Sample records for catalyzed silica polymerization

  1. Silica nanospheres formation induced by peroxidase-catalyzed phenol polymerization

    Institute of Scientific and Technical Information of China (English)


    To examine whether lignin-like compound is correlated with silica precipitation in grass, a series of simulated chemical experiments were carried out at ambient temperature and pressure, close to cell wall pH, with phenol polymerization catalyzed by peroxidase in silicon solution. The experiments showed that phenol polymer (a kind of lignin-like substance) caused silica nanosphere precipitation similar to those caused by protein in diatom cell wall previously reported by other authors. The sphere diameter varied with different kinds of phenol and the concentrations of phenol and silicon. Silicon precipitation had phenol and silicon saturation effect, meaning that when the concentration ratio of soluble silicon to phenol exceeded a certain value, the amount of silicon precipitation would decrease.

  2. 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


    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

  3. Kinetics of silica polymerization

    Energy Technology Data Exchange (ETDEWEB)

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


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

  4. Radiation-induced polymerization and grafting of {beta}(-)pinene on silica surface

    Energy Technology Data Exchange (ETDEWEB)

    Cataldo, Franco [Lupi Chemical Research Institute, Via Casilina 1626/A, 00133 Rome (Italy)], E-mail:; Ursini, Ornella; Lilla, Edo; Angelini, Giancarlo [CNR, Institute of Chemical Metodologies, Area della Ricerca di Roma 1, Monterotondo Scalo, Rome (Italy)


    Poly-{beta}-pinene (pBp) was obtained on silica surface by {gamma} radiation-induced polymerization of {beta}(-)pinene in presence of silica gel with a specific surface area of 300 m{sup 2}/g. Different radiation doses were employed in the range 50-332 kGy. The pBp-silica hybrid samples obtained have been characterized by FT-IR spectroscopy and the amount of pBp on silica surface has been determined both by gravimetric and TGA measurements. The fraction of pBp chemically grafted on silica surface has been determined by the extraction of the pBp-silica hybrid with boiling toluene and was found to be 10-20% of the total pBp formed on silica surface. The optical activity of pBp extracted from the hybrid was studied by polarimetric measurements and found slightly lower than the typical specific optical rotation of pBp polymerized in bulk with radiation. The thermal stability of the pBp-silica hybrid materials was studied by thermogravimetric and differential thermal analysis. The results show lower thermal stability for the pBp-silica hybrid in comparison to pure pBp. Evidently, silica catalyzes the thermal decomposition of pBp at lower temperatures. Use of the pBp-silica hybrid as stationary phase for liquid chromatography for chiral separations has been proposed.

  5. Preparation of polyamide 6/silica nanocomposites from silica surface initiated ring-opening anionic polymerization

    Directory of Open Access Journals (Sweden)


    Full Text Available Polyamide 6/silica nanocomposites were synthesized by in situ ring-opening anionic polymerization of ε-caprolactam in the presence of sodium caprolactamate as a catalyst and caprolactam-functionalized silica as an initiator. The initiator precursor, isocyanate-functionalized silica, was prepared by directly reacting commercial silica with excess toluene 2,4-diisocyanate. This polymerization was found to occur in a highly efficient manner at relatively low reaction temperature (170°C and short reaction times (6 h. FTIR spectroscopy was utilized to follow the introduction and consumption of isocyanate groups on the silica surface. Thermogravimetric analysis indicated that the polyamide 6 was successfully grown from the silica surface. Transmission electron microscopy was utilized to image polymer-functionalized silica, showing fine dispersion of silica particles and their size ranging from 20 to 40 nm.

  6. Polymerization of phenols catalyzed by peroxidase in nonaqueous media

    Energy Technology Data Exchange (ETDEWEB)

    Dordick, J.S.; Marletta, M.A.; Klibanov, A.M.


    Polymers produced by horseradish-peroxidase-catalyzed coupling of phenols have been explored as potential substitutes for phenol-formaldehyde resins. To overcome low substrate solubilities and product molecular weights in water, enzymatic polymerizations in aqueous-organic mixtures have been examined. Peroxidase vigorously polymerizes a number of phenols in mixtures of water with water-miscible solvents such as dioxane, acetone, dimethylformamide, and methyl formate with the solvent content up to 95%. As a result, various phenolic polymers with average molecular weights from 400 to 2.6 x 10/sup 4/ D were obtained depending on the reaction medium composition and the nature of the phenol. Peroxidase-catalyzed copolymerization of different phenols in 85% dioxane was demonstrated. Poly(p-phenylphenol) and poly(p-cresol) were enzymatically prepared on a gram scale. They had much higher melting points, and in addition, poly(p-phenylphenol) was found to have a much higher electrical conductivity than phenol-formaldehyde resins.

  7. 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


    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

  8. Kinetics of phenolic polymerization catalyzed by peroxidase in organic media

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Y.P.; Huang, G.L; Yu, Y.T. [Nankai Univ., Tianjin (China). Inst. for Molecular Biology


    Phenolic polymerization was carried out by enzymatic catalysis in organic media, and its kinetics was studied by using high-pressure liquid chromatography (HPLC). Phenols and aromatic amines with electron-withdrawing groups could hardly be polymerized by HRP catalysis, but phenols and aromatic amines with electron-donating groups could easily by polymerized. The reaction rate of either the para-substituted substrate or meta-substituted substrate was higher than that of ortho-substituted substrate. When ortho-position of hydroxy group of phenols was occupied by an electron-donating group and if another electron-donating group occupied para-position of hydroxy group, the reaction rate increased. Horseradish peroxidase and lactoperoxidase could easily catalyze the polymerization, but chloroperoxidase and laccase failed to yield polymers. Metallic ions such as Mn{sup 2+}, Fe{sup 2+}, or Fe{sup 3+}, and Cu{sup 2+} could poison horseradish peroxidase to various extents, but ions such as Co{sup 2+}, Cd{sup 2+}, Zn{sup 2+}, and K{sup +} were not found to inhibit the reaction.


    Institute of Scientific and Technical Information of China (English)

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


    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.

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

    Directory of Open Access Journals (Sweden)

    Bérangère Bailly


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

  11. Plasma polymerization of acetylene onto silica: an approach to control the distribution of silica in single elastomers and immiscible blends

    NARCIS (Netherlands)

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


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

  12. Polymeric bionanocomposite cast thin films with in situ laccase-catalyzed polymerization of dopamine for biosensing and biofuel cell applications. (United States)

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


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

  13. Rate equations for sodium catalyzed amorphous silica dissolution (United States)

    Rimstidt, J. Donald; Zhang, Yilun; Zhu, Chen


    Newly measured amorphous silica dissolution rate data were combined with data from the literature to produce an equation that predicts the dissolution flux (J, mol/m2 s) of amorphous silica as a function of temperature (T, K), sodium concentration (mNa+, molal), and hydrogen ion activity (aH+).

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

    Institute of Scientific and Technical Information of China (English)


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

  15. Polymerization of isoprene catalyzed by neodymium heterocyclic Schiff base complex

    Institute of Scientific and Technical Information of China (English)

    Lei Zhang; Xu Feng Ni; Wei Lin Sun; Zhi Quan Shen


    Neodymium-based heterocyclic Schiff base complex was prepared and applied for the coordination polymerization of isoprene. This complex polymerized isoprene to afford products featuring high cis-1,4 stereospecificity (ca. 95%) and high molecular weight (ca. 105) in the presence of the triisobutyl aluminium (AliBu3) as cocatalyst. The microstructure of obtained polyisoprene was investigated by FTIR, 1H NMR. Two different kinds of active centers in the catalyst system were examined by GPC method.

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

    Directory of Open Access Journals (Sweden)

    Shen Ruoping


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

  17. Acid-catalyzed Furfuryl Alcohol Polymerization: Characterizations of Molecular Structure and Thermodynamic Properties

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Taejin; Assary, Rajeev A; Marshall, Christopher L; Gosztola, David J.; Curtiss, Larry A; Stair, Peter C


    The liquid-phase polymerization of furfuryl alcohol catalyzed by sulfuric acid catalysts and the identities of molecular intermediates were investigated by using Raman spectroscopy and density functional theory calculation. At room temperature, with an acid catalyst, a vigorous furfuryl alcohol polymerization reaction was observed, whereas even at a high water concentration, furfuryl alcohol was very stable in the absence of an acid catalyst. Theoretical studies were carried out to investigate the thermodynamics of protonation of furfuryl alcohol, initiation of polymerization, and formation of conjugated dienes and diketonic species by using the B3LYP level of theory. A strong aliphatic C=C band observed in the calculated and measured Raman spectra provided crucial evidence to understand the polymerization reaction mechanism. It is confirmed that the formation of a conjugated diene structure rather than a diketone structure is involved in the furfuryl alcohol polymerization reaction.

  18. Kinetics and Mechanism of Bulk Polymerization of Styrene Catalyzed by Rare Earth Catalyst

    Institute of Scientific and Technical Information of China (English)

    吴林波; 李伯耿; 李宝芳; 曹堃


    The bulk polymerization of styrene catalyzed by Nd(P204)3/MgBu2/HMPA (hexamethyl phospho-ramide) was carried out in capped glass tubes. The effects of reaction conditions on polymerization conversion and molecular weight in the range of high conversion were investigated. The molecular weight of the resultant polymers is dramatically high and its distribution is relatively narrow. The polymerization process demonstrates the feature of living polymerization and auto-acceleration phenomenon. The auto-acceleration phenomenon is attributed to the non-instantaneous formation of the active species. The experimental data suggest that chain transfer to MgBu2 is one of the factors governing the molecular weight development. A mechanism of polymerization is presented with the chain transfer process incorporated.

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

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


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

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


    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.

  1. Silica-supported Copper(Ⅱ) Catalyzed Coupling of Arylboronic Acids with Imidazoles

    Institute of Scientific and Technical Information of China (English)

    ZHANG Li-Yuan; WANG Lei


    Immobilized copper(Ⅱ) in organic-inorganic hybrid materials catalyzed Ar-N coupling of arylboronic acids with imidazoles has been developed. Arylboronic acids reacted with imidazoles smoothly in the presence of a 3-(2-aminoethylamino)propyl functionalized silica gel immobilized copper(Ⅱ) catalyst (10 mol%) in methanol without any additives and bases. The reactions generated the corresponding cross-coupling products in good yields.Furthermore, silica-supported copper can be recovered and recycled by a simple filtration procedure and used for five consecutive trials without decreases in activity.

  2. Room temperature polymerization of alkyl isocyanates catalyzed by rare earth Schiff base complexes

    Institute of Scientific and Technical Information of China (English)

    YANG XiongFa; NI XuFeng; SHEN ZhiQuan


    The polymerization of alkyl isocyanates catalyzed by rare earth chloride salen complexes/triisobutyl aluminum (Ln(H_2salen)_2Cl_3·2C_2H_7OH/Al(i-Bu)_3) at room temperature was investigated.The influences of ligand structure,catalyst composition,polymerization temperature,polymerization time,the concentration of catalyst and monomer,and the polymerization solvent on the polymerization of isocyanates were studied.It was found that under the polymerization conditions,examined La(H_2salen_A)_2Cl_3·2C_(2-)H_7OH/Al(i-Bu)_3 (H_2salen_A=N,N'-disalicylideneethylene diamine) is a fairly high efficient catalyst for the polymerization of n-hexyl isocyanate (n-HexNCO) to prepare high molecular weight poly(n-hexyl isocyanate) (PHNCO) with narrower molecular weight distribution at room temperature.PHNCO could be prepared with yield of 74.0%,number-average molecular weight (M_n) of 40.20×10~4 and MWD of 1.79 under the following optimum conditions:[Al]/[La]=30 (molar ratio),[n-HexNCO]/[La]=100 (molar ratio),[n-HexNCO]=3.43 mol/L polymerization at 20℃ for 12 h in toluene.In the same polymerization conditions,poly (n-octyl isocyanate) (PONCO) with yield of 67.3%,and poly(n-butyl isocyanate) (PBNCO) with yield of 45.5%,could be prepared respectively.The kinetics of the polymerization of n-HexNCO was also investigated and found to be first-order with respect to both monomer and catalyst concentrations.

  3. 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


    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.

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

    DEFF Research Database (Denmark)

    Monnard, Pierre-Alain; Szostak, Jack W.


    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...... elongate RNA hairpins whose 5’-overhangs served as the templating sequence. The same applies for every other pyrimidine and purine nucleobase. Moreover, the initial elongation rates were always higher in the presence of a template complementary to the nucleotide than in systems without proper base...

  5. Water and oil repellency of flexible silica-coated polymeric substrates (United States)

    Hsieh, Chien-Te; Cheng, Yu-Shun; Hsu, Shu-Min; Lin, Jia-Yi


    A facile coating technique was used for the one-step creation of silica-sphere layers onto flexible polypropylene (PP) substrates, which showed the enhanced repellency toward liquid droplets with different surface tensions, ranging from 25.6 to 72.3 mN/m. One-step solution preparation comprised the homogenous mixing of colloidal silica nanospheres and perfluoroalkyl methacrylic copolymer, and the resulting F-silica slurry was subsequently deposited over the PP films, which showed good adhesion. The flexible silica-coated polymeric film displayed a remarkable repellency toward water and oil drops, when compared with the F-coated PP flat film. The silica-stacking layers on the PP substrate generated a roughened surface, owing to the creation of bionic surface hierarchically combined with multiple-scale architecture. To clarify this, the wetted fraction was determined from Cassie-Baxter equation, and the work of adhesion, based on Young-Duprè equation, was used to examine the sliding ability of the resulting polymeric films. The cross-cut test incorporated with film bending proved the excellent adherence between silica layer and PP substrate. A satisfactory durability in water and oil immersions for 10 days showed that the resulting PP film possesses strong adhesion and better repellency for a long period, confirming a promising commercial feasibility.

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

    KAUST Repository

    Zhao, Junpeng


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


    Institute of Scientific and Technical Information of China (English)

    QIN Wei; HUANG Zhitang


    The bulk polymerization of benzonitrile catalyzed by Co (Ⅱ), Co (Ⅲ) and Fe(Ⅲ)acetylacetonate was studied. The results of kinetics study show that the rate of polymerization was proportional to first power of the concentration of catalyst and second power of the concentration of monomer.


    Institute of Scientific and Technical Information of China (English)

    QIN Wei; HUANG Zhitang


    The polymerization kinetics of 4,4'-biphenyldicarbonitrile and other substituted benzonitriles catalyzed by cobaltic acetylacetonate was studied. The structure of polymer of different substituted benzonitrile was also determined. It is found that the rate of polymerization and the structure of polymer is greatly affected by the substituent of benzonitriles.

  9. Immobilization of Chiral Ferrocenyl Ligands on Silica Gel and their Testing in Pd-catalyzed Allylic Substitution and Rh-catalyzed Hydrogenation

    Directory of Open Access Journals (Sweden)

    Duncan J. Macquarrie


    Full Text Available Five different silica gels containing two chiral ferrocenyl ligands were prepared by various synthetic routes and tested in an enantioselective Pd(0-catalyzed allylic substitution and Rh-catalyzed hydrogenation. All the prepared anchored ligands were characterized by porosimetry data, DRIFTS spectra, thermal data and AAS. The aim of the work was to compare the influence of the carrier, surface properties and immobilization strategy on the performance of the catalyst.

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

    Institute of Scientific and Technical Information of China (English)

    WAN; Xiaolong


    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

  11. Mechanism of horseradish peroxidase-catalyzed heme oxidation and polymerization (beta-hematin formation). (United States)

    Trivedi, Vishal; Chand, Prem; Maulik, Prakas R; Bandyopadhyay, Uday


    Horseradish peroxidase (HRP) catalyzes the polymerization of free heme (beta-hematin formation) through its oxidation. Heme when added to HRP compound II (FeIV=O) causes spectral shift from 417 nm (Compound II) to 402 nm (native, FeIII) indicating that heme may be oxidized via one-electron transfer. Direct evidence for one-electron oxidation of heme by HRP intermediates is provided by the appearance of an E.s.r signal of a 5,5-dimethyl-1-pyrroline N-oxide (spin trap)-heme radical adduct (a1H=14.75 G, a2H=4.0 G) in E.s.r studies. Heme-polymerization by HRP is inhibited by spin trap indicating that one-electron oxidation product of heme ultimately leads to the formation of heme-polymer. HRP, when incubated with diethyl pyrocarbonate (DEPC), a histidine specific reagent, shows concentration dependent loss of heme-polymerization indicating the role of histidine residues in the process. We suggest that HRP catalyzes the formation of heme-polymer through one-electron oxidation of free heme.

  12. Graft polymerization of styrene initiated by covalently bonded peroxide groups on silica. (United States)

    Bachmann, Stefan; Wang, Hongyu; Albert, Klaus; Partch, Richard


    The graft polymerization of styrene initiated by immobilized peroxide groups was investigated. Three different types of modification reactions were used to introduce peroxide groups which are directly attached onto the surface of two different silica supports. Silanol groups were chlorinated using thionyl chloride or tetrachlorosilane. In another reaction pathway 1,3,5-benzenetricarbonyl chloride enabled the introduction of free acid chloride residues bonded onto the surface of silica. tert-Butyl hydroperoxide (TBHP) was used to transform the chlorosilyl and the acid chloride groups into peroxide residues. In a further reaction step the covalently bonded peroxides initiated the polymerization of styrene to form grafted polystyrene directly attached onto the silica support. Solid-state 13C CP/MAS NMR spectroscopy, and thermogravimetric and scanning electron microscope measurements enabled a clear structure and property elucidation of the different bonded phases. The highest amount of grafted polystyrene was achieved employing the acid chloride synthesis pathway with silica-gel, whereas modification of spherical silica only led to minor amounts of grafted polymer. The results contribute to the evolving need to understand particle surface modifications and may have positive impact on development of new HPLC stationary phases for improved elutant resolution.

  13. Silica aerogels as support for lipase catalyzed esterifications at sub- and supercritical conditions



    The enzymes (lipases from Candida rugosa and porcine pancreas) were immobilized on silica aerogels by sol-gel procedure followed by supercritical drying with CO2. Such immobilized enzymes were used as biocatalysts for esterification in supercritical CO2 and near critical propane at 40 °C and 100 bar. It was found out that the initial reaction rates in propane rose two to three times in comparison with the same reaction, catalyzed by free lipase. SC CO2 deactivated the non-immobilized lipase i...

  14. Hydrogenation of Toluidines Catalyzed by Silica-supported Carboxymethylcellulose-platinum Complex

    Institute of Scientific and Technical Information of China (English)

    WANG Xin; YANG Ji-huo; HUANG Mei-yu; JIANG Ying-yan


    The hydrogenation of toluidines catalyzed by silica-supported carboxymethyl cellulose platinum complex forms methylcyclohexlamines in high yields, such as m-toluidine to 3-methylcyclohexylamine, o-toluidine to 2-methylcyclohexylamine, and p-toluidine to 4-methylcyclohexylamine in 97%, 96.7% and 98.2% yields,respectively, at 30 C and under atmospheric hydrogen pressure. The yields were remarkably affected by the Pt content in the complex, the kind of solvent and the reaction temperature. The catalyst was very stable and could be reused several times without remarkable change in the catalytic activity.

  15. Polymerization of Dimethylaminoethyl Methacrylate Catalyzed by Substituted Indenyl Lanthanide(Ⅱ) Complexes

    Institute of Scientific and Technical Information of China (English)


    The polymerization of dimethylaminoethyl methacrylate (DMAEMA) catalyzed by the 1-cyclopentylindenyl lanthanide (Ⅱ) complex (1-C5H9C9H6)2Yb (THF)2 was investigated.The results indicated that the complex (1-C5H9C9H6)2Yb (THF)2 as a single component catalyst showed high activity.The conversion of the polymerization and the molecular weight of the polymer were affected by temperature, time, amount of catalyst and solvent in the polymerization process.The catalytic activity of (1-C5H9C9H6)2Yb (THF)2 enhanced significantly when a small amount of polar solvent THF was added into the polymerization system in which toluene was selected as the solvent.The optimal temperature of polymerization was about 0 ℃.Other modified substituted indenyl lanthanide (Ⅱ) complexes also showed good catalytic activity.The order of catalytic activity of the complexes was as follows: (1-C5H9C9H6)2Sm(THF)≈(1-C2H5C9H6)2Sm(THF)2>(1-C5H9C9H6)2Yb(THF)2>(1-PhCH2C9H6)2Sm(THF)2.The steric regularity of poly (dimethylaminoethyl methacrylate) (PDMAEMA) was characterized by 1H NMR spectra.The polymerization provided syndiotacticity-rich PDMAEMA.The molecular weight and the molecular weight distribution of PDMAEMA were measured by gel permeation chromatography.

  16. Effect of enzyme impurities on phenol removal by the method of polymerization and precipitation catalyzed by Coprinus cinereus peroxidase. (United States)

    Masuda, M; Sakurai, A; Sakakibara, M


    The removal of phenol by peroxidase-catalyzed polymerization was examined using the Coprinus cinereus peroxidases at different levels of impurity with respect to contamination. The phenol removal efficiency was improved by lowering the peroxidase purity. Acidic and high molecular weight proteins present as impurities in the peroxidase solution had some positive effect on the phenol-polymerizing reaction. The residual enzyme activity, either only in the solution or both in the solution and on the precipitate during the polymerizing reaction, was measured. The results indicate that the main effect of impurities in the peroxidase solution was the suppression of the adsorption of peroxidase molecules on the polymerized precipitate.

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

    Directory of Open Access Journals (Sweden)

    J. Lv


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

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

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

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


    Institute of Scientific and Technical Information of China (English)

    Hua Li; Shu-xue Zhou; Bo You; Li-min Wu


    Poly(St-co-BuA)/silica nanocomposite latexes were synthesized via conventional emulsion polymerization in the presence of 3-(trimethoxysilyl)propyl methacrylate modified colloidal nano-silica. The effects of surface property, particle size and content of colloidal nano-silica as well as the concentrations of monomer and surfactant on the morphology of nanocomposite latex particles were investigated by transmission electron microscope (TEM) and scanning electron microscope (SEM) in detail. Various interesting morphologies such as grape-like, Chinese gooseberry-like, pomegranate-like and normal core-shell structures were observed. Droplet nucleation mechanism competing with micelle nucleation mechanism was proposed to explain the morphological evolution of the nanocomposite particles.

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

    DEFF Research Database (Denmark)

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


    This article presents a novel type of flame-retardant biohybrid foam with good insulation properties based on wheat gluten and silica, the latter polymerized in situ from hydrolysed tetraethyl orthosilicate (TEOS). This led to the formation of intimately mixed wheat gluten and silica phases, where...

  1. Polymerization contraction of light-cured composite resins containing silica/polymethylmethacrylate bonded microstructured networks. (United States)

    Pefferkorn, A; Haïkel, Y; Pefferkorn, E


    The adsorption of methylmethacrylate polymer at silica/methylmethacrylate interfaces was determined to provide microstructured networks whose structural characteristics were determined to be controlled by the amount of polymer initially supplied to the system. First, the microstructure was investigated by determining as a function of the amount of polymer (i) the shrinking rate due to evaporation of the methylmethacrylate monomer, (ii) the rate of sedimentation of the silica/polymer complexes in the methylmethacrylate monomer, and (iii) the height of the sediment in the long term. These different characteristics were found to be strongly correlated. Second, the sedimentation characteristics were determined as a function of the amount of polymer initially supplied to the dispersion of the same silica/polymer system in the ethylene glycol dimethacrylate monomer. Then the rate of the polymerization contraction during light-curing of the resin was determined for the sediment recovered after centrifugation. The slowest polymerization contraction and the smallest contraction were obtained with the filler/polymer/resin system composed of aggregates of medium porosity and size.

  2. Trace the polymerization induced by gamma-ray irradiated silica particles (United States)

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


    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Jinyu; Zhou, Guowei, E-mail:; Jiang, Bin; Zhao, Minnan; Zhang, Yan


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

  4. 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


    @@ 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.

  5. Metal-catalyzed simultaneous chain- and step-growth radical polymerization: marriage of vinyl polymers and polyesters. (United States)

    Mizutani, Masato; Satoh, Kotaro; Kamigaito, Masami


    All polymerization reactions are categorized into two large different families, chain- and step-growth polymerizations, which are typically incompatible. Here, we report the simultaneous chain- and step-growth polymerization via the metal-catalyzed radical copolymerization of conjugated vinyl monomers and designed monomers possessing unconjugated C horizontal lineC and active C-Cl bonds. Especially, almost ideal linear random copolymers containing both vinyl polymer and polyester units in a single polymer chain were formed by the CuCl/1,1,4,7,10,10-hexamethyltriethylenetetramine- or RuCp*Cl(PPh(3))(2)-catalyzed copolymerization of methyl acrylate (MA) for the chain-growth polymerization and 3-butenyl 2-chloropropionate (1) for the step-growth polymerization. In contrast, other transition metal catalysts, such as CuCl with tris[2-(dimethylamino)ethyl]amine or N,N,N',N'',N''-pentamethyldiethylenetriamine and FeCl(2)/PnBu(3), resulted in branched structures via the concomitant chain-growth copolymerization of 1 with MA. The polymerization mechanism was studied in detail by NMR and MALDI-TOF-MS analyses of the polymerizations as well as the model reactions. Furthermore, a series of copolymers changing from random to multiblock polymer structures were obtained by varying the feed ratios of the two monomers. These copolymers can be easily degraded into lower molecular weight oligomers or polymers via methanolysis of the ester-linkages in the main chain using sodium carbonate.

  6. Enzyme-Catalyzed Polymerization of Beta-alanine Esters, A Sustainable Route Towards the Formation of Poly-Beta-alanine

    NARCIS (Netherlands)

    Steunenberg, P.; Uiterweerd, M.; Sijm, M.; Scott, E.L.; Zuilhof, H.; Sanders, J.P.M.; Franssen, M.C.R.


    The synthesis of poly-ß-alanine by a lipase catalyzed polycondensation reaction between ß-alanine esters is reported. The effect of different solvents, reaction temperatures and substrate/enzyme concentrations on polymer yield and degree of polymerization (DP) was determined. Also the effect of meth

  7. The molecular structure of interfaces formed between plasma polymerized silica-like films and epoxy adhesives (United States)

    Bengu, Basak

    The molecular structure of the interphase formed by curing a model adhesive system consisting of the diglycidyl ether of bisphenol-A (DGEBA) and dicyandiamide (DDA) against inorganic substrates, including mechanically polished aluminum, electrogalvanized steel (EGS) and plasma polymerized silica-like primer films, was determined using reflection--absorption infrared spectroscopy (RAIR) and X-ray photoelectron spectroscopy (XPS). RAIR analysis suggested that DGEBA/DDA mixtures created an interphase with a different molecular structure from the bulk of the adhesive when cured in contact with aluminum. The formation of this unique interphase was mainly due to interactions between DDA and the Al surface. XPS analysis indicated that aluminum ions exposed by heating the substrate surface were necessary for this interaction. DDA was found to adsorb onto the aluminum surface via the lone pair of electrons on the nitrogen atoms of the nitrile groups. A slight decrease in the nitrile stretching frequency indicated an additional back-bonding interaction between aluminum ions and the nitrile groups. Slight back donation of electrons from the metal to DDA resulted in a reduction product that led to the formation of the carbodiimide form of DDA. This specific reaction caused a decrease in the concentration of nitrile groups in the interphase and changed the network structure of the epoxy adhesive in the regions close to the oxide surface. The interaction of DDA with EGS surfaces followed a similar trend. However, the effects were much more pronounced with EGS and the path of the curing reaction and the network structure near the metal surface were strongly affected by EGS/DDA interactions. Two types of plasma polymerized silica-like films were prepared from hexamethyldisiloxane (HMDSO) monomer and oxygen by varying the gas compositions. One of the films was high and the other was low in hydroxyl content. XPS results showed that adjacent to the silica-like primer films, the

  8. Influence of ultrasonic condition on phase transfer catalyzed radical polymerization of methyl methacrylate in two phase system - A kinetic study. (United States)

    Marimuthu, Elumalai; Murugesan, Vajjiravel


    An ultrasonic condition assisted phase transfer catalyzed radical polymerization of methyl methacrylate was investigated in an ethyl acetate/water two phase system at 60±1°C and 25kHz, 300W under inert atmosphere. The influence of monomer, initiator, catalyst and temperature, volume fraction of aqueous phase on the rate of polymerization was examined in detail. The reaction order was found to be unity for monomer, initiator and catalyst. Generally, the reaction rate was relatively fast in two phase system, when a catalytic amount of phase transfer catalyst was used. The combined approach, use of ultrasonic and PTC condition was significantly enhances the rate of polymerization. An ultrasonic and phase transfer catalyzed radical polymerization of methyl methacrylate has shown about three fold enhancements in the rate compared with silent polymerization of MMA using cetyltrimethylammonium bromide as PTC. The resultant kinetics was evaluated with silent polymerization and an important feature was discussed. The activation energy and other thermodynamic parameters were computed. Based on the obtained results an appropriate radical mechanism has been derived. TGA showed the polymer was stable up to 150°C. The FT-IR and DSC analysis validates the atactic nature of the obtained polymer. The XRD pattern reveals the amorphous nature of polymer was dominated.

  9. Development of mechano-responsive polymeric scaffolds using functionalized silica nano-fillers for the control of cellular functions. (United States)

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


    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% (PScaffolds 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) (Ppolymeric scaffolds, which can help to customize cellular responses for biomaterial applications.

  10. 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: [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)


    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.

  11. Effect of polyvinylpyrrolidone on mesoporous silica morphology and esterification of lauric acid with 1-butanol catalyzed by immobilized enzyme (United States)

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


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

  12. 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


    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Shahabi, Shakiba; Treccani, Laura, E-mail:; Rezwan, Kurosch [University of Bremen, Advanced Ceramics (Germany)


    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.

  14. Synthesis of composite particles through emulsion polymerization based on silica/fluoroacrylate-siloxane using anionic reactive and nonionic surfactants. (United States)

    Qu, Ailan; Wen, Xiufang; Pi, Pihui; Cheng, Jiang; Yang, Zhuoru


    The composite particles with core/shell structure resulting from the combination of silica seed and hydrophobic copolymer (dodecafluoroheptyl methacrylate (DFMA), gamma-methacryloxypropyltriisopropoxidesilane (MAPTIPS), methyl methacrylate, butyl acrylate) were synthesized by emulsion polymerization. The amount of the silica seeds, concentration of reactive surfactant, as well as the addition of DFMA and MAPTIPS, have strong influences on the morphology of composite particles. It has been shown that it would be possible to produce stable organic/inorganic composite particles with inhomogeneous core/shell structure encapsulated by hydrophobic fluorinated acrylate even though using unmodified silica particles and admixture of anionic and nonionic surfactants. However, there was an obvious difference on the morphologies of core-shell structure whether the DFMA and MAPTIPS were added or not. It was concluded that two kinds of polymerization approaches might coexist in the presence of DFMA and MAPTIPS for raw silica. One clear advantage of this process is that there is only one silica bead for each composite particle. This kind of stable core-shell structural hybrid latex is useful for preparing high performance hydrophobic coating.

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

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


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

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

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


    The inorganic matrix of the siliceous skeletal elements of sponges, that is, spicules, is formed of amorphous biosilica. Until a decade ago, it remained unclear how the hard biosilica monoliths of the spicules are formed in sponges that live in a silica-poor (<50 μM) aquatic environment. The following two discoveries caused a paradigm shift and allowed an elucidation of the processes underlying spicule formation; first the discovery that in the spicules only one major protein, silicatein, exists and second, that this protein displays a bio-catalytical, enzymatic function. These findings caused a paradigm shift, since silicatein is the first enzyme that catalyzes the formation of an inorganic polymer from an inorganic monomeric substrate. In the present review the successive steps, following the synthesis of the silicatein product, biosilica, and resulting in the formation of the hard monolithic spicules is given. The new insight is assumed to open new horizons in the field of biotechnology and also in biomedicine.

  17. In vitro polymerization of mussel polyphenolic proteins catalyzed by mushroom tyrosinase. (United States)

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


    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.

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

    Institute of Scientific and Technical Information of China (English)


    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.

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

    KAUST Repository

    Alamri, Haleema


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

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

    Energy Technology Data Exchange (ETDEWEB)

    Gommes, Cedric J. [Universite de Liege, Laboratoire de Genie Chimique, Bat B6a, Allee du 6 aout 3, B-4000 Sart Tilman Liege (Belgium)]. E-mail:; Blacher, Silvia [Universite de Liege, Laboratoire de Genie Chimique, Bat B6a, Allee du 6 aout 3, B-4000 Sart Tilman Liege (Belgium); Goderis, Bart [Katholieke Universiteit Leuven, Laboratorium voor Macromoleculaire Structuurchemie, Celestijnenlann 200F, B-3001 Heverlee (Belgium); Pirard, Jean-Paul [Universite de Liege, Laboratoire de Genie Chimique, Bat B6a, Allee du 6 aout 3, B-4000 Sart Tilman Liege (Belgium)


    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.

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

    Directory of Open Access Journals (Sweden)

    Lihua Guo


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

  2. Enzyme-catalyzed ring-opening polymerization of unsubstituted beta-lactam

    NARCIS (Netherlands)

    Schwab, Leendert W.; Kroon, Renee; Schouten, Arend Jan; Loos, Katja


    The synthesis of poly(beta-alanine) by Candida antarctica lipase B immobilized as novozyme 435 catalyzed ring-opening of 2-azetidinone is reported. After removal of cyclic side products and low molecular weight species pure linear poly(beta-alanine) is obtained. The formation of the polymer is confi

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

    Energy Technology Data Exchange (ETDEWEB)

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


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

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

    Directory of Open Access Journals (Sweden)

    K. Sasipriya


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

  5. Silica Chloride Nano Particle Catalyzed Ring Opening of Epoxides by Aromatic Amines

    Institute of Scientific and Technical Information of China (English)

    Karimian Ramin; Piri Farideh; Karimi Babak; Moghimi Abolghasem


    Silica chloride nano particle (nano SiO2-Cl), has been found to be heterogeneous catalyst for facile, simple and mild ring opening of epoxides with aromatic amines to afford β-amino alcohols in dry CH2Cl2 at room temperature.

  6. Synthesis of Mixed-ring Zirconocene Complexes Containing Alkenyl Group and Ethylene Polymerization Catalyzed with Them

    Institute of Scientific and Technical Information of China (English)

    钱延龙; 孙俊全; 等


    Four new mixed-ring zirconium complexes,[CH2=CH(CH2)n·C5H4](RC5H4)ZrCl2[n=1,R=CH3OCH2CH2(3);n=2,R=CH3OCH2CH2(4);n=2,R=Me3Si(5);n=2,R=allyl(6)],have been prepared by the reaction of CH2=CH(CH2)nC5H4ZrCl3·DME[n=1(1);n=2(2)] with RC5H4Li.When activated with methylaluminoxane(MAO),the catalytic activities of the above complexes in ethylene polymerization were tested.Complexes 5 and 6 show high activities similar to Cp2ZrCl2.Introduction of methoxyethyl group into Cp-ligand dramatically decreases the catalytic activities of complexes 3 and 4,which can be overcome by increasing the amount of MAO.For complex 5,the dependence of activity and molecular weight(Mη) on the Al/Zr ratio,the polymerization time(tp).polymerization temperature(Tp) and the polymerization solvent volume(V) was investigated.

  7. Zirconium-allyl complexes as resting states in zirconocene-catalyzed α-olefin polymerization. (United States)

    Panchenko, Valentina N; Babushkin, Dmitrii E; Brintzinger, Hans H


    UV-vis spectroscopic data indicate that zirconocene cations with Zr-bound allylic chain ends are generally formed during olefin polymerization with zirconocene catalysts. The rates and extent of their formation and of their re-conversion to the initial pre-catalyst cations depend on the types of zirconocene complexes and activators used.

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

    KAUST Repository

    Ladelta, Viko


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


    Institute of Scientific and Technical Information of China (English)

    Bijayashree Samal; Prafulla K.Sahoo


    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.

  10. Template polymerization synthesis of hydrogel and silica composite for sorption of some rare earth elements. (United States)

    Borai, E H; Hamed, M G; El-kamash, A M; Siyam, T; El-Sayed, G O


    New sorbents containing 2-acrylamido 2-methyl propane sulphonic acid monomer onto poly(vinyl pyrilidone) P(VP-AMPS) hydrogel and P(VP-AMPS-SiO2) composite have been synthesized by radiation template polymerization. The effect of absorbed dose rate (kGy), crosslinker concentration and polymer/monomer ratio on the degree of template polymerization of P(VP-AMPS) hydrogel was studied. The degree of polymerization was evaluated by the calculated percent conversion and swelling degree. The maximum capacity of P(VP-AMPS) hydrogel toward Cu(+2) metal ion found to be 91 mg/gm. The polymeric composite P(VP-AMPS-SiO2) has been successfully synthesized. The structure of the prepared hydrogel and composite were confirmed by FTIR, thermal analysis (TGA and DTA) and SEM micrograph. Batch adsorption studies for La(3+), Ce(3+), Nd(3+), Eu(3+) and Pb(+2) metal ions on the prepared hydrogel and composite were investigated as a function of shaking time, pH and metal ion concentration. The sorption efficiency of the prepared hydrogel and composite toward light rare earth elements (LREEs) are arranged in the order La(3+)>Ce(3+)>Nd(3+)>Eu(3+). The obtained results demonstrated the superior adsorption capacity of the composite over the polymeric hydrogel. The maximum capacity of the polymeric composite was found to be 116, 103, 92, 76, 74 mg/gm for La(3+), Ce(3+), Nd(3+), Eu(3+) and Pb(2+) metal ions respectively.

  11. Efficient polymerization of acrylonitrile catalyzed by diValent lanthanide complex/sodium phenolate systems

    Institute of Scientific and Technical Information of China (English)


    Four divalent lanthanide complexes Sm(ArO)2(THF)4, Yb(ArO)2(THF)3, Eu(ArO)2(THF)3 (ArO = 2,6-ditert-butyl-4-methylphenolate) and (ButCp)2Sm(THF)2 were synthesized. Their catalytic activities on the polymerization of acrylonitrile were studied. The catalytic activities were influenced by the central metal ions involved. The catalytic activities of these divalent lanthanide complexes can be greatly increased by adding NaOC~H2-2,6-But2-4-Me,NaOC6H4-4-But, or NaOC10H6-2-Me. The amount of additive has apparent effect on the catalytic activity, but the additive has no effect on the tacticity of the resulting polyacrylonitrile

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

    Energy Technology Data Exchange (ETDEWEB)

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


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

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

    KAUST Repository

    Riache, Nassima


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

  14. From the N-Heterocyclic Carbene-Catalyzed Conjugate Addition of Alcohols to the Controlled Polymerization of (Meth)acrylates. (United States)

    Ottou, Winnie Nzahou; Bourichon, Damien; Vignolle, Joan; Wirotius, Anne-Laure; Robert, Fredéric; Landais, Yannick; Sotiropoulos, Jean-Marc; Miqueu, Karinne; Taton, Daniel


    Among various N-heterocyclic carbenes (NHCs) tested, only 1,3-bis(tert-butyl)imidazol-2-ylidene (NHC(tBu) ) proved to selectively promote the catalytic conjugate addition of alcohols onto (meth)acrylate substrates. This rather rare example of NHC-catalyzed 1,4-addition of alcohols was investigated as a simple means to trigger the polymerization of both methyl methacrylate and methyl acrylate (MMA and MA, respectively). Well-defined α-alkoxy poly(methyl (meth)acrylate) (PM(M)A) chains, the molar masses of which could be controlled by the initial [(meth)acrylate]0/[ROH]0 molar ratio, were ultimately obtained in N,N-dimethylformamide at 25 °C. A hydroxyl-terminated poly(ethylene oxide) (PEO-OH) macro-initiator was also employed to directly access PEO-b-PMMA amphiphilic block copolymers. Investigations into the reaction mechanism by DFT calculations revealed the occurrence of two competitive concerted pathways, involving either the activation of the alcohol or that of the monomer by NHC(tBu) .

  15. 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


    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.

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

    KAUST Repository

    Khokhar, Munir


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

  17. Unexpectedly Facile Rh(I) Catalyzed Polymerization of Ethynylbenzaldehyde Type Monomers: Synthesis of Polyacetylenes Bearing Reactive and Easy Transformable Pendant Carbaldehyde Groups. (United States)

    Sedláček, Jan; Havelková, Lucie; Zedník, Jiří; Coufal, Radek; Faukner, Tomáš; Balcar, Hynek; Brus, Jiří


    The chain coordination polymerization of (ethynylarene)carbaldehydes with unprotected carbaldehyde groups, namely ethynylbenzaldehydes, 1-ethynylbenzene-3,5-dicarboxaldehyde, and 3-[(4-ethynylphenyl)ethynyl]benzaldehyde, is reported for the first time. Polymerization is catalyzed with various Rh(I) catalysts and yields poly(arylacetylene)s with one or two pendant carbaldehyde groups per monomeric unit. Surprisingly, the carbaldehyde groups of the monomers do not inhibit the polymerization unlike the carbaldehyde group of unsubstituted benzaldehyde that acts as a strong inhibitor of Rh(I) catalyzed polymerization of arylacetylenes. The inhibition ability of carbaldehyde groups in (ethynylarene)carbaldehydes seems to be eliminated owing to a simultaneous presence of unsaturated ethynyl groups in (ethynylarene)carbaldehydes. The reactive carbaldehyde groups make poly[(ethynylarene)carbaldehyde]s promising for functional appreciation via various postpolymerization modifications. The introduction of photoluminescence or chirality to poly(ethynylbenzaldehyde)s via quantitative modification of their carbaldehyde groups in reaction with either photoluminescent or chiral primary amines under formation of the polymers with Schiff-base-type pendant groups is given as an example.

  18. A combined approach of experiments and computational docking simulation to the Coprinus cinereus peroxidase-catalyzed oxidative polymerization of alkyl phenols. (United States)

    Park, Jong Chul; Joo, Jeong Chan; An, Eun Suk; Song, Bong Keun; Kim, Yong Hwan; Yoo, Young Je


    The characteristics of the oxidative polymerization of alkyl phenol derivatives catalyzed by Coprinus cinereus peroxidase (CIP) were studied qualitatively and quantitatively using a combined approach of experiments and computational docking simulations. As determined by docking study of CIP and alkyl phenols, the binding interaction was found to be important for the determination of substrate specificity. The distant binding and indirect orientation of o-isopropyl phenol and o-tertiary butyl phenol to the catalytic residue (56His) could explain the inability of CIP to polymerize these substrates. Three hydrophobic residues (156Pro, 192Leu, and 230Phe) at the entrance of the binding pocket were also found to be crucial in binding and orientation of alkyl phenols. A two-parameter QSAR equation with the binding distance and the molecular volume of the substrates was proposed and the polymerization yield was accurately predicted by two-parameter QSAR equation.


    Institute of Scientific and Technical Information of China (English)

    殷明志; 张良莹; 姚熹


    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Kato, Katsuya, E-mail: [National Institute of Advanced Industrial Science and Technology (AIST), 2266-98 Anagahora, Shimoshidami, Moriyama-ku, Nagoya 463-8560 (Japan); Nishida, Masakazu [National Institute of Advanced Industrial Science and Technology (AIST), 2266-98 Anagahora, Shimoshidami, Moriyama-ku, Nagoya 463-8560 (Japan); Ito, Kimiyasu; Tomita, Masahiro [Division of Chemistry for Materials, Graduate School of Engineering, Mie University, 1577 Kurimamachiya-cho, Tsu, Mie 514-8570 (Japan)


    Highlights: Black-Right-Pointing-Pointer Silica precipitation occurred via urease-catalytic reactions. Black-Right-Pointing-Pointer Higher urease activity for silica synthesis enables mesostructure of silica-urease composites. Black-Right-Pointing-Pointer 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 {approx}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 Degree-Sign C is relatively high (324 m{sup 2}/g and 1.0 cm{sup 3}/g). These values are equivalent to those of usual mesoporous silica materials synthesized from the self-assembly of triblock copolymers as organic templates. In addition, after encapsulating in a sol-gel silica matrix, urease retained high activity ({approx}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.

  1. Multifunctional mesoporous silica catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Lin, Victor Shang-Yi; Tsai, Chih-Hsiang; Chen, Hung-Ting; Pruski, Marek; Kobayashi, Takeshi


    The present invention provides bifunctional silica mesoporous materials, including mesoporous silica nanoparticles ("MSN"), having pores modified with diarylammonium triflate and perfluoroaryl moieties, that are useful for the acid-catalyzed esterification of organic acids with organic alcohols.

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

    KAUST Repository

    Chen, Xia


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

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

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


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

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

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


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

  5. Influences of Alkyl and Aryl Substituents on Iminopyridine Fe(II- and Co(II-Catalyzed Isoprene Polymerization

    Directory of Open Access Journals (Sweden)

    Lihua Guo


    Full Text Available A series of alkyl- and aryl-substituted iminopyridine Fe(II complexes 1a–7a and Co(II complexes 2b, 3b, 5b, and 6b were synthesized. The activator effect, influence of temperature, and, particularly, the alkyl and aryl substituents’ effect on catalytic activity, polymer molecular weight, and regio-/stereoselectivity were investigated when these complexes were applied in isoprene polymerization. All of the Fe(II complexes afforded polyisoprene with high molecular weight and moderate cis-1,4 selectivity. In contrast, the Co(II complexes produced polymers with low molecular weight and relatively high cis-1,4 selectivity. In the iminopyridine Fe(II system, the alkyl and aryl substituents’ effect exhibits significant variation on the isoprene polymerization. In the iminopyridine Co(II system, there is little influence observed on isoprene polymerization by alkyl and aryl substituents.

  6. 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)


    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.

  7. The Oxidative Coupling of 2,6-Xylenol Catalyzed by Polymeric Complexes of Copper, 1. Kinetic Study of the Catalysis by Copper(II)-Complexes of Partially Aminated Polystyrene

    NARCIS (Netherlands)

    Schouten, Arend Jan; Prak, Nanno; Challa, Ger


    The oxidative coupling reaction of 2,6-xylenol catalyzed by copper(II) complexes of chemically modified polystyrene was investigated. Under the applied reaction conditions the main reaction product was 2,6,2',6'-tetramethyl-1,1'-dioxo-4,4'-bicyclohexa-2,5-dienylidene. It was found that the polymeric

  8. 稀土催化苯乙烯本体聚合机理与动力学%Kinetics and Mechanism of Bulk Polymerization of Styrene Catalyzed by Rare Earth Catalyst

    Institute of Scientific and Technical Information of China (English)

    吴林波; 李伯耿; 李宝芳; 曹堃


    The bulk polymerization of styrene catalyzed by Nd(P204)3/MgBu2/HMPA (hexamethyl phosphoramide) was carried out in capped glass tubes. The effects of reaction conditions on polymerization conversion and molecular weight in the range of high conversion were investigated. The molecular weight of the resultant polymers is dramatically high and its distribution is relatively narrow. The polymerization process demonstrates the feature of living polymerization and auto-acceleration phenomenon. The auto-acceleration phenomenon is attributed to the non-instantaneous formation of the active species. The experimental data suggest that chain transfer to MgBu2 is one of the factors governing the molecular weight development. A mechanism of polymerization is presented with the chain transfer process incorporated. ``

  9. Metal-silica sol-gel materials (United States)

    Stiegman, Albert E. (Inventor)


    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.

  10. 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


    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.

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

    KAUST Repository

    Riache, Nassima


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

  12. Effect of the Polymeric Stabilizer in the Aqueous Phase Fischer-Tropsch Synthesis Catalyzed by Colloidal Cobalt Nanocatalysts

    Directory of Open Access Journals (Sweden)

    Jorge A. Delgado


    Full Text Available A series of small and well defined cobalt nanoparticles were synthesized by the chemical reduction of cobalt salts in water using NaBH4 as a reducing agent and using various polymeric stabilizers. The obtained nanocatalysts of similar mean diameters (ca. 2.6 nm were fully characterized and tested in the aqueous phase Fischer-Tropsch Synthesis (AFTS. Interestingly, the nature and structure of the stabilizers used during the synthesis of the CoNPs affected the reduction degree of cobalt and the B-doping of these NPs and consequently, influenced the performance of these nanocatalysts in AFTS.

  13. A water-soluble polycarbonate with dimethylamino pendant groups prepared by enzyme-catalyzed ring-opening polymerization. (United States)

    Zhang, Xiaojin; Cai, Mengmeng; Zhong, Zhenlin; Zhuo, Renxi


    A water-soluble polycarbonate with dimethylamino pendant groups, poly(2-dimethylaminotrimethylene carbonate) (PDMATC), is synthesized and characterized. First, the six-membered carbonate monomer, 2-dimethylaminotrimethylene carbonate (DMATC), is prepared via the cyclization reaction of 2-(dimethylamino)propane-1,3-diol with triphosgene in the presence of triethylamine. Although the attempted ring-opening polymerization (ROP) of DMATC with Sn(Oct)(2) as a catalyst fails, the ROP of DMATC is successfully carried out with Novozym-435 as a catalyst to give water-soluble aliphatic polycarbonate PDMATC with low cytotoxicity and good degradability.

  14. Effect of the Polymeric Stabilizer in the Aqueous Phase Fischer-Tropsch Synthesis Catalyzed by Colloidal Cobalt Nanocatalysts (United States)

    Delgado, Jorge A.; Claver, Carmen; Castillón, Sergio; Curulla-Ferré, Daniel; Godard, Cyril


    A series of small and well defined cobalt nanoparticles were synthesized by the chemical reduction of cobalt salts in water using NaBH4 as a reducing agent and using various polymeric stabilizers. The obtained nanocatalysts of similar mean diameters (ca. 2.6 nm) were fully characterized and tested in the aqueous phase Fischer-Tropsch Synthesis (AFTS). Interestingly, the nature and structure of the stabilizers used during the synthesis of the CoNPs affected the reduction degree of cobalt and the B-doping of these NPs and consequently, influenced the performance of these nanocatalysts in AFTS. PMID:28336892

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

    Energy Technology Data Exchange (ETDEWEB)

    Bercaw, John E. [California Institute of Technology


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

  16. A High-Fidelity Codon Set for the T4 DNA Ligase-Catalyzed Polymerization of Modified Oligonucleotides. (United States)

    Lei, Yi; Kong, Dehui; Hili, Ryan


    In vitro selection of nucleic acid polymers can readily deliver highly specific receptors and catalysts for a variety of applications; however, it is suspected that the functional group deficit of nucleic acids has limited their potential with respect to proteinogenic polymers. This has stimulated research toward expanding their chemical diversity to bridge the functional gap between nucleic acids and proteins to develop a superior biopolymer. In this study, we investigate the effect of codon library size and composition on the sequence specificity of T4 DNA ligase in the DNA-templated polymerization of both unmodified and modified oligonucleotides. Using high-throughput DNA sequencing of duplex pairs, we have uncovered a 256-membered codon set that yields sequence-defined modified ssDNA polymers in high yield and with high fidelity.

  17. Catalyzed oxidative degradation of methyl orange over Au catalyst prepared by ionic liquid-polymer modified silica (United States)

    Wang, Y.; Guo, J. S.


    A new type of hybrid material was prepared by grafting an ionic liquid monomer, 1-(p-vinylbenzyl)-3-methylimidazolium chloride, on the surface of the porous silica which was synthesized via sodium silicate hydrolysis. The as-synthesized products were characterized by scanning electron microscope, nitrogen physisorption experiment, thermogravimetric analysis and Fourier transform infrared spectra. A catalyst with Au was prepared using the hybrid material as carrier. The experimental results show that the catalyst exhibits a better catalytic effect of hydrogen peroxide on the degradation of methyl orange. The reason may be that the metal component of the catalyst facilitated the dissociation of hydrogen peroxide to produce abundant highly active free radicals which can rapidly ruin the structure of methyl orange molecules in water. Finally, a probable catalytic degradation mechanism based on diffusion was discussed.

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

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


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

  19. 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


    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.

  20. Structure-property relationships of solid polymeric catalysts: isopropanol dehydration to propylene catalyzed by sulfonated polyethylene-grafted styrene

    Energy Technology Data Exchange (ETDEWEB)

    Cooper, C.A.


    Isopropanol dehydration to propylene catalyzed by sulfonated polyethylene-grafted styrene was used to measure the effects on the catalytic activity of structural charges induced in the membranes by constant-rate, cold drawing by 75, 150, and 200 3< of their initial lengths. The form of the rate expression for the reaction with undrawn and drawn membranes at 100/sup 0/C and 1 atm under differential reaction conditions was the same and could be explained by a concerted reaction mechanism involving intermediate isopropanol hydrogen bonded to about four -SO/sub 3/H groups. The maximum reaction rate (based on catalyst acidity) increased by approx. 80% from the undrawn membrane to the 150% drawn membrane and then decreased by approx. 70% from the maximum observed for the 150% drawn membrane to the 200% drawn membrane. A structural model was developed on the basis that the -SO/sub 3/H groups are confined to the amorphous phase due to steric exclusion but that they redistribute to more favorable arrangements during drawing. Model predictions were supported by X-ray and birefringence studies.

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

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


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

  2. Study on Antioxidant Activity of Catalyzed Hydrogen Degradation Product of Polymeric Proanthocyanidins (LPPC from Larix gmelinii Bark

    Directory of Open Access Journals (Sweden)

    Gui-quan Jiang


    Full Text Available A grading countercurrent extraction method was used to separate polymeric proanthocyanidins (LPPC from degreased Larix gmelinii bark, and the purification of LPPC was performed using HP-2MGL resin. The purity of LPPC was 26.37%. The cumulative recovery rate of purified product (LPPC-1 was 98.54% by the adsorption method of HP-2MGL resin. The purity of LPPC-1 was 99.79%. Catalytic hydrogenolysis tests of LPPC-1 were performed by means of a palladium carbon catalyst. The degradation rate was 67.5%, and the residual rate was 72.1%. The results of antioxidant ability showed that the degradation product (LHOPC had more excellent antioxidant ability compared with LPPC-1, VC, TBHQ, grape seed extract, and pine bark extract. The results, through the analysis of the linear model of MALDI-TOF/TOF MS, revealed that LHOPC was oligomeric with the tetramer as the major component and the distribution ranging from the trimer to eleven units.

  3. Surface initiated polymerization of a cationic monomer on inner surfaces of silica capillaries: analyte separation by capillary electrophoresis versus polyelectrolyte behavior. (United States)

    Witos, Joanna; Karesoja, Mikko; Karjalainen, Erno; Tenhu, Heikki; Riekkola, Marja-Liisa


    [2-(Methacryloyl)oxyethyl]trimethylammonium chloride was successfully polymerized by surface-initiated atom transfer radical polymerization method on the inner surface of fused-silica capillaries resulting in a covalently bound poly([2-(methacryloyl)oxyethyl]trimethylammonium chloride) coating. The coated capillaries provided in capillary electrophoresis an excellent run-to-run repeatability, capillary-to-capillary and day-to-day reproducibility. The capillaries worked reliably over 1 month with EOF repeatability below 0.5%. The positively charged coated capillaries were successfully applied to the capillary electrophoretic separation of three standard proteins and five β-blockers with the separation efficiencies ranging from 132,000 to 303,000 plates/m, and from 82,000 to 189,000 plates/m, respectively. In addition, challenging high- and low-density lipoprotein particles could be separated. The hydrodynamic sizes of free polymer chains in buffers used in the capillary electrophoretic experiments were measured for the characterization of the coatings.

  4. Synthesis of vanadium complexes and butadiene polymerization catalyzed by the complexes%钒配合物的合成及其催化丁二烯聚合

    Institute of Scientific and Technical Information of China (English)

    黄贵秋; 陈敏娥; 熊拯


    采用N-亚硝基苯胲铵、二乙基二硫代氨基甲酸钠合三水和8-羟基喹啉三种萃取剂,萃取合成了三个双配位基配体钒配合物,将其用于催化丁二烯聚合获得聚丁二烯产品.用元素分析及红外光谱分析测定了钒配合物的结构,用凝胶渗透色谱、红外光谱及核磁共振波谱分析了聚合产物结构.所得聚丁二烯的数均分子量为(0.96~1.36)×104,相对分子质量分布为3.5~4.3,1,2-结构单元的摩尔分数高于60%,且构型为间同立构和无规结构.%Three vanadium complexes were synthesized via extraction with cupferron, sodium diethyl dithiocarbamate and 8-hydroxyquinoline as extraction reagents. The resultant vanadium complex with bifunctional ligand was successfully applied in catalyzing butadiene polymerization through which the corresponding polymer was acquired. The structure of the vanadium complexes was tested by elemental analyses and infrared spectroscopy (IR). The structure of the resultant polybutadiene was analysized with gel permeation chromatography (GPC), IR, nuclear magnetic resonance spectroscopy (1H-NMR and 13C-NMR). The polybutadiene possessed number average molecular mass of (0.96-1.36)xl04 and relative molecular mass distribution of 3.5-4.3. The molar content of 1,2-configuration unit, in either syndiotactie or atactic microstructure, was higher than 60% of the polybutadiene.

  5. Development of a solid-phase microextraction fiber by chemical binding of polymeric ionic liquid on a silica coated stainless steel wire. (United States)

    Pang, Long; Liu, Jing-Fu


    A novel approach was developed for the fabrication of solid-phase microextraction (SPME) fiber by coating stainless steel fiber with a polymeric ionic liquid (PIL) through covalent bond. The stainless steel fiber was sequentially coated with a gold film by replacement reaction between Fe and Au when immerged in chloroauric acid, assembled with a monolayer of 3-(mercaptopropyl) triethoxysilane on the gold layer through the Au-S bond, and coated with a silica layer by the hydrolysis and polycondensation reaction of the surface-bonded siloxane moieties and the active silicate solution. Then, 1-vinyl-3-(3-triethoxysilylpropyl)-4,5-dihydroimidazolium chloride ionic liquid was anchored on the silica layer by covalent bond, and the PIL film was further formed by free radical copolymerization between 1-vinyl-3-(3-triethoxysilylpropyl)-4,5-dihydroimidazdium and vinyl-substituted imidazolium with azobisisobutyronitrile (AIBN) as initiator. Parameters influencing the preparation of PIL fiber were optimized, and the developed SPME fiber has a coating thickness of ~20 μm with good thermal stability and long lifetime. The performance of the PIL fiber was evaluated by analysis of polycyclic aromatic hydrocarbons (PAHs) in water samples. The developed PIL fiber showed good linearity between 0.5 and 20 μg l(-1) with regression coefficient in the range of 0.963-0.999, detection limit ranging from 0.05 to 0.25 μg l(-1), and relative standard deviation of 9.2-29% (n=7). This developed PIL fiber exhibited comparable analytical performance to commercial 7 μm thickness PDMS fiber in the extraction of PAHs. The spiked recoveries for three real water samples at 0.5-5 μg l(-1) levels were 49.6-111% for the PIL fiber and 40.8-103% for the commercial PDMS fiber.

  6. Synthesis of well-defined structurally silica-nonlinear polymer core-shell nanoparticles via the surface-initiated atom transfer radical polymerization (United States)

    Chen, Jiucun; Hu, Min; Zhu, Wendong; Li, Yaping


    We report on the synthesis of the well-defined structurally silica-nonlinear polymer core-shell nanoparticles via the surface-initiated atom transfer radical polymerization. At first, 3-(2-bromoisobutyramido)propyl(triethoxy)-silane (the ATRP initiator) was prepared by the reaction of 3-aminopropyltriethoxysilane with 2-bromoisobutyryl bromide. The ATRP initiator was covalently attached onto the nanosilica surface. The subsequent ATRP of HEMA from the initiator-attached SiO 2 surface was carried out in order to afforded functional nanoparticles bearing a hydroxyl moiety at the chain end, SiO 2-g-PHEMA-Br. The esterification reaction of pendent hydroxyl moieties of PHEMA segment with 2-bromoisobutyryl bromide afforded the SiO 2-based multifunctional initiator, SiO 2-g-PHEMA(-Br)-Br, bearing one bromine moiety on each monomer repeating unit within the PHEMA segment. Finally, the synthesis of SiO 2-g-PHEMA(-g-PSt)-b-PSt was accomplished by the ATRP of St monomer using SiO 2-g-PHEMA(-Br)-Br as multifunctional initiator. These organic/inorganic hybrid materials have been extensively characterized by FT-IR, XPS, TG, and TEM.

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

    Institute of Scientific and Technical Information of China (English)

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


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


    Institute of Scientific and Technical Information of China (English)

    SUN Luying; HUANG Zhitang


    The polymerization kinetics of 4,4 '-biphenyldicarbonitrile using cuprous chloride-zinc system as catafyst was investigated .the concentration of unreacted cyano group was measured by infrared spectroscopic analysis using potassium ferricyanide as the internal reference. It was found that the polymerization rate is directly proportional to the concentrations ofcyano group, cuprous chloride and zinc, and the activation energy of the polymerization is as low as 18.4 KJ/mol. In addition, the other kinetics parameters were obtained and discussed.


    Institute of Scientific and Technical Information of China (English)

    陶敬奇; 李景宁; 王广洪; 曾广益


    The Polysuccinimide is Synthesized by means of pyrocondensation catalyze polymerization,using L-aspartic acid as a monomer.Poly-aspartic Acid is achieved by hydrolization of Polysuccinimide.The effect of temperature,time,catalyzer and condition of hydrolization on yield and quality is studied.The research results show that the method has the advantages of simple equipment and high yield.

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

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


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

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

    Directory of Open Access Journals (Sweden)

    Takashi Morinaga


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

  12. Ruthenium-catalyzed metathesis reactions of ortho- and meta-dialkenyl-carboranes: efficient ring-closing and acyclic diene polymerization reactions. (United States)

    Guron, Marta; Wei, Xiaolan; Carroll, Patrick J; Sneddon, Larry G


    The ruthenium-catalyzed metathesis reactions of dialkenyl-substituted ortho- and meta-carboranes provide excellent routes to both cyclic-substituted o-carboranes and new types of main-chain m-carborane polymers. The adjacent positions of the two olefins in the 1,2-(alkenyl)(2)-o-carboranes strongly favor the formation of ring-closed (RCM) products with the reactions of 1,2-(CH(2)=CHCH(2))(2)-1,2-C(2)B(10)H(10) (1), 1,2-(CH(2)=CH(CH(2))(3)CH(2))(2)-1,2-C(2)B(10)H(10) (2), 1,2-(CH(2)=CHSiMe(2))(2)-1,2-C(2)B(10)H(10) (3), 1,2-(CH(2)=CHCH(2)SiMe(2))(2)-1,2-C(2)B(10)H(10) (4), and 1,2-[CH(2)=CH(CH(2))(4)SiMe(2)](2)-1,2-C(2)B(10)H(10) (5) affording 1,2-(-CH(2)CH=CHCH(2)-)-C(2)B(10)H(10) (10), 1,2-[-CH(2)(CH(2))(3)CH=CH(CH(2))(3)CH(2)-]-1,2-C(2)B(10)H(10) (11), 1,2-[-SiMe(2)CH=CHSiMe(2)-]-1,2-C(2)B(10)H(10) (12), 1,2-[-SiMe(2)CH(2)CH=CHCH(2)SMe(2)-]-C(2)B(10)H(10) (13), and 1,2-[-SiMe(2)(CH(2))(4)CH=CH(CH(2))(4)SiMe(2)-]-C(2)B(10)H(10) (14), respectively, in 72-97% yields. On the other hand, the reaction of 1,2-(CH(2)-CHCH(2)OC(=O))(2)-1,2-C(2)B(10)H(10) (6) gave cyclo-[1,2-(1',8'-C(=O)OCH(2)CH=CHCH(2)OC(=O))-1,2-C(2)B(10)H(10)](2) (15a) and polymer 15b resulting from intermolecular metathesis reactions. The nonadjacent positions of the alkenyl groups in the 1,7-(alkenyl)(2)-m-carboranes, 1,7-(CH(2)=CHCH(2))(2)-1,7-C(2)B(10)H(10) (7), 1,7-(CH(2)=CH(CH(2))(3)CH(2))(2)-1,7-C(2)B(10)H(10) (8), and 1,7-(CH(2)=CHCH(2)SiMe(2))(2)-1,7-C(2)B(10)H(10) (9), disfavor the formation of RCM products, and in these cases, acyclic diene metathesis polymerizations (ADMET) produced new types of main chain m-carborane polymers. The structures of 3, 9, 11, 12, 13, and 15a were crystallographically confirmed.

  13. Polymerization Using Phosphazene Bases

    KAUST Repository

    Zhao, Junpeng


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


    Institute of Scientific and Technical Information of China (English)

    孙燕; 孙晋; 宋瑾; 黄文艳; 蒋必彪; 翟光群


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


    Institute of Scientific and Technical Information of China (English)

    Chi-fei Wu


    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.

  16. Fractals of Silica Aggregates

    Institute of Scientific and Technical Information of China (English)

    ZhinhongLi; DongWu; Yuhansun; JunWang; YiLiu; BaozhongDong; Zhinhong


    Silica aggregates were prepared by base-catalyzed hydrolysis and condensation of alkoxides in alcohol.Polyethylene glycol(PEG) was used as organic modifier.The sols were characterized using Small Angle X-ray Scattering (SAXS) with synchrotron radiation as X-ray source.The structure evolution during the sol-gel process was determined and described in terms of the fractal geometry.As-produced silica aggregates were found to be mass fractals.The fractl dimensions spanned the regime 2.1-2.6 corresponding to more branched and compact structures.Both RLCA and Eden models dominated the kinetic growth under base-catalyzed condition.


    Institute of Scientific and Technical Information of China (English)

    颜明发; 王涛; 黄永凯; 强娜; 全大萍


    In order to study the structure and the catalytic activity of aliphatic tertiary amines, the ring-opening polymerizations of trimethylene carbonate ( TMC ) and L-lactide ( L-LA) were catalyzed by aliphatic tertiary amines,including triethylamine ( TEA) , N, N, N', N'-tetramethylethylenediamine ( TMEDA ) , 1, 1,4,7, 7-pentamethyldiethylenetriamine (PMDTA) and 4-( dimethylamino) pyridine (DMAP) , using benzyl alcohol as initiator in THF at 551. Studies revealed the catalytic activity of these tertiary amines was increased according to the order; TEA < TMEDA ≈ PMDTA < DMAP. The relationships of polymer molecular weight with the conversion of monomer were linear, which were consistent with a living polymerization character. Finally, the plausible polymerization pathway was through an alcohol-activating mechanism. Aliphatic tertiary amines which were abundant in source and cheap in price were suitable for catalyzing the ring-opening bulk polymerization of lactone in low temperature because of their low boiling point, being liquid under ordinary conditions and being easy to get rid of.%为研究脂肪叔胺结构对内酯开环聚合规律的影响,以三乙胺( TEA)、N,N,N′,N′-四甲基乙二胺(TMEDA)、N,N,N′,N″,N″-五甲基二亚乙基三胺(PM DTA)3种不同结构的叔胺催化碳酸三亚甲基酯(TMC)和左旋丙交酯( L-LA)开环聚合.结果显示,在55℃的THF溶液中,以苄醇为引发剂,3种叔胺均能催化TMC和L-LA的开环聚合,聚合物的分子量与单体转化率成线性关系,表现出活性聚合特征.三者催化能力为TEA< TMEDA<PMDTA.对聚合物进行端基分析发现聚合反应可能是一个由醇活化机理引发的过程.

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

    Directory of Open Access Journals (Sweden)

    Perumberkandgai A. Vivekanand


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

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

    KAUST Repository

    Wang, De


    A novel arsonium ylide, ω-2-methylallylarsonium ylide, was synthesized and used as monomer for polyhomologation with triethyborane as initiator. It was found that the terminal methyl group leads to C3 polymerization. Furthermore, the copolyhomologation of arsonium ylide with dimethylsulfoxonium methylide is reported for the first time. (Chemical Equation Presented). © 2016 American Chemical Society.

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

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


    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.


    Institute of Scientific and Technical Information of China (English)

    Elhussein A.Taha; Jun-tao Wu; Kai Gao; Lin Guo


    Fumed silica/bisphenol A dicyanate ester (BADCy) nanocomposites were prepared by introducing different contents of nano-sized fumed SiO2 into the BADCy matrix.Two different average primary particle diameters of 12 and 40 nm were chosen.Dibutyltindilaurate (DBTDL) catalyst was chosen to catalyze the cyanate ester group into triazine group via cyclotrimerization reaction.The SEM micrographs indicated that the fumed SiO2 particles were homogeneously dispersed in the poly(bisphenol A dicyanate) matrix by means of ultrasonic treatment and the addition of a coupling agent.The FTIR spectroscopy shows that,not only DBTDL catalyzes the polymerization reaction but also-OH groups of the SiO2 particles surface help the catalyst for the complete polymerization of BADCy monomer.The thermal stability of the cured BADCy can be improved by adequate addition of fumed SiO2.A slight increase in the dielectric constant and dielectric loss values were identified by testing the dielectric properties of the prepared nanocomposite samples.By increasing the SiO2 content,there was a slight increasing in the thermal conductivity values of the tested samples.The obtained results proved that the fumed silica/BADCy nanocomposites had good thermal and dielectrical properties and can be used in many applications such as in the thermal insulation field.

  2. Ethylene Polymerization Catalyzed by Monocyclopentadienyl Titanium Complex Containing 8-Quinolinolato Ligand and ADF Study on the Formation Mechanism of Active Species

    Institute of Scientific and Technical Information of China (English)

    Jianjun Yi; Xiaoguang Zhao; Han Zhou; Zhenhua Jing


    A monocyclopentadienyl titanium complex containing 8-quinolinolato (QCpTiCl2) was synthesized. Its activities in ethylene polymerization at various Al/Ti molar ratios, different temperatures and activation time were investigated. The activity with a Al/Ti molar ratio of 500 exhibited a maximum of 2.8× 105 g/(mol.h) at 30 ℃. The activation time of QCpTiCl2 with MAO before polymerization also plays a role on the activity. The structural properties of the produced polyethylene (molecular weight, molecular weight distribution and melting point) were discussed. Kinetic behaviors of ethylene polymerization with the QCpTiCl2/MAO system at different Al/Ti molar ratios were studied. For the QCpTiMeCl/MAO system and the CpTiMe2Cl/MAO system, binding energies of the examined intermediates were calculated by quantum-mechanical method based on ADF program, respectively. It is confirmed that the chlorinebridged adduct formed by the reaction of QCpTiMeCl with MAO is thermodynamically steady. In the case of the QCpTiMeCl/MAO system, olefin-separated ion pair (OSIP) mechanism is much favorable than ion-pair dissociation (IPD) mechanism. The experimental result on the CpTiMe2Cl/MAO system showed lower activity for ethylene polymerization than that on the QCpTiMeCl/MAO system, which revealed that the CpTiMe2Cl/MAO system is unfavorable to form active species with ethylene.

  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)



    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. 苯丙-硅溶胶纳米复合乳液的制备及其性能%Study on polymerization and performance of styrene acrylate/silica nanocomposite latex

    Institute of Scientific and Technical Information of China (English)

    嵇胜全; 孔凡桃; 朱爱萍; 钟涛; 钱晓燕


    采用原位乳液聚合法制备了苯丙-硅溶胶纳米复合乳液,系统研究了乳化剂种类和用量对乳液稳定性、乳胶膜吸水率以及乳胶粒子粒径的影响.结果表明:相比单独使用,十二烷基硫酸钠(SDS)与壬基酚聚氧化乙烯基醚(OP-10)按质量比为2:1复配时制备的乳液稳定性最好;当乳化剂用量为0.75%~1.5%时,所制复合乳液稳定性好,乳胶膜的吸水率为3.64%~5.72%.与共混乳液(硅溶胶和苯丙乳液的共混物)和苯丙乳液的乳胶膜相比,复合乳胶膜的吸水率显著降低;透射电子显微镜(TEM)检测结果表明:与共混乳液相比,复合乳液中游离的纳米SiO2粒子数大大减少.%The styrene-acrylate/silica nanocomposite latex was synthesized by in-situ emulsion polymerization. The influence of the type and content of emulsifier on the emulsion polymerization stabilities, water absorption rate of latex film and the size of the latex were studied systematically. The results indicated that the emulsion polymerization stabilities were best when the emulsifier of SDS and OP-10 were used with a mass ratio of 2 : 1; when the emulsifier content used was in the range of 0. 75%~l. 5%, the obtained latex showed good stability and the water absorption rate was as low as 3. 64%~5. 72%. The nanocomposite latex film showed lower water absorption rate than those formed by the pure styrene-acrylic emulsion and the physical mixture of styrene-acrylic emulsion and silica sol. The TEM results showed that the number of free SiO2 particles in nanocomposite latex was much less than that in the mixture of styrene-acrylic emulsion and silica sol.


    Institute of Scientific and Technical Information of China (English)

    Qi-song Shi; Wei-wei Zuo


    The catalytic system of[2-(2-benzimidazolyl)-6-((1-arylirninoethyl)pyridyl)]nickel chloride/MAO (methylalu-minoxane)was found to be good active for vinyl polymerization of norbornene and provided polymers with relative narrow molecular distributions.Various reaction parameters,such as the ratios of nickel precursor to MAO or monomer norbornene,and the nature of the ligands in complexes were carefully investigated to realize their effects on the catalytic activities,polymer molecular weight and molecular weight distributions.

  6. Structural evolution of silica sols modified with formamide

    Directory of Open Access Journals (Sweden)

    Lenza R.F.S.


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

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

    Directory of Open Access Journals (Sweden)

    Norio Nakata


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

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

    KAUST Repository

    Gong, Dirong


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

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

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


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

  10. Catalytic Conversion of Bio-Oil to Oxygen-Containing Fuels by Acid-Catalyzed Reaction with Olefins and Alcohols over Silica Sulfuric Acid

    Directory of Open Access Journals (Sweden)

    Qingwen Wang


    Full Text Available Crude bio-oil from pine chip fast pyrolysis was upgraded with olefins (1-octene, cyclohexene, 1,7-octadiene, and 2,4,4-trimethylpentene plus 1-butanol (iso-butanol, t-butanol and ethanol at 120 °C using a silica sulfuric acid (SSA catalyst that possesses a good catalytic activity and stability. Gas chromatography-mass spectrometry (GC-MS, Fourier transform infrared spectroscopy (FT-IR and proton nuclear magnetic resonance (1H-NMR analysis showed that upgrading sharply increased ester content and decreased the amounts of levoglucosan, phenols, polyhydric alcohols and carboxylic acids. Upgrading lowered acidity (pH value rose from 2.5 to >3.5, removed the unpleasant odor and increased hydrocarbon solubility. Water content dramatically decreased from 37.2% to about 7.0% and the heating value increased from 12.6 MJ·kg−1 to about 31.9 MJ·kg−1. This work has proved that bio-oil upgrading with a primary olefin plus 1-butanol is a feasible route where all the original heating value of the bio-oil plus the added olefin and alcohol are present in the resulting fuel.

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

    KAUST Repository

    Gong, Dirong


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

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

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


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

  13. Development of high efficiency silica coated β-cyclodextrin polymeric adsorbent for the removal of emerging contaminants of concern from water. (United States)

    Bhattarai, Bikash; Muruganandham, M; Suri, Rominder P S


    This article reports the removal of several emerging contaminants (ECs) from water using novel adsorbent comprising of β-cyclodextrin (β-CD) coated on silica. Fourteen different adsorbents were synthesized under different experimental conditions using two different crosslinking agents (hexamethylene diisocyanate (HMDI) and epichlorohydrin (EPI)) and co-polymers (glycidoxypropyl trimethoxysilane (GPTS) and aminopropyl triethoxysilane (APTES). The adsorption capacities of the synthesized adsorbents were initially evaluated using 17β-estradiol, perfluorooctanoic acid (PFOA), and bisphenol-A (BPA) as adsorbates. The adsorbent prepared by using HMDI as crosslinking agent with DMSO as solvent was observed to perform the best, and removed more than 90% of 17β-estradiol, PFOA, and BPA. Furthermore, the β-CD loading on the ECs removal was studied which showed that the adsorbate removal increases with increase in loading of β-CD on the substrate. The best adsorbent was resynthesized in seven batches and its performance was reproducible for the removal of ten steroid hormones. The adsorbent showed very good regeneration potential for four successive adsorption-regeneration cycles to remove steroid hormones and PFOA. A plausible mechanism of adsorption is proposed. The synthesized best adsorbent is characterized using FTIR, HR-TEM, TGA and nitrogen adsorption analysis. The TGA results showed that the adsorbent has thermal stability of upto 300°C.

  14. Horseradish peroxidase catalyzed free radical cannot free move in reaction solution



    Mechanism of Horseradish Peroxidase -catalyzed phenol compound oxidizing reaction is a radical polymerization. Many polymer preparation are also carry on through the radical polymerization mechanism We deduce if free radical produced by peroxidasecatalyzed phenol polymerization could apply on polymer preparation? Could the phenol–oxygen free radical leave off the peroxidase and catalyze other compounds polymerization? The free radical in phenol oxidation process was investigated in homo...

  15. Recent developments in lipase-catalyzed synthesis of polyesters. (United States)

    Kobayashi, Shiro


    Polyester synthesis by lipase catalyst involves two major polymerization modes: i) ring-opening polymerization of lactones, and, ii) polycondensation. Ring-opening polymerization includes the finding of lipase catalyst; scope of reactions; polymerization mechanism; ring-opening polymerization reactivity of lactones; enantio-, chemo- and regio-selective polymerizations; and, chemoenzymatic polymerizations. Polycondensation includes polymerizations involving condensation reactions between carboxylic acid and alcohol functional groups to form an ester bond. In most cases, a carboxylic acid group is activated as an ester form, such as a vinyl ester. Many recently developed polymerizations demonstrate lipase catalysis specific to enzymatic polymerization and appear very useful. Also, since lipase-catalyzed polyester synthesis provides a good opportunity for conducting "green polymer chemistry", the importance of this is described.

  16. Polymeric microspheres (United States)

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


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

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

    Institute of Scientific and Technical Information of China (English)


    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.

  18. Evolution of microstructure in mixed niobia-hybrid silica thin films from sol-gel precursors. (United States)

    Besselink, Rogier; Stawski, Tomasz M; Castricum, Hessel L; ten Elshof, Johan E


    The evolution of structure in sol-gel derived mixed bridged silsesquioxane-niobium alkoxide sols and drying thin films was monitored in situ by small-angle X-ray scattering. Since sol-gel condensation of metal alkoxides proceeds much faster than that of silicon alkoxides, the incorporation of d-block metal dopants into silica typically leads to formation of densely packed nano-sized metal oxide clusters that we refer as metal oxide building blocks in a silica-based matrix. SAXS was used to study the process of niobia building block formation while drying the sol as a thin film at 40-80°C. The SAXS curves of mixed niobia-hybrid silica sols were dominated by the electron density contrast between sol particles and surrounding solvent. As the solvent evaporated and the sol particles approached each other, a correlation peak emerged. Since TEM microscopy revealed the absence of mesopores, the correlation peak was caused by a heterogeneous system of electron-rich regions and electron poor regions. The regions were assigned to small clusters that are rich in niobium and which are dispersed in a matrix that mainly consisted of hybrid silica. The correlation peak was associated with the typical distances between the electron dense clusters and corresponded with distances in real space of 1-3 nm. A relationship between the prehydrolysis time of the silica precursor and the size of the niobia building blocks was observed. When 1,2-bis(triethoxysilyl)ethane was first hydrolyzed for 30 min before adding niobium penta-ethoxide, the niobia building blocks reached a radius of 0.4 nm. Simultaneous hydrolysis of the two precursors resulted in somewhat larger average building block radii of 0.5-0.6 nm. This study shows that acid-catalyzed sol-gel polymerization of mixed hybrid silica niobium alkoxides can be rationalized and optimized by monitoring the structural evolution using time-resolved SAXS.


    Institute of Scientific and Technical Information of China (English)

    LEIYanohui; LIHong; 等


    Asymmetric hydrisilylation catalyzed by polymeric thiazolidine rhodium catalysts was conducted.Almost the same optical yields have been obtained when comb-shaped polymeric ligands and their corresponding monomer complexed rhodium cataltysts were used to asymmetric hydrosilylation of acetophenone.Optical yield of chiral 1-methylbenzyl alcohol reaches as high as 71.5%.Temperature dependence of enantioselective hydrosilylation of acetophenone was discussed.

  20. One-Pot and Efficient Synthesis of Triazolo[1,2-a]indazole-triones via Reaction of Arylaldehydes with Urazole and Dimedone Catalyzed by Silica Nanoparticles Prepared from Rice Husk


    Asadollah Hassankhani; Sayed Zia Mohammadi; Hooshang Hamidian; Samieh Fozooni


    A novel synthesis of triazolo[1,2-a]indazole-1,3,8-trione derivatives by reaction of urazole, dimedone and aromatic aldehydes under conventional heating and microwave irradiation and solvent-free conditions using silica nanoparticles prepared from rice husk ash as catalyst is described. The new method features high yields, multicomponent reactions and environmental friendliness.

  1. One-Pot and Efficient Synthesis of Triazolo[1,2-a]indazole-triones via Reaction of Arylaldehydes with Urazole and Dimedone Catalyzed by Silica Nanoparticles Prepared from Rice Husk

    Directory of Open Access Journals (Sweden)

    Asadollah Hassankhani


    Full Text Available A novel synthesis of triazolo[1,2-a]indazole-1,3,8-trione derivatives by reaction of urazole, dimedone and aromatic aldehydes under conventional heating and microwave irradiation and solvent-free conditions using silica nanoparticles prepared from rice husk ash as catalyst is described. The new method features high yields, multicomponent reactions and environmental friendliness.

  2. One-pot and efficient synthesis of triazolo[1,2-a]indazole-triones via reaction of arylaldehydes with urazole and dimedone catalyzed by silica nanoparticles prepared from rice husk. (United States)

    Hamidian, Hooshang; Fozooni, Samieh; Hassankhani, Asadollah; Mohammadi, Sayed Zia


    A novel synthesis of triazolo[1,2-a]indazole-1,3,8-trione derivatives by reaction of urazole, dimedone and aromatic aldehydes under conventional heating and microwave irradiation and solvent-free conditions using silica nanoparticles prepared from rice husk ash as catalyst is described. The new method features high yields, multicomponent reactions and environmental friendliness.

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

    Directory of Open Access Journals (Sweden)

    Basudeb Basu


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

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

    KAUST Repository

    Werghi, Baraa


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

  5. Structure of silica xerogels synthesized with organoalkoxysilane co-reactants hints at multiple phase separation. (United States)

    Gommes, Cédric J; Basiura, Monika; Goderis, Bart; Pirard, Jean-Paul; Blacher, Silvia


    The microstructure of hybrid silica xerogels synthesized by the base-catalyzed polymerization of tetraethoxysilane (TEOS) in ethanol in the presence of 3-aminopropyltriethoxysilane (AES) and of 3-(2-aminoethylamino)propyltrimethoxysilane (EDAS) as co-reactants, and dried in subcritical conditions, is analyzed. A thorough structural characterization of the samples is performed combining nitrogen adsorption, small-angle X-ray scattering (SAXS), and transmission electron microscopy coupled with digital image analysis. The use of these methods shows that, for both co-reactants, the xerogels are made of macropores supported by filaments, with each filament being formed of smaller structures. The quantitative impact of the additive on each structural level is assessed. The data are compared with a previous time-resolved SAXS study conducted during the formation of the gels (J. Phys. Chem. B 2004, 108, 8983-8991). The results are analyzed in the framework of a double phase separation model.

  6. Silica Nephropathy

    Directory of Open Access Journals (Sweden)

    N Ghahramani


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


    Institute of Scientific and Technical Information of China (English)

    杨亮亮; 殷明志; 常亮亮


    采取溶胶-凝胶成膜技术,以正硅酸乙酯(TEOS)为原料,分别以水为溶剂NH3催化、乙醇为溶剂HC1催化和冰醋酸为溶剂各自制备出粒状结构、簇状结构和网状结构的二氧化硅溶胶,丙三醇作为添加剂与TEOS水解中间体以氢键结合控制二氧化硅溶胶形态,聚乙烯醇(PVA)与二氧化硅溶胶形成有机/无机互穿网络结构,易于成膜.热处理能使二氧化硅凝胶薄膜中的添加剂逸出并形成疏松结构,塑性形变使硅胶薄膜形成多孔、疏松、致密结构二氧化硅薄膜.实验表明,催化剂和溶剂效应直接影响着二氧化硅溶胶微观结构,从而影响着所形成的硅胶薄膜的微结构.多孔硅胶膜的平衡吸湿量是致密硅胶薄膜的3倍;而疏松结构的硅胶薄膜的吸湿量高于多孔硅胶薄膜的吸湿量,且其吸附速率明显大于多孔硅胶薄膜的吸附速率.%Colloidal silica sol, clustered silica sol, and polymeric silica sol were made by sol-gel processes of tetraethylorthosilicate (TEOS) catalyzing with NH3-H2O in water, with HC1 in ethanol and in glacial acetic acid, respectively. Glycerol as a template combining with the hydrolyzing intermediates controlled the silica intermediate state, while poly(vinyl alcohol) (PVA) compatibilizing and cross-linking with silica polymers made the silica sol a co-polymeric and spinning easily. Heating processes made the gel silica membrances into loosen structure after the organic templates being escaped, and plastic deformation forced the silica gel membrances into microporous, loosen, and compact structure. The experiment results indicated microstructures of the silica membrances were affected by catalyst and solvent. Absorbed amount of the microporous silica membrances was triple that of the compact, while the loosen silica membrance's was more than that of the microporous and the absorbed ratio higher than that of the microporous.

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

    Directory of Open Access Journals (Sweden)

    Masako Miki


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

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

    KAUST Repository

    Kermagoret, Anthony


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

  10. 茂金属催化剂Cpt2MCl2(Cpt=tBuC5H4,M=Ti、zr、Hf)聚合丁烯-1的研究%Polymerization of Butene-1 Catalyzed byCpt2MCl2[Cpt=tBuC5H4,M=Ti(Ⅰ),Zr(Ⅱ),Hf(Ⅲ)

    Institute of Scientific and Technical Information of China (English)

    周光远; 程延祥; 金国新


    The synthesis and characterization of metallocene complexes Cpt2MC12[Cpt=tBuC5H4,M=Ti(Ⅰ), Zr(Ⅱ), Hr(Ⅲ)] are presented in catalyzation polymerization of butene-1. The metallocenecatalysts and polybutenes have been characterized by IR, 1H NMR and EI-MS spectra and DSCmeasurements. The catalytic features for butene-1 polymerization were studied under differentconditions. The results showed that Cpt2MCl2/MAO had high activity for butene-1 polymerization,improving the tacticity and molecular weight of the polymers obtained.%探讨了茂金属催化剂Cpt2MCl2(CPt=tBuC5H4,M=Ti,zr,Hf)的合成以及用于聚合丁烯-1的研究,研究了几种不同的茂金属催化剂和不同聚合条件下的催化行为,并通过IR、1H NMR、EI-MS、DSC、粘度法测分子量和正庚烷抽提等测试手段对催化剂和聚合物进行了表征.结果表明,叔丁基取代的茂金属催化剂催化丁烯-1聚合具有较高的催化活性,叔丁基的引入提高了聚合物的等规度和分子量.

  11. Horseradish peroxidase catalyzed free radical cannot free move in reaction solution

    Directory of Open Access Journals (Sweden)

    Cai Xialing


    Full Text Available Mechanism of Horseradish Peroxidase -catalyzed phenol compound oxidizing reaction is a radical polymerization. Many polymer preparation are also carry on through the radical polymerization mechanism We deduce if free radical produced by peroxidasecatalyzed phenol polymerization could apply on polymer preparation? Could the phenol–oxygen free radical leave off the peroxidase and catalyze other compounds polymerization? The free radical in phenol oxidation process was investigated in homogeneous reaction and in immobilized HRP catalyzed reaction. The results showed the free radical produced by peroxidase only move on the surface of enzyme, can’t free move in solution in both experiment. Evidence showed the phenol polymerization is enzyme reaction process, different from general chemistry free radical chain reaction.Keywords: Horseradish Peroxidase, free radical polymerization, mechanismReceived: 17 March 2008 / Received in revised form: 5 February 2009, Accepted: 31 April 2009 Published online: 14 May 2009

  12. Saccharide modified silica particles by enzymatic grafting

    NARCIS (Netherlands)

    Loos, Katja; Braunmühl, Volker von; Stadler, Reimund; Landfester, K; Spiess, HW


    The surface of silica particles has been chemically modified with oligo- or poly-(α,1→4)-D-glucopyranose (amylose) chains of various length by covalently attaching maltoheptaose derivatives to the solid support and enzymatic polymerization of glucose-1-phosphate with a potato phosphorylase as cataly

  13. Glycine Polymerization on Oxide Minerals (United States)

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


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

  14. Complex coacervation between colloidal silica and polyacrylamide

    Energy Technology Data Exchange (ETDEWEB)

    Kawase, Kaoru; Sakami, Hiroshi; Hayakawa, Kiyoshi


    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).

  15. Recent Progress on Molecular Modeling of Ethylene Polymerization/Oligomerization Catalyzed by Chromium-Based Catalysts%铬系催化乙烯配位聚合/齐聚分子模拟研究进展

    Institute of Scientific and Technical Information of China (English)

    刘振; 程瑞华; 何雪莲; 田洲; 刘柏平


    Phillips chromium-based catalysts are widely used in industrial production of polyethylene andα-olefins through ethylene selective oligomerization. Recently, molecular modeling has been playing more and more important role in understanding the mechanism of ethylene polymerization and selective trimerization. From this point of view, the active site transformation from polymerization to metathesis during the induction period of the Phillips catalyst, the effect of Ti-modification on the Phillips catalyst, the transformation from ethylene polymerization to selective trimerization of the Cr(III) 2-EH/PIBAO/DME system, and the effect of deprotonation and Cr oxidation states in the Cr-SNS system on the ethylene selective trimerization were reviewed. A much profound mechanistic understanding has been achieved through combination of molecular modeling with experiments.%针对工业中广泛应用的 Phillips 铬系乙烯聚合催化剂和铬系乙烯选择性齐聚催化体系,从分子模拟角度对近期相关研究进展进行综述。主要介绍了分子模拟在 Phillips 铬系催化剂诱导期内乙烯聚合活性中心向乙烯易位活性中心转换机理、Ti改性Phillips铬系催化剂的乙烯聚合行为、Cr(III)2-EH/PIBAO/DME体系乙烯聚合和三聚转换机理以及 Cr-SNS 体系去质子化对乙烯三聚活性的影响等方面的研究进展。通过计算机分子模拟和实验手段相结合,可以获得对催化反应机理更为深刻的认识,从而为新型催化剂的设计与开发提供理论指导。

  16. Ester Exchange Polymerization of 3-Hydroxyl Propionic Acid Methyl Ester Catalyzed by SO3 H-functionalized Ionic Liquids%磺酸功能化离子液体催化3-羟基丙酸甲酯酯交换聚合反应

    Institute of Scientific and Technical Information of China (English)

    徐国荣; 刘建华; 宋大勇; 陈静; 夏春谷


    Employing SO3 H-functionalized ionic liquids as catalysts, the biodegradable poly [ 3-hydroxypropionic acid] (PHP) was obtained by ester exchange polymerization of 3-Hydroxyl propionie acid methyl ester(3-HPM). The effects of various ionic liquids, reaction temperature and reaction time on the polymerization performance were discussed in detail. Meanwhile, the FFIR, NMR and TG-DSC were applied to characterize the products. The PHP with Mw above 1.0×104 and yield above 82% could be obtained when catalyzed by [ BsMIm] [ OTf] under the opti- mal reaction conditions. In addition, the catalyst in the polymer could be removed completely after washing with water, efficiently avoiding the pollution of the product.%以磺酸功能化咪唑离子液体为催化剂,以3-羟基丙酸甲酯为原料,采用自身酯交换法合成了具有生物可降解性能的聚羟基脂肪酸酯.系统考察了离子液体种类、反应温度以及聚合反应时间对反应性能的影响,同时采用红外、核磁、热分析等手段对产物进行表征.研究结果表明:阴离子为CF3SO-3的磺酸功能化离子液体在120℃的低温下催化聚合反应所得聚酯Mw可达10 159,收率82.1%;通过水洗方法可有效去除产物中的离子液体催化剂,从而避免催化剂污染产物.

  17. Liquid nitration of benzene catalyzed by ammonium molybdophosphat catalyst supported on silica%二氧化硅负载磷钼酸铵催化苯液相硝化反应的研究

    Institute of Scientific and Technical Information of China (English)

    耿辉; 刘丽君; 李考真; 崔庆新; 龚树文


    Ammonium molybdophosphat (S-AMPA) catalyst supported on silica was synthesized by sol-gel method with ethyl silicate as silicon source. The properties were characterized by XRD, IR spectra and the potentiometric titration method. The influences of various parameters such as reaction time and temperature on liquid nitration of benzene have also been systematically studied. XRD and IR indicated that the Keggin structure was retained after AMPA catalyst supported on silica. And the results of potentiometric titration revealed that the maximum acid strength and the total number of acid sites of S-AMPA were more than these of unsupported catalyst. The catalyst exhibited high catalytic activity for nitration reaction and the highest yield is up to 96%. The phase and structure of catalyst have not obvious change after used, although the active component had some loss in the reaction progress.%以正硅酸乙酯为硅源,采用溶胶-凝胶法制备了负载磷钼杂多酸铵催化剂(S-AMPA),利用XRD、IR以及电位滴定等方法对催化剂进行了表征,并考察了催化剂用量、反应时间和温度等反应参数对催化剂的苯液相硝化反应催化性能的影响.结果表明,溶胶-凝胶法制备的S-AMPA具有典型的Keggin结构,而且负载后催化剂的酸度和酸性点总量都明显增大;反应时间等反应参数对苯催化硝化反应有明显的影响,在优化实验条件下,苯硝化转化率可达96%;反应后催化剂活性组分有所损失,但催化剂整体物相和结构没有发生明显变化.

  18. 白炭黑原位复合聚丙烯酰胺水凝胶的合成及次级网络对流变行为的影响%Synthesis and the Second Networks Effects on Rheological Behaviors of Polyacrylamide Hydrogel by Silica In-Situ Polymerization

    Institute of Scientific and Technical Information of China (English)

    苏智青; 何佳; 姜祖明; 黄光速


    Polyacrylamide(PAM)/SiO2 hybird hydrogels were synthesized by silica-acrylamide in-situ composit via aqueous solution polymerization. Potassium persulfate was used as the initiator, acrylamide(AM) as main monomer and polyethylene glycol diacrylate as the crsosslinker. Analysis to the tests by oscillation rheometer and infraed spectrometer demonstrate existence of the second networks formed by silica and polyacrylamide. And the influence of the second networks is found on modulus, zero shear viscosity, flow coefficient and tanδ of the PAM hydrogels with the different ratio of Silica. Through comparison on the zero shear viscosity and the flow coefficient of AM/silica hydrogel with different diploid water-absorbent, the principle reinforced from the second networks and its origin are presented.%采用水溶液聚合法,通过丙烯酰胺与白炭黑原位复合,制备出复合聚丙烯酰胺凝胶.采用高级流变仪和红外吸收光谱证实了白炭黑与聚丙烯酰胺形成的次级网络的存在,通过对比不同白炭黑填充量和不同吸水倍数对聚丙烯酰胺水凝胶模量、损耗角正切、零切黏度和流动指数的影响,发现白炭黑的加入对聚丙烯酰胺凝胶力学性能的贡献,随着白炭黑用量在0%~3%范围内增加,凝胶交联密度增大,弹性增强,流动性降低.当亲水型白炭黑T40用量在3%时,水凝胶的弹性模量在0.1Hz时达100 Pa,而疏水型白炭黑H2000填充的水凝胶在0.1 Hz时弹性模量小于0.1 Pa,确切反映了次级网络的明显影响.


    Institute of Scientific and Technical Information of China (English)

    SUN Luying; HUANG Zhitang


    Various catalysts for the polymerization ot aromatic nitriles were investigated. It was found that Lewis acid - metal is a preferable catalyst system for the polymerization of aromatic nitriles,and the polymerization rate is about 10 times faster than Lewis acid alone. The polymerization rate of benzonitrile catalyzed by Lewis acid and different metals was measured, and the activity of metals was in the following decreasing order ,magnesium, zinc, sodium, calcium. Furthermore, the polymerization of benzonitrile catalyzed by different Lewis acid and zinc was also investigated.


    Institute of Scientific and Technical Information of China (English)

    SUN Luying; HUANG Zhitang


    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.

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

    NARCIS (Netherlands)

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


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

  2. Biokompatible Polymere (United States)

    Ha, Suk-Woo; Wintermantel, Erich; Maier, Gerhard

    Der klinische Einsatz von synthetischen Polymeren begann in den 60-er Jahren in Form von Einwegartikeln, wie beispielsweise Spritzen und Kathetern, vor allem aufgrund der Tatsache, dass Infektionen infolge nicht ausreichender Sterilität der wiederverwendbaren Artikel aus Glas und metallischen Werkstoffen durch den Einsatz von sterilen Einwegartikeln signifikant reduziert werden konnten [1]. Die Einführung der medizinischen Einwegartikel aus Polymeren erfolgte somit nicht nur aus ökonomischen, sondern auch aus hygienischen Gründen. Wegen der steigenden Anzahl synthetischer Polymere und dem zunehmenden Bedarf an ärztlicher Versorgung reicht die Anwendung von Polymeren in der Medizin von preisgünstigen Einwegartikeln, die nur kurzzeitig intrakorporal eingesetzt werden, bis hin zu Implantaten, welche über eine längere Zeit grossen Beanspruchungen im menschlichen Körper ausgesetzt sind. Die steigende Verbreitung von klinisch eingesetzten Polymeren ist auf ihre einfache und preisgünstige Verarbeitbarkeit in eine Vielzahl von Formen und Geometrien sowie auf ihr breites Eigenschaftsspektrum zurückzuführen. Polymere werden daher in fast allen medizinischen Bereichen eingesetzt.

  3. Synthesis of cyclohexanone ethylene ketal catalyzed by silica supported ammonium molybdophosphate catalyst%二氧化硅负载磷钼杂多酸铵催化合成环己酮乙二醇缩酮

    Institute of Scientific and Technical Information of China (English)

    于丽敏; 王佳佳; 周卫卫; 刘丽君; 龚树文; 尹汉东


    采用溶胶-凝胶法制备系列二氧化硅负载磷钼杂多酸铵固体酸催化剂,以环己酮和乙二醇为原料、环己烷为带水荆,合成环己酮乙二醇缩酮,考察催化剂负载量、原料配比、催化剂用量、带水剂用量以及反应时间等因素对反应收率的影响.得到较佳工艺条件:n(环己酮):n(乙二醇)=1:1.5,催化剂用量0.5 g,环已烷用量10 mL,回流反应45 min,产品平均收率97.1%.催化剂重复使用性实验结果表明,随着使用次数的增多,二氧化硅负载磷钼杂多酸铵催化剂催化活性下降,但使用6次后,仍表现出较高的缩酮收率.%Cyclohexanone glycol ketal was synthesized from cyclohexanone and ethylene glycol using silica supported ammonium molybdophosphate as the catalyst,which was prepared by sol-gel method. The influence of catalyst dosage, molar ratio of cyclohexanone to ethylene glycol, amount of water carrying agent and reaction time on the yield was investigated. The results showed that the product yield of 97.1%was attained under the optimal condition as follows: n ( cyclohexanone ): n ( glycol ) = 1: 1.5, catalyst dosage 0.5 g,the amount of water carrying agent cyclohexane 10 mL,and reflux time 45 min. The catalyst exhibited higher catalytic activity after being repeated use 6 times.

  4. 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)



    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.

  5. A bioinspired strategy for surface modification of silica nanoparticles (United States)

    Tian, Jianwen; Zhang, Haoxuan; Liu, Meiying; Deng, Fengjie; Huang, Hongye; Wan, Qing; Li, Zhen; Wang, Ke; He, Xiaohui; Zhang, Xiaoyong; Wei, Yen


    Silica nanoparticles have become one of the most promising nanomaterials for a vast of applications. In this work, a novel strategy for surface modification of silica nanoparticles has been developed for the first time via combination of mussel inspired chemistry and Michael addition reaction. In this procedure, thin polydopamine (PDA) films were first coated on the bare silica nanoparticles via self-polymerization of dopamine in alkaline condition. And then amino-containing polymers were introduced onto the PDA coated silica nanoparticles through Michael addition reaction, that are synthesized from free radical polymerization using poly(ethylene glycol) methyl methacrylate (PEGMA) and N-(3-aminopropyl) methacrylamide (NAPAM) as monomers and ammonium persulfate as the initiator. The successful modification of silica nanoparticles was evidenced by a series of characterization techniques. As compared with the bare silica nanoparticles, the polymers modified silica nanoparticles showed remarkable enhanced dispersibility in both aqueous and organic solution. This strategy is rather simple, effective and versatile. Therefore, it should be of specific importance for further applications of silica nanoparticles and will spark great research attention of scientists from different fields.

  6. Reaction mechanism and structure-reactivity relationships in the stereospecific 1,4-polymerization of butadiene catalyzed by neutral dimeric allylnickel(II) halides [Ni(C3H5)X]2 (X- = Cl-, Br-, I-): a comprehensive density functional theory study. (United States)

    Tobisch, S; Taube, R


    For the first time, a comprehensive and consistent picture of the catalytic cycle of 1,4-polymerization of butadiene with neutral dimeric allylnickel(II) halides [Ni(C3H5)X]2 (X = Cl- (I), Br- (II), and I- (III)) as single-site catalysts has been derived by means of quantum chemical calculations that employ a gradient-corrected density-functional method. All crucial reaction steps of the entire catalytic course have been scrutinized, taking into account butadiene pi complex formation, symmetrical and asymmetrical splitting of dimeric pi complexes, cis-butadiene insertion, and anti-syn isomerization. The present investigation examines, in terms of located structures, energies and activation barriers, the participation of postulated intermediates, in particular it aimed to clarify whether monomeric or dimeric species are the catalytically active species. Prior qualitative mechanistic assumptions are substituted by the presented theoretically well-founded and detailed analysis of both the thermodynamic and the kinetic aspects, that substantially improve the insight into the reaction course and enlarge them with novel mechanistic proposals. From a mechanistic point of view, all three catalysts exhibit common characteristics. First, chain propagation occurs by cis-butadiene insertion into the pi-butenylnickel(II) bond with nearly identical intrinsic free-energy activation barriers. Second, the reactivity of syn-butenyl forms is distinctly higher than that of anti forms. Third, the chain-propagation step is rate-determining in the entire polymerization process, and the pre-established anti-syn equilibrium can always be regarded as attained. Accordingly, neutral dimeric allylnickel(II) halides catalyze the formation of a stereo-regular trans-1,4-polymer under kinetic control following the k1t channel with butenyl(halide)(butadiene)NiII complexes being the catalytically active species. Production of a stereoregular cis-1,4-polymer with allylnickel chloride can only be

  7. Preparation of Hyperbranched Polyethyleneimine Composite Membrane Using Interfacial Polymerization Catalyzed by 4-Dimethylamiopryidine%4-二甲氨基吡啶催化的界面聚合法制备超支化聚乙烯亚胺复合膜

    Institute of Scientific and Technical Information of China (English)

    张林; 林赛赛; 魏平; 程丽华; 陈欢林


    The promoting effect of 4-dimethylaminopyridine (DMAP) on the interfacial polymerization between trimesoyl chloride (TMC) and hyperbranched polyethyleneimine (PEI) was investigated. The solubility of DMAP in organic phase and aqueous phase was examined and the mass fraction of DMAP to PEI was optimized to 8%. Fourier transform infrared spectroscopy and scanning electron microscopy results showed that when catalyzed by DMAP, almost all the amino groups of PEI were cross-linked with TMC into amide groups, and thus a smooth and integrated layer was formed on the polysulfone support membrane. The rejection of PEI/TMC composite membrane against NaCl was improved to 85.4% as compared with 45.2%. Combined with the donating electron effects of 1-tertiary amine and 4-methylamino groups, the catalytic mechanism for DMAP in this PEI-based interfacial polymerization was proposed.%为了提高超支化聚合物在界面聚合反应中的成膜性能,选择4-二甲氨基吡啶(DMAP)作为空间位阻催化剂,用于催化超支化聚乙烯亚胺(PEI)与均苯三甲酰氯(TMC)界面聚合成膜.研究了DMAP在水油两相中的溶解性能,发现DMAP的适宜用量为底物PEI的8%.傅里叶红外光谱和扫描电镜表征结果表明,DMAP能够催化PEI上更多氨基参与酰化交联,在聚砜底膜上形成光滑连续的网络状结构.该复合分离膜对NaCl的截留率由无DMAP催化成膜的45.2%提高至85.4%,水通量高达60.8 L/(m2·h).结合吡啶环上1-叔胺基团及环外的4-二甲氨基团,推测了DMAP在PEI界面聚合反应过程中消除强空间位阻效应的催化机理.

  8. Sono-enzymatic polymerization of catechol


    Fernandes, Margarida M.; Basto, Carlos; Zille, Andrea; Munteanu, Florentina-Daniela; Gübitz, Georg M.; Paulo, Artur Cavaco


    "Abstracts of papers presented at the 232nd American Chemical Society National Meeting" The potential of laccase enzymes for polymerizing, crosslinking and functionalizing various compounds was studied extensively and increasing interest has been focused on the application of this enzyme as a new biocatalyst in organic synthesis.[1-6] Laccases (EC are a class of multi-copper-containing oxidoreductase enzymes able to catalyze the transformation of various aromatic c...

  9. Supramolecular Assembly of pH-Sensitive Triphenylene Derived π-Gelators and Their Application as Molecular Template for the Preparation of Silica Nanotubes

    Directory of Open Access Journals (Sweden)

    Ignacio Muñoz Resta


    Full Text Available The gelation properties and mode of self-assembly of six asymmetrical hexaether triphenylene derivatives mono-functionalized with carboxylic and primary amine groups were investigated. The presence of a carboxylic and amine group attached to the triphenylene core generated stable, thermo- and pH-sensitive supramolecular π-organogels with a reversible response to both stimuli. In order to understand the gelation process, we studied the effect of the spacer length and found a different gelation scope for the acid and basic derivatives that accounts for a different supramolecular self-assembly. The presence of the basic group on the amino derivatives was used to guide and catalyze the templated in situ sol-gel polymerization of TEOS and allowed us, under controlled hydrolytic conditions, to prepare an entangled fibrillar network of silica nanotubes.

  10. 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


    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.

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

    Directory of Open Access Journals (Sweden)

    Mu Bin


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

  12. Hollow silica spheres: synthesis and mechanical properties. (United States)

    Zhang, Lijuan; D'Acunzi, Maria; Kappl, Michael; Auernhammer, Günter K; Vollmer, Doris; van Kats, Carlos M; van Blaaderen, Alfons


    Core-shell polystyrene-silica spheres with diameters of 800 nm and 1.9 microm were synthesized by soap-free emulsion and dispersion polymerization of the polystyrene core, respectively. The polystyrene spheres were used as templates for the synthesis of silica shells of tunable thickness employing the Stöber method [Graf et al. Langmuir 2003, 19, 6693]. The polystyrene template was removed by thermal decomposition at 500 degrees C, resulting in smooth silica shells of well-defined thickness (15-70 nm). The elastic response of these hollow spheres was probed by atomic force microscopy (AFM). A point load was applied to the particle surface through a sharp AFM tip, and successively increased until the shell broke. In agreement with the predictions of shell theory, for small deformations the deformation increased linearly with applied force. The Young's modulus (18 +/- 6 GPa) was about 4 times smaller than that of fused silica [Adachi and Sakka J. Mater. Sci. 1990, 25, 4732] but identical to that of bulk silica spheres (800 nm) synthesized by the Stöber method, indicating that it yields silica of lower density. The minimum force needed to irreversibly deform (buckle) the shell increased quadratically with shell thickness.

  13. Functional Films from Silica/Polymer Nanoparticles

    Directory of Open Access Journals (Sweden)

    Tânia Ribeiro


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


    Institute of Scientific and Technical Information of China (English)

    Xiao-hu Qiang; Li-bang Feng; Yan-ping Wang; Shun-hua Wang


    Waterborne polyurethane composites containing silica nanoparticles are synthesized successfully via the in situ polymerization.The structure,thermal stability,surface hardness,tensile strength,UV-Vis absorbance,dynamic mechanical properties and chemicals resistance of the resulting composites are investigated by FTIR,TEM,TGA,UV-Vis,DMA and chemicals soakage measurements.Results show that polyurethane molecules and silica nanoparticles are linked with covalent bonds.As a result,physical properties of polyurethane composites,such as thermal stability,surface hardness,weather and chemicals resistance are all improved when an appropriate concentration of silica nanoparticles are incorporated.

  15. Synthesis of Polymeric Microcapsule Arrays and Their Use for Enzyme Immobilization (United States)


    acetyl L-phenyl alanine ethyl ester and propanol; subtilisin should catalyze the transesterification reaction. Transesterification is 3 observed when...template- based synthetic method that yields hollow polymeric microcapsules of uniform diameter and length. These microcapsules are arranged in a high...immobilization that satisfies all of these criteria. We have developed a template- based synthetic method that yields hollow polymeric microcapsules of

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

    NARCIS (Netherlands)

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


    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

  17. Towards copper-free nanocapsules obtained by orthogonal interfacial "click" polymerization in miniemulsion. (United States)

    Siebert, Joerg Max; Baier, Grit; Musyanovych, Anna; Landfester, Katharina


    A facile method to produce nanocapsules by copper-free interfacial "click"-polymerization as orthogonal reaction for the encapsulation of functional molecules is successfully performed using stable miniemulsion droplets. Difunctional azides and alkynes have been used for polymerization around the miniemulsion droplets, leading to the formation of nanocapsules. The results were compared with copper-catalyzed systems.

  18. Insights into relevant mechanistic aspects about the induction period of Cu(0)/Me(6)TREN-mediated reversible-deactivation radical polymerization. (United States)

    Gao, Yongsheng; Zhao, Tianyu; Zhou, Dezhong; Greiser, Udo; Wang, Wenxin


    There is a controversial debate about the mechanism of the Cu(0)-catalyzed radical polymerization. Herein, a comparative analysis of a series of reactions catalyzed by different valent copper shows that the induction period and the subsequent autoaccelerated polymerization of a Cu(0)/Me6TREN-catalyzed system originate from the accumulation of soluble copper species, and Cu(I) is still a powerful activator under its disproportionation favored conditions.

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

    Institute of Scientific and Technical Information of China (English)


    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.

  20. 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. (United States)

    Wang, Wei; He, Maofang; Wang, Chaozhan; Wei, Yinmao


    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.


    Institute of Scientific and Technical Information of China (English)

    Yi Yi; Xing-he Fan; Yong-feng Zhao; Xiao-fang Chen; Xin-hua Wan; Qi-feng Zhou


    A side-on liquid crystalline monomer, 2,5-bis[(4-hexyloxyphenyl)oxycarbonyl]styrene) (HPCS), was successfully polymerized via atom transfer radical polymerization (ATRP). The polymerization was catalyzed by CuBr/PMDETA in chlorobenzene at 90℃ with (1-bromoethyl)benzene as the initiator. The polymers have narrow MWD. It is the second example of mesogen-jacketed liquid crystalline polymer (MJLCP) prepared by ATRP.

  2. Catalyzing RE Project Development

    Energy Technology Data Exchange (ETDEWEB)

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


    This poster details how screenings done with REopt - NREL's software modeling platform for energy systems integration and optimization - are helping to catalyze the development of hundreds of megawatts of renewable energy.

  3. Muon Catalyzed Fusion (United States)

    Armour, Edward A.G.


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

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

    Energy Technology Data Exchange (ETDEWEB)

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


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

  5. 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


    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...


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


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

  8. Silica extraction from geothermal water (United States)

    Bourcier, William L; Bruton, Carol J


    A method of producing silica from geothermal fluid containing low concentration of the silica of less than 275 ppm includes the steps of treating the geothermal fluid containing the silica by reverse osmosis treatment thereby producing a concentrated fluid containing the silica, seasoning the concentrated fluid thereby producing a slurry having precipitated colloids containing the silica, and separating the silica from the slurry.

  9. Polymeric materials for neovascularization (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

  10. Enzyme-catalysis breathes new life into polyester condensation polymerizations. (United States)

    Gross, Richard A; Ganesh, Manoj; Lu, Wenhua


    Traditional chemical catalysts for polyester synthesis have enabled the generation of important commercial products. Undesirable characteristics of chemically catalyzed condensation polymerizations include the need to conduct reactions at high temperatures (150-280 degrees C) with metal catalysts that are toxic and lack selectivity. The latter is limiting when aspiring towards synthesis of increasingly complex and well-defined polyesters. This review describes an exciting technology that makes use of immobilized enzyme-catalysts for condensation polyester synthesis. Unlike chemical catalysts, enzymes function under mild conditions (< or =100 degrees C), which enables structure retention when polymerizing unstable monomers, circumvents the introduction of metals, and also provides selectivity that avoids protection-deprotection steps and presents unique options for structural control. Examples are provided that describe the progress made in enzyme-catalyzed polymerizations, as well as current limitations and future prospects for developing more efficient enzyme-catalysts for industrial processes.

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

    Directory of Open Access Journals (Sweden)

    Jun-ichi Kadokawa


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

  12. Janus Silica Hollow Spheres Prepared via Interfacial Biosilicification. (United States)

    Sheng, Li; Chen, Hong; Fu, Wenxin; Li, Zhibo


    A poly(ethylene glycol)-b-poly(L-lysine)-b-poly(styrene) (PEG-PLL-PS) triblock copolymer, which contains a cationic PLL block as the middle block, is synthesized via a combination of ring-opening polymerization (ROP) and atom-transfer radical polymerization (ATRP). The PEG-PLL-PS (ELS) triblock is employed as a macromolecular surfactant to form a stable oil-in-water (O/W) emulsion, which is subsequently used as the template to prepare Janus silica hollow spheres (JHS) via a one-pot biosilicification reaction. For the emulsion template, the middle PLL block assembles at the O/W interface and directs the biomimetic silica synthesis in the presence of phosphate buffer and silicic acid precursors. This biosilicification process takes place only in the intermediate layer between water and the organic interior phase, leading to the formation of silica JHSs with hydrophobic PS chains tethered to the inner surface and PEG attached to the outer surface. The three-layer JHSs, namely, PEG/silica-polylysine/PS composites, were verified by electron microscopy. Upon further breaking these JHSs into species, polymer-grafted Janus silica nanoplates (JPLs) can be obtained. Our studies provide an efficient one-step method for preparing hybrid silica Janus structures within minutes.

  13. Highly efficient palladium-catalyzed hydrostannation of ethyl ethynyl ether. (United States)

    Andrews, Ian P; Kwon, Ohyun


    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 ethyl ethynyl ether using 0.1% palladium(0) catalyst and 1.0 equiv of tributyltin hydride. The product obtained is a mixture of regioisomers that can be carried forward with exclusive reaction of the beta-isomer. This method is highly reproducible; relative to previously reported procedures, it is more economical and involves a more facile purification procedure.

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

    Energy Technology Data Exchange (ETDEWEB)

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


    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.

  15. Porous Properties of Nano-fibriform Silica from Natural Chrysotile

    Institute of Scientific and Technical Information of China (English)

    WANG Lijuan; LU Anhuai; WANG Changqiu; LI Xuejun; ZHENG Xishen; ZHAO Dongjun; LIU Rui


    With the TEM and physical gas adsorption techniques, porous properties of nano-fibriform silica (MLD: 92.73 %) from natural chrysotile are studied in this paper. The results indicate that porous nano-fibriform silica results from brucite octahedral sheets of nature chrysotile dissolved completely and Si-O tetrahedral sheets collapsed by acid leaching. Its length is at a micron or nanometer scale.There are two types of pores: pores among neighboring fibers and pores in nanofiber. These pores (less than 6.5 nm in diameter, mostly 2.1 nm and 3.8 nm) all belong to mesopores. The pores in fibers consist of those among SiO2 particles, those among aggregates, remnant nanotubes and capillary tubes. Nanofibriform silica proves better than the traditional silica as a carrier of catalyzer and a filler for reinforce rubber and plastics.

  16. Predictive Modeling of Metal-Catalyzed Polyolefin Processes


    Khare, Neeraj Prasad


    This dissertation describes the essential modeling components and techniques for building comprehensive polymer process models for metal-catalyzed polyolefin processes. The significance of this work is that it presents a comprehensive approach to polymer process modeling applied to large-scale commercial processes. Most researchers focus only on polymerization mechanisms and reaction kinetics, and neglect physical properties and phase equilibrium. Both physical properties and phase equilib...

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

    Institute of Scientific and Technical Information of China (English)


    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.

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

    Institute of Scientific and Technical Information of China (English)


    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.

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

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


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

  20. Soluble polymers in sol-gel silica (United States)

    Beaudry, Christopher Laurent

    In the last few years, the inherent versatility of sol-gel processing has led to a significant research effort on inorganic/organic materials. One method of incorporating an organic phase into sol-gel silica is dissolving an organic polymer in a tetraethylorthosilicate (TEOS) solution, followed by in situ polymerization of silica in the presence of organic polymer. The first part of the study involved the development of a two-step (acid-base) synthesis procedure to allow systematic control of acidity in TEOS solutions. With this procedure, it was possible to increase the pH of the TEOS solution while correlating the acidity and properties. The properties were the gelation time, syneresis rate, drying behavior, and xerogel pore structure, as determined by nitrogen sorption. Furthermore, controlling the acidity was shown to control the silica xerogel pore structure. In the second part of the study, the two-step procedure was used to synthesize silica/poly(ethylene glycol) (PEG), and silica/poly(vinyl acetate) (PVAc) composite materials. The content of organic polymer and the molecular weight were varied. The gelation time, the syneresis rate, the drying behavior, and the pore structure were determined for compositions with 10% PEG (M.W. 2,000), 5, 10, and 15% PEG (M.W. 3,400), and 10 and 25% PVAc (M.W. 83,000). Other compositions and molecular weights of PEG lead to sedimentation. In the PEG compositions, the tendency to phase separate was correlated with the effects of the processing variables on the segregation strength and polymerization rate. The PVAc compositions did not show any visible phase separation during processing, giving the composite xerogels an appearance similar to pure silica. The property differences between gels with PEG and gels with PVAc show the relative strength of the interactions with silica. Both polymers exhibit hydrogen bonding between the phases. In the case of PEG, hydrogen bonding between the ether oxygens of the polymer and silanol

  1. Luminescence of Terbium Complexes Incorporated into Silica Matrix

    Institute of Scientific and Technical Information of China (English)

    闫冰; 游佳勇


    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.

  2. Preparation of Composite Microporous Silica Membranes Using TEOS and 1, 2-Bis(triethoxysilyl)ethane as Precursors for Gas Separation%以正硅酸乙酯和1,2-二(三乙氧基硅基)乙烷为前驱体制备微孔SiO2复合膜及其气体分离性能

    Institute of Scientific and Technical Information of China (English)



    This paper reports on a new microporous composite silica membrane prepared via acid-catalyzed polymeric route of sol-gel method with tetraethylorthosilicate (TEOS) and a bridged silsesquioxane [1, 2-bis(triethoxysilyl)ethane,BTESE] as precursors. A stable nano-sized composite silica sol with a mean volume size of~5 nm was synthesized.A 150 nm-thick defect-free composite silica membrane was deposited on disk support consisting of macroporous α-Al2O3 and mesoporous γ-Al2O3 intermediate layer by using dip-coating approach, followed by calcination under pure nitrogen atmosphere. The composite silica membranes exhibit molecular sieve properties for small gases like H2, CO2, O2, N2, CH4 and SF6 with hydrogen permeances in the range of (l-4)× 10-7 mol.m-2·s-1·Pa-1 (measured at 200 ℃, 3.0×105 Pa). With respect to the membrane calcined at 500 ℃, it is found that the permselectivities of H2 (0.289 mn) with respect to N2 (0.365 mn), CH4 (0.384 nm) and SF6 (0.55 mn) are 22.9, 42 and >1000, respectively,which are all much higher than the corresponding Knudsen values (H2/N2 = 3.7, H2/CH4 = 2.8, and H2/SF6 = 8.5).

  3. Muon catalyzed fusion

    Energy Technology Data Exchange (ETDEWEB)

    Ishida, K. [Advanced Meson Science Laboratory, RIKEN, 2-1 Hirosawa, Wako, Saitama 351-0198 (Japan); Nagamine, K. [Muon Science Laboratory, IMSS-KEK, 1-1 Oho, Tsukuba, Ibaraki 305-0801 (Japan); Matsuzaki, T. [Advanced Meson Science Laboratory, RIKEN, 2-1 Hirosawa, Wako, Saitama 351-0198 (Japan); Kawamura, N. [Muon Science Laboratory, IMSS-KEK, 1-1 Oho, Tsukuba, Ibaraki 305-0801 (Japan)


    The latest progress of muon catalyzed fusion study at the RIKEN-RAL muon facility (and partly at TRIUMF) is reported. The topics covered are magnetic field effect, muon transfer to {sup 3}He in solid D/T and ortho-para effect in dd{mu} formation.

  4. Lipase-catalyzed polyester synthesis – A green polymer chemistry (United States)

    Kobayashi, Shiro


    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 synthesis is, therefore, a reaction in reverse way of in vivo lipase catalysis of ester bond-cleavage with hydrolysis. The lipase-catalyzed polymerizations show very high chemo-, regio-, and enantio-selectivities and involve various advantageous characteristics. Lipase is robust and compatible with other chemical catalysts, which allows novel chemo-enzymatic processes. New syntheses of a variety of functional polyesters and a plausible reaction mechanism of lipase catalysis are mentioned. The polymerization characteristics are of green nature currently demanded for sustainable society, and hence, desirable for conducting ‘green polymer chemistry’. PMID:20431260

  5. Lipase-catalyzed polyester synthesis--a green polymer chemistry. (United States)

    Kobayashi, Shiro


    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 synthesis is, therefore, a reaction in reverse way of in vivo lipase catalysis of ester bond-cleavage with hydrolysis. The lipase-catalyzed polymerizations show very high chemo-, regio-, and enantio-selectivities and involve various advantageous characteristics. Lipase is robust and compatible with other chemical catalysts, which allows novel chemoenzymatic processes. New syntheses of a variety of functional polyesters and a plausible reaction mechanism of lipase catalysis are mentioned. The polymerization characteristics are of green nature currently demanded for sustainable society, and hence, desirable for conducting 'green polymer chemistry'.

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

    Institute of Scientific and Technical Information of China (English)


    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.


    carbon fibers . Several economical and simple processes were developed for obtaining research quantities of silica surfaced carbon filaments. Vat dipping processes were utilized to deposit an oxide such as silica onto the surface and into the micropores of available carbon or graphite base fibers. High performance composite materials were prepared with the surface treated carbon fibers and various resin matrices. The ablative characteristics of these composites were very promising and exhibited fewer limitations than either silica or...treated

  8. Silica in higher plants. (United States)

    Sangster, A G; Hodson, M J


    Opaline silica deposits are formed by many vascular (higher) plants. The capacity of these plants for silica absorption varies considerably according to genotype and environment. Plant communities exchange silica between soil and vegetation, especially in warmer climates. Silica deposition in epidermal cell walls offers mechanical and protective advantages. Biogenic silica particles from plants are also implicated in the causation of cancer. Recent techniques are reviewed which may aid in the identification of plant pathways for soluble silica movement to deposition sites and in the determination of ionic environments. Botanical investigations have focused on silicification of cell walls in relation to plant development, using scanning and transmission electron microscopy combined with X-ray microanalysis. Silica deposition in macrohair walls of the lemma of canary grass (Phalaris) begins at inflorescence emergence and closely follows wall thickening. The structure of the deposited silica may be determined by specific organic polymers present at successive stages of wall development. Lowering of transpiration by enclosure of Phalaris inflorescences in plastic bags reduced silica deposition in macrohairs. Preliminary freeze-substitution studies have located silicon, as well as potassium and chloride, in the cell vacuole and wall deposition sites during initial silicification.

  9. Toward one-pot lipase-catalyzed synthesis of poly(ε-caprolactone) particles in aqueous dispersion. (United States)

    Inprakhon, Pranee; Panlawan, Pabhangkon; Pongtharankul, Thunyarat; Marie, Emmanuelle; Wiemann, Lars O; Durand, Alain; Sieber, Volker


    The preparation of polyester particles using enzyme-catalyzed (lipase from Candida antarctica B, CALB) ring-opening polymerization of ε-caprolactone (ε-CL) in aqueous dispersion was demonstrated for the first time. Immobilization of CALB enabled a significant increase of the number-average degree of polymerization of ε-CL oligomers (up to 38) as compared to dissolved CALB (8 at the maximum). The nature and amount of lipase, as well as the nature of the support material were identified as key parameters controlling ring-opening polymerization of ε-CL in aqueous dispersion. In addition, the involvement of solubilized monomers in polymerization elementary reactions was demonstrated and the consequences on oligomers average length were detailed. An overall mechanism of lipase-catalyzed ε-CL polymerization in aqueous dispersion taking into account the colloidal nature of reaction medium was proposed on the basis of experimental results.

  10. Facile synthesis of small crystal ZSM-5 zeolite by acid-catalyzed hydrolysis of tetraethylorthosilicate

    Institute of Scientific and Technical Information of China (English)


    Small crystal zeolites ZSM-5 with sizes of 150-300 nm were synthesized using the colloidal silicate precursors as the silica source created by the acid-catalyzed hydrolysis of tetraethylorthosilicate with tetrapropylammonium bromide as the structure-directing agent within a short crystallization time of 20-35 h. The precursors and final products were detected by XRD, SEM, ICP and DLS.

  11. Polymerization in emulsion microdroplet reactors (United States)

    Carroll, Nick J.

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

  12. Click on silica: systematic immobilization of Co(II) Schiff bases to the mesoporous silica via click reaction and their catalytic activity for aerobic oxidation of alcohols. (United States)

    Rana, Bharat S; Jain, Suman L; Singh, Bhawan; Bhaumik, Asim; Sain, Bir; Sinha, Anil K


    The systematic immobilization of cobalt(II) Schiff base complexes on SBA-15 mesoporous silica via copper catalyzed [3 + 2] azide-alkyne cycloaddition (CuAAC) "click reaction" involving either step-wise synthesis of silica-bound Schiff base ligand followed by its subsequent complexation with cobalt ions, or by the direct immobilization of preformed Co(II) Schiff base complex to the silica support is described. The catalytic activity of the prepared complexes was studied for the oxidation of alcohols to carbonyl compounds using molecular oxygen as oxidant. The immobilized complexes were recycled for several runs without loss in catalytic activity and no leaching was observed during this course.

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

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


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

  14. Fabrication of monodisperse hollow silica spheres and effect on water vapor permeability of polyacrylate membrane. (United States)

    Bao, Yan; Yang, Yongqiang; Ma, Jianzhong


    Polystyrene/silica core-shell spheres were fabricated using polystyrene as templates by hydrolysis and condensation of tetraethyl orthosilicate through a sol-gel process, in which polystyrene was synthesized by emulsion polymerization. Then, hollow silica spheres were obtained after selective removal of the organic polystyrene core from the polystyrene/silica core-shell spheres by tetrahydrofuran etching. The effect of hollow silica spheres on water vapor permeability, mechanical property, and water uptake of polyacrylate membrane were investigated. The microstructure analysis shows that the mean size and wall thickness of hollow silica spheres are 170 nm and 20 nm, respectively. The silica shells consist of amorphous silica seed assembly with a broad size distribution, which roughen the surfaces of hollow silica spheres greatly. The specific surface area of hollow silica spheres is bigger than that of polystyrene/silica core-shell spheres. Hollow silica spheres can significantly improve water vapor permeability of polyacrylate membrane, but lead to the reduction in mechanical property.

  15. Speciation characterization and coagulation of poly-silica-ferric-chloride: The role of hydrolyzed Fe(Ⅲ) and silica interaction

    Institute of Scientific and Technical Information of China (English)

    Jian Shi; Yan Zhang; Kaiyun Zou; Feng Xiao


    The highly efficient inorganic polymer flocculants (IPFs) of the ferric-silica system is a new and promising coagulant.Interactions between ferric species and silica play a large part in the coagulation of suspensions.These effects are quite distinct from those associated with polymeric or colloid silica.However, although these species are key to coagulation efficiency, they have not been comprehensively discussed.A new type of coagulant, poly-silica-ferric-chloride (PFSC), was synthesized by co-polymerization and characterized by time complexation spectroscopy and photon correlation spectroscopy.Compared with traditional ferric salt, the results indicated that PFSC had a higher molecular weight, lesser positive charge, lower Feb and higher Fec.The higher the Si/Fe ratio, the higher the silica and lower the silicac found.The PFSC with appropriate polysilica acid not only obtained better coagulation/flocculation efficiency in turbidity removal, enhanced the flocculation index (FI) and provided less residual ferric, it also lowered water treatment costs compared to traditional ferric salt.Results showed that PFSC could remove colloid particles in water by charge neutralization and sweeping, adsorption bridging mechanism.

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

    2010-04-29 (1) De Gennes, P. G. Rev. Mod. Phys. 1992, 64, 645. (2) Perro , A.; Reculusa, S.; Ravaine, S.; Bourgeat-Lami, E.; Duguet, E. J. Mater...Rubner,M. F.; Cohen, R. E.Macromolecules 2005, 38, 7876. (12) Perro ,A.;Meunier, F.; Schmitt, V.;Ravaine, S.Colloid. Surface.A. 2009, 332, 57. (13

  17. Silica Refractory Bricks

    Institute of Scientific and Technical Information of China (English)

    Yu Lingyan; Peng Xigao


    @@ 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.

  18. Crystalline Silica Primer (United States)



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

  19. Dimethylsilanone generation from pyrolysis of polysiloxanes filled with nanosized silica and ceria/silica

    CERN Document Server

    Kulyk, Kostiantyn; Gatchell, Michael; Alexander, John D; Borysenko, Mykola; Palianytsia, Borys; Larsson, Mats; Kulik, Tetiana


    Polydimethylsiloxane (PDMS) is a widely used organosilicon polymer often employed in formulations with fine oxide particles for various high temperature applications. Although PDMS is considered to be thermally stable and chemically inert, it is not always clear how the oxide filler influences its thermoresistance, decomposition chemistry and what reactive products are formed in the underlying thermal reactions. In this work we use temperature programmed desorption mass spectrometry (TPD MS) to study the pyrolysis of PDMS and its composites with nanosized silica and ceria/silica. Our results suggest that the elusive organosilicon compound - dimethylsilanone is generated from PDMS over a broad temperature range (in some cases starting at 70${\\deg}$C). The presence of nano-oxides catalyzed this process. Ions characteristic of the fragmentation of dimethylsilanone under electron ionization were assigned with the aid of DFT structure calculations. Possible reaction mechanisms for generating dimethylsilanone were ...

  20. Making Polymeric Microspheres (United States)

    Rhim, Won-Kyu; Hyson, Michael T.; Chung, Sang-Kun; Colvin, Michael S.; Chang, Manchium


    Combination of advanced techniques yields uniform particles for biomedical applications. Process combines ink-jet and irradiation/freeze-polymerization techniques to make polymeric microspheres of uniform size in diameters from 100 to 400 micrometer. Microspheres used in chromatography, cell sorting, cell labeling, and manufacture of pharmaceutical materials.

  1. Applied bioactive polymeric materials

    CERN Document Server

    Carraher, Charles; Foster, Van


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

  2. Preparation of Stable Photopatternable Polymeric Materials for Non- linear Optics (United States)


    of limited versatility and is incompatible with the azobenzene and stilbene based chromo- phores.6’ 7 In addition it has proven extremely difficult...could not be achieved using dibutyltin dilaurate as a catalyst due to the occurrence of a trou- blesome transesterification side reaction of the...methacrylate moiety. Therefore, diazab- icyclo[2.2.2]-octane was used to catalyze the polymerization of monomer Q with iso- phorone diisocyanate. After

  3. 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


    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.

  4. Mesoporous silica and organosilica films templated by nanocrystalline chitin. (United States)

    Nguyen, Thanh-Dinh; Shopsowitz, Kevin E; MacLachlan, Mark J


    Liquid crystalline phases can be used to impart order into inorganic solids, creating materials that mimic natural architectures. Herein, mesoporous silica and organosilica films with layered structures and high surface areas have been templated by nanocrystalline chitin. Aqueous suspensions of spindle-shaped chitin nanocrystals were prepared by sequential deacetylation and hydrolysis of chitin fibrils isolated from king crab shells. The nanocrystalline chitin self-assembles into a nematic liquid-crystalline phase that has been used to template silica and organosilica composites. Removal of the chitin template by either calcination or sulfuric-acid-catalyzed hydrolysis gave mesoporous silica and ethylene-bridged organosilica films. The large, crack-free mesoporous films have layered structures with features that originate from the nematic organization of the nanocrystalline chitin.


    Institute of Scientific and Technical Information of China (English)

    CHENG Rongshi; HU Huizhen; JIANG Liansheng


    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.

  6. Catalyzed Ceramic Burner Material

    Energy Technology Data Exchange (ETDEWEB)

    Barnes, Amy S., Dr.


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

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

    Energy Technology Data Exchange (ETDEWEB)

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


    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.

  8. 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


    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.

  9. Electrostatic Discharge Properties of Fused Silica Coatings (United States)

    Andersen, Allen; Sim, Charles; Dennison, J. R.


    The electric field value at which electrostatic discharge (ESD) occurs was studied for thin coatings of fused silica (highly disordered SiO2/SiOx) on conductive substrates, such as those encountered as optical coatings and in Si microfabrication. The electrostatic breakdown field was determined using an increasing voltage, while monitoring the leakage current. A simple parallel-plate capacitor geometry was used, under medium vacuum and at temperatures down to ˜150 K using a liquid N2 reservoir. The breakdown field, pre-breakdown arcing and I-V curves for fused silica samples are compared for ˜60 nm and ˜80 μm thick, room and low temperature, and untreated and irradiated samples. Unlike typical I-V results for polymeric insulators, the thin film silica samples did not exhibit pre-breakdown arcing, displayed transitional resistivity after initial breakdown, and in many cases showed evidence of a second discontinuity in the I-V curves. This diversity of observed discharge phenomena is discussed in terms of breakdown modes and defect generation on a microscopic scale.

  10. Silicification and biosilicification: The role of macromolecules in bioinspired silica synthesis (United States)

    Patwardhan, Siddharth Vijay

    Diatoms, sponges and grasses are all known to produce ornate biogenic silica structures under ambient conditions. Some aspects of the molecular mechanism controlling biosilicification have recently been elucidated. The entrapment of the catalyzing/templating/scaffolding biomacromolecules enables them to be recovered by selective dissolution of biosilica. The proteins extracted from the diatom Cylindrotheca fusiformis (silaffins) and the sponge Tethya aurantia (silicateins) have been shown to precipitate silica from silica precursors in vitro. The identification of synthetic macromolecules that can act as catalysts/templates/scaffolds for silica formation gives exciting possibilities for bioinspired silica synthesis. Herein, the role of various synthetic (bio)macromolecules in silicification is studied. Attempts have also been made to understand the mechanism(s) governing (bio)macromolecule mediated (bio)silicification. Furthermore, the results and the understanding gained from various synthetic systems are used to demonstrate the potential of such bioinspired routes to develop new materials.

  11. Facile Method for Preparation of Silica Coated Monodisperse Superparamagnetic Microspheres

    Directory of Open Access Journals (Sweden)

    Xuan-Hung Pham


    Full Text Available This paper presents a facile method for preparation of silica coated monodisperse superparamagnetic microsphere. Herein, monodisperse porous polystyrene-divinylbenzene microbeads were prepared by seeded emulsion polymerization and subsequently sulfonated with acetic acid/H2SO4. The as-prepared sulfonated macroporous beads were magnetized in presence of Fe2+/Fe3+ under alkaline condition and were subjected to silica coating by sol-gel process, providing water compatibility, easily modifiable surface form, and chemical stability. FE-SEM, TEM, FT-IR, and TGA were employed to characterize the silica coated monodisperse magnetic beads (~7.5 μm. The proposed monodisperse magnetic beads can be used as mobile solid phase particles candidate for protein and DNA separation.

  12. 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:; Tavares, Maria I.B. [Universidade Federal do Rio de Janeiro, RJ (Brazil). Inst. de Macromoleculas]. E-mail:


    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.


    Institute of Scientific and Technical Information of China (English)

    黄吉玲; 克莱伯特·多诺; 马海燕; 钱延龙


    @@ 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.

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

    DEFF Research Database (Denmark)

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


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

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

    DEFF Research Database (Denmark)

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


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

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

    DEFF Research Database (Denmark)

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


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

  17. Chelating polymeric membranes

    KAUST Repository

    Peinemann, Klaus-Viktor


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

  18. Modeling three-dimensional network formation with an atomic lattice model: application to silicic acid polymerization. (United States)

    Jin, Lin; Auerbach, Scott M; Monson, Peter A


    We present an atomic lattice model for studying the polymerization of silicic acid in sol-gel and related processes for synthesizing silica materials. Our model is based on Si and O atoms occupying the sites of a body-centered-cubic lattice, with all atoms arranged in SiO(4) tetrahedra. This is the simplest model that allows for variation in the Si-O-Si angle, which is largely responsible for the versatility in silica polymorphs. The model describes the assembly of polymerized silica structures starting from a solution of silicic acid in water at a given concentration and pH. This model can simulate related materials-chalcogenides and clays-by assigning energy penalties to particular ring geometries in the polymerized structures. The simplicity of this approach makes it possible to study the polymerization process to higher degrees of polymerization and larger system sizes than has been possible with previous atomistic models. We have performed Monte Carlo simulations of the model at two concentrations: a low density state similar to that used in the clear solution synthesis of silicalite-1, and a high density state relevant to experiments on silica gel synthesis. For the high concentration system where there are NMR data on the temporal evolution of the Q(n) distribution, we find that the model gives good agreement with the experimental data. The model captures the basic mechanism of silica polymerization and provides quantitative structural predictions on ring-size distributions in good agreement with x-ray and neutron diffraction data.

  19. Multipod-like silica/polystyrene clusters (United States)

    Désert, Anthony; Morele, Jérémy; Taveau, Jean-Christophe; Lambert, Olivier; Lansalot, Muriel; Bourgeat-Lami, Elodie; Thill, Antoine; Spalla, Olivier; Belloni, Luc; Ravaine, Serge; Duguet, Etienne


    Multipod-like clusters composed of a silica core and PS satellites are prepared according to a seeded-growth emulsion polymerization of styrene in the presence of size-monodisperse silica particles previously surface-modified with methacryloxymethyltriethoxysilane. Tuning the diameter and concentration of the silica seeds affords homogeneous batches of tetrapods, hexapods, octopods, nonapods and dodecapods with morphology yields as high as 80%. Three-dimensional reconstructions by cryo-electron tomography are presented on large fields for the first time to show the high symmetry and regularity of the clusters demonstrating the good control of the synthesis process. These synthesis experiments are visited again digitally, in order to successfully refine an original simulation model and better understand the correlation between the history of the cluster growth and the final composition of the cluster mixture. Finally, using the model as a predictive tool and varying the extra experimental conditions, e.g. the composition of the surfactant mixture and the styrene concentration, result in trapping other cluster morphologies, such as tripods.Multipod-like clusters composed of a silica core and PS satellites are prepared according to a seeded-growth emulsion polymerization of styrene in the presence of size-monodisperse silica particles previously surface-modified with methacryloxymethyltriethoxysilane. Tuning the diameter and concentration of the silica seeds affords homogeneous batches of tetrapods, hexapods, octopods, nonapods and dodecapods with morphology yields as high as 80%. Three-dimensional reconstructions by cryo-electron tomography are presented on large fields for the first time to show the high symmetry and regularity of the clusters demonstrating the good control of the synthesis process. These synthesis experiments are visited again digitally, in order to successfully refine an original simulation model and better understand the correlation between the

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

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


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

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

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


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

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

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


    Institute of Scientific and Technical Information of China (English)

    Ning Zhu; Yong Cui; Zi-long Li; Yong Chen; Wen-Hua Sun


    8-Aminoquinoline nickel dichloride and bis(cyclopentadienyl)zirconium dichloride (Cp2ZrC12) were supported simultaneously on silica to produce branched polyethylene successfully by combined polymerization. The supported polymerization results showed that the molecular weight of polyethylene increased while the molecular weight distribution became wider and the molecular chains of oligomers remaining in the final solution became shorter as compared to the oligomers obtained in polymerization processes with pure 8-aminoquinoline nickel dichloride catalysis, as well as the Cp2ZrC12 and nickel combination system. With decreasing amount of Ni catalyst in the supported catalyst, the molecular chains of oligomers in the resulting solution became shorter, while a-olefin selectivity increased.

  4. Conformation and assembly of polypeptide scaffolds in templating the synthesis of silica: an example of a polylysine macromolecular "switch". (United States)

    Patwardhan, Siddharth V; Maheshwari, Ronak; Mukherjee, Niloy; Kiick, Kristi L; Clarson, Stephen J


    Although the role of polycationic macromolecules in catalyzing the synthesis of silica structures is well established, detailed understanding of the mechanisms behind the production of silica structures of controlled morphologies remains unclear. In this study, we have used both poly-L-lysine (PLL) and/or poly-D-lysine (PDL) for silica synthesis to investigate mechanisms controlling inorganic morphologies. The formation of both spherical silica particles and hexagonal plates was observed. The formation of hexagonal plates was suggested, via circular dichroic spectroscopy (CD), to result from the assembly of helical polylysine molecules. We confirm that the formation of PLL helices is a prerequisite to the hexagonal silica synthesis. In addition, we present for the first time that the handedness of the helicity of the macromolecule does not affect the formation of hexagonal silica. We also show, by using two different silica precursors, that the precursor does not have a direct effect on the formation of hexagonal silica plates. Furthermore, when polylysine helices were converted to beta-sheet structure, only silica particles were obtained, thus suggesting that the adoption of a helical conformation by PLL is required for the formation of hexagonally organized silica. These results demonstrate that the change in polylysine conformation can act as a "switch" in silica structure formation and suggest the potential for controlling morphologies and structures of inorganic materials via control of the conformation of soft macromolecular templates.

  5. 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


    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.

  6. Catalyzing alignment processes

    DEFF Research Database (Denmark)

    Lauridsen, Erik Hagelskjær; Jørgensen, Ulrik


    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......, the networks of environmental professionals that work in the environmental organisation, in consulting and regulatory enforcement, and dominating business cultures. These have previously been identified in the literature as individually significant in relation to the evolving environmental agendas....... They are here used to describe the context in which environmental management is implemented. Based on findings from contributions to a research program studying the implementation and impact of EMS in different settings, we highlight the diverse roles that these systems play in the Thai context. EMS may over...

  7. 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)



    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.

  8. Stereoselective synthesis of 3,3-diarylacrylonitriles as tubulin polymerization inhibitors. (United States)

    Fang, Zhenglai; Song, Yunlong; Sarkar, Taradas; Hamel, Ernest; Fogler, William E; Agoston, Gregory E; Fanwick, Phillip E; Cushman, Mark


    A series of 3,3-diarylacrylonitriles were synthesized stereoselectively as tubulin polymerization inhibitors for potential use in cancer chemotherapy. This synthetic route features stannylcupration and palladium-catalyzed Stille cross-coupling chemistry, allowing both E and Z isomers of 3,3-diarylacrylonitriles to be prepared in a very short sequence of reactions.

  9. Mechanistic Insight in the Enzymatic Ring-Opening Polymerization of beta-Propiolactam

    NARCIS (Netherlands)

    Schwab, Leendert W.; Baum, Iris; Fels, Gregor; Loos, Katja; Cheng, HN; Gross, RA


    Here we report the polymerization of beta-propiolactam to poly(beta-alanine) catalyzed by the immobilized Candida antarctica lipase B (N435). The polymer is characterized by (1)H-NMR spectroscopy and MALDI-ToF mass spectrometry. The best results were obtained with N435 (dried for 24 hours in vacua a

  10. Plasma polymerization by Softplasma

    DEFF Research Database (Denmark)

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


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

  11. Investigations of silica alcogel aging using coherent light

    Energy Technology Data Exchange (ETDEWEB)

    Hunt, Arlon J.; Ayers, Michael R.


    Light scattering methods have previously been used to monitor the formation of gels. In this report we present new light scattering techniques to study the properties of silica alcogels during the aging process. Monitoring one particular polarization transformation of scattered light with time reveals a clear increase in internal strain in standing alcogels with time. The stress birefringence coefficient of an acid-catalyzed SiO{sub 2} gel was found to be 3.4 x 10{sup 12} Brewsters. Additionally, the evolution of the stiffness of alcogels was investigated using laser speckle methods. Specifically, image analysis of specklegrams obtained during multi-frequency acoustic excitation of aging gels was used to non-destructively measure the hardening of alcogels. For an acid catalyzed gel with a theoretical density of {approx}0.05 g/cm{sup 3} SiO{sub 2}, the rate of hardening is found to be greatest between gelation and 2X the gel time, and drops considerably thereafter. The Young's modulus of the gel can be monitored over time with this method and was found to range from 6.2 x 10{sup 3} N/m{sup 2} after 6 hours to 2.2 x 10{sup 5} N/m{sup 2} after 24 hours for acid-catalyzed silica gels.

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

    KAUST Repository

    Li, Fuyue Stephanie


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

  13. Conducting Polymeric Materials

    DEFF Research Database (Denmark)

    Hvilsted, Søren


    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 charge transfer elements are intrinsically conducting polymers, where the electrical conductivity is a result of delocalized electrons along the polymer backbone, with polyaniline, polypyrrole, and PEDOT as prominent examples. Already in 2000 Alan Heeger, Alan MacDiarmid, and Hideki Shirakawa were...


    Institute of Scientific and Technical Information of China (English)

    P.M. Saville; J.W. White


    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.

  15. Incorporation of 5-hydroxyindazole into the self-polymerization of dopamine for novel polymer synthesis. (United States)

    Peterson, Matthew B; Le-Masurier, Solomon P; Lim, Khoon; Hook, James M; Martens, Penny; Granville, Anthony M


    Investigation into the mussel-inspired polymerization of dopamine has led to the realization that other compounds possessing potential quinone structures could undergo similar self-polymerizations in mild buffered aqueous conditions. To this end, 5-hydroxyindazole was added to a dopamine polymerization matrix in varying amounts, to study its incorporation into a polydopamine coating of silica particles. Solid-state (13) C NMR spectroscopy confirmed the presence of the indazole in the polymer shell when coated onto silica gel. SEM and DLS analysis also confirmed that the presence of the indazole in the reaction matrix yielded monodisperse polymer-coated particles, which retained their polymer shell upon HF etching, except when high levels of the indazole were used. Characterization data and examination of incorporation mechanism suggests that the 5-hydroxyindazole performs the function of a chain-terminating agent. Cytotoxicity studies of the polymer particles containing 5-hydroxyindazole showed dramatically lower toxicity levels compared to polydopamine alone.

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

    DEFF Research Database (Denmark)

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


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

  17. Particle seeding enhances interconnectivity in polymeric scaffolds foamed using supercritical CO(2). (United States)

    Collins, Niki J; Bridson, Rachel H; Leeke, Gary A; Grover, Liam M


    Foaming using supercritical CO(2) is a well-known process for the production of polymeric scaffolds for tissue engineering. However, this method typically leads to scaffolds with low pore interconnectivity, resulting in insufficient mass transport and a heterogeneous distribution of cells. In this study, microparticulate silica was added to the polymer during processing and the effects of this particulate seeding on the interconnectivity of the pore structure and pore size distribution were investigated. Scaffolds comprising polylactide and a range of silica contents (0-50 wt.%) were produced by foaming with supercritical CO(2). Scaffold structure, pore size distributions and interconnectivity were assessed using X-ray computed microtomography. Interconnectivity was also determined through physical measurements. It was found that incorporation of increasing quantities of silica particles increased the interconnectivity of the scaffold pore structure. The pore size distribution was also reduced through the addition of silica, while total porosity was found to be largely independent of silica content. Physical measurements and those derived from X-ray computed microtomography were comparable. The conclusion drawn was that the architecture of foamed polymeric scaffolds can be advantageously manipulated through the incorporation of silica microparticles. The findings of this study further establish supercritical fluid foaming as an important tool in scaffold production and show how a previous limitation can be overcome.

  18. Insitu grafting silica nanoparticles reinforced nanocomposite hydrogels (United States)

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


    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

  19. Thin supported silica membranes

    NARCIS (Netherlands)

    Zivkovic, Tijana


    This thesis discusses several transport-related aspects relevant for the application of thin supported silica membranes for gas separation and nanofiltration. The influence of support geometry on overall membrane performance is investigated. Planar (i.e., flat plate), tubular, and multichannel suppo

  20. Polymerized and functionalized triglycerides (United States)

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

  1. Waterborne Polymeric Films. (United States)


    Skydrol 500B is a fire resistant hydraulic fluid available from Monsanto and which is primarily tricresyl phosphate. In most cases, the above table...Makromol. Chem. 1979, 82 149.- 23. Ger. Offen 2,804,609; (8/9/79). Bayer AG. 24. Odian, G. "Principles of Polymerization; "McGraw-Hill Book Co.: New York

  2. 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


    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.

  3. Preparation of poly(oxybutyleneoxymaleoyl) catalyzed by a proton exchanged montmorillonite clay. (United States)

    Ferrahi, Mohammed Issam; Belbachir, Mohammed


    The polycondensation of tetrahydrofuran with maleic anhydride catalyzed by Maghnite-H+ (Mag-H) was investigated. Maghnite is a montmorillonite sheet silicate clay that is exchanged with protons to produce Maghnite-H [1]. It was found that the polymerization in bulk is initiated by Mag-H in the presence of acetic anhydride at 40 degrees C. The effects of the amounts of Mag-H and acetic anhydride were studied. The polymerization yield increased as the proportions of catalyst and acetic anhydride were increased.

  4. Asymmetric transfer hydrogenation of imines catalyzed by a polymer-immobilized chiral catalyst. (United States)

    Haraguchi, Naoki; Tsuru, Keiichi; Arakawa, Yukihiro; Itsuno, Shinichi


    The asymmetric transfer hydrogenation of imines was performed with the use of a polymer-immobilized chiral catalyst. The chiral catalyst, prepared from crosslinked polystyrene-immobilized chiral 1,2-diamine monosulfonamide, was effective in the asymmetric transfer hydrogenation of N-benzyl imines in CH(2)Cl(2) to give a chiral amine in high yield and good enantioselectivity. Furthermore, an amphiphilic polymeric catalyst prepared from crosslinked polystyrene containing sulfonated groups successfully catalyzed the asymmetric transfer hydrogenation of cyclic imines in water. Enantioenriched secondary amines with up to 94% ee were obtained by using a polymeric catalyst.

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

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


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

  6. Biomimetic mineral self-organization from silica-rich spring waters (United States)

    García-Ruiz, Juan Manuel; Nakouzi, Elias; Kotopoulou, Electra; Tamborrino, Leonardo; Steinbock, Oliver


    Purely inorganic reactions of silica, metal carbonates, and metal hydroxides can produce self-organized complex structures that mimic the texture of biominerals, the morphology of primitive organisms, and that catalyze prebiotic reactions. To date, these fascinating structures have only been synthesized using model solutions. We report that mineral self-assembly can be also obtained from natural alkaline silica-rich water deriving from serpentinization. Specifically, we demonstrate three main types of mineral self-assembly: (i) nanocrystalline biomorphs of barium carbonate and silica, (ii) mesocrystals and crystal aggregates of calcium carbonate with complex biomimetic textures, and (iii) osmosis-driven metal silicate hydrate membranes that form compartmentalized, hollow structures. Our results suggest that silica-induced mineral self-assembly could have been a common phenomenon in alkaline environments of early Earth and Earth-like planets. PMID:28345049

  7. 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


    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.

  8. 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)


    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.

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

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


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

  10. Photopolymerization of acrylamide as a new functionalization way of silica monoliths for hydrophilic interaction chromatography and coated silica capillaries for capillary electrophoresis. (United States)

    El-Debs, R; Marechal, A; Dugas, V; Demesmay, C


    A simple, rapid and localizable photochemical process for the preparation of hydrophilic coated capillary and silica-based monolithic capillary columns is described. The process involves the free radical polymerization of acrylamide monomers onto acrylate pre-activated silica surface triggered by UV photoinitiation. The experimental conditions (monomer content, time of irradiation) were optimized on silica monolithic columns by monitoring the evolution of the chromatographic properties (retention, permeability, efficiency) in HILIC mode using a set of nucleosides as test solutes. Compared to thermal polymerization process, the photoinitiation allows the preparation of highly retentive and efficient HILIC monolithic columns in less than 10min of irradiation. This process was then successfully applied to the surface coating of fused silica capillary walls. In addition to its relative high stability and ability to reduce the electroosmotic flow, this polyacrylamide coating is localizable. Benefits of this localizable photochemical process are highlighted through the conception of an in-line integrated bimodal microseparation tool combining a SPE preconcentration step on a photografted silica monolith and an electrokinetic separation step in a polyacrylamide photopolymerized capillary section. Two neuropeptides are used as model solutes to illustrate the suitability of this approach.

  11. Optical patterning of photosensitive thin film silica mesophases

    Energy Technology Data Exchange (ETDEWEB)



    Photosensitive films incorporating molecular photoacid generators compartmentalized within a silica-surfactant mesophase were prepared by an evaporation-induced self-assembly process. UV-exposure promoted localized acid-catalyzed siloxane condensation, enabling selective etching of unexposed regions, thereby serving as a resistless technique to prepare patterned mesoporous silica. The authors also demonstrated an optically-defined mesophase transformation (hexagonal {r_arrow} tetragonal) and patterning of refractive index and wetting behavior. Spatial control of structure and function on the macro- and mesoscales is of interest for sensor arrays, nano-reactors, photonic and fluidic devices, and low dielectric constant films. More importantly, it extends the capabilities of conventional lithography from spatially defining the presence or absence of film to spatial control of film structure and function.

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

    Directory of Open Access Journals (Sweden)

    Hang Zhou


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

  13. Protection of wood from microorganisms by laccase-catalyzed iodination. (United States)

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


    In the present work, Norway spruce wood (Picea abies L.) was reacted with a commercial Trametes versicolor laccase in the presence of potassium iodide salt or the phenolic compounds thymol and isoeugenol to impart an antimicrobial property to the wood surface. In order to assess the efficacy of the wood treatment, a leaching of the iodinated and polymerized wood and two biotests including bacteria, a yeast, blue stain fungi, and wood decay fungi were performed. After laccase-catalyzed oxidation of the phenols, the antimicrobial effect was significantly reduced. In contrast, the enzymatic oxidation of iodide (I(-)) to iodine (I(2)) in the presence of wood led to an enhanced resistance of the wood surface against all microorganisms, even after exposure to leaching. The efficiency of the enzymatic wood iodination was comparable to that of a chemical wood preservative, VP 7/260a. The modification of the lignocellulose by the laccase-catalyzed iodination was assessed by the Fourier transform infrared spectroscopy-attenuated total reflectance (FTIR-ATR) technique. The intensities of the selected lignin-associated bands and carbohydrate reference bands were analyzed, and the results indicated a structural change in the lignin matrix. The results suggest that the laccase-catalyzed iodination of the wood surface presents an efficient and ecofriendly method for wood protection.


    Institute of Scientific and Technical Information of China (English)

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


    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.

  15. Structural Formation Studies of UV-Catalyzed Gels and Aerogels byLight Scattering

    Energy Technology Data Exchange (ETDEWEB)

    Hunt, Arlon J.; Ayers, Michael R.


    The skeletal structure of aerogel is determined before, during, and after the gel is formed. Supercritical drying of aerogel largely preserves the pore structure that is determined near the time of gelation. To better understand these gel formation mechanisms we carried out measurements of the time evolution of light scattering in a series of gels prepared without conventional acid or base catalysis. Instead, ultraviolet light was used to catalyze the formation of silica gels made from the hydrolysis of tetraethylorthosilicate and partly prehydrolyzed tetraethylorthosilicate in ethanol. Time evolution of light scattering provides information regarding the rate and geometrical nature of the assembly of the primary silica particles formed in the sol. UV-catalyzed gels show volumetric growth typical of acid-catalyzed gels, except when UV exposure is discontinued at the gel point, where gels then show linear chain formation typical of base-catalyzed gels. Long term UV exposure leads to coarsening of the pore network, a decrease in the clarity of the aerogel, and an increase in the surface area of the aerogel. Additionally, UV exposure up to the gel point leads to increased crystallinity in the final aerogel.

  16. 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: [Centro de Tecnologia, Instituto de Macromoleculas Professora Eloisa Mano, Universidade Federal do Rio de Janeiro, Rio de Janeiro, RJ (Brazil)


    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)

  17. Aniline incorporated silica nanobubbles

    Indian Academy of Sciences (India)

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


    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.

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


    Kenjiro Yazawa; Keiji Numata


    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 ...

  19. 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)



    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.

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

    DEFF Research Database (Denmark)

    Zhang, Hong; Xu, Xuebing; Nilsson, Jörgen


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

  1. 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


    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Jun, E-mail:; Fan, Shaohua; Zhao, Weiqian; Lu, Xuelian; Li, Wuke


    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 Eu{sup 3+} ions.

  3. Direct Synthesis of Telechelic Polyethylene by Selective Insertion Polymerization

    KAUST Repository

    Jian, Zhongbao


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

  4. Iron Oxide Silica Derived from Sol-Gel Synthesis

    Directory of Open Access Journals (Sweden)

    João Carlos Diniz da Costa


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

  5. Enhanced formaldehyde-vapor adsorption capacity of polymeric amine-incorporated aminosilicas. (United States)

    Nomura, Akihiro; Jones, Christopher W


    Airborne formaldehyde, which is a highly problematic volatile organic compound (VOC) pollutant, is adsorbed by polymeric amine-incorporated silicas (aminosilicas), and the factors that affect the adsorption performance are systematically investigated. Three different types of polymeric amines 1) poly(ethyleneimine) branched (PEIBR); 2) poly(ethyleneimine) linear (PEILI); and 3) poly(allylamine) (PAA) are impregnated into two types of porous silicas [SBA-15 and mesocellular foam (MCF) silicas] with systematic changes of the amine loadings. The adsorption results demonstrate that the adsorption capacity increases along with the amine loading until the polymeric amines completely fill the silica pores. This results in the MCF silica, which has a larger pore volume and hence can accommodate more polymeric amine before completely filling the pore, giving materials that adsorb more formaldehyde, with the largest adsorption capacity, q, of up to 5.7 mmolHCHO  g(-1) among the samples studied herein. Of the three different types of polymers, PAA, comprised of 100 % primary amines, showed the highest amine efficiency μ (mmolHCHO/mmolN) for capturing formaldehyde. The chemical structures of the adsorbed formaldehyde are analyzed by (13)C cross-polarization magic-angle spinning (CP-MAS) NMR, and it is demonstrated that the adsorbed formaldehyde is chemically attached to the aminosilica surface, forming hemiaminal and imine species. Because the chemical adsorption of formaldehyde forms covalent bonds, it is not desorbed from the aminosilicas below 130 °C based on temperature-programed-desorption (TPD) analysis. The high formaldehyde-adsorption capacity and stability of the trapped formaldehyde on the amine surface in this study reveal the potential utility of aminosilicas as formaldehyde abatement materials.

  6. Silica reinforced triblock copolymer gels

    DEFF Research Database (Denmark)

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


    The effect of silica and polymer coated silica particles as reinforcing agents on the structural and mechanical properties of polystyrene-poly(ethylene/butylene)-polystyrene (PS-PEB-PS) triblock gel has been investigated. Different types of chemically modified silica have been compared in order...... to evaluate the influence of the compatibility between gel and filler. Time-resolved SANS and small-angle X-ray scattering (SAXS) shows that the presence of silica particles affects the ordering of the polystyrene domains during gelsetting. The scattering pattern of silica-reinforced gels reveals strong...... 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....

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

    Directory of Open Access Journals (Sweden)

    Tomás Cuenca


    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.

  8. Monolithic molecularly imprinted polymeric capillary columns for isolation of aflatoxins. (United States)

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


    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.

  9. A model for the effects of germanium on silica biomineralization in choanoflagellates (United States)

    Chappell, Helen; Ratcliffe, Sarah; Goldstein, Raymond E.


    Silica biomineralization is a widespread phenomenon of major biotechnological interest. Modifying biosilica with substances like germanium (Ge) can confer useful new properties, although exposure to high levels of Ge disrupts normal biosilicification. No clear mechanism explains why this disruption occurs. Here, we study the effect of Ge on loricate choanoflagellates, a group of protists that construct a species-specific extracellular lorica from multiple siliceous costal strips. High Ge exposures were toxic, whereas lower Ge exposures produced cells with incomplete or absent loricae. These effects can be ameliorated by restoring the germanium : silicon ratio, as observed in other biosilicifying organisms. We developed simulations of how Ge interacts with polymerizing silica. In our models, Ge is readily incorporated at the ends of silica forming from silicic acid condensation, but this prevents further silica polymerization. Our ‘Ge-capping’ model is supported by observations from loricate choanoflagellates. Ge exposure terminates costal strip synthesis and lorica formation, resulting in disruption to cytokinesis and fatal build-up of silicic acid. Applying the Ge-capping model to other siliceous organisms explains the general toxicity of Ge and identifies potential protective responses in metalloid uptake and sensing. This can improve the design of new silica biomaterials, and further our understanding of silicon metabolism. PMID:27655668

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

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


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

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

    Directory of Open Access Journals (Sweden)

    Li Hua-Rong


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

  12. Living olefin polymerization processes (United States)

    Schrock, Richard R.; Baumann, Robert


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

  13. Phosphazene-promoted anionic polymerization

    KAUST Repository

    Zhao, Junpeng


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

  14. Silica Micro Encapsulation

    Energy Technology Data Exchange (ETDEWEB)

    Mitchell, P.; Whitbread-Jordan, M. [KEECO (United Kingdom)


    The article explains how Silica Micro Encapsulation (SME) water treatment technology may be transferred from metal mining to coal mining operations. KEECO has been developing a unique solution for treating acid rock drainage in the metal sulphide mining sector and following trials in metal mining operations (described in the article), is preparing to transfer the technology to the coal industry. SME technology comprises metal precipitation and encapsulation accomplished with proprietary chemical, KB-1, and a group of patented chemical dosing systems, the K-series, to dose KB-1 into contaminated liquid wastes as a dry powder. 4 figs., 4 tabs.

  15. ZBLAN, Silica Fiber Comparison (United States)


    This graph depicts the increased signal quality possible with optical fibers made from ZBLAN, a family of heavy-metal fluoride glasses (fluorine combined zirconium, barium, lanthanum, aluminum, and sodium) as compared to silica fibers. NASA is conducting research on pulling ZBLAN fibers in the low-g environment of space to prevent crystallization that limits ZBLAN's usefulness in optical fiber-based communications. In the graph, a line closer to the black theoretical maximum line is better. Photo credit: NASA/Marshall Space Flight Center

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

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


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

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

    NARCIS (Netherlands)

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


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

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

    NARCIS (Netherlands)

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


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

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

    DEFF Research Database (Denmark)

    Brandt, Rasmus Guldbæk; Yu, Donghong

    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......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...

  20. Exploring chain length selectivity in HIC-catalyzed polycondensation reactions. (United States)

    Feder, David; Gross, Richard A


    Polyester synthesis activity of immobilized Humicola insolens (HiC) was systematically studied with three-series of substrates varying in (i) omega-hydroxyalkanoic acid (omegaHA), (ii) alpha,omega-n-alkane diol, and (iii) alpha,omega-n-alkane diacid chain length. Covalent immobilization of HiC on Amberzyme oxirane (AO) resin (i.e., AO-HiC) was prepared. HiC-AO's activity for omegaHA substrates with 6, 10, 12, and 16 carbons was C16 > C12, where C10-omegaHA and C6-omegaHA were not polymerized. In contrast, N435's activity for omegaHA substrates was C16 = C12 > C10, where C6-omegaHA was not polymerized. HiC-AO activity for copolymerization of sebacic acid (C10-diacid) with alpha,omega-n-alkane diols with 3-, 4-, 5-, 6-, and 8-carbon chain lengths was C8 > C6, where C3, C4, and C5 diols were not polymerized. N435's relative activity for diol substrates was C8 = C6 = C5 > C4 > C3. HiC-AO activity for copolymerizations of 1,8-octanediol with alpha,omega-n-alkane diacids with 6-, 8-, 9-, 10-, and 13-carbon chain lengths was C13 = C10, where HiC showed little activity for C6, C8, and C9 diacid copolymerization. N435 displayed similar activity for all these diacid chain lengths. Thus, N435 has a broader substrate promiscuity than HiC-AO. This is most apparent for shorter chain length omegaHA, diol, and diacid monomers. These trends were similarly observed for a series of small molecule esterification reactions. Comparison of HiC-AO- and N435-catalyzed C16-HA homopolymerization at 8 h gave polymers with M(n) 40.4 and 25.5 kg/mol, respectively. Furthermore, HiC-AO- and N435-catalyzed copolymerization of 1,8-octanediol/C13-diacid polymerizations at 8 h gave polymers with M(n) of 11.0 and 9.6 kg/mol, respectively.

  1. Gratings in polymeric waveguides (United States)

    Mishakov, G.; Sokolov, V.; Kocabas, A.; Aydinli, A.


    Laser-induced formation of polymer Bragg grating filters for Dense Wavelength Division Multiplexing (DWDM) applications is discussed. Acrylate monomers halogenated with both fluorine and chlorine, which possess absorption losses less than 0.25 dB/cm and wide choice of refractive indices (from 1.3 to 1.5) in the 1.5 μm telecom wavelength region were used. The monomers are highly intermixable thus permitting to adjust the refractive index of the composition within +/-0.0001. Moreover they are photocurable under UV exposure and exhibit high contrast in polymerization. These properties make halogenated acrylates very promising for fabricating polymeric waveguides and photonic circuits. Single-mode polymer waveguides were fabricated on silicon wafers using resistless contact lithography. Submicron index gratings have been written in polymer waveguides using holographic exposure with He-Cd laser beam (325 nm) through a phase mask. Both uniform and apodized gratings have been fabricated. The gratings are stable and are not erased by uniform UV exposure. The waveguide gratings possess narrowband reflection spectra in the 1.5 μm wavelength region of 0.4 nm width, nearly rectangular shape of the stopband and reflectivity R > 99%. The fabricated Bragg grating filters can be used for multiplexing/demultiplexing optical signals in high-speed DWDM optical fiber networks.

  2. Cu催化的单电子转移活性自由基聚合制备石墨烯/聚N,N-二甲基丙烯酰胺复合体系%Preparation of Graphene/Poly(N,N-dimethylacrylamide) Nanocomposite via Cu-Catalyzed Single-Electron Transfer Living Radical Polymerization

    Institute of Scientific and Technical Information of China (English)

    王凇旸; 郭冠南; 杨东; 胡建华


    Exfoliated graphene oxide (GO) sheets were prepared from natural graphite by a modified Hummer’s method, which included oxidative hydrolysis under strong acidic conditions and ultrasonic dispersing. GO was firstly reduced by hy-drazine and then followed by a diazonium addition reaction to give graphene containing hydroxyls (G-OH), which was con-verted to graphene with singel eclectron transfer-living radical polymerization (SET-LRP) initiating groups via esterification with 2-chloropropionyl chloride. Finally, poly(N,N-dimethylacrylamide) (PDMAA) chains were grown from the surface of graphene via in situ SET-LRP to obtain graphene/PDMAA (G-PDMAA) nanocomposite. G-PDMAA nanocomposite showed good dispersity in common organic solvents and aqueous solution.%以天然石墨为起始原料,采用改进的 Hummer 方法,通过强酸氧化水解和超声分散制备了氧化石墨烯,然后通过肼还原和重氮化反应得到含有羟基的石墨烯(G-OH),再通过酯化反应在石墨烯表面上引入了α-氯代羰基,从而得到了含有单电子转移活性自由基聚合(SET-LRP)引发基团的石墨烯(G-Cl)。最后,在石墨烯表面原位引发N,N-二甲基丙烯酰胺(DMAA)单体的SET-LRP聚合,得到了G-PDMAA复合材料, G-PDMAA在常规的有机溶剂和水中具有良好的分散性。

  3. Gold-Catalyzed Synthesis of Heterocycles (United States)

    Arcadi, Antonio


    The following sections are included: * Introduction * Synthesis of Heterocycles via Gold-Catalyzed Heteroatom Addition to Unsaturated C-C Bonds * Synthesis of Heterocyclic Derivatives through Gold-Catalyzed Cyclization of Polyunsaturated Compounds * Synthesis of Heterocyclic Compounds via α-Oxo Gold Carbenoid * Synthesis of Heterocyclic Derivatives through Gold-Catalyzed Cycloaddition Reactions * Synthesis of Heterocyclic Derivatives through Gold-Catalyzed Activation of Carbonyl Groups and Alcohols * Synthesis of Heterocyclic Compounds through Gold-Mediated C-H Bond Functionalization * Gold-Catalyzed Domino Cyclization/Oxidative Coupling Reactions * Conclusions * References

  4. Synergism and Mutualism in Non-Enzymatic RNA Polymerization

    Directory of Open Access Journals (Sweden)

    Hussein Kaddour


    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.

  5. Synergism and Mutualism in Non-Enzymatic RNA Polymerization (United States)

    Kaddour, Hussein; Sahai, Nita


    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. PMID:25370531

  6. Silaffins in Silica Biomineralization and Biomimetic Silica Precipitation

    Directory of Open Access Journals (Sweden)

    Carolin C. Lechner


    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.

  7. 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.


    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

  8. Synthesis and characterization of hybrid silica/PMMA nanoparticles and their use as filler in dental composites. (United States)

    Canché-Escamilla, G; Duarte-Aranda, S; Toledano, M


    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 1,730 cm(-1), corresponding to carbonyl groups (CO) 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.

  9. 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: [Petroceramics S.p.A., Kilometro Rosso Science Park (Italy); Rezwan, Kurosch [University of Bremen, Advanced Ceramics (Germany)


    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.

  10. 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:; Pak, Joonsung [Hallym University, Department of Chemistry (Korea, Republic of)


    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.

  11. Synthesis of polymeric fluorinated sol-gel precursor for fabrication of superhydrophobic coating (United States)

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


    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.

  12. Biogenic nanostructured silica

    Institute of Scientific and Technical Information of China (English)


    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.

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

    Kerdi, Fatmé; Caps, Valérie; Tuel, Alain

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

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

    KAUST Repository

    Kerdi, Fatmé


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

  15. Organic and composite aerogels through ring opening metathesis polymerization (ROMP) (United States)

    Mohite, Dhairyashil P.

    Aerogels are open-cell nanoporous materials, unique in terms of low density, low thermal conductivity, low dielectric constants and high acoustic attenuation. Those exceptional properties stem from their complex hierarchical solid framework (agglomerates of porous, fractal secondary nanoparticles), but they also come at a cost: low mechanical strength. This issue has been resolved by crosslinking silica aerogels with organic polymers. The crosslinking polymer has been assumed to form a conformal coating on the surface of the skeletal framework by covalent bridging elementary building blocks. However, "assuming" is not enough: for correlating nanostructure with bulk material properties, it is important to know the exact location of the polymer on the aerogel backbone. For that investigation, we synthesized a new norbornene derivative of triethoxysilane (Si-NAD) that can be attached to skeletal silica nanoparticles. Those norbornene-modified silica aerogels were crosslinked with polynorbornene by ring opening metathesis polymerization (ROMP). The detailed correlation between nanostructure and mechanical strength was probed with a wide array of characterization methods ranging from molecular to bulk through nano. Subsequently, it was reasoned that since the polymer dominates the exceptional mechanical properties of polymer crosslinked aerogels, purely organic aerogels with the same nanostructure and interparticle connectivity should behave similarly. That was explored and confirmed by: (a) synthesis of a difunctional nadimide monomer (bis-NAD), and preparation of robust polyimide aerogels by ROMP of its norbornene end-caps; and, (b) synthesis of dimensionally stable ROMP-derived polydicyclopentadiene aerogels by grafting the nanostructure with polymethylmethacrylate (PMMA) via free radical chemistry.

  16. 碱式碳酸镁催化酚醛聚合制备多孔炭及其CO2吸附性能%Synthesis of porous carbon through polymerization catalyzed by basic magnesium carbonate and their CO2 adsorption performance

    Institute of Scientific and Technical Information of China (English)

    王恩民; 李文翠; 雷成; 陆安慧


    利用碱式碳酸镁的催化功能及易分解特性,实现间苯二酚、甲醛的快速凝胶,炭化得到孔隙发达的整体式多孔炭(MCM-Mg),其轴向抗压强度达9.4 MPa。与普通碳酸盐催化的样品相比,MCM-Mg孔隙更为发达。273 K下该系列样品的静态CO2吸附量可达3.49~4.50 mmol·g−1(0.1 MPa),0.015 MPa最高可达1.87 mmol·g−1。研究发现,微孔对材料吸附性能起主导作用;MCM-Mg的单位微孔比表面积可吸附7.15μmol CO2,超过了大部分活化法制备的炭材料。多组分动态穿透实验表明,该系列材料可实现CO2/N2的完全分离;材料具有良好的耐水汽性能和循环吸附-脱附性能,室温下经惰性气体吹扫即可实现再生。%By taking the advantages of easy decomposition and catalytic function of basic magnesium carbonate, the mechanically stable porous carbon materials (MCM-Mg) are synthesized through rapid gelation of resorcinol with formaldehyde and subsequently carbonization. Compared with samples catalyzed by traditional carbonates, the synthesis process can obtain a well-developed porous structure. The resulted samples can withstand a pressure of up to 9.4 MPa. At 273 K, the equilibrium CO2 adsorption capacities of MCM-Mg are in the range of 3.49—4.50 mmol·g−1 at 0.1 MPa and can reach 1.87 mmol·g−1 at 0.015 MPa. Experimental test of the MCM-Mg shows that the micropores play a major role in contribution of the amount of adsorbed CO2. Importantly, MCM-Mg can adsorb 7.15 μmol CO2 per Smicro, which surpasses most of the carbons prepared by activation. Dynamic breakthrough tests show that over such series of samples, CO2/N2 streams can be fully separated. The CO2 release is achieved facilely in Ar purge at 298 K. The samples also exhibit stable performance for CO2 separation under humid conditions and exhibit good regeneration capability.

  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


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


    Basudeb Basu; Susmita Paul


    Solid-phase organic synthesis (SPOS) and catalysis have gained impetus after the seminal discovery of Merrifield’s solid-phase peptide synthesis and also because of wide applicability in combinatorial and high throughput chemistry. A large number of organic, inorganic, or organic-inorganic hybrid materials have been employed as polymeric solid supports to promote or catalyze various organic reactions. This review article provides a concise account on our approaches involving the use of (i) al...

  19. 21 CFR 582.1711 - Silica aerogel. (United States)


    ... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Silica aerogel. 582.1711 Section 582.1711 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL DRUGS....1711 Silica aerogel. (a) Product. Silica aerogel as a finely powdered microcellular silica foam...

  20. 21 CFR 182.1711 - Silica aerogel. (United States)


    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Silica aerogel. 182.1711 Section 182.1711 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD FOR HUMAN....1711 Silica aerogel. (a) Product. Silica aerogel as a finely powdered microcellular silica foam...

  1. 21 CFR 584.700 - Hydrophobic silicas. (United States)


    ... 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....

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

    Energy Technology Data Exchange (ETDEWEB)

    Hari Babu, B., E-mail:, E-mail:; 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:, E-mail: [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)


    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.

  3. Application of Super-Amphiphilic Silica-Nanogel Composites for Fast Removal of Water Pollutants. (United States)

    Atta, Ayman M; Al-Lohedan, Hamad A; Tawfik, Ahmed M; Ezzat, Abdelrahman O


    This work first reports the preparation of super-amphiphilic silica-nanogel composites to reduce the contact angle of water to increase the diffusion of pollutant into adsorbents. In this respect, the silica nanoparticles were encapsulated into nanogels based on ionic and nonionic polyacrylamides by dispersion polymerization technique. The morphologies and the dispersion stability of nanogel composites were investigated to clarify the ability of silica-nanogel composites to adsorb at different interfaces. The feasibility of silica polyacrylamide nanogel composites to act as a high-performance adsorbent for removal of methylene blue (MB) dye and heavy metals (Co(2+) and Ni(2+)) from aqueous solution was investigated. The surface tension, contact angle, average pore size, and zeta potential of the silica-nanogel composites have been evaluated. The MB dye and heavy metal adsorption capacity achieved Qmax = 438-387 mg/g which is considerably high. The adsorption capacity results are explained from the changes in the morphology of the silica surfaces as recorded from scanning electron microscopy (SEM).

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

    Directory of Open Access Journals (Sweden)

    Ayman M. Atta


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

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

    Directory of Open Access Journals (Sweden)

    Wei Yan


    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.

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

    Directory of Open Access Journals (Sweden)

    Ronald Okoth


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

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

    Directory of Open Access Journals (Sweden)

    Qian CHEN


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

  8. Organometallic Polymeric Conductors (United States)

    Youngs, Wiley J.


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

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

    Energy Technology Data Exchange (ETDEWEB)

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


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

  10. Functionalized silica materials for electrocatalysis

    Indian Academy of Sciences (India)

    Vellaichamy Ganesan


    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

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

    Energy Technology Data Exchange (ETDEWEB)

    Li, Qianqian; Yan, Yuheng; Yu, Miao; Song, Botao; Shi, Suqing, E-mail:; Gong, Yongkuan


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

  12. Silica exposure and systemic vasculitis.


    Mulloy, Karen B


    Work in Department of Energy (DOE) facilities has exposed workers to multiple toxic agents leading to acute and chronic diseases. Many exposures were common to numerous work sites. Exposure to crystalline silica was primarily restricted to a few facilities. I present the case of a 63-year-old male who worked in DOE facilities for 30 years as a weapons testing technician. In addition to silica, other workplace exposures included beryllium, various solvents and heavy metals, depleted uranium, a...

  13. 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


    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.

  14. Synthesis of N-halamine-functionalized silica-polymer core-shell nanoparticles and their enhanced antibacterial activity (United States)

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


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

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

    Energy Technology Data Exchange (ETDEWEB)

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


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

  16. Thermodynamics of Enzyme-Catalyzed Reactions Database (United States)

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

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

    Akhavan, Behnam; Jarvis, Karyn; Majewski, Peter


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

  18. Rapid "one-pot" preparation of polymeric monolith via photo-initiated thiol-acrylate polymerization for capillary liquid chromatography. (United States)

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


    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.

  19. Electroactivity in Polymeric Materials

    CERN Document Server


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

  20. Cationic ring-opening polymerization of 3,3-bis(chloromethyl)oxacyclobutane in ionic liquids

    Institute of Scientific and Technical Information of China (English)


    Cationic ring-opening polymerization of 3,3-bis(chloromethyl)oxacyclobutane catalyzed by BF3·OEt2 was carried out in ionic liquids [bmim]BF4 and [bmim]PF6. The influences of BCMO concentration and molar ratio of BCMO/BF3·OEt2 on the molecular weights and yield of PBCMO were investigated. The polymerization in ionic liquids proceed to high conversions, although molecular weights are limited, similar to polymerization in organic solvent such as CH2C12. Follow a viewpoint of green chemistry,we feel ionic liquid [bmim]BF4 is superior to [bmim]PF6. Extracting [bmim]PF6 from the product using organic solvent as extractant limits its advantage as a green reaction media.

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

    Directory of Open Access Journals (Sweden)

    Valdemiro P. Carvalho Jr.


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

  2. Polymerization of anionic wormlike micelles. (United States)

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


    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.

  3. 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


    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.

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

    KAUST Repository

    Polshettiwar, Vivek


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

  5. Surface glycosylation of polymeric membranes

    Institute of Scientific and Technical Information of China (English)

    DAI ZhengWei; WAN LingShu; XU ZhiKang


    Surface glycosylation of polymeric membranes has been inspired by the structure of natural biomembranes. It refers to that glycosyl groups are introduced onto the membrane surface by various strategies, which combine the separation function of the membrane with the biological function of the saccharides 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 surface-glycosylated membranes.

  6. Silica research in Glasgow

    CERN Document Server

    Barr, B W; Casey, M M; Clubley, D; Crooks, D R M; Danzmann, K; Elliffe, E J; Gossler, S; Grant, A; Grote, H; Heptonstall, A; Hough, J; Jennrich, O; Lück, H B; McIntosh, S A; Newton, G P; Palmer, D A; Plissi, M V; Robertson, D I; Robertson, N A; Rowan, S; Skeldon, K D; Sneddon, P; Strain, K A; Torrie, C I; Ward, H; Willems, P A; Willke, B; Winkler, W


    The Glasgow group is involved in the construction of the GEO600 interferometer as well as in R and D activity on technology for advanced gravitational wave detectors. GEO600 will be the first GW detector using quasi-monolithic silica suspensions in order to decrease thermal noise significantly with respect to steel wire suspensions. The results concerning GEO600 suspension mounting and performance will be shown in the first section. Section 2 is devoted to the present results from the direct measurement of thermal noise in mirrors mounted in the 10 m interferometer in Glasgow which has a sensitivity limit of 4 x 10 sup - sup 1 sup 9 m Hz sup - sup 1 sup / sup 2 above 1 kHz. Section 3 presents results on the measurements of coating losses. R and D activity has been carried out to understand better how thermal noise in the suspensions affects the detector sensitivity, and in section 4 a discussion on the non-linear thermoelastic effect is presented.

  7. 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: [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)


    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.

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

    Directory of Open Access Journals (Sweden)

    Alessandro Mandoli


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

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

    DEFF Research Database (Denmark)

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


    Immobilized lipases can be used in biodiesel production to overcome many disadvantages of the conventional base-catalyzed process. However, the glycerol by-product poses a potential problem for the biocatalytic process as it is known to inhibit immobilized lipases, most likely by clogging...... to illustrate the interaction of glycerol with immobilized lipases and thus provided an aid for screening supports for lipase immobilization according to their interaction with glycerol. Glycerol was found to have great affinity for silica, less for polystyrene and no affinity for supports made from...


    Institute of Scientific and Technical Information of China (English)

    TANG Liming; HUANG Meiyu; JIANG Yingyan


    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.

  11. Iridium-Catalyzed Allylic Substitution (United States)

    Hartwig, John F.; Pouy, Mark J.

    Iridium-catalyzed asymmetric allylic substitution has become a valuable method to prepare products from the addition of nucleophiles at the more substituted carbon of an allyl unit. The most active and selective catalysts contain a phosphoramidite ligand possessing at least one arylethyl substituent on the nitrogen atom of the ligand. In these systems, the active catalyst is generated by a base-induced cyclometalation at the methyl group of this substituent to generate an iridium metalacycle bound by the COD ligand of the [Ir(COD)Cl]2 precursor and one additional labile dative ligand. Such complexes catalyze the reactions of linear allylic esters with alkylamines, arylamines, phenols, alcohols, imides, carbamates, ammonia, enolates and enolate equivalents, as well as typical stabilized carbon nucleophiles generated from malonates and cyanoesters. Iridium catalysts for enantioselective allylic substitution have also been generated from phosphorus ligands with substituents bound by heteroatoms, and an account of the studies of such systems, along with a description of the development of iridium catalysts is included.


    Institute of Scientific and Technical Information of China (English)

    Andrea R. Szkurhan; Michael K. Georges


    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.

  13. Enzyme-Catalyzed Synthesis of Water-Soluble Conjugated Poly[2-(3-thienyl-Ethoxy-4-Butylsulfonate

    Directory of Open Access Journals (Sweden)

    Yun Zhao


    Full Text Available An environmentally friendly water-soluble conjugated polythiophene poly[2-(3-thienyl-ethoxy-4-butylsulfonate] (PTEBS has been found to be effective for making hybrid solar cells. In this work, we first report the enzyme-catalyzed polymerization of (3-thienyl-ethoxy-4-butylsulfonate (TEBS using horseradish peroxidase (HRP enzyme as a catalyst and hydrogen peroxide (H2O2 as an oxidant in an aqueous buffer. This enzyme-catalyzed polymerization is a “green synthesis process” for the synthesis of water-soluble conjugated PTEBS, the benefits of which include a simple setting, high yields, and an environmentally friendly route. Fourier transform infrared spectra (FTIR and UV–Vis absorption spectra confirm the successful enzyme-catalyzed polymerization of TEBS. The thermo gravimetric (TG data show the obtained PTEBS is stable over a fairly high range of temperatures. The present PTEBS has a good solubility in water and ethanol, and photoluminescence quenching of PTEBS/titanium dioxide (TiO2 composite implies that the excitons dissociate and separate successfully at the interface of PTEBS and TiO2, which help to build solar cells using green processing methods.

  14. Transition metal-catalyzed functionalization of pyrazines

    NARCIS (Netherlands)

    Nikishkin, Nicolai I.; Huskens, Jurriaan; Verboom, Willem


    Transition metal-catalyzed reactions are generally used for carbon–carbon bond formation on pyrazines and include, but are not limited to, classical palladium-catalyzed reactions like Sonogashira, Heck, Suzuki, and Stille reactions. Also a few examples of carbon–heteroatom bond formation in pyrazine

  15. Infrared spectra of silica polymorphs (United States)

    Koike, C.; Noguchi, R.; Chihara, H.; Suto, H.; Ohtaka, O.; Imai, Y.; Matsumoto, T.; Tsuchiyama, A.

    The existence of silica within several debris disks has been suggested. We investigate the annealing conditions of α-cristobalite, and further prepare various types of silica, including α-cristobalite, α-quartz, coesite, stishovite, and fused quartz, which are natural, synthetic or commercial samples. We compare the results to previous studies and find that α-cristobalite synthesized at higher temperature than annealed silica. The interesting result of features similar to those of forsterite should be highlighted, where αcristobalite and coesite showed similar peaks at 16, 33, and 69 μm as forsterite. The 69 μm band for αcristobalite is especially very broad and strong, and shifts largely to a shorter wavelengths under cooling to low temperatures. The band for coesite, however, is very sharp, and shifts only a small amount to longer wavelengths under cooling to low temperatures. The peak positions of 16 and 69-μm band due to α-cristobalite can become index for temperature of silica dust. We discuss the possibility of silica detection around debris disks.

  16. Exposure to crystalline silica in abrasive blasting operations where silica and non-silica abrasives are used. (United States)

    Radnoff, Diane L; Kutz, Michelle K


    Exposure to respirable crystalline silica is a hazard common to many industries in Alberta but particularly so in abrasive blasting. Alberta occupational health and safety legislation requires the consideration of silica substitutes when conducting abrasive blasting, where reasonably practicable. In this study, exposure to crystalline silica during abrasive blasting was evaluated when both silica and non-silica products were used. The crystalline silica content of non-silica abrasives was also measured. The facilities evaluated were preparing metal products for the application of coatings, so the substrate should not have had a significant contribution to worker exposure to crystalline silica. The occupational sampling results indicate that two-thirds of the workers assessed were potentially over-exposed to respirable crystalline silica. About one-third of the measurements over the exposure limit were at the work sites using silica substitutes at the time of the assessment. The use of the silica substitute, by itself, did not appear to have a large effect on the mean airborne exposure levels. There are a number of factors that may contribute to over-exposures, including the isolation of the blasting area, housekeeping, and inappropriate use of respiratory protective equipment. However, the non-silica abrasives themselves also contain silica. Bulk analysis results for non-silica abrasives commercially available in Alberta indicate that many contain crystalline silica above the legislated disclosure limit of 0.1% weight of silica per weight of product (w/w) and this information may not be accurately disclosed on the material safety data sheet for the product. The employer may still have to evaluate the potential for exposure to crystalline silica at their work site, even when silica substitutes are used. Limited tests on recycled non-silica abrasive indicated that the silica content had increased. Further study is required to evaluate the impact of product recycling

  17. Stereospecific olefin polymerization catalysts (United States)

    Bercaw, John E.; Herzog, Timothy A.


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

  18. Thermo-mechanical properties of high aspect ratio silica nanofiber filled epoxy composites (United States)

    Ren, Liyun

    The optimization of thermo-mechanical properties of polymer composites at low filler loadings is of great interest in both engineering and scientific fields. There have been several studies on high aspect ratio fillers as novel reinforcement phase for polymeric materials. However, facile synthesis method of high aspect ratio nanofillers is limited. In this study, a scalable synthesis method of high aspect ratio silica nanofibers is going to be presented. I will also demonstrate that the inclusion of high aspect ratio silica nanofibers in epoxy results in a significant improvement of epoxy thermo-mechanical properties at low filler loadings. With silica nanofiber concentration of 2.8% by volume, the Young's modulus, ultimate tensile strength and fracture toughness of epoxy increased ~23, ~28 and ~50%, respectively, compared to unfilled epoxy. At silica nanofiber volume concentration of 8.77%, the thermal expansion coefficient decreased by ˜40% and the thermal conductivity was improved by ˜95% at room temperature. In the current study, the influence of nano-sized silica filler aspect ratio on mechanical and thermal behavior of epoxy nanocomposites were studied by comparing silica nanofibers to spherical silica nanoparticles (with aspect ratio of one) at various filler loadings. The significant reinforcement of composite stiffness is attributed to the variation of the local stress state in epoxy due to the high aspect ratio of the silica nanofiber and the introduction of a tremendous amount of interfacial area between the nanofillers and the epoxy matrix. The fracture mechanisms of silica nanofiber filled epoxy were also investigated. The existence of high aspect ratio silica nanofiber promotes fracture energy dissipation by crack deflection, crack pinning as well as debonding with fiber pull-out leading to enhanced fracture toughness. High aspect ratio fillers also provide significant reduction of photon scattering due to formation of a continuous fiber network

  19. 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


    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.

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

    Institute of Scientific and Technical Information of China (English)


    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

  1. Studies of Immobilized Homogeneous Metal Catalysts on Silica Supports

    Energy Technology Data Exchange (ETDEWEB)

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


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

  2. Radiation hardening of sol gel-derived silica fiber preforms through fictive temperature reduction. (United States)

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


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

  3. Bioactive organic-inorganic poly(CLMA-co-HEA)/silica nanocomposites. (United States)

    Ivashchenko, Sergiy; Escobar Ivirico, Jorge L; García Cruz, Dunia M; Campillo-Fernández, Alberto; Gallego Ferrer, Gloria; Monleón Pradas, Manuel


    A series of novel poly(CLMA-co-HEA)/silica nanocomposites is synthesized from caprolactone 2-(methacryloyloxy)ethyl ester (CLMA) and 2-hydroxyethyl acrylate (HEA) as organic comonomers and the simultaneous sol-gel polymerization of tetraethyloxysilane (TEOS) as silica precursor, in different mass ratios up to a 30 wt% of silica. The nanocomposites are characterized as to their mechanical and thermal properties, water sorption, bioactivity and biocompatibility, reflecting the effect on the organic matrix provided by the silica network formation. The nanocomposites nucleate the growth of hydroxyapatite (HAp) on their surfaces when immersed in the simulated body fluid of the composition used in this work. Proliferation of the MC3T3 osteoblast-like cells on the materials was assessed with the MTS assay showing their biocompatibility. Immunocytochemistry reveals osteocalcin and type I collagen production, indicating that osteoblast differentiation was promoted by the materials, and calcium deposition was confirmed by von Kossa staining. The results indicate that these poly(CLMA-co-HEA)/silica nanocomposites could be a promising biomaterial for bone tissue engineering.

  4. 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: [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)


    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.

  5. Dynamics of Methyl Methacrylate Nanoconfined in Silica Sol Glasses Studied by Optical Kerr Effect Spectroscopy (United States)

    Meng, Dujuan; Xue, Lianjie; Tamas, George; Quitevis, Edward; Simon, Sindee


    Nanoconfinement has been found to have an effect on polymerization processes [1,2] and on the glass transition temperature Tg [3]. Here we report studies of the nanoconfinement effect on the dynamics of monomers in the pores of silica sol-gel glass. The samples were prepared under a vacuum and studied by using optical Kerr effect (OKE) spectroscopy. The reorientational dynamics of methyl methacrylate (MMA) confined in silica sol-gel glasses with pore diameters of 32, 41, and 82 Å was studied. The decays of the reorientational correlation function C(t) became longer as the pore size decreased. Based on the analysis of the reorientational correlation functions using a two-state model [4], the nanoconfinement effect is due to the interaction of molecules with the surface of the silica-gel glass. In a study of the effect of nanoconfinement in modified silica sol-gel glasses, which were obtained by refluxing the sol-gel glasses in methanol to give hydrophobic pore surfaces, the decay is faster in the modified silica gel glass than in the unmodified sol-gel glass. This work is supported by NSF Grant CMMI-1235346.

  6. Effect of concentrated epoxidised natural rubber and silica masterbatch for tyre application (United States)

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


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

  7. 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


    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.

  8. Silica Aerogel: Synthesis and Applications

    Directory of Open Access Journals (Sweden)

    Jyoti L. Gurav


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

  9. Kinetics of Coloration in Photochromic Tungsten(VI) Oxide/Silicon Oxycarbide/Silica Hybrid Xerogel: Insight into Cation Self-diffusion Mechanisms. (United States)

    Adachi, Kenta; Tokushige, Masataka; Omata, Kaoru; Yamazaki, Suzuko; Iwadate, Yoshiaki


    Silicon oxycarbide/silica composites with well-dispersed tungsten(VI) oxide (WO3) nanoparticles were obtained as transparent hybrid xerogels via an acid-catalyzed sol-gel process (hydrolysis/condensation polymerization) of 3-(triethoxysilyl)propyl methacrylate (TESPMA) and tetraethoxysilane (TEOS). The self-diffusion mechanism of alkali-metal cations and the kinetics of the photochromic coloration process in the WO3/TESPMA/TEOS hybrid xerogel systems have been systematically investigated. Under continuous UV illumination, a gradual color change (colorless → blue) corresponding to the reduction of W(6+) into W(5+) states in WO3 nanoparticles can be confirmed from the WO3/TESPMA/TEOS hybrid xerogels containing alkali-metal sulfates, although no coloration of the hybrid xerogel without alkali-metal sulfate was observed. The coloration behavior depended exclusively on a variety of alkali-metal cations present in the hybrid xerogel system. Furthermore, a detailed analysis of the self-diffusion mechanism confirmed that the alkali-metal cations electrostatically interact with a layer of unreacted silanol groups on the TESPMA/TEOS matrix surface, and subsequently pass through the interconnected pore network of the hybrid xerogel. More interestingly, in the context of an Arrhenius analysis, we found a good coincidence between the activation energies for alkali-metal cation self-diffusion and UV-induced coloration in the WO3/TESPMA/TEOS hybrid xerogel system containing the corresponding alkali-metal sulfate. It is experimentally obvious that the photochromic properties are dominated by the diffusion process of alkali-metal cations in the WO3/TESPMA/TEOS hybrid xerogel system. Such hybrid materials with cation-controlled photochromic properties will show promising prospects in applications demanding energy-efficient "smart windows" and "smart glasses".

  10. Synthesis and Characterization of Bimodal Mesoporous Silica

    Institute of Scientific and Technical Information of China (English)

    ZHANG Xiaofang; GUO Cuili; WANG Xiaoli; WU Yuanyuan


    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.

  11. Optothermal nonlinearity of silica aerogel

    CERN Document Server

    Braidotti, Maria Chiara; Fleming, Adam; Samuels, Michiel C; Di Falco, Andrea; Conti, Claudio


    We report on the characterization of silica aerogel thermal optical nonlinearity, obtained by z-scan technique. The results show that typical silica aerogels have nonlinear optical coefficient similar to that of glass $(\\simeq 10^{-12} $m$^2/$W), with negligible optical nonlinear absorption. The non\\-li\\-near coefficient can be increased to values in the range of $10^{-10} $m$^2/$W by embedding an absorbing dye in the aerogel. This value is one order of magnitude higher than that observed in the pure dye and in typical highly nonlinear materials like liquid crystals.

  12. Niobia-silica and silica membranes for gas separation

    NARCIS (Netherlands)

    Boffa, Vittorio


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

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

    Energy Technology Data Exchange (ETDEWEB)

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


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

  14. Surface glycosylation of polymeric membranes

    Institute of Scientific and Technical Information of China (English)


    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.

  15. Synthesis and properties of Chitosan-silica hybrid aerogels

    Energy Technology Data Exchange (ETDEWEB)

    Ayers, Michael R.; Hunt, Arlon J.


    Chitosan, a polymer that is soluble in dilute aqueous acid, is derived from chitin, a natural polyglucosamide. Aquagels where the solid phase consists of both chitosan and silica can be easily prepared by using an acidic solution of chitosan to catalyze the hydrolysis and condensation of tetraethylorthosilicate. Gels with chitosan/TEOS mass ratios of 0.1-1.1 have been prepared by this method. Standard drying processes using CO{sub 2} give the corresponding aerogels. The amount of chitosan in the gel plays a role in the shrinkage of the aerogel during drying. Gels with the lowest chitosan/silica ratios show the most linear shrinkage, up to 24%, while those with the highest ratios show only a 7% linear shrinkage. Pyrolysis at 700 C under nitrogen produces a darkened aerogel due to the thermal decomposition of the chitosan, however, the aerogel retains its monolithic form. The pyrolyzed aerogels absorb slightly more infrared radiation in the 2-5 {micro}m region than the original aerogels. B.E.T. surface areas of these aerogels range from 470-750 m{sup 2}/g. Biocompatibility screening of this material shows a very high value for hemolysis, but a low value for cytotoxicity.

  16. 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


    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.


    Institute of Scientific and Technical Information of China (English)

    Zhao-bin Zhang; Xiao-long Wan; Chun-pu Hu; Sheng-kang Ying


    Atom transfer radical polymerization (ATRP) of styrene catalyzed by cuprous (CuX)/1,10-phenanthroline (Phen)and CuX/CuX2/Phen was conducted in an aqueous dispersed system. A stable latex was obtained by using ionic surfactant sodium lauryl sulfonate (SLS) or composite surfactants, such as SLS/polyoxyethylene nonyl phenyl ether (OP-10),SLS/hexadecanol and SLS/OP-10/hexadecanol. Among which SLS and SLS/OP-10/hexadecanol systems established better dispersed effect during the polymerization. It was found that Phen was a more suitable ligand than N,N,N',N",N"-pentamethyldiethylenetriamine (PMDETA) to maintain an appropriate equilibrium of the activator Cu(Ⅰ) and the deactivator Cu(Ⅱ) between the organic phase and the water phase. The effect of several initiators (such as EBiB, CCl4 and 1-PEBr) and the temperature on such a kind of ATRP system was also observed. The number-average molar mass (Mn) of polystyrene (PS)increased with the conversion and the molar mass distribution (Mw/Mn) remained narrow. These experimental data show that the polymerization could be controlled except for the quick increase of monomer conversion and the number-average molar mass of PS in the initial stage of polymerization. Furthermore, the initiator efficiency was found to be low (~57%) in CuX/Phen catalyzed system. To overcome this problem, Cu(Ⅱ )X2 (20 mol%-50 mol% based on CuX) was introduced into the polymerization system. In this case, higher initiator efficiency (60%-90%), low Mw/Mn of PS (as low as 1.08) were achieved and the molar masses of the PS fit with the theoretical ones.

  18. The Effect of Microporous Polymeric Support Modification on Surface and Gas Transport Properties of Supported Ionic Liquid Membranes. (United States)

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


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

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

    Directory of Open Access Journals (Sweden)

    Alsu A. Akhmetshina


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

  20. Effect of base monomer's refractive index on curing depth and polymerization conversion of photo-cured resin composites. (United States)

    Fujita, Kou; Nishiyama, Norihiro; Nemoto, Kimiya; Okada, Tamami; Ikemi, Takuji


    In this study, we examined the effect of the transmitted amount of visible light through a resin composite on the curing depth and polymerization conversion. Transmitted amount of visible light was strongly dependent on the magnitude of refractive index difference that existed between the resin and silica filler. More specifically, the differences arose from the type of base monomer used. The transmitted amount of visible light exhibited a good correlation with the curing depth and Knoop hardness ratio of the bottom surface against the top surface of the resin composite. To improve the polymerization conversion of the cavity floor, it is important to reduce the refractive index difference that exists between the base resin and silica filler.

  1. Functionalization and Polymerization on the CNT Surfaces

    KAUST Repository

    Albuerne, Julio


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

  2. Ringing phenomenon in silica microspheres

    Institute of Scientific and Technical Information of China (English)

    Chunhua Dong; Changling Zou; Jinming Cui; Yong Yang; Zhengfu Han; Guangcan Guo


    Whispering gallery modes in silica microspheres are excited by a tunable continuous-wave laser through the fiber taper. Ringing phenomenon can be observed with high frequency sweeping speed. The thermal nonlinearity in the microsphere can enhance this phenomenon. Our measurement results agree very well with the theoretical predictions by the dynamic equation.

  3. Syndiospecific Polymerization of Styrene Catalyzed by IndTiCl2(OR)/Methylaluminoxane System

    Institute of Scientific and Technical Information of China (English)


    @@Since Ishihara et al[1] reported that a new macromolecule syndiotact ic polystyrene (s-PS) could be produced with high stereoregularity by using ( η5-Cp)TiCl3 activated with methylaluminoxane (MAO), more efforts were de voted to syntheses of new kinds of half-sandwich titanocenes and to elucidation of the relationship of precursor structure to its catalytic behavior[2~4]. The effect of the substituents attached to π-ligand on the styrene polym erization has been discussed[2~4], but the effect of σ-bonded ligands has not been reported properly.

  4. Polymeric Inverse Glasses for Development of Noniridescent Structural Colors in Full Visible Range. (United States)

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


    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.

  5. Biodegradable polymeric prodrugs of naltrexone

    NARCIS (Netherlands)

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


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

  6. Buckling of polymerized monomolecular films (United States)

    Bourdieu, L.; Daillant, J.; Chatenay, D.; Braslau, A.; Colson, D.


    The buckling of a two-dimensional polymer network at the air-water interface has been evidenced by grazing incidence x-ray scattering. A comprehensive description of the inhomogeneous octadecyltrichlorosilane polymerized film was obtained by atomic force microscopy and x-ray scattering measurements. The buckling occurs with a characteristic wavelength ~=10 μm.

  7. Novel polymeric materials from triglycerides (United States)

    Triglycerides are good platforms for new polymeric products that can substitute for petroleum-based materials. As part of our research emphasis in sustainability and green polymer chemistry, we have explored a number of reactions in efforts to produce a wide range of value-added products. In this ...

  8. The Viscosity of Polymeric Fluids. (United States)

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


    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…

  9. The absorption of polymeric composites (United States)

    Řídký, R.; Popovič, M.; Rolc, S.; Drdlová, M.; Krátký, J.


    An absorption capacity of soft, viscoelastic materials at high strain rates is important for wide range of practical applications. Nowadays there are many variants of numerical models suitable for this kind of analysis. The main difficulty is in selection of the most realistic numerical model and a correct setup of many unknown material constants. Cooperation between theoretical simulations and real testing is next crucial point in the investigation process. Standard open source material database offer material properties valid for strain rates less than 250 s-1. There are experiments suitable for analysis of material properties with strain rates close to 2000 s-1. The high strain-rate characteristics of a specific porous blast energy absorbing material measured by modified Split Hopkinson Pressure Bar apparatus is presented in this study. Testing these low impedance materials using a metallic split Hopkinson pressure bar setup results in poor signal to noise ratios due to impedance mismatching. These difficulties are overcome by using polymeric Hopkinson bars. Conventional Hopkinson bar analysis cannot be used on the polymeric bars due to the viscoelastic nature of the bar material. One of the possible solution leads to complex and frequency depended Young modulus of testing bars material. This testing technique was applied to materials composed of porous glass/ceramic filler and polymeric binder, with density of 125 - 300 kg/m3 and particle size in range of 50 µm - 2 mm. The achieved material model was verified in practical application of sandwich structure includes polymeric composites under a blast test.

  10. Silica-Coated Liposomes for Insulin Delivery

    Directory of Open Access Journals (Sweden)

    Neelam Dwivedi


    Full Text Available Liposomes coated with silica were explored as protein delivery vehicles for their enhanced stability and improved encapsulation efficiency. Insulin was encapsulated within the fluidic phosphatidylcholine lipid vesicles by thin film hydration at pH 2.5, and layer of silica was formed above lipid bilayer by acid catalysis. The presence of silica coating and encapsulated insulin was identified using confocal and electron microscopy. The native state of insulin present in the formulation was evident from Confocal Micro-Raman spectroscopy. Silica coat enhances the stability of insulin-loaded delivery vehicles. In vivo study shows that these silica coated formulations were biologically active in reducing glucose levels.

  11. Biguanide-functionalized mesoporous SBA-15 silica as an efficient solid catalyst for interesterification of vegetable oils. (United States)

    Xie, Wenlei; Hu, Libing


    The biguanide-functionalized SBA-15 materials were fabricated by grafting of organic biguanide onto the SBA-15 silica through covalent attachments, and then this organic-inorganic hybrid material was employed as solid catalysts for the interesterification of triacylglycerols for the modification of vegetable oils. The prepared catalyst was characterized by FTIR, XRD, SEM, TEM, nitrogen adsorption-desorption and elemental analysis. The biguanide base was successfully tethered onto the SBA-15 silica with no damage to the ordered mesoporous structure of the silica after the organo-functionalization. The solid catalyst had stronger base strength and could catalyze the interesterification of triacylglycerols. The fatty acid compositions and triacylglycerol profiles of the interesterified products were noticeably varied following the interesterification. The reaction parameters, namely substrate ratio, reaction temperature, catalyst loading and reaction time, were investigated for the interesterification of soybean oil with methyl decanoate. The catalyst could be reused for at least four cycles without significant loss of activity.

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

    Directory of Open Access Journals (Sweden)

    B. Lantaño


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


    Institute of Scientific and Technical Information of China (English)

    HUANG Zhitang


    This review is a concise survey about the works in our laboratory on the polymerization of aromatic and heterocyclic dinitriles, including the polymerization kinetics and mechanism, synthesis of heterocyclic dinitriles, the structure of polymers, and the correlation between the structures of dinitriles and polymerization rates and thermal performances of polymers.

  14. Polymeric amines and biomedical uses thereof

    NARCIS (Netherlands)

    Broekhuis, Antonius; Zhang, Youchum; Picchioni, Francesco; Roks, Antonius


    The invention relates to the field of polymers and biomedical applications thereof. In particular, it relates to the use of polymeric amines derived from alternating polyketones.Provided is the use of a polymeric amine for modulating or supporting cellular behavior, said polymeric amine being an alt

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

    Directory of Open Access Journals (Sweden)

    Jun Yin


    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.

  16. Polymerization of Polar Monomers from a Theoretical Perspective

    KAUST Repository

    Alghamdi, Miasser


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

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

    Directory of Open Access Journals (Sweden)

    Genoveva Hernández-Padrón


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

  18. Synthesis and characterization of guar gum templated hybrid nano silica. (United States)

    Singh, V; Singh, S K; Pandey, S; Sanghi, R


    The objective of the present study was the fabrication of green adsorbent hybrids for which native guar gum was used as template to polymerize tetraethoxysilane. The properties and performances of the hybrids could be tailored by using varying molecular sizes of the partially depolymerized guar gum templates of various molecular sizes as control. Zn(II) uptake from aqueous solution was used as a criterion for evaluating the adsorbent efficiency. The optimum material (H4) in terms of maximum Zn(II) uptake, was obtained when the template size used was 375 kDa at a calcination temperature of 700°C. H4 was also evaluated for Ca(II), Mg(II), Cd(II) and Hg(II) adsorption. To explore the other applicability areas, the hybrids have been extensively characterized using FTIR, XRD, TGA-DTA, PL, SEM, TEM and BET analyses. H4 was found to be as efficient as previously reported vinyl modified-silica nanohybrids. It had a high surface area (264 m(2)/g) with silica nanoparticles in the size range of 90-140 nm. Being thermally very stable and photoluminescent, the material can be potentially used for many biological, medical and environmental applications.

  19. 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


    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.

  20. The Pozzolanic reaction of silica fume

    DEFF Research Database (Denmark)

    Jensen, Ole Mejlhede


    Silica fume is a very important supplementary cementitious binder in High-Performance and Ultra High-Performance Concretes. Through its pozzolanic reaction the silica fume densifies the concrete micro-structure, in particular it strengthens the paste-aggregate interfacial transition zone. In the ...... of activation of the pozzolanic reaction of silica fume is estimated. The results show that the pozzolanic reaction of silica fume has notable differences from Portland cement hydration.......Silica fume is a very important supplementary cementitious binder in High-Performance and Ultra High-Performance Concretes. Through its pozzolanic reaction the silica fume densifies the concrete micro-structure, in particular it strengthens the paste-aggregate interfacial transition zone....... In the present paper different aspects of the pozzolanic reaction of silica fume are investigated. These include chemical shrinkage, isothermal heat development and strength development. Key data for these are given and compared with theoretical calculations, and based on presented measurements the energy...

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

    Energy Technology Data Exchange (ETDEWEB)

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


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

  2. Advances in lipase-catalyzed esterification reactions. (United States)

    Stergiou, Panagiota-Yiolanda; Foukis, Athanasios; Filippou, Michalis; Koukouritaki, Maria; Parapouli, Maria; Theodorou, Leonidas G; Hatziloukas, Efstathios; Afendra, Amalia; Pandey, Ashok; Papamichael, Emmanuel M


    Lipase-catalyzed esterification reactions are among the most significant chemical and biochemical processes of industrial relevance. Lipases catalyze hydrolysis as well as esterification reactions. Enzyme-catalyzed esterification has acquired increasing attention in many applications, due to the significance of the derived products. More specifically, the lipase-catalyzed esterification reactions attracted research interest during the past decade, due to an increased use of organic esters in biotechnology and the chemical industry. Lipases, as hydrolyzing agents are active in environments, which contain a minimum of two distinct phases, where all reactants are partitioned between these phases, although their distribution is not fixed and changes as the reaction proceeds. The kinetics of the lipase-catalyzed reactions is governed by a number of factors. This article presents a thorough and descriptive evaluation of the applied trends and perspectives concerning the enzymatic esterification, mainly for biofuel production; an emphasis is given on essential factors, which affect the lipase-catalyzed esterification reaction. Moreover, the art of using bacterial and/or fungal strains for whole cell biocatalysis purposes, as well as carrying out catalysis by various forms of purified lipases from bacterial and fungal sources is also reviewed.

  3. Shape Memory Properties of PBS-Silica Hybrids

    Directory of Open Access Journals (Sweden)

    Katia Paderni


    Full Text Available A series of novel Si–O–Si crosslinked organic/inorganic hybrid semi-crystalline polymers with shape memory properties was prepared from alkoxysilane-terminated poly(butylene succinate (PBS by water-induced silane crosslinking under organic solvent-free and catalyst-free conditions. The hydrolyzation and condensation of alkoxysilane end groups allowed for the generation of silica-like crosslinking points between the polymeric chains, acting not only as chemical net-points, but also as inorganic filler for a reinforcement effect. The resulting networks were characterized using differential scanning calorimetry (DSC, thermogravimetric analysis (TGA, dynamic-mechanical analysis (DMA and tensile and shape memory tests to gain insight into the relationship between the polymeric structure, the morphology and the properties. By controlling the molecular weight of the PBS precursor, a fine tuning of the crosslinking density and the inorganic content of the resulting network was possible, leading to different thermal, mechanical and shape memory properties. Thanks to their suitable morphology consisting of crystalline domains, which represent the molecular switches between the temporary and permanent shapes, and chemical net-points, which permit the shape recovery, the synthesized materials showed good shape memory characteristics, being able to fix a significant portion of the applied strain in a temporary shape and to restore their original shape above their melting temperature.

  4. Photophysical studies of newly derivatized mono substituted phthalocyanines grafted onto silica nanoparticles via click chemistry (United States)

    Fashina, Adedayo; Amuhaya, Edith; Nyokong, Tebello


    This work reports on the synthesis, characterization and photophysical studies of newly derived phthalocyanine complexes and the phthalocyanine-silica nanoparticles conjugates. The derived phthalocyanine complexes have one terminal alkyne group. The derived phthalocyanine complexes showed improved photophysical properties (ФF, ФT, ΦΔ and τT) compared to the respective phthalocyanine complexes from which they were derived. The derived phthalocyanine complexes were conjugated to the surface of an azide functionalized silica nanoparticles via copper (1) catalyzed cyclo-addition reaction. All the conjugates showed lower triplet quantum yields ranging from 0.37 to 0.44 compared to the free phthalocyanine complexes. The triplet lifetimes ranged from 352 to 484 μs for the conjugates and from 341 to 366 μs for the free phthalocyanine complexes.

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

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


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

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

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


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

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

    Directory of Open Access Journals (Sweden)

    Kenjiro Yazawa


    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.

  8. Rate equation approach to understanding the ion-catalyzed formation of peptides (United States)

    Dubrovskii, V. G.; Sibirev, N. V.; Eliseev, I. E.; Vyazmin, S. Yu; Boitsov, V. M.; Natochin, Yu. V.; Dubina, M. V.


    The salt-induced peptide formation is important for assessing and approaching schemes of molecular evolution. Here, we present experimental data and an exactly solvable kinetic model describing the linear polymerization of L-glutamic amino acid in water solutions with different concentrations of KCl and NaCl. The length distributions of peptides are well fitted by the model. Strikingly, we find that KCl considerably enhances the peptide yield, while NaCl does not show any catalytic effect in most cases under our experimental conditions. The greater catalytic effect of potassium ions is entirely interpreted by one and single parameter, the polymerization rate constant that depends on the concentration of a given salt in the reaction mixture. We deduce numeric estimates for the rate constant at different concentrations of the ions and show that it is always larger for KCl. This leads to an exponential increase of the potassium- to sodium-catalyzed peptide concentration ratio with length. Our results show that the ion-catalyzed peptides have a higher probability to emerge in excess potassium rather than in sodium-rich water solutions.

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

    Guan, Yinyan; Meng, Xiaohui; Qiu, Dong


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

  10. Evaluation of the interactions between polymeric chains and surfaces with different structures performed by an atomic force microscope

    Directory of Open Access Journals (Sweden)

    Oréfice Rodrigo Lambert


    Full Text Available Interactions between polymers and inorganic surfaces are present in a series of phenomena involving processes such as coagulation and deffloculation of ceramic powder and adsorption of organic macromolecules on the surface of implants, among others. In this work, Atomic Force Microscopy (AFM was modified to allow the evaluation of interactions between polymeric chains and inorganic surfaces (silica with different structures. Polymers (sulfonated polysulfone were grafted onto AFM cantilevers. AFM force-distance curves were obtained for this modified tip against a series of substrates produced by depositing silica films on silicon wafers. The structure of the silica layer was modified by employing heat treatments at different temperatures. The results showed that the interactions between polymer and surfaces are dependent on the structure of the surfaces. Penetration of the polymeric chains can occur through a soft gel layer (substrates treated at low temperature, 110 °C. For surfaces with dense silica layers, the results showed that not only the concentration of hydroxy groups but also their spatial distribution along the surfaces are important in defining the magnitude of interactions between polymers and surfaces. A model involving a molecular recognition process, in which interactions are maximized for inorganic surfaces with structures that can match the chemical architecture of the polymer, was then used to explain the obtained results.

  11. Surface Modification of Fillers and Curatives by Plasma Polymerization for Enhanced Performance of Single Rubbers and Dissimilar Rubber/Rubber Blends (United States)

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

    Plasma polymerization is a technique for modifying the surface characteristics of fillers and curatives for rubber from essentially polar to nonpolar. Acetylene, thiophene, and pyrrole are employed to modify silica and carbon black reinforcing fillers. Silica is easy to modify because its surface contains siloxane and silanol species. On carbon black, only a limited amount of plasma deposition takes place, due to its nonreactive nature. Oxidized gas blacks, with larger oxygen functionality, and particularly carbon black left over from fullerene production, show substantial plasma deposition. Also, carbon/silica dual-phase fillers react well because the silica content is reactive. Elemental sulfur, the well-known vulcanization agent for rubbers, can also be modified reasonably well.

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

    Cacciotti, Ilaria; Nanni, Francesca


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

  13. Effect of chemically modified silicas on the properties of hybrid gel electrolyte for Li-ion batteries (United States)

    Walkowiak, Mariusz; Zalewska, Aldona; Jesionowski, Teofil; Waszak, Daniel; Czajka, Bogdan

    The aim of the presented work was to perform a preliminary study the physico-chemical properties of hybrid organic-inorganic gel electrolytes for Li-ion batteries based on the PVdF-HFP polymeric matrix and surface modified fumed silicas. Modifications were done by means of the so-called dry method using seven different silanes differing in the nature of the principal functional group: N-2-(aminoethyl)-3-amino propyltrimethoxysilane, 3-glycidoxypropyltrimetoxysilane, 3-mercaptopropyltrimetoxysilane, n-octyltriethoxysilane, 3-(chloropropyl)trimethoxysilane, 3-methacryloxypropyltrimetoxysilane, vinyltrimethoxysilane. The PVdF-HFP gels were prepared according to the so-called Bellcore process (two-step method). Impact of the silicas surface functionality on the degree of crystallinity of the polymeric membranes was studied using the differential scanning calorimetry technique. Applicability of the prepared gel electrolytes for the Li-ion technology was estimated on the basis of specific conductivity measurements. It was shown that modification of the silica surface by most of the silanes causes an increase in the gel specific conductivity by about two orders of magnitude as compared to gel with unmodified silica.

  14. Effect of chemically modified silicas on the properties of hybrid gel electrolyte for Li-ion batteries

    Energy Technology Data Exchange (ETDEWEB)

    Walkowiak, Mariusz; Waszak, Daniel; Czajka, Bogdan [Central Laboratory of Batteries and Cells, ul. Forteczna 12, 61-362 Poznan (Poland); Zalewska, Aldona [Warsaw University of Technology, Department of Chemistry, ul. Noakowskiego 3, 00-664 Warsaw (Poland); Jesionowski, Teofil [Poznan University of Technology, Institute of Chemical Technology and Engineering, Pl. Marii Sklodowskiej-Curie 2, 60-965 Poznan (Poland)


    The aim of the presented work was to perform a preliminary study the physico-chemical properties of hybrid organic-inorganic gel electrolytes for Li-ion batteries based on the PVdF-HFP polymeric matrix and surface modified fumed silicas. Modifications were done by means of the so-called dry method using seven different silanes differing in the nature of the principal functional group: N-2-(aminoethyl)-3-amino propyltrimethoxysilane, 3-glycidoxypropyltrimetoxysilane, 3-mercaptopropyltrimetoxysilane, n-octyltriethoxysilane, 3-(chloropropyl)trimethoxysilane, 3-methacryloxypropyltrimetoxysilane, vinyltrimethoxysilane. The PVdF-HFP gels were prepared according to the so-called Bellcore process (two-step method). Impact of the silicas surface functionality on the degree of crystallinity of the polymeric membranes was studied using the differential scanning calorimetry technique. Applicability of the prepared gel electrolytes for the Li-ion technology was estimated on the basis of specific conductivity measurements. It was shown that modification of the silica surface by most of the silanes causes an increase in the gel specific conductivity by about two orders of magnitude as compared to gel with unmodified silica. (author)

  15. 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


    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.

  16. Ordered mesoporous silica: microwave synthesis

    Energy Technology Data Exchange (ETDEWEB)

    Fantini, M.C.A. [IF-USP, CP 66318, 05315-970, Sao Paulo, SP (Brazil)]. E-mail:; Matos, J.R. [IQ-USP, CP 26077, 05599-970, Sao Paulo, SP (Brazil); Silva, L.C. Cides da [IQ-USP, CP 26077, 05599-970, Sao Paulo, SP (Brazil); Mercuri, L.P. [IQSC-USP, CP 780, 13560-970, Sao Carlos, SP (Brazil); Chiereci, G.O. [IQSC-USP, CP 780, 13560-970, Sao Carlos, SP (Brazil); Celer, E.B. [Department of Chemistry, Kent State University, Kent, OH 44240 (United States); Jaroniec, M. [Department of Chemistry, Kent State University, Kent, OH 44240 (United States)


    Ordered mesoporous silicas, FDU-1, synthesized by using triblock copolymer, EO{sub 39}BO{sub 47}EO{sub 39}, as template were hydrothermally treated in a microwave oven at 373 K for different periods of time. The structural and morphological properties of these silicas were investigated by X-ray diffraction and nitrogen adsorption and compared with those for the FDU-1 samples prepared by conventional hydrothermal treatment at 373 K. All samples were calcined at 813 K in N{sub 2} and air. This procedure succeeded in producing ordered cage-like mesoporous structures even after 15 min of the microwave treatment. The best sample was obtained after 60 min of the microwave treatment, which is reflected by narrow pore size distribution, uniform pore size entrances and thick mesopore walls. Longer time of the microwave treatment increased nonuniformity of the pore entrance sizes as evidenced by changes in the hysteresis loops of nitrogen adsorption isotherms.

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

    Institute of Scientific and Technical Information of China (English)

    Dong Jinyong


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


    Directory of Open Access Journals (Sweden)



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

  19. 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: [Instituto de Investigaciones en Materiales, Universidad Nacional Autonoma de Mexico, Apartado Postal 70-360, Ciudad Universitaria, Mexico DF 04510 (Mexico)


    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.

  20. 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)



    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.

  1. Regioselective ring opening of epoxides using NH4SCN/silica sulfuric acid: An efficient approach for the synthesis of β-hydroxy thiocyanate under solvent-free conditions

    Institute of Scientific and Technical Information of China (English)

    Ali R. Kiasat; Maryam Zayadi; Mehdi Fallah Mehrjardi


    Silica sulfuric acid was developed as a stable and efficient heterogeneous catalyst in organic synthesis. This solid acid catalyzed the regioselective ring opening of epoxides by thiocyanate anion to give thiocyanohydrins as key intermediates in agricultural and pharmaceutical chemistry in high yields under solvent-free conditions.

  2. Polymeric Microspheres for Medical Applications

    Directory of Open Access Journals (Sweden)

    Ketie Saralidze


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

  3. Silica exposure and systemic vasculitis. (United States)

    Mulloy, Karen B


    Work in Department of Energy (DOE) facilities has exposed workers to multiple toxic agents leading to acute and chronic diseases. Many exposures were common to numerous work sites. Exposure to crystalline silica was primarily restricted to a few facilities. I present the case of a 63-year-old male who worked in DOE facilities for 30 years as a weapons testing technician. In addition to silica, other workplace exposures included beryllium, various solvents and heavy metals, depleted uranium, and ionizing radiation. In 1989 a painful macular skin lesion was biopsied and diagnosed as leukocytoclastic vasculitis. By 1992 he developed gross hematuria and dyspnea. Blood laboratory results revealed a serum creatinine concentration of 2.1 mg/dL, ethrythrocyte sedimentation rate of 61 mm/hr, negative cANCA (antineutrophil cytoplasmic antibody cytoplasmic pattern), positive pANCA (ANCA perinuclear pattern), and antiglomerular basement membrane negative. Renal biopsy showed proliferative (crescentric) and necrotizing glomerulonephritis. The patient's diagnoses included microscopic polyangiitis, systemic necrotizing vasculitis, leukocytoclastic vasculitis, and glomerulonephritis. Environmental triggers are thought to play a role in the development of an idiopathic expression of systemic autoimmune disease. Crystalline silica exposure has been linked to rheumatoid arthritis, scleroderma, systemic lupus erythematosus, rapidly progressive glomerulonephritis and some of the small vessel vasculitides. DOE workers are currently able to apply for compensation under the federal Energy Employees Occupational Illness Compensation Program (EEOICP). However, the only diseases covered by EEOICP are cancers related to radiation exposure, chronic beryllium disease, and chronic silicosis.

  4. Preparation of polystyrene/SiO2 nanocomposites by surface-initiated nitroxide-mediated radical polymerization

    Institute of Scientific and Technical Information of China (English)

    NI Gang; YANG Wu; BO Lili; GUO Hao; ZHANG Wenhao; GAO Jinzhang


    Polystyrene/SiO2 composite nanoparticles (PS-g-Silica) were prepared by an in-situ surface-initiated nitroxide-mediated radical polymerization. After SiO2 nanoparticles were treated by thionyl chloride (SOCl2), peroxide initiation groups were immobilized on their surfaces through a reaction with tertiary butyl hydroperoxide (TBHP). Then surface nitroxide-mediated radical polymerization was initiated and polystyrene was grafted on the surface of SiO2 particles. Composite nanoparticles were characterized by IR spectra, transmission electron microscopy (TEM), atomic force microscopy (AFM) and thermogravimetry (TGA) and the results indicated that the surface-initiated nitroxide-mediated radical polymerization could be successfully used to synthesize well-dispersive PS/SiO2 nanocomposites.

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

    Directory of Open Access Journals (Sweden)

    Lotta Bergman


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

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

    Directory of Open Access Journals (Sweden)

    Marcello Iacono


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

  7. Silica entrapment for significantly stabilized, energy-conducting light-harvesting complex (LHCII). (United States)

    Roeder, Sebastian; Hobe, Stephan; Paulsen, Harald


    The major light-harvesting chlorophyll a/b complex (LHCII) of the photosynthetic apparatus in green plants consists of a membrane protein and numerous noncovalently bound pigments that make up about one-third of the molecular mass of the pigment-protein complex. Due to this high pigment density, LHCII is potentially interesting as a light-harvesting component in synthetic constructs. However, for such applications its stability needs to be significantly improved. In this work, LHCII was dramatically stabilized by enclosing it within polymerizing colloidal silica. The entrapped LHCII stayed functional at 50 °C for up to 24 h instead of a few minutes in detergent solution and clearly showed energy transfer between complexes. Entrapment yield was enhanced by a polycationic peptide attached to the N terminus. Both the extent of stabilization and the yield of entrapment strongly increased with decreasing diameters of the silica particles.

  8. Instantaneous Click Chemistry by a Copper-Containing Polymeric-Membrane-Installed Microflow Catalytic Reactor. (United States)

    Yamada, Yoichi M A; Ohno, Aya; Sato, Takuma; Uozumi, Yasuhiro


    The copper(I)-catalyzed Huisgen cycloaddition (azide-alkyne cycloaddition) is an important reaction in click chemistry that ideally proceeds instantaneously. An instantaneous Huisgen cycloaddition has been developed that uses a novel catalytic dinuclear copper complex-containing polymeric membrane-installed microflow device. A polymeric membranous copper catalyst was prepared from poly(4-vinylpyridine), copper(II) sulfate, sodium chloride, and sodium ascorbate at the interface of two laminar flows inside microchannels. Elucidation of the structure by XANES, EXAFS, and elemental analysis, as well as second-order Møller-Plesset perturbation theory (MP2) calculations and density functional theory (DFT) calculations assigned the local structure near Cu as a μ-chloro dinuclear Cu(I) complex. The microflow device promotes the instantaneous click reaction of a variety of alkynes and organic azides to afford the corresponding triazoles in quantitative yield.

  9. 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)


    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.

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

    DEFF Research Database (Denmark)

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

    Enzymatic polymerization has been gradually building up during the last 30 years as an alternative to classical polyesterificaiton processes, which permits preparation of polyesters under more benign conditions with high selectivity1. In particular, the high selectivity is an interesting property...... of the enzymatic catalysts that can provide control over polymer structure in functional polymers. Lipase catalyzed polymerizations (specifically CALB) has been applied to prepare functional polyesters and to evaluate the possibilities of using less stable bio-based monomers such as itaconic acid or its...... on PEG have been prepared and functionalized through aza-michael additions as well as through thiol-ene chemistry2. Thereby the enzymatically prepared polymer backbone can be considered a scaffold for functional water soluble materials. Finally, these polymers have been applied for preparation...

  11. Synthesis of Cross-Linked Polymeric Micelle pH Nanosensors

    DEFF Research Database (Denmark)

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


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

  12. Ribozyme Activity of RNA Nonenzymatically Polymerized from 3′,5′-Cyclic GMP

    Directory of Open Access Journals (Sweden)

    Samanta Pino


    Full Text Available 3′,5′-Cyclic GMP spontaneously nonenzymatically polymerizes in a base-catalyzed reaction affording G oligonucleotides. When reacted with fully or partially sequence-complementary RNA (oligo C, the abiotically generated oligo G RNA displays a typical ribozyme activity consisting of terminal ligation accompanied by cleavage of an internal phosphate site of the donor oligonucleotide stem upon attack of the acceptor 3′ terminal OH. This reaction is dubbed Ligation following Intermolecular Cleavage (LIC. In a prebiotic perspective, the ability of oligo G polynucleotides to react with other sequences outlines a simple and possible evolutionary scenario based on the autocatalytic properties of RNA.

  13. Question of the possible asymmetric polymerization of aspartic acid on kaolinite

    Energy Technology Data Exchange (ETDEWEB)

    McCullough, J.J.; Lemmon, R.M.


    McCullough and Lemmon have been unable to confirm the recent report that kaolinite catalyzes the polymerization of aqueous D- and L-aspartic acid at different rates. In experiments where DL-Asp was used, no induced optical rotation was found in the reaction solution. No evidence for polymer (or other product) formation was found when L-Asp-2-/sup 14/C was used, and products were searched by paper chromatography and x-ray film autoradiography. Asp is adsorbed by kaolinite, but no selectivity for one or the other enantiomer was observed.

  14. Enzymatic regioselective symthesis of vinthesis of vinyl lactose ester and its chemical polymerization

    Institute of Scientific and Technical Information of China (English)


    Transesterification reaction of lactose with divinyladipate in pyridine catalyzed by an alkaline protease from Bacillus subtilis at 50(C for 3 days gave 6(-O-vinyladipoyl-lactose (yield 35%). Poly(6(-O-vinyladipoyl-lactose) with Mn = 21,200, Mw = 32,900, Mw/Mn = 1.56 could be obtained by chemical polymerization. Poly(vinyl alcohol) containing lactose branch was biodegradable. After 6 days in aqueous buffer (PH 7), this alkaline protease could degrade the polymer to an Mn of ca. 2100, Mw/Mn = 2.56.


    Institute of Scientific and Technical Information of China (English)

    Xue Jiang; Zhi-qiang Fan


    A series of Ti/Mg supported catalysts are prepared by using ball-milled mixtures of MgCl2-ethanol adducts and NaCl as supports, and 1-hexene polymerizations catalyzed by the novel catalysts are studied. It is found that the molecular weight distribution of poly(1-hexene) becomes apparently narrower when catalysts with doped supports are used, indicating that changing the structure of the support is an effective way to regulate the active center distribution of heterogeneous Ziegler-Natta catalyst.

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

    Energy Technology Data Exchange (ETDEWEB)

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


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

  17. Tailoring Elastic Properties of Silica Aerogels Cross-Linked with Polystyrene (United States)

    Nguyen, Baochau N.; Meador, Mary Ann B.; Tousley, Marissa E.; Shonkwiler, Brian; McCorkle, Linda; Scheiman, Daniel A.; Palczer, Anna


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

    Directory of Open Access Journals (Sweden)

    Mohammed Kadhom


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

  19. Synthesis of novel porous magnetic silica microspheres as adsorbents for isolation of genomic DNA. (United States)

    Zhang, Zhichao; Zhang, Liming; Chen, Lei; Chen, Ligong; Wan, Qian-Hong


    An improved procedure is described for preparation of novel mesoporous microspheres consisting of magnetic nanoparticles homogeneously dispersed in a silica matrix. The method is based on a three-step process, involving (i) formation of hematite/silica composite microspheres by urea-formaldehyde polymerization, (ii) calcination of the composite particles to remove the organic constituents, and (iii) in situ transformation of the iron oxide in the composites by hydrogen reductive reaction. The as-synthesized magnetite/silica composite microspheres were nearly monodisperse, mesoporous, and magnetizable, with as typical values an average diameter of 3.5 microm, a surface area of 250 m(2)/g, a pore size of 6.03 nm, and a saturation magnetization of 9.82 emu/g. These magnetic particles were tested as adsorbents for isolation of genomic DNA from Saccharomyces cerevisiae cells and maize kernels. The results are quite encouraging as the magnetic particle based protocols lead to the extraction of genomic DNA with satisfactory integrity, yield, and purity. Being hydrophilic in nature, the porous magnetic silica microspheres are considered a good alternative to polystyrene-based magnetic particles for use in biomedical applications where nonspecific adsorption of biomolecules is to be minimized.

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

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


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

  1. Advanced polymer-inorganic hybrid hard coatings utilizing in situ polymerization method. (United States)

    Takaki, Toshihiko; Nishiura, Katsunori; Mizuta, Yasushi; Itou, Yuichi


    Hard coatings are frequently used to give plastics high scratch resistance. Coating hardness and adhesion to the substrate are considered to be key factors influencing scratch resistance, but it is difficult to produce coatings that have both properties. Hybridization of polymers and inorganic materials is a promising approach for solving this problem. We prepared polymer-silica hybrid coatings by using in situ polymerization to carry out radical polymerization of vinyl monomers in a sol-gel solution of alkoxysilanes, and measured the abrasion resistance of the coatings. However, the expected properties were not obtained because the sol-gel reaction did not perfectly proceed on the surface of the coatings under the N2 conditions. We found that curing the hybrid coatings by UV irradiation in air promoted the sol-gel reaction on the surface, resulting in coatings having excellent abrasion resistance.

  2. Silica-based 2-(N,N-dimethylamino)-1,3-propanediol hydrophilic interaction liquid chromatography stationary phase for separating cephalosporins and carbapenems. (United States)

    Yin, Wei; Cheng, Lingping; Chai, Huihui; Guo, Ruiqiang; Liu, Renhua; Chu, Changhu; Palasota, John A; Cai, Xiaohui


    A silica-based stationary phase bearing both hydrophilic hydroxyl and amino groups was developed by covalently bonding a small molecular N,N-dimethylamino 1,3-propanediol moiety onto silica beads via copper(I)-catalyzed Huisgen azide-alkyne 1,3-dipolar cycloaddition (CuAAC). This new stationary phase showed good HILIC characteristics and high column efficiency (the theoretical plate number is up to 37000 plates m(-1) in the case of inosine) in the separation of polar compounds, such as nucleosides and bases, organic acids, cephalosporins, and carbapenems.

  3. Ultrasound-Mediated Polymeric Micelle Drug Delivery. (United States)

    Xia, Hesheng; Zhao, Yue; Tong, Rui


    The synthesis of multi-functional nanocarriers and the design of new stimuli-responsive means are equally important for drug delivery. Ultrasound can be used as a remote, non-invasive and controllable trigger for the stimuli-responsive release of nanocarriers. Polymeric micelles are one kind of potential drug nanocarrier. By combining ultrasound and polymeric micelles, a new modality (i.e., ultrasound-mediated polymeric micelle drug delivery) has been developed and has recently received increasing attention. A major challenge remaining in developing ultrasound-responsive polymeric micelles is the improvement of the sensitivity or responsiveness of polymeric micelles to ultrasound. This chapter reviews the recent advance in this field. In order to understand the interaction mechanism between ultrasound stimulus and polymeric micelles, ultrasound effects, such as thermal effect, cavitation effect, ultrasound sonochemistry (including ultrasonic degradation, ultrasound-initiated polymerization, ultrasonic in-situ polymerization and ultrasound site-specific degradation), as well as basic micellar knowledge are introduced. Ultrasound-mediated polymeric micelle drug delivery has been classified into two main streams based on the different interaction mechanism between ultrasound and polymeric micelles; one is based on the ultrasound-induced physical disruption of the micelle and reversible release of payload. The other is based on micellar ultrasound mechanochemical disruption and irreversible release of payload.

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

    KAUST Repository

    Guillois, Kevin


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

  5. Mesoporous Silica: A Suitable Adsorbent for Amines

    Directory of Open Access Journals (Sweden)

    Abdollahzadeh-Ghom Sara


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

  6. 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)


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

  7. Hydrogen Silsesquioxane based silica glass coatings for the corrosion protection of austenitic stainless steel

    DEFF Research Database (Denmark)

    Lampert, Felix; Jensen, Annemette Hindhede; Din, Rameez Ud


    The application of stainless steels in hostile environments, such as concentrated acid or hot sea water, requires additional surface treatments, considering that the native surface oxide does not guarantee sufficient corrosion protection under these conditions. In the present work, silica-like thin......-film barrier coatings were deposited on AISI 316L grade austenitic stainless steel with 2B surface finish from Hydrogen Silsesquioxane (HSQ) spin-on-glass precursor and thermally cured to tailor the film properties. Results showed that curing at 500 °C resulted in a film-structure with a polymerized siloxane...

  8. Determination of particle size distribution and elastic properties of silica microcapsules by ultrasound spectroscopy (United States)

    Nguyen Tran, Thao; Shibata, Daisuke; Norisuye, Tomohisa; Nakanishi, Hideyuki; Tran-Cong-Miyata, Qui


    The acoustical properties of silica microcapsules synthesized by the interfacial polymerization of sodium silicate were studied by ultrasound spectroscopy. The experimental data were reproduced by the Waterman-Truell dispersion relation with the scattering function theory proposed by Goodman and Stern for hollow particles in liquid. The particle size distributions were successfully evaluated by the analysis and were found to be in good agreement with those obtained by scanning electron microscopy (SEM). The formation of such silicate microcapsules synthesized through water/oil/water emulsion as a template was also monitored.

  9. Construction of Nontoxic Polymeric UV-Absorber with Great Resistance to UV-Photoaging (United States)

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


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

    DEFF Research Database (Denmark)

    Boffa, Vittorio; Magnacca, Giualiana; Yue, Yuanzheng

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

  11. Practical Hydrogen Loading of Air Silica Fibres

    DEFF Research Database (Denmark)

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


    A method for hydrogen-loading air-silica optical fibres has been developed allowing out-diffusion times comparable to standard step-index fibres. Examples of the first grating written in Ge-doped air-silica fibres using a 266nm UV-laser are shown.......A method for hydrogen-loading air-silica optical fibres has been developed allowing out-diffusion times comparable to standard step-index fibres. Examples of the first grating written in Ge-doped air-silica fibres using a 266nm UV-laser are shown....

  12. Cellular membrane trafficking of mesoporous silica nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

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


    This dissertation mainly focuses on the investigation of the cellular membrane trafficking of mesoporous silica nanoparticles. We are interested in the study of endocytosis and exocytosis behaviors of mesoporous silica nanoparticles with desired surface functionality. The relationship between mesoporous silica nanoparticles and membrane trafficking of cells, either cancerous cells or normal cells was examined. Since mesoporous silica nanoparticles were applied in many drug delivery cases, the endocytotic efficiency of mesoporous silica nanoparticles needs to be investigated in more details in order to design the cellular drug delivery system in the controlled way. It is well known that cells can engulf some molecules outside of the cells through a receptor-ligand associated endocytosis. We are interested to determine if those biomolecules binding to cell surface receptors can be utilized on mesoporous silica nanoparticle materials to improve the uptake efficiency or govern the mechanism of endocytosis of mesoporous silica nanoparticles. Arginine-glycine-aspartate (RGD) is a small peptide recognized by cell integrin receptors and it was reported that avidin internalization was highly promoted by tumor lectin. Both RGD and avidin were linked to the surface of mesoporous silica nanoparticle materials to investigate the effect of receptor-associated biomolecule on cellular endocytosis efficiency. The effect of ligand types, ligand conformation and ligand density were discussed in Chapter 2 and 3. Furthermore, the exocytosis of mesoporous silica nanoparticles is very attractive for biological applications. The cellular protein sequestration study of mesoporous silica nanoparticles was examined for further information of the intracellular pathway of endocytosed mesoporous silica nanoparticle materials. The surface functionality of mesoporous silica nanoparticle materials demonstrated selectivity among the materials and cancer and normal cell lines. We aimed to determine

  13. Silica deactivation of bead VOC catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Libanati, C.; Pereira, C.J. [Research Division, W. R. Grace and Co., Columbia, MD (United States); Ullenius, D.A. [Grace TEC Systems, De Pere, WI (United States)


    Catalytic oxidation is a key technology for controlling the emissions of Volatile Organic Compounds (VOCs) from industrial plants. The present paper examines the deactivation by silica of bead VOC catalysts in a flexographic printing application. Post mortem analyses of field-aged catalysts suggest that organosilicon compounds contained in the printing ink diffuse into the catalyst and deposit as silica particles in the micropores. Laboratory activity evaluation of aged catalysts suggests that silica deposition is non-selective and that silica masks the noble metal active site

  14. Investigation of tribological properties of biobased polymers and polymeric composites (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

  15. Core-shell-structured silica/polyacrylate particles prepared by Pickering emulsion: influence of the nucleation model on particle interfacial organization and emulsion stability. (United States)

    Ji, Jing; Shu, Shi; Wang, Feng; Li, Zhilin; Liu, Jingjun; Song, Ye; Jia, Yi


    This work reports a new evidence of the versatility of silica sol as a stabilizer for Pickering emulsions. The organization of silica particles at the oil-water interface is a function of the nucleation model. The present results show that nucleation model, together with monomer hydrophobicity, can be used as a trigger to modify the packing density of silica particles at the oil-water interface: Less hydrophobic methylmethacrylate, more wettable with silica particles, favors the formation of core-shell-structured composite when the composite particles are prepared by miniemulsion polymerization in which monomers are fed in batch (droplet nucleation). By contrast, hydrophobic butylacrylate promotes the encapsulating efficiency of silica when monomers are fed dropwise (homogeneous nucleation). The morphologies of polyacrylate-nano-SiO2 composites prepared from different feed ratio of methylmethacrylate/butylacrylate (with different hydrophobicity) and by different feed processes are characterized by transmission electron microscopy (TEM) and scanning electron microscopy (SEM) techniques. The results from SEM and TEM show that the morphologies of the as-prepared polyacrylate/nano-SiO2 composite can be a core-shell structure or a bare acrylic sphere. The stability of resulting emulsions composed of these composite particles is strongly dependent on the surface coverage of silica particles. The emulsion stability is improved by densely silica-packed composite particles.

  16. Polymerization rate and mechanism of ultrasonically initiated emulsion polymerization of n-butyl acrylate. (United States)

    Xia, Hesheng; Wang, Qi; Liao, Yongqin; Xu, Xi; Baxter, Steven M; Slone, Robert V; Wu, Shuguang; Swift, Graham; Westmoreland, David G


    The factors affecting the induction period and polymerization rate in ultrasonically initiated emulsion polymerization of n-butyl acrylate (BA) were investigated. The induction period takes only an instant in ultrasonically initiated emulsion polymerization of BA without any added initiator by enhancing the N2 flow rate. Increasing temperature, power output and SDS concentration, decreasing the monomer concentration results in further decreasing induction period and enhanced polymerization rate. Under optimized reaction conditions the conversion of BA reaches 92% in 11 min. The polymerization rate can be controlled by varying reaction parameters. The apparatus of ultrasonically initiated semi-continuous and continuous emulsion polymerization were set up and the feasibility was first studied. Based on the experimental results, a free radical polymerization mechanism for ultrasonically initiated emulsion polymerization was proposed, including the sources of the radicals, the process of radical formation, the locus of polymerization and the polymerization process. Compared with conventional emulsion polymerization, where the radicals come from thermal decomposition of a chemical initiator, ultrasonically initiated emulsion polymerization has attractive features such as no need for a chemical initiator, lower reaction temperature, faster polymerization rate, and higher molecular weight of the polymer prepared.

  17. Attractor Explosions and Catalyzed Vacuum Decay

    Energy Technology Data Exchange (ETDEWEB)

    Green, Daniel; Silverstein, Eva; Starr, David


    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.

  18. Enantioselective, iridium-catalyzed monoallylation of ammonia. (United States)

    Pouy, Mark J; Stanley, Levi M; Hartwig, John F


    Highly enantioselective, iridium-catalyzed monoallylations of ammonia are reported. These reactions occur with electron-neutral, -rich, and -poor cinnamyl carbonates, alkyl and trityloxy-substituted allylic carbonates, and dienyl carbonates in moderate to good yields and excellent enantioselectivities. This process is enabled by the use of an iridium catalyst that does not require a Lewis acid for activation and that is stable toward a large excess of ammonia. This selective formation of primary allylic amines allows for one-pot syntheses of heterodiallylamines and allylic amides that are not otherwise accessible via iridium-catalyzed allylic amination without the use of blocking groups and protective group manipulations.


    Institute of Scientific and Technical Information of China (English)

    DONG Jianhua; QIU Kunyuan; FENG Xinde


    Polymerization of acrylamide initiated by ceric ammonium nitrate alone has been studied in aqueous medium. The effects of UV light irradiation on the initial rates of polymerization, the activation energy and on the polymer molecular weights have been investigated. Compared with that in the dark, the rate of polymerization under UV light was accelerated to eleven times higher, and the overall activation energy was lowered markedly.

  20. Copper-catalyzed azide alkyne cycloaddition polymer networks (United States)

    Alzahrani, Abeer Ahmed

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

  1. Charge transport in polymeric transistors

    Directory of Open Access Journals (Sweden)

    Alberto Salleo


    Full Text Available Polymeric semiconductors have attracted much attention because of their possible use as active materials in printed electronics. Thin-film transistors (TFTs are a convenient tool for studying charge-transport physics in conjugated polymers. Two families of materials are reviewed here: fluorene copolymers and polythiophenes. Because charge transport is highly anisotropic in molecular conductors, the electrical properties of conjugated polymers are strongly dependent on microstructure. Molecular weight, polydispersity, and regioregularity all affect morphology and charge-transport in these materials. Charge transport models based on microstructure are instrumental in identifying the electrical bottlenecks in these materials.

  2. Directional Growth of Polymeric Nanowires (United States)

    Thapa, Prem; Flanders, Bret


    This work establishes an innovative electrochemical approach to the template free growth of conducting polypyrrole and polythiophene wires. These polymeric wires exhibit a knobby structure, but persistent growth in a given direction up to 30 μm in length. A long-range component of the applied voltage signal defines the growth-path. Moreover, the presence of this component enables the growth of amorphous nanowires with wire-like geometries. Such wires are employed in a non-invasive methodology for attaining strong mechanical attachments to live cells. This capability is of potential use in the electro-mechanical probing of cell physiological processes.

  3. Marketing NASA Langley Polymeric Materials (United States)

    Flynn, Diane M.


    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.

  4. High Vacuum Techniques for Anionic Polymerization

    KAUST Repository

    Ratkanthwar, Kedar


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

  5. Effect of Polymerization Condition on Particle Size Distribution in St/BA/MAA Emulsion Polymerization Process

    Institute of Scientific and Technical Information of China (English)


    A series of St/BA/MAA emulsion polymerizations was carried out. By using PCS (photon correlation spectroscopy), the particle size distribution(PSD) of the whole St/BA/MAA emulsion polymerization process was gotten easily and quickly. The effect of polymerization condition on PSD in St/BA/MAA emulsion process was discussed.

  6. Twin screw extruders as polymerization reactors for a free radical homo polymerization

    NARCIS (Netherlands)

    Ganzeveld, K.J.; Janssen, L.P.B.M.


    The bulk polymerization of n-butylmethacrylate was investigated in a counter-rotating twin screw extruder. It appeared that the gel effect, occurring with bulk polymerizations, affected the polymerization progress very strongly. Due to this effect the conversion of the reaction is independent of the

  7. Silica- and perfluoro-based nanoparticular polymeric network for the skin protection against organophosphates (United States)

    Bignon, Cécile; Amigoni, Sonia; Guittard, Frédéric


    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.

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

    Elliott, Douglas C.; Hu, Jianli; Hart, Todd R.; Neuenschwander, Gary G.


    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.

  9. Silica-Immobilized Enzyme Reactors (Postprint) (United States)


    Non-solubilized UDPGT from rat liver microsomes was covalently immobilized to a func- tionalized silica support by Schiff base chemistry and a number...activity within a day. GADPH isolated from rabbit was covalently immobilized to a wide-pore silica support by glutaraldehyde activation and Schiff - base chemistry

  10. Biomimetic silica encapsultation of living cells (United States)

    Jaroch, David Benjamin

    Living cells perform complex chemical processes on size and time scales that artificial systems cannot match. Cells respond dynamically to their environment, acting as biological sensors, factories, and drug delivery devices. To facilitate the use of living systems in engineered constructs, we have developed several new approaches to create stable protective microenvironments by forming bioinspired cell-membrane-specific silica-based encapsulants. These include vapor phase deposition of silica gels, use of endogenous membrane proteins and polysaccharides as a site for silica nucleation and polycondensation in a saturated environment, and protein templated ordered silica shell formation. We demonstrate silica layer formation at the surface of pluripotent stem-like cells, bacterial biofilms, and primary murine and human pancreatic islets. Materials are characterized by AFM, SEM and EDS. Viability assays confirm cell survival, and metabolite flux measurements demonstrate normal function and no major diffusion limitations. Real time PCR mRNA analysis indicates encapsulated islets express normal levels of genetic markers for β-cells and insulin production. The silica glass encapsulant produces a secondary bone like calcium phosphate mineral layer upon exposure to media. Such bioactive materials can improve device integration with surrounding tissue upon implantation. Given the favorable insulin response, bioactivity, and long-term viability observed in silica-coated islets, we are currently testing the encapsulant's ability to prevent immune system recognition of foreign transplants for the treatment of diabetes. Such hybrid silica-cellular constructs have a wide range of industrial, environmental, and medical applications.

  11. Chemical immobilisation of humic acid on silica

    NARCIS (Netherlands)

    Koopal, L.K.; Yang, Y.; Minnaard, A.J.; Theunissen, P.L.M.; Riemsdijk, W.H. van


    Immobilisation of purified Aldrich humic acid (PAHA) on aminopropyl silica and glutaraldehyde-activated aminopropyl silica has been investigated. In general the humic acid is bound to the solid by both physical and chemical bonds. The physically adsorbed HA can be released to a large extent at high

  12. Magnetic core-shell silica particles

    NARCIS (Netherlands)

    Claesson, E.M.


    This thesis deals with magnetic silica core-shell colloids and related functionalized silica structures. Synthesis routes have been developed and optimized. The physical properties of these colloids have been investigated, such as the magnetic dipole moment, dipolar structure formation and rotationa

  13. Active and passive silica waveguide integration

    DEFF Research Database (Denmark)

    Hübner, Jörg; Guldberg-Kjær, Søren Andreas


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

  14. Zeolite 5A Catalyzed Etherification of Diphenylmethanol (United States)

    Cooke, Jason; Henderson, Eric J.; Lightbody, Owen C.


    An experiment for the synthetic undergraduate laboratory is described in which zeolite 5A catalyzes the room temperature dehydration of diphenylmethanol, (C[subscript 6]H[subscript 5])[subscript 2]CHOH, producing 1,1,1',1'-tetraphenyldimethyl ether, (C[subscript 6]H[subscript 5])[subscript 2]CHOCH(C[subscript 6]H[subscript 5])[subscript 2]. The…

  15. Catalyzing curriculum evolution in graduate science education. (United States)

    Gutlerner, Johanna L; Van Vactor, David


    Strategies in life science graduate education must evolve in order to train a modern workforce capable of integrative solutions to challenging problems. Our institution has catalyzed such evolution through building a postdoctoral Curriculum Fellows Program that provides a collaborative and scholarly education laboratory for innovation in graduate training.

  16. Mechanochemical ruthenium-catalyzed olefin metathesis. (United States)

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


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

  17. Pinacol Coupling Reactions Catalyzed by Active Zinc

    Institute of Scientific and Technical Information of China (English)

    Hui ZHAO; Wei DENG; Qing Xiang GUO


    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. Rhodium-catalyzed restructuring of carbon frameworks. (United States)

    Murakami, Masahiro


    Metal-catalyzed reactions involving an elementary step which cleaves a carbon-carbon bond provide unique organic transformations. Restructuring reactions recently developed in our laboratory, through which the carbon framework of a starting substance is restructured into a totally different carbon framework, are discussed, with the possibility of applying such methods to the synthesis of natural products.

  19. Lysophosphatidylcholine synthesis by lipase-catalyzed ethanolysis. (United States)

    Yang, Guolong; Yang, Ruoxi; Hu, Jingbo


    Lysophosphatidylcholine (LPC) is amphiphilic substance, and possesses excellent physiological functions. In this study, LPC was prepared through ethanolysis of phosphatidylcholine (PC) in n-hexane or solvent free media catalyzed by Novozym 435 (from Candida antarctica), Lipozyme TLIM (from Thermomcyces lanuginosus) and Lipozyme RMIM (from Rhizomucor miehei). The results showed that three immobilized lipases from Candida Antarctica, Thermomcyces lanuginosus and Rhizomucor miehei could catalyze ethanolysis of PC efficiently. In n-hexane, the LPC conversions of ethanolysis of PC catalyzed by Novozyme 435, Lipozyme TLIM and Lipozyme RMIM could reach to 98.5 ± 1.6%, 94.6 ± 1.4% and 93.7 ± 1.8%, respectively. In solvent free media, the highest LPC conversions of ethanolysis of PC catalyzed by Novozyme 435, Lipozyme TL IM and Lipozyme RM IM were 97.7 ± 1.7%, 93.5 ± 1.2% and 93.8 ± 1.9%, respectively. The catalytic efficiencies of the three lipases were in the order of Novozyme 435 > Lipozyme TLIM > Lipozyme RMIM. Furthermore, their catalytic efficiencies in n-hexane were better than those in solvent free media.

  20. Biodiesel production by enzyme-catalyzed transesterification

    Directory of Open Access Journals (Sweden)

    Stamenković Olivera S.


    Full Text Available The principles and kinetics of biodiesel production from vegetable oils using lipase-catalyzed transesterification are reviewed. The most important operating factors affecting the reaction and the yield of alkyl esters, such as: the type and form of lipase, the type of alcohol, the presence of organic solvents, the content of water in the oil, temperature and the presence of glycerol are discussed. In order to estimate the prospects of lipase-catalyzed transesterification for industrial application, the factors which influence the kinetics of chemically-catalysed transesterification are also considered. The advantages of lipase-catalyzed transesterification compared to the chemically-catalysed reaction, are pointed out. The cost of down-processing and ecological problems are significantly reduced by applying lipases. It was also emphasized that lipase-catalysed transesterification should be greatly improved in order to make it commercially applicable. The further optimization of lipase-catalyzed transesterification should include studies on the development of new reactor systems with immobilized biocatalysts and the addition of alcohol in several portions, and the use of extra cellular lipases tolerant to organic solvents, intracellular lipases (i.e. whole microbial cells and genetically-modified microorganisms ("intelligent" yeasts.

  1. Electrochemical Polymerization of Methylene Green

    Institute of Scientific and Technical Information of China (English)

    ZHU,Hong-Ping; MU,Shao-Lin


    The electrochemical polymerization of methylene green has been carried out using cyclic voltammetry. The electrolytic so lution consisted of 4 × 10-3 mol/L methylene green, 0.1 mol/L NaNO3 and 1 × 10-2 mol/L sodium tetraborate with pH 11.0. The temperature for polymerization is controlled at 60℃. The scan potential is set between -0.2 and 1.2 V (vs. Ag/AgCl with saturated KCl solution). There are an anodic peak and a cathodic peak on the cyclic voltammogram of poly(methylene green) at pH≤3.8. Both peak potentials shift towards nega tive potentials with increasing pH value, and their peak cur rents decrease with increasing pH value. Poly(methylene green) has a good electrochemical activity and stability in aqueous solutions with pH ≤ 3.8. The UV-Visible spectrum and FTIR spectrum of poly (methylene green) are different from those of methylene green.

  2. Schlenk Techniques for Anionic Polymerization

    KAUST Repository

    Ratkanthwar, Kedar


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

  3. Palladium-Catalyzed Intramolecular Aminofluorination of Styrenes%Palladium-Catalyzed Intramolecular Aminofluorination of Styrenes

    Institute of Scientific and Technical Information of China (English)

    徐涛; 邱水发; 刘国生


    A novel palladium-catalyzed intramolecular oxidative aminofluorination of styrenes has been developed by using NFSI as fluorinating reagent. This reaction represented an efficient method for the synthesis of 2-aryl-3-fluoropyrrolidine derivatives.

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

    Institute of Scientific and Technical Information of China (English)

    Wang Hai-Feng; Lin Zhen-Quan; Gao Yan


    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 < 0 case, the irreversible aggregation dominates the process, and ak(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.

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

    KAUST Repository

    Hu, Xian-Lei


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

  6. 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.


    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.

  7. 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


    an elevated pressure was required. Carboxylic acids, such as benzoic acid or p-toluic acid, additionally increased the reaction rate while CeO2 could act both as a promoter and an inhibitor depending on the substrate and the reaction conditions. Silver catalysts were prepared both by standard impregnation......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...... and flame spray pyrolysis. Addition of a Ce precursor to the FSP catalyst resulted in significantly smaller silver particles. Ce-doped FSP catalysts in general exhibited a superior catalytic performance with TONs up to 2000 except for cumene oxidation that appeared to proceed mainly by homogeneous catalysis...


    Institute of Scientific and Technical Information of China (English)

    Wei-jun Ye; Jason S. Keiper; Joseph M. DeSimone


    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.

  9. Spherical Resorcinol-Formaldehyde Synthesis by Inverse Suspension Polymerization

    Energy Technology Data Exchange (ETDEWEB)

    Ray, Robert J.; Scrivens, Walter A.; Nash, Charles


    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{reg_sign} 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.

  10. Inflation and Instability of a Polymeric Membrane

    DEFF Research Database (Denmark)

    Hassager, Ole; Kristensen, Susanne Brogaard; Larsen, Johannes Ruben


    We consider an axisymmetric polymeric membrane inflated by a uniform pressure difference acting across the membrane. The polymeric material is described by an arbitrary combination of a viscoelastic and a purely viscous component to the stress. Some viscoelastic materials described by a Mooney...

  11. Inflation and Instability of a Polymeric Membrane

    DEFF Research Database (Denmark)

    Neergaard, Jesper; Hassager, Ole


    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...

  12. Single "click" synthesis of a mixed-mode silica sorbent and application in matrix solid-phase dispersion extraction of β-agonists from porcine liver. (United States)

    Zhu, Yuling; Yang, Siwen; Chen, Gang; Xing, Jun


    A single "click" strategy is proposed for the preparation of a reversed-phase/weak cation-exchange mixed-mode silica-based sorbent (silica-WCX). Upon this strategy, both 1-dodecyne and 5-hexynoic acid were simultaneously immobilized onto azide-silica in varied ratio via Cu (I)-catalyzed azide-alkyne cycloaddition click reaction. The chemical compositions of silica-WCXs were characterized by elemental analysis, acid-base titration and Fourier transform-infrared spectroscopy. The results indicated that the actual mole ratio of n-dodecyl to carboxylic group on the sorbent is almost the same as the reactant ratio of 1-dodecyne to 5-hexynoic acid, and the repeatability of synthesis method is good. After that, two β-agonists, clenbuterol and ractopamine, were selected as model drug residues to evaluate the applicability of silica-WCX in matrix solid-phase dispersion extraction for the determination of basic drug residues in porcine liver by HPLC/UV. In comparison with some commercial sorbents, silica-WCX exhibited higher recoveries and better purification capability. Under the optimized conditions, linearity ranges were between 0.04 and 8.0μg/g for both analytes with coefficients of determination (R(2)) higher than 0.9997. The average recoveries at three spiked levels ranged from 92.5% to 105.0% with RSDs less than 6.6%.

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

    Energy Technology Data Exchange (ETDEWEB)

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


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

  14. Photoacoustic analysis of dental resin polymerization (United States)

    Coloiano, E. C. R.; Rocha, R.; Martin, A. A.; da Silva, M. D.; Acosta-Avalos, D.; Barja, P. R.


    In this work, we use the photoacoustic technique to monitor the curing process of diverse dental materials, as the resins chemically activated (RCA). The results obtained reveal that the composition of a determined RCA significantly alters its activation kinetics. Photoacoustic data also show that temperature is a significant parameter in the activation kinetics of resins. The photoacoustic technique was also applied to evaluate the polymerization kinetics of photoactivated resins. Such resins are photoactivated by incidence of continuous light from a photodiode. This leads to the polymerization of the resin, modifying its thermal properties and, consequently, the level of the photoacoustic signal. Measurements show that the polymerization of the resin changes the photoacoustic signal amplitude, indicating that photoacoustic measurements can be utilized to monitor the polymerization kinetic and the degree of polymerization of photoactivated dental resins.

  15. Fluid Effects in Polymers and Polymeric Composites

    CERN Document Server

    Weitsman, Y Jack


    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...

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

    Directory of Open Access Journals (Sweden)

    Qinghuang Wang


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

  17. Approaches to nanostructure control and functionalizations of polymer@silica hybrid nanograss generated by biomimetic silica mineralization on a self-assembled polyamine layer

    Directory of Open Access Journals (Sweden)

    Jian-Jun Yuan


    Full Text Available We report the rational control of the nanostructure and surface morphology of a polyamine@silica nanoribbon-based hybrid nanograss film, which was generated by performing a biomimetic silica mineralization reaction on a nanostructured linear polyethyleneimine (LPEI layer preorganized on the inner wall of a glass tube. We found that the film thickness, size and density of the nanoribbons and the aggregation/orientation of the nanoribbons in the film were facile to tune by simple adjustment of the biomimetic silicification conditions and LPEI self-assembly on the substrate. Our LPEI-mediated nanograss process allows the facile and programmable generation of a wide range of nanostructures and surface morphologies without the need for complex molecular design or tedious techniques. This ribbon-based nanograss has characteristics of a LPEI@silica hybrid structure, suggesting that LPEI, as a polymeric secondary amine, is available for subsequent chemical reaction. This feature was exploited to functionalize the nanograss film with three representative species, namely porphyrin, Au nanoparticles and titania. Of particular note, the novel silica@titania composite nanograss surface demonstrated the ability to convert its wetting behavior between the extreme states (superhydrophobic–superhydrophilic by surface hydrophobic treatment and UV irradiation. The anatase titania component in the nanograss film acts as a highly efficient photocatalyst for the decomposition of the low-surface-energy organic components attached to the nanosurface. The ease with which the nanostructure can be controlled and facilely functionalized makes our nanograss potentially important for device-based application in microfluidic, microreactor and biomedical fields.

  18. Radical polymerization of vinyl acetate with bis(tetramethylheptadionato)cobalt(II): coexistence of three different mechanisms. (United States)

    Santhosh, Kumar; Gnanou, Yves; Champouret, Yohan; Daran, Jean-Claude; Poli, Rinaldo


    The complex [Co(II)(tmhd)(2)] (4; tmhd = 2,2,6,6-tetramethylhepta-3,5-dionato) has been investigated as a mediator for controlled radical polymerization of vinyl acetate (VAc) and compared with the analogue [Co(II)(acac)(2)] (1; acac = acetylacetonato). A relatively well controlled process occurs, after an induction time, with 2,2'-azobis(4-methoxyl-2,4-dimethylvaleronitrile) (V-70) as radical initiator at 30 degrees C. However, whereas the polymerization essentially stops after about six initiator half-lives in the presence of 1, it continues with a first-order rate law in the presence of 4. The successful simulation of the kinetic data shows that 4 operates simultaneously by associative (degenerative transfer, DT) and dissociative (organometallic radical polymerization, OMRP) mechanisms. The occurrence of OMRP was confirmed by an independent polymerization experiment starting from an isolated and purified [Co(tmhd)(2)](PVAc) macroinitiator. The polymer molecular weight evolves linearly with conversion in accordance with the expected values for one chain per Co atom when DT is the predominant mechanism and also during the pure OMRP process; however, observation of stagnating molecular weights at long reaction times with concomitant breakdown of the first-order rate law for monomer consumption indicates a competitive chain-transfer process catalyzed by an increasing amount of Co(II). In the presence of external donors L (water, pyridine, triethylamine) the DT pathway is blocked and the OMRP pathway is accelerated, and polymerization with complex 4 is then about five times slower than with complex 1. The reversal of relative effective OMRP rate constants k(eff) (4>1 in the absence of external donors, 4<1 in their presence) is rationalized through competitive steric effects on Co(III)-C and Co(II)-L bond strengths. These propositions are supported by (1)H NMR studies and by DFT calculations.

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

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


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

  20. Anhydrous proton conducting materials based on sulfonated dimethylphenethylchlorosilane grafted mesoporous silica/ionic liquid composite. (United States)

    Amiinu, Ibrahim Saana; Liang, Xinmiao; Tu, Zhengkai; Zhang, Haining; Feng, Jiwen; Wan, Zhongmin; Pan, Mu


    Efficient membrane proton conductivity at elevated temperatures (>100 °C) and reduced humidification conditions is a critical issue hindering fuel cell commercialization. Herein, proton conducting materials consisting of high surface area acid catalyzed mesoporous silica functionalized with sulfonated dimethylphenethylchlorosilane was investigated under anhydrous conditions. The organic moiety covalently bonded to the silica substrate via active hydroxyl groups on the silica pore surface. The structure and dynamic phases of the attached organic molecule were characterized and qualitatively determined by XRD, TEM, FT-IR, and solid state NMR. The amount of grafted organic molecules was estimated to be 2.45 μmol m(-2) by carbon elemental analysis. The so-formed composite materials showed adequate thermal stability up to 300 °C as determined by TGA. Under anhydrous conditions, ionic conductivity of the composite material upon ionic liquid impregnation reaches a peak value of 1.14 × 10(-2) S cm(-1) at 160 °C associated with the activation energy of 9.24 kJ mol(-1) for proton transport.