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Sample records for catalyzed silica polymerization

  1. Understanding amine catalyzed silica polymerization : diatoms as bioarchitects.

    Energy Technology Data Exchange (ETDEWEB)

    Spoerke, Erik David; Aubry, Sylvie; Lane, Pamela; Robinson, David B; Bauer, Christina A.; Zendejas, Frank; Tran, Huu; Lane, Todd W.; Simmons, Blake Alexander

    2007-10-01

    phytoplankton critical to global carbon fixation. The silicified cell wall of the diatom is called the frustule, and the intricate silica structure characteristic of a given species is known as the valve. There are two general classes of diatoms, based on their overall morphologies, the pennate and centric. Diatoms achieve their silicified structures in exact fashion through genetically inspired design rules coupled with precisely directed biochemistry occurring at temperatures ranging from a few degrees Celsius (polar species) to temperatures just over room temperature (tropical species). Different species of diatoms produce markedly different structures. To start with, there are two basic types of frustule macromorphologies: pennate diatoms display bilateral symmetry and centric diatoms show radial symmetry. There are thousands of permutations of these two basic forms and the micromorphology of the valve can be quite complex with all types of pore arrangements and morphologies (Figure 1.1). The detailed morphology of the cell wall of a given diatom species is reproduced with exactness, because the process is genetically encoded. Three types of cell wall proteins have been identified in diatoms; the frustulins, pleuralins, and silaffins. Frustulins are cell wall proteins that form an organic coat to protect the silica structures from dissolution into the aqueous environment. Pleuralins are associated with a specific subcomponent of the frustule during cell division, and play a role in hypotheca-epitheca development. Silaffins from Cylindrotheca fusiformis are short chain-length peptides that play a direct role in the silica polymerization process, and possess unique biochemical post-translation functionalization. Larger proteins with silaffin activity have recently been described in Thalassiosira pseudonana. Frustulins and pleuralins play no role in silica polymerization or structure formation in diatoms, whereas the silaffins are one of the primary polymerization determinants

  2. 介孔SBA-15负载磷钨酸催化四氢呋喃聚合的研究%Study on THF Polymerization Catalyzed by Phosphotungstic Heteropolyacid on Mesoporous Silica SBA-15 Support

    Institute of Scientific and Technical Information of China (English)

    邓杭军; 邓佳; 陈纪忠

    2014-01-01

    以SBA-15为载体负载磷钨酸(HPW),用于催化四氢呋喃(THF)开环聚合,采用在线反应红外分析仪(ReactIR)测定THF转化率,实验考察了HPW负载质量百分比、3-氨丙基三乙氧基硅烷(APTES)/SBA-15质量比和载体SBA-15孔径等因素对催化剂的催化性能和THF转化率的影响。结果表明:采用直接浸渍法负载HPW,HPW最优负载质量百分比为40%;将SBA-15进行氨基改性后负载HPW,最优APTES/SBA-15质量比为mAPTES/mSBA-15=0.0712,且通过氨基改性可有效改善催化剂的重复利用性能;当载体 SBA-15的比表面积较大时(853 m2⋅g-1)或孔径较大(比表面积较小498~585 m2⋅g-1)时,所制备的催化剂具有较高的催化效率、聚合产物平均分子量较大,催化剂的催化效率和聚合产物分子量随着孔径增大而增大。%A catalyst synthesized by loading phosphotungstic heteropolyacid on mesoporous silica material SBA-15 support was used in ring-opening polymerization of tetrahydrofuran (THF). The polymerization of THF was monitored in real-time by ReactIR. The effects of mass fraction of HPW, the mass ratio of 3-aminopropyl-triethoxysilane (APTES) to SBA-15, and the pore diameter of SBA-15 on catalytic performance and the conversion of THF were investigated. It was found that the supported catalyst HPW/SBA-15 prepared by impregnation with 40% mass fraction of HPW exhibits the highest activity. The amino-functionalized SBA-15 can effectively improve the catalytic performance of catalyst HPW/NH2-SBA-15 for repeated use in THF polymerization. And the catalyst HPW/NH2-SBA-15 has the highest activity when the mass ratio of mAPTES/mSBA-15=0.0712. It shows good catalytic performance. Its PTHF product has higher molecular weight when SBA-15 has larger specific surface area or larger pore sizes (specific surface area=498~585 m2⋅g-1). Also, the catalytic performance of catalysts and the molecular weight of PTHF product increase with the pore size of

  3. Rubber products prepared from silica modified by radiation-induced admicellar polymerization

    International Nuclear Information System (INIS)

    Unmodified silica, silica modified with Si69, silica modified by thermal admicellar polymerization and silica modified by radiation-induced admicellar polymerization were applied as rubber reinforcement. Mechanical properties of these different rubber formulae were subsequently tested. The results revealed that the mechanical properties of rubber reinforced with silica modified by admicellar polymerization were superior to those reinforced with unmodified silica or silica modified with Si69. As for the silica modified by admicellar polymerization, cetyltrimethyl ammonium bromide (CTAB) proved to be the most effective surfactant, compared to dodecyltrimethyl ammonium bromide (DTAB) and tetradecyltrimethyl ammonium bromide (TTAB). - Highlights: ► Rubber is reinforced with silica modified by radiation-induced admicellar polymerization. ► The modified silica noticeably improves the mechanical properties of the rubber. ► CTAB proves to be the most effective surfactant for the modified silica.

  4. Metallocene-catalyzed alkene polymerization and the observation of Zr-allyls

    OpenAIRE

    Landis, Clark R.; Christianson, Matthew D.

    2006-01-01

    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 zirconoce...

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

    OpenAIRE

    Jun-ichi Kadokawa

    2013-01-01

    This paper reviews the architecture of amylose supramolecules in form of inclusion complexes with synthetic polymers by phosphorylase-catalyzed enzymatic polymerization. Amylose is known to be synthesized by enzymatic polymerization using α-d-glucose 1-phosphate as a monomer, by phosphorylase catalysis. When the phosphorylase-catalyzed enzymatic polymerization was conducted in the presence of various hydrophobic polymers, such as polyethers, polyesters, poly(ester-ether), and polycarbonates a...

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

    International Nuclear Information System (INIS)

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

  7. Catalyzed ring-opening polymerization of epoxidized soybean oil by hydrated and anhydrous fluoroantimonic acids

    Science.gov (United States)

    Ring-opening polymerization of epoxidized soybean oil (ESO) catalyzed by the super acid, fluroantimonic acid hexahydrate (HSbF6-6H2O), and the anhydrous form (HSbF6) in ethyl acetate was conducted in an effort to develop useful biodegradable polymers. The resulting polymerized ESO (SA-RPESO and SAA-...

  8. GRAFTING OF POLYSTYRENE ONTO A NANOMETER SILICA SURFACE BY MICROEMULSION POLYMERIZATION

    Institute of Scientific and Technical Information of China (English)

    Jian Yu; Jie Yu; Yan-fang Gao; Zhao-xia Guo

    2002-01-01

    The grafting of polystyrene onto a nanometer silica surface by microemulsion polymerization is described. Silica was functionalized with 3-methacryloxypropyltrimethoxysilane coupling agent before polymerization. A mixture of ionic and non-ionic surfactants as well as water-soluble and oil-soluble initiators were used. The effect of the amount of silica and ionic surfactant on the graft polymerization was studied. The graft polymerization procedure for styrene was also applied to methyl methacrylate. Composite particles with a core-shell structure were obtained and the yield and grafting efficiency of monomer were high.

  9. Horseradish peroxidase-catalyzed polymerization of cardanol in the presence of redox mediators.

    Science.gov (United States)

    Won, Keehoon; Kim, Yong Hwan; An, Eun Suk; Lee, Yeon Soo; Song, Bong Keun

    2004-01-01

    Horseradish peroxidase-catalyzed polymerization of cardanol in aqueous organic solvent was investigated in the presence of a redox mediator. Cardanol is a phenol derivative from a renewable resource mainly having a C15 unsaturated hydrocarbon chain with mostly 1-3 double bonds at a meta position. Unlike soybean peroxidase (SBP), it has been shown that horseradish peroxidase (HRP) is not able to perform oxidative polymerization of phenol derivatives having a bulky meta substituent such as cardanol. For the first time, redox mediators have been applied to enable horseradish peroxidase to polymerize cardanol. Veratryl alcohol, N-ethyl phenothiazine, and phenothiazine-10-propionic acid were tested as a mediator. It is surprising that the horseradish peroxidase-catalyzed polymerization of cardanol took place in the presence of N-ethyl phenothiazine or phenothiazine-10-propionic acid. However, veratryl alcohol showed no effect. FT-IR and GPC analysis of the product revealed that the structure and properties of polycardanol formed by HRP with a mediator were similar to those by SBP. This is the first work to apply a redox mediator to enzyme-catalyzed oxidative polymerization. Our new finding that oxidative polymerization of a poor substrate, which the enzyme is not active with, can take place in the presence of an appropriate mediator will present more opportunities for the application of enzyme-catalyzed polymerization. PMID:14715000

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

    International Nuclear Information System (INIS)

    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.

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

    DEFF Research Database (Denmark)

    Monnard, Pierre-Alain; Szostak, Jack W.

    2008-01-01

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

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

    Science.gov (United States)

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

    1999-01-01

    Lipase catalysis induced a ring-opening polymerization of lactones with different ring-sizes. Small-size (four-membered) and medium-size lactones (six- and seven-membered) as well as macrolides (12-, 13-, 16-, and 17-membered) were subjected to lipase-catalyzed polymerization. The polymerization behaviors depended primarily on the lipase origin and the monomer structure. The macrolides showing much lower anionic polymerizability were enzymatically polymerized faster than epsilon-caprolactone. The granular immobilized lipase derived from Candida antartica showed extremely efficient catalysis in the polymerization of epsilon-caprolactone. Single-step terminal functionalization of the polyester was achieved by initiator and terminator methods. The enzymatic polymerizability of lactones was quantitatively evaluated by Michaelis-Menten kinetics. PMID:10416661

  13. Amylase catalyzed synthesis of glycosyl acrylates and their polymerization

    OpenAIRE

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

    2014-01-01

    The enzymatic synthesis of novel (di)saccharide acrylates from starch and 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate and 4-hydroxybutyl acrylate (2-HEA, 2-HEMA and 4-HBA) catalyzed by various commercially available amylase preparations is demonstrated. Both liquefaction and saccharification amylases were tested as biocatalysts. Transglycosidation products were only detected in reaction mixtures containing saccharification amylases. The glycoamylase from Aspergillus niger was found t...

  14. Palladium (Ii) Catalyzed Polymerization Of Norbornene And Acrylates

    Science.gov (United States)

    Sen, Ayusman; Kacker, Smita; Hennis, April; Polley, Jennifer D.

    2001-10-09

    Homopolymers or copolymers of acrylates, homopolymers or copolymers of norbornenes, and copolymers of acrylates with norbornenes, may be prepared by contacting acrylate and/or norbornene monomer reactant under polymerization conditions and in the presence of a solvent with a catalyst system consisting essentially of a Pd(II) dimer component having the formula: where L is a monodentate phosphorus or nitrogen ligand, X is an anionic group, and R is an alkyl or aryl group.

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

    Directory of Open Access Journals (Sweden)

    Shen Ruoping

    2009-01-01

    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.

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

    Directory of Open Access Journals (Sweden)

    Elodie Bourgeat-Lami

    2007-01-01

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

  17. Luminescent silica nanoparticles for sensing acetylcholinesterase-catalyzed hydrolysis of acetylcholine.

    Science.gov (United States)

    Mukhametshina, Alsu R; Fedorenko, Svetlana V; Zueva, Irina V; Petrov, Konstantin A; Masson, Patrick; Nizameev, Irek R; Mustafina, Asiya R; Sinyashin, Oleg G

    2016-03-15

    This work highlights the H-function of Tb(III)-doped silica nanoparticles in aqueous solutions of acetic acid as a route to sense acetylcholinesterase-catalyzed hydrolysis of acetylcholine (ACh). The H-function results from H(+)-induced quenching of Tb(III)-centered luminescence due to protonation of Tb(III) complexes located close to silica/water interface. The H-function can be turned on/switched off by the concentration of complexes within core or nanoparticle shell zones, by the silica surface decoration and adsorption of both organic and inorganic cations on silica surface. Results indicate the optimal synthetic procedure for making nanoparticles capable of sensing acetic acid produced by enzymatic hydrolysis of acetylcholine. The H-function of nanoparticles was determined at various concentrations of ACh and AChE. The measurements show experimental conditions for fitting the H-function to Michaelis-Menten kinetics. Results confirm that reliable fluorescent monitoring AChE-catalyzed hydrolysis of ACh is possible through the H-function properties of Tb(III)-doped silica nanoparticles. PMID:26516688

  18. Utilizing advanced polymerization techniques for simplifying polymer grafting from silica colloidal crystal substrates

    Science.gov (United States)

    Yerneni, Charu K.

    Polyacrylamide has been well established as a biocompatible material when Polyacrylamide gel electrophoresis (PAGE) came into existence in the 1960s. Under aqueous buffer conditions it becomes non-adsorptive to proteins and due to its molecular level pore forming nature could be used in size based biomolecule separations. Since then considerable research has been done to explore the non-adsorptive nature of polyacrylamide on a platform or substrate. Attempts were made to grow polyacrylamide chains from silica as a substrate which can then be used in various protein separation techniques. Based on an ionic polymerization method which was used for gel casting in PAGE, polymers were grown on silica gel. Though considerable thickness could be achieved, polymerization was not just confined to the surface. Therefore a rigid polymer brush layer could not be achieved. Atom transfer radical polymerization (ATRP) method showed the solution to this problem. Polymer brush layers with acceptable thickness could now be achieved for growing polyacrylamide from silica gel. Yet it still suffered from several disadvantages such as the need of an inert atmosphere for polymerization and limited thickness. Many developments have taken place in the past decade which led to improvements in substrate and polymerization methods. This research used non porous sub-micron silica as the substrate and AGET ATRP (Activator generated electron transfer atom transfer radical polymerization) for surface grafting polyacrylamide. Non porous submicron silica has been shown to be a better stationary phase substrate for protein separations than conventional substrates. AGET ATRP enables polymerization to be performed under ambient conditions and in water based solutions which gives thicknesses much higher than conventional ATRP. Data from various analytical techniques showed that within the experimental range the polymerization is linear and has decent control. This means silica nanoparticles coated with

  19. Polymerization of o-Phenylenediamine Catalyzed by Hemeproteins Encapsulated in Reversed Micelle

    Institute of Scientific and Technical Information of China (English)

    YANG Yong; MAO Lu-yuan; LI Liu-zhu; LIU Xiao-guang; SHI Jun; CAO Shao-kui

    2004-01-01

    Hemeproteins encapsulated in reversed micelle formulated with di-2-ethylhexyl sulfosuccinate (AOT)was found to catalyze the polymerization of o-phenylenediamine (o-PDA) with hydrogen peroxide, whereas o-PDA catalyzed by hemeproteins dissolved in water could only form its trimers. As the nanostructural environment in reversed micelle acts as a certain orientation surrounding medium, it offers a strong electrostatic field that alters the reductive potential of Fe3+/Fe2+ (Em7) in the heme of hemeproteins and thus increases the catalytic activity of peroxidase accordingly. According to the results of UV-Vis, 1H NMR and FTIR, the polymer catalyzed by hemoglobin(Hb) in reversed micelle was presumed to be constructed of lines and trapeziforms alternatively.

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

    KAUST Repository

    Zhao, Junpeng

    2015-02-04

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

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

    Institute of Scientific and Technical Information of China (English)

    WAN; Xiaolong

    2001-01-01

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

  2. Characterization of transparent silica films deposited on polymeric materials

    International Nuclear Information System (INIS)

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

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

    Directory of Open Access Journals (Sweden)

    J. Lv

    2012-10-01

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

  4. Molecular Dynamics Simulations of Aldol Condensation Catalyzed by Alkylamine-Functionalized Crystalline Silica Surfaces.

    Science.gov (United States)

    Kim, Ki Chul; Moschetta, Eric G; Jones, Christopher W; Jang, Seung Soon

    2016-06-22

    Molecular dynamics simulations are performed to investigate the cooperatively catalyzed aldol condensation between acetone and 4-nitrobenzaldehyde on alkylamine (or alkylenamine)-grafted silica surfaces, focusing on the mechanism of the catalytic activation of the acetone and 4-nitrobenzaldehyde by the acidic surface silanols followed by the nucleophilic attack of the basic amine functional group toward the activated reactant. From the analysis of the correlations between the catalytically active acid-base sites and reactants, it is concluded that the catalytic cooperativity of the acid-base pair can be affected by two factors: (1) the competition between the silanol and the amine (or enamine) to form a hydrogen bond with a reactant and (2) the flexibility of the alkylamine (or alkylenamine) backbone. Increasing the flexibility of the alkylamine facilitates the nucleophilic attack of the amine on the reactants. From the molecular dynamics simulations, it is found that C3 propylamine and C4 butylamine linkers exhibit the highest probability of reaction, which is consistent with the experimental observation that the activity of the aldol reaction on mesoporous silica depends on the length of alkylamine grafted on the silica surface. This simulation work serves as a pioneering study demonstrating how the molecular simulation approach can be successfully employed to investigate the cooperative catalytic activity of such bifunctional acid-base catalysts. PMID:27238580

  5. Synthesis and silica coating of calcia-doped ceria/mica nanocomposite by seeded polymerization technique

    Energy Technology Data Exchange (ETDEWEB)

    El-Toni, Ahmed Mohamed [Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, Sendai 980-8577 (Japan)]. E-mail: el-toni@mail.tagen.tohoku.ac.jp; Yin, Shu [Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, Sendai 980-8577 (Japan); Sato, Tsugio [Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, Sendai 980-8577 (Japan)

    2006-05-15

    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 platy particles are required to enhance the covering ability of inorganic materials. This can be accomplished by synthesis of calcia-doped ceria/mica nanocomposite with subsequent silica coating to control catalytic activity of calcia-doped ceria. Calcia-doped ceria/mica nanocomposite was prepared by soft solution chemical method followed by silica coating via seeded polymerization technique. Silica coated calcia-doped ceria/mica nanocomposite was characterized by X-ray diffraction, SEM, TEM, XPS and FT-IR.

  6. Polymerization of ethylene by silica-supported dinuclear Cr(III) sites through an initiation step involving C-H bond activation.

    Science.gov (United States)

    Conley, Matthew P; Delley, Murielle F; Siddiqi, Georges; Lapadula, Giuseppe; Norsic, Sébastien; Monteil, Vincent; Safonova, Olga V; Copéret, Christophe

    2014-02-10

    The insertion of an olefin into a preformed metal-carbon bond is a common mechanism for transition-metal-catalyzed olefin polymerization. However, in one important industrial catalyst, the Phillips catalyst, a metal-carbon bond is not present in the precatalyst. The Phillips catalyst, CrO3 dispersed on silica, polymerizes ethylene without an activator. Despite 60 years of intensive research, the active sites and the way the first CrC bond is formed remain unknown. We synthesized well-defined dinuclear Cr(II) and Cr(III) sites on silica. Whereas the Cr(II) material was a poor polymerization catalyst, the Cr(III) material was active. Poisoning studies showed that about 65 % of the Cr(III) sites were active, a far higher proportion than typically observed for the Phillips catalyst. Examination of the spent catalyst and isotope labeling experiments showed the formation of a Si-(μ-OH)-Cr(III) species, consistent with an initiation mechanism involving the heterolytic activation of ethylene at Cr(III) O bonds. PMID:24505006

  7. Development of mechano-responsive polymeric scaffolds using functionalized silica nano-fillers for the control of cellular functions

    OpenAIRE

    Griffin, M.; Nayyer, L.; Butler, P. E.; R.G. Palgrave; Seifalian, A. M.; Kalaskar, D. M.

    2016-01-01

    We demonstrate an efficient method to produce mechano-responsive polymeric scaffolds which can alter cellular functions using two different functionalized (OH and NH2) silica nano-fillers. Fumed silica-hydroxyl and fumed silica-amine nano-fillers were mixed with a biocompatible polymer (POSS-PCU) at various wt% to produce scaffolds. XPS and mechanical testing demonstrate that bulk mechanical properties are modified without changing the scaffold's surface chemistry. Mechanical testing showed s...

  8. Synthesis and characterization of sulfonated polyphenylene containing benzophenone moiety via nickel catalyzed polymerization

    International Nuclear Information System (INIS)

    Graphical abstract: Synthesis and characterization of sulfonated polyphenylene containing benzophenone moiety via nickel catalyzed polymerization. - Highlights: • The active new monomer, 1,6-dichloro-2,5-dibenzoylbenzene, was synthesized. • The sulfonated polyphenylenes containing benzoyl moiety were synthesized with high molecular weight using Ni(II) and Zn catalysts. • Carbon-carbon structures membranes showed good performance with high proton conductivity. - Abstract: The synthesis of polyphenylenes containing benzoyl moiety (PPBP), their functionalization with sulfonic acid groups, and the measurement of properties for PEMs are described. The new monomer was synthesized from an oxidation reaction of 2,5-dichloro-p-xylene, followed by Fridel-craft reaction with benzene. The polymerization was performed by a Ni-catalyzed carbon-carbon coupling reaction of 1,6-dichloro-2,5-dibenzoylbenzene, followed by a sulfonation reaction with chlorosulfuric acid. Compared with Nafion 211® membrane, these SPPBPs showed rational IECs from 1.47 to 2.51 meq./g, water uptake from 54.1 to 88.4%, proton conductivity from 80.6 to 108.6 mS/cm, and high thermal stability. The proton conductivity was higher than Nafion 211®. These results showed that the morphology of the polymer matrix was greatly affected by the membranes’ properties and stability. Membranes, including benzoyl segments without ether linkage, also provided good dimensional stability in spite of high IEC values. The properties of SPPBPs were very remarkable for fuel cell membrane application. This research demonstrated the possibility of promising SPPBP membranes for excellent proton conductivity

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-05-01

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

  10. An Efficient Procedure for Esterification of Aryloxyacetic Acid and Arylthioacetic Acid Catalyzed by Silica Sulfuric Acid

    Institute of Scientific and Technical Information of China (English)

    LI,Hong-Ya; LI,Ji-Tai; LI,Hui-Zhang

    2004-01-01

    @@ Aryloxyacetate and arylthioacetate are wildly used in herbicides, plant regulator and insecticides. Recently, Wille et al. have reported that methyl aryloxyacetate is an efficient agent to prevent and treat allergic contact dermatitis.[1] The most popular synthesis is by heating sodium phenoxide (mercaptide) with ethyl chloroacetate in DMF,[2] or by the esterification of acid with alcohol using concentrated H2SO4 as catalyst.[3] In this paper, synthesis of aryloxyacetate and aryl thioacetate from aryloxyacetic acid and arylthioacetic acid respectively in ether catalyzed by silica sulfuric acid in 83%~94% yields is described. The catalyst is reused for 3 times without significant loss of activity (Entry 4). Compared with common procedures, the present procedure possesses the advantages of the operational simplicity, short reaction time,less-corrosion, high yield and reusable catalyst.

  11. Trace the polymerization induced by gamma-ray irradiated silica particles

    Science.gov (United States)

    Lee, Hoik; Ryu, Jungju; Kim, Myungwoong; Im, Seung Soon; Kim, Ick Soo; Sohn, Daewon

    2016-08-01

    A γ-ray irradiation to inorganic particles is a promising technique for preparation of organic/inorganic composites as it offers a number of advantages such as an additive-free polymerizations conducted under mild conditions, avoiding undesired damage to organic components in the composites. Herein, we demonstrated a step-wise formation mechanism of organic/inorganic nanocomposite hydrogel in detail. The γ-ray irradiation to silica particles dispersed in water generates peroxide groups on their surface, enabling surface-initiated polymerization of acrylic acid from the inorganic material. As a result, poly(acrylic acid) (PAA) covers the silica particles in the form of a core-shell at the initial stage. Then, PAA-coated silica particles associate with each other by combination of radicals at the end of chains on different particles, leading to micro-gel domains. Finally, the micro-gels are further associated with each other to form a 3D network structure. We investigated this mechanism using dynamic light scattering (DLS) and transmission electron microscopy (TEM). Our result strongly suggests that controlling reaction time is critical to achieve specific and desirable organic/inorganic nanocomposite structure among core-shell particles, micro-gels and 3D network bulk hydrogel.

  12. Strong, low-density nanocomposites by chemical vapor deposition and polymerization of cyanoacrylates on aminated silica aerogels.

    Science.gov (United States)

    Boday, Dylan J; Stover, Robert J; Muriithi, Beatrice; Keller, Michael W; Wertz, Jason T; Defriend Obrey, Kimberly A; Loy, Douglas A

    2009-07-01

    Strong polymer-silica aerogel composites were prepared by chemical vapor deposition of cyanoacrylate monomers onto amine-modified aerogels. Amine-modified silica aerogels were prepared by copolymerizing small amounts of (aminopropyl)triethoxysilane with tetraethoxysilane. After silation of the aminated gels with hexamethyldisilazane, they were dried as aerogels using supercritical carbon dioxide processing. The resulting aerogels had only the amine groups as initiators for the cyanoacrylate polymerizations, resulting in cyanoacrylate macromolecules that were higher in molecular weight than those observed with unmodified silica and that were covalently attached to the silica surface. Starting with aminated silica aerogels that were 0.075 g/cm(3) density, composite aerogels were made with densities up to 0.220 g/cm(3) and up to 31 times stronger (flexural strength) than the precursor aerogel and about 2.3 times stronger than an unmodified silica aerogel of the same density. PMID:20355935

  13. Removal of benzene from wastewater via Fenton pre-treatment followed by enzyme catalyzed polymerization.

    Science.gov (United States)

    Saha, Beeta; Taylor, K E; Bewtra, J K; Biswas, N

    2011-01-01

    This study investigated the feasibility of a two-step process for the removal of benzene from buffered synthetic wastewater. Benzene is outside the scope of enzymatic removal. In order to remove it from wastewater using enzyme, its pretreatment by modified Fenton reaction was employed to generate the corresponding phenolic compounds. In the first phase, the optimum pH, H2O2 and Fe2+ concentrations and reaction time for the Fenton reaction were determined to maximize the conversion of benzene to phenolic compounds without causing significant mineralization. The pretreatment process was followed by oxidative polymerization of the phenolic compounds catalyzed by a laccase from Trametes villosa. Factors of interest for the three-hour enzymatic treatment were pH and laccase concentration. Under optimum Fenton reaction conditions, 80% conversion of the initial benzene concentration was achieved, giving a mixture containing oxidative dimerization product (biphenyl) and hydroxylation products (phenol, catechol, resorcinol, benzoquinone and hydroquinone). Enzymatic removal of biphenyl and benzoquinone was not possible but 2.5 U/mL laccase was successful in removal of the rest of the phenolic PMID:21866766

  14. Quarternization of 3-azido-1-propyne oligomers obtained by copper(I)-catalyzed azide–alkyne cycloaddition polymerization

    OpenAIRE

    Shun Nakano; Akihito Hashidzume; Takahiro Sato

    2015-01-01

    3-Azido-1-propyne oligomer (oligoAP) samples, prepared by copper(I)-catalyzed azide–alkyne cycloaddition (CuAAC) polymerization, were quarternized quantitatively with methyl iodide in sulfolane at 60 °C to obtain soluble oligomers. The conformation of the quarternized oligoAP in dilute DMSO-d6 solution was examined by pulse-field-gradient spin-echo NMR based on the touched bead model.

  15. Chemical and mechanical properties of silica hybrid films from NaOH catalyzed sols for micromachining with diamond cutting tools

    International Nuclear Information System (INIS)

    Manufacturing of microstructured mold surfaces was realized by the micromachining of thick sol–gel silica hybrid coatings. The films were deposited onto pre-machined steel molds by spin coating using NaOH-catalyzed sols from organosilicate precursors. The effect of the sol synthesis and the heat treatment on the mechanical and chemical properties of these films was studied in order to develop thick and crack-free films with appropriate properties for micromachining with diamond cutting tools. The hardness was measured by nanoindentation as a function of the heat treatment temperature. The transition from soft organic gel films to hard glass-like films due to the thermal treatment was characterized by X-ray photoelectron spectroscopy, elastic recoil detection, and Raman and infrared spectroscopies. The films from NaOH catalyzed sols showed a complex transition from aliphatic carbon originating from hydrocarbon groups to carbonates, carboxylates and disordered carbon clusters. - Highlights: ► Thick silica hybrid films were micromachined with diamond cutting tools. ► The nanoindentation hardness increased with the heat treatment temperature. ► The role of sodium hydroxide in base catalyzed silica sols was studied. ► Formation of carbonates, carboxylates and disordered carbon was observed

  16. Chemical and mechanical properties of silica hybrid films from NaOH catalyzed sols for micromachining with diamond cutting tools

    Energy Technology Data Exchange (ETDEWEB)

    Prenzel, T., E-mail: tprenzel@uni-bremen.de [Stiftung Institut für Werkstofftechnik, Badgasteiner Str. 3, 28359 Bremen (Germany); Mehner, A. [Stiftung Institut für Werkstofftechnik, Badgasteiner Str. 3, 28359 Bremen (Germany); Lucca, D.A.; Qi, Y.; Harriman, T.A. [School of Mechanical and Aerospace Engineering, 218 Engineering North, Oklahoma State University, Stillwater, OK 74078 (United States); Mutlugünes, Y. [Labor für Mikrozerspanung — LFM, Badgasteiner Str. 2, 28359 Bremen (Germany); Shojaee, S.A. [School of Mechanical and Aerospace Engineering, 218 Engineering North, Oklahoma State University, Stillwater, OK 74078 (United States); Wang, Y.Q.; Williams, D. [Los Alamos National Laboratory, Los Alamos, NM 87545 (United States); Nastasi, M. [Nebraska Center for Energy Sciences Research, University of Nebraska, 230 Whittier Research Center, 2200 Vine Street Lincoln, NE 68583-0857 (United States); Zoch, H.-W. [Stiftung Institut für Werkstofftechnik, Badgasteiner Str. 3, 28359 Bremen (Germany); Swiderek, P. [Institute of Applied and Physical Chemistry, University of Bremen, Leobener Straße, 28359 Bremen (Germany)

    2013-03-01

    Manufacturing of microstructured mold surfaces was realized by the micromachining of thick sol–gel silica hybrid coatings. The films were deposited onto pre-machined steel molds by spin coating using NaOH-catalyzed sols from organosilicate precursors. The effect of the sol synthesis and the heat treatment on the mechanical and chemical properties of these films was studied in order to develop thick and crack-free films with appropriate properties for micromachining with diamond cutting tools. The hardness was measured by nanoindentation as a function of the heat treatment temperature. The transition from soft organic gel films to hard glass-like films due to the thermal treatment was characterized by X-ray photoelectron spectroscopy, elastic recoil detection, and Raman and infrared spectroscopies. The films from NaOH catalyzed sols showed a complex transition from aliphatic carbon originating from hydrocarbon groups to carbonates, carboxylates and disordered carbon clusters. - Highlights: ► Thick silica hybrid films were micromachined with diamond cutting tools. ► The nanoindentation hardness increased with the heat treatment temperature. ► The role of sodium hydroxide in base catalyzed silica sols was studied. ► Formation of carbonates, carboxylates and disordered carbon was observed.

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

    Science.gov (United States)

    Zhang, Jinyu; Zhou, Guowei; Jiang, Bin; Zhao, Minnan; Zhang, Yan

    2014-05-01

    Mesoporous silica materials with a range of morphology evolution, i.e., from curved rod-shaped mesoporous silica to straight rod-shaped mesoporous silica, were successfully prepared using polyvinylpyrrolidone (PVP) and triblock copolymer as dual template. The effects of PVP molecular weight and concentration on mesoporous silica structure parameters were studied. Results showed that surface area and pore volume continuously decreased with increased PVP molecular weight. Mesoporous silica prepared with PVP K30 also possessed larger pore diameter, interplanar spacing (d100), and cell parameter (a0) than that prepared with PVP K15 and PVP K90. In addition, with increased PVP concentration, d100 and a0 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%.

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

    Institute of Scientific and Technical Information of China (English)

    BAO Yongzhong; ZHAO Wenting; HUANG Zhiming

    2013-01-01

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

  19. Amino acid-catalyzed seed regrowth synthesis of photostable high fluorescent silica nanoparticles with tunable sizes for intracellular studies

    International Nuclear Information System (INIS)

    Size-controlled fluorescence silica nanoparticles (NPs) are widely used for nanotoxicological studies, and diagnostic and targeted therapies. Such particles can be easily visualized and localized within cell environments and their interactions with cellular components can be monitored. We developed an amino acid-catalyzed seed regrowth technique (ACSRT) to synthesize spherical rhodamine-doped silica NPs with tunable sizes, low polydispersity index as well as high labeling efficiency and enhanced fluorescence photostability. Via ACSRT, fluorescent silica NPs can be obtained by introducing the fluorophore in seed formation step, while a precise control over particle size can be achieved by simply adjusting the concentration of reactants in the regrowth step. Unlike the conventional methods, the proposed ACSRT permits the synthesis of fluorescent silica NPs in a water-based system, without the use of any surfactants and co-surfactants. By this approach, additional linkers for covalent coupling of the fluorophore to silica matrix can be omitted, while a remarkable doping efficiency is achieved. The suitability of these particles for biomedical application is demonstrated by in vitro tests with normal and malignant bone cells. We show that the particles can be easily and unambiguously visualized by a conventional fluorescence microscope, localized, and distinguished within intracellular components. In addition, it is presented that the cellular uptake and cytotoxic profile of silica NPs are strongly correlated to the particle size, concentration, and cell line. The results of in vitro experiments demonstrate that tunable fluorescent silica NPs synthesized with ACSRT can be potentially used for toxicological assessments and nanomedical studies

  20. Development and characterization of stabilized, polymerized phospholipid bilayers on silica particles for specific immobilization of His-tagged proteins

    Indian Academy of Sciences (India)

    Seid M Adem

    2015-04-01

    Stabilized phospholipid bilayer (PLB) coated silica microspheres were prepared via polymerization of lipid monomers. These lipid coated silica microspheres are stable to both extended storage in solution at 4°C and dry storage at room temperature. These stabilized lipid coated microspheres have also been functionalized with nickel-chelating lipids, a commonly used tool for immobilizing polyhistidine-tagged proteins. 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, these biocompatible (poly)bis-SorbPC coated microspheres were able to minimize non-specific protein adsorption.

  1. Half-sandwich rare-earth-catalyzed olefin polymerization, carbometalation, and hydroarylation.

    Science.gov (United States)

    Nishiura, Masayoshi; Guo, Fang; Hou, Zhaomin

    2015-08-18

    -site catalysts. This Account is intended to give an overview of our recent studies on organo rare-earth catalysis, in particular the synthesis and application of half-sandwich rare-earth alkyl complexes bearing monocyclopentadienyl ligands for olefin polymerization, carbometalation, and hydroarylation. Treatment of half-sandwich rare-earth dialkyl complexes having the general formula CpMR2 with an equimolar amount of an appropriate borate compound such as [Ph3C][B(C6F5)4] can generate the corresponding cationic monoalkyl species, which serve as excellent single-site catalysts for the polymerization and copolymerization of a wide range of olefin monomers such as ethylene, 1-hexene, styrene, conjugated and nonconjugated dienes, and cyclic olefins. The cationic half-sandwich rare-earth alkyl complexes can also catalyze the regio- and stereoselective alkylative alumination of alkenes and alkynes through insertion of the unsaturated C-C bond into the metal-alkyl bond followed by transmetalation between the resulting new alkyl or alkenyl species and an alkylaluminum compound. Moreover, a combination of deprotonative C-H bond activation of appropriate organic compounds such as anisoles and pyridines by the rare-earth alkyl species and insertion of alkenes into the resulting new metal-carbon bond can lead to catalytic C-H bond alkylation of the organic substrates. Most of these transformations are unique to the rare-earth catalysts with selectivity and functional group tolerance different from those of late-transition-metal catalysts. PMID:26214733

  2. RAFT Polymerization of N-[3-(Trimethoxysilyl)-propyl]acrylamide and Its Versatile Use in Silica Hybrid Materials.

    Science.gov (United States)

    Maçon, Anthony L B; Greasley, Sarah L; Becer, C Remzi; Jones, Julian R

    2015-12-01

    Reversible addition-fragmentation chain transfer (RAFT) polymerization and characterization of an alkoxysilane acrylamide monomer using a trithiocarbonate chain transfer agent are described. Poly(N-[3-(trimethoxysilyl)propyl]acrylamide) (PTMSPAA) homopolymers are obtained with good control over the polymerization. A linear increase in the molecular weight is observed whereas the polydispersity values do not exceed 1.2 regardless of the monomer conversion. Moreover, PTMSPAA is used as a macro-RAFT agent to polymerize N-isopropylacrylamide (NIPAM). By varying the degree of polymerization of NIPAM within the block copolymer, different sizes of thermoresponsive particles are obtained. These particles are stabilized by the condensation of the alkoxysilane moieties of the polymers. Furthermore, a co-network of silica and PTMSPAA is prepared using the sol-gel process. After drying, transparent mesoporous hybrids are obtained with a surface area of up to 400 m(2) g(-1). PMID:26288010

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

    International Nuclear Information System (INIS)

    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 Tg 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−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 analysis shows that

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-11-15

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

  5. Development of mechano-responsive polymeric scaffolds using functionalized silica nano-fillers for the control of cellular functions.

    Science.gov (United States)

    Griffin, Michelle; Nayyer, Leila; Butler, Peter E; Palgrave, Robert G; Seifalian, Alexander M; Kalaskar, Deepak M

    2016-08-01

    We demonstrate an efficient method to produce mechano-responsive polymeric scaffolds which can alter cellular functions using two different functionalized (OH and NH2) silica nano-fillers. Fumed silica-hydroxyl and fumed silica-amine nano-fillers were mixed with a biocompatible polymer (POSS-PCU) at various wt% to produce scaffolds. XPS and mechanical testing demonstrate that bulk mechanical properties are modified without changing the scaffold's surface chemistry. Mechanical testing showed significant change in bulk properties of POSS-PCU scaffolds with an addition of silica nanofillers as low as 1% (P<0.01). Scaffolds modified with NH2 silica showed significantly higher bulk mechanical properties compared to the one modified with the OH group. Enhanced cell adhesion, proliferation and collagen production over 14days were observed on scaffolds with higher bulk mechanical properties (NH2) compared to those with lower ones (unmodified and OH modified) (P<0.05) during in vitro analysis. This study provides an effective method of manufacturing mechano-responsive polymeric scaffolds, which can help to customize cellular responses for biomaterial applications. PMID:27013128

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

    OpenAIRE

    Roos, Peter; Meier, Gerben B.; Samson, Job Jan C.; Weickert, Günter; Westerterp, K. Roel

    1997-01-01

    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 catalyst. the average catalyst activity is reproducible within 10% for low temperatures. The polymerization rate and the rate of deactivation increase with increasing temperature. The deactivation ...

  7. In vitro polymerization of mussel polyphenolic proteins catalyzed by mushroom tyrosinase.

    Science.gov (United States)

    Burzio, L A; Burzio, V A; Pardo, J; Burzio, L O

    2000-07-01

    The in vitro enzymatic polymerization of the polyphenolic protein purified from the mussels Aulacomya ater, Mytilus edulis chilensis and Choromytilus chorus was studied. Mushroom tyrosinase was used to oxidize the dopa residues present in these proteins, and polymerization was monitored by acid-urea polyacrylamide gel electrophoresis. The protein from A. ater polymerized at a faster rate than the other two. Amino acid analysis of the crosslinked protein showed a notable decrease in the content of dopa, but no significant change of other amino acids. This suggests that crosslink formation may be limited to the oxidized dopa derivatives of the protein molecules. PMID:11007180

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

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    No matter what the polymerization manner was, polystyrene withunique high Tm (Tm = 170-285℃) was obtained through polymerization of styrene if the amount of BDE/CuCl catalyst was highly increased (mol ratio: St:CuCl = 25:1-2.5:1). Partial crystallinity of the PSt was observed by characterizations of X-ray diffraction and DSC. Spectra of 1H-NMR and 13C-NMR showed that syndiotactic structure contained in the obtained PSt was 5% more than that in aPSt (atactic polystyrene). According to the proposed "coordinated radical cage" mechanism, the coordinated state between radical and catalyst center metal Cu should be more closely packed with increasing the BDE/CuCl catalyst amount, which was induced to partial stereospecific polymerization in the coordinated radical polymerization of St.

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

    International Nuclear Information System (INIS)

    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 N2 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 oC and stable up to about 350-400 oC 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.

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

    Science.gov (United States)

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

    2015-12-01

    We present a new method for the preparation of superhydrophobic materials by in situ aggregation of silica nanoparticles on a surface during a urea-formaldehyde (UF) polymerization. This is a one-step process in which a two-tier topography is obtained. The polymerization is carried out for 30, 60, 120, 180, and 240 min on silicon shards. Silicon surfaces are sintered to remove the polymer. SEM and AFM show both an increase in the area covered by the nanoparticles and their aggregation with increasing polymerization time. Chemical vapor deposition of a fluorinated silane in the presence of a basic catalyst gives these surfaces hydrophobicity. Deposition of this low surface energy silane is confirmed by the F 1s signal in XPS. The surfaces show advancing water contact angles in excess of 160 degrees with very low hysteresis (< 7) after 120 min and 60 min polymerization times for 7 nm and 14 nm silica, respectively. Depositions are successfully demonstrated on glass substrates after they are primed with a UF polymer layer. Superhydrophobic surfaces can also be prepared on unsintered substrates. PMID:26682448

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

    KAUST Repository

    Alamri, Haleema

    2014-01-01

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

  12. Controlled Radical Polymerization of Methyl Methacrylate Catalyzed by Hybrid Supported Iron Catalyst

    Institute of Scientific and Technical Information of China (English)

    LI Zhong-hui; ZHANG Yong-ming; XUE Min-zhao; ZHOU Lei; LIU Yan-gang

    2005-01-01

    A supported iron catalyst, which was prepared by anchoring FeCl2/FeCl3 on the cross-linking macroporous polyacrylate ion exchange resin, was evaluated via the controlled radical polymerization. When a small amount of CuCl2/Me6TREN was added, the controllability of the polymerization over the iron-mediated catalyst was significantly improved(Mw/Mn=1.23-1.73), affording a polymer with a low residual metal via a simple catalyst separation procedure. After suitable regeneration, the supported iron catalyst could also be recycled. UV-Vis analysis showed that the additional copper catalyst could facilitate the radical deactivation process.

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

    Science.gov (United States)

    Sivalingam, G; Madras, Giridhar

    2004-01-01

    Enzymatic ring-opening polymerization of epsilon-caprolactone by various lipases was investigated in toluene at various temperatures. The determination of molecular weight and structural identification was carried out with gel permeation chromatography and proton NMR, respectively. Among the various lipases employed, an immobilized lipase from Candida antartica B (Novozym 435) showed the highest catalytic activity. The polymerization of epsilon-caprolactone by Novozym 435 showed an optimal temperature of 65 degrees C and an optimum toluene content of 50/50 v/v of toluene and epsilon-caprolactone. As lipases can degrade polyesters, a maximum in the molecular weight with time was obtained due to the competition of ring opening polymerization and degradation by specific chain end scission. The optimum temperature, toluene content, and the variation of molecular weight with time are consistent with earlier observations. A comprehensive model based on continuous distribution kinetics was developed to model these phenomena. The model accounts for simultaneous polymerization, degradation and enzyme deactivation and provides a technique to determine the rate coefficients for these processes. The dependence of these rate coefficients with temperature and monomer concentration is also discussed. PMID:15003027

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

    International Nuclear Information System (INIS)

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

  15. New Diketopyrrolopyrrole(DPP)-Based Conjugated Polymers Prepared upon Palladium Catalyzed Polymerization and Electropolymerization Reactions

    OpenAIRE

    Zhu, Yu

    2006-01-01

    Synthesis and characteristic properties of new conjugated polymers and polyelectrolytes containing DPP-units in the main chain are described. The polymers are synthesized upon palladium-catalyzed Suzuki, Stille and Buchwald-Hartwig polycondensation and electropolymerization. Characteristic properties such as molecular weight, structure, optical and electrooptical properties of the polymers are studied using gel permeation chromatography, spectroscopic methods (UV/vis, Fluorescence, NMR spectr...

  16. Silicatein filaments and subunits from a marine sponge direct the polymerization of silica and silicones in vitro.

    Science.gov (United States)

    Cha, J N; Shimizu, K; Zhou, Y; Christiansen, S C; Chmelka, B F; Stucky, G D; Morse, D E

    1999-01-19

    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. PMID:9892638

  17. Phase separation during silica gel formation followed by time-resolved SAXS

    International Nuclear Information System (INIS)

    Time-resolved small angle X-ray scattering data are collected during the formation of silica gels from the base catalyzed polymerization of tetraethoxysilane in ethanol with 3-(2-aminoethylamino)propyltrimethoxysilane and 3-aminopropyltriethoxysilane as additives. It is shown that a polymerization-induced spinodal demixing occurs during the gel formation

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2013-11-01

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

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

    International Nuclear Information System (INIS)

    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)

  20. NONCONVENTIONAL EMULSION POLYMERIZATION OF ACRYLONITRILE CATALYZED BY in situ METAL COMPLEX

    Institute of Scientific and Technical Information of China (English)

    Bijayashree Samal; Prafulla K.Sahoo

    2007-01-01

    Nano-sized polyacrylonitrile (PAN) particles were prepared under the catalytic effect of in situ developed CoCl2/EDTA complex with ammonium persulfate as the initiator in the absence of any added emulsifier.The emulsion polymerization was studied at varying concentrations of the initiator,monomer,complex and solvent over a temperature range of 30-70℃.The overall activation energy(Ea,49.79 kJ/mol),energy of dissociation of initiator(Ed,82.68kJ/mol),number of micelles(0.163 × 1018)and the viscosity average molecular weight of the polymer were computed.The distribution of particle sizes was determined by transmission electron microscopy(TEM).It was found that the oil-in-water polymerization was stabilized by the presence of the CoCl2/EDTA in situ complex reducing the particle size into the nano order.The average diameters of PAN nano particles,obtained by TEM,were in the range of 50-150 nm at the maximum conversion.The experimental particle size was mainly dependent on the concentration of the complex and temperature.

  1. Synthesis of N-aryl imidazoles catalyzed by copper nanoparticles on nanosized silica-coated maghemite

    OpenAIRE

    Nador, Fabiana; Volpe, María A.; Alonso Valdés, Francisco; Radivoy, Gabriel

    2014-01-01

    A magnetically recoverable catalyst consisting of copper nanoparticles (CuNPs) on nanosized silica-coated maghemite is presented. The catalyst has been prepared under mild conditions by mixing the magnetic support with a freshly prepared suspension of CuNPs obtained by fast reduction of anhydrous CuCl2 with lithium sand and a catalytic amount of DTBB (4,4′-di-tert-butylbiphenyl) as electron carrier. This copper-based catalyst has shown to be very efficient in the N-(hetero)arylation of imidaz...

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

    International Nuclear Information System (INIS)

    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

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

    KAUST Repository

    Riache, Nassima

    2015-11-14

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

  4. New antifouling silica hydrogel.

    Science.gov (United States)

    Beltrán-Osuna, Ángela A; Cao, Bin; Cheng, Gang; Jana, Sadhan C; Espe, Matthew P; Lama, Bimala

    2012-06-26

    In this work, a new antifouling silica hydrogel was developed for potential biomedical applications. A zwitterionic polymer, poly(carboxybetaine methacrylate) (pCBMA), was produced via atom-transfer radical polymerization and was appended to the hydrogel network in a two-step acid-base-catalyzed sol-gel process. The pCBMA silica aerogels were obtained by drying the hydrogels under supercritical conditions using CO(2). To understand the effect of pCBMA on the gel structure, pCBMA silica aerogels with different pCBMA contents were characterized using scanning electron microscopy (SEM), nuclear magnetic resonance (NMR) spectroscopy, and the surface area from Brauner-Emmet-Teller (BET) measurements. The antifouling property of pCBMA silica hydrogel to resist protein (fibrinogen) adsorption was measured using enzyme-linked immunosorbent assay (ELISA). SEM images revealed that the particle size and porosity of the silica network decreased at low pCBMA content and increased at above 33 wt % of the polymer. The presence of pCBMA increased the surface area of the material by 91% at a polymer content of 25 wt %. NMR results confirmed that pCBMA was incorporated completely into the silica structure at a polymer content below 20 wt %. A protein adsorption test revealed a reduction in fibrinogen adsorption by 83% at 25 wt % pCBMA content in the hydrogel compared to the fibrinogen adsorption in the unmodified silica hydrogel. PMID:22607091

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

    KAUST Repository

    Khokhar, Munir

    2015-05-01

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

  6. Phenylsulfonic Acid Functionalized Mesoporous Silica Catalyzed Transetherification of Alcohols with Dimethoxymethane

    Institute of Scientific and Technical Information of China (English)

    杨建明; 吕剑

    2005-01-01

    Phenylsulfonic acid functionalized mesoporous silica was synthesized by condensation of tetraethylorthosilicate with phenyltrimethoxysilane, and then sulfonation using 30% fuming sulfuric acid. The material was characterized using FT-IR, DSC, XPS, TEM and N2 adsorption/desorption measurements. DSC revealed that sulfonic acid group of the catalyst was decomposed at 354.8℃, indicating that the catalyst exhibited high thermal stability. XPS showed that there existed three kinds of different silicon species on surface of the catalyst. The catalytic performance of the catalyst was evaluated using transetherification of alcohols with dimethoxymethane. It was found that among primary alcohols, the selectivities of the two long-chain alcohols for n-dedocanol and n-tetradecyl alcohol were higher than 97.0% at the conversions of 43.6% and 65.3%, respectively, while the selectivities of the short-chain alcohols except for n-hexanol were less than 90.0% at the conversions of over 80.0%. Due to steric bartier, the secondary alcohols such as /so-butanol and cyclohexanol afforded conversions of 79.4% and 60.5%, and the selectivities of the two alcohols were more than 90.0%. The sequence in conversion of the substituted phenols isas follows: p-nitrophenol>p-fluorophenol≥p-bromophenol>p-cresol>m-cresol.

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

    International Nuclear Information System (INIS)

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

  8. Fabrication of superhydrophobic silica-based surfaces with high transmittance by using tetraethoxysilane precursor and different polymeric species

    International Nuclear Information System (INIS)

    The preparation of superhydrophobic silica-based surfaces via the sol-gel process through the addition of different polymeric species into the precursor solution was done in this study. The surface roughness of the films was obtained by removing the organic polymer at a high temperature, and then the hydrophobic groups were bonded onto the films with a monolayer by chemical reaction with hexamethyldisilazane (HMDS). The characteristic properties of the as-prepared films were analyzed by contact angle measurements, scanning electron microscopy (SEM), atomic force microscopy (AFM), nitrogen adsorption/desorption, and UV-vis scanning spectrophotometer. The experimental results revealed that the superhydrophobic thin films with high transmittance could easily be prepared using polypropylene (PPG), polyethylene (PEG), and poly(vinylpyrrolidone) (PVP). Surface roughness and pore size were enhanced using PPG polymeric species. The distribution of pore size was from the microporous to the mesoporous and marcoporous regions. In addition, the contact angles of the rough surfaces prepared at 500 deg. C without modification of HMDS were smaller than 5o but larger than 156o after modified by HMDS.

  9. The Use of Functionalized Zirconocenes as Precursors to Silica-Supported Zirconocene Olefin Polymerization Catalysts

    OpenAIRE

    Cheng, Xu

    2001-01-01

    Deck and coworkers previously showed that Me3Si substituents adjacent to group 4 metallocene dichlorides (M = Ti, Zr, Hf) are converted to corresponding BrMe2Si groups using BBr3, and that these BrMe2Si substituents are highly reactive to nucleophilic reagents such as water. The high reactivity of the Si-Br bonds suggested that these substituents could react with hydroxyl groups on the surface of partially dehydroxylated silica, forming covalently immobilized metallocene catalysts. This diss...

  10. FABRICATION AND CHARACTERATION OF NANOPOROUS SILICA FILM

    Institute of Scientific and Technical Information of China (English)

    殷明志; 张良莹; 姚熹

    2003-01-01

    Colloidal silica sol is formed by a novel hydrolyzing procedure of tetraethyl-orthosilicate(TEOS) catalyzing with NH3*H2O in aqueous mediums. Glycerol, combining with the hydrolyzed intermediates of TEOS, controls growing of the silica particles; poly(vinyl-vinyl alcohol makes the colloidal silica sol with polymeric structure and spinning, thermal strain makes the gel silica film changed into a nanoporous structure with diameter ranging 50-150 nm. Morphologies of the nanoporous silica film have been characterized; the porosities (%) is 32-64; the average dielectric constant at 1MHz region is 2.0 and 2.1; the thermal conductivity is less than 0.8. Chemical mechanism of the sol-gel process is discussed.

  11. N-Heterocyclic Carbene-Catalyzed Ring Opening Polymerization of ε-Caprolactone with and without Alcohol Initiators: Insights from Theory and Experiment.

    Science.gov (United States)

    Jones, Gavin O; Chang, Young A; Horn, Hans W; Acharya, Ashwin K; Rice, Julia E; Hedrick, James L; Waymouth, Robert M

    2015-04-30

    Computational investigations with density functional theory (DFT) have been performed on the N-heterocyclic carbene (NHC) catalyzed ring-opening polymerization of ε-caprolactone in the presence and in the absence of a methanol initiator. Much like the zwitterionic ring opening (ZROP) of δ-valerolactone which was previously reported, calculations predict that the mechanism of the ZROP of caprolactone that occurs without an alcohol present involves a high-barrier step involving ring opening of the zwitterionic tetrahedral intermediate formed after the initial nucleophilic attack of NHC on caprolactone. However, the operative mechanism by which caprolactone is polymerized in the presence of an alcohol initiator does not involve the analogous mechanism involving initial nucleophilic attack by the organocatalytic NHC. Instead, the NHC activates the alcohol through hydrogen bonding and promotes nucleophilic attack and the subsequent ring-opening steps that occur during polymerization. The largest free energy barrier for the hydrogen-bonding mechanism in alcohol involves nucleophilic attack, while that for both ZROP processes involves ring opening of the initially formed zwitterionic tetrahedral intermediate. The DFT calculations predict that the rate of polymerization in the presence of alcohol is faster than the reaction performed without an alcohol initiator; this prediction has been validated by experimental kinetic studies. PMID:25848823

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

    International Nuclear Information System (INIS)

    Highlights: ► Silica precipitation occurred via urease-catalytic reactions. ► Higher urease activity for silica synthesis enables mesostructure of silica–urease composites. ► Urease encapsulating in silica matrix retained high activity. - Abstract: Urease templated precipitation of silica synthesized by sol–gel chemistry produces a composite material allowing high urease activity. This study investigates the structural properties of the composite material that allow for the retention of the urease hydrolysis activity. Scanning (SEM) and transmission (TEM) electron microscopy reveal that the composite has a mesoporous structure composed of closely packed spherical structures ∼20–50 nm in diameter. Brunauer–Emmett–Teller (BET) analysis revealed that the surface area and pore volume of the composite prepared under the conditions of 50 mM urea and 25 °C is relatively high (324 m2/g and 1.0 cm3/g). These values are equivalent to those of usual mesoporous silica materials synthesized from the self-assembly of triblock copolymers as organic templates. In addition, after encapsulating in a sol–gel silica matrix, urease retained high activity (∼90% of the activity compared with native urease). Our results suggest a new method for synthesizing mesoporous silica materials with highly tunable pore sizes and shapes under mild conditions.

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

    KAUST Repository

    Chen, Xia

    2012-05-02

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

  14. Loading of Silica Nanoparticles in Block Copolymer Vesicles during Polymerization-Induced Self-Assembly: Encapsulation Efficiency and Thermally Triggered Release.

    Science.gov (United States)

    Mable, Charlotte J; Gibson, Rebecca R; Prevost, Sylvain; McKenzie, Beulah E; Mykhaylyk, Oleksandr O; Armes, Steven P

    2015-12-30

    Poly(glycerol monomethacrylate)-poly(2-hydroxypropyl methacrylate) diblock copolymer vesicles can be prepared in the form of concentrated aqueous dispersions via polymerization-induced self-assembly (PISA). In the present study, these syntheses are conducted in the presence of varying amounts of silica nanoparticles of approximately 18 nm diameter. This approach leads to encapsulation of up to hundreds of silica nanoparticles per vesicle. Silica has high electron contrast compared to the copolymer which facilitates TEM analysis, and its thermal stability enables quantification of the loading efficiency via thermogravimetric analysis. Encapsulation efficiencies can be calculated using disk centrifuge photosedimentometry, since the vesicle density increases at higher silica loadings while the mean vesicle diameter remains essentially unchanged. Small angle X-ray scattering (SAXS) is used to confirm silica encapsulation, since a structure factor is observed at q ≈ 0.25 nm(-1). A new two-population model provides satisfactory data fits to the SAXS patterns and allows the mean silica volume fraction within the vesicles to be determined. Finally, the thermoresponsive nature of the diblock copolymer vesicles enables thermally triggered release of the encapsulated silica nanoparticles simply by cooling to 0-10 °C, which induces a morphological transition. These silica-loaded vesicles constitute a useful model system for understanding the encapsulation of globular proteins, enzymes, or antibodies for potential biomedical applications. They may also serve as an active payload for self-healing hydrogels or repair of biological tissue. Finally, we also encapsulate a model globular protein, bovine serum albumin, and calculate its loading efficiency using fluorescence spectroscopy. PMID:26600089

  15. Sub-femtomolar electrochemical detection of DNA using surface circular strand-replacement polymerization and gold nanoparticle catalyzed silver deposition for signal amplification.

    Science.gov (United States)

    Gao, Fenglei; Zhu, Zhu; Lei, Jianping; Geng, Yao; Ju, Huangxian

    2013-01-15

    A highly sensitive method was developed for detection of target DNA. This method combined circular strand-displacement polymerization (CSRP) with silver enhancement to achieve dual signal amplification. After molecular beacon (MB) hybridized with target DNA, the reporter gold nanoparticle (Au NPs) was attached to an electrode surface by hybridization between Au NP labeled primer and stem part of the MB to initiate a polymerization of DNA strand, which led to the release of target and another polymerization cycle. Thus the CSRP produced the multiplication of target-related reporter Au NPs on the surface. The Au NPs then catalyzed silver deposition for subsequent stripping analysis of silver. The dual signal amplification offered a dramatic enhancement of the stripping response. This signal could discriminate perfect matched target DNA from 1-base mismatch DNA. The dynamic range of the sequence-specific DNA detection was from 10(-16) to 10(-12)mol L(-1) with a detection limit down to sub-femtomolar level. This proposed method exhibited an efficient amplification performance, and would open new opportunities for sensitive detection of other biorecognition events. PMID:22883748

  16. The effects of zeolite and silica gel on synthesis of amylisobutyrate catalyzed by lipase from Candida rugosa

    OpenAIRE

    Stojaković Sanja B.; Bezbradica Dejan I.; Mijin Dušan Ž.; Knežević Zorica D.; Šiler-Marinković Slavica S.

    2008-01-01

    Lipase-catalyzed synthesis of esters has been widely investigated due to numerous advantages in comparison with the conventional chemical process catalyzed with concentrated acids since use of chemical catalysts leads to several problems. The most important disadvantages are corrosion of equipment, hazards of handling of the corrosive acids that are not reused, loss of conversion, yield and selectivity. The activity of water in reaction mixture seems to be one of the crucial factors affecting...

  17. Heck Arylation of Acrylonitrile with Aryl Iodides Catalyzed by a Silica-bound Arsine Palladium(0) Complex

    Institute of Scientific and Technical Information of China (English)

    Ming Zhong CAI; Hong ZHAO; Rong Li ZHANG

    2005-01-01

    Acrylonitrile reacts with aryl iodides in the presence of tri-n-butylamine and a catalytic amount of a silica-bound arsine palladium(0) complex to afford stereoselectively (E)-cinnamonitriles in high yields.

  18. Propylene Polymerization Catalyzed by Bis (R3-indenyl) Zirconium Dichloride/Aluminoxane--Synthesis of Metallocenes and Influence of Sol vent Polarity on Poi ymerization

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    Three unbridged metallocenes, bis(2,4,7-Mea-indenyl)zirconium dichloride (1), bis (2-Me4,7-Etz-indenyl) zirconium dichloride (2) and bis (2,4,6-Me3-indenyl) zirconium dichloride (3)were synthesized. The effect of solvent polarity on propylene polymerization catalyzed by the metallocenes in the presence of methylaluminoxane(MAO) and triisobutylaluminum(TIBA) was investigated in the toluene/CH2Cl2 mixed solvent. Changing the solvent polarity was found to influence the catalytic activity, polymer molecular weight and stereospecificity of the catalysts.The changes in the position of the substituents on the ligand caused the different responses of the catalyst to the changes in solvent polarity. The isotactic stereosequence of polypropylene was found to increase with the increase in the polarity of the reaction medium.

  19. TARTARIC ACID TEMPLATED SYNTHESIS OF MESOPOROUS Ti-INCORPORATED SILICA AND ITS CATALYTIC ACTIVITY FOR THE RING-OPENING POLYMERIZATION OF ε-CAPROLACTONE

    Institute of Scientific and Technical Information of China (English)

    Jie-bin Pang; Chang-ming Dong; Kun-yuan Qiu; Yen Wei

    2002-01-01

    Ti-incorporated mesoporous silica materials with pore diameters of 3-4 nm have been prepared via the co-hydrolysis and co-condensation reactions, that is the sol-gel reactions, of titanium (Ⅳ) tetrabutoxide and tetraethylorthosilicate in the presence of tartaric acid as template, followed by extraction with ethanol to remove the templatemolecules. The materials were characterized in detail by Fourier transform infrared spectroscopy, nitrogen adsorption-desorption test, powder X-ray diffraction, transmission electron microscopy and X-ray energy dispersive spectroscopy. Theresults indicate that the Ti-containing silica materials have large specific surface areas (ca. 1200 m2 g-1) and pore volumes(ca. 0.900 cm3 g-1). The mesoporosity arises from disordered interconnecting channels or pores. The Ti-incorporated silicasexhibit catalytic activity for the ring-opening polymerization of ε-caprolactone, otherwise, the pure mesoporous silicamaterial shows no catalytic activity under the identical conditions.

  20. Direct coating for layered double hydroxide/4,4'-diaminostilbene-2,2'-disulfonic acid nanocomposite with silica by seeded polymerization technique

    International Nuclear Information System (INIS)

    Organic ultraviolet (UV) ray absorbents have been used as sunscreen materials, but may pose a safety problem when used at high concentration. In order to prevent direct contact of organic UV rays absorbent by the human skin, an organic UV absorbent such as 4,4'-diaminostilbene-2,2'-disulfonic acid (DASDSA) was intercalated into Zn2Al-layered double hydroxide (Zn2Al-LDHs) by coprecipiation reaction. The problem of deintercalation of organic molecules from LDHs by the anion exchange reaction with carbonate ion could be greatly depressed by forming a protection film of silica on the surface. Zn2Al-LDH/DASDSA was directly coated with silica by means of a polymerization technique based on the Stoeber method. The deintercalation behavior as well as UV-shielding properties were investigated for coated particles

  1. Regioselectivity Study on Propylene Polymerization Catalyzed by Neutral Salicyladiminato Pd(Ⅱ) Model Complex with DFT Method

    Institute of Scientific and Technical Information of China (English)

    YANG Zhao-Di; LIU Yue; LIU Ying

    2005-01-01

    Many attempts have been made to control the regioselectivity for olefin poly- merization by varying the structures of ligands in catalysts. The regioselectivity of propylene polymerization was investigated by replacing a nitrogen atom in the Pd(II) diimine catalyst with an oxygen atom from density functional theory method at the B3LYP/LANL2DZ level. The results show that the 1,2-insertion becomes a rival mechanism to the 2,1-insertion when the nitrogen atom is replaced by the oxygen atom leading to an asymmetric environment in the catalyst, and that the steric effect in the asymmetrical catalyst plays an important part in the polymerization. The insertion barrier from 2-O is much higher than that from 2-N. A pyramid transition state was characterized for the catalyst to convert 2-O back to 2-N through internal rotation. The propylene prefers to coordinate at the opposite side of O in the catalyst. This is the driving force for the internal rotation. The results are significant for isotactic and syndiotactic polymerization.

  2. All-acrylic film-forming colloidal polymer/silica nanocomposite particles prepared by aqueous emulsion polymerization.

    Science.gov (United States)

    Fielding, Lee A; Tonnar, Jeff; Armes, Steven P

    2011-09-01

    The efficient synthesis of all-acrylic, film-forming, core-shell colloidal nanocomposite particles via in situ aqueous emulsion copolymerization of methyl methacrylate with n-butyl acrylate in the presence of a glycerol-functionalized ultrafine silica sol using a cationic azo initiator at 60 °C is reported. It is shown that relatively monodisperse nanocomposite particles can be produced with typical mean weight-average diameters of 140-330 nm and silica contents of up to 39 wt %. The importance of surface functionalization of the silica sol is highlighted, and it is demonstrated that systematic variation of parameters such as the initial silica sol concentration and initiator concentration affect both the mean particle diameter and the silica aggregation efficiency. The nanocomposite morphology comprises a copolymer core and a particulate silica shell, as determined by aqueous electrophoresis, X-ray photoelectron spectroscopy, and electron microscopy. Moreover, it is shown that films cast from n-butyl acrylate-rich copolymer/silica nanocomposite dispersions are significantly more transparent than those prepared from the poly(styrene-co-n-butyl acrylate)/silica nanocomposite particles reported previously. In the case of the aqueous emulsion homopolymerization of methyl methacrylate in the presence of ultrafine silica, a particle formation mechanism is proposed to account for the various experimental observations made when periodically sampling such nanocomposite syntheses at intermediate comonomer conversions. PMID:21776995

  3. Structural Determination of Copolymers from the Cross-catalyzed Reactions of Phenol-formaldehyde and Polymeric Methylenediphenyl Diisocyanate

    OpenAIRE

    Haupt, Robert A

    2013-01-01

    This work reports the elucidation of the structure of a copolymer generated by the cross- catalyzed reactions of PF and pMDI prepolymers.  The electronic behavior of phenolic monomers as perturbed by alkali metal hydroxides in an aqueous environment was studied with 1H and 13C NMR.  Changes in electronic structure and thus reactivity were related to solvated ionic radius, solvent dielectric constant, and their effect on ion generated electric field strength. NMR chemical shifts were used to p...

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

    Energy Technology Data Exchange (ETDEWEB)

    Bercaw, John E. [California Institute of Technology

    2014-05-23

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

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

    KAUST Repository

    Riache, Nassima

    2014-10-03

    Metathesis of cyclic alkanes catalyzed by the new surface complex [(ΞSiO)W(Me)5] affords a wide distribution of cyclic and macrocyclic alkanes. The major products with the formula CnH2n are the result of either a ring contraction or ring expansion of cyclooctane leading to lower unsubstituted cyclic alkanes (5≤n≤7) and to an unprecedented distribution of unsubstituted macrocyclic alkanes (12≤n≤40), respectively, identified by GC/MS and by NMR spectroscopies.

  6. Horseradish peroxidase-catalyzed polymerization of L-DOPA for mono-/bi-enzyme immobilization and amperometric biosensing of H2O2 and uric acid.

    Science.gov (United States)

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

    2016-03-01

    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. PMID:26717822

  7. Effect of surface acidity and pore size of Al-substituted plugs-containing SBA-15 and MCM-41 silicas on the polymerization of THF

    Institute of Scientific and Technical Information of China (English)

    Zhi Qi Jia; Ming Zhao; Chun Guang Gao; Yong Xiang Zhao

    2011-01-01

    We reported here the simultaneous influence of surface acidity and pore size of Al-substituted hexagonal mesoporous silicas (Aldoped plugs-containing SBA-15 and Al-doped MCM-41) on polymerization of THF.These materials were directly synthesized by introduced aluminum isopropoxide into reaction mixture including surfactant and siliceous precursor.Al-doped plugs-containing SBA-15 (denotes as PAS) samples not only possess typical two-step desorption isotherms,which implied PAS materials generated plugs in their mesochannel,but also exhibit larger pore size and thicker wall than that of Al-doped MCM-41 (denotes as ACM),which implied PAS would have a great advantage on catalytic reaction involving large molecular (e.g.polymer of TI-IF) in industrial point'of view.To investigate catalytic activity of PAS and ACM with moderate acidic sites the polymerization of THF in the presence of acetic anhydride was carded out.The results showed PAS exhibiting good performance on polymerization of THF.Such result could be related to the large pore size and moderate acidic sites.

  8. Metal-silica sol-gel materials

    Science.gov (United States)

    Stiegman, Albert E. (Inventor)

    2002-01-01

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

  9. Ag-deposited silica-coated Fe3O4 magnetic nanoparticles catalyzed reduction of p-nitrophenol

    International Nuclear Information System (INIS)

    In this paper, a novel approach was successfully developed for advanced catalyst Ag-deposited silica-coated Fe3O4 magnetic nanoparticles, which possess a silica coated magnetic core and growth active silver nanoparticles on the outer shell using n-butylamine as the reductant of AgNO3 in ethanol. The as-synthesized nanoparticles have been characterized by X-ray powder diffraction (XRD), transmission electron microscopy (TEM), energy dispersive X-ray analysis (EDX), Fourier transform infrared spectra (FT-IR), vibration sample magnetometer (VSM), and have been exploited as a solid phase catalyst for the reduction of p-nitrophenol in the presence of NaBH4 by UV-vis spectrophotometry. The obtained products exhibited monodisperse and bifunctional with high magnetization and excellent catalytic activity towards p-nitrophenol reduction. As a result, the as-obtained nanoparticles showed high performance in catalytic reduction of p-nitrophenol to p-aminophenol with conversion of 95% within 14 min in the presence of an excess amount of NaBH4, convenient magnetic separability, as well as remained activity after recycled more than 6 times. The Fe3O4-SiO2-Ag functional nanostructure could hold great promise for various catalytic reactions.

  10. Synthesis of chitin and chitosan stereoisomers by thermostable α-glucan phosphorylase-catalyzed enzymatic polymerization of α-D-glucosamine 1-phosphate.

    Science.gov (United States)

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

    2015-04-14

    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. PMID:25766841

  11. OXIDATIVE ETHOXYCARBONYLATION OF ANILINE TO ETHYL PHENYLCARBAMATE CATALYZED BY SILICA-SUPPORTED POLY-γ-AMINOPROPYLSILOXANE-METAL COMPLEXES

    Institute of Scientific and Technical Information of China (English)

    GUAN Shiyou; HUANG Meiyu; JIANG Yingyan

    1993-01-01

    Several silica-supported poly-γ-aminopropylsiloxane-monometal and bimetal complexes (Si-NH2-M,M=Cu or Co;Si-NH2-Cu-M',M'=Co,Sn,Mn,Ni or Fe)have been prepared.Their catalytic properties for oxidative ethoxycarbonylation of aniline to ethyl phenylcarbamate have been investigated.The catalytic reaction was carried out under relatively mild conditions.The catalyst Si-NH2-Cu-Co had high activity and selectivity,and the turn-over number(molar of aniline converted/molar of metal in Si-NH2-Cu-Coadded)could amount to 450 under the conditions:150 ℃,4MPa(CO/O2=3) and 40 hours.The results of XPS and IR indicated that the coordination bonds were formed between nitrogen and metals in Si-NH2-Cu,Si-NH2-Co and Si-NH2-Cu-Co,and the coordination pattern was not single.In the oxidative ethoxycarbonylation of aniline to ethyl phenylcarbamate,the catalytic property of Si-NH2-Cu-Co bimetallic complex was better than Si- NH2-Cu or Si-NH2-Co monometallic complex.This indicated that there was synergistic action between different metals in the bimetallic complex.

  12. Controlled radical polymerization of vinyl acetate in presence of mesoporous silica supported TiCl4 heterogeneous catalyst

    Indian Academy of Sciences (India)

    M A Semsarzadeh; S Amiri; M Azadeh

    2012-10-01

    The heterogeneous TiCl4 catalysts supported on mesoporous mobile composition of matter (MCM-41) and mesoporous silicone particles synthesized from block copolymer of PPG–PEG–PPG (SPB) complexed with dimethyl formamide (DMF) ligand were used in a controlled free radical reaction with benzoyl peroxide (BPO) initiator in bulk polymerization of vinyl acetate (VAc). In this polymerization process, mesoporous particle of SPB increased the reactivity of TiCl4 catalyst with DMF ligand. The active site formed on the surface and the pores of the catalyst produced specific sequences of VAc on the chain with different thermal and microstructural properties and crystallinity.

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

    Science.gov (United States)

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

    2011-08-15

    Myoglobin (Mb) is among the cardiac biomarkers playing a major role in urgent diagnosis of cardiovascular diseases. Its monitoring in point-of-care is therefore fundamental. Pursuing this goal, a novel biomimetic ionophore for the potentiometric transduction of Mb is presented. It was synthesized by surface molecular imprinting (SMI) with the purpose of developing highly efficient sensor layers for near-stereochemical recognition of Mb. The template (Mb) was imprinted on a silane surface that was covalently attached to silica beads by means of self-assembled monolayers. First the silica was modified with an external layer of aldehyde groups. Then, Mb was attached by reaction with its amine groups (on the external surface) and subsequent formation of imine bonds. The vacant places surrounding Mb were filled by polymerization of the silane monomers 3-aminopropyltrimethoxysilane (APTMS) and propyltrimethoxysilane (PTMS). Finally, the template was removed by imine cleavage after treatment with oxalic acid. The results materials were finely dispersed in plasticized PVC selective membranes and used as ionophores in potentiometric transduction. The best analytical features were found in HEPES buffer of pH 4. Under this condition, the limits of detection were of 1.3 × 10(-6)mol/L for a linear response after 8.0 × 10(-7) mol/L with an anionic slope of -65.9 mV/decade. The imprinting effect was tested by preparing non-imprinted (NI) particles and employing these materials as ionophores. The resulting membranes showed no ability to detect Mb. Good selectivity was observed towards creatinine, sacarose, fructose, galactose, sodium glutamate, and alanine. The analytical application was conducted successfully and showed accurate and precise results. PMID:21683568

  14. Non-isothermal crystallization kinetic of poly(ethylene terephthalate)/fumed silica (PET/SiO{sub 2}) prepared by in situ polymerization

    Energy Technology Data Exchange (ETDEWEB)

    Antoniadis, G.; Paraskevopoulos, K.M. [School of Physics, Solid State Physics Department, Aristotle University of Thessaloniki, 54124 Thessaloniki (Greece); Bikiaris, D. [Department of Chemistry, Aristotle University of Thessaloniki, 54124 Thessaloniki (Greece); Chrissafis, K., E-mail: hrisafis@physics.auth.gr [School of Physics, Solid State Physics Department, Aristotle University of Thessaloniki, 54124 Thessaloniki (Greece)

    2010-10-20

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

  15. Synthesis and silica coating of calcia-doped ceria/plate-like titanate (K{sub 0.8}Li{sub 0.27}Ti{sub 1.73}O{sub 4}) nanocomposite by seeded polymerization technique

    Energy Technology Data Exchange (ETDEWEB)

    El-Toni, Ahmed Mohamed [Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, Sendai 980-8577 (Japan)]. E-mail: el-toni@mail.tagen.tohoku.ac.jp; Yin, Shu [Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, Sendai 980-8577 (Japan); Sato, Tsugio [Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, Sendai 980-8577 (Japan)

    2007-06-15

    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{sub 0.8}Li{sub 0.27}Ti{sub 1.73}O{sub 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.

  16. Synthesis and properties of epoxy-polyurethane/silica nanocomposites by a novel sol method and in-situ solution polymerization route

    Energy Technology Data Exchange (ETDEWEB)

    Lin, Jing, E-mail: linjin00112043@126.com [School of Chemistry and Chemical Engineering, Guangzhou University, Guangzhou 510006 (China); Wu, Xu; Zheng, Cheng [School of Chemistry and Chemical Engineering, Guangzhou University, Guangzhou 510006 (China); Zhang, Peipei [Worcester Polytechnic Institute, Worcester, MA 01605 (United States); Huang, Bowei; Guo, Ninghai; Jin, LiYazi [School of Chemistry and Chemical Engineering, Guangzhou University, Guangzhou 510006 (China)

    2014-06-01

    In this work, a novel nonaqueous sol method for preparing 3-methacryloxypropyltrimethoxysilane modified nano-SiO{sub 2} (MPS-SiO{sub 2}) 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/SiO{sub 2}) 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/SiO{sub 2} (EPUAs/SiO{sub 2}) were finally obtained by curing action among as-prepared EPAc/SiO{sub 2}, isocyanate and anhydride curing agent. The obtained EA and MPS-SiO{sub 2} were also characterized using Fourier transform infrared spectroscopy (FTIR), {sup 1}H nuclear magnetic resonance spectra ({sup 1}H NMR), thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy(XPS), and surface contact angle analysis(CA). Microstructures of MPS-SiO{sub 2} and EPAc/SiO{sub 2} in DMF were observed by transmission electron microscope (TEM). Furthermore, the influence of MPS-SiO{sub 2} on the properties of EPUAs/SiO{sub 2} including fracture surface morphology, thermal stability, glass transition temperature (T{sub g}), tensile strength, elongation at break, cross-linking density, shore hardness, water absorption, etc. were also investigated. The results demonstrate that colloidal MPS-SiO{sub 2} with DMF as solvent can be directly added into polyurethane system and has industrial application value, EPAc/SiO{sub 2} with core–shell morphologies have good individual dispersion in DMF, and incorporating MPS-SiO{sub 2} into EPUAs/SiO{sub 2} greatly enhances physico-chemical properties of EPUAs/SiO{sub 2} composites.

  17. Synthesis and properties of epoxy-polyurethane/silica nanocomposites by a novel sol method and in-situ solution polymerization route

    Science.gov (United States)

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

    2014-06-01

    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.

  18. SYNTHESIS OF POLY(5,5-DIMETHYL-1,3-DIOXAN-2-ONE) BY LIPASE-CATALYZED RING-OPENING POLYMERIZATION

    Institute of Scientific and Technical Information of China (English)

    Chi-fei Wu

    2003-01-01

    Porcine pancreas lipase (PPL) and PPL immobilized on narrow distributed micron-sized glass beads were employed successfully for the ring-opening polymerization of 5,5-dimethyl-1,3-dioxan-2-one (DTC) for the first time.Different polymerization conditions such as enzyme concentration and reaction temperature were studied. Immobilized PPL exhibits higher activity than native PPL. Along with the increasing enzyme concentration, the molecular weight of resulting PDTC decreases. PPL immobilized on narrow distributed micron-sized glass beads has outstanding recyclability. For the third recycle time, immobilized PPL exhibits the highest catalytic activity and with high activity even after the fifth recyle time for the synthesis of PDTC. The 1H-NMR spectra indicate that decarboxylation does not occur during the ring-opening polymerization.

  19. Blue-light activated rapid polymerization for defect-free bulk Cu(i)-catalyzed azide-alkyne cycloaddition (CuAAC) crosslinked networks.

    Science.gov (United States)

    Shete, Abhishek U; El-Zaatari, Bassil M; French, Jonathan M; Kloxin, Christopher J

    2016-08-18

    A visible-light (470 nm wavelength) sensitive Type II photoinitiator system is developed for bulk Cu(i)-catalyzed azide-alkyne cycloaddition (CuAAC) reactions in crosslinked networks. The accelerated photopolymerization eliminates UV-mediated azide decomposition allowing for the formation of defect-free glassy networks which exhibit a narrow glass transition temperature. PMID:27499057

  20. Sonolytic and Silent Polymerization of Methacrlyic Acid Butyl Ester Catalyzed by a New Onium Salt with bis-Active Sites in a Biphasic System — A Comparative Investigation

    Directory of Open Access Journals (Sweden)

    Perumberkandgai A. Vivekanand

    2013-02-01

    Full Text Available Currently, ingenious new analytical and process experimental techniques which are environmentally benign techniques, viz., ultrasound irradiation, have become immensely popular in promoting various reactions. In this work, a novel soluble multi-site phase transfer catalyst (PTC viz., 1,4-bis-(propylmethyleneammounium chloridebenzene (BPMACB was synthesized and its catalytic efficiency was assessed by observing the kinetics of sonolytic polymerization of methacrylic acid butyl ester (MABE using potassium persulphate (PPS as an initiator. The ultrasound–multi-site phase transfer catalysis (US-MPTC-assisted polymerization reaction was compared with the silent (non-ultrasonic polymerization reaction. The effects of the catalyst and various reaction parameters on the catalytic performance were in detail investigated by following the kinetics of polymerization of MABE in an ethyl acetate-water biphasic system. From the detailed kinetic investigation we propose a plausible mechanism. Further the kinetic results demonstrate clearly that ultrasound-assisted phase-transfer catalysis significantly increased the reaction rate when compared to silent reactions. Notably, this environmentally benign and cost-effective process has great potential to be applied in various polymer industries.

  1. The Oxidative Coupling of 2,6-Xylenol Catalyzed by Polymeric Complexes of Copper, 2. Physicochemical Study on Copper(II) Complexes of Partially Dimethylaminomethylated Polystyrene

    NARCIS (Netherlands)

    Schouten, Arend Jan; Wiedijk, Dick; Challa, Ger; Borkent, J.

    1977-01-01

    The polymeric catalyst formed by complexation of copper(II) chloride and partially dimethylaminomethylated polystyrene was investigated to explain its behaviour in the oxidative coupling of 2,6-xylenol. Viscometric studies indicated that at low polymer concentrations coordination of tertiary amine g

  2. Synthesis of two novel macroporous silica-based impregnated polymeric composites and their application in highly active liquid waste partitioning by extraction chromatography.

    Science.gov (United States)

    Zhang, Anyun; Kuraoka, Etsusyo; Hoshi, Harutaka; Kumagai, Mikio

    2004-12-24

    Two kinds of novel macroporous silica-based chelating polymeric adsorption materials, TODGA/SiO2-P and CMPO/SiO2-P, were synthesized by impregnating and immobilizing two chelating agents, N,N,N',N'-tetraoctyl-3-oxapentane-1,5-diamide (TODGA) and octyl(phenyl)-N,N-diisobutylcarbamoylmethylphoshine oxide (CMPO), into the pores of SiO2-P particles. To separate minor actinides (MA(III)) such as Am(III) and Cm(III), the adsorption and elution of 13 typically simulated fission products from a 3 M HNO3 were performed. It was found that in the first column packed with TODGA/SiO2-P, all of the simulated elements were separated effectively into four groups: (1) Cs(I), Mo(VI), and the most portion of Ru(III) (non-adsorption group), (2) Sr(II), small portion of Gd(III) and all of light REs(III) (MA-lRE-Sr group), (3) most of Gd(III) and all heavy RE(III) (hRE group), and (4) Zr(IV), Pd(II), and a little of Ru(III) (Zr-Pd group) by eluting with 3.0 M HNO3, 1.0M HNO3, distilled water, and 0.5 M H2C2O4, respectively, at 298 K. MA(III) was predicted to flow into the second group along with Nd(III) because of their close adsorption-elution onto TODGA/SiO2-P. In the second column packed with CMPO/SiO2-P, MA-lRE-Sr group was separated into (1) Sr(II), (2) middle RE(III) such as Gd(III), Eu(III), Sm(III), and quite small portion of Nd(III) (MA-mRE), and (3) light RE(III) such as La(III), Ce(III), and most of Nd(III) by eluting with 3.0 M HNO3 and 0.05 M DTPA-pH 2.0, respectively, at 323 K. MA(III) was believed to flow into MA-mRE group along with Gd(III) due to their similar adsorption properties towards CMPO/SiO2-P. Based on positions of MA(III) appeared in light and heavy RE(III), an improved MAREC process for MA(III) partitioning from HLW was proposed. PMID:15641360

  3. Modeling and Simulation of Heterogeneous Catalyzed Propylene Polymerization%非均相催化丙稀聚合的建模与仿真

    Institute of Scientific and Technical Information of China (English)

    刘兴高

    2007-01-01

    A novel mathematical model for single particle slurry propylene polymerization using heterogeneous Ziegler-Natta catalysts has been developed to describe the kinetic behavior, the molecular weight distribution, the monomer concentration, the degree of polymerization, the polydispersity index (PDI), etc. This model provides a more valid mathematical description by accounting for the monomer diffusion phenomena at two levels as multigrain model counts, and obtains results that are more applicable to the conditions existing in most polymerizations of industrial interest. Considering that some models on the mesoscale phenomena are so complex that some existing modeling aspects have to be simplified or even neglected to make the model convenient for use in interesting engineering studies, it is very important to put some effort into determining what sort of numerical analysis works best for these problems. For this reason, special attention is paid to these studies to explore an efficient algorithm using adaptive grid-point spacing in a finite-difference technique to figure out more practical mass transport models and convection-diffusion models efficiently. The reasonable outcomes, as well as the significant computation time saving, have been achieved, thereby displaying the advantage of this calculation method.

  4. Formation of hollow silica nanospheres by reverse microemulsion

    Science.gov (United States)

    Lin, Cheng-Han; Chang, Jen-Hsuan; Yeh, Yi-Qi; Wu, Si-Han; Liu, Yi-Hsin; Mou, Chung-Yuan

    2015-05-01

    Uniform hollow silica nanospheres (HSNs) synthesized with reverse microemulsion have great application potential as nanoreactors because enzymes or nanocatalysts can be easily encapsulated de novo in synthesis. Water-in-oil (w/o) reverse microemulsions comprising the polymeric surfactant polyoxyethylene (5) isooctylphenyl ether (Igepal CA-520), ammonia and water in a continuous oil phase (alkanes) coalesce into size-tunable silica nanoparticles via diffusion aggregation after the introduction of silica precursors. Here, we elucidate in detail the growth mechanism for silica nanoparticles via nucleation of ammonium-catalyzed silica oligomers from tetraethylorthosilicate (TEOS) and nanoporous aminopropyltrimethoxy silane (APTS) in the reverse microemulsion system. The formation pathway was studied in situ with small-angle X-ray scattering (SAXS). We find a four-stage process showing a sigmoidal growth behavior in time with a crossover from the induction period, early nucleation stage, coalescence growth and a final slowing down of growth. Various characterizations (TEM, N2 isotherm, dynamic light scattering, zeta potential, NMR, elemental analysis) reveal the diameters, scattering length density (SLD), mesoporosity, surface potentials and chemical compositions of the HSNs. Oil phases of alkanes with different alkyl chains are systematically employed to tune the sizes of HSNs by varying oil molar volumes, co-solvent amounts or surfactant mixture ratios. Silica condensation is incomplete in the core region, with the silica source of TEOS and APTS leading to the hollow silica nanosphere after etching with warm water.Uniform hollow silica nanospheres (HSNs) synthesized with reverse microemulsion have great application potential as nanoreactors because enzymes or nanocatalysts can be easily encapsulated de novo in synthesis. Water-in-oil (w/o) reverse microemulsions comprising the polymeric surfactant polyoxyethylene (5) isooctylphenyl ether (Igepal CA-520), ammonia and

  5. The design of a bipodal bis(pentafluorophenoxy)aluminate supported on silica as an activator for ethylene polymerization using surface organometallic chemistry.

    Science.gov (United States)

    Sauter, Dominique W; Popoff, Nicolas; Bashir, Muhammad Ahsan; Szeto, Kai C; Gauvin, Régis M; Delevoye, Laurent; Taoufik, Mostafa; Boisson, Christophe

    2016-04-01

    A new class of well-defined activating supports for olefin polymerization was obtained via the surface organometallic chemistry approach. High activities in slurry polymerization of ethylene along with industrial-grade physical properties of the resulting polyethylene were obtained when these activators were combined with metallocene complexes in the presence of triisobutylaluminium. PMID:26899986

  6. Processable polyaniline/titania nanocomposites with good photocatalytic and conductivity properties prepared via peroxo-titanium complex catalyzed emulsion polymerization approach

    Science.gov (United States)

    Li, Yuzhen; Yu, Yuan; Wu, Liangzhuan; Zhi, Jinfang

    2013-05-01

    The homogeneous polyaniline (PAni)/TiO2 nanocomposites were successfully synthesized via a facile emulsion polymerization with the assistance of peroxo-titanium complex (PTC), where PTC was used as both the TiO2 precursor and the oxidant for the polymerization of PAni/TiO2 nanocomposites. Comprehensive analysis indicated that anatase TiO2 nanocrystals (about 4-6 nm) were well-dispersed in the PAni chains without aggregation, and the TiO2 were anchored on the polymer chains through chemical interactions, such as Tisbnd Osbnd Nsbnd C and Tisbnd Osbnd C, which made the PAni/TiO2 composite possess better thermal stability. The PAni/TiO2 composite could be well dispersed in common solvent, such as acetone, and stay stability without any precipitation for a month. Since the PAni/TiO2 composite could be well dispersed in common solvent, the PAni/TiO2 dispersion may be coated on the surface of Poly (ethylene terephthalate) (PET) film, showing good processable properties, and the prepared PAni/TiO2/PET films exhibit good photocatalysis and best conductivity (2.08 × 10-2 s cm-1), when the molar ratio of aniline (AN) and Ti in the PAni/TiO2 composite is 1/1. The possible reaction mechanism was also discussed. The facile synthesized method proposed can also be used for the preparation of other conducting polymer/semiconductor nanocomposites.

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

    OpenAIRE

    Piyasan Praserthdam; Nichapat Senso; Bunjerd Jongsomjit; Supaporn Khaubunsongserm

    2010-01-01

    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,...

  8. Highly Active and Isospecific Styrene Polymerization Catalyzed by Zirconium Complexes Bearing Aryl-substituted [OSSO]-Type Bis(phenolate Ligands

    Directory of Open Access Journals (Sweden)

    Norio Nakata

    2016-01-01

    Full Text Available [OSSO]-type dibenzyl zirconium(IV complexes 9 and 10 possessing aryl substituents ortho to the phenoxide moieties (ortho substituents, phenyl and 2,6-dimethylphenyl (Dmp were synthesized and characterized. Upon activation with dMAO (dried methylaluminoxane, complex 9 was found to promote highly isospecific styrene polymerizations ([mm] = 97.5%–99% with high molecular weights Mw up to 181,000 g·mmol−1. When the Dmp-substituted pre-catalyst 10/dMAO system was used, the highest activity, over 7700 g·mmol(10−1·h−1, was recorded involving the formation of precisely isospecific polystyrenes of [mm] more than 99%.

  9. Processable polyaniline/titania nanocomposites with good photocatalytic and conductivity properties prepared via peroxo-titanium complex catalyzed emulsion polymerization approach

    Energy Technology Data Exchange (ETDEWEB)

    Li, Yuzhen [Key Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing, 100190 (China); Graduate University of Chinese Academy of Sciences, Beijing, 100190 (China); Yu, Yuan [Key Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing, 100190 (China); Wu, Liangzhuan, E-mail: wuliangzhuan@mail.ipc.ac.cn [Key Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing, 100190 (China); Zhi, Jinfang, E-mail: zhi-mail@mail.ipc.ac.cn [Key Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing, 100190 (China)

    2013-05-15

    The homogeneous polyaniline (PAni)/TiO{sub 2} nanocomposites were successfully synthesized via a facile emulsion polymerization with the assistance of peroxo-titanium complex (PTC), where PTC was used as both the TiO{sub 2} precursor and the oxidant for the polymerization of PAni/TiO{sub 2} nanocomposites. Comprehensive analysis indicated that anatase TiO{sub 2} nanocrystals (about 4–6 nm) were well-dispersed in the PAni chains without aggregation, and the TiO{sub 2} were anchored on the polymer chains through chemical interactions, such as Ti-O-N-C and Ti-O-C, which made the PAni/TiO{sub 2} composite possess better thermal stability. The PAni/TiO{sub 2} composite could be well dispersed in common solvent, such as acetone, and stay stability without any precipitation for a month. Since the PAni/TiO{sub 2} composite could be well dispersed in common solvent, the PAni/TiO{sub 2} dispersion may be coated on the surface of Poly (ethylene terephthalate) (PET) film, showing good processable properties, and the prepared PAni/TiO{sub 2}/PET films exhibit good photocatalysis and best conductivity (2.08 × 10{sup −2} s cm{sup −1}), when the molar ratio of aniline (AN) and Ti in the PAni/TiO{sub 2} composite is 1/1. The possible reaction mechanism was also discussed. The facile synthesized method proposed can also be used for the preparation of other conducting polymer/semiconductor nanocomposites.

  10. Effective Liquid-phase Nitration of Benzene Catalyzed by a Stable Solid Acid Catalyst: Silica Supported Cs2.5H0.5PMo12O40

    International Nuclear Information System (INIS)

    Silica supported Cs2.5H0.5PMo12O40 catalyst was prepared through sol-gel method with ethyl silicate-40 as silicon resource and characterized by X-ray diffraction, infrared spectroscopy, scanning electron microscopy, nitrogen adsorption-desorption and potentiometric titration methods. The Cs2.5H0.5PMo12O40 particles with Keggin-type structure well dispersed on the surface of silica, and the catalyst exhibited high surface area and acidity. The catalytic performance of the catalysts for benzene liquid-phase nitration was examined with 65% nitric acid as nitrating agent, and the effects of various parameters were tested, which including temperature, time and amount of catalyst, reactants ratio, especially the recycle of catalyst was emphasized. Benzene was effectively nitrated to mononitro-benzene with high conversion (95%) in optimized conditions. Most importantly, the supported catalyst was proved has excellent stability in the nitration progress, and there were no any other organic solvent and sulfuric acid were used in the reaction system, so the liquid-phase nitration of benzene that we developed was an eco-friendly and attractive alternative for the commercial technology

  11. Can laccases catalyze bond cleavage in lignin?

    DEFF Research Database (Denmark)

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

    2015-01-01

    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...

  12. Rapid reduction in gelation time and impregnation of hydrophobic property in the tetraethoxysilane (TEOS) based silica aerogels using NH4F catalyzed single step sol-gel process

    International Nuclear Information System (INIS)

    The experimental results on the synthesis and physical properties of tetraethoxysilane (TEOS) based superhydrophobic silica aerogels, obtained by single step sol-gel process, are reported and discussed. Superhydrophobic silica aerogels were prepared by varying the molar ratio of MeOH/TEOS (M) from 11 to 275, molar ratio of NH4F/TEOS (A) from 1.2 to 9.6 and concentration of NH4F from 0.001 to 1 M, respectively. All the alcogels were dried under supercritical conditions. The remarkable results were obtained in terms of drastic reduction in the gelation time which is less than 1 min, using single step sol-gel process. Further, the obtained aerogels are hydrophobic (θ = 155 deg.) without use of any hydrophobic reagents. The obtained hydrophobic property of the aerogels was improved using mono, di and tri-functional methoxysilanes as co-precursor such as, trimethylmethoxysilane (TMMS), dimethyldimethoxysilane (DMMS) and methyltrimethoxysilane (MTMS), respectively. It was observed that as the order of functional groups of methoxysilane decreases, the contact angle of the water droplet on the aerogel surface increases, indicating the aerogel become more hydrophobic. The highest contact angle of (θ = 168 deg.) was observed for trimethylmethoxysilane as a co-precursor. The aerogels were characterized by bulk density, volume shrinkage, porosity, optical transmission and thermal conductivity measurements. The effect of humidity on the aerogel samples was studied using programmable environmental test chamber. The hydrophobicity of the aerogels was quantified by contact angle measurements and FTIR studies while microstructural studies were done using Transmission Electron Microscopy (TEM).

  13. Structural evolution of silica sols modified with formamide

    Directory of Open Access Journals (Sweden)

    Lenza R.F.S.

    2001-01-01

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

  14. 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

    2013-08-01

    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.

  15. 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

    2010-12-01

    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.

  16. The influence of mixed activators on ethylene polymerization and ethylene/1-hexene copolymerization with silica-supported Ziegler-Natta catalyst.

    Science.gov (United States)

    Senso, Nichapat; Khaubunsongserm, Supaporn; Jongsomjit, Bunjerd; Praserthdam, Piyasan

    2010-01-01

    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. PMID:21169883

  17. Bioinspired thermo- and pH-responsive polymeric amines: multimolecular aggregates in aqueous media and matrices for silica/polymer nanocomposites.

    Science.gov (United States)

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

    2015-05-15

    Polymeric amines have been intensively studied for application in smart systems and as matrices for the design of composite materials, including bioinspired substances. A new thermo- and pH-responsive polymer was obtained by radical polymerization of N-(3-(diethylamino)propyl)-N-methylacrylamide. Upon heating, the polymer precipitated from aqueous solutions above pH 9; the observed cloud point was dependent on the polymer concentration and decreased from 95°C at pH 9 to 40°C at pH 11. The basicity of the polymer decreased at elevated temperatures owing to an increase in the hydrophobicity-driven compaction of the macromolecules. Dynamic light scattering analysis demonstrated that the formation of large multimolecular associates with radius 1000-2000 nm was initiated from 1 to 2°C below the cloud point. The new polymer is demonstrated to be an effective matrix for various siliceous composite structures, including 200-300 nm solid spherical raspberry-like particles and hollow hemispherical particles of more than 1000 nm diameter. Condensation of silicic acid in the presence of polymeric amines is a model reaction in biosilicification studies, and the obtained data are also discussed from the perspective of the matrix hypothesis for biosilica formation. PMID:25646785

  18. Comparative studies on electrochemical cycling behavior of two different silica-based ionogels

    Science.gov (United States)

    Wang, Shuang; Hsia, Ben; Alper, John P.; Carraro, Carlo; Wang, Zhe; Maboudian, Roya

    2016-01-01

    We report a comparative study of two silica-based ionogel electrolytes for electrochemical cycling applications. The ionogels considered represent two classes of gel networks, a covalently formed network generated by the polymerization of tetramethoxysilane catalyzed by formic acid, and a network formed by weak intermolecular forces obtained by mixing fumed silica nanopowder with ionic liquid. In both cases, 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide is utilized as the ion conductor in the gel network. With increasing temperature it is shown that the electrochemical stability window is reduced, the conductivity of the electrolyte is increased, and the double layer capacitance is increased for both types of ionogels. Long-term stability of the two ionogels is excellent, with 90% capacitance retained after 10,000 repetitive CV cycles at 100 °C. Our results indicate that both of these ionogel electrolytes are promising for application in solid-state electrochemical systems at high temperature.

  19. Fluoropolymer materials and architectures prepared by controlled radical polymerizations

    DEFF Research Database (Denmark)

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

    2007-01-01

    This review initially summarizes the mechanisms, merits and limitations of the three controlled radical polymerizations: nitroxide mediated polymerization (NMP), atom transfer radical polymerization (ATRP) or metal catalyzed living radical polymerization, and reversible addition–fragmentation chain...... transfer (RAFT) polymerization. This is followed by two parts, one dealing with homo- and copolymerizations of fluorinated methacrylates and acrylates, and a second where fluorinated styrenes, alone or in combination with other monomers, are the main issues. In these parts, initiators (including...

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

    Science.gov (United States)

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

    2016-07-22

    A solid-phase extraction method for the efficient analysis of the excretion-dynamics of flavonoids in urine was established and described. In this work, in situ surface radical chain-transfer polymerization and in situ anion exchange were utilized to tune the extraction performance of poly(1-vinyl-3-hexylimidazolium bromide)-graphene oxide-grafted silica (poly(VHIm(+)Br(-))@GO@Sil). Graphene oxide (GO) was first coated onto the silica using a layer-by-layer fabrication method, and then the anion of poly(VHIm(+)Br(-))@GO@Sil was changed into hexafluorophosphate (PF6(-)) by in situ anion exchange. The interaction energies between two PILs and four flavonoids were calculated with the Gaussian09 suite of programs. A Box-Behnken design was used for the optimization of four greatly influential parameters after single-factor experiments to obtain more accurate and precise results. Coupled to high performance liquid chromatography, the poly(VHIm(+)PF6(-))@GO@Sil method showed acceptable extraction recoveries for the four flavonoids, with limits of detection in the range of 0.1-0.5μgL(-1), and wide linear ranges with correlation coefficients (R) ranging from 0.9935 to 0.9987. Under the optimum conditions, the proposed method was applied to analyze the urines collected from a healthy volunteer. The excretion amount-time profiles revealed that 4-15h was the main excretion time for the detected flavonoids. The results indicated that the newly developed method offered the advantages of being feasible, green and cost-effective, and could be successfully applied to the extraction and enrichment of flavonoids in human body systems allowing the study of the metabolic kinetics. PMID:27295963

  1. Retention behavior of silica-bonded and novel polymeric reversed-phase sorbents in studies on flavones as chemotaxonomic markers of Scutellaria L. genus.

    Science.gov (United States)

    Zgórka, Grazyna

    2006-07-01

    In this study, the effectiveness of both classical and novel polymeric sorbents used in solid-phase extraction (SPE) for isolation of pharmacologically active flavones (baicalin, luteolin, apigenin, wogonin and chrysin) from aerial parts of 13 species of Scutellaria L. (Skullcap) genus was assessed. The highest recoveries of hydrophilic (baicalin, luteolin) flavones for Oasis HLB were obtained, whereas for medium hydrophobic (apigenin) and hydrophobic (wogonin, chrysin) flavones better quantitative results for BakerBond phenyl cartridges were stated. Eluates were analysed using reversed-phase high-performance liquid chromatography with diode array detection (RP-HPLC-DAD). For the five target compounds the determined concentrations ranged from approximately 4 to approximately 15,500 microg/g dry wt. Very good linearities (r(2)>0.9995) of calibration curves were achieved for each flavone. The accuracy was below 5% for most compounds examined. This is the first method reported that enabled simultaneous qualification and quantitation of five flavones (being chemotaxonomic markers) in 13 species of Scutellaria L. genus. PMID:16364344

  2. Structure of random porous materials: Silica aerogel

    International Nuclear Information System (INIS)

    Using small-angle x-ray scattering, we show that porous silica aerogel has a fractal backbone structure. The observed structure is traced to the underlying chemical (polymerization) and physical (colloid aggregation) growth processes. Comparison of scattering curves for aerogel with silica aggregates confirms this interpretation

  3. Process for preparing polymer reinforced silica aerogels

    Science.gov (United States)

    Meador, Mary Ann B. (Inventor); Capadona, Lynn A. (Inventor)

    2011-01-01

    Process for preparing polymer-reinforced silica aerogels which comprises a one-pot reaction of at least one alkoxy silane in the presence of effective amounts of a polymer precursor to obtain a silica reaction product, the reaction product is gelled and subsequently subjected to conditions that promotes polymerization of the precursor and then supercritically dried to obtain the polymer-reinforced monolithic silica aerogels.

  4. Highly efficient palladium-catalyzed hydrostannation of ethyl ethynyl ether

    OpenAIRE

    Andrews, Ian P.; Kwon, Ohyun

    2008-01-01

    The palladium-catalyzed hydrostannation of acetylenes is widely exploited in organic synthesis as a means of forming vinyl stannanes for use in palladium-catalyzed cross-coupling reactions. Application of this methodology to ethyl ethynyl ether results in an enol ether that is challenging to isolate from the crude reaction mixture because of incompatibility with typical silica gel chromatography. Reported here is a highly efficient procedure for the palladium-catalyzed hydrostannation of ethy...

  5. Molecular modification of a novel macroporous silica-based impregnated polymeric composite by tri-n-butyl phosphate and its application in the adsorption for some metals contained in a typical simulated HLLW

    International Nuclear Information System (INIS)

    Using tri-n-butyl phosphate (TBP) as a molecular modifier, a novel macroporous silica-based 4,4',(5')-di-(tert-butylcyclohexano)-18-crown-6 (DtBuCH18C6) polymeric composite (DtBuCH18C6 + TBP/SiO2-P) was synthesized. It was done by impregnating and immobilizing DtBuCH18C6 and TBP molecules into the pores of SiO2-P particles utilizing an advanced vacuum sucking technique. The adsorption of 10 fission and non-fission products Sr(II), Ba(II), Ru(III), Mo(VI), Na(I), K(I), Pd(II), La(III), Cs(I), and Y(III) onto (DtBuCH18C6 + TBP)/SiO2-P was investigated by examining the influence of contact time and the HNO3 concentration in a range of 0.1-5.0 M at 298 K. It was found that at the optimum concentration of 2.0 M HNO3 (DtBuCH18C6 + TBP)/SiO2-P exhibited strong adsorption ability and high selectivity for Sr(II) over all of the tested elements, which showed very weak or almost no adsorption except Ba(II). Moreover, the quantity of DtBuCH18C6 leaked from (DtBuCH18C6 + TBP)/SiO2-P in 2.0 M HNO3, 326.2 ppm, was obviously lower than 658.4 ppm that leaked from DtBuCH18C6/SiO2-P. This was ascribed to the effective association of DtBuCH18C6 and TBP through intermolecular interaction, i.e., hydrogen bonding. The significant reduction of DtBuCH18C6 leakage by molecular modification with TBP was achieved. It was of great benefit to application of the (DtBuCH18C6 + TBP)/SiO2-P polymeric composite in chromatographic partitioning of Sr(II), one of the main heat generators, from high level liquid waste (HLLW) in reprocessing of nuclear spent fuel in MAREC process developed recently

  6. Allyl-silica Hybrid Monoliths For Chromatographic Application

    Science.gov (United States)

    Guo, Wenjuan

    Column technology continues to be the most investigated topics in the separation world, since the column is the place where the chromatographic separation happens, making it the heart of the separation system. Allyl-silica hybrid monolithic material has been exploited as support material and potential stationary phases for liquid chromatography; the stationary phase anchored to the silica surface by Si-C bond, which is more pH stable than traditional stationary phase. First, nuclear magnetic resonance spectroscopy has been used to study the sol in the synthesis of allyl-silica hybrid monoliths. Allyl-trimethoxysilane (allyl-TrMOS), dimethyldimethoxysilane (DMDMOS) and tetramethoxysilane (TMOS) have been served as co-precursors in the sol-gel synthesis of organo-silica hybrid monolithic columns for liquid chromatography (LC). 29Si nuclear magnetic resonance (NMR) and 1H NMR spectroscopy were employed to monitor reaction profiles for the acid-catalyzed hydrolysis and initial condensation reactions of the individual precursor and the hybrid system. 29Si-NMR has also been used to identify different silane species formed during the reactions. The overall hydrolysis rate has been found to follow the trend DMDMOS > allyl-TrMOS > TMOS, if each precursor is reacted individually (homo-polymerization). Precursors show different hydrolysis rate when reacted together in the hybrid system than they are reacted individually. Cross-condensation products of TMOS and DMDMOS (QD) arise about 10 minutes of initiation of the reaction. The allyl-silica monolithic columns for capillary liquid chromatography can only be prepared in capillaries with 50 im internal diameter with acceptable performance. One of the most prominent problems related to the synthesis of silica monolithic structures is the volume shrinkage. The synthesis of allylfunctionalized silica hybrid monolithic structures has been studied in an attempt to reduce the volume shrinkage during aging, drying and heat treatment

  7. Preparation of polystyrene/silica nanocomposites by radical copolymerization of styrene with silica macromonomer

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    A two-stage process has been developed to generate the silica-based macromonomer through surface-modification of silica with polymerizable vinyl groups. The silica surfaces were treated with excess 2,4-toluene diisocynate (TDI), after which the residual isocyanate groups were converted into polymerizable vinyl groups by reaction with hydroxypropylacrylate (HPA). Thus, polystyrene/silica nanocomposites were prepared by conventional radical copolymerization of styrene with silica macromonomer. The main effecting factors, such as ratios of styrene to the macromonomer, together with polymerization time on the copolymerization were studied in detail. FTIR, DSC and TGA were utilized to characterize the nanocomposites. Experimental results revealed that the silica nanoparticles act as cross-linking points in the polystytene/silica nanocomposites, and the glass transition temperatures of the nanocomposites are higher than that of the corresponding pure polystyrene. The glass transition temperatures of nanocomposites increased with the increasing of silica contents, which were further ascertained by DSC.

  8. In Situ Determination of Tacticity, Deactivation, and Kinetics in [rac-(C2H4(1-Indenyl)2)ZrMe][B(C6F5)4] and [Cp2ZrMe][B(C6F5)4]-Catalyzed Polymerization of 1-Hexene Using (13)C Hyperpolarized NMR.

    Science.gov (United States)

    Chen, Chia-Hsiu; Shih, Wei-Chun; Hilty, Christian

    2015-06-01

    The stereochemistry, kinetics, and mechanism of olefin polymerization catalyzed by a set of zirconium-based metallocenes was studied by NMR using dissolution dynamic nuclear polarization (DNP). Hyperpolarized 1-hexene was polymerized in situ with a C2 symmetric catalyst, [(EBI)ZrMe][B(C6F5)4] (EBI = rac-(C2H4(1-indenyl)2)), and a C2v symmetric catalyst, [(Cp)2ZrMe][B(C6F5)4] (Cp = cyclopentadienyl). Hyperpolarized (13)C NMR spectra were used to characterize product tacticity following initiation of the reaction. At the same time, a signal gain of 3 orders of magnitude from (13)C hyperpolarization enabled the real time observation of catalyst-polymeryl species and deactivation products, such as vinylidene and a Zr-allyl complex. The compounds appearing in the reaction provide evidence for the existence of β-hydride elimination and formation of a dormant site via a methane-generating mechanism. The presence of a deactivating mechanism was incorporated in a model used to determine kinetic parameters of the reaction. On this basis, rate constants were measured between 0.8 and 6.7 mol % of catalyst. The concentration dependence of the rate constants obtained indicates a second-order process for polymerization concomitant with a first-order process for deactivation. The simultaneous observation of both processes in the time evolution of (13)C NMR signals over the course of several seconds underlines the utility of hyperpolarized NMR for quantifying early events in polymerization reactions. PMID:25961793

  9. Preparation of a novel macroporous silica-based 2,6-bis(5,6-diisobutyl-1,2,4-triazine-3-yl)pyridine impregnated polymeric composite and its application in the adsorption for trivalent rare earths

    International Nuclear Information System (INIS)

    A novel macroporous silica-based 2,6-bis(5,6-diisobutyl-1,2,4-triazine-3-yl)pyridine (iso-Bu-BTP), a neutral chelating agent having several softatom nitrogen, polymeric composite (iso-Bu-BTP/SiO2-P) was synthesized. It was done through impregnation and immobilization of iso-Bu-BTP molecule into the pores of SiO2-P particles with 40-60 μm of bead diameter and 0.6 μm of mean pore size. The effective impregnation resulted from the intermolecular interaction of iso-Bu-BTP and co-polymer inside the SiO2-P particles by a vacuum sucking technique. To understand the possibility of applying iso-Bu-BTP in the MAREC process developed, the adsorption behavior of a few representative rare earths (REs) such as Ce(III), Nd(III), Gd(III), Dy(III), Er(III), Yb(III), and Y(III) towards iso-Bu-BTP/SiO2-P was investigated at 298 K. The influence of the HNO3 concentration in a wide range of pH 5.52-3.0M and a few chelating agents such as formic acid, citric acid, and diethylenetriaminepentaacetic acid (DTPA) on the adsorption of RE(III) was examined. It was found that in the presence of chelating agent, the adsorption ability of the tested RE(III) towards iso-Bu-BTP/SiO2-P decreased due to two competition reactions of RE(III) with iso-Bu-BTP/SiO2-P and chelating agents. In a 0.01M HNO3 solution containing 1M formic acid or 1M citric acid, light RE(III) showed lower adsorption towards iso-Bu-BTP/SiO2-P than that of the heavy one. This makes the separation of light RE(III) from the heavy one possible. Based on the similarity of minor actinides and heavy RE(III) in chemical properties and the results of column separation experiments, chromatographic partitioning of light RE(III) from a simulated high level liquid waste solution composed of the heavy RE(III) and minor actinides in MAREC process is promising. (author)

  10. Application of silica hydrogel and silica gel comprising chromium(III) ions for synthesis of organo mineral cation exchangers

    International Nuclear Information System (INIS)

    Present article is devoted to application of silica hydrogel and silica gel comprising chromium(III) ions for synthesis of organo mineral cation exchangers. Thus, the polymerization of methacrylic acid on the surface of porous silica is studied. Porous sorbents are obtained by polymerizing of methacrylic acid in the medium of precipitated silica hydrogel treated by Cr(III) salts. The dependence of sorbents porosity on different factors, including conditions of hydrogel precipitation, its treatment by chromium salts, its ageing in the medium of methacrylic acid, quantity of methacrylic acid is studied as well.

  11. Microwave-assisted solvent-free synthesis of 14-aryl/alkyl-14H-dibenzo[a,j]xanthenes and tetrahydrobenzo[a]xanthen-11-ones catalyzed by nano silica phosphoric acid

    OpenAIRE

    Abdolhamid Bamoniri; Bi Bi Fatemeh Mirjalili; Sedigeh Nazemian

    2013-01-01

    Nano silica phosphoric acid (nano SPA) was applied as a catalyst for synthesis of 14-aryl/alkyl-14H-dibenzo[a,j]xanthenes and tetrahydrobenzo[a]xanthen-11-ones in microwave oven under solvent free conditions. High efficiency, easy availability and reusability are some advantages of this catalyst.

  12. Preparation of monodisperse polystyrene/silica core-shell nano-composite abrasive with controllable size and its chemical mechanical polishing performance on copper

    International Nuclear Information System (INIS)

    Monodisperse silica-coated polystyrene (PS) nano-composite abrasives with controllable size were prepared via a two-step process. Monodisperse positively charged PS colloids were synthesized via polymerization of styrene by using a cationic initiator. In the subsequent coating process, silica formed shell on the surfaces of core PS particles via the ammonia-catalyzed hydrolysis and condensation of tetraethoxysilane. Neither centrifugation/water wash/redispersion cycle process nor surface modification or addition surfactant was needed in the whole process. The morphology of the abrasives was characterized by scanning electron microscope. Transmission electron microscope and energy dispersive X-ray analysis results indicated that silica layer was successfully coated onto the surfaces of PS particles. Composite abrasive has a core-shell structure and smooth surface. The chemical mechanical polishing performances of the composite abrasive and conventional colloidal silica abrasive on blanket copper wafers were investigated. The root mean square roughness decreases from 4.27 nm to 0.56 nm using composite abrasive. The PS/SiO2 core-shell composite abrasives exhibited little higher material removal rate than silica abrasives.

  13. Elektroaktive polymerer

    DEFF Research Database (Denmark)

    West, K.

    Traditionelt tænker vi på polymerer (plastik) som elektrisk isolerende materialer - det som er udenpå ledningerne. I dag kender vi imidlertid også polymerer med intrinsisk elektrisk ledningsevne, og plast er på vej ind i anvendelser, der tidligereudelukkende var baseret på metaller og uorganiske...... halvledere. Hertil kommer, at en del af de ledende polymerer kan stimuleres til at skifte mellem en ledende og en halvledende tilstand, hvorved de ændret både form og farve. I foredraget gives der enrække eksempler på anvendelse af polymerer som elektriske komponenter - rækkende fra polymer elektronik over...

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2013-10-15

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

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

    International Nuclear Information System (INIS)

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

  16. 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

    2014-05-01

    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.

  17. Process for Preparing Epoxy-Reinforced Silica Aerogels

    Science.gov (United States)

    Meador, Mary Ann B (Inventor)

    2016-01-01

    One-pot reaction process for preparing epoxy-reinforced monolithic silica aerogels comprising the reaction of at least one silicon compound selected from the group consisting of alkoxysilanes, orthosilicates and combination thereof in any ratio with effective amounts of an epoxy monomer and an aminoalkoxy silane to obtain an epoxy monomer-silica sol in solution, subsequently preparing an epoxy-monomer silica gel from said silica sol solution followed by initiating polymerization of the epoxy monomer to obtain the epoxy-reinforced monolithic silica aerogel.

  18. Silica nephropathy.

    Science.gov (United States)

    Ghahramani, N

    2010-07-01

    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. PMID:23022796

  19. Silica Nephropathy

    Directory of Open Access Journals (Sweden)

    N Ghahramani

    2010-06-01

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

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

    Directory of Open Access Journals (Sweden)

    Masako Miki

    2013-12-01

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

  1. Immobilization of Polymeric Luminophor on Nanoparticles Surface

    Science.gov (United States)

    Bolbukh, Yuliia; Podkoscielna, Beata; Lipke, Agnieszka; Bartnicki, Andrzej; Gawdzik, Barbara; Tertykh, Valentin

    2016-04-01

    Polymeric luminophors with reduced toxicity are of the priorities in the production of lighting devices, sensors, detectors, bioassays or diagnostic systems. The aim of this study was to develop a method of immobilization of the new luminophor on a surface of nanoparticles and investigation of the structure of the grafted layer. Monomer 2,7-(2-hydroxy-3-methacryloyloxypropoxy)naphthalene (2,7-NAF.DM) with luminophoric properties was immobilized on silica and carbon nanotubes in two ways: mechanical mixing with previously obtained polymer and by in situ oligomerization with chemisorption after carrier's modification with vinyl groups. The attached polymeric (or oligomeric) surface layer was studied using thermal and spectral techniques. Obtained results confirm the chemisorption of luminophor on the nanotubes and silica nanoparticles at the elaborated synthesis techniques. The microstructure of 2,7-NAF.DM molecules after chemisorption was found to be not changed. The elaborated modification approach allows one to obtain nanoparticles uniformly covered with polymeric luminophor.

  2. Lipase-catalyzed polyester synthesis – A green polymer chemistry

    OpenAIRE

    Kobayashi, Shiro

    2010-01-01

    This article is a short comprehensive review describing in vitro polyester synthesis catalyzed by a hydrolysis enzyme of lipase, most of which has been developed for these two decades. Polyesters are prepared by repeated ester bond-formation reactions; they include two major modes, ring-opening polymerization (ROP) of cyclic monomers such as cyclic esters (lactones) and condensation polymerization via the reaction between a carboxylic acid or its ester group and an alcohol group. Polyester sy...

  3. Silica/Polymer and Silica/Polymer/Fiber Composite Aerogels

    Science.gov (United States)

    Ou, Danny; Stepanian, Christopher J.; Hu, Xiangjun

    2010-01-01

    carboxyl groups of the organic phase. The polymerization process has been adapted to create interpenetrating PMA and silica-gel networks from monomers and prevent any phase separations that could otherwise be caused by an overgrowth of either phase. Typically, the resulting PMA/silica aerogel, without or with fiber reinforcement, has a density and a thermal conductivity similar to those of pure silica aerogels. However, the PMA enhances mechanical properties. Specifically, flexural strength at rupture is increased to 102 psi (=0.7 MPa), about 50 times the flexural strength of typical pure silica aerogels. Resistance to compression is also increased: Applied pressure of 17.5 psi (=0.12 MPa) was found to reduce the thicknesses of several composite PMA/silica aerogels by only about 10 percent.

  4. On the Origin and Underappreciated Effects of Ion Doping in Silica.

    Science.gov (United States)

    Song, Xiaohui; Ding, Tao; Yao, Lin; Lin, Ming; Siew Tan, Rachel Lee; Liu, Cuicui; Sokol, Katarzyna; Yu, Le; Lou, Xiong Wen David; Chen, Hongyu

    2015-09-01

    The origin of selectivity in the hollowing of silica nanoparticles is investigated to further understand silica. It is realized that, during the synthesis, the silica precursors are essentially ion-paired polyelectrolytes, whose nucleation depends on the concentration of the counter ions, and most importantly, the size/length of the poly(silicic acid). Thus, the "silica" that nucleates out at the different stages of synthesis has different degrees of ion doping, which explains its solubility in water, its microporosity, and the selective etching phenomena. The etching of silica in water is shown to be a matter of silica solubility, which correlates to the relative amounts of solvent and to the solvent quality (the water/isopropanol ratio). Hollowing does not occur when the silica nanoparticles are incubated in solutions presaturated with "silica," ruling out surface reposition and Ostwald ripening as the hollowing mechanism. The embedded ions in silica are confirmed by elemental analysis (CHNS) and inductively coupled plasma-mass spectrometry. The high ionic doping ratios (N/Si = 2.3% for NH3 -catalyzed silica; Na/Si = 11.2% for NaOH-catalyzed silica) explain the unusual solubility of silica in neutral water. The new view of silica with the ionic impurities on the central stage allows for insights in silica properties and versatility in synthetic design. PMID:26068983

  5. Complex coacervation between colloidal silica and polyacrylamide

    International Nuclear Information System (INIS)

    Complex coacervation introduced by gamma-ray induced polymerization of acrylamide in colloidal silica was studied. The complex coaservate was formed by polymerization of acrylamide dissolved in a colloidal silica and methanol mixture. Complex coacervation (two-phase separation of the mixture) was observed only when the concentration of methanol was between 33 and 41 percent by volume, and the concentration of colloidal silica did not affect it. Although two phase separation was not influenced by pH change, the content of polyacrylamide was bigger in the equilibrated solution in acidic regions. It was, however, bigger in the complex coacervate at neutral and in alkaline regions. The content of polyacrylamide was also calculated from the particle diameter of complex coacervate measured by small angle X-ray scattering, and the result was well coincided with the analytical result. The stability of the complex coacervate against the addition of salts was better than that of the untreated colloidal silica. The rate of electrophoretic transport of the complex coacervate was also lower than that of the colloidal silica. From these observation it was concluded that the hydrophobic colloidal silica particles were protected by the surrounding hydrophilic polyacrylamide. (author)

  6. Synthesis of polymeric and hybrid nanoparticles for electroplating applications

    International Nuclear Information System (INIS)

    Monodisperse polymeric particles with diameters in the range of 60-1400 nm were prepared by (emulsifier-free) emulsion polymerization and incorporated into electrolytic zinc coatings aiming to improve the corrosion resistance of electrogalvanized steel. Various types of polymeric nanoparticles were thus synthesized in order to assess the effect of the emulsifier, initiator and comonomer type on the particle morphology, stability and codeposition behavior. The polymerization experiments were carried out in laboratory-scale glass reactors and the most promising recipes were successfully scaled-up in a fully automated pilot-scale reactor. Replicates of some representative experiments, which were run both in lab and pilot-scale reactors, indicated excellent reproducibility of the polymerization process. Uniform, polymer-containing zinc coatings were produced by electrolytic codeposition of the nanoparticles from an acid zinc plating bath using a rotating disk electrode (RDE). Hybrid polystyrene/silica nanoparticles with increased silica content were also prepared via emulsifier-free emulsion polymerization, in the presence of an ultrafine aqueous silica sol, to be used in electrocoating applications. The effect of key process parameters, such as initial monomers molar ratio and pH on the size, morphology and silica content of the produced hybrid nanoparticles was investigated

  7. AROMATIC AND HETEROCYCLIC NITRILES AND THEIR POLYMERS XⅦ. THE POLYMERIZATION KINETICS OF CYANOPYRIDINES AND CHARACTERIZATION OF THE FORMED POLYMER

    Institute of Scientific and Technical Information of China (English)

    SUN Luying; HUANG Zhitang

    1990-01-01

    The polymerization rates of three cyanopyridines catalyzed by cuprous chloride-zinc system are measured,and the structure of the formed polymer is also determined. Compared with aromatic nitrile,cyanopyridines polymerize faster and form polyconjugated polymer with skeleton -(C=N)- n insteadoftriazine structure. This chain-polymer possesses semiconductive property, and can be converted into conductive material by thermal treatment. In addition, the polymerization kinetics of 3-cyanopyridine catalyzed by 3-cyanopyridinium perchlorate is investigated. It is found that the polymerization rate is directly proportional to the concentrations of monomer and catalyst, and the activation energy of the polymerization is 103.1 KJ/mol.

  8. Chain Reaction Polymerization.

    Science.gov (United States)

    McGrath, James E.

    1981-01-01

    The salient features and importance of chain-reaction polymerization are discussed, including such topics as the thermodynamics of polymerization, free-radical polymerization kinetics, radical polymerization processes, copolymers, and free-radical chain, anionic, cationic, coordination, and ring-opening polymerizations. (JN)

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

    OpenAIRE

    Sebastian Wilhelm; Matthias Kind

    2015-01-01

    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)...

  10. 二氧化硅负载高氯酸催化合成香兰素缩1,2-丙二醇%Synthesis of Vanillin 1,2-propylene glycol acetal catalyzed by silica supported perchloric acid

    Institute of Scientific and Technical Information of China (English)

    王宏社

    2013-01-01

    以二氧化硅负载高氯酸(HClO4/SiO2)为催化剂,香兰素和1,2-丙二醇经缩合反应合成香兰素缩1,2-丙二醇.考察了醛醇物质的量比、催化剂用量、反应温度和反应时间对产品收率的影响.实验表明,较佳反应条件为:当香兰素的用量为0.1 mol,1,2-丙二醇的用量为0.16 mol,即n(香兰素)∶n(1,2-丙二醇)=1∶1.6,催化剂用量1.5g,反应温度80℃,反应时间45 min,香兰素缩1,2-丙二醇的收率达87.1%以上.HClO4/SiO2是一种热稳定性好、简单易制、可循环使用的高效非均相催化剂.%Vanillin 1, 2-propylene glycol acetal was synthesized through the condensation of Vanillin with 1, 2-propylene glycol using silica supported perchloric acid (HClO4/SiO2) as a catalyst. The effects of the molar ratio of reactant, the amount of catalyst, reaction temperature and reaction time on the yield of product were discussed. The results showed that the optimized reaction conditions are as follows; the molar ratio of Vanillin (0.1 mol) to 1, 2-propylene glycol (0.16 mol) is 1:1.6; the amount of catalyst is 1.5 g, reaction temperature is 80 ℃ and the reaction time is 45 min. Under the optimum conditions mentioned above, the yield of Vanillin 1, 2-propylene glycol acetal reached more than 87.1%. HClO4/SiO2 as a heterogeneous catalyst has many advantages of high thermal stability, ease of preparation and reusability.

  11. 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

    Science.gov (United States)

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

    2016-01-01

    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

  12. 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.

    Science.gov (United States)

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

    2016-01-28

    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. PMID:26785674

  13. Experimental determination of quartz solubility and melting in the system SiO2-H2O-NaCl at 15-20 kbar and 900-1100 °C: implications for silica polymerization and the formation of supercritical fluids

    Science.gov (United States)

    Cruz, Miguel F.; Manning, Craig E.

    2015-10-01

    We investigated quartz solubility and melting in the system SiO2-NaCl-H2O at 15-20 kbar and 900-1100 °C using hydrothermal piston-cylinder methods. The solubility of natural, high-purity quartz was determined by weight loss. Quartz solubility decreases with increasing NaCl mole fraction ( X NaCl) at fixed pressure and temperature. The decline is greatest at low X NaCl. The solubility patterns can be explained by changes in the concentration and identity of silica oligomers. Modeling of results at 1000 °C, 15 kbar, reveals that silica monomers and dimers predominate at low Si concentration (high X NaCl), that higher oligomers assumed to be trimers become detectable at X NaCl = 0.23, and that the trimers contain >50 % of dissolved Si at X NaCl = 0. The modeling further implies a hydration number for the silica monomer of 1.6, significantly lower than is observed in previous studies. Results at 15 kbar and 1100 °C provide evidence of two coexisting fluid phases. Although solubility could not be determined directly in these cases, the presence or absence of phases over a range of bulk compositions permitted mapping of the topology of the phase diagram. At 1100 °C, 15 kbar, addition of only a small amount of NaCl ( X NaCl = 0.05) leads to separation of two fluid phases, one rich in H2O and SiO2, the other rich in NaCl with lower SiO2. Textural identification of two fluids is supported by very low quench pH due to preferential partitioning of Na into the fluid that is rich in SiO2 and H2O, confirmed by electron microprobe analyses. The addition of NaCl causes the upper critical end point on the SiO2-H2O melting curve to migrate to significantly higher pressure. Correspondence between depolymerization and phase separation of SiO2-H2O-NaCl fluids indicates that polymerization plays a fundamental role in producing critical mixing behavior in silicate-fluid systems.

  14. Distribution of active centers by catalytic activity in diene polymerization with lanthanide systems

    International Nuclear Information System (INIS)

    In the ion coordination polymerization of dienes catalyzed by lanthanides systems NdCl3 · TBP-triisobutylaluminium, the kinetic-activity distribution of active sites were determined using the molecular mass distribution curves obtained by the Tikhonov regularization method. The polymodal pattern of distributions suggests the presence of several types of active centers, which change their kinetic activity during polymerization

  15. Clickable Polylactic Acids by Fast Organocatalytic Ring-Opening Polymerization in Continuous Flow

    NARCIS (Netherlands)

    Berg, van den Sebastiaan A.; Zuilhof, Han; Wennekes, Tom

    2016-01-01

    The use of microreactor technology for the ring-opening polymerization of l-lactide catalyzed by 1,5,7-triazabicyclo[4.4.0]dec-5-ene allows for rapid optimization of reaction parameters (reaction temperature and residence time). At moderate catalyst loading, good control over the polymerization i

  16. Muon Catalyzed Fusion

    Science.gov (United States)

    Armour, Edward A.G.

    2007-01-01

    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.

  17. A novel fabrication of meso-porous silica film by sol-gol of TEOS

    Institute of Scientific and Technical Information of China (English)

    殷明志; 姚熹; 张良莹

    2004-01-01

    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≥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 ℃ to 850 ℃; 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.

  18. A novel fabrication of meso-porous silica film by sol-gol of TEOS

    Institute of Scientific and Technical Information of China (English)

    殷明志; 姚熹; 张良莹

    2004-01-01

    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≥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℃ to 850℃;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.

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

    OpenAIRE

    Valdemiro P. Carvalho Jr.; Camila P. Ferraz; José Luiz S. Sá; Benedito S. Lima-Neto

    2012-01-01

    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 ...

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

    Science.gov (United States)

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

    2006-02-01

    Silica/polystyrene nanocomposite particles with different morphologies were synthesized through emulsion polymerization of styrene in the presence of silica particles previously modified by gamma-methacryloxypropyltrimethoxysilane (MPS). Grafting of the silane molecule was performed by direct addition of MPS to the aqueous silica suspension in the presence of an anionic surfactant under basic conditions. The MPS grafting density on the silica surface was determined using the depletion method and plotted against the initial MPS concentration. The influence of the MPS grafting density, the silica particles size and concentration and the nature of the surfactant on the polymerization kinetics and the particles morphology was investigated. When the polymerization was performed in the presence of an anionic surfactant, transmission electron microscopy images showed the formation of polymer spheres around silica for MPS grafting densities lower than typically 1 micromole x m(-2) while the conversion versus time curves indicated a strong acceleration effect under such conditions. In contrast, polymerizations performed in the presence of a larger amount of MPS moieties or in the presence of a non ionic emulsifier resulted in the formation of "excentered" core-shell morphologies and lower polymerization rates. The paper identifies the parameters that allow to control particles morphology and polymerization kinetics and describes the mechanism of formation of the nanocomposite colloids. PMID:16573042

  1. COPPER(I)-CATALYZED ATOM TRANSFER RADICAL POLYMERIZATIONS. (R826735)

    Science.gov (United States)

    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...

  2. TRANSITION METAL CATALYZED ATOM TRANSFER RADICAL POLYMERIZATION. (R826735)

    Science.gov (United States)

    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...

  3. Transition Metal Catalyzed Polymerization of 1,3,5-Trioxane

    OpenAIRE

    Henes, Michael

    2002-01-01

    We highlighted that transition metal complexes can serve as mediators for the cationic ROP of 1,3,5-trioxane. As examples cyclopentadienyl molybdenum complexes of different Lewis acidity were employed tolerating considerable more water than classical Lewis acid catalysts like BF3 · OEt2 or tBuClO4. They are less active than iridium or palladium catalysts, but [CpMo(CO)3OTf] (2a) was an excellent example to carry out time-dependent 1H NMR spectroscopic studies to follow the course of the polym...

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

    Science.gov (United States)

    Philipp, Warren H.

    1990-01-01

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

  5. Functional Films from Silica/Polymer Nanoparticles

    Directory of Open Access Journals (Sweden)

    Tânia Ribeiro

    2014-05-01

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

    Directory of Open Access Journals (Sweden)

    Jun-ichi Kadokawa

    2016-04-01

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

  7. Polymeric materials for neovascularization

    Science.gov (United States)

    DeVolder, Ross John

    Revascularization therapies have emerged as a promising strategy to treat various acute and chronic wounds, cardiovascular diseases, and tissue defects. It is common to either administer proangiogenic growth factors, such as vascular endothelial growth factor (VEGF), or transplant cells that endogenously express multiple proangiogenic factors. Additionally, these strategies utilize a wide variety of polymeric systems, including hydrogels and biodegradable plastics, to deliver proangiogenic factors in a sophisticated manner to maintain a sustained proangiogenic environment. Despite some impressive results in rebuilding vascular networks, it is still a challenging task to engineer mature and functional neovessels in target tissues, because of the increasing complexities involved with neovascularization applications. To resolve these challenges, this work aims to design a wide variety of proangiogenic biomaterial systems with tunable properties used for neovascularization therapies. This thesis describes the design of several biomaterial systems used for the delivery of proangiogenic factors in neovascularization therapies, including: an electrospun/electrosprayed biodegradable plastic patch used for directional blood vessel growth (Chapter 2), an alginate-g-pyrrole hydrogel system that biochemically stimulates cellular endogenous proangiogenic factor expression (Chapter 3), an enzyme-catalyzed alginate-g-pyrrole hydrogel system for VEGF delivery (Chapter 4), an enzyme-activated alginate-g-pyrrole hydrogel system with systematically controllable electrical and mechanical properties (Chapter 5), and an alginate-g-pyrrole hydrogel that enables the decoupled control of electrical conductivity and mechanical rigidity and is use to electrically stimulate cellular endogenous proangiogenic factor expression (Chapter 6). Overall, the biomaterial systems developed in this thesis will be broadly useful for improving the quality of a wide array of molecular and cellular based

  8. Catalytic Polymerization of Acrylonitrile by Khulays Bentonite

    Directory of Open Access Journals (Sweden)

    Matar M. Al-Esaimi

    2007-04-01

    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.2.1.4.6-10][How to Link/DOI: http://dx.doi.org/10.9767/bcrec.2.1.4.6-10 || or local: http://ejournal.undip.ac.id/index.php/bcrec/article/view/4] 

  9. Synthesis of 3D ordered porous polystyrene using silica template

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    A rigid colloidal silica template was formed by self-assembly ofthe monodispersed silica spheres prepared according to St-ber method. The silica template is highly ordered, which was verified by bright color effect due to Bragg diffraction and the results of SEM. The free radical polymerization of styrene was allowed within the interstices of the rigid template to result in the formation of the three- dimensional periodic silica/polystyrene nano-composites. The titled porous polystyrene was prepared by chemical decom- position of the template with concentrated aqueous hydro- fluoric acid. Scanning electron microscopy characterization showed that the macroporous polystyrene has ordered arrays of the uniform pores replicated from the template. Moreover, it was found that the morphology of the as-synthesized macroporous polystyrene was greatly affected by the connectivity of the silica spheres treated under different conditions.

  10. Polymerization in emulsion microdroplet reactors

    Science.gov (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

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

    Directory of Open Access Journals (Sweden)

    Kaushal Rege

    2010-02-01

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

  12. "Click" i polymerer 2

    DEFF Research Database (Denmark)

    Hvilsted, Søren

    2012-01-01

    "Click"-reaktioner til fremstilling af ledende polymerer med funktionelle håndtag og bipolymermaterialer......"Click"-reaktioner til fremstilling af ledende polymerer med funktionelle håndtag og bipolymermaterialer...

  13. 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: ymwei@nwu.edu.cn

    2015-07-30

    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.

  14. 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

    International Nuclear Information System (INIS)

    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−1 for catechol and 736.8 μmol g−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

  15. Polymerization Reactor Engineering.

    Science.gov (United States)

    Skaates, J. Michael

    1987-01-01

    Describes a polymerization reactor engineering course offered at Michigan Technological University which focuses on the design and operation of industrial polymerization reactors to achieve a desired degree of polymerization and molecular weight distribution. Provides a list of the course topics and assigned readings. (TW)

  16. Immobilization of Polymeric Luminophor on Nanoparticles Surface.

    Science.gov (United States)

    Bolbukh, Yuliia; Podkoscielna, Beata; Lipke, Agnieszka; Bartnicki, Andrzej; Gawdzik, Barbara; Tertykh, Valentin

    2016-12-01

    Polymeric luminophors with reduced toxicity are of the priorities in the production of lighting devices, sensors, detectors, bioassays or diagnostic systems. The aim of this study was to develop a method of immobilization of the new luminophor on a surface of nanoparticles and investigation of the structure of the grafted layer. Monomer 2,7-(2-hydroxy-3-methacryloyloxypropoxy)naphthalene (2,7-NAF.DM) with luminophoric properties was immobilized on silica and carbon nanotubes in two ways: mechanical mixing with previously obtained polymer and by in situ oligomerization with chemisorption after carrier's modification with vinyl groups. The attached polymeric (or oligomeric) surface layer was studied using thermal and spectral techniques. Obtained results confirm the chemisorption of luminophor on the nanotubes and silica nanoparticles at the elaborated synthesis techniques. The microstructure of 2,7-NAF.DM molecules after chemisorption was found to be not changed. The elaborated modification approach allows one to obtain nanoparticles uniformly covered with polymeric luminophor. PMID:27090657

  17. Polymerization of organized monomers

    Directory of Open Access Journals (Sweden)

    Stoiljković Dragoslav M.

    2004-01-01

    Full Text Available The current explanations of olefin and vinyl monomer polymerization propose that monomer molecules are successively added one by one to the growing polymer chain. This may be true if the monomer molecules exist as individual species in a polymerizing system, e.g. in dilute solutions of monomer. There are cases, however, in which monomer molecules are organized: bulk liquid monomer, solid monomer, a monomer monolayer adsorbed on a support, etc. Various supra-molecular species and particles of monomer exist in such cases. In the 1960-ties, Semenov, Kargin and Kabanov proposed a theory of organized monomer polymerization. In the last 25 years, our research group has further developed and applied that theory to various polymerizing systems: the radical polymerization of compressed ethene gas, the radical polymerization of liquid methyl methacrylate, olefin polymerization by transition metals and by Al-based catalysts. An outline of the main achievements are presented in this article.

  18. Silica in Protoplanetary Disks

    CERN Document Server

    Sargent, B A; Tayrien, C; McClure, M K; Li, A; Basu, A R; Manoj, P; Watson, D M; Bohac, C J; Furlan, E; Kim, K H; Green, J D; Sloan, G C

    2008-01-01

    Mid-infrared spectra of a few T Tauri stars (TTS) taken with the Infrared Spectrograph (IRS) on board the Spitzer Space Telescope show prominent narrow emission features indicating silica (crystalline silicon dioxide). Silica is not a major constituent of the interstellar medium; therefore, any silica present in the circumstellar protoplanetary disks of TTS must be largely the result of processing of primitive dust material in the disks surrouding these stars. We model the silica emission features in our spectra using the opacities of various polymorphs of silica and their amorphous versions computed from earth-based laboratory measurements. This modeling indicates that the two polymorphs of silica, tridymite and cristobalite, which form at successively higher temperatures and low pressures, are the dominant forms of silica in the TTS of our sample. These high temperature, low pressure polymorphs of silica present in protoplanetary disks are consistent with a grain composed mostly of tridymite named Ada found...

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

    International Nuclear Information System (INIS)

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

  20. 78 FR 14540 - Cyromazine, Silica Silicates (Silica Dioxide and Silica Gel), Glufosinate Ammonium, Dioctyl...

    Science.gov (United States)

    2013-03-06

    ... AGENCY Cyromazine, Silica Silicates (Silica Dioxide and Silica Gel), Glufosinate Ammonium, Dioctyl Sodium... the registration review of cyromazine, silica silicates (silica dioxide and silica gel), glufosinate..., consistent with the notice published in the Federal Register of August 17, 2012, (77 FR 49792)...

  1. Tritium catalyzed deuterium tokamaks

    International Nuclear Information System (INIS)

    A preliminary assessment of the promise of the Tritium Catalyzed Deuterium (TCD) tokamak power reactors relative to that of deuterium-tritium (D-T) and catalyzed deuterium (Cat-D) tokamaks is undertaken. The TCD mode of operation is arrived at by converting the 3He from the D(D,n)3He reaction into tritium, by neutron capture in the blanket; the tritium thus produced is fed into the plasma. There are three main parts to the assessment: blanket study, reactor design and economic analysis and an assessment of the prospects for improvements in the performance of TCD reactors (and in the promise of the TCD mode of operation, in general)

  2. Kinase-Catalyzed Biotinylation

    OpenAIRE

    Senevirathne, Chamara; Green, Keith D.; Pflum, Mary Kay H.

    2012-01-01

    Kinase-catalyzed protein phosphorylation plays an essential role in a variety of biological processes. Methods to detect phosphoproteins and phosphopeptides in cellular mixtures will aid in cell biological and signaling research. Our laboratory recently discovered the utility of γ-modified ATP analogues as tools for studying phosphorylation. Specifically, ATP-biotin can be used for labeling and visualizing phosphoproteins from cell lysates. Because the biotin tag is suitable for protein detec...

  3. Preparation of well-defined polystyrene/silica hybrid nanoparticles by ATRP

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    Immobilization of the atom transfer radical polymerization (ATRP) macroinitiators at the silica nanoparticle surfaces was achieved through surface modification with excess toluene-2,4-diisocynate (TDI), after which the residual isocyanate groups were converted into ATRP macroinitiators. Structurally well-defined polystyrene chains were grown from the nanoparticle surfaces to yield individual particles composed of a silica core and a well-defined, densely grafted outer polystyrene by ATRP, which was initiated by the as-synthesized silica-based macroinitiator. FTIR, NMR and gel permeation chro-matography (GPC) were used to characterize the polystyrene/silica hybrid particles.

  4. Preparation of well-defined polystyrene/silica hybrid nanoparticles by ATRP

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    Immobilization of the atom transfer radical polymerization(ATRP)macroinitiators at the silica nanoparticle surfaces was achieved through surface modification with excess toluene-2,4-diisocynate(TDI),after which the residual isocyanate groups were converted into ATRP macroinitiators.Structurally well-defined polystyrene chains were grown from the nanoparticle surfaces to yield individual particles composed of a silica core and a well-defined,densely grafted outer polystyrene by ATRP,which was initiated by the as-synthesized silica-based macroinitiator.FTIR,NMR and gel permeation chromatography(GPC)were used to characterize the polystyrene/silica hybrid particles.

  5. Polymerization in emulsion microdroplet reactors

    Science.gov (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

  6. Development of Filler Structure in Colloidal Silica-Polymer Nanocomposites

    Energy Technology Data Exchange (ETDEWEB)

    Meth, Jeffrey S; Zane, Stephen G; Chi, Changzai; Londono, J David; Wood, Barbara A; Cotts, Patricia; Keating, Mimi; Guise, William; Weigand, Steven [NWU; (Dupont)

    2012-02-07

    The realization of the full potential for polymeric nanocomposites to manifest their entitled property improvements relies, for some properties, on the ability to achieve maximum particle-matrix interfacial area. Well-dispersed nanocomposites incorporating colloidal silica as the filler can be realized in both polystyrene and poly(methyl methacrylate) matrices by exploiting the charge stabilized nature of silica in nonaqueous solvents which act as Bronsted bases. We demonstrate that dispersions of colloidal silica in dimethylformamide are charge stabilized, regardless of organosilyl surface functionalization. When formulated with polymer solutions, the charge stabilized structure is maintained during drying until the charged double layer collapses. Although particles are free to diffuse and cluster after this neutralization, increased matrix viscosity retards the kinetics. We demonstrate how high molecular weight polymers assist in immobilizing the structure of the silica to produce well-dispersed composites. The glass transition temperatures of these composites do not vary, even at loadings up to 50 vol %.

  7. Luminescence of Terbium Complexes Incorporated into Silica Matrix

    Institute of Scientific and Technical Information of China (English)

    闫冰; 游佳勇

    2002-01-01

    Binary and ternary terbium complexes were synthesized: Tb(N-PA)3*4H2O and Tb(N-PA)3(phen*2H2O (N-HPA = N-phenyl-2-aminobenzoic acid and phen = 1,10-phenanthroline). These complexes were introduced into inorganic polymeric porous silica matrix by the sol-gel method. The luminescence behavior of the complexes in silica gels was compared with the corresponding solid state complexes by means of emission, excitation spectra and luminescence lifetimes. The result indicates that the terbium ions show fewer emission lines and lower emission intensities in the silica gel than those in pure terbium complexes. The lifetimes of terbium ions in silica gel doped with terbium complexes become longer than those of terbium complexes.

  8. Phosphotungstate-Based Ionic Silica Nanoparticles Network for Alkenes Epoxidation

    Directory of Open Access Journals (Sweden)

    Xiaoting Li

    2015-12-01

    Full Text Available An inorganic-organic porous silica network catalyst was prepared by linking silica nanoparticles using ionic liquid and followed by anion-exchange with phosphotungstate. Characterization methods of FT-IR, TG, SEM, TEM, BET, etc., were carried out to have a comprehensive insight into the catalyst. The catalyst was used for catalyzing cyclooctene epoxidation with high surface area, high catalytic activity, and convenient recovery. The conversion and selectivity of epoxy-cyclooctene could both reach over 99% at 70 °C for 8 h using hydrogen peroxide (H2O2 as an oxidant, and acetonitrile as a solvent when the catalyst was 10 wt. % of cyclooctene.

  9. Catalyzed Ceramic Burner Material

    Energy Technology Data Exchange (ETDEWEB)

    Barnes, Amy S., Dr.

    2012-06-29

    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

  10. Dispersion of "guava-like" silica/polyacrylate nanocomposite particles in polyacrylate matrix

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    A series of "guava-like" silica/polyacrylate nanocomposite particles with close silica content and different grafting degrees were prepared via mini-emulsion polymerization using 3-(trimethoxysilyl)propyl methacrylate (TSPM) modified silica/acrylate dispersion.The silica/polyacrylate composite particles were melt-mixed with unfilled polyacrylate (PA) resin to prepare corresponding silica/polyacrylate molded composites and the dispersion mechanism of these silica particles from the "guava-like" composite particles into polyacrylate matrix was studied.It was calculated that about 110 silica particles were accumulated in the bulk of every silica/polyacrylate composite latex particle.Both the solubility tests of silica/polyacrylate composite latex particles in tetrahydrofuran (THF) and the section transmission electron microscope (TEM) micrographs of silica/polyacrylate molded composites indicated that the grafting degree of silica particles played a crucial role in the dispersion of silica/polyacrylate composite particles into the polyacrylate matrix.When the grafting degree of polyacrylate onto silica was in a moderate range (ca.20%-70%),almost all of silica particles in these "guava-like" composite particles were dispersed into the polyacrylate matrix in a primary-particle-level.However,at a lower grafting degree,massive silica aggregations were found in molded composites because of the lack of steric protection.At a greater grafting degree (i.e.,200%),a cross-linked network was formed in the silica/polyacrylate composite particles,which prevented the dispersion of composite particles in THF and polyacrylate matrix as primary particles.

  11. Correlating the Morphological Properties and Structural Organization of Monodisperse Spherical Silica Nanoparticles Grown on a Commercial Silica Surface.

    Science.gov (United States)

    Moreno, Yolice P; Cardoso, Mateus B; Moncada, Edwin A; dos Santos, João H Z

    2015-10-01

    A variety of nanosilicas have been widely used to fabricate rough surfaces with superhydrophobic and superhydrophilic properties. In this context, we prepared mixed silica and mixed nanosilica that were generated by the growth and self-assembly of synthesized monodisperse silica nanospheres (11-30 nm, 363 m(2)  g(-1) ) on the surface of Sylopol-948 and Dispercoll S3030 by using a base-catalyzed sol-gel route. Using this process, the interactions and hierarchical structure between the nano- and microsized synthesized silica particles were studied by changing the amount of tetraethoxysilane. The resulting materials were characterized by BET analysis, small-angle X-ray scattering (SAXS), dynamic light scattering, FTIR spectroscopy, and SEM. The mixed silica presented a higher specific surface area (326 m(2)  g(-1) ), a six-fold higher percentage of (SiO)6 (44-68 %), and a higher amount of silanol groups (14.0-30.7 %) than Sylopol-948 (271 m(2)  g(-1), 42.6 %, and 12.5 %, respectively). The morphological and hierarchical structural differences in the silica nanoparticles synthesized on the surface of commercial silica (micrometric or nanometric) were identified by SAXS. Mixed micrometric silica exhibited a higher degree of structural organization between particles than mixed nanosilica. PMID:26287309

  12. Conducting Polymeric Materials

    DEFF Research Database (Denmark)

    Hvilsted, Søren

    2016-01-01

    The overall objective of this collection is to provide the most recent developments within the various areas of conducting polymeric materials. The conductivity of polymeric materials is caused by electrically charged particles, ions, protons and electrons. Materials in which electrons are the ch...... awarded the Nobel Prize in chemistry “for the discovery and development of conductive polymers”....

  13. Step-Growth Polymerization.

    Science.gov (United States)

    Stille, J. K.

    1981-01-01

    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)

  14. Polymerization of cardanol using soybean peroxidase and its potential application as anti-biofilm coating material.

    Science.gov (United States)

    Kim, Yong Hwan; An, Eun Suk; Song, Bong Keun; Kim, Dong Shik; Chelikani, Rahul

    2003-09-01

    Soybean peroxidase (20 mg) catalyzed the oxidative polymerization of cardanol in 2-propanol/phospate buffer solution (25 ml, 1:1 v/v) and yielded 62% polycardanol over 6 h. Cobalt naphthenate (0.5% w/w) catalyzed the crosslinking of polycardanol and the final hardness of crosslinked polycardanol film exceeded 9 H scale as pencil scratch hardness, which shows a high potential as a commercial coating material. In addition, it showed an excellent anti-biofouling activity to Pseudomonas fluorescens compared to other polymeric materials such as polypropylene. PMID:14571976

  15. Microporous silica membranes

    DEFF Research Database (Denmark)

    Boffa, Vittorio; Yue, Yuanzheng

    2012-01-01

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

  16. Synthesis and Characterization of Polyvinylpyrrolidone Silica Core-Shell Nanocomposite Particles.

    Science.gov (United States)

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

    2015-03-01

    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. PMID:26413650

  17. Applied bioactive polymeric materials

    CERN Document Server

    Carraher, Charles; Foster, Van

    1988-01-01

    The biological and biomedical applications of polymeric materials have increased greatly in the past few years. This book will detail some, but not all, of these recent developments. There would not be enough space in this book to cover, even lightly, all of the major advances that have occurred. Some earlier books and summaries are available by two of this book's Editors (Gebelein & Carraher) and these should be consul ted for additional information. The books are: "Bioactive Polymeric Systems" (Plenum, 1985); "Polymeric Materials In Medication" (Plenum, 1985); "Biological Acti vi ties of Polymers" (American Chemical Society, 1982). Of these three, "Bioacti ve Polymeric Systems" should be the most useful to a person who is new to this field because it only contains review articles written at an introductory level. The present book primarily consists of recent research results and applications, with only a few review or summary articles. Bioactive polymeric materials have existed from the creation of life...

  18. Confined Polymerization in Highly Ordered Mesoporous Organosilicas.

    Science.gov (United States)

    Comotti, Angiolina; Bracco, Silvia; Beretta, Mario; Perego, Jacopo; Gemmi, Mauro; Sozzani, Piero

    2015-12-01

    Hybrid mesoporous organosilica exhibiting crystal-like order in the walls provided an ideal channel reaction vessel for the confined polymerization of acrylonitrile (PAN). The resulting high-molecular-mass PAN fills the channels at high yield and forms an ordered nanostructure of polymer nanobundles enclosed into the hybrid matrix. The in situ thermal transformation of PAN into rigid polyconjugated and, eventually, into condensed polyaromatic carbon nanofibers, retains the periodic architecture. Simultaneously, the matrix evolves showing the fusion of the p-phenylene rings and the cleavage of carbonsilicon bonds: this gives rise to graphitic-carbon/silica nanocomposites containing hyper-oxydrylated silica nanophases. Interestingly, the 3D hexagonal mesostructure survives in the carbonaceous material. The exploitation of porous materials of high capacity and a hybrid nature, for polymerization in the confined state, followed by high temperature treatments, allowed us to achieve unique and precisely fabricated nanostructures, thus paving the way for the construction of fine-tuned electronic and light-harvesting materials. PMID:26559381

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

    OpenAIRE

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

    2016-01-01

    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...

  20. THE BIMODAL MOLECULAR WEIGHT DISTRIBUTION OF cis-POLYBUTADIENE POLYMERIZED WITH LANTHANIDE COMPLEX CATALYSTS

    Institute of Scientific and Technical Information of China (English)

    CHENG Rongshi; HU Huizhen; JIANG Liansheng

    1987-01-01

    The variation of the molecular weight and molecular weight distribution of cis-polybutadiene in the course of polymerization catalyzed by lanthanide complex composed of triisobutyl aluminium or diisobutyl aluminium hydride was investigated by osmometry, viscometry and size exclusion chromatography. By analyzing the experimental data, the reasons of the appearance of bimodal molecular weight distribution were elucidated and the possible mechanisms of polymerization were discussed.

  1. Functional Virus-Based Polymer-Protein Nanoparticles by Atom Transfer Radical Polymerization

    OpenAIRE

    Pokorski, Jonathan K.; Breitenkamp, Kurt; Finn, M. G.

    2011-01-01

    Viruses and virus-like particles (VLPs) are useful tools in biomedical research. Their defined structural attributes make them attractive platforms for engineered interactions over large molecular surface areas. In this report, we describe the use of VLPs as multivalent macroinitiators for atom transfer radical polymerization (ATRP). The introduction of chemically reactive monomers during polymerization provides a robust platform for post-synthetic modification via the copper-catalyzed azide-...

  2. Synthesis of multivalent silica nanoparticles combining both enthalpic and entropic patchiness.

    Science.gov (United States)

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

    2015-01-01

    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. PMID:25920418

  3. Improved imide polymerization catalyst

    Science.gov (United States)

    Estrella, C. A.; Riccitiello, S. R.; Sawko, P. M.

    1979-01-01

    Catalyzation of imide polymers with metallic salts of 2-ethyl hexanoic acid allows reaction in production of flame resistant foams to proceed in one step without formation of undesirable heat-sensitive byproducts.

  4. Preparation of isospecific metallocene catalysts for olefin polymerization that are covalently tethered on solid surface

    OpenAIRE

    Suzuki, Noriyuki; Yu, Jian; Shioda, Nobuyuki; Asami, Hayato; Nakamura, Takashi; Huhn, Thomas; Fukuoka, Atsushi; Ichikawa, Masaru; Saburi, Masahiko; Wakatsuki, Yasuo

    2002-01-01

    A novel methodology was developed for the preparation of isospecific metallocene catalysts for olefin polymerization that are tethered on silica surfaces with covalent bonds. A racemic ansa-zirconocene complex that has a Si Cl moiety on its bridge was immobilized on SiO2 by the reaction of the Si Cl anchor with Si OH on the solid surface. The prepared solid catalyst was found to be effective for isospecific propene polymerization (catalyst A). Pretreatment of silica surfaces with Me3SiCl impr...

  5. 四氯化钛配合物/甲基锂体系催化降冰片烯开环移位聚合的研究%RING OPENING METATHESIS POLYMERIZATION OF NORBORNENE CATALYZED BY MCl4·2L/CH3Li

    Institute of Scientific and Technical Information of China (English)

    黄吉玲; 克莱伯特·多诺; 马海燕; 钱延龙

    1999-01-01

    @@ The ring opening metathesis polymerization of cyclic monomers is relatively a newcomer to the field of polymer chemistry. Depending on the monomer and the catalyst used, this type of reaction yields a wide range of products that have found important industrial applications.

  6. Catalyzing alignment processes

    DEFF Research Database (Denmark)

    Lauridsen, Erik Hagelskjær; Jørgensen, Ulrik

    2004-01-01

    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 implemented in and how the changing context is reflected in the environmental objectives that are established and prioritised. Our argument is, that the ability of the standard to achieve an impact is dependant on the constitution of ’coherent’ environmental issues in the context, where the management system...

  7. Preparation of Poly(MA-alt--olefin-C6,8,12,18)/Silica Nanohybrids via in situ generated nanofillers for use as a dual function organonanofiller

    Indian Academy of Sciences (India)

    Deni̇z Demi̇rcan; Günay Ki̇barer; Zaki̇r M O Rzayev

    2015-11-01

    Four types of copolymer-silica nanocomposites have been prepared via ring-opening grafting of -aminopropyltrimethoxysilane (APTS) as reactive coupling agent onto preformed copolymers of maleic anhydride (MA) with 1-hexene, 1-octene, 1-dodecene and 1-octadecene and in situ hydrolysis (polycondensation) of side-chain ethoxysilane groups and tetraethoxysilane as a precursor in the presence of HCl catalyst. The copolymers of MA with 1-hexene, 1-octene and 1-dodecene were synthesized by free radical polymerization and another MA copolymer with 1-octadecene was supplied commercially as matrix copolymer. Chemical/physical structures, thermal behavior and morphology investigations of the generated hybrids were performed by FTIR, 13C, 29Si-NMR, TGA, SEM and TEM analysis methods. Nano-level hybridization through covalent bonding (amidization) between the anhydride unit of copolymers and amine group of APTS was observed, and nanosilica networks (hydrolysis) were obtained through acid catalyzed co-polycondensation of TEOS and ethoxysilane fragments from both coupling agent and precursor. Agreeing with 29Si-NMR and TGA quantitative analysis results, the degree of hydrolysis of ethoxysilane groups varied from 51.0 to 60.9%, and the content of in situ generated silica particles was found to be around 70.7-75.7%. Thermal properties and thermal stability of the obtained hybrids were found to be enhanced with silica content. SEM analysis confirmed the formation of nanostructural hybrids with relatively fine distributed nanoparticles. TEM analyses of all the nanohybrids indicate the formation of spherical morphologies. These novel copolymer hybrids are expected to be a promising and efficient organonanofiller for the preparation of polymer nanocomposites with both dual functionality and compatibilizer effects.

  8. Silica Refractory Bricks

    Institute of Scientific and Technical Information of China (English)

    Yu Lingyan; Peng Xigao

    2011-01-01

    @@ 1.Scope This standard specifies the classification,technical requirements,test methods,quality appraisal procedures,packing,marking,transportation,storage,and quality certificate of silica refractory bricks.This standard is applicable to silica refractory bricks with single weight≤40 kg.

  9. Crystalline Silica Primer

    Science.gov (United States)

    Staff- Branch of Industrial Minerals

    1992-01-01

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

  10. Comparison of Base-catalyzed Silica Antireflective Coatings Modified by Different Surface Treatments of Water-NH3 and/or Hexamethyldisilazane Vapors%水氨或/和六甲基二硅氮烷表面处理碱催化二氧化硅增透膜结果的对比研究

    Institute of Scientific and Technical Information of China (English)

    霍艳芳; 罗荣辉; 苏永钢

    2013-01-01

    Aiming at the shortcoming that base-catalyzed quarter-wave silica antireflective coatings,prepared by sol-gel method,are porous and therefore low environment-resistant,water/NH3 vapor and/or hexamethyldisilazane vapor were utilized to modify the surface of these coatings to obtain high hydrophobicity and abrasion-resistance.Otherwise,comparison between different modified results from single vapor and combined vapors,were carried out to show the changes of coatings' physical properties and microstructures after different surface modifications and the influence of the treated order of combined vapors to the result coatings.According to the investigations,some conclusion can be drawn that water-ammonia vapor treatment facilitates the cross-link between hydroxyl groups in coatings,which reduces the film thickness,strengthens the abrasion-resistance,and simultaneously maintains the high transmittance; hexamethyldisilazane vapor treatment introduces methyl groups into coatings,making the polarity of coating surface and the interaction between particles decreased obviously,leading to poorer abrasion-resistance but fortunately,distinctly improved hydrophobicity; when coatings are treated by water-ammonia combined hexamethyldisilazane vapor,the water-ammonia vapor firstly strengthens the abrasion-resistance and meanwhile reduces the amount of hydroxyl groups which hindered the later hexamethyldisilazane vapor treatment,finally obtaining AR coatings with good abrasion-resistance and a certain extent of hydrophobicity; when coatings are treated by hexamethyldisilazane combined water-ammonia vapor,the hexamethyldisilazane vapor obviously improves the hydrophobicity but weakens the effect of water-ammonia vapor,resulting in a slight weaker abrasion-resistance compared to that after single water-ammonia vapor treatment.%针对溶胶-凝胶法制备的1/4波长二氧化硅增透膜耐环境性差的缺点,对其进行了水氨或/和六甲基二硅氮烷的表面处理,并对单

  11. Sorption of cadmium to bacterial extracellular polymeric sediment coatings under estuarine conditions

    Energy Technology Data Exchange (ETDEWEB)

    Schlekat, C.E.; Decho, A.W.; Chandler, G.T. [Univ. of South Carolina, Columbia, SC (United States). Dept. of Environmental Health Sciences

    1998-09-01

    Microbial extracellular polymeric substances (EPS) are ubiquitous features in aquatic environments. Produced by surface-adherent bacteria and microalgae, EPS are often present as coatings on surfaces of sediment particles and exhibit high affinities for divalent cationic metals. Thus, EPS sediment coatings may participate in the fate of potentially toxic metals. The authors coated particulate silica with EPS produced by NISC1, a bacterium isolated from estuarine sediments, in order to measure the metal binding characteristics of these coatings. They used the radioisotope {sup 109}Cd to measure effects of salinity, Cd concentration, and pH on Cd sorption to EPS-coated (EPS-silica) silica and to noncoated silica (NC-silica). Also, Cd sorption by NISC1 EPS coatings was compared to coatings of polymers formed by the bacterium, Alteromonas atlantica and the alga, Macrocystis porifera. Under all circumstances, EPS coatings increased the affinity of silica for Cd. Extracellular polymeric substance-particulate aggregates rapidly sorbed up to 90% of Cd from aqueous solution. Extracellular polymeric substance sediment coatings exhibited a maximum log distribution coefficient (K{sub d}) of 6.5 at 2.5%. Sorption of Cd to NC-silica was affected by salinity and metal concentration, whereas sorption of Cd to EPS-silica was only affected by salinity under high metal concentrations. Changes in pH had a dramatic effect on Cd sorption, with the proportion of free Cd to sorbed Cd changing from approximately 90% at pH 5 to 5% at pH 9. Desorption of Cd from EPS-silica was enhanced with increasing salinity. These experiments suggest that EPS coatings actively participate in binding dissolved overlying and pore-water metals in estuarine sediments.

  12. Silica, Silicosis, and Autoimmunity.

    Science.gov (United States)

    Pollard, Kenneth Michael

    2016-01-01

    Inhalation of dust containing crystalline silica is associated with a number of acute and chronic diseases including systemic autoimmune diseases. Evidence for the link with autoimmune disease comes from epidemiological studies linking occupational exposure to crystalline silica dust with the systemic autoimmune diseases systemic lupus erythematosus, systemic sclerosis, and rheumatoid arthritis. Although little is known regarding the mechanism by which silica exposure leads to systemic autoimmune disease, there is a voluminous literature on silica exposure and silicosis that may help identify immune processes that precede development of autoimmunity. The pathophysiology of silicosis consists of deposition of silica particles in the alveoli of the lung. Ingestion of these particles by macrophages initiates an inflammatory response, which stimulates fibroblasts to proliferate and produce collagen. Silica particles are encased by collagen leading to fibrosis and the nodular lesions characteristic of the disease. The steps in the development of silicosis, including acute and chronic inflammation and fibrosis, have different molecular and cellular requirements, suggesting that silica-induced inflammation and fibrosis may be mechanistically separate. Significantly, it is unclear whether silica-induced inflammation and fibrosis contribute similarly to the development of autoimmunity. Nonetheless, the findings from human and animal model studies are consistent with an autoimmune pathogenesis that begins with activation of the innate immune system leading to proinflammatory cytokine production, pulmonary inflammation leading to activation of adaptive immunity, breaking of tolerance, and autoantibodies and tissue damage. The variable frequency of these immunological features following silica exposure suggests substantial genetic involvement and gene/environment interaction in silica-induced autoimmunity. However, numerous questions remain unanswered. PMID:27014276

  13. Silica, Silicosis and Autoimmunity.

    Directory of Open Access Journals (Sweden)

    Kenneth Michael Pollard

    2016-03-01

    Full Text Available Inhalation of dust containing crystalline silica is associated with a number of acute and chronic diseases including systemic autoimmune diseases. Evidence for the link with autoimmune disease comes from epidemiological studies linking occupational exposure to crystalline silica dust with the systemic autoimmune diseases SLE, SSc and RA. Although little is known regarding the mechanism by which silica exposure leads to systemic autoimmune disease, there is a voluminous literature on silica exposure and silicosis that may help identify immune processes that precede development of autoimmunity. The pathophysiology of silicosis consists of deposition of silica particles in the alveoli of the lung. Ingestion of these particles by macrophages initiates an inflammatory response which stimulates fibroblasts to proliferate and produce collagen. Silica particles are encased by collagen leading to fibrosis and the nodular lesions characteristic of the disease. The steps in the development of silicosis, including acute and chronic inflammation and fibrosis, have different molecular and cellular requirements suggesting that silica-induced inflammation and fibrosis may be mechanistically separate. Significantly, it is unclear whether silica-induced inflammation and fibrosis contribute similarly to the development of autoimmunity. Nonetheless, the findings from human and animal model studies are consistent with an autoimmune pathogenesis that begins with activation of the innate immune system leading to proinflammatory cytokine production, pulmonary inflammation leading to activation of adaptive immunity, breaking of tolerance, autoantibodies and tissue damage. The variable frequency of these immunological features following silica exposure suggests substantial genetic involvement and gene/environment interaction in silica-induced autoimmunity. However numerous questions remain unanswered.

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

    OpenAIRE

    Sebastian Wilhelm; Matthias Kind

    2014-01-01

    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 o...

  15. Tailoring of thermomechanical properties of thermoplastic nanocomposites by surface modification of nanoscale silica particles

    OpenAIRE

    Becker, Carsten; Krug, Herbert; Schmidt, Helmut K.

    1996-01-01

    Thermoplastic nanocomposites based on linear polymethacrylates as matrix materials and spherical silica particles as fillers have been synthesized using the in situ free radical polymerization technqiue of methacrylate monomers in presence of specially functionalized SiO2 nanoparticulate fillers. Uncoated monodisperse silica particles with particle sizes 100 nm and 10 nm were used as reference fillers. For surface modification, the alcoholic dispersions of the fillers were treated with approp...

  16. Chelating polymeric membranes

    KAUST Repository

    Peinemann, Klaus-Viktor

    2015-01-22

    The present application offers a solution to the current problems associated with recovery and recycling of precious metals from scrap material, discard articles, and other items comprising one or more precious metals. The solution is premised on a microporous chelating polymeric membrane. Embodiments include, but are not limited to, microporous chelating polymeric membranes, device comprising the membranes, and methods of using and making the same.

  17. Lewis-Acid-Mediated Stereospecific Radical Polymerization of Acrylimides Bearing Chiral Oxazolidinones.

    Science.gov (United States)

    Fujita, Takehiro; Yamago, Shigeru

    2015-12-14

    Lewis acid (MgBr2)-catalyzed radical polymerization of acrylimides bearing chiral oxazolidinones gave highly isotactic polyacrylimides with up to >99% meso tetrad (mmm) selectivity. Polymerization in the absence of Lewis acid gave atactic polymers with 80% racemo diad (r) selectivity; the selectivity was deliberately tuned from 80% r to >99% mmm by varying the polymerization conditions. The polyacrylimide was quantitatively converted to corresponding polyacrylates while preserving the stereoregularity, thus providing a general method for the synthesis of atactic to isotactic polyacrylates. PMID:26500040

  18. Radical polymerization of monoethyl itaconate

    OpenAIRE

    Katsikas Lynne; Nišević Nataša; Ignjatović Milka; Adamović Vladimir; Đakov Tatjana A.; Popović Ivanka G.

    2003-01-01

    The radical polymerization of monoethyl itaconate (MEI) was investigated in bulk and in solution at 60°C using a,a'-azobisisobutyronitrile as initiator. It was established that the obtained polymer poly(monoethyl itaconate) was insoluble in its monomer, implying that the bulk polymerization of MEI was a precipitation polymerization. The polymerization kinetics of MEI were discussed and compared to the polymerization kinetics of structurally similar alkyl itaconates. The homogeneous radical po...

  19. Enhancing water flux of thin-film nanocomposite (TFN) membrane by incorporation of bimodal silica nanoparticles

    OpenAIRE

    Jun Yin; Baolin Deng; Zhe Yang

    2016-01-01

    Modern reverse osmosis (RO)/nanofiltration (NF) membranes are primarily made of thin-film composites (TFC) fabricated through interfacial polymerization of m-phenylene diamine (MPD) and trimesoyl chloride (TMC) on a polysulfone (PSF) supporting membrane. In this study, two types of bimodal silica nanoparticles (~80 nm) with different internal pore structures were synthesized and incorporated into the polyamide (PA) thin-film layer during interfacial polymerization at concentrations varying fr...

  20. Adsorption of polyelectrolytes on silica and gold surfaces

    OpenAIRE

    Altamirano, M. A. Balderas; Camacho, R.; E. Pérez; Goicochea, A. Gama

    2016-01-01

    The results of a study that helps understand the mechanisms of adsorption of polyelectrolytes on particles, using numerical simulation methods, specifically the one known as dissipative particle dynamics are reported here. The adsorption of cationic polyelectrolytes of two different polymerization degrees interacting with two types of surfaces, one made of gold and the other of silica is predicted and compared. We find that a more negatively charged wall does not necessarily adsorb more catio...

  1. Flue gas injection control of silica in cooling towers.

    Energy Technology Data Exchange (ETDEWEB)

    Brady, Patrick Vane; Anderson, Howard L., Jr.; Altman, Susan Jeanne

    2011-06-01

    Injection of CO{sub 2}-laden flue gas can decrease the potential for silica and calcite scale formation in cooling tower blowdown by lowering solution pH to decrease equilibrium calcite solubility and kinetic rates of silica polymerization. Flue gas injection might best inhibit scale formation in power plant cooling towers that use impaired makeup waters - for example, groundwaters that contain relatively high levels of calcium, alkalinity, and silica. Groundwaters brought to the surface for cooling will degas CO{sub 2} and increase their pH by 1-2 units, possibly precipitating calcite in the process. Recarbonation with flue gas can lower the pHs of these fluids back to roughly their initial pH. Flue gas carbonation probably cannot lower pHs to much below pH 6 because the pHs of impaired waters, once outgassed at the surface, are likely to be relatively alkaline. Silica polymerization to form scale occurs most rapidly at pH {approx} 8.3 at 25 C; polymerization is slower at higher and lower pH. pH 7 fluids containing {approx}220 ppm SiO{sub 2} require > 180 hours equilibration to begin forming scale whereas at pH 8.3 scale formation is complete within 36 hours. Flue gas injection that lowers pHs to {approx} 7 should allow substantially higher concentration factors. Periodic cycling to lower recoveries - hence lower silica concentrations - might be required though. Higher concentration factors enabled by flue gas injection should decrease concentrate volumes and disposal costs by roughly half.

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

    Energy Technology Data Exchange (ETDEWEB)

    Stael, Giovanni Chaves [Observatorio Nacional, Rio de Janeiro, RJ (Brazil). Dept. de Geofisica (DGE)]. E-mail: stael@on.br; Tavares, Maria I.B. [Universidade Federal do Rio de Janeiro, RJ (Brazil). Inst. de Macromoleculas]. E-mail: mibt@ima.ufrj.br

    2005-07-01

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

  3. Polymerization of euphorbia oil with Lewis acid in carbon dioxide media

    Science.gov (United States)

    Boron trifluoride diethyl etherate (BF3-OEt2) Lewis acid catalyzed ring-opening polymerization of euphorbia oil (EO), a natural epoxy oil, in liquid carbon dioxide was conducted in an effort to develop useful vegetable oil based polymers. The resulting polymers (RPEO) were characterized by FTIR, 1H-...

  4. Solid-Phase Synthesis of 2-Arylbenzothiazole Using Silica Sulfuric Acid under Microwave Irradiation

    International Nuclear Information System (INIS)

    The condensation of several aromatic/heteroaromatic aldehydes with 2-aminothiophenol catalyzed by silica sulfuric acid under microwave irradiation afforded 2-arylbenzothiazoles in high yields and short reaction times under solvent- free conditions. The major advantages of the present method are good yields, ecofriendly, reusable catalyst, mild and solvent-free reaction conditions

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

    DEFF Research Database (Denmark)

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

    1992-01-01

    The specific heat C(p) and the thermal conductivity lambda of a series of base-catalyzed silica aerogels have been measured at temperatures between 0.05 and 20 K. The results confirm that the different length-scale regions observed in the aerogel structure are reflected in the dynamic behavior of...

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

    DEFF Research Database (Denmark)

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

    1992-01-01

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

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

    DEFF Research Database (Denmark)

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

    1991-01-01

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

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

    DEFF Research Database (Denmark)

    Bernasconi, A.; Sleator, T.; Posselt, D.; Kjems, Jørgen; Ott, H.R.

    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 in...

  9. 溴化钾催化硫化物、硝酸铵和 SiO2-OSO3H 固体酸的氧化反应%Chemoselective Oxidation of Sulfides with Ammonium Nitrate and Silica Sulfuric Acid Catalyzed by KBr

    Institute of Scientific and Technical Information of China (English)

    Arash GHORBANI-CHOGHAMARANI; Mohammad Ali ZOLFIGOL; Toktam RASTEGAR

    2009-01-01

    A convenient and selective catalytic method for the sulfoxidation of aliphatic and aromatic sulfides by treatment of NH4NO3, silica sulfuric acid, wet SiO2 (50% w/w) and a catalytic amount of KBr in CH2Cl2 at room temperature was developed. Many sulfides can be selectively oxidized at room temperature in good to excellent yields. The reaction proceeds without over-oxidation to sulfones under mild conditions.

  10. What Is Crystalline Silica?

    Science.gov (United States)

    ... 1926.55, 1910.1000). OSHA also requires hazard communication training for workers exposed to crystalline silica, and ... identify, reduce, and eliminate health hazards associated with occupational ... safety and health? OSHA has various publications, standards, technical ...

  11. Cellulose-silica aerogels.

    Science.gov (United States)

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

    2015-05-20

    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. PMID:25817671

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

    DEFF Research Database (Denmark)

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

    2011-01-01

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

  13. Peptide catalysed prebiotic polymerization of RNA

    DEFF Research Database (Denmark)

    Wieczorek, Rafal; Luisi, Pier Luigi; Monnard, Pierre-Alain

    A short peptide composed of only two amino acid residues, serine and histidine, is here reported to enable oligomerization of RNA monomers. SerHis dipeptide was previously reported to catalyse formation of peptide bonds (Gorlero et al. 2009) as well as possessing broad hydrolytic activities...... oligomers from imidazole derivatives of mononucleotides. The thermodynamic shift towards condensation was achieved using water/ice eutectic phase environment (Monnard and Ziock 2008). To obtain such an environment, a reaction solution is cooled below its freezing point, but above the eutectic point. Under....... (2000) Dipeptide seryl-histidine and related oligopeptides cleave DNA, protein, and a carboxyl ester. Bioorg. Med. Chem. 8(12): 2675-80. Monnard PA, Ziock H. (2008) Eutectic phase in water-ice: a self-assembled environment conducive to metal-catalyzed non-enzymatic RNA polymerization. Chem Biodivers. 5...

  14. From molecular precursors in solution to microstructured optical fiber: a sol-gel polymeric route

    OpenAIRE

    El Hamzaoui, Hicham; Bigot, Laurent; Bouwmans, Géraud; Razdobreev, Igor,; Bouazaoui, Mohamed; Capoen, Bruno

    2011-01-01

    Solid-core photonic crystal fibers with the core derived from non-doped or Erbium-doped sol-gel silica rods are fabricated. The results demonstrate that the direct polymeric sol-gel route constitutes a promising method to prepare large high quality glass pieces that can be integrated into microstructured optical fibers suitable for passive and active optical fiber applications.

  15. Synthesis and characterization of aluminum particles coated with uniform silica shell

    Institute of Scientific and Technical Information of China (English)

    CHENG Zhi-peng; YANG Yi; LI Feng-sheng; PAN Zhen-hua

    2008-01-01

    The silica coated aluminum composite particles were prepared by hydrolysis-condensation polymerization of tetraethylorthosilicate(TEOS) on the surface of aluminum particle. The structure, morphology, and properties of the silica coated aluminum were studied. The peaks of Si-O-Si are presented in the Fourier transform infrared (FT-IR) spectrum of the composite particles. The thickness of the silica shell is about 80 nm according to the results of transmission electron microscopy(TEM) and laser particle size analysis, while the mean diameter of the aluminum particle is 7.13 μm. The mass fraction of silica in the sample was determined by fluorescent X-ray spectrometry(XRF). Result of the thermogravimetric analysis(TGA) indicates that thermal stability of silica coated aluminum particles is better than that of pure aluminum particles at low temperature while more reactive at high temperature.

  16. POLYMERIC SURFACTANT STRUCTURE

    Institute of Scientific and Technical Information of China (English)

    P.M. Saville; J.W. White

    2001-01-01

    Polymeric surfactants are amongst the most widespread of all polymers. In nature, proteins and polysaccharides cause self organization as a result of this surfactancy; in industry, polymeric surfactants play key roles in the food, explosives and surface coatings sectors. The generation of useful nano- and micro-structures in films and emulsions as a result of polymer amphiphilicity and the application of mechanical stress is discussed. The use of X-ray and neutron small angle scattering and reflectivity to measure these structures and their dynamic properties will be described. New results on linear and dendritic polymer surfactants are presented.

  17. A facile synthesis of terminal arylacetylenes via Sonogashira coupling reactions catalyzed by MCM-41-supported mercapto palladium(0) complex

    Institute of Scientific and Technical Information of China (English)

    Ya Ping Xu; Rong Hua Hu; Ramesh C.Kamboj

    2008-01-01

    A variety of terminal arylacetylenes have been conveniently synthesized in good to high yields via Sonogashira coupling of aryl iodides with (trimethylsilyl)acetylene catalyzed by MCM-41-supported mercapto palladium(0) complex,followed by desilylation under mild conditions.This polymeric palladium catalyst can be reused many times without any decrease in activity.

  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;

    2001-01-01

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

    Science.gov (United States)

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

    2016-01-12

    We investigated the relationship between unfolded proteins, silica nanoparticles and chaperonin to determine whether unfolded proteins could stick to silica surfaces and how this process could impair heat shock protein activity. The HSP60 catalyzed green fluorescent protein (GFP) folding was used as a model system. The adsorption isotherms and adsorption kinetics of denatured GFP were measured, showing that denaturation increases GFP affinity for silica surfaces. This affinity is maintained even if the surfaces are covered by a protein corona and allows silica NPs to interfere directly with GFP folding by trapping it in its unstructured state. We determined also the adsorption isotherms of HSP60 and its chaperonin activity once adsorbed, showing that SiO2 NP can interfere also indirectly with protein folding through chaperonin trapping and inhibition. This inhibition is specifically efficient when NPs are covered first with a layer of unfolded proteins. These results highlight for the first time the antichaperonin activity of silica NPs and ask new questions about the toxicity of such misfolded proteins/nanoparticles assembly toward cells. PMID:26649773

  20. Inflation of a Polymeric Menbrane

    DEFF Research Database (Denmark)

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

    1998-01-01

    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....

  1. Preparation and characterization of montmorillonite-silica nanocomposites: A sol-gel approach to modifying clay surfaces

    International Nuclear Information System (INIS)

    Montmorillonite-silica nanocomposites were prepared by a sol-gel approach involving hydrolysis reaction of alkoxysilanes (TEOS) and subsequent condensation reaction with hydroxyl groups of the clay, resulting in the formation of the mesoporous silica network and silica nanoparticles covered or attached on the clay surfaces. According to X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM) and nitrogen adsorption isotherms, the structure and surface properties of the sol-gel-modified clay can be controlled by varying the TEOS/clay mass ratio and/or adding trace amounts of acid as catalyst. In the case of acid-catalyzed procedures, large continuous mesoporous silica was covered on the clay surfaces, resulting in delamination of clay platelets in silica matrix at higher TEOS/clay ratio, and attaching of isolated mesoporous silica on the clay surface at lower TEOS/clay ratio, respectively. In the case of non-catalyzed procedures, silica nanoparticles were attached on the two-dimensional (2D) clay platelets, while the stack order of the clay was maintained regardless of the TEOS/clay ratios. This sol-gel modification approach combines the surface properties of mesoporous silica and nanoparticles with layered clay, while inheriting the structural properties of the pristine clay such as further intercalation with organic compounds and polymers

  2. Variable Effect during Polymerization

    Science.gov (United States)

    Lunsford, S. K.

    2005-01-01

    An experiment performing the polymerization of 3-methylthiophene(P-3MT) onto the conditions for the selective electrode to determine the catechol by using cyclic voltammetry was performed. The P-3MT formed under optimized conditions improved electrochemical reversibility, selectivity and reproducibility for the detection of the catechol.

  3. Synthesis of Highly Branched Poly(ε-caprolactone) by Self-condensing Atom Transfer Radical Polymerization of Macroinimers

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    Branched poly(ε-caprolactone) was synthesized by self-condensing atom transfer radical polymerization of macroinimer, α-acryloyoxy-ω-2-bromopropionyloxy poly(ε-caprolactone),which was prepared by enzyme-catalyzed ring-opening polymerization of ε-caprolactone with 2-hydroxylethyl acrylate as initiator and esterification of the ω-hydroxyl group of the obtained poly(ε-caprolactone) by 2-bromopropionyl bromide.

  4. CLAY CATALYZED SYNTHESIS OF BIO-DEGRADABLE POLY(GLYCOLIC ACID)

    Institute of Scientific and Technical Information of China (English)

    K. Durai Murugan; S. Radhika; I. Baskaran; R. Anbarasan

    2008-01-01

    Glycolic acid was polymerized under vacuum in the presence and absence of nano sized clay. The added clay catalyzed the condensation polymerization which can be confirmed by recording FT1R spectroscopy and intrinsic viscosity (Ⅳ) values. The relative intensity of C =O/CH is increased while increasing the amount of clay. DSC showed the appearance of multiple endotherms of poly(glycolic acid). TGA showed the percentage weight residue remain above 750℃ for polymer-nano composite system was 21% and hence proved the flame retardancy (char forming) nature. TEM confirmed the nano size of the clay used to catalyze the condensation reaction. The intrinsic viscosity value was increased with the increase of percentage weight of Hectorite type clay.

  5. Controllable synthesis of hollow mesoporous silica spheres and application as support of nano-gold

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Tao; Ma, Weihua, E-mail: maweiuan@163.com; Shangguan, Junnan; Jiang, Wei; Zhong, Qin

    2014-07-01

    Hollow silica spheres with mesoporous structure were synthesized by sol–gel/emulsion method. In the process, the surfactant, cetyltrimethylammonium bromide (CTAB) was used to stabilize the oil droplet and also used as structure direct agent. The diameter of the hollow silica spheres, ranging from 895 nm to 157 nm, can be controlled by changing the ratio of ethanol to water and the concentration of the surfactant as well. The shell thickness of the spheres decreased when the ratio of ethanol to water decreased. The proposed mechanism of the formation of silica spheres could elucidate the experimental results well. Furthermore, the resultant hollow mesoporous silica spheres were then employed as support of nano-gold which was used to catalyze the isomerization reaction of propylene oxide to produce allyl alcohol. - Graphical abstract: It is the schematic mechanism for the formation of hollow mesoporous silica spheres. - Highlights: • The formation mechanism of the hollow spheres is proposed. • The isomerization of propylene oxide can be catalyzed by the nano-gold/SiO{sub 2}. • The hollow silica spheres can be prepared controllably.

  6. Controllable synthesis of hollow mesoporous silica spheres and application as support of nano-gold

    International Nuclear Information System (INIS)

    Hollow silica spheres with mesoporous structure were synthesized by sol–gel/emulsion method. In the process, the surfactant, cetyltrimethylammonium bromide (CTAB) was used to stabilize the oil droplet and also used as structure direct agent. The diameter of the hollow silica spheres, ranging from 895 nm to 157 nm, can be controlled by changing the ratio of ethanol to water and the concentration of the surfactant as well. The shell thickness of the spheres decreased when the ratio of ethanol to water decreased. The proposed mechanism of the formation of silica spheres could elucidate the experimental results well. Furthermore, the resultant hollow mesoporous silica spheres were then employed as support of nano-gold which was used to catalyze the isomerization reaction of propylene oxide to produce allyl alcohol. - Graphical abstract: It is the schematic mechanism for the formation of hollow mesoporous silica spheres. - Highlights: • The formation mechanism of the hollow spheres is proposed. • The isomerization of propylene oxide can be catalyzed by the nano-gold/SiO2. • The hollow silica spheres can be prepared controllably

  7. Control of particle size and morphology in compatiblized self-catalyzed co-polyimide/sio/sub 2/ nanocomposites

    International Nuclear Information System (INIS)

    The size of the silica particles and morphology of hybrids were controlled in copolyimide based hybrids through amino-silane functionalization of silica particles prepared in situ through a self-catalyzed sol-gel process using atmospheric moisture. The particles were generated using tetraethoxysilane in the uncompatiblized (UPISH) system whereas a mixture of 3-aminopropyltrietoxysilane and tetraethoxysilane was used in the compatiblized Co-PI/silica hybrid (CPISH) system. The properties of resulting hybrid films were measured by Fourier Transform Infrared Spectroscopy, Scanning Electron Microscopy, Thermogravimetirc Analysis, Dynamic Mechanical Analysis and Universal Testing Machine. FTIR results confirmed the formation of silica particles and Co-PI matrix. FE-SEM images revealed spherical silica particles with sharp boundaries in UPISH; whereas nano-sized coupled silica network structures with totally different morphologies were observed in CPISH system. The CPISH system exhibited better thermal stability, higher modulus and Tg values than UPISH system. The improvement in thermal and mechanical properties has been discussed with reference to morphological changes due to incorporation of 3-aminopropyltrietoxysilane in aerobic condition and in a self-catalyzed sol-gel process. (author)

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

    KAUST Repository

    Li, Fuyue Stephanie

    2014-03-01

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

  9. Papain-Catalyzed Synthesis of Polyglutamate Containing a Nylon Monomer Unit

    OpenAIRE

    Kenjiro Yazawa; Keiji Numata

    2016-01-01

    Peptides have the potential to serve as an alternative for petroleum-based polymers to support a sustainable society. However, they lack thermoplasticity, owing to their strong intermolecular interactions. In contrast, nylon is famous for its thermoplasticity and chemical resistance. Here, we synthesized peptides containing a nylon unit to modify their thermal properties by using papain-catalyzed chemoenzymatic polymerization. We used l-glutamic acid alkyl ester as the amino acid monomer and ...

  10. Silica in alkaline brines

    Science.gov (United States)

    Jones, B.F.; Rettig, S.L.; Eugster, H.P.

    1967-01-01

    Analysis of sodium carbonate-bicarbonate brines from closed basins in volcanic terranes of Oregon and Kenya reveals silica contents of up to 2700 parts per million at pH's higher than 10. These high concentrations of SiO 2 can be attributed to reaction of waters with silicates, and subsequent evaporative concentration accompanied by a rise in pH. Supersaturation with respect to amorphous silica may occur and persist for brines that are out of contact with silicate muds and undersaturated with respect to trona; correlation of SiO2 with concentration of Na and total CO2 support this interpretation. Addition of moredilute waters to alkaline brines may lower the pH and cause inorganic precipitation of substantial amounts of silica.

  11. 碱/酸两步催化法制备耐候性SiO2增透膜的研究%Preparation and Characterization of Environment-Resistant Silica Antireflective Coating by Base/Acid Two-Step Catalyzed Sol-Gel Process

    Institute of Scientific and Technical Information of China (English)

    业海平; 张欣向; 肖波; 晏良宏; 江波

    2011-01-01

    Antireflective (AR) coatings with high transmittance and abrasion-resistance were prepared by a two-step base/acid catalyzed sol-gel process using tetraethylorthosilicate (TEOS) as precursor. It was found that addition of 50% acid-catalyzed SiO2 in the sol afforded the AR coatings relatively high transmittance and enhanced abrasion-resistance. It provided the AR coating with highest transmittance while the mole ratio of nH2O/nHCl was 1∶0.001 0. The water contact angle of base/acid two-step catalyzed AR coating was 11.3°, in this work,hexamethyldisiloxane (HMDS) was further used to modify the hydrophobicity of AR coatings. After HMDS treatment, the hydroxyl groups of AR coating were replaced by -OSi (CH3)3, which greatly increases the hydrophobicity of the coating, affording HMDS modified AR coating excellent environment resistance.%以正硅酸乙酯(TEOS)为先驱体,采用碱/酸两步催化溶胶-凝胶法制备出一种兼具碱催化增透膜的高透过率和酸催化增透膜的良好耐摩擦性能的优点的SiO2增透膜.对酸碱催化SiO2相对比例及酸催化时水含量的系统研究表明,当酸催化SiO2的含量为50%时,增透膜综合性能最好,即具有高透过率和高耐摩擦性;当nH2o/nHCI=1∶0.0010时,增透膜的透过率最高.碱/酸两步催化法制备的增透膜与水的接触角仅为11.3°,本文进一步用六甲基二硅氧烷(HMDS)对增透膜表面进行了修饰,修饰后增透膜的接触角提高至52.5°,增透膜的疏水性及环境稳定性得到较大的提高.

  12. Insitu grafting silica nanoparticles reinforced nanocomposite hydrogels

    Science.gov (United States)

    Yang, Jun; Han, Chun-Rui; Duan, Jiu-Fang; Xu, Feng; Sun, Run-Cang

    2013-10-01

    Highly flexible nanocomposite hydrogels were prepared by using silica nanoparticles (SNPs) as fillers and multi-functional cross-links to graft hydrophilic poly(acrylic acid) (PAA) by free radical polymerization from an aqueous solution. The SNPs were collected by neighboring polymer chains and dispersed uniformly within a PAA matrix. The mechanical properties of the nanocomposite hydrogels were tailored by the concentration of SNPs according to the percolation model. It was proposed that covalent bonds of adsorbed chains on the filler surface resulted in the formation of a shell of an immobilized glassy layer and trapped entanglements, where the glassy polymer layer greatly enhanced the elastic modulus and the release of trapped entanglements at deformation contributed to the viscoelastic properties.Highly flexible nanocomposite hydrogels were prepared by using silica nanoparticles (SNPs) as fillers and multi-functional cross-links to graft hydrophilic poly(acrylic acid) (PAA) by free radical polymerization from an aqueous solution. The SNPs were collected by neighboring polymer chains and dispersed uniformly within a PAA matrix. The mechanical properties of the nanocomposite hydrogels were tailored by the concentration of SNPs according to the percolation model. It was proposed that covalent bonds of adsorbed chains on the filler surface resulted in the formation of a shell of an immobilized glassy layer and trapped entanglements, where the glassy polymer layer greatly enhanced the elastic modulus and the release of trapped entanglements at deformation contributed to the viscoelastic properties. Electronic supplementary information (ESI) available: FTIR spectra of SNP after silane treatment, dynamic oscillatory shear measurements as a function of frequency, constrained polymer chain analysis by a change in the peak height in loss factor spectra, molecular weight of grafted chains at different stages of gelation, prediction of the SNP reinforcing mechanism in the

  13. Frontal Polymerization in Microgravity

    Science.gov (United States)

    Pojman, John A.

    1999-01-01

    Frontal polymerization systems, with their inherent large thermal and compositional gradients, are greatly affected by buoyancy-driven convection. Sounding rocket experiments allowed the preparation of benchmark materials and demonstrated that methods to suppress the Rayleigh-Taylor instability in ground-based research did not significantly affect the molecular weight of the polymer. Experiments under weightlessness show clearly that bubbles produced during the reaction interact very differently than under 1 g.

  14. Polymeric bicontinuous microemulsions

    DEFF Research Database (Denmark)

    Bates, F.S.; Maurer, W.W.; Lipic, P.M.; Hillmyer, M.A.; Almdal, K.; Mortensen, K.; Fredrickson, G.H.; Lodge, T.P.

    1997-01-01

    High molecular weight block copolymers can be viewed as macromolecular surfactants when blended with thermodynamically incompatible homopolymers. This Letter describes the formation of polymeric bicontinuous microemulsions in nurtures containing a model diblock copolymer and two homopolymers. Alt....... Although we attribute development of this equilibrium morphology to the effects of fluctuations, mean-field theory provides a quantitative strategy for preparing the bicontinuous state at blend compositions near an isotropic Lifshitz point....

  15. Polymeric bicontinuous microemulsions

    DEFF Research Database (Denmark)

    Bates, F.S.; Maurer, W.W.; Lipic, P.M.;

    1997-01-01

    High molecular weight block copolymers can be viewed as macromolecular surfactants when blended with thermodynamically incompatible homopolymers. This Letter describes the formation of polymeric bicontinuous microemulsions in nurtures containing a model diblock copolymer and two homopolymers....... Although we attribute development of this equilibrium morphology to the effects of fluctuations, mean-field theory provides a quantitative strategy for preparing the bicontinuous state at blend compositions near an isotropic Lifshitz point....

  16. Polymeric Bicontinuous Microemulsions

    Science.gov (United States)

    Bates, Frank S.; Maurer, Wayne W.; Lipic, Paul M.; Hillmyer, Marc A.; Almdal, Kristoffer; Mortensen, Kell; Fredrickson, Glenn H.; Lodge, Timothy P.

    1997-08-01

    High molecular weight block copolymers can be viewed as macromolecular surfactants when blended with thermodynamically incompatible homopolymers. This Letter describes the formation of polymeric bicontinuous microemulsions in mixtures containing a model diblock copolymer and two homopolymers. Although we attribute development of this equilibrium morphology to the effects of fluctuations, mean-field theory provides a quantitative strategy for preparing the bicontinuous state at blend compositions near an isotropic Lifshitz point.

  17. Polymerization on the rocks: beta-amino acids and arginine

    Science.gov (United States)

    Liu, R.; Orgel, L. E.; Bada, J. L. (Principal Investigator)

    1998-01-01

    We have studied the accumulation of long oligomers of beta-amino acids on the surface of minerals using the 'polymerization on the rocks' protocol. We find that long oligopeptides of beta-glutamic acid which cannot be formed in homogeneous aqueous solution are accumulated efficiently on the surface of hydroxylapatite using 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide (EDAC) as condensing agent. The EDAC-induced oligomerization of aspartic acid on hydroxylapatite proceeds even more efficiently. Hydroxylapatite can also facilitate the ligation of the tripeptide (glu)3. The 'polymerization on the rocks' scenario is not restricted to negatively-charged amino acids. Oligoarginines are accumulated on the surface of illite using carbonyldiimidizole (CDI) as condensing agent. We find that FeS2 catalyzes the CDI-induced oligomerization of arginine, although it does not adsorb oligoarginines. These results are relevant to the formation of polypeptides on the primitive earth.

  18. Influence of hydrophobic characteristic of organo-modified precursor on wettability of silica film

    Indian Academy of Sciences (India)

    Violeta Purcar; Otilia Cinteza; Marius Ghiurea; Adriana Balan; Simona Caprarescu; Dan Donescu

    2014-02-01

    The objective of this study is to design new hybrid silica materials as templates with hydrophobic properties, prepared at room temperature by a base catalyzed sol–gel process. As silica sources, organoalkoxysilanes functionalized with short hydrophobic chains were used: tetraethylorthosilicate (TEOS), methyltriethoxysilane (MTES), vinyltriethoxysilane (VTES), octyltriethoxysilane (OTES) and isobutyltriethoxysilane (iTES). It was shown that hydrophobicity of the functionalized silica nanoparticles increased as a function of length of the aliphatic chains (MTES < iTES < OTES) or when, instead of a hydrophobic alkyl chains (substituting group of silica precursors), a monounsaturated group was used (VTES). It was observed that the samples responded in a specific way to each type (hydrophilic or hydrophobic) of the dropped liquid. Even though the experiments were limited to short hydrocarbon chains, they showed that there is a threshold to reach high hydrophobicity of the hybrid surface.

  19. Production of silica aerogel

    International Nuclear Information System (INIS)

    A production facility for silica aerogel has been set up in Lund. Aerogel is now produced in large quantities with the refractive indices of 1.03 and 1.05. The standard block size is 18 x 18 x 3 cm3. (Auth.)

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

    International Nuclear Information System (INIS)

    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

  1. Functional nanocomposites prepared by self-assembly and polymerization of diacetylene surfactants and silicic acid

    Science.gov (United States)

    Yang, Yi; Lu, Yunfeng; Lu, Mengcheng; Huang, Jinman; Haddad, Raid; Xomeritakis, George; Liu, Nanguo; Malanoski, Anthony P.; Sturmayr, Dietmar; Fan, Hongyou; Sasaki, Darryl Y.; Assink, Roger A.; Shelnutt, John A.; van Swol, Frank; Lopez, Gabriel P.; Burns, Alan R.; Brinker, C. Jeffrey

    2003-01-01

    Conjugated polymer/silica nanocomposites with hexagonal, cubic, or lamellar mesoscopic order were synthesized by self-assembly using polymerizable amphiphilic diacetylene molecules as both structure-directing agents and monomers. The self-assembly procedure is rapid and incorporates the organic monomers uniformly within a highly ordered, inorganic environment. By tailoring the size of the oligo(ethylene glycol) headgroup of the diacetylene-containing surfactant, we varied the resulting self-assembled mesophases of the composite material. The nanostructured inorganic host altered the diacetylene polymerization behavior, and the resulting nanocomposites show unique thermo-, mechano-, and solvatochromic properties. Polymerization of the incorporated surfactants resulted in polydiacetylene (PDA)/silica nanocomposites that were optically transparent and mechanically robust. Molecular modeling and quantum calculations and (13)C spin-lattice relaxation times (T(1)) of the PDA/silica nanocomposites indicated that the surfactant monomers can be uniformly organized into precise spatial arrangements prior to polymerization. Nanoindentation and gas transport experiments showed that these nanocomposite films have increased hardness and reduced permeability as compared to pure PDA. Our work demonstrates polymerizable surfactant/silica self-assembly to be an efficient, general approach to the formation of nanostructured conjugated polymers. The nanostructured inorganic framework serves to protect, stabilize, and orient the polymer, mediate its performance, and provide sufficient mechanical and chemical stability to enable integration of conjugated polymers into devices and microsystems.

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

    Science.gov (United States)

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

    2015-04-01

    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.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. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr01439e

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

    Directory of Open Access Journals (Sweden)

    Tomás Cuenca

    2010-02-01

    Full Text Available 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.

  4. Monolithic molecularly imprinted polymeric capillary columns for isolation of aflatoxins.

    Science.gov (United States)

    Szumski, Michał; Grzywiński, Damian; Prus, Wojciech; Buszewski, Bogusław

    2014-10-17

    Monolithic molecularly imprinted polymers extraction columns have been prepared in fused-silica capillaries by UV or thermal polymerization in a two-step process. First, a poly-(trimethylolpropane trimethacrylate) (polyTRIM) core monolith was synthesized either by UV or thermal polymerization. Then it was grafted with the mixture of methacrylic acid (MAA) as a functional monomer, ethylene dimethacrylate (EDMA) as a cross-linking agent, 5,7-dimethoxycoumarin (DMC) as an aflatoxin-mimicking template, toluene as a porogen solvent and 2,2-azobis-(2-methylpropionitrile) (AIBN) as an initiator of the polymerization reaction. Different thermal condition of the photografting and different concentrations of the grafting mixture were tested during polymerization. The extraction capillary columns were evaluated in the terms of their hydrodynamic and chromatographic properties. Retention coefficients for aflatoxin B1 and DMC were used for assessment of the selectivity and imprinting factor. The obtained results indicate that the temperature of photografting and concentration of the grafting mixture are key parameters that determine the quality of the prepared MIPs. From the MIP columns characterized by the highest permeability the column of the highest imprinting factor was applied for isolation of aflatoxins B1, B2, G1 and G2 from the model aqueous sample followed by on-line chromatographic separation. The process was performed using a micro-MISPE-microLC-LIF system of a novel design, which allowed for detection of the eluates from the sample preparation part as well as from the chromatographic separation. PMID:25218633

  5. Immortal Ring-Opening Polymerization of rac-Lactide Using Polymeric Alcohol as Initiator to Prepare Graft Copolymer

    Directory of Open Access Journals (Sweden)

    Na Liu

    2016-01-01

    Full Text Available In the presence of a small molecular protic initiator, immortal ring-opening polymerization (ROP of lactide (LA is a highly efficient strategy to synthesize polylactide in a controllable manner, while using polymeric alcohol as an initiator has been less investigated. A series of polymeric alcohols (PS–OH composed of styrene and 4.3%–18% hydroxyl functional styrene (diethyl(hydroxy(4-vinylphenylmethylphosphonate, St–OH were synthesized through reversible addition-fragmentation transfer (RAFT polymerization. Using PS–OH as an initiator, the immortal ROP of rac-LA was catalyzed by dibutylmagnesium (MgnBu2 under various ratios of monomer to hydroxyl group within PS–OH to generate polystyrene-g-polylactide (PS–g–PLA copolymers with different graft lengths. After thermal annealing at 115 °C, the PLA domain aggregated to nanospheres among the PS continuum. The size of the nanospheres, varying from 130.1 to 224.2 nm, was related to the graft density and length of PS–g–PLA. Nanoporous films were afforded through chemical etching of the PLA component.

  6. Solid acid catalyzed biodiesel production from waste cooking oil

    Energy Technology Data Exchange (ETDEWEB)

    Jacobson, Kathlene; Gopinath, Rajesh; Meher, Lekha Charan; Dalai, Ajay Kumar [Catalysis and Chemical Reaction Engineering Laboratories, Department of Chemical Engineering, University of Saskatchewan, 57 Campus Drive, Saskatoon, SK, S7N 5A9 (Canada)

    2008-12-17

    Various solid acid catalysts were evaluated for the production of biodiesel from low quality oil such as waste cooking oil (WCO) containing 15 wt.% free fatty acids. The zinc stearate immobilized on silica gel (ZS/Si) was the most effective catalyst in simultaneously catalyzing the transesterification of triglycerides and esterification of free fatty acid (FFA) present in WCO to methyl esters. The optimization of reaction parameters with the most active ZS/Si catalyst showed that at 200 C, 1:18 oil to alcohol molar ratio and 3 wt.% catalysts loading, a maximum ester yield of 98 wt.% could be obtained. The catalysts were recycled and reused many times without any loss in activity. (author)

  7. 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; Mu, Huiling; Adler-Nissen, Jens; Høy, Carl-Erik

    2001-01-01

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

  8. Iodine Supported on 3-Aminopropyl Silica Gel as Efficient Catalyst for Acetylation of Alcohols under Solvent-free Conditions

    Institute of Scientific and Technical Information of China (English)

    MAHDAVI Hossein; GHAEMY Mosa; ZERAATPISHEH Fatemeh

    2009-01-01

    3-Aminopropyl silica gel (I2/APSG) was found to catalyze the acetylation of alcohols and phenols efficiently with acetic anhydride. The reaction is mild and selective with high yields. A wide variety of alcohols and phenols are selectively converted into the corresponding acetates using I2/APSG under solvent-free conditions at room tem-perature.

  9. Diketene-based neat four-component synthesis of the dihydropyrimidinones and dihydropyridine backbones using silica sulfuric acid (SSA)

    Institute of Scientific and Technical Information of China (English)

    Sadegh Rostamnia; Kamran Lamei

    2012-01-01

    Heterocyclic skeleton building blocks to afford dihydropyrimidinones and dihydropyridines based on neat adducts of diketene,alcohols and aldehydes via silica sulfuric acid (SSA) catalyzed ring opening of diketene in four-c6mponent Biginelli-type and Hantzsch-type reactions are presented.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2011-07-01

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

  11. Packaging based on polymeric materials

    OpenAIRE

    Jovanović Slobodan M.; Živković Predrag M.; Stoiljković Dragoslav M.

    2005-01-01

    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 m...

  12. Mesoporous and biocompatible surface active silica aerogel synthesis using choline formate ionic liquid.

    Science.gov (United States)

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

    2011-09-01

    In this paper, we report the preparation and characterization of mesoporous and biocompatible transparent silica aerogel by the sol-gel polymerization of tetraethyl orthosilicate using ionic liquid. Choline cation based ionic liquid allows the silica framework to form in a non collapsing environment and controls the pore size of the gel. FT-IR spectra reveal the interaction of ionic liquid with surface -OH of the gel. DSC thermogram giving the evidence of confinement of ionic liquid within the silica matrix, which helps to avoid the shrinkage of the gel during the aging process. Nitrogen sorption measurements of gel prepared with ionic liquid exhibit a low surface area of 100.53 m2/g and high average pore size of 3.74 nm. MTT assay proves the biocompatibility and cell viability of the prepared gels. This new nanoporous silica material can be applied to immobilize biological molecules, which may retain their stability over a longer period. PMID:21565470

  13. Bifunctional composite microspheres of silica/lanthanide-polyoxometalates/Au: Study on luminescence and catalytic properties

    International Nuclear Information System (INIS)

    In this paper, the synthesis and properties of composite silica microspheres grafted with gold nanoparticles and lanthanide-polyoxometalates are described. This synthesis employs polyethyleneimine as the crosslink polymer to immobilize the Au nanoparticles and lanthanide-polyoxometalates on silica spheres, which results in the formation of bifunctional composite microspheres of silica/lanthanide-polyoxometalates/Au. The composite material was found to be catalytically active in the oxidation of styrene, and benzaldehyde and styrene oxide were the main products. Catalyzed oxidation of styrene demonstrates the size-dependent activity of catalysts and the smaller catalyst shows the higher selectivity. Moreover, the composite particles show bright red luminescence under UV light, which could be seen by naked eyes. The luminescence properties of composite material and the effect of Au nanoparticles on the luminescence of Eu ion were investigated, and energy could be more effectively transferred from ligand to lanthanide ion when Au nanoparticles were grafted on silica spheres. The integration of luminescent components and Au particles makes it possible to label catalyst and monitor the catalyzed reactions. - Highlights: • The bifunctional composite microspheres were fabricated. • Both polyoxometalates and Au nanoparticles could be grafted on silica spheres. • The composite particles exhibit the excellent luminescence and catalytic activity. • The Au nanoparticles affect the luminescence properties of Eu3+ ions

  14. Optical nonlinearity and structural phase-transition observation of organic dye-doped polymer silica hybrid material.

    Science.gov (United States)

    Xu, L; Hou, Z; Liu, L; Xu, Z; Wang, W; Li, F; Ye, M

    1999-10-01

    The optical nonlinearity of organic dye-doped poly(methyl methacrylate) (PMMA)-silica-gel hybrid material was investigated by second-harmonic-generation measurement. We found that incorporation of in situ polymerized solgel precursors into the organic dye-doped PMMA significantly improved the nonlinear optical stability of the system. However, improvement of thermal stability occurred only when a sufficient amount of silica gel was incorporated. A structural phase transition from pure polymer to a hybrid system was found near a 10-mol.% silica-gel concentration. The optimum polymer/tetraethoxysilane molar ratio is 2:1 to 1:1. PMID:18079805

  15. Sustainable polymerizations in recoverable microemulsions.

    Science.gov (United States)

    Chen, Zhenzhen; Yan, Feng; Qiu, Lihua; Lu, Jianmei; Zhou, Yinxia; Chen, Jiaxin; Tang, Yishan; Texter, John

    2010-03-16

    Free radical and atom-transfer radical polymerizations were conducted in monomer/ionic liquid microemulsions. After the polymerization and isolation of the resultant polymers, the mixture of the catalyst and ionic liquids (surfactant and continuous phase) can be recovered and reused, thereby dramatically improving the environmental sustainability of such chemical processing. The addition of monomer to recovered ionic liquid mixtures regenerates transparent, stable microemulsions that are ready for the next polymerization cycle upon addition of initiator. The method combines the advantages of IL recycling and microemulsion polymerization and minimizes environmental disposable effects from surfactants and heavy metal ions. PMID:20170175

  16. Polymerization Evaluation by Spectrophotometric Measurements.

    Science.gov (United States)

    Dunach, Jaume

    1985-01-01

    Discusses polymerization evaluation by spectrophotometric measurements by considering: (1) association degrees and molar absorptivities; (2) association degrees and equilibrium constants; and (3) absorbance and equilibrium constants. (JN)

  17. Radiation polymerization of unsaturated polyester

    International Nuclear Information System (INIS)

    Radiation polymerization of unsaturated polyester has been studied, either under electron beams or gamma rays. Addition of reducing agents of dyes will reduce the rate of polymerization. Rate of polymerization is proportional to 1sup(a), where the value of ''a'' is dependent on the composition of the monomer and polymer (1= dose rate). Infrared examinations indicated that for higher dose of irradiation, 8,5 Mrad in the case of unsaturated polyester STRATYL under electron beams, either polymerization or degradation of ester groups can take place. (author)

  18. Phosphazene-promoted anionic polymerization

    KAUST Repository

    Zhao, Junpeng

    2014-01-01

    In the recent surge of metal-free polymerization techniques, phosphazene bases have shown their remarkable potential as organic promoters/catalysts for the anionic polymerization of various types of monomers. By complexation with the counterion (e.g. proton or lithium cation), phosphazene base significantly improve the nucleophilicity of the initiator/chain-end resulting in rapid and usually controlled anionic/quasi-anionic polymerization. In this review, we will introduce the general mechanism, i.e. in situ activation (of initiating sites) and polymerization, and summarize the applications of such a mechanism on macromolecular engineering toward functionalized polymers, block copolymers and complex macromolecular architectures.

  19. Iodine-catalyzed coal liquefaction

    Energy Technology Data Exchange (ETDEWEB)

    Joseph, J.T.; Duffield, J.E.; Davidson, M.G. (Amoco Oil Company, Naperville, IL (USA). Research and Development Dept.)

    Coals of two different ranks were liquefied in high yields using catalytic quantities of elemental iodine or iodine compounds. Iodine monochloride was found to be especially effective for enhancing both coal conversion and product quality. It appears that enhancement in coal conversion is due to the unique ability of iodine to catalyze radical-induced bond scission and hydrogen addition to the coal macromolecule or coal-derived free radicals. The starting iodine can be fully accounted for in the reaction products as both organic-bound and water-soluble forms. Unconverted coal and the heavy product fractions contain the majority of the organic-bound iodine. The results of iodine-catalyzed coal reactions emphasize the need for efficient hydrogen atom transfer along with bond scission to achieve high conversion and product quality. 22 refs., 12 tabs.

  20. Living olefin polymerization processes

    Science.gov (United States)

    Schrock, Richard R.; Baumann, Robert

    1999-01-01

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

  1. 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...

  2. Aniline incorporated silica nanobubbles

    Indian Academy of Sciences (India)

    M J Rosemary; V Suryanarayanan; Ian Maclaren; T Pradeep

    2006-09-01

    We report the synthesis of stearate functionalized nanobubbles of SiO2 with a few aniline molecules inside, represented as C6H5NH2@SiO2@stearate, exhibiting fluorescence with red-shifted emission. Stearic acid functionalization allows the materials to be handled just as free molecules, for dissolution, precipitation, storage etc. The methodology adopted involves adsorption of aniline on the surface of gold nanoparticles with subsequent growth of a silica shell through monolayers, followed by the selective removal of the metal core either using sodium cyanide or by a new reaction involving halocarbons. The material is stable and can be stored for extended periods without loss of fluorescence. Spectroscopic and voltammetric properties of the system were studied in order to understand the interaction of aniline with the shell as well as the monolayer, whilst transmission electron microscopy has been used to study the silica shell.

  3. Modified silicas with different structure of grafted methylphenylsiloxane layer.

    Science.gov (United States)

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

    2016-12-01

    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. PMID:27295258

  4. Modified silicas with different structure of grafted methylphenylsiloxane layer

    Science.gov (United States)

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

    2016-06-01

    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.

  5. Zeolite Catalyzed Aldol Condensation Reactions

    OpenAIRE

    Adedayo I. Inegbenebor; Raphael C. Mordi; Oluwakayode M. Ogunwole

    2015-01-01

    The review is based on the description of zeolite structure, uses, synthesis, and catalytic aldol reaction in aldol condensation. An internal aldolcondensation reaction has been achieved over ZSM-5 zeolite with high silica-alumina ratio at 350oC. It therefore follows that zeolite canfunction as a catalyst in aldol type condensation reactions and that weak acid sites as well as a small number of active sites favor the aldolcondensation reaction of carbonyl compounds. However, the mixed condens...

  6. The mechanisms of platinum-catalyzed silicon nanowire growth

    International Nuclear Information System (INIS)

    Platinum (Pt) has been known as a catalyst material for vapor-liquid-solid (VLS) synthesis since the mid 1960s with the potential to grow electronic grade silicon nanowires (SiNWs). In contrast to gold-based growth, Pt-catalyzed SiNW synthesis has rarely been studied, most likely due to higher synthesis temperatures and the formation of multiple Pt silicide phases. Here we present the growth of SiNWs from a Pt catalyst deposited by a focused ion or electron beam, which opens new strategies for the assembly of Pt-catalyzed SiNW-based devices, as well as SiNW growth from Pt nanoparticles and thin films. We show that single-crystalline SiNWs exhibit either the well-known catalyst tip or a polycrystalline silicon tip so far not reported. The local Pt concentration was found to be one key parameter triggering the growth mode. The proposed growth model for both types of SiNWs is based on a solid-state silicide-mediated crystallization rather than VLS. The discussion of the growth modes is supported by a variation of several growth parameters and SiNW synthesis using the substrate materials silicon nitride, single-crystalline silicon, fused silica, and sapphire. (paper)

  7. The mechanisms of platinum-catalyzed silicon nanowire growth

    Science.gov (United States)

    Hibst, N.; Knittel, P.; Biskupek, J.; Kranz, C.; Mizaikoff, B.; Strehle, S.

    2016-02-01

    Platinum (Pt) has been known as a catalyst material for vapor-liquid-solid (VLS) synthesis since the mid 1960s with the potential to grow electronic grade silicon nanowires (SiNWs). In contrast to gold-based growth, Pt-catalyzed SiNW synthesis has rarely been studied, most likely due to higher synthesis temperatures and the formation of multiple Pt silicide phases. Here we present the growth of SiNWs from a Pt catalyst deposited by a focused ion or electron beam, which opens new strategies for the assembly of Pt-catalyzed SiNW-based devices, as well as SiNW growth from Pt nanoparticles and thin films. We show that single-crystalline SiNWs exhibit either the well-known catalyst tip or a polycrystalline silicon tip so far not reported. The local Pt concentration was found to be one key parameter triggering the growth mode. The proposed growth model for both types of SiNWs is based on a solid-state silicide-mediated crystallization rather than VLS. The discussion of the growth modes is supported by a variation of several growth parameters and SiNW synthesis using the substrate materials silicon nitride, single-crystalline silicon, fused silica, and sapphire.

  8. Synergism and Mutualism in Non-Enzymatic RNA Polymerization

    Directory of Open Access Journals (Sweden)

    Hussein Kaddour

    2014-11-01

    Full Text Available The link between non-enzymatic RNA polymerization and RNA self-replication is a key step towards the “RNA world” and still far from being solved, despite extensive research. Clay minerals, lipids and, more recently, peptides were found to catalyze the non-enzymatic synthesis of RNA oligomers. Herein, a review of the main models for the formation of the first RNA polymers is presented in such a way as to emphasize the cooperation between life’s building blocks in their emergence and evolution. A logical outcome of the previous results is a combination of these models, in which RNA polymerization might have been catalyzed cooperatively by clays, lipids and peptides in one multi-component prebiotic soup. The resulting RNAs and oligopeptides might have mutualistically evolved towards functional RNAs and catalytic peptides, preceding the first RNA replication, thus supporting an RNA-peptide world. The investigation of such a system is a formidable challenge, given its complexity deriving from a tremendously large number of reactants and innumerable products. A rudimentary experimental design is outlined, which could be used in an initial attempt to study a quaternary component system.

  9. 21 CFR 582.1711 - Silica aerogel.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Silica aerogel. 582.1711 Section 582.1711 Food and....1711 Silica aerogel. (a) Product. Silica aerogel as a finely powdered microcellular silica foam having a minimum silica content of 89.5 percent. (b) (c) Limitations, restrictions, or explanation....

  10. 21 CFR 182.1711 - Silica aerogel.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Silica aerogel. 182.1711 Section 182.1711 Food and....1711 Silica aerogel. (a) Product. Silica aerogel as a finely powdered microcellular silica foam having a minimum silica content of 89.5 percent. (b) (c) Limitations, restrictions, or explanation....

  11. pH dependent polymeric micelle adsorption

    International Nuclear Information System (INIS)

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

  12. Acrylic coatings exhibiting improved hardness, solvent resistance and glossiness by using silica nano-composites

    Science.gov (United States)

    Dashtizadeh, Ahmad; Abdouss, Majid; Mahdavi, Hossein; Khorassani, Manuchehr

    2011-01-01

    To prepare nano-composite emulsion acrylic resins with improved surface hardness and solvent resistance, nano-silica particles were treated with surfactants. The monomers of methyl methacrylate/butylacrylate were co-polymerized on the surface of dispersed silica particles. Several emulsions with different silica contents and copolymer mole fractions were prepared. Finally the emulsions were modified to water-based acrylic coatings and improved properties such as surface hardness, solvent resistance and glossiness were determined. The study of coatings was directed to find the improved resin by optimum surface properties. Size distribution and morphology of latexes were characterized by Fourier transform infrared spectroscopy, dynamic light scattering, transmission electron microscopy and scanning electron microscopy. The glass transition temperature of nano-composites was measured and discussed its relation with silica contents, monomer mole fractions and improved properties of coatings. The optimum pendulum hardness of coatings was on 0.46 methyl methacrylate mole fraction and 120 g silica content. An increase in pendulum hardness of nano-composites with the addition of modified silica was observed. DLS and TEM studies indicate that silica particles were dispersed homogenously through the polymer matrix.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2013-11-01

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

  14. Plasma polymerization by Softplasma

    DEFF Research Database (Denmark)

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

    2008-01-01

    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...... reactive splvent (as shown in Figure 1). 1] H. Biederman, in Plasma Polymer Films. (ed.) H. Biederman. Imperial College Press, Singapore, 13-24 ~OO~· '. , [2] R. d'Agostino et.a!. in Plasma Depd~itiqn, 'Treatment, and Etching ofPolymers. (ed.) R. d'Agostino, Academic Press, U.S. (1990). [3] F. F. Shi....... Recent advances in polymer thin films prepared by plasma polymerization synthesis, structural characterization, properties and applications. Surface and Coating Technology 82, 1 (1996). [4] B. Winther-Jensen. WOO0235895A2. A method and apparatus for excitation of a plasma, (2002). [5]. K. Glejbol. EP...

  15. Silica microsphere: synthesis and its application to remove traces of Cs and Sr from potable water

    International Nuclear Information System (INIS)

    This study presents a simple method to prepare silica microspheres based on a PVP (Polyvinylpyrrolidone) involved emulsion polymerization and subsequent sol-gel process. The product was characterized by measuring their size, zeta potential, taking SEM images and recording their FTIR spectrum. Silica microspheres removed 75-100% of cesium and strontium in the concentration range of 1 μg mL-1 to 10 μg mL-1 from the groundwater in the batch process. Effects of pH, contact time on the sorption were studied. Drinking water quality parameters were tested before and after the uptake which didn't show significant variation. (author)

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

    International Nuclear Information System (INIS)

    The effects of surface treatment method of unreacted N-[3-(trimethoxysilyl)propyl]ethylenediamine (2NS), N1-(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 SiO2/2NS/(n-BuCp)2ZrCl2>SiO2/1NCy/(n-BuCp)2ZrCl2>SiO2/3NS/(n-BuCp)2ZrCl2. The ethylene polymerization activity was increased as the surface treatment temperature of aminosilane on silica increased

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

    KAUST Repository

    Zhao, Junpeng

    2014-01-01

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

  18. Isocyanate Cross-Linked Silica: Structurally Strong Aerogels

    Science.gov (United States)

    Leventis, Nicholas; Sotiriou-Leventis, Chariklia; Zhang, Guo-Hui; Rawashdeh, Abdel-Monem M.

    2002-01-01

    Molecular-level synergism between the silica nanoparticles of pre-formed monoliths and molecular cross-linkers inverts the relative host-guest roles in glass-polymer composites, leading to new strong low-density materials. Attempts to load gels with variable amounts of polyurethane precursors such as di-ISO and diol end-capped polybutylene adipate followed by heat treatment, washing, and supercritical drying led to opaque materials, somewhat stronger than silica but still quite brittle and much inferior to the materials described above. Direct mixing of a diisocyanate and an alcohol-free sol has been attempted recently by Yim et al. Reportedly, that procedure leads to week-long gelation times and requires an at least equally long aging period. In our attempt to add various amounts of di-ISO in a base-catalyzed sol in PC, we also noticed a week-long gelation time. The resulting aerogels were translucent but no less brittle than native silica. According to more recent studies, if propylene carbonate is replaced with acetone, it leads not only to shorter processing times, but also to much stronger gels that can tolerate loads in excess of 40 kg in the arrangement presented. We attribute that behavior to the lower viscosity of acetone, that allows faster diffusion of the di-ISO solution within the pores before di-ISO has time to react with the surface of silica. Further studies are underway to vary the chemical identity of the diisocyanate, as well as the composition and density of silica.

  19. Synthesis of antireflective silica coatings through the synergy of polypeptide layer-by-layer assemblies and biomineralization

    Science.gov (United States)

    Lee, Yung-Lun; Lin, Ting-Xuan; Hsu, Feng-Ming; Jan, Jeng-Shiung

    2016-01-01

    We report a versatile approach to synthesize silica coatings with antireflective (AR) characteristics through the combination of a layer-by-layer (LbL) assembly technique and biomineralization. LbL assembled decanoyl-modified poly(l-lysine)/poly(l-glutamic acid) (PLL-g-Dec/PLGA) multilayer films were used as templates for silica mineralization, followed by calcination. The specific deposition of silica onto the LbL polypeptide assemblies through amine-catalyzed polycondensation resulted in silica coatings that exhibited the transcription of the nano-/microstructured polypeptide films and their film thickness and porosity can be tuned by varying the number of bilayers, degree of substitution, and PLL molecular weight. AR silica coatings exhibiting more than 6% increase in transmittance in the near UV/visible spectral range can be obtained at an optimized refractive index, thickness, and surface roughness. The abrasion test showed that the silica coatings exhibited sufficient structural durability due to continuous silica nanostructures and low surface roughness. This study demonstrated that nanostructured thin films can be synthesized for AR coatings using the synergy between the LbL assembly technique and biomineralization.We report a versatile approach to synthesize silica coatings with antireflective (AR) characteristics through the combination of a layer-by-layer (LbL) assembly technique and biomineralization. LbL assembled decanoyl-modified poly(l-lysine)/poly(l-glutamic acid) (PLL-g-Dec/PLGA) multilayer films were used as templates for silica mineralization, followed by calcination. The specific deposition of silica onto the LbL polypeptide assemblies through amine-catalyzed polycondensation resulted in silica coatings that exhibited the transcription of the nano-/microstructured polypeptide films and their film thickness and porosity can be tuned by varying the number of bilayers, degree of substitution, and PLL molecular weight. AR silica coatings exhibiting

  20. Stau-catalyzed Nuclear Fusion

    OpenAIRE

    Hamaguchi, K.; Hatsuda, T.(Theoretical Research Division, Nishina Center, RIKEN, Saitama, 351-0198, Japan); Yanagida, T. T.

    2006-01-01

    We point out that the stau may play a role of a catalyst for nuclear fusions if the stau is a long-lived particle as in the scenario of gravitino dark matter. In this letter, we consider d d fusion under the influence of stau where the fusion is enhanced because of a short distance between the two deuterons. We find that one chain of the d d fusion may release an energy of O(10) GeV per stau. We discuss problems of making the stau-catalyzed nuclear fusion of practical use with the present tec...

  1. Gold-catalyzed naphthalene functionalization

    OpenAIRE

    Iván Rivilla; M. Mar Díaz-Requejo; Pedro J. Pérez

    2011-01-01

    The complexes IPrMCl (IPr = 1,3-bis(diisopropylphenyl)imidazol-2-ylidene, M = Cu, 1a; M = Au, 1b), in the presence of one equiv of NaBAr'4 (Ar' = 3,5-bis(trifluoromethyl)phenyl), catalyze the transfer of carbene groups: C(R)CO2Et (R = H, Me) from N2C(R)CO2Et to afford products that depend on the nature of the metal center. The copper-based catalyst yields exclusively a cycloheptatriene derivative from the Buchner reaction, whereas the gold analog affords a mixture of products derived either f...

  2. Thermodynamics of Enzyme-Catalyzed Reactions Database

    Science.gov (United States)

    SRD 74 Thermodynamics of Enzyme-Catalyzed Reactions Database (Web, free access)   The Thermodynamics of Enzyme-Catalyzed Reactions Database contains thermodynamic data on enzyme-catalyzed reactions that have been recently published in the Journal of Physical and Chemical Reference Data (JPCRD). For each reaction the following information is provided: the reference for the data, the reaction studied, the name of the enzyme used and its Enzyme Commission number, the method of measurement, the data and an evaluation thereof.

  3. The catalytic mechanism of benzoxazine to the polymerization of cyanate ester

    International Nuclear Information System (INIS)

    Two model compounds, 3-Phenyl-3,4-dihydro-2H-1,3-benzoxazine (PA) and 6,8-dimethyl-3-(2,4,6-trimethyl-phenyl)-3,4-dihydro-2H-1,3-benzoxazine (s-PA), were successfully synthesized and purificated. Compared with PA, s-PA also catalyzed the polymerization of BADCy even though there was no phenolic hydroxyl in its final ring-opened structures. It was confirmed that the real mechanism of benzoxazine catalyzing the polymerization of cyanate ester is the nucleophilic addition reaction of the oxygen anion on ring-opened benzoxazine to the positively charged carbon atom on cyano group. The catalytic effect also contains the contribution from the phenolic hydroxyl, but it is a secondary factor. - Highlights: • Two model compounds, PA and s-PA, were successfully synthesized and purificated. • There is no phenolic hydroxyl in the final ring-opened structures of s-PA. • Compared with PA, s-PA also can catalyze the polymerization of BADCy. • The main catalytic process is caused by the oxygen anion. • The catalytic effect from the phenolic hydroxyl is a secondary factor

  4. The catalytic mechanism of benzoxazine to the polymerization of cyanate ester

    Energy Technology Data Exchange (ETDEWEB)

    Li, Xiaodan, E-mail: 12345ruby@163.com [Chongqing Key Laboratory of Catalysis and Functional Organic Molecules, College of Environment and Biological Engineering, Chongqing Technology and Business University, Chongqing 400067 (China); Luo, Xiaoyong; Liu, Ming [State Key Laboratory of Polymer Materials Engineering, College of Polymer Science and Engineering, Sichuan University, Sichuan, Chengdu 610065 (China); Ran, Qichao, E-mail: qichaoran@126.com [State Key Laboratory of Polymer Materials Engineering, College of Polymer Science and Engineering, Sichuan University, Sichuan, Chengdu 610065 (China); Gu, Yi, E-mail: guyi@scu.edu.cn [State Key Laboratory of Polymer Materials Engineering, College of Polymer Science and Engineering, Sichuan University, Sichuan, Chengdu 610065 (China)

    2014-11-14

    Two model compounds, 3-Phenyl-3,4-dihydro-2H-1,3-benzoxazine (PA) and 6,8-dimethyl-3-(2,4,6-trimethyl-phenyl)-3,4-dihydro-2H-1,3-benzoxazine (s-PA), were successfully synthesized and purificated. Compared with PA, s-PA also catalyzed the polymerization of BADCy even though there was no phenolic hydroxyl in its final ring-opened structures. It was confirmed that the real mechanism of benzoxazine catalyzing the polymerization of cyanate ester is the nucleophilic addition reaction of the oxygen anion on ring-opened benzoxazine to the positively charged carbon atom on cyano group. The catalytic effect also contains the contribution from the phenolic hydroxyl, but it is a secondary factor. - Highlights: • Two model compounds, PA and s-PA, were successfully synthesized and purificated. • There is no phenolic hydroxyl in the final ring-opened structures of s-PA. • Compared with PA, s-PA also can catalyze the polymerization of BADCy. • The main catalytic process is caused by the oxygen anion. • The catalytic effect from the phenolic hydroxyl is a secondary factor.

  5. Gel-silica science

    International Nuclear Information System (INIS)

    Sol-gel techniques can be used to produce two new types of optical silicas, termed Type V for the full density material and Type VI for the optically transparent porous material. This paper summarizes the processing differences between these six types of commercial silicas. The primary emphasis of this paper is to discuss the scientific basis for the processing of Types V and VI optical silica. First, however, the use of sol-gel processing of other systems will be briefly reviewed. The controlled hydrolysis of alkoxides has also been used to produce submicrometer TiO2, doped TiO2 (17), ZrO2 (18), doped ZrO2 (18), doped SiO2 (19), SrTiO3 (20), and corderite (20) powders. Emulsions have been employed to produce spherical powders of mixed cation oxides, such as yttrium aluminum garnets (YAG) and many other systems (20). Sol-gel powder processes have also been applied to fissile elements (21) where spray form sols UO2, and rigid gel spheres of UO-PuO2 are formed during passage through a column of heated liquid. Both crystalline and vitreous ceramic fibers have been prepared using the sol-gel method. Compositions include TiO2-SiO2 and ZrO2-SiO2 glass fibers (22), high purity SiO2 waveguide fibers (23), Al2O3, ZrO2, ThO2, MgO, TiO2, ZrSiO4, 3AlO3-2SiO2 fibers (24). Sol-gel derived alumina grains are important commercial products (25)

  6. Synthesis of polymeric fluorinated sol-gel precursor for fabrication of superhydrophobic coating

    Science.gov (United States)

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

    2016-03-01

    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.

  7. High-Voltage Insulation Organic-Inorganic Nanocomposites by Plasma Polymerization

    Directory of Open Access Journals (Sweden)

    Wei Yan

    2014-01-01

    Full Text Available In organic-inorganic nanocomposites, interfacial regions are primarily influenced by the dispersion uniformity of nanoparticles and the strength of interfacial bonds between the nanoparticles and the polymer matrix. The insulating performance of organic-inorganic dielectric nanocomposites is highly influenced by the characteristics of interfacial regions. In this study, we prepare polyethylene oxide (PEO-like functional layers on silica nanoparticles through plasma polymerization. Epoxy resin/silica nanocomposites are subsequently synthesized with these plasma-polymerized nanoparticles. It is found that plasma at a low power (i.e., 10 W can significantly increase the concentration of C–O bonds on the surface of silica nanoparticles. This plasma polymerized thin layer can not only improve the dispersion uniformity by increasing the hydrophilicity of the nanoparticles, but also provide anchoring sites to enable the formation of covalent bonds between the organic and inorganic phases. Furthermore, electrical tests reveal improved electrical treeing resistance and decreased dielectric constant of the synthesized nanocomposites, while the dielectric loss of the nanocomposites remains unchanged as compared to the pure epoxy resin.

  8. Electrochemically Formed Porous Silica

    Directory of Open Access Journals (Sweden)

    Jean-Noël Chazalviel

    2011-04-01

    Full Text Available Controlled electrochemical formation of porous silica can be realized in dilute aqueous, neutral-pH, fluoride medium. Formation of a porous film is initiated by sweeping the potential applied to silicon to values higher than 20 V. Film formation, reaching a steady state, may be pursued in a wide range of potentials, including lower potentials. The origin of a threshold potential for porous film initiation has been explained quantitatively. All of the films appear mesoporous. Films grown at high potentials exhibit a variety of macrostructures superimposed on the mesoporosity. These macrostructures result from selective dissolution of silica induced by local pH lowering due to oxygen evolution. Films grown at potentials lower than 15 V appear uniform on the micrometer scale. However, all of the films also exhibit a stratified structure on the scale of a few tens of nanometres. This periodic structure can be traced back to the oscillatory behavior observed during the electrochemical dissolution of silicon in fluoride medium. It suggests that periodic breaking of the growing film may be responsible for this morphology.

  9. Silica aerogel Cherenkov counter

    International Nuclear Information System (INIS)

    A practical method for making silica aerogel Cherenkov counters has been developed at KEK, and some tests were performed to evaluate the performance of the counters. The method for making silica aerogel with refractive index between 1.01 and 1.06 is explained in detail. Chemical reaction with methanol, pressure and temperature conditions, and the structure of the autoclave are described together with the whole process. About 20 l aerogel is now produced per week at KEK. The dimensions of the aerogel module is 200 x 100 x 300 mm3. The aerogel with refractive index larger than 1.06 is produced from the aerogel with refractive index 1.06 by heating it up to about 900 deg C. The refractive index can be controlled by the temperature and duration of heating. Refractive index in relation to these conditions is listed in a table. However, the dispersion of the index is about ten times as large as that for the aerogel with lower index (<1.06). The wave length dependence of the transmission length of light for the aerogel was measured and compared with other data obtained at various laboratories. The performance of the counter was evaluated through the experiment with π beam. Average number of photoelectrons gathered is plotted in relation to momentum. It is deduced from the experiment that the saturation thickness of the aerogel is about 10 cm. Two examples of the practical use of the aerogel counter at KEK are also shortly described. (Aoki, K.)

  10. Organometallic Polymeric Conductors

    Science.gov (United States)

    Youngs, Wiley J.

    1997-01-01

    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

  11. Preparation of polymeric nanocapsules by γ-ray initiated miniemulsion polymerization stabilized by polymeric surfactant

    International Nuclear Information System (INIS)

    An alkali soluble polymeric surfactant, copolymer of butyl methacrylate and methacrylic acid, has been prepared by free radical solution polymerization initiated by γ-ray and used as stabilizer in preparation of polymeric nanocapsules by γ-ray initiated miniemulsion polymerization. Effect of the amount of surfactant and costabilizer (hexadecane) and the styrene/hexadecane ratio on the morphological characteristics of the polymer/oil composite particle was systematically studied. The morphologies of final latexes particles were compared with those obtained by γ-ray initiated miniemulsion polymerization used SDS as surfactant. The results indicated that the structure can be adjusted to cover the whole range from independent particles over partially engulfed structures to structurally integer nanocapsules by varying the parameters such as the type and amount of surfactant and the styrene/hexadecane ratio, as well as dose rate. The use of this polymeric surfactant leads to large amounts of nanocapsules in the case of a lower concentration of hexadecane, which is due to the graft reaction between polymer and polymeric surfactant. (authors)

  12. Composite polymer electrolytes using fumed silica fillers: synthesis, rheology and electrochemistry

    Energy Technology Data Exchange (ETDEWEB)

    Khan, Saad A.; Fedkiw, Peter S.; Baker, Gregory L.

    1999-06-28

    The goal of the synthesis research was to devise routes to PEG/fumed silica/lithium salt composites that can be processed and then photochemically cross-linked to form mechanically stable electrolytes. An essential feature of the system is that the ionic conductivity and the mechanical properties must be de-coupled from each other, i.e., cross-linking of the fumed silica matrix must not cause a significant deterioration of the conductivity of the composite. As shown in Figure 2, we prepared a range of surface-modified fumed silicas and investigated their ability to form mechanically stable composite electrolytes. The groups used to modify the surface properties of the silica ranged from simple linear alkyls that render the silica hydrophobia to polyethers that promote compatibility with the electrolyte. From these materials we developed a cross-linkable system that satisfies the criteria of processibility and high-conductivity. The key material needed for the cross-linking reaction are silicas that bear surface-attached monomers. As shown schematically in Figure 3a, we prepared fumed silicas with a combination of surface groups, for example, an octyl chain with different coverages of tethered methacrylates. The length of the tether was varied, and we found that both C{sub 3} and C{sub 8} tethers gave useful composites. The functionalized silicas were combined with PEG-DM, AIBN or benzophenone (free radical initiators), LiClO{sub 4} or Li imide, and either methyl, butyl, or octyl, methacrylate to form stable clear gels. Upon irradiation with UV light, polymerization of both the tethered methacrylate and the added methacrylate took place, yielding a cross-linked rubbery composite material. Ionic conductivity measurements before and after cross-linking showed only a slight decrease (see Figure 9 later), thereby offering strong experimental evidence that the mechanical properties conferred by the silica matrix are de-coupled from the ionic conductivity of the PEG

  13. Controlled free radical polymerization of styrene initiated from the alkoxyamine-functionalized silicon surface

    Institute of Scientific and Technical Information of China (English)

    CHEN; Zhijun; ZHOU; Sikai; LU; Wenzhong; FANG; Shaoming; J

    2005-01-01

    We describe a new method of fabricating a brush-like polystyrene layer anchored on the surface of the silicon substrate, which involves three steps, namely (I) the attachment of 3-methacryloxypropyltrimethoxysilane onto the silicon surface; (ii) the reaction of vinyl moiety at another extremity of the anchored 3-methacryloxypropyltrimethoxysilane to 4-Hydroxyl-2, 2, 6, 6-tetramethyl-1-piperidinyloxy (HTEMPO·) catalyzed by azobisisobutyronitrile (AIBN); (iii) living free radical grafting polymerization of styrene in the presence of HTEMPO·. The controllable living free radical polymerization permits accurate control of both the molecular weight and the polydispersity. X-photoelectron spectroscopy measurement proved that the alkoxyamine initiator layer forms on the silicon surface. XPS and Ellipsometry measurements showed that the polystyrene chains were covalently anchored onto the silicon surface. The thickness of the grafted polymer layer can be accurately manipulated by altering the polymerization time. The new method allows synthesizing random copolymer and block copolymers by the sequential growth of monomers from the substrate surface.

  14. Titanium(IV) catalysts with ancillary imino-spiroketonato ligands: synthesis, structure and olefin polymerization.

    Science.gov (United States)

    Ma, Yuguo; Lobkovsky, Emil B; Coates, Geoffrey W

    2015-07-21

    New titanium(IV) complexes having two bidentate β-iminoethyl-spiro[4,5]decan-6-onato ligands with various N-aryl substituents have been synthesized. X-ray crystal structure analysis reveals that these titanium complexes all exhibit a C2-symmetric conformation with a distorted octahedral geometry, although the specific orientation of the ligands around the titanium center varies with the identity of the N-aryl moiety. Upon activation with methylaluminoxane (MAO), these complexes catalyze the polymerization of ethylene and propylene. In the case of ethylene, most complexes exhibit the characteristics of a living polymerization between 0 °C and 25 °C, producing polyethylenes with narrow molecular weight distributions and number average molecular weights up to 100,000 g/mol. Depending on the N-aryl substituents, polymerizations of propylene result in products with tacticity ranging from slightly syndiotactic to slightly isotactic. PMID:25984908

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

    Directory of Open Access Journals (Sweden)

    Valdemiro P. Carvalho Jr.

    2012-01-01

    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. Silaffins in Silica Biomineralization and Biomimetic Silica Precipitation

    Directory of Open Access Journals (Sweden)

    Carolin C. Lechner

    2015-08-01

    Full Text Available Biomineralization processes leading to complex solid structures of inorganic material in biological systems are constantly gaining attention in biotechnology and biomedical research. An outstanding example for biomineral morphogenesis is the formation of highly elaborate, nano-patterned silica shells by diatoms. Among the organic macromolecules that have been closely linked to the tightly controlled precipitation of silica in diatoms, silaffins play an extraordinary role. These peptides typically occur as complex posttranslationally modified variants and are directly involved in the silica deposition process in diatoms. However, even in vitro silaffin-based peptides alone, with and without posttranslational modifications, can efficiently mediate biomimetic silica precipitation leading to silica material with different properties as well as with encapsulated cargo molecules of a large size range. In this review, the biomineralization process of silica in diatoms is summarized with a specific focus on silaffins and their in vitro silica precipitation properties. Applications in the area of bio- and nanotechnology as well as in diagnostics and therapy are discussed.

  17. Modification of surface properties of silica-alumina by irradiation with gamma-rays

    International Nuclear Information System (INIS)

    Coprecipitated silica-alumina gel was prepared to contain 11.8 mol.% alumina. The gel was calcined at 523, 673, 823, 973 and 1173 K. The calcination products were irradiated by γ-rays (15-75 Mrad). Nitrogen adsorption at 77 K, water vapour adsorption at 303 K, pyridine chemisorption at 423 K were measured for non-irradiated and γ irradiated silica-alumina samples. The dehydration of isopropanol was measured at 553 K and at a carrier gas flow rate = 25 ml/min. ''gamma-Irradiation (30-75 Mrad) caused appreciable changes in textural properties of silica-alumina. The extents of these changes depend on the irradiation dose and on the pre-calcination temperature. Irradiation with γ-rays decreased the surface acid density and consequently the activity of the irradiated sample towards acid catalyzed reactions decreased. (author)

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

    International Nuclear Information System (INIS)

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

  19. Preparation of modified silica aerogel and its appilication in inertial confinement fusion (ICF) experiment

    International Nuclear Information System (INIS)

    The silica alco-gel was obtained by the 2-step acid-base catalyzed TEOS. Aging in a solution of methyltrimethoxylsilane and trimethylating Si-OH groups increased the strength and stiffness of the wet gel by hexamethyldisilazane (HMDSA) on the surface of silica matrix. The modified silica aerogel was obtained by CO2 supercritical drying method. The bulk densities of aerogels were between 30-100 mg/cm3. FTIR and some other experiment methods were used to investigate the structure and hydrophobic properties. The experiment results showed that the aerogel possessed perfect size-stability and hydrophobic properties. The aerogel micro-cylinder for ICF targets was manufactured by lathe machine. (authors)

  20. Fabrication of silica aerogel micro-cylinder for inertial confinement fusion target

    International Nuclear Information System (INIS)

    The silica alco-gel was obtained by the 2-step acid-base catalyzed TEOS. Aging in a solution of tetraethoxylsilane and trimethylating Si-OH groups increases the strength and stiffness of the wet gel due to the hexanethyldisilazane (HMDSA) on the surface of silica matrix. The modified silica aerogels were obtained by CO2 supercritical drying method. The bulk density of aerogels is in the range of 30-100 mg/cm3. FTIR and some other methods were used to investigate the structure and hydrophobic properties. The results show that the aerogel possesses perfect size-stability and hydrophobic properties. The aerogel micro-cylinder for inertial confinement fusion targets were manufactured by lathe machine. (authors)

  1. Laser-induced damage of sol-gel silica acid and basic thin films

    International Nuclear Information System (INIS)

    The sol-gel monolayer silica acid and basic thin films on K9 glass substrates were prepared with the dip method from acid and basic catalyzed silica sols, respectively. Both films have nearly similar optical thickness. The laser-induced damage thresholds(LIDT) of the two kinds of films were measured. Thermal absorption, porous ratio and surface morphologies of films were investigated by Stanford photo-thermal solutions, ellipsometer, atomic force microscope(AFM) and scanning electron micro-scope(SEM), respectively. Optical microscope was used to characterize the defects and impurities of films before laser irradiation and damage morphology after laser irradiation. The experimental results showed that compared with basic film, the silica acid film had larger absorption, smaller porous ratio, and smaller LIDT. Different damage morphologies of films were relative to their different absorption and microstructures. (authors)

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-01-15

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

  3. Changes in alveolar lavage materials and lung microsomal xenobiotic metabolism following exposures to HCl-washed or unwashed crystalline silica.

    Science.gov (United States)

    Miles, P R; Bowman, L; Jones, W G; Berry, D S; Vallyathan, V

    1994-12-01

    Intratracheal exposures of rats to crystalline silica washed with HCl to remove iron contaminants have previously been shown to increase lung surfactant phospholipids (PL) and proteins and to alter the pulmonary microsomal cytochrome P450 system. We compared these effects of HCl-washed silica with those produced by exposures to unwashed silica and alumina. Both silica preparations produce increases in lung weights and alveolar lavage PL and proteins, but to different degrees. The increases produced by HCl-washed vs unwashed silica are lung weights, 2.2- vs 1.3-fold; lavage PL, 25.9- vs 3.7-fold; and lavage proteins, 11.1- vs 3.2-fold, respectively. Although the two silica particles increase lung microsomal protein concentrations (expressed per gram lung) by 50-60%, their effects on cytochrome P-450-mediated xenobiotic metabolism are quite different. Exposure to HCl-washed silica leads to a 2.3-fold increase in 7-ethoxyresorufin O-deethylation, a reaction catalyzed by cytochrome P4501A1, and a 0.5- to 0.6-fold reduction in 7-ethoxycoumarin O-deethylation, a reaction which may be catalyzed by cytochrome P-4502B1. Unwashed silica does not alter the metabolism of either xenobiotic when results are expressed per milligram microsomal protein. Administration of alumina produces only minor increases in lung weight and lavage PL and no effect on microsomal xenobiotic metabolism. These results show that the increases in alveolar lavage PL and proteins induced by administration of unwashed silica are exaggerated by 3- to 7-fold if the silica is treated with HCl. Furthermore, exposure to HCl-washed silica results in significant alterations of the lung microsomal cytochrome P450 system, but the unwashed silica has little effect. Although the reason(s) for these different effects is not known, measurements of iron levels and formation of hydroxyl radicals using ESR demonstrate that there is more iron associated with the unwashed than with the HCl-washed silica. PMID:7992313

  4. Polymerization of anionic wormlike micelles.

    Science.gov (United States)

    Zhu, Zhiyuan; González, Yamaira I; Xu, Hangxun; Kaler, Eric W; Liu, Shiyong

    2006-01-31

    Polymerizable anionic wormlike micelles are obtained upon mixing the hydrotropic salt p-toluidine hydrochloride (PTHC) with the reactive anionic surfactant sodium 4-(8-methacryloyloxyoctyl)oxybenzene sulfonate (MOBS). Polymerization captures the cross-sectional radius of the micelles (approximately 2 nm), induces micellar growth, and leads to the formation of a stable single-phase dispersion of wormlike micellar polymers. The unpolymerized and polymerized micelles were characterized using static and dynamic laser light scattering, small-angle neutron scattering, 1H NMR, and stopped-flow light scattering. Stopped-flow light scattering was also used to measure the average lifetime of the unpolymerized wormlike micelles. A comparison of the average lifetime of unpolymerized wormlike micelles with the surfactant monomer propagation rate was used to elucidate the mechanism of polymerization. There is a significant correlation between the ratio of the average lifetime to the monomer propagation rate and the average aggregation number of the polymerized wormlike micelles. PMID:16430253

  5. Electroactivity in Polymeric Materials

    CERN Document Server

    2012-01-01

    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. Positronium at polymeric surface

    International Nuclear Information System (INIS)

    Annihilation of slow positrons at a polymeric surface has been discussed in terms of positron diffusion and trapping of positronium into free volume holes. The above model has been used to calculate the ortho-positronium lifetime (τ3) in polystyrene (PS), epoxy resin film, polyurethane (PU) and polytetrafluroethylene (PTFE) as a function of temperature, incident positron energy and mean implantation depth. The results have been compared with the experimental observations of other authors. The variation in τ3 with respect to temperature clearly demonstrates a discontinuity in the curve at Tg corresponding to the glass transition temperature. The variation of calculated τ3 shows that the lifetime increases significantly above Tg however, below Tg it increases only slowly. This is a direct consequence of the change in the size of free volume holes. The Tg has been found to be dependent both on positron energy and density of the polymer. Large variation in τ3 has been observed at low energies suggesting a significant structure of free volume holes near the surface. (copyright 2004 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

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

    KAUST Repository

    Kerdi, Fatmé

    2011-12-23

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

  8. HYDROGENATION OF PHENOL AND CRESOLS CATALYZED BY CHITOSAN SUPPORTED PALLADIUM COMPLEX AT MILD CONDITIONS

    Institute of Scientific and Technical Information of China (English)

    TANG Liming; HUANG Meiyu; JIANG Yingyan

    1996-01-01

    A natural polymer catalyst, silica-supported chitosan palladium complex (abbr. as SiO2-CS-Pd) was found to catalyze the hydrogenation of phenol and cresols to corresponding cyclohexanones in high yield and 100% selectivity at 70℃ and 1.01325 × 105 Pa mild conditions. N/Pd molar ratio in the complex, temperature and solvents have much influence on the reaction. The reactivity order of reactants was found to be: phenol >m->p->ocresol. The catalyst is stable during the reaction and could be repeatedly used for several times without much decrease in its catalytic activity.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2013-05-15

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

  10. Rapid "one-pot" preparation of polymeric monolith via photo-initiated thiol-acrylate polymerization for capillary liquid chromatography.

    Science.gov (United States)

    Bai, Jingyao; Wang, Hongwei; Ou, Junjie; Liu, Zhongshan; Shen, Yehua; Zou, Hanfa

    2016-06-21

    A facile approach was exploited for fast preparation of polymer-based monoliths in UV-transparent fused-silica capillaries via "one-pot" photo-initiated thiol-acrylate polymerization reaction of dipentaerythritolpenta-/hexaacrylate (DPEPA) and 1-octadecanethiol (ODT) in the presence of porogenic solvents (1-butanol and ethylene glycol). Due to relative insensitivity of oxygen inhibition in thiol-ene free-radical polymerization, the polymerization could be performed within 5 min. The effects of composition of prepolymerization solution on the morphology and permeability of poly(ODT-co-DPEPA) monoliths were investigated in detail by adjusting the content of monomer and binary porogen ratio. The physical properties of poly(ODT-co-DPEPA) monoliths were characterized by Fourier transform infrared spectroscopy (FT-IR), mercury intrusion porosimetry (MIP) and nitrogen adsorption/desorption measurement. The evaluation of chromatographic performance was carried out by capillary liquid chromatography (cLC). The results indicated that the poly(ODT-co-DPEPA) monolith was homogeneous and permeable, and also possessed a typical reversed-phase retention mechanism in cLC with high efficiency (∼75,000 N m(-1)) for separation of alkylbenzenes. Eventually, the further separation of tryptic digest of proteins by cLC tandem mass spectrometry (cLC-MS/MS) demonstrated its potential in the analysis of biological samples. PMID:27188321

  11. Microwave pyrolisis of polymeric materials

    OpenAIRE

    A.Undri; L.Rosi; M. FREDIANI; P. Frediani

    2011-01-01

    The polymeric materials consumption are growing ceaselessly in the world even in spite of the financial crisis. World rubber demand, for instance, is foreseen to increase up to 4% annually to 26.5 million metric tons in 2011. Therefore the disposal of waste polymers is a serious environmental problem against which public is becoming more aware. The interest of waste polymeric materials disposal is focused on new ways of dealing rather than land filling or incineration. The pyrolysis of polyme...

  12. Polyolefin nanocomposites in situ polymerization

    Energy Technology Data Exchange (ETDEWEB)

    Galland, Griselda Barrera; Fim, Fabiana de C.; Milani, Marceo A.; Silva, Silene P. da; Forest, Tadeu; Radaelli, Gislaine, E-mail: griselda.barrera@ufrgs.br [Universidade Federal do Rio Grande de Sul - UFRGS, Porto Alegre, RS (Brazil); Basso, Nara R.S. [Pontificia Universidade Catolica do Rio Grande do Sul, Porto Alegre, RS (Brazil); Quijada, Raul [Universidad de Chile, Santiago (Chile)

    2011-07-01

    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)

  13. Ethylene polymerization and polyethylene functionalization

    OpenAIRE

    Marín Càmara, Ariadna

    2010-01-01

    Polyolefins have become ubiquitous and are large volume commodity materials. Of current interest is the preparation of speciality polymers incorporating polyethylene (PE), which often requires polymer chain-end manipulation. Ethylene polymerization by a neodymium catalyst in conjunction with n-butyloctylmagnesium (BOMg) is based on a reversible chain-transfer between Nd (where PE chains grow) and Mg (where PE chains rest). Using a large BOMg/Nd ratio for ethylene polymerization leads to m...

  14. Donor Schiff Base Polymeric Complexes

    Directory of Open Access Journals (Sweden)

    Shubhangi N. Kotkar

    2013-01-01

    Full Text Available A series of new polymeric complexes of Mn(II, Co(II, Ni(II, Cu(II, and Zn(II were prepared with a Schiff base ligand derived from condensation of 2,4-dihydroxy acetophenone and p-phenylene diamine and characterized by elemental analysis and IR and NMR spectral data. The antimicrobial activity of the Schiff base and its polymeric complexes have been studied.

  15. Nanocomposites obtained by embedding of conjugated polymers in porous silicon and silica

    Science.gov (United States)

    Errien, N.; Vellutini, L.; Froyer, G.; Louarn, G.; Simos, C.; Skarka, V.; Haesaert, S.; Joubert, P.

    2005-06-01

    Porous silicon and porous silica matrices are filled up by conjugated polymers in order to obtain nanocomposite with enhanced third order optical nonlinearity. The active component is either PDA-TS thermally polymerized in situ or PT12 electropolymerized in porous silicon. The first measurements of the nonlinear properties of these nanocomposites give evidence of a significant increase of the nonlinear refractive index with respect to the standard optical materials.

  16. Catalyzed electrolytic plutonium oxide dissolution

    International Nuclear Information System (INIS)

    Catalyzed electrolytic plutonium oxide dissolution (CEPOD) was first demonstrated at Pacific Northwest Laboratory (PNL) in early 1974 in work funded by the Exxon Corporation. The work, aimed at dissolution of Pu-containing residues remaining after the dissolution of spent mixed-oxide reactor fuels, was first publicly disclosed in 1981. The process dissolves PuO2 in an anolyte containing small (catalytic) amounts of elements that form kinetically fast, strongly oxidizing ions. These are continuously regenerated at the anode. Catalysts used, in their oxidized form, include Ag2+, Ce4+, Co3+, and AmO22+. This paper reviews the chemistry involved in CEPOD and the results of its application to the dissolution of the Pu content of a variety of PuO2-containing materials such as off-standard oxide, fuels dissolution residues, incinerator ash, contaminated soils, and other scraps or wastes. Results are presented for both laboratory-scale and plant-scale dissolves

  17. Gold-catalyzed naphthalene functionalization

    Directory of Open Access Journals (Sweden)

    Iván Rivilla

    2011-05-01

    Full Text Available The complexes IPrMCl (IPr = 1,3-bis(diisopropylphenylimidazol-2-ylidene, M = Cu, 1a; M = Au, 1b, in the presence of one equiv of NaBAr'4 (Ar' = 3,5-bis(trifluoromethylphenyl, catalyze the transfer of carbene groups: C(RCO2Et (R = H, Me from N2C(RCO2Et to afford products that depend on the nature of the metal center. The copper-based catalyst yields exclusively a cycloheptatriene derivative from the Buchner reaction, whereas the gold analog affords a mixture of products derived either from the formal insertion of the carbene unit into the aromatic C–H bond or from its addition to a double bond. In addition, no byproducts derived from carbene coupling were observed.

  18. Hydrogen evolution catalyzed by cobaloximes.

    Science.gov (United States)

    Dempsey, Jillian L; Brunschwig, Bruce S; Winkler, Jay R; Gray, Harry B

    2009-12-21

    Natural photosynthesis uses sunlight to drive the conversion of energy-poor molecules (H(2)O, CO(2)) to energy-rich ones (O(2), (CH(2)O)(n)). Scientists are working hard to develop efficient artificial photosynthetic systems toward the "Holy Grail" of solar-driven water splitting. High on the list of challenges is the discovery of molecules that efficiently catalyze the reduction of protons to H(2). In this Account, we report on one promising class of molecules: cobalt complexes with diglyoxime ligands (cobaloximes). Chemical, electrochemical, and photochemical methods all have been utilized to explore proton reduction catalysis by cobaloxime complexes. Reduction of a Co(II)-diglyoxime generates a Co(I) species that reacts with a proton source to produce a Co(III)-hydride. Then, in a homolytic pathway, two Co(III)-hydrides react in a bimolecular step to eliminate H(2). Alternatively, in a heterolytic pathway, protonation of the Co(III)-hydride produces H(2) and Co(III). A thermodynamic analysis of H(2) evolution pathways sheds new light on the barriers and driving forces of the elementary reaction steps involved in proton reduction by Co(I)-diglyoximes. In combination with experimental results, this analysis shows that the barriers to H(2) evolution along the heterolytic pathway are, in most cases, substantially greater than those of the homolytic route. In particular, a formidable barrier is associated with Co(III)-diglyoxime formation along the heterolytic pathway. Our investigations of cobaloxime-catalyzed H(2) evolution, coupled with the thermodynamic preference for a homolytic route, suggest that the rate-limiting step is associated with formation of the hydride. An efficient water splitting device may require the tethering of catalysts to an electrode surface in a fashion that does not inhibit association of Co(III)-hydrides. PMID:19928840

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

    International Nuclear Information System (INIS)

    The aim of the present paper is to report the effect of radiation on the Er3+-doped sol-gel silica glasses. A possible application of these sol-gel glasses could be their use in harsh radiation environments. The sol-gel glasses are fabricated by densification of erbium salt-soaked nanoporous silica xerogels through polymeric sol-gel technique. The radiation-induced attenuation of Er3+-doped sol-gel silica is found to increase with erbium content. Electron paramagnetic resonance studies reveal the presence of E′δ point defects. This happens in the sol-gel aluminum-silica glass after an exposure to γ-rays (kGy) and in sol-gel silica glass after an exposure to electrons (MGy). The concentration levels of these point defects are much lower in γ-ray irradiated sol-gel silica glasses. When the samples are co-doped with Al, the exposure to γ-ray radiation causes a possible reduction of the erbium valence from Er3+ to Er2+ ions. This process occurs in association with the formation of aluminum oxygen hole centers and different intrinsic point defects

  20. Radiation hardening in sol-gel derived Er{sup 3+}-doped silica glasses

    Energy Technology Data Exchange (ETDEWEB)

    Hari Babu, B., E-mail: hariphy2012@gmail.com, E-mail: matthieu.lancry@u-psud.fr; León Pichel, Mónica [Laboratoire des Solides Irradiés, UMR CEA-CNRS 7642, Ecole Polytechnique, Université Paris Saclay, 91128 Palaiseau (France); Institut de Chimie Moléculaire et des Matériaux d' Orsay, UMR CNRS-UPSud 8182, Université Paris Sud, 91405 Orsay (France); Ollier, Nadège [Laboratoire des Solides Irradiés, UMR CEA-CNRS 7642, Ecole Polytechnique, Université Paris Saclay, 91128 Palaiseau (France); El Hamzaoui, Hicham; Bigot, Laurent; Savelii, Inna; Bouazaoui, Mohamed [Laboratoire PhLAM (UMR CNRS 8523), IRCICA (USR CNRS 3380), CERLA - FR CNRS 2416, Université Lille 1, Villeneuve d' Ascq Cedex F-59655 (France); Poumellec, Bertrand; Lancry, Matthieu, E-mail: hariphy2012@gmail.com, E-mail: matthieu.lancry@u-psud.fr [Institut de Chimie Moléculaire et des Matériaux d' Orsay, UMR CNRS-UPSud 8182, Université Paris Sud, 91405 Orsay (France); Ibarra, Angel [National Fusion Laboratory, CIEMAT, Avda Complutense 40, 28040 Madrid (Spain)

    2015-09-28

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

  1. AQUEOUS STABLE FREE RADICAL POLYMERIZATION PROCESSES

    Institute of Scientific and Technical Information of China (English)

    Andrea R. Szkurhan; Michael K. Georges

    2004-01-01

    An overview of aqueous polymerizations, which include emulsion, miniemulsion and suspension polymerizations,under stable free radical polymerization (SFRP) conditions is presented. The success of miniemulsion and suspension SFRP polymerizations is contrasted with the difficulties associated with obtaining a stable emulsion polymerization. A recently developed unique microprecipitation technique is referenced as a means of making submicron sized particles that can be used to achieve a stable emulsion SFRP process.

  2. Biogenic nanostructured silica

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    Silicon is by far the most abundant element in the earth crust and also is an essential element for higher plants, yet its biology and mechanisms in plant tolerance of biotic and abiotic stresses are poorly understood. Based on the molecular mechanisms of the biosilicification in marine organisms such as diatoms and sponges, the cell wall template-mediated self-assembly of nanostructured silica in marine organisms and higher plants as well as the related organic molecules are discussed. Understanding of the templating and structure-directed effects of silicon-processing organic molecules not only offers the clue for synthesizing silicon-based materials, but also helps to recognize the anomaly of silicon in plant biology.

  3. Silica aerogel core waveguide.

    Science.gov (United States)

    Grogan, M D W; Leon-Saval, S G; England, R; Birks, T A

    2010-10-11

    We have selectively filled the core of hollow photonic crystal fibre with silica aerogel. Light is guided in the aerogel core, with a measured attenuation of 0.2 dB/cm at 1540 nm comparable to that of bulk aerogel. The structure guides light by different mechanisms depending on the wavelength. At long wavelengths the effective index of the microstructured cladding is below the aerogel index of 1.045 and guidance is by total internal reflection. At short wavelengths, where the effective cladding index exceeds 1.045, a photonic bandgap can guide the light instead. There is a small region of crossover, where both index- and bandgap-guided modes were simultaneously observed. PMID:20941148

  4. Zeolite Catalyzed Aldol Condensation Reactions

    Directory of Open Access Journals (Sweden)

    Adedayo I. Inegbenebor

    2015-03-01

    Full Text Available The review is based on the description of zeolite structure, uses, synthesis, and catalytic aldol reaction in aldol condensation. An internal aldolcondensation reaction has been achieved over ZSM-5 zeolite with high silica-alumina ratio at 350oC. It therefore follows that zeolite canfunction as a catalyst in aldol type condensation reactions and that weak acid sites as well as a small number of active sites favor the aldolcondensation reaction of carbonyl compounds. However, the mixed condensation product was found to be favored at temperatures above 300oCand the self-condensation of ethanal to crotonaldehyde was favored at temperatures below 300oC. It has also been suggested that both Brønstedand Lewis acids are involved in aldol reactions with Lewis acid sites the most probable catalytic sites. The zeolite group of minerals has founduse in many chemical and allied industries.

  5. Synthesis and characterization of hollow silica particles from tetraethyl orthosilicate and sodium silicate.

    Science.gov (United States)

    Kim, Jiwoong; Lee, Jinwoo; Choi, Jeong-Woo; Jang, Hee Dong

    2013-03-01

    We herein introduce an effective method to synthesize hollow silica particles (HSPs) from tetraethyl orthosilicate (TEOS) and sodium silicate (Na2SiO3) as silica sources using a sacrificial template method with a simple modification. The advantage of the method is that it can be applied to synthesize HSPs from not only TEOS but also Na2SiO3 silica sources without changing the method adopted to obtain the sacrificial polymeric templates. Polystyrene particles are adopted as sacrificial templates to synthesize the HSPs, and a conventional dispersion polymerization method is used to synthesis polystyrene particles in an oil medium. Size control of HSPs is enabled by modulation of the polymerization initiator content (2,2'-Azoisobutyronitrile). The particle size, shell thickness, and morphology are analyzed. Light reflection spectra are measured to obtain the light reflection properties of the HSPs. The results indicate that the hollow architecture is the most important factor in determining the light reflection properties of the particles. Such particles are potential candidates for use in light reflectors and heat insulators, as they may reduce energy consumption in heating and cooling applications. PMID:23755680

  6. 21 CFR 584.700 - Hydrophobic silicas.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Hydrophobic silicas. 584.700 Section 584.700 Food... DRINKING WATER OF ANIMALS Listing of Specific Substances Affirmed as GRAS § 584.700 Hydrophobic silicas. (a) Product. Amorphous fumed hydrophobic silica or precipitated hydrophobic silica (CAS Reg. No....

  7. Structural study of spray dried silica-germanate nanoparticles

    International Nuclear Information System (INIS)

    Noncrystalline materials belonging to 0.005Gd2O3.0.995[(1 - x)SiO2.xGeO2] system, with Si/Ge ratio ranging from 1:1 to 1:4 (x = 0.5; 0.667; 0.75; 0.8) were prepared by sol-gel and spray drying method. The samples were characterized by X-ray diffraction, scanning electron microscopy, electron paramagnetic resonance and nuclear magnetic resonance. The XRD patterns indicate that all prepared samples have an amorphous structure. The SEM imagines show that the samples are quite spherical conglomerates of amorphous nanoparticles. Gd3+ EPR spectra recorded from the gadolinium doped silica-germanate samples are specific for noncrystalline systems and show that gadolinium ions are mainly clustered on the nanoparticles surface. Solid-state 29Si MAS-NMR results indicate the Si/Ge ratio depending presence of Q2, Q3 and Q4 units in the silica-germanate samples, and a less polymerized silica network with increasing of germanium content.

  8. Hydrolysis of carboxylate ester catalyzed by a new artificial abzyme based on molecularly imprinted polymer

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    A new kind of artificial abzyme MIP-3, which contains N-phenyl benzonic amide group and “nanochannel” formed by embedded ZnO nano materials, and is imprinted by a transition-state analogue of p-nitrophenyl methyphosphonate in the hydrolysis of p-nitrophenyl acetate, was prepared by radical co-polymerization. Hydrolytic kinetics of p-nitrophenyl carboxylate catalyzed by MIP-3 was investigated. The results showed that the artificial abzyme exhibited notable substructure selectivity and strong catalytic ability in hydrolysis of p-nitrophenyl acetate

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

    Directory of Open Access Journals (Sweden)

    Qian CHEN

    2012-03-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

    Oliveira, Larissa H., E-mail: larissahelena2009@gmail.com [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)

    2013-12-05

    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

  11. Silaffins in Silica Biomineralization and Biomimetic Silica Precipitation

    OpenAIRE

    Lechner, Carolin C.; Becker, Christian F. W.

    2015-01-01

    Biomineralization processes leading to complex solid structures of inorganic material in biological systems are constantly gaining attention in biotechnology and biomedical research. An outstanding example for biomineral morphogenesis is the formation of highly elaborate, nano-patterned silica shells by diatoms. Among the organic macromolecules that have been closely linked to the tightly controlled precipitation of silica in diatoms, silaffins play an extraordinary role. These peptides typic...

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

    KAUST Repository

    Polshettiwar, Vivek

    2011-02-18

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

  13. Silica-bonded N-propylsulfamic acid as a recyclable catalyst for the synthesis of 2,3-dihydroquinazolin-4(1H)-ones

    Institute of Scientific and Technical Information of China (English)

    Khodabakhsh Niknam; Nasrolah Jafarpour; Ebrahim Niknam

    2011-01-01

    2,3-Dihydroquinazolin-4(1H)-one derivatives are synthesized via a one-pot,three component reaction of isatoic anhydride and an aromatic aldehyde with ammonium acetate or primary amine catalyzed by silica-bonded N-propylsulfamic acid(SBNPSA)in refluxing ethanol.

  14. Nanocomposite electrolytes with fumed silica in poly(methyl methacrylate): thermal, rheological and conductivity studies

    Energy Technology Data Exchange (ETDEWEB)

    Ahmad, Shahzada; Agnihotry, S.A. [Electronic Materials Division, National Physical Laboratory, Dr. K.S. Krishnan Marg, New Delhi 110012 (India); Ahmad, Sharif [Materials Research Laboratory, Department of Chemistry, Jamia Millia Islamia, New Delhi 110025 (India)

    2005-01-10

    Composite polymer electrolytes (CPEs), were prepared by adding hydrophilic fumed silica in different proportions upto 5wt.% to gel polymeric electrolyte (GPE) comprising liquid electrolyte (1M LiClO{sub 4} in propylene carbonate) immobilized with 15wt.% poly(methyl methacrylate) (PMMA). The effect of fumed silica content in the CPEs on the ionic conductivity and viscosity over a wide temperature range was investigated. The resultant CPEs showed room temperature conductivity ({sigma}{sub 25}) as high as 3.8mScm{sup -1} along with viscosity value of 3700P for 2wt.% SiO{sub 2} addition. Fumed silica addition both to the liquid electrolyte and to the GPE exhibits similar conductivity behaviour and this suggests a passive role of PMMA. The shear thinning behaviour, pointing towards easy processablity, high thermal stability and low volatility, makes these CPEs potential candidates as solid-like electrolytes for electrochemical devices. (author)

  15. Fabrication of silver-coated silica microspheres through mussel-inspired surface functionalization.

    Science.gov (United States)

    Wang, Wencai; Jiang, Yi; Liao, Yuan; Tian, Ming; Zou, Hua; Zhang, Liqun

    2011-06-15

    A facile method was developed to prepare silica-silver core-shell composite microspheres with continuous, compact, and conductive silver layers. The procedure involves dopamine oxidative self-polymerization and electroless plating. The poly(dopamine) layer was used as the chemi-sorption sites for silver ions and promoted the silver deposition. The electroless plating procedure involves a combination of surface activation, seeding growth, and deposition. The chemical composition and the crystal structure of the silica-silver core-shell composite microspheres were studied by X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD), respectively. In addition, the surface morphology and chemical composition of each composite microsphere were confirmed by scanning electron microscopy and energy dispersive X-ray spectroscopy. The results demonstrated that the silver layer on the silica surface was continuous and compacted. PMID:21481409

  16. Effect of Catalyst on the Formation of Silica Coating on Nickel Substrate by Sol -Gel Processing

    Institute of Scientific and Technical Information of China (English)

    Ali Ghasemi; F.Ashrafizadeh; M.A.Golozar; Ali Ashrafi

    2004-01-01

    In this research work silica coating was produced on nickel substrates by a sol-gel process. In order to increase the rate of hydrolysis and to reduce the rate of polymerization several acid catalysts including nitric acid-hydrochloric acid,acetic acid, hydrochloric acid and nitric acid were add to silica sol. Conversely, in order to control the rate of hydrolysis and to increase the rate of polymerization, basic catalyst of ammonia and ammonia hydroxyl were introduced in to the solution.Nickel specimens of known surface roughness were chemically cleaned and prepared by dipping in the sols. In order to produce a suitable silica coating the drying and firing cycles were optimized on these substrates. The structure and uniformity of the coatings produced were examined by scanning electron microscopy. Coatings composition was determined using glow discharge optical spectroscopy and EDAX microanalysis. Experimental result showed that hydrochloric acid, acetic acid, ammonia and acetic acid - ammonia are suitable catalytic agents for silica coating formation on nickel type substrate.

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

    Science.gov (United States)

    Akhavan, Behnam; Jarvis, Karyn; Majewski, Peter

    2015-02-25

    Highly negatively charged particles were fabricated via an innovative plasma-assisted approach for the removal of heavy metal ions. Thiophene plasma polymerization was used to deposit sulfur-rich films onto silica particles followed by the introduction of oxidized sulfur functionalities, such as sulfonate and sulfonic acid, via water-plasma treatments. Surface chemistry analyses were conducted by X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectroscopy. Electrokinetic measurements quantified the zeta potentials and isoelectric points (IEPs) of modified particles and indicated significant decreases of zeta potentials and IEPs upon plasma modification of particles. Plasma polymerized thiophene-coated particles treated with water plasma for 10 min exhibited an IEP of less than 3.5. The effectiveness of developed surfaces in the adsorption of heavy metal ions was demonstrated through copper (Cu) and zinc (Zn) removal experiments. The removal of metal ions was examined through changing initial pH of solution, removal time, and mass of particles. Increasing the water plasma treatment time to 20 min significantly increased the metal removal efficiency (MRE) of modified particles, whereas further increasing the plasma treatment time reduced the MRE due to the influence of an ablation mechanism. The developed particulate surfaces were capable of removing more than 96.7% of both Cu and Zn ions in 1 h. The combination of plasma polymerization and oxidative plasma treatment is an effective method for the fabrication of new adsorbents for the removal of heavy metals. PMID:25603034

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

    Science.gov (United States)

    Kumar, A; Gross, R A

    2000-01-01

    Engineering of the reaction medium and study of an expanded range of reaction temperatures were carried out in an effort to positively influence the outcome of Novozyme-435 (immobilized Lipase B from Candida antarctica) catalyzed epsilon-CL polymerizations. A series of solvents including acetonitrile, dioxane, tetrahydrofuran, chloroform, butyl ether, isopropyl ether, isooctane, and toluene (log P from -1.1 to 4.5) were evaluated at 70 degrees C. Statistically (ANOVA), two significant regions were observed. Solvents having log P values from -1.1 to 0.49 showed low propagation rates (< or = 30% epsilon-CL conversion in 4 h) and gave products of short chain length (Mn < or = 5200 g/mol). In contrast, solvents with log P values from 1.9 to 4.5 showed enhanced propagation rates and afforded polymers of higher molecular weight (Mn = 11,500-17,000 g/mol). Toluene, a preferred solvent for this work, was studied at epsilon-CL to toluene (wt/vol) ratios from 1:1 to 10:1. The ratio 1:2 was selected since, for polymerizations at 70 degrees C, 0.3 mL of epsilon-CL and 4 h, gave high monomer conversions and Mn values (approximately 85% and approximately 17,000 g/mol, respectively). Increasing the scale of the reaction from 0.3 to 10 mL of CL resulted in a similar isolated product yield, but the Mn increased from 17,200 to 44,800 g/mol. Toluene appeared to help stabilize Novozyme-435 so that lipase-catalyzed polymerizations could be conducted effectively at 90 degrees C. For example, within only 2 h at 90 degrees C (toluene-d8 to epsilon-CL, 5:1, approximately 1% protein), the % monomer conversion reached approximately 90%. Also, the controlled character of these polymerizations as a function of reaction temperature was evaluated. PMID:11709835

  19. Silica Brick for Coke Oven

    Institute of Scientific and Technical Information of China (English)

    Wang Jing

    2007-01-01

    @@ 1 Scope This standard specifies the classification,specification,test method,quality appraisal procedure,labeling,packing,transportation,storage and quality certification of silica brick for coke oven.

  20. Silica reinforced triblock copolymer gels

    DEFF Research Database (Denmark)

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

    2004-01-01

    scattering at very low q, but no structure and formfactor information. However, on heating above the viscoelastic to plastic transition, the 'typical' scattering pattern of the copolymer gel builds-up. All reinforced gels are strengthened by the addition of the reinforcing agent. The transitions from a...... viscoclastic rubber to a plastic fluid and from a plastic fluid to a viscoelastic liquid are shifted to more elevated temperatures when silica is added to the triblock copolymer gel. (C) 2004 Elsevier Ltd. All rights reserved.......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 to...

  1. Functionalized silica materials for electrocatalysis

    Indian Academy of Sciences (India)

    Vellaichamy Ganesan

    2015-02-01

    Electrocatalysis is an important phenomenon which is utilized in metal–air batteries, fuel cells, electrochemical sensors, etc. 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 catalysts and/or catalyst supports. Owing to the uniform dispersion of electrocatalysts (metal complex and/or metal nanoparticles (NPs)) on the functionalized and non-functionalized silica, an enormous increase in the redox current is observed. Long range channels of silica materials with pore diameter of 15–100 Å allowed metal NPs to accommodate in a specified manner in addition to other catalysts. The usefulness of MCM-41-type silica in increasing the efficiency of electrocatalysisis demonstrated by selecting oxygen, carbon dioxide and nitrite reduction reactions as examples

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

    Science.gov (United States)

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

    2006-09-01

    Highly ordered mesoporous polymer-silica and carbon-silica nanocomposites with interpenetrating networks have been successfully synthesized by the evaporation-induced triconstituent co-assembly method, wherein soluble resol polymer is used as an organic precursor, prehydrolyzed TEOS is used as an inorganic precursor, and triblock copolymer F127 is used as a template. It is proposed for the first time that ordered mesoporous nanocomposites have "reinforced concrete"-structured frameworks. By adjusting the initial mass ratios of TEOS to resol, we determined the obtained nanocomposites possess continuous composition with the ratios ranging from zero to infinity for the two constituents that are "homogeneously" dispersed inside the pore walls. The presence of silicates in nanocomposites dramatically inhibits framework shrinkage during the calcination, resulting in highly ordered large-pore mesoporous carbon-silica nanocomposites. Combustion in air or etching in HF solution can remove carbon or silica from the carbon-silica nanocomposites and yield ordered mesoporous pure silica or carbon frameworks. The process generates plenty of small pores in carbon or/and silica pore walls. Ordered mesoporous carbons can then be obtained with large pore sizes of approximately 6.7 nm, pore volumes of approximately 2.0 cm(3)/g, and high surface areas of approximately 2470 m(2)/g. The pore structures and textures can be controlled by varying the sizes and polymerization degrees of two constituent precursors. Accordingly, by simply tuning the aging time of TEOS, ordered mesoporous carbons with evident bimodal pores at 2.6 and 5.8 nm can be synthesized. PMID:16939291

  3. Magnetic silica colloids for catalysis

    OpenAIRE

    Claesson, E.M.; Mehendale, N.C.; Klein Gebbink, R. J. M.; van Koten, G; Philipse, A. P.

    2007-01-01

    Monodisperse magnetizable colloidal silica particles in a stable dispersion have been functionalized with a homogeneous catalyst: a PCP–pincer Pd-complex. In a proof-of-principle experiment we demonstrate the catalytic activity of the colloids in a C–C bond formation reaction. Advantages of the magnetic silica carriers are the large surface-to-volume ratio and the easy recovery by magnetic separation. After magnetic separation, the catalyst-loaded particles are readily redispersed for further...

  4. Synthesis and characterization of hybrid silica/PMMA nanoparticles and their use as filler in dental composites

    Energy Technology Data Exchange (ETDEWEB)

    Canché-Escamilla, G., E-mail: gcanche@cicy.mx [Unidad de Materiales, Centro de Investigación Científica de Yucatán A.C. Calle 43 No. 130 Col. Chuburná de Hidalgo, Mérida, Yucatán 97200 (Mexico); Duarte-Aranda, S. [Unidad de Materiales, Centro de Investigación Científica de Yucatán A.C. Calle 43 No. 130 Col. Chuburná de Hidalgo, Mérida, Yucatán 97200 (Mexico); Toledano, M. [Facultad de Odontología, Universidad de Granada, Campus Universitario de Cartuja s/n, Granada 18071 (Spain)

    2014-09-01

    The effect of hybrid silica/poly(methylmethacrylate) (PMMA) nanoparticles on the properties of composites for dental restoration was evaluated. Hybrid nanoparticles with silica as core and PMMA as shell were obtained by a seeded emulsion polymerization process. Fourier transform infrared spectrum of the hybrid nanoparticles shows an intense peak at 1730 cm{sup −1}, corresponding to carbonyl groups (C=O) of the ester. The thermal stability of the hybrid particles decreases with increasing amounts of PMMA and the residual mass at 700 °C corresponds to the silica content in the hybrid particles. Composites were obtained by dispersing nanoparticles (silica or hybrid), as fillers, in a resin—bis glycidyl dimethacrylate (Bis-GMA)/triethylene glycol dimethacrylate (TEGDMA) (40%/60% (w/w)). The paste was then placed in a mold and polymerized under light irradiation. During the preparation of the composites, with the hybrid nanoparticles, the monomers swell the PMMA shell and after photo-curing, a semi-interpenetrating network (semi-IPN) is obtained around the silica core. The properties of the composites, obtained using the hybrid nanoparticles, depend on the filler content and the amount of PMMA in the semi-IPN matrix. For composites with similar inorganic filler contents, the composites with low amounts of PMMA shell had higher modulus than those in which silica was used as the filler. - Highlights: • Hybrid nanoparticles silica/PMMA were used as fillers in dental composites. • The properties of the hybrid nanoparticle depend on the silica/PMMA content ratio. • A higher content of inorganic filler was obtained using hybrid nanoparticle. • Composites with higher modulus were obtained using hybrid nanoparticles. • A semi-IPN matrix between the PMMA shell and the resin is obtained.

  5. Synthesis and characterization of hybrid silica/PMMA nanoparticles and their use as filler in dental composites

    International Nuclear Information System (INIS)

    The effect of hybrid silica/poly(methylmethacrylate) (PMMA) nanoparticles on the properties of composites for dental restoration was evaluated. Hybrid nanoparticles with silica as core and PMMA as shell were obtained by a seeded emulsion polymerization process. Fourier transform infrared spectrum of the hybrid nanoparticles shows an intense peak at 1730 cm−1, corresponding to carbonyl groups (C=O) of the ester. The thermal stability of the hybrid particles decreases with increasing amounts of PMMA and the residual mass at 700 °C corresponds to the silica content in the hybrid particles. Composites were obtained by dispersing nanoparticles (silica or hybrid), as fillers, in a resin—bis glycidyl dimethacrylate (Bis-GMA)/triethylene glycol dimethacrylate (TEGDMA) (40%/60% (w/w)). The paste was then placed in a mold and polymerized under light irradiation. During the preparation of the composites, with the hybrid nanoparticles, the monomers swell the PMMA shell and after photo-curing, a semi-interpenetrating network (semi-IPN) is obtained around the silica core. The properties of the composites, obtained using the hybrid nanoparticles, depend on the filler content and the amount of PMMA in the semi-IPN matrix. For composites with similar inorganic filler contents, the composites with low amounts of PMMA shell had higher modulus than those in which silica was used as the filler. - Highlights: • Hybrid nanoparticles silica/PMMA were used as fillers in dental composites. • The properties of the hybrid nanoparticle depend on the silica/PMMA content ratio. • A higher content of inorganic filler was obtained using hybrid nanoparticle. • Composites with higher modulus were obtained using hybrid nanoparticles. • A semi-IPN matrix between the PMMA shell and the resin is obtained

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

    OpenAIRE

    Raúl Quijada; Paula Zapata

    2012-01-01

    Polypropylene nanocomposites containing silica nanospheres based on the sol-gel methods were produced via in situ polymerization using a rac-Et(Ind)2ZrCl2/methylaluminoxane (MAO) system. Two different routes were used depending on the interaction between the silica nanoparticles with the catalytic system. In route 1 the nanoparticles were added together with the catalytic system (rac-Et(Ind)2ZrCl2)/(MAO) directly into the reactor, and in route 2 the metallocene rac-Et(Ind)2ZrCl2 was supported...

  7. Muon catalyzed fusion under compressive conditions

    International Nuclear Information System (INIS)

    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 1017 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.)

  8. 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.

    2005-01-01

    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

  9. Surface glycosylation of polymeric membranes

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    Surface glycosylation of polymeric membranes has been inspired by the structure of natural biomem-branes. It refers to that glycosyl groups are introduced onto the membrane surface by various strate-gies, which combine the separation function of the membrane with the biological function of the sac-charides in one system. In this review, progress in the surface glycosylation of polymeric membranes is highlighted in two aspects, i.e. the glycosylation methods and the potential applications of the sur-face-glycosylated membranes.

  10. On-demand photoinitiated polymerization

    Science.gov (United States)

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

    2013-12-10

    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.

  11. Palladium-Catalyzed Carbonylation and Arylation Reactions

    OpenAIRE

    Sävmarker, Jonas

    2012-01-01

    Palladium-catalyzed reactions have found widespread use in contemporary organic chemistry due to their impressive range of functional group tolerance and high chemo- and regioselectivity. The pioneering contributions to the development of the Pd-catalyzed C-C bond forming cross-coupling reaction were rewarded with the Nobel Prize in Chemistry in 2010. Today, this is a rapidly growing field, and the development of novel methods, as well as the theoretical understanding of the various processes...

  12. Enzymatic Polymerization of Cyclic Monomers in Ionic Liquids as a Prospective Synthesis Method for Polyesters Used in Drug Delivery Systems

    Directory of Open Access Journals (Sweden)

    Urszula Piotrowska

    2014-12-01

    Full Text Available Biodegradable or bioresorbable polymers are commonly used in various pharmaceutical fields (e.g., as drug delivery systems, therapeutic systems or macromolecular drug conjugates. Polyesters are an important class of polymers widely utilized in pharmacy due to their biodegradability and biocompatibility features. In recent years, there has been increased interest in enzyme-catalyzed ring-opening polymerization (e-ROP of cyclic esters as an alternative method of preparation of biodegradable or bioresorbable polymers. Ionic liquids (ILs have been presented as green solvents in enzymatic ring-opening polymerization. The activity, stability, selectivity of enzymes in ILs and the ability to catalyze polyester synthesis under these conditions are discussed. Overall, the review demonstrates that e-ROP of lactones or lactides could be an effective method for the synthesis of useful biomedical polymers.

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

    International Nuclear Information System (INIS)

    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

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

    Energy Technology Data Exchange (ETDEWEB)

    Chemtob, Abraham, E-mail: abraham.chemtob@uha.fr [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)

    2014-01-01

    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.

  15. Covalently anchored sulfonic acid on silica gel (SiO2-R-SO3H) as an efficient and reusable heterogeneous catalyst for the one-pot synthesis of 1,8-dioxooctahydroxanthenes under solvent-free conditions

    Institute of Scientific and Technical Information of China (English)

    Gholam Hossein Mahdavinia; Mohammad A.Bigdeli; Yaser Saeidi Hayeniaz

    2009-01-01

    A highly efficient one-pot synthesis of 1,8-dioxooctahydroxanthenes under solvent-free conditions catalyzed by sulfonic acid covalently anchored onto the surface of silica gel is reported.All types of aldehydes,including aromatic,unsaturated,and heterocyclic,are used.The silica gel/sulfonic acid catalyst (SiO2-R-SO3H) is completely heterogeneous and can be recycled.

  16. Functionalization and Polymerization on the CNT Surfaces

    KAUST Repository

    Albuerne, Julio

    2013-07-01

    In this review we focus on the current status of using carbon nanotube (CNT) as a filler for polymer nanocomposites. Starting with the historical background of CNT, its distinct properties and the surface functionalization of the nanotube, the three different surface polymerization techniques, namely grafting "from", "to" and "through/in between" were discussed. Wider focus has been given on "grafting from" surface initiated polymerizations, including atom transfer radical polymerization (ATRP), reversible addition fragmentation chain-transfer (RAFT) Polymerization, nitroxide mediated polymerization (NMP), ring opening polymerization (ROP) and other miscellaneous polymerization methods. The grafting "to" and "through / in between" also discussed and compared with grafting from polymerization. The merits and shortcomings of all three grafting methods were discussed and the bottleneck issue in grafting from method has been highlighted. Furthermore the current and potential future industrial applications were deliberated. Finally the toxicity issue of CNTs in the final product has been reviewed with the limited available literature knowledge. © 2013 Bentham Science Publishers.

  17. Thermally Stable, Piezoelectric and Pyroelectric Polymeric Substrates

    Science.gov (United States)

    Simpson, Joycely O. (Inventor); St.Clair, Terry L. (Inventor)

    1999-01-01

    A thermally stable, piezoelectric and pyroelectric polymeric substrate was prepared. This thermally stable, piezoelectric and pyroelectric polymeric substrate may be used to prepare electromechanical transducers, thermomechanical transducers, accelerometers. acoustic sensors, infrared sensors, pressure sensors, vibration sensors, impact sensors, in-situ temperature sensors, in-situ stress/strain sensors, micro actuators, switches, adjustable fresnel lenses, speakers, tactile sensors. weather sensors, micro positioners, ultrasonic devices, power generators, tunable reflectors, microphones, and hydrophones. The process for preparing these polymeric substrates includes: providing a polymeric substrate having a softening temperature greater than 1000 C; depositing a metal electrode material onto the polymer film; attaching a plurality of electrical leads to the metal electrode coated polymeric substrate; heating the metal electrode coated polymeric substrate in a low dielectric medium; applying a voltage to the heated metal electrode coated polymeric substrate to induce polarization; and cooling the polarized metal electrode coated polymeric electrode while maintaining a constant voltage.

  18. Solid state polymerization of pet/pc extruded blend: effect of reaction temperature on thermal, morphological and viscosity properties

    OpenAIRE

    Luis Claudio Mendes; Isaac Albert Mallet; Sibele Piedade Cestari; Frederico Gonçalves de Albuquerque Dias; Patricia Soares da Costa Pereira

    2014-01-01

    A systematic study of solid state polymerization (SSP), concerning the melt extruded blend of poly(ethylene terephthalate)/polycarbonate (catalyzed PET/PC, 80/20 wt %), as a function of temperature range (180-190°C) for a fixed time (6 h) is presented. The materials obtained were evaluated by differential scanning calorimetry (DSC), thermogravimetry/derivative thermogravimetry (TG/DTG), optical microscopy (OM) and intrinsic viscosity (IV) analysis. After SSP, at all reaction temperatures, PET...

  19. Papain-Catalyzed Synthesis of Polyglutamate Containing a Nylon Monomer Unit

    Directory of Open Access Journals (Sweden)

    Kenjiro Yazawa

    2016-05-01

    Full Text Available Peptides have the potential to serve as an alternative for petroleum-based polymers to support a sustainable society. However, they lack thermoplasticity, owing to their strong intermolecular interactions. In contrast, nylon is famous for its thermoplasticity and chemical resistance. Here, we synthesized peptides containing a nylon unit to modify their thermal properties by using papain-catalyzed chemoenzymatic polymerization. We used l-glutamic acid alkyl ester as the amino acid monomer and nylon 1, 3, 4, and 6 alkyl esters as the nylon unit. Papain catalyzed the copolymerization of glutamic acid with nylon 3, 4, and 6 alkyl esters, whereas the nylon 1 unit could not be copolymerized. Other proteases used in this study, namely, bromelain, proteinase K, and Candida antarctica lipase (CALB, were not able to copolymerize with any nylon units. The broad substrate specificity of papain enabled the copolymerization of l-glutamic acid with a nylon unit. The peptides with nylon units demonstrated different thermal profiles from that of oligo(l-glutamic acid. Therefore, the resultant peptides with various nylon units are expected to form fewer intermolecular hydrogen bonds, thus altering their thermal properties. This finding is expected to broaden the applications of peptide materials and chemoenzymatic polymerization.

  20. Studies of Immobilized Homogeneous Metal Catalysts on Silica Supports

    Energy Technology Data Exchange (ETDEWEB)

    Keith James Stanger

    2003-05-31

    The tethered, chiral, chelating diphosphine rhodium complex, which catalyzes the enantioselective hydrogenation of methyl-{alpha}-acetamidocinnamate (MAC), has the illustrated structure as established by {sup 31}P 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]{sub 4}, [Rh(COD){sub 2}]{sup +}BF{sub 4}{sup -}, [Rh(COD)Cl]{sub 2}, and RhCl{sub 3} {center_dot} 3H{sub 2}O, adsorbed on SiO{sub 2} are optimally activated for toluene hydrogenation by pretreatment with H{sub 2} at 200 C. The same complexes on Pd-SiO{sub 2} 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(CH{sub 2}){sub 3}s-]Re(O)(Me)(PPh{sub 3}) 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.

  1. The Viscosity of Polymeric Fluids.

    Science.gov (United States)

    Perrin, J. E.; Martin, G. C.

    1983-01-01

    To illustrate the behavior of polymeric fluids and in what respects they differ from Newtonian liquids, an experiment was developed to account for the shear-rate dependence of non-Newtonian fluids. Background information, procedures, and results are provided for the experiment. Useful in transport processes, fluid mechanics, or physical chemistry…

  2. Low vibration polymeric composite engine

    Science.gov (United States)

    Guimond, David P.; Muench, Rolf K.

    1994-12-01

    An internal combustion engine is constructed with metallic parts in its regions which are subjected to high stress (temperature, pressure) during combustion and polymeric materials in its regions which are subjected to relatively lower stresses. The integrated construction helps realize increased power densities and reductions on engine noise without compromising engine performance. V-configuration Diesel engines particularly benefit from this construction.

  3. Sleeving nanocelluloses by admicellar polymerization.

    Science.gov (United States)

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

    2013-10-15

    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. PMID:23921337

  4. 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...

  5. Chemical oxidative polymerization of benzocaine

    Czech Academy of Sciences Publication Activity Database

    Marjanovic, B.; Juranic, I.; Ciric-Marjanovic, G.; Pašti, I.; Trchová, Miroslava; Holler, Petr

    2011-01-01

    Roč. 71, č. 7 (2011), s. 704-712. ISSN 1381-5148 R&D Projects: GA ČR GA203/08/0686 Institutional research plan: CEZ:AV0Z40500505 Keywords : benzocaine * electro-active oligomer * oxidative polymerization Subject RIV: CD - Macromolecular Chemistry Impact factor: 2.479, year: 2011

  6. Rheological behavior of novel polyamide 6/silica nanocomposites containing epoxy resins

    Institute of Scientific and Technical Information of China (English)

    赵才贤; 张平; 陈广兵; 王霞瑜

    2008-01-01

    A novel polyamide 6/silica nanocomposite containing epoxy resins(EPA6N) was prepared via in situ polymerization using tetraethoxysilane(TEOS) as the precursor of silica.The dynamic rheological properties of pure PA6 and EPA6N at temperatures of 225 and 235 ℃ were investigated.The results of transmission electron microscopy(TEM) and atomic force microscopy(AFM) indicate that the silica particles are well dispersed in the polyamide 6 matrix on about 30 nm in diameter,which demonstrates that this method can effectively avoid agglomeration of the inorganic particles.The rheological results suggest that pure PA6 shows Newtonian behavior.However,the novel EPA6N exhibits a solid-like rheological behavior,which is due to the small size,large surface of silica particles and the stronger polyamide 6-silica chemical bond formed through the reactions of epoxy resins with end groups of PA6 molecular chains.The EPA6N also exhibits higher melt viscosity,storage modulus and loss modulus than those of pure PA6.

  7. Nanomechanical properties of silica-coated multiwall carbon nanotubes-poly(methyl methacrylate) composites.

    Science.gov (United States)

    Olek, M; Kempa, K; Jurga, S; Giersig, M

    2005-03-29

    The mechanical properties of polymer composites, reinforced with silica-coated multiwall carbon nanotubes (MWNTs), have been studied using the nanoindentation technique. The hardness and the Young's modulus have been found to increase strongly with the increasing content of these nanotubes in the polymer matrix. Similar experiments conducted on thin films containing MWNTs, but without a silica shell, revealed that the presence of these nanotubes does not affect the nanomechanical properties of the composites. While carbon nanotubes (CNTs) have a very high tensile strength due to the nanotube stiffness, composites fabricated with CNTs may exhibit inferior toughness. The silica shell on the surface of a nanotube enhances its stiffness and rigidity. Our composites, at 4 wt % of the silica-coated MWNTs, display a maximum hardness of 120 +/- 20 MPa, and a Young's modulus of 9 +/- 1 GPa. These are respectively 2 and 3 times higher than those for the polymeric matrix. Here, we describe a method for the silica coating of MWNTs. This is a simple and efficient technique, adaptable to large-scale production, and might lead to new advanced polymer based materials, with very high axial and bending strength. PMID:15779997

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

    Science.gov (United States)

    Timin, Alexander S; Khashirova, Svetlana Yu; Rumyantsev, Evgeniy V; Goncharenko, Alexander A

    2016-07-01

    Guanidine containing co-polymers grafted onto silica nanoparticles to form core-shell structure were prepared by sol-gel method in the presence of γ-Fe2O3 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-Fe2O3 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±0.14mg/g respectively. The maximum drug release of molsidomine is achieved at pH1.6 (approximately 71-75% release at 37°C), whereas at pH7.4 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. PMID:27127024

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-02-15

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

  10. Thermal Polymerization of N-Butyl Acrylate

    Science.gov (United States)

    Ingham, J. D.

    1982-01-01

    Simple new polymerization method enables production of n-butyl acrylate polymer of desired high molecular weight, without disadvantages that usually attend more conventional methods. Process, which is hybrid of thermal, solution, and emulsion polymerization methods, involves controlled thermal polymerization of monomer at moderate temperatures without use of catalysts or additives.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2013-06-07

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

  12. Polymeric Inverse Glasses for Development of Noniridescent Structural Colors in Full Visible Range.

    Science.gov (United States)

    Lee, Gun Ho; Sim, Jae Young; Kim, Shin-Hyun

    2016-05-18

    Amorphous colloidal array with short-range order displays noniridescent structural colors due to the isotropic nature of the colloidal arrangement. The low angle dependence renders the colloidal glasses, which is promising for various coloration applications. Nevertheless, the colloidal glasses are difficult to develop red structural color due to strong cavity-like resonance from individual particles in the blue region. To suppress the cavity mode and develop the colors in the full visible range, we prepare inverse glasses composed of amorphous array of air cavities with short-range order. To produce the structures in a simple and reproducible manner, monodisperse silica particles are dispersed in a photocurable resin of poly(ethylene glycol) dimethacrylate (PEGDMA) at a volume fraction of 0.3. The particles spontaneously form the amorphous array with short-range order, which is rapidly captured in polymeric films by photopolymerization of the resin. Selective removal of silica particles from the polymerized resin leaves behind amorphous array of air cavities. The inverse glasses display structural colors with negligible backscattering in blue due to short optical path and low index in each cavity. Therefore, the colors can be tuned in full visible range by simply controlling the cavity size. The photocurable suspensions of silica particles can be patterned by photolithography, which enables the production of freestanding films containing patterned inverse glasses with noniridescent structural colors. PMID:27124719

  13. Metal Nanoparticles Catalyzed Selective Carbon-Carbon Bond Activation in the Liquid Phase.

    Science.gov (United States)

    Ye, Rong; Yuan, Bing; Zhao, Jie; Ralston, Walter T; Wu, Chung-Yeh; Unel Barin, Ebru; Toste, F Dean; Somorjai, Gabor A

    2016-07-13

    Understanding the C-C bond activation mechanism is essential for developing the selective production of hydrocarbons in the petroleum industry and for selective polymer decomposition. In this work, ring-opening reactions of cyclopropane derivatives under hydrogen catalyzed by metal nanoparticles (NPs) in the liquid phase were studied. 40-atom rhodium (Rh) NPs, encapsulated by dendrimer molecules and supported in mesoporous silica, catalyzed the ring opening of cyclopropylbenzene at room temperature under hydrogen in benzene, and the turnover frequency (TOF) was higher than other metals or the Rh homogeneous catalyst counterparts. Comparison of reactants with various substitution groups showed that electron donation on the three-membered ring boosted the TOF of ring opening. The linear products formed with 100% selectivity for ring opening of all reactants catalyzed by the Rh NP. Surface Rh(0) acted as the active site in the NP. The capping agent played an important role in the ring-opening reaction kinetics. Larger particle size tended to show higher TOF and smaller reaction activation energy for Rh NPs encapsulated in either dendrimer or poly(vinylpyrrolidone). The generation/size of dendrimer and surface group also affected the reaction rate and activation energy. PMID:27322570

  14. Silica Aerogel: Synthesis and Applications

    International Nuclear Information System (INIS)

    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.

  15. Silica Aerogel: Synthesis and Applications

    Directory of Open Access Journals (Sweden)

    Jyoti L. Gurav

    2010-01-01

    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.

  16. Effect of Polymerization Temperature on Polymerization Degree and Structure of Calcium Polyphosphate

    OpenAIRE

    WU Hang, ZHANG Li-Fang, BAI Wei, MA Chi, XIONG Cheng-Dong

    2012-01-01

    The properties of calcium polyphosphate (CPP) were greatly affected by its polymerization degree. A series of CPP with different polymerization degree were prepared by polymerization of calcium phosphate monobasic monohydrate (MCP) at different temperatures. Polymerization degree was analyzed by liquid state 31P nuclear magnetic resonance (31P―NMR). The effect of different temperature on polymerization degree and structure of CPP was discussed. MCP was ana...

  17. Synthesis and Characterization of Bimodal Mesoporous Silica

    Institute of Scientific and Technical Information of China (English)

    ZHANG Xiaofang; GUO Cuili; WANG Xiaoli; WU Yuanyuan

    2012-01-01

    Mesoporous silica with controllable bimodal pore size distribution was synthesized with cetyltrimethylammonium bromide (CTAB) as chemical template for small mesopores and silica gel as physical template for large mesopores.The structure of synthesized samples were characterized by Fourier transform infrared (FT-IR) spectroscopy,X-ray diffraction (XRD),scanning electron microscopy (SEM),transmission electron microscopy (TEM) and N2 adsorption-desorption measurements.The experimental results show that bimodal mesoporous silica consists of small mesopores of about 3 nm and large mesopores of about 45 nm.The small mesopores which were formed on the external surface and pore walls of the silica gel had similar characters with those of MCM-41,while large mesopores were inherited from parent silica gel material.The pore size distribution of the synthesized silica can be adjusted by changing the relative content of TEOS and silica gel or the feeding sequence of silica gel and NH4OH.

  18. Physisorbed Water on Silica at Mars Temperatures

    Science.gov (United States)

    Sutter, B.; Sriwatanapongse, W.; Quinn, R.; Klug, C.; Zent, A.

    2002-01-01

    The usefulness of nuclear magnetic resonance spectroscopy in probing water interactions on silica at Mars temperatures is discussed. Results indicate that two types of water occur with silica at Mars temperatures. Additional information is contained in the original extended abstract.

  19. Polyurethane reinforced by silica and silica filled with polyurethane

    Czech Academy of Sciences Publication Activity Database

    Serkis, Magdalena; Špírková, Milena; Poreba, Rafal

    Prague : Institute of Macromolecular Chemistry AS CR, 2015. L9. ISBN 978-80-85009-83-5. [Workshop "Career in Polymers" /7./. 03.07.2015, Prague] R&D Projects: GA ČR(CZ) GA13-06700S Institutional support: RVO:61389013 Keywords : polyurethane water dispersion * polycarbonate macrodiol * colloidal silica Subject RIV: CD - Macromolecular Chemistry

  20. The influence of pH over topography and spectroscopic properties of silica hybrid materials embedding meso-tetratolylporphyrin

    International Nuclear Information System (INIS)

    Hybrid porphyrin-silica materials consisting in 5,10,15,20-tetratolyl-21H,23H-porphine, encapsulated in silica matrices were obtained by sol-gel method. The hydrolysis and condensation reactions were performed by using tetraethylorthosilicate as precursor, either in one-step acid or in two steps acid-base catalysis, assisted or not by an ultrasonic field. The porphyrin-silica hybrid materials were monitored and characterized by AFM, FT-IR, fluorescence and UV-vis spectroscopy. As a result of porphyrin entrapping into silica gels, a general phenomenon regarding hyperchromic effects of the Q bands, occurs. UV-vis study revealed that during the sol-gel process, major changes regarding porphyrin ring structure occur, especially at acidic pH, when the dicationic species of porphyrin are formed. During acid-base catalyzed method the dye molecules tend to aggregate by π-π and hydrophobic co-facial interactions of sandwich H-type. In acid catalyzed process, the protonation of the porphyrins prevent the formation of aggregates, due to increased electrostatic repulsion between the molecules

  1. Magnetic properties of polymerized diphenyloctatetrayne

    International Nuclear Information System (INIS)

    A new type of metal-free ferromagnetic carbon material was obtained by thermal polymerization and electron beam irradiation of diphenyloctatetrayne (DPOT). The isothermal magnetic measurements showed hysteresis loops indicating weak but intrinsic ferromagnetism with Curie temperatures of around 600 K. Electron spin resonance spectroscopy showed that the material contained stable free radicals in the range of 1017–1020 radicals g−1 depending on the polymerization process. The ferromagnetism should be due to high radical concentration although no correlation was observed between them. It was shown that an amorphous ferromagnetic carbon could be obtained from a simple crystalline solid by heating at moderate temperatures. Highlights: ► Diphenyloctatetrayne as a precursor for carbon with high radical concentration. ► The carbon material consists of sp2 configuration. ► A weak intrinsic metal-free ferromagnetism was observed for the carbon products.

  2. Magnetic properties of polymerized diphenyloctatetrayne

    Energy Technology Data Exchange (ETDEWEB)

    Beristain, Miriam F.; Jimenez-Solomon, Maria F.; Ortega, Alejandra; Escudero, Roberto [Instituto de Investigaciones en Materiales, Universidad Nacional Autonoma de Mexico, Apartado Postal 70-360, Ciudad Universitaria, Mexico DF 04510 (Mexico); Munoz, Eduardo [Instituto de Fisica, Universidad Nacional Autonoma de Mexico, Apartado Postal 20-364, Ciudad Universitaria, Mexico DF 01000 (Mexico); Maekawa, Yasunari; Koshikawa, Hiroshi [High Performance Polymer Group, Quantum Beam Science Directorate, Japan Atomic Energy Agency, 1233 Watanuki, Takasaki, Gunma 370-1292 (Japan); Ogawa, Takeshi, E-mail: ogawa@unam.mx [Instituto de Investigaciones en Materiales, Universidad Nacional Autonoma de Mexico, Apartado Postal 70-360, Ciudad Universitaria, Mexico DF 04510 (Mexico)

    2012-10-15

    A new type of metal-free ferromagnetic carbon material was obtained by thermal polymerization and electron beam irradiation of diphenyloctatetrayne (DPOT). The isothermal magnetic measurements showed hysteresis loops indicating weak but intrinsic ferromagnetism with Curie temperatures of around 600 K. Electron spin resonance spectroscopy showed that the material contained stable free radicals in the range of 10{sup 17}-10{sup 20} radicals g{sup -1} depending on the polymerization process. The ferromagnetism should be due to high radical concentration although no correlation was observed between them. It was shown that an amorphous ferromagnetic carbon could be obtained from a simple crystalline solid by heating at moderate temperatures. Highlights: Black-Right-Pointing-Pointer Diphenyloctatetrayne as a precursor for carbon with high radical concentration. Black-Right-Pointing-Pointer The carbon material consists of sp{sup 2} configuration. Black-Right-Pointing-Pointer A weak intrinsic metal-free ferromagnetism was observed for the carbon products.

  3. SCATTERING FROM RAMIFIED POLYMERIC SYSTEMS

    Directory of Open Access Journals (Sweden)

    M.Benhamou

    2004-01-01

    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.

  4. Microemulsion Polymerization of Methyl Methacrylat

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    The microemulsion polymerization of methyl methacrylate was studied. The effects of feeding modes on the structure and the properties of the obtained polymer microlatex were investigated by measuring the conversion, the transmittance and the refractive index of the latex, and by measuring the particle size, the molecular weight and the glass transition temperature (Tg) of the polymers. The results show that compared to the batch feeding mode, the semi-continuous feeding mode is more favorable to form a PMMA microlatex with a higher transmittance, a smaller particle size, a higher molecular weight and a higher Tg. And the obtained PMMA microlatex has a 30 %-40 % (mass fraction) polymer content, a 0.03 emulsifier/water weight ratio, a 0.05emulsifier/monomer weight ratio and a 17 nm average particle diameter, which is very important for the industrialization of the microemulsion polymerization technique.

  5. Enhancing water flux of thin-film nanocomposite (TFN membrane by incorporation of bimodal silica nanoparticles

    Directory of Open Access Journals (Sweden)

    Jun Yin

    2016-03-01

    Full Text Available Modern reverse osmosis (RO/nanofiltration (NF membranes are primarily made of thin-film composites (TFC fabricated through interfacial polymerization of m-phenylene diamine (MPD and trimesoyl chloride (TMC on a polysulfone (PSF supporting membrane. In this study, two types of bimodal silica nanoparticles (~80 nm with different internal pore structures were synthesized and incorporated into the polyamide (PA thin-film layer during interfacial polymerization at concentrations varying from 0 to 0.1 wt%. The as-prepared membranes were characterized by scanning electron microscopy (SEM, atomic force microscopy (AFM, and attenuated total reflection Fourier transform infrared (ATR FT-IR spectroscopy, and their performances were evaluated in terms of the water permeability and salt rejection. The results showed the water permeability increased with increasing BSN concentrations, reaching a maximum of 53.5 L m−2 h−1 at a bimodal silica nanoparticle (BSN concentration of 0.5 wt% (pressure at 300 psi, NaCl concentration: 2000 ppm. This represented a flux increase of approximately 40%, while a near constant salt rejection of 95% was maintained. The study demonstrated that the internal micro-mesoporous structures of bimodal silica nanoparticles contributed significantly to the membrane performance, which is consistent with previous studies with relatively uniform internal pores.

  6. New Hybrid Organic/Inorganic Polysilsesquioxane-Silica Particles as Sunscreens.

    Science.gov (United States)

    Tolbert, Stephanie H; McFadden, Peter D; Loy, Douglas A

    2016-02-10

    Effectiveness of organic sunscreens is limited by phototoxicity and degradation. Both of which can be significantly reduced by encapsulation in hollow particles or covalent incorporation into the solid structure of particles, but direct comparisons of the two methods have not been reported. In this study, physical encapsulation and covalent incorporation of sunscreens were compared with 1 mol % salicylate and curcumeroid sunscreens. 2-Ethylhexyl salicylate was physically encapsulated in hollow silica nanoparticles prepared by oil-in-water (O/W) microemulsion polymerizations (E-Sal). Some of these particles were coated with an additional shell or cap of silica to reduce leaking of sunscreen (cap-E-Sal). Covalent incorporation involved co-polymerizing tetraethoxysilane (TEOS) with 0.2 mol % of new salicylate and curcuminoid sunscreen monomers with triethoxsilyl groups. Particles were prepared with the salicylate attached to the silica matrix through single silsesquioxane groups (pendant; P-Sal) and two silsesquioxane groups (bridged; B-Sal). Particles based on a new curcuminoid-bridged monomer were also prepared (B-Curc). Sunscreen leaching, photodegradation, and sunscreen performance were determined for the E-Sal, cap-E-Sal, P-Sal, B-Sal, and B-Curc particles. Covalent attachment, particularly with bridged sunscreen monomers, reduced leaching and photodegradation over physical encapsulation, even with capping. PMID:26730573

  7. Chemical oxidative polymerization of aminodiphenylamines

    Czech Academy of Sciences Publication Activity Database

    Ciric-Marjanovic, G.; Trchová, Miroslava; Konyushenko, Elena; Holler, Petr; Stejskal, Jaroslav

    2008-01-01

    Roč. 112, č. 23 (2008), s. 6976-6987. ISSN 1520-6106 R&D Projects: GA ČR GA203/08/0686 Grant ostatní: Ministry of Science and Environmental Protection of Serbia(CS) 142047 Institutional research plan: CEZ:AV0Z40500505 Keywords : aminodiphenylamine * polymerization * FTIR and Raman spectroscopy Subject RIV: CD - Macromolecular Chemistry Impact factor: 4.189, year: 2008

  8. Tunnel magnetoresistance of polymeric chains

    OpenAIRE

    Walczak, Kamil

    2004-01-01

    Coherent spin-dependent electronic transport is investigated in a molecular junction made of polymeric chain attached to ferromagnetic electrodes (Ni and Co, respectively). Molecular system is described by a simple Huckel model, while the coupling to the electrodes is treated through the use of a broad-band theory. The current flowing through the device is calculated within non-equilibrium Green's function approach. It is shown that tunnel magnetoresistance of molecular junction can be quite ...

  9. Alcohol polymerization using electron emission

    International Nuclear Information System (INIS)

    We report a means of instantaneous alcohol polymerization using electron emission at room temperature. We selected 1-butanol as a source of alcohol polymer. A 1-butanol molecule has a simple molecular structure and is a good candidate for analyzing reaction mechanisms. Direct electron emission onto the surface of volatile 1-butanol prevented intense discharge and gently composed 1-butanol-polymer at room temperature in air. The strategy enabled exciting liquids and instantaneously composing new materials at room temperature

  10. Polymeric Microspheres for Medical Applications

    Directory of Open Access Journals (Sweden)

    Ketie Saralidze

    2010-06-01

    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.

  11. Polystyrene-supported triphenylarsines: Useful ligands in palladium-catalyzed aryl halide homocoupling reactions and a catalyst for alkene epoxidation using hydrogen peroxide

    OpenAIRE

    Song He, H; Zhang, C; Ng, CKW; Toy, PH

    2005-01-01

    The utility of both soluble (non-cross-linked) and insoluble (cross-linked) polystyrene-supported triphenylarsine reagents were examined. These reagents were prepared by standard radical polymerization methodology and used in palladium-catalyzed homocoupling reactions of aryl halides. The insoluble reagent was also used as a catalyst precursor in heterogeneous alkene epoxidation reactions in which aqueous hydrogen peroxide was the stoichiometric oxidant. For the aryl halide homocoupling react...

  12. Poling of Planar Silica Waveguides

    DEFF Research Database (Denmark)

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

    1999-01-01

    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...

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-05-15

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

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

    International Nuclear Information System (INIS)

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

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

    Science.gov (United States)

    Arumugasamy, Senthil Kumar; Ahmad, Z.

    2015-05-01

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

  16. Elastic behavior of silica/poly(dimethylsiloxane) nanocomposites: nano-size effects

    Science.gov (United States)

    Ibrahim, I. A. M.; Zikry, A. A. F.; Sharaf, M. A.; Mark, J. E.; Jacob, K.; Jasiuk, I. M.; Tannenbaumn, R.

    2012-09-01

    Elastomeric materials require the incorporation of reinforcing fillers in order to improve their mechanical properties. The enhancement of properties is very much dependent on the size and any surface modification of the reinforcing agent. It is widely accepted that the reinforcement effects are primarily due to molecular interactions of the polymeric matrix and the filler inclusions and it involves both chemical and physical interactions. Herein, we have incorporated silica nano fillers (Stober silica) into poly (dimethylsiloxane) (PDMS) elastomeric networks. The mechanical and swelling properties of the networks were investigated as a function of filler sizes (50, 130, and 170 nm), volume fraction of the filler inclusions, and surface treatment of the particles by were analyzed to give the Mooney-Rivlin constants 2C1 and 2C2. These properties were found to be dependent on the size of the nano inclusions. Thus, a nano size phenomenon had been discerned and was one of the highlights of this investigation. This phenomenon was largely attributed to the high specific surface area of the nano fillers used that leads to significant increase in the interfacial interactions. Also, and as would be expected, the properties of the polymeric networks filled with unmodified particles were different than those obtained for the polymeric networks filled with surface-modified particles. This has been primarily attributed to changes in the surface properties, and as would be expected, the elastic properties of the networks were thus shown to be strongly dependent on type and concentration.

  17. Dielectric behavior of Silica/Poly(dimethylsiloxane) nanocomposites. nano size effects

    International Nuclear Information System (INIS)

    The enhancement of properties of elastomeric composite materials is very much dependent on the size and the surface modification of the reinforcing filler inclusions. It is well accepted that the reinforcement effects are primarily due to molecular interactions of the polymeric matrix and the filler inclusions and it involves both chemical and physical interactions. In the present study, we have incorporated silica nano fillers (Stober silica) into poly(dimethylsiloxane) (PDMS) elastomeric networks. The dielectric properties of the networks were investigated as a function of filler nano filler size, volume fraction, and surface treatment by hexamethyldisilazane. The broad-spectrum dielectric properties (in particular, the dielectric constant, the dielectric loss, and tan δ) were characterized. These properties were found to be dependent on the size of the nano inclusions; thus, the results clearly showed a nano size phenomenon that was a highlight of the present research. Certainly, that can be largely attributed to the high specific surface area of the nano fillers, which significantly leads to a pronounced increase in interfacial interactions. Also, and as would be expected, the dielectric properties of the polymeric networks filled with unmodified particles were different from those for the polymeric networks filled with surface-modified particles. Again, this is mainly attributed to changes in the surface properties. The expected dependence of properties of the nanocomposite networks on the nature of the filler and its concentration has thus been demonstrated.

  18. Dielectric behavior of Silica/Poly(dimethylsiloxane) nanocomposites. nano size effects

    Science.gov (United States)

    Ibrahim, I. A. M.; Zikry, A. A. F.; Sharaf, M. A.; Mark, J. E.; Jacob, K.; Jasiuk, I. M.; Tannenbaumn, R.

    2012-09-01

    The enhancement of properties of elastomeric composite materials is very much dependent on the size and the surface modification of the reinforcing filler inclusions. It is well accepted that the reinforcement effects are primarily due to molecular interactions of the polymeric matrix and the filler inclusions and it involves both chemical and physical interactions. In the present study, we have incorporated silica nano fillers (Stober silica) into poly(dimethylsiloxane) (PDMS) elastomeric networks. The dielectric properties of the networks were investigated as a function of filler nano filler size, volume fraction, and surface treatment by hexamethyldisilazane. The broad-spectrum dielectric properties (in particular, the dielectric constant, the dielectric loss, and tan δ) were characterized. These properties were found to be dependent on the size of the nano inclusions; thus, the results clearly showed a nano size phenomenon that was a highlight of the present research. Certainly, that can be largely attributed to the high specific surface area of the nano fillers, which significantly leads to a pronounced increase in interfacial interactions. Also, and as would be expected, the dielectric properties of the polymeric networks filled with unmodified particles were different from those for the polymeric networks filled with surface-modified particles. Again, this is mainly attributed to changes in the surface properties. The expected dependence of properties of the nanocomposite networks on the nature of the filler and its concentration has thus been demonstrated.

  19. Elastic behavior of silica/poly(dimethylsiloxane) nanocomposites: nano-size effects

    International Nuclear Information System (INIS)

    Elastomeric materials require the incorporation of reinforcing fillers in order to improve their mechanical properties. The enhancement of properties is very much dependent on the size and any surface modification of the reinforcing agent. It is widely accepted that the reinforcement effects are primarily due to molecular interactions of the polymeric matrix and the filler inclusions and it involves both chemical and physical interactions. Herein, we have incorporated silica nano fillers (Stober silica) into poly (dimethylsiloxane) (PDMS) elastomeric networks. The mechanical and swelling properties of the networks were investigated as a function of filler sizes (50, 130, and 170 nm), volume fraction of the filler inclusions, and surface treatment of the particles by were analyzed to give the Mooney-Rivlin constants 2C1 and 2C2. These properties were found to be dependent on the size of the nano inclusions. Thus, a nano size phenomenon had been discerned and was one of the highlights of this investigation. This phenomenon was largely attributed to the high specific surface area of the nano fillers used that leads to significant increase in the interfacial interactions. Also, and as would be expected, the properties of the polymeric networks filled with unmodified particles were different than those obtained for the polymeric networks filled with surface-modified particles. This has been primarily attributed to changes in the surface properties, and as would be expected, the elastic properties of the networks were thus shown to be strongly dependent on type and concentration.

  20. Attractor Explosions and Catalyzed Vacuum Decay

    Energy Technology Data Exchange (ETDEWEB)

    Green, Daniel; Silverstein, Eva; Starr, David

    2006-05-05

    We present a mechanism for catalyzed vacuum bubble production obtained by combining moduli stabilization with a generalized attractor phenomenon in which moduli are sourced by compact objects. This leads straightforwardly to a class of examples in which the Hawking decay process for black holes unveils a bubble of a different vacuum from the ambient one, generalizing the new endpoint for Hawking evaporation discovered recently by Horowitz. Catalyzed vacuum bubble production can occur for both charged and uncharged bodies, including Schwarzschild black holes for which massive particles produced in the Hawking process can trigger vacuum decay. We briefly discuss applications of this process to the population and stability of metastable vacua.

  1. Palladium-Catalyzed Amination of Bromoanthancene

    Institute of Scientific and Technical Information of China (English)

    YU Ming-Xin; CHEN Xiao-Hang; CHENG Chien-Hong

    2003-01-01

    @@ Triarylamines are an important class of compounds, because they have been used as the hole-transport layer in electroluminescent devices. [1] New palladium catalyzed methods to form arylamines have emerged recently from Hartwing and Bucchwald . [2,3] Our group have investigated unusual diboration of allenes catalyzed by palladium complex and organic iodides. [4] Here we will report that arylamines react with bromoanthrancene (or dibromoanthancene) to afford triarylamines in the presence of Ligand-palladium complex. The structures of products were de termined by 1H NMR, 13C NMR, 13C (DEPT), IR and MS (HREI and EI) spectra.

  2. Silica-Coated Liposomes for Insulin Delivery

    Directory of Open Access Journals (Sweden)

    Neelam Dwivedi

    2010-01-01

    Full Text Available Liposomes coated with silica were explored as protein delivery vehicles for their enhanced stability and improved encapsulation efficiency. Insulin was encapsulated within the fluidic phosphatidylcholine lipid vesicles by thin film hydration at pH 2.5, and layer of silica was formed above lipid bilayer by acid catalysis. The presence of silica coating and encapsulated insulin was identified using confocal and electron microscopy. The native state of insulin present in the formulation was evident from Confocal Micro-Raman spectroscopy. Silica coat enhances the stability of insulin-loaded delivery vehicles. In vivo study shows that these silica coated formulations were biologically active in reducing glucose levels.

  3. Montmorillonite-based porous clay heterostructures (PCHs) intercalated with silica-titania pillars-synthesis and characterization

    International Nuclear Information System (INIS)

    Porous clay heterostructures (PCHs) were synthesized using natural montmorillonite as a raw material. Apart from pure silica pillars also silica-titania pillars were intercalated into the interlayer space of the parent clay. The detailed studies of the calcination process of the as-prepared PCH samples as well as thermal stability of the pillared structure of these materials were performed. The pillared structure of PCHs intercalated with both silica and silica-titania clusters was found to be thermally stable up to temperatures exceeding 600 deg. C. It was found that titanium incorporated into the silica pillars was present mainly in the form of separated tetracoordinated cations. For the samples with the higher Ti loading also small contribution of titanium in the form of the polymeric oxide species was detected. Titanium incorporated into the PCH materials significantly increased their surface acidity forming mainly Bronsted acid sites. - Graphical abstract: Synthesis of the montmorillonite based porous clay heterostructures (PCHs) intercalated with silica-titania pillars has been performed. The mechanism of the thermal degradation of organic templates in the pore system of PCHs was studied. PCHs were characterized with respect to structure, texture, composition, surface acidity, thermal stability and form of introduced titanium.

  4. Simulation of the tensile properties of silica aerogels: the effects of cluster structure and primary particle size.

    Science.gov (United States)

    Liu, Qiang; Lu, Zixing; Zhu, Man; Yuan, Zeshuai; Yang, Zhenyu; Hu, Zijun; Li, Junning

    2014-09-01

    A new two-level model is proposed to investigate the relationship between the mechanical properties and microstructure of silica aerogels. This two-level model consists of the particle-particle interaction model and the cluster structure model. The particle-particle interaction model is proposed to describe interactions between primary particles, in which the polymerization reaction between primary particles is considered. The cluster structure model represents the geometrical structure of silica aerogels, and it is established using a modified diffusion-limited colloid aggregation (DLCA) algorithm. This two-level model is used to investigate the tensile behavior of silica aerogels based on the discrete element method (DEM). The numerical results show that the primary particle size has significant effects on the elastic modulus and tensile strength of silica aerogels. Moreover, the power-law relationships between tensile properties and aerogel density are dependent on the variation of the primary particle radius with density. The present results can explain the difference among different experimental exponents to a certain extent. In comparison with experimental data within a wide density range, this two-level model provides good quantitative estimations of the elastic modulus and tensile strength of silica aerogels after the size effects of the primary particle are considered. This paper provides a fundamental understanding of the relationship between the mechanical properties and microstructure of silica aerogels. The two-level model can be extended to study the mechanical properties of other aerogels and aerogel composites. PMID:25022232

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

    KAUST Repository

    Guillois, Kevin

    2012-02-01

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

  6. Preparation and characterizaion of CTAB-templated large pore silica nanocomposite films

    Science.gov (United States)

    Yao, Lan-fang; Tian, Lin-lin; Wang, Shuo; Li, Lin; Xu, Ruiqing; Fang, Xueling

    2011-02-01

    CTAB-templated large pore silica nano-composite films were prepared by means of a two-step acid-catalyzed and solgel process using tetraethoxysilane (TEOS) as the precursor, Surfactant cetyltrimethy- ammonium bromide (CTAB) as an organic template to generate the uniformity pore structure and 1,3,5-trimethyl benzene (TMB) as organic swelling agent. The obtained samples were characterized by XRD, Fourier-transform infrared (FTIR) and Atomic Force Microscopy (AFM). We found that the TMB/CTAB mol ratio must be controlled well for producing large pore materials.

  7. Catalytic Synthesis of Pyrano- and Furoquinolines Using Nano Silica Chromic Acid at Room Temperature

    Directory of Open Access Journals (Sweden)

    Ali Gharib

    2013-01-01

    Full Text Available Nano silica chromic acid (nano-SCA is found to catalyze efficiently the three component-coupling reactions of aldehydes, amines, and cyclic enol ethers such as 3,4-dihydro-2H-pyran and 2,3-dihydrofuran under mild conditions to afford the corresponding pyrano- and furanoquinolines in excellent yields with high endoselectivity. Interestingly, 2,3-dihydrofuran afforded selectively endoproducts under the similar reaction conditions. Heterogeneous reaction conditions, easy procedure, short reaction time, and high yields are some important advantages of this method.

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

    DEFF Research Database (Denmark)

    Bernasconi, A.; Sleator, T.; Posselt, D.; Kjems, Jørgen; Ott, H.R.

    1992-01-01

    The specific heat C(p) and the thermal conductivity lambda of a series of base-catalyzed silica aerogels have been measured at temperatures between 0.05 and 20 K. The results confirm that the different length-scale regions observed in the aerogel structure are reflected in the dynamic behavior of...... the possibility of two spectral dimensions characterizing the fracton modes. Our data imply important differences between the physical mechanisms dominating the low-temperature behavior of aerogels and dense glasses, respectively. From our analysis we also conclude that the low-temperature properties...

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

    Science.gov (United States)

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

    2016-05-01

    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-ynyloxy)phenyl)(phenyl)methanone at ambient temperature for affording the desired PVC-based UV-absorbers (PVC-UV) with different amounts of benzophenone moieties, which displayed great resistance to photoaging without degradation while exposed to UV irradiation. These polymeric UV-absorbers also showed good solubilities in common organic solvents and no cytotoxicity vs. HaCat cell. Small amounts of PVC-UV were homogeneously mixed with PVC as additive for stabilizing PVC against UV-photoaging without degradation and releasing small molecule even after 200 h while keeping thermal stability. This route of polymeric additive clearly paved an efficient way for solving the puzzle of separation of small molecule additive.

  10. Silica Pigments for Glossy Ink Jet Media

    Institute of Scientific and Technical Information of China (English)

    Sun Qi; Michael R. Sestrick; Yoshi Sugimoto; William A. Welsh

    2004-01-01

    Silica is a versatile pigment for ink jet media. Micronized silica gel is the worldwide standard for high performance matte ink jet media. For glossy ink jet media, several different forms of silica are widely used. Submicron silica gel dispersions, with either anionic or cationic surfaces, can be employed in either absorptive basecoat layers or in the glossy ink receptive top layer. Colloidal silica, with a variety of particle sizes and surface modifications, is utilized extensively in glossy top layers. It will show how various silica pigments can be utilized in glossy ink receptive coatings, both in cast based glossy media and RC based glossy media. Several novel silica pigments will be examined by relating the physical properties of the pigments and the formula variables to the print quality of the ink jet media.

  11. Investigation of tribological properties of biobased polymers and polymeric composites

    Science.gov (United States)

    Bhuyan, Satyam Kumar

    Worldwide potential demands for replacing petroleum derived raw materials with renewable plant-based ones in the production of valuable polymeric materials and composites are quite significant from the social and environmental standpoints. Therefore, using low-cost renewable resources has deeply drawn the attention of many researchers. Among them, natural oils are expected to be ideal alternative feedstock since oils, derived from plant and animal sources, are found in profusion in the world. The important feature of these types of materials is that they can be designed and tailored to meet different requirements. The real challenge lies in finding applications which would use sufficiently large quantities of these materials allowing biodegradable polymers to compete economically in the market. Lack of material and tribological characterizations have created an awareness to fulfill this essential objective. In order to understand the viability of biobased polymers in structural applications, this thesis work elucidates the study of friction and wear characteristics of polymers and polymeric composites made out of natural oil available profusely in plants and animals. The natural oils used in this study were soybean and tung oil. Various monomeric components like styrene, divinely benzene etc. were used in the synthesis of biobased polymers through Rh-catalyzed isomerization techniques. For the different polymeric composites, spent germ, a byproduct of ethanol production, is used as the filler and an organoclay called montmorillonite is used as the reinforcing agent in the polymer matrix. The effect of crosslinker concentration, filler composition and reinforcement agent concentration was studied under dry sliding. A ball-on-flat tribometer with a probe made out of steel, silicon nitride or diamond was used for most of the experimental work to measure friction and generate wear. The wear tracks were quantified with an atomic force microscope and a contact

  12. A Novel Catalytic Method for the Oxidation of Sulfides to Sulfoxides with Silica Sulfuric Acid and Sodium Nitrite in the Presence of KBr and/or NaBr as Catalyst

    Institute of Scientific and Technical Information of China (English)

    GOUDARZIAFSHAR Hamid; GHORBANI-CHOGHAMARANI Arash; NIKOORAZM Mohsen; NASERIFAR Zahra

    2009-01-01

    Highly efficient selective oxidation of sulfides to sulfoxides by NaNO2 and silica sulfuric acid catalyzed with KBr or NaBr has been reported.This oxidation was carried out in the presence of wet SiO2(50% w/w)in acetonitrile at room temperature with good to excellent yields.

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

    Science.gov (United States)

    Cacciotti, Ilaria; Nanni, Francesca

    2016-06-01

    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.

  14. Radiation curing of silica for silica-rubber composites

    International Nuclear Information System (INIS)

    The functional modification of silica samples based on the reaction of '' grafting '' of polybutadiene oligomers carried out by gamma-irradiation in the presence of air at room temperature has been investigated. The yield of grafted PB reaches a maximum at doses of about 30 kGy, then decreases as a consequence of the oxidative degradation. The reaction is accompanied by the build up of carbonyls and peroxides up to 0.1 moles/kg and it leads to a rapid consumption of the double bonds concentration as determined by both FTIR and Raman spectroscopy. The results of the EPR analysis are diagnostic of a mechanism of immobilization of the oligomer based on cross-linking of polybutadiene which is initiated by the SiO2 radiolytic species. Depending on the nature of the SiO2 species, the mechanism of initiation leads to immobilized PB either really grafted to the silica surface or simply physically absorbed. (authors)

  15. Photocatalytic Surface-Initiated Polymerization on TiO2 toward Well-Defined Composite Nanostructures.

    Science.gov (United States)

    Wang, Xin; Lu, Qipeng; Wang, Xuefei; Joo, Jibong; Dahl, Michael; Liu, Bo; Gao, Chuanbo; Yin, Yadong

    2016-01-13

    We demonstrate the use of TiO2 nanospheres as the photoinitiator for photocatalytic surface-initiated polymerization for the synthesis of various inorganic/polymer nanocomposites with well-defined structures. The excitation of TiO2 by UV-light irradiation produces electrons and holes which drive the free radical polymerization near its surface, producing core/shell composite nanospheres with eccentric or concentric structures that can be tuned by controlling the surface compatibility between the polymer and the TiO2. When highly porous TiO2 nanospheres were employed as the photoinitiator, polymerization could disintegrate the mesoporous framework and give rise to nanocomposites with multiple TiO2 nanoparticles evenly distributed in the polymer spheres. Thanks to the well-developed sol-gel chemistry of titania, this synthesis is well-extendable to the coating of the polymers on many other substrates of interest such as silica and ZnS by simply premodifying their surface with a thin layer of titania. In addition, this strategy could be easily applied to coating of different types of polymers such as polystyrene, poly(methyl methacrylate), and poly(N-isopropylacrylamide). We expect this photocatalytic surface-initiated polymerization process could provide a platform for the synthesis of various inorganic/polymer hybrid nanocomposites for many interesting applications. PMID:26671186

  16. Enyne Metathesis Catalyzed by Ruthenium Carbene Complexes

    DEFF Research Database (Denmark)

    Poulsen, Carina Storm; Madsen, Robert

    2003-01-01

    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...

  17. Pinacol Coupling Reactions Catalyzed by Active Zinc

    Institute of Scientific and Technical Information of China (English)

    Hui ZHAO; Wei DENG; Qing Xiang GUO

    2005-01-01

    Pinacol coupling reactions catalyzed by active zinc revealed high activity and extensive suitability. The efficiency of the reaction was improved apparently owing to decreasing reductive potential of zinc. In addition, the results indicated that the zinc activity has a direct relation to the coupling reactivity compared to untreated zinc or other general active zinc.

  18. Palladium Catalyzed Allylic C-H Alkylation

    DEFF Research Database (Denmark)

    Engelin, Casper Junker; Fristrup, Peter

    2011-01-01

    The atom-efficiency of one of the most widely used catalytic reactions for forging C-C bonds, the Tsuji-Trost reaction, is limited by the need of preoxidized reagents. This limitation can be overcome by utilization of the recently discovered palladium-catalyzed C-H activation, the allylic C...

  19. Sulfilimimines in metal-catalyzed redox reactions

    Czech Academy of Sciences Publication Activity Database

    Voltrová, Svatava; Šrogl, Jiří

    Praha : -, 2009. s. 593-593. ISBN 978-80-02-02160-5. [ESOC 2009. European Symposium on Organic Chemistry /16./. 12.07.2009-16.07.2009, Praha] Institutional research plan: CEZ:AV0Z40550506 Keywords : sulfilimines * metal catalyzed oxidations * benzoisothiazolone Subject RIV: CC - Organic Chemistry

  20. Biodiesel production by enzyme-catalyzed transesterification

    Directory of Open Access Journals (Sweden)

    Stamenković Olivera S.

    2005-01-01

    Full Text Available The principles and kinetics of biodiesel production from vegetable oils using lipase-catalyzed transesterification are reviewed. The most important operating factors affecting the reaction and the yield of alkyl esters, such as: the type and form of lipase, the type of alcohol, the presence of organic solvents, the content of water in the oil, temperature and the presence of glycerol are discussed. In order to estimate the prospects of lipase-catalyzed transesterification for industrial application, the factors which influence the kinetics of chemically-catalysed transesterification are also considered. The advantages of lipase-catalyzed transesterification compared to the chemically-catalysed reaction, are pointed out. The cost of down-processing and ecological problems are significantly reduced by applying lipases. It was also emphasized that lipase-catalysed transesterification should be greatly improved in order to make it commercially applicable. The further optimization of lipase-catalyzed transesterification should include studies on the development of new reactor systems with immobilized biocatalysts and the addition of alcohol in several portions, and the use of extra cellular lipases tolerant to organic solvents, intracellular lipases (i.e. whole microbial cells and genetically-modified microorganisms ("intelligent" yeasts.

  1. Palladium catalyzed hydrogenation of bio-oils and organic compounds

    Science.gov (United States)

    Elliott, Douglas C.; Hu, Jianli; Hart, Todd R.; Neuenschwander, Gary G.

    2008-09-16

    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.

  2. Effect of Catalyst on the Formation of Silica Coating on Nickel Substrate by Sol-Gel Processing

    Institute of Scientific and Technical Information of China (English)

    AliGhasemi; F.Ashrafizadeh; M.A.Golozar; AliAshrafi

    2004-01-01

    In this research work silica coating was produced on nickel substrates by a sol-gel process. In order to increase the rate of hydrolysis and to reduce the rate of polymerization several acid catalysts including nitric acid-hydrochloric acid, acetic acid, hydrochloric acid and nitric acid were add to silica sol. Conversely, in order to control the rate of hydrolysis and to increase the rate of polymerization, basic catalyst of ammonia and ammonia hydroxyl were introduced in to the solution. Nickel specimens of known surface roughness were chemically cleaned and prepared by dipping in the sols. In order to produce a suitable silica coating the drying and firing cycles were optimized on these substrates. The structure and uniformity of the coatings produced were examined by scanning electron microscopy. Coatings composition was determined using glow discharge optical spectroscopy and EDAX microanalysis. Experimental result showed that hydrochloric acid, acetic acid, ammonia and acetic acid-ammonia are suitable catalytic agents for silica coating formation on nickel type substrate.

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

    International Nuclear Information System (INIS)

    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 In(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) = Kkjv 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)=Lkjv, 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 ak(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, ak(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

  4. Structural basis of reverse nucleotide polymerization

    OpenAIRE

    Nakamura, Akiyoshi; Nemoto, Taiki; Heinemann, Ilka U.; Yamashita, Keitaro; Sonoda, Tomoyo; Komoda, Keisuke; Tanaka, Isao; Söll, Dieter; Yao, Min

    2013-01-01

    Template-dependent RNA and DNA polymerization is a vital reaction in the cell and is believed to occur exclusively in the forward direction (5′-3′), which poses significant challenges to the cell in, for example, lagging strand synthesis. Although cells are mostly limited to unidirectional polymerization, we find that reverse polymerization is structurally and chemically possible utilizing the same structural core, the conserved palm domain of canonical polymerases. The structure of a unique ...

  5. Stimulation of Actin Polymerization by Filament Severing

    OpenAIRE

    Carlsson, A E

    2005-01-01

    The extent and dynamics of actin polymerization in solution are calculated as functions of the filament severing rate, using a simple model of in vitro polymerization. The model is solved by both analytic theory and stochastic-growth simulation. The results show that severing essentially always enhances actin polymerization by freeing up barbed ends, if barbed-end cappers are present. Severing has much weaker effects if only pointed-end cappers are present. In the early stages of polymerizati...

  6. Fluidized bed reactor for catalytic olefin polymerization

    OpenAIRE

    Meier, Gerhardus Bernardus

    2000-01-01

    Due to the continuous improvement of catalysts and processes, polyolefins have become one of the most important plastics in the world. Polyolefins can be produced at low costs with a variety of end-use properties. Nowadays, the most important propylene polymerization processes are executed in the liquid or the gas phase or a combination of both. In contrast to propylene polymerizations in slurry phase, only a few studies have been published concerning gas or liquid phase polymerization. Espec...

  7. Radiation polymerization of allyl derivatives of glycerin

    International Nuclear Information System (INIS)

    Radiation polymerization of 1 allyloxi-3-(chlorine)-alkoxipropanol-2, 1-cro otoxy-3=ethyloxypropanol-2, 1-allylamino-3-amyloxypropanol-2, 1-butoxy-2-allyloxi-3-chlorpropane has been carried out. Some kinetic character ristics of the polymerization process have been obtained. A dependence of the polymerization rate on exposure doze rate, on the persence of modifier (orthopho osphoric acid) and its ratio to the manometer has been studied

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

    Science.gov (United States)

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

    2016-02-01

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

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

    International Nuclear Information System (INIS)

    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

  10. 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: nakashik@cc.saga-u.ac.jp [Department of Chemistry, Faculty of Science and Engineering, Saga University, 1 Honjo-machi, Saga 840-8502 (Japan)

    2014-09-30

    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.

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

    Directory of Open Access Journals (Sweden)

    Marcello Iacono

    2015-08-01

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

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

    Directory of Open Access Journals (Sweden)

    Lotta Bergman

    2008-01-01

    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.

  13. Computational studies of polymeric systems

    Science.gov (United States)

    Carrillo, Jan-Michael Y.

    Polymeric systems involving polyelectrolytes in surfaces and interfaces, semiflexible polyelectrolytes and biopolymers in solution, complex polymeric systems that had applications in nanotechnology were modeled using coarse grained molecular dynamics simulation. In the area of polyelectrolytes in surfaces and interfaces, the phenomena of polyelectrolyte adsorption at oppositely charge surface was investigated. Simulations found that short range van der Waals interaction was a major factor in determining morphology and thickness of the adsorbed layer. Hydrophobic polyelectrolytes adsorbed in hydrophobic surfaces tend to be the most effective in forming multi-layers because short range attraction enhances the adsorption process. Adsorbed polyelectrolytes could move freely along the surface which was in contrast to polyelectrolyte brushes. The morphologies of hydrophobic polyelectrolyte brushes were investigated and simulations found that brushes had different morphologies depending on the strength of the short range monomer-monomer attraction, electrostatic interaction and counterion condensation. Planar polyelectrolyte brushes formed: (1) vertically oriented cylindrical aggregates, (2) maze-like aggregate structures, or (3) thin polymeric layer covering a substrate. While, the spherical polyelectrolyte brushes could be in any of the previous morphologies or be in a micelle-like conformation with a dense core and charged corona. In the area of biopolymers and semiflexible polyelectrolytes in solution, simulations demonstrated that the bending rigidity of these polymers was scale-dependent. The bond-bond correlation function describing a chain's orientational memory could be approximated by a sum of two exponential functions manifesting the existence of the two characteristic length scales. The existence of the two length scales challenged the current practice of describing chain stretching experiments using a single length scale. In the field of nanotechnology

  14. Template polymerization of nucleotide analogues

    Science.gov (United States)

    Orgel, L. E.

    1991-01-01

    Recent work on the template-directed reactions of the natural D-nucleotides has made it clear that l-nucleotides and nucleotide-like derivatives of other sugars would strongly inhibit the formation of long oligonucleotides. Consequently, attention is focusing on molecules simpler than nucleotides that might have acted as monomers of an information transfer system. We have begun a general exploration of the template directed reactions of diverse peptide analogues. I will present work by Dr. Taifeng Wu on oxidative oligomerization of phosphorothioates and of Dr. Mary Tohidi on the cyclic polymerization of nucleoside and related cyclic pyrophosphates.

  15. Marketing NASA Langley Polymeric Materials

    Science.gov (United States)

    Flynn, Diane M.

    1995-01-01

    A marketing tool was created to expand the knowledge of LaRC developed polymeric materials, in order to facilitate the technology transfer process and increase technology commercialization awareness among a non-technical audience. The created brochure features four materials, LaRC-CP, LaRC-RP46, LaRC-SI, and LaRC-IA, and highlights their competitive strengths in potential commercial applications. Excellent opportunities exist in the $40 million per year microelectronics market and the $6 billion adhesives market. It is hoped that the created brochure will generate inquiries regarding the use of the above materials in markets such as these.

  16. Silica aerogel and space astrophysics

    International Nuclear Information System (INIS)

    Silica aerogels have been produced in large and transparent blocks for space astrophysics experiments since the beginning of the 1970's. They were used in cosmic ray experiments on board balloons by the Saclay group. A new space venture where aerogel Cerenkov radiators will play a decisive role is currently being prepared by a large collaboration of European and US Institutes. It will be part of the so-called International Solar Polar Mission (ISPM) which will explore the heliosphere over the full range of solar latitudes from the ecliptic (equatorial) plane to the magnetic poles of the sun. Comments on properties and long term behaviour of silica aerogel cerenkov radiators in space environment are given

  17. Tailoring Elastic Properties of Silica Aerogels Cross-Linked with Polystyrene

    Science.gov (United States)

    Nguyen, Baochau N.; Meador, Mary Ann B.; Tousley, Marissa E.; Shonkwiler, Brian; McCorkle, Linda; Scheiman, Daniel A.; Palczer, Anna

    2009-01-01

    The effect of incorporating an organic linking group, 1,6-bis(trimethoxysilyl)hexane (BTMSH), into the underlying silica structure of a styrene cross-linked silica aerogel is examined. Vinyltrimethoxysilane (VTMS) is used to provide a reactive site on the silica backbone for styrene polymerization. Replacement of up to 88 mol 1 of the silicon from tetramethoxyorthosilicate with silicon derived from BTMSH and VTMS during the making of silica gels improves the elastic behavior in some formulations of the crosslinked aerogels, as evidenced by measurement of the recovered length after compression of samples to 251 strain. This is especially true for some higher density formulations, which recover nearly 100% of their length after compression to 251 strain twice. The compressive modulus of the more elastic monoliths ranged from 0.2 to 3 MPa. Although some of these monoliths had greatly reduced surface areas, changing the solvent used to produce the gels from methanol to ethanol increased the surface area in one instance from 6 to 220 sq m2/g with little affect on the modulus, elastic recovery, porosity, or density.

  18. Gain functionalization of silica microresonators.

    Science.gov (United States)

    Yang, Lan; Vahala, K J

    2003-04-15

    Erbium-doped solgel films are applied to the surface of silica microspheres to create low-threshold microactivity lasers. This gain functionalization can be applied by use of a number of different dopants, thereby extending the wavelength range of this class of device. Also, by varying the doping concentration and thickness of the applied solgel layer, one can vary the laser dynamics so that both continuous-wave and pulsating modes of operation are possible. PMID:12703910

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

    International Nuclear Information System (INIS)

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-02-15

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

  1. Ternary europium mesoporous polymeric hybrid materials Eu(β-diketonate)3pvpd-SBA-15(16): host–guest construction, characterization and photoluminescence

    International Nuclear Information System (INIS)

    Novel organic–inorganic mesoporous luminescent polymeric hybrid materials containing europium(III) complexes incorporated to mesoporous silica SBA-15/SBA-16 have been prepared by simple physical doping (impregnation) methods, followed by the addition polymerization reaction of the monomer 4-vinylpyridine (vpd) extending along the mesoporous channels. The precursor europium(III) complexes are synthesized by β-diketonate (β-diketonate=2-thenoyltrifluoroacetonate (tta), hexafluoroacetylacetonate (hfac), trifluoroacetylacetonate (taa)) and monomer 4-vinylpyridine (vpd) coordinated to Eu3+, and SBA-15/SBA-16 are obtained via a sol–gel process. After the physical doping and the polymerization reaction, the final ternary materials Eu(β-diketonate)3pvpd-SBA-15/Eu(β-diketonate)3pvpd-SBA-16 (β-diketonate=tta, hfac, taa) are received. The physical properties and espeically the photoluminescence of these hybrids are characterized, and the XRD and BET results reveal that all of these hybrid materials have uniformity in the mesostructure. The detailed luminescence investigation on all the materials show that Eu(tta)3pvpd-SBA-16 have the highest luminescence intensity and the materials with taa ligands have longer lifetimes. - Grapical abstract: Luminescent mesoporous polymeric hybrid materials containing europium complexes hydrogen bonding to silica SBA-15/SBA-16 followed by the addition polymerization reaction of 4-vinylpyridine (vpd) extending along the mesoporous channels. Highlights: ► Functional mesoporous with simple impregnation method. ► New lanthanide mesoporous hybrids with polymer ligands. ► Luminescence in visible region.

  2. Substrate inhibition in the heterogeneous catalyzed aldol condensation: A mechanistic study of supported organocatalysts

    Energy Technology Data Exchange (ETDEWEB)

    Kandel, Kapil; Althaus, Stacey M.; Peeraphatdit, Chorthip; Kobayashi, Takeshi; Trewyn, Brian G.; Pruski, Marek; Slowing, Igor I.

    2012-05-23

    In this study, we demonstrate how materials science can be combined with the established methods of organic chemistry to find mechanistic bottlenecks and redesign heterogeneous catalysts for improved performance. By using solid-state NMR, infrared spectroscopy, surface and kinetic analysis, we prove the existence of a substrate inhibition in the aldol condensation catalyzed by heterogeneous amines. We show that modifying the structure of the supported amines according to the proposed mechanism dramatically enhances the activity of the heterogeneous catalyst. We also provide evidence that the reaction benefits significantly from the surface chemistry of the silica support, which plays the role of a co-catalyst, giving activities up to two orders of magnitude larger than those of homogeneous amines. This study confirms that the optimization of a heterogeneous catalyst depends as much on obtaining organic mechanistic information as it does on controlling the structure of the support.

  3. 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; Andersen, Jens Enevold Thaulov; Pratsinis, Sotiris E.; Grunwaldt, Jan-Dierk

    2010-01-01

    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...... catalysis. 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...

  4. Copper-catalyzed coupling of oxime acetates with sodium sulfinates: an efficient synthesis of sulfone derivatives.

    Science.gov (United States)

    Tang, Xiaodong; Huang, Liangbin; Xu, Yanli; Yang, Jidan; Wu, Wanqing; Jiang, Huanfeng

    2014-04-14

    Sulfone derivatives are important synthetic intermediates. However, the general method for their preparation is through traditional coupling reaction: the alkylation of sodium sulfinates with phenacyl halides. Based on our previous work on sodium sulfinates and oxime acetates, we herein report a novel method for sulfone derivatives by oxidative coupling with sodium sulfinates and oxime acetates using copper as catalyst. The sulfonylvinylamine products could be formed in excellent yields. Upon hydrolysis by silica gel in CH2 Cl2 , β-ketosulfones could also be efficiently constructed. Various sulfonylvinylamines and β-ketosulfones were obtained in good to excellent yields under the optimized reaction conditions. Mechanistic studies indicated that this transformation involved copper-catalyzed N-O bond cleavage, activation of a vinyl sp(2) C-H bond, and C-S bond formation. The oxime acetates act as both a substrate and an oxidant, thus the reaction needs no additional oxidants or additives. PMID:24677481

  5. Nanomechanical testing of polymeric nanofibers

    Science.gov (United States)

    Tan, E. P. S.; Lim, C. T.

    2005-04-01

    Biodegradable polymeric nanofibrous scaffold comprises individual nanofibers where their stiffnesses can promote or undermine the various cellular functions as well as structural integrity of the scaffold. As such, there is a need to investigate the nanomechanical properties of these individual nanofibers. However, conducting mechanical tests of individual fibers at the nanometer scale can pose great challenges and difficulties. Here, we present novel techniques to perform nanomechanical testing of individual polymeric nanofibers. For demonstration of the nano tensile tests, polycaprolactone (PCL) nanofibers were produced via electrospinning. These fibers were deposited across two parallel edges of a cardboard frame so that a single nanofiber can be isolated for tensile test using a nano tensile tester. For nanoscale three-point bend test, a Poly (L-lactic acid) (PLLA) nanofiber was suspended across a microsized groove etched on a silicon wafer. An atomic force microscope (AFM) tip was then used to apply a point load on the mid-span of the suspended fiber. Beam bending theory was then used to calculate the elastic modulus of the nanofiber. For nanoindentation test, a PLLA nanofiber was deposited on a mica substrate and an AFM tip used to indent the nanofiber. Modified Hertz theory for normal contact was then used to evaluate the elastic modulus of the nanofiber.

  6. Non-occupational exposure to silica dust

    Directory of Open Access Journals (Sweden)

    L J Bhagia

    2012-01-01

    Full Text Available Occupational exposure to silica occurs at workplaces in factories like quartz crushing facilities (silica flour milling, agate, ceramic, slate pencil, glass, stone quarries and mines, etc., Non-occupational exposure to silica dust can be from industrial sources in the vicinity of the industry as well as non-industrial sources. Recently, public concern regarding non-occupational or ambient exposure to crystalline silica has emerged making it important to gather information available on non-occupational exposures to silica dust and non-occupational silicosis. This paper reviews various non-occupational exposures reported in literature including some studies by the author. Methodology used in assessment of non-occupational exposures, standards for non-occupational exposures to silica dust and indirect estimation of cumulative risk % are also discussed.

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

    Directory of Open Access Journals (Sweden)

    2007-02-01

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

  8. Silica-based cationic bilayers as immunoadjuvants

    OpenAIRE

    Carmona-Ribeiro Ana M; da Costa Maria; Faquim-Mauro Eliana; Santana Mariana RA; Lincopan Nilton

    2009-01-01

    Abstract Background Silica particles cationized by dioctadecyldimethylammonium bromide (DODAB) bilayer were previously described. This work shows the efficiency of these particulates for antigen adsorption and presentation to the immune system and proves the concept that silica-based cationic bilayers exhibit better performance than alum regarding colloid stability and cellular immune responses for vaccine design. Results Firstly, the silica/DODAB assembly was characterized at 1 mM NaCl, pH 6...

  9. Mesoporous Silica from Rice Husk Ash

    OpenAIRE

    V.R. Shelke; S.S. Bhagade; S.A. Mandavgane

    2011-01-01

    Mesoporous silica is used as a raw material in several areas: in preparation of catalysts, in inks, as a concrete hardening accelerator, as a component of detergents and soaps, as a refractory constituent etc. Sodium silicate is produced by reacting rice hull ash (RHA) with aqueous NaOH and silica is precipitated from the sodium silicate by acidification. In the present work, conversion of about 90% of silica contained in RHA into sodium silicate was achieved in an open system at temperatures...

  10. Influence of Silica Fume on Normal Concrete

    OpenAIRE

    Debabrata Pradhan

    2013-01-01

    The incorporation of silica fume into the normal concrete is a routine one in the present days to produce the tailor made high strength and high performance concrete. The design parameters are increasing with the incorporation of silica fume in conventional concrete and the mix proportioning is becoming complex. The main objective of this paper has been made to investigate the different mechanical properties like compressive strength, compacting factor, slump of concrete incorporating silica ...

  11. Spherical Resorcinol-Formaldehyde Synthesis by Inverse Suspension Polymerization

    International Nuclear Information System (INIS)

    Base catalyzed sol-gel polycondensation of resorcinol (1,3-dihydroxybenzene) with formaldehyde by inverse suspension polymerization leads to the formation of uniform, highly cross-linked, translucent, spherical gels, which have increased selectivity and capacity for cesium ion removal from high alkaline solutions. Because of its high selectivity for cesium ion, resorcinol-formaldehyde (R-F) resins are being considered for process scale column radioactive cesium removal by ion-exchange at the Waste Treatment and Immobilization Plant (WTP), which is now under construction at the Hanford site. Other specialty resins such as Superlig(regsign) 644 have been ground and sieved and column tested for process scale radioactive cesium removal but show high pressure drops across the resin bed during transition from column regeneration to loading and elution. Furthermore, van Deemter considerations indicate better displacement column chromatography by the use of spherical particle beads rather than irregularly shaped ground or granular particles. In our studies batch contact equilibrium experiments using a high alkaline simulant show a definite increase in cesium loading onto spherical R-F resin. Distribution coefficient (Kd) values ranged from 777 to 429 mL/g in the presence of 0.1M and 0.7M potassium ions, respectively. Though other techniques for making R-F resins have been employed, to our knowledge no one has made spherical R-F resins by inverse suspension polymerization. Moreover, in this study we discuss the data comparisons to known algebraic isotherms used to evaluate ion-exchange resins for WTP plant scale cesium removal operations

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

    Science.gov (United States)

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

    2014-09-01

    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.

  13. POLYMERIC NANOPARTICLES FROM SUPERCRITICAL CO2 MICROEMULSION POLYMERIZATION

    Institute of Scientific and Technical Information of China (English)

    Wei-jun Ye; Jason S. Keiper; Joseph M. DeSimone

    2006-01-01

    Herein, we reported the microemulsion polymerization in supercritical carbon dioxide. With the aid of an anionic phosphate fluorosurfactant (bis-[2-(F-hexyl)ethyl]phosphate sodium), water-soluble/CO2-insoluble acryloxyethyltrimethyl ammonium chloride monomer and N,N'-methylene-bisacrylamide cross-linker were solubilized into CO2 continuous phase via the formation of water-in-CO2 (w/c) microemulsion water pools. Initiated by a CO2-soluble initiator, 2,2'-azo-bisisobutyronitrile (AIBN), cross-linked poly(acryloxyethyltrimethyl ammonium chloride) particles were produced and stabilized in these w/c internal water pools. Nano-sized particles with sizes less than 20 nm in diameter and narrow particle size distributions were obtained.

  14. Parameters critical to muon-catalyzed fusion

    International Nuclear Information System (INIS)

    We have demonstrated that muon catalysis cycling rates increase rapidly with increasing deuterium-tritium gas temperatures and densities. Furthermore, muon-capture losses are significantly smaller than predicted before the experiments. There remains a significant gap between observation and theoretical expectation for the muon-alpha sticking probability in dense d-t mixtures. We have been able to achieve muon-catalyzed yields of 150 fusion/muon (average). While the fusion energy thereby released significantly exceeds expectations, enhancements by nearly a factor of twenty would be needed to realize energy applications for a pure (non-hybrid) muon-catalyzed fusion reactor. The process could be useful in tritium-breeding schemes. We have also explored a new form of cold nuclear fusion which occurs when hydrogen isotopes are loaded into metals. 22 refs., 10 figs

  15. Cold fusion catalyzed by muons and electrons

    International Nuclear Information System (INIS)

    Two alternative methods have been suggested to produce fusion power at low temperature. The first, muon catalyzed fusion or MCF, uses muons to spontaneously catalyze fusion through the muon mesomolecule formation. Unfortunately, this method fails to generate enough fusion energy to supply the muons, by a factor of about ten. The physics of MCF is discussed, and a possible approach to increasing the number of MCF fusions generated by each muon is mentioned. The second method, which has become known as ''Cold Fusion,'' involves catalysis by electrons in electrolytic cells. The physics of this process, if it exists, is more mysterious than MCF. However, it now appears to be an artifact, the claims for its reality resting largely on experimental errors occurring in rather delicate experiments. However, a very low level of such fusion claimed by Jones may be real. Experiments in cold fusion will also be discussed

  16. Palladium-Catalyzed Environmentally Benign Acylation.

    Science.gov (United States)

    Suchand, Basuli; Satyanarayana, Gedu

    2016-08-01

    Recent trends in research have gained an orientation toward developing efficient strategies using innocuous reagents. The earlier reported transition-metal-catalyzed carbonylations involved either toxic carbon monoxide (CO) gas as carbonylating agent or functional-group-assisted ortho sp(2) C-H activation (i.e., ortho acylation) or carbonylation by activation of the carbonyl group (i.e., via the formation of enamines). Contradicting these methods, here we describe an environmentally benign process, [Pd]-catalyzed direct carbonylation starting from simple and commercially available iodo arenes and aldehydes, for the synthesis of a wide variety of ketones. Moreover, this method comprises direct coupling of iodoarenes with aldehydes without activation of the carbonyl and also without directing group assistance. Significantly, the strategy was successfully applied to the synthesis n-butylphthalide and pitofenone. PMID:27377566

  17. Hydrophobic transition in porous amorphous silica

    International Nuclear Information System (INIS)

    Realistic models of amorphous silica surfaces with different silanol densities are built using Monte Carlo annealing. Water-silica interfaces are characterized by their energy interaction maps, adsorption isotherms, self-diffusion coefficients, and Poiseuille flows. A hydrophilic to hydrophobic transition appears as the surface becomes purely siliceous. These results imply significant consequences for the description of surfaces. First, realistic models are required for amorphous silica interfaces. Second, experimental amorphous silica hydrophilicity is attributed to charged or uncharged defects, and not to amorphousness. In addition, auto irradiation in nuclear waste glass releases hydrogen atoms from silanol groups and can induce such a transition. (authors)

  18. Airborne silica levels in an urban area

    International Nuclear Information System (INIS)

    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 μg/m3. The mean diameter of silica particles ranged from 0.3 to 10.5 μm, with more than 87% of particles having a diameter of less than 2.5 μm. 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

  19. Cellular membrane trafficking of mesoporous silica nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

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

    2012-01-01

    This dissertation mainly focuses on the investigation of the cellular membrane trafficking of mesoporous silica nanoparticles. We are interested in the study of endocytosis and exocytosis behaviors of mesoporous silica nanoparticles with desired surface functionality. The relationship between mesoporous silica nanoparticles and membrane trafficking of cells, either cancerous cells or normal cells was examined. Since mesoporous silica nanoparticles were applied in many drug delivery cases, the endocytotic efficiency of mesoporous silica nanoparticles needs to be investigated in more details in order to design the cellular drug delivery system in the controlled way. It is well known that cells can engulf some molecules outside of the cells through a receptor-ligand associated endocytosis. We are interested to determine if those biomolecules binding to cell surface receptors can be utilized on mesoporous silica nanoparticle materials to improve the uptake efficiency or govern the mechanism of endocytosis of mesoporous silica nanoparticles. Arginine-glycine-aspartate (RGD) is a small peptide recognized by cell integrin receptors and it was reported that avidin internalization was highly promoted by tumor lectin. Both RGD and avidin were linked to the surface of mesoporous silica nanoparticle materials to investigate the effect of receptor-associated biomolecule on cellular endocytosis efficiency. The effect of ligand types, ligand conformation and ligand density were discussed in Chapter 2 and 3. Furthermore, the exocytosis of mesoporous silica nanoparticles is very attractive for biological applications. The cellular protein sequestration study of mesoporous silica nanoparticles was examined for further information of the intracellular pathway of endocytosed mesoporous silica nanoparticle materials. The surface functionality of mesoporous silica nanoparticle materials demonstrated selectivity among the materials and cancer and normal cell lines. We aimed to determine

  20. Practical Hydrogen Loading of Air Silica Fibres

    DEFF Research Database (Denmark)

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

    2005-01-01

    A method for hydrogen-loading air-silica optical fibres has been developed allowing out-diffusion times comparable to standard step-index fibres. Examples of the first grating written in Ge-doped air-silica fibres using a 266nm UV-laser are shown.......A method for hydrogen-loading air-silica optical fibres has been developed allowing out-diffusion times comparable to standard step-index fibres. Examples of the first grating written in Ge-doped air-silica fibres using a 266nm UV-laser are shown....

  1. Spring-loaded polymeric gel actuators

    Science.gov (United States)

    Shahinpoor, M.

    1995-02-14

    Spring-loaded electrically controllable polymeric gel actuators are disclosed. The polymeric gels can be polyvinyl alcohol, polyacrylic acid, or polyacrylamide, and are contained in an electrolytic solvent bath such as water plus acetone. The action of the gel is mechanically biased, allowing the expansive and contractile forces to be optimized for specific applications. 5 figs.

  2. Inflation and Instability of a Polymeric Membrane

    DEFF Research Database (Denmark)

    Neergaard, Jesper; Hassager, Ole

    1999-01-01

    We consider an axisymmetric polymeric membrane inflated by a uniform pressure difference acting across the membrane. The polymeric materialis described by an arbitrary combination of a viscoelastic and a purely viscous component to the stress. Some viscoelastic materials described by a Mooney...

  3. Ion exchange behaviour of polymeric zirconium cations

    International Nuclear Information System (INIS)

    Polymeric zirconium cations formed in weakly acid solutions (pH2) are taken up strongly into macroporous cation exchange resins, while uptake into normal cation exchange resins (pore diameter about 1 nm) is low. Macroporous cation exchange resins loaded with polymeric Zr cations are shown to function as ligand exchange sorbents. (Authors)

  4. Transition-metal catalyzed valorization of lignin: the key to a sustainable carbon-neutral future.

    Science.gov (United States)

    Kärkäs, Markus D; Matsuura, Bryan S; Monos, Timothy M; Magallanes, Gabriel; Stephenson, Corey R J

    2016-02-14

    The development of a sustainable, carbon-neutral biorefinery has emerged as a prominent scientific and engineering goal of the 21st century. As petroleum has become less accessible, biomass-based carbon sources have been investigated for utility in fuel production and commodity chemical manufacturing. One underutilized biomaterial is lignin; however, its highly crosslinked and randomly polymerized composition have rendered this biopolymer recalcitrant to existing chemical processing. More recently, insight into lignin's molecular structure has reinvigorated chemists to develop catalytic methods for lignin depolymerization. This review examines the development of transition-metal catalyzed reactions and the insights shared between the homogeneous and heterogeneous catalytic systems towards the ultimate goal of valorizing lignin to produce value-added products. PMID:26732312

  5. Copolymerization of Ethylene and Vinyl Amino Acidic Ester Catalyzed by Titanium and Zirconium Complexes

    Directory of Open Access Journals (Sweden)

    Jing Wang

    2015-10-01

    Full Text Available A series of titanium and zirconium complexes with ligands based on di-isopropyl phosphorus-phenylamine and their derivatives were synthesized and characterized. These catalysts were utilized to catalyze the copolymerization of ethylene with N-acetyl-O-(dec-9-enyl-L-tyrosine ethyl ester with high catalytic activity of 6.63 × 104 g P (mol Ti−1 h−1 after activation by methylaluminoxane (MAO. The effects of ligand structure, metal atoms (Ti, Zr and polymerization conditions were investigated in detail. The obtained polymers were characterized by 13C-NMR, DSC, FT-IR, and GPC. The results showed that the obtained copolymer had a high comonomer incorporation rate of 2.56 mol % within the copolymer chain. The melting temperature of the copolymer was up to 138.9 °C, higher than that of the obtained homopolyethylene.

  6. Preliminary Study on Lipase-catalyzed Synthesis of Polyesters Containing L-Malic Acid Units

    Institute of Scientific and Technical Information of China (English)

    Da Hu YAO; Guang Ji LI

    2006-01-01

    Terpolymer of 1, 8-octanediol, adipic acid, and L-malic acid was synthesized via a lipase-catalyzed direct polycondensation. The products were characterized by GPC and 1H NMR.The results indicated that the molecular weight of the prepared polymers decreased with increasing L-malic acid content in the monomer feed ratio, and that change in the L-malic acid content from 0to 20 mol % did not remarkably influenced on the molecular weight distribution Mw/Mn of the prepared samples. The 1H NMR spectra of the obtained copolymer samples showed that hydroxyl groups of L-malic acid did not take part in the polymerization reaction.

  7. Copper Catalyzed Oceanic Methyl Halide Production

    OpenAIRE

    Robin Kim, Jae Yun; Rhew, Robert

    2014-01-01

    Methyl halides are found in all of Earth’s biomes, produced naturally or through manmade means. Their presence in the atmosphere is problematic, as they catalyze depletion of stratospheric ozone. To understand the full environmental impact of these compounds, it is important to identify their chemical cycling processes. Iron increases methyl halide production in soils and oceans, yet copper’s influence remains unknown despite its similar chemical oxidation properties to iron. I experimentally...

  8. Antibody-Catalyzed Degradation of Cocaine

    Science.gov (United States)

    Landry, Donald W.; Zhao, Kang; Yang, Ginger X.-Q.; Glickman, Michael; Georgiadis, Taxiarchis M.

    1993-03-01

    Immunization with a phosphonate monoester transition-state analog of cocaine provided monoclonal antibodies capable of catalyzing the hydrolysis of the cocaine benzoyl ester group. An assay for the degradation of radiolabeled cocaine identified active enzymes. Benzoyl esterolysis yields ecgonine methyl ester and benzoic acid, fragments devoid of cocaine's stimulant activity. Passive immunization with such an artificial enzyme could provide a treatment for dependence by blunting reinforcement.

  9. Palladium(II)-Catalyzed Coupling Reactions

    OpenAIRE

    Lindh, Jonas

    2010-01-01

    Sustainable chemical processes are becoming increasingly important in all fields of synthetic chemistry. Catalysis can play an important role in developing environmentally benign chemical processes, and transition metals have an important role to play in the area of green chemistry. In particular, palladium(II) catalysis includes many key features for successful green chemistry methods, as demonstrated by a number of eco-friendly oxidation reactions catalyzed by palladium(II). The aim of the ...

  10. Palladium-catalyzed oxidative carbonylation reactions.

    Science.gov (United States)

    Wu, Xiao-Feng; Neumann, Helfried; Beller, Matthias

    2013-02-01

    Palladium-catalyzed coupling reactions have become a powerful tool for advanced organic synthesis. This type of reaction is of significant value for the preparation of pharmaceuticals, agrochemicals, as well as advanced materials. Both, academic as well as industrial laboratories continuously investigate new applications of the different methodologies. Clearly, this area constitutes one of the major topics in homogeneous catalysis and organic synthesis. Among the different palladium-catalyzed coupling reactions, several carbonylations have been developed and widely used in organic syntheses and are even applied in the pharmaceutical industry on ton-scale. Furthermore, methodologies such as the carbonylative Suzuki and Sonogashira reactions allow for the preparation of interesting building blocks, which can be easily refined further on. Although carbonylative coupling reactions of aryl halides have been well established, palladium-catalyzed oxidative carbonylation reactions are also interesting. Compared with the reactions of aryl halides, oxidative carbonylation reactions offer an interesting pathway. The oxidative addition step could be potentially avoided in oxidative reactions, but only few reviews exist in this area. In this Minireview, we summarize the recent development in the oxidative carbonylation reactions. PMID:23307763

  11. Silica- and perfluoro-based nanoparticular polymeric network for the skin protection against organophosphates

    Science.gov (United States)

    Bignon, Cécile; Amigoni, Sonia; Guittard, Frédéric

    2016-06-01

    Due to their small size, nanoparticles possess unique properties such as high absorption or pollutant degradation, making them useful for skin protection against chemicals. By covalently grafting to a hydrophobically modified alkali-soluble emulsion (HASE), a thickening polymer, nanoparticles can be dispersed as gels in water at neutral pH. With this modification the potential aggregation and toxicity typical of nanoparticles are avoided. Once integrated into a cosmetic formula, these gels can be spread onto skin to afford protective barriers. This paper reports (1) the benefit of SiO2 nanoparticles grafted to a perfluorocarbon HASE polymer (HASE-F/SiO2) which is then integrated into a new formula and it is influence on the efficacy against the penetration of paraoxone, as well as (2) the stability of the barrier cream (BC) and (3) how the homogenous dispersion of nanoparticles maintains a high active surface area of SiO2 nanoparticles. The efficiency of the new active topical skin protectant was proved at different doses (5–27 mg cm‑2), under occlusive conditions and validated on human skin. Therefore, the combination of the HASE-F polymer, nanoparticle grafting, and polyvinylpyrrolidone and glycerol formulation led to a very effective active BC.

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

    OpenAIRE

    Smith, Joseph V.

    1998-01-01

    Catalysis at mineral surfaces might generate replicating biopolymers from simple chemicals supplied by meteorites, volcanic gases, and photochemical gas reactions. Many ideas are implausible in detail because the proposed mineral surfaces strongly prefer water and other ionic species to organic ones. The molecular sieve silicalite (Union Carbide; = Al-free Mobil ZSM-5 zeolite) has a three-dimensional, 10-ring channel system whose electrically neutral Si-O surface strongly adsorbs organic spec...

  13. Fluid Effects in Polymers and Polymeric Composites

    CERN Document Server

    Weitsman, Y Jack

    2012-01-01

    Fluid Effects in Polymers and Polymeric Composites, written by the late Dr. Y. Jack Weitsman, addresses the wide range of parameters that affect the interaction of fluids with polymers and polymeric composites. The book aims at broadening the scope of available data, mostly limited up to this time to weight-gain recordings of fluid ingress into polymers and composites, to the practical circumstances of fluctuating exposure. Various forms of experimental data are given, in conjunction with theoretical models derived from basic scientific principles, and correlated with severity of exposure conditions and interpreted by means of rationally based theoretical models. The practical implications of the effects of fluids are discussed. The issue of fluid effects on polymers and polymeric composites is of concern to engineers and scientists active in aerospace and naval structures, as an increasing portion of these structures are made of polymeric composites and employ polymeric adhesives as a joining device. While...

  14. Synthesis of star and H-shape polymers via a combination of cobalt-mediated radical polymerization and nitrone-mediated radical coupling reactions

    OpenAIRE

    Detrembleur, Christophe; Debuigne, Antoine; Altintas, Ozcan; Conradi, Matthias; Wong, Edgar H. H.; Jerome, Christine; Barner-Kowollik, Christopher; Junkers, Thomas

    2012-01-01

    Via consecutive cobalt-mediated radical polymerization (CMRP), nitrone-mediated radical coupling (NMRC) and copper catalyzed azide-alkyne cycloaddition (CuAAC), polymers with mikto-arm star and H-shape architecture were synthesized. Poly(vinyl acetate)(40)-block-poly(acrylonitrile)(78)-Co(acac)(2) polymers were synthesized via CMRC and subsequently coupled using an alkyne functional nitrone. The coupling efficiency of the NMRC process was assessed employing N-tert-butyl alpha-phenyl nitrone (...

  15. HEALTH EFFECTS OF INHALED CRYSTALLINE AND AMORPHOUS SILICA

    Science.gov (United States)

    Recently, public concern regarding nonoccupational or ambient silica exposure, mainly to crystalline silica, has emerged making it important to evaluate background and ambient concentrations. Ambient emissions of silica rarely are estimated or measured in air pollution studies of...

  16. Radiation Polymerization of Acetylene Hydrocarbons. Special Features

    International Nuclear Information System (INIS)

    The synthesis and study of the properties of polymers with conjugated bond systems offers new and extremely promising prospects in the chemistry of high molecular compounds. A high degree of de-localization of p-electrons in the macromolecule is characteristic of such polymer systems. The decrease in the energy excited in the triplet state, just like the diminished ionization potential with large conjugated bonds, conditions the semiconductor and specific magnetic properties of such compounds. In addition, polymer systems with conjugated bonds have proved to be extremely effective stabilizers in the thermo- and photo-oxidation destruction of polymers. The radiation polymerization of acetylene derivatives offers one suitable method of obtaining such polymers and is the only one which ensures that the polymers obtained are free of contamination from initiators at low temperatures. The kinetics of the radiation polymerization of ethynyl benzene and other acetylene derivatives have a number of features typical of ion polymerization quite rare in radical polymerization (speed of polymerization linearly proportional to speed of initiation: very low activation energy; no oxygen inhibition). Nevertheless this polymerization is obviously radical. We reached that conclusion on the basis of a study of polymerization initiation for acetylene hydrocarbons by typical radical initiators - benzoyl peroxide and the dinitrile of azoisobutyric acid. They investigated the kinetic features and mechanism of peroxide decomposition in the presence of acetylene hydrocarbons (e.g. ethynyl benzene, deutero-ethynyl benzene and phenylpropyne). The kinetics of radiation co-polymerization of ethynyl benzene with different vinyl monomers and the composition of copolymers in different initial mixtures were also studied. These data and the results of a study of the kinetics of inhibited ethynyl benzene polymerization (benzoquinone initiator) indicate a small reactivity capacity of the ethynyl

  17. Enhancement of T1 and T2 relaxation by paramagnetic silica-coated nanocrystals

    International Nuclear Information System (INIS)

    We present the first comprehensive investigation on water-soluble nanoparticles embedded into a paramagnetic shell and their properties as an MRI contrast agent. The nanoprobes are constructed with an inorganic core embedded into an ultra-thin silica shell covalently linked to chelated Gd3+ paramagnetic ions that act as an MRI contrast agent. The chelator contains the molecule DOTA and the inorganic core contains a fluorescent CdSe/ZnS qdots in Au nanoparticles. Optical properties of the cores (fluorescence emission or plasmon position) are not affected by the neither the silica shell nor the presence of the chelated paramagnetic ions. The resulting complex is a MRI/fluorescence probe with a diameter of 8 to 15 nm. This probe is highly soluble in high ionic strength buffers at pH ranging from ∼4 to 11. In MRI experiments at clinical field strengths of 60 MHz, the QDs probes posses spin-lattice (T1) and a spin-spin (T2) relaxivities of 1018.6 +/- 19.4 mM-1 s-1 and 2438.1 +/- 46.3 mM-1 s-1 respectively for probes having ∼8 nm. This increase in relaxivity has been correlated to the number of paramagnetic ions covalently linked to the silica shell, ranging from approximately 45 to over 320. We found that each bound chelated paramagnetic species contributes by over 23 mM-1 s-1 to the total T1 and by over 54 mM-1 s-1 to the total T2 relaxivity respectively. The contrast power is modulated by the number of paramagnetic moieties linked to the silica shell and is only limited by the number of chelated paramagnetic species that can be packed on the surface. So far, the sensitivity of our probes is in the 100 nM range for 8-10 nm particles and reaches 10 nM for particles with approximately 15-18 nm in diameter. The sensitivities values in solutions are equivalent of those obtained with small superparamagnetic iron oxide nanoparticles of 7 nm diameter clustered into a 100 nm polymeric shell. A thin paramagnetic silica shell as interface with the bioworld presents several

  18. Environment-Responsive Polymeric Hydrogels

    Institute of Scientific and Technical Information of China (English)

    Zhn X. X.; M. Nichifor; Lin H.Y.; D. Avoce

    2004-01-01

    Some polymers may respond by changing their physico-chemical perperties when the environmental conditions such as pH, temperature and ionic strength are varied. For example,thermosensentive polymers can exhibit a sharp change in solubility in a solvent such as water at a certain temperature known as the lower critical solution temperature (LCST). The responsiveness of the polymeric materials has important technological implications since they can be employed for various applications. The responsiveness of such polymers can be varied by means of copolymerization, chemical modification of the polymer, or the addition of reagents into the solutions. It is interesting and important to tune predictably the responsiveness of the polymers for the different applications. The sensitivity towards the external environment can be modulated by the relative hydrophilicity of the copolymers, hence the chemical structure and composition of the comonomers used.

  19. MESO-STRUCTURED POLYMERIC HYDROGELS

    Institute of Scientific and Technical Information of China (English)

    Zhen-zhong Yang; Jian-hua Rong; Dan Li

    2003-01-01

    Meso-structured (opal and inverse opal) polymeric hydrogels of varied morphology and composition were prepared by using two methods: post-modification of the template-synthesized structured polymers and templatepolymerization of functional monomers. A polyacrylic acid based inverse opal hydrogel was chosen to demonstrate its fast pH response by changing color, which is important in designing tunable photonic crystals. Template effects of the hydrogels on controlling structure of the template-synthesized inorganic materials were discussed. The catalytic effect of acid groups inthe templates was emphasized for a preferential formation of TiO2 in the region containing acid groups, which allowed duplicating inorganic colloidal crystals from colloidal crystal hydrogels (or macroporous products from macroporous hydrogels) via one step duplication.

  20. MESO—STRUCTURED POLYMERIC HYDROGELS

    Institute of Scientific and Technical Information of China (English)

    Zhen-zhongYang; Jian-huaRong; DanLi

    2003-01-01

    Meso-structured(opal and inverse opal) polymeric hydrogels of varied morphology and composition were prepared by using two methods:post-modification of the template-synthesized structured polymers and templatepolymerization of functional monomers.A polyacrylic acid based inverse opal hydrogel was chosen to demonstrate its fast pH response by changing color,which is important in designing tunable photonic crystals.Template effects of the hydrogels on controlling structure of the template-synthesized inorganic materials were discussed.The catalytic effect of acid groups in the templates was emphasized for a preferential formation of TiO2 in the region containing acid groups,which allowed duplicating inorganic colloidal crystals from colloidal crystal hydrogels (or macroporous products from macroporous hydrogels) via one step duplication.