mixture is used for firing boilers. The RHA therefore, usually contains carbon particles. Activated carbon embedded on silica has been prepared using the carbon already present in RHA. This carbon shows good adsorption capacity. ©2010 BCREC UNDIP. All rights reserved(Received: 25th April 2010, Revised: 17th June 2010, Accepted: 24th June 2010[How to Cite: V.R. Shelke, S.S. Bhagade, S.A. Mandavgane. (2010. Mesoporous Silica from Rice Husk Ash. Bulletin of Chemical Reaction Engineering and Catalysis, 5 (2: 63-67. doi:10.9767/bcrec.5.2.793.63-67][DOI: http://dx.doi.org/10.9767/bcrec.5.2.793.63-67

  16. Representing Rate Equations for Enzyme-Catalyzed Reactions

    Science.gov (United States)

    Ault, Addison

    2011-01-01

    Rate equations for enzyme-catalyzed reactions are derived and presented in a way that makes it easier for the nonspecialist to see how the rate of an enzyme-catalyzed reaction depends upon kinetic constants and concentrations. This is done with distribution equations that show how the rate of the reaction depends upon the relative quantities of…

  17. Production and Application of Olivine Nano-Silica in Concrete

    Science.gov (United States)

    Mardiana, Oesman; Haryadi

    2017-05-01

    The aim of this research was to produce nano silica by synthesis of nano silica through extraction and dissolution of ground olivine rock, and applied the nano silica in the design concrete mix. The producing process of amorphous silica used sulfuric acid as the dissolution reagent. The separation of ground olivine rock occurred when the rock was heated in a batch reactor containing sulfuric acid. The results showed that the optimum mole ratio of olivine- acid was 1: 8 wherein the weight ratio of the highest nano silica generated. The heating temperature and acid concentration influenced the mass of silica produced, that was at temperature of 90 °C and 3 M acid giving the highest yield of 44.90%. Characterization using Fourier Transform Infrared (FTIR ) concluded that amorphous silica at a wavenumber of 1089 cm-1 indicated the presence of siloxane, Si-O-Si, stretching bond. Characterization using Scanning Electron Microscope - Energy Dispersive Spectroscopy (SEM-EDS) showed the surface and the size of the silica particles. The average size of silica particles was between 1-10 μm due to the rapid aggregation of the growing particles of nano silica into microparticles, caused of the pH control was not fully achieved.

  18. Pumping Iron and Silica Bodybuilding

    Science.gov (United States)

    Mcnair, H.; Brzezinski, M. A.; Krause, J. W.; Parker, C.; Brown, M.; Coale, T.; Bruland, K. W.

    2016-02-01

    The availability of dissolved iron influences the stoichiometry of nutrient uptake by diatoms. Under nutrient replete conditions diatoms consume silicic acid and nitrate in a 1:1 ratio, this ratio increases under iron stress. Using the tracers 32Si and PDMPO, the total community and group-specific silica production rates were measured along a gradient of dissolved iron in an upwelling plume off the California coast. At each station, a control (ambient silicic acid) and +20 µM silicic acid treatment were conducted with each tracer to determine whether silicic acid limitation controlled the rate of silica production. Dissolved iron was 1.3 nmol kg-1 nearshore and decreased to 0.15 nmol kg-1 offshore. Silicic acid decreased more rapidly than nitrate, it was nearly 9 µM higher in the nearshore and 7 µM lower than nitrate in the middle of the transect where the iron concentration had decreased. The rate of diatom silica production decreased in tandem with silicic acid concentration, and silica production limitation by low silicic acid was most pronounced when iron concentrations were >0.4 nmol kg-1. The composition of the diatom assemblage shifted from Chaetoceros spp. dominated nearshore to a more sparse pennate-dominated assemblage offshore. Changes in taxa-specific silica production rates will be reported based on examination of PDMPO labeled cells using confocal microscopy.

  19. Application of acid-catalyzed hydrolysis of dispersed organic solvent in developing new microencapsulation process technology.

    Science.gov (United States)

    Lee, Honghwa; Lee, Sunhwa; Bhattacharjee, Himanshu; Sah, Hongkee

    2012-01-01

    The aim of this study was to evaluate a new microencapsulation technology employing an acid-catalyzed solvent extraction method in conjunction to an emulsion-based microencapsulation process. Its process consisted of emulsifying a dispersed phase of poly(D,L-lactide-co-glycolide) and isopropyl formate in an aqueous phase. This step was followed by adding hydrochloric acid to the resulting oil-in-water emulsion, in order to initiate the hydrolysis of isopropyl formate dissolved in the aqueous phase. Its hydrolysis caused the liberation of water-soluble species, that is, isopropanol and formic acid. This event triggered continual solvent leaching out of emulsion droplets, thereby initiating microsphere solidification. This new processing worked well for encapsulation of progesterone and ketoprofen that were chosen as a nonionizable model drug and a weakly acidic one, respectively. Furthermore, the structural integrity of poly(D,L-lactide-co-glycolide) was retained during microencapsulation. The new microencapsulation technology, being conceptually different from previous approaches, might be useful in preparing various polymeric particles.

  20. Functionalization and Polymerization on the CNT Surfaces

    KAUST Repository

    Albuerne, Julio

    2013-07-01

    In this review we focus on the current status of using carbon nanotube (CNT) as a filler for polymer nanocomposites. Starting with the historical background of CNT, its distinct properties and the surface functionalization of the nanotube, the three different surface polymerization techniques, namely grafting "from", "to" and "through/in between" were discussed. Wider focus has been given on "grafting from" surface initiated polymerizations, including atom transfer radical polymerization (ATRP), reversible addition fragmentation chain-transfer (RAFT) Polymerization, nitroxide mediated polymerization (NMP), ring opening polymerization (ROP) and other miscellaneous polymerization methods. The grafting "to" and "through / in between" also discussed and compared with grafting from polymerization. The merits and shortcomings of all three grafting methods were discussed and the bottleneck issue in grafting from method has been highlighted. Furthermore the current and potential future industrial applications were deliberated. Finally the toxicity issue of CNTs in the final product has been reviewed with the limited available literature knowledge. © 2013 Bentham Science Publishers.

  1. Rheological behavior of oil well cements slurries containing polyurethane and silica flour; Estudo reologico de pastas de cimento com adicao de poliuretana e silica flour

    Energy Technology Data Exchange (ETDEWEB)

    Fernandes, M.R.P.; Silva, P.D.; Martinelli, A.E.; Melo, D.M.A.; Silva, B.N. [Universidade Federal do Rio Grande do Norte (UFRN), Natal, RN (Brazil); Araujo, R.G.S. [Universidade Estadual de Campinas (UNICAMP), SP (Brazil)

    2008-07-01

    A number of heat-resistant polymeric admixtures have been tested in the search of new cementing materials for adverse field conditions, including advanced recovery by steam injection. High-temperature applications also involve the use of silica as anti-retrogression agent in the composition of cement slurries. However, the addition of polymers to the cement usually affects the rheological behavior of the slurry, especially increasing its plastic viscosity. The rheological properties play an important role in determining the success of a cementing or squeeze project. The major rheological parameters of a cement slurry include its yield strength, plastic viscosity and gel strength. The rheological parameters of a cement slurry are determined following API SPEC 10A and NBR 9830:1993, using a coaxial viscosimeter. The data recorded from the viscosimeter is used to fit a rheological model, e.g., Bingham, power-law, de Herschel-Bulkley, Newton, Casson or Vocadlo. Portland-based cement slurries are mainly fitted either by Bingham, power-law or Herschel-Bulkley models. The present study aimed at determining the rheological behavior of cementing slurries as a function of the contents of polyurethane (5 - to 25% BWOC) and 40% BWOC silica flour. The slurries also contained 0.015 gpc antifoaming. The specific weight of the slurries was preset at 15.6 lb/gal. The rheological tests were carried out at 30.5 deg C (87 deg F) using a Chandler 3500 viscosimeter. After the homogenization of the slurries during 20 min in the atmospheric consistometer, the slurries were poured into a thermal recipient and sheared in the viscosimeter at different speeds ranging from 3 to 300 rpm, both in the ascending and descending way. Readings were taken after 10 s intervals and averaged. Filter loss tests were also carried out to study the effect of polyurethane and silica in the slurry using a Fann HPHT Filter Press. The results obtained in the rheological tests revealed that increasing the

  2. Effect of silica particle size on macrophage inflammatory responses.

    Directory of Open Access Journals (Sweden)

    Toshimasa Kusaka

    Full Text Available Amorphous silica particles, such as nanoparticles (<100 nm diameter particles, are used in a wide variety of products, including pharmaceuticals, paints, cosmetics, and food. Nevertheless, the immunotoxicity of these particles and the relationship between silica particle size and pro-inflammatory activity are not fully understood. In this study, we addressed the relationship between the size of amorphous silica (particle dose, diameter, number, and surface area and the inflammatory activity (macrophage phagocytosis, inflammasome activation, IL-1β secretion, cell death and lung inflammation. Irrespective of diameter size, silica particles were efficiently internalized by mouse bone marrow-derived macrophages via an actin cytoskeleton-dependent pathway, and induced caspase-1, but not caspase-11, activation. Of note, 30 nm-1000 nm diameter silica particles induced lysosomal destabilization, cell death, and IL-1β secretion at markedly higher levels than did 3000 nm-10000 nm silica particles. Consistent with in vitro results, intra-tracheal administration of 30 nm silica particles into mice caused more severe lung inflammation than that of 3000 nm silica particles, as assessed by measurement of pro-inflammatory cytokines and neutrophil infiltration in bronchoalveolar lavage fluid of mice, and by the micro-computed tomography analysis. Taken together, these results suggest that silica particle size impacts immune responses, with submicron amorphous silica particles inducing higher inflammatory responses than silica particles over 1000 nm in size, which is ascribed not only to their ability to induce caspase-1 activation but also to their cytotoxicity.

  3. Pecan drying with silica gel

    Energy Technology Data Exchange (ETDEWEB)

    Ghate, S.R.; Chhinnan, M.S.

    1983-07-01

    High moisture in-shell pecans were dried by keeping them in direct and indirect contact with silica gel to investigate their drying characteristics. In-shell pecans were also dried with ambient air from a controlled environment chamber and with air dehumidified by silica gel. Direct contact and dehumidified air drying seemed feasible approaches.

  4. Catalyzing RE Project Development

    Energy Technology Data Exchange (ETDEWEB)

    Anderson, Kate; Elgqvist, Emma; Walker, Andy; Cutler, Dylan; Olis, Dan; DiOrio, Nick; Simpkins, Travis

    2016-09-01

    This poster details how screenings done with REopt - NREL's software modeling platform for energy systems integration and optimization - are helping to catalyze the development of hundreds of megawatts of renewable energy.

  5. Influence of organic solvents on interfacial water at surfaces of silica gel and partially silylated fumed silica

    International Nuclear Information System (INIS)

    Turov, V.V.; Gun'ko, V.M.; Tsapko, M.D.; Bogatyrev, V.M.; Skubiszewska-Zieba, J.; Leboda, R.; Ryczkowski, J.

    2004-01-01

    The effects of organic solvents (dimethylsulfoxide-d 6 (DMSO-d 6 ), chloroform-d, acetone-d 6 , and acetonitrile-d 3 ) on the properties of interfacial water at surfaces of silica gel Si-40 and partially silylated fumed silica A-380 were studied by means of the 1 H NMR spectroscopy with freezing-out of adsorbed water at 180 1 H NMR investigations were also analysed on the basis of the structural characteristics of silicas and quantum chemical calculations of the chemical shifts δ H and solvent effects. DMSO-d 6 and acetonitrile-d 3 are poorly miscible with water in silica gel pores in contrast to the bulk liquids. DMSO-d 6 and chloroform-d affect the structure of the interfacial water weaker than acetone-d 6 and acetonitrile-d 3 at amounts of liquids greater than the pore volume. Acetone-d 6 and acetonitrile-d 3 can displace water from pores under this condition. The chemical shift of protons in water adsorbed on silica gel is 3.5-6.5 ppm, which corresponds to the formation of two to four hydrogen bonds per molecule. Water adsorbed on partially silylated fumed silica has two 1 H NMR signals at 5 and 1.1-1.7 ppm related to different structures (droplets and small clusters) of the interfacial water

  6. New Palladium-Catalyzed Approaches to Heterocycles and Carbocycles

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Qinhua [Iowa State Univ., Ames, IA (United States)

    2004-12-19

    The tert-butylimines of o-(1-alkynyl)benzaldehydes and analogous pyridinecarbaldehydes have been cyclized under very mild reaction conditions in the presence of I2, ICl, PhSeCl, PhSCl and p-O2NC6H4SCl to give the corresponding halogen-, selenium- and sulfur-containing disubstituted isoquinolines and naphthyridines, respectively. Monosubstituted isoquinolines and naphthyridines have been synthesized by the metal-catalyzed ring closure of these same iminoalkynes. This methodology accommodates a variety of iminoalkynes and affords the anticipated heterocycles in moderate to excellent yields. The Pd(II)-catalyzed cyclization of 2-(1-alkynyl)arylaldimines in the presence of various alkenes provides an efficient way to synthesize a variety of 4-(1-alkenyl)-3-arylisoquinolines in moderate to excellent yields. The introduction of an ortho-methoxy group on the arylaldimine promotes the Pd-catalyzed cyclization and stabilizes the resulting Pd(II) intermediate, improving the yields of the isoquinoline products. Highly substituted naphthalenes have been synthesized by the palladium-catalyzed annulation of a variety of internal alkynes, in which two new carbon-carbon bonds are formed in a single step under relatively mild reaction conditions. This method has also been used to synthesize carbazoles, although a higher reaction temperature is necessary. The process involves arylpalladation of the alkyne, followed by intramolecular Heck olefination and double bond isomerization. This method accommodates a variety of functional groups and affords the anticipated highly substituted naphthalenes and carbazoles in good to excellent yields. Novel palladium migratiodarylation methodology for the synthesis of complex fused polycycles has been developed, in which one or more sequential Pd-catalyzed intramolecular migration processes involving C-H activation are employed. The chemistry works best with electron-rich aromatics, which is in agreement

  7. Silica and lung cancer: a controversial issue.

    Science.gov (United States)

    Pairon, J C; Brochard, P; Jaurand, M C; Bignon, J

    1991-06-01

    The role of crystalline silica in lung cancer has long been the subject of controversy. In this article, we review the main experimental and epidemiological studies dealing with this problem. Some evidence for a genotoxic potential of crystalline silica has been obtained in the rare in vitro studies published to date. In vivo studies have shown that crystalline silica is carcinogenic in the rat; the tumour types appear to vary according to the route of administration. In addition, an association between carcinogenic and fibrogenic potency has been observed in various animal species exposed to crystalline silica. An excess of lung cancer related to occupational exposure to crystalline silica is reported in many epidemiological studies, regardless of the presence of silicosis. However, most of these studies are difficult to interpret because they do not correctly take into account associated carcinogens such as tobacco smoke and other occupational carcinogens. An excess of lung cancer is generally reported in studies based on silicosis registers. Overall, experimental and human studies suggest an association between exposure to crystalline silica and an excess of pulmonary malignancies. Although the data available are not sufficient to establish a clear-cut causal relationship in humans, an association between the onset of pneumoconiosis and pulmonary malignancies is probable. In contrast, experimental observations have given rise to a pathophysiological mechanism that might account for a putative carcinogenic potency of crystalline silica.

  8. Nanoporous Polymeric Grating-Based Biosensors

    KAUST Repository

    Gao, Tieyu; Hsiao, Vincent; Zheng, Yue Bing; Huang, Tony Jun

    2012-01-01

    We demonstrate the utilization of an interferometrically created nanoporous polymeric gratings as a platform for biosensing applications. Aminopropyltriethoxysilane (APTES)-functionalized nanoporous polymeric gratings was fabricated by combining holographic interference patterning and APTES-functionalization of pre-polymer syrup. The successful detection of multiple biomolecules indicates that the biofunctionalized nanoporous polymeric gratings can act as biosensing platforms which are label-free, inexpensive, and applicable as high-throughput assays. Copyright © 2010 by ASME.

  9. Nanoporous Polymeric Grating-Based Biosensors

    KAUST Repository

    Gao, Tieyu

    2012-05-02

    We demonstrate the utilization of an interferometrically created nanoporous polymeric gratings as a platform for biosensing applications. Aminopropyltriethoxysilane (APTES)-functionalized nanoporous polymeric gratings was fabricated by combining holographic interference patterning and APTES-functionalization of pre-polymer syrup. The successful detection of multiple biomolecules indicates that the biofunctionalized nanoporous polymeric gratings can act as biosensing platforms which are label-free, inexpensive, and applicable as high-throughput assays. Copyright © 2010 by ASME.

  10. New Silica Magnetite Sorbent: The Influence of Variations of Sodium Silicate Concentrations on Silica Magnetite Character

    Science.gov (United States)

    Azmiyawati, C.; Pratiwi, P. I.; Darmawan, A.

    2018-04-01

    The adsorption capacity of an adsorbent is determined by the adsorbent and the adsorbate properties. The character of the adsorbent will play a major role in its ability to adsorb the corresponding adsorbate. Therefore, in this study we looked at the effects of variations of sodium silicate concentrations on the resulting magnetite silica adsorbent properties. The application of silica coating on the magnetite was carried out through a sol-gel process with sodium silicate and HCl precursors. Based on the characterization data obtained, it was found that the silica coating on magnetite can increase the resistance to acid leaching, increase the particle size, but decrease the magnetic properties of the magnetite. Based on Gas Sorption Analyzer (GSA) and X-ray Difraction (XRD) data it can successively be determined that increase in concentration of sodium silicate will increase the surface area and amorphous structure of the Silica Magnetie.

  11. cis,cis-Muconic acid: separation and catalysis to bio-adipic acid for nylon-6,6 polymerization

    Energy Technology Data Exchange (ETDEWEB)

    Vardon, Derek R.; Rorrer, Nicholas A.; Salvachúa, Davinia; Settle, Amy E.; Johnson, Christopher W.; Menart, Martin J.; Cleveland, Nicholas S.; Ciesielski, Peter N.; Steirer, K. Xerxes; Dorgan, John R.; Beckham, Gregg T.

    2016-01-01

    cis,cis-Muconic acid is a polyunsaturated dicarboxylic acid that can be produced renewably via the biological conversion of sugars and lignin-derived aromatic compounds. Subsequently, muconic acid can be catalytically converted to adipic acid -- the most commercially significant dicarboxylic acid manufactured from petroleum. Nylon-6,6 is the major industrial application for adipic acid, consuming 85% of market demand; however, high purity adipic acid (99.8%) is required for polymer synthesis. As such, process technologies are needed to effectively separate and catalytically transform biologically derived muconic acid to adipic acid in high purity over stable catalytic materials. To that end, this study: (1) demonstrates bioreactor production of muconate at 34.5 g L-1 in an engineered strain of Pseudomonas putida KT2440, (2) examines the staged recovery of muconic acid from culture media, (3) screens platinum group metals (e.g., Pd, Pt, Rh, Ru) for activity and leaching stability on activated carbon (AC) and silica supports, (4) evaluates the time-on-stream performance of Rh/AC in a trickle bed reactor, and (5) demonstrates the polymerization of bio-adipic acid to nylon-6,6. Separation experiments confirmed AC effectively removed broth color compounds, but subsequent pH/temperature shift crystallization resulted in significant levels of Na, P, K, S and N in the crystallized product. Ethanol dissolution of muconic acid precipitated bulk salts, achieving a purity of 99.8%. Batch catalysis screening reactions determined that Rh and Pd were both highly active compared to Pt and Ru, but Pd leached significantly (1-9%) from both AC and silica supports. Testing of Rh/AC in a continuous trickle bed reactor for 100 h confirmed stable performance after 24 h, although organic adsorption resulted in reduced steady-state activity. Lastly, polymerization of bio-adipic acid with hexamethyldiamine produced nylon-6,6 with comparable properties to its petrochemical counterpart

  12. Dispersibility of silica fume in mortar and its effect on properties of mortar. Silica fume no bunsan to mortar no shotokusei

    Energy Technology Data Exchange (ETDEWEB)

    Oga, H; Uomoto, T [The University of Tokyo, Tokyo (Japan). Institute of Industrial Science

    1992-08-01

    Effect of silica fume dispersibility on concrete characteristics was discussed. Properties of mortar mixed with silica fume to exhibit compression strength varied with displacement rates, patterns, and mixing time of silica fume. In submerged curing age of 28 days, the compression strength in a mortar mixed with silica fume at 10% was affected only very little by the mixing time for both pelletizing and non-pelletizing types for up to 180 seconds. The strength increased thereafter with the mixing time. The compression strength at 1020 seconds showed higher value by about 150 kgf/cm [sup 2] than when no silica fume is added, with a difference because of patterns disappearing. In the case of a mixing time of 1020 seconds, neutralization depth receives very little effect from a pattern difference, and decreases with increasing displacement rate. Neutralization coefficient of the mortar mixed with silica fume at 10% decreased with the mixing time, and it was possible to suppress the neutralization coefficient to 25% of the case without silica fume addition in a 1020-second mixing. 7 refs., 8 figs., 1 tab.

  13. Well-defined polyethylene-based graft terpolymers by combining nitroxide-mediated radical polymerization, polyhomologation and azide/alkyne “click” chemistry†

    KAUST Repository

    Alkayal, Nazeeha

    2016-03-30

    Novel well–defined polyethylene–based graft terpolymers were synthesized via the “grafting onto” strategy by combining nitroxide-mediated radical polymerization (NMP), polyhomologation and copper (I)-catalyzed azide-alkyne cycloaddition (CuAAC) “click” chemistry. Three steps were involved in this approach: (i) synthesis of alkyne-terminated polyethylene-b-poly(ε-caprolactone) (PE-b-PCL-alkyne) block copolymers (branches) by esterification of PE-b-PCL-OH with 4-pentynoic acid; the PE-b-PCL-OH was obtained by polyhomologation of dimethylsulfoxonium methylide to afford PE-OH, followed by ring opening polymerization of ε-caprolactone using the PE-OH as macroinitiator, (ii) synthesis of random copolymers of styrene (St) and 4-chloromethylstyrene (4-CMS) with various CMS contents, by nitroxide-mediated radical copolymerization (NMP), and conversion of chloride to azide groups by reaction with sodium azide (NaN3) (backbone) and (iii) “click” linking reaction to afford the PE-based graft terpolymers. All intermediates and final products were characterized by high-temperature size exclusion chromatography (HT-SEC), Fourier transform infrared spectroscopy (FTIR), proton nuclear magnetic resonance spectroscopy (1H NMR) and differential scanning calorimetry (DSC).

  14. Synthesis of Silica Nanoparticles by Sol-Gel: Size-Dependent Properties, Surface Modification, and Applications in Silica-Polymer Nano composites-A Review

    International Nuclear Information System (INIS)

    Ismail, A.R.; Vejayakumaran, P.

    2012-01-01

    Application of silica nanoparticles as fillers in the preparation of nano composite of polymers has drawn much attention, due to the increased demand for new materials with improved thermal, mechanical, physical, and chemical properties. Recent developments in the synthesis of monodispersed, narrow-size distribution of nanoparticles by sol-gel method provide significant boost to development of silica-polymer nano composites. This paper is written by emphasizing on the synthesis of silica nanoparticles, characterization on size-dependent properties, and surface modification for the preparation of homogeneous nano composites, generally by sol-gel technique. The effect of nano silica on the properties of various types of silica-polymer composites is also summarized.

  15. Silica sol as grouting material: a physio-chemical analysis.

    Science.gov (United States)

    Sögaard, Christian; Funehag, Johan; Abbas, Zareen

    2018-01-01

    At present there is a pressing need to find an environmentally friendly grouting material for the construction of tunnels. Silica nanoparticles hold great potential of replacing the organic molecule based grouting materials currently used for this purpose. Chemically, silica nanoparticles are similar to natural silicates which are essential components of rocks and soil. Moreover, suspensions of silica nanoparticles of different sizes and desired reactivity are commercially available. However, the use of silica nanoparticles as grouting material is at an early stage of its technological development. There are some critical parameters such as long term stability and functionality of grouted silica that need to be investigated in detail before silica nanoparticles can be considered as a reliable grouting material. In this review article we present the state of the art regarding the chemical properties of silica nanoparticles commercially available, as well as experience gained from the use of silica as grouting material. We give a detailed description of the mechanisms underlying the gelling of silica by different salt solutions such as NaCl and KCl and how factors such as particle size, pH, and temperature affect the gelling and gel strength development. Our focus in this review is on linking the chemical properties of silica nanoparticles to the mechanical properties to better understand their functionality and stability as grouting material. Along the way we point out areas which need further research.

  16. Preparation of thick silica coatings on carbon fibers with fine-structured silica nanotubes induced by a self-assembly process

    Directory of Open Access Journals (Sweden)

    Benjamin Baumgärtner

    2017-05-01

    Full Text Available A facile method to coat carbon fibers with a silica shell is presented in this work. By immobilizing linear polyamines on the carbon fiber surface, the high catalytic activity of polyamines in the sol–gel-processing of silica precursors is used to deposit a silica coating directly on the fiber’s surface. The surface localization of the catalyst is achieved either by attaching short-chain polyamines (e.g., tetraethylenepentamine via covalent bonds to the carbon fiber surface or by depositing long-chain polyamines (e.g., linear poly(ethylenimine on the carbon fiber by weak non-covalent bonding. The long-chain polyamine self-assembles onto the carbon fiber substrate in the form of nanoscopic crystallites, which serve as a template for the subsequent silica deposition. The silicification at close to neutral pH is spatially restricted to the localized polyamine and consequently to the fiber surface. In case of the linear poly(ethylenimine, silica shells of several micrometers in thickness can be obtained and their morphology is easily controlled by a considerable number of synthesis parameters. A unique feature is the hierarchical biomimetic structure of the silica coating which surrounds the embedded carbon fiber by fibrillar and interconnected silica fine-structures. The high surface area of the nanostructured composite fiber may be exploited for catalytic applications and adsorption purposes.

  17. Ordered nanoporous silica as carriers for improved delivery of water insoluble drugs: a comparative study between three dimensional and two dimensional macroporous silica

    Directory of Open Access Journals (Sweden)

    Wang Y

    2013-10-01

    Full Text Available Ying Wang, Qinfu Zhao, Yanchen Hu, Lizhang Sun, Ling Bai, Tongying Jiang, Siling WangDepartment of Pharmaceutics, Shenyang Pharmaceutical University, Liaoning Province, People’s Republic of ChinaAbstract: The goal of the present study was to compare the drug release properties and stability of the nanoporous silica with different pore architectures as a matrix for improved delivery of poorly soluble drugs. For this purpose, three dimensional ordered macroporous (3DOM silica with 3D continuous and interconnected macropores of different sizes (200 nm and 500 nm and classic mesoporous silica (ie, Mobil Composition of Matter [MCM]-41 and Santa Barbara Amorphous [SBA]-15 with well-ordered two dimensional (2D cylindrical mesopores were successfully fabricated and then loaded with the model drug indomethacin (IMC via the solvent deposition method. Scanning electron microscopy (SEM, N2 adsorption, differential scanning calorimetry (DSC, and X-ray diffraction (XRD were applied to systematically characterize all IMC-loaded nanoporous silica formulations, evidencing the successful inclusion of IMC into nanopores, the reduced crystallinity, and finally accelerated dissolution of IMC. It was worth mentioning that, in comparison to 2D mesoporous silica, 3DOM silica displayed a more rapid release profile, which may be ascribed to the 3D interconnected pore networks and the highly accessible surface areas. The results obtained from the stability test indicated that the amorphous state of IMC entrapped in the 2D mesoporous silica (SBA-15 and MCM-41 has a better physical stability than in that of 3DOM silica. Moreover, the dissolution rate and stability of IMC loaded in 3DOM silica was closely related to the pore size of macroporous silica. The colorimetric 3-(4,5-Dimethylthiazol-2-yl-2,5-diphenyltetrazolium bromide (MTT and Cell Counting Kit (CCK-8 assays in combination with direct morphology observations demonstrated the good biocompatibility of nanoporous

  18. Measurement and modelization of silica opal optical properties

    OpenAIRE

    Avoine , Amaury; Ngoc Hong , Phan; Frederich , Hugo; Aregahegn , Kifle; Bénalloul , Paul; Coolen , Laurent; Schwob , Catherine; Thu Nga , Pham; Gallas , Bruno; Maître , Agnès

    2014-01-01

    International audience; We present the synthesis process and optical characterization of artificial silica opals. The specular reflection spectra are analyzed and compared to band structure calculations and finite difference time domain (FDTD) simulations. The silica optical index is a key parameter to correctly describe an opal and is usually not known and treated as a free parameter. Here we propose a method to infer the silica index, as well as the silica spheres diameter, from the reflect...

  19. Functionalized mesoporous silica materials for molsidomine adsorption: Thermodynamic study

    International Nuclear Information System (INIS)

    Alyoshina, Nonna A.; Parfenyuk, Elena V.

    2013-01-01

    A series of unmodified and organically modified mesoporous silica materials was prepared. The unmodified mesoporous silica was synthesized via sol–gel synthesis in the presence of D-glucose as pore-forming agent. The functionalized by phenyl, aminopropyl and mercaptopropyl groups silica materials were prepared via grafting. The fabricated adsorbent materials were characterized by Fourier transform infrared spectroscopy (FTIR) analysis, N 2 adsorption/desorption and elemental analysis methods. Then their adsorption properties for mesoionic dug molsidomine were investigated at 290–313 K and physiological pH value. Thermodynamic parameters of molsidomine adsorption on the synthesized materials have been calculated. The obtained results showed that the adsorption process of molsidomine on the phenyl modified silica is the most quantitatively and energetically favorable. The unmodified and mercaptopropyl modified silica materials exhibit significantly higher adsorption capacities and energies for molsidomine than the aminopropyl modified sample. The effects are discussed from the viewpoint of nature of specific interactions responsible for the adsorption. - Graphical abstract: Comparative analysis of the thermodynamic characteristics of molsidomine adsorption showed that the adsorption process on mesoporous silica materials is controlled by chemical nature of surface functional groups. Molsidomine adsorption on the phenyl modified silica is the most quantitatively and energetically favorable. Taking into account ambiguous nature of mesoionic compounds, it was found that molsidomine is rather aromatic than dipolar. Display Omitted - Highlights: • Unmodified and organically modified mesoporous silica materials were prepared. • Molsidomine adsorption on the silica materials was studied. • Phenyl modified silica shows the highest adsorption capacity and favorable energy. • Molsidomine exhibits the lowest affinity to aminopropyl modified silica

  20. Functionalized Mesoporous Silica Membranes for CO2 Separation Applications

    Directory of Open Access Journals (Sweden)

    Hyung-Ju Kim

    2015-01-01

    Full Text Available Mesoporous silica molecular sieves are emerging candidates for a number of potential applications involving adsorption and molecular transport due to their large surface areas, high pore volumes, and tunable pore sizes. Recently, several research groups have investigated the potential of functionalized mesoporous silica molecular sieves as advanced materials in separation devices, such as membranes. In particular, mesoporous silica with a two- or three-dimensional pore structure is one of the most promising types of molecular sieve materials for gas separation membranes. However, several important challenges must first be addressed regarding the successful fabrication of mesoporous silica membranes. First, a novel, high throughput process for the fabrication of continuous and defect-free mesoporous silica membranes is required. Second, functionalization of mesopores on membranes is desirable in order to impart selective properties. Finally, the separation characteristics and performance of functionalized mesoporous silica membranes must be further investigated. Herein, the synthesis, characterization, and applications of mesoporous silica membranes and functionalized mesoporous silica membranes are reviewed with a focus on CO2 separation.