Sample records for catalyzed silica polymerization

  1. Kinetics of silica polymerization

    Energy Technology Data Exchange (ETDEWEB)

    Weres, O.; Yee, A.; Tsao, L.


    The polymerization of silicic acid in geothermal brine-like aqueous solutions to produce amorphous silica in colloidal form has been studied experimentally and theoretically. A large amount of high quality experimental data has been generated over the temperature rang 23 to 100{sup 0}C. Wide ranges of dissolved silica concentration, pH, and sodium chloride concentration were covered. The catalytic effects of fluoride and the reaction inhibiting effects of aluminum and boron were studied also. Two basic processes have been separately studied: the formation of new colloidal particles by the homogeneous nucleation process and the deposition of dissolved silica on pre-existing colloidal particles. A rigorous theory of the formation of colloidal particles of amorphous silica by homogeneous nucleation was developed. This theory employs the Lothe-Pound formalism, and is embodied in the computer code SILNUC which quantitatively models the homogeneous nucleation and growth of colloidal silica particles in more than enough detail for practical application. The theory and code were extensively used in planning the experimental work and analyzing the data produced. The code is now complete and running in its final form. It is capable of reproducing most of the experimental results to within experimental error. It is also capable of extrapolation to experimentally inaccessible conditions, i.e., high temperatures, rapidly varying temperature and pH, etc.

  2. Structure and growth of polymeric niobia-silica mixed-oxide sols for microporous molecular sieving membranes: A SAXS study

    NARCIS (Netherlands)

    Boffa, V.; Castricum, H.L.; Garcia, Ruben; Schmuhl, R.; Petukhov, Andrei V.; Blank, David H.A.; ten Elshof, Johan E.


    Branched polymeric niobia-silica (NS) mixed-oxide sols with a Nb:Si molar ratio between 0.33 and 0.8 were made by acid-catalyzed sol−gel synthesis and characterized using small-angle X-ray scattering (SAXS) and dynamic light scattering (DLS). The growth rate of NS sols after addition of a niobium

  3. Bioengineering of the silica-polymerizing enzyme silicatein-alpha for a targeted application to hydroxyapatite. (United States)

    Natalio, Filipe; Link, Thorben; Müller, Werner E G; Schröder, Heinz C; Cui, Fu-Zhai; Wang, Xiaohong; Wiens, Matthias


    Since its discovery, numerous biotechnological approaches have aimed to explore the silica-polymerizing catalytic activity of the enzyme silicatein. In vivo, silicatein catalyzes polymerization of amorphous silica nanospheres from soluble precursors. In vitro, it directs the formation of nanostructured biosilica. This is of interest for various applications that strive to benefit from both the advantages of the biological system (i.e., silica synthesis under physiological conditions) and the cell mineralization-stimulating effect of biosilica. However, so far immobilization of silicatein has been hampered by the complex multistep procedure required. In addition, the chemical surface modifications involved not only restrict the choice of carrier materials but also render application of silicatein to hydroxyapatite (HA) of mineralized tissue impossible. Here we describe the bioengineering of silicatein, adapted for application in the fields of bone regeneration, tissue engineering, and dental care. Inspired by Glu-rich sequences of mammalian proteins that confer binding affinity to HA, a novel protein-tag was developed, the Glu-tag. Following expression of Glu-tagged silicatein, the HA-binding capacity of the enzyme is demonstrated in combination with synthetic and dental HA. Furthermore, immobilized Glu-tagged silicatein catalyzes synthesis of biosilica coatings on both synthetic HA nanofibrils and dental HA. Hence, Glu-tagged silicatein reveals a considerable biomedical potential with regenerative and prophylactic implementations. 2010 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

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

    National Research Council Canada - National Science Library

    Chua, David


    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...

  5. Studies of Olefin Dimerization, Oligomerization, and Polymerization Catalyzed by Cationic (alpha-Diimine)Ni(II) Complexes

    National Research Council Canada - National Science Library

    Svejda, Steven


    .... The development of cationic (alpha-diimine)nickel(II) and palladium(II) complexes which catalyze the polymerization of both ethylene and alpha-olefins to high polymers represents a major advance in the field of olefin polymerization catalysis...

  6. 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.


    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

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

    Directory of Open Access Journals (Sweden)

    Bérangère Bailly


    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.

  8. 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.


    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.

  9. Effect of Oxygen and Initiator Solubility on Admicellar Polymerization of Styrene on Silica Surfaces

    Directory of Open Access Journals (Sweden)

    Pohlee Cheah


    Full Text Available Although admicellar polymerization has been termed the surface analog of emulsion polymerization, previous reports utilizing free radical-initiated admicellar polymerization relied on high levels of the free radical initiator when compared to emulsion polymerization, likely due to the presence of oxygen in the reported admicellar polymerization systems. Admicellar polymerizations of styrene on the surface of precipitated silica initiated by either a water-soluble or a water-insoluble initiator were studied to determine the effect of dissolved oxygen and free radical initiator solubility on the kinetics, yield, and molecular weight of the polymer formed. Results show that the presence of oxygen reduces the polymer yield and limits molecular weight. The solubility of the initiator also affected the polymer formed in the admicellar polymerization of styrene. While monomer conversions and polymer yield were similar, the molecular weights of polymerizations initiated by a water-soluble initiator were higher than comparable polymerizations initiated by a water-insoluble initiator.

  10. Amylase catalyzed synthesis of glycosyl acrylates and their polymerization

    NARCIS (Netherlands)

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


    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

  11. 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.


    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)

  12. Surface modification of silica nanoparticles by UV-induced graft polymerization of methyl methacrylate. (United States)

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


    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.

  13. Polymeric Nanocapsule from Silica Nanoparticle@Cross-linked Polymer Nanoparticles via One-Pot Approach

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    Shen Ruoping


    Full Text Available Abstract A facile strategy was developed here to prepare cross-linked polymeric nanocapsules (CP nanocapsules with silica nanoparticles as templates. The silica nanoparticle@cross-linked polymer nanoparticles were prepared by the encapsulation of the silica nanoparticles by the one-pot approach via surface-initiated atom transfer radical polymerization of hydroxyethyl acrylate in the presence ofN,N′-methylenebisacrylamide as a cross-linker from the initiator-modified silica nanoparticles. After the silica nanoparticle templates were etched with hydrofluoric acid, the CP nanocapsules with particle size of about 100 nm were obtained. The strategy developed was confirmed with Fourier transform infrared, thermogravimetric analysis and transmission electron microscopy.

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

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


    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. The effect of high temperature sol-gel polymerization parameters on the microstructure and properties of hydrophobic phenol-formaldehyde/silica hybrid aerogels. (United States)

    Seraji, Mohamad Mehdi; Sameri, Ghasem; Davarpanah, Jamal; Bahramian, Ahmad Reza


    Phenol-formaldehyde/silica hybrid aerogels with different degree of hydrophobicity were successfully synthesized via high temperature sol-gel polymerization. Tetraethoxysilane (TEOS) and methyltriethoxysilane (MTES) were used as precursor and co-precursor of the hydrophobic silica-based phase, respectively. The hydrolysis step of silica based sols were conducted by acid catalyzed reactions and HCl was used as hydrolysis catalyst. The chemical structure of prepared hybrid aerogels was characterized by Fourier Transform Infrared spectroscopy (FT-IR). The effect of MTES/TEOS proportion and catalyst content on the morphology and microstructure of samples were investigated by FE-SEM and C, Si mapping analysis. The acid catalyzed hydrolysis of TEOS and MTES sols leads to formation of a sol with primarily silica particles in the organic-inorganic hybrid sol and varying colloid growth mechanisms were occurred with change in MTES and HCl molar ratio. With the increasing of MTES content, the microstructure of samples changed from uniform colloidal network, core-shell structure to polymeric structure with a huge phase separation. The increasing of HCl mole fraction leads to smaller particle size. Moreover, the shrinkage of samples was decreased and water contact angles of the resulted aerogels were increased from 40 to 156.8° with the increases of MTES content. Copyright © 2017 Elsevier Inc. All rights reserved.

  16. Highly Branched Polypropylene via Li(+)-Catalyzed Radical Polymerization

    Czech Academy of Sciences Publication Activity Database

    Braunecker, W. A.; Akdag, A.; Boon, B. A.; Michl, Josef


    Roč. 44, č. 6 (2011), s. 1229-1232 ISSN 0024-9297 Grant - others:NSF(US) CHE-0715374; GA MŠk(CZ) ME09001 Program:ME Institutional research plan: CEZ:AV0Z40550506 Keywords : radical polymerization * 13C NMR spectroscopy * Li+ coordination * polyhedral anion CB11Me12- Subject RIV: CC - Organic Chemistry Impact factor: 5.167, year: 2011

  17. Metallocene-catalyzed alkene polymerization and the observation of Zr-allyls (United States)

    Landis, Clark R.; Christianson, Matthew D.


    Single-site polymerization catalysts enable exquisite control over alkene polymerization reactions to produce new materials with unique properties. Knowledge of catalyst speciation and fundamental kinetics are essential for full mechanistic understanding of zirconocene-catalyzed alkene polymerization. Currently the effect of activators on fundamental polymerization steps is not understood. Progress in understanding activator effects requires determination of fundamental kinetics for zirconocene catalysts with noncoordinating anions such as [B(C6F5)4]−. Kinetic NMR studies at low temperature demonstrate a very fast propagation rate for 1-hexene polymerization catalyzed by [(SBI)Zr(CH2SiMe3)][B(C6F5)4] [where SBI is rac-Me2Si(indenyl)2] with complete consumption of 1-hexene before the first NMR spectrum. Surprisingly, the first NMR spectrum reveals, aside from uninitiated catalyst, Zr-allyls as the sole catalyst-containing species. These Zr-allyls, which exist in two diastereomeric forms, have been characterized by physical and chemical methods. The mechanism of Zr-allyl formation was probed with a trapping experiment, leading us to favor a mechanism in which Zr-polymeryl undergoes β-H transfer to metal without dissociation of coordinated alkene followed by σ-bond metathesis to form H2 and Zr-allyl. Zr-allyl species undergo slow reactions with alkene but react rapidly with H2 to form hydrogenation products. PMID:17032772

  18. Polymerization of Ethylene Catalyzed by Vanadium(III Complexes

    Directory of Open Access Journals (Sweden)

    Hamdi Ali Elagab


    Full Text Available Thirty five  complexes of 1,2- bis(benzimidazole, benzothiazole and benzoxazolebenzene,  1,2-bis(benzimidazole, benzothiazole and benzoxazole-4-methyl-benzene, 1,2-bis  (benzimidazole, benzothiazole and benzoxazole4-bromobenzene, 1, 2-bis(benzimidazole, benzothiazole and benzoxazole 4- chlorobenzene,  and 2, 6-bis(benzimidazole, benzothiazole and benzoxazole pyridine compounds with V (III metal centers were synthesized, characterized, activated with methylalumoxane (MAO and then tested for catalytic ethylene polymerization. The catalysts generally show moderate to good activities compared to the benchmark catalyst Cp2ZrCl2. The activities of the various catalysts were found to be function of the hetero atoms in the ligand frameworks and also strongly influenced by the bridging unit of the ligand. The highest activity was obtained with 36 / MAO (442 kg PE / mol cat. h. The produced polyethylenes showed high molecular weights (up to 2.7 × 106 g/mol and broad molecular weight distributions (PD = 1.4 - 16.6. Thermal analysis of polyethylenes produced with vanadium complexes revealed that the catalyst systems were capable to produce high density polyethylenes with melting temperatures > 135 °C and crystallization temperatures range from 117-120 °C with high degree of crystallinity. DOI: 

  19. 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.


    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

  20. 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.


    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

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

    KAUST Repository

    Zhao, Junpeng


    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.

  2. Robust Plasma Polymerized-Titania/Silica Janus Microparticles (United States)


    the assembly of two diffe- rent components combined into a single unit along an interface which allows the design of multifaceted micro- particles... microcapsules .21 In addition to spherical Janus particles, discs, cylinders, and other biphasic structures have also been fabri- cated.22,23 Other...complete, uniform layer, which conformally coats on the designated and highly curved surface areas. Different plasma polymerized coatings can be em- ployed

  3. Preparation of epoxy-acrylate copolymer/nano-silica via Pickering emulsion polymerization and its application as printing binder (United States)

    Gao, Dangge; Chang, Rui; Lyu, Bin; Ma, Jianzhong; Duan, Xiying


    This paper presents a facile and efficient synthesis method to fabricate epoxy-acrylate copolymer/nano-silica latex via Pickering emulsion polymerization stabilized by silica sol. The effects of solid contents, silica concentration and polymerization time on emulsion polymerization were studied. The core-shell epoxy-acrylate copolymer/nano-silica was obtained with average diameter 690 nm, was observed by Transmission Electron Microscopy (TEM) and Dynamic Light Scattering (DLS). The formation mechanism of epoxy-acrylate copolymer/nano-silica emulsion polymerization was proposed through observing the morphology of latex particles at different polymerization time. Fourier Transformation Infrared (FT-IR) and Thermogravimetric Analysis (TGA) were used to study structure and thermostability of the composites. Morphology of the latex film was characterized by Scanning Electron Microscope (SEM). The results indicated that nano-silica particles existed in the composite emulsion and could improve the thermal stability of the film. The epoxy-acrylate copolymer/nano-silica latex was used as binder applied to cotton fabric for pigment printing. The application results demonstrated that Pickering emulsion stabilized by silica sol has good effects in the pigment printing binder without surfactant. Compared with commodity binder, the resistance to wet rubbing fastness and soaping fastness were improved half grade.

  4. 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: [Universidade do Vale do Rio dos Sinos (UNISINOS), Sao Leopoldo, RS (Brazil). Pos-Graduacao em Engenharia Civil


    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)

  5. Cu-catalyzed multicomponent polymerization to synthesize a library of poly(N-sulfonylamidines). (United States)

    Lee, In-Hwan; Kim, Hyunseok; Choi, Tae-Lim


    We report a versatile Cu-catalyzed multicomponent polymerization (MCP) technique that enables the synthesis of high-molecular-weight, defect-free poly(N-sulfonylamidines) from monomers of diynes, sulfonyl azides, and diamines. Through a series of optimizations, we discovered that the addition of excess triethylamine and the use of N,N'-dimethylformamide as a solvent are key factors to ensure efficient MCP. Formation of cyclic polyamidines was a side reaction during polymerization, but it was readily controlled by using diynes or diamines with long or rigid moieties. In addition, this polymerization is highly selective for three-component reactions over click reactions. The combination of the above factors enables the synthesis of high-molecular-weight polymers, which was challenging in previous MCPs. All three kinds of monomers (diynes, sulfonyl azides, and diamines) are readily accessible and stable under the reaction conditions, with various monomers undergoing successful polymerization regardless of their steric and electronic properties. Thus, we synthesized various high-molecular-weight, defect-free polyamidines from a broad range of monomers while overcoming the limitations of previous MCPs, such as low conversion and defects in the polymer structures.

  6. Molecular Imprinting of Silica Nanoparticle Surfaces via Reversible Addition-Fragmentation Polymerization for Optical Biosensing Applications (United States)

    Oluz, Zehra; Nayab, Sana; Kursun, Talya Tugana; Caykara, Tuncer; Yameen, Basit; Duran, Hatice

    Azo initiator modified surface of silica nanoparticles were coated via reversible addition-fragmentation polymerization (RAFT) of methacrylic acid and ethylene glycol dimethacrylate using 2-phenylprop 2-yl dithobenzoate as chain transfer agent. Using L-phenylalanine anilide as template during polymerization led molecularly imprinted nanoparticles. RAFT polymerization offers an efficient control of grafting process, while molecularly imprinted polymers shows enhanced capacity as sensor. L-phenylalanine anilide imprinted silica particles were characterized by X-Ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM). Performances of the particles were followed by surface plasmon resonance spectroscopy (SPR) after coating the final product on gold deposited glass substrate against four different analogous of analyte molecules: D-henylalanine anilide, L-tyrosine, L-tryptophan and L-phenylalanine. Characterizations indicated that silica particles coated with polymer layer do contain binding sites for L-phenylalanine anilide, and are highly selective for the molecule of interest. This project was supported by TUBITAK (Project No:112M804).

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

    Directory of Open Access Journals (Sweden)

    J. Lv


    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.

  8. 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:; Jiang, Bin; Zhao, Minnan; Zhang, Yan


    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.

  9. Transition metal catalyzed polymerization of butadiene in supercritical CO{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Borkowsky, S. [Los Alamos National Lab., NM (United States)]|[Stanford Univ., CA (United States); Tumas, W. [Los Alamos National Lab., NM (United States); Waymouth, R.M. [Stanford Univ., CA (United States)


    A class of Ni(II) catalysts has been shown to stereoselectively catalyze the 1,4-polymerization of butadiene. The authors have been investigating the use of supercritical CO{sub 2} as an environmentally benign replacement solvent for conventional hydrocarbon and halocarbon solvents for a variety of chemical transformations. Above 31 C, CO{sub 2} enters a supercritical phase, where its physical properties are both liquid-like and gas-like. Importantly, the solvent properties such as dielectric constant for supercritical fluids can be varied by changing the pressure of the fluid. In this report, the authors present results of an investigation of the polymerization of 1,3-butadiene using [({pi}-allyl) Ni(CF{sub 3}CO{sub 2})]{sub 2} in supercritical CO{sub 2}. They conducted 1,3-butadiene polymerizations in CO{sub 2} to determine whether or not they could systematically and predictably adjust the regiochemistry/stereochemistry of the polybutadiene product by varying the solution properties at different pressures. They also mention experiments with CO catalysts that are known to give 1,2-syndiotactic polybutadiene, and with a Pd catalyst system that is known to copolymerize olefin with CO to give perfectly alternating copolymers.

  10. A water-soluble precursor for efficient silica polymerization by silicateins. (United States)

    Povarova, Natalia V; Markina, Nadezda M; Baranov, Mikhail S; Barinov, Nikolay A; Klinov, Dmitry V; Kozhemyako, Valery B; Lukyanov, Konstantin A


    Silicateins, the spicule-forming proteins from marine demosponges capable to polymerize silica, are popular objects of biomineralization studies due to their ability to form particles varied in shape and composition under physiological conditions. Despite the occurrence of the many approaches to nanomaterial synthesis using silicateins, biochemical properties of this protein family are poorly characterized. The main reason for this is that tetraethyl orthosilicate (TEOS), the commonly used silica acid precursor, is almost insoluble in water and thus is poorly available for the protein. To solve this problem, we synthesized new water-soluble silica precursor, tetra(glycerol)orthosilicate (TGS), and characterized biochemical properties of the silicatein A1 from marine sponge Latrunculia oparinae. Compared to TEOS, TGS ensured much greater activity of silicatein and was less toxic for the mammalian cell culture. We evaluated optimum conditions for the enzyme - pH range, temperature and TGS concentration. We concluded that TGS is a useful silica acid precursor that can be used for silica particles synthesis and in vivo applications. Copyright © 2017 Elsevier Inc. All rights reserved.


    Directory of Open Access Journals (Sweden)

    N. G. Leonova


    Full Text Available The polymer and composites were received using epoxy resin EPONEX 1510 – diglycidyl ether of dicyclohexylolpropane and 15 % solution of boron trifluoride in diethylene glycol. The silica particles were formed in situ via the sol-gel method using hydrolytic polycondensation of tetraethoxysilane. The silica sol was obtained in acetone as the organic solvent. Silica filler content in the composites varied from 0.5 to 3 wt%. The effect of the nanofiller on the thermophysical and thermal properties of the obtained polymers was studied. Thermophysical characteristics were determined by differential scanning calorimetry on a TA Instruments DSC Q2000 apparatus at a rate of heating of 20 °С/min in the temperature range from 5 to 190 °C. With the objective of decreasing the influence of the technological (kinetic and thermal prehistory of the sample on its thermophysical characteristics, the scanning was done twice. The glass transition temperature and heat capacity jump of the composite coatings based on epoxy-silica prepared by cationic polymerization were studied. It was established that with an increase of filler content the glass transition temperature of composites increases, and the value of the heat capacity jump remains almost unchanged. Parameters of thermostability of polymer and composites were determined by thermogravimetric analysis on a TA Instruments Q50 apparatus at a rate of heating of 20 °С/min in the temperature range from 20 to 1000 °C in an atmosphere of oxygen. The destruction process of epoxy-silica composites proceeds in several stages. In the deep stages of the thermo-oxidative destruction of obtained composites the effect of the silica filler is insignificant. The obtained polymer coatings were subjected to a long-term (100 hours isothermal aging at 160 °C in an atmosphere of oxygen. It was determined that the maximum rate of mass loss rate of epoxy-silica composites is 1.5 times lower than that of unmodified polymer.

  12. Study of radiation-induced polymerization of vinyl monomers adsorbed on inorganic substances. IX. Preirradiation polymerization of styrene--silica gel system

    International Nuclear Information System (INIS)

    Fukano, K.; Kageyama, E.


    Preirradiation polymerization of the styrene-silica gel system was studied in detail. Both graft polymers and homopolymers have bimodal GPC spectra. High molecular weight peaks were formed in a radical mechanism and the low molecular weight peaks were formed in a cationic mechanism as same as those in the simultaneous irradiation polymerization. The rate of formation of the low molecular weight peaks was very high compared with that of the high molecular weight peaks. Monomer conversion and percent grafting leveled off at about 1--2 Mrad. Radiation dose dependence of the four peaks were different from each other. Monomer conversion and percent grafting decreased as the preheating temperature of silica gel increased. The amount of the low molecular weight peaks of graft polymers depended on the number of silanol groups, as in the case of the simultaneous irradiation polymerization. A reaction mechanism for the preirradiation polymerization is proposed based on the results obtained

  13. Constrained Geometry Organotitanium Catalysts Supported on Nanosized Silica for Ethylene (co)Polymerization. (United States)

    Li, Kuo-Tseng; Wu, Ling-Huey


    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.

  14. The polymerizations of alkylsilane and bis-(γ-triethoxysilylpropyl)-tetrasulfide catalyzed by copper nanoparticles and the effects of transition metal ions on the polymerizations of alkylsilane catalyzed by silver nanoparticles

    International Nuclear Information System (INIS)

    Yan Jiangmei; Zi Guoli; Yang Feng; Mi Yangli; Yang Xikun; Wang Wei; Zou Qinpeng; Wang Jiaqiang


    Poly(vinylpyrrolidone) (PVP)-capped copper nanoparticles synthesized by solvent-based polyol reduction were found to be effective catalysts for the polymerization of octadecylsilane and bis-(γ-triethoxysilylpropyl)-tetrasulfide. Comparing with PVP-capped silver nanoparticles, copper nanoparticles exhibited different catalytic activity, and the polymerization products also showed different morphologies. The effects of transition metal ions on the polymerization of octadecylsilane catalyzed by PVP-capped silver nanoparticles were also investigated. It was found that transition of metal ions not only had strong effects on the morphologies of the products of polymerizations, but also resulted in the disappearance of silver oxide. The products were characterized by scanning electron microscopy (SEM), Fourier transform infrared (FT-IR) and X-ray powder diffraction (XRD).

  15. Improved Synthesis of 5-Substituted 1H-Tetrazoles via the [3+2] Cycloaddition of Nitriles and Sodium Azide Catalyzed by Silica Sulfuric Acid (United States)

    Du, Zhenting; Si, Changmei; Li, Youqiang; Wang, Yin; Lu, Jing


    A silica supported sulfuric acid catalyzed [3+2] cycloaddition of nitriles and sodium azide to form 5-substituted 1H-tetrazoles is described. The protocol can provide a series of 5-substituted 1H-tetrazoles using silica sulfuric acid from nitriles and sodium azide in DMF in 72%–95% yield. PMID:22606004

  16. Half-sandwich group 4 metal siloxy and silsesquioxane complexes : Soluble model systems for silica-grafted olefin polymerization catalysts

    NARCIS (Netherlands)

    Duchateau, R; Cremer, U; Harmsen, RJ; Mohamud, SI; Abbenhuis, HCL; van Santen, RA; Meetsma, A; Thiele, SKH; van Tol, MFH; Kranenburg, M


    The cuboctameric hydroxysilsesquioxane (c-C5H9)(7)Si8O12(OH) (2), obtained after hydrolysis of (c-C5H9)(7)Si8O12Cl (1), and triphenylsilanol have been applied as model supports for silica-grafted olefin polymerization catalysts. The ligands were introduced on group 4 metals by either chloride


    NARCIS (Netherlands)



    The kinetics of the L-lactide bulk polymerization was studied using tin(II) bis(2-ethylhexanoate) and zinc bis(2,2-dimethyl-3,5-heptanedionato-O,O'). Up to 80% conversion, the rate of polymerization using tin(II) bis(2-ethylhexanoate) is higher than that with the zinc-containing catalyst, while at

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

    Directory of Open Access Journals (Sweden)

    Stavroula Nanaki


    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.

  19. Polymeric carbon nitride/mesoporous silica composites as catalyst support for Au and Pt nanoparticles. (United States)

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


    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.

  20. 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: [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)


    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

  1. Formation of silver nanoparticles in an acid-catalyzed silica colloidal solution (United States)

    Jiang, Zhong-Jie; Liu, Chun-Yan; Liu, Yun


    In a weak basic, weak acidic or neutral water-alcohol solution, silver nanoparticles were generated by the reduction of Ag + ions in the present of colloidal silica. Silica as a substrate played an important role in the formation of Silver particles. The plasmon band of silver particles supported on the surface of silica was considerably shifted to longer wavelength compared with the pure silver sol. The shift in absorption spectra was explained in terms of surface effects induced by the interaction of silver and silica, as well as size effects and irregular shape.

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

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


    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.

  3. 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


    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.

  4. Gas phase polymerization of ethylene with a silica-supported metallocene catalyst: influence of temperature on deactivation.

    NARCIS (Netherlands)

    Roos, P.; Meier, G.B.; Samson, J.J.C.; Samson, Job Jan C.; Weickert, G.; Westerterp, K.R.


    Ethylene was polymerized at 5 bar in a stirred powder bed reactor with silica supported rac-Me2Si[Ind]2ZrCl2/methylaluminoxane (MAO) at temperatures between 40°C and 80°C using NaCl as support bed and triethylaluminium (TEA) as a scavenger for impurities. For this fixed recipe and a given charge of

  5. Adsorption properties of carbonized polyacrylonitrile deposited on γ-alumina and silica gel by precipitation polymerization

    International Nuclear Information System (INIS)

    Kustrowski, Piotr; Janus, Rafal; Kochanowski, Andrzej; Chmielarz, Lucjan; Dudek, Barbara; Piwowarska, Zofia; Michalik, Marek


    The precipitation polymerization method was used for the deposition of various contents of polyacrylonitrile on two oxide-type supports (γ-alumina and silica gel). The synthesized materials were characterized by thermal analysis performed in inert and oxidizing atmospheres. The mechanism of polyacrylonitrile decomposition was proposed. In order to gain effective adsorbents of volatile organic compounds the polyacrylonitrile/support composites were carbonized at elevated temperatures. The texture and morphology of the calcined materials were examined by low-temperature sorption of N 2 and scanning electron microscopy, respectively. An influence of thermal treatment conditions and carbonaceous species loading on adsorption capacity of methyl-ethyl ketone vapour was also determined. Attenuated total reflection Fourier transform infrared spectroscopy measurements revealed that the ladder-type polyacrylonitrile species formed above 250 o C and stable up to about 350-400 o C are the most effective sites for methyl-ethyl ketone sorption. The carbonaceous species dispersion was found to be an additional factor influencing the adsorption capacity of the carbonized polyacrylonitrile/support composites.

  6. Silicatein Filaments and Subunits from a Marine Sponge Direct the Polymerization of Silica and Silicones in vitro (United States)

    Cha, Jennifer N.; Shimizu, Katsuhiko; Zhou, Yan; Christiansen, Sean C.; Chmelka, Bradley F.; Stucky, Galen D.; Morse, Daniel E.


    Nanoscale control of the polymerization of silicon and oxygen determines the structures and properties of a wide range of siloxane-based materials, including glasses, ceramics, mesoporous molecular sieves and catalysts, elastomers, resins, insulators, optical coatings, and photoluminescent polymers. In contrast to anthropogenic and geological syntheses of these materials that require extremes of temperature, pressure, or pH, living systems produce a remarkable diversity of nanostructured silicates at ambient temperatures and pressures and at near-neutral pH. We show here that the protein filaments and their constituent subunits comprising the axial cores of silica spicules in a marine sponge chemically and spatially direct the polymerization of silica and silicone polymer networks from the corresponding alkoxide substrates in vitro, under conditions in which such syntheses otherwise require either an acid or base catalyst. Homology of the principal protein to the well known enzyme cathepsin L points to a possible reaction mechanism that is supported by recent site-directed mutagenesis experiments. The catalytic activity of the "silicatein" (silica protein) molecule suggests new routes to the synthesis of silicon-based materials.

  7. Electrophilic reactions at single bonds. Ionic chlorination of hydrocarbons catalyzed by silica gel

    International Nuclear Information System (INIS)

    Gonzalez, A.G.; La Fuente, G. de; Trujillo, J.


    Chlorination of adamantane, bicyclo(3.3.1)nonane, bicyclo(2.2.2)octane, bicyclo(3.2.1)octane, norbornane and 2,5-dimethylhexane, absorbed on silica gel with chlorine, was studied. High yield of ionic chlorination at bridgehead carbon was achieved with the less-strained hydrocarbons. (author)

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

    KAUST Repository

    Alamri, Haleema


    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.

  9. Investigations of the Ligand Electronic Effects on α-Diimine Nickel(II Catalyzed Ethylene Polymerization

    Directory of Open Access Journals (Sweden)

    Lihua Guo


    Full Text Available The synthesis and characterization of a series of dibenzhydryl-based α-diimine Ni(II complexes bearing a range of electron-donating or -withdrawing groups are described. Polymerization with ethylene is investigated in detail, involving the activator effect, influence of polymerization conditions on catalyst activity, thermal stability, polymer molecular weight and melting point. All of these Ni(II complexes show great activity (up to 6 × 106 g of PE (mol of Ni−1·h−1, exceptional thermal stability (stable at up to 100 °C and generate polyethylene with very high molecular weight (Mn up to 1.6 × 106 and very narrow molecular weight distribution. In the dibromo Ni(II system, the electronic perturbations exhibit little variation on the ethylene polymerization. In the Ni(acac system, dramatic ligand electronic effects are observed in terms of catalytic activity and polyethylene molecular weight.

  10. 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: [Centre for Nanoscience and Technology, K. S. Rangasamy College of Technology, Tamil Nadu (India)


    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)

  11. 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


    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.

  12. 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.


    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)

  13. Polyisoprene-Silica Nanoparticles Synthesized via RAFT Emulsifier-Free Emulsion Polymerization Using Water-Soluble Initiators

    Directory of Open Access Journals (Sweden)

    Dusadee Tumnantong


    Full Text Available Polyisoprene-silica (PIP-co-RAFT-SiO2 nanoparticles were prepared via reversible addition–fragmentation chain-transfer (RAFT emulsifier-free emulsion polymerization using water-soluble initiators, 4,4′-Azobis (4-cyanopentanoic acid (ACP and 2,2′-Azobis (2-methylpropionamidine dihydrochloride (V50. The particle size of emulsion prepared using ACP initiator was smaller than that using V50 initiator because the V50 initiator was more active toward decomposition than the ACP initiator. A high monomer conversion (84%, grafting efficiency (83% and small particle size (38 nm with narrow size distribution were achieved at optimum condition. The PIP-co-RAFT-SiO2 nanoparticles exhibited core–shell morphology with silica encapsulated with polyisoprene (PIP. The new PIP-SiO2 nanoparticles could be applied as effective filler in rubber composites that possess good mechanical and thermal properties.

  14. Efficient conversion of levulinic acid into alkyl levulinates catalyzed by sulfonic mesostructured silicas


    Melero, J.A.; Morales, G.; Iglesias, J.; Paniagua, M.; Hernández, B.; Penedo, S.


    Línea Investigación: Línea 8. Producción de biocombustibles Sulfonic mesoporous silicas have demonstrated an outstanding catalytic performance in the esterification of levulinic acid with different alcohols to produce alkyl levulinates, a family of chemicals considered to be excellent oxygenated fuel extenders for gasoline, diesel and biodiesel. Catalyst screening indicated that propylsulfonic acid-modified SBA-15 material was the most active one, among tested materials, due to a combinati...

  15. Modeling of lipase catalyzed ring-opening polymerization of epsilon-caprolactone. (United States)

    Sivalingam, G; Madras, Giridhar


    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.

  16. Mechanistic Studies of Hafnium-Pyridyl Amido-Catalyzed 1-Octene Polymerization and Chain Transfer Using Quench-Labeling Methods. (United States)

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


    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.

  17. Characterization of physical structure of silica nanoparticles encapsulated in polymeric structure of polyamide films. (United States)

    Singh, Puyam S; Aswal, Vinod K


    Polyamide nanocomposite films were prepared from nanometer sized silica particles and trimesoyl chloride-m-phenylene diamine based polyamides. The type of silica nanoparticles used is commercial LUDOX HS-40 and the particle size characterized by the radius of gyration (R(g)) is about 66 A. The immediately prepared films were easily broken into particles to form colloidal-like dilute suspension of the silica-polyamide composite particles in D(2)O-H(2)O solutions for SANS measurements, that in this dilute system SANS data the complication of scattering data from the interacting particles is minimized. At about 60% D(2)O of the sample solution, the silica is contrasted out, therefore the SANS profiles are predominantly from the organic polyamide scattering. The SANS profile of the sample solutions measured at 90% D(2)O clearly indicates scattering from both silica and polymer. The scattering heterogeneities for two-phase system were evident from the validity of the Debye-Bueche expression in case of the nanocomposite with high silica loading. At limited silica loading of the nanocomposite, interaction between the silica and polymer chains forming core-shell morphology was observed. The transport properties of the membranes made from the nanocomposite films were measured on a batch type test kit with an aqueous solution of 500 ppm dioxane concentration at pressures ranging from 50 to 200 psig, and correlated to their composite structure.

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

    KAUST Repository

    Ladelta, Viko


    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.

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

    KAUST Repository

    Riache, Nassima


    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.

  20. 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)


    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.

  1. Ru-Catalyzed Isomerization Provides Access to Alternating Copolymers via Ring-Opening Metathesis Polymerization (United States)


    We describe an isomerization–alternating ROMP protocol that gives linear copolymers with rigorous sequence alternation. Bicyclo[4.2.0]oct-7-ene-7-carboxamides of primary amines are isomerized in the presence of (3-BrPyr)2Cl2(H2IMes)Ru=CHPh to the corresponding bicyclo[4.2.0]oct-1(8)-ene-8-carboxamides in which the olefinic bond is tetrasubstituted. The isomerized amides undergo alternating ring-opening metathesis polymerization with cyclohexene to provide soluble and linear copolymers with molecular weights up to ∼130 kDa. This process provides efficient entry to strictly alternating copolymers that can display diverse functional groups. PMID:26243969

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

    KAUST Repository

    Khokhar, Munir


    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.

  3. Lipase catalyzed HEMA initiated ring-opening polymerization: in situ formation of mixed polyester methacrylates by transesterification. (United States)

    Takwa, Mohamad; Xiao, Yan; Simpson, Neil; Malmström, Eva; Hult, Karl; Koning, Cor E; Heise, Andreas; Martinelle, Mats


    2-Hydroxyethyl methacrylate (HEMA) was used as initiator for the enzymatic ring-opening polymerization (ROP) of omega-pentadecalactone (PDL) and epsilon-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, resulting in two major transesterification processes, methacrylate transfer and polyester transfer. This resulted in a number of different polyester methacrylate structures, such as polymers without, with one, and with two methacrylate end groups. Furthermore, the 1,2-ethanediol moiety (from HEMA) was found in the polyester products as an integral part of HEMA, as an end group (with one hydroxyl group) and incorporated within the polyester (polyester chains acylated on both hydroxyl groups). After 72 h, as a result of the methacrylate transfer, 79% (48%) of the initial amount of the methacrylate moiety (from HEMA) was situated (acylated) on the end hydroxyl group of the PPDL (PCL) polyester. In order to prepare materials for polymer networks, fully dimethacrylated polymers were synthesized in a one-pot procedure by combining HEMA-initiated ROP with end-capping using vinyl methacrylate. The novel PPDL dimethacrylate (>95% incorporated methacrylate end groups) is currently in use for polymer network formation. Our results show that initiators with cleavable ester groups are of limited use to obtain well-defined monomethacrylated macromonomers due to the enzyme-based transesterification processes. On the other hand, when combined with end-capping, well-defined dimethacrylated polymers (PPDL, PCL) were prepared.

  4. 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


    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.

  5. Bioinspired control of colloidal silica in vitro by dual polymeric assemblies of zwitterionic phosphomethylated chitosan and polycations or polyanions. (United States)

    Demadis, Konstantinos D; Pachis, Konstantinos; Ketsetzi, Antonia; Stathoulopoulou, Aggeliki


    This paper focuses on the effects of biological and synthetic polymers on the formation of amorphous silica. A concise review of relevant literature related to biosilicification is presented. The importance of synergies between polyelectrolytes on the inhibition of silicic acid condensation is discussed. A specific example of a zwitterionic polymer phosphonomethylated chitosan (PCH) is further analyzed for its inhibitory activity. Specifically, the ability of PCH to retard silicic acid condensation at circumneutral pH in aqueous supersaturated solutions is explored. It was discovered that in short-term studies (0-8 h) the inhibitory activity is PCH dosage-independent, but for longer condensation times (>24 h) there is a clear increase in inhibition upon PCH dosage increase. Soluble silicic acid levels reach 300 ppm after 24 h in the presence of 160 ppm PCH. Furthermore, the effects of either purely cationic (polyethyleneimine, PEI) or purely anionic (carboxymethylinulin, CMI) polyelectrolytes on the inhibitory activity of PCH is systematically studied. It was found that the action of inhibitor blends is not cumulative. PCH/PEI blends stabilize the same level of silicic acid as PCH alone in both short-term (8 h) and long-term (72 h) experiments. PCH/CMI combinations on the other hand can only achieve short-term inhibition of silicic acid polymerization, but fail to extend this over the first 8 h. PCH and its combinations with PEI or CMI affect silica particle morphology, studied by SEM. Spherical particles and their aggregates, irregularly shaped particles and porous structures are obtained depending on additive or additive blend. It was demonstrated by FT-IR that PCH is trapped in the colloidal silica matrix.

  6. Silicateins--a novel paradigm in bioinorganic chemistry: enzymatic synthesis of inorganic polymeric silica. (United States)

    Müller, Werner E G; Schröder, Heinz C; Burghard, Zaklina; Pisignano, Dario; Wang, Xiaohong


    The inorganic matrix of the siliceous skeletal elements of sponges, that is, spicules, is formed of amorphous biosilica. Until a decade ago, it remained unclear how the hard biosilica monoliths of the spicules are formed in sponges that live in a silica-poor (inorganic polymer from an inorganic monomeric substrate. In the present review the successive steps, following the synthesis of the silicatein product, biosilica, and resulting in the formation of the hard monolithic spicules is given. The new insight is assumed to open new horizons in the field of biotechnology and also in biomedicine. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. 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


    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.

  8. Silyl Ketene Acetals/B(C₆F₅)₃ Lewis Pair-Catalyzed Living Group Transfer Polymerization of Renewable Cyclic Acrylic Monomers. (United States)

    Hu, Lu; Zhao, Wuchao; He, Jianghua; Zhang, Yuetao


    This work reveals the silyl ketene acetal (SKA)/B(C₆F₅)₃ 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(C₆F₅)₃ 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(C₆F₅)₃-activated monomer, while the silyl group is transferred to the carbonyl group of the B(C₆F₅)₃-activated monomer to generate the single-monomer-addition species or the active propagating species; the coordinated B(C₆F₅)₃ 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 ( M n ) and narrow molecular weight distribution (MWD).

  9. 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


    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.

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

    KAUST Repository

    Chen, Xia


    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.

  11. Stereoselectivity in metallocene-catalyzed coordination polymerization of renewable methylene butyrolactones: from stereo-random to stereo-perfect polymers. (United States)

    Chen, Xia; Caporaso, Lucia; Cavallo, Luigi; Chen, Eugene Y-X


    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

  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


    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. 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


    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

  14. 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: [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)


    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.

  15. Trapping of Intermediates with Substrate Analog HBOCoA in the Polymerizations Catalyzed by Class III Polyhydroxybutyrate (PHB) Synthase from Allochromatium Vinosum (United States)

    Shrestha, Ruben; Ward, Christina; Katz, Benjamin B.; Fischer, Christopher J.; Tomich, John M.; Li, Ping


    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 hr−1. This extremely slow rate is due to thermodynamically unfavorable steps that involve 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 [3H]-sT-PhaECAv and HBOCoA yielded [3H]-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. PMID:25686368

  16. Ultrafast synthesis of ultrahigh molar mass polymers by metal-catalyzed living radical polymerization of acrylates, methacrylates, and vinyl chloride mediated by SET at 25 degrees C. (United States)

    Percec, Virgil; Guliashvili, Tamaz; Ladislaw, Janine S; Wistrand, Anna; Stjerndahl, Anna; Sienkowska, Monika J; Monteiro, Michael J; Sahoo, Sangrama


    Conventional metal-catalyzed organic radical reactions and living radical polymerizations (LRP) performed in nonpolar solvents, including atom-transfer radical polymerization (ATRP), proceed by an inner-sphere electron-transfer mechanism. One catalytic system frequently used in these polymerizations is based on Cu(I)X species and N-containing ligands. Here, it is reported that polar solvents such as H(2)O, alcohols, dipolar aprotic solvents, ethylene and propylene carbonate, and ionic liquids instantaneously disproportionate Cu(I)X into Cu(0) and Cu(II)X(2) species in the presence of a diversity of N-containing ligands. This disproportionation facilitates an ultrafast LRP in which the free radicals are generated by the nascent and extremely reactive Cu(0) atomic species, while their deactivation is mediated by the nascent Cu(II)X(2) species. Both steps proceed by a low activation energy outer-sphere single-electron-transfer (SET) mechanism. The resulting SET-LRP process is activated by a catalytic amount of the electron-donor Cu(0), Cu(2)Se, Cu(2)Te, Cu(2)S, or Cu(2)O species, not by Cu(I)X. This process provides, at room temperature and below, an ultrafast synthesis of ultrahigh molecular weight polymers from functional monomers containing electron-withdrawing groups such as acrylates, methacrylates, and vinyl chloride, initiated with alkyl halides, sulfonyl halides, and N-halides.

  17. Preparation and Structural Studies on Hybrid Core-Shell Nanoparticles Consisting of Silica Core and Conjugated Block Copolymer Shell Prepared by Surface-Initiated Polymerization (United States)

    Chatterjee, Sourav; Karam, Tony; Rosu, Cornelia; Li, Xin; Do, Changwoo; Youm, Sang Gil; Haber, Louis; Russo, Paul; Nesterov, Evgueni

    Controlled Kumada catalyst-transfer polymerization occurring by chain-growth mechanism was developed for the synthesis of conjugated polymers and block copolymers from the surface of inorganic substrates such as silica nanoparticles. Although synthesis of conjugated polymers via Kumada polymerization became an established method for solution polymerization, carrying out the same reaction in heterogeneous conditions to form monodisperse polymer chains still remains a challenge. We developed and described a simple and efficient approach to the preparation of surface-immobilized layer of catalytic Ni(II) initiator, and demonstrated using it to prepare polymers and block copolymers on silica nanoparticle. The structure of the resulting hybrid nanostructures was thoroughly studied using small-angle neutron and X-ray scattering, thermal analysis, and optical spectroscopy. The photoexcitation energy transfer processes in the conjugated polymer shell were studied via steady-state and time resolved transient absorption spectroscopy. This study uncovered important details of the energy transfer, which will be discussed in this presentation.

  18. Different mechanisms at different temperatures for the ring-opening polymerization of lactide catalyzed by binuclear magnesium and zinc alkoxides. (United States)

    Sun, Yangyang; Cui, Yaqin; Xiong, Jiao; Dai, Zhongran; Tang, Ning; Wu, Jincai


    Two binuclear magnesium and zinc alkoxides supported by a bis-salalen type dinucleating heptadentate Schiff base ligand were synthesized and fully characterized. The two complexes are efficient initiators for the ring-opening polymerization (ROP) of L-lactide, affording polymers with narrow polydispersities and desirable molecular weights. Interestingly, the mechanisms for the ROP of lactide are different at different temperatures. At a high temperature of 130 °C, a coordination-insertion mechanism is reasonable for the bulk melt polymerization of lactide. At a low temperature, the alkoxide cannot initiate the ROP reaction; however, upon the addition of external benzyl alcohol into the system, the ROP of lactide can smoothly proceed via an "activated monomer" mechanism. In addition, these complexes display slight stereo-selectivity for the ring-opening polymerization of rac-lactide, affording partially isotactic polylactide in toluene with a Pm value of 0.59.

  19. Comonomer-induced stereo-selectivity enhancement in a c2 -symmetric metallocene-catalyzed propylene polymerization. (United States)

    Ma, Lin; Dong, Jin-Yong


    Propylene polymerization is carried out with a C 2 -symmetric metallocene catalyst of rac-Et(Ind)2 ZrCl2 /MAO at 40 °C in the presence of a cyclo-triene of trans,trans,cis-1,5,9-cyclododecatriene ((E,E,Z)-CDT). Comonomer incorporations are rather low (7% in [mmmm]). (E,E,Z)-CDT is speculated to coordinate to the metal center forming comonomer-complexed active sites in charge of the entire polymerization reaction with decreased activity however increased propylene -enantiomorphic selectivity. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Cyclic Multiblock Copolymers via Combination of Iterative Cu(0)-Mediated Radical Polymerization and Cu(I)-Catalyzed Azide-Alkyne Cycloaddition Reaction. (United States)

    Xiao, Lifen; Zhu, Wen; Chen, Jiqiang; Zhang, Ke


    Cyclic multiblock polymers with high-order blocks are synthesized via the combination of single-electron transfer living radical polymerization (SET-LRP) and copper-catalyzed azide-alkyne cycloaddition (CuAAC). The linear α,ω-telechelic multiblock copolymer is prepared via SET-LRP by sequential addition of different monomers. The SET-LRP approach allows well control of the block length and sequence as A-B-C-D-E, etc. The CuAAC is then performed to intramolecularly couple the azide and alkyne end groups of the linear copolymer and produce the corresponding cyclic copolymer. The block sequence and the cyclic topology of the resultant cyclic copolymer are confirmed by the characterization of 1 H nuclear magnetic resonance spectroscopy, gel permeation chromatography, Fourier transform infrared spectroscopy, and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. 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


    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

  2. Polymeric ionic liquid-assembled graphene-immobilized silica composite for selective isolation of human serum albumin from human whole blood. (United States)

    Liu, Jiawei; Liang, Yixun; Shen, Jiwei; Bai, Quan


    Polymeric ionic liquids (PILs) with 1-vinyl-3-ethylimidazolium cations and two different anions of Br - and PF 6 - were assembled onto the surface of graphene (G) nanosheets. The derived two composites, i.e., PIL(Br)-G and PIL(PF 6 )-G, were further efficiently immobilized onto the surface of silica nanoparticles via self-assembly technique. The obtained two PIL-G/SiO 2 nanocomposites exhibited diverse adsorption performances toward proteins through adjusting the anions of PILs. Electrostatic attractions between proteins and the nanocomposites dominated protein adsorption, while the presence of PF 6 - anions weakened electrostatic interactions and deteriorated the selective adsorption of target protein, i.e., bovine serum albumin (BSA) in this case. Specifically, PIL(Br)-G/SiO 2 nanocomposite displayed high selectivity toward BSA and a high adsorption efficiency of ca. 98% was achieved for 100 mg L -1 BSA in a Britton-Robinson (B-R) buffer at pH 5. HPLC analysis demonstrated the selectivity of PIL(Br)-G/SiO 2 nanocomposite toward BSA in the presence of abundant hemoglobin and cytochrome c. The practical applicability was verified by performing selective isolation of human serum albumin (HSA) from human whole blood. Graphical abstract Selective isolation of human serum albumin from blood by polymeric ionic liquid assembled graphene immobilized silica nanocomposite with tunable anions.

  3. Bio-based alkyds by direct enzymatic bulk polymerization

    DEFF Research Database (Denmark)

    Nguyen, Hiep Dinh

    materials before a 100% bio-based alkyd paint can be realized. In this project an enzyme catalyzed bulk polymerization method for direct production of alkyds has been developed. The objective has been to make it possible to produce binders at much lower temperatures as well as to achieve a higher degree....... Bio-based alkyds prepared from a combination of glycerol, and tall oil fatty acids, and azelaic acid by enzymatic polymerization show improved hydrophobicity and lower glass transition temperatures compared to an alkyd prepared from the same raw materials by a classical boiling method. The enzymatic...... working on the coupling between reinforcement agents and the binder in alkyd coatings. For this purpose, two different types of silica particles were modified with rape seed oil fatty acids or tall oil fatty acids (TOFA-silica), respectively. Tests of TOFA-silica particles have demonstrated...

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

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


    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.

  5. Cyclooctane metathesis catalyzed by silica-supported tungsten pentamethyl [(ΞSiO)W(Me)5]: Distribution of macrocyclic alkanes

    KAUST Repository

    Riache, Nassima


    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.

  6. 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


    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.

  7. Redox-Controlled Olefin (Co)Polymerization Catalyzed by Ferrocene-Bridged Phosphine-Sulfonate Palladium Complexes. (United States)

    Chen, Min; Yang, Bangpei; Chen, Changle


    The facile and reversible interconversion between neutral and oxidized forms of palladium complexes containing ferrocene-bridged phosphine sulfonate ligands was demonstrated. The activity of these palladium complexes could be controlled using redox reagents during ethylene homopolymerization, ethylene/methyl acrylate copolymerization, and norbornene oligomerization. Specifically in norbornene oligomerization, the neutral complexes were not active at all whereas the oxidized counterparts showed appreciable activity. In situ switching between the neutral and oxidized forms resulted in an interesting "off" and "on" behavior in norbornene oligomerization. This work provides a new strategy to control the olefin polymerization process. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. 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


    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.

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

    Directory of Open Access Journals (Sweden)

    M. Pakizeh


    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.

  10. Horseradish peroxidase-catalyzed polymerization of L-DOPA for mono-/bi-enzyme immobilization and amperometric biosensing of H2O2 and uric acid. (United States)

    Dai, Mengzhen; Huang, Ting; Chao, Long; Xie, Qingji; Tan, Yueming; Chen, Chao; Meng, Wenhua


    Horseradish peroxidase (HRP)-catalyzed polymerization of L-DOPA (vs. dopamine) in the presence of H2O2 (and uricase (UOx)) was exploited to immobilize mono-/bi-enzymes for hydroquinone-mediated amperometric biosensing of H2O2 and uric acid (UA). The relevant polymeric biocomposites (PBCs) were prepared in phosphate buffer solution containing HRP and L-DOPA (or plus UOx) after adding H2O2. The mono-/bi-enzyme amperometric biosensors were prepared simply by casting some of the PBCs on Au-plated Au (Au(plate)/Au) electrodes, followed by coating with an outer-layer chitosan (CS) film for each. UV-vis spectrophotometry, scanning electron microscopy, cyclic voltammetry and electrochemical impedance spectroscopy were used for film characterization and/or process monitoring. The HRP immobilized by enzyme catalysis well preserved its bioactivity, as confirmed by UV-vis spectrophotometry. Under optimized conditions, the monoenzyme CS/HRP-poly(L-DOPA) (PD)/Au(plate)/Au electrode potentiostated at -0.1V responded linearly to H2O2 concentration from 0.001 to 1.25mM with a sensitivity of 700μA mM(-1)cm(-2) and a limit of detection (LOD) of 0.1μM, and the bienzyme CS/UOx-HRP-PD/Au(plate)/Au electrode at -0.1V responded linearly to UA concentration from 0.001 to 0.4mM with a sensitivity of 349μA mM(-1)cm(-2) and a LOD of 0.1μM. The mono-/bi-enzyme biosensors based on biosynthesized PD performed better than many reported analogues and those based on similarly biosynthesized polydopamine. Copyright © 2015 Elsevier B.V. All rights reserved.

  11. Sol-gel synthesis and characterization of microporous silica membranes I: SAXS study on the growth of polymeric structures

    NARCIS (Netherlands)

    Nair, Balagopal N.; Elferink, Wilma (Johanna); Keizer, Klaas; Verweij, H.


    Silica-based microporous membranes can be successfully processed by sol¿gel techniques. However tailor making of such membranes is still not possible because of the unavailability of systematic studies on membrane oriented sol processing and characterization. The present series of papers aims to

  12. Direct surface grafting of mesoporous silica nanoparticles with phospholipid choline-containing copolymers through chain transfer free radical polymerization and their controlled drug delivery. (United States)

    Huang, Long; Wu, Jing; Liu, Meiying; Mao, Liucheng; Huang, Hongye; Wan, Qing; Dai, Yanfeng; Wen, Yuanqing; Zhang, Xiaoyong; Wei, Yen


    Mesoporous silica nanoparticles have attracted considerable research attention due to their various applications. Surface modification of these mesoporous silica nanoparticles with polymers not only can improve their water dispersity but can also endow several new functions, such as drug loading and delivery or targeting capability. In this work, we report a novel strategy for the direct surface grafting of phospholipid choline-containing copolymers onto Santa Barbara Amorphous-15 (SBA-15) through surface-initiated chain transfer free radical polymerization. The SBA-15 was synthesized by hydrolysis of tetraethoxysilane in the presence of poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) (P123) under acidic synthetic conditions. Next, SBA-15 was subsequently modified with thiol groups by co-condensation with γ-mercaptopropyltrimethoxysilane to obtain SBA-15-SH. Finally, the copolymers were grafted on SBA-15-SH through chain transfer free radical polymerization using 2-methacryloyloxy ethyl phosphorylcholine (MPC) and itaconic acid (IA) as monomers. The SBA-15-based polymer composites (SBA-15-SH-poly(MPC-co-IA)) were used as matrices for controlled release of cisplatin (CDDP). The data from a series of characterization techniques indicated that the monomers were successfully grafted onto SBA-15. The resultant SBA-15-SH-poly(MPC-co-IA) composites showed many remarkable physicochemical properties, such as high water dispersity, desirable biocompatibility and high drug loading capacity. These features provide the SBA-15-SH-poly(MPC-co-IA) composites with considerable potential for biomedical applications. Copyright © 2017 Elsevier Inc. All rights reserved.

  13. Initial steps of the peroxidase-catalyzed polymerization of coniferyl alcohol and/or sinapyl aldehyde: capillary zone electrophoresis study of pH effect. (United States)

    Fournand, David; Cathala, Bernard; Lapierre, Catherine


    Capillary zone electrophoresis has been used to monitor the first steps of the dehydrogenative polymerization of coniferyl alcohol, sinapyl aldehyde, or a mixture of both, catalyzed by the horseradish peroxidase (HRP)-H(2)O(2) system. When coniferyl alcohol was the unique HRP substrate, three major dimers were observed (beta-5, beta-beta, and beta-O-4 interunit linkages) and their initial formation velocity as well as their relative abundance varied with pH. The beta-O-4 interunit linkage was thus slightly favored at lower pH values. In contrast, sinapyl aldehyde turned out to be a very poor substrate for HRP except in basic conditions (pH 8). The major dimer observed was the beta,beta'-di-sinapyl aldehyde, a red-brown exhibiting compound which might partly participate in the red coloration usually observed in cinnamyl alcohol dehydrogenase-deficient angiosperms. Finally, when a mixture of coniferyl alcohol and sinapyl aldehyde was used, it looked as if sinapyl aldehyde became a very good substrate for HRP. Indeed, coniferyl alcohol turned out to serve as a redox mediator (i.e. "shuttle oxidant") for the sinapyl aldehyde incorporation in the lignin-like polymer. This means that in particular conditions the specificity of oxidative enzymes might not hinder the incorporation of poor substrates into the growing lignin polymer.

  14. Synthesis of chitin and chitosan stereoisomers by thermostable α-glucan phosphorylase-catalyzed enzymatic polymerization of α-D-glucosamine 1-phosphate. (United States)

    Kadokawa, Jun-ichi; Shimohigoshi, Riko; Yamashita, Kento; Yamamoto, Kazuya


    The relationship between two aminopolysaccharide stereoisomers, namely α-(1→4)- and β-(1→4)-linked (N-acetyl)-D-glucosamine polymers, is of significant interest within the field of polysaccharide science, as they correspond to amino analogs of the representative abundant natural polysaccharides, viz. amylose and cellulose. While the latter glucosamine polymer is the basis of well-known natural polysaccharides, chitin and chitosan (linear polysaccharides composed of β-(1→4)-linked N-acetyl-D-glucosamine and D-glucosamine), to the best of our knowledge, the former (α-(1→4)-linked) has not been observed in nature. For the purpose of these studies, the synthesis of such non-natural aminopolysaccharides was performed by the thermostable α-glucan phosphorylase (from Aquifex aeolicus VF5)-catalyzed enzymatic polymerization of α-D-glucosamine 1-phosphate (GlcN-1-P), via successive α-glucosaminylations, in ammonia buffer containing Mg(2+) ions, resulting in the production of the α-(1→4)-linked D-glucosamine polymers, corresponding to the structure of the chitosan stereoisomer. Subsequent N-acetylation of the products gave the aminopolysaccharides, corresponding to the chitin stereoisomer.

  15. Tuning preparation conditions towards optimized separation performance of thermally polymerized organo-silica monolithic columns in capillary liquid chromatography. (United States)

    Gharbharan, Deepa; Britsch, Denae; Soto, Gabriela; Weed, Anna-Marie Karen; Svec, Frantisek; Zajickova, Zuzana


    Tuning of preparation conditions, such as variations in the amount of a porogen, concentration of an aqueous acid catalyst, and adjustment in polymerization temperature and time, towards optimized chromatographic performance of thermally polymerized monolithic capillaries prepared from 3-(methacryloyloxy)propyltrimethoxysilane has been carried out. Performance of capillary columns in reversed-phase liquid chromatography was assessed utilizing various sets of solutes. Results describing hydrophobicity, steric selectivity, and extent of hydrogen bonding enabled comparison of performance of hybrid monolithic columns prepared under thermal (TSG) and photopolymerized (PSG) conditions. Reduced amounts of porogen in the polymerization mixture, and prolonged reaction times were necessary for the preparation of monolithic columns with enhanced retention and column efficiency that reached to 111,000 plates/m for alkylbenzenes with shorter alkyl chains. Both increased concentration of catalyst and higher temperature resulted in faster polymerization but inevitably in insufficient time for pore formation. Thermally polymerized monoliths produced surfaces, which were slightly more hydrophobic (a methylene selectivity of 1.28±0.002 TSG vs 1.20±0.002 PSG), with reduced number of residual silanols (a caffeine/phenol selectivity of 0.13±0.001 TSG vs 0.17±0.003 PSG). However, steric selectivity of 1.70±0.01 was the same for both types of columns. The batch-to-batch repeatability was better using thermal initiation compared to monolithic columns prepared under photopolymerized conditions. RSD for retention factor of benzene was 3.7% for TSG capillaries (n=42) vs. 6.6% for PSG capillaries (n=18). A similar trend was observed for columns prepared within the same batch. Copyright © 2015 Elsevier B.V. All rights reserved.

  16. Fluoropolymer materials and architectures prepared by controlled radical polymerizations

    DEFF Research Database (Denmark)

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


    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...

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

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


    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.

  18. Developments of Chiral Metallocenes as Polymerization Catalysts

    Directory of Open Access Journals (Sweden)

    Takeshi Shiono


    Full Text Available This review article describes developments in chiral metallocenes as polymerization catalysts focusing on C2 symmetric ansa-zirconocene complexes. Selective synthesis of rac-isomers of ansa-zirconocenes are surveyed. Isospecific polymerizations of propylene catalyzed by chiral zirconocenes are summarized. Advanced series of polymerizations by chiral metallocenes such as asymmetric polymerization and polymerization of polar monomers are also introduced.

  19. 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


    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

  20. Evidence of coexistence of micro and nanoporosity of organo-silica polymeric films deposited on silicon by plasma deposition

    International Nuclear Information System (INIS)

    Purohit, Viswas; Mielczarski, Ela; Mielczarski, Jerzy A.; Akesso, Laurent


    A range of hybrid, SiOCH films were deposited on silicon substrates within a radio frequency plasma reactor using hexamethyldisiloxane (HMDSO) as a precursor. The plasma polymerized films were deposited at various HMDSO/argon/oxygen ratios. The composition and structure, at microscopic and nanoscopic levels, of the deposited films were determined by external reflection and transmission Fourier Transform Infrared (FTIR) spectroscopy as well as by X-Ray Photoelectron Spectroscopy (XPS). The content of carbon and oxygen in films were found to be inversely proportional to each other. XPS results showed that the outermost surface of the deposited films are nanoporous and coexist with microporosity which was revealed by electron microscopy. The structure of deposited coatings is anisotropic as was documented by polarized external reflection FTIR spectroscopy. Several correlations between the film chemical composition, surface structure, and macroscopic properties of the films such as: hydrophobicity and hydrophilicity were established. - Highlights: • Hybrid organo-polymer silicon films deposited by RF plasma on silicon substrates. • FTIR and XPS reveal porosity by interpreting bonding between Si and –O. • Quantification of nano and microporosity are identified with bonding of Si with –O

  1. Synthesis and properties of epoxy-polyurethane/silica nanocomposites by a novel sol method and in-situ solution polymerization route (United States)

    Lin, Jing; Wu, Xu; Zheng, Cheng; Zhang, Peipei; Huang, Bowei; Guo, Ninghai; Jin, LiYazi


    In this work, a novel nonaqueous sol method for preparing 3-methacryloxypropyltrimethoxysilane modified nano-SiO2 (MPS-SiO2) in N,N-dimethylformamide (DMF) substituting alcoholic solvents was developed, and epoxy acrylate resins (EA) based on novolac epoxy resin (EP) were prepared. Epoxy acrylate copolymers (EPAc/SiO2) with core/shell structure were prepared by one-step in-situ solution polymerization of EA, acrylic monomers and a certain amount of modified silica sol as core. Epoxy acrylate based polyurethane composites/SiO2 (EPUAs/SiO2) were finally obtained by curing action among as-prepared EPAc/SiO2, isocyanate and anhydride curing agent. The obtained EA and MPS-SiO2 were also characterized using Fourier transform infrared spectroscopy (FTIR), 1H nuclear magnetic resonance spectra (1H NMR), thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy(XPS), and surface contact angle analysis(CA). Microstructures of MPS-SiO2 and EPAc/SiO2 in DMF were observed by transmission electron microscope (TEM). Furthermore, the influence of MPS-SiO2 on the properties of EPUAs/SiO2 including fracture surface morphology, thermal stability, glass transition temperature (Tg), tensile strength, elongation at break, cross-linking density, shore hardness, water absorption, etc. were also investigated. The results demonstrate that colloidal MPS-SiO2 with DMF as solvent can be directly added into polyurethane system and has industrial application value, EPAc/SiO2 with core-shell morphologies have good individual dispersion in DMF, and incorporating MPS-SiO2 into EPUAs/SiO2 greatly enhances physico-chemical properties of EPUAs/SiO2 composites.

  2. Synthesis of Monodisperse Silica Particles Grafted with Concentrated Ionic Liquid-Type Polymer Brushes by Surface-Initiated Atom Transfer Radical Polymerization for Use as a Solid State Polymer Electrolyte

    Directory of Open Access Journals (Sweden)

    Takashi Morinaga


    Full Text Available A polymerizable ionic liquid, N,N-diethyl-N-(2-methacryloylethyl-N-methylammonium bis(trifluoromethylsulfonylimide (DEMM-TFSI, was polymerized via copper-mediated atom transfer radical polymerization (ATRP. The polymerization proceeded in a living manner producing well-defined poly(DEMM-TFSI of target molecular weight up to about 400 K (including a polycation and an counter anion. The accurate molecular weight as determined by a GPC analysis combined with a light scattering measurement, and the molecular weight values obtained exhibited good agreement with the theoretical values calculated from the initial molar ratio of DEMM-TFSI and the monomer conversion. Surface-initiated ATRP on the surface of monodisperse silica particles (SiPs with various diameters was successfully performed, producing SiPs grafted with well-defined poly(DEMM-TFSI with a graft density as high as 0.15 chains/nm2. Since the composite film made from the silica-particle-decorated polymer brush and ionic liquid shows a relatively high ionic conductivity, we have evaluated the relationship between the grafted brush chain length and the ionic conductivity.

  3. Polymerization Using Phosphazene Bases

    KAUST Repository

    Zhao, Junpeng


    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.

  4. 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.


    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)

  5. 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


    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.

  6. Boron-Catalyzed C3-Polymerization of ω-2-Methyl Allylarsonium Ylide and Its C3/C1 Copolymers with Dimethylsulfoxonium Methylide

    KAUST Repository

    Wang, De


    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.

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

    Directory of Open Access Journals (Sweden)

    Yanzhao Nie


    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.

  8. 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


    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

  9. Tentacle-type zwitterionic stationary phase prepared by surface-initiated graft polymerization of 3-[N,N-dimethyl-N-(methacryloyloxyethyl)-ammonium] propanesulfonate through peroxide groups tethered on porous silica. (United States)

    Jiang, Wen; Irgum, Knut


    A novel stationary phase with tentacle-type zwitterionic interaction layer was synthesized by free radical graft polymerization of 3-[N,N-dimethyl-N-(methacryloyloxyethyl)ammonium]propanesulfonate (SPE) from the surface of Kromasil porous silica particles. The polymerization was initiated by thermal cleavage of tert-butylperoxy groups covalently attached to the particle surface, and the material therefore carries a tentacle-type polymeric interaction layer with 3-sulfopropylbetaine functional moieties. The composition of the surface graft was determined by elemental analysis, and the surface charge was measured using photon correlation spectroscopy. The measured zeta-potentials were close to 0 and nearly independent of pH, and the tentacle character of the interactive layers were evident from the lack of colloidal stability in the absence of salt (antipolyelectrolytic behavior) and a marked increase in column back-pressure when the concentration of perchloric acid or perchlorate salt was increased. The chromatographic properties were evaluated on columns packed with the functionalized material, and it was shown that this zwitterionic stationary phase could simultaneously and independently separate inorganic anions and cations using aqueous solutions of perchloric acid or perchlorate salts as eluents. The material was also capable of separating two acidic and three basic proteins in a single run, using gradient salt elution at constant pH.

  10. 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


    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.

  11. Synthesis and spectroscopic characterization of azoic dyes based on pyrazolone derivatives catalyzed by an acidic ionic liquid supported on silica-coated magnetite nanoparticle (United States)

    Isaad, Jalal; El Achari, Ahmida


    Novel family of azoic dyes pyrazolone based were prepared by an efficient and rapid methodology through diazotization reaction of different pyrazolone amine derivatives, in the presence of acidic ionic liquid supported on silica-coated magnetite nanoparticles as acidic catalyst at room temperature and under solvent-free conditions. The attractive advantages of the present process include short reaction times, milder and cleaner conditions, higher purity and yields, easy isolation of products, easier work-up procedure and lower generation of waste or pollution. This catalyst was easily separated by an external magnet and the recovered catalyst was reused several times without any significant loss of activity. Therefore, this method provides improved protocol over the existing methods.

  12. Structural evolution of silica sols modified with formamide

    Directory of Open Access Journals (Sweden)

    Lenza R.F.S.


    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.

  13. 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


    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%.

  14. Polymerization of Methyl Methacrylate Catalyzed by Co(II), Cu(II), and Zn(II) Complexes Bearing N-Methyl-N-((pyridin-2-yl)methyl) cyclohexanamine

    Energy Technology Data Exchange (ETDEWEB)

    Ahn, Seoung Hyun; Lee, Hyosun [Kyungpook National University, Daegu (Korea, Republic of); Shin, Jongwon [POSTECH, Pohang (Korea, Republic of); Nayab, Saira [Shaheed Benazir Bhutto University, Sheringal (Pakistan)


    We demonstrated the synthesis and characterization of Co(II), Cu(II), and Zn(II) complexes ligated to N-methyl-N-((pyridin-2-yl)methyl)cyclohexanamine. The complex [Co(nmpc)Cl{sub 2}] in the presence of MMAO showed the highest catalytic activity for MMA polymerization at 60 °C compared with its Zn(II) and Cu(II) analogs. The metal center showed an obvious influence on the catalytic activity, although this appeared to have no effect on the stereo-regularity of the resultant PMMA. X-ray diffraction analysis revealed that [Co(nmpc)Cl{sub 2}] and [Zn(nmpc)Cl{sub 2}] crystallized in the monoclinic system with space group P2{sub 1}/c and existed as monomeric and solvent-free complexes.

  15. Non-hydrolytic formation of silica and polysilsesquioxane particles from alkoxysilane monomers with formic acid in toluene/tetrahydrofuran solutions (United States)

    Boday, Dylan J.; Tolbert, Stephanie; Keller, Michael W.; Li, Zhe; Wertz, Jason T.; Muriithi, Beatrice; Loy, Douglas A.


    Silica and polysilsesquioxane particles are used as fillers in composites, catalyst supports, chromatographic separations media, and even as additives to cosmetics. The particles are generally prepared by hydrolysis and condensation of tetraalkoxysilanes and/or organotrialkoxysilanes, respectively, in aqueous alcohol solutions. In this study, we have discovered a new, non-aqueous approach to prepare silica and polysilsesquioxane particles. Spherical, nearly monodisperse, silica particles (600-6,000 nm) were prepared from the reaction of tetramethoxysilane with formic acid (4-8 equivalents) in toluene or toluene/tetrahydrofuran solutions. Polymerization of organotrialkoxysilanes with formic acid failed to afford particles, but bridged polysilsesquioxane particles were obtained from monomers with two trialkoxysilyl group attached to an organic-bridging group. The mild acidic conditions allowed particles to be prepared from monomers, such as bis(3-triethoxysilylpropyl)tetrasulfide, which are unstable to Stöber or base-catalyzed emulsion polymerization conditions. The bridged polysilsesquioxane particles were generally less spherical and more polydisperse than silica particles. Both silica and bridged polysilsesquioxane nanoparticles could be prepared in good yields at monomer concentrations considerably higher than used in Stöber or emulsion approaches.

  16. Regio- and stereo-selective polymerization of 1,3-butadiene catalyzed by phosphorus–nitrogen PN3-pincer cobalt(ii) complexes

    KAUST Repository

    Gong, Dirong


    A new family of cobalt complexes (CoCl2-H, CoCl2-Me, CoCl2-iPr, CoBr2-H, CoBr2-Me, CoBr2-iPr, CoI2-H, CoI2-Me, and CoI2-iPr) supported by a PN3 ligand (6-(N,N′-di-t-butylphosphino)-2-pyrazol-yl-aminopyridine) have been prepared and fully characterized by FT-IR, elemental analysis, and X-ray analysis. The X-ray analysis reveals a trigonal bipyramidal conformation in the solid state for all representative complexes, CoCl2-H, CoBr2-H, CoBr2-iPr and CoI2-Me. The cobalt center is chelated by the PN3 ligand through the pyridinyl nitrogen, the pyrazol nitrogen and the phosphorus donor, with a long Co-P bond distance indicating a labile character. On activation with AlEt2Cl, Al2Et3Cl3, MAO, [Ph3C]+[B(C6F5)4]-/AliBu3 or AliBu3, cis-1,4 selective butadiene polymerization was achieved with up to 98.6% selectivity. The polymerization results show that the cis-1,4 selectivity is influenced by the steric hindrance, increasing with the bulkiness of the substituent groups (CoX2-iPr > CoX2-Me > CoX2-H) at the 3,5-positions of the pyrazole moiety, together with a slight decrease in activity. The activity changes in the order CoCl2L ≈ CoBr2L > CoI2L (for the same ligand L) when MAO is used as the activator, while the high level of cis-1,4 selectivity is maintained. It is possible to switch the selectivity from cis-1,4 to syndiotactic-1,2 by adding PPh3 © The Royal Society of Chemistry.

  17. The Influence of Mixed Activators on Ethylene Polymerization and Ethylene/1-Hexene Copolymerization with Silica-Supported Ziegler-Natta Catalyst

    Directory of Open Access Journals (Sweden)

    Piyasan Praserthdam


    Full Text Available This article reveals the effects of mixed activators on ethylene polymerization and ethylene/1-hexene copolymerization over MgCl2/SiO2-supported Ziegler-Natta (ZN catalysts. First, the conventional ZN catalyst was prepared with SiO2 addition. Then, the catalyst was tested for ethylene polymerization and ethylene/1-hexene (E/H co-polymerization using different activators. Triethylaluminum (TEA, tri-n-hexyl aluminum (TnHA and diethyl aluminum chloride (DEAC, TEA+DEAC, TEA+TnHA, TnHA+ DEAC, TEA+DEAC+TnHA mixtures, were used as activators in this study. It was found that in the case of ethylene polymerization with a sole activator, TnHA exhibited the highest activity among other activators due to increased size of the alkyl group. Further investigation was focused on the use of mixed activators. The activity can be enhanced by a factor of three when the mixed activators were employed and the activity of ethylene polymerization apparently increased in the order of TEA+ DEAC+TnHA > TEA+DEAC > TEA+TnHA. Both the copolymerization activity and crystallinity of the synthesized copolymers were strongly changed when the activators were changed from TEA to TEA+DEAC+TnHA mixtures or pure TnHA and pure DEAC.  As for ethylene/1-hexene copolymerization the activity apparently increased in the order of TEA+DEAC+TnHA > TEA+TnHA > TEA+DEAC > TnHA+DEAC > TEA > TnHA > DEAC. Considering the properties of the copolymer obtained with the mixed TEA+DEAC+TnHA, its crystallinity decreased due to the presence of TnHA in the mixed activator. The activators thus exerted a strong influence on copolymer structure. An increased molecular weight distribution (MWD was observed, without significant change in polymer morphology.

  18. Harvesting silica nanoparticles from rice husks

    International Nuclear Information System (INIS)

    Wang Weixing; Martin, Jarett C.; Zhang Ning; Ma Chao; Han Aijie; Sun Luyi


    Biogenic silica nanoparticles were synthesized using rice husks (RHs) as the raw material via controlled pyrolysis. The characterization results showed that the morphology of the synthesized silica was highly related to the pretreatment of RHs and the pyrolysis conditions. Particularly, potassium cations in RHs were found to catalyze the melting of silica, during which the amorphous silica were converted to crystalline phase. Two hours of pyrolysis at 700 °C appeared to be ideal to synthesize silica nanoparticles with a diameter of ca. 20–30 nm. Higher temperature and longer duration of pyrolysis led to undesired melting of silica nanoparticles, while too low a temperature cannot effectively remove carbonous residues. Such amorphous silica nanoparticles with narrow size distribution and high purity are expected to replace silica gel and fumed silica for various applications.

  19. 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.


    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

  20. Polymerization of 1,3-butadiene catalyzed by pincer cobalt(II) complexes derived from 2-(1-arylimino)-6-(pyrazol-1-yl)pyridine ligands

    KAUST Repository

    Gong, Dirong


    A new class of air stable and structurally well-defined cobalt complexes with unsymmetrical pincer type ligands ([2-(ArNCMe)-6-(Py)C5H 3N]CoCl2) (Ar = C6H5, Py = pyrazol-1-yl, 5a; Ar = 2,4,6-Me3C6H2, Py = pyrazol-1-yl, 5b; Ar = 2,6-iPr2C6H3, Py = pyrazol-1-yl, 5c; Ar = C6H5, Py = 3,5-Me 2pyrazol-1-yl, 5d; Ar = 2,4,6-Me3C6H 2, Py = 3,5-Me2pyrazol-1-yl, 5e; Ar = 2,6- iPr2C6H3, Py = 3,5-Me 2pyrazol-1-yl, 5f; Ar = 2,6-iPr2C 6H3, Py = 3,5-iPr2pyrazol-1-yl, 5g and [2-(OCMe)-6-(3,5-diphenylpyrazol-1-yl)C5H3N]CoCl 2 5h) were prepared and the molecular structures of 5a, 5c and 5f were determined by single crystal X-ray crystallography. Upon activation by methylaluminoxane (MAO) in toluene at room temperature, all complexes initiate polymerization of 1,3-butadiene (polymer yields: 65-99%), affording polybutadiene with excellent cis-1,4 regularity (97.5-98.7%). The polymer yields and properties in terms of molecular weight and distribution are well controlled by the substituents on iminoaryl rings and pyrazole rings. Selectivity switch from cis-1,4 to syndio-1,2 was also achievable by adding phosphine as microstructure regulator. © 2013 Elsevier B.V. All rights reserved.

  1. Bioinspired thermo- and pH-responsive polymeric amines: multimolecular aggregates in aqueous media and matrices for silica/polymer nanocomposites. (United States)

    Danilovtseva, Elena N; Aseyev, Vladimir; Belozerova, Olga Yu; Zelinskiy, Stanislav N; Annenkov, Vadim V


    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.

  2. 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. (United States)

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


    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.

  3. Acetylation and oxygenation transformations catalyzed by silica ...

    African Journals Online (AJOL)

    Acetylation of alcohols in refluxing ethyl acetate, and oxidation of aniline and cyclohexanol with 34 % H2O2 in the presence of H3PW12O40 and its supported forms on SiO2 (20 %, 40 %, and 60 % by weight) as active solid acid catalysts were performed under mild reaction conditions with moderate to good yields and with ...

  4. Polymeric microspheres (United States)

    Walt, David R.; Mandal, Tarun K.; Fleming, Michael S.


    The invention features core-shell microsphere compositions, hollow polymeric microspheres, and methods for making the microspheres. The microspheres are characterized as having a polymeric shell with consistent shell thickness.

  5. Solid-Phase Organic Synthesis and Catalysis: Some Recent Strategies Using Alumina, Silica, and Polyionic Resins

    Directory of Open Access Journals (Sweden)

    Basudeb Basu


    Full Text Available Solid-phase organic synthesis (SPOS and catalysis have gained impetus after the seminal discovery of Merrifield’s solid-phase peptide synthesis and also because of wide applicability in combinatorial and high throughput chemistry. A large number of organic, inorganic, or organic-inorganic hybrid materials have been employed as polymeric solid supports to promote or catalyze various organic reactions. This review article provides a concise account on our approaches involving the use of (i alumina or silica, either having doped with metal salts or directly, and (ii polyionic resins to either promote various organic reactions or to immobilize reagents/metal catalysts for subsequent use in hydrogenation and cross-coupling reactions. The reaction parameters, scopes, and limitations, particularly in the context of green chemistry, have been highlighted with pertinent approaches by other groups.

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

    KAUST Repository

    Werghi, Baraa


    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.

  7. Silica Nephropathy

    Directory of Open Access Journals (Sweden)

    N Ghahramani


    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.

  8. Can laccases catalyze bond cleavage in lignin?

    DEFF Research Database (Denmark)

    Munk, Line; Sitarz, Anna Katarzyna; Kalyani, Dayanand


    Modification of lignin is recognized as an important aspect of the successful refining of lignocellulosic biomass, and enzyme-assisted processing and upcycling of lignin is receiving significant attention in the literature. Laccases (EC 1.103.2) are taking the centerstage of this attention, since...... these enzymes may help degrading lignin, using oxygen as the oxidant. Laccases can catalyze polymerization of lignin, but the question is whether and how laccases can directly catalyze modification of lignin via catalytic bond cleavage. Via a thorough review of the available literature and detailed...... 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...

  9. Synthesis of a fluorine-free polymeric water-repellent agent for creation of superhydrophobic fabrics (United States)

    Shen, Keke; Yu, Miao; Li, Qianqian; Sun, Wei; Zhang, Xiting; Quan, Miao; Liu, Zhengtang; Shi, Suqing; Gong, Yongkuan


    A non-fluorinated polymeric alkylsilane, poly(isobutyl methacrylate-co-3-methacryloxypropyltrimethoxysilane) (PIT), is designed and synthesized to replace the commercial long-chain perfluoroalkylsilane (FAS) water-repellent agent. The superhydrophobic polyester fabrics are prepared by anchoring sol-gel derived silica nanoparticles onto alkali-treated polyester fabric surfaces and subsequently hydrophobilizing with PIT, using FAS as control. The surface chemical composition, surface morphology, wetting behavior and durability of the modified polyester fabrics are characterized by scanning electron microscopy (SEM), X-ray photoelectron spectrophotometer (XPS) and video-based contact angle goniometer, respectively. The results show that a porous silica layer could be successfully fabricated onto the surface of polyester fabric through base-catalyzed sol-gel process with tetraethoxysilane (TEOS) as precursor, incorporating additional nanostructured roughness essential for superhydrophobicity. At the same time, such a silica primer layer could provide both secondary reactive moieties (-Si - OH) for the subsequent surface hydrophobization and acceptable adhesion at the silica-polyester fabric interface. When silica modified polyester fabric (SiO2@ fabric) is hydrophobized by PIT solution (10 mg/mL), excellent water-repellency could be obtained. The water contact angle is up to 154° and the sliding angle is about 5°. Compared with small molecule water-repellent agent FAS, PIT modified SiO2@ fabric exhibits greatly improved solvent resistance under ultra-sonication, abrasion and simulated laundering durability. The anti-stain property of PIT-modified SiO2@ fabric is also evaluated by using different aqueous colored solutions.

  10. 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


    ...) 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...

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

    Directory of Open Access Journals (Sweden)

    Masako Miki


    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.

  12. Chlorodiethylaluminum supported on silica: A dinuclear aluminum surface species with bridging μ2-Cl-ligand as a highly efficient co-catalyst for the Ni-catalyzed dimerization of ethene

    KAUST Repository

    Kermagoret, Anthony


    Silica-supported chloro alkyl aluminum co-catalysts (DEAC@support) were prepared via Surface Organometallic Chemistry by contacting diethylaluminum chloride (DEAC) and high specific surface silica materials, i.e. SBA-15, MCM-41, and Aerosil SiO2. Such systems efficiently activate NiCl 2(PBu3)2 for catalytic ethene dimerization, with turnover frequency (TOF) reaching up to 498,000 molC2H4/ (molNi h) for DEAC@MCM-41. A detailed analysis of the DEAC@SBA-15 co-catalyst structure by solid-state aluminum-27 NMR at high-field (17.6 T and 20.0 T) and ultrafast spinning rates allows to detect six sites, characterized by a distribution of quadrupolar interaction principal values CQ and isotropic chemical shifts δiso. Identification of the corresponding Al-grafted structures was possible by comparison of the experimental NMR signatures with these calculated by DFT on a wide range of models for the aluminum species (mono- versus di-nuclear, mono- versus bis-grafted with bridging Cl or ethyl). Most of the sites were identified as dinuclear species with retention of the structure of DEAC, namely with the presence of μ2-Cl-ligands between two aluminum, and this probably explains the high catalytic performance of this silica-supported co-catalysts. © 2014 Elsevier Inc. All rights reserved.

  13. Can laccases catalyze bond cleavage in lignin? (United States)

    Munk, Line; Sitarz, Anna K; Kalyani, Dayanand C; Mikkelsen, J Dalgaard; Meyer, Anne S


    Modification of lignin is recognized as an important aspect of the successful refining of lignocellulosic biomass, and enzyme-assisted processing and upcycling of lignin is receiving significant attention in the literature. Laccases (EC are taking the centerstage of this attention, since these enzymes may help degrading lignin, using oxygen as the oxidant. Laccases can catalyze polymerization of lignin, but the question is whether and how laccases can directly catalyze modification of lignin via catalytic bond cleavage. Via a thorough review of the available literature and detailed 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 model compounds; ii) For laccases to catalyze inter-unit bond cleavage in lignin substrates, the presence of a mediator system is required. Clearly, the higher the redox potential of the laccase enzyme, the broader the range of substrates, including o- and p-diphenols, aminophenols, methoxy-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 is proposed. Copyright © 2015 Elsevier Inc. All rights reserved.

  14. Ultrasound promoted rapid and green synthesis of thiiranes from epoxides in water catalyzed by chitosan-silica sulfate nano hybrid (CSSNH) as a green, novel and highly proficient heterogeneous nano catalyst. (United States)

    Behrouz, Somayeh; Soltani Rad, Mohammad Navid; Piltan, Mohammad Amin


    The synthesis and characterization of chitosan-silica sulfate nano hybrid (CSSNH) as a novel, green and highly efficient heterogeneous nano catalyst is described. The catalytic activity of this new biopolymeric nano catalyst was investigated in the ultrasonic assisted green synthesis of structurally diverse thiiranes from epoxides using thiourea in water at room temperature. CSSNH was characterized using some different microscopic and spectroscopic techniques such as scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), N 2 adsorption isotherm, Fourier transform infrared spectroscopy (FT-IR), and thermogravimetric analysis (TGA). The green nature, cheapness, efficiency, ease of preparation, handling and reusability of this new catalyst makes this catalyst to be useful for green industrial processes. Copyright © 2017 Elsevier B.V. All rights reserved.

  15. Glycine Polymerization on Oxide Minerals (United States)

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


    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. The Electrochemical Behavior in Aqueous Media of Conducting Polymers. 2. The Insoluble Fractions Obtained on the Cu(II) Catalyzed Polymerization of (2,5-Dibromo-3-Group IV Substituted) Thiophenes. (United States)


    using anhydrous CuCI 2 as the promoter in the polymerization of 2,5-dilithiothiophene (23). We shall demonstrate that the broad peaks are due to the...Poly(thienylene) and Its Derivatives. Scan rate 100 mVs -1 . Polymer Catalyst E ° mV / \\ CuCI 2 -28 S n 6- CH 3 CuCI2 -56 Sn S i / \\ CuCl2 -24 S n G...e CuCI 2 -33 S n ’V Sn / \\ CuCI 2 -23 S S C H3 CuCI -185 S L:’ 0 Figures Figure 1: Cyclic voltammograms of Cu(l1)-poly(2,5-thienylene) in 0.1 N NaCI0

  17. Condensation Polymerization

    Indian Academy of Sciences (India)

    building blocks, is essentially the process of polycondensation or step-growth polymerization. Before we leave this LEGO-style discussion, I would leave you with two alternate scenarios; one is to use building blocks bearing two sockets and two balls, as de- picted in the figure, and the other is to use blocks that contain two.

  18. Condensation Polymerization

    Indian Academy of Sciences (India)

    At first, let us begin by treating molecules as LEGO-type building blocks with certain strict rules for linking them; a ball can readily fit with a socket, ... is essentially the process of polycondensation or step-growth polymerization. Before we leave this LEGO-style discussion, I would leave you with two alternate scenarios; one is.

  19. Polymerization catalyst, production and use

    International Nuclear Information System (INIS)

    Best, S.A.


    A process is described for polymerization of ethylene and alpha-olefins having from 1 to 20 carbon atoms or mixtures of ethylene, alpha-olefins and diolefins. The process comprises polymerizing one or more olefins in the presence of the catalyst system comprising (a) an organoaluminum cocatalyst, and (b) a vanadium containing a catalyst component obtained by treating an inert solid support material in an inert solvent with (i) an organoaluminum compound represented by the formula R/sub m/AIX/sub 3-m/, wherein R represents an alkyl group, cycloalkyl group or aryl group having from 1 to 18 carbon atoms, X represents halogen atoms, and 1≤m≤3, (ii) an acyl halide, and (iii) a vanadium compound. Another process is identified wherein the inert solid support material is an inorganic oxide or mixtures of inorganic oxides. Also a process wherein the inorganic oxide is silica is described

  20. Atomistic Model for the Polyamide Formation from beta-Lactam Catalyzed by Candida antarctica Lipase B

    NARCIS (Netherlands)

    Baum, Iris; Elsaesser, Brigitta; Schwab, Leendert W.; Loos, Katja; Fels, Gregor; Elsässer, Brigitta

    Candida antarctica lipase B (CALB) is an established biocatalyst for a variety of transesterification, amidation, and polymerization. reactions. In contrast to polyesters, poly amides are not yet generally accessible via enzymatic polymerization. In this regard, an enzyme-catalyzed ring-opening

  1. Emulsion droplets as a dynamic interface for the direct and large-scale synthesis of ultrathin free-standing mesoporous silica films as well as 2D polymeric and carbon nanomaterials (United States)

    Li, Jian; Zhu, Wei; Ji, Jingwei; Wang, Peng; Wang, Chen; Yin, Xianpeng; Wang, Hui; Lan, Yue; Gao, Ning; Li, Guangtao


    The efficient synthesis of free-standing mesostructured two-dimensional (2D) nanofilms with high-yield as well as good control of composite, mesophase structure, orientation of the pore channel and thickness represents a big challenge. In this work, it was serendipitously found that microemulsion droplets of tetraethylorthosilicate (TEOS) could serve as a novel dynamic interface for continuous growth of nanofilms. Based on this finding, a general, efficient strategy for the direct and large-scale synthesis of free-standing mesoporous silica films (FSMSFs) was developed. Remarkably, with the careful control of the synthesis conditions, the FSMSFs with high-yield as well as good control of composite, mesophase structure, orientation of the pore channel and thickness could be efficiently achievable. More importantly, by using polymerizable surfactants the preorganized monomers in the nanochannels of the resultant silica films could be further converted into 2D polymers and carbon nanomaterials as well as metal particle-decorated forms, as exemplified by using pyrrole-terminated surfactants, demonstrating a powerful method to create 2D inorganic, organic or hybrid functional nanomaterials.The efficient synthesis of free-standing mesostructured two-dimensional (2D) nanofilms with high-yield as well as good control of composite, mesophase structure, orientation of the pore channel and thickness represents a big challenge. In this work, it was serendipitously found that microemulsion droplets of tetraethylorthosilicate (TEOS) could serve as a novel dynamic interface for continuous growth of nanofilms. Based on this finding, a general, efficient strategy for the direct and large-scale synthesis of free-standing mesoporous silica films (FSMSFs) was developed. Remarkably, with the careful control of the synthesis conditions, the FSMSFs with high-yield as well as good control of composite, mesophase structure, orientation of the pore channel and thickness could be efficiently

  2. A novel fabrication of meso-porous silica film by sol-gol of TEOS. (United States)

    Yin, Ming-zhi; Yao, Xi; Zhang, Liang-ying


    A homogeneous crack-free nano- or meso-porous silica films on silicon was fabricated by colloidal silica sol derived by hydrolyzing tetraethyl orthosilicate (TEOS) catalyzing with (C4H9)4N+OH- in water medium. The solution with ratio of H2O/TEOS> or =15, R4N+ and glycerol as templates, combining with the hydrolyzed intermediate, controlled the silica aggregating; the templated silica film with heterostructure was developed into homogeneous nano-porous then meso-porous silica films after being annealed from 750 degrees C to 850 degrees C; the formation mechanism of the porous silica films was discussed; morphologies of the silica films were characterized. The refractive indexes of the porous silica films were 1.256-1.458, the thermal conductivity < 0.7 W/m/K. The fabricating procedure and the sequence had not been reported before.

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


    Ma, Huan; Luo, Mingxiang; Sanyal, Sriya; Rege, Kaushal; Dai, Lenore L.


    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-hydroxyethyl)propionamide (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 e...

  4. Nucleation of polystyrene latex particles in the presence of gamma-methacryloxypropyltrimethoxysilane: functionalized silica particles. (United States)

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


    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.

  5. Functional Films from Silica/Polymer Nanoparticles

    Directory of Open Access Journals (Sweden)

    Tânia Ribeiro


    Full Text Available High performance functional coatings, based on hybrid organic/inorganic materials, are being developed to combine the polymer flexibility and ease of processing with the mechanical properties and versatility of inorganic materials. By incorporating silica nanoparticles (SiNPs in the polymeric matrices, it is possible to obtain hybrid polymer films with increased tensile strength and impact resistance, without decreasing the flexural properties of the polymer matrix. The SiNPs can further be used as carriers to impart other functionalities (optical, etc. to the hybrid films. By using polymer-coated SiNPs, it is possible to reduce particle aggregation in the films and, thus, achieve more homogeneous distributions of the inorganic components and, therefore, better properties. On the other hand, by coating polymer particles with silica, one can create hierarchically structured materials, for example to obtain superhydrophobic coatings. In this review, we will cover the latest developments in films prepared from hybrid polymer/silica functional systems.

  6. Single-Molecule Visualization of Living Polymerization (United States)


    77 (2011). 11 D. P. Allen , M. M. Van Wingerden & R. H. Grubbs. Well-defined silica-supported olefin metathesis catalysts. Org Lett 11, 1261-1264...magnet position), we can also probe how mechanical tension affects the catalytic kinetics of the polymerization. When the magnets are positioned far...the setup include: two rectangular NdFeB magnets mounted on a rotatable base controlled by a motor via a timing belt , collimated LED illumination

  7. Synthesis of novel carbon/silica composites based strong acid ...

    Indian Academy of Sciences (India)

    hydrophobic acid-catalyzed reactions proceed in poor or with no catalytic activity (Nakajima et al 2009). The novel car- bon/silica composites based solid acid was synthesized for the purpose. However, the new method added the step of impregnating sucrose to the channels of SBA-15, which fur- ther added to the cost for ...

  8. Mesoporous silica supported Pd/Ag bimetallic nanoparticles as a ...

    Indian Academy of Sciences (India)

    Priyanka Verma


    Sep 19, 2017 ... bUnit of Elements Strategy Initiative for Catalysts and Batteries, Kyoto University, Katsura, Kyoto 615-8520,. Japan. cJST, PRESTO, 4-1-8 Honcho, Kawaguchi, ... Silver-based bimetallic Pd/Ag plasmonic catalysts supported on mesoporous silica catalyze the chemoselective reduction of nitrostyrene (NS) to ...

  9. Facile Preparation of Crosslinked Polymeric Nanocapsules via Combination of Surface-Initiated Atom Transfer Radical Polymerization and Ultraviolet Irradiated Crosslinking Techniques

    Directory of Open Access Journals (Sweden)

    Mu Bin


    Full Text Available Abstract A facile approach for the preparation of crosslinked polymeric nanocapsules was developed by the combination of the surface-initiated atom transfer radical polymerization and ultraviolet irradiation crosslinking techniques. The well-defined polystyrene grafted silica nanoparticles were prepared via the SI-ATRP of styrene from functionalized silica nanoparticles. Then the grafted polystyrene chains were crosslinked with ultraviolet irradiation. The cross-linked polystyrene nanocapsules with diameter of 20–50 nm were achieved after the etching of the silica nanoparticle templates with hydrofluoric acid. The strategy developed was confirmed with Fourier transform infrared, thermogravimetric analysis, and transmission electron microscopy.

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

    Directory of Open Access Journals (Sweden)

    Jianbo Tan


    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.

  11. Polysiloxanes derived from the controlled hydrolysis of tetraethoxysilane as precursors to silica for use in ceramic processing (United States)

    Philipp, Warren H.


    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.

  12. Templated growth of gold satellites on dimpled silica cores. (United States)

    Chomette, C; Duguet, E; Mornet, S; Yammine, E; Manoharan, V N; Schade, N B; Hubert, C; Ravaine, S; Perro, A; Tréguer-Delapierre, M


    We synthesize robust clusters of gold satellites positioned with tetrahedral symmetry on the surface of a patchy silica core by adsorption and growth of gold on the patches. First we conduct emulsion polymerization of styrene in the presence of 52 nm silica seeds whose surface has been modified with methacryloxymethyltriethoxysilane (MMS). We derive four-dimple particles from the resulting silica/polystyrene tetrapods. Polystyrene chains are covalently bound to the silica surface within the dimples due to the MMS grafts and they may be thiolated to induce adsorption of 12 nm gold particles. Using chloroauric acid, ascorbic acid and sodium citrate at room temperature, we grow gold from these 12 nm seeds without detachment from or deformation of the dimpled silica surface. We obtain gold satellites of tunable diameter up to 140 nm.

  13. Calculation of 29Si NMR shifts of silicate complexes with carbohydrates, amino acids, and muhicarboxylic acids: potential role in biological silica utilization (United States)

    Sahai, Nita


    The existence of ether or ester-like complexes of silicate with organic compounds has long been debated in the literature on biological utilization of silicon. Comparison of theoretically calculated 29Si NMR chemical shifts for such complexes with experimentally measured values in biological systems could provide a diagnostic tool for identifying which, if any of these molecules exist under physiological conditions. Results are presented here for ab initio molecular orbital calculations of 29Si NMR shifts and formation energies of silicate complexes with polyalcohols, sugar-acids, pyranose sugars, amino acids and multicarboxylic acids. The effects of functional group and molecular structure including ligand size, denticity, ring size, silicon polymerization and coordination number on calculated 29Si shifts were considered. The potential role of such compounds in biological silica utilization pathways is discussed. 29Si NMR shifts and energies were calculated at the HF/6-311+G(2d,p)//HF/6-31G* level. The main result is that only five-membered rings containing penta- and hexa-coordinated Si can explain experimentally observed resonances at ˜ -101 and -141 ppm. Further, the heptet observed in 1H- 29Si coupled spectra can only be explained by structures where Si bonds to oxygens atoms in H-C-O-Si linkages with six symmetrically equivalent H atoms. While compounds containing quadra-coordinated silicon may exist in intracellular silicon storage pools within diatoms, calculated reaction energies suggest that the organism has no thermodynamic advantage in taking up extracellular organ-silicate compounds, instead of silicic acid, from the ambient aqueous environment. Hyper-coordinated complexes are deemed unlikely for transport and storage, though they may exist as transient reactive intermediates or activated complexes during enzymatically- catalyzed silica polymerization, as known previously from sol-gel silica synthesis studies.

  14. Catalyzing RE Project Development

    Energy Technology Data Exchange (ETDEWEB)

    Anderson, Kate; Elgqvist, Emma; Walker, Andy; Cutler, Dylan; Olis, Dan; DiOrio, Nick; Simpkins, Travis


    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.

  15. Muon Catalyzed Fusion (United States)

    Armour, Edward A.G.


    Muon catalyzed fusion is a process in which a negatively charged muon combines with two nuclei of isotopes of hydrogen, e.g, a proton and a deuteron or a deuteron and a triton, to form a muonic molecular ion in which the binding is so tight that nuclear fusion occurs. The muon is normally released after fusion has taken place and so can catalyze further fusions. As the muon has a mean lifetime of 2.2 microseconds, this is the maximum period over which a muon can participate in this process. This article gives an outline of the history of muon catalyzed fusion from 1947, when it was first realised that such a process might occur, to the present day. It includes a description of the contribution that Drachrnan has made to the theory of muon catalyzed fusion and the influence this has had on the author's research.

  16. 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...

  17. A joint experimental/theoretical investigation of the MMA polymerization initiated by yttrium phenoxyamine complexes. (United States)

    Fang, Jian; Tschan, Mathieu J-L; Brulé, E; Robert, Carine; Thomas, Christophe M; Maron, Laurent


    A joint experimental/theoretical study has been carried out on the putative MMA polymerization catalyzed by an yttrium isopropyloxide complex. Despite its high activity in lactone polymerization, this catalyst is found to be unreactive on methyl methacrylate (MMA) polymerization. This surprising result is rationalized using a computational approach at the DFT level. Indeed, the endothermicity of the initiation step explains this lack of reactivity. The theoretical proposal of yttrium amido complexes as catalysts allows overcoming this initiation problem.

  18. Immobilized Ionic Liquid-Catalyzed Synthesis of Pyrano[3,2-b]indole Derivatives

    Directory of Open Access Journals (Sweden)

    Saman Damavandi


    Full Text Available An ionic liquid-catalyzed synthesis of 2-amino-4,5-dihydro-4-arylpyrano[3,2-b]indole-3-carbonitrile derivatives through a novel three-component condensation of 3-hydroxyindole, aromatic aldehydes and malononitrile in the presence of silica supported ionic liquid of [pmim]HSO4SiO2 (silica supported 1-methyl-3-(triethoxysilylpropylimidazolium hydrogensulfate as an efficient catalyst is described.

  19. Catalytic olefin polymerization with early transition metal compounds

    NARCIS (Netherlands)

    Eshuis, Johan Jan Willem


    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

  20. Characterization of Plasma Polymerized Hexamethyldisiloxane Films Prepared by Arc Discharge

    NARCIS (Netherlands)

    Lazauskas, A.; Baltrusaitis, Jonas; Grigaliunas, V.; Jucius, D; Guobiene, A.; Prosycevas, I.; Narmontas, P.


    Herein, we present a simple method for fabricating plasma polymerized hexamethyldisiloxane films (pp-HMDSO) possessing superhydrophobic characteristics via arc discharge. The pp-HMDSO films were deposited on a soda–lime–silica float glass using HMDSO monomer vapor as a precursor. A detailed surface

  1. Controlled radical polymerization of vinyl acetate in presence of ...

    Indian Academy of Sciences (India)

    Mesoporous silica; heterogeneous catalyst; specific sequences; controlled free radical polymerization; ... copolymers. CRP is a common technique for synthesis of (co)polymers with well-defined molecular parameters. (Mw/Mn), reactive end groups, composition and ... bulk copolymerization of vinyl acetate with butyl acrylate.

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


    The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...


    The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

  5. Enhanced binding capacity of boronate affinity adsorbent via surface modification of silica by combination of atom transfer radical polymerization and chain-end functionalization for high-efficiency enrichment of cis-diol molecules

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Wei; He, Maofang; Wang, Chaozhan; Wei, Yinmao, E-mail:


    Boronate affinity materials have been widely used for specific separation and preconcentration of cis-diol molecules, but most do not have sufficient capacity due to limited binding sites on the material surface. In this work, we prepared a phenylboronic acid-functionalized adsorbent with a high binding capacity via the combination of surface-initiated atom transfer radical polymerization (SI-ATRP) and chain-end functionalization. With this method, the terminal chlorides of the polymer chains were used fully, and the proposed adsorbent contains dense boronic acid polymers chain with boronic acid on the chain end. Consequently, the proposed adsorbent possesses excellent selectivity and a high binding capacity of 513.6 μmol g{sup −1} for catechol and 736.8 μmol g{sup −1} for fructose, which are much higher than those of other reported adsorbents. The dispersed solid-phase extraction (dSPE) based on the prepared adsorbent was used for extraction of three cis-diol drugs (i.e., epinephrine, isoprenaline and caffeic acid isopropyl ester) from plasma; the eluates were analyzed by HPLC-UV. The reduced amount of adsorbent (i.e., 2.0 mg) could still eliminate interferences efficiently and yielded a recovery range of 85.6–101.1% with relative standard deviations ranging from 2.5 to 9.7% (n = 5). The results indicated that the proposed strategy could serve as a promising alternative to increase the density of surface functional groups on the adsorbent; thus, the prepared adsorbent has the potential to effectively enrich cis-diol substances in real samples. - Highlights: • Boronate adsorbent is prepared via ATRP and chain-end functionalization. • The adsorbent has quite high binding capacity for cis-diols. • Binding capacity is easily manipulated by ATRP condition. • Chain-end functionalization can improve binding capacity significantly. • Reduced adsorbent is consumed in dispersed solid-phase extraction of cis-diols.

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

    Directory of Open Access Journals (Sweden)

    Kaushal Rege


    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.

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

    Directory of Open Access Journals (Sweden)

    Jun-ichi Kadokawa


    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

  8. Fibrinogen Matsumoto V: a variant with Aalpha19 Arg-->Gly (AGG-->GGG). Comparison between fibrin polymerization stimulated by thrombin or reptilase and fibrin monomer polymerization. (United States)

    Tanaka, H; Terasawa, F; Ito, T; Tokunaga, S; Ishida, F; Kitano, K; Kiyosawa, K; Okumura, N


    Fibrinogen Matsumoto V (M-V) is a dysfibrinogen identified in a 52-year-old woman with systemic lupus erythematous. The triplet AGG encoding the amino acid residue Aalpha19 was replaced by GGG, resulting in the substitution of Arg-->Gly. Residue Aalpha19 has been shown to be one of the most important amino acids in the so-called 'A' site or alpha-chain knob. The thrombin-catalyzed release of fibrinopeptide A from M-V fibrinogen was only slightly delayed yet release of fibrinopeptide B was significantly delayed. Both thrombin-catalyzed fibrin polymerization and fibrin monomer polymerization were markedly impaired compared to normal fibrinogen. In addition, reptilase-catalyzed fibrin polymerization of M-V was much more impaired than thrombin-catalyzed fibrin polymerization. These results indicate 'B' and/or 'b' site of M-V fibrinogen play a more important role in thrombin-catalyzed fibrin polymerization than that of normal control fibrinogen.

  9. Catalytic Polymerization of Acrylonitrile by Khulays Bentonite

    Directory of Open Access Journals (Sweden)

    Matar M. Al-Esaimi


    Full Text Available The aqueous polymerization of acrylonitrile (AN catalyzed with exchanged Khulays bentonite . The influence of various polymerization parameters ( e.g., concentrations of Potassium Persulfate (K2S2O8 and monomer , various of organic solvents, and different temperature has been investigated. It was found that the rate of polymerization of AN was found to be dependent on monomer concentration, initiator and temperature. The activation energy of polymerization was calculated .Thermal properties of the polymer were studied by TGA and DSC techniques. © 2007 CREC UNDIP. All rights reserved.Received: 5 February 2007; Received in revised: 19 April 2007; Accepted: 7 May 2007[How to Cite: M. M. Al-Esaimi. (2007. Catalytic Polymerization of Acrylonitrile by Khulays Bentonite. Bulletin of Chemical Reaction Engineering and Catalysis, 2 (2-3: 32-36.  doi:10.9767/bcrec.][How to Link/DOI: || or local:] 

  10. Silica Synthesis by Sponges: Unanticipated Molecular Mechanism (United States)

    Morse, D. E.; Weaver, J. C.


    Oceanic diatoms, sponges and other organisms synthesize gigatons per year of silica from silicic acid, ultimately obtained from the weathering of rock. This biogenic silica exhibits a remarkable diversity of structures, many of which reveal a precision of nanoarchitectural control that exceeds the capabilities of human engineering. In contrast to the conditions of anthropogenic and industrial manufacture, the biological synthesis of silica occurs under mild physiological conditions of low temperatures and pressures and near-neutral pH. In addition to the differentiation between biological and abiotic processes governing silica formation, the biomolecular mechanisms controlling synthesis of these materials may offer insights for the development of new, environmentally benign routes for synthesis of nanostructurally controlled silicas and high-performance polysiloxane composites. We found that the needle-like silica spicules made by the marine sponge, Tethya aurantia, each contain an occluded axial filament of protein composed predominantly of repeating assemblies of three similar subunits we named "silicateins." To our surprise, analysis of the purified protein subunits and the cloned silicatein DNAs revealed that the silicateins are highly homologous to a family of hydrolytic enzymes. As predicted from this finding, we discovered that the silicatein filaments are more than simple, passive templates; they actively catalyze and spatially direct polycondensation to form silica, (as well as the phenyl- and methyl-silsesquioxane) from the corresponding silicon alkoxides at neutral pH and low temperature. Catalytic activity also is exhibited by the silicatein subunits obtained by disaggregation of the protein filaments and those produced from recombinant DNA templates cloned in bacteria. This catalytic activity accelerates the rate-limiting hydrolysis of the silicon alkoxide precursors. Genetic engineering, used to produce variants of the silicatein molecule with

  11. Rhodium Catalyzed Decarbonylation

    DEFF Research Database (Denmark)

    Garcia Suárez, Eduardo José; Kahr, Klara; Riisager, Anders


    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...

  12. Microporous silica membranes

    DEFF Research Database (Denmark)

    Boffa, Vittorio; Yue, Yuanzheng


    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....

  13. Metal content determination in polymerization catalysts by direct methods

    International Nuclear Information System (INIS)

    Bichinho, K.M.; Pires, Gilvan P.; Stedile, F.C.; Santos, J.H.Z. dos


    Metal contents in polymerization catalysts were comparatively determined by Rutherford backscattering spectrometry (RBS), X-ray photoelectron spectroscopy (XPS) and X-ray fluorescence (XRF) spectroscopy. Catalysts were prepared by grafting metallocene onto bare silica or onto silica chemically modified with methylaluminoxane (MAO). Catalysts were compressed as self-supporting pellets (RBS and XRF), or mounted on adhesive copper tape (XPS). The proximity of the mass of the atomic nuclei did not allow resolution by RBS of the signals corresponding to Zr and Nb, nor Si and Al in catalyst systems such as (nBuCp) 2 ZrCl 2 /Cp 2 NbCl 2 /MAO/SiO 2 . On the other hand, Zr, Nb, Si and Al lines were completely resolved in an XRF spectrum. For supported metallocenes on bare silica, XPS measurement was ca. 40% higher than that obtained by RBS. Silica-supported zirconocene showed good agreement in Zr content determination by XRF and RBS

  14. Synthesis and Characterization of Polyvinylpyrrolidone Silica Core-Shell Nanocomposite Particles. (United States)

    Chen, Lian-Xi; Li, Jie; Li, Xi; Zhang, Zhong-Min; Jiao, Cai-Bin


    In this work, a novel and facile strategy for making a new type of polymer/silica nanocomposte particle was proposed. Colloidally stable polyvinypyrrolidone (PVP)/silica core-shell nanocomposite particles have been successfully synthesized using an azo initiator via seed polymerization of N-vinyl-2-pyrrolidone (NVP) and VFSs (VFSs) that were derived from vinyl triethoxysilane (VTES). It was suggested from the FTIR and TGA analysis that the copolymerization reaction of NVP with VFSs has been thoroughly carried out. In addition, SEM images showed that PVP/silica nanocomposite particles have relatively rough surface due to surface polymerization in comparison with VFSs. Furthermore, TEM results proved that the size of VFSs had considerable effects on the appearance of PVP/silica nanocomposite particles. Generally, it presented that several silica nanoparticle cores with an average size of 78 nm mainly pack together within each nanocomposite particle after seed polymerization. Interestingly, the average shell thickness was 59 nm for most PVP/silica nanocomposite particles with cores about 242 nm. However, when the core size was large enough to about 504 nm, a series of PVP/silica nanocomposite particles with a relative thin shell were observed.

  15. Synthesis of multivalent silica nanoparticles combining both enthalpic and entropic patchiness. (United States)

    Hubert, Céline; Chomette, Cyril; Désert, Anthony; Sun, Ming; Treguer-Delapierre, Mona; Mornet, Stéphane; Perro, Adeline; Duguet, Etienne; Ravaine, Serge


    Silica particles with a controlled number of entropic patches, i.e. dimples, are synthesized through the growth of the silica core of binary multipods that have been produced by a seeded-growth emulsion polymerization reaction. Transmission electron microscopy studies indicate that the silica surface conforms to the shape of the polystyrene (PS) nodules of the multipods while growing, allowing good control of the final shape of the dimpled silica particles. The PS nodules are also used as protecting masks to regioselectively graft amino groups, as revealed by the adsorption of gold markers. After dissolution of the PS nodules, some polymer chains remain grafted onto the silica surface, forming organic bumps. These residues are also selectively functionalized, leading to silica particles with both entropic and enthalpic patches.

  16. Crystalline Silica Primer (United States)



    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

  17. Silica from Ash

    Indian Academy of Sciences (India)

    Silica (SiOz) is one of the valuable inorganic multipurpose chemical compounds. It can exist in gel, crystalline and amorphous forms. It is the most abundant material on the earth's crust. However, manufacture of pure silica is energy intensive. A variety of industrial processes, involving conven- tional raw materials require ...

  18. Polymerization in emulsion microdroplet reactors (United States)

    Carroll, Nick J.

    The goal of this research project is to utilize emulsion droplets as chemical reactors for execution of complex polymerization chemistries to develop unique and functional particle materials. Emulsions are dispersions of immiscible fluids where one fluid usually exists in the form of drops. Not surprisingly, if a liquid-to-solid chemical reaction proceeds to completion within these drops, the resultant solid particles will possess the shape and relative size distribution of the drops. The two immiscible liquid phases required for emulsion polymerization provide unique and complex chemical and physical environments suitable for the engineering of novel materials. The development of novel non-ionic fluorosurfactants allows fluorocarbon oils to be used as the continuous phase in a water-free emulsion. Such emulsions enable the encapsulation of almost any hydrocarbon compound in droplets that may be used as separate compartments for water-sensitive syntheses. Here, we exemplify the promise of this approach by suspension polymerization of polyurethanes (PU), in which the liquid precursor is emulsified into droplets that are then converted 1:1 into polymer particles. The stability of the droplets against coalescence upon removal of the continuous phase by evaporation confirms the formation of solid PU particles. These results prove that the water-free environment of fluorocarbon based emulsions enables high conversion. We produce monodisperse, cross-linked, and fluorescently labeled PU-latexes with controllable mesh size through microfluidic emulsification in a simple one-step process. A novel method for the fabrication of monodisperse mesoporous silica particles is presented. It is based on the formation of well-defined equally sized emulsion droplets using a microfluidic approach. The droplets contain the silica precursor/surfactant solution and are suspended in hexadecane as the continuous oil phase. The solvent is then expelled from the droplets, leading to

  19. Fouling behavior during microfiltration of silica nanoparticles and polymeric stabilizers

    NARCIS (Netherlands)

    Trzaskus, Krzystof; Zdeb, Aneta; de Vos, Wiebe Matthijs; Kemperman, Antonius J.B.; Nijmeijer, Dorothea C.


    Nanotechnology applications give rise to new forms of water pollution, resulting in a need for reliable technologies that can remove nanoparticles from water. Membrane filtration is an obvious candidate. The tendency of nanoparticles to become instable in suspension and form aggregates strongly

  20. Synthesis and characterization of polyaniline-silica composites: Raspberry vs core-shell structures. Where do we stand? (United States)

    Roosz, Nicolas; Euvard, Myriam; Lakard, Boris; Buron, Cédric C; Martin, Nicolas; Viau, Lydie


    The synthesis of polyaniline-silica composites has been reinvestigated in view of the opposing results found in the literature. Firstly, we synthesized silica particles with tunable size using the Stöber process. These silica particles have been fully characterized before being used as solid support for the polymerization of aniline. This polymerization was performed according to a published procedure where the pH of the reaction mixture was below the pKa of aniline but at a value where the silica particles surface was still slightly negatively charged. The objective of this procedure was to favor electrostatic interactions between anilinium cations and the silica surface to lead to the formation of silica-polyaniline core-shell particles. Several sets of nanocomposites were prepared under different experimental conditions (oxidant/aniline ratio, silica concentration, temperature, silica particles diameters). The study evidenced that under all the conditions used the formation of core-shell nanoparticles is impossible. However, using different particle sizes, noticeable morphological differences were observed. The use of large silica particles led to the formation of non-uniform polyaniline-silica composites whereas the use of smaller particles always led to raspberry-like morphology as reported by other groups in highly acidic media. The difference in morphology led to different electrical properties with electrical conductivities measured at room temperature ranging from 1.6×10 -3 to 2.5×10 -5 S cm -1 . Copyright © 2017 Elsevier Inc. All rights reserved.

  1. Polymeric Membrane Reactors


    José M. Sousa; Luís M. Madeira; João C. Santos; Adélio Mendes


    The aim of this chapter is the study of membrane reactors with polymeric membranes, particularly catalytic polymeric membranes. After an introduction where the main advantages and disadvantages of the use of polymeric membranes are summarised, a review of the main areas where they have been applied, integrated in chemical reactors, is presented. This excludes the field of bio-membranes processes, which is analysed in a specific chapter of this book. Particular attention is then given to model...

  2. Catalyzed Ceramic Burner Material

    Energy Technology Data Exchange (ETDEWEB)

    Barnes, Amy S., Dr.


    Catalyzed combustion offers the advantages of increased fuel efficiency, decreased emissions (both NOx and CO), and an expanded operating range. These performance improvements are related to the ability of the catalyst to stabilize a flame at or within the burner media and to combust fuel at much lower temperatures. This technology has a diverse set of applications in industrial and commercial heating, including boilers for the paper, food and chemical industries. However, wide spread adoption of catalyzed combustion has been limited by the high cost of precious metals needed for the catalyst materials. The primary objective of this project was the development of an innovative catalyzed burner media for commercial and small industrial boiler applications that drastically reduce the unit cost of the catalyzed media without sacrificing the benefits associated with catalyzed combustion. The scope of this program was to identify both the optimum substrate material as well as the best performing catalyst construction to meet or exceed industry standards for durability, cost, energy efficiency, and emissions. It was anticipated that commercial implementation of this technology would result in significant energy savings and reduced emissions. Based on demonstrated achievements, there is a potential to reduce NOx emissions by 40,000 TPY and natural gas consumption by 8.9 TBtu in industries that heavily utilize natural gas for process heating. These industries include food manufacturing, polymer processing, and pulp and paper manufacturing. Initial evaluation of commercial solutions and upcoming EPA regulations suggests that small to midsized boilers in industrial and commercial markets could possibly see the greatest benefit from this technology. While out of scope for the current program, an extension of this technology could also be applied to catalytic oxidation for volatile organic compounds (VOCs). Considerable progress has been made over the course of the grant

  3. Synthesis of hollow asymmetrical silica dumbbells with a movable inner core. (United States)

    Nagao, Daisuke; van Kats, Carlos M; Hayasaka, Kentaro; Sugimoto, Maki; Konno, Mikio; Imhof, Arnout; van Blaaderen, Alfons


    Hollow asymmetrical silica dumbbells containing a movable inner core were fabricated by a template-assisted method. Three different templates were employed for the fabrication of the hollow asymmetrical dumbbells. For the preparation of the first template, silica particles were uniformly covered with a cross-linked polymethylmethacrylate (PMMA) shell and the polymerization of styrene was conducted to induce a protrusion of polystyrene (PSt) from the PMMA shell. Anisotropic colloids composed of silica, PMMA, and PSt were used as templates, coated with a silica shell, and held at 500 degrees C for 2 h to remove the polymer interior components of the template colloid. The heat treatment successfully produced hollow asymmetrical silica dumbbells containing an inner silica core. After being dried, approximately 50% of the inner silica particles that were originally coated with PMMA ended up in the other hollow sphere in which the PSt component existed before heat treatment, indicating that the inner silica particles could pass through the hollow asymmetrical dumbbells' necks and were free to move in the interior. In the preparation of the second and third asymmetrical dumbbell templates, magnetic silica particles and titania particles, respectively, were covered with a PMMA shell to incorporate externally responsive particles into the hollow silica shells as above. The successful syntheses demonstrated the generality of our approach. The passage of the responsive particles through the dumbbell's neck enabled active control of the position of the responsive particles inside the asymmetrical dumbbells by external fields.

  4. Design of water-repellant coating using dual scale size of hybrid silica nanoparticles on polymer surface (United States)

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


    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.

  5. High residue contents indebted by platinum and silica synergistic action during the pyrolysis of silicone formulations. (United States)

    Delebecq, Etienne; Hamdani-Devarennes, Siska; Raeke, Julia; Lopez Cuesta, José-Marie; Ganachaud, François


    The synergistic role of platinum and silica as a way to increase the final residue of pyrolized silicone was investigated and explained, giving new interpretations. Conditions were first set to study the thermal degradation of silicones in the presence of platinum based on the simplest silicone/silica/platinum formulation. Numerous parameters, e.g., platinum and silica content or silica surface modifications, were varied to track their influences on the final residues. A thorough DSC study, together with SEM/EDX and Pyrolysis/GC-MS analyses, led us to propose a three-stage process. The key parameter governing thermal stability and final content of the residue is the conjugated actions of immobilizing/cross-linking PDMS chains. Silica particles tether silicone chains through physical interactions, i.e., hydrogen bonding, facilitating a platinum radically catalyzed cross-linking reaction. Practical implications and possible improvements on LSR formulations are finally given.

  6. Silica aerogel Cerenkov counter

    International Nuclear Information System (INIS)

    Yasumi, S.; Masaike, A.; Yamamoto, A.; Yoshimura, Y.; Kawai, H.


    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)

  7. Cellulose-silica aerogels. (United States)

    Demilecamps, Arnaud; Beauger, Christian; Hildenbrand, Claudia; Rigacci, Arnaud; Budtova, Tatiana


    Aerogels based on interpenetrated cellulose-silica networks were prepared and characterised. Wet coagulated cellulose was impregnated with silica phase, polyethoxydisiloxane, using two methods: (i) molecular diffusion and (ii) forced flow induced by pressure difference. The latter allowed an enormous decrease in the impregnation times, by almost three orders of magnitude, for a sample with the same geometry. In both cases, nanostructured silica gel was in situ formed inside cellulose matrix. Nitrogen adsorption analysis revealed an almost threefold increase in pores specific surface area, from cellulose aerogel alone to organic-inorganic composite. Morphology, thermal conductivity and mechanical properties under uniaxial compression were investigated. Thermal conductivity of composite aerogels was lower than that of cellulose aerogel due to the formation of superinsulating mesoporous silica inside cellulose pores. Furthermore, composite aerogels were stiffer than each of reference aerogels. Copyright © 2015 Elsevier Ltd. All rights reserved.

  8. Electrochemical Sensors: Functionalized Silica

    Energy Technology Data Exchange (ETDEWEB)

    Fryxell, Glen E.; Lin, Yuehe; Yantasee, Wassana


    This chapter summarizes recent devellopment of electrochemical sensors based on functionlized mesoporous silica materials. The nanomatrials based sensors have been developed for sensitive and selective enrironmental detection of toxic heavy metal and uranium ions.

  9. Silica Coating of Nonsilicate Nanoparticles for Resin-Based Composite Materials. (United States)

    Kaizer, M R; Almeida, J R; Gonçalves, A P R; Zhang, Y; Cava, S S; Moraes, R R


    This study was designed to develop and characterize a silica-coating method for crystalline nonsilicate ceramic nanoparticles (Al 2 O 3 , TiO 2 , and ZrO 2 ). The hypothesis was that the coated nonsilicate nanoparticles would stably reinforce a polymeric matrix due to effective silanation. Silica coating was applied via a sol-gel method, with tetraethyl orthosilicate as a silica precursor, followed by heat treatment. The chemical and microstructural characteristics of the nanopowders were evaluated before and after silica coating through x-ray diffraction, BET (Brunauer-Emmett-Teller), energy-dispersive x-ray spectroscopy, field emission scanning electron microscopy, and transmission electron microscopy analyses. Coated and noncoated nanoparticles were silanated before preparation of hybrid composites, which contained glass microparticles in addition to the nanoparticles. The composites were mechanically tested in 4-point bending mode after aging (10,000 thermal cycles). Results of all chemical and microstructural analyses confirmed the successful obtaining of silica-coated nanoparticles. Two distinct aspects were observed depending on the type of nanoparticle tested: 1) formation of a silica shell on the surface of the particles and 2) nanoparticle clusters embedded into a silica matrix. The aged hybrid composites formulated with the coated nanoparticles showed improved flexural strength (10% to 30% higher) and work of fracture (35% to 40% higher) as compared with composites formulated with noncoated nanoparticles. The tested hypothesis was confirmed: silanated silica-coated nonsilicate nanoparticles yielded stable reinforcement of dimethacrylate polymeric matrix due to effective silanation. The silica-coating method presented here is a versatile and promising novel strategy for the use of crystalline nonsilicate ceramics as a reinforcing phase of polymeric composite biomaterials.

  10. Step-Growth Polymerization. (United States)

    Stille, J. K.


    Following a comparison of chain-growth and step-growth polymerization, focuses on the latter process by describing requirements for high molecular weight, step-growth polymerization kinetics, synthesis and molecular weight distribution of some linear step-growth polymers, and three-dimensional network step-growth polymers. (JN)

  11. Construction of Nontoxic Polymeric UV-Absorber with Great Resistance to UV-Photoaging


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


    In this article, we developed a series of new nontoxic polymeric UV-absorbers through covalently attaching a benzophenone derivative onto the main chain of poly(vinyl chloride) (PVC) via mild and quantitative click chemistry. Azide groups were firstly introduced into the backbone of PVC via a nucleophilic reaction without affecting polymeric skeleton. Copper-catalyzed Husigen-Click cycloaddition reaction was performed between the pendant azide groups of PVC and alkynyl of (2-hydroxy-4-(prop-2...

  12. Applied bioactive polymeric materials

    CERN Document Server

    Carraher, Charles; Foster, Van


    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...

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

    DEFF Research Database (Denmark)

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


    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...

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

    DEFF Research Database (Denmark)

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


    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...

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

    DEFF Research Database (Denmark)

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


    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...

  16. Multifunctional antireflection coatings based on novel hollow silica-silica nanocomposites. (United States)

    Zhang, Xianpeng; Lan, Pinjun; Lu, Yuehui; Li, Jia; Xu, Hua; Zhang, Jing; Lee, YoungPak; Rhee, Joo Yull; Choy, Kwang-Leong; Song, Weijie


    Antireflection (AR) coatings that exhibit multifunctional characteristics, including high transparency, robust resistance to moisture, high hardness, and antifogging properties, were developed based on hollow silica-silica nanocomposites. These novel nanocomposite coatings with a closed-pore structure, consisting of hollow silica nanospheres (HSNs) infiltrated with an acid-catalyzed silica sol (ACSS), were fabricated using a low-cost sol-gel dip-coating method. The refractive index of the nanocomposite coatings was tailored by controlling the amount of ACSS infiltrated into the HSNs during synthesis. Photovoltaic transmittance (TPV) values of 96.86-97.34% were obtained over a broad range of wavelengths, from 300 to 1200 nm; these values were close to the theoretical limit for a lossy single-layered AR coating (97.72%). The nanocomposite coatings displayed a stable TPV, with degradation values of less than 4% and 0.1% after highly accelerated temperature and humidity stress tests, and abrasion tests, respectively. In addition, the nanocomposite coatings had a hardness of approximately 1.6 GPa, while the porous silica coatings with an open-pore structure showed more severe degradation and had a lower hardness. The void fraction and surface roughness of the nanocomposite coatings could be controlled, which gave rise to near-superhydrophilic and antifogging characteristics. The promising results obtained in this study suggest that the nanocomposite coatings have the potential to be of benefit for the design, fabrication, and development of multifunctional AR coatings with both omnidirectional broadband transmission and long-term durability that are required for demanding outdoor applications in energy harvesting and optical instrumentation in extreme climates or humid conditions.

  17. Catalyzing alignment processes

    DEFF Research Database (Denmark)

    Lauridsen, Erik Hagelskjær; Jørgensen, Ulrik


    time and in combination with other social processes establish more aligned and standardized environmental performance between countries. However, examples of the introduction of environmental management suggests that EMS’ only plays a minor role in developing the actual environmental objectives......This paper describes how environmental management systems (EMS) spur the circulation of processes that support the constitution of environmental issues as specific environ¬mental objects and objectives. EMS catalyzes alignmentprocesses that produce coherence among the different elements involved....... They are here used to describe the context in which environmental management is implemented. Based on findings from contributions to a research program studying the implementation and impact of EMS in different settings, we highlight the diverse roles that these systems play in the Thai context. EMS may over...

  18. 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


    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 and reusa......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...

  19. A new type of self-supported, polymeric Ru-carbene complex for homogeneous catalysis and heterogeneous recovery: synthesis and catalytic activities for ring-closing metathesis. (United States)

    Chen, Shu-Wei; Kim, Ju Hyun; Shin, Hyunik; Lee, Sang-Gi


    A novel 2nd generation Grubbs-type catalyst tethering an isopropoxystyrene has been synthesized and automatically polymerized in solution to form a self-supported polymeric Ru-carbene complex, which catalyzed ring-closing metathesis homogeneously, but was recovered heterogeneously.

  20. Fluoroantimonic acid hexahydrate (HSbF6-6H2O) catalysis: The ring-opening polymerization of epoxidized soybean oil (United States)

    Ring-opening polymerization of epoxidized soybean oil (ESO) catalyzed by a super acid, fluroantimonic acid hexahydrate (HSbF6-6H2O), in ethyl acetate was conducted in an effort to develop useful biodegradable polymers. The resulting polymerized ESO (SA-RPESO) were characterized by using infrared (IR...

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

    African Journals Online (AJOL)

    Silica coated ionic liquid templated mesoporous silica nanoparticles. E.D.M. Isa, M. B. A. Rahman, H. Ahmad. Abstract. 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 ...

  2. Chelating polymeric membranes

    KAUST Repository

    Peinemann, Klaus-Viktor


    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.

  3. Polymeric coordination compounds

    Indian Academy of Sciences (India)


    Ce(dipic)3Sr(dipicH2)(OH2)3·5H2O (4) (dipicH2 – dipicolinic acid) exhibits 1-D polymeric chain structure, built up of alternating nine coordinate Ce and eight coordinate. Sr polyhedra. The analogous Ce–Ba compound (5) exhibits a polymeric chain built up of nine coordinate Ba units only, arranged in a hexagonal lattice.

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

    KAUST Repository

    Li, Fuyue Stephanie


    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.

  5. Silica reinforced triblock copolymer gels

    DEFF Research Database (Denmark)

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


    The effect of silica and polymer coated silica particles as reinforcing agents on the structural and mechanical properties of polystyrene-poly(ethylene/butylene)-polystyrene (PS-PEB-PS) triblock gel has been investigated. Different types of chemically modified silica have been compared in order...

  6. Catalyzed deuterium fueled tokamak reactors

    International Nuclear Information System (INIS)

    Southworth, F.H.


    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

  7. 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)


    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}

  8. Recent advances in preparation and application of hybrid organic-silica monolithic capillary columns. (United States)

    Ou, Junjie; Lin, Hui; Zhang, Zhenbin; Huang, Guang; Dong, Jing; Zou, Hanfa


    Hybrid organic-silica monolithic columns, regarded as a second generation of silica-based monoliths, have received much interest due to their unique properties over the pure silica-based monoliths. This review mainly focuses on development in the fields of preparation of hybrid monolithic columns in a capillary and their application for CEC and capillary liquid chromatography separation, as well as for sample pretreatment of solid-phase microextraction and immobilized enzyme reactor since July 2010. The preparation approaches are comprehensively summarized with three routes: (i) general sol-gel process using trialkoxysilanes and tetraalkoxysilanes as coprecursors; (ii) "one-pot" process of alkoxysilanes and organic monomers concomitantly proceeding sol-gel chemistry and free radical polymerization; and (iii) other polymerization approaches of organic monomers containing silanes. The modification of hybrid monoliths containing reactive groups to acquire the desired surface functionality is also described. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    DEFF Research Database (Denmark)

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


    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...

  10. Silica from Ash

    Indian Academy of Sciences (India)

    and may change the product characteristics (colour, etc.). This method of quality assessment is more suitable to workers at the processing site as it does not involve lab-scale analysis. Process. The initial step is extraction of silica from ash as sodium silicate using caustic soda. This reaction is carried out at a temperature.

  11. Aniline incorporated silica nanobubbles

    Indian Academy of Sciences (India)



    Sep 14, 2006 ... persed in diverse media. 2. Experimental. 2.1 Materials. Chloroauric acid, trisodium citrate, ... molecules such as ciprofloxacin, we could see the same kind of carbon onion structures inside the silica .... molecule. The supernatant, after precipitation of ani- line@SiO2 by centrifugation, did not show aniline.

  12. Carbanion as a Superbase for Catalyzing Thiol–Epoxy Photopolymerization

    Directory of Open Access Journals (Sweden)

    Xiaoqing Dong


    Full Text Available Photobase generator (PBG-mediated thiol–epoxy photopolymerization has received widedspread attention due to its versatility in various applications. Currently, nearly all reported PBGs release amines as active species. The formed amines induce odor, yellowing, and potential toxicity. In this study, a series of novel thioxanthone-based PBGs, which were able to generate carbanion via decarboxylation under LED light irradiation, were designed and straightforwardly prepared. The formed carbanion can be used as a superbase to catalyze thiol–epoxy polymerization efficiently. Investigation on 1H NMR and FT-IR confirmed the generation of carbanion intermediates. The counteranion significantly affected the photodecarboxylation efficiency. The study of photopolymerization tests, based on real-time FT-IR and dielectric analysis measurements, indicated that the generated carbanion exhibited faster polymerization rate and higher epoxy conversion than traditional superbase 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU. In differential scanning calorimeter, thermogravimetric, and nanoindentation tests, comparable thermal and mechanical properties of the photocured films catalyzed by novel PBGs were obtained. The high initiation ability combined with straightforward synthesis makes these PBGs promising candidates for commercialization.

  13. 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


    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

  14. Poly(2-aminothiazole)-silica nanocomposite particles: Synthesis and morphology control (United States)

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


    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.

  15. 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.


    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)

  16. 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. (United States)

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


    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.

  17. Plasma polymerization by Softplasma

    DEFF Research Database (Denmark)

    Jiang, J.; Wu, Zhenning; Benter, Maike


    In the late 19th century, the first depositions - known today as plasma polymers, were reported. In the last century, more and more research has been put into plasma polymers. Many different deposition systems have been developed. [1, 2] Shi F. F. broadly classified them into internal electrode......, external electrode, and electrodeless microwave or high frequency reactors. [3] Softplasma™ is an internal electrode plasma setup powered by low frequenc~ gower supply. It was developed in late 90s for surface treatment of silicone rubber. [ ]- 5] It is a low pressure, low electron density, 3D homogenous...... plasma. In this study, we are presenting the surface modification"pf polymers by plasma polymerization using Softplasma™. Softplasma™ can be used for two major types of polymerization: polymerization of vinyl monomers, where plasma acts as initiator; chemical vapour deposition, where plasma acts...

  18. Silica precipitation in acidic solutions: mechanism, pH effect, and salt effect. (United States)

    Gorrepati, Elizabeth A; Wongthahan, Pattanapong; Raha, Sasanka; Fogler, H Scott


    This study is the first to show that silica precipitation under very acidic conditions ([HCl] = 2-8 M) proceeds through two distinct steps. First, the monomeric form of silica is quickly depleted from solution as it polymerizes to form primary particles approximately 5 nm in diameter. Second, the primary particles formed then flocculate. A modified Smoluchowski equation that incorporates a geometric population balance accurately describes the exponential growth of silica flocs. Variation of the HCl concentration between 2 and 8 M further showed that polymerization to form primary particles and subsequent particle flocculation become exponentially faster with increasing acid concentration. The effect of salt was also studied by adding 1 M chloride salts to the solutions; it was found that salts accelerated both particle formation and growth rates in the order: AlCl(3) > CaCl(2) > MgCl(2) > NaCl > CsCl > no salt. It was also found that ionic strength, over cation identity, determines silica polymerization and particle flocculation rates. This research reveals that precipitation of silica products from acid dissolution of minerals can be studied apart from the mineral dissolution process. Thus, silica product precipitation from mineral acidization follows a two-step process--formation of 5 nm primary particles followed by particle flocculation--which becomes exponentially faster with increasing HCl concentration and with salts accelerating the process in the above order. This result has implications for any study of acid dissolution of aluminosilicate or silicate material. In particular, the findings are applicable to the process of acidizing oil-containing rock formations, a common practice of the petroleum industry where silica dissolution products encounter a low-pH, salty environment within the oil well.

  19. Protection of Wood from Microorganisms by Laccase-Catalyzed Iodination (United States)

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


    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

  20. Surface Immobilization of pH-Responsive Polymer Brushes on Mesoporous Silica Nanoparticles by Enzyme Mimetic Catalytic ATRP for Controlled Cargo Release

    Directory of Open Access Journals (Sweden)

    Hang Zhou


    Full Text Available Peroxidase mimetic catalytic atom transfer radical polymerization (ATRP was first used to install tertiary amine-functionalized polymer brushes on the surface of mesoporous silica nanoparticles (MSNs in a facile and highly efficient manner. Poly(N,N-dimethylaminoethyl methacrylate (PDMAEMA brushes-grafted MSNs were fabricated by biocompatible deuterohemin-β-Ala-His-Thr-Val-Glu-Lys (DhHP-6-catalyzed surface-initiated ATRP (SI-ATRP. The resulting organic–inorganic hybrid nanocarriers were fully characterized by Fourier transform-infrared spectroscopy (FT-IR, thermogravimetric analysis (TGA, X-ray photoelectron spectroscopy (XPS, powder X-ray diffraction (XRD, SEM, TEM, Elemental analysis, Zeta-potential, and N2 adsorption–desorption isotherms, which demonstrated the successful coating of pH-responsive polymers on the MSN surface. Rhodamine 6G (Rh6G dyes were further loaded within the mesopores of this nanocarrier, and the release of Rh6G out of MSNs in a controlled fashion was achieved upon lowing the solution pH. The electrostatic repulsion of positively-charged tertiary ammonium of PDMAEMAs in acidic environments induced the stretching out of polymer brushes on MSN surfaces, thus opening the gates to allow cargo diffusion out of the mesopores of MSNs.

  1. Microwave assisted highly efficient one-pot multi-component synthesis of novel 2-(tetrasubstituted-1H-pyrrol-3-yl-4H-chroman-4-ones catalyzed by heterogeneous reusable silica gel supported polyphosphoric acid (PPA/SiO2

    Directory of Open Access Journals (Sweden)

    Sumit Kumar


    Full Text Available A solvent-free, eco-friendly and facile approach for the synthesis of highly functionalized tetrasubstituted pyrroles has been reported through one-pot four-component reaction of aldehyde, amine, nitroalkane and 1,3-diketone using silica gel supported polyphosphoric acid (PPA–SiO2 under microwave condition. The reaction occured through the in situ formation of β-keto enamine and nitrostyrene analog following Michael addition and finally intramolecular annulation affording the products in good yields. The key features of the present method include clean reaction, mild conditions, low catalyst loading, straightforward, high to excellent yields, short reaction time, avoiding use of harmful metal catalyst and organic solvent, environmentally friendly compared to the existing methods, recovery and reusability of catalyst and easy workup procedure.

  2. Inflation of a Polymeric Menbrane

    DEFF Research Database (Denmark)

    Kristensen, Susanne B.; Larsen, Johannes R.; Hassager, Ole


    We consider an axisymmetric polymeric membrane inflated by a uniform pressure difference acting across the membrane.......We consider an axisymmetric polymeric membrane inflated by a uniform pressure difference acting across the membrane....

  3. 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


    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...

  4. One pot glucose detection by [Fe(III)(biuret-amide)] immobilized on mesoporous silica nanoparticles: an efficient HRP mimic. (United States)

    Malvi, Bharmana; Panda, Chakadola; Dhar, Basab B; Gupta, Sayam Sen


    An [Fe(III)(biuret-amide)] complex has been immobilized onto mesoporous silica nanoparticles via Cu(I) catalyzed azide-alkyne click chemistry. This hybrid material functions as an efficient peroxidase mimic and was successfully used for the quantitative determination of hydrogen peroxide and glucose via a one-pot colorimetric assay. This journal is © The Royal Society of Chemistry 2012

  5. Pore Structure of Macroporous Polymers Using Polystyrene/Silica Composite Particles as Pickering Stabilizers. (United States)

    Tu, Shuhua; Zhu, Chenxu; Zhang, Lingyun; Wang, Haitao; Du, Qiangguo


    A novel approach for the preparation of interconnected macroporous polymers with a controllable pore structure was reported. The method was based on the polymerization of water-in-oil Pickering high internal phase emulsion (HIPE) stabilized by polystyrene (PS)/silica composite particles. The composite Pickering stabilizers were facilely obtained by mixing positively charged PS microspheres and negatively charged silica nanoparticles, and their amphiphilicity could be delicately tailored by varying the ratio of PS and silica. The droplet size of Pickering HIPEs was characterized using an optical microscope. The pore structure of polymer foams was observed using a scanning electron microscope. The interconnectivity of macroporous polymers was evaluated upon their gas permeability, which was greatly improved after etching PS microspheres included in the Pickering stabilizers with tetrahydrofuran. As a result, fine tailoring of the pore structure of polymer foams could be realized by simply tuning the ratio of PS to silica particles in the composite stabilizer.

  6. Polymeric coordination compounds

    Indian Academy of Sciences (India)


    Metal coordination polymers with one- and two-dimensional structures are of current interest due to their possible relevance to material science 1. In continuation of our previous studies 2,3, several new polymeric compounds are reported here. Among the complexes of silver with aminomethyl pyridine (amp) ...

  7. Polymerized and functionalized triglycerides (United States)

    Plant oils are useful sustainable raw materials for the development of new chemical products. As part of our research emphasis in sustainability and green polymer chemistry, we have explored a new method for polymerizing epoxidized triglycerides with the use of fluorosulfonic acid. Depending on the ...

  8. Iron Oxide Silica Derived from Sol-Gel Synthesis

    Directory of Open Access Journals (Sweden)

    João Carlos Diniz da Costa


    Full Text Available In this work we investigate the effect of iron oxide embedded in silica matrices as a function of Fe/Si molar ratio and sol pH. To achieve homogeneous dispersion of iron oxide particles, iron nitrate nonahydrate was dissolved in hydrogen peroxide and was mixed with tetraethyl orthosilicate and ethanol in a sol-gel synthesis method. Increasing the calcination temperature led to a reduction in surface area, although the average pore radius remained almost constant at about 10 Å, independent of the Fe/Si molar ratio or sol pH. Hence, the densification of the matrix was accompanied by similar reduction in pore volume. However, calcination at 700 °C resulted in samples with similar surface area though the iron oxide content increased from 5% to 50% Fe/Si molar ratio. As metal oxide particles have lower surface area than polymeric silica structures, these results strongly suggest that the iron oxides opposed the silica structure collapse. The effect of sol pH was found to be less significant than the Fe/Si molar ratio in the formation of molecular sieve structures derived from iron oxide silica.

  9. Iron Oxide Silica Derived from Sol-Gel Synthesis. (United States)

    Darmawan, Adi; Smart, Simon; Julbe, Anne; Diniz da Costa, João Carlos


    In this work we investigate the effect of iron oxide embedded in silica matrices as a function of Fe/Si molar ratio and sol pH. To achieve homogeneous dispersion of iron oxide particles, iron nitrate nonahydrate was dissolved in hydrogen peroxide and was mixed with tetraethyl orthosilicate and ethanol in a sol-gel synthesis method. Increasing the calcination temperature led to a reduction in surface area, although the average pore radius remained almost constant at about 10 Å, independent of the Fe/Si molar ratio or sol pH. Hence, the densification of the matrix was accompanied by similar reduction in pore volume. However, calcination at 700 °C resulted in samples with similar surface area though the iron oxide content increased from 5% to 50% Fe/Si molar ratio. As metal oxide particles have lower surface area than polymeric silica structures, these results strongly suggest that the iron oxides opposed the silica structure collapse. The effect of sol pH was found to be less significant than the Fe/Si molar ratio in the formation of molecular sieve structures derived from iron oxide silica.

  10. Modified silicas with different structure of grafted methylphenylsiloxane layer (United States)

    Bolbukh, Yuliia; Terpiłowski, Konrad; Kozakevych, Roman; Sternik, Dariusz; Deryło-Marczewska, Anna; Tertykh, Valentin


    The method of a chemical assembly of the surface polymeric layer with high contents of the modifying agent was developed. Powders of nanodispersed silica with chemisorbed polymethylphenylsiloxane (PMPS) were synthesized by solvent-free chemical assembly technique with a dimethyl carbonate (DMC) as scission agent. Samples were characterized using FTIR spectroscopy, transmission electron microscopy (TEM), atomic force microscopy (AFM), and elemental analysis (CHN analysis). Coating microstructure, morphology, and hydrophilic-hydrophobic properties of nanoparticles were estimated. The results indicate a significant effect of the PMPS/DMC ratio at each modification stage on hydrophobic properties of modified silicas. Modification with a similar composition of the PMPS/DMC mixture, even with different polymer amount at each stage, provides the worst hydrophobicity. Results suggest that the highest hydrophobicity (contact angle θ = 135°-140°) is achieved in the case when silica modified with the PMPS/DMC mixture using multistage approach that providing a formation of the monomolecular layer of polysiloxane at the first modification step. The characteristics of surface structure were interpreted in terms of density of polymer-silica bonds at the interfaces that, usually, are reduced for modified surfaces, in a coupling with conformation model that accented the shape of chains (arch- and console-like) adsorbed on solid surfaces.

  11. Faraday rotation measurements in maghemite-silica aerogels

    International Nuclear Information System (INIS)

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


    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

  12. Fabrication of superhydrophobic fluorinated silica nanoparticles for multifunctional liquid marbles (United States)

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


    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. Kinetic and thermal analysis of polymeric materials (United States)

    Peterson, Jeffery David


    Thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) techniques have been used to study the thermal degradation of polymeric materials. These polymers were subjected to a variety of heating programs as well as numerous types of atmospheric conditions. The results from these analyses were then used to determine activation energies as a function of an extent of reaction variable, alpha. This technique, known as the model-free isoconversional method, allows for changes in energies to occur as decomposition pathways change. This produces a more realistic means of observing complex kinetic schemes and is a better representation of kinetic analysis. Chapters 1 and 2 provide introductory backgrounds into both polymer chemistry and the isoconversional analysis technique, respectively. A brief description of the research goals and motivations is also discussed. Thermal analysis of pure polystyrene (PS), polyethylene (PE), and polypropylene (PP) samples are presented in Chapter 3. The obtained activation energy dependencies are interpreted in terms of degradation mechanisms. These mechanisms vary greatly according to the gaseous environment in which they were analyzed. The thermal degradation of poly(methyl methacrylate) (PMMA) in both pure nitrogen and in various oxygen-containing atmospheres is discussed in Chapter 4. It was observed that oxygen exhibits a stabilizing effect on PMMA decomposition. Activation energies for these processes, and their mechanistic interpretations, will also be presented. Chapter 5 builds off the understanding gained in Chapter 4 by investigating the char-forming effects of silica gel and potassium carbonate additives on PMMA. These additives are known for their fire-resistant properties when combined in a 3:1 silica gel to potassium carbonate ratio. The effects of these additives, and their respective ratio amounts, on PMMA char formation are reported. Chapters 6 and 7 conclude the dissertation by looking at the thermal

  14. Antibacterial activity of N-halamine decorated mesoporous silica nanoparticles (United States)

    Xu, Jiarong; Zhang, Yu; Zhao, Yanbao; Zou, Xueyan


    N-halamine decorated mesoporous silica nanoparticles (mSiO2/halamine NPs) were prepared by coating mSiO2 NPs with poly (1-allylhydantoin-co-methyl methacrylate) (AH-co-MMA) by the aid of the radical polymerization, followed by chlorination treatment. The sterilizing effect on the bacterial strain is investigated by incubating Staphylococcus aureus (S. aureus) and Escherichia coli (E. coli). Results indicated that the mSiO2/halamine NPs had excellent antibacterial activity and no significant change occurred in antibacterial efficiency after five recycle experiments.

  15. Iodine-Catalyzed Polysaccharide Esterification (United States)

    A review is provided of the recent reports to use iodine-catalyzed esterification reaction to produce esters from polysaccharides. The process entails reaction of the polysaccharide with an acid anhydride in the presence of a catalytic level of iodine, and in the absence of additional solvents. T...

  16. Radiation-induced heterophase polymerizations

    International Nuclear Information System (INIS)

    Carenza, M.; Palma, G.


    Investigations were carried out on the morphology of particles produced in the early stages of radiation-induced heterophase polymerization of acrylonitrile in quiescent conditions over a wide temperature range both in bulk and with addition of a solvent or a comonomer. The data were compared with the corresponding data obtained in the polymerization of vinyl chloride, producing an amorphous polymer, taking into account also the kinetic behaviours of the two polymerization systems. The particle morphologies in the two systems were quite similar at low polymerization temperatures but there were considerable differences when higher temperatures were involved. This change was interpreted on the basis of differences in compatability between the liquid phase and the polymer particle phase for the two systems. In order to account for the two different kinetic behaviours, a two-phase polymerization model was formulated and also a polymerization model in which the surface of the polymer particles was the locus of polymerization. (author)

  17. Hydrothermal stability of microporous silica and niobia-silica membranes

    NARCIS (Netherlands)

    Boffa, V.; Blank, David H.A.; ten Elshof, Johan E.


    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

  18. Development of acid stable, hyper-crosslinked, silica-based reversed-phase liquid chromatography supports for the separation of organic bases. (United States)

    Ma, Lianjia; Luo, Hao; Dai, Jun; Carr, Peter W


    A new generation of extremely acid stable "hyper-crosslinked" (HC) phases have been developed with good plate counts for basic drug separations. In our previous work, we successfully developed an approach for synthesizing HC stationary phases on silica substrates using aluminum trichloride catalyzed Friedel-Crafts (F-C) chemistry to improve the stability of silica-based RPLC stationary phases at low pH. However, the performance of basic analytes on these HC phases under acidic conditions was unusually poor compared to that of conventional silica-based C18 phases. The effects of the specific F-C catalysts used and the specific silica substrate on the chromatographic properties of HC phases have been studied. Modified synthetic strategies that give both good observed plate counts for basic analytes under acidic conditions and very good low pH stability without compromising other chromatographic properties of the hyper-crosslinked phases have been developed. Replacement of aluminum trichloride with tin tetrachloride as the catalyst for the F-C chemistry and use of a very high purity silica result in significantly improved plate counts for basic analytes. In formic acid buffered mobile phases, which are highly compatible with electrospray ionization LC-MS, basic analytes showed much better performance on the tin tetrachloride catalyzed HC phases than on any conventional commercial phase tested. The tin tetrachloride catalyzed HC phase is as stable as the original aluminum trichloride catalyzed HC phases, and much more stable than the bench mark acid stable commercial phase.

  19. Biomimetic synthesis of raspberry-like hybrid polymer-silica core-shell nanoparticles by templating colloidal particles with hairy polyamine shell. (United States)

    Pi, Mengwei; Yang, Tingting; Yuan, Jianjun; Fujii, Syuji; Kakigi, Yuichi; Nakamura, Yoshinobu; Cheng, Shiyuan


    The nanoparticles composed of polystyrene core and poly[2-(diethylamino)ethyl methacrylate] (PDEA) hairy shell were used as colloidal templates for in situ silica mineralization, allowing the well-controlled synthesis of hybrid silica core-shell nanoparticles with raspberry-like morphology and hollow silica nanoparticles by subsequent calcination. Silica deposition was performed by simply stirring a mixture of the polymeric core-shell particles in isopropanol, tetramethyl orthosilicate (TMOS) and water at 25 degrees C for 2.5h. No experimental evidence was found for nontemplated silica formation, which indicated that silica deposition occurred exclusively in the PDEA shell and formed PDEA-silica hybrid shell. The resulting hybrid silica core-shell particles were characterized by transmission electron microscopy (TEM), thermogravimetry, aqueous electrophoresis, and X-ray photoelectron spectroscopy. TEM studies indicated that the hybrid particles have well-defined core-shell structure with raspberry morphology after silica deposition. We found that the surface nanostructure of hybrid nanoparticles and the composition distribution of PDEA-silica hybrid shell could be well controlled by adjusting the silicification conditions. These new hybrid core-shell nanoparticles and hollow silica nanoparticles would have potential applications for high-performance coatings, encapsulation and delivery of active organic molecules. 2010 Elsevier B.V. All rights reserved.

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

    DEFF Research Database (Denmark)

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


    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....... 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...

  1. Direct Synthesis of Telechelic Polyethylene by Selective Insertion Polymerization

    KAUST Repository

    Jian, Zhongbao


    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.

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

    Directory of Open Access Journals (Sweden)

    Ahmad Rabiee


    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.

  3. 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.


    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

  4. Silicoaluminates as “Support Activator” Systems in Olefin Polymerization Processes (United States)

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


    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.

  5. Thermally bisignate supramolecular polymerization (United States)

    Venkata Rao, Kotagiri; Miyajima, Daigo; Nihonyanagi, Atsuko; Aida, Takuzo


    One of the enticing characteristics of supramolecular polymers is their thermodynamic reversibility, which is attractive, in particular, for stimuli-responsive applications. These polymers usually disassemble upon heating, but here we report a supramolecular polymerization that occurs upon heating as well as cooling. This behaviour arises from the use of a metalloporphyrin-based tailored monomer bearing eight amide-containing side chains, which assembles into a highly thermostable one-dimensional polymer through π-stacking and multivalent hydrogen-bonding interactions, and a scavenger, 1-hexanol, in a dodecane-based solvent. At around 50 °C, the scavenger locks the monomer into a non-polymerizable form through competing hydrogen bonding. On cooling, the scavenger preferentially self-aggregates, unlocking the monomer for polymerization. Heating also results in unlocking the monomer for polymerization, by disrupting the dipole and hydrogen-bonding interactions with the scavenger. Analogous to 'upper and lower critical solution temperature phenomena' for covalently bonded polymers, such a thermally bisignate feature may lead to supramolecular polymers with tailored complex thermoresponsive properties.

  6. Peptide bond formation of alanine on silica and alumina surfaces as a catalyst (United States)

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


    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.

  7. Synthetic aspects and characterization of polypropylene-silica nanocomposites prepared via solid-state modification and sol-gel reactions

    NARCIS (Netherlands)

    Jain, S; Goossens, H; Picchioni, F; Magusin, P; Mezari, B


    A new route is developed by combining solid-state modification (SSM) by grafting vinyl triethoxysilane (VTES) with a sol-gel method to prepare PP/silica nanocomposites with varying degree of adhesion between filler and matrix. VTES was grafted via SSM in porous PP particles. Bulk polymerization

  8. Synthetic aspects and characterization of polypropylene–silica nanocomposites prepared via solid-state modification and sol–gel reactions

    NARCIS (Netherlands)

    Jain, Sachin; Goossens, Han; Picchioni, Francesco; Magusin, Pieter; Mezari, Brahim; Duin, Martin van


    A new route is developed by combining solid-state modification (SSM) by grafting vinyl triethoxysilane (VTES) with a sol–gel method to prepare PP/silica nanocomposites with varying degree of adhesion between filler and matrix. VTES was grafted via SSM in porous PP particles. Bulk polymerization

  9. Radiation chemistry of polymeric system

    International Nuclear Information System (INIS)

    Machi, Sueo; Ishigaki, Isao


    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.)

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

    Directory of Open Access Journals (Sweden)


    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.

  11. Post-Polymerization Modifications of Polymeric Monolithic Columns: A Review

    Directory of Open Access Journals (Sweden)

    Sinéad Currivan


    Full Text Available The vast cache of methods used in polymeric monolithic column modification is presented herein, with specific attention to post-polymerization modification reactions. The modification of polymeric monolithic columns is defined and can include the modification of pre-existing surface groups, the addition of polymeric chains or indeed the addition of structures such as nano-particles and nano-structures. The use of these modifications can result in the specific patterning of monoliths, useful in microfluidic device design or in the investigation of modification optimization.

  12. 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


    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.

  13. Improvement of thermal stability of polypropylene using DOPO-immobilized silica nanoparticles. (United States)

    Dong, Quanxiao; Ding, Yanfen; Wen, Bin; Wang, Feng; Dong, Huicong; Zhang, Shimin; Wang, Tongxin; Yang, Mingshu


    After the surface silylation with 3-methacryloxypropyltrimethoxysilane, silica nanoparticles were further modified by 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO). The immobilization of DOPO on silica nanoparticles was confirmed by Fourier transform infrared spectroscopy, UV-visible spectroscopy, magic angle spinning nuclear magnetic resonance, and thermogravimetric analysis. By incorporating the DOPO-immobilized silica nanoparticles (5 wt%) into polypropylene matrix, the thermal oxidative stability exhibited an improvement of 62 °C for the half weight loss temperature, while that was only 26 °C increment with incorporation of virgin silica nanoparticles (5 wt%). Apparent activation energies of the polymer nanocomposites were estimated via Flynn-Wall-Ozawa method. It was found that the incorporation of DOPO-immobilized silica nanoparticles improved activation energies of the degradation reaction. Based on the results, it was speculated that DOPO-immobilized silica nanoparticles could inhibit the degradation of polypropylene and catalyze the formation of carbonaceous char on the surface. Thus, thermal stability was significantly improved.

  14. Trypsin-Catalyzed Deltamethrin Degradation


    Xiong, Chunrong; Fang, Fujin; Chen, Lin; Yang, Qinggui; He, Ji; Zhou, Dan; Shen, Bo; Ma, Lei; Sun, Yan; Zhang, Donghui; Zhu, Changliang


    To explore if trypsin could catalyze the degradation of non-protein molecule deltamethrin, we compared in vitro hydrolytic reactions of deltamethrin in the presence and absence of trypsin with ultraviolet-visible (UV/Vis) spectrophotometry and gas chromatography-mass spectrometry (GC/MS). In addition, acute oral toxicity of the degradation products was determined in Wistar rats. The results show that the absorption peak of deltamethrin is around 264 nm, while the absorption peaks of deltameth...

  15. Self-Propagating Frontal Polymerization in Water at Ambient Pressure (United States)

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


    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.

  16. 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


    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...

  17. 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...

  18. 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


    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)

  19. Packaging based on polymeric materials

    Directory of Open Access Journals (Sweden)

    Jovanović Slobodan M.


    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. 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)


    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. Synthesis of magnetic polymeric microspheres

    International Nuclear Information System (INIS)

    Gervald, A Yu; Gritskova, Inessa A; Prokopov, Nikolai I


    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.

  2. Phosphazene-promoted anionic polymerization

    KAUST Repository

    Zhao, Junpeng


    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.

  3. Luminescent SiO 2-coated Gd 2O 3:Eu 3+ nanorods/poly(styrene) nanocomposites by in situ polymerization (United States)

    Macedo, Andreia G.; Martins, Manuel A.; Fernandes, Sílvia E. M.; Barros-Timmons, Ana; Trindade, Tito; Carlos, Luís D.; Rocha, João


    Europium doped gadolinium oxide nanorods have been coated with silica via a sol-gel approach. The silica coating increases the Eu 3+ absolute emission quantum yields from 0.51 to 0.86 (255 nm excitation) and decay times from 1.43 to 1.80 ms (394.4 nm excitation). Subsequently the silica coating was modified with 3-(trimethoxysilyl)-propyl-methacrylate. Grafting of silica with the MPS coupling agent was confirmed by FTIR and contact angle measurements. The functionalized nanoparticles were used as core structures in the in situ radical polymerization of styrene via miniemulsion and solution routes. Depending on the polymerization technique used the morphology of the polymer coating consisted in isolated spheres or a homogenous film respectively. Although the optical properties of the ensuing nanocomposites were reduced the synthetic strategy developed to process this type of luminescent nanoparticles proved efficient and can be explored using different vinyl or (meth)acrylate monomers.

  4. Living olefin polymerization processes (United States)

    Schrock, Richard R.; Baumann, Robert


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

  5. Living olefin polymerization processes (United States)

    Schrock, Richard R.; Bauman, Robert


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

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

    KAUST Repository

    Kerdi, Fatmé


    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.

  7. Periodic mesoporous silica gels

    Energy Technology Data Exchange (ETDEWEB)

    Anderson, M.T.; Martin, J.E.; Odinek, J.G. [and others


    We have synthesized monolithic particulate gels of periodic mesoporous silica by adding tetramethoxysilane to a homogeneous alkaline micellar precursor solution. The gels exhibit 5 characteristic length scales over 4 orders of magnitude: fractal domains larger than the particle size (>500 nm), particles that are {approximately}150 to 500 nm in diameter, interparticle pores that are on the order of the particle size, a feature in the gas adsorption measurements that indicates pores {approximately}10-50 nm, and periodic hexagonal arrays of {approximately}3 nm channels within each particle. The wet gel monoliths exhibit calculated densities as low as {approximately}0.02 g/cc; the dried and calcined gels have bulk densities that range from {approximately}0.3-0.5 g/cc. The materials possess large interparticle ({approximately}1.0-2.3 cc/g) and intraparticle ({approximately}0.6 cc/g) porosities.

  8. 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


    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

  9. Carbon dioxide adsorption on polyacrylamide-impregnated silica gel and breakthrough modeling (United States)

    Zhao, Yi; Shen, Yanmei; Bai, Lu; Ni, Shiqing


    Polyacrylamide-impregnated silica gel was prepared to capture CO2 from flue gas. The polymerization of acrylamide was carried out in AN solvent using AIBN as initiator and EGDMA as crosslinker. The adsorbents were characterized by N2 adsorption, FTIR analysis, SEM analysis, and thermal gravimetric analysis. The results showed that the polymer was not only occupying the porosity of the silica, but necessarily surrounding silica particles, and the amide groups was successfully loaded on the support silica. The impregnated silica displayed good thermal-stability at 250 °C. The CO2 adsorption isotherms were measured to examine CO2 adsorption on adsorbents, and the results showed that the capacity was increased significantly after modification. The CO2 isosteric adsorption heats calculated from the isotherms showed that the adsorption interaction of CO2 with the functionalized material may be mainly an intermolecular force or hydrogen bond. Fixed-bed breakthrough model of CO2 adsorption on functionalized silica was successfully developed to describe the breakthrough curves under different adsorption temperature, CO2 concentration, and gas flow rate. The mass transfer coefficients of CO2 were calculated from the breakthrough model, the results showed that adsorption rate could be promoted by increasing temperature, flow rate and CO2 concentration, among which the effect of gas flow rate is the most obvious.

  10. Behaviour of Silica during Metal Recovery from Bauxite Residue by Acidic Leaching


    Marin Rivera, Rodolfo; Ulenaers, Brecht; Ounoughene, Ghania; Binnemans, Koen; Van Gerven, Tom


    Bauxite residue represents an interesting source for not only major elements such as aluminium, iron and titanium, but also for rare earths (REEs), while the residue after metal recovery can be used for low-carbon building materials and cementitious binders. Several methods based on direct acidic leaching for recovering metals from bauxite residue have been reported. The co-dissolution of iron represents a significant drawback for REEs recovery upon silica polymerization. The behaviour of sil...

  11. End-labeled amino terminated monotelechelic glycopolymers generated by ROMP and Cu(I-catalyzed azide–alkyne cycloaddition

    Directory of Open Access Journals (Sweden)

    Ronald Okoth


    Full Text Available Functionalizable monotelechelic polymers are useful materials for chemical biology and materials science. We report here the synthesis of a capping agent that can be used to terminate polymers prepared by ring-opening metathesis polymerization of norbornenes bearing an activated ester. The terminating agent is a cis-butene derivative bearing a Teoc (2-trimethylsilylethyl carbamate protected primary amine. Post-polymerization modification of the polymer was accomplished by amidation with an azido-amine linker followed by Cu(I-catalyzed azide–alkyne cycloaddition with propargyl sugars. Subsequent Teoc deprotection and conjugation with pyrenyl isothiocyanates afforded well-defined end-labeled glycopolymers.

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

    Directory of Open Access Journals (Sweden)

    Qian CHEN


    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:

  13. Functionalization of Silica Nanoparticles for Polypropylene Nanocomposite Applications

    Directory of Open Access Journals (Sweden)

    Diego Bracho


    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.

  14. 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:


    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

  15. Thermodynamics of Enzyme-Catalyzed Reactions Database (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.

  16. Silica-Immobilized Enzyme Reactors (United States)


    metal affinity binding between the ‘his- tag’ and a metal coating ( cobalt ) upon the agarose packing material. The peptide forms silica in situ and...of a nitro group to hydroxylamine resulting in a large electronic change which can be exploited for a variety of biotechnological applications...combined system, or individually as single sequential units will allow for development of complex catalytic sequences. Biologically-derived silica

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

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


    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.

  18. 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


    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.

  19. Fabrication of robust crystal balls from the electrospray of soft polymer spheres/silica dispersion. (United States)

    Shen, Zhehong; Zhu, Yue; Wu, Limin; You, Bo; Zi, Jian


    This paper presents a novel and facile approach to fabricate robust crystal balls directly through the self-assembly of soft colloidal polymer spheres by the aid of nano silica using an electrospraying technique. In this approach, soft colloidal polymer spheres are synthesized by emulsion polymerization and then blended with colloidal silica to obtain nanocomposite dispersion. When this dispersion is loaded into an injector and forced to flow through the nozzle under direct electric field, the detached droplets are collected by an oil solvent. As water and solvent evaporate, the colloidal polymer spheres and silica beads can directly self-assemble into robust crystal balls. Neither soft matrix nor post-treatment is needed. The obtained crystal balls have not only excellent mechanical properties to withstand external forces such as cutting, puckering, and bending, but also reversible deformation.

  20. "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


    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.

  1. 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


    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.

  2. Plasma polymer-functionalized silica particles for heavy metals removal. (United States)

    Akhavan, Behnam; Jarvis, Karyn; Majewski, Peter


    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.

  3. Polymerization with freezing

    International Nuclear Information System (INIS)

    Ben-Naim, E; Krapivsky, P L


    Irreversible aggregation processes involving reactive and frozen clusters are investigated using the rate equation approach. In aggregation events, two clusters join irreversibly to form a larger cluster; additionally, reactive clusters may spontaneously freeze. Frozen clusters do not participate in merger events. Generally, freezing controls the nature of the aggregation process, as demonstrated by the final distribution of frozen clusters. The cluster mass distribution has a power-law tail, F k ∼k -γ , when the freezing process is sufficiently slow. Different exponents, γ = 1 and 3, are found for the constant and the product aggregation rates, respectively. For the latter case, the standard polymerization model, either no gels, or a single gel, or even multiple gels, may be produced

  4. Collaborative Research: Polymeric Multiferroics

    Energy Technology Data Exchange (ETDEWEB)

    Ren, Shenqiang [Temple Univ., Philadelphia, PA (United States). College of Engineering


    The goal of this project is to investigate room temperature magnetism and magnetoelectric coupling of polymeric multiferroics. A new family of molecular charge-transfer crystals has been emerged as a fascinating opportunity for the development of all-organic electrics and spintronics due to its weak hyperfine interaction and low spin-orbit coupling; nevertheless, direct observations of room temperature magnetic spin ordering have yet to be accomplished in organic charge-transfer solids. Furthermore, room temperature magnetoelectric coupling effect hitherto known multiferroics, is anticipated in organic donor-acceptor complexes because of magnetic field effects on charge-transfer dipoles, yet this is also unexplored. The PI seeks to fundamental understanding of the control of organic crystals to demonstrate and explore room temperature multiferroicity. The experimental results have been verified through the theoretical modeling.

  5. Characterization of Water-Clear Polymeric Gels for Use as Radiotherapy Bolus. (United States)

    Adamson, Justus D; Cooney, Tabitha; Demehri, Farokh; Stalnecker, Andrew; Georgas, Debra; Yin, Fang-Fang; Kirkpatrick, John


    Our purpose was to investigate polymeric gels for use as a highly transparent radiotherapy bolus and determine the relevant physical and dosimetric properties. We first quantified tensile properties (maximum stress, strain, and Young modulus) for various polymeric gels, along with a commercial bolus product in order to illustrate the wide variety of potential materials. For a select polymeric gel with tensile properties similar to currently used radiotherapy bolus, we also evaluated mass and electron density, effective atomic number, optical transparency, and percent depth dose in clinical megavoltage photon and electron beams. For this polymeric gel, mass density was 872 ± 12 and 896 ± 13 g/cm 3 when measured via weight/volume and computed tomography Hounsfield units, respectively. Electron density was 2.95 ± 0.04 ×10 23 electrons/cm 3 . Adding fused silica (9% by weight) increases density to that of water. The ratio of the effective atomic number to that of water without and with added silica was 0.780 and 0.835 at 1 MeV, 0.767 and 0.826 at 6 MeV, and 0.746 and 0.809 at 20 MeV. Percent depth dose for 6 MV photons was within 2% of water within the first 2.5 cm and after scaling by the density coincided within 1% out to >7 cm. For 6 and 20 MeV electrons, after scaling for density D 80% was within 1.3 and 1.5 mm of water, respectively. The high transparency and mechanical flexibility of polymeric gels indicate potential for use as a radiotherapy bolus; differences in density from water may be managed via either using "water equivalent thickness" or by incorporating fused silica into the material.

  6. Synthesis of oxide-supported vanadium catalysts and their activity in ethylene polymerization

    International Nuclear Information System (INIS)

    Czaja, K.; Korach, L.; Bialek, M.


    The activity of oxide supported vanadium-based catalyst system (VOCl 3 /Et 2 AlCl) in low-pressure ethylene polymerization and the properties of the resulting polyethylenes were studied in relation to the type and mode of modification of the oxide support. Alumina and silica and an unconventional silica-type material prepared by sol-gel process were used as supports. Results are compared with those obtained earlier with a catalyst supported on MgCl 2 (THF) 2 . Of the oxides studied, the silica-type sol-gel material dehydrated and subsequently modified with Et 2 AlCl proved to be the best carrier for the vanadium catalyst. The polyethylene prepared by using this catalyst support was found to exhibit good morphology, especially as compared with the polymer prepared over the more active Mg-V-Al catalyst. (author)

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

    Directory of Open Access Journals (Sweden)

    Alessandro Mandoli


    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.

  8. 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


    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.

  9. Amorphous Silica-Promoted Lysine Dimerization: a Thermodynamic Prediction (United States)

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


    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.

  10. Gas Separation through Bilayer Silica, the Thinnest Possible Silica Membrane. (United States)

    Yao, Bowen; Mandrà, Salvatore; Curry, John O; Shaikhutdinov, Shamil; Freund, Hans-Joachim; Schrier, Joshua


    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.

  11. Polymeric micelles for drug targeting. (United States)

    Mahmud, Abdullah; Xiong, Xiao-Bing; Aliabadi, Hamidreza Montazeri; Lavasanifar, Afsaneh


    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.

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

    Directory of Open Access Journals (Sweden)

    Lin Yang


    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.

  13. High temperature structural, polymeric foams from high internal emulsion polymerization

    Energy Technology Data Exchange (ETDEWEB)

    Hoisington, M.A.; Duke, J.R.; Apen, P.G.


    In 1982, a high internal phase emulsion (HIPE) polymerization process to manufacture microcellular, polymeric foam systems was patented by Unilever. This patent discloses a polymerization process that occurs in a water-in-oil emulsion in which the water represents at least 76% of the emulsion by volume. The oil phase consists of vinyl monomers such as styrene and acrylates that are crosslinked by divinyl monomers during polymerization. After polymerization and drying to remove the water phase, the result is a crosslinked polymer foam with an open cell microstructure that is homogeneous throughout in terms of morphology, density, and mechanical properties. Since 1982, numerous patents have examined various HIPE polymerized foam processing techniques and applications that include absorbents for body fluids, cleaning materials, and ion exchange systems. All the published HIPE polymerized foams have concentrated on materials for low temperature applications. Copolymerization of styrene with maleic anhydride and N-substituted maleimides to produce heat resistant thermoplastics has been studied extensively. These investigations have shown that styrene will free radically copolymerize with N-substituted maleimides to create an alternating thermoplastic copolymer with a Tg of approximately 200{degrees}C. However, there are many difficulties in attempting the maleimide styrene copolymerization in a HIPE such as lower polymerization temperatures, maleimide solubility difficulties in both styrene and water, and difficulty obtaining a stable HIPE with a styrene/maleimide oil phase. This work describes the preparation of copolymer foams from N-ethylmaleimide and Bis(3-ethyl-5-methyl-4-maleimide-phenyl)methane with styrene based monomers and crosslinking agents.

  14. Proton-transfer polymerization (HTP): converting methacrylates to polyesters by an N-heterocyclic carbene. (United States)

    Hong, Miao; Chen, Eugene Y-X


    A new polymerization termed proton (H)-transfer polymerization (HTP) has been developed to convert dimethacrylates to unsaturated polyesters. HTP is catalyzed by a selective N-heterocyclic carbene capable of promoting intermolecular Umpolung condensation through proton transfer and proceeds through the step-growth propagation cycles via enamine intermediates. The role of the added suitable phenol, which is critical for achieving an effective HTP, is twofold: shutting down the radically induced chain-growth addition polymerization under HTP conditions (typically at 80-120 °C) and facilitating proton transfer after each monomer enchainment. The resulting unsaturated polyesters have a high thermal stability and can be readily cross-linked to robust polyester materials. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Romp as a versatile method for the obtention of differentiated polymeric materials

    Directory of Open Access Journals (Sweden)

    Valdemiro P. Carvalho Jr.


    Full Text Available Ring Opening Metathesis Polymerization (ROMP of cyclic olefins is a powerful transition metal-catalyzed reaction for syntheses of polymers and copolymers. The key feature of this reaction is the [2+2]-cycloaddition mechanism, with retention of the olefinic unsaturation in the polymer chain and occurrence of living polymerization. With the development of metal-carbene type catalysts for this process, many addressed polymeric materials have been successfully prepared to be employed in several fields of the science and technology. This review summarizes recent examples of syntheses of polymers with amphiphilic features such as block, graft, brush or star copolymers; as well syntheses of biomaterials, dendronized architectures, photoactive polymers, cross-linked or self-healing materials, and polymers from renewed supplies.

  16. Coordination Polymerization of Renewable 3-Methylenecyclopentene with Rare-Earth-Metal Precursors. (United States)

    Liu, Bo; Li, Shihui; Wang, Meiyan; Cui, Dongmei


    Coordination polymerization of renewable 3-methylenecyclopentene has been investigated for the first time using rare-earth metal-based precursors bearing various bulky ligands. All the prepared complexes catalyze controllable polymerization of 3-methylenecyclopentene into high molecular weight polymers, of which the NPN- and NSN-tridentate non-Cp ligated lutetium-based catalytic systems exhibited extremely high activities up to 11 520 kg/(mol Lu ⋅h) in a dilute toluene solution (3.2 g/100 mL) at room temperature. The resultant polymers have pure 1,4-regioregularity (>99 %) and tailorable number average molecular weights (1-20×10 4 ) with narrow molecular weight distributions (polydispersity index (PDI)=1.45-1.79). DFT simulations were employed to study the polymerization mechanism and stereoregularity control. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    Directory of Open Access Journals (Sweden)

    M. Soto


    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. Organometallic Polymeric Conductors (United States)

    Youngs, Wiley J.


    For aerospace applications, the use of polymers can result in tremendous weight savings over metals. Suitable polymeric materials for some applications like EMI shielding, spacecraft grounding, and charge dissipation must combine high electrical conductivity with long-term environmental stability, good processability, and good mechanical properties. Recently, other investigators have reported hybrid films made from an electrically conductive polymer combined with insulating polymers. In all of these instances, the films were prepared by infiltrating an insulating polymer with a precursor for a conductive polymer (either polypyrrole or polythiophene), and oxidatively polymerizing the precursor in situ. The resulting composite films have good electrical conductivity, while overcoming the brittleness inherent in most conductive polymers. Many aerospace applications require a combination of properties. Thus, hybrid films made from polyimides or other engineering resins are of primary interest, but only if conductivities on the same order as those obtained with a polystyrene base could be obtained. Hence, a series of experiments was performed to optimize the conductivity of polyimide-based composite films. The polyimide base chosen for this study was Kapton. 3-MethylThiophene (3MT) was used for the conductive phase. Three processing variables were identified for producing these composite films, namely time, temperature, and oxidant concentration for the in situ oxidation. Statistically designed experiments were used to examine the effects of these variables and synergistic/interactive effects among variables on the electrical conductivity and mechanical strength of the films. Multiple linear regression analysis of the tensile data revealed that temperature and time have the greatest effect on maximum stress. The response surface of maximum stress vs. temperature and time (for oxidant concentration at 1.2 M) is shown. Conductivity of the composite films was measured for

  19. Simulation of Peptide Binding to Silica and Silica Mineralization (United States)

    Emami, F. S.; Heinz, H.; Berry, R. J.; Varshney, V.; Farmer, B. L.; Naik, R. R.; Patwardhan, S. V.; Perry, C. C.


    The purpose of this study is to identify the nature of the interaction of peptides with silica surfaces and their effect on mineralization. Classical force fields (CVFF, PCFF) have been extended for silica aiming at the computation of surface properties in quantitative agreement with experiment, taking explicitly into account water molecules, pH, and surface coverage with peptides. We focus on the interaction of five short peptides (pep1, pep4, 82-4, H4, R5) identified by biopanning with regular and amorphous silica surfaces (Q3 and Q2) to understand the relation between peptide sequence and affinity to the surface. Results of the atomistic molecular dynamics simulation indicate adsorption energies, binding constants and conformational changes upon adsorption. The comparison of NMR chemical shifts in solution and on the surface in computation and experiment further aids in understanding the mechanism of binding.

  20. Pumping Iron and Silica Bodybuilding (United States)

    Mcnair, H.; Brzezinski, M. A.; Krause, J. W.; Parker, C.; Brown, M.; Coale, T.; Bruland, K. W.


    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.

  1. Luminescent properties of hybrid materials prepared by the polymeric precursor method

    Energy Technology Data Exchange (ETDEWEB)

    Oliveira, Larissa H., E-mail: [LIEC-UNESP, Institute of Chemistry, Caixa Postal 355, 14800-900 Araraquara, SP (Brazil); Moura, Ana Paula de; Longo, Elson; Varela, José A. [LIEC-UNESP, Institute of Chemistry, Caixa Postal 355, 14800-900 Araraquara, SP (Brazil); Rosa, Ieda L.V. [LIEC-UFSCar, Department of Chemistry, Caixa Postal 676, 13560-905 São Carlos, SP (Brazil)


    Highlights: •The Eu{sup 3+} ions are chelating to the 2-hydroxynicotinic acid via O,O-coordination. •A Class II hybrid material was formed by increasing the temperature to 300 °C. •The 2-hydroxynicotinic acid insert in a silica matrix became thermally stable. •PL emission showed a charge transference from 2-hydroxynicotinic to Eu{sup 3+} ions. -- Abstract: Rare earth complexes (RE) can be incorporated in silica matrixes, originating organic/inorganic hybrid materials with good thermal stability and high rare earth emission lines. In this work, the hybrid material was obtained by the polymeric precursor method and ultrasonic dispersed with spherical silica particles prepared by the Stöber Method. The Raman spectra indicated that the Eu{sup 3+} ions are involved in a polymeric structure formed as consequence of the chelation and polyesterification reactions of this ion with citric acid and ethylene glycol. After the ultrasonic stirring, 2-hydroxynicotinic ligand will also compose this polymeric rigid structure. The TGA/DTA analysis showed that this polymeric material was thermal decomposed at 300 °C. Moreover, this process allows the chelating process of the 2-hydroxynicotinic acid ligand to the Eu{sup 3+} ions. The {sup 29}Si NMR showed that the ultrasonic dispersion of the reactants was not able to promote the functionalization of the silica particles with the 2-hydroxynicotinic acid ligand. Moreover, heat treatment promotes the [Eu(HnicO{sub 2}){sub 3}] complex particles incorporation into silica pores. At this temperature, the TGA curve showed that only the thermal degradation of ethylene glycol and citric acid used during the experimental procedure occurs. The silica and hybrid materials are composed by spherical and aggregated particles with particle size of approximately 450 nm, which can be influenced by the heat treatment. These materials also present an absorption band located at 337 nm. The photoluminescent study showed that when the hybrid

  2. Optimization of polymerization process conditions during development of micro- and nanocapsules of hydrophobic agents based on Pickering emulsions

    Directory of Open Access Journals (Sweden)

    Saule Aidarova


    Full Text Available The polymerization process is one of the most important processes to obtain stable emulsions. This is especially important when the emulsion evaporates. In the work, the protocol of optimum polymerization conditions was developed, which comprises carrying out the polymerization at a temperature of 80°C using potassium persulfate as an initiator at a concentration 0.4 mM. It was found that the formed monodisperse particles with an average size of 200 nm have a distinct morphology capsules, which according cryo-SEM pictures have spherical shape, similar to the morphology of raspberry. These results are also consistent with the data of TEM images, whereby submicrocapsules were densely coated by silica particles. It was proved by zeta-potential measurements according to which, after polymerization the disperse systems become more colloidally stable and less prone to aggregation and sedimentation.

  3. Stabilizing Single Sites on Solid Supports: Robust Grafted Ti(IV)-Calixarene Olefin Epoxidation Catalysts via Surface Polymerization and Cross-Linking


    Guo, Yijun; Solovyov, Andrew; Grosso-Giordano, Nicolás A.; Hwang, Son-Jong; Katz, Alexander


    This manuscript develops a surface polymerization and cross-linking approach for the stabilization of single-site catalysts on solid surfaces, which is demonstrated here for grafted Ti(IV)-calixarene Lewis acids on silica. Our approach relies on cationic polymerization that is initiated by an adsorbed B(C_6F_5)_3 and uses styrene as the monomer and diisopropenylbenzene as the cross-linking agent. The mildness of this polymerization method is demonstrated by its lack of blocking micropores and...

  4. On the problem of silica solubility at high pH

    International Nuclear Information System (INIS)

    Eikenberg, J.


    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

  5. Electroactivity in Polymeric Materials

    CERN Document Server


    Electroactivity in Polymeric Materials provides an in-depth view of the theory of electroactivity and explores exactly how and why various electroactive phenomena occur. The book explains the theory behind electroactive bending (including ion-polymer-metal-composites –IPMCs), dielectric elastomers, electroactive contraction, and electroactive contraction-expansion cycles.  The book also balances theory with applications – how electroactivity can be used – drawing inspiration from the manmade mechanical world and the natural world around us.  This book captures: A complete introduction to electroactive materials including examples and recent developments The theory and applications of numerous topics like electroactive bending of dielectric elastomers and electroactive contraction and expansion New topics, such as biomimetic applications and energy harvesting This is a must-read within the electroactive community, particularly for professionals and graduate students who are interested in the ...

  6. Polyolefin nanocomposites in situ polymerization

    International Nuclear Information System (INIS)

    Galland, Griselda Barrera; Fim, Fabiana de C.; Milani, Marceo A.; Silva, Silene P. da; Forest, Tadeu; Radaelli, Gislaine; Basso, Nara R.S.; Quijada, Raul


    Polyethylene and polypropylene nanocomposites using grapheme nanosheets and treated chrysotile have been synthesized by in situ polymerization using metallocene catalysts. The fillers have been submitted to acid, thermal and/ou ultrasound treatments before to introduce them into the polymerization reactor. A complete characterization of the fillers has been done. The nanocomposites have been characterized by SEM, TEM, DRX and AFM. The thermal, mechanic -dynamic, mechanical and electrical properties of the nanocomposites are discussed. (author)

  7. Studies of Immobilized Homogeneous Metal Catalysts on Silica Supports

    Energy Technology Data Exchange (ETDEWEB)

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


    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.

  8. Tailored Cyclic and Linear Polycarbosilazanes by Barium-Catalyzed N-H/H-Si Dehydrocoupling Reactions. (United States)

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


    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.

  9. Silica Aerogel: Synthesis and Applications

    Directory of Open Access Journals (Sweden)

    Jyoti L. Gurav


    Full Text Available Silica aerogels have drawn a lot of interest both in science and technology because of their low bulk density (up to 95% of their volume is air, hydrophobicity, low thermal conductivity, high surface area, and optical transparency. Aerogels are synthesized from molecular precursors by sol-gel processing. Special drying techniques must be applied to replace the pore liquid with air while maintaining the solid network. Supercritical drying is most common; however, recently developed methods allow removal of the liquid at atmospheric pressure after chemical modification of the inner surface of the gels, leaving only a porous silica network filled with air. Therefore, by considering the surprising properties of aerogels, the present review addresses synthesis of silica aerogels by the sol-gel method, as well as drying techniques and applications in current industrial development and scientific research.

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

    Energy Technology Data Exchange (ETDEWEB)

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


    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.

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

    KAUST Repository

    Hu, Xian-Lei


    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.

  12. 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.


    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.

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

    Directory of Open Access Journals (Sweden)

    Daniela B. van den Heuvel


    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.

  14. 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.


    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

  15. Development of silica RO membranes

    International Nuclear Information System (INIS)

    Ikeda, Ayumi; Kawamoto, Takashi; Matsuyama, Emi; Utsumi, Keisuke; Nomura, Mikihiro; Sugimoto, Masaki; Yoshikawa, Masato


    Silica based membranes have been developed by using a counter diffusion CVD method. Effects of alkyl groups in the silica precursors and deposition temperatures had investigated in order to control pore sizes of the silica membranes. In this study, this type of a silica membrane was applied for RO separation. Effects of silica sources, deposition temperatures and post treatments had been investigated. Tetramethoxysilane (TMOS), Ethyltrimethoxysilane (ETMOS) and Phenyltrimethoxysilane (PhTMOS) were used as silica precursors. A counter diffusion CVD method was carried out for 90 min at 270 - 600degC on γ-alumina capillary substrates (effective length: 50 mm, φ: 4 nm: NOK Co.). O 3 or O 2 was introduced into the inside of the substrate at the O 2 rate of 0.2 L min -1 . Ion beam irradiation was carried out for a post treatment using Os at 490 MeV for 1.0 x 10 10 ions cm -2 or 3.0 x 10 10 ions cm -2 . Single gas permeance was measured by using H 2 , N 2 and SF 6 . RO tests were employed at 3.0 or 5.4 MPa for 100 mg L -1 of feed NaCl solution. First, effects of the silica sources were investigated. The total fluxes increased by increasing N 2 permeance through the silica membrane deposited by ETMOS. The maximum NaCl rejection was 28.2% at 12.2 kg m -2 h -1 of the total flux through the membrane deposited at 270degC. N 2 permeance was 9.6 x 10 -9 mol m -2 s -1 Pa -1 . While, total fluxes through the membrane deposited by using PhTMOS were smaller than those through the ETMOS membranes. The phenyl groups for the PhTMOS membrane must be important for the hydrophobic properties through the membrane. Next, effects of ion beam irradiation were tested for the TMOS membranes. Water is difficult to permeate through the TMOS membranes due to the low N 2 permeance through the membrane (3.1 x 10 -11 mol m -2 s -1 Pa -1 ). N 2 permeance increased to 7.3 x 10 -9 mol m -2 s -1 Pa -1 by the irradiation. Irradiation amounts had little effects on N 2 permeance. However, NaCl rejections

  16. Synthesis of colloidal silica dumbbells. (United States)

    Johnson, Patrick M; van Kats, Carlos M; van Blaaderen, Alfons


    We describe the synthesis and characterization of stable suspensions of monodisperse fluorescently labeled silica dumbbell particles. Pure dispersions of silica dumbbells with center-to-center lengths from 174 nm to 2.3 microm were produced with a variety of aspect ratios. Individual particles in concentrated dispersions of these particles could be imaged with confocal microscopy. These particles can be used as a colloidal model system for addressing fundamental questions about crystal and glass formation of low-aspect-ratio anisotropic particles. They also have potential in photonic applications and electro-optical devices.

  17. Candida antartica lipase B catalyzed polycaprolactone synthesis: effects of organic media and temperature. (United States)

    Kumar, A; Gross, R A


    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.

  18. Niobia-silica and silica membranes for gas separation

    NARCIS (Netherlands)

    Boffa, V.


    This thesis describes the development of ceramic membranes suitable for hydrogen separation and CO2 recovery from gaseous streams. The research work was focused on the three different parts of which gas selective ceramic membranes are composed, i.e., the microporous gas selective silica layer, the

  19. Secondary structure and dynamics study of the intrinsically disordered silica-mineralizing peptide P 5 S 3 during silicic acid condensation and silica decondensation

    Energy Technology Data Exchange (ETDEWEB)

    Zerfass, Christian; Buchko, Garry W.; Shaw, Wendy J.; Hobe, Stephan; Paulsen, Harold


    The silica forming repeat R5 of sil1 from Cylindrotheca fusiformis was the blueprint for the design of P5S3, a 50-residue peptide which can be produced in large amounts by recombinant bacterial expression. It contains five protein kinase A target sites and is highly cationic due to 10 lysine and 10 arginine residues. In the presence of supersaturated ortho silicic acid P5S3 strongly enhances silica-formation whereas it retards the dissolution of amorphous silica (SiO2) at globally undersaturated concentrations. The secondary structure of P5S3 during these different functions was studied by circular dichroism (CD), complemented by nuclear magnetic resonance (NMR) studies of the peptide in the absence of silicate. The NMR studies of dual-labeled (13C, 15N) P5S3 revealed a disordered structure at pH 2.8 and 4.5. Within the pH range of 4.5 to 9.5, the CD data verified the disordered secondary structure but also suggested the presence of some polyproline II character in the absence of silicic acid. Upon silicic acid polymerization and during dissolution of preformed silica, the CD spectrum of P5S3 indicated partial transition into an α-helical conformation which was transient during silica-dissolution. Consequently, the secondary structural changes observed for P5S3 correlate with the presence of oli-gomeric/polymeric silicic acid, presumably due to P5S3-silicic acid interactions. These interactions appear, at least in part, ionic in nature since dodecylsulfate micelles, which are negatively charged, cause similar conformational shifts to P5S3 in the absence of silica while ß-D-dodecyl maltoside micelles, which are neutral, do not. Thus, P5S3 influences both the condensation of silicic acid into silica and its decondensation back to silicic acid. Moreover, the dynamics of these pro-cesses may be indirectly monitored by following structural changes to P5S3 with CD spectroscopy.

  20. Atomistic Model for the Polyamide Formation from β-Lactam Catalyzed by Candida Antarctica Lipase B

    Energy Technology Data Exchange (ETDEWEB)

    Baum, Iris; Elsasser, Brigitta M.; Schwab, Leendert; Loos, Katja; Fels, Gregor


    Candida antarctica lipase B (CALB) is an established biocatalyst for a variety of transesterification, amidation, and polymerization reactions. In contrast to polyesters, polyamides are not yet generally accessible via enzymatic polymerization. In this regard, an enzyme-catalyzed ring-opening polymerization of {beta}-lactam (2-azetidinone) using CALB is the first example of an enzymatic polyamide formation yielding unbranched poly({beta}-alanine), nylon 3. The performance of this polymerization, however, is poor, considering the maximum chain length of 18 monomer units with an average length of 8, and the molecular basis of the reaction so far is not understood. We have employed molecular modeling techniques using docking tools, molecular dynamics, and QM/MM procedures to gain insight into the mechanistic details of the various reaction steps involved. As a result, we propose a catalytic cycle for the oligomerization of {beta}-lactam that rationalizes the activation of the monomer, the chain elongation by additional {beta}-lactam molecules, and the termination of the polymer chain. In addition, the processes leading to a premature chain termination are studied. Particularly, the QM/MM calculation enables an atomistic description of all eight steps involved in the catalytic cycle, which features an in situ-generated {beta}-alanine as the elongating monomer and which is compatible with the experimental findings.

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

    Directory of Open Access Journals (Sweden)

    Leila Mazaheri


    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Timin, Alexander S., E-mail: [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)


    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.

  3. Structure of silica-supported catalysts

    International Nuclear Information System (INIS)

    Gladden, L.F.; Vignaux, M.; Griffiths, R.W.; Jackson, S.D.; Jones, J.R.; Sharratt, A.P.; Robertson, F.J.; Webb, G.


    Neutron diffraction and SANS studies of silica supported metal catalysts have indicated that more active metal:silica catalysts are produced when the silica support has a relatively high content of three-membered rings in its network structure. SANS studies also suggest that the more active catalysts possess a bimodal metal particle size distribution. (orig.)

  4. Sonochemical coating of magnetite nanoparticles with silica. (United States)

    Dang, Feng; Enomoto, Naoya; Hojo, Junichi; Enpuku, Keiji


    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. 21 CFR 584.700 - Hydrophobic silicas. (United States)


    ...) 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...

  6. Anisotropic silica mesostructures for DNA encapsulation

    Indian Academy of Sciences (India)

    functionalizing the pores of silica with amine group, the amount of DNA loaded on the rods decreases which is due to a reduction in the pore size upon grafting of amine groups. Keywords. Surfactant; reverse micellar method; silica mesostructures; surface area. 1. Introduction. Amorphous silica nanoparticles are important ...

  7. Omega-3 PUFA concentration by a novel PVDF nano-composite membrane filled with nano-porous silica particles. (United States)

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


    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.

  8. Covalent immobilization of oxylipin biosynthetic enzymes on nanoporous rice husk silica for production of cis(+)-12-oxophytodienoic acid. (United States)

    Le, Thu Bao; Han, Chong Soo; Cho, Kyoungwon; Han, Oksoo


    Soybean lipoxygenase, recombinant rice allene oxide synthase-1 and rice allene oxide cyclase were covalently immobilized on nanoporous rice husk silica using two types of linkers: glutardialdehyde and polyethylene glycol. The immobilization efficiency achieved using glutardialdehyde-linked rice husk silica was higher than that achieved using polyethylene glycol-linked rice husk silica (50-92% and 25-50%, respectively). Immobilization on both types of matrices significantly decreased the specific activities of the immobilized enzymes. Solid-phase reaction yields of the enzymes were determined relative to the yields observed for the solution-phase reactions. Yields of the solid-phase reactions catalyzed by immobilized soybean lipoxygenase, rice allene oxide synthase-1, and rice allene oxide cyclase ranged from 50% to 230% and were dependent on both the enzymes and linkers used. Production of cis(+)-12-oxophytodienoic acid from α-linolenic acid by consecutive reactions using all three enzymes in a co-immobilization system resulted in 83.6% and 65.1% yields on glutardialdehyde-linked and epichlorohydrin-polyethylene glycol-linked rice husk silica, respectively. Our results suggest that immobilization of biosynthetic enzymes of the octadecanoid pathway on rice husk silica may be an efficient method for the in vitro production of oxylipins. Additionally, enzyme immobilizations on rice husk silica matrices may be more broadly applicable for producing physiologically important compounds in other biosynthetic pathways.

  9. Functionalized silica materials for electrocatalysis

    Indian Academy of Sciences (India)

    electrochemical sensors and biosensors.1–5 Templated routes to synthesize silica materials give rise to well- ordered structures with pores and interconnected chan- nels, whereas a .... 2.2 Fabrication of electrodes. An aqueous colloidal solution (0.5–1.0%) of the res- pective material was prepared together with 0.01% poly.

  10. Poling of Planar Silica Waveguides

    DEFF Research Database (Denmark)

    Arentoft, Jesper; Kristensen, Martin; Jensen, Jesper Bo


    UV-written planar silica waveguides are poled using two different poling techniques, thermal poling and UV-poling. Thermal poling induces an electro-optic coefficient of 0.067 pm/V. We also demonstrate simultaneous UV-writing and UV-poling. The induced electro-optic effect shows a linear dependence...

  11. Functionalized silica materials for electrocatalysis

    Indian Academy of Sciences (India)

    To increase the efficiency of the electrocatalytic process and to increase the electrochemical accessibility of the immobilized electrocatalysts, functionalized and non-functionalized mesoporous organo-silica (MCM41-type-materials) are used in this study. These materials possess several suitable properties to be durable ...

  12. High surface area Au-SBA-15 and Au-MCM-41 materials synthesis: tryptophan amino acid mediated confinement of gold nanostructures within the mesoporous silica pore walls. (United States)

    Selvakannan, Pr; Mantri, Kshudiram; Tardio, James; Bhargava, Suresh K


    Advantages of confining the gold nanostructures formation within the mesoporous silica pore walls during its silica condensation and consequent improvement in the textural properties such as specific surface area, pore volume, pore diameter have been demonstrated, while retaining gold nanostructures within the silica walls. This has been achieved by tryptophan mediated confinement of gold nanoparticles formation within the condensing silica framework, to obtain Au-SBA-15 (SSA 1247 m(2)/g, V(t)~1.37 cm(3)/g) and Au-MCM-41 (SSA 1287 m(2)/g, V(t)~1.1 cm(3)/g), mesoporous silica materials having the combination of very high surface area from the porous support as well as gold nanoparticles infiltrated silica walls. Choice of tryptophan for this purpose is that it has an indole group, which was known to reduce gold ions to form gold nanoparticles and its amine and carboxylic acid groups, catalyze the hydrolysis of silica precursors in a wide range of pH. These properties have been utilized in restricting the gold nanostructures formation inside the condensing silica phase without affecting the self assembly between the silica precursors and the triblock copolymer (for SBA-15) or cetyltrimethylammonium bromide template (for MCM-41). The polytryptophan and the gold nanostructures, which were encapsulated within the silica framework and upon removal of the template by calcination resulting in the formation mesoporous materials wherein the silica walls become microporous due to the removal of occluded polytryptophan and the resulting microchannels contain very small gold nanostructures. Hence, the resulting materials have very high surface area, high pore volume and narrow pore size distribution as compared to their parent SBA-15, MCM-41 and SBA-15, MCM-41 post functionalized with gold nanoparticles inside the pores. Copyright © 2012 Elsevier Inc. All rights reserved.

  13. Trypsin-catalyzed deltamethrin degradation.

    Directory of Open Access Journals (Sweden)

    Chunrong Xiong

    Full Text Available To explore if trypsin could catalyze the degradation of non-protein molecule deltamethrin, we compared in vitro hydrolytic reactions of deltamethrin in the presence and absence of trypsin with ultraviolet-visible (UV/Vis spectrophotometry and gas chromatography-mass spectrometry (GC/MS. In addition, acute oral toxicity of the degradation products was determined in Wistar rats. The results show that the absorption peak of deltamethrin is around 264 nm, while the absorption peaks of deltamethrin degradation products are around 250 nm and 296 nm. In our GC setting, the retention time of undegraded deltamethrin was 37.968 min, while those of deltamethrin degradation products were 15.289 min and 18.730 min. The LD50 of deltamethrin in Wistar rats is 55 mg/kg, while that of deltamethrin degradation products is 3358 mg/kg in female rats and 1045 mg/kg in male rates (61-fold and 19-fold reductions in toxicity, suggesting that trypsin could directly degrade deltamethrin, which significantly reduces the toxicity of deltamethrin. These results expand people's understanding of the functions of proteases and point to potential applications of trypsin as an attractive agent to control residual pesticides in the environment and on agricultural products.

  14. Silica-Coated Liposomes for Insulin Delivery

    Directory of Open Access Journals (Sweden)

    Neelam Dwivedi


    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.

  15. Uranium incorporation into amorphous silica. (United States)

    Massey, Michael S; Lezama-Pacheco, Juan S; Nelson, Joey M; Fendorf, Scott; Maher, Kate


    High concentrations of uranium are commonly observed in naturally occurring amorphous silica (including opal) deposits, suggesting that incorporation of U into amorphous silica may represent a natural attenuation mechanism and promising strategy for U remediation. However, the stability of uranium in opaline silicates, determined in part by the binding mechanism for U, is an important factor in its long-term fate. U may bind directly to the opaline silicate matrix, or to materials such as iron (hydr)oxides that are subsequently occluded within the opal. Here, we examine the coordination environment of U within opaline silica to elucidate incorporation mechanisms. Precipitates (with and without ferrihydrite inclusions) were synthesized from U-bearing sodium metasilicate solutions, buffered at pH ∼ 5.6. Natural and synthetic solids were analyzed with X-ray absorption spectroscopy and a suite of other techniques. In synthetic amorphous silica, U was coordinated by silicate in a double corner-sharing coordination geometry (Si at ∼ 3.8-3.9 Å) and a small amount of uranyl and silicate in a bidentate, mononuclear (edge-sharing) coordination (Si at ∼ 3.1-3.2 Å, U at ∼ 3.8-3.9 Å). In iron-bearing synthetic solids, U was adsorbed to iron (hydr)oxide, but the coordination environment also contained silicate in both edge-sharing and corner-sharing coordination. Uranium local coordination in synthetic solids is similar to that of natural U-bearing opals that retain U for millions of years. The stability and extent of U incorporation into opaline and amorphous silica represents a long-term repository for U that may provide an alternative strategy for remediation of U contamination.

  16. Acetylation and oxygenation transformations catalyzed by silica-supported dodecatungstophosphoric acid

    Directory of Open Access Journals (Sweden)

    Reza Tayebee


    Full Text Available Acetylation of alcohols in refluxing ethyl acetate, and oxidation of aniline and cyclohexanol with 34 % H2O2 in the presence of H3PW12O40 and its supported forms on SiO2 (20 %, 40 %, and 60 % by weight as active solid acid catalysts were performed under mild reaction conditions with moderate to good yields and with 100 % selectivity. It is found that the supported H3PW12O40 was in general 1.4-2.3 times more efficient than the unsupported catalyst in the acetylation and oxygenation reactions. Easy work-up and effective recycling of the heterogeneous catalyst were distinct advantages of the catalytic heterogeneous system.

  17. Ni/Silica catalyzed acetylation of phenols and naphthols: An eco-friendly approach

    Directory of Open Access Journals (Sweden)

    Manawwer Alam


    Full Text Available A method for 10% Ni/SiO2 catalyst is developed for acetylation of phenol, substituted phenols, naphthols, substituted alcohols under mild liquid phase conditions affording aromatic esters with maximum conversions of 50–80% and 100% selectivity. The catalyst showed remarkable reusability for up to 4 cycles. This methodology is eco-friendly, economic with Ni/SiO2 catalysts exhibiting no loss of activity the first report for acetylation of substituted phenols to esters with 10% Ni/SiO2 catalyst.

  18. Cyclodimerization of Stilbenes and Styrenes Catalyzed by Heteropolyacid Supported on Silica

    Directory of Open Access Journals (Sweden)

    B. Lantaño


    Full Text Available Several stilbenes and styrenes have been treated with heteropolyacid] (HPA supported over silice. The compounds obtained were characterized by 1H and 13C- NMR and the yields were compared with those obtained using H2SO4 (c and ethyl poliphosphate] (PPE.

  19. Biodiesel production by enzyme-catalyzed transesterification


    Stamenković Olivera S.; Lazić Miodrag L.; Veljković Vlada B.; Skala Dejan U.


    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 appli...

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

    Directory of Open Access Journals (Sweden)

    Agnieszka Kierys


    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. 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


    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

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

    Directory of Open Access Journals (Sweden)

    Genoveva Hernández-Padrón


    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.

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

    International Nuclear Information System (INIS)

    Ishak Manaf


    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)

  4. Studies of Olefin Dimerization, Oligomerization, and Polymerization Catalyzed by Cationic (alpha-Diimine)Ni(II) Complexes

    National Research Council Canada - National Science Library

    Svejda, Steven


    .... Over the past twenty years, substantial improvements have been made in the design and industrial employment of these catalysts, especially with the development of early transition-metal metallocenes...

  5. Degradation of polycyclic aromatic hydrocarbons by hydrogen peroxide catalyzed by heterogeneous polymeric metal chelates

    Czech Academy of Sciences Publication Activity Database

    Baldrian, Petr; Cajthaml, Tomáš; Merhautová, Věra; Gabriel, Jiří; Nerud, František; Stopka, P.; Hrubý, Martin; Beneš, Milan J.


    Roč. 59, - (2005), s. 267-274 ISSN 0926-3373 R&D Projects: GA AV ČR IBS5020306; GA ČR GA203/01/0944 Institutional research plan: CEZ:AV0Z7090911 Keywords : degradation * polycyclic aromatic hydrocarbon * hydrogen peroxide Subject RIV: EE - Microbiology, Virology Impact factor: 3.809, year: 2005

  6. Synthesis and characterization of polyimide silica hybrids

    International Nuclear Information System (INIS)

    Ullah, S.M.


    Flexible-chain polyimide (PIF) was synthesized from 4, 4'-oxydianiline (ODA) and pyromellitic dianhydride (PMDA) and the stiff-chain polyimide (PI S ) was derived from 1, 5-diaminonepthaline (DAN) and pyromellitic anhydride (PMDA). Molecular composites of polyimide were prepared by embedding the stiff-chain polyimide (PIS) in to ductile matrix of flexible-polyimide (PI F ) by blending their respective poly(amic acid) solution (20:80). Blend of rigid and flexible polyimide (20:80) was reinforced with silica up to 35 wt % by sol-gel process to form the silica reinforced molecular composite (SRMC). Silica reinforced molecular composite (SRMC) were characterized by Fourier transform infrared spectroscopy (FTIR), thermogravimetry (TG) and tensile testing (TT). FTIR results showed the shifting of Si - O - Si peak toward lower wave number with the increase in the silica wt % indicates the increase in the silica particle size. The oxidative degradation of SRMC showed an improvement of 23 degree C in composite having 30 wt% silica contents. Similarly, modulus of SRMC was increased as the concentration of silica was increased. Silica reinforced (co-)polyimide (SRCO) was prepared from the same monomers DAN, ODA and PMDA (20:80:100) and reinforced with different of silica up to 35 wt%. Comparison of thermo-mechanical properties of SRMC with SRCO was also done. Both the composite showed similar peak shift to low wave number with the increase in the wt% of silica was observed as in the case of SRMC. TG results of SRCO showed the 13 degree C improvement in the oxidative degradation with 30 wt% silica content. Tensile testing shows the 80% increase in the modulus with 35 wt% silica content. The result showed that SRMC are 15 degree C more stable than SRCO with 30 wt% silica. SRMC have 15% more modulus than SRCO with 30 wt% silica. This shows that thermo mechanical stability of SRMC's over SRCO's composites. (author)

  7. Immobilized Bis-Indenyl Ligands for Stable and Cost-Effective Metallocene Catalysts of Hydrogenation and Polymerization Reactions (United States)

    Simerly, Thomas Max

    Reactions of catalytic hydrogenations and polymerizations are widely used in industry for manufacture of fine chemicals, pharmaceuticals, and plastics. Homogeneous catalysts for the processes that have low stability and their separation is difficult. Therefore, the development of new highly active and stable catalysts for hydrogenations and polymerizations is a necessity. The objective of this research was the development of a strategy for immobilization of heterogeneous metallocene catalysts. First, a methodology of immobilization of bis-indenyl ligands on the surface of mesoporous silica gel was designed. Four bis-indenyl ligands containing functionalized tethers of various lengths with terminal alkene groups were synthesized. All bis-indenyl ligands were immobilized on the surface of mesoporous functionalized silica gel by two methods: hydrosilylation and thiol-ene coupling of the double bond. After comparing the results, the second strategy was chosen as more efficient. The materials can be used further as intermediates for synthesis of supported metallocene catalysts.

  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


    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. Bioinspired enzymatic synthesis of silica nanocrystals provided by recombinant silicatein from the marine sponge Latrunculia oparinae. (United States)

    Shkryl, Yury N; Bulgakov, Victor P; Veremeichik, Galina N; Kovalchuk, Svetlana N; Kozhemyako, Valery B; Kamenev, Dmitrii G; Semiletova, Irina V; Timofeeva, Yana O; Shchipunov, Yury A; Kulchin, Yury N


    The process of silica formation in marine sponges is thought to be mediated by a family of catalytically active structure-directing enzymes called silicateins. It has been demonstrated in biomimicking syntheses that silicateins facilitated the formation of amorphous SiO2. Here, we present evidence that the silicatein LoSiLA1 from the marine sponge Latrunculia oparinae catalyzes the in vitro synthesis of hexa-tetrahedral SiO2 crystals of 200–300 nm. This was possible in the presence of the silica precursor tetrakis-(2-hydroxyethyl)-orthosilicate that is completely soluble in water and biocompatible, experiences hydrolysis–condensation at neutral pH and ambient conditions.

  10. Preparation of hollow silica nanospheres in O/W microemulsion system by hydrothermal temperature changes (United States)

    Wang, Dandan; Li, Xiuyan; Liu, Zuohua; Shi, Xue; Zhou, Guowei


    Hollow silica nanospheres with wrinkled or smooth surfaces were successfully fabricated through a hydrothermal method. In this method, oil-in-water microemulsion (composed of cyclohexane, water, ethanol, and cetyltrimethylammonium bromide), and polyvinylpyrrolidone were utilized as template and capping agent, respectively. In such a facile synthesis, we can well realize the morphological transformation of spheres with radially oriented mesochannels to hollow structures of silica nanoparticle only by regulating the hydrothermal temperature from 100 °C to 200 °C. Synthesized samples with different mesostructures were then used as supports to immobilize Candida rugosa lipase (CRL). The immobilized CRL was employed as a new biocatalyst for biodiesel production through the esterification of heptanoic acid with ethanol. The conversion ratio of heptanoic acid with ethanol catalyzed by the immobilized CRL was also evaluated. Results of this study suggest that the prepared samples have potential applications in biocatalysis.

  11. Thermodynamics of Silica Dissolution From In-situ Raman +Spectroscopy (United States)

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


    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.

  12. A highly reactive photobase catalytic system for sol–gel polymerization

    Energy Technology Data Exchange (ETDEWEB)

    Chemtob, Abraham, E-mail: [Laboratory of Macromolecular Photochemistry and Engineering, University of Haute-Alsace, ENSCMu, 3 rue Alfred Werner, 68093 Mulhouse Cedex (France); De Paz-Simon, Héloïse; Dietlin, Céline; Croutxé-Barghorn, Céline; Salmi, Hanène; Allonas, Xavier [Laboratory of Macromolecular Photochemistry and Engineering, University of Haute-Alsace, ENSCMu, 3 rue Alfred Werner, 68093 Mulhouse Cedex (France); Chany, Anne-Caroline [Laboratory of Organic and Bioorganic Chemistry, University of Haute Alsace, ENSCMu, 3 rue Alfred Werner, 68093 Mulhouse Cedex (France); Vidal, Loïc; Rigolet, Séverinne [Institute of Mulhouse Material Science, UMR-CNRS 7361, University of Haute-Alsace, 3 rue Alfred Werner 68093, Mulhouse Cedex (France)


    In sol–gel polymerization of alkoxysilane precursors, base catalysts are usually employed to introduce textural properties. Herein, we show the feasibility and interest of a photobase-catalyzed sol–gel reaction to afford silicate films. Our inorganic polymerization is solvent-free, single-step and UV activatable with a mixture of α-aminoacetophenone (photobase generator), benzophenone (photosensitizer) and triphenylphosphine (oxygen scavenger). To date, the present tricomponent photolatent system generating N-alkyl morpholine tertiary amines represents one of the most efficient photobase generators reported so far in sol–gel chemistry. A combination of spectroscopic and electron microscopy techniques enabled to investigate the fundamental chemistry underlying alkoxysilane photopolymerization: reaction mechanism, hydrolysis kinetics and siloxane microstructure. Systematic comparison with a photoacid-catalyzed process revealed also the impact of the photocatalyst nature on film texture, morphology and optical properties. - Highlights: • A very efficient UV-driven photobase-catalyzed sol–gel process. • Single-step film formation without transition through a sol. • Comparison of film properties under photoacid and photobase catalysis.

  13. On-demand photoinitiated polymerization (United States)

    Boydston, Andrew J; Grubbs, Robert H; Daeffler, Chris; Momcilovic, Nebojsa


    Compositions and methods for adjustable lenses are provided. In some embodiments, the lenses contain a lens matrix material, a masking compound, and a prepolymer. The lens matrix material provides structure to the lens. The masking compound is capable of blocking polymerization or crosslinking of the prepolymer, until photoisomerization of the compound is triggered, and the compound is converted from a first isomer to a second isomer having a different absorption profile. The prepolymer is a composition that can undergo a polymerization or crosslinking reaction upon photoinitiation to alter one or more of the properties of the lenses.

  14. Pentafluorosulfanyl Substituents in Polymerization Catalysis. (United States)

    Kenyon, Philip; Mecking, Stefan


    Highly electron-withdrawing pentafluorosulfanyl groups were probed as substituents in an organometallic catalyst. In Ni(II) salicylaldiminato complexes as an example case, these highly electron-withdrawing substituents allow for polymerization of ethylene to higher molecular weights with reduced branching due to significant reductions in β-hydrogen elimination. Combined with the excellent functional group tolerance of neutral Ni(II) complexes, this suppression of β-hydrogen elimination allows for the direct polymerization of ethylene in water to nanocrystal dispersions of disentangled, ultrahigh-molecular-weight linear polyethylene.

  15. Sol-gel synthesis and characterization of silica polyamine composites: applications to metal ion capture. (United States)

    Allen, Jesse J; Rosenberg, Edward; Johnston, Erik; Hart, Carolyn


    A sol-gel method has been developed for the synthesis of composite materials analogous to the previously reported and commercialized silica polyamine composite (SPC) materials made from amorphous silica. Monolithic xerogels were formed using a two-step procedure with no templating agent using acid catalyzed followed by base catalyzed hydrolysis. This reaction was followed by (1)H NMR. Initial sol-gels were formed using a methyltrimethoxysilane (MTMOS) and 3-chloropropyltrimethoxysilane (CPTMOS) mixture. Elemental analyses and (13)C CPMAS NMR confirmed incorporation of both monomeric units into the surface structure. Some control over surface morphology was achieved by adjusting synthetic conditions. The resulting xerogels were reacted with poly(allylamine) (PAA) to give composite materials which showed much lower metal ion capacities than the commercially available amorphous silica analogs. The low degree of reaction of the chloropropyl groups indicated they were not surface-available to the polyamine. Addition of tetramethoxysilane (TMOS) produced a structural matrix and resulted in higher chloride utilization (reaction of surface chloropropyl groups with the polyamine). The ratio of the three siloxane monomeric components was varied until the resulting polyamine composite xerogels had metal capacities comparable with the commercialized SPC materials. These composites had narrower average pore size distributions and fewer small pores. Further modification of these composites with metal selective ligands showed material characteristics similar to those of commercially available SPC materials. Subjecting a composite made by the sol-gel route to one thousand load-strip cycles with Cu(2+) shows essentially no loss in metal capacity, and this robustness compares favorably with that observed for the SPC made from amorphous silica gels. © 2012 American Chemical Society

  16. Precision synthesis of poly(3-hexylthiophene) from catalyst-transfer Suzuki-Miyaura coupling polymerization. (United States)

    Yokozawa, Tsutomu; Suzuki, Ryosuke; Nojima, Masataka; Ohta, Yoshihiro; Yokoyama, Akihiro


    (t)Bu(3) PPd(Ph)Br (1)-catalyzed Suzuki-Miyaura coupling polymerization of 2-(4-hexyl-5-iodo-2-thienyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2) was investigated. Monomer 2 was polymerized with 1 at 0 °C in the presence of CsF and 18-crown-6 in THF containing a small amount of water to yield P3HT with a narrow molecular weight distribution and almost perfect head-to-tail regioregularity. The M(n) values increased up to 11,400 g · mol(-1) in proportion to the feed ratio of 2 to 1. The MALDI-TOF mass spectra showed that P3HT with moderate molecular weight uniformly had a phenyl group at one end and a hydrogen atom at the other, indicating involvement of a catalyst-transfer mechanism. Successive 1-catalyzed polymerization of fluorene monomer 3 and then 2 yielded a well-defined block copolymer of polyfluorene and P3HT. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Preparation and controlled drug delivery applications of mesoporous silica polymer nanocomposites through the visible light induced surface-initiated ATRP (United States)

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


    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.

  18. synthesis of microporous polymers by frontal polymerization

    Indian Academy of Sciences (India)


    EGDM) copolymers of varying compositions were synthesized by free-radically triggered thermal frontal polymerization (FP) as well as by suspension polymerization (SP) using azobisisobutyronitrile [AIBN] as initiator. The two sets of copolymers.

  19. Functionalization and Polymerization on the CNT Surfaces

    KAUST Repository

    Albuerne, Julio


    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.

  20. Poly(lactic) acid fibers loaded with mesoporous silica for potential applications in the active food packaging (United States)

    Cacciotti, Ilaria; Nanni, Francesca


    Multifunctional fibrous systems based on poly(lactic) acid (PLA), mesoporous silica (SiO2) and ascorbic acid (AA) were produced by means of electrospinning technique, for potential applications in the active food packaging sector, as platform for the controlled release of antioxidant and/or antimicrobial agents with the additional filtering function. The ascorbic acid was physisorbed on the surface of mesoporous silica in order to stabilize it and to extend its antioxidant action. The influence of mesoporous silica and ascorbic acid on the microstructural and mechanical properties was investigated, revealing a revelant mechanical reinforcement in the case of fibers loaded only with SiO2 and a decrement in the case of SiO2 with physisorbed ascorbic acid, due to the worse interface between the fillers and the polymeric matrix.

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

    Directory of Open Access Journals (Sweden)

    Hiep Dinh Nguyen


    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. 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


    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.

  3. High-Yield Synthesis of Janus Dendritic Mesoporous Silica@Resorcinol-Formaldehyde Nanoparticles: A Competing Growth Mechanism. (United States)

    Qu, Lili; Hu, Huicheng; Yu, Jiaqi; Yu, Xiaoya; Liu, Jian; Xu, Yong; Zhang, Qiao


    Recently, Janus nanostructures that possess two or more different surface functions have attracted enormous attention because of their unique structures and promising applications in diverse fields. In this work, we present that Janus structured dendritic mesoporous silica@resorcinol-formaldehyde (DMS@RF) nanoparticles can be prepared through a simple one-pot colloidal method. The Janus DMS@RF nanoparticle shows a bonsai-like morphology which consists of a dendritic mesoporous silica part and a spherical RF part. After a systematic study on the growth process, we proposed a competing growth mechanism that accounts for the formation of Janus nanostructures. It is believed that suitable polymerization rate of silica and RF resin is critical. Based on the competing growth mechanism, eccentric and concentric core-shell nanostructures have been successfully prepared by tuning the polymerization rates of silica and RF, respectively. Metal-contained ternary Janus nanoparticles that might be used for catalysis have also been prepared. This research may pave the way for the practical applications of delicate nanomaterials with desired structures and properties.

  4. Polymerization of Polar Monomers from a Theoretical Perspective

    KAUST Repository

    Alghamdi, Miasser


    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

  5. Capillary thinning of polymeric filaments

    DEFF Research Database (Denmark)

    Kolte, Mette Irene; Szabo, Peter; Hassager, Ole


    The capillary thinning of a polymeric filament is analysed experimentally as well as by means of numerical simulation. The experimental procedure is as follows. Initially a liquid sample is kept between two cylindrical plates. Then the bottom plate is lowered under gravity to yield a given strain...

  6. Actin Polymerization and ATP Hydrolysis (United States)

    Korn, Edward D.; Carlier, Marie-France; Pantaloni, Dominique


    F-actin is the major component of muscle thin filaments and, more generally, of the microfilaments of the dynamic, multifunctional cytoskeletal systems of nonmuscle eukaryotic cells. Polymeric F-actin is formed by reversible noncovalent self-association of monomeric G-actin. To understand the dynamics of microfilament systems in cells, the dynamics of polymerization of pure actin must be understood. The following model has emerged from recent work. During the polymerization process, adenosine 5'-triphosphate (ATP) that is bound to G-actin is hydrolyzed to adenosine 5'-diphosphate (ADP) that is bound to F-actin. The hydrolysis reaction occurs on the F-actin subsequent to the polymerization reaction in two steps: cleavage of ATP followed by the slower release of inorganic phosphate (Pi). As a result, at high rates of filament growth a transient cap of ATP-actin subunits exists at the ends of elongating filaments, and at steady state a stabilizing cap of ADP \\cdot Pi-actin subunits exists at the barbed ends of filaments. Cleavage of ATP results in a highly stable filament with bound ADP \\cdot Pi, and release of Pi destabilizes the filament. Thus these two steps of the hydrolytic reaction provide potential mechanisms for regulating the monomer-polymer transition.

  7. Biodegradable polymeric prodrugs of naltrexone

    NARCIS (Netherlands)

    Bennet, D.B.; Li, X.; Adams, N.W.; Kim, S.W.; Hoes, C.J.T.; Hoes, C.J.T.; Feijen, Jan


    The development of a biodegradable polymeric drug delivery system for the narcotic antagonist naltrexone may improve patient compliance in the treatment of opiate addiction. Random copolymers consisting of the ¿-amino acids N5-(3-hydroxypropyl--glutamine and -leucine were synthesized with equimolar

  8. The effect of impeller type on silica sol formation in laboratory scale agitated tank (United States)

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


    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.

  9. Silica precipitation by synthetic minicollagens. (United States)

    Weiher, Felix; Schatz, Michaela; Steinem, Claudia; Geyer, Armin


    Oligomeric Pro-Hyp-Gly- (POG-) peptides, wherein the collagenous triple helix is supported by C-terminal capping, exhibit silica precipitation properties (O, Hyp = (2S,4R)hydroxyproline). As quantified by a molybdate assay, the length of the covalently tethered triple helix (number of POG units) determines the amount of amorphous silica obtained from silicic acid solution. Although lacking charged side chains, the synthetic collagens precipitate large quantities of silicic acid resulting in micrometer-sized spheres of varying surface morphologies as analyzed by scanning electron microscopy. Similar precipitation efficiencies on a fast time scale of less than 10 min were previously described only for biogenic diatom proteins and sponge collagen, respectively, which have a considerably higher structural complexity and limited accessibility. The minicollagens described here provide an unexpected alternative to the widely used precipitation conditions, which generally depend on (poly-)amines in phosphate buffer. Collagen can form intimate connections with inorganic matter. Hence, silica-enclosed collagens have promising perspectives as composite materials.

  10. Hollow microsphere with mesoporous shell by Pickering emulsion polymerization as a potential colloidal collector for organic contaminants in water. (United States)

    Guan, Yinyan; Meng, Xiaohui; Qiu, Dong


    Submicrometer hollow microspheres with mesoporous shells were prepared by a simple one-pot strategy. Colloidal silica particles were used as a particle stabilizer to emulsify the oil phase, which was composed of a polymerizable silicon monomer (TPM) and an inert organic solvent (PEA). The low interfacial tension between colloidal silica particles and TPM helped to form a Pickering emulsion with small droplet sizes. After the polymerization of TPM, the more hydrophobic PEA formed a liquid core, leading to a hollow structure after its removal by evaporation. BET results indicated that the shell of a hollow particle was mesoporous with a specific surface area over 400 m(2)·g(-1). With PEA as the core and silica as the shell, each resultant hollow particle had a hydrophobic cavity and an amphiphilic surface, thus serving as a good colloidal collector for hydrophobic contaminants in water.

  11. Preparations of spherical polymeric particles from Tanzanian ...

    African Journals Online (AJOL)

    Spherical Polymeric Particles (SPP) have been prepared from Tanzanian Cashew Nut Shell Liquid (CNSL) by suspension polymerization technique involving either step-growth or chain- growth polymerization mechanisms. The sizes of the SPP, which ranged from 0.1 to 2.0 mm were strongly influenced by the amounts of ...

  12. Sol-gel network silica/modified montmorillonite clay hybrid nanocomposites for hydrophobic surface coatings. (United States)

    Meera, Kamal Mohamed Seeni; Sankar, Rajavelu Murali; Murali, Adhigan; Jaisankar, Sellamuthu N; Mandal, Asit Baran


    Sol-gel silica/nanoclay composites were prepared through sol-gel polymerization technique using tetraethylorthosilicate precursor and montmorillonite (MMT) clay in aqueous media. In this study, both montmorillonite-K(+) and organically modified MMT (OMMT) clays were used. The prepared composites were coated on glass substrate by making 1 wt% solution in ethyltrichlorosilane. The incorporation of nanoclay does not alter the intensity of characteristic Si-O-Si peak of silica network. Thermogravimetric studies show that increasing clay content increased the degradation temperature of the composites. Differential scanning calorimetry (DSC) results of organically modified MMT nanoclay incorporated composite show a shift in the melting behavior up to 38°C. From DSC thermograms, we observed that the ΔH value decreased with increasing clay loading. X-ray diffraction patterns prove the presence of nanoclay in the composite and increase in the concentration of organically modified nanoclay from 3 to 5 wt% increases the intensity of the peak at 2θ=8° corresponds to OMMT. Morphology of the control silica gel composite was greatly influenced by the incorporation of OMMT. The presence of nanoclay changed the surface of control silica gel composite into cleaved surface with brittle in nature. Contact angle measurements were done for the coatings to study their surface behavior. These hybrid coatings on glass substrate may have applications for hydrophobic coatings on leather substrate. Copyright © 2011 Elsevier B.V. All rights reserved.

  13. Green binding material using alkali activated blast furnace slag with silica fume

    Directory of Open Access Journals (Sweden)

    Mohamad Sayed


    Full Text Available Recently million tons of cement is produced in Egypt accompanied with million tons of CO2 emission which causes annually negative impact on the environment. Granulated blast furnace slag and silica fume are produced as by-product from iron and chemical industries with limited recycling facility. This paper represents an experimental study aimed to safe ferrosilicon alloy of slag and silica fume to produce cementless binding material using both of Sodium Hydroxide and water glass liquid (Sodium Silicate as alkaline activator. Experimental program was designed to study silica/slag ratio, percentage of alkali activator, water/binding ratio, incorporation of superplasticizer, and curing condition on the properties of the produced binding material. Compressive strength and mineralogical analysis were conducted on the polymeric binding material to asses the effectiveness of the main variables. The tests were divided into two stages; in the first stage compressive strength was conducted for all mixes while X-ray, microscopic scan (SEM, and infrared analysis (IR were carried out for the most pronounced promising mixes. The results showed that ratio of 25% of silica/slag is the most effective ratio and 5% of each of Sodium Hydroxide and Sodium Silicate was the optimum percentage of the alkaline activator. Additionally the use of superplasticizer is essential as it positively reduces the mixing water and maintains the binding material with acceptable workability.

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

    Directory of Open Access Journals (Sweden)

    Mohammed Kadhom


    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.

  15. Synthesis of hollow silica nanosphere with high accessible surface area and their hybridization with carbon matrix for drastic enhancement of electrochemical property

    Energy Technology Data Exchange (ETDEWEB)

    Alam, Mohammad Mydul; Yamahana, Haruki [Department of Chemistry, Faculty of Science and Engineering, Saga University, 1 Honjo-machi, Saga 840-8502 (Japan); Bastakoti, Bishnu Prasad [World Premier International (WPI) Research Center for Materials Nanoarchitectonics (MANA), National Institute for Materials Science - NIMS, 1-1 Namiki, Tsukuba, Ibaraki 305-0044 (Japan); Luitel, Hom Nath; Zhao, Wenwen [Department of Chemistry, Faculty of Science and Engineering, Saga University, 1 Honjo-machi, Saga 840-8502 (Japan); Yamauchi, Yusuke [World Premier International (WPI) Research Center for Materials Nanoarchitectonics (MANA), National Institute for Materials Science - NIMS, 1-1 Namiki, Tsukuba, Ibaraki 305-0044 (Japan); Department of Nanoscience and Nanoengineering, Faculty of Science and Engineering, Waseda University, 3-4-1 Okubo, Shinjuku, Tokyo 169-8555 (Japan); Watari, Takanori; Noguchi, Hideyuki [Department of Chemistry, Faculty of Science and Engineering, Saga University, 1 Honjo-machi, Saga 840-8502 (Japan); Nakashima, Kenichi, E-mail: [Department of Chemistry, Faculty of Science and Engineering, Saga University, 1 Honjo-machi, Saga 840-8502 (Japan)


    Highlights: • Hollow silica nanosphere with large void space and high surface area is synthesized. • Carbon was doped into silica layer through glucose solution and resulting carbon/silica composite drastically enhanced electrochemical property. • Combination of core–shell–corona micelle template and doping method could be a new platform for developing functional materials. - Abstract: Hollow silica nanospheres with high accessible surface area have been synthesized by using core–shell–corona polymeric micelle of poly (styrene-b-2-vinyle pyridine-b-ethylene oxide) (PS45k-PVP26k-PEO82k) as a template. The size of the template polymeric micelle depends on the pH of the solution, i.e. ≈100 nm at pH 7 whereas ≈300 nm at pH 4. The enlarged size of the micelle is possibly due to the protonation of the PVP block, which also serves as reaction sites for silica precursor. The size of the obtained silica nanosphere measured with transmission electron microscope (TEM) is around ≈70 nm and shell thickness is ≈20 nm. Fourier transformed infrared spectroscopy (FTIR) data confirms that the polymer template is completely removed during calcination. Conductive carbon is doped into the silica nanosphere through glucose solution followed by hydrothermal treatment and pyrolysis. It is found that the electrochemical performance and stability of the silica nanosphere is dramatically enhanced after carbon doping. The combined strategy of the core–shell–corona micelle as template and carbon doping could represent a new platform for the researchers to develop functional nanomaterials.

  16. On the Complexity of Electrostatic Suspension Stabilization of Functionalized Silica Nanoparticles for Biotargeting and Imaging Applications

    Directory of Open Access Journals (Sweden)

    Lotta Bergman


    Full Text Available Different means of attaching streptavidin to surface functionalized silica particles with a diameter of 240 nm were investigated with special focus on suspension stability for electrostatically stabilized suspensions. The influence of two different fluorescent dyes covalently linked to the streptavidin on suspension stability was also studied. The results clearly show that the stability of the suspensions is crucially dependent on all functional groups present on the surface. The surface functions may either directly affect the effective surface charge if the functions contain charged groups, or indirectly by affecting the relative concentration of charged groups on the particle surface. Poly(ethylene imine-functionalized silica particles, where the polymer is grown by surface hyperbranching polymerization, are shown to be promising candidates for bioapplications, as the zeta-potential can remain strongly positive even under biologically relevant conditions.

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

    Directory of Open Access Journals (Sweden)

    Marcello Iacono


    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.

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

    KAUST Repository

    Guillois, Kevin


    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.

  19. Silica supported nickel catalysts : Tracer studies.


    Sharratt, Andrew Paul.


    A series of silica supported catalysts were prepared by impregnation of the support materials with a nickel(II) nitrate precursor under standard conditions. The catalysts and silicas were characterised using temperature programmed reduction (TPR) techniques, neutron diffraction, small angle neutron scattering, and 29Si magic angle spinning nuclear magnetic resonance (MAS-NMR). These analyses revealed one significant variable in the silicas:- the surface concentration of strained siloxane ring...

  20. Mesoporous Silica: A Suitable Adsorbent for Amines

    Directory of Open Access Journals (Sweden)

    Abdollahzadeh-Ghom Sara


    Full Text Available Abstract Mesoporous silica with KIT-6 structure was investigated as a preconcentrating material in chromatographic systems for ammonia and trimethylamine. Its adsorption capacity was compared to that of existing commercial materials, showing its increased adsorption power. In addition, KIT-6 mesoporous silica efficiently adsorbs both gases, while none of the employed commercial adsorbents did. This means that KIT-6 Mesoporous silica may be a good choice for integrated chromatography/gas sensing micro-devices.

  1. Preparations of bifunctional polymeric beads simultaneously incorporated with fluorescent quantum dots and magnetic nanocrystals

    International Nuclear Information System (INIS)

    Tu Chifeng; Yang Yunhua; Gao Mingyuan


    Bifunctional polystyrene beads simultaneously incorporated with fluorescent CdTe quantum dots (Q-dots) and superparamagnetic Fe 3 O 4 nanocrystals were prepared by a modified mini-emulsion polymerization method, in which polymerizable surfactants were used as both phase transfer agent for aqueous colloidal nanoparticles and emulsifier. In addition, silica coating was also introduced to Fe 3 O 4 nanocrystals for regulating the internal structure of the composite beads. Transmission electron microscopy, confocal fluorescence microscopy and conventional spectroscopy were used to characterize the composite beads, as well as the polymerizable surfactant-coated CdTe Q-dots and silica-coated Fe 3 O 4 nanoparticles. Different mixing methods were also attempted in order to vary the size of the resultant bifunctional beads

  2. Cellular membrane trafficking of mesoporous silica nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Fang, I-Ju [Iowa State Univ., Ames, IA (United States)


    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

  3. Airborne silica levels in an urban area

    Energy Technology Data Exchange (ETDEWEB)

    De Berardis, B. [Dipartimento di Tecnologie e Salute, Istituto Superiore di Sanita, Viale Regina Elena, 299, 00161 Rome (Italy)]. E-mail:; Incocciati, E. [CONTARP Consulenza Tecnica Accertamento Rischi e Prevenzione, INAIL Direzione Generale, 00143 Rome (Italy); Massera, S. [CONTARP Consulenza Tecnica Accertamento Rischi e Prevenzione, INAIL Direzione Generale, 00143 Rome (Italy); Gargaro, G. [CONTARP Consulenza Tecnica Accertamento Rischi e Prevenzione, INAIL Direzione Generale, 00143 Rome (Italy); Paoletti, L. [Dipartimento di Tecnologie e Salute, Istituto Superiore di Sanita, Viale Regina Elena, 299, 00161 Rome (Italy)


    In order to evaluate the exposure levels of the general population we studied the concentrations of silica particles in the inhalable particulate fraction (PM10) in different meteorological-climate periods in an urban area of Rome. In order to determine the concentration and the granulometric spectrum of silica particles, PM10 sampled by a cascade impactor was analysed by X-ray diffractometry (XRD) and by scanning electron microscopy equipped with a thin-window system for X-ray microanalysis (SEM/EDX). Over the period September 2004-October 2005 the abundance of silica particles as evaluated by SEM/EDX ranged from 1.6 to 10.4% of the total PM10 particulate, with a weight concentration of free crystalline silica, evaluated by XRD, in the range 0.25-2.87 {mu}g/m{sup 3}. The mean diameter of silica particles ranged from 0.3 to 10.5 {mu}m, with more than 87% of particles having a diameter of less than 2.5 {mu}m. The correlations between SEM/EDX and XRD data seem to suggest that the airborne silica particles in the urban location studied were mainly in the form crystalline silica. A strong relationship was found between the meteorological-climate conditions and the concentration level of free crystalline silica. This result suggests that the Southern winds from the Sahara desert carry an important amount of silica particles into Mediterranean Europe.

  4. Nanoporous silica membranes with high hydrothermal stability

    DEFF Research Database (Denmark)

    Boffa, Vittorio; Magnacca, Giualiana; Yue, Yuanzheng

    Despite the use of sol-gel derived nanoporous silica membranes in substitution of traditional separation processes is expected leading to vast energy savings, their intrinsic poor steam-stability hampers their application at an industrial level. Transition metal ions can be used as dopant...... to improve the stability of nanoporous silica structure. This work is a quantitative study on the impact of type and concentration of transition metal ions on the microporous structure and stability of amorphous silica-based membranes, which provides information on how to design chemical compositions...... and synthetic paths for the fabrication of silica-based membranes with a well accessible and highly stabile nanoporous structure...

  5. Oil absorption in mesoporous silica particles

    Directory of Open Access Journals (Sweden)

    Radislav Filipović


    Full Text Available Mesoporous silica particles were prepared from highly basic sodium silicate solutions, having different silica modulus and SiO2 concentrations, by adding sulphuric acid at different temperatures. Pore structure of prepared silica particles (aggregates is strongly influenced by processing conditions and easy controllable in broad range of the specific surface area, pore size, pore volume and size distribution. It is shown that there is a clear correlation between volume of absorbed oil and processing parameters used in preparation of silica aggregates. Thus, oil absorption is higher in the samples prepared from sodium silicate solution with higher SiO2 concentration and at higher synthesis temperature.

  6. Practical Hydrogen Loading of Air Silica Fibres

    DEFF Research Database (Denmark)

    Sørensen, Henrik Rokkjær; Jensen, Jesper Bevensee; Jensen, Jesper Bo Damm


    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....

  7. Expanded corn starch as a versatile material in atom transfer radical polymerization (ATRP) of styrene and methyl methacrylate. (United States)

    Bansal, Ankushi; Kumar, Arvind; Latha, Patnam Padma; Ray, Siddharth Sankar; Chatterjee, Alok Kumar


    Polymerization of styrene (St) and methyl methacrylate (MMA) was performed by surface initiated (SI) and activator generated by electron transfer (AGET) systems of atom transfer radical polymerization (ATRP) using renewable expanded corn starch (ECS) as a support. This prepared ECS is found to have V type crystallinity with 50 m(2)g(-1) surface area (<1m(2)g(-1) for corn starch (CS)) and average pore volume of 0.43 cm(3)g(-1) (<0.1cm(3)g(-1) for CS). In SI-ATRP, hydroxyl groups on ECS were converted into macro-initiator by replacing with 2-bromoisobutyryl bromide (BIBB) with a 0.06 degree of substitution determined from NMR. In AGET-ATRP, CuBr2/ligand complex get adsorbed on ECS (Cu(II)/ECS=10 wt.%) to catalyze the polymerization. Synthesized PS/PMMA was characterized by SEM, FT-IR, (1)H NMR. Copyright © 2015 Elsevier Ltd. All rights reserved.

  8. 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)


    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)

  9. 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.


    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...... is attractive because it should ensure good dispersion of LDH in the polymer. The effect of adding either LDH carbonate (LDH-CO3) or laurate-modified LDH (LDH-C12) was investigated. X-ray diffraction, scanning electron microscopy, and transmission electron microscopy revealed that exfoliated nanocomposites were...... 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....

  10. Synthesis of hollow silica nanosphere with high accessible surface area and their hybridization with carbon matrix for drastic enhancement of electrochemical property (United States)

    Alam, Mohammad Mydul; Yamahana, Haruki; Bastakoti, Bishnu Prasad; Luitel, Hom Nath; Zhao, Wenwen; Yamauchi, Yusuke; Watari, Takanori; Noguchi, Hideyuki; Nakashima, Kenichi


    Hollow silica nanospheres with high accessible surface area have been synthesized by using core-shell-corona polymeric micelle of poly (styrene-b-2-vinyle pyridine-b-ethylene oxide) (PS45k-PVP26k-PEO82k) as a template. The size of the template polymeric micelle depends on the pH of the solution, i.e. ≈100 nm at pH 7 whereas ≈300 nm at pH 4. The enlarged size of the micelle is possibly due to the protonation of the PVP block, which also serves as reaction sites for silica precursor. The size of the obtained silica nanosphere measured with transmission electron microscope (TEM) is around ≈70 nm and shell thickness is ≈20 nm. Fourier transformed infrared spectroscopy (FTIR) data confirms that the polymer template is completely removed during calcination. Conductive carbon is doped into the silica nanosphere through glucose solution followed by hydrothermal treatment and pyrolysis. It is found that the electrochemical performance and stability of the silica nanosphere is dramatically enhanced after carbon doping. The combined strategy of the core-shell-corona micelle as template and carbon doping could represent a new platform for the researchers to develop functional nanomaterials.

  11. Ring opening metathesis polymerization catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Grubbs, R.H.; Johnson, L.K.; Novak, B.M.; Hillmyer, M.; Benedicto, A.; France, M.; Nguyen, S.T. [California Institute of Technology, Pasadena, CA (United States)


    Over the past eight years, a number of new catalysts for the ring opening metathesis polymerization of cyclic olefins have been developed. These catalysts are simple organometallic complexes containing metal carbon multiple bonds that in most cases polymerize olefins by a living process. These catalysts have been used to prepare a family of near monodispersed and structurally homogeneous polymers, a series of telechelic polymers with controlled molecular weight and functionality and triblock polymers with segments with potentially interesting electronic properties. A series of new group VIII catalysts are being developed that allow a wide range of functionality to be incorporated into the polymer side chains. The same catalysts can also be used in the synthesis of fine chemicals.


    Directory of Open Access Journals (Sweden)



    Full Text Available Here, of great interest to us is a quantitative study of the scattering properties from ramified polymeric systems of arbitrary topology. We consider three types of systems, namely ramified polymers in solution, ramified polymer blends, or ternary mixtures made of two ramified polymers of different chemical nature immersed in a good solvent. To achieve the goal of the study, use is made of the Random Phase Approximation. First we determine the exact expression of the form factor of an ideal ramified polymer of any topology, from which we extract the exact expression of its gyration radius. Using the classical Zimm's formulae and the exact form factor, we determine all scattering properties of these three types of ramified polymeric systems. The main conclusion is that ramification of the chains induces drastic changes of the scattering properties.

  13. Polymerization catalyst, production and use

    International Nuclear Information System (INIS)

    Best, S.A.


    A process is described for the polymerization of ethylene and alpha-olefins having from 1 to 2 carbon atoms of mixtures of ethylene, alpha-olefins or diolefins. The process comprises polymerizing one or more olefins in the presence of the catalyst system comprising (A) an organo aluminum cocatalyst, and (B) a vanadium-containing catalyst component obtained by sequentially treating an inert solid support material in an inert solvent with (i) a dihydrocarbyl magnesium compound, (ii) optionally an oxygen-containing compound which is an alcohol, ketone or aldehyde, (iii) a vanadium compound, and (iv) a Group IIIa metal halide. The process as above is described wherein the inert solid support material is an inorganic oxide or mixtures of inorganic oxides

  14. Sleeving nanocelluloses by admicellar polymerization. (United States)

    Trovatti, Eliane; Ferreira, Adriane de Medeiros; Carvalho, Antonio José Felix; Ribeiro, Sidney José Lima; Gandini, Alessandro


    This investigation reports the first application of admicellar polymerization to cellulose nanofibers in the form of bacterial cellulose, microfibrillated cellulose, and cellulose nanowhiskers using styrene and ethyl acrylate. The success of this physical sleeving was assessed by SEM, FTIR, and contact angle measurements, providing an original and simple approach to the modification of cellulose nanofibers in their pristine aqueous environment. Copyright © 2013 The Authors. Published by Elsevier Inc. All rights reserved.

  15. Polymeric Microspheres for Medical Applications

    Directory of Open Access Journals (Sweden)

    Ketie Saralidze


    Full Text Available Synthetic polymeric microspheres find application in a wide range of medical applications. Among other applications, microspheres are being used as bulking agents, embolic- or drug-delivery particles. The exact composition of the spheres varies with the application and therefore a large array of materials has been used to produce microspheres. In this review, the relation between microsphere synthesis and application is discussed for a number of microspheres that are used for different treatment strategies.

  16. Microwave-assisted ADMET polymerization


    Rojas Jiménez, Giovanni


    Microwave-assisted ADMET polymerization is reported on a series of α,ω-diene monomers, both polar and non-polar. Investigations indicate that of the multiple microwave modes possible, constant power is the most advantageous, providing polymers up to M‾w=31,000g/mol. Molecular weight values are nearly triple in comparison with conventional oil bath heating. Polymers are characterized by NMR, GPC, TGA, and DSC. Microwave irradiation provides a highly controllable and energy efficient ADMET poly...

  17. Copper-catalyzed azide alkyne cycloaddition polymer networks (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

  18. Non-equilibrium supramolecular polymerization. (United States)

    Sorrenti, Alessandro; Leira-Iglesias, Jorge; Markvoort, Albert J; de Greef, Tom F A; Hermans, Thomas M


    Supramolecular polymerization has been traditionally focused on the thermodynamic equilibrium state, where one-dimensional assemblies reside at the global minimum of the Gibbs free energy. The pathway and rate to reach the equilibrium state are irrelevant, and the resulting assemblies remain unchanged over time. In the past decade, the focus has shifted to kinetically trapped (non-dissipative non-equilibrium) structures that heavily depend on the method of preparation (i.e., pathway complexity), and where the assembly rates are of key importance. Kinetic models have greatly improved our understanding of competing pathways, and shown how to steer supramolecular polymerization in the desired direction (i.e., pathway selection). The most recent innovation in the field relies on energy or mass input that is dissipated to keep the system away from the thermodynamic equilibrium (or from other non-dissipative states). This tutorial review aims to provide the reader with a set of tools to identify different types of self-assembled states that have been explored so far. In particular, we aim to clarify the often unclear use of the term "non-equilibrium self-assembly" by subdividing systems into dissipative, and non-dissipative non-equilibrium states. Examples are given for each of the states, with a focus on non-dissipative non-equilibrium states found in one-dimensional supramolecular polymerization.

  19. Characteristics of zinc sulphide nanostructures grown onsilica modified-polyaniline with polymerization time-dependent (United States)

    Potestas, M.; Alguno, A.; Vequizo, R.; Sambo, B. R.; Odarve, M. K.


    Growth of zinc sulphide (ZnS) nanostructures on silica modified-polyaniline (SM- PAni) with polymerization time-dependent was prepared using chemical bath deposition (CBD) technique. The grown samples were characterized by scanning electron microscopy (SEM) equipped with energy dispersive x-ray spectroscopy (EDS) and fourier transform infrared spectroscopy (FTIR). SEM images revealed that polyaniline rod-like nanostructures and ZnS nanospheres were successfully grown. The average diameter of the grown ZnS nanospheres did not significantly change by changing the growth time of the polyaniline. However, ZnS nanospheres grown with longer polymerization time of PAni is less dense and loosely bound as compared to shorter polymerization time of PAni. The less density of ZnS nanostructures with longer polymerization time of PAni may be due to the presence of PAni agglomerates that hinders the growth of ZnS nanospheres. Furthermore, FTIR spectra confirmed that the grown polyaniline is of emeraldine salt oxidation state which is the most conductive state of PAni.

  20. Palladium catalyzed hydrogenation of bio-oils and organic compounds (United States)

    Elliott, Douglas C [Richland, WA; Hu, Jianli [Kennewick, WA; Hart, Todd R [Kennewick, WA; Neuenschwander, Gary G [Burbank, WA


    The invention provides palladium-catalyzed hydrogenations of bio-oils and certain organic compounds. Experimental results have shown unexpected and superior results for palladium-catalyzed hydrogenations of organic compounds typically found in bio-oils.

  1. Enyne Metathesis Catalyzed by Ruthenium Carbene Complexes

    DEFF Research Database (Denmark)

    Poulsen, Carina Storm; Madsen, Robert


    Enyne metathesis combines an alkene and an alkyne into a 1,3-diene. The first enyne metathesis reaction catalyzed by a ruthenium carbene complex was reported in 1994. This review covers the advances in this transformation during the last eight years with particular emphasis on methodology...

  2. Biodiesel production by enzyme-catalyzed transesterification

    Directory of Open Access Journals (Sweden)

    Stamenković Olivera S.


    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.

  3. Enzyme-Catalyzed Transetherification of Alkoxysilanes

    Directory of Open Access Journals (Sweden)

    Peter G. Taylor


    Full Text Available We report the first evidence of an enzyme-catalyzed transetherification of model alkoxysilanes. During an extensive enzymatic screening in the search for new biocatalysts for silicon-oxygen bond formation, we found that certain enzymes promoted the transetherification of alkoxysilanes when tert-butanol or 1-octanol were used as the reaction solvents.

  4. Muon catalyzed fusion under compressive conditions

    International Nuclear Information System (INIS)

    Cripps, G.; Goel, B.; Harms, A.A.


    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

  5. 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


    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

  6. Silica gel matrix immobilized Chlorophyta hydrodictyon africanum ...

    African Journals Online (AJOL)



    Aug 5, 2015 ... immobilization of 300 mg per gram silica. Maximum immobilization was 400 mg biomass per gram silica. Sorption capacity increased with an increase in initial dye concentration and reached equilibrium within. 30 min. Three models were used to simulate kinetic data and the pseudo–second order model ...

  7. Subclinical nephrotoxicity associated with occupational silica ...

    African Journals Online (AJOL)

    Objective: To determine early signs of renal injury due to occupational silica exposure. Design: Cross-sectional analytical research. Settings: Kenyatta National Hospital for the referent population and Clayworks ceramics, bricks and tiles factory for the assessment of occupational silica exposure. Subjects: Thirty three ...

  8. Medium-range order in metamict silicas

    International Nuclear Information System (INIS)

    Qin, L.C.; Hobbs, L.W.


    The first sharp diffraction peak from various forms of aperiodic silica was studied. Materials examined include vitreous silica, electron-metallic quartz, neutron-metallic quartz, and Si + ion-implanted quartz. The peak is attributed to the dominant structural rings existing in the materials, or modification thereof. The anomalous behavior of this peak is also discussed

  9. Bioinspired synthesis of new silica structures. (United States)

    Patwardhan, Siddharth V; Mukherjee, Niloy; Steintz-Kannan, Miriam; Clarson, Stephen J


    Silicon and oxygen are the two most abundant elements in the Earth's crust but despite the vast scientific literature on crystalline and amorphous silica, new chemistries, structures and applications continue to be discovered for compounds formed from these elements--thus we present here for the first time the formation of new amorphous silica structures that were uniquely synthesized by a bioinspired synthetic system.

  10. Silica gel matrix immobilized Chlorophyta hydrodictyon africanum ...

    African Journals Online (AJOL)

    Chlorophyta hydrodictyon africanum was immobilized on a silica gel matrix to improve its mechanical properties. The algae-silica gel adsorbent was used for batch sorption studies of a cationic dye, methylene blue (MB). Optimum adsorption was obtained with a dosage of 0.8 g bio sorbent. Results from sorption studies ...

  11. Active and passive silica waveguide integration

    DEFF Research Database (Denmark)

    Hübner, Jörg; Guldberg-Kjær, Søren Andreas


    in existing and future networks without affecting the power budget of the system. Silica on silicon technology offers a unique possibility to selectively dope sections of the integrated circuit with erbium where amplification is desired. Some techniques for active/passive integration are reviewed and a silica...

  12. Magnetic core-shell silica particles

    NARCIS (Netherlands)

    Claesson, E.M.


    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

  13. FTIR thermal analysis on organofunctionalized silica gel

    Directory of Open Access Journals (Sweden)

    Foschiera José L.


    Full Text Available Silica gel modified with organic groups is widely used as a stationary phase for liquid chromatography. Grafting synthesis can be used to obtain stable modified silica gel surfaces. In this work, silica gel (10 nm of pore diameter and surface area of 320 m² g-1 was chemically modified with 3-chloropropyltrimethoxysilane or 3-aminopropyltrimethoxysilane and reacted with aniline, p-anisidine, benzylamine and 3-phenylpropylchloride in order to yield aromatic groups immobilized on the silica gel surface. Infrared spectroscopy was utilized for characterization of the aromatic groups grafted on the silica gel surface, using a quartz cell. The solids were heated at several temperatures in high vacuum and the infrared band areas of the organic groups were used to evaluate the thermal stability.

  14. The Pozzolanic reaction of silica fume

    DEFF Research Database (Denmark)

    Jensen, Ole Mejlhede


    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...... of activation of the pozzolanic reaction of silica fume is estimated. The results show that the pozzolanic reaction of silica fume has notable differences from Portland cement hydration....

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

    International Nuclear Information System (INIS)

    Wang Haifeng; Gao Yan; Lin Zhenquan


    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

  16. In situ visualization and effect of glycerol in lipase-catalyzed ethanolysis of rapeseed oil

    DEFF Research Database (Denmark)

    Xu, Yuan; Nordblad, Mathias; Nielsen, Per M.


    Immobilized lipases can be used in biodiesel production to overcome many disadvantages of the conventional base-catalyzed process. However, the glycerol by-product poses a potential problem for the biocatalytic process as it is known to inhibit immobilized lipases, most likely by clogging...... of the catalyst particles. In this paper, this negative effect was further investigated and confirmed in ethanolysis of rapeseed oil. A dyeing method was developed for in situ visualization of glycerol in order to study its partitioning and accumulation during the ethanolysis reaction. The method was used...... to illustrate the interaction of glycerol with immobilized lipases and thus provided an aid for screening supports for lipase immobilization according to their interaction with glycerol. Glycerol was found to have great affinity for silica, less for polystyrene and no affinity for supports made from...

  17. Selective side-chain oxidation of alkyl aromatic compounds catalyzed by cerium modified silver catalysts

    DEFF Research Database (Denmark)

    Beier, Matthias Josef; Schimmoeller, Bjoern; Hansen, Thomas Willum


    . In addition, flame-made catalysts were more stable against silver leaching compared to the impregnated catalysts. The structure of the silver catalysts was studied in detail both by X-ray absorption spectroscopy and transmission electron microscopy suggesting metallic silver to be required for catalytic......Silver supported on silica effectively catalyzes the aerobic side-chain oxidation of alkyl aromatic compounds under solvent-free conditions. Toluene, p-xylene, ethylbenzene and cumene were investigated as model substrates. Typically, the reaction was performed at ambient pressure; only for toluene...... an elevated pressure was required. Carboxylic acids, such as benzoic acid or p-toluic acid, additionally increased the reaction rate while CeO2 could act both as a promoter and an inhibitor depending on the substrate and the reaction conditions. Silver catalysts were prepared both by standard impregnation...

  18. Patchy micelles based on coassembly of block copolymer chains and block copolymer brushes on silica particles. (United States)

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


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

  19. Development and characterization of stabilized, polymerized ...

    Indian Academy of Sciences (India)

    It is shown that 6xHis-EGFP interacts with (poly)bis-SorbPC/DOGS-NTA-Ni2+ coated silica and this interaction was interrupted by washing with imidazole indicating the reversibility of the interaction. No interaction was observed between the functionalized silica substrate and EGFP, which lacks the 6xHis-tag. Furthermore ...

  20. Dispersion Polymerizations in Supercritical Carbon Dioxide (United States)

    Desimone, J. M.; Maury, E. E.; Menceloglu, Y. Z.; McClain, J. B.; Romack, T. J.; Combes, J. R.


    Conventional heterogeneous dispersion polymerizations of unsaturated monomers are performed in either aqueous or organic dispersing media with the addition of interfacially active agents to stabilize the colloidal dispersion that forms. Successful stabilization of the polymer colloid during polymerization results in the formation of high molar mass polymers with high rates of polymerization. An environmentally responsible alternative to aqueous and organic dispersing media for heterogeneous dispersion polymerizations is described in which supercritical carbon dioxide (CO_2) is used in conjunction with molecularly engineered free radical initiators and amphipathic molecules that are specifically designed to be interfacially active in CO_2. Conventional lipophilic monomers, exemplified by methyl methacrylate, can be quantitatively (>90 percent) polymerized heterogeneously to very high degrees of polymerization (>3000) in supercritical CO_2 in the presence of an added stabilizer to form kinetically stable dispersions that result in micrometer-sized particles with a narrow size distribution.

  1. Rearrangement of micelle structures during polymerization

    International Nuclear Information System (INIS)

    Chatjaroenporn, K.; Baker, R.; FitzGerald, P.; Warr, G.


    Full text: Using small angle neutron scattering (SANS), we studied the shape transition of micelles of 11(methacryloyloxy)undecyltrimethylammonium bromide (MUTAB) as this tail-polymerisable cationic surfactant polymerized. Previous studies of such systems have suggested kinetic 'locking' of the micelle structure during polymerization. However, we found a transition from spheres (unpolymerised) to rods (at intermediate conversions) back to spheres (fully polymerized), see Figure 1. By comparing these results to the micelle shapes formed by the mixtures of 100% polymerized and unpolymerised MUTAB, we show that the shape transitions observed during polymerization are due to equilibrium structures that undergo rearrangement as the composition changes. In addition, atomic force microscopy (AFM) reveals that besides the monolayer of unpolymerised MUTAB, the rearranged structures of this surfmer in bulk, when polymerization proceeded, retained their shapes after adsorbing at mica/solution interface, providing potential for the manipulating of thin film structures. This understanding assists design of templating or encapsulating nanostructured materials.

  2. Thermal conductivity of pressure polymerized C60

    International Nuclear Information System (INIS)

    Soldatov, A.; Andersson, O.


    We have studied the kinetics of C 60 polymerization in the temperature interval 450-500 K at pressures below 1 GPa by measurements of the time dependence of the thermal conductivity. It has been found at 450 K that the polymerization process at 0.8 GPa is slower than the reverse transformation from ''polymeric'' to ''monomeric'' phase at 0.08 GPa. The thermal conductivity λ of polymerized C 60 was measured in the temperature range 100-430 K and found to increase with increasing temperature, which reflects strong phonon scattering. Both the presence of non-bonded C 60 molecules and a high degree of structural disorder in the crystalline lattice of the polymeric phase might be responsible for the behaviour of λ(T). The results for λ(T) are qualitatively similar to those reported previously for C 60 polymerized at higher p, T but an order of magnitude smaller. (orig.)

  3. Effect of silica coating and silane surface treatment on the bond strength of soft denture liner to denture base material. (United States)

    Atsü, Saadet; Keskın, Yasemin


    This study investigated the effects of different surface treatments on the tensile bond strength of an autopolymerizing silicone denture liner to a denture base material after thermocycling. Fifty rectangular heat-polymerized acrylic resin (QC-20) specimens consisting of a set of 2 acrylic blocks were used in the tensile test. Specimens were divided into 5 test groups (n=10) according to the bonding surface treatment as follows: Group A, adhesive treatment (Ufi Gel P adhesive) (control); Group S, sandblasting using 50-µm Al2O3; Group SCSIL, silica coating using 30-µm Al2O3 modified by silica and silanized with silane agent (CoJet System); Group SCA, silica coating and adhesive application; Group SCSILA, silica coating, silane and adhesive treatment. The 2 PMMA blocks were placed into molds and the soft lining materials (Ufi Gel P) were packed into the space and polymerized. All specimens were thermocycled (5,000 cycles) before the tensile test. Bond strength data were analyzed using 1-way ANOVA and Duncan tests. Fracture surfaces were observed by scanning electron microscopy. X-ray photoelectron spectrometer (XPS) and Fourier Transform Infrared spectrometer (FTIR) analysis were used for the chemical analysis and a profilometer was used for the roughness of the sample surfaces. The highest bond strength test value was observed for Group A (1.35±0.13); the lowest value was for Group S (0.28±0.07) and Group SCSIL (0.34±0.03). Mixed and cohesive type failures were seen in Group A, SCA and SCSILA. Group S and SCSIL showed the least silicone integrations and the roughest surfaces. Sandblasting, silica coating and silane surface treatments of the denture base resin did not increase the bond strength of the silicone based soft liner. However, in this study, the chemical analysis and surface profilometer provided interesting insights about the bonding mechanism between the denture base resin and silicone soft liner.

  4. Chalcedony (a crystalline variety of silica): biogenic origin in electric organs from living Psammobatis extenta (family Rajidae). (United States)

    Prado Figueroa, María; Barrera, Facundo; Cesaretti, Nora N


    The electric organs of electric fish have been used extensively for the study of peripheral cholinergic synapses. Aluminum and silicon have been observed in the electrocytes of Psammobatis extenta, a fish belonging to the family Rajidae, using a combination of scanning electron microscopy and X-ray spectrometry. Based on this evidence, the presence of silica minerals has been documented by means of mineralogical techniques. Electric organ cryostat sections and subcellular fractions were observed using a Leica DMLP mineralogical microscope. The shape, size and color, among other properties, were analyzed in plane-polarized light, while birefringence and the extinction angle, which allow for mineral identification, were observed through crossed-polarized illumination. The distribution of chalcedony, an oxide silicon mineral, in the sections and all the fractions of the electric organ was recorded. X-ray diffraction analysis of the electric organ segments showed a similar result, with a low-quartz variety. Chalcedony precipitation occurred at a specific pH (7-8) and oxidation potential (Eh; 0.0 to -0.2). This observation supports the important role played by pH and Eh conditions in silica precipitation in electrocytes, as has been reported in geological environments. It is possible that silica formation and silica degradation in electric organs are also related to the enzymes, silicatein and silicase, that direct the polymerization and depolymerization of amorphous silica in sponges. Carbonic anhydrases (silicase) are involved in physiological pH regulation. Crystallization of chalcedony via spiral growth from a partially polymerized fluid is consistent with processes known to occur in organic systems. This is the first time that a biogenically produced crystalline mineral phase (i.e., chalcedony) has been observed in the electrocytes and cholinergic nerves from living electric fish.

  5. Morphological Control of Multifunctional Mesoporous Silica Nanomaterials for Catalysis Applications

    Energy Technology Data Exchange (ETDEWEB)

    Huh, Seong [Iowa State Univ., Ames, IA (United States)


    I found an efficient method to control the morphology of the organically monofunctionalized mesoporous silica materials by introducing different types of organoalkoxysilanes in a base-catalyzed co-condensation reaction. The monofunctionalized materials exhibit different particle morphologies relative to the pure MCM-41 material. The concentration dependence of the morphology is a critical factor to determine the final particle shape. A proposed mechanism of the shape evolution is also offered. After understanding the role of organoalkoxysilanes in producing various well-shaped nanomaterials, I also obtained a series of bifunctional mesoporous silica materials with certain particle morphology. A series of bifunctional mesoporous silica nanospheres (MSNs) whose physicochemical properties was investigated via solid state NMR techniques and Cu2+ adsorption capacity tests, The ratio of two different organic groups inside of mesopores of these MSNs could be fine-tuned. These MSNs serve as a useful model system to study substrate selectivity in catalytic reactions and sorption phenomena. For example, the Cu2+ adsorption capacity of these materials was dictated by the chemical nature of the mesopores generated by the different organic functional groups. An investigation of the substrate selectivity of the bifunctionalized MSNs in a competitive nitroaldol reaction using an equimolar amount of two competing 4-nitrobenzaldehyde derivatives was performed. Shape-controlled bifunctional MSNs were employed as the catalysts. The properties of the MSNs were investigated using various spectroscopic methods and electron microscopy. The more hydrophobic the surface organic groups are, the higher the ratio of hydrophobic final product. This is the first example to demonstrate the selection of substrate using physicochemical nature of the mesopore surface other than the conventional shape selection in zeolite systems. I also created a cooperative dual catalyst

  6. Morphological control of multifunctionalized mesoporous silica nanomaterials for catalysis applications (United States)

    Huh, Seong

    I found an efficient method to control the morphology of the organically monofunctionalized mesoporous silica materials by introducing different types of organoalkoxysilanes in a base-catalyzed co-condensation reaction. The monofunctionalized materials exhibit different particle morphologies relative to the pure MCM-41 material. The concentration dependence of the morphology is a critical factor to determine the final particle shape. A proposed mechanism of the shape evolution is also offered. After understanding the role of organoalkoxysilanes in producing various well-shaped nanomaterials, I also obtained a series of bifunctional mesoporous silica materials with certain particle morphology. A series of bifunctional mesoporous silica nanospheres (MSNs) whose physicochemical properties was investigated via solid state NMR techniques and Cu 2+ adsorption capacity tests. The ratio of two different organic groups inside of mesopores of these MSNs could be fine-tuned. These MSNs serve as a useful model system to study substrate selectivity in catalytic reactions and sorption phenomena. For example, the Cu2+ adsorption capacity of these materials was dictated by the chemical nature of the mesopores generated by the different organic functional groups. An investigation of the substrate selectivity of the bifunctionalized MSNs in a competitive nitroaldol reaction using an equimolar amount of two competing 4-nitrobenzaldehyde derivatives was performed. Shape-controlled bifunctional MSNs were employed as the catalysts. The properties of the MSNs were investigated using various spectroscopic methods and electron microscopy. The more hydrophobic the surface organic groups are, the higher the ratio of hydrophobic final product. This is the first example to demonstrate the selection of substrate using physicochemical nature of the mesopore surface other than the conventional shape selection in zeolite systems. I also created a cooperative dual catalyst system that is capable of

  7. Polymeric Micelles for Acyclovir Drug Delivery


    Sawdon, Alicia J.; Peng, Ching-An


    Polymeric prodrug micelles for delivery of acyclovir (ACV) were synthesized. First, ACV was used directly to initiate ring-opening polymerization of ε-caprolactone to form ACV-polycaprolactone (ACV-PCL). Through conjugation of hydrophobic ACV-PCL with hydrophilic methoxy poly(ethylene glycol) (MPEG) or chitosan, polymeric micelles for drug delivery were formed. 1H NMR, FTIR, and gel permeation chromatography were employed to show successful conjugation of MPEG or chitosan to hydrophobic ACV-P...

  8. Nanoporous Polymeric Grating-Based Biosensors

    KAUST Repository

    Gao, Tieyu


    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. Volumetric polymerization shrinkage of contemporary composite resins


    Nagem Filho, Halim; Nagem, Haline Drumond; Francisconi, Paulo Afonso Silveira; Franco, Eduardo Batista; Mondelli, Rafael Francisco Lia; Coutinho, Kennedy Queiroz


    The polymerization shrinkage of composite resins may affect negatively the clinical outcome of the restoration. Extensive research has been carried out to develop new formulations of composite resins in order to provide good handling characteristics and some dimensional stability during polymerization. The purpose of this study was to analyze, in vitro, the magnitude of the volumetric polymerization shrinkage of 7 contemporary composite resins (Definite, Suprafill, SureFil, Filtek Z250, Fill ...

  10. Lipase immobilization for catalytic applications obtained using fumed silica deposited with MAPLE technique (United States)

    Bloisi, Francesco; Califano, Valeria; Perretta, Giuseppe; Nasti, Libera; Aronne, Antonio; Di Girolamo, Rocco; Auriemma, Finizia; De Rosa, Claudio; Vicari, Luciano R. M.


    Lipases are enzymes used for catalyzing reactions of acylglycerides in biodiesel production from lipids, where enzyme immobilization on a substrate is required. Silica nanoparticles in different morphologies and configurations are currently used in conjunction with biological molecules for drug delivery and catalysis applications, but up to date their use for triglycerides has been limited by the large size of long-chain lipid molecules. Matrix assisted pulsed laser evaporation (MAPLE), a laser deposition technique using a frozen solution/suspension as a target, is widely used for deposition of biomaterials and other delicate molecules. We have carried out a MAPLE deposition starting from a frozen mixture containing fumed silica and lipase in water. Deposition parameters were chosen in order to increase surface roughness and to promote the formation of complex structures. Both the target (a frozen thickened mixture of nanoparticles/catalyst in water) and the deposition configuration (a small target to substrate distance) are unusual and have been adopted in order to increase surface contact of catalyst and to facilitate access to long-chain molecules. The resulting innovative film morphology (fumed silica/lipase cluster level aggregation) and the lipase functionality (for catalytic biodiesel production) have been studied by FESEM, FTIR and transesterification tests.

  11. Sol-gel derived flexible silica aerogel as selective adsorbent for water decontamination from crude oil. (United States)

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


    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.

  12. High Vacuum Techniques for Anionic Polymerization

    KAUST Repository

    Ratkanthwar, Kedar


    Anionic polymerization high vacuum techniques (HVTs) are the most suitable for the preparation of polymer samples with well-defined complex macromolecular architectures. Though HVTs require glassblowing skill for designing and making polymerization reactor, it is the best way to avoid any termination of living polymers during the number of steps for the synthesis of polymers with complex structure. In this chapter, we describe the different polymerization reactors and HVTs for the purification of monomers, solvents, and other reagents for anionic polymerization as well as few model reactions for the synthesis of polymers with simple to complex structure.

  13. Polymer-modified fibrous mesoporous silica nanoparticles as coating material for open-tubular capillary electrochromatography. (United States)

    Liu, Yuanyuan; Liu, Qing; Yu, Haiyan; Sun, Shujun; Xue, Yun; Wang, Yan; Qu, Qishu; Yan, Chao


    A novel fibrous mesoporous silica nanoparticles (fSiO 2 ) stationary phase grafted with polymer (Poly (2-(dimethylamino) ethyl methacrylate) (PDMAEMA) was developed for open tubular capillary electrochromatography (OT-CEC). The preparation procedure included synthesizing fSiO 2 through biphase stratification approach, removing the surfactants, silanization and in situ graft polymerization with monomers via atom transfer radical polymerization (ATRP). Subsequently, PDMAEMA-modified mesoporous silica nanoparticles (P-fSiO 2 )/ethanol solution was immobilized onto the inner surface of the pretreated capillary and functionalized with octadecylsilane to fabricate the open-tubular column. Separation of polycyclic aromatic hydrocarbons (PAHs) and proteins were carried out to evaluate the performance of the column in CEC. The run-to-run, day-to-day and column-to-column reproducibility in terms retention time of naphthalene was 1.9%, 2.2%, and 3.7%, respectively. The effects of solvent concentration and pH on the separation were evaluated. The method was also used for the separation of real bio-sample, egg white proteins. Copyright © 2017 Elsevier B.V. All rights reserved.

  14. Effect of filler porosity on the abrasion resistance of nanoporous silica gel/polymer composites. (United States)

    Luo, J; Lannutti, J J; Seghi, R R


    This laboratory study was designed to investigate the effect of controlled nanoporosity on the wear resistance of polymeric composites reinforced with silica gel powders and to determine the mechanisms controlling the abrasive wear properties of these unique nanostructured materials. Silica gels were prepared by hydrolysis and condensation of tetraethylorthosilicate (TEOS) using four different catalysts to modify the porous structure of the resulting polysilicate silanation, an organic monomer (TEGDMA) containing various initiators was introduced into the gel powders to form a paste. The various pastes were then polymerized inside a glass mold. A pin-on-disk apparatus was then used to record the specimen length and number of revolutions. Abrasive wear rates were determined by regression analysis and statistical differences were determined by analysis of variance and multiple comparisons. BET was used to characterize the filler pore structure and scanning electron microscopy was used used to visually examine the abraded surfaces. Significant differences (p particle pullout. Porous particles prepared via sol-gel show some promise as fillers that improve the wear resistance of photopolymerized resins. The wear resistance of the fillers appears to be directly related to nanoporous structure of the gel particles. Unlike conventional dental composites, these materials rely primarily on nanomechanical coupling for improved wear resistance. This new principle should benefit subsequent investigations.

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

    Directory of Open Access Journals (Sweden)

    Qinghuang Wang


    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.

  16. 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: [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Zhang, Xiaoyong, E-mail: [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Wei, Yen, E-mail: [Department of Chemistry and The Tsinghua Center for Frontier Polymer Research, Tsinghua University, Beijing, 100084 (China)


    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

  17. Silica-Gentamicin Nanohybrids: Synthesis and Antimicrobial Action

    Directory of Open Access Journals (Sweden)

    Dina Ahmed Mosselhy


    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.

  18. Silica-Gentamicin Nanohybrids: Synthesis and Antimicrobial Action. (United States)

    Mosselhy, Dina Ahmed; Ge, Yanling; Gasik, Michael; Nordström, Katrina; Natri, Olli; Hannula, Simo-Pekka


    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.

  19. Olefin polymerization from single site catalysts confined within porous media (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

  20. Experimental investigation of muon-catalyzed fusion

    International Nuclear Information System (INIS)

    Jones, S.E.


    Data will be presented from the first experimental determination of the total yield of the muon-catalyzed fusion reaction: μ - + d + t → μ - + 4 He + n + 17.6 MeV. In this reaction, an elementary particle known as the muon induces fusion without being affected by the nuclear reaction. Thus, it serves as a catalyst in the usual sense. The muon catalyzes many fusion reactions before decaying into an electron and neutrinos. The process is known as cold fusion since it proceeds rapidly for temperatures in the range from room temperature to about 800 0 C. An obvious advantage over thermal fusion approaches is that there is no plasma to contain. On the other hand, the muons which drive the reaction must be continually produced using a particle accelerator

  1. Analytical rheology of metallocene-catalyzed polyethylenes (United States)

    Shanbhag, Sachin; Takeh, Arsia


    A computational algorithm that seeks to invert the linear viscoelastic spectrum of single-site metallocene-catalyzed polyethylenes is presented. The algorithm uses a general linear rheological model of branched polymers as its underlying engine, and is based on a Bayesian formulation that transforms the inverse problem into a sampling problem. Given experimental rheological data on unknown single-site metallocene- catalyzed polyethylenes, it is able to quantitatively describe the range of values of weight-averaged molecular molecular weight, MW , and average branching density, bm , consistent with the data. The algorithm uses a Markov-chain Monte Carlo method to simulate the sampling problem. If, and when information about the molecular weight is available through supplementary experiments, such as chromatography or light scattering, it can easily be incorporated into the algorithm, as demonstrated. Financial support from NSF DMR 0953002.

  2. Conjugation of diisocyanate side chains to dimethacrylate reduces polymerization shrinkage and increases the hardness of composite resins. (United States)

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


    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.

  3. Fluorine-Based DRIE of Fused Silica (United States)

    Yee, Karl; Shcheglov, Kirill; Li, Jian; Choi, Daniel


    A process of deep reactive-ion etching (DRIE) using a fluorine-based gas mixture enhanced by induction-coupled plasma (ICP) has been demonstrated to be effective in forming high-aspect-ratio three-dimensional patterns in fused silica. The patterns are defined in part by an etch mask in the form of a thick, high-quality aluminum film. The process was developed to satisfy a need to fabricate high-aspect-ratio fused-silica resonators for vibratory microgyroscopes, and could be used to satisfy similar requirements for fabricating other fused-silica components.

  4. Fused Silica and Other Transparent Window Materials (United States)

    Salem, Jon


    Several transparent ceramics, such as spinel and AlONs are now being produced in sufficient large areas to be used in space craft window applications. The work horse transparent material for space missions from Apollo to the International Space Station has been fused silica due in part to its low coefficient of expansion and optical quality. Despite its successful use, fused silica exhibits anomalies in its crack growth behavior, depending on environmental preconditioning and surface damage. This presentation will compare recent optical ceramics to fused silica and discuss sources of variation in slow crack growth behavior.

  5. Effect of Surface Treatment Condition of Aminosilane on Ethylene Polymerization of Supported Metallocene

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Sang Yun; Lee, Jeong Suk; Ko, Young Soo [Kongju National University, Cheonan (Korea, Republic of)


    The effects of surface treatment method of unreacted N-[3-(trimethoxysilyl)propyl]ethylenediamine (2NS), N{sup 1}-(3-trimethoxysilylpropyl)diethylenetriamine (3NS), and 3-cyanopropyltriethoxysilane (1NCy) after grafting on the surface of silica and of the surface treatment temperature on ethylene polymerization were investigated. The Zr content of supported catalyst employing filtering method was higher than that of washing method, and the activities of supported catalysts prepared by washing method were higher than those of filtering methods significantly. Regardless of surface treatment methods the activities were in order by SiO{sub 2}/2NS/(n-BuCp){sub 2}ZrCl{sub 2}>SiO{sub 2}/1NCy/(n-BuCp){sub 2}ZrCl{sub 2}>SiO{sub 2}/3NS/(n-BuCp){sub 2}ZrCl{sub 2}. The ethylene polymerization activity was increased as the surface treatment temperature of aminosilane on silica increased.

  6. Selective and recyclable depolymerization of cellulose to levulinic acid catalyzed by acidic ionic liquid. (United States)

    Ren, Huifang; Girisuta, Buana; Zhou, Yonggui; Liu, Li


    Cellulose depolymerization to levulinic acid (LA) was catalyzed by acidic ionic liquids (ILs) selectively and recyclably under hydrothermal conditions. The effects of reaction temperature, time, water amount and cellulose intake were investigated. Dilution effect becomes more pronounced at lower cellulose intake, dramatically improving the yield of LA to 86.1%. A kinetic model has been developed based on experimental data, whereby a good fit was obtained and kinetic parameters were derived. The relationships between IL structure, polymeric structure and depolymerization efficiency were established, shedding light on the in-depth catalytic mechanism of IL, inclusive of acidity and hydrogen bonding ability. The LA product can be readily separated through extraction by methyl isobutyl ketone (MIBK) and IL can be reused over five cycles without loss of activity. This environmentally friendly methodology can be applied to selective production of LA from versatile biomass feedstocks, including cellulose and derivatives, glucose, fructose and HMF. Copyright © 2014 Elsevier Ltd. All rights reserved.

  7. Schlenk Techniques for Anionic Polymerization

    KAUST Repository

    Ratkanthwar, Kedar


    Anionic polymerization-high vacuum techniques (HVTs) are doubtlessly the most prominent and reliable experimental tools to prepare polymer samples with well-defined and, in many cases, complex macromolecular architectures. Due to the high demands for time and skilled technical personnel, HVTs are currently used in only a few research laboratories worldwide. Instead, most researchers in this filed are attracted to more facile Schlenk techniques. The basic principle of this technique followed in all laboratories is substantially the same, i.e. the use of alternate vacuum and inert gas atmosphere in glass apparatus for the purification/charging of monomer, solvents, additives, and for the manipulation of air-sensitive compounds such as alkyl metal initiators, organometallic or organic catalysts. However, it is executed quite differently in each research group in terms of the structure of Schlenk apparatus (manifolds, connections, purification/storage flasks, reactors, etc.), the use of small supplementary devices (soft tubing, cannulas, stopcocks, etc.) and experimental procedures. The operational methods are partly purpose-oriented while also featured by a high flexibility, which makes it impossible to describe in detail each specific one. In this chapter we will briefly exemplify the application of Schlenk techniques for anionic polymerization by describing the performance of a few experiments from our own work.

  8. Amorphous silica biomineralizations in Schoenoplectus californicus (Cyperaceae): their relation with maturation stage and silica availability


    Fernández Honaine, Mariana; Borrelli, Natalia Lorena; Osterrieth, Margarita Luisa; del Río, Laura Sombra


    The factors involved on the silicification process in Cyperaceae are scarcely known. In this study we analyse the effect of maturation stage and silica availability on the production of amorphous silica biomineralizations in culms of Schoenoplectus californicus. Young and senescent culms were collected from ponds with different silica availability. Two complementary methodologies (calcination and staining techniques), light and scanning electron microscopy and EDS were applied for amorpho...

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

    Directory of Open Access Journals (Sweden)

    Sebastian Wilhelm


    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.

  10. Polymerized Paired Ions as Polymeric Ionic Liquid-Proton Conductivity. (United States)

    Gu, Hong; Yan, Feng; Texter, John


    A new polymerized ionic liquid has been derived by photopolymerization of a stimuli-responsive ionic liquid surfactant, ILAMPS, which is composed of polymerizable, paired ions. The cation is 1-methyl-3-[11-(acryloyloxy)undecyl] imidazolium (IL), and the anion is 2-acrylamido-2-methyl-1-propanesulfonate (AMPS). This ion combination is a new ionic liquid. The resulting hygroscopic resins are highly polarizable, suitable for sensor design and for ultracapacitor fabrication and proton conducting. Interactions of imidazolium with anions provide basis for stimuli-responsiveness, and are used to promote proton transport. Doping with one equivalent of HPF6 at 0% relative humidity produces a 100-fold increase in proton conductivity at 100-125 °C and activation energies for proton transport lower than those of Nafion at water loadings less than 5 per sulfonate. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. IR spectral similarity studies of geothermal silica-bentonite based geopolymer (United States)

    Olvianas, Muhammad; Widiyatmoko, Achmad; Petrus, Himawan Tri Bayu Murti


    The geopolymer structures are formed through polymerization of silicate and aluminate species. The resulted structure is predicted to be similar with zeolite. In this study, geopolymer samples were made from mix powder of geothermal silica and bentonite, then activated with sodium hydroxide and sodium silicate. The effect of silica content, NaOH molarity and curing temperature effect were investigated on geopolymer IR spectra and compared with 3A zeolite IR spectra. Pearson correlation value (r) and spectral similarity correlation (Corr) were used to assess spectra similarity between geopolymer samples and zeolite. The development of geopolymer bond and microstructure of samples were then investigated by FTIR technique. IR spectra of geopolymer samples show that Si-O-Al absorption bands are formed around 900-1300 cm-1 and 400-800 cm-1. The optimum of silica contents, NaOH molarity and curing temperature obtained from the experiment were 140 grams, 10 M and 80°C with Corr value of 922 and compressive strength of 7,59 MPa. Corr value is proven to have relation with material strength. Higher Corr value is identified to have higher aluminosilicate species which contributes to higher compressive strength.

  12. Investigation of dielectric breakdown in silica-epoxy nanocomposites using designed interfaces. (United States)

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


    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.

  13. Nano-structured silica coated mesoporous carbon micro-granules for potential application in water filtration (United States)

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


    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.

  14. Cerasomes and Bicelles: Hybrid Bilayered Nanostructures with Silica-like Surface in Cancer Theranostics (United States)

    Hameed, Sadaf; Bhattarai, Pravin; Dai, Zhifei


    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.

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

    Directory of Open Access Journals (Sweden)

    Sebastian Wilhelm


    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.

  16. Preparation, characterization and selective recognition for vanillic acid imprinted mesoporous silica polymers

    Energy Technology Data Exchange (ETDEWEB)

    Li, Hui, E-mail: [College of Chemistry and Chemical Engineering, Jishou University, Jishou 416000 (China); Key laboratory of plant resource and utilization, Jishou University, Hunan Jishou 416000 (China); Xu, Miaomiao; Wang, Susu; Lu, Cuimei; Li, Zhiping [College of Chemistry and Chemical Engineering, Jishou University, Jishou 416000 (China)


    Highlights: • Preparation of a vanillic acid imprinted mesoporous silica polymers. • Improved selectivity and adsorption capability of this MIPs. • Excellent mass transfer dynamics for the MIPs. • High solid phase extraction applicability toward real sample. - Abstract: A vanillic acid imprinted mesoporous silica polymer (MIPs) was prepared by copolymerizing a modified mesoporous silica molecular sieve with template molecule, functional monomer and cross-linker in present work. Interaction between the template and functional monomer was investigated by ultraviolet/visible spectrophotometry. These MIPs were characterized by Fourier transmission infrared spectrometry (FTIR) and scanning electron microscopy (SEM). Adsorption dynamics and thermodynamic behavior of MIPs was explored and the selective recognition capability evaluated. Also, the applicability for the MIPs as solid phase extraction media was tested. Results indicated the 1:1 (mole ratio) complex of vanillic acid-4-vinylpyridine might predominate in the pre-polymerization mixture and the MIPs obtained possessed rapid binding dynamics and higher affinity toward template molecules, reaching adsorption equilibrium within 230 min with the highest adsorption amount of 50.7 mg g{sup −1}. Freundlich model was shown best to describe isotherm adsorption for the MIPs. The MIPs could selectively bind template molecule with selectivity coefficients of 1.36–1.50. In addition, a higher enrichment capability when using it for gathering target compound from methanol extract of Artemisia stelleriana and a good reusability during adsorption–desorption recycling use could be observed.

  17. Self-Strengthening Hybrid Dental Adhesive via Visible-light Irradiation Triple Polymerization. (United States)

    Song, Linyong; Ye, Qiang; Ge, Xueping; Misra, Anil; Tamerler, Candan; Spencer, Paulette


    A self-strengthening methacrylate-based dental adhesive system was developed by introducing an epoxy cyclohexyl trimethoxysilane (TS) which contains both epoxy and methoxysilyl functional groups. The experimental formulation, HEMA/BisGMA/TS (22.5/27.5/50, wt%), was polymerized by visible-light. Real-time Fourier transform infrared spectroscopy (FTIR) was used to investigate in situ the free radical polymerization of methacrylate, ring-opening cationic polymerization of epoxy, and photoacid-induced sol-gel reactions. Among the three simultaneous reactions, the reaction rate of the free radical polymerization was the highest and the hydrolysis/condensation rate was the lowest. With 40s-irradiation, the degrees of conversion of the double bond and epoxy groups at 600 s were 73.2±1.2%, 87.9±2.4%, respectively. Hydrolysis of the methoxysilyl group was initially induced reaction were effective in catalyzing both epoxy ring-opening polymerization and methoxysilyl sol-gel reaction. The mechanical properties of copolymers made with TS concentrations from 5 to 35 wt% were obtained using dynamic mechanical analysis (DMA). In wet conditions, the storage moduli at 70 °C and glass transition temperature were significantly higher than that of the control (p<0.05); these properties increased with TS concentration and storage time. The post reaction of hydrolysis/condensation of alkoxysilane could provide persistent strengthening whether in a neutral or acidic environment and these characteristics could lead to enhanced mechanical properties in the oral environment. The cumulative amount of leached species decreased significantly in the TS-containing copolymers. These results provide valuable information for the development of dental adhesives with reduced leaching of methacrylate monomers and enhanced mechanical properties under the wet, oral environment.

  18. Diffusion of coloured silica nanoparticles into human hair


    Gomes, Jaime Rocha; Sampaio, Sandra; Maia, Frederico


    A novel method for dyeing human hair fibres using coloured silica nanoparticles of 206 nm has been developed. Diffusion of coloured silica nanoparticles into hair fibres has been investigated; silica nanoparticles do not penetrate at all, or do so only sparingly, into the structure of Caucasian virgin hair. However, coloured silica nanoparticles diffused readily into bleached hair fibres. Scanning electron microscopy showed that coloured silica nanoparticles were present mainly in...

  19. 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: [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)


    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.

  20. Imidazole catalyzes chlorination by unreactive primary chloramines (United States)

    Roemeling, Margo D.; Williams, Jared; Beckman, Joseph S.; Hurst, James K.


    Hypochlorous acid and simple chloramines (RNHCl) are stable biologically-derived chlorinating agents. In general, the chlorination potential of HOCl is much greater than that of RNHCl, allowing it to oxidize or chlorinate a much wider variety of reaction partners. However, in this study we demonstrate by kinetic analysis that the reactivity of RNHCl can be dramatically promoted by imidazole and histidyl model compounds via intermediary formation of the corresponding imidazole chloramines. Two biologically relevant reactions were investigated—loss of imidazole-catalyzed chlorinating capacity and phenolic ring chlorination using fluorescein and the tyrosine analog, 4-hydroxyphenylacetic acid (HPA). HOCl reacted stoichiometrically with imidazole, N-acetylhistidine (NAH), or imidazoleacetic acid to generate the corresponding imidazole chloramines which subsequently decomposed. Chloramine (NH2Cl) also underwent a markedly accelerated loss in chlorinating capacity when NAH was present, although in this case NAHCl did not accumulate, indicating that the catalytic intermediate must be highly reactive. Mixing HOCl with 1-methylimidazole (MeIm) led to very rapid loss in chlorinating capacity via formation of a highly reactive chlorinium ion (MeImCl+) intermediate; this behavior suggests that the reactive forms of the analogous imidazole chloramines are their conjugate acids, e.g., the imidazolechlorinium ion (HImCl+). HOCl-generated imidazole chloramine (ImCl) reacted rapidly with fluorescein in a specific acid-catalyzed second order reaction to give 3′-monochloro and 3′,5′-dichloro products. Equilibrium constants for the transchlorination reactions: HOCl + HIm = H2O + ImCl and NH2Cl + HIm = NH3 + ImCl were estimated from the dependence of the rate constants upon [HIm]/[HOCl] and literature data. Acid catalysis again suggests that the actual chlorinating agent is HImCl+; consistent with this interpretation, MeIm markedly catalyzed fluorescein chlorination by HOCl

  1. Thermal bulk polymerization of cholesteryl acrylate

    NARCIS (Netherlands)

    de Visser, A.C.; de Groot, K.; Feijen, Jan; Bantjes, A.


    The thermal bulk polymerization of cholesteryl acrylate was carried out in the solid phase, the mesomorphic phase, and the liquid phase to study the effect of monomer ordering on polymerization rate and polymer properties. The rate increased with decreasing ordering (or enhanced mobility) of the

  2. Polymeric implant of methylprednisolone for spinal injury ...

    African Journals Online (AJOL)

    Polymeric implant of methylprednisolone for spinal injury: preparation and characterization. Bo Yin, Jian-Jun Ji, Ming Yang. Abstract. Purpose: To improve the effectiveness and reduce the systemic side effects of methylprednisolone in traumatic spinal injuries, its polymeric implants were prepared using chitosan and sodium ...

  3. Transformation kinetics of mixed polymeric substrates under ...

    African Journals Online (AJOL)

    Transformation kinetics of mixed polymeric substrates under transitory conditions by Aspergillus niger. ... Abstract. A mixture of polymeric substrates (simulating a complex wastewater) was transformed under sewer conditions and aerobiosis by Aspergillus niger in a tanks-in-series reactor at a hydraulic retention time of 14 h.

  4. Effective thermal conductivity of condensed polymeric nanofluids ...

    Indian Academy of Sciences (India)

    Polymeric nanosolids; thermal conductivity; photothermal techniques; effective medium theory; interfacial scattering. PACS Nos 66.70.−f; 65.80.−g; 81.07.−b; 66.70.Hk. 1. Introduction. The polymeric nanosolids presented in this work are uniform dispersions of a single-phase nanomaterial dispersed uniformly in a polymer ...

  5. Sodium metabisulphite induced polymerization of sickle cell ...

    African Journals Online (AJOL)

    The present in vitro study ascertained the capacity of three medicinal plants, namely, Anacardium occidentale, Psidium guajava and Terminalia catappa, to alter polymerization of sickle cell haemoglobin (HbS). Spectrophotometric method was used to monitor the level of polymerization of haemolysate HbS molecules ...

  6. Microscopic polyangiitis secondary to silica exposure. (United States)

    Vega Miranda, Juliana; Pinto Peñaranda, Luis Fernando; Márquez Hernández, Javier Darío; Velásquez Franco, Carlos Jaime


    There is sufficient evidence of the capacity of silica to induce autoimmunity in patients with some type of genetic susceptibility. There are several autoimmune diseases related to this exposure (rheumatoid arthritis, Sjögren's syndrome, sarcoidosis, systemic sclerosis). Nodular silicosis (clinical expression of this exposure in lungs) generates apoptosis, inflammation, loss of tolerance and a respiratory burst. There is evidence that relates silica with induction of antineutrophil cytoplasmic antibodies, but, until it is better explained, the reports of systemic vasculitis secondary to silica exposure are inconclusive. We describe a case of a patient with a history of occupational exposure to silica who developed microscopic polyangiitis. Copyright © 2013 Elsevier España, S.L. All rights reserved.

  7. Nanoengineered silica: Properties, applications and toxicity. (United States)

    Mebert, Andrea M; Baglole, Carolyn J; Desimone, Martin F; Maysinger, Dusica


    Silica nanoparticles are widely used for biomedical purposes, but also in cosmetic products, food, the car industry, paints, etc. Considering their mega production, one should not ignore their potential hazardous effects on humans, flora and fauna. Human exposure to nanosilica can occur unintentionally in daily life and in industrial settings. Here, we review the common methods of silica nanoparticle production and its applications in biomedical investigations and nanotoxicology. The use of silica nanoparticles in biomedicine is discussed in terms of drug delivery, their responsiveness to different stimuli, theranostic applications and their uses in the food and cosmetic industries. Advantages and limitations of silica nanoparticles are presented and the effects of these nanoparticles are discussed in relation to their route of entry and impact on biochemical and epigenetic processes in human and animal cells. Copyright © 2017 Elsevier Ltd. All rights reserved.

  8. Influence of Nano Silica on Alkyd Films

    DEFF Research Database (Denmark)

    Nikolic, Miroslav

    . The present work centers on the reinforcement of alkyd binders emulsified in water and used in exterior wood coatings with nano silica. Raman spectroscopy was used throughout the study to maintain the reproducibility of results as it was found that colloidal nano silica can increase or decrease the speed...... of alkyd curing affecting the tested mechanical properties. Hydrophilic, colloidal nano silica was seen to have limited effect in improving the mechanical properties due to problems in properly dispersing and attaining good surface interactions with the hydrophobic alkyd polymer. Efforts in increasing...... nano silica which was incorporated in the pure alkyd and then subsequently emulsified. When the change in the coating formulation increases the stiffness of the exterior wood coating, as happens with the addition of nano particles, there is a concern for the long term performance due to possibility...

  9. Nanoparticles from a controlled polymerization process

    International Nuclear Information System (INIS)

    Tirumala, V.R.; Caneba, G.T.; Dar, Y.; Wang, H.-H.; Mancini, D.C.


    Free-radical retrograde precipitation polymerization process in the past has shown excellent control characteristics over reaction rate, molecular weight, and in the entrapment of live radicals for the generation of block copolymers. The same principle has now been extended to study the reaction confinement to a nanoscale region. Nanosized polymer particles have been reported to form from block copolymers, conventional precipitation polymerization methods, or through emulsion polymerization approaches. In this work, we present a new method of generating nanosized polymer particles by polymerizing the monomer in an environment that precipitates the polymer above the lower critical solution temperature. The nanoparticles have been characterized by both tapping-mode atomic force microscopy observations and in situ synchrotron time-resolved small-angle X-ray scattering analysis. The results from both the techniques showed the formation of nanoparticles in the size range of 15-30 nm, directly from the polymerization process.

  10. Nonporous Silica Nanoparticles for Nanomedicine Application


    Tang, Li; Cheng, Jianjun


    Nanomedicine, the use of nanotechnology for biomedical applications, has potential to change the landscape of the diagnosis and therapy of many diseases. In the past several decades, the advancement in nanotechnology and material science has resulted in a large number of organic and inorganic nanomedicine platforms. Silica nanoparticles (NPs), which exhibit many unique properties, offer a promising drug delivery platform to realize the potential of nanomedicine. Mesoporous silica NPs have bee...

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

    International Nuclear Information System (INIS)

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


    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)

  12. Carbon Isotope Systematics in Mineral-Catalyzed Hydrothermal Organic Synthesis Processes at High Temperature and Pressures (United States)

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


    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.

  13. Grassy Silica Nanoribbons and Strong Blue Luminescence (United States)

    Wang, Shengping; Xie, Shuang; Huang, Guowei; Guo, Hongxuan; Cho, Yujin; Chen, Jun; Fujita, Daisuke; Xu, Mingsheng


    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.

  14. 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


    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.

  15. Polymerization of lanthanide acrylonitrile complexes. (United States)

    el-Mossalamy, El-Sayed H; Khalil, Ahmed A


    The molecular complexes of some lanthanides scandium (Sc3+), yttrium (Y3+), lanthanum (La3+), gadolinium (Gd3+), cerium (Ce3+) and ytterbium (Yb3) have been studies in dimethyl formamide (DMF) spectrophtometrically equilibrium constants (K), molar extintion coefficient (epsilon), energy of transition (E) and free energy (delta G*) were calculated. The polymerization of acrylonitrile has been studied and investigated in the presence of Sc3+, Y3+, La3+, Gd3+, Ce3+, and Yb3+ ions. The IR spectra of the formed AN-M (III) Br3 polymer complexes show the absence of the C identical to N band and the presence of two new bands corresponding to NH2 and OH groups. Magnetic moment values and the thermal stabilities of homopolymer and the polymer complexes were studied by means of thermogravimetric analysis and the activation energies for degradation were calculated.

  16. Polymeric materials from renewable resources (United States)

    Frollini, Elisabete; Rodrigues, Bruno V. M.; da Silva, Cristina G.; Castro, Daniele O.; Ramires, Elaine C.; de Oliveira, Fernando; Santos, Rachel P. O.


    The goals of our studies have been the use of renewable raw materials in the preparation of polymeric materials with diversified properties. In this context, lignosulfonate, which is produced in large scale around the world, but not widely used in the production of polymeric materials, was used to replace phenol and polyols in the preparation of phenolic- (Ligno-PH) and polyurethane-type (Ligno-PU) polymers, respectively. These polymers were used to prepare composites reinforced with sisal lignocellulosic fibers. The use of lignosulfonate in the formulation of both types of polymers was beneficial, because in general composites with improved properties, specially impact strength, were obtained. Composites were also prepared from the so called "biopolyethylene" (HDPE), curaua lignocellulosic fiber, and castor oil (CO). All composites HDBPE/CO/Fiber exhibited higher impact strength, when compared to those of the corresponding HDBPE/Fiber. These results, combined with others (eg SEM images of the fractured surfaces) indicated that, in addition to acting as a plasticizer, this oil may have acted as a compatibilizer of the hydrophilic fiber with the hydrophobic polymer. The set of results indicated that (i) mats with nano (diameter ≤ 100nm) and/or ultrafine (submicron scale) fibers were produced, (ii) hybrid fibers were produced (bio-based mats composites), (iii) cellulosic pulp (CP) and/or lignin (Lig) can be combined with PET matrices to control properties such as stiffness and hydrophilicity of the respective mats. Materials with diversified properties were prepared from high content of renewable raw materials, thus fulfilling the proposed targets.

  17. Polymeric materials from renewable resources

    Energy Technology Data Exchange (ETDEWEB)

    Frollini, Elisabete; Rodrigues, Bruno V. M.; Silva, Cristina G. da; Castro, Daniele O.; Ramires, Elaine C.; Oliveira, Fernando de; Santos, Rachel P. O. [Macromolecular Materials and Lignocellulosic Fibers Group, Center for Research on Science and Technology of BioResources, Institute of Chemistry of São Carlos, University of São Paulo, CP 780, 13560-970 São Carlos, São Paulo (Brazil)


    The goals of our studies have been the use of renewable raw materials in the preparation of polymeric materials with diversified properties. In this context, lignosulfonate, which is produced in large scale around the world, but not widely used in the production of polymeric materials, was used to replace phenol and polyols in the preparation of phenolic- (Ligno-PH) and polyurethane-type (Ligno-PU) polymers, respectively. These polymers were used to prepare composites reinforced with sisal lignocellulosic fibers. The use of lignosulfonate in the formulation of both types of polymers was beneficial, because in general composites with improved properties, specially impact strength, were obtained. Composites were also prepared from the so called “biopolyethylene” (HDPE), curaua lignocellulosic fiber, and castor oil (CO). All composites HDBPE/CO/Fiber exhibited higher impact strength, when compared to those of the corresponding HDBPE/Fiber. These results, combined with others (eg SEM images of the fractured surfaces) indicated that, in addition to acting as a plasticizer, this oil may have acted as a compatibilizer of the hydrophilic fiber with the hydrophobic polymer. The set of results indicated that (i) mats with nano (diameter ≤ 100nm) and/or ultrafine (submicron scale) fibers were produced, (ii) hybrid fibers were produced (bio-based mats composites), (iii) cellulosic pulp (CP) and/or lignin (Lig) can be combined with PET matrices to control properties such as stiffness and hydrophilicity of the respective mats. Materials with diversified properties were prepared from high content of renewable raw materials, thus fulfilling the proposed targets.

  18. Radiation polymerization of vinylene carbonate

    International Nuclear Information System (INIS)

    Schnautz, N.G.; Lustig, A.; Roesch, H.


    The radiation-induced polymerization of vinylene carbonate of 99,97% purity has been investigated. The relationship between conversion and irradiation time is strictly linear, even at the lowest conversions, thus proving that the normal induction period observed for the polymerization of lower-purity vinylene carbonate indeed results from the presence of an inhibitor. Although the identity of the inhibitor has not been established, it has been shown that it is not dichlorovinylene carbonate. An activation energy of 15,1 kJ/mole was calculated for the homopolymerization process. The radiation-induced copolymerization of vinylene carbonate (M 1 ) with isobutyl vinyl ether (M 2 ) has been investigated over the temperature range of 40-80 degrees Celcius. The monomer reactivity ratios r 1 and r 2 were determined to be 0,118 and 0,148 respectively, and an activation energy of 31,8kJ/mole was calculated for the copolymerization process. The radiation-induced telomerization of vinylene carbonate with carbon tetrachloride has been investigated over a telogen to monomer concentration ratio range of 4 to 20. The rate of formation of the n=1 adduct was found to be independent of monomer concentration, directly proportional to the telogen concentration, and exhibiting a 0,38 order power dependence on the radiation intensity, in general agreement with the derived rate equations. The rate of formation of the n=2 telomer was found to be independent of both monomer and telogen concentrations and radiation intensity, which is not in agreement with the derived rate equations. The first and second chain-transfer coefficients C 1 and C 2 were determined to be 0,116 and 0,34 respectively, and the activation energies for the formation of the n=1 adduct and n=2 telomer were calculated to be 17,6 and 64,9 kJ/mole respectively [af

  19. 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


    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.

  20. Preparação e caracterização de compósitos poliméricos baseados em amido termoplástico e materiais de alta área superficial: zeólita ZSM-5 e sílica coloidal Preparation and characterization of polymeric composites based on thermoplastic starch and high surface area materials: ZSM-5 zeolite and colloidal silica

    Directory of Open Access Journals (Sweden)

    Fábio Plotegher


    Full Text Available Foram produzidas amostras de amido termoplástico (TPS reforçadas com materiais de alta área superficial, com o intuito de verificar a variação nas propriedades do polímero, com especial enfoque na sua permeabilidade a vapor d'água. Foram utilizadas como carga a sílica coloidal (área superficial de 122,7 m²/g e uma zeólita do tipo ZSM-5, produzida em laboratório (área superficial de 261,3 m²/g, em teores de 2 a 10% em massa. Os resultados demonstraram que a adição de ambos os materiais melhorou as propriedades mecânicas do TPS, embora nos maiores teores houve redução da qualidade das interfaces e dessas propriedades, principalmente para a ZSM-5. Em todos os casos a introdução da carga inorgânica reduziu a permeabilidade ao vapor d'água em até 20% quando comparada à permeabilidade do TPS, porém a melhor dispersão da sílica coloidal na matriz permitiu as maiores reduções, apesar da área superficial inferior.Compositions of thermoplastic starch (TPS reinforced by high surface area materials were produced, intending to study the variation in polymer properties, focusing on the permeability to water vapor. Colloidal silica (surface area 122.7 m²/g and a ZSM-5 zeolite (surface area 261.3 m²/g were used, in loadings from 2 to 10% weight. The results demonstrated that the addition of both materials was favorable to the TPS mechanical properties, however in higher loadings the quality of polymer interfaces and these properties were negatively affected, especially for ZSM-5. In all the cases the inorganic particles reduced the permeability to water vapor in levels below 20% when compared to pure TPS, although the best dispersion of colloidal silica determined better reductions, despite its lower surface area.

  1. Enzyme-catalyzed synthesis of unsaturated aliphatic polyesters based on green monomers from renewable resources. (United States)

    Jiang, Yi; Woortman, Albert J J; van Ekenstein, Gert O R Alberda; Loos, Katja


    Bio-based commercially available succinate, itaconate and 1,4-butanediol are enzymatically co-polymerized in solution via a two-stage method, using Candida antarctica Lipase B (CALB, in immobilized form as Novozyme® 435) as the biocatalyst. The chemical structures of the obtained products, poly(butylene succinate) (PBS) and poly(butylene succinate-co-itaconate) (PBSI), are confirmed by 1H- and 13C-NMR. The effects of the reaction conditions on the CALB-catalyzed synthesis of PBSI are fully investigated, and the optimal polymerization conditions are obtained. With the established method, PBSI with tunable compositions and satisfying reaction yields is produced. The 1H-NMR results confirm that carbon-carbon double bonds are well preserved in PBSI. The differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA) results indicate that the amount of itaconate in the co-polyesters has no obvious effects on the glass-transition temperature and the thermal stability of PBS and PBSI, but has significant effects on the melting temperature.

  2. Silica ecosystem for synergistic biotransformation (United States)

    Mutlu, Baris R.; Sakkos, Jonathan K.; Yeom, Sujin; Wackett, Lawrence P.; Aksan, Alptekin


    Synergistical bacterial species can perform more varied and complex transformations of chemical substances than either species alone, but this is rarely used commercially because of technical difficulties in maintaining mixed cultures. Typical problems with mixed cultures on scale are unrestrained growth of one bacterium, which leads to suboptimal population ratios, and lack of control over bacterial spatial distribution, which leads to inefficient substrate transport. To address these issues, we designed and produced a synthetic ecosystem by co-encapsulation in a silica gel matrix, which enabled precise control of the microbial populations and their microenvironment. As a case study, two greatly different microorganisms: Pseudomonas sp. NCIB 9816 and Synechococcus elongatus PCC 7942 were encapsulated. NCIB 9816 can aerobically biotransform over 100 aromatic hydrocarbons, a feat useful for synthesis of higher value commodity chemicals or environmental remediation. In our system, NCIB 9816 was used for biotransformation of naphthalene (a model substrate) into CO2 and the cyanobacterium PCC 7942 was used to provide the necessary oxygen for the biotransformation reactions via photosynthesis. A mathematical model was constructed to determine the critical cell density parameter to maximize oxygen production, and was then used to maximize the biotransformation rate of the system.

  3. Rheoreversible polymeric organogels: the art of science for art conservation. (United States)

    Carretti, Emiliano; Dei, Luigi; Macherelli, Azzurra; Weiss, Richard G


    A new category of gels where gelification and breaking of the gels are chemically induced is presented. In particular, the latent gellant polyallylamine produced stable gels with some organic solvents after reaction with CO2 at room temperature, giving the gellant polyallylammonium carbamate. The rheological behavior switches from solution-type to gel-type. After weak acid-catalyzed displacement of CO2, the gel character disappears in a few seconds, making these polymeric organogels rheoreversible by a simple chemical action. This "intelligent" chemical switch between solution-type and gel-type rheological behavior has been exploited to clean pictorial surfaces in art conservation. In fact, during the cleaning procedure, there is a need for the gel supporting the cleaning solvent to have a very high viscosity. After cleaning has been successful, there is a strong necessity to reduce the viscosity, to better eliminate traces of the gellant that must be completely removed from the work of art. In the present study, we show that the art of science, in the sense of designing new physicochemical systems exploiting the "science palette", can lead to an improvement in the techniques used to protect and conserve the results of the "artists' palette".

  4. Encapsulation and permeability characteristics of plasma polymerized hollow particles. (United States)

    Shahravan, Anaram; Matsoukas, Themis


    In this protocol, core-shell nanostructures are synthesized by plasma enhanced chemical vapor deposition. We produce an amorphous barrier by plasma polymerization of isopropanol on various solid substrates, including silica and potassium chloride. This versatile technique is used to treat nanoparticles and nanopowders with sizes ranging from 37 nm to 1 micron, by depositing films whose thickness can be anywhere from 1 nm to upwards of 100 nm. Dissolution of the core allows us to study the rate of permeation through the film. In these experiments, we determine the diffusion coefficient of KCl through the barrier film by coating KCL nanocrystals and subsequently monitoring the ionic conductivity of the coated particles suspended in water. The primary interest in this process is the encapsulation and delayed release of solutes. The thickness of the shell is one of the independent variables by which we control the rate of release. It has a strong effect on the rate of release, which increases from a six-hour release (shell thickness is 20 nm) to a long-term release over 30 days (shell thickness is 95 nm). The release profile shows a characteristic behavior: a fast release (35% of the final materials) during the first five minutes after the beginning of the dissolution, and a slower release till all of the core materials come out.

  5. Salix daphnoides: A Screening for Oligomeric and Polymeric Proanthocyanidins

    Directory of Open Access Journals (Sweden)

    Stefan Wiesneth


    Full Text Available In the present study, a qualitative analysis of proanthocyanidins (PAs from an aqueous-methanolic extract of Salix daphnoides VILL. bark is described. Procyanidin B1 (1, B2 (2, B3 (3, B4 (4, C1 (5, epicatechin-(4β→8-epicatechin-(4β→8-catechin (6 and epicatechin-(4β→8-epicatechin-(4β→8-epicatechin-(4β→8-catechin (7 have been isolated by a combination of different chromatographic separations on Sephadex® LH-20-, MCI®-, Diol-and RP-18-phases. Mass spectrometry, 1D- and 2D-NMR, circular dichroism and polarimetry were used for their structure elucidation and verification by comparison with the literature. Additionally, two fractions of very polar flavan-3-ols were compared: “regular” polymeric PAs received at the very end of the Sephadex® LH-20 chromatography showing no mobility on silica TLC and “unusual” PAs with the same RF-value but already eluting together with flavonoids in the Sephadex® LH-20 system. These “unusual” PAs were subsequently enriched by centrifugal partition chromatography (CPC. 13C-NMR, polarimetry, thiolysis, acid hydrolysis and phloroglucinol degradation were used to characterize both fractions. Differences in the composition of different flavan-3-ol units and the middle chain length were observed.

  6. Preparation of fused-silica columns with phases immobilized by cobalt-60 gamma radiation; application to essential oil analysis

    Energy Technology Data Exchange (ETDEWEB)

    Hubball, J.A.


    Cobalt-60 gamma-radiation was used to immobilize polymeric stationary phases in fused silica capillary columns for gas chromatography. Surface studies of the uncoated fused silica tubing by optical and scanning electron microscopy indicated some irregularities, but overall the tubing maintained its strength and flexibility at dosages up to 25 MRads. A polydimethylsiloxane phase (OV-1) and a polyethylene glycol phase (Carbowax 20 M) were effectively immobilized on the inner surface of fused silica capillary tubing without altering the properties of the phases. The optimum radiation dosage for OV-1 was 7 MRads, while Carbowax 20 M required 25 MRads to immobilize 33% of the coated layer. Fused silica capillary columns prepared with both phases were evaluated for deactivation, efficiency, and thermal stability. Immobilization of Carbowax 20 M extended the low and high temperature limits by 30 C in each direction. Columns prepared in this study were used to analyze the essential oil of Siparuna guianensis. Several key components of the oil were identified by GC/MS and gas chromatographic techniques.

  7. 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.


    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

  8. 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)


    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.

  9. Nature of active tin species and promoting effect of nickle in silica supported tin oxide for dehydrogenation of propane (United States)

    Wang, Haoren; Wang, Hui; Li, Xiuyi; Li, Chunyi


    Different with Wang et. al.'s study, we found that polymeric Si-O-Sn2+ rather than Ni-Sn alloy and metallic Sn are active species in silica-supported tin oxide catalysts for dehydrogenation of propane. The results showed that high surface area of mesoporous silica brought about high dispersion of tin oxide species, as a result, catalytic activity and stability were both improved. DRUV-vis, XPS, TPR and XRD studies of fresh and reduced catalysts indicated that the deactivation was related to the reduction of active species rather than the coke formation since active tin species cannot maintain its oxidation state at reaction conditions (high temperature and reducing atmosphere). The formed Ni3Sn2 alloy after reduction just functioned as promoter which accelerated the desorption of H2 and regeneration of active site. A synergy effect between active tin species and Ni3Sn2 alloy were observed.

  10. Polyaniline-grafted silica nanocomposites-based gel electrolytes for quasi-solid-state dye-sensitized solar cells (United States)

    Ma, Pin; Tan, Jing; Cheng, Hongbo; Fang, Yanyan; Wang, Yanan; Dai, Yuhua; Fang, Shibi; Zhou, Xiaowen; Lin, Yuan


    Polyaniline-grafted silica nanocomposites (PANI-SiO2), which are synthesized through in-situ surface chemical oxidative polymerization of aniline with the NH2-modified silica nanoparticles, are exploited as gelators in the ionic-liquid electrolytes for dye-sensitized solar cells (DSCs). It can be clearly seen that the PANI-SiO2 nanocomposites have the well-interconnected network structure, which not only serve as gelators to effectively solidfy the ionic-liquid electrolytes, but also significantly improve the ion conductivity of electrolytes and the diffusion coefficient of I3- ions. As a result, an optimal efficiency of 7.15% for DSC using gel electrolyte is achieved due to the enhancement of photocurrent density (Jsc) and fill factor (FF), which is increased by 18.99% than that of the cell using ionic-liquid electrolyte.

  11. Cationic Ring Opening polymerization of ε-caprolactam by a Montmorillonite Clay Catalyst

    Directory of Open Access Journals (Sweden)

    Djamal Eddine Kherroub


    Full Text Available The ring opening bulk polymerization of ε-caprolactam catalyzed by Maghnite-H+ was reported. Maghnite-H+ is a montmorillonite silicate sheet clay was prepared through a straight forward proton exchange process. The effect of the amount of catalyst, and temperature was studied. Increasing Maghnite-H+ proportion and temperature produced the increase in ε-caprolactam conversion. The kinetics indicated that the polymerization rate is first order with respect to monomer concentration. Mechanism studies showed that monomer inserted into the growing chains with the acyl–oxygen bond scission rather than the break of alkyl–oxygen bond. © 2014 BCREC UNDIP. All rights reservedSubmitted: 3rd October 2013; Revised: 28th February 2014; Accepted: 1st March 2014[How to Cite: Kherroub, D.E., Belbachir, M., Lamouri, S. (2014. Cationic Ring Opening Polymeriza-tion of ε-caprolactam by a Montmorillonite Clay Catalyst. Bulletin of Chemical Reaction Engineering & Catalysis, 9 (1: 74-79. (doi:10.9767/bcrec.9.1.5555.74-80][Permalink/DOI:

  12. Sequence-regulated copolymers via tandem catalysis of living radical polymerization and in situ transesterification. (United States)

    Nakatani, Kazuhiro; Ogura, Yusuke; Koda, Yuta; Terashima, Takaya; Sawamoto, Mitsuo


    Sequence regulation of monomers is undoubtedly a challenging issue as an ultimate goal in polymer science. To efficiently produce sequence-controlled copolymers, we herein developed the versatile tandem catalysis, which concurrently and/or sequentially involved ruthenium-catalyzed living radical polymerization and in situ transesterification of methacrylates (monomers: RMA) with metal alkoxides (catalysts) and alcohols (ROH). Typically, gradient copolymers were directly obtained from the synchronization of the two reactions: the instantaneous monomer composition in feed gradually changed via the transesterification of R(1)MA into R(2)MA in the presence of R(2)OH during living polymerization to give R(1)MA/R(2)MA gradient copolymers. The gradient sequence of monomers along a chain was catalytically controlled by the reaction conditions such as temperature, concentration and/or species of catalysts, alcohols, and monomers. The sequence regulation of multimonomer units was also successfully achieved in one-pot by monomer-selective transesterification in concurrent tandem catalysis and iterative tandem catalysis, providing random-gradient copolymers and gradient-block counterparts, respectively. In contrast, sequential tandem catalysis via the variable initiation of either polymerization or in situ transesterification led to random or block copolymers. Due to the versatile adaptability of common and commercially available reagents (monomers, alcohols, catalysts), this tandem catalysis is one of the most efficient, convenient, and powerful tools to design tailor-made sequence-regulated copolymers. © 2012 American Chemical Society

  13. Microscopic structure of nanometer-sized silica particles

    International Nuclear Information System (INIS)

    Uchino, T.; Aboshi, A.; Kohara, S.; Ohishi, Y.; Sakashita, M.; Aoki, K.


    We have studied the structure of nanometer-sized silica particles called fumed silica, which is a synthetic amorphous silicon dioxide produced by burning silicon tetrachloride in an oxygen-hydrogen flame, using infrared and Raman spectroscopies and a high-energy x-ray diffraction method. It has been demonstrated that the structure of fumed silica is not identical to that of the normal bulk silica glass in terms especially of the distribution of the size of silica rings. Three- and four-membered rings are more frequent in fumed silica than in the bulk silica glass. It has also been shown that the network structure of fumed silica is more flexible than that of the bulk one, probably explaining the reason why fumed silica can accommodate a large number of three- and four-membered rings in the structure

  14. The Management of Silica in Los Alamos National Laboratory Tap Water - A Study of Silica Solubility

    Energy Technology Data Exchange (ETDEWEB)

    Wohlberg, C.; Worland, V.P.; Kozubal, M.A.; Erickson, G.F.; Jacobson, H.M.; McCarthy, K.T.


    Well water at Los Alamos National Laboratory (LANL) has a silica (SiO{sub 2}) content of 60 to 100 mg/L, with 4 mg/L of magnesium, 13 mg/L calcium and lesser concentrations of other ions. On evaporation in cooling towers, when the silica concentration reaches 150 to 220 mg/L, silica deposits on heat transfer surfaces. When the high silica well water is used in the reprocessing of plutonium, silica remains in solution at the end of the process and creates a problem of removal from the effluent prior to discharge or evaporation. The work described in this Report is divided into two major parts. The first part describes the behavior of silica when the water is evaporated at various conditions of pH and in the presence of different classes of anions: inorganic and organic. In the second part of this work it was found that precipitation (floccing) of silica was a function of solution pH and mole ratio of metal to silica.

  15. Aluminum Hydride Catalyzed Hydroboration of Alkynes. (United States)

    Bismuto, Alessandro; Thomas, Stephen P; Cowley, Michael J


    An aluminum-catalyzed hydroboration of alkynes using either the commercially available aluminum hydride DIBAL-H or bench-stable Et 3 Al⋅DABCO as the catalyst and H-Bpin as both the boron reagent and stoichiometric hydride source has been developed. Mechanistic studies revealed a unique mode of reactivity in which the reaction is proposed to proceed through hydroalumination and σ-bond metathesis between the resultant alkenyl aluminum species and HBpin, which acts to drive turnover of the catalytic cycle. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Titanium catalyzed silicon nanowires and nanoplatelets

    Directory of Open Access Journals (Sweden)

    Mohammad A. U. Usman


    Full Text Available Silicon nanowires, nanoplatelets, and other morphologies resulted from silicon growth catalyzed by thin titanium layers. The nanowires have diameters down to 5 nm and lengths to tens of micrometers. The two-dimensional platelets, in some instances with filigreed, snow flake-like shapes, had thicknesses down to the 10 nm scale and spans to several micrometers. These platelets grew in a narrow temperature range around 900 celsius, apparently representing a new silicon crystallite morphology at this length scale. We surmise that the platelets grow with a faceted dendritic mechanism known for larger crystals nucleated by titanium silicide catalyst islands.

  17. Preparation of New Conductive Nanocomposites of Polyaniline and Silica under Solid-State Condition

    Directory of Open Access Journals (Sweden)

    Ali Reza Modarresi-Alam


    Full Text Available The novel conductive nanocomposite and composite from polyaniline (PANI were prepared. The composites were synthesized by in situ oxidative chemical polymerization of aniline on silica- and nanosilica-supported sulfuric acid. The reaction was carried out in a mortar and ammonium persulfate was used as oxidant under solvent-free condition at room temperature. Structure, size and morphology of the synthesized nanocomposite and composite were determined by Fourier transform infrared (FTIR spectroscopy, ultraviolet-visible (UV-Vis spectroscopy, scanning electron microscopy (SEM, transmission electron microscopy (TEM and atomic force microscopy (AFM. Conductivity was measured by four-probe technique and revealed that the samples not only had the conductivity in the range of conductive polymers (~ 0.4 S/cm but also they showed high conductivity as composites and blends of polyaniline reported by others. Synthesis of composites (nanocomposites and formation of polarons were confirmed by FTIR and UV-Vis. SEM images showed that silica particles were thoroughly coated by PANI and all were amorphous. According to the TEM and AFM images, particle size in composite and nanocomposite was in the range of 1-5 μm and 35-49 nm, respectively. Furthermore, the surface morphology, shape and dimensions of particles obtained by AFM strongly supported the SEM and TEM observations related to polymer deposition on the silica particles. The key benefits of the approach used in this research are the preparation of novel conductive composite and nanocomposites with the polaron structure under green chemistry condition of dopant solid acids including silica- and nanosilica-supported sulfuric acid.

  18. Organic layer formation and sorption of U(vi) on acetamide diethylphosphonate-functionalized mesoporous silica. (United States)

    Uribe, Eva C; Mason, Harris E; Shusterman, Jennifer A; Lukens, Wayne W


    Acetamide diethylphosphonate (AcPhos)-functionalized silica has been shown to have a high affinity for U(vi) in pH 2-3 nitric acid. Previous work with AcPhos-functionalized silica has focused on actinide and lanthanide extraction under various conditions, but has shown poor reproducibility in the functionalization process. For this work, four AcPhos-functionalized SBA-15 materials were synthesized and evaluated based on their U(vi) sorption capacity and their stability in nitric acid. Materials synthesized using pyridine as a basic catalyst were shown to form a greater fraction of polymeric structures at the silica surface, which correlated with higher structural integrity upon contact with acidic solutions. Single-pulse 31 P and 1 H NMR spectra of these materials show evidence of phosphonic acid groups, as well as hydrogen-bonding interactions either between ligands or with the silica surface. Additionally, these materials were found to have significantly higher U(vi) sorption capacities and K eq values than the materials synthesized without pyridine, most likely due to the ion-exchange properties of the phosphonic acid groups. The 31 P- 31 P DQ-DRENAR NMR technique was used to compare the average strength of dipolar coupling interactions between phosphorus atoms for the four materials. Because the strength of dipolar coupling interactions depends on the number and proximity of neighboring spins, this technique provides information about the average density of ligands on the surface. The conventional functionalization procedure yielded materials with the lowest average surface ligand density, while those using extended reaction times and the pyridine base catalyst yielded materials with higher surface ligand densities.

  19. 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


    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.

  20. Discovery and Development of Pyridine-bis(imine) and Related Catalysts for Olefin Polymerization and Oligomerization. (United States)

    Small, Brooke L


    For over 40 years following the polyolefin catalyst discoveries of Hogan and Banks (Phillips) and Ziegler (Max Planck Institute), chemists traversed the periodic table searching for new transition metal and lanthanide-based olefin polymerization systems. Remarkably, none of these "hits" employed iron, that is, until three groups independently reported iron catalysts for olefin polymerization in the late 1990's. The history surrounding the discovery of these catalysts was only the beginning of their uniqueness, as the ensuing years have proven these systems remarkable in several regards. Of primary importance are the pyridine-bis(imine) ligands (herein referred to as PDI), which produced iron catalysts that are among the world's most active for ethylene polymerization, demonstrated "staying power" despite over 15 years of ligand improvement efforts, and generated highly active polymerization systems with cobalt, chromium, and vanadium. Although many ligands have been employed in iron-catalyzed polymerization, the PDI family has thus far provided the most information about iron's capabilities and tendencies. For example, iron systems tend to be highly selective for ethylene over higher olefins, making them strong candidates for producing highly crystalline polyethylene, or highly linear α-olefins. Iron PDI polymerizes propylene with 2,1-regiochemistry via a predominantly isotactic, chain end control mechanism. Because the first insertion proceeds via 1,2-regiochemistry, iron (and cobalt) PDI systems can be tailored to make highly linear dimers of α-olefins by "head-to-head" coupling, resulting from a switch in regiochemistry after the first insertion. Finally, PDI ligands, while not being surpassed in activity, have inspired the development of related ligand families and complexes, such as pendant donor diimines (PDD), which are also highly efficient at producing linear α-olefins. This Account will detail a variety of oligomerization and polymerization results