Sample records for cationically polymerizable monomers

  1. Synthesis and Polymerizability of Atom-Bridged Bicyclic Monomers

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    Henry K. Hall


    Full Text Available ¨The synthesis and polymerizability of atom-bridged bicyclic monomers was surveyed. The monomers included lactams, ureas, urethanes, lactones, carbonates, ethers, acetals, orthoesters, and amines. Despite widely-varying structures, they almost all polymerized to give polymers with monocyclic rings in the chain. The polymerizations are grouped by mechanism: uncoordinated anionic, coordinated anionic, and cationic.

  2. Synthesis of Polymerizable Cyclodextrin Derivatives for Use in Adhesion-Promoting Monomer Formulations

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    Bowen, Rafael L.


    Full Text Available The synthesis of the cyclodextrin derivatives reported herein was assisted by extensive literature research together with structure-property relationships derived from three-dimensional molecular modeling. These studies led to the hypothesis that many of the 21 hydroxyl groups on beta-cyclodextrin molecules could be derivatized to form a closely related family of analogous chemical compounds containing both polymerizable groups and hydrophilic ionizable ligand (substrate-binding groups, each attached via hydrolytically-stable ether-linkages. The vinylbenzylether polymerizable groups should readily homopolymerize and also copolymerize with methacrylates. This could be highly useful for dental applications because substantially all contemporary dental resins and composites are based on methacrylate monomers. Due to hydrophilic ligands and residual hydroxyl groups, these cyclodextrin derivatives should penetrate hydrated layers of dentin and enamel to interact with collagen and tooth mineral. Analyses indicated that the diverse reaction products resulting from the method of synthesis reported herein should comprise a family of copolymerizable molecules that collectively contain about 30 different combinations of vinylbenzyl and hexanoate groups on the various molecules, with up to approximately seven of such groups combined on some of the molecules. Although the hypothesis was supported, and adhesive bonding to dentin is expected to be significantly improved by the use of these polymerizable cyclodextrin derivatives, other efforts are planned for improved synthetic methods to ensure that each of the reaction-product molecules will contain at least one copolymerizable moiety. The long-term objective is to enable stronger and more durable attachments of densely cross-linked polymers to hydrated hydrophilic substrates. Capabilities for bonding of hydrolytically stable polymers to dental and perhaps other hydrous biological tissues could provide

  3. Radiation polymerizable compositions

    International Nuclear Information System (INIS)

    Stvan, O.J.; Brodie, M.G.


    This invention relates to radiation polymerizable compositions particularly useful in the preparation of printing inks and to a method of preparing said radiation polymerizable compositions which comprises (1) a condensation product with (2) up to about 90% by weight thereof of at least one ethylenically unsaturated monomer and (3) up to about 50% by weight thereof of at least one sensitizer. The condensation products are prepared by condensing at least one alkoxy-methyl aminotriazine or methylol aminotriazine with one or more polyols, e.g., raw caster oil and at least one hydroxy-alkyl acrylate. The polymerizable composition may be cured with radiation, e.g., light or electrons, to obtain coatings useful for a variety of purposes

  4. Radiation polymerizable coating composition containing an unsaturated phosphoric ester

    International Nuclear Information System (INIS)

    Dickie, R.A.; Cassatta, J.C.


    A radiation polymerizable protective coating composition or paint consists essentially of a binder solution of: (1) between about 90 and about 10 parts of a saturated, thermoplastic vinyl polymer prepared from at least about 85 weight percent of monofunctional vinyl monomers; (2) between about 10 and about 90 parts of vinyl solvent monomers for the vinyl polymer, at least about 10 weight percent, preferably at least about 30 weight percent, of the solvent monomers being selected from the group consisting of divinyl monomers, trivinyl monomers, tetravinyl monomers and mixtures of these; and (3) between about 1.0 and about 15.0 parts per 100 parts of the total of the thermoplastic vinyl polymer and the vinyl solvent monomers of a triester of phosphoric acid bearing one or more sites of vinyl unsaturation. The composition exhibits excellent quality and good adhesion to a variety of substrates, in particular metals, including vapor deposited metals. Preferred articles bearing such a coating are prepared by applying a base coat to a substrate and curing the same; vapor depositing a coating of metal over the surface of the base coat; and applying to and curing on the surface of the deposited metal the radiation polymerizable topcoat, preferably with little or no pigment contained therein. 7 claims, no drawings

  5. Efecto de surfactantes polimerizables en la distribución de tamaño de partícula, pH, viscosidad, contenidos de sólidos y de monómero residual de una resina estireno-butilacrilato Effect of polymerizable surfactants on particle size distribution, pH, viscosity, contents of solids and residual monomer of a styrene-butylacrylate resin

    Directory of Open Access Journals (Sweden)

    Luis A. Rios


    Full Text Available Se presentan los resultados de la polimerización en emulsión de una resina acrílica estirenada usando surfactantes polimerizables, los cuales presentan ventajas técnicas como baja formación de espuma, alta resistencia de la película al contacto con agua y buena estabilidad en la polimerización. Se evaluó el efecto de estos surfactantes polimerizables en la distribución de tamaños de partícula de la resina; además se determinaron propiedades finales de la resina tales como porcentaje de sólidos, porcentaje de monómero libre, viscosidad y pH. Estos resultados se compararon con los obtenidos usando surfactantes convencionales no polimerizables del tipo alquil fenol etoxilado y alquilarilpoliglicol éter sulfato de sodio. Los resultados indican que que se pueden remplazar totalmente los surfactantes convencionales no polimerizables por los surfactantes poliméricos evaluados sin afectar significativamente las propiedades de la resina, mientras que la sustitución parcial de los surfactantes no polimerizables por los polimerizables induce, en algunos casos, a la formación de partículas con mayor tamaño a las presentes en la muestra estándar.Results on the emulsion polymerization of a styrenated acrylic resin using polymerizable surfactants are presented. These surfactants exhibit low foaming, high film strength upon contact with water and good stability in the polymerization. A comparison was made with results for conventional non-polymerizable alkyl aryl polyglycol ether sulphate, sodium salt and nonylphenolethoxylate surfactants. The effect of these polymerizable surfactants on the particle size distribution of the resin was evaluated; in addition to determining the final properties of the resin such as solids content, free monomer content, viscosity and pH. It is feasible to totally replace non-polymerizable surfactants by the polymerizable surfactants evaluated without affecting significantly the properties of the resin, while

  6. Electron Transfer Triggers Fast Dimer/Monomer Switching of Pyridinium and Quinolinium Cations

    Czech Academy of Sciences Publication Activity Database

    Teplý, Filip; Čížková, Martina; Slavíček, P.; Kolivoška, Viliam; Tarábek, Ján; Hromadová, Magdaléna; Pospíšil, Lubomír


    Roč. 116, č. 5 (2012), s. 3779-3786 ISSN 1932-7447 R&D Projects: GA ČR GA203/09/0705; GA ČR GA203/09/1614 Institutional research plan: CEZ:AV0Z40550506; CEZ:AV0Z40400503 Keywords : electrochemical reduction * dimerization * radicals * mechanism * N-heteroaromatic cations Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 4.814, year: 2012

  7. Interaction of Refractory Dibenzothiophenes and Polymerizable Structures

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    Jose L. Rivera


    Full Text Available We carried out first principles calculations to show that polymerizable structures containing hydroxyl (alcoholic chain and amino groups are suitable to form stable complexes with dibenzothiophene (DBT and its alkyl derivates. These sulfur pollutants are very difficult to eliminate through traditional catalytic processes. Spontaneous and exothermic interactions at 0 K primarily occur through the formation of stable complexes of organosulfur molecules with monomeric structures by hydrogen bonds. The bonds are formed between the sulfur atom and the hydrogen of the hydroxyl group; additional hydrogen bonds are formed between the hydrogen atoms of the organosulfur molecule and the nitrogen atoms of the monomers. We vary the number of methylene groups in the alcoholic chain containing the hydroxyl group of the monomer and find that the monomeric structure with four methylene groups has the best selectivity towards the interaction with the methyl derivates with reference to the interaction with DBT. Even this study does not consider solvent and competitive adsorption effects; our results show that monomeric structures containing amino and hydroxyl groups can be used to develop adsorbents to eliminate organosulfur pollutants from oil and its derivates.

  8. Polymerizable Ionic Liquid Crystals Comprising Polyoxometalate Clusters toward Inorganic-Organic Hybrid Solid Electrolytes

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    Takeru Ito


    Full Text Available Solid electrolytes are crucial materials for lithium-ion or fuel-cell battery technology due to their structural stability and easiness for handling. Emergence of high conductivity in solid electrolytes requires precise control of the composition and structure. A promising strategy toward highly-conductive solid electrolytes is employing a thermally-stable inorganic component and a structurally-flexible organic moiety to construct inorganic-organic hybrid materials. Ionic liquids as the organic component will be advantageous for the emergence of high conductivity, and polyoxometalate, such as heteropolyacids, are well-known as inorganic proton conductors. Here, newly-designed ionic liquid imidazolium cations, having a polymerizable methacryl group (denoted as MAImC1, were successfully hybridized with heteropolyanions of [PW12O40]3− (PW12 to form inorganic-organic hybrid monomers of MAImC1-PW12. The synthetic procedure of MAImC1-PW12 was a simple ion-exchange reaction, being generally applicable to several polyoxometalates, in principle. MAImC1-PW12 was obtained as single crystals, and its molecular and crystal structures were clearly revealed. Additionally, the hybrid monomer of MAImC1-PW12 was polymerized by a radical polymerization using AIBN as an initiator. Some of the resulting inorganic-organic hybrid polymers exhibited conductivity of 10−4 S·cm−1 order under humidified conditions at 313 K.

  9. Surface active monomers synthesis, properties, and application

    CERN Document Server

    Borzenkov, Mykola


    This brief includes information on the background?of and development of synthesis of various types of surface active monomers. The authors explain the importance of utilization of surface active monomers for creation of surface active polymers? and the various biomedical applications of such compounds . This brief introduces techniques for the synthesis of novel types of surface active monomers, their colloidal and polymerizable properties and application for needs of medicine and biology.

  10. Novel polymerizable bent-shaped monomeric molecules

    Czech Academy of Sciences Publication Activity Database

    Kozmik, V.; Kovářová, A.; Kuchař, M.; Svoboda, Jiří; Novotná, Vladimíra; Glogarová, Milada; Kroupa, Jan


    Roč. 33, č. 1 (2006), s. 41-56 ISSN 0267-8292 R&D Projects: GA ČR(CZ) GA202/05/0431; GA MŠk(CZ) OC D14.50 Institutional research plan: CEZ:AV0Z10100520 Keywords : mesogens * polymerizable * bent-shaped molecules * liquid crystals * ferroelectricity Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.417, year: 2006

  11. Low temperature irradiation of vitrifiable mixtures of unsaturated monomers

    International Nuclear Information System (INIS)

    Kaetsu, I.; Ito, A.; Hayashi, K.


    A specific mixture containing at least one polymerizable unsaturated monomer which is not vitrifiable by itself can advantageously be polymerized by irradiating the mixture at a temperature not higher than 100 0 C above glass transition temperature of the mixture with an ionizing radiation and/or a light. 12 claims, 6 drawings, figures

  12. Ionic Liquid Epoxy Resin Monomers (United States)

    Paley, Mark S. (Inventor)


    Ionic liquid epoxide monomers capable of reacting with cross-linking agents to form polymers with high tensile and adhesive strengths. Ionic liquid epoxide monomers comprising at least one bis(glycidyl) N-substituted nitrogen heterocyclic cation are made from nitrogen heterocycles corresponding to the bis(glycidyl) N-substituted nitrogen heterocyclic cations by a method involving a non-nucleophilic anion, an alkali metal cation, epichlorohydrin, and a strong base.

  13. Radiation-polymerizable mixture and recording material containing it

    International Nuclear Information System (INIS)

    Gersdorf, J.; Kleiner, H-J.


    Esters of dihydric alcohols with alkenylphosphonic or alkenylphosphinic acids which are polymerizable by free radicals are described. They are combined with polymer binders, in particular water-soluble polymers, and photoinitiators forming free radicals to give photopolymerizable mixtures which are suitable for the production of photoresists and printing plates. The mixtures display low heat-sensitivity and have long shelf lives. (author) 1 tab

  14. Tailored cationic palladium(II) compounds as catalysts for highly selective dimerization and polymerization of vinylic monomers: Synthetic and mechanistic aspects

    Energy Technology Data Exchange (ETDEWEB)

    Jiang, Z.; Sen, A. (Pennsylvania State Univ., University Park (United States))


    The electrophilic palladium(II)compounds Pd(2,6-di-tert-butylpyridine)[sub 2](CH[sub 3]NO[sub 2])[sub 2](BF[sub 4])[sub 2] (1), Pd(PPh[sub 3])[sub 2](BF[sub 4])[sub 2] (2), and Pd(Ph[sub 2]PCH[sub 2]CH[sub 2]PPh[sub 2])(BF[sub 4])[sub 2] (3) were found to be highly selective catalysts for the acyclic dimerization of vinyl monomers (styrene, ethylene, and propylene) and the linear polymerization of p-divinylbenzene, the reactions proceeding through a carbocationic mechanism. One manifestation of the high selectivity was the ability to catalyze the dimerization of ethylene in the presence of propylene and styrene in the presence of [alpha]-methylstyrene even though the second member of each pair was normally significantly more reactive in reactions involving carbocationic intermediates. The linear polymerization of p-divinylbenzene involved in step-growth mechanism. The synthesis of a telechelic polymer through cross-coupling between the terminal vinyl groups of linear poly(p-divinylbenzene) and the vinyl group of a functionalized styrene derivative was also achieved. The reaction rates for the linear dimerization of styrene and the linear polymerization of p-divinylbenzene were found to be first order in the monomer concentration and fractional order in the catalyst concentration. Mathematical modeling indicated that the fractional order in the catalyst concentration was due to preequilibria involving anion dissociation from the metal center, and actually, the catalytic species in the case of 2 was found to be the dication, Pd(PPh[sub 3])[sub 2][sup 2+]. 17 refs., 6 figs., 4 tabs.

  15. Synthesis and studies of novel high metal content organic aerogels obtained from a polymerizable titanium complex

    International Nuclear Information System (INIS)

    Cadra, S.


    Inertial Confinement Fusion (ICF) is a technique widely studied by the French atomic commission (CEA). Experiments will be performed within the Laser Megajoule (LMJ). They require innovative materials like organic aerogels that constitute laser targets. Such polymeric material must provide both a high porosity and a significant titanium percentage (1 atom %). Moreover, the monomers developed must be compatible with the synthesis procedure already in use. According to these specifications, a new polymerizable titanium complex was synthesized and fully characterized. This air and moisture-stable monomer provides a high metal percentage. Its free-radical cross-linked copolymerization affords several titanium-containing polymers. These gels were dried under supercritical conditions and organic aerogels were obtained. The chemical compositions of these materials were investigated by NMR, IR and elemental analysis while their structure was characterized by MEB-EDS, MET, N 2 adsorption/desorption isotherms measurements and SAXS. The data collected fit the specification requirements. Moreover, the mechanisms responsible of the foam nano-structure formation were discussed. (author) [fr

  16. Novel self-healing dental resin with microcapsules of polymerizable triethylene glycol dimethacrylate and N,N-dihydroxyethyl-p-toluidine. (United States)

    Wu, Junling; Weir, Michael D; Zhang, Qiang; Zhou, Chuanjian; Melo, Mary Anne S; Xu, Hockin H K


    Bulk fracture is one of the primary reasons for resin-based dental restoration failures. To date, there has been no report on the use of polymerizable dental monomers with acceptable biocompatibility to develop a resin with substantial self-healing capability. The objectives of this study were to: (1) develop a self-healing resin containing microcapsules with triethylene glycol dimethacrylate (TEGDMA)-N,N-dihydroxyethyl-p-toluidine (DHEPT) healing liquid in poly(urea-formaldehyde) (PUF) shells for the first time, and (2) determine the physical and mechanical properties, self-healing efficiency, and fibroblast cytotoxicity. Microcapsules of polymerizable TEGDMA-DHEPT in PUF were prepared via an in situ polymerization method. Microcapsules were added into a BisGMA-TEGDMA resin at microcapsule mass fractions of 0%, 5%, 10%, 15% and 20%. A flexural test was used to measure composite strength and elastic modulus. A single edge V-notched beam method was used to measure fracture toughness KIC and self-healing efficiency. Flexural strength and elastic modulus (mean±sd; n=6) of resin containing 5-15% microcapsules were similar to control without microcapsules (p>0.1). Adding microcapsules into the resin increased the virgin KIC, which was about 40% higher at 15% microcapsules than that with 0% microcapsules (pmicrocapsules. All specimens with 0-20% microcapsules had fibroblast viability similar to control without resin eluents (p>0.1). Self-healing dental resin containing microcapsules with polymerizable TEGDMA-DHEPT healing liquid in PUF shells were prepared for the first time with excellent self-healing capability. These microcapsules and self-healing resins containing them may be promising for dental restorations to heal cracks/damage and increase durability. Copyright © 2015 Academy of Dental Materials. All rights reserved.

  17. Crystal structures of expressed non-polymerizable monomeric actin in the ADP and ATP states. (United States)

    Rould, Mark A; Wan, Qun; Joel, Peteranne B; Lowey, Susan; Trybus, Kathleen M


    Actin filament growth and disassembly, as well as affinity for actin-binding proteins, is mediated by the nucleotide-bound state of the component actin monomers. The structural differences between ATP-actin and ADP-actin, however, remain controversial. We expressed a cytoplasmic actin in Sf9 cells, which was rendered non-polymerizable by virtue of two point mutations in subdomain 4 (A204E/P243K). This homogeneous monomer, called AP-actin, was crystallized in the absence of toxins, binding proteins, or chemical modification, with ATP or ADP at the active site. The two surface mutations do not perturb the structure. Significant differences between the two states are confined to the active site region and sensor loop. The active site cleft remains closed in both states. Minor structural shifts propagate from the active site toward subdomain 2, but dissipate before reaching the DNase binding loop (D-loop), which remains disordered in both the ADP and ATP states. This result contrasts with previous structures of actin made monomeric by modification with tetramethylrhodamine, which show formation of an alpha-helix at the distal end of the D-loop in the ADP-bound but not the ATP-bound form (Otterbein, L. R., Graceffa, P., and Dominguez, R. (2001) Science 293, 708-711). Our reanalysis of the TMR-modified actin structures suggests that the nucleotide-dependent formation of the D-loop helix may result from signal propagation through crystal packing interactions. Whereas the observed nucleotide-dependent changes in the structure present significantly different surfaces on the exterior of the actin monomer, current models of the actin filament lack any actin-actin interactions that involve the region of these key structural changes.

  18. Activated ERK2 is a monomer in vitro with or without divalent cations and when complexed to the cytoplasmic scaffold PEA-15. (United States)

    Kaoud, Tamer S; Devkota, Ashwini K; Harris, Richard; Rana, Mitra S; Abramczyk, Olga; Warthaka, Mangalika; Lee, Sunbae; Girvin, Mark E; Riggs, Austen F; Dalby, Kevin N


    The extracellular signal-regulated protein kinase, ERK2, fully activated by phosphorylation and without a His(6) tag, shows little tendency to dimerize with or without either calcium or magnesium ions when analyzed by light scattering or analytical ultracentrifugation. Light scattering shows that ~90% of ERK2 is monomeric. Sedimentation equilibrium data (obtained at 4.8-11.2 μM ERK2) with or without magnesium (10 mM) are well described by an ideal one-component model with a fitted molar mass of 40180 ± 240 Da (without Mg(2+) ions) or 41290 ± 330 Da (with Mg(2+) ions). These values, close to the sequence-derived mass of 41711 Da, indicate that no significant dimerization of ERK2 occurs in solution. Analysis of sedimentation velocity data for a 15 μM solution of ERK2 with an enhanced van Holde-Weischet method determined the sedimentation coefficient (s) to be ~3.22 S for activated ERK2 with or without 10 mM MgCl(2). The frictional coefficient ratio (f/f(0)) of 1.28 calculated from the sedimentation velocity and equilibrium data is close to that expected for an ~42 kDa globular protein. The translational diffusion coefficient of ~8.3 × 10(-7) cm(2) s(-1) calculated from the experimentally determined molar mass and sedimentation coefficient agrees with the value determined by dynamic light scattering in the absence and presence of calcium or magnesium ions and a value determined by NMR spectrometry. ERK2 has been proposed to homodimerize and bind only to cytoplasmic but not nuclear proteins [Casar, B., et al. (2008) Mol. Cell 31, 708-721]. Our light scattering data show, however, that ERK2 forms a strong 1:1 complex of ~57 kDa with the cytoplasmic scaffold protein PEA-15. Thus, ERK2 binds PEA-15 as a monomer. Our data provide strong evidence that ERK2 is monomeric under physiological conditions. Analysis of the same ERK2 construct with the nonphysiological His(6) tag shows substantial dimerization under the same ionic conditions.

  19. Synthesis and characterization of high molecular weight hydrophobically modified polyacrylamide nanolatexes using novel nonionic polymerizable surfactants

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    A.M. Al-Sabagh


    Full Text Available In this article, nine hydrophobically modified polyacrylamides (HM-PAM nanolatexes, were synthesized by copolymerizing the acrylamide monomer and novel polymerizable surfactants (surfmers. The reaction was carried out by inverse microemulsion copolymerization technique. The copolymerization was initiated by redox initiators composed of potassium peroxodisulphate and sodium bisulfite. The emulsion was stabilized using mixed tween 85 and span 80 as nonionic emulsifiers. The prepared HM-PAMs were classified into three groups according to the surfmers used in the copolymerization. The chemical structures of the prepared HM-PAMs were confirmed by FT-IR, 1H NMR and 13C NMR. The thermal properties were estimated with the thermal gravimetric analysis (TGA. The size and morphology of the prepared latexes were investigated by the dynamic light scattering (DLS and the High Resolution Transmission Electron Microscope (HRTEM. Finally, the molecular weights of the prepared copolymers were determined by the GPC and the viscosity average molecular weight method. They were situated between 1.58 × 106 and 0.89 × 106.

  20. Method of improving the physical properties of moulded parts of ethylene-trifluoromonochloroethylene mixed polymerizates by treatment with ionizing radiation

    International Nuclear Information System (INIS)

    Carlson, D.P.; West, N.E.


    Supplement to patent 1957993 describing irradiation of formed bodies of fluorous hydrocarbon polymerizates (in particular, ethylene monochlorotrifluoroethylene mixed polymerizates) with a dose of 2 to 80 megarad. The polymerizates are used as wire coatings and should have a high soldering iron resistance. It is now proposed to subject the formed bodies to a heat treatment in the absence of oxygen after irradiation. The mechanical properties of the mixed polymerizate are thus improved and the radiation dose can therefore be reduced to 12 to 50 megarad. (UWI) [de

  1. Polymerizable Supramolecular Approach to Highly Conductive PEDOT:PSS Patterns. (United States)

    Kim, Tae Geun; Ha, Su Ryong; Choi, Hyosung; Uh, Kyungchan; Kundapur, Umesha; Park, Sumin; Lee, Chan Woo; Lee, Sang-Hwa; Kim, Jaeyong; Kim, Jong-Man


    Owing to its high conductivity, solution processability, mechanical flexibility, and transparency, poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) has been extensively explored for use in functional devices including solar cells, sensors, light-emitting diodes, and supercapacitors. The ability to fabricate patterned PEDOT:PSS on a solid substrate is of significant importance to develop practical applications of this conducting polymer. Herein, we describe a new approach to obtain PEDOT:PSS patterns that are based on a polymerizable supramolecular concept. Specifically, we found that UV irradiation of a photopolymerizable diacetylene containing PEDOT:PSS film followed by development in deionized water and subsequent treatment with sulfuric acid (glass and silicon wafer) or formic acid (PET) produces micron-sized PEDOT:PSS patterns on solid substrates. The newly designed photolithographic method, which can be employed to generate highly conductive (>1000 S/cm) PEDOT:PSS patterns, has many advantages including the use of aqueous process conditions, a reduced number of process steps, and no requirement for plasma etching procedures.

  2. Recovery of olefin monomers (United States)

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


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

  3. Liquid organic scintillator in a polymerizable emulsion, its application to radioactive counting and process for its destruction

    International Nuclear Information System (INIS)

    O'Brien, R.E.; Krieger, J.K.


    Scintillation organic liquid mixture for performing very efficient counts on compound solutions labelled with a radioactive indicator containing up to 10% water by volume and which is easily polymerizable into a solid substance, in order to facilitate its elimination. The mixture includes a polymerizable organic solvent, a solubilizing agent, an intermediate solvent and an organic scintillator [fr

  4. Amino-Acid-Based Polymerizable Surfactants for the Synthesis of Chiral Nanoparticles. (United States)

    Preiss, Laura C; Wagner, Manfred; Mastai, Yitzhak; Landfester, Katharina; Muñoz-Espí, Rafael


    Amino-acid-based chiral surfactants with polymerizable moieties are synthesized, and a versatile approach to prepare particles thereof with a chiral surface functionality is presented. As an example of an application, the synthesized particles are tested for their ability as nucleating agents in the enantioselective crystallization of amino acid conglomerate systems, taking rac-asparagine as a model system. Particles resulting from chiral surfactants with different tail groups are compared and the results demonstrate that only the chiral nanoparticles made of the polymerizable surfactant are able to act efficiently as nucleation agent in enantioselective crystallization. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Method of analysis of polymerizable monomeric species in a complex mixture (United States)

    Hermes, Robert E


    Method of selective quantitation of a polymerizable monomeric species in a well spacer fluid, said method comprising the steps of adding at least one solvent having a refractive index of less than about 1.33 to a sample of the complex mixture to produce a solvent phase, and measuring the refractive index of the solvent phase.

  6. Novel 2-(ω-phosphonooxy-2-oxaalkylacrylate monomers for self-etching self-priming one part adhesive

    Directory of Open Access Journals (Sweden)

    Joachim E. Klee


    Full Text Available Novel hydrolysis stable 2-(ω-phosphonooxy-2-oxaalkylacrylate monomers 3 with phosphoric acid moieties were synthesized by a three step synthesis via Baylis–Hillman reaction of ethyl acrylate and formaldehyde, and subsequent etherification of the obtained product with diols and phosphorylation using POCl3. The polymerization enthalpy of 2-(ω-phosphonooxy-2-oxaalkylacrylates 3 as measured by DSC ranges from −29 to −53 kJ·mol−1. The shear bond strength of adhesive compositions 4, comprising of polymerizable acids 3, ranges from 5.8 to 19.3 MPa on enamel and from 8.7 to 16.9 MPa on dentin.

  7. Comparative evaluation of effect of polymerizable and non-polymerizable desensitizing agents on crown-retentive-strength of zinc-phosphate, glass-ionomer and compomer cements. (United States)

    Patil, P G; Parkhedkar, R D; Patil, S P; Bhowmik, H S


    The Purpose of this study was to evaluate the effect of polymerizable and non-polymerizable dentine desensitizers on retention of complete cast crowns cemented with three different types of cements. Freshly extracted human molars (n = 90) were prepared for standardized crown preparation (6-degree taper 4-mm height). The axial surface area of each preparation was determined and specimens were distributed equally among groups (n = 10). Dentine desensitizers, cementing agents, glass ionomer cement and compomer cement. Teeth were prepared and individual castings were made using high noble porcelain-metal alloy. Castings were cemented, thermo-cycled and removed along the path of insertion using a universal testing machine. Tooth surface as well as inner surface of the casting was examined and nature of cement failure was determined. Compomer cement exhibited the highest retentive strength and all dentine treatments resulted in significantly different retentive values. Zinc phosphate was the least retentive. Crown retentive values of Compomer cement were improved with Prime & Bond NT and Gluma Desensitizer Retentive values of zinc phosphate cement with Prime & Bond NT were decreased and not affected with Gluma Desensitizer Retentive values of Glass ionomer cement were not affected by any of the desensitizers used in the study.

  8. Microhardness of light- and dual-polymerizable luting resins polymerized through 7.5-mm-thick endocrowns. (United States)

    Gregor, Ladislav; Bouillaguet, Serge; Onisor, Ioana; Ardu, Stefano; Krejci, Ivo; Rocca, Giovanni Tommaso


    The complete polymerization of luting resins through thick indirect restorations is still questioned. The purpose of this study was to evaluate the degree of polymerization of light- and dual-polymerizable luting resins under thick indirect composite resin and ceramic endocrowns by means of Vickers microhardness measurements. The Vickers microhardness measurements of a light-polymerizable microhybrid composite resin and a dual-polymerizable luting cement directly polymerized in a natural tooth mold for 40 seconds with a high-power light-emitting diode lamp (control) were compared with measurements after indirect irradiation through 7.5-mm-thick composite resin and ceramic endocrowns for 3 × 90 seconds. A test-to-control microhardness values ratio of 0.80 at a depth of 0.5 mm below the surface was assumed as the criterion for adequate conversion. For the Vickers microhardness measurements of a dual-polymerizable luting cement, no differences (P>.05) were found between Vickers microhardness control values and values reported after polymerization through composite resin and ceramic endocrowns. For The Vickers microhardness measurements (±SD) of a light-polymerizable microhybrid composite resin, control values were significantly (P.05). Under the conditions of this in vitro study, Vickers microhardness values of the dual-polymerizable resin cement and the light-polymerizable restorative composite resin irradiated for 3 × 90 seconds with a high irradiance light-emitting diode lamp through 7.5-mm-thick endocrowns reached at least 80% of the control Vickers microhardness values, which means that both materials can be adequately polymerized when they are used for luting thick indirect restorations. Copyright © 2014 Editorial Council for the Journal of Prosthetic Dentistry. Published by Elsevier Inc. All rights reserved.

  9. Cationic polymers and porous materials

    KAUST Repository

    Han, Yu


    According to one or more embodiments, cationic polymers may be produced which include one or more monomers containing cations. Such cationic polymers may be utilized as structure directing agents to form mesoporous zeolites. The mesoporous zeolites may include micropores as well as mesopores, and may have a surface area of greater than 350 m2/g and a pore volume of greater than 0.3 cm3/g. Also described are core/shell zeolites, where at least the shell portion includes a mesoporous zeolite material.

  10. Actinide cation-cation complexes

    International Nuclear Information System (INIS)

    Stoyer, N.J.; Seaborg, G.T.


    The +5 oxidation state of U, Np, Pu, and Am is a linear dioxo cation (AnO 2 + ) with a formal charge of +1. These cations form complexes with a variety of other cations, including actinide cations. Other oxidation states of actinides do not form these cation-cation complexes with any cation other than AnO 2 + ; therefore, cation-cation complexes indicate something unique about AnO 2 + cations compared to actinide cations in general. The first cation-cation complex, NpO 2 + ·UO 2 2+ , was reported by Sullivan, Hindman, and Zielen in 1961. Of the four actinides that form AnO 2 + species, the cation-cation complexes of NpO 2 + have been studied most extensively while the other actinides have not. The only PuO 2 + cation-cation complexes that have been studied are with Fe 3+ and Cr 3+ and neither one has had its equilibrium constant measured. Actinides have small molar absorptivities and cation-cation complexes have small equilibrium constants; therefore, to overcome these obstacles a sensitive technique is required. Spectroscopic techniques are used most often to study cation-cation complexes. Laser-Induced Photacoustic Spectroscopy equilibrium constants for the complexes NpO 2 + ·UO 2 2+ , NpO 2 + ·Th 4+ , PuO 2 + ·UO 2 2+ , and PuO 2 + ·Th 4+ at an ionic strength of 6 M using LIPAS are 2.4 ± 0.2, 1.8 ± 0.9, 2.2 ± 1.5, and ∼0.8 M -1

  11. Development of a novel resin-based dental material with dual biocidal modes and sustained release of Ag+ ions based on photocurable core-shell AgBr/cationic polymer nanocomposites. (United States)

    Cao, Weiwei; Zhang, Yu; Wang, Xi; Chen, Yinyan; Li, Qiang; Xing, Xiaodong; Xiao, Yuhong; Peng, Xuefeng; Ye, Zhiwen


    Research on the incorporation of cutting-edge nano-antibacterial agent for designing dental materials with potent and long-lasting antibacterial property is demanding and provoking work. In this study, a novel resin-based dental material containing photocurable core-shell AgBr/cationic polymer nanocomposite (AgBr/BHPVP) was designed and developed. The shell of polymerizable cationic polymer not only provided non-releasing antibacterial capability for dental resins, but also had the potential to polymerize with other methacrylate monomers and prevented nanoparticles from aggregating in the resin matrix. As a result, incorporation of AgBr/BHPVP nanocomposites did not adversely affect the flexural strength and modulus but greatly increased the Vicker's hardness of resin disks. By continuing to release Ag + ions without the impact of anaerobic environment, resins containing AgBr/BHPVP nanoparticles are particularly suitable to combat anaerobic cariogenic bacteria. By reason of the combined bactericidal effect of the contact-killing cationic polymers and the releasing-killing Ag + ions, AgBr/BHPVP-containing resin disks had potent bactericidal activity against S. mutans. The long-lasting antibacterial activity was also achieved through the sustained release of Ag + ions due to the core-shell structure of the nanocomposites. The results of macrophage cytotoxicity showed that the cell viability of dental resins loading less than 1.0 wt% AgBr/BHPVP was close to that of neat resins. The AgBr/BHPVP-containing dental resin with dual bactericidal capability and long term antimicrobial effect is a promising material aimed at preventing second caries and prolonging the longevity of resin composite restorations.

  12. Surface Enrichment by Conventional and Polymerizable Sulfated Nonylphenol Ethoxylate Emulsifiers in Water-Based Pressure-Sensitive Adhesive (United States)

    Jilin Zhang; Yuxi Zhao; Matthew R. Dubay; Steven J. Severtson; Larry E. Gwin; Carl J. Houtman


    Comparisons of properties are made for pressure-sensitive adhesives (PSAs) generated via emulsion polymerization using both conventional and reactive emulsifiers. The emulsifiers are ammonium salts of sulfated nonylphenol ethoxylates with similar chemical structures and hydrophilic−lipophilic balances. The polymerizable surfactant possesses a reactive double...

  13. Monomers of cutin biopolymer: sorption and esterification on montmorillonite surfaces (United States)

    Olshansky, Yaniv; Polubesova, Tamara; Chefetz, Benny


    One of the important precursors for soil organic matter is plant cuticle, a thin layer of predominantly lipids that cover all primary aerial surfaces of vascular plants. In most plant species cutin biopolymer is the major component of the cuticle (30-85% weight). Therefore cutin is the third most abundant plant biopolymer (after lignin and cellulose). Cutin is an insoluble, high molecular weight bio-polyester, which is constructed of inter-esterified cross linked hydroxy-fatty acids and hydroxyepoxy-fatty acids. The most common building blocks of the cutin are derivatives of palmitic acid, among them 9(10),16 dihydroxy palmitic acid (diHPA) is the main component. These fatty acids and their esters are commonly found in major organo-mineral soil fraction-humin. Hence, the complexes of cutin monomers with minerals may serve as model of humin. Both cutin and humin act as adsorption efficient domains for organic contaminants. However, only scarce information is available about the interactions of cutin with soil mineral surfaces, in particular with common soil mineral montmorillonite. The main hypothesize of the study is that adsorbed cutin monomers will be reconstituted on montmorillonite surface due to esterification and oligomerization, and that interactions of cutin monomers with montmorillonite will be affected by the type of exchangeable cation. Cutin monomers were obtained from the fruits of tomato (Lycopersicon esculentum). Adsorption of monomers was measured for crude Wyoming montmorillonites and montmorillonites saturated with Fe3+ and Ca2+. To understand the mechanism of monomer-clay interactions and to evaluate esterification on the clay surface, XRD and FTIR analyses of the montmorillonite-monomers complexes were performed. Our results demonstrated that the interactions of cutin monomers with montmorillonite are affected by the type of exchangeable cation. Isotherms of adsorption of cutin monomers on montmorillonites were fitted by a dual mode model of

  14. Synthesis of Cationic Core-Shell Latex Particles

    NARCIS (Netherlands)

    Dziomkina, N.; Hempenius, Mark A.; Vancso, Gyula J.


    Surfactant-free seeded (core-shell) polymerization of cationic polymer colloids is presented. Polystyrene core particles with sizes between 200 nm and 500 nm were synthesized. The number average diameter of the colloidal core particles increased with increasing monomer concentration. Cationic shells

  15. A practical method for the synthesis of peptoids containing both lysine-type and arginine-type monomers. (United States)

    Bolt, H L; Cobb, S L


    Peptoids are a promising class of peptidomimetics that exhibit the key chemical and physical properties of peptides but without being hampered by susceptibility towards enzymatic degradation. Biologically active peptoids are often designed to be amphipathic in nature, consisting of hydrophobic monomers interspersed with either cationic lysine-type or arginine-type monomers. Access to amphipathic peptoids that contain both lysine-type and arginine-type monomers is highly desirable as it offers a route to further modulate the biological properties of this class of molecule. However, the lack of a suitable synthetic route to prepare mixed cationic peptoids has meant that their biological potential has remained almost largely unexplored. Herein, we present an efficient synthetic route that can be used to access novel cationic peptoids containing both lysine-type and arginine-type monomers within the same sequence.

  16. Synthesis of Thermal Polymerizable Alginate-GMA Hydrogel for Cell Encapsulation

    Directory of Open Access Journals (Sweden)

    Xiaokun Wang


    Full Text Available Alginate is a negative ionic polysaccharide that is found abundantly in nature. Calcium is usually used as a cross-linker for alginate. However, calcium cross-linked alginate is used only for in vitro culture. In the present work, alginate was modified with glycidyl methacrylate (GMA to produce a thermal polymerizable alginate-GMA (AA-GMA macromonomer. The molecular structure and methacrylation (%DM of the macromonomer were determined by 1H NMR. After mixing with the correct amount of initiator, the AA-GMA aqueous solution can be polymerized at physiological temperature. The AA-GMA hydrogels exhibited a three-dimensional porous structure with an average pore size ranging from 50 to 200 μm, directly depending on the macromonomer concentration. Biocompatibility of the AA-GMA hydrogel was determined by in vivo muscle injection and cell encapsulation. Muscle injection in vivo showed that the AA-GMA solution mixed with initiator could form a hydrogel in situ and had a mild inflammatory effect. Human umbilical vein endothelial cells (HUVECs were encapsulated in the AA-GMA hydrogels in situ at 37°C. Cell viability and proliferation were unaffected by macromonomer concentrations, which suggests that AA-GMA has a potential application in the field of tissue engineering, especially for myocardial repair.

  17. Design, synthesis and characterization of a highly luminescent Eu-complex monomer featuring thenoyltrifluoroacetone and 5-acryloxyethoxymethyl-8-hydroxyquinoline

    Energy Technology Data Exchange (ETDEWEB)

    Xu Cunjin [State Key Laboratory of Chemical Engineering, Department of Chemical and Biochemical Engineering, Zhejiang University, Hangzhou 310027 (China); College of Material, Chemistry and Chemical Engineering, Hangzhou Normal University, Hangzhou 310036 (China); Li Bogeng, E-mail: [State Key Laboratory of Chemical Engineering, Department of Chemical and Biochemical Engineering, Zhejiang University, Hangzhou 310027 (China); Wan Jintao; Bu Zhiyang [State Key Laboratory of Chemical Engineering, Department of Chemical and Biochemical Engineering, Zhejiang University, Hangzhou 310027 (China)


    A multi-functional ligand, 5-acryloxyethoxymethyl-8-hydroxyquinoline (Hamq), was synthesized, which contained a polymerizable C=C double bond for the copolymerization with other vinyl monomers and acted as photon antenna able to transfer energy to Eu{sup 3+} ions effectively. The triplet state energy of Hamq was determined to be 22,370 cm{sup -1} via the phosphorescence spectra of Hamq and its gadolinium complex. The title complex monomer Eu(tta){sub 2}(amq) was prepared by coordination reaction of Hamq with europium isopropoxide and 2-thenoyltrifluoroacetone (Htta) in dry organic solvents under argon atmosphere and characterized by elemental analysis and IR spectrum. The photophysical properties of the complex were studied in detail with UV-vis, luminescence spectra, luminescence lifetime and quantum yield. The complex exhibited nearly monochromatic red emission at 612 nm, a remarkable luminescence quantum yield at room temperature (30.6%) upon ligand excitation and a long {sup 5}D{sub 0} lifetime (389 {mu}s), which indicated that the ligand Hamq could sensitize the luminescence of Eu(III) ion efficiently in Eu(tta){sub 2}(amq), resulting in a strong luminescence of its copolymer poly[MMA-co-Eu(TTA){sub 2}(amq)] under UV excitation. The excellent luminescence properties of the complex made it not only a promising light-conversion molecular device but also an excellent luminescent monomer. - Highlights: >iWe designed and synthesized a highly luminescent Eu-complex monomer. > Quantum yield and lifetime of the complex are 30.6% and 389 {mu}s, respectively. > Excellent luminescence of the complex made it an excellent luminescent monomer.

  18. Preparation, characterization and thermal properties of nanocapsules containing phase change material n-dodecanol by miniemulsion polymerization with polymerizable emulsifier

    International Nuclear Information System (INIS)

    Chen, Zhong-Hua; Yu, Fei; Zeng, Xing-Rong; Zhang, Zheng-Guo


    Highlights: ► We prepare nanocapsules containing n-dodecanol via miniemulsion polymerization. ► Polymerizable emulsifier plays important role in the preparation of nanocapsules. ► Adding co-emulsifier into water phase is helpful to encapsulate n-dodecanol. ► The phase change latent heat of nanocapsule is 98.8 J/g with temperature of 18.2 °C. -- Abstract: Nanocapsules containing phase change material (PCM) n-dodecanol as core and polymethyl methacrylate (PMMA) as shell were synthesized by miniemulsion polymerization with polymerizable emulsifier DNS-86 and co-emulsifier hexadecane (HD). The nanocapsules were characterized by using Fourier transform infrared spectroscopy (FTIR), transmission electron microscope (TEM), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and laser particle diameter analyzer. The effects of polymerizable emulsifier and co-emulsifier on the properties of nanocapsules were studied. The results show that thermal properties of nanocapsules are affected greatly by the addition methods of HD and the amounts of DNS-86 and HD. Adding HD into water phase is helpful for the encapsulation of n-dodecanol. When the mass ratios of DNS-86 to n-dodecanol and the mass ratios of HD to n-dodecanol were 3% and 2%, the phase change latent heat and the encapsulation efficiency of nanocapsules reached to the maximum value of 98.8 J/g and 82.2%, respectively. Spherical nanocapsules with mean diameter of 150 nm and phase change temperature of 18.2 °C are obtained, which are sure to have a good potential for energy storage.

  19. Radical cations in condensed phases

    Energy Technology Data Exchange (ETDEWEB)

    Symons, M.C.R. (Leicester Univ. (UK). Dept. of Chemistry)

    The subject is covered in sections, entitled: introduction (scope of present Review); preparative procedures; alkane and cycloalkane cations; alkene and cyclic alkene cations; alkyl-halide cations; alcohol and ether cations; carbonyl cations (aldehyde, ketone and ester cations); sulphur-centred cations; selenium-centred cations; nitrogen-centred cations; phosphorus-centred cations; tin- and lead-centred cations; aromatic cations; five membered hetero-aromatic cations; vinyl cations; inorganic cations.

  20. Preparation of a Fluorocarbon Polymerizable Surfactant and Its Application in Emulsion Polymerization of Fluorine-Containing Acrylate

    Directory of Open Access Journals (Sweden)

    Meng Zhao


    Full Text Available A novel polymerizable fluorocarbon surfactant, perfluoro (4–methyl–3, 6–dioxaoct–7–ene sodium sulfonate (PSVNa, was synthesized and characterized. The fluorocarbon surfactant PSVNa and its mixture PSVNa/SDS were used as emulsifiers during the emulsion polymerization of DFHMA/MMA. The investigation of polymerization kinetics, particle size, and stability of the emulsions revealed that PSVNa has excellent emulsifying properties. The NMR spectrum of the copolymer and the detection of residual PSVNa show that more than 95% of the fluorocarbon surfactants have been linked to the polymer chains by radical polymerization, which will greatly reduce the environmental pollution caused by fluorinated surfactants.

  1. On the intrinsic optical absorptions by tetrathiafulvalene radical cations and isomers

    DEFF Research Database (Denmark)

    Kirketerp, Maj-Britt Suhr; Leal, Leonardo Andrés Espinosa; Varsano, Daniele


    Gas-phase action spectroscopy shows unambiguously that the low-energy absorptions by tetramethylthiotetrathiafulvalene and tetrathianaphthalene cations in solution phase are due to monomers and not π-dimers....

  2. Donor And Acceptor Containing Monomers


    Gülfidan, Damla


    Bu çalışmanın amacı; farklı zincir uzunluklarına sahip donör ve akseptör monomerlerinden oluşturulan kopolimerlerin, düşük enerji tüketimiyle iyi elektron transferi vermesini sağlamaktır. Bu konudan yola çıkarak; farklı zincir uzunluklarında, yan zincirinde karbazol ve naftalimit içeren stirene ve akrilata dayalı donör monomerler (CzMS, CEA, VBEC) ve akseptör monomer (AM) literatüre uygun olarak sentezlenmiştir. Sentezlenen monomerler ve bu monomerlerin radikal polimerizasyon yöntemi ile oluş...

  3. Flash evaporation of liquid monomer particle mixture (United States)

    Affinito, John D.; Darab, John G.; Gross, Mark E.


    The present invention is a method of making a first solid composite polymer layer. The method has the steps of (a) mixing a liquid monomer with particles substantially insoluble in the liquid monomer forming a monomer particle mixture; (b) flash evaporating the particle mixture and forming a composite vapor; and (c) continuously cryocondensing said composite vapor on a cool substrate and cross-linking the cryocondensed film thereby forming the polymer layer.

  4. Visible Light Curable Restorative Composites for Dental Applications Based on Epoxy Monomer. (United States)

    Vitale, Alessandra; Sangermano, Marco; Bongiovanni, Roberta; Burtscher, Peter; Moszner, Norbert


    A cationic photo-curable cycloaliphatic epoxy resin has been investigated as reactive monomer in blue light crosslinking process. We have demonstrated that camphorquinone is able to abstract labile hydrogen from the epoxy monomer, giving rise to the formation of carbon-centered radicals that are oxidized by the onium salt; a complete epoxy group conversion was reached after 50 s of irradiation. The presence of water up to 1 wt% was tolerated without any important detrimental effect on the kinetics of light-curing. The presence of the inorganic filler up to 65 wt% did not significantly influence the curing process.

  5. Visible Light Curable Restorative Composites for Dental Applications Based on Epoxy Monomer

    Directory of Open Access Journals (Sweden)

    Alessandra Vitale


    Full Text Available A cationic photo-curable cycloaliphatic epoxy resin has been investigated as reactive monomer in blue light crosslinking process. We have demonstrated that camphorquinone is able to abstract labile hydrogen from the epoxy monomer, giving rise to the formation of carbon-centered radicals that are oxidized by the onium salt; a complete epoxy group conversion was reached after 50 s of irradiation. The presence of water up to 1 wt% was tolerated without any important detrimental effect on the kinetics of light-curing. The presence of the inorganic filler up to 65 wt% did not significantly influence the curing process.

  6. Fluxional Monomers for Enhanced Thermoset Materials.

    Energy Technology Data Exchange (ETDEWEB)

    Jones, Brad Howard [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Alam, Todd M. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Black, Hayden T [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Celina, Mathias C. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Wheeler, David R. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)


    This report catalogues the results of a project exploring the incorporation of organometallic compounds into thermosetting polymers as a means to reduce their residual stress. Various syntheses of polymerizable ferro cene derivatives were attempted with mixed success. Ultimately, a diamine derivative of ferrocene was used as a curing agen t for a commercial epoxy resin, where it was found to give similar cure kinetics and mechanical properties in comparison to conventional curing agents. T he ferrocen e - based material is uniquely able to relax stress above the glass transition, leading to reduced cure stress. We propose that this behavior arises from the fluxional capacity of ferrocene. In support of this notion, nuclear magnetic resonance spectroscopy indicates a substantial increase in chain flexibility in the ferrocene - containing network. Although t he utilization of fluxionality is a novel approach to stress management in epoxy thermosets, it is anticipated to have greater impact in radical - cured ther mosets and linear polymers.

  7. Step growth of two flexible ABf monomers

    DEFF Research Database (Denmark)

    Cameron, Colin; Fawcett, Allan H.; Hetherington, Cecil R.


    A three-dimensional lattice model was used to simulate the competition between the growth of hyperbranched structures and cycle formation that occurs when flexible ABf monomers undergo step growth. The monomers in the model are mapped onto several lattice sites. The effect of functionality was st...... was studied by performing studies with f = 2 and 4....

  8. Muonium addition to vinyl monomers

    International Nuclear Information System (INIS)

    Stadlbauer, J.M.; Ng, B.W.; Walker, D.C.; Jean, Y.C.; Ito, Y.


    The chemical rate constants for the addition of the muonium atom (Mu) across the vinyl double bonds of acrylamide, acrylic acid, acrylonitrile, methylmethacrylate, and styrene were determined in aqueous solution; they are, respectively, ksub(m) = 1.9x10 10 M -1 s -1 ,1.6x10 10 M -1 s -1 , 1.1x10 10 M -1 s -1 , 9.5x10 9 M -1 s -1 , and 1.1 x 10 9 M -1 . Since muonium can be considered a very light isotope of hydrogen, the kinetic isotope effects, ksub(M)/ksub(H), for acrylamide (1.1) and acrylonitrile (2.8) were calculated. The muonium rate constants of these monomers are also compared to those of hydroxyl and methyl radical addition where available. The muonium substituted free radical formed by reaction with styrene is represented by two peaks in the Fourier Transform of the μSR spectrum at 500, 1500 and 2500 G with a hyperfine coupling constant of 213.5 MHz. This spectrum shows that Mu addition to styrene occurs at the vinyl bond only and not at the benzene ring

  9. Synthesis of nanostructured LiTi2(PO4)3 powder by a Pechini-type polymerizable complex method

    International Nuclear Information System (INIS)

    Mariappan, C.R.; Galven, C.; Crosnier-Lopez, M.-P.; Le Berre, F.; Bohnke, O.


    The nanostructured NASICON-type LiTi 2 (PO 4 ) 3 (LTP) material has been synthesized by Pechini-type polymerizable complex method. The use of water-soluble ammonium citratoperoxotitanate (IV) metal complex instead of alkoxides as precursor allows to prepare monophase material. Thermal analyses have been carried out on the powder precursor to check the weight loss and synthesis temperature. X-ray powder diffraction analysis (XRD) has been performed on the LTP powder obtained after heating the powder precursor over a temperature range from 550 to 1050 deg. C for 2 h. By varying the molar ratio of citric acid to metal ion (CA/Ti) and citric acid to ethylene glycol (CA/EG), the grain size of the LTP powder could be modified. The formation of small and well-crystalline grains, in the order of 50-125 nm in size, has been determined from the XRD patterns and confirmed by transmission electron microscopy

  10. Small angle neutron scattering studies on the interaction of cationic

    Indian Academy of Sciences (India)

    The structure of the protein–surfactant complex of bovine serum albumin (BSA) and cationic surfactants has been studied by small angle neutron scattering. At low concentrations, the CTAB monomers are observed to bind to the protein leading to an increase in its size. On the other hand at high concentrations, surfactant ...


    Directory of Open Access Journals (Sweden)

    A. V. Tkachev


    Full Text Available The preconditions of use in the manufacture of automobile tyres of vulcanizates-based mortar butadienestyrene rubber with a high content of 1.2 links butadiene and statistical distribution of styrene are formulated. Set out scientific researches in the field of anionic co-polymerization of diene and vinyl aromatic monomers. Formulation of catalytic systems applied in processes of anionic copolymerization of monomers are given. The reasons of formation of gel in the process of anionic polymerization of monomers and terms of their elimination are considered.

  12. Synthesize and polymerization of novel photocurable vinyl ether monomers containing perfluorinated aromatic units (United States)

    Li, Wei; Zou, Ying Quan


    A series of novel UV-curable vinyl ether monomers with perfluorinated aromatic units for photoresist had been designed and synthesized. Perfluorinated vinyl ether monomer I-1was prepared from the reactions of 2-vinyloxy ethanol and hexafluorobenzene in the presence of sodium hydride in DMF. And perfluorinated vinyl ether monomer I-2 was prepared from the reactions of I-1 and 2,2,2-trifluoroethanol in the presence of sodium carbonate in DMF. The photocrosslinked perfluorinated polymers obtained by PAG201 (a kind of cationic photo-initiator) initiating. When PAG201 was introduced into the monomers, the conversion of vinyl ether double bond increased sharply. The final conversion was close to 90%, and when the light intensity was 478μW/cm2, at 25 sec, the polymerization achieved maximum. Generally, the UV-curing performance of monomers with 3wt.% PAG201 concentration is superior to 2wt.% PAG201 concentration. And their physical and chemical properties satisfied the material requirements for photoresist or UV imaging materials.

  13. Polymerizable Molecular Silsesquioxane Cage Armored Hybrid Microcapsules with In Situ Shell Functionalization. (United States)

    Xing, Yuxiu; Peng, Jun; Xu, Kai; Lin, Weihong; Gao, Shuxi; Ren, Yuanyuan; Gui, Xuefeng; Liang, Shengyuan; Chen, Mingcai


    We prepared core-shell polymer-silsesquioxane hybrid microcapsules from cage-like methacryloxypropyl silsesquioxanes (CMSQs) and styrene (St). The presence of CMSQ can moderately reduce the interfacial tension between St and water and help to emulsify the monomer prior to polymerization. Dynamic light scattering (DLS) and TEM analysis demonstrated that uniform core-shell latex particles were achieved. The polymer latex particles were subsequently transformed into well-defined hollow nanospheres by removing the polystyrene (PS) core with 1:1 ethanol/cyclohexane. High-resolution TEM and nitrogen adsorption-desorption analysis showed that the final nanospheres possessed hollow cavities and had porous shells; the pore size was approximately 2-3 nm. The nanospheres exhibited large surface areas (up to 486 m 2  g -1 ) and preferential adsorption, and they demonstrated the highest reported methylene blue adsorption capacity (95.1 mg g -1 ). Moreover, the uniform distribution of the methacryloyl moiety on the hollow nanospheres endowed them with more potential properties. These results could provide a new benchmark for preparing hollow microspheres by a facile one-step template-free method for various applications. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Isomerization of propargyl cation to cyclopropenyl cation ...

    Indian Academy of Sciences (India)

    step) for isomerization of the linear propargyl cation to the aromatic cyclopropenyl cation, also probing the phenomenon of solvation of this reaction by simple lone pair donors (NH3, H2O, H2S and HF) which bind to the substrate at two sites.

  15. The crystalline and magnetic properties of Zn doped strontium Z-type hexaferrite synthesized by polymerizable complex method

    Directory of Open Access Journals (Sweden)

    Jung Tae Lim


    Full Text Available Polycrystalline samples of Sr3Co2-xZnxFe24O41 (x = 0.0, 0.5, 1.0, 1.5, 2.0 were synthesized by a polymerizable complex method. The crystallographic, and magnetic properties of samples were investigated using x-ray diffractometer (XRD, vibrating sample magnetometer (VSM, and Mössbauer spectroscopy. The crystal structures of all samples were determined to be hexagonal with the space group P63/mmc. The hysteresis curves under 10 kOe at 295 K showed that all samples were not saturated due to the high planar anisotropy of Sr ions. In addition, the coercivity (Hc of samples decreased with increasing Zn ion contents. Mössbauer spectra of all samples were obtained at 295 K, and least-squares fitted below TC as six distinguishable sextets (4fIV, 4fIV*, 12kVI*, 4fVI*+ 4eIV, 12kVI, and 2dV + 2aVI + 4fVI + 4eVI.

  16. Sustainable Poly(Ionic Liquids) for CO2 Capture Based on Deep Eutectic Monomers

    KAUST Repository

    Isik, Mehmet


    The design of high performance solid sorbent materials for CO2 capture is a technology which has been employed to mitigate global warming. However, the covalent incorporation of functionalities into polymeric supports usually involves multistep energy-intensive chemical processes. This fact makes the net CO2 balance of the materials negative even though they possess good properties as CO2 sorbents. Here we show a new family of polymers which are based on amines, amidoximes, and natural carboxylic acids and can be obtained using sustainable low energy processes. Thus, deep eutectic monomers based on natural carboxylic acids, amidoximes, and amines have been prepared by just mixing with cholinium type methacrylic ammonium monomer. The formation of deep eutectic monomers was confirmed by differential scanning calorimetry measurements. In all cases, the monomers displayed glass transition temperatures well below room temperature. Computational studies revealed that the formation of eutectic complexes lengthens the distance between the cation and the anion causing charge delocalization. The liquid nature of the resulting deep eutectic monomers (DEMs) made it possible to conduct a fast photopolymerization process to obtain the corresponding poly(ionic liquids). Materials were characterized by means of nuclear magnetic resonance, differential scanning calorimetry, thermogravimetric analysis, and X-ray diffraction to evaluate the properties of the polymers. The polymers were then used as solid sorbents for CO2 capture. It has been shown that the polymers prepared with citric acid displayed better performance both experimentally and computationally. The current endeavor showed that sustainable poly(ionic liquids) based on deep eutectic monomers can be easily prepared to produce low-energy-cost alternatives to the materials currently being researched for CO2 capture. © 2016 American Chemical Society.

  17. Softening and elution of monomers in ethanol

    DEFF Research Database (Denmark)

    Benetti, Ana Raquel; Asmussen, Erik; Munksgaard, E Christian


    The purpose of this study was to investigate the effect of light-curing protocol on softening and elution of monomers in ethanol as measured on a model polymer. It was a further aim to correlate the measured values with previously reported data on degree of conversion and glass transition...

  18. BD monomer and elastomer production processes. (United States)

    Lynch, J


    The monomer 1,3 butadiene (BD) is a product of the petrochemical industry. It is used to make several elastomers including the very high volume styrene butadiene rubber (SBR) that comprises the bulk of automobile tires. It is also used to make polybutadiene rubber that is used in parts of tires, coatings, composites and other products. The monomer can be converted to chlorobutadiene (chloroprene) and used to make polychloroprene (neoprene). BD is one of the several olefins created by cracking hydrocarbons in the presence of steam. A mixed C4 stream from the steam cracker is then sent to a BD monomer extraction unit. Modern units typically use dimethyl formamide as the extraction solvent. SBR is commonly made by the copolymerization of BD and styrene, along with various additives to control the reaction, in a water emulsion. The reaction proceeds in a continuous chain of reactors until it is 'shortstopped' by a strong reducing agent. After removing unreacted monomers from the stabilized latex, it is blended, coagulated and dewatered. The resulting dry rubber crumb is bailed, film wrapped and stored in crates. The polymerization of BD to make polybutadiene rubber can be conducted as a water suspension type polymerization similar to SBR or in a solvent system followed by solvent recovery and transfer into water suspension.

  19. Membranes prepared by radiation grafting of binary monomers for adsorption of heavy metals from industrial wastes (United States)

    Hegazy, El-Sayed A.; Kamal, H.; Maziad, N.; Dessouki, A. M.


    Preparation of synthetic membranes using simultaneous radiation grafting of acrylic acid (AAc) and styrene (Sty) as individually and in binary monomer mixture onto low density polyethylene (LDPE) has been carried out. The effect of preparation conditions such as irradiation dose, monomer concentration, comonomer composition, and solvent on the grafting yield was investigated. Characterization and some properties of the prepared membranes using different analytical techniques are studied, accordingly the possibility of its practical use in industrial waste treatment is determined. The swelling behavior, electrical conductivity, thermal stability, and mechanical properties of the membranes were investigated as a function of the grafting degree. The prepared cation-exchange membranes possessed good electrical and mechanical properties, high thermal stability and possess good characteristics for separation processes. These membranes have also good affinity toward the adsorption or chelation with Fe 3+ and Pb 2+ ions either in mixture containing other metals or if exists alone in the waste solution.

  20. Photokopolimerisasi monomer akrilat degan kulit kras sapi

    Directory of Open Access Journals (Sweden)

    Dwi Wahini Nurhajati


    Full Text Available The research on photocopolymerization of acrylate monomer with cow crust hide had object to observe the resulted copolymer onto cow crust hide. Crust hides, saturated with aqueous emulsions containing 25 wt % of n-butyl acrylate (n-BA or tripropylene glycol diacrylate (TPGDA were irradiated by cobalt – 60 gamma rays with doses ranges from 5 to 25 kGy. The irradiated hides were washed with water, dried in air and extracted in soxhlet apparatus for 48 hours to remove homopolymer. The highest yield of photocopolymerization of n – butyl acrylate monomer with crust hides was found 17,7878% at dose 25 kGy, and for photocopolymerization of tripropylene glycol diacrylate with crust hides was found 39,4245% at dose 20 kGy.

  1. Elution of Monomers from Provisional Composite Materials

    Directory of Open Access Journals (Sweden)

    Simon Daniel Schulz


    Full Text Available The aim of this study was to evaluate the elution of substances from different materials used for the manufacturing of temporary indirect restorations, after storage in saliva and ethanol 75%. 10 samples of three chemically cured materials (Protemp 3 Garant, Systemp.c&b, and Trim and one light-cured material (Clip F were stored in saliva and ethanol 75% for 24 h, 7, and days 28 days. From the storage media at each time period, samples were prepared and analysed by LC-MS/MS, in order to access the elution of monomers. The results differed among the materials (P ≤ 0.05. No monomers were detected in the samples of Protemp 3 Garant and Clip F. Substances were detected only in ethanol samples of Systemp.c&b and Trim. The amount of BisGMA, TEGDMA, and UDMA 2 released from Systemp.c&b was higher compared to Trim. Storage time affected the release of substances (P ≤ 0.05. The highest release was observed within the first 24 h. It can be concluded that provisional resin composite materials do not show high release of monomers and this release is material dependent. However, the detection of additional peaks during the analysis, suggesting the formation of by-products of the eluted substances, may not be in favour of these materials with respect to their toxicity.

  2. 21 CFR 888.4220 - Cement monomer vapor evacuator. (United States)


    ... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Cement monomer vapor evacuator. 888.4220 Section... (CONTINUED) MEDICAL DEVICES ORTHOPEDIC DEVICES Surgical Devices § 888.4220 Cement monomer vapor evacuator. (a) Identification. A cement monomer vapor evacuator is a device intended for use during surgery to contain or remove...

  3. Isomerization of propargyl cation to cyclopropenyl cation ...

    Indian Academy of Sciences (India)

    step) for isomeri- zation of the linear propargyl cation to ..... C3, C4 and C5. The ZPE corrections in each case are derived from the. B3LYP calculations. ..... the converse of which gives the relative capacity of the. LPD's to stabilize TS6 with respect ...

  4. Dimer/monomer switching of pyridinium and quinolinium cations by electron transfer

    Czech Academy of Sciences Publication Activity Database

    Pospíšil, Lubomír; Teplý, Filip; Hromadová, Magdaléna; Čížková, Martina; Kolivoška, Viliam; Slavíček, P.; Tarábek, Ján


    Roč. 2012, - (2012), s. 75 ISSN 0872-1904. [Iberic Meeting of Electrochemistry /14./ and Meeting of the Portuguese Electrochemical Society /17./. 11.04.2012-14.04.2012, Madeira Island] R&D Projects: GA ČR GA203/09/0705; GA AV ČR IAA400400802; GA ČR GA203/09/1614 Source of funding: I - inštitucionálna podpora na rozvoj VO Institutional support: RVO:61388955 Keywords : electron transfer * electrochemistry Subject RIV: CG - Electrochemistry

  5. Cation Exchange Water Softeners (United States)

    WaterSense released a notice of intent to develop a specification for cation exchange water softeners. The program has made the decision not to move forward with a spec at this time, but is making this information available.

  6. X-ray structure determination of new monomers to establish their polymerizability: copolymerization of two tetrasubstituted electrophilic olefins with electron-rich styrenes giving polymers with an average 1.25 functional groups per chain carbon atom

    International Nuclear Information System (INIS)

    Hall, H.K. Jr.; Reineke, K.E.; Ried, J.H.; Sentman, R.C.; Miller, D.


    X-ray crystal structure determination for two tetrasubstituted electrophilic olefins, tetramethyl ethylenetetracarboxylate TMET and dimethyl dicyanofumarate DDCF, revealed two fundamentally different molecular structures. TMET is a nonplanar molecule that possesses two opposite ester groups planar and the others above and below the molecular plane. In contrast, DDCF is a molecule for which both ester groups lie in the plane of the double bond and nitrile groups. DDCF underwent thermal spontaneous copolymerization with electron-rich styrenes to give 1:1 alternating copolymers in moderate yields and molecular weights. These copolymers, which result from the first copolymerization of a tetrasubstituted olefin, possess an average functionality of 1.25 per chain carbon atom. Polymerization is made possible by low steric hindrance and the high delocalization in the propagating radical. The yields were limited by competing cycloaddition reaction. The corresponding diethyl ester also copolymerized, but not so well. Neither electrophilic olefin homopolymerized under γ-irradiation. TMET did not copolymerize at all when treated under identical conditions

  7. Formation and reactions of cation-radicals of aliphatic ketones in freon matrices at low temperatures

    International Nuclear Information System (INIS)

    Belevskii, V.N.; Belopushkin, S.I.; Fel'dman, V.I.


    In solutions of acetone and methyl ethyl ketone in CFCl 3 (0.1-22%) γ-irradiated at 77 K, monomeric and dimeric cation-radicals of the ketones, as well as RCHCOMe radicals, are stabilized with yields dependent on the ketone concentration in the CFCl 3 . On exposure to light the dimeric cation-radicals are converted to RCHCOMe while the monomers disappear without forming radicals. It is shown that different types of ion-molecule reactions occur in the solid phase in which the monomeric and dimeric cation-radicals participate

  8. Cation-cation interaction in neptunyl(V) compounds

    Energy Technology Data Exchange (ETDEWEB)

    Krot, N.N. [Russian Academy of Sciences, Institute of Physical Chemistry (Russian Federation); Saeki, Masakatsu [Japan Atomic Energy Research Inst., Tokai, Ibaraki (Japan). Tokai Research Establishment


    The original manuscript was prepared by Professor N.N. Krot of Institute of Physical Chemistry, Russian Academy of Sciences, in 1997. Saeki tried to translate that into Japanese and to add some new data since 1997. The contents include the whole picture of cation-cation interactions mainly in 5-valence neptunium compounds. Firstly, characteristic structures of neptunium are summarized of the cation-cation bonding in compounds. Secondly, it is mentioned how the cation-cation bonding affects physical and chemical properties of the compounds. Then, characterization-methods for the cation-cation bonding in the compounds are discussed. Finally, the cation-cation interactions in compounds of other actinide-ions are shortly reviewed. (author)

  9. Controlled Release of Benzocaine from Monomer and Copolymer Carriers in Synthetic Gastro-intestinal Media

    Directory of Open Access Journals (Sweden)

    Houaria Merine


    Full Text Available New dosage forms able to control drug release in the gastro-intestinal media have been prepared and investigated in this paper. Two different type of medicinal agent bonding (MA, in our case Benzocaine (Bz, were chosen in order to examine drug release. i MA attached to ethylenic monomer (m,p-vinylbenzaldehyde, condensation reaction. ii The copolymer carrier (Cp is obtained by copolymerizing this monomer. These two carriers were well characterized by microanalysis, FTIR, DSC (Tg and GPC (Ip and the two fraction α and β were calculated from elemental analyses of Cp. The results showed good polydispersity and low average molecular weight. MA linked to an organic product by the azomethine function (C=N, hydrolytically sensitive, allowed controlled release of Bz, from the monomer carrier and from the bending Schiff bases groups. Theoretical and experimental analyses of controlled release of Bz kinetics from monomer and copolymer carriers were conducted for the case of contact with synthetic gastro-intestinal fluids at various pH (1,2; 6,0 and 8,0 at 37°C. The process was found to be controlled by the nature of media (heterogeneous, which involved the preliminary hydrolysis, and the drug (Bz diffusing out of structure of copolymer (Cp to the external aqueous media. The results obtained on the rate of delivery showed a clear difference between pH = 1,2 and pH = 6,0 and 8,0 based on: i The cation of p-aminoniumbenzoic acid (PABAH+ release at pH = 1,2 ii Bz release at pH = 6,0 and 8,0

  10. The effect of monomer molecular weight on grafting reaction

    International Nuclear Information System (INIS)

    Wu Minghong; Ding Zhongli; Ma Zueteh


    In this paper, some condensed ethylene glycol acrylate monomers with different molecular weight being grafted to the PE film by means of pre-irradiation is reported. The effect of molecular weight of monomer on grafting reaction and the hydrophilicity of grafting sample have been discussed. The experimental results show: molar degrees of grafting decreased non-linearly with the increasement of molecular weight of monomer, the grafting reaction of polymer is greater effected by the swelling degree of PE film, the greater the swelling degree of grafting material, the higher the grating degree grafting is, the initial rate of grafting reaction decreased with the increasement of molecular weight of monomer. (author)

  11. Reaction kinetics and modeling of photoinitiated cationic polymerization of an alicyclic based diglycidyl ether

    International Nuclear Information System (INIS)

    Harikrishna, R.; Ponrathnam, S.; Tambe, S.S.


    Highlights: • Photocationic polymerization of alicyclic based diglycidyl ether was carried out. • Kinetic parameters were influenced by gelation and diffusional restrictions. • Applicability of autocatalytic model was established by nonlinear regression. • System showed higher activation energy than cycloaliphatic and aromatic diepoxides. -- Abstract: Photoinitiated cationic polymerization of cycloaliphatic diepoxides had received tremendous attention, while studies with lesser polymerizable diglycidyl ethers are comparatively less reported. The present work deals with the photoinitiated cationic polymerization of cyclohexane dimethanol diglycidyl ether followed by estimation of kinetic parameters. The effects of concentration of photoinitiator and temperature on curing performance were studied using photo differential scanning calorimeter or photo DSC with polychromatic radiation. It was observed that the rate of polymerization as well as ultimate conversion increased with increasing concentration of photoinitiator and temperature. The influences of gelation as well as diffusional restrictions have remarkable effect on cure performance. The kinetic parameters as per autocatalytic kinetic model were studied by Levenberg–Marquardt nonlinear regression method instead of conventional linear method for obtaining more accurate values of apparent rate constant. It was observed that the model fits with data from initial stages to almost towards the end of the reaction. The activation energy was found to be higher than the values reported for more reactive cycloaliphatic diepoxides. The value of pre-exponential factor increased with increase in activation energy showing influence of gelation at early stages of reaction

  12. Measurement of in situ monomer sorption in polyu(propylene)

    NARCIS (Netherlands)

    Pater, J.T.M.; Weickert, G.; Fait, Anna; Mei, Gabriele


    An experimental method has been developed to compare the amount of monomer absorbed in freshly produced poly(propylene) with the amount of monomer absorbed in the same material after degassing. It has been found that propylene sorption in freshly produced poly(propylene) is significantly higher than

  13. Oligonucleotides with 1,4-dioxane-based nucleotide monomers

    DEFF Research Database (Denmark)

    Madsen, Andreas S; Wengel, Jesper


    An epimeric mixture of H-phosphonates 5R and 5S has been synthesized in three steps from known secouridine 1. Separation of the epimers has been accomplished by RP-HPLC, allowing full characterization and incorporation of monomers X and Y into 9-mer oligonucleotides using H-phosphonates building...... blocks 5R and 5S, respectively. A single incorporation of either monomer X or monomer Y in the central position of a DNA 9-mer results in decreased thermal affinity toward both DNA and RNA complements (ΔT(m) = -3.5 °C/-3.5 °C for monomer X and ΔT(m) = -11.0 °C/-6.5 °C for monomer Y). CD measurements do...

  14. Identifi cation of Sectarianism

    Directory of Open Access Journals (Sweden)

    Martinovich Vladimir


    Full Text Available «New religious movements and society» is traditionally one of the most sophisticated topics in the area of new religions studies. Its problem field is so huge that up to now by far not all important research themes where even touched by scientists from all over the world. The problem of the process of the identification of sectarianism by diff erent societal institutions is one of such untouched themes that is taken as the main subject of this article. This process by itself is an inseparable part of the every societal deliberate reaction to the very existence of unconventional religiosity, its unstructured and mainly structured types. The focal point of the article is step-by-step analysis of the general structure elements of the process of the identification of sectarianism without any reference to the specific time and place of its flow. Special attention is paid to the analysis of the subjects of the identification of sectarianism, to the criteria for religious groups to be qualified as new religious movements, and to the specific features of the process of documents filtration. The causes of selective perception of sectarianism are disclosed. Some main consequences and unpredictable outcomes of the process of the identification of sectarianism are described.

  15. Low temperature synthesis of Y3NbO7 by polymerizable complex method: utilization of a methanol-citric acid solution of NbCl5 as a novel niobium precursor

    International Nuclear Information System (INIS)

    Okubo, T.; Kakihana, M.


    A modified polymerizable complex method was used to prepare pure Y 3 NbO 7 powders at reduced temperature. To acquire a niobium-containing solution stable enough for the polymerizable complex processing, methanol was chosen to solvate NbCl 5 . Dissolution of NbCl 5 in methanol gave a colorless transparent solution, to which citric acid (CA), yttrium carbonate and ethylene glycol (EG) were added successively to produce a transparent solution containing yttrium-CA complexes and niobium-CA complexes. The solution was heated at ∝130 C to remove excess methanol and promote esterification between CA and EG to yield a transparent polymeric resin without precipitation; this material was used subsequently as a precursor for Y 3 NbO 7 . The formation of Y 3 NbO 7 occurred when the resin precursor was heat-treated at 500 C for 2 h in static air. (orig.)

  16. New Horizons in Cationic Photopolymerization

    Directory of Open Access Journals (Sweden)

    Marco Sangermano


    Full Text Available In this review, we report some recent advances and new horizons in UV-induced cationic photopolymerization. In particular, after a brief introduction on the discovery and affirmation of the cationic photopolymerization process, new efforts in the synthesis of cationic photoinitiators are reported. Subsequently, an interesting and absolutely new application is reported, related to the combination of Radical-Induced Cationic Photopolymerization with Frontal Polymerization, achieving the cross-linking of epoxy composites.

  17. Redesign of the monomer-monomer interface of Cre recombinase yields an obligate heterotetrameric complex. (United States)

    Zhang, Chi; Myers, Connie A; Qi, Zongtai; Mitra, Robi D; Corbo, Joseph C; Havranek, James J


    Cre recombinase catalyzes the cleavage and religation of DNA at loxP sites. The enzyme is a homotetramer in its functional state, and the symmetry of the protein complex enforces a pseudo-palindromic symmetry upon the loxP sequence. The Cre-lox system is a powerful tool for many researchers. However, broader application of the system is limited by the fixed sequence preferences of Cre, which are determined by both the direct DNA contacts and the homotetrameric arrangement of the Cre monomers. As a first step toward achieving recombination at arbitrary asymmetric target sites, we have broken the symmetry of the Cre tetramer assembly. Using a combination of computational and rational protein design, we have engineered an alternative interface between Cre monomers that is functional yet incompatible with the wild-type interface. Wild-type and engineered interface halves can be mixed to create two distinct Cre mutants, neither of which are functional in isolation, but which can form an active heterotetramer when combined. When these distinct mutants possess different DNA specificities, control over complex assembly directly discourages recombination at unwanted half-site combinations, enhancing the specificity of asymmetric site recombination. The engineered Cre mutants exhibit this assembly pattern in a variety of contexts, including mammalian cells. © The Author(s) 2015. Published by Oxford University Press on behalf of Nucleic Acids Research.

  18. Difunctional polyisobutylene prepared by polymerization of monomer on molecular sieve (United States)

    Midler, J. A., Jr.


    Process yields difunctional isobutylene polymers ranging in molecular weight from 1150 to 3600. These polymers have the potential for copolymerization and cross-linking with other monomers to form elastomeric materials.

  19. Ultrasonic cleaning reduces the residual monomer in acrylic resins


    Charasseangpaisarn, Taksid; Wiwatwarrapan, Chairat; Leklerssiriwong, Nonthida


    Background/purpose: The residual monomer remaining in acrylic resin can cause an allergic reaction and is toxic to oral soft tissue. This study determined the effect of the duration of ultrasonic cleaning on the amount of residual methyl methacrylate monomer in one heat-polymerized acrylic resin, Meliodent, and three autopolymerized acrylic resins, Unifast Trad Ivory, Unifast Trad Pink, and Unifast III. Materials and methods: Thirty-six disc-shaped specimens of each brand were prepared and...

  20. Complex Macromolecular Architectures by Living Cationic Polymerization

    KAUST Repository

    Alghamdi, Reem D.


    Poly (vinyl ether)-based graft polymers have been synthesized by the combination of living cationic polymerization of vinyl ethers with other living or controlled/ living polymerization techniques (anionic and ATRP). The process involves the synthesis of well-defined homopolymers (PnBVE) and co/terpolymers [PnBVE-b-PCEVE-b-PSiDEGVE (ABC type) and PSiDEGVE-b-PnBVE-b-PSiDEGVE (CAC type)] by sequential living cationic polymerization of n-butyl vinyl ether (nBVE), 2-chloroethyl vinyl ether (CEVE) and tert-butyldimethylsilyl ethylene glycol vinyl ether (SiDEGVE), using mono-functional {[n-butoxyethyl acetate (nBEA)], [1-(2-chloroethoxy) ethyl acetate (CEEA)], [1-(2-(2-(t-butyldimethylsilyloxy)ethoxy) ethoxy) ethyl acetate (SiDEGEA)]} or di-functional [1,4-cyclohexanedimethanol di(1-ethyl acetate) (cHMDEA), (VEMOA)] initiators. The living cationic polymerizations of those monomers were conducted in hexane at -20 0C using Et3Al2Cl3 (catalyst) in the presence of 1 M AcOEt base.[1] The PCEVE segments of the synthesized block terpolymers were then used to react with living macroanions (PS-DPE-Li; poly styrene diphenyl ethylene lithium) to afford graft polymers. The quantitative desilylation of PSiDEGVE segments by n-Bu4N+F- in THF at 0 °C led to graft co- and terpolymers in which the polyalcohol is the outer block. These co-/terpolymers were subsequently subjected to “grafting-from” reactions by atom transfer radical polymerization (ATRP) of styrene to afford more complex macromolecular architectures. The base assisted living cationic polymerization of vinyl ethers were also used to synthesize well-defined α-hydroxyl polyvinylether (PnBVE-OH). The resulting polymers were then modified into an ATRP macro-initiator for the synthesis of well-defined block copolymers (PnBVE-b-PS). Bifunctional PnBVE with terminal malonate groups was also synthesized and used as a precursor for more complex architectures such as H-shaped block copolymer by “grafting-from” or

  1. Primary processes of the radiation-induced cationic polymerization of aromatic olefins studied by pulse radiolysis

    International Nuclear Information System (INIS)

    Brede, O.; Boes, J.; Helmstreit, W.; Mehnert, R.


    By pulse radiolysis of solutions of aromatic olefins (styrene, 1-methylstyrene, 1,1-diphenylethylene) in non-polar solvents (cyclohexane, carbon tetrachloride, n-butylchloride) the mechanism and kinetics of primary processes of radiation-induced cationic polymerization were investigated. In cyclohexane, radical cations of the olefins are generated by charge transfer from solvent cations. These cations dimerize in a diffusion-controlled reaction. The next step of chain-growth is slower by 3 to 4 orders of magnitude. In carbon tetrachloride and in n-butyl chloride growing olefin cations are produced by a reaction of radical cations with solvent as well as by addition of solvent carbonium ions to the monomer. In strongly acidic aqueous solution of olefins radical cations produced indirectly from hydroxycyclohexadienyl radicals dimerize and react in a subsequent step by deprotonation forming non-saturated dimer radicals. The reaction mechanism established shows that in the case of radiation-induced cationic polymerization it is not possible to define a uniform first step of the chain reaction. (author)

  2. Primary processes of the radiation-induced cationic polymerization of aromatic olefins studied by pulse radiolysis

    International Nuclear Information System (INIS)

    Brede, O.; Boes, J.; Helmstreit, W.; Mehnert, R.


    By pulse radiolysis of solutions of aromatic olefins (styrene, 1-methylstyrene, 1,1-diphenylethylene) in nonpolar solvents (cyclohexane, carbon tetrachloride, n-butyl chloride) the mechanism and kinetics of primary processes of radiation-induced cationic polymerization were investigated. In cyclohexane, radical cations of the olefins are generated by charge transfer from solvent cations (k about 10 11 l mol -1 s -1 ). These cations dimerize in a diffusion-controlled reaction (k approximately 10 10 l mol -1 s -1 ). The next step of chain-growth is slower by 3 to 4 orders of magnitude. Furthermore, in carbon tetrachloride and in n-butyl chloride growing olefin cations are produced by a reaction of the radical cations with the solvent as well as by addition of solvent carbonium ions to the monomer. In strongly acidic aqueous solution of olefins radical cations produced indirectly from hydroxycyclohexadienyl radicals dimerize and react in a subsequent step by deprotonation forming non-saturated dimer radicals. The established reaction mechanism shows that in the case of radiation-induced cationic polymerization it is not possible to define a uniform first step of the chain reaction. (author)

  3. Perturbation of the Monomer-Monomer Interfaces of the Benzoylformate Decarboxylase Tetramer

    Energy Technology Data Exchange (ETDEWEB)

    Andrews, Forest H.; Rogers, Megan P.; Paul, Lake N.; McLeish, Michael J. [IUPUI; (Purdue)


    The X-ray structure of benzoylformate decarboxylase (BFDC) from Pseudomonas putida ATCC 12633 shows it to be a tetramer. This was believed to be typical of all thiamin diphosphate-dependent decarboxylases until recently when the structure of KdcA, a branched-chain 2-keto acid decarboxylase from Lactococcus lactis, showed it to be a homodimer. This lent credence to earlier unfolding experiments on pyruvate decarboxylase from Saccharomyces cerevisiae that indicated that it might be active as a dimer. To investigate this possibility in BFDC, we sought to shift the equilibrium toward dimer formation. Point mutations were made in the noncatalytic monomer–monomer interfaces, but these had a minimal effect on both tetramer formation and catalytic activity. Subsequently, the R141E/Y288A/A306F variant was shown by analytical ultracentrifugation to be partially dimeric. It was also found to be catalytically inactive. Further experiments revealed that just two mutations, R141E and A306F, were sufficient to markedly alter the dimer–tetramer equilibrium and to provide an ~450-fold decrease in kcat. Equilibrium denaturation studies suggested that the residual activity was possibly due to the presence of residual tetramer. The structures of the R141E and A306F variants, determined to <1.5 Å resolution, hinted that disruption of the monomer interfaces will be accompanied by movement of a loop containing Leu109 and Leu110. As these residues contribute to the hydrophobicity of the active site and the correct positioning of the substrate, it seems that tetramer formation may well be critical to the catalytic activity of BFDC.

  4. Proof of Concept Analysis of Using Photo-Click Chemistry on Ionic Liquid Monomers with Propargyl Functionality (United States)

    Kattekola, Samhita

    Click chemistry refers to a specific set of organic chemistry reactions that proceed under mild conditions, are high yielding, and are extremely selective. Due to their orthogonality, these types of reactions have opened doors for the fabrication of materials of many kinds. This work explores the applicability of click chemistry used in conjunction with ionic liquids. The kinetics of light initiated click chemistry reactions of CuAAC and thiol-yne on ionic liquids functionalized with alkyne are examined, setting up the foundation for many applications including but not limited to ion-containing membranes, adhesives, and organic catalysts. Photo-click chemistry is a recent discovery and all its facets have not been explored yet. While it is evident that photo-click reactions have made the already friendly click reactions even more amicable, there is a vast gap in the literature on the fundamentals of this reaction. It was observed that the cationic structure of the ionic liquid monomer and the presence of the anion significantly affect the kinetics of the click reactions. For the CuAAC reaction, the fastest kinetics were produced by a weakly coordinating anion and aromatic structure cation combination and it was deduced that anions which strongly interact with Cu(I) inhibit the reaction. Additionally, it was discovered that the polarity of the thiol monomer has an effect on the thiol-yne click reaction. A more polar thiol in thiol-yne reactions with ionic liquids appears to facilitate the reaction to proceed to full conversion.

  5. Photoinitiated Polymerization of Cationic Acrylamide in Aqueous Solution: Synthesis, Characterization, and Sludge Dewatering Performance

    Directory of Open Access Journals (Sweden)

    Huaili Zheng


    Full Text Available A copolymer of acrylamide (AM with acryloyloxyethyl trimethyl ammonium chloride (DAC as the cationic monomer was synthesized under the irradiation of high-pressure mercury lamp with 2,2-azobis(2-amidinopropane dihydrochloride (V-50 as the photoinitiator. The compositions of the photoinduced copolymer were characterized by Fourier transform infrared spectra (FTIR, ultraviolet spectra (UV, and scanning electron microscope (SEM. The effects of 6 important factors, that is, photo-initiators concentration, monomers concentration, CO(NH22 (urea concentrations, pH value, mass ratio of AM to DAC, and irradiation time on the molecular weight and dissolving time, were investigated. The optimal reaction conditions were that the photo-initiators concentration was 0.3%, monomers concentration was 30 wt.%, irradiation time was 60 min, urea concentration was 0.4%, pH value was 5.0, and mass ratio of AM to DAC was 6 : 4. Its flocculation properties were evaluated with activated sludge using jar test. The zeta potential of supernatant at different cationic monomer contents was simultaneously measured. The results demonstrated the superiority of the copolymer over the commercial polyacrylamide as a flocculant.

  6. Simultaneous membrane interaction of amphipathic peptide monomers, self-aggregates and cargo complexes detected by fluorescence correlation spectroscopy. (United States)

    Vasconcelos, Luís; Lehto, Tõnis; Madani, Fatemeh; Radoi, Vlad; Hällbrink, Mattias; Vukojević, Vladana; Langel, Ülo


    Peptides able to translocate cell membranes while carrying macromolecular cargo, as cell-penetrating peptides (CPPs), can contribute to the field of drug delivery by enabling the transport of otherwise membrane impermeable molecules. Formation of non-covalent complexes between amphipathic peptides and oligonucleotides is driven by electrostatic and hydrophobic interactions. Here we investigate and quantify the coexistence of distinct molecular species in multiple equilibria, namely peptide monomer, peptide self-aggregates and peptide/oligonucleotide complexes. As a model for the complexes, we used a stearylated peptide from the PepFect family, PF14 and siRNA. PF14 has a cationic part and a lipid part, resembling some characteristics of cationic lipids. Fluorescence correlation spectroscopy (FCS) and fluorescence cross-correlation spectroscopy (FCCS) were used to detect distinct molecular entities in solution and at the plasma membrane of live cells. For that, we labeled the peptide with carboxyrhodamine 6G and the siRNA with Cyanine 5. We were able to detect fluorescent entities with diffusional properties characteristic of the peptide monomer as well as of peptide aggregates and peptide/oligonucleotide complexes. Strategies to avoid peptide adsorption to solid surfaces and self-aggregation were developed and allowed successful FCS measurements in solution and at the plasma membrane. The ratio between the detected molecular species was found to vary with pH, peptide concentration and the proximity to the plasma membrane. The present results suggest that the diverse cellular uptake mechanisms, often reported for amphipathic CPPs, might result from the synergistic effect of peptide monomers, self-aggregates and cargo complexes, distributed unevenly at the plasma membrane. Copyright © 2017 Elsevier B.V. All rights reserved.

  7. Sorption by cation exchange

    International Nuclear Information System (INIS)

    Bradbury, M.H.; Baeyens, B.


    A procedure for introducing exchange into geochemical/surface complexation codes is described. Beginning with selectivity coefficients, K c , defined in terms of equivalent fractional ion occupancies, a general expression for the molar based exchange code input parameters, K ex , is derived. In natural systems the uptake of nuclides onto complex sorbents often occurs by more than one mechanism. The incorporation of cation exchange and surface complexation into a geochemical code therefore enables sorption by both mechanisms to be calculated simultaneously. The code and model concepts are tested against sets of experimental data from widely different sorption studies. A proposal is made to set up a data base of selectivity coefficients. Such a data base would form part of a more general one consisting of sorption mechanism specific parameters to be used in conjunction with geochemical/sorption codes to model and predict sorption. (author) 6 figs., 6 tabs., 26 refs

  8. Mechanism of prion propagation: amyloid growth occurs by monomer addition.

    Directory of Open Access Journals (Sweden)

    Sean R Collins


    Full Text Available Abundant nonfibrillar oligomeric intermediates are a common feature of amyloid formation, and these oligomers, rather than the final fibers, have been suggested to be the toxic species in some amyloid diseases. Whether such oligomers are critical intermediates for fiber assembly or form in an alternate, potentially separable pathway, however, remains unclear. Here we study the polymerization of the amyloidogenic yeast prion protein Sup35. Rapid polymerization occurs in the absence of observable intermediates, and both targeted kinetic and direct single-molecule fluorescence measurements indicate that fibers grow by monomer addition. A three-step model (nucleation, monomer addition, and fiber fragmentation accurately accounts for the distinctive kinetic features of amyloid formation, including weak concentration dependence, acceleration by agitation, and sigmoidal shape of the polymerization time course. Thus, amyloid growth can occur by monomer addition in a reaction distinct from and competitive with formation of potentially toxic oligomeric intermediates.

  9. Evaluation of level of impregnation monomers in hydrotalcite

    International Nuclear Information System (INIS)

    Carmo, Danieli M. do; Machado, Jacson S.C.; Oliveira, Marcelo F.L.; Oliveira, Marcia G.; Soares, Bluma G.


    To evaluate the impregnation degree of 1,6-hexamethylene diisocyanate and 1,4-butanediol monomers in hydrotalcite clays it was prepared dispersions with mixing ratio 1:100 (clay/monomer), using the Ultraturrax and Ultrasound. Subsequently the samples were characterized by Fourier Transform Infrared Spectroscopy and X-ray Diffraction. Swelling tests and Tyndall effect were used to illustrate the different dispersions. The results indicated a strong interaction between the hydrotalcite with 1,6-hexamethylene diisocyanate, favoring the formation of intercalated structures. (author)

  10. Highly Efficient Synthesis of Allopurinol Locked Nucleic Acid Monomer by C6 Deamination of 8-Aza-7-bromo-7-deazaadenine Locked Nucleic Acid Monomer

    DEFF Research Database (Denmark)

    Kosbar, Tamer Reda El-Saeed; Sofan, M.; Abou-Zeid, L.


    An allopurinol locked nucleic acid (LNA) monomer was prepared by a novel strategy through C6 deamination of the corresponding 8-aza-7-bromo-7-deazaadenine LNA monomer with aqueous sodium hydroxide. An 8-aza-7-deazaadenine LNA monomer was also synthesized by a modification of the new synthetic...

  11. Influence of vinyl chloride monomer and vinyl chloride monomer derivatives on hepatic DNA synthesis

    International Nuclear Information System (INIS)

    Brenner, E.A.


    Vinyl chloride monomer (VCM) is used extensively in the chemical industry, mainly in the production of polyvinyl chloride. It has recently been found to cause hepatic angiosarcoma. As VCM has also been shown to be mutagenic after metabolic activation the effect of VCM on DNA synthesis was investigated. [ 3 H]Thymidine incorporation into DNA was used to measure the rate of DNA synthesis in regenerating rat liver. A possible direct toxic effect of VCM or its metabolites on liver cell metabolism was examined by two unrelated techniques, viz. the measurement of adenine nucleotide concentrations in regenerating livers and the influence on transmembrane potentials in hepatocytes. The distribution of radioactivity in subcellular fractions following [ 14 C]VCM administration suggested microsomal conversion of VCM to an active form which was selectively retained in the nuclear fraction. Measurement of the activities of thymidine kinase and DNA polymerase in regenerating liver indicated that the induction of these enzymes which normally occurs after partial hepatectomy was not prevented by VCM treatment. Three techniques were used to test the hypothesis that the retardation in DNA synthesis was due to DNA damage: the prophage lambda induction test for DNA damage, autoradiographic detection of unscheduled thymidine incorporation into DNA, and detection of DNA strand breaks in alkaline sucrose gradients. All three provided evidence of DNA damage and led to the development of a novel technique to confirm these findings. This involved centrifugation in neutral sucrose gradients on intact double-stranded DNA contained in hepatocyte nucleoids and showed conclusively that VCM administration causes DNA strand breaks. Subsequent repair of DNA was also assessed by this technique. The site of the VCM/metabolite: DNA reaction was characterized by DNA thermal denaturation and renaturation studies

  12. From cation to oxide: hydroxylation and condensation of aqueous complexes

    International Nuclear Information System (INIS)

    Jolivet, J.P.


    Hydroxylation, condensation and precipitation of metal cations in aqueous solution are briefly reviewed. Hydroxylation of aqueous complexes essentially depends on the format charge (oxidation state), the size and the pH of the medium. It is the step allowing the condensation reaction. Depending on the nature of complexes (aqua-hydroxo, oxo-hydroxo), the. mechanism of condensation is different, olation or ox-olation respectively. The first one leads to poly-cations or hydroxides more or less stable against dehydration. The second one leads to poly-anions or oxides. Oligomeric species (poly-cations, poly-anions) are form from charged monomer complexes while the formation of solid phases requires non-charged precursors. Because of their high lability, charged oligomers are never the precursors of solids phases. The main routes for the formation of solid phases from solution are studied with two important and representative elements, Al and Si. For Al 3+ ions, different methods (base addition in solution, thermo-hydrolysis, hydrothermal synthesis) are discussed in relation to the crystal structure of the solid phase obtained. For silicic species condensing by ox-olation, the role of acid or base catalysis on the morphology of gels is studied. The influence of complexing ligands on the processes and on the characteristics of solids (morphology of particles, basic salts and polymetallic oxides formation) is studied. (author)

  13. Calcium phosphate nanoparticles functionalized with a dimethacrylate monomer

    Energy Technology Data Exchange (ETDEWEB)

    Rodrigues, Marcela Charantola, E-mail: [University of São Paulo, School of Dentistry, Department of Biomaterials and Oral Biology, Av. Prof. Lineu Prestes, 2227, 05508-000 São Paulo, SP (Brazil); Hewer, Thiago Lewis Reis, E-mail: [University of São Paulo, Department of Chemical Engineering, Av. Prof. Lineu Prestes, 580, Bloco 18, 05508-000 São Paulo, SP (Brazil); Espósito de Souza Brito, Giancarlo, E-mail: [University of São Paulo, Institute of Physics, Department of Applied Physics, Rua do Matão Travessa R #187, 05508-090 São Paulo, SP (Brazil); Arana-Chavez, Victor Elias, E-mail: [University of São Paulo, School of Dentistry, Department of Biomaterials and Oral Biology, Av. Prof. Lineu Prestes, 2227, 05508-000 São Paulo, SP (Brazil); Braga, Roberto Ruggiero, E-mail: [University of São Paulo, School of Dentistry, Department of Biomaterials and Oral Biology, Av. Prof. Lineu Prestes, 2227, 05508-000 São Paulo, SP (Brazil)


    The synthesis of calcium phosphate nanoparticles may include modifying agents to tailor particle size, reduce agglomeration and add specific functionalities. This study describes the synthesis of dicalcium phosphate dihydrate (DCPD) nanoparticles functionalized with triethylene glycol dimethacrylate (TEGDMA), added to one of the reacting solutions, with the purpose of reducing agglomeration and improving the compatibility with vinyl-based resin matrices. The nanoparticles were characterized by X-ray diffraction (XRD), Fourier-transformed infrared spectroscopy (FTIR), elemental analysis, thermogravimetric analysis (TGA), transmission electronic microscopy (TEM), dynamic light scattering (DLS), and surface area (BET). As controls, proprietary DCPD nanoparticles and nanoparticles synthesized without the addition of TEGDMA (“bare”) were subjected to the same analytical methods. XRD revealed a similar crystalline structure of the synthesized materials in comparison to the proprietary nanoparticles. The presence of a TEGDMA layer was confirmed by elemental analysis and TGA, corresponding to a mass fraction of 8.5%. FTIR analysis of the functionalized nanoparticles revealed the suppression of some absorbance bands found in the neat TEGDMA. A chemisorption mechanism between TEGDMA and the surface of primary particles by ion–dipole interaction involving TEGDMA oxyethylene, and also an interaction mechanism between the particle surface and terminal-CH{sub 3} groups are proposed. Functionalized nanoparticles showed 3 to 11 times higher surface area than the controls, in agreement with DLS data, indicating lower agglomeration. - Highlights: • Dicalcium phosphate (DCPD) nanoparticles were functionalized ab initio using TEGDMA. • Triethylene glycol dimethacrylate was chosen due to its polymerizable vinyl groups. • These nanoparticles would have a better interaction with dimethacrylate resins. • An ion–dipole chemisorption mechanism between DCPD and TEGDMA is

  14. Base-catalyzed depolymerization of lignin : separation of monomers

    Energy Technology Data Exchange (ETDEWEB)

    Vigneault, A. [Sherbrooke Univ., PQ (Canada). Dept. of Chemical Engineering; Johnson, D.K. [National Renewable Energy Laboratory, Golden, CO (United States); Chornet, E. [Sherbrooke Univ., PQ (Canada). Dept. of Chemical Engineering; National Renewable Energy Laboratory, Golden, CO (United States)


    Biofuels produced from residual lignocellulosic biomass range from ethanol to biodiesel. The use of lignin for the production of alternate biofuels and green chemicals has been studied with particular emphasis on the structure of lignin and its oxyaromatic nature. In an effort to fractionate lignocellulosic biomass and valorize specific constitutive fractions, the authors developed a strategy for the separation of 12 added value monomers produced during the hydrolytic base catalyzed depolymerization (BCD) of a Steam Exploded Aspen Lignin. The separation strategy was similar to vanillin purification to obtain pure monomers, but combining more steps after the lignin depolymerization such as acidification, batch liquid-liquid-extraction (LLE), followed by vacuum distillation, liquid chromatography (LC) and crystallization. The purpose was to develop basic data for an industrial size process flow diagram, and to evaluate both the monomer losses during the separation and the energy requirements. Experimentally testing of LLE, vacuum distillation and flash LC in the laboratory showed that batch vacuum distillation produced up to 4 fractions. Process simulation revealed that a series of 4 vacuum distillation columns could produce 5 distinct monomer streams, of which 3 require further chromatography and crystallization operations for purification. 22 refs., 4 tabs., 8 figs.


    African Journals Online (AJOL)

    Chinese herbal drugs have been proved to be effective agents in myocardial protection by preventing ischemia-reperfusion injury. The underlying mechanisms as to how these agents work were however poorly elucidated. Studies on the monomers or on the single drugs have highlighted the possible rationales, leading to ...

  16. A CO2-switchable amidine monomer: synthesis and characterization. (United States)

    Liu, Hanbin; Yin, Hongyao; Feng, Yujun


    Smart system employed CO 2 gas as new trigger has been attracting enormous attention in recent years, but few monomers that are capable of switching their hydrophobicity/hydrophility upon CO 2 stimulation have been reported. A novel CO 2 responsive monomer, 4-vinylbenzyl amidine, is designed and synthesized in this work with N,N -dimethylacetamide dimethyl acetal and 4-vinylbenzyl amine that is prepared through the Gabriel reaction. In bi-phase solvent of n -hexane and water, the monomer dissolves in n -hexane first and then transforms into water upon the CO 2 treatment, indicating a hydrophobic to hydrophilic transition. This transformation is demonstrated as reversible by monitoring the conductivity variation of its wet dimethyl formamide solution during alternate bubbling/removing CO 2 . The protonation of 4-vinylbenzyl amidine upon CO 2 treatment is demonstrated by 1 H NMR which also accounts for the dissolubility change. The reversible addition-fragmentation chain-transfer polymerization of this monomer is also performed, finding the reaction only occurs in glacial acetic acid. The reason can be ascribed to the different radical structure produced in different solvent.

  17. Influence of the Diene Monomer on Devulcanization of EPDM Rubber

    NARCIS (Netherlands)

    Verbruggen, M.A.L.; van der Does, L.; Noordermeer, Jacobus W.M.; van Duin, M.


    Ethylene–propylene–diene rubbers (EPDM) with 2-ethylidene-5-norbornene (ENB), dicyclopentadiene (DCPD), and 1,4-hexadiene (HD) as third monomers have been vulcanized with peroxide and with a conventional sulfur vulcanization recipe, and their devulcanization was subsequently investigated for

  18. Plasma-Enhanced Copolymerization of Amino Acid and Synthetic Monomers (United States)


    dielectrics to successfully deposit a wide range of monomers covering many traditional polymers, ranging from styrene , acrylonitrile, and benzene to...dispersive spectroscopy (EDS) was performed with an Oxford system on a Hitachi S-3400 scanning electron microscope. Fourier transform infrared ( FTIR ...spectroscopy measurements were conducted using a Bruker FTIR spectrometer (Vertex 70) equipped with a narrow-band mercury cadmium telluride detector

  19. Two Populations Mean-Field Monomer-Dimer Model (United States)

    Alberici, Diego; Mingione, Emanuele


    A two populations mean-field monomer-dimer model including both hard-core and attractive interactions between dimers is considered. The pressure density in the thermodynamic limit is proved to satisfy a variational principle. A detailed analysis is made in the limit of one population is much smaller than the other and a ferromagnetic mean-field phase transition is found.

  20. The LOMOsup(R) process: a solution for residual monomers

    International Nuclear Information System (INIS)

    Derbyshire, R.L.


    Regulatory activity over the last several years has addressed the potential problems associated with the migration of residual monomers from a number of commodity food packages. Regardless of the outcome of current debates, it will always be desirable to reduce monomer levels to as low a level as economically practicable so that they do not become indirect additives. The LOMO process is a body of technology inclusive of an ionizing radiation treatment which can result in sharp reduction of residual monomer levels in commodity plastic resins. The process may be applicable to factory intermediates, raw resins, or finished articles. Depending upon the individual system and its monomers, LOMO treatment can result in reductions to levels which press today's analytical test capability. Industrial radiation processing is normally accomplished with electron beam accelerators. Electron beam processing continues to gain in understanding and acceptance as one of the very few basic methods by which energy can be imparted to an industrial process system. Typically, whole factories are constructed around one accelerator. (author)

  1. Epoxy resin monomers with reduced skin sensitizing potency. (United States)

    O'Boyle, Niamh M; Niklasson, Ida B; Tehrani-Bagha, Ali R; Delaine, Tamara; Holmberg, Krister; Luthman, Kristina; Karlberg, Ann-Therese


    Epoxy resin monomers (ERMs), especially diglycidyl ethers of bisphenol A and F (DGEBA and DGEBF), are extensively used as building blocks for thermosetting polymers. However, they are known to commonly cause skin allergy. This research describes a number of alternative ERMs, designed with the aim of reducing the skin sensitizing potency while maintaining the ability to form thermosetting polymers. The compounds were designed, synthesized, and assessed for sensitizing potency using the in vivo murine local lymph node assay (LLNA). All six epoxy resin monomers had decreased sensitizing potencies compared to those of DGEBA and DGEBF. With respect to the LLNA EC3 value, the best of the alternative monomers had a value approximately 2.5 times higher than those of DGEBA and DGEBF. The diepoxides were reacted with triethylenetetramine, and the polymers formed were tested for technical applicability using thermogravimetric analysis and differential scanning calorimetry. Four out of the six alternative ERMs gave polymers with a thermal stability comparable to that obtained with DGEBA and DGEBF. The use of improved epoxy resin monomers with less skin sensitizing effects is a direct way to tackle the problem of contact allergy to epoxy resin systems, particularly in occupational settings, resulting in a reduction in the incidence of allergic contact dermatitis.

  2. Binding interactions between suberin monomer components and pesticides

    Energy Technology Data Exchange (ETDEWEB)

    Olivella, M.À., E-mail: [Department of Chemical Engineering, Escola Politècnica Superior, Universitat de Girona, Maria Aurèlia Capmany, 61, 17071 Girona (Spain); Bazzicalupi, C.; Bianchi, A. [Department of Chemistry “Ugo Schiff”, University of Florence, Via della Lastruccia, 3, 50019 Sesto Fiorentino (Italy); Río, J.C. del [Instituto de Recursos Naturales y Agrobiología de Sevilla, Consejo Superior de Investigaciones Científicas, P.O. Box 1052, 41080 Seville (Spain); Fiol, N.; Villaescusa, I. [Department of Chemical Engineering, Escola Politècnica Superior, Universitat de Girona, Maria Aurèlia Capmany, 61, 17071 Girona (Spain)


    Understanding the role of biomacromolecules and their interactions with pollutants is a key for elucidating the sorption mechanisms and making an accurate assessment of the environmental fate of pollutants. The knowledge of the sorption properties of the different constituents of these biomacromolecules may furnish a significant contribution to this purpose. Suberin is a very abundant biopolymer in higher plants. In this study, suberin monomers isolated from cork were analyzed by thermally-assisted methylation with tetramethylammonium hydroxide (TMAH) in a pyrolysis unit coupled to gas chromatography–mass spectrometry (GC/MS). The isolated monomer mixture was used to study the sorption of three pesticides (isoproturon, methomyl and oxamyl). The modes of pesticide–sorbent interactions were analyzed by means of two modeling calculations, the first one representing only the mixture of suberin monomers used in the sorption study, and the second one including glycerol to the mixture of suberin monomers, as a building block of the suberin molecule. The results indicated that the highest sorption capacity exhibited by the sorbent was for isoproturon (33%) being methomyl and oxamyl sorbed by the main suberin components to a lesser extent (3% and < 1%, respectively). In addition to van der Waals interactions with the apolar region of sorbent and isoproturon, modeling calculations evidenced the formation of a hydrogen bond between the isoproturon NH group and a carboxylic oxygen atom of a suberin monomer. In the case of methomyl and oxamyl only weak van der Waals interactions stabilize the pesticide–sorbent adducts. The presence of glycerol in the model provoked significant changes in the interactions with isoproturon and methomyl. - Highlights: • Suberin has low affinity to retain pesticides of aliphatic character. • Suberin has a moderate affinity to adsorb isoproturon. • Modeling calculations show that apolar portion of suberin interacts with isoproturon.

  3. Surfactant-free, cationic latices of poly(BMA-co-MMA) using AIBA initiator. (United States)

    Lee, Ki-Chang


    When polymer particles come into use, especially, for photonic crystal applications, their diameter, dispersivity, and refractive indices become very important. Poly(benzyl methacrylate) is known to be a kind of high refracive materials (n = 1.57) compared to poly(methyl methacrylate) (n = 1.49). Not many work was concerned for surfactant-free emulsion polymerization of benzyl methacrylate or its copolymerization using cationic initiators. Narrowly dispersed cationic poly(BMA-co-MMA) and PBMA latices were synthesized successfully by surfactant-free emulsion polymerization with AIBA. The influences of BMA/MMA ratio, BMA/MMA monomer and initiator concentrations, addition of DVB/EGDMA crosslink agent, and polymerization temperature on the kinetics and on the particle size and molecular weight were studied. Monodisperse cationic charged PBMA and poly(BMA-coMMA) latices with particle diameters varying between 160-494 nm and polymer molecular weights of the order 1.25 x 10(4) to 7.55 x 10(4) g/mol were prepared. The rate of polymerization increased with increasing MMA concentration in BMA/MMA ratio, AIBA concentration, DVB crosslink agent, and polymerization temperature. The particle diameter increased with BMA concentration in BMA/MMA ratio, AIBA concentration, and BMA/MMA monomer concentration. The molecular weight increased with BMA concentration in BMA/MMA ratio and BMA/MMA monomer concentration. The glass transition temperature of the latex copolymers decreased with increasing amount of BMA from 375 K for PMMA to 321 K for PBMA. It was, thus, found that the particle diameter and rate of polymerization as well as the polymer molecular weight for surfactant-free emulsion polymerization of BMA and MMA can be controlled easily by controlling the BMA/MMA ratio, BMA/MMA monomer concentration, AIBA concentration, and polymerization temperature.

  4. Multifunctional monomers based on vinyl sulfonates and vinyl sulfonamides for crosslinking thiol-Michael polymerizations: monomer reactivity and mechanical behavior. (United States)

    Sinha, Jasmine; Podgórski, Maciej; Huang, Sijia; Bowman, Christopher N


    Multifunctional vinyl sulfonates and vinyl sulfonamides were conveniently synthesized and assessed in thiol-Michael crosslinking polymerizations. The monomer reactivities, mechanical behavior and hydrolytic properties were analyzed and compared with those of analogous thiol-acrylate polymerizations. Materials with a broad range of mechanical properties and diverse hydrolytic stabilities were obtained.

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

    International Nuclear Information System (INIS)

    Fukano, K.; Kageyama, E.


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

  6. Asymmetric cation-binding catalysis

    DEFF Research Database (Denmark)

    Oliveira, Maria Teresa; Lee, Jiwoong


    solvents, thus increasing their applicability in synthesis. The expansion of this concept to chiral polyethers led to the emergence of asymmetric cation-binding catalysis, where chiral counter anions are generated from metal salts, particularly using BINOL-based polyethers. Alkali metal salts, namely KF...... and KCN, are selectively bound to the catalyst, providing exceptionally high enantioselectivities for kinetic resolutions, elimination reactions (fluoride base), and Strecker synthesis (cyanide nucleophile). Asymmetric cation-binding catalysis was recently expanded to silicon-based reagents, enabling...

  7. Zero kinetic energy photoelectron spectroscopy of tryptamine and the dissociation pathway of the singly hydrated cation cluster (United States)

    Gu, Quanli; Knee, J. L.


    The relative ionization energies of tryptamine conformations are determined by zero kinetic energy photoelectron spectroscopy and photoionization efficiency measurements. The relative cationic conformational stabilities are compared to the published results for the neutral molecule. In the cation, the interaction strength changes significantly between amino group and either the phenyl or the pyrrole moiety of the indole chromophore where most of the positive charge is located, leading to different conformational structures and relative conformer energies in the cation. In particular, the measured adiabatic ionization potential of isomer B is 60 928 ± 5 cm-1, at least 400 cm-1 higher than any of the 6 other tryptamine isomers which all have ionization potentials within 200 cm-1 of each other. In addition to the monomer, measurements were made on the A conformer of the tryptamine+-H2O complex including the ionization threshold and cation dissociation energy measured using a threshold photoionization fragmentation method. The water cluster exhibits an unexpectedly high ionization potential of 60 307 ± 100 cm-1, close to the conformer A monomer of 60 320 ± 100 cm-1. It also exhibits surprisingly low dissociation energy of 1750 ± 150 cm-1 compared to other H-bonding involved cation-H2O complexes which are typically several thousands of wavenumbers higher. Quantum chemical calculations indicate that upon ionization the structure of the parent molecule in the water complex remains mostly unchanged due to the rigid intermolecular double hydrogen bonded water molecule bridging the monomer backbone and its side chain thus leading to the high ionization potential in the water cluster. The surprisingly low dissociation energy measured in the cationic water complex is attributed to the formation of a much more stable structural isomer H+ in the exit channel.

  8. Calculation of vibrational spectra for dioxouranium monochloride monomer and dimers (United States)

    Umreiko, D. S.; Shundalau, M. B.; Zazhogin, A. P.; Komyak, A. I.


    Structural models were built and spectral characteristics were calculated based on ab initio calculations for the monomer and dimers of dioxouranium monochoride UO2Cl. The calculations were carried out in the effective core potential LANL2DZ approximation for the uranium atom and all-electron basis sets using DFT methods for oxygen and chlorine atoms (B3LYP/cc-pVDZ). The monomer UO2Cl was found to possess an equilibrium planar (close to T-shaped) configuration with C2v symmetry. The obtained spectral characteristics were analyzed and compared with experimental data. The adequacy of the proposed models and the qualitative agreement between calculation and experiment were demonstrated.

  9. Liquid-solid extraction of cationic metals by cationic amphiphiles

    International Nuclear Information System (INIS)

    Muller, W.


    In the field of selective separation for recycling of spent nuclear fuel, liquid-liquid extraction processes are widely used (PUREX, DIAMEX..) in industrial scale. In order to guarantee a sustainable nuclear energy for the forthcoming generations, alternative reprocessing techniques are under development. One of them bases on the studies from Heckmann et al in the 80's and consists in selectively precipitating actinides from aqueous waste solutions by cationic surfactants (liquid-solid extraction). This technique has some interesting advantages over liquid-liquid extraction techniques, because several steps are omitted like stripping or solvent washing. Moreover, the amount of waste is decreased considerably, since no contaminated organic solvent is produced. In this thesis, we have carried out a physico-chemical study to understand the specific interactions between the metallic cations with the cationic surfactant. First, we have analysed the specific effect of the different counter-ions (Cl - , NO 3 - , C 2 O 4 2- ) and then the effect of alkaline cations on the structural properties of the surfactant aggregation in varying thermodynamical conditions. Finally, different multivalent cations (Cu 2+ , Zn 2+ , UO 2 2+ , Fe 3+ , Nd 3+ , Eu 3+ , Th 4+ ) were considered; we have concluded that depending on the anionic complex of these metals formed in acidic media, we can observe either an adsorption at the micellar interface or not. This adsorption has a large influence of the surfactant aggregation properties and determines the limits of the application in term of ionic strength, temperature and surfactant concentration. (author) [fr

  10. Cationic Polymerization of 1,2-Epoxypropane by an Acid Exchanged Montmorillonite Clay in the Presence of Ethylene Glycol

    Directory of Open Access Journals (Sweden)

    Aïcha Hachemaoui


    Full Text Available Abstract: The polymerization of propylene oxide (PO catalysed by maghnite-H+ (mag-H+ in the presence of ethylene glycol was investigated. Mag-H+ is a montmorillonite silicate sheet clay was prepared through a straight forward proton exchange process. It was found that the cationic polymerization of PO was initiated by mag-H+ at 20 °C both in bulk and in solution. The effect of the amount of mag-H+ and solvent was studied. These results indicated the cationic nature of the polymerization A possible initiation pathway, via the transfer of protons from mag-H+ to the monomer, is proposed.

  11. Ortho-substituted triptycene-based diamines, monomers, and polymers, methods of making and uses thereof

    KAUST Repository

    Ghanem, Bader Saleh


    Described herein are ortho-dimethyl-substituted and tetramethyi-substituted triptycene-containing diamine monomers and microporous triptycene-based poiyimides and poiyamides, and methods of making the monomers and polymers.

  12. Effect of adhesion promoting monomer addition to MMA-TBBO resin on bonding to pure palladium. (United States)

    Minami, Hiroyuki; Murahara, Sadaaki; Muraguchi, Koichi; Sakoguchi, Kenji; Suzuki, Shiro; Tanaka, Takuo


    This study evaluated the effects of combined use of metal primers and modified monomers on the bonding of MMA-TBBO resins to pure palladium (Pd). Bonding surface was polished with 600-grit silicon carbide paper and primed with one of these four metal primers: V-Primer, M. L. Primer, Metaltite, or Alloy Primer. Four monomers, including three modified ones, were added to MMATBBO resin. One was a methyl methacrylate monomer containing no adhesion promoting monomers, while the other two modified monomers contained the functional monomer of either V-Primer or Alloy Primer. Bonded specimens were prepared by incremental build-up of MMA-TBBO resin on primed Pd surfaces. Shear bond strengths were measured after thermal cycling. Bonding to Pd was significantly improved when modified monomer containing the functional monomer of Alloy Primer was used in combination with M. L. Primer or Metaltite applied on the bonding surface.

  13. Monomer dynamics in single- and double-stranded DNA coils (United States)

    Tothova, J.; Brutovsky, B.; Lisy, V.


    In our paper (Tothova et al., Czech. J. Phys. 55, 221 (2005)), the first observation of the kinetics of individual polymer monomers using the fluorescence correlation technique (R. Shusterman et al., Phys. Rev. Lett. 92, 048303 (2004)) has been interpreted within the bead-spring theory. Optimizing the joint Rouse-Zimm model to the experimental data, the phenomenological parameters for the statistical-mechanical description of the universal behavior of double- and single-stranded DNA and the dominant types of their dynamics have been determined. Recently, these data have been corrected (R. Shusterman et al., Phys. Rev. Lett. 98, 029901 (2007)). In the present work, the fits of the theory to the new data are given. The main conclusions of our preceding paper remain unchanged but some of the polymer parameters have changed. The new data allow a significantly better agreement with the theory than the previous ones. Our calculations confirm that dsDNA follows mainly the classical Zimm-type kinetics rather than the Rouse one as it was proposed by Shusterman et al. Single-stranded DNA also behaves predominantly as the Zimm polymer. To support these conclusions, we analyze the draining effects on the monomer dynamics and the applicability of simple “universal” laws, according to which the monomer mean square displacement scales with the time as t1/2 and t2/3 for the Rouse and Zimm polymers, respectively.

  14. Structure of human insulin monomer in water/acetonitrile solution

    Energy Technology Data Exchange (ETDEWEB)

    Bocian, Wojciech; Sitkowski, Jerzy; Bednarek, Elzbieta [National Medicines Institute (Poland); Tarnowska, Anna; Kawecki, Robert [Institute of Organic Chemistry Polish Academy of Sciences (Poland); Kozerski, Lech [National Medicines Institute (Poland)], E-mail:


    Here we present evidence that in water/acetonitrile solvent detailed structural and dynamic information can be obtained for important proteins that are naturally present as oligomers under native conditions. An NMR-derived human insulin monomer structure in H{sub 2}O/CD{sub 3}CN, 65/35 vol%, pH 3.6 is presented and compared with the available X-ray structure of a monomer that forms part of a hexamer (Acta Crystallogr. 2003 Sec. D59, 474) and with NMR structures in water and organic cosolvent. Detailed analysis using PFGSE NMR, temperature-dependent NMR, dilution experiments and CSI proves that the structure is monomeric in the concentration and temperature ranges 0.1-3 mM and 10-30 deg. C, respectively. The presence of long-range interstrand NOEs, as found in the crystal structure of the monomer, provides the evidence for conservation of the tertiary structure. Starting from structures calculated by the program CYANA, two different molecular dynamics simulated annealing refinement protocols were applied, either using the program AMBER in vacuum (AMBER{sub V}C), or including a generalized Born solvent model (AMBER{sub G}B)

  15. Structure of human insulin monomer in water/acetonitrile solution

    International Nuclear Information System (INIS)

    Bocian, Wojciech; Sitkowski, Jerzy; Bednarek, Elzbieta; Tarnowska, Anna; Kawecki, Robert; Kozerski, Lech


    Here we present evidence that in water/acetonitrile solvent detailed structural and dynamic information can be obtained for important proteins that are naturally present as oligomers under native conditions. An NMR-derived human insulin monomer structure in H 2 O/CD 3 CN, 65/35 vol%, pH 3.6 is presented and compared with the available X-ray structure of a monomer that forms part of a hexamer (Acta Crystallogr. 2003 Sec. D59, 474) and with NMR structures in water and organic cosolvent. Detailed analysis using PFGSE NMR, temperature-dependent NMR, dilution experiments and CSI proves that the structure is monomeric in the concentration and temperature ranges 0.1-3 mM and 10-30 deg. C, respectively. The presence of long-range interstrand NOEs, as found in the crystal structure of the monomer, provides the evidence for conservation of the tertiary structure. Starting from structures calculated by the program CYANA, two different molecular dynamics simulated annealing refinement protocols were applied, either using the program AMBER in vacuum (AMBER V C), or including a generalized Born solvent model (AMBER G B)

  16. Controllable synthesis, crystal structure and magnetic properties of Monomer-Dimer Cocrystallized MnIII Salen-type composite material (United States)

    Wu, Qiong; Wu, Wei; Wu, Yongmei; Li, Weili; Qiao, Yongfeng; Wang, Ying; Wang, Baoling


    By the reaction of manganese-Schiff-base complexes with penta-anionic Anderson heteropolyanion, a new supramolecular architecture [Mn2(Salen)2(H2O)2][Mn(Salen)(H2O)2]2Na[IMo6O24]·8H2O (1) (salen = N,N‧-ethylene-bis (salicylideneiminate) has been isolated. Compound 1 was characterized by the single-crystal X-ray diffraction, elemental, IR and thermal gravimetric analyses. Structural analysis reveals that the unit cell simultaneously contains MnIII-Salen dimer and monomer cation fragments, for which the Anderson-type polyanions serve as counter anions. In the packing arrangement, all the MnIII dimers are well separated by polyoxometalate units and form tertiary structure together with MnIII monomers. Interestingly, different from the previous work, in the exact same reaction conditions, we are able to template MnIII-Salen complexes into different configurations by varying the charge state of polyanions. Besides, the magnetic properties of 1 were also examined by using both dc and ac magnetic field of the superconducting quantum interference devices. Most importantly, our fitting of the experimental data to a Heisenberg-type spin model shows that there exists a ferromagnetic exchange interaction ∼5 K between the spins (S = 2) on MnIII in the dimer, while antiferromagnetic ones exist among monomers and dimer (∼2 K). This meta-magnetic state could induce a slight spin frustration at low temperature, which would in turn affect the magnetic behavior. In addition, our ac field measurement of the susceptibilities suggests a typical signature for a single-molecule magnet.

  17. Effects of monomer size on polymer mass transport at a crystalline interface (United States)

    Cadilhe, Antonio; Coura, P. Z.; Costa, B. V.


    The relevance of surface structure to polymer diffusion was considered in a few cases. In this work extensive Monte Carlo simulations are done to study the diffusion of a polymer on a crystalline surface. We study models for which we vary the monomer size, thus, allowing us to define a parameter γ as the ratio of the equilibrium distances between monomers to substrate particles. Physically, distinct γ values represent different materials. Two different models are considered: one (Model A) where the equilibrium distance between monomers and substrate particles remains constant as we vary the size of the monomers and another (Model B) where this distance scales with the monomer-monomer equilibrium distance. In Model A the monomer-monomer and monomer-substrate interactions have different ranges, which makes it anisotropic, while in Model B these ranges are the same, which makes it isotropic. Our results for Model A show that the presence of the crystalline substrate significantly affects the diffusion coefficient introducing an oscillation in the diffusion coefficient that depends on the ratio monomer size to lattice spacing (γ). When γ is a multiple integer of some lattice vectors the diffusion constant diminishes dramatically suggesting that the monomers settle. In Model B monomers do settle for γ= \\sqrt 5 , but otherwise the behavior of the diffusion coefficient stays monotonic. Additionally, this model shows that larger γ values give similar diffusion coefficients, which might be of use to experimentalists.

  18. Influence of template/functional monomer/cross‐linking monomer ratio on particle size and binding properties of molecularly imprinted nanoparticles

    DEFF Research Database (Denmark)

    Yoshimatsu, Keiichi; Yamazaki, Tomohiko; Chronakis, Ioannis S.


    A series of molecularly imprinted polymer nanoparticles have been synthesized employing various template/functional monomer/crosslinking monomer ratio and characterized in detail to elucidate the correlation between the synthetic conditions used and the properties (e.g., particle size and template...... binding properties) of the obtained nanoparticles. In brief, the presence of propranolol (template) in the polymerization mixture turned out to be a critical factor on determination of the size as well as the binding properties of the imprinted nanoparticles. The functional monomer/crosslinking monomer...... tuning of particle size and binding properties are required to fit practical applications. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012...

  19. Studies on cationic UV curing of epoxidised palm oil (EPO) for surface coatings

    International Nuclear Information System (INIS)

    Mek Zah Salleh; Mohd Hilmi Mahmood; Wan Rosli Wan Daud; Kumar, R.N.


    Epoxidised palm oil (EPO) resin can be cured by ultraviolet (UV) radiation either by radical, cationic or hybrid system. Cationic curing system has been chosen in this study due to the fact that epoxy groups present in EPO can be utilised directly to form crosslinking. Curing was done by means of a 20 cm wide UV IST machine with the conditions of 7.5 A current and 4 m/min conveyor speed. Sulphonium and ferrocenium salts were used as cationic photoinitiator. A formulations study was performed on the selected grades of EPO with other materials. These include types and concentration of photoinitiator, monomers, concentration of EPO and post-cure. The properties of the cured film such as pendulum hardness, percentage of gel content and tensile strength were determined. It was found that triarylsulphonium hexafluorophosphate has a very low solubility in EPO. Addition of vinyl ether monomer to the formulation did not enhance pendulum hardness and gel content of the cured films. It is also found that the post cure temperature has no significant effect on the cured film

  20. Cationic quaternization of cellulose with methacryloyloxy ethyl trimethyl ammonium chloride via ATRP method

    Energy Technology Data Exchange (ETDEWEB)

    Supeno [Cenderawasih University, Jayapura, Papua, Indonesia and School of Chemical Sciences and Food Technology, Faculty of Science and Technology, Universiti Kebangsaan Malaysia, 43600 Bangi, Selangor (Malaysia); Daik, Rusli, E-mail: [School of Chemical Sciences and Food Technology, Faculty of Science and Technology, Universiti Kebangsaan Malaysia, 43600 Bangi, Selangor (Malaysia); El-Sheikh, Said M. [Nano-Structured Materials Division, Advanced Materials Department, Central Metallurgical Research and Development Institute, Cairo (Egypt)


    The synthesis of a cationic cellulose copolymer from cellulose macro-initiator (MCC-BiB) and quaternary compound monomer (METMA) via atom transfer radical polymerization (ATRP) was studied. By using dimethylformamide (DMF), the optimum condition for successful synthesis was at the mole ratio of MCC-BIB:Catalyst:METMA = 1:1:26. The highest copolymer recovery was 93.2 % for 6 h and at 40°C. The copolymer was insoluble in weak polar solvents such as THF and DMF but soluble in methanol and water. The chemistry of cellulose copolymer was confirmed by the FTIR and TGA in which the METMA monomer was used as a reference. The absence of CC bond in the CiB-g-METMA spectrum indicated that graft copolymerization occurred.

  1. Effects of phenolic monomers on growth of Acidothermus cellulolyticus. (United States)

    Joh, Lawrence D; Rezaei, Farzaneh; Barabote, Ravi D; Parales, Juanito V; Parales, Rebecca E; Berry, Alison M; Vandergheynst, Jean S


    Previous studies on biological pretreatment of switchgrass by solid-state fermentation with Acidothermus cellulolyticus 11B have shown that inhibitory compounds prevent growth on untreated switchgrass. A. cellulolyticus was grown in liquid medium containing cellobiose with phenolic monomers added to determine if the phenolic compounds are one possible source of inhibition. Cinnamic acid derivatives (trans-p-coumaric, trans-ferulic, and hydrocinnamic acids), hydroxybenzoic acids (p-hydroxybenzoic, syringic, and vanillic acids), benzaldehydes (vanillin and p-hydroxybenzaldehyde), and condensed tannin monomers (catechin and epicatechin) were tested at levels up to 20 mM. All compounds exhibited a dose-response relationship and strongly inhibited growth at 20 mM. trans-p-Coumaric acid was found to be the strongest inhibitor of A. cellulolyticus growth, with a specific growth rate of 0.004 h(-1) at 1 mM (0.18 h(-1) without phenolic monomer). GC-MS and HPLC methods were used to confirm the presence of these phenolic compounds in switchgrass and measure the amounts extracted using different conditions. The amounts of phenolic compounds measured were found to be higher than the threshold for growth inhibition. Leaching with water at 55°C was inefficient at removing bound phenolics, whereas NaOH treatment improved efficiency. Phenolic compounds spiked into alkaline pretreated switchgrass were also found to inhibit growth of A. cellulolyticus in solid-state fermentation. However, addition of insoluble polyvinylpolypyrrolidone (PVPP) to switchgrass improved growth of A. cellulolyticus in liquid cultures, providing a possible approach for alleviating microbial inhibition due to phenolic compounds in lignocellulose. Copyright © 2010 American Institute of Chemical Engineers (AIChE).

  2. [Migration of monomers and primary aromatic amines from nylon products]. (United States)

    Mutsuga, Motoh; Yamaguchi, Miku; Ohno, Hiroyuki; Kawamura, Yoko


    Migration of 2 kinds of monomer and 21 kinds of primary aromatic amines (PAAs) from 21 kinds of nylon products such as turners, ladles and wrap film were determined. Samples were classified as regards materials by mean of pyrolysis-GC/MS. One sample was classified as nylon 6, 15 samples as nylon 66 and three samples as nylon 6/66 copolymers, while two samples were laminate of nylon 6 with polyethylene or polypropylene. All of the nylon 66 samples contained a small amount of ε-caprolactam (CPL), which is the nylon 6 monomer. Migration levels of monomers and PAAs at 60°C for 30 min into 20% ethanol were measured by LC/MS/MS. CPL was detected at the level of 0.015-38 µg/mL from all samples, excluding one wrap film sample, and 1,6-hexamethylenediamine was detected at the level of 0.002-0.013 µg/mL from all nylon 66 samples and one nylon 6/66 sample. In addition, 0.006-4.3 µg/mL of 4,4'-diaminodiphenylmethane from three samples, 0.032-0.23 µg/mL of aniline from four samples, 0.001 µg/mL of 4-chloroaniline from two samples, and 0.002 µg/mL of 2-toluidine and 0.066 mg/mL of 1-naphthylamine from one sample each were detected. The migration levels at 95 or 121°C were about 3 and 10 times the 60°C levels, respectively.

  3. Synthesis of acrylic and allylic bifunctional cross-linking monomers derived from PET waste

    International Nuclear Information System (INIS)

    Cruz-Aguilar, A; Herrera-González, A M; Vázquez-García, R A; Coreño, J; Navarro-Rodríguez, D


    An acrylic and two novel allylic monomers synthesized from bis (hydroxyethyl) terephthalate, BHET, are reported. This was obtained by glycolysis of post-consumer PET with boiling ethylene glycol. The bifunctional monomer bis(2-(acryloyloxy)ethyl) terephthalate was obtained from acryloyl chloride, while the allylic monomers 2-(((allyloxi)carbonyl)oxy) ethyl (2-hydroxyethyl) terephthalate and bis(2-(((allyloxi)carbonyl)oxy)ethyl) terephthalate, from allyl chloroformate. Cross-linking was studied in bulk polymerization using two different thermal initiators. Monomers were analyzed by means of 1 H NMR and the cross-linked polymers by infrared spectroscopy. Gel content higher than 90% was obtained for the acrylic monomer. In the case of the mixture of the allylic monomers, the cross-linked polymer was 80 % using BPO initiator, being this mixture 24 times less reactive than the acrylic monomer.

  4. Breathing zone concentrations of methylmethacrylate monomer during joint replacement operations

    DEFF Research Database (Denmark)

    Darre, E; Jørgensen, L G; Vedel, P


    By use of a methylmethacrylate (MMA) Dräger tube and bellow bump, the breathing zone concentrations of MMA monomer were measured for the operating surgeon during cementation of the components of hip and knee joint prostheses. The highest recordings (50-100 p.p.m.) were encountered during...... cementation of the acetabular cups with conventional polymethylmethacrylate cement. Such exposure could be eliminated by the use of personal protection equipment, local punctual field suction or change to a MMA/n-decylmethacrylate/isobornylmethacrylate bone cement....

  5. Breathing zone concentrations of methylmethacrylate monomer during joint replacement operations

    DEFF Research Database (Denmark)

    Darre, E; Jørgensen, L G; Vedel, P


    By use of a methylmethacrylate (MMA) Dräger tube and bellow bump, the breathing zone concentrations of MMA monomer were measured for the operating surgeon during cementation of the components of hip and knee joint prostheses. The highest recordings (50-100 p.p.m.) were encountered during cementat...... cementation of the acetabular cups with conventional polymethylmethacrylate cement. Such exposure could be eliminated by the use of personal protection equipment, local punctual field suction or change to a MMA/n-decylmethacrylate/isobornylmethacrylate bone cement....

  6. Preparation of cation-exchange stir bar sorptive extraction based on monolithic material and its application to the analysis of soluble cations in milk by ion chromatography. (United States)

    Huang, Xiaojia; Lin, Jianbin; Yuan, Dongxing


    In this study, a new cation-exchange coating for stir bar sorptive extraction (SBSE) based on poly (acrylic acid-ethylene dimethacrylate) monolithic material was synthesized. The effect of polymerization conditions such as the ratio of functional monomer to cross-linker and the content of porogenic solvent on the extraction efficiencies were investigated in detail. The monolithic material was characterized by elemental analysis, scanning electron microscopy and infrared spectroscopy. In order to evaluate the usability of the new coating for the extraction of inorganic cations, the analysis of soluble K(+), Mg(2+) and Ca(2+) in milk by ion chromatography with conductivity detection was selected as a paradigm. Several extractive parameters, including pH value in sample matrix, desorption solvent, extraction and desorption time were optimized. Under the optimum conditions, low detection limits (S/N = 3) and quantification limits (S/N = 10) of the proposed method for the target cations were achieved within the range of 0.12-0.28 and 0.4-0.92 μg L(-1), respectively. The method also showed good linearity, simplicity, practicality and low cost for the extraction of inorganic cations. Finally, the proposed method was successfully used to analyse three different trademarks of commercial milk samples with satisfactory recoveries in the range of 71.1% to 102.8%.

  7. Shelf Life of PMR Polyimide Monomer Solutions and Prepregs Extended (United States)

    Alston, William B.; Scheiman, Daniel A.


    PMR (Polymerization of Monomeric Reactants) technology was developed in the mid-1970's at the NASA Glenn Research Center at Lewis Field for fabricating high-temperature stable polyimide composites. This technology allowed a solution of polyimide monomers or prepreg (a fiber, such as glass or graphite, impregnated with PMR polyimide monomers) to be thermally cured without the release of volatiles that cause the formation of voids unlike the non-PMR technology used for polyimide condensation type resins. The initial PMR resin introduced as PMR 15 is still commercially available and is used worldwide by aerospace industries as the state-of-the-art resin for high-temperature polyimide composite applications. PMR 15 offers easy composite processing, excellent composite mechanical property retention, a long lifetime at use temperatures of 500 to 550 F, and relatively low cost. Later, second-generation PMR resin versions, such as PMR II 50 and VCAP 75, offer improvements in the upper-use temperature (to 700 F) and in the useful life at temperature without major compromises in processing and property retention but with significant increases in resin cost. Newer versions of nontoxic (non-methylene dianiline) PMR resins, such as BAX PMR 15, offer similar advantages as originally found for PMR 15 but also with significant increases in resin cost. Thus, the current scope of the entire PMR technology available meets a wide range of aeronautical requirements for polymer composite applications.

  8. Elution of monomer from different bulk fill dental composite resins. (United States)

    Cebe, Mehmet Ata; Cebe, Fatma; Cengiz, Mehmet Fatih; Cetin, Ali Rıza; Arpag, Osman Fatih; Ozturk, Bora


    The purpose of this study was to evaluate the elution of Bis-GMA, TEGDMA, HEMA, and Bis-EMA monomers from six bulk fill composite resins over four different time periods, using HPLC. Six different composite resin materials were used in the present study: Tetric Evo Ceram Bulk Fill (Ivoclar Vivadent, Amherst, NY), X-tra Fill (VOCO, Cuxhaven, Germany), Sonic Fill (Kerr, Orange, CA, USA), Filtek Bulk Fill (3M ESPE Dental Product, St. Paul, MN), SDR (Dentsply, Konstanz, Germany), EQUIA (GC America INC, Alsip, IL). The samples (4mm thickness, 5mm diameter) were prepared and polymerized for 20s with a light emitted diode unit. After fabrication, each sample was immediately immersed in 75wt% ethanol/water solution used as extraction fluid and stored in the amber colored bottles at room temperature. Ethanol/water samples were taken (0.5mL) at predefined time intervals:10m (T1), 1h (T2), 24h (T3) and 30 days (T4). These samples were analyzed by HPLC. The obtained data were analyzed with one-way ANOVA and Tukey HSD at significance level of pcomposites (pcomposite resins in all time periods and the amount of eluted monomers was increased with time. Copyright © 2015 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

  9. An Efficient Method for the Synthesis of Peptoids with Mixed Lysine-type/Arginine-type Monomers and Evaluation of Their Anti-leishmanial Activity. (United States)

    Bolt, Hannah L; Denny, Paul W; Cobb, Steven L


    This protocol describes the manual solid-phase synthesis of linear peptoids that contain two differently functionalized cationic monomers. In this procedure amino functionalized 'lysine' and guanido functionalized 'arginine' peptoid monomers can be included within the same peptoid sequence. This procedure uses on-resin (N-(1-(4,4-dimethyl-2,6-dioxocyclohexylidene)ethyl) or Dde protection, orthogonal conditions to the Boc protection of lysine monomers. Subsequent deprotection allows an efficient on-resin guanidinylation reaction to form the arginine residues. The procedure is compatible with the commonly used submonomer method of peptoid synthesis, allowing simple peptoids to be made using common laboratory equipment and commercially available reagents. The representative synthesis, purification and characterization of two mixed peptoids is described. The evaluation of these compounds as potential anti-infectives in screening assays against Leishmania mexicana is also described. The protozoan parasite L. mexicana is a causative agent of cutaneous leishmaniasis, a neglected tropical disease that affects up to 12 million people worldwide.

  10. Micronutrient Fortification of Foods

    African Journals Online (AJOL)

    Micronutrient Fortification of Foods: Developing A Program. Mahshid Lotti, M.G. Venkatesh Manar, Richard J. H. M. .... Develop the fortification technology. 11. Perform studies on interactions, potency, stability, ... Fortification with vitamin A is a long-term strategy capable of maintaining adequate vitamin A status over time.

  11. Cationic electrodepositable coating composition comprising lignin (United States)

    Fenn, David; Bowman, Mark P; Zawacky, Steven R; Van Buskirk, Ellor J; Kamarchik, Peter


    A cationic electrodepositable coating composition is disclosed. The present invention in directed to a cationic electrodepositable coating composition comprising a lignin-containing cationic salt resin, that comprises (A) the reaction product of: lignin, an amine, and a carbonyl compound; (B) the reaction product of lignin, epichlorohydrin, and an amine; or (C) combinations thereof.

  12. 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

  13. Conformational and dynamic differences between actin filaments polymerized from ATP- or ADP-actin monomers. (United States)

    Nyitrai, M; Hild, G; Hartvig, N; Belágyi, J; Somogyi, B


    Conformational and dynamic properties of actin filaments polymerized from ATP- or ADP-actin monomers were compared by using fluorescence spectroscopic methods. The fluorescence intensity of IAEDANS attached to the Cys(374) residue of actin was smaller in filaments from ADP-actin than in filaments from ATP-actin monomers, which reflected a nucleotide-induced conformational difference in subdomain 1 of the monomer. Radial coordinate calculations revealed that this conformational difference did not modify the distance of Cys(374) from the longitudinal filament axis. Temperature-dependent fluorescence resonance energy transfer measurements between donor and acceptor molecules on Cys(374) of neighboring actin protomers revealed that the inter-monomer flexibility of filaments assembled from ADP-actin monomers were substantially greater than the one of filaments from ATP-actin monomers. Flexibility was reduced by phalloidin in both types of filaments.

  14. Graft copolimerization of hydrophilic monomers onto irradiated polypropylene fibers

    International Nuclear Information System (INIS)

    Sundardi, F.


    A method of graft copolymerization of hydrophilic monomers, such as 1-vinyl-2-pyrrolidone, acrylonitrile, acrylic acid, and acrylamide, onto irradiated polypropylene fibers has been studied. γ ray as well as electron beam were employed for the irradiation processes. Graft-copolymerization kinetics and the properties of grafted fibers have been investigated. Moisture regain, dyes absorption, and melting point of the grafted fibers were found to increase with the increasing of the degree of grafting. Polypropylene for 1-vinyl-2-pyrrolidone grafted fibers showed excellent dye absorption for almost all kinds of dyes such as direct, basic, acid, reactive, disper, and naphthol dyes. However, for polypropylene acrylic acid grafted fibers, the colorfastness to washing was found to be unsatisfactory. The colorfastness to washing for polypropylene 1-vinyl-2-pyrrolidone grafted fibers was found to be fairly good for certain types of dyes such as vat and naphthol dyes. (author)

  15. Molecular recognition at methyl methacrylate/n-butyl acrylate (MMA/nBA) monomer unit boundaries of phospholipids at p-MMA/nBA copolymer surfaces. (United States)

    Yu, Min; Urban, Marek W; Sheng, Yinghong; Leszczynski, Jerzy


    Lipid structural features and their interactions with proteins provide a useful vehicle for further advances in membrane proteins research. To mimic one of potential lipid-protein interactions we synthesized poly(methyl methacrylate/ n-butyl acrylate) (p-MMA/nBA) colloidal particles that were stabilized by phospholipid (PLs). Upon the particle coalescence, PL stratification resulted in the formation of surface localized ionic clusters (SLICs). These entities are capable of recognizing MMA/nBA monomer interfaces along the p-MMA/nBA copolymer backbone and form crystalline SLICs at the monomer interface. By utilizing attenuated total reflectance Fourier transform infrared (ATR FT-IR) spectroscopy and selected area electron diffraction (SAD) combined with ab initio calculations, studies were conducted that identified the origin of SLICs as well as their structural features formed on the surface of p-MMA/nBA copolymer films stabilized by 1,2-dilauroyl-sn-glycero-3-phosphocholine (DLPC) PL. Specific entities responsible for SLIC formation are selective noncovalent bonds of anionic phosphate and cationic quaternary ammonium segments of DLPC that interact with two neighboring carbonyl groups of nBA and MMA monomers of the p-MMA/nBA polymer backbone. To the best of our knowledge this is the first example of molecular recognition facilitated by coalescence of copolymer colloidal particles and the ability of PLs to form SLICs at the boundaries of the neighboring MMA and nBA monomer units of the p-MMA/nBA chain. The dominating noncovalent bonds responsible for the molecular recognition is a combination of H-bonding and electrostatic interactions.

  16. Pyrolysis of polyolefins for increasing the yield of monomers' recovery. (United States)

    Donaj, Pawel J; Kaminsky, W; Buzeto, F; Yang, W


    Pyrolysis of plastic waste is an alternative way of plastic recovery and could be a potential solution for the increasing stream of solid waste. The objective of this work was to increase the yield the gaseous olefins (monomers) as feedstock for polymerization process and to test the applicability of a commercial Ziegler-Natta (Z-N): TiCl(4)/MgCl(2) for cracking a mixture of polyolefins consisted of 46%wt. of low density polyethylene (LDPE), 30%wt. of high density polyethylene (HDPE) and 24%wt. of polypropylene (PP). Two sets of experiments have been carried out at 500 and 650°C via catalytic pyrolysis (1% of Z-N catalyst) and at 650 and 730°C via only-thermal pyrolysis. These experiments have been conducted in a lab-scale, fluidized quartz-bed reactor of a capacity of 1-3kg/h at Hamburg University. The results revealed a strong influence of temperature and presence of catalyst on the product distribution. The ratios of gas/liquid/solid mass fractions via thermal pyrolysis were: 36.9/48.4/15.7%wt. and 42.4/44.7/13.9%wt. at 650 and 730°C while via catalytic pyrolysis were: 6.5/89.0/4.5%wt. and 54.3/41.9/3.8%wt. at 500 and 650°C, respectively. At 650°C the monomer generation increased by 55% up to 23.6%wt. of total pyrolysis products distribution while the catalyst was added. Obtained yields of olefins were compared with the naphtha steam cracking process and other potentially attractive processes for feedstock generation. The concept of closed cycle material flow for polyolefins has been discussed, showing the potential benefits of feedstock recycling in a plastic waste management. Copyright © 2011 Elsevier Ltd. All rights reserved.

  17. Glassy dynamics of model colloidal polymers: The effect of "monomer" size (United States)

    Li, Jian; Zhang, Bo-kai; Li, Hui-shu; Chen, Kang; Tian, Wen-de; Tong, Pei-qing


    In recent years, attempts have been made to assemble colloidal particles into chains, which are termed "colloidal polymers." An apparent difference between molecular and colloidal polymers is the "monomer" size. Here, we propose a model to represent the variation from molecular polymer to colloidal polymer and study the quantitative differences in their glassy dynamics. For chains, two incompatible local length scales, i.e., monomer size and bond length, are manifested in the radial distribution function and intramolecular correlation function. The mean square displacement of monomers exhibits Rouse-like sub-diffusion at intermediate time/length scale and the corresponding exponent depends on the volume fraction and the monomer size. We find that the threshold volume fraction at which the caging regime emerges can be used as a rescaling unit so that the data of localization length versus volume fraction for different monomer sizes can gather close to an exponential curve. The increase of monomer size effectively increases the hardness of monomers and thus makes the colloidal polymers vitrify at lower volume fraction. Static and dynamic equivalences between colloidal polymers of different monomer sizes have been discussed. In the case of having the same peak time of the non-Gaussian parameter, the motion of monomers of larger size is much less non-Gaussian. The mode-coupling critical exponents for colloidal polymers are in agreement with that of flexible bead-spring chains.

  18. Studies on the Influence of Monomers on the Performance Properties of Epoxy Acrylate Resin

    Directory of Open Access Journals (Sweden)

    Amrita Sharma


    Full Text Available Twelve blend samples were prepared by physical mixing of epoxy acrylate resins with various monomers viz. ethoxylated phenol monoacrylate (EOPA, tripropylene glycol diacrylate (TPGDA and trimethylol propane tri acrylate(TMPTA, having weight ratio of epoxy acrylate resin and monomers are 50:50, 60:40, 70:30, 80:20. These samples were cured under UV radiation using 5% photo initiator by weight. These blends were evaluated for mechanical, chemical & thermal properties. It was found that the sample having mono & tri functional monomers shows better properties than the samples having di functional monomer.

  19. Rate constants for some electrophilic reactions of benzyl, benzhydryl, and trityl cations in solution

    International Nuclear Information System (INIS)

    Ujdak, R.J.; Jones, R.L.; Dorfman, L.M.


    Absolute rate constants have been determined by the pulse radiolysis technique for several electrophilic reactions of the benzyl, the benzhydryl, and the trityl cation in 1,2-dichloroethane solution. The rate constants for the reactions of these carbonium ions with chloride ion, with bromide ion, and with iodide ion are all very nearly the same, namely 6 x 10 10 M -1 s -1 at 24 0 C. The values very likely represent the diffusion controlled limit for the ion combination reactions. The rate constants for the reactions with triethylamine, tri-n-propylamine, and tri-n-butylamine range from 2.0 x 10 9 to 7 x 10 6 M -1 s -1 at 24 0 C. With increasing phenyl substitution, the decreasing trend in the magnitude of the rate constant is consistent with the combined electronic and steric effects. With increasing size of the amine, the decrease in the value of the rate constant seems to indicate that the steric effect predominates. The values of the rate constants for reactions of benzyl and benzhydryl cation with methanol, ethanol, and 2-propanol indicate the following. The rate constant is higher for reaction with the alcohol dimer in solution than with alcohol monomer. The rate constants for reaction with alcohol monomer have values of 1 x 10 8 M -1 s -1 or lower

  20. Mechanisms of radiation induced cationic polymerization in the presence of onium salts (United States)

    Malmström, E.; Sundell, P. E.; Hult, A.; Jönsson, S. E.


    Cationic polymerization of various monomers in the presence of onium salts were induced by hv, EB and γ irradiation. The mechanism for the initiation process involves the photoreduction of onium salts by a direct photolysis or by an indirect redox reaction from organic free radicals or solvated electrons depending on the reduction potentials of the onium salts. For EB and γ irradiation only solvated electrons were capable of reducing the onium salts with reduction potentials lower than approximately -100 kJ/mol. An enhanced production of protons and/or carbenium ions takes place if the reduction potentials of the onium salts are higher than -60 kJ/mol. This paper will give some indications of useful onium structures that fulfill the needs in EB and γ induced cationic polymerization. Typical examples are fragmenting type of dialkylphenacyl and cyclic ringopening phenacylic sulfonium salts. The influence of typical "polymer or monomer backbone" structural groups, such as esters and ethers on the proton formation under high energy irradiation, was studied by UV spectroscopy at 540 nm. The formation of acid was monitored in the presence of various onium salts, and α-naphtylred was used as an indicator. By comparing aromatic versus aliphatic structural group influences on the generation of protons and carbenium ions a good correlation was found between experimental data and theoretical calculations on nucleophilicity, electron charge density distributions and electron scavenging effects by the use of simplified Hückel calculations (SHMO).

  1. Synthesis of Grafted Hydrogels as Mono-Divalent Cation Exchange and Drug Delivery

    International Nuclear Information System (INIS)

    El-Arnaouty, M.B.; Eid, M.


    ph-sensitive grafted poly vinyl alcohol-poly acrylic acid (PVA-PAA) hydrogels has been prepared by direct radiation grafting of acrylic acid (AA) onto PVA hydrogels. The grafting percent increase as the monomer concentration and irradiation dose increase. The maximum grafting yield was obtained at monomer concentration 50 % and irradiation dose 50 kGy. The swelling, thermogravimetric analysis, activation energy and scanning electron microscope of the grafted copolymer hydrogels were studied. The swelling of co-polymeric hydrogel was studied at different ph, and the gel demonstrate high swelling at ph 6.8. The de swelling of the swollen hydrogel in Ni 2+ and Cu 2+ cations solution was explained on the basis of mono-divalent cation exchange. The hydrogel was loaded by antihistaminic chlorphenamine maleate hydrochloride (CPM) as drug model. The release of (CPM) was faster in stimulated gastric fluid (SGF) of ph 1.1 than in stimulated intestinal fluid (SIF) of ph 6.8

  2. Preparation, characterization, and DNA interaction studies of cationic europium luminescent copolymer. (United States)

    Deng, Ziwei; Hu, Xiaoxi; Wang, Yun; Yin, Yanzhen; Peng, Bo; Xu, Zushun


    This paper proposed a simple synthetic strategy towards a novel cationic europium luminescent copolymer, poly(METAC-co-NIPAm-co-Eu(AA)3Phen) (PMNEu), and investigation about their complexation ability with DNA. In this approach, first, Eu(AA)3Phen complex monomer containing Eu(3+), acrylic acid (AA), and 1,10-phenanthroline (Phen) was synthesized, and subsequently, free radical copolymerization of Eu(AA)3Phen complex monomer with other two functional monomers, [2-(methacryloyloxy) ethyl] trimethylammonium chloride (METAC) and N-isopropylarylamide (NIPAm), was carried out in methanol using azodiisobutyronitrile (AIBN) as the initiator. (1)HNMR, GPC, fluorescence spectroscopy, UV-vis spectroscopy, and TEM were used to investigate the chemical structures, molecular weight and molecular weight distribution, fluorescence properties, UV spectra, and morphologies of PMNEu copolymer, respectively. Furthermore, the interaction of PMNEu with DNA was also studied with fluorescence spectroscopy, UV-vis spectroscopy, and agarose gel electrophoresis. These results indicated that PMNEu could interact with DNA via an electrostatic bonding mode and the bonding constant was 2.2 × 10(5) L/mol. Additionally, TEM observation showed that pure PMNEu formed micelles in water solution, while the size-controllable aggregations of PMNEu with DNA were obtained when PMNEu was mixed with DNA at various concentration ratios. A good biocompability of PMNEu was demonstrated through in vitro cytotoxicity assays.

  3. Effect of the intercalated cation-exchanged on the properties of nanocomposites prepared by 2-aminobenzene sulfonic acid with aniline and montmorillonite

    Energy Technology Data Exchange (ETDEWEB)

    Toumi, I. [Laboratoire de Chimie Organique, Macromoleculaire et des Materiaux, Universite de Mascara, Bp 763 Mascara 29000 (Algeria); Benyoucef, A., E-mail: [Laboratoire de Chimie Organique, Macromoleculaire et des Materiaux, Universite de Mascara, Bp 763 Mascara 29000 (Algeria); Yahiaoui, A. [Laboratoire de Chimie Organique, Macromoleculaire et des Materiaux, Universite de Mascara, Bp 763 Mascara 29000 (Algeria); Quijada, C. [Departamento de Ingenieria Textil y Papelera, Universidad Politecnica de Valencia, Pza Ferrandiz i Carbonel, E-03801 Alcoy, Alicante (Spain); Morallon, E. [Departamento de Quimica Fisica e Instituto Universitario de Materiales, Universidad de Alicante, Apartado 99, E-03080 Alicante (Spain)


    Polymer/montmorillonite nanocomposites were prepared. Intercalation of 2-aminobenzene sulfonic acid with aniline monomers into montmorillonite modified by cation was followed by subsequent oxidative polymerization of monomers in the interlayer spacing. The clay was prepared by cation exchange process between sodium cation in (M-Na) and copper cation (M-Cu). XRD analyses show the manifestation of a basal spacing (d-spacing) for M-Cu changes depending on the inorganic cation and the polymer intercalated in the M-Cu structure. TGA analyses reveal that polymer/M-Cu composites is less stable than M-Cu. The conductivity of the composites is found to be 10{sup 3} times higher than that for M-Cu. The microscopic examinations including TEM picture of the nanocomposite demonstrated an entirely different and more compatible morphology. Remarkable differences in the properties of the polymers have also been observed by UV-Vis and FTIR, suggesting that the polymer produced with presence of aniline has a higher degree of branching. The electrochemical behavior of the polymers extracted from the nanocomposites has been studied by cyclic voltammetry which indicates the electroactive effect of nanocomposite gradually increased with aniline in the polymer chain.

  4. Cation-Coupled Bicarbonate Transporters


    Aalkjaer, Christian; Boedtkjer, Ebbe; Choi, Inyeong; Lee, Soojung


    Cation-coupled HCO3− transport was initially identified in the mid-1970s when pioneering studies showed that acid extrusion from cells is stimulated by CO2/HCO3− and associated with Na+ and Cl− movement. The first Na+-coupled bicarbonate transporter (NCBT) was expression-cloned in the late 1990s. There are currently five mammalian NCBTs in the SLC4-family: the electrogenic Na,HCO3-cotransporters NBCe1 and NBCe2 (SLC4A4 and SLC4A5 gene products); the electroneutral Na,HCO3-cotransporter NBCn1 ...

  5. The Free Tricoordinated Silyl Cation Problem

    Directory of Open Access Journals (Sweden)

    Čičak, H.


    Full Text Available As the importance and abundance of silicon in our environment is large, it has been thought that silicon might take the place of carbon in forming a host of similar compounds and silicon-based life. However, until today there is no experimental evidence for such a hypothesis and carbon is still unique among the elements in the vast number and variety of compounds it can form. Also, the corresponding derivatives of the two elements show considerable differences in their chemical properties.The essential debate concerning organosilicon chemistry relates to the existence of the free planar tricoordinated silyl cations in condensed phase (R3Si+, in analogy to carbocations (R3C+ which have been known and characterized as free species. Although silyl cations are thermodynamically more stable than their carbon analogs, they are very reactive due to their high inherent electrophilicity and the ability of hypervalent coordination. On the other hand, stabilization by inductive and hyperconjugative effects and larger steric effects of carbocations make them less sensitive to solvation or other environmental effects than silyl cations. Hence, observation of free silyl cations in the condensed phase proved extremely difficult and the actual problem is the question of the degree of the (remaining silyl cation character.The first free silyl cation, trimesitylsilyl cation, and in analogy with it tridurylsilyl cation, were synthesized by Lambert et al. Free silyl cations based on analogy to aromatic ions (homocyclopropenylium and tropylium have also been prepared. However, in these silyl cations the cationic character is reduced by internal π -conjugation. Čičak et al. prepared some silyl-cationic intermediates (Me3Si--CH≡CR+in solid state. With the help of quantum-mechanical calculations it was concluded that these adducts have much more silyl cation than carbocation character.

  6. Effect of the combination of dithiooctanoate monomers and acidic adhesive monomers on adhesion to precious metals, precious metal alloys and non-precious metal alloys. (United States)

    Ikemura, Kunio; Kojima, Katsunori; Endo, Takeshi; Kadoma, Yoshinori


    This study investigated the effect of the combination of a dithiooctanoate monomer and an acidic adhesive monomer on adhesion to precious metals, precious and non-precious metal alloys. From a selection of four dithiooctanoate monomers and six acidic adhesive monomers, 14 experimental primers containing a combination of 5.0 wt% of a dithiooctanoate monomer and 1.0 wt% of an acidic adhesive monomer in acetone were prepared. Tensile bond strengths (TBSs) of MMA-PMMA/TBBO resin to nine kinds of precious metals, precious metal alloys, and non-precious metal alloys after 2,000 thermal cycles were measured. Results showed that there were no significant differences in TBS among the primers to all the precious and non-precious metal adherends tested (p>0.05). Highest TBS values (46.5-55.8 MPa) for bonding to Au alloy, Au-Ag-Pd alloy, Co-Cr alloy, and Ni-Cr alloy were achieved with the primer which contained 5.0 wt% 10-methacryloyloxydecyl 6,8-dithiooctanoate (10-MDDT) and 1.0 wt% 6-methacryloyloxyhexyl phosphonoacetate (6-MHPA). Therefore, 5.0 wt% 10-MDDT and 1.0 wt% 6-MHPA was determined as the optimal combination for bonding to precious metals, precious and non-precious metal alloys.

  7. Interactions of Phospholipid Vesicles with Cationic and Anionic Oligomeric Surfactants. (United States)

    Chen, Yao; Qiao, Fulin; Fan, Yaxun; Han, Yuchun; Wang, Yilin


    This work studied the interactions of 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) with cationic ammonium surfactants and anionic sulfate or sulfonate surfactants of different oligomeric degrees, including cationic monomeric DTAB, dimeric C 12 C 3 C 12 Br 2 , and trimeric DDAD as well as anionic monomeric SDS, dimeric C 12 C 3 C 12 (SO 3 ) 2 , and trimeric TED-(C 10 SO 3 Na) 3 . The partition coefficient P of these surfactants between the DOPC vesicles and water was determined with isothermal titration microcalorimetry (ITC) by titrating concentrated DOPC solution into the monomer solution of these surfactants. It was found that the P value increases with the increase of the surfactant oligomeric degree. Moreover, the enthalpy change and the Gibbs free energy for the transition of these surfactants from water into the DOPC bilayer become more negative with increasing the oligomeric degree. Meanwhile, the calcein release experiment proves that the surfactant with a higher oligomeric degree shows stronger ability of changing the permeability of the DOPC vesicles. Furthermore, the solubilization of the DOPC vesicles by these oligomeric surfactants was studied by ITC, turbidity, and dynamic light scattering, and thus the phase boundaries for the surfactant/lipid mixtures have been determined. The critical surfactant to lipid ratios for the onset and end of the solubilization for the DOPC vesicles derived from the phase boundaries decrease remarkably with increasing the oligomeric degree. Overall, the surfactant with a larger oligomerization degree shows stronger ability in incorporating into the lipid bilayer, altering the membrane permeability and solubilizing lipid vesicles, which provides comprehensive understanding about the effects of structure and shape of oligomeric surfactant molecules on lipid-surfactant interactions.

  8. Ligustrazine monomer against cerebral ischemia-reperfusion injury

    Directory of Open Access Journals (Sweden)

    Hai-jun Gao


    Full Text Available Ligustrazine (2,3,5,6-tetramethylpyrazine is a major active ingredient of the Szechwan lovage rhizome and is extensively used in treatment of ischemic cerebrovascular disease. The mechanism of action of ligustrazine use against ischemic cerebrovascular diseases remains unclear at present. This study summarizes its protective effect, the optimum time window of administration, and the most effective mode of administration for clinical treatment of cerebral ischemia/reperfusion injury. We examine the effects of ligustrazine on suppressing excitatory amino acid release, promoting migration, differentiation and proliferation of endogenous neural stem cells. We also looked at its effects on angiogenesis and how it inhibits thrombosis, the inflammatory response, and apoptosis after cerebral ischemia. We consider that ligustrazine gives noticeable protection from cerebral ischemia/reperfusion injury. The time window of ligustrazine administration is limited. The protective effect and time window of a series of derivative monomers of ligustrazine such as 2-[(1,1-dimethylethyloxidoimino]methyl]-3,5,6-trimethylpyrazine, CXC137 and CXC195 after cerebral ischemia were better than ligustrazine.


    Khym, J.X.


    The chromatographic separation of fission product cations is discussed. By use of this method a mixture of metal cations containing Zr, Cb, Ce, Y, Ba, and Sr may be separated from one another. Mentioned as preferred exchange adsorbents are resins containing free sulfonic acid groups. Various eluants, such as tartaric acid, HCl, and citric acid, used at various acidities, are employed to effect the selective elution and separation of the various fission product cations.

  10. Use of Monomer Fraction Data in the Parametrization of Association Theories

    DEFF Research Database (Denmark)

    Kontogeorgis, Georgios; Tsivintzelis, Ioannis; von Solms, Nicolas


    the monomer fraction of hydrogen bonding compounds and their mixtures. Monomer fraction data are obtained from spectroscopic measurements and they are available for a few compounds such as pure water and alcohols as well as for some alcohol–alkane and similar mixtures. These data are useful...... “improved” model parameters can be obtained if monomer fraction data are included in the parameter estimation together with vapor pressures and liquid densities. The expression “improved” implies parameters which can represent several pure compound properties as well as monomer fraction data for pure......, liquid densities and monomer fractions of water and alcohols. The 4C scheme is the best choice for water, while for methanol there is small difference between the 2B and 3B association schemes....

  11. Afrikaans Syllabification Patterns

    Directory of Open Access Journals (Sweden)

    Tilla Fick


    Full Text Available In contrast to English, automatic hyphenation by computer of Afrikaans words is a problem that still needs to be addressed, since errors are still often encountered in printed text. An initial step in this task is the ability to automatically syllabify words. Since new words are created continuously by joining words, it is necessary to develop an “intelligent” technique for syllabification. As a first phase of the research, we consider only the orthographic information of words, and disregard both syntactic and morphological information. This approach allows us to use machine-learning techniques such as artificial neural networks and decision trees that are known for their pattern recognition abilities. Both these techniques are trained with isolated patterns consisting of input patterns and corresponding outputs (or targets that indicate whether the input pattern should be split at a certain position, or not. In the process of compiling a list of syllabified words from which to generate training data for the  syllabification problem, irregular patterns were identified. The same letter patterns are split differently in different words and complete words that are spelled identically are split differently due to meaning. We also identified irregularities in and between  the different dictionaries that we used. We examined the influence range of letters that are involved in irregularities. For example, for their in agter-ente and vaste-rente we have to consider three letters to the left of r to be certain where the hyphen should be inserted. The influence range of the k in verstek-waarde and kleinste-kwadrate is four to the left and three to the right. In an analysis of letter patterns in Afrikaans words we found that the letter e has the highest frequency overall (16,2% of all letters in the word list. The frequency of words starting with s is the highest, while the frequency of words ending with e is the highest. It is important to

  12. Detection and architecture of small heat shock protein monomers.

    Directory of Open Access Journals (Sweden)

    Pierre Poulain

    Full Text Available BACKGROUND: Small Heat Shock Proteins (sHSPs are chaperone-like proteins involved in the prevention of the irreversible aggregation of misfolded proteins. Although many studies have already been conducted on sHSPs, the molecular mechanisms and structural properties of these proteins remain unclear. Here, we propose a better understanding of the architecture, organization and properties of the sHSP family through structural and functional annotations. We focused on the Alpha Crystallin Domain (ACD, a sandwich fold that is the hallmark of the sHSP family. METHODOLOGY/PRINCIPAL FINDINGS: We developed a new approach for detecting sHSPs and delineating ACDs based on an iterative Hidden Markov Model algorithm using a multiple alignment profile generated from structural data on ACD. Using this procedure on the UniProt databank, we found 4478 sequences identified as sHSPs, showing a very good coverage with the corresponding PROSITE and Pfam profiles. ACD was then delimited and structurally annotated. We showed that taxonomic-based groups of sHSPs (animals, plants, bacteria have unique features regarding the length of their ACD and, more specifically, the length of a large loop within ACD. We detailed highly conserved residues and patterns specific to the whole family or to some groups of sHSPs. For 96% of studied sHSPs, we identified in the C-terminal region a conserved I/V/L-X-I/V/L motif that acts as an anchor in the oligomerization process. The fragment defined from the end of ACD to the end of this motif has a mean length of 14 residues and was named the C-terminal Anchoring Module (CAM. CONCLUSIONS/SIGNIFICANCE: This work annotates structural components of ACD and quantifies properties of several thousand sHSPs. It gives a more accurate overview of the architecture of sHSP monomers.

  13. Mathematical modeling of cross-linking monomer elution from resin-based dental composites. (United States)

    Manojlovic, Dragica; Radisic, Marina; Lausevic, Mila; Zivkovic, Slavoljub; Miletic, Vesna


    Elution of potentially toxic substances, including monomers, from resin-based dental composites may affect the biocompatibility of these materials in clinical conditions. In addition to the amounts of eluted monomers, mathematical modeling of elution kinetics reveals composite restorations as potential chronic sources of leachable monomers. The aim of this work was to experimentally quantify elution of main cross-linking monomers from four commercial composites and offer a mathematical model of elution kinetics. Composite samples (n = 7 per group) of Filtek Supreme XT (3M ESPE), Tetric EvoCeram (Ivoclar Vivadent), Admira (Voco), and Filtek Z250 (3M ESPE) were prepared in 2-mm thick Teflon moulds and cured with halogen or light-emitting diode light. Monomer elution in ethanol and water was analyzed using high-performance liquid chromatography up to 28 days postimmersion. The mathematical model was expressed as a sum of two exponential regression functions representing the first-order kinetics law. Elution kinetics in all cases followed the same mathematical model though differences in rate constants as well as the extent of monomer elution were material-, LCU-, medium-dependent. The proposed mechanisms of elution indicate fast elution from surface and subsurface layers and up to 100 times slower monomer extraction from the bulk polymer. Copyright © 2012 Wiley Periodicals, Inc.

  14. Investigation on physical behavior of styrene wood-polymer in different concentrations of monomer

    Directory of Open Access Journals (Sweden)

    maryam ghorbani


    Full Text Available This research was conducted to study the effect of different concentrations of styrene lumen monomer on the physical properties of beech wood. Physical test samples were prepared according to ASTM-D1037 standard and treated with vacuum-pressure method at five concentration levels; 0, 40, 60, 80 and 100 percent of soluble monomer. For polymerization, treated samples were heated in oven for two 24-hour period at 90 and 103ºC respectively. Monomer and polymer absorption, density variation, water absorption, swelling and anti-swelling efficiency (ASE were determined. According to the results, Monomer and polymer absorption were increment by monomer concentration increase, and they were reported 38.2% and 26% in highest level. With polymer absorption enhancement, density of wood increased from 0/63g/cm³ in control to 0/91g/cm³ in the highest monomer concentration level that reduces pores in wood-polymer structure. Absorbed polymer enhancement decreased hydrophilicity and dimensional changes of treated samples, so that water absorption and swelling volume of the samples saturated with 100% concentration of monomer were decreased 64% and 45.3% after the longest immersion time. Highest Anti-swelling efficiency of Styrene-saturated samples was determined 56.15% in the maximum concentration level of treatment.

  15. Surface forces between hydrophilic silica surfaces in a moisture-sensitive oleophilic diacrylate monomer liquid (United States)

    Ito, Shunya; Kasuya, Motohiro; Kurihara, Kazue; Nakagawa, Masaru


    We measured the surface forces generated between fused silica surfaces in a low-viscosity oleophilic diacrylate monomer for reliably repeated ultraviolet (UV) nanoimprinting, and studied the influence of water in monomer liquids on the forces. Fused silica surfaces, with a static contact angle of 52.6 ± 1.7° for water, owing to the low degree of hydroxylation, hardly showed reproducible surface forces with repeated scan cycles, comprising approach and separation, even in an identical liquid monomer medium with both of low and high water content. The monomer liquid with a high water content of approximately 420 ppm showed a greater tendency to increase the surface forces at longer surface-surface distances compared with the monomer liquid with a low water content of approximately 60 ppm. On the other hand, silica surfaces with a water contact angle of < 5° after exposure to vacuum UV (VUV) light under a reduced air pressure showed reproducible profiles of surfaces forces using the monomer with a low water concentration of approximately 60 ppm for repeated surface forces scan cycles even in separately prepared silica surfaces, whilst they showed less reproducible profiles in the liquids with high water content of 430 ppm. These results suggested that water possibly adsorbed on the hydrophilic and hydrophobic silica surfaces in the monomer liquid of the high water concentration influenced the repeatability of the surface forces profiles.

  16. Optimization of divalent cation in Saccharomyces pastorianus ...

    African Journals Online (AJOL)

    Cassava starch fermentations were conducted in batch cultures to optimize the effect of divalent cations on ethanol production with Saccharomyces pastorianus using the central composite rotatable response surface design. Divalent cations used were magnesium (Mg2+), zinc (Zn2+) and calcium (Ca2+). Maximum ethanol ...

  17. Characterization of urethane-dimethacrylate derivatives as alternative monomers for the restorative composite matrix. (United States)

    Barszczewska-Rybarek, Izabela M


    The aim was accomplished by a comparative analysis of the physicochemical properties of urethane-dimethacrylate (UDMA) monomers and their homopolymers with regard to the properties of basic dimethacrylates used presently in dentistry. The homologous series of UDMA were obtained from four oligoethylene glycols monomethacrylates (HEMA, DEGMMA, TEGMMA and TTEGMMA) and six diisocyanates (HMDI, TMDI, IPDI, CHMDI, TDI and MDI). Photopolymerization was light-initiated with the camphorquinone/tertiary amine system. Monomers were tested for viscosity and density. Flexural strength, flexural modulus, hardness, water sorption and polymerization shrinkage of the polymers were studied. The glass transition temperature and the degree of conversion were also discussed. HEMA/IPDI appeared to be the most promising alternative monomer. The monomer exhibited a lower viscosity and achieved higher degree of conversion, the polymer had lower water sorption as well as higher modulus, glass temperature and hardness than Bis-GMA. The polymer of DEGMMA/CHMDI exhibited lower polymerization shrinkage, lower water sorption and higher hardness, however it exhibited lower modulus when compared to HEMA/TMDI. The remaining monomers obtained from HEMA were solids. Monomers with longer TEGMMA and TTEGMMA units polymerized to rubbery networks with high water sorption. The viscosity of all studied UDMA monomers was too high to be used as reactive diluents. The systematic, comparative analysis of the homologous UDMA monomers and corresponding homopolymers along with their physico-mechanical properties are essential for optimizing the design process of new components desirable in dental formulations. Some of the studied UDMA monomers may be simple and effective alternative dimethacrylate comonomers. Copyright © 2014 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

  18. The potential dermal irritating effect of residual (meth)acrylic monomers in pressure sensitive adhesive tapes. (United States)

    Tokumura, Fumio; Matsui, Tetsuya; Suzuki, Yasuko; Sado, Masashi; Taniguchi, Masaharu; Kobayashi, Ichiro; Kamiyama, Masashi; Suda, Shin; Nakamura, Atsushi; Yamazaki, Yuhiro; Yamori, Akira; Igarashi, Ryosuke; Kawai, Jun; Oka, Keiji


    It is generally thought that residual unpolymerized (meth)acrylic monomers commonly found in pressure sensitive adhesive tapes for medical use may cause dermal irritation, but a systematic study has never been carried out. Therefore, we assessed the potential dermal irritating effect of residual (meth)acrylic monomers. We studied seven acrylic monomers, acrylic acid (AA), methyl acrylate (MA), ethyl acrylate (EA), n-butyl acrylate (n-BA), n-hexyl acrylate (n-HA), 2-ethylhexyl acrylate (2-EHA) and 2-hydroxyethyl acrylate (HEA), as well as three methacrylic monomers, methacrylic acid (MAA), methyl methacrylate (MMA) and 2-hydroxyethyl methacrylate (2-HEMA). We first examined their cytotoxic effect on a cultured dermis model using the MTT method to determine their EC(50) and then performed a primary irritation test in rabbits using the monomers at three different concentrations (i.e., EC(50) , one-tenth EC(50) and 10 times EC(50)). Marked variations were found in cytotoxic and dermal irritating activities among the (meth)acrylic monomers tested. HEA exhibited the most potent dermal irritation having the lowest erythema dose (the concentration which gives a primary dermal irritation index of 1.00) of 460 ppm. But the other monomers exhibited less potent dermal irritation (lowest erythema doses > or =1000 ppm). For the monomers, significant correlation was found between cytotoxic activity and in vivo dermal irritating activity. Our results show that residual unpolymerized (meth)acrylic monomers in adhesive tapes are unlikely to induce skin irritation except for HEA. This study also suggests that cultured skin models are extremely useful as a screening method for chemical substances that could potentially cause dermal irritating activity.

  19. Irradiation of monomer-impregnated sawdust to produce new construction materials

    International Nuclear Information System (INIS)

    de Burillo, V.G.; Loyola, V.V.M.; Echenique-Manrique, R.; Galvez, C.L.; Azamar, B.J.A.


    A new construction material was prepared by gamma radiation with or without heat curing, of methyl methacrylate monomer mixed with foaming agent and pine sawdust. The composite with the greatest hardness, bending strength, dimensional stability and lowest water absorption was prepared at a total dose of 1.0 Mrad, a ratio of sawdust/monomer of 8 g/20 ml, and VAZO to monomer of 1.5 percent. The composite appears to be a promising material for use in housing construction for items such as window and door frames, studs, wall partitions, furniture components, etc. (U.S.)

  20. Pengaruh radiasi kopolimer dengan monomer metil metakrilat (MMA pada lateks sebagai lem terhadap sifat kuat rekat

    Directory of Open Access Journals (Sweden)

    Sri Nadilah


    Full Text Available Vulcanizing process of copolymer radiation with methyl methacrylate monomer 75 (per hundred parts of rubbers of natural latex was done, and to application like adhesive for rubber shoes. This research was centered to find the influence of radiation copolymerization process of methyl methacrylate monomer, with the methods to compare the peel strength with natural latex. Natural latex was copolymer radiation processed with methyl methyl methacrylate monomer 75 (per hundred parts of rubbers, the radiation doses 5 kGy have peel strength as adhesives on rubber shoe more than natural latex, and the result fulfill the requirements of SNI. 12. 0172-1987 “Super Kanvas Umum”.

  1. Synthesis and characterization of novel organotin carboxylate maleimide monomers and copolymers

    Directory of Open Access Journals (Sweden)


    Full Text Available Two novel tributyltin carboxylate maleimide monomers, tributyltin(maleimidoacetate and tributyltin(4-maleimidobenzoate, were synthesized by condensation reaction of maleimidoacetic acid or 4-maleimidobenzoic acid with bis(tributyltin oxide. Copolymerization of these monomers with styrene was carried in dioxane at 70°C using asobisisobutyronitrile as free radical initiator. The structures of monomers and copolymers were confirmed by FT-IR (Fourier Transform Infrared, 1H and 13C NMR (nuclear magnetic resonance spectroscopy and elemental analysis. The copolymers were characterized by solubility and thermal analysis.

  2. Dynamic conformations of nucleophosmin (NPM1 at a key monomer-monomer interface affect oligomer stability and interactions with granzyme B.

    Directory of Open Access Journals (Sweden)

    Wei D Duan-Porter

    Full Text Available Nucleophosmin (NPM1 is an abundant, nucleolar tumor antigen with important roles in cell proliferation and putative contributions to oncogenesis. Wild-type NPM1 forms pentameric oligomers through interactions at the amino-terminal core domain. A truncated form of NPM1 found in some hepatocellular carcinoma tissue formed an unusually stable oligomer and showed increased susceptibility to cleavage by granzyme B. Initiation of translation at the seventh methionine generated a protein (M7-NPM that shared all these properties. We used deuterium exchange mass spectrometry (DXMS to perform a detailed structural analysis of wild-type NPM1 and M7-NPM, and found dynamic conformational shifts or local "unfolding" at a specific monomer-monomer interface which included the β-hairpin "latch." We tested the importance of interactions at the β-hairpin "latch" by replacing a conserved tyrosine in the middle of the β-hairpin loop with glutamic acid, generating Y67E-NPM. Y67E-NPM did not form stable oligomers and further, prevented wild-type NPM1 oligomerization in a dominant-negative fashion, supporting the critical role of the β-hairpin "latch" in monomer-monomer interactions. Also, we show preferential cleavage by granzyme B at one of two available aspartates (either D161 or D122 in M7-NPM and Y67E-NPM, whereas wild-type NPM1 was cleaved at both sites. Thus, we observed a correlation between the propensity to form oligomers and granzyme B cleavage site selection in nucleophosmin proteins, suggesting that a small change at an important monomer-monomer interface can affect conformational shifts and impact protein-protein interactions.

  3. Exploring backbone-cation alkyl spacers for multi-cation side chain anion exchange membranes (United States)

    Zhu, Liang; Yu, Xuedi; Hickner, Michael A.


    In order to systematically study how the arrangement of cations on the side chain and length of alkyl spacers between cations impact the performance of multi-cation AEMs for alkaline fuel cells, a series of polyphenylene oxide (PPO)-based AEMs with different cationic side chains were synthesized. This work resulted in samples with two or three cations in a side chain pendant to the PPO backbone. More importantly, the length of the spacer between cations varied from 3 methylene (-CH2-) (C3) groups to 8 methylene (C8) groups. The highest conductivity, up to 99 mS/cm in liquid water at room temperature, was observed for the triple-cation side chain AEM with pentyl (C5) or hexyl (C6) spacers. The multi-cation AEMs were found to have decreased water uptake and ionic conductivity when the spacer chains between cations were lengthened from pentyl (C5) or hexyl (C6) to octyl (C8) linking groups. The triple-cation membranes with pentyl (C5) or hexyl (C6) groups between cations showed greatest stability after immersion in 1 M NaOH at 80 °C for 500 h.

  4. PPP and CNDO calculations on the free radical cations of styrene

    International Nuclear Information System (INIS)

    Helmstreit, W.


    Open shell calculations were carried out on the styrene monomer radical cation St/sup +./, the associated dimer radical cation St 2 /sup +./, and the covalently bonded dimer radical cation (St-St)/sup +./, using a PPP and CNDO/INDO method. St 2 /sup +./ was assumed to have a sandwich structure with different overlapping of the π-orbitals. Calculated transition energies are in agreement with the experimental data. The calculations suggest that St 2 /sup +./ has electronic transitions in the IR and UV/VIS range whereas those of (St-St)/sup +./ lie only within the UV/VIS range. The molecular diagrams of the investigated ions are discussed in the framework of general structure principles. The change of the total energy calculated for the reaction steps St/sup +./ + St → St 2 + → (St-St) + as well as the similarity of the electronic structures of St 2 /sup +./ and (St-St)/sup +./ suggest that the former is a precursor of the latter ion. (author)

  5. Electron beam induced cationic polymerization of epoxy resins. Dependence of Tg on conversion

    International Nuclear Information System (INIS)

    Degrand, H.; Cazaux, F.; Coqueret, X.


    Complete text of publication follows. The high-energy radiation curing of monomer blends polymerizing by a free radical or by a cationic mechanism receives increasing attention in the perspective of high performance composite materials. In the present work, we have focused our attention on epoxy formulations as models of the matrices polymerizing by a cationic mechanism that could be used in fiber-reinforced composites for aerospace applications. We have examined the progress of the electron beam (EB) induced polymerization of diglycidylether of bisphenol A (DGEBA) in the presence of a diaryliodonium salt (DAIS) by FTIR spectroscopy and by dynamic mechanical thermal analysis (DMA). The obtained results allow to draw the gradual increase of the temperature for the network thermomechanical transition (T a , associated with the glass transition temperature T g ) over a broad range of conversion (p) and reveal a peculiar behavior at high conversion. In this domain (p > 0.90), the material's T g is shown to decrease when conversion approaches unity. Moreover, the post-irradiation thermal treatment of the materials, that generally yields effective 'dark curing', appears to induce a decrease of T g , with an amplitude correlated with the amount of DAIS in the formulation. Owing to the particular nature of the propagating centers in cationic polymerisation, the thermal relaxation of ionic clusters trapped in the glassy matrix can be reasonably invoked as a possible cause for this behavior

  6. Intracellular trafficking mechanism of cationic phospholipids including cationic liposomes in HeLa cells. (United States)

    Un, K; Sakai-Kato, K; Goda, Y


    The development of gene delivery methods is essential for the achievement of effective gene therapy. Elucidation of the intracellular transfer mechanism for cationic carriers is in progress, but there are few reports regarding the intracellular trafficking processes of the cationic phospholipids taken up into cells. In the present work, the trafficking processes of a cationic phospholipid (1,2-dioleoyl-3-trimethylammonium-propane, DOTAP) were investigated from intracellular uptake to extracellular efflux using cationic liposomes in vitro. Following intracellular transport of liposomes via endocytosis, DOTAP was localized in the endoplasmic reticulum, Golgi apparatus, and mitochondria. Moreover, the proteins involved in DOTAP intracellular trafficking and extracellular efflux were identified. In addition, helper lipids of cationic liposomes were found to partially affect this intracellulartrafficking. These findings might provide valuable information for designing cationic carriers and avoiding unexpected toxic side effects derived from cationic liposomal components.

  7. Cation transport in isomeric pentanes

    International Nuclear Information System (INIS)

    Gyoergy, Istvan; Gee, Norman; Freeman, G.R.


    The cation mobility μsub(+) is measured in n-pentane, isopentane, neo-pentane, and mixtures of n- and neo-pentane over conditions from the normal liquid, through the critical fluid, to the low density gas. Most of the liquid data correlate with the reduced temperature T/Tsub(c). The T/Tsub(c) reflects free volume and viscosity changes. Comparison is made to neutral molecule diffusion. The transition from viscosity control of mobility in the liquid to density control in the dilute gas occurs over the reduced viscosity region 3 > eta/etasub(c) > 0.6, which corresponds to the reduced density region 1.9 > eta/etasub(c) > 0.5. In the saturated gas etaμsub(+) is similar in all pentanes, but iso- approximately> n- > neo-pentane. At constant density dμsub(+)/dT >= 0 for gases. The average gas nμsub(+) is similar in all pentanes, but iso- approximately> n- > neo-pentane. At constant density dμsub(+)/dT >= 0 for gases. The average momentum transfer cross sections in the n-/neo-pentane mixtures are similar to those in neo-pentane at low T but similar to those in n-pentane at high T. The present findings are combined with previous electron mobility data in addressing the effect of hydrocarbon molecular (external) shape on the electric breakdown strength of gases

  8. Cationic Bolaamphiphiles for Gene Delivery (United States)

    Tan, Amelia Li Min; Lim, Alisa Xue Ling; Zhu, Yiting; Yang, Yi Yan; Khan, Majad


    Advances in medical research have shed light on the genetic cause of many human diseases. Gene therapy is a promising approach which can be used to deliver therapeutic genes to treat genetic diseases at its most fundamental level. In general, nonviral vectors are preferred due to reduced risk of immune response, but they are also commonly associated with low transfection efficiency and high cytotoxicity. In contrast to viral vectors, nonviral vectors do not have a natural mechanism to overcome extra- and intracellular barriers when delivering the therapeutic gene into cell. Hence, its design has been increasingly complex to meet challenges faced in targeting of, penetration of and expression in a specific host cell in achieving more satisfactory transfection efficiency. Flexibility in design of the vector is desirable, to enable a careful and controlled manipulation of its properties and functions. This can be met by the use of bolaamphiphile, a special class of lipid. Unlike conventional lipids, bolaamphiphiles can form asymmetric complexes with the therapeutic gene. The advantage of having an asymmetric complex lies in the different purposes served by the interior and exterior of the complex. More effective gene encapsulation within the interior of the complex can be achieved without triggering greater aggregation of serum proteins with the exterior, potentially overcoming one of the great hurdles faced by conventional single-head cationic lipids. In this review, we will look into the physiochemical considerations as well as the biological aspects of a bolaamphiphile-based gene delivery system.

  9. The effect of monomers on the formulation of polymeric nanocapsules based on polyureas and polyamides. (United States)

    Montasser, I; Briançon, S; Fessi, H


    Formulation of nanocapsules based on polyureas and polyamides have been tested using a patented process. This method based on polycondensation reaction of two complementary monomers and spontaneous formation of oil in water emulsion, is an alternative concept to the known technique based on the same type of reaction used for the formulation of microcapsules, and in which the lipophilic monomer was emulsified in the organic phase before the formation of the polymeric membrane. Nanocapsules can be prepared from different monomers. Wall based on cross-linked polymer contributes to the stability of nanocapsules during and after formulation. The permeability of the polymeric wall is related to its crystallinity and contributes to the growth of nanocapsule membrane by the diffusion of the hydrophilic monomers to get stable colloidal suspensions.

  10. Determination of caprolactam and residual vinyl caprolactam monomer in soluplus by mixed mode gel permeation chromatography. (United States)

    Soman, Ashish; Jerfy, Madhuri


    Soluplus, a graft copolymer of polyethylene glycol, vinyl caprolactam and vinyl acetate, is designed to solubilize poorly soluble active pharmaceutical ingredients. A straightforward aqueous gel permeation chromatography method that exploits both size exclusion and adsorption modes of separation was used to separate and quantify the related residual vinyl caprolactam monomer and caprolactam impurity present in Soluplus. This methodology offers a single step analysis of caprolactam and the residual vinyl caprolacatam monomer, yielding similar results to reversed-phase chromatography measurements, which are time-consuming and may involve multi-step sample preparation. The results of this study demonstrate that gel permeation chromatography provides a viable option to traditional reversed-phase chromatography in the quantitative analysis of residual caprolactam and vinyl caprolactam monomers and can be extended to other monomer-polymeric systems.

  11. Resin adhesion strengths to zirconia ceramics after primer treatment with silane coupling monomer or oligomer. (United States)

    Okada, Masahiro; Inoue, Kazusa; Irie, Masao; Taketa, Hiroaki; Torii, Yasuhiro; Matsumoto, Takuya


    Resin bonding to zirconia ceramics is difficult to achieve using the standard methods for conventional silica-based dental ceramics, which employ silane coupling monomers as primers. The hypothesis in this study was that a silane coupling oligomer -a condensed product of silane coupling monomers- would be a more suitable primer for zirconia. To prove this hypothesis, the shear bond strengths between a composite resin and zirconia were compared after applying either a silane coupling monomer or oligomer. The shear bond strength increased after applying a non-activated ethanol solution of the silane coupling oligomer compared with that achieved when applying the monomer. Thermal treatment of the zirconia at 110°C after application of the silane coupling agents was essential to improve the shear bond strength between the composite resin cement and zirconia.

  12. Neodymium Catalyst for the Polymerization of Dienes and Polar Vinyl Monomers. (United States)

    Kularatne, Ruvanthi N; Yang, Annie; Nguyen, Hien Q; McCandless, Gregory T; Stefan, Mihaela C


    Ziegler-Natta catalysts have played a major role in industry for the polymerization of dienes and vinyl monomers. However, due to the deactivation of the catalyst, this system fails to polymerize polar vinyl monomers such as vinyl acetate, methyl methacrylate, and methyl acrylate. Herein, a catalytic system composed of NdCl 3 ⋅3TEP/TIBA is reported, which promotes a quasi-living polymerization of dienes and is also active for the homopolymerization of polar vinyl monomers. Additionally, this catalytic system generates polymyrcene-b-polyisoprene and poly(myrcene)-b-poly(methyl methacrylate) diblock copolymers by sequential monomer addition. To encourage the replacement of petroleum-based polymers by environmentally benign biobased polymers, polymerization of β-myrcene is demonstrated with a catalytic activity of ≈106 kg polymer mol Nd -1 h -1 . © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. A comment on water’s structure using monomer fraction data and theories

    DEFF Research Database (Denmark)

    Liang, Xiaodong; Maribo-Mogensen, Bjørn; Tsivintzelis, Ioannis


    Monomer fraction data for water (and other compounds) can provide useful information about their structure and can be used in “advanced” equations of state, which account explicitly for association phenomena. Recent findings about the performance of association theories in representing the monomer...... fraction of water are reviewed. Three such theories are considered and all of them perform qualitatively similar. They can all represent phase equilibria for water solutions qualitatively well but with parameters which are not in good agreement with Luck’s famous monomer fraction data. While this could set...... the theoretical basis of these theories in doubt, we also show in this work that the findings with these association models are in agreement with a recently presented theory which links monomer fraction to dielectric constants. This new theory, like the three thermodynamic models, predicts more hydrogen bonding...

  14. Evaluation of UV Curing Properties of Mixture Systems with Differently Sized Monomers

    Directory of Open Access Journals (Sweden)

    Ji-Won Park


    Full Text Available Ultraviolet (UV curing is a photopolymerization technique resulting in a three-dimensional polymer network from monomers and oligomers after exposure to UV light, which is often used for fusion industry. However, shrinkage is an issue that needs to be resolved. Studies of single substances have been extensively conducted, but studies of mixture systems have not sufficiently been undertaken. In this study, we evaluate the shrinkage phenomenon by studying a monomer/monomer binary system and monomer/macromer composite systems. Shrinkage tends to increase when compounds varying in size are used. Similar to the shrinkage phenomenon, the curing rate is also relatively higher in such systems. These synergistic effects are evaluated to be due to the nano-porous effect, and vary with the composition ratio and material structure.

  15. Effect of food simulating liquids on release of monomers from two dental resin composites

    Directory of Open Access Journals (Sweden)

    Ghavam M


    Full Text Available "nBackground and Aims: The elution of residual monomers from cured dental composites to oral cavity has a harmful effect on human health and can affect their clinical durability. The purpose of this study was to evaluate the amount of eluted monomers (Bis-GMA, TEGDMA, UDMA from two types of composites (Gradia and P60 after exposure to food simulating liquids such as ethanol (25, 50, 75 % and heptane 50 % for 24 hours and 7 days. "nMaterials and Methods: Forty specimens of each composite were prepared. Equal numbers of each composite were immersed in tubes containing 2cc volumes of 25, 50, 75 % ethanole and 50 % heptane. The amount of eluted monomers in standard condition such as Bis-GMA, TEGDMA and UDMA was measured by GC/MS (Gas Chromatography/Mass Spectroscopy and results were statistically analysed by three way and one way ANOVA. P<0.05 was considered as the level of significancy. "nResults: The results showed that Gradia released more TEGDMA than P60. In assessing the effect of environment, the result showed that ethanol caused releasing monomers more than heptane and the concentration rate of 75 % ethanole resulted in most releasing of monomers. In assessing the effect of time, the observation showed that more monomers were released 7 days compared to 24 hours. Bis-GMA and UDMA were not detected in any solutions in these conditions. "nConclusion: Ethanole caused more release of monomers than heptane and 75 % ethanole released the most amount of monomers. Gradia released more amount of TEGDMA than P60.

  16. Triptycene-based ladder monomers and polymers, methods of making each, and methods of use

    KAUST Repository

    Pinnau, Ingo


    Embodiments of the present disclosure provide for a triptycene-based A-B monomer, a method of making a triptycene-based A-B monomer, a triptycene-based ladder polymer, a method of making a triptycene-based ladder polymers, a method of using triptycene-based ladder polymers, a structure incorporating triptycene-based ladder polymers, a method of gas separation, and the like.

  17. Radiation Induced Crosslinking of Polyethylene in the Presence of Bifunctional Vinyl Monomers

    DEFF Research Database (Denmark)

    Joshi, M. S.; Singer, Klaus Albert Julius; Silverman, J.


    Several reports have been published showing that the radiation induced grafting of bifunctional vinyl monomers to low density polyethylene results in a product with an unusually high density of crosslinks. The same grafting reactions are shown to reduce the incipient gel dose by more than a factor...... of fifty. This paper is concerned with the apparent crosslinking produced by the radiation grafting of two monomers to polyethylene: acrylic acid and acrylonitrile....

  18. Oxidative pyrolysis of polystyrene into styrene monomers in an autothermal fixed-bed catalytic reactor. (United States)

    Sun, Hui; Rosenthal, Corey; Schmidt, Lanny D


    Styrene monomer recovery: A selective stream of styrene from fast pyrolysis of polystyrene is obtained with an autothermal fixed-bed reactor containing noble-metal (Rh, Pt) catalysts. Autothermal fast pyrolysis of polystyrene is an efficient means of recovering monomers from waste polystyrene in a continuous, high-throughput process without external heating. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Inhibition of odontogenic differentiation of human dental pulp cells by dental resin monomers


    Kwon, Ji Hyun; Park, Hee Chul; Zhu, Tingting; Yang, Hyeong-Cheol


    Background Dental resin monomers that are leached from the resin matrix due to incomplete polymerization can affect the viability and various functions of oral tissues and cells. In this study, the effects of triethylene glycol dimethacrylate (TEGDMA) and 2-hydroxyethyl methacrylate (HEMA) on odontogenic differentiation of human dental pulp cells (HDPCs) were examined. To mimic clinical situations, dental pulp cells were treated with resin monomers for 24?h prior to the analysis of alkaline p...

  20. Qualitative and quantitative analysis of monomers in polyesters for food contact materials. (United States)

    Brenz, Fabrian; Linke, Susanne; Simat, Thomas


    Polyesters (PESs) are gaining more importance on the food contact material (FCM) market and the variety of properties and applications is expected to be wide. In order to acquire the desired properties manufacturers can combine several FCM-approved polyvalent carboxylic acids (PCAs) and polyols as monomers. However, information about the qualitative and quantitative composition of FCM articles is often limited. The method presented here describes the analysis of PESs with the identification and quantification of 25 PES monomers (10 PCA, 15 polyols) by HPLC with diode array detection (HPLC-DAD) and GC-MS after alkaline hydrolysis. Accurate identification and quantification were demonstrated by the analysis of seven different FCM articles made of PESs. The results explained between 97.2% and 103.4% w/w of the polymer composition whilst showing equal molar amounts of PCA and polyols. Quantification proved to be precise and sensitive with coefficients of variation (CVs) below 6.0% for PES samples with monomer concentrations typically ranging from 0.02% to 75% w/w. The analysis of 15 PES samples for the FCM market revealed the presence of five different PCAs and 11 different polyols (main monomers, co-monomers, non-intentionally added substances (NIAS)) showing the wide variety of monomers in modern PESs. The presented method provides a useful tool for commercial, state and research laboratories as well as for producers and distributors facing the task of FCM risk assessment. It can be applied for the identification and quantification of migrating monomers and the prediction of oligomer compositions from the identified monomers, respectively.

  1. ENDOR and ESEEM of the 15N labelled radical cations of chlorophyll a and the primary donor P 700 in photosystem I (United States)

    Käβ, H.; Bittersmann-Weidlich, E.; Andréasson, L.-E.; Bönigk, B.; Lubitz, W.


    The hyperfine couplings of the nitrogen nuclei in the radical cations of both 15N-labelled chlorophyll a and the primary donor P 700 in Photosystem I of Synechococcus elongatus and spinach ( Spinacea oleracea) in frozen solutions were investigated by ENDOR and, for confirmation, by two-dimensional ESEEM techniques. In addition, 1H ENDOR experiments were performed on these compounds. The experimental 15N hyperfine couplings of the chlorophyll a radical cation are compared with theoretical ones obtained by RHF-INDO/SP calculations and with the respective hyperfine couplings in the closely related 15N-bacteriochlorophyll a radical cation. Based on the observed 15N and 1H hyperfine couplings two possible models are discussed for P 700+: (a) the special pair model with a strongly asymmetric spin density distribution over the dimer halves; (b) the model of a strongly perturbed chlorophyll a monomer.

  2. Residual monomer content determination in some acrylic denture base materials and possibilities of its reduction

    Directory of Open Access Journals (Sweden)

    Kostić Milena


    Full Text Available Background/Aim. Polymethyl methacrylate is used for producing a denture basis. It is a material made by the polymerization process of methyl methacrylate. Despite of the polymerization type, there is a certain amount of free methyl methacrylate (residual monomer incorporated in the denture, which can cause irritation of the oral mucosa. The aim of this study was to determine the amount of residual monomer in four different denture base acrylic resins by liquid chromatography and the possibility of its reduction. Methods. After the polymerization, a postpolymerization treatment was performed in three different ways: in boiling water for thirty minutes, with 500 W microwaves for three minutes and in steam bath at 22º C for one to thirty days. Results. The obtained results showed that the amount of residual monomer is significantly higher in cold polymerizing acrylates (9.1-11%. The amount of residual monomer after hot polymerization was in the tolerance range (0.59- 0.86%. Conclusion. The obtained results denote a low content of residual monomer in the samples which have undergone postpolymerization treatment. A lower percent of residual monomer is established in samples undergone a hot polymerization.

  3. Scattering properties of alumina particle clusters with different radius of monomers in aerocraft plume (United States)

    Li, Jingying; Bai, Lu; Wu, Zhensen; Guo, Lixin; Gong, Yanjun


    In this paper, diffusion limited aggregation (DLA) algorithm is improved to generate the alumina particle cluster with different radius of monomers in the plume. Scattering properties of these alumina clusters are solved by the multiple sphere T matrix method (MSTM). The effect of the number and radius of monomers on the scattering properties of clusters of alumina particles is discussed. The scattering properties of two types of alumina particle clusters are compared, one has different radius of monomers that follows lognormal probability distribution, another has the same radius of monomers that equals the mean of lognormal probability distribution. The result show that the scattering phase functions and linear polarization degrees of these two types of alumina particle clusters are of great differences. For the alumina clusters with different radius of monomers, the forward scatterings are bigger and the linear polarization degree has multiple peaks. Moreover, the vary of their scattering properties do not have strong correlative with the change of number of monomers. For larger booster motors, 25-38% of the plume being condensed alumina. The alumina can scatter radiation from other sources present in the plume and effect on radiation transfer characteristics of plume. In addition, the shape, size distribution and refractive index of the particles in the plume are estimated by linear polarization degree. Therefore, accurate scattering properties calculation is very important to decrease the deviation in the related research.

  4. Spectrophotometric studies on cation-cation interactions between Np(V) and Th(IV) cations in nitric acid medium

    International Nuclear Information System (INIS)

    Verma, P.K.; Pathak, P.N.; Bhattacharyya, A.; Prabhu, D.R.; Mohapatra, P.K.


    The higher-valent actinide cations exhibit fascinating coordination chemistry essentially due to the flexibility in their electronic structures. This is particularly applicable for the dioxo penta- and hexavalent lighter actinides such as U, Np, Pu, and Am. Even though the oxo moiety is assumed to be chemically inert in these cations, there are several studies which show that pentavalent Np cation (NpO 2 + ) displays a tendency of bonding with charged metal ions. This class of weak bond formation has been classified as cation-cation interactions (CCI). Initial studies suggested that these types of interactions of Np(V) with polyvalent metal ions are more probable in non complexing perchloric acid solutions. Majority of these studies have been performed in perchlorate media and the stability constant values have been calculated. On the other hand, these studies in nitric acid medium are rather few. Our recent spectrophotometric study has shown that Np(V) cation undergoes disproportionation reaction and the tendency for CCI becomes less favorable at elevated temperature in nitric acid media. This study has been extended for understanding possible CCI between Np(V)O 2 + and Th 4 + ions under varying conditions such as nitric acid (1-6 M HNO 3 ). Th concentration (up to 0.86 M), and temperature (293-343K). An attempt has been made to calculate the stability constant values and compare with those reported in other media

  5. Biodegradable cationic poly(carbonates): Effect of varying side chain hydrophobicity on key aspects of gene transfection. (United States)

    Ong, Zhan Yuin; Yang, Chuan; Cheng, Wei; Voo, Zhi Xiang; Chin, Willy; Hedrick, James L; Yang, Yi Yan


    The degree of hydrophobicity in cationic polymers plays an important but often underappreciated role in the safety and efficacy of gene delivery processes. In order to further elucidate structure-activity relationships of biodegradable cationic poly(carbonate) gene carriers, we synthesized a series of narrowly dispersed homo-polymers via metal-free organocatalytic living ring-opening polymerization (ROP) of cyclic carbonate monomers bearing either alkyl (propyl, hexyl or nonyl) or 4-methyl benzyl halide side chains. The polymers were then quaternized using bis-tertiary amines to install both quaternary ammoniums and tertiary amines for DNA binding and endosomal escape, respectively. Among the polymers with similar molecular lengths and charge densities, it was found that an increase in side chain alkyl spacer length from 3 to 6 carbons significantly enhanced cellular uptake and luciferase gene expression in HepG2 and HeLa cell lines without causing overt hemolysis and cytotoxicity. A further increase of side chain alkyl length to 9 carbons, however, led to a drastic decline in gene expression due to increased cellular toxicity, which was correlated with an increased disruption and lysis of red blood cell membranes. Interestingly, the incorporation of an aromatic 4-methyl benzyl spacer increased DNA binding strength, reduced particle sizes of resultant DNA complexes, and enhanced cellular uptake, leading to improved luciferase gene expression, albeit with higher levels of hemolysis and cytotoxicity. Taken together, the findings of this study demonstrate that a delicate balance between cationic charge density and hydrophobicity could be achieved by utilizing a hexyl spacer in the side chains of cationic poly(carbonates), hence providing insights on the future development of non-viral cationic polymeric gene delivery systems. Owing to their ease of synthesis and well-controlled polymerization, biodegradable cationic poly(carbonates) have emerged as a highly promising

  6. Cationization of heparin for film applications

    Czech Academy of Sciences Publication Activity Database

    Šimkovic, I.; Mendichi, R.; Kelnar, Ivan; Filip, J.; Hricovíni, M.


    Roč. 115, 22 January (2015), s. 551-558 ISSN 0144-8617 Institutional support: RVO:61389013 Keywords : heparin * cationization * NMR Subject RIV: CD - Macromolecular Chemistry Impact factor: 4.219, year: 2015

  7. Test procedure for cation exchange chromatography

    International Nuclear Information System (INIS)

    Cooper, T.D.


    The purpose of this test plan is to demonstrate the synthesis of inorganic antimonate ion exchangers and compare their performance against the standard organic cation exchangers. Of particular interest is the degradation rate of both inorganic and organic cation exchangers. This degradation rate will be tracked by determining the ion exchange capacity and thermal stability as a function of time, radiation dose, and chemical reaction

  8. Cationic surfactants as the hydrolytic micellar catalysts


    Janošcová, Petra


    Cationic surfactants as the hydrolytic micellar catalysts Petra Janošcová The effectiveness of hydrolytic cleavage of the pesticide fenitrothionin cationic surfactants micellar media has been tested. All used surfactants increased the rate of fenitrothionhydrolysis, which was the evidence of micellar catalysis. For some surfactants decreases has been evident at the highest rate of hydrolysis concentrations. It has been the result of a phenomenon called the effect of empty micelles. High hydro...

  9. Asymmetric Aminalization via Cation-Binding Catalysis

    DEFF Research Database (Denmark)

    Park, Sang Yeon; Liu, Yidong; Oh, Joong Suk


    Asymmetric cation-binding catalysis, in principle, can generate "chiral" anionic nucleophiles, where the counter cations are coordinated within chiral environments. Nitrogen-nucleophiles are intrinsically basic, therefore, its use as nucleophiles is often challenging and limiting the scope...... of the reaction. Particularly, a formation of configurationally labile aminal centers with alkyl substituents has been a formidable challenge due to the enamine/imine equilibrium of electrophilic substrates. Herein, we report enantioselective nucleophilic addition reactions of potassium phthalimides to Boc-protected...

  10. Cycloaliphatic epoxide resins for cationic UV - cure

    International Nuclear Information System (INIS)

    Verschueren, K.; Balwant Kaur


    This paper introduces the cyclo - aliphatic epoxide resins used for the various applications of radiation curing and their comparison with acrylate chemistry. Radiation curable coatings and inks are pre - dominantly based on acrylate chemistry but over the last few years, cationic chemistry has emerged successfully with the unique properties inherent with cyclo - aliphatic epoxide ring structures. Wide variety of cationic resins and diluents, the formulation techniques to achieve the desired properties greatly contributes to the advancement of UV - curing technology

  11. Cationized Carbohydrate Gas-Phase Fragmentation Chemistry (United States)

    Bythell, Benjamin J.; Abutokaikah, Maha T.; Wagoner, Ashley R.; Guan, Shanshan; Rabus, Jordan M.


    We investigate the fragmentation chemistry of cationized carbohydrates using a combination of tandem mass spectrometry, regioselective labeling, and computational methods. Our model system is D-lactose. Barriers to the fundamental glyosidic bond cleavage reactions, neutral loss pathways, and structurally informative cross-ring cleavages are investigated. The most energetically favorable conformations of cationized D-lactose were found to be similar. In agreement with the literature, larger group I cations result in structures with increased cation coordination number which require greater collision energy to dissociate. In contrast with earlier proposals, the B n -Y m fragmentation pathways of both protonated and sodium-cationized analytes proceed via protonation of the glycosidic oxygen with concerted glycosidic bond cleavage. Additionally, for the sodiated congeners our calculations support sodiated 1,6-anhydrogalactose B n ion structures, unlike the preceding literature. This affects the subsequent propensity of formation and prediction of B n /Y m branching ratio. The nature of the anomeric center (α/β) affects the relative energies of these processes, but not the overall ranking. Low-energy cross-ring cleavages are observed for the metal-cationized analytes with a retro-aldol mechanism producing the 0,2 A 2 ion from the sodiated forms . Theory and experiment support the importance of consecutive fragmentation processes, particularly for the protonated congeners at higher collision energies.

  12. Luminescent sulfides of monovalent and trivalent cations

    International Nuclear Information System (INIS)


    The invention discloses a family of luminescent materials or phosphors having a rhombohedral crystal structure and consisting essentially of a mixed host sulfide of at least one monovalent host cation and at least one trivalent host cation, and containing, for each mole of phosphor, 0.0005 to 0.05 mole of at least one activating cation. The monovalent host cations may be Na, K or Rb and Cs. The trivalent host cations may be Gd, La, Lu, Sc and Y. The activating cations may be one or more of trivalent As, Bi, Ce, Dy, Er, Pr, Sb, Sm, Tb and Tm; divalent Lu, Mn, Pb and Sn; and monovalent Ag, Cu and Tl. The novel phosphors may be used in devices to convert electron-beam, ultraviolet or x-ray energy to light in the visible spectrum. Such energy conversion can be employed for example in fluoroscopic screens, and in viewing screens of cathode-ray tubes and other electron tubes

  13. Novel Alkyd-Type Coating Resins Produced Using Cationic Polymerization [PowerPoint

    Energy Technology Data Exchange (ETDEWEB)

    Chisholm, Bret; Kalita, Harjyoti; Alam, Samim; Jayasooriyamu, Anurad; Fernando, Shashi; Samanata, Satyabrata; Bahr, James; Selvakumar, Sermadurai; Sibi, Mukund; Vold, Jessica; Ulven, Chad


    Novel, partially bio-based poly(vinyl ether) copolymers derived from soybean oil and cyclohexyl vinyl ether (CHVE) were produced by cationic polymerization and investigated for application as alkyd-type surface coatings. Compared to conventional alkyd resins, which are produced by high temperature melt condensation polymerization, the poly(vinyl ether)s provide several advantages. These advantages include miler, more energy efficient polymer synthesis, elimination of issues associated with gelation during polymer synthesis, production of polymers with well-defined composition and relatively narrow molecular weight distribution, and elimination of film formation and physical property issues associated with entrained monomers, dimers, trimmers, etc. The results of the studied showed that the thermal, mechanical, and physical properties of the coatings produced from these novel polymers varied considerable as a function of polymer composition and cure temperature. Overall, the results suggest a good potential for these novel copolymers to be used for coatings cured by autoxidation.

  14. Thermodynamically stable amyloid-β monomers have much lower membrane affinity than the small oligomers

    Directory of Open Access Journals (Sweden)

    Bidyut eSarkar


    Full Text Available Amyloid beta (Aβ is an extracellular 39-43 residue long peptide present in the mammalian cerebrospinal fluid, whose aggregation is associated with Alzheimer’s disease. Small oligomers of Aβ are currently thought to be the key to toxicity. However, it is not clear why the monomers of Aβ are non-toxic, and at what stage of aggregation toxicity emerges. Interactions of Aβ with cell membranes is thought to be the initiator of toxicity, but membrane-binding studies with different preparations of monomers and oligomers have not settled this issue. We have earlier found that thermodynamically stable Aβ monomers emerge spontaneously from oligomeric mixtures upon long term incubation in physiological solutions (Nag et al, JBC, 2011. Here we show that the membrane-affinity of these stable Aβ monomers is much lower than that of a mixture of small oligomers (containing dimers to decamers, providing a clue to the emergence of toxicity. Fluorescently labeled Aβ40 monomers show negligible binding to cell membranes of a neuronal cell line (RN46A at physiological concentrations (250 nM, while oligomers at the same concentrations show strong binding within 30 minutes of incubation. The increased affinity most likely does not require any specific neuronal receptor, since this difference in membrane-affinity was also observed in a somatic cell-line (HEK 293T. Similar results are also obtained for Aβ42 monomers and oligomers. Minimal amount of cell death is observed at these concentrations even after 36 hours of incubation. It is likely that membrane binding precedes subsequent slower toxic events induced by Aβ. Our results a provide an explanation for the non-toxic nature of Aβ monomers, b suggest that Aβ toxicity emerges at the initial oligomeric phase, and c provide a quick assay for monitoring the benign-to-toxic transformation of Aβ.

  15. Comparison of Cyclooxygenase-1 Crystal Structures: Cross-Talk between Monomers Comprising Cyclooxygenase-1 Homodimers

    Energy Technology Data Exchange (ETDEWEB)

    Sidhu, Ranjinder S.; Lee, Jullia Y.; Yuan, Chong; Smith, William L. (Michigan)


    Prostaglandin endoperoxide H synthases (PGHSs)-1 and -2 (also called cyclooxygenases (COXs)-1 and -2) catalyze the committed step in prostaglandin biosynthesis. Both isoforms are targets of nonsteroidal antiinflammatory drugs (NSAIDs). PGHSs are homodimers that exhibit half-of-sites COX activity; moreover, some NSAIDs cause enzyme inhibition by binding only one monomer. To learn more about the cross-talk that must be occurring between the monomers comprising each PGHS-1 dimer, we analyzed structures of PGHS-1 crystallized under five different conditions including in the absence of any tightly binding ligand and in the presence of nonspecific NSAIDs and of a COX-2 inhibitor. When crystallized with substoichiometric amounts of an NSAID, both monomers are often fully occupied with inhibitor; thus, the enzyme prefers to crystallize in a fully occupied form. In comparing the five structures, we only observe changes in the positions of residues 123-129 and residues 510-515. In cases where one monomer is fully occupied with an NSAID and the partner monomer is incompletely occupied, an alternate conformation of the loop involving residues 123-129 is seen in the partially occupied monomer. We propose, on the basis of this observation and previous cross-linking studies, that cross-talk between monomers involves this mobile 123-129 loop, which is located at the dimer interface. In ovine PGHS-1 crystallized in the absence of an NSAID, there is an alternative route for substrate entry into the COX site different than the well-known route through the membrane binding domain.

  16. Residual methyl methacrylate monomer, water sorption, and water solubility of hypoallergenic denture base materials. (United States)

    Pfeiffer, Peter; Rosenbauer, Ernst-Ulrich


    Denture base materials have the potential to cause irritation and allergic reaction to the oral mucosa. Water sorption and water solubility of denture base resins affect dimensional behavior and denture stability. A correlation between residual monomer and water sorption exists. This in vitro study compared the amount of residual monomer, quantity of water sorption, and solubility of 4 denture base materials purported to be hypoallergenic with those of a polymethyl methacrylate-based (PMMA) heat-polymerizing acrylic resin. The denture base resins Sinomer (heat-polymerized, modified methacrylate), Polyan (thermoplastic, modified methacrylate), Promysan (thermoplastic, enterephthalate-based), and Microbase (microwave polymerized, polyurethane-based), which are purported to be hypoallergenic, and Paladon 65 (heat-polymerized, methacrylate, control group) were examined. Specimens of each material were tested for residual methyl methacrylate (MMA) monomer (% wt, n=3), amount of water sorption (microg/mm3, n=5) and water solubility (microg/mm3, n=5), according to ISO 1567:2000. The residual MMA monomer concentrations were determined by gas chromatography (GC). The data were analyzed with 1-way ANOVA and the Bonferroni-Dunn multiple comparisons post hoc analysis for each test variable (alpha=.05). Significantly lower residual MMA monomer was shown for Sinomer and Polyan compared to the PMMA control group (0.90 +/- 0.20% wt, Pdenture base materials (0.34-0.84 +/- 0.05-0.09 microg/mm3) was not significantly lower than the PMMA material (0.40 +/- 0.06 microg/mm3, P>.05). Except for Sinomer, the tested denture base resins passed the requirements of ISO 1567 regarding residual MMA monomer (denture base materials fulfilled the requirements regarding water sorption (denture base materials exhibited significantly lower residual monomer content than PMMA. Promysan and Microbase showed no detectable residual MMA.

  17. Net expansion of dried demineralized dentin matrix produced by monomer/alcohol saturation and solvent evaporation. (United States)

    Agee, Kelli A; Becker, Thomas D; Joyce, Anthony P; Rueggeberg, Frederick A; Borke, James L; Waller, Jennifer L; Tay, Franklin R; Pashley, David H


    The purpose of this work was to determine if nonaqueous methacrylate monomer/alcohol mixtures could expand dried collapsed demineralized dentin matrix. Thin disks (ca. 200 microm) of human dentin were demineralized and placed in wells beneath contact probes of linear variable differential transformers. The probes were placed on water-saturated expanded matrices to record the shrinkage associated with drying. Monomer mixtures containing hydroxyethyl methacrylate, 2,2-bis[4-(2-hydroxy-3 methacryloyloxy)propoxyphenyl] propane, or triethyleneglycol dimethacrylate were mixed with methanol or ethanol at alcohol/monomer mass fraction % of 90/10, 70/30, 50/50, or 30/70. They were randomly applied to the dried matrices to determine the rate and magnitude of expansion; then shrinkage was recorded during evaporation of the alcohols. The results indicated that matrix expansion was positively correlated with the Hoy's solubility parameters for hydrogen bonding forces (delta(h)) of the monomer/solvent mixtures (p methanol-containing than with ethanol-containing monomer mixtures. For the test solutions, triethyleneglycol dimethacrylate-containing mixtures produced the slowest rate of matrix expansion and hydroxyethyl methacrylate-containing mixtures the most rapid expansion. When the solvents were evaporated, the matrix shrank in proportion to the solvent content and the delta(h) of the monomer-solvent mixtures. The results indicate that expansion of dried, collapsed dentin matrices requires that the delta(h) of the mixtures be larger than 17 (J/cm(3))(1/2). The greater the delta(h) of the monomer solutions, the greater the rate and extent of expansion.

  18. Cu K-edge X-ray Absorption Spectroscopy Reveals Differential Copper Coordimation Within Amyloid-beta Oligomers Compared to Amyloid-beta Monomers

    Energy Technology Data Exchange (ETDEWEB)

    J Shearer; P Callan; T Tran; V Szalai


    The fatal neurodegenerative disorder Alzheimer's disease (AD) has been linked to the formation of soluble neurotoxic oligomers of amyloid-{beta} (A{beta}) peptides. These peptides have high affinities for copper cations. Despite their potential importance in AD neurodegeneration few studies have focused on probing the Cu{sup 2+/1+} coordination environment within A{beta} oligomers. Herein we present a Cu K-edge X-ray absorption spectroscopic study probing the copper-coordination environment within oligomers of A{beta}(42) (sequence: DAEFRHDSGYEVHHQKLVFFAEDVGSNKGAIIGLMVGGVVIA). We find that the Cu{sup 2+} cation is contained within a square planar mixed N/O ligand environment within A{beta}(42) oligomers, which is similar to the copper coordination environment of the monomeric forms of {l_brace}Cu{sup II}A{beta}(40){r_brace} and {l_brace}Cu{sup II}A{beta}(16){r_brace}. Reduction of the Cu{sup 2+} cation within the A{beta}(42) oligomers to Cu{sup 1+} yields a highly dioxygen sensitive copper-species that contains Cu{sup 1+} in a tetrahedral coordination geometry. This can be contrasted with monomers of {l_brace}Cu{sup I}A{beta}(40){r_brace} and {l_brace}Cu{sup I}A{beta}(16){r_brace}, which contain copper in a dioxygen inert linear bis-histidine ligand environment [Shearer and Szalai, J. Am. Chem. Soc., 2008, 130, 17826]. The biological implications of these findings are discussed.

  19. Cationic Ring Opening polymerization of ε-caprolactam by a Montmorillonite Clay Catalyst

    Directory of Open Access Journals (Sweden)

    Djamal Eddine Kherroub


    Full Text Available The ring opening bulk polymerization of ε-caprolactam catalyzed by Maghnite-H+ was reported. Maghnite-H+ is a montmorillonite silicate sheet clay was prepared through a straight forward proton exchange process. The effect of the amount of catalyst, and temperature was studied. Increasing Maghnite-H+ proportion and temperature produced the increase in ε-caprolactam conversion. The kinetics indicated that the polymerization rate is first order with respect to monomer concentration. Mechanism studies showed that monomer inserted into the growing chains with the acyl–oxygen bond scission rather than the break of alkyl–oxygen bond. © 2014 BCREC UNDIP. All rights reservedSubmitted: 3rd October 2013; Revised: 28th February 2014; Accepted: 1st March 2014[How to Cite: Kherroub, D.E., Belbachir, M., Lamouri, S. (2014. Cationic Ring Opening Polymeriza-tion of ε-caprolactam by a Montmorillonite Clay Catalyst. Bulletin of Chemical Reaction Engineering & Catalysis, 9 (1: 74-79. (doi:10.9767/bcrec.9.1.5555.74-80][Permalink/DOI:

  20. Interactions of bovine serum albumin with cationic imidazolium and quaternary ammonium gemini surfactants: effects of surfactant architecture. (United States)

    Zhou, Ting; Ao, Mingqi; Xu, Guiying; Liu, Teng; Zhang, Juan


    The interactions of BSA with a series of cationic imidazolium gemini surfactants ([C(n)-s-C(n)im]Br(2), n=10, 12, 14, s=2, 4, 6), quaternary ammonium surfactants (C(12)C(2)C(12)), and their corresponding monomers ([C(12)mim]Br and DTAB) are investigated by fluorescence using pyrene as a molecular probe, synchronous fluorescence, circular dichroism (CD), and UV-visible absorption spectra. These surfactants are used to elucidate the effects of surfactant hydrophilic head group, spacer length, and hydrophobic chain length on the conformation of BSA. The results of fluorescence spectra and CD show that the imidazolium gemini surfactants with shorter spacers or with longer hydrophobic chains have a larger effect on BSA unfolding, and the imidazolium gemini surfactant interacts with BSA more strongly than its corresponding monomer and the quaternary ammonium gemini surfactant. These conclusions have been confirmed by the binding constants (K(a)) and binding sites (n) for the BSA/surfactant system. Stern-Volmer quenching constants K(SV) of cationic surfactants binding to BSA are obtained, indicating that the probable quenching mechanism is initiated by ground-state complex formation rather than by dynamic collision. Moreover, the synchronous fluorescence spectra show that the surfactants mainly interact with tryptophan residues of BSA. Copyright © 2012 Elsevier Inc. All rights reserved.

  1. Cation Exchange in the Presence of Oil in Porous Media

    NARCIS (Netherlands)

    Farajzadeh, R.; Guo, H.; van Winden, J.L.; Bruining, J.


    Cation exchange is an interfacial process during which cations on a clay surface are replaced by other cations. This study investigates the effect of oil type and composition on cation exchange on rock surfaces, relevant for a variety of oil-recovery processes. We perform experiments in which brine

  2. Photopolymerizable phosphate acrylates as comonomers in dental adhesives with or without triclosan monomer units

    International Nuclear Information System (INIS)

    Melinte, Violeta; Buruiana, Tinca; Aldea, Horia; Matiut, Simona; Silion, Mihaela; Buruiana, Emil C.


    Phosphate diacrylates (CO-DAP, TMP-DAP) based on castor oil or trimethylolpropane were synthesized and evaluated in dental adhesive formulations in comparison with 3-acryloyloxy-2-hydroxypropyl methacrylate phosphate (AMP-P). In an attempt to promote antibacterial activity, another photopolymerizable monomer (TCS-UMA) containing 5-chloro-2-(2,4-dichlorophenoxy)phenol moiety (triclosan) was prepared and incorporated in adhesive resins. Each of these monomers had a molecular structure confirmed by spectral methods. The photopolymerization rates for monomers (0.063–0.088 s −1 ) were lower than those determined in the monomer combinations (0.116–0.158 s −1 ) incorporating phosphate diacrylate (11 wt.%), BisGMA (33 wt.%), TEGDMA (10 wt.%), UDMA (10 wt.%) and HEMA (15 wt.%), the degree of conversion varying between 63.4 and 74.5%. The formed copolymers showed high values for water sorption (18.65–57.02 μg/mm 3 ) and water solubility (3.51–13.38 μg/mm 3 ), and the contact angle was dependent on the presence of CO-DAP (θ F1 : 66.67°), TMP-DAP (θ F2 : 55.05°) or AMP-P (θ F3 : 52.90°) in the photocrosslinked specimens compared to the sample without phosphate monomer (θ F4 : 82.14°). The scanning electron microscopy image of the dentin–resin composite interface after applying our F1 formulation (pH: 4.1) and its light-curing for 20 s supports the evidence of the formation of the hybrid layer with the tooth structure created by self-etching approach, with no gaps or cracks in the adhesive. A comparative analysis of the adhesion achieved with commercial adhesive systems (Single Bond Universal, C-Bond) rather indicates similarities than differences between them. The addition of triclosan methacrylate (1 wt.%) into the formulation inhibited the bacterial growth of the Streptococcus mutans and Escherichia coli in the direct contact area due to the covalently linked antibacterial monomer. - Highlights: • Synthesis of photopolymerizable phosphate acrylate

  3. Photopolymerizable phosphate acrylates as comonomers in dental adhesives with or without triclosan monomer units

    Energy Technology Data Exchange (ETDEWEB)

    Melinte, Violeta [Petru Poni Institute of Macromolecular Chemistry, 41 A Gr. Ghica Voda Alley, 700487 Iasi (Romania); Buruiana, Tinca, E-mail: [Petru Poni Institute of Macromolecular Chemistry, 41 A Gr. Ghica Voda Alley, 700487 Iasi (Romania); Aldea, Horia [Gr. T. Popa University of Medicine and Pharmacy, Faculty of Dentistry, Iasi (Romania); Matiut, Simona [Praxis Medical Investigations, 33 Independence, 700102 Iasi (Romania); Silion, Mihaela; Buruiana, Emil C. [Petru Poni Institute of Macromolecular Chemistry, 41 A Gr. Ghica Voda Alley, 700487 Iasi (Romania)


    Phosphate diacrylates (CO-DAP, TMP-DAP) based on castor oil or trimethylolpropane were synthesized and evaluated in dental adhesive formulations in comparison with 3-acryloyloxy-2-hydroxypropyl methacrylate phosphate (AMP-P). In an attempt to promote antibacterial activity, another photopolymerizable monomer (TCS-UMA) containing 5-chloro-2-(2,4-dichlorophenoxy)phenol moiety (triclosan) was prepared and incorporated in adhesive resins. Each of these monomers had a molecular structure confirmed by spectral methods. The photopolymerization rates for monomers (0.063–0.088 s{sup −1}) were lower than those determined in the monomer combinations (0.116–0.158 s{sup −1}) incorporating phosphate diacrylate (11 wt.%), BisGMA (33 wt.%), TEGDMA (10 wt.%), UDMA (10 wt.%) and HEMA (15 wt.%), the degree of conversion varying between 63.4 and 74.5%. The formed copolymers showed high values for water sorption (18.65–57.02 μg/mm{sup 3}) and water solubility (3.51–13.38 μg/mm{sup 3}), and the contact angle was dependent on the presence of CO-DAP (θ{sub F1}: 66.67°), TMP-DAP (θ{sub F2}: 55.05°) or AMP-P (θ{sub F3}: 52.90°) in the photocrosslinked specimens compared to the sample without phosphate monomer (θ{sub F4}: 82.14°). The scanning electron microscopy image of the dentin–resin composite interface after applying our F1 formulation (pH: 4.1) and its light-curing for 20 s supports the evidence of the formation of the hybrid layer with the tooth structure created by self-etching approach, with no gaps or cracks in the adhesive. A comparative analysis of the adhesion achieved with commercial adhesive systems (Single Bond Universal, C-Bond) rather indicates similarities than differences between them. The addition of triclosan methacrylate (1 wt.%) into the formulation inhibited the bacterial growth of the Streptococcus mutans and Escherichia coli in the direct contact area due to the covalently linked antibacterial monomer. - Highlights: • Synthesis of

  4. Using monomer vibrational wavefunctions to compute numerically exact (12D) rovibrational levels of water dimer (United States)

    Wang, Xiao-Gang; Carrington, Tucker


    We compute numerically exact rovibrational levels of water dimer, with 12 vibrational coordinates, on the accurate CCpol-8sf ab initio flexible monomer potential energy surface [C. Leforestier et al., J. Chem. Phys. 137, 014305 (2012)]. It does not have a sum-of-products or multimode form and therefore quadrature in some form must be used. To do the calculation, it is necessary to use an efficient basis set and to develop computational tools, for evaluating the matrix-vector products required to calculate the spectrum, that obviate the need to store the potential on a 12D quadrature grid. The basis functions we use are products of monomer vibrational wavefunctions and standard rigid-monomer basis functions (which involve products of three Wigner functions). Potential matrix-vector products are evaluated using the F matrix idea previously used to compute rovibrational levels of 5-atom and 6-atom molecules. When the coupling between inter- and intra-monomer coordinates is weak, this crude adiabatic type basis is efficient (only a few monomer vibrational wavefunctions are necessary), although the calculation of matrix elements is straightforward. It is much easier to use than an adiabatic basis. The product structure of the basis is compatible with the product structure of the kinetic energy operator and this facilitates computation of matrix-vector products. Compared with the results obtained using a [6 + 6]D adiabatic approach, we find good agreement for the inter-molecular levels and larger differences for the intra-molecular water bend levels.

  5. Do CAD/CAM dentures really release less monomer than conventional dentures? (United States)

    Steinmassl, Patricia-Anca; Wiedemair, Verena; Huck, Christian; Klaunzer, Florian; Steinmassl, Otto; Grunert, Ingrid; Dumfahrt, Herbert


    Computer-aided design (CAD)/computer-aided manufacturing (CAM) dentures are assumed to have more favourable material properties than conventionally fabricated dentures, among them a lower methacrylate monomer release. The aim of this study was to test this hypothesis. CAD/CAM dentures were generated from ten different master casts by using four different CAD/CAM systems. Conventional, heat-polymerised dentures served as control group. Denture weight and volume were measured; the density was calculated, and the denture surface area was assessed digitally. The monomer release after 7 days of water storage was measured by high-performance liquid chromatography. Whole You Nexteeth and Wieland Digital Dentures had significantly lower mean volume and weight than conventional dentures. Baltic Denture System and Whole You Nexteeth had a significantly increased density. Baltic Denture System had a significantly smaller surface area. None of the CAD/CAM dentures released significantly less monomer than the control group. All tested dentures released very low amounts of methacrylate monomer, but not significantly less than conventional dentures. A statistically significant difference might nevertheless exist in comparison to other, less recommendable denture base materials, such as the frequently used autopolymerising resins. CAD/CAM denture fabrication has numerous advantages. It enables the fabrication of dentures with lower resin volume and lower denture weight. Both could increase the patient comfort. Dentures with higher density might exhibit more favourable mechanical properties. The hypothesis that CAD/CAM dentures release less monomer than conventional dentures could, however, not be verified.

  6. Monomer diffusion into static and evolving polymer networks during frontal photopolymerisation. (United States)

    Hennessy, Matthew G; Vitale, Alessandra; Matar, Omar K; Cabral, João T


    Frontal photopolymerisation (FPP) is a directional solidification process that converts monomer-rich liquid into crosslinked polymer solid by light exposure and finds applications ranging from lithography to 3D printing. Inherent to this process is the creation of an evolving polymer network that is exposed to a monomer bath. A combined theoretical and experimental investigation is performed to determine the conditions under which monomer from this bath can diffuse into the propagating polymer network and cause it to swell. First, the growth and swelling processes are decoupled by immersing pre-made polymer networks into monomer baths held at various temperatures. The experimental measurements of the network thickness are found to be in good agreement with theoretical predictions obtained from a nonlinear poroelastic model. FPP propagation experiments are then carried out under conditions that lead to swelling. Unexpectedly, for a fixed exposure time, swelling is found to increase with incident light intensity. The experimental data is well described by a novel FPP model accounting for mass transport and the mechanical response of the polymer network, providing key insights into how monomer diffusion affects the conversion profile of the polymer solid and the stresses that are generated during its growth. The predictive capability of the model will enable the fabrication of gradient materials with tuned mechanical properties and controlled stress development.

  7. Inhibition of odontogenic differentiation of human dental pulp cells by dental resin monomers. (United States)

    Kwon, Ji Hyun; Park, Hee Chul; Zhu, Tingting; Yang, Hyeong-Cheol


    Dental resin monomers that are leached from the resin matrix due to incomplete polymerization can affect the viability and various functions of oral tissues and cells. In this study, the effects of triethylene glycol dimethacrylate (TEGDMA) and 2-hydroxyethyl methacrylate (HEMA) on odontogenic differentiation of human dental pulp cells (HDPCs) were examined. To mimic clinical situations, dental pulp cells were treated with resin monomers for 24 h prior to the analysis of alkaline phosphatase (ALP) activity and mRNA expression of genes related to pulp cell differentiation. To elucidate the underlying signaling pathways, regulation of mitogen-activated protein (MAP) kinases by resin monomers was also investigated. The ALP activity of HDPCs was reduced by TEGDMA and HEMA at noncytotoxic concentrations. The mRNA expression of dentin sialophosphoprotein (DSPP), osteocalcin (OCN), and osteopontin (OPN) was also downregulated by resin monomers. However, DSPP expression was not affected by hydrogen peroxide (H2O2). Among the MAP kinases examined, ERK activation (ERK phosphorylation) was not affected by either resin monomers or H2O2, whereas JNK was phosphorylated by TEGDMA and HEMA. Phospho-p38 was upregulated by HEMA, while TEGDMA and H2O2 suppressed p38 phosphorylation. Exposure to TEGDMA and HEMA for a limited period suppresses differentiation of HDPCs via different signaling pathways.

  8. Radiation-induced graft polymerization of amphiphilic monomers with different polymerization characteristics onto hydrophobic polysilane

    Energy Technology Data Exchange (ETDEWEB)

    Tanaka, Hidenori; Iwasaki, Isao; Kunai, Yuichiro [Research Reactor Institute, Kyoto University, Asashironishi 2-1010, Kumatori-cho, Sennan-gun, Osaka 590-0494 (Japan); Sato, Nobuhiro, E-mail: [Research Reactor Institute, Kyoto University, Asashironishi 2-1010, Kumatori-cho, Sennan-gun, Osaka 590-0494 (Japan); Matsuyama, Tomochika [Research Reactor Institute, Kyoto University, Asashironishi 2-1010, Kumatori-cho, Sennan-gun, Osaka 590-0494 (Japan)


    The structures of poly(methyl-n-propylsilane) (PMPrS) amphiphilically modified through {gamma}-ray-induced graft polymerization were investigated with {sup 1}H NMR measurement. By the use of methyl methacrylate (MMA) or diethyl fumarate (DEF) as monomers for the graft polymerization, grafting yield rose with increasing total absorption dose and monomer concentrations, but decreased with increasing dose rate. This result means that grafting yield of modified PMPrS can be controlled by changing irradiation conditions. However, the number of PMMA or PDEF graft chains per PMPrS chain was estimated to be less than 1.0 by analysis of {sup 1}H NMR spectra, and this value was lower than that we had expected. To improve graft density, maleic anhydride (MAH), which is known as a non-homopolymerizable monomer in radical polymerization, was used as a monomer for grafting. As a result, high density grafting (one MAH unit for 4.2 silicon atoms) was attained. It demonstrates that the structure of {gamma}-ray-modified polysilane strongly depends on the polymerization characteristics of grafted monomers.

  9. Design and Applications of Biodegradable Polyester Tissue Scaffolds Based on Endogenous Monomers Found in Human Metabolism

    Directory of Open Access Journals (Sweden)

    Devin G. Barrett


    Full Text Available Synthetic polyesters have deeply impacted various biomedical and engineering fields, such as tissue scaffolding and therapeutic delivery. Currently, many applications involving polyesters are being explored with polymers derived from monomers that are endogenous to the human metabolism. Examples of these monomers include glycerol, xylitol, sorbitol, and lactic, sebacic, citric, succinic, α-ketoglutaric, and fumaric acids. In terms of mechanical versatility, crystallinity, hydrophobicity, and biocompatibility, polyesters synthesized partially or completely from these monomers can display a wide range of properties. The flexibility in these macromolecular properties allows for materials to be tailored according to the needs of a particular application. Along with the presence of natural monomers that allows for a high probability of biocompatibility, there is also an added benefit that this class of polyesters is more environmentally friendly than many other materials used in biomedical engineering. While the selection of monomers may be limited by nature, these polymers have produced or have the potential to produce an enormous number of successes in vitro and in vivo.

  10. Pathway and mechanism of pH dependent human hemoglobin tetramer-dimer-monomer dissociations.

    Directory of Open Access Journals (Sweden)

    Yao-Xiong Huang

    Full Text Available Hemoglobin dissociation is of great interest in protein process and clinical medicine as well as in artificial blood research. However, the pathway and mechanisms of pH-dependent human Hb dissociation are not clear, whether Hb would really dissociate into monomers is still a question. Therefore, we have conducted a multi-technique investigation on the structure and function of human Hb versus pH. Here we demonstrate that tetramer hemoglobin can easily dissociate into dimer in abnormal pH and the tetramer → dimer dissociation is reversible if pH returns to normal physiological value. When the environmental pH becomes more acidic (8.0, Hb can further dissociate from dimer to monomer. The proportion of monomers increases while the fraction of dimers decreases as pH declines from 6.2 to 5.4. The dimer → monomer dissociation is accompanied with series changes of protein structure thus it is an irreversible process. The structural changes in the dissociated Hbs result in some loss of their functions. Both the Hb dimer and monomer cannot adequately carry and release oxygen to the tissues in circulation. These findings provide a comprehensive understanding on the pH-dependent protein transitions of human Hb, give guideline to explain complex protein processes and the means to control protein dissociation or re-association reaction. They are also of practical value in clinical medicine, blood preservation and blood substitute development.

  11. Precision design of ethylene- and polar-monomer-based copolymers by organometallic-mediated radical polymerization (United States)

    Kermagoret, Anthony; Debuigne, Antoine; Jérôme, Christine; Detrembleur, Christophe


    The copolymerization of ethylene with polar monomers is a major challenge when it comes to the manufacture of materials with potential for a wide range of commercial applications. In the chemical industry, free-radical polymerization is used to make a large proportion of such copolymers, but the forcing conditions result in a lack of fine control over the architecture of the products. Herein we introduce a synthetic tool, effective under mild experimental conditions, for the precision design of unprecedented ethylene- and polar-monomer-based copolymers. We demonstrate how an organocobalt species can control the growth of the copolymer chains, their composition and the monomer distribution throughout the chain. By fine tuning the ethylene pressure during polymerization and by exploiting a unique reactive mode of the end of the organometallic chain, novel block-like copolymer structures can be prepared. This highly versatile synthetic platform provides access to a diverse range of polymer materials.

  12. Testing of residual monomer content reduction possibility on acrilic resins quality

    Directory of Open Access Journals (Sweden)

    Kostić Milena


    Full Text Available Poly (methyl methacrylate (PMMA is material widely used in dentistry. Despite the various methods used to initiate the polymerization of acrylic resins, the conversion of monomer to polymer is not complete thus leaving some unreacted methyl methacrylate (MMA, known as residual monomer (RM, in denture structure. RM in dental acrylic resins has deleterious effects on their mechanical properties and their biocompatibility. The objective of the work was to test the residual monomer reduction possibility by applying the appropriate postpolymerization treatment as well as to determine the effects of this reduction on pressure yields stress and surface structure characteristics of the acrylic resins. Postpolymerization treatments and water storage induced reduction of RM amount in cold-polymerized acrylic resins improved their mechanical properties and the homogenized surface structure. After the polymerization of heat-polymerized acrylic resins the post-polymerization treatments for improving the quality of this material type are not necessary.

  13. Dynamic mechanical properties of photopolymerizable poly(vinyl alcohol)-acrylate monomer blends

    International Nuclear Information System (INIS)

    Koshiba, M.; Yamaoka, T.; Tsunoda, T.


    Dynamic mechanical properties of photopolymerizable poly(vinyl alcohol) (PVA)-monoacrylate blends were investigated by measuring dynamic shear modulus G' and loss tangent, tan delta. The dynamic mechanical properties of the blends before being exposed to UV irradiation were governed by the weight percent of the monomers which act as plasticizers. On the other hand, the UV-irradiated blends seemed to be typical two-phase materials since they revealed two tan delta maxima whose positions were independent of the monomer content. Those two maxima were assigned to PVA and photopolymerized acrylates with reference to the dynamic mechanical data of PVA and a PVA-polyacrylamide polyblend. Those dynamic mechanical data suggested that insolubilization of the blend type photopolymers should be caused by a decrease in solubility due to graft polymerization of acrylate monomers onto PVA. 9 figures, 3 tables

  14. Distinct Internalization Pathways of Human Amylin Monomers and Its Cytotoxic Oligomers in Pancreatic Cells (United States)

    Trikha, Saurabh; Jeremic, Aleksandar M.


    Toxic human amylin oligomers and aggregates are implicated in the pathogenesis of type 2 diabetes mellitus (TTDM). Although recent studies have shown that pancreatic cells can recycle amylin monomers and toxic oligomers, the exact uptake mechanism and trafficking routes of these molecular forms and their significance for amylin toxicity are yet to be determined. Using pancreatic rat insulinoma (RIN-m5F) beta (β)-cells and human islets as model systems we show that monomers and oligomers cross the plasma membrane (PM) through both endocytotic and non-endocytotic (translocation) mechanisms, the predominance of which is dependent on amylin concentrations and incubation times. At low (≤100 nM) concentrations, internalization of amylin monomers in pancreatic cells is completely blocked by the selective amylin-receptor (AM-R) antagonist, AC-187, indicating an AM-R dependent mechanism. In contrast at cytotoxic (µM) concentrations monomers initially (1 hour) enter pancreatic cells by two distinct mechanisms: translocation and macropinocytosis. However, during the late stage (24 hours) monomers internalize by a clathrin-dependent but AM-R and macropinocytotic independent pathway. Like monomers a small fraction of the oligomers initially enter cells by a non-endocytotic mechanism. In contrast a majority of the oligomers at both early (1 hour) and late times (24 hours) traffic with a fluid-phase marker, dextran, to the same endocytotic compartments, the uptake of which is blocked by potent macropinocytotic inhibitors. This led to a significant increase in extra-cellular PM accumulation, in turn potentiating amylin toxicity in pancreatic cells. Our studies suggest that macropinocytosis is a major but not the only clearance mechanism for both amylin’s molecular forms, thereby serving a cyto-protective role in these cells. PMID:24019897

  15. Distinct internalization pathways of human amylin monomers and its cytotoxic oligomers in pancreatic cells.

    Directory of Open Access Journals (Sweden)

    Saurabh Trikha

    Full Text Available Toxic human amylin oligomers and aggregates are implicated in the pathogenesis of type 2 diabetes mellitus (TTDM. Although recent studies have shown that pancreatic cells can recycle amylin monomers and toxic oligomers, the exact uptake mechanism and trafficking routes of these molecular forms and their significance for amylin toxicity are yet to be determined. Using pancreatic rat insulinoma (RIN-m5F beta (β-cells and human islets as model systems we show that monomers and oligomers cross the plasma membrane (PM through both endocytotic and non-endocytotic (translocation mechanisms, the predominance of which is dependent on amylin concentrations and incubation times. At low (≤ 100 nM concentrations, internalization of amylin monomers in pancreatic cells is completely blocked by the selective amylin-receptor (AM-R antagonist, AC-187, indicating an AM-R dependent mechanism. In contrast at cytotoxic (µM concentrations monomers initially (1 hour enter pancreatic cells by two distinct mechanisms: translocation and macropinocytosis. However, during the late stage (24 hours monomers internalize by a clathrin-dependent but AM-R and macropinocytotic independent pathway. Like monomers a small fraction of the oligomers initially enter cells by a non-endocytotic mechanism. In contrast a majority of the oligomers at both early (1 hour and late times (24 hours traffic with a fluid-phase marker, dextran, to the same endocytotic compartments, the uptake of which is blocked by potent macropinocytotic inhibitors. This led to a significant increase in extra-cellular PM accumulation, in turn potentiating amylin toxicity in pancreatic cells. Our studies suggest that macropinocytosis is a major but not the only clearance mechanism for both amylin's molecular forms, thereby serving a cyto-protective role in these cells.

  16. The effect of various frequencies of ultrasonic cleaner in reducing residual monomer in acrylic resin. (United States)

    Charasseangpaisarn, Taksid; Wiwatwarrapan, Chairat


    Monomer remaining in denture base acrylic can be a major problem because it may cause adverse effects on oral tissue and on the properties of the material. The purpose of this study was to compare the effect of various ultrasonic cleaner frequencies on the amount of residual monomer in acrylic resin after curing. Forty-two specimens each of Meliodent heat-polymerized acrylic resin (M) and Unifast Trad Ivory auto-polymerized acrylic resin (U) were prepared according to their manufacturer's instructions and randomly divided into seven groups: Negative control (NC); Positive control (PC); and five ultrasonic treatment groups: 28 kHz (F1), 40 kHz (F2), 60 kHz (F3) (M=10 min, U=5 min), and 28 kHz followed by 60 kHz (F4: M=5 min per frequency, U=2.5 min per frequency, and F5: M=10 min followed by 5 min per frequency, U=5 min followed by 2.5 min per frequency). Residual monomer was determined by HPLC following ISO 20795-1. The data were analyzed by One-way ANOVA and Tukey HSD. There was significantly less residual monomer in the auto-polymerized acrylic resin in all ultrasonic treatment groups and the PC group than that of the NC group (pacrylic resin (p>0.05). The amount of residual monomer in heat-polymerized acrylic resin was significantly lower than that of auto-polymerized acrylic resin. In conclusion, ultrasonic treatment at low frequencies is recommended to reduce the residual monomer in auto-polymerized acrylic resin and this method is more practical in a clinical situation than previously recommended methods because of reduced chairside time. Copyright © 2015 Elsevier B.V. All rights reserved.

  17. High-speed atomic force microscopy reveals structural dynamics of α -synuclein monomers and dimers (United States)

    Zhang, Yuliang; Hashemi, Mohtadin; Lv, Zhengjian; Williams, Benfeard; Popov, Konstantin I.; Dokholyan, Nikolay V.; Lyubchenko, Yuri L.


    α-Synuclein (α-syn) is the major component of the intraneuronal inclusions called Lewy bodies, which are the pathological hallmark of Parkinson's disease. α-Syn is capable of self-assembly into many different species, such as soluble oligomers and fibrils. Even though attempts to resolve the structures of the protein have been made, detailed understanding about the structures and their relationship with the different aggregation steps is lacking, which is of interest to provide insights into the pathogenic mechanism of Parkinson's disease. Here we report the structural flexibility of α-syn monomers and dimers in an aqueous solution environment as probed by single-molecule time-lapse high-speed AFM. In addition, we present the molecular basis for the structural transitions using discrete molecular dynamics (DMD) simulations. α-Syn monomers assume a globular conformation, which is capable of forming tail-like protrusions over dozens of seconds. Importantly, a globular monomer can adopt fully extended conformations. Dimers, on the other hand, are less dynamic and show a dumbbell conformation that experiences morphological changes over time. DMD simulations revealed that the α-syn monomer consists of several tightly packed small helices. The tail-like protrusions are also helical with a small β-sheet, acting as a "hinge". Monomers within dimers have a large interfacial interaction area and are stabilized by interactions in the non-amyloid central (NAC) regions. Furthermore, the dimer NAC-region of each α-syn monomer forms a β-rich segment. Moreover, NAC-regions are located in the hydrophobic core of the dimer.

  18. A nine-year follow up study of a population occupationally exposed to vinyl chloride monomer. (United States)

    Fucić, A; Barković, D; Garaj-Vrhovac, V; Kubelka, D; Ivanic, B; Dabo, T; Mijić, A


    The presence of structural chromosome aberrations and sister chromatid exchange frequencies (SCE) were studied in lymphocytes from 28 male subjects occupationally exposed to vinyl chloride monomer for a period of 9 years. A significant increase in chromosomal damages and elevated SCE frequencies was detected during the third and fourth year of the follow-up study. During the last 2 years, all examined parameters are approaching control values. This is a result of decreasing vinyl chloride monomer concentrations in the working environment without interrupting the working process.

  19. Synthesis and ATRP of novel fluorinated aromatic monomer with pendant sulfonate group

    DEFF Research Database (Denmark)

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


    Novel, fluorinated monomer with pendant sulfonate group was synthesized utilizing a two-step derivatization of 2,3,4,5,6-pentafluorostyrene (FS). The first step was a nucleophilic substitution of the fluorine atom in para position by hydroxyl group followed by sulfopropylation. The monomer...... was polymerized under aqueous ATRP conditions to yield phenyl-fluorinated aromatic homopolymer bearing pendant sulfonates on each repeating unit. Furthermore, this polymer was used as macroinitiator for the ATRP of poly(ethylene glycol) methacrylate. The polymers were characterized by 1H NMR, SEC and FTIR...

  20. Sulfonated copolyimide membranes derived from a novel diamine monomer with pendant benzimidazole groups for fuel cells

    DEFF Research Database (Denmark)

    Li, Wei; Guo, Xiaoxia; Aili, David


    Sulfonated polyimides are among the most interesting proton exchange membrane materials with high proton conductivity and good mechanical characteristics. As a major challenge the hydrolytic instability of the polymer backbone is addressed by introducing basic moieties in the polymer main chain....... A series of sulfonated copolyimides (SPI) are prepared via random copolymerizatio of 1,4,5,8-naphthalenetetracarboxylic dianhydride (NTDA) with a new diamine monomer with pendant benzimidazole groups, 2,2'-bis(4-(1H-benzo[d]imidazol-2-yl)phenoxy)benzidine (BIPOB), and a sulfonated diamine monomer 4,4'-bis...

  1. Kinetics of the monomer-dimer reaction of yeast hexokinase PI.


    Hoggett, J G; Kellett, G L


    Kinetic studies of the glucose-dependent monomer-dimer reaction of yeast hexokinase PI at pH 8.0 in the presence of 0.1 M-KCl have been carried out using the fluorescence temperature-jump technique. A slow-relaxation effect was observed which was attributed from its dependence on enzyme concentration to the monomer-dimer reaction; the reciprocal relaxation times tau-1 varied from 3 s-1 at low concentrations of glucose to 42 s-1 at saturating concentrations. Rate constants for association (kas...

  2. Preparation of poly (vinyl alcohol) membranes grafted with n-vinyl pyridine/ acrylic acid binary monomers

    International Nuclear Information System (INIS)

    Ajji, A.; Ali, A.


    Poly(vinyl alcohol) films were grafted with two monomers using gamma radiation, acrylic acid and N-vinyl pyridine. The influence of different parameters on the grafting yield was investigated as: the comonomer concentration and composition, and irradiation dose. The suitable conditions of the process had been determined to prepare PVA membranes have both properties of the two monomers, acrylic acid and vinyl pyridine as comonomer concentration and composition, and irradiation dose. Some properties of the membranes had been investigated as maximum swelling and grafting. Also the ability of the grafted films to adsorb some heavy metals and dyes was elaborated and discussed.(author)

  3. Radiation-induced cationic polymerization of limonene oxide, α-pinene oxide, and β-pinene oxide

    International Nuclear Information System (INIS)

    Aikins, J.A.; Williams, F.


    After suitable drying, the subject monomers in the form of neat liquids undergo radiation-induced polymerization with no apparent side reactions and high conversions to precipitatable polymers of low molecular weight. A cationic mechanism is evidenced by the strongly retarding effect of tri-n-propylamine on the polymerization rate. At 25 0 C, limonene oxide gives the highest polymerization rates, an average conversion of 36% per Mrad being obtained in comparison with values of 5.7 and 7.3% per Mrad for the α-pinene and β-pinene oxides, respectively. Similarly, the average anti DP/sub n/ decreases from 11.8 for the limonene oxide polymer to 5.6 and 4.0 for the α-pinene oxide and β-pinene oxide polymers, respectively. A high frequency of chain transfer to monomer is indicated in each case by the fact that the kinetic chain lengths are estimated to be on the order of a hundred times larger than the anti DP/sub n/ values. Structural characterization of the limonene oxide polymer by 1 H and 13 C NMR spectroscopy provides conclusive evidence that the polymerization proceeds by the opening of the epoxide ring to yield a 1,2-trans polyether. Similar NMR studies on the polymers formed from the α-pinene and β-pinene oxides show that in the polymerization of these monomers, the opening of the epoxide ring is generally accompanied by the concomitant ring opening of the cyclobutane ring structure to yield a gem-dimethyl group in the main chain. The detection of isopropenyl end groups in the pinene oxide polymers is also consistent with this mode of propagation being followed by chain (proton) transfer to monomer

  4. Mechanism of bacterial inactivation by cationic surfactants

    Energy Technology Data Exchange (ETDEWEB)

    Pavlova, I.B.; Samoylenko, I.I.


    The mechanism of bacteriocidal action of the cationic surfactant dimethylbenzylammonium chloride was studied on exposure of Staphylococcus aureus, Streptococcus faecium, Bacillus subtilis and Escherichia coli to different concentrations of the agent and determinations of survival plots. The data showed that the surfactant was bacteriocidal for all the bacteria tested at a concentration of 0.0001%, but more efficient in the case of the gram positives. Electron microscopy showed considerable damage and dissarrangement of the cytoplasmic membrane, indicating that the killing mechanism involved this organelle. It appears that cationic surfactants may constitute effective disinfectant preparations. 9 references, 2 figures.

  5. Cationic Poly(benzyl ether)s as Self-Immolative Antimicrobial Polymers. (United States)

    Ergene, Cansu; Palermo, Edmund F


    Self-immolative polymers (SIMPs) are macromolecules that spontaneously undergo depolymerization into small molecules when triggered by specific external stimuli. We report here the first examples of antimicrobial SIMPs with potent, rapid, and broad-spectrum bactericidal activity. Their antibacterial and hemolytic activities were examined as a function of cationic functionality. Polymers bearing primary ammonium cationic groups showed more potent bactericidal activity against Escherichia coli, relative to tertiary and quaternary ammonium counterparts, whereas the quaternary ammonium polymers showed the lowest hemolytic toxicity. These antibacterial polycations undergo end-to-end depolymerization when triggered by an externally applied stimulus. Specifically, poly(benzyl ether)s end-capped with a silyl ether group and bearing pendant allyl side chains were converted to polycations by photoinitiated thiol-ene radical addition using cysteamine HCl. The intact polycations are stable in solution, but they spontaneously unzip into their component monomers upon exposure to fluoride ions, with excellent sensitivity and selectivity. Upon triggered depolymerization, the antibacterial potency was largely retained but the hemolytic toxicity was substantially reduced. Thus, we reveal the first example of a self-immolative antibacterial polymer platform that will enable antibacterial materials to spontaneously unzip into biologically active small molecules upon the introduction of a specifically designed stimulus.

  6. Green Synthesis of Cationic Polyacrylamide Composite Catalyzed by An Ecologically Catalyst Clay Called Maghnite-H+ (Algerian MMT Under Microwave Irradiation.

    Directory of Open Access Journals (Sweden)

    Rahmouni Abdelkader


    Full Text Available In this study, a novel green cationic hydrogel of cationic polyacrylamide composite have been prepared and investigated. The synthesis of green cationic polyacrylamide composite was evaluated for its solubility in water. The reactions were performed using acrylamide monomer, solvent, catalyst (clay fin called maghnite and solution of  H2SO4 (0.25 M, with the system under microwave irradiation (160 ºC for 4 min. Major factors affecting the polymerization reaction were studied with a view to discover appropriate conditions for preparation of the composite. The cationic polyacrylamide obtained is the subject of future studies of modification and transformation. The resulting polymer has been characterized by a variety of characterization techniques, such as: Fourier Transform Infrared Spectra and 1H NMR spectra.  Copyright © 2016 BCREC GROUP. All rights reserved Received: 10th June 2015; Revised: 2nd September 2015; Accepted: 5th January 2016 How to Cite: Abdelkader, R., Mohammed, B. (2016. Green Synthesis of Cationic Polyacrylamide Composite Catalyzed by An Ecologically  Catalyst Clay Called Maghnite-H+ (Algerian MMT Under Microwave Irradiation. Bulletin of Chemical Reaction Engineering & Catalysis, 11 (2: 170-175 (doi:10.9767/bcrec.11.2.543.170-175 Permalink/DOI:

  7. Effect of cations on the hydrated proton. (United States)

    Ottosson, Niklas; Hunger, Johannes; Bakker, Huib J


    We report on a strong nonadditive effect of protons and other cations on the structural dynamics of liquid water, which is revealed using dielectric relaxation spectroscopy in the frequency range of 1-50 GHz. For pure acid solutions, protons are known to have a strong structuring effect on water, leading to a pronounced decrease of the dielectric response. We observe that this structuring is reduced when protons are cosolvated with salts. This reduction is exclusively observed for combinations of protons with other ions; for all studied solutions of cosolvated salts, the effect on the structural dynamics of water is observed to be purely additive, even up to high concentrations. We derive an empirical model that quantitatively describes the nonadditive effect of cosolvated protons and cations. We argue that the effect can be explained from the special character of the proton in water and that Coulomb fields exerted by other cations, in particular doubly charged cations like Mg(2+)aq and Ca(2+)aq, induce a localization of the H(+)aq hydration structures.

  8. NMR studies of cation transport across membranes

    Energy Technology Data Exchange (ETDEWEB)

    Shochet, N.R.


    /sup 23/Na NMR Studies of cation transport across membranes were conducted both on model and biological membranes. Two ionophores, the carrier monensin and the channel-former gramicidin, were chosen to induce cation transport in large unilamellar phosphatidylcholine vesicles. The distinction between the NMR signals arising from the two sides of the membrane was achieved by the addition of an anionic paramagnetic shift reagent to the outer solution. The kinetics of the cation transport across the membrane was observed simultaneously monitoring the changes in the /sup 23/Na NMR signals of both compartments. Two mathematical models were developed for the estimation of the transport parameters of the monensin- and gramicidin-induced cation transport. The models were able to fit the experimental data very well. A new method for the estimation of the volume trapped inside the vesicles was developed. The method uses the relative areas of the intra- and extravesicular NMR signals arising from a suspension of vesicles bathed in the same medium they contain, as a measure for the relative volumes of these compartments. Sodium transport across biological membranes was studied by /sup 23/ NMR, using suspensions of cultured nerve cells. The sodium influx through voltage-gated channels was studied using the channel modifier batrachotoxin in combination with scorpion toxin.

  9. Mixed cation effect in sodium aluminosilicate glasses

    DEFF Research Database (Denmark)

    Kjeldsen, Jonas; Smedskjær, Morten Mattrup; Mauro, John C.

    , network structure, and the resistances associated with the deformation processes in mixed cation glasses by partially substituting magnesium for calcium and calcium for lithium in sodium aluminosilicate glasses. We use Raman and 27Al NMR spectroscopies to obtain insights into the structural...

  10. Resonance raman studies of phenylcyclopropane radical cations

    NARCIS (Netherlands)

    Godbout, J.T.; Zuilhof, H.; Heim, G.; Gould, I.R.; Goodman, J.L.; Dinnocenzo, J.P.; Myers Kelley, A.


    Resonance Raman spectra of the radical cations of phenylcyclopropane and trans-1-phenyl-2-methylcyclopropane are reported. A near-UV pump pulse excites a photosensitizer which oxidizes the species of interest, and a visible probe pulse delayed by 35 ns obtains the spectrum of the radical ion. The

  11. Water Adsorption on Free Cobalt Cluster Cations

    NARCIS (Netherlands)

    Kiawi, Denis M.; Bakker, Joost M.; Oomens, Jos; Buma, Wybren Jan; Jamshidi, Zahra; Visscher, Lucas; Waters, L. B. F. M.


    Cationic cobalt clusters complexed with water Con+–H2O (n = 6–20) are produced through laser ablation and investigated via infrared multiple photon dissociation (IR-MPD) spectroscopy in the 200–1700 cm–1 spectral range. All spectra exhibit a resonance close to the 1595 cm–1 frequency of the free

  12. Water adsorption on free cobalt cluster cations

    NARCIS (Netherlands)

    Kiawi, D.M.; Bakker, J.M.; Oomens, J.; Buma, W.J.; Jamshidi, Z.; Visscher, L.; Waters, L.B.F.M.


    Cationic cobalt clusters complexed with water Con+-​H2O (n = 6-​20) are produced through laser ablation and investigated via IR multiple photon dissocn. (IR-​MPD) spectroscopy in the 200-​1700 cm-​1 spectral range. All spectra exhibit a resonance close to the 1595 cm-​1 frequency of the free water

  13. Simultaneous anion and cation mobility in polypyrrole

    DEFF Research Database (Denmark)

    Skaarup, Steen; Bay, Lasse; Vidanapathirana, K.


    Polypyrrole (PPy) polymer films permanently doped with large, immobile anion dodecyl benzene sulfonate (DBS) have been characterized by cyclic voltammetry in order to clarify the roles of cations and anions in the aqueous electrolyte as mobile ions in the film. Aqueous solutions of 0.05-0.1 M...

  14. Cationic flotation of some lithium ores

    International Nuclear Information System (INIS)

    Valadao, G.E.S.; Peres, A.E.C.; Silva, H.C. da


    The cationic flotation of some lithium ores (spodumene, amblygonite, petalite, lepidolite) is studied by the measure of zeta potential and micro-flotation tests in Hallimond tube. The effect of some modifier agents (corn starch, meta sodium silicate) on the lithium flotation is studied. (M.A.C.) [pt

  15. The Off-rate of Monomers Dissociating from Amyloid-β Protofibrils* (United States)

    Grüning, Clara S. R.; Klinker, Stefan; Wolff, Martin; Schneider, Mario; Toksöz, Küpra; Klein, Antonia N.; Nagel-Steger, Luitgard; Willbold, Dieter; Hoyer, Wolfgang


    The interconversion of monomers, oligomers, and amyloid fibrils of the amyloid-β peptide (Aβ) has been implicated in the pathogenesis of Alzheimer disease. The determination of the kinetics of the individual association and dissociation reactions is hampered by the fact that forward and reverse reactions to/from different aggregation states occur simultaneously. Here, we report the kinetics of dissociation of Aβ monomers from protofibrils, prefibrillar high molecular weight oligomers previously shown to possess pronounced neurotoxicity. An engineered binding protein sequestering specifically monomeric Aβ was employed to follow protofibril dissociation by tryptophan fluorescence, precluding confounding effects of reverse or competing reactions. Aβ protofibril dissociation into monomers follows exponential decay kinetics with a time constant of ∼2 h at 25 °C and an activation energy of 80 kJ/mol, values typical for high affinity biomolecular interactions. This study demonstrates the high kinetic stability of Aβ protofibrils toward dissociation into monomers and supports the delineation of the Aβ folding and assembly energy landscape. PMID:24247242

  16. Polyimide, dianhydride monomers, and polymers, methods of making and uses thereof

    KAUST Repository

    Pinnau, Ingo


    Embodiments of the present disclosure include, a dianhydride monomer, a polyimide, a method of making a dianhydride, a method of making a polyimide, and the like. Embodiments of the present disclosure can be used in membrane-based gas separation applications.

  17. Evaluation of residual monomer release and toxicity of self-adhesive resin cements. (United States)

    Kurt, Aysegul; Altintas, Subutay Han; Kiziltas, Mustafa Volkan; Tekkeli, Serife Evrim; Guler, Eray Metin; Kocyigit, Abdurrahim; Usumez, Aslihan


    The aim of this study was to evaluate the amount of leached residual monomers from self-adhesive resin cements and evaluate their toxicity in-vitro. A total of 60 disk-shaped specimens (5 mm in diameter and 0.5 mm in thickness) were prepared from each cement (RelyX U200, SpeedCEM, G-Cem) (n=20). Specimens were immersed in artificial saliva and the amount of released monomers [urethane dimethacrylate (UDMA) and triethyleneglycol dimethacrylate (TEGDMA)] was identified. Then, the cytotoxicity and genotoxicity effect on cells were evaluated using the defined amounts of released monomers from cements. The highest monomer release was detected in G-Cem (p<0.05). The highest cytotoxicity value was identified from SpeedCEM (p<0.01) and the highest genotoxicity values were calculated from RelyX U200 (p<0.05). Released UDMA and TEGDMA from self-adhesive resin cements induced cytotoxicity and genotoxicity effect on cells.

  18. Regulation of the PI3K pathway through a p85a monomer-homodimer equilibrium

    KAUST Repository

    Aljedani, Safia Salim Eid


    The phosphatidylinositol-3-kinase a (PI3Ka) is heterodimeric enzyme that is composed of p85a regulatory subunit and a p110a catalytic subunit. PI3Ka plays a key role in cell survival, growth and differentation. Owing to its role as a key regulator, the PI3Ka pathway is the most frequently mutated pathway in human cancers, and is targeted by many viruses to insure their survival and successful reproduction. Previous studies have shown that the equilibrium of p85 monomers and dimers regulates the PI3K pathway, suggesting that interrupting this equilibrium could lead to disease development. Moreover, studies suggest that the p85a monomers and dimers have opposing effects on PI3Ka signaling as only the p85a dimers bind to the PTEN phosphatase, whereas p85a monomers bind to the catalytic p110 subunit. However, the mechanism for dimerisation is controversial, and it is unknown why PTEN or p110a bind only dimer or monomer. Therefore, we combine molecular biology, biophsical, computational and structural methods to investigate the suprosingly complex p85 dimerisation mechanism and its control by ligands. Results may inspire novel theraputic approaches.

  19. Effect of operation variables and monomers on the properties of polyamide microcapsules. (United States)

    Zhang, M; Ni, P; Yan, N


    Oil containing microcapsules were prepared by using phthaloyl dichloride as an oil-soluble monomer and diethylene triamine (DETA) as a water-soluble monomer. The diameter of the microcapsules decreased and their distribution became narrower and sharper as the emulsifying time was increased within the initial period of 45 s, beyond which no appreciable changes in the diameter and its distribution were observed. Once DETA was introduced into the aqueous solution to initiate the interfacial polycondensation reaction, reducing the stirring speed diminished the formation of the membrane fragments, but resulted in an increase in the microcapsule diameter. This indicates that the strength of the initial membrane is not strong enough to prevent the microcapsules from coalescing. Raising the volume fraction of the dispersed phase led to a larger diameter and a wider distribution of the microcapsules. When ortho-, meta- or para-phthaloyl dichloride was used as the oil-soluble monomer, both the diameter and the zeta-potential of the microcapsules decreased in the order: ortho-->meta-->para-, indicating that the steric effect of the monomers plays an important role in the microencapsulation process.

  20. Pseudomonas syringae evades host immunity by degrading flagellin monomers with alkaline protease AprA

    NARCIS (Netherlands)

    Pel, Michiel J C; van Dijken, Anja J H; Bardoel, Bart W; Seidl, Michael F; van der Ent, Sjoerd; van Strijp, Jos A G; Pieterse, Corné M J

    Bacterial flagellin molecules are strong inducers of innate immune responses in both mammals and plants. The opportunistic pathogen Pseudomonas aeruginosa secretes an alkaline protease called AprA that degrades flagellin monomers. Here, we show that AprA is widespread among a wide variety of

  1. Pseudomonas syringae evades host Immunity by degrading flagellin monomers with alkaline protease AprA

    NARCIS (Netherlands)

    Pel, M.J.C.; Van Dijken, A.J.H.; Bardoel, B.W.; Seidl, M.F; Van der Ent, S.; Van Strijp, J.A.G.


    Bacterial flagellin molecules are strong inducers of innate immune responses in both mammals and plants. The opportunistic pathogen Pseudomonas aeruginosa secretes an alkaline protease called AprA that degrades flagellin monomers. Here, we show that AprA is widespread among a wide variety of

  2. High-resolution structure of a retroviral protease folded as a monomer

    Czech Academy of Sciences Publication Activity Database

    Gilski, M.; Kazmierczyk, M.; Krzywda, S.; Zábranská, Helena; Cooper, S.; Popovic, Z.; Khatíb, F.; Dímaio, F.; Thompson, J.; Baker, D.; Pichová, Iva; Jaskolski, M.

    D67, č. 11 (2011), s. 907-914 ISSN 0907-4449 R&D Projects: GA MŠk 1M0508 Institutional research plan: CEZ:AV0Z40550506 Keywords : M-PMV protease * crystal structure * monomer * dimerization inhibitors Subject RIV: CE - Biochemistry Impact factor: 12.619, year: 2011

  3. Heterogeneous glycoform separation by process chromatography: I: Monomer purification and characterization. (United States)

    Li, Yi; Xu, Xuankuo; Shupe, Alan; Yang, Rong; Bai, Kevin; Das, Tapan; Borys, Michael C; Li, Zheng Jian


    Fc fusion proteins with high and low sialylation were purified and separated by preparative ion-exchange and hydrophobic interaction chromatography. Heterogeneity in sialylation and glycosylation led to variation in surface charge and hydrophobicity, and resulted in multiple distinct glycoform populations in response to various purification conditions. Monomer with high sialic acid content has higher surface charge and adsorbs stronger to ion-exchange resin, while the less sialylated monomer interacts more favorably with hydrophobic resin. Extensive biophysical characterization was carried out for purified monomers at different level of sialylation. In general, different monomeric glycoforms have different surface charge and hydrophobicity, different thermal stability, and different aggregation propensity. The surface charge corresponds well with sialic acid content, as evidenced by electrophoresis, N-link domain analysis, and zeta potential results. The sialylation also contributes to minor modification of protein size, molecular mass and tertiary structure. Notably, fluorescence emission spectra and thermal transition became less distinguishable when the monomers containing low and high sialic acid were prepared in high ionic strength solution. Such finding reiterates the fact that the electrostatic forces, which are largely dependent on sialic acid content of protein, plays a dominant role in many intra- and inter-molecular interactions. Overall, the characterization data agreed well with separation behaviors and provided valuable insight to control of glycoform profile in purification process. Copyright © 2015 Elsevier B.V. All rights reserved.

  4. Theoretical investigation on monomer and solvent selection for molecular imprinting of nitrocompounds. (United States)

    Saloni, Julia; Walker, Kiara; Hill, Glake


    The aim of this work is to serve as a guideline for the initial selection of monomer and solvent for the synthesis of the nitrocompound-based molecularly imprinted polymers, MIPs. Reported data include evaluation of six systems with the ability to form noncovalently bonded monomer-template complexes. These systems are represented by the following aliphatic and aromatic molecules: acrolein, acrylonitrile, 2,6-bisacrylamide, 4-ethylenebenzoic acid, methyl methacrylate, and 2-vinylpyridine. Cave models for selected monomers are also presented and supported by binding energy analysis under various conditions. Solvent effects on monomer-template binding energy have been studied for four solvents: acetone, acetonitrile, chloroform, and methanol. Additionally, systems such as 2,4-dinitrotoluene (2,4-DNT), 2,6-dinitrotoluene (2,6-DNT), pentachlorophenol (PCP), and 3,6-dichloro-2-methoxybenzoic acid (Dicamba) have been used to study selectivity of acrolein-based MIP toward TNT detection. The density functional theory, DFT, method has been used for all structural, vibrational frequency, and solvent calculations.

  5. Migration of formaldehyde and melamine monomers from kitchen- and tableware made of melamine plastic

    DEFF Research Database (Denmark)

    Lund, K.H.; Petersen, J.H.


    Migration of one or both formaldehyde and/or melamine monomers was found in seven of ten tested melamine samples bought on the Danish market. The samples were a bowl, a jug, a mug, a ladle, and different cups and plates. No violation of the European Union-specific migration limits for melamine (30...

  6. Selective crystallization of cations with crown ethers

    International Nuclear Information System (INIS)

    Heffels, Dennis Egidius


    The aim of this work was to study the selectivity and preferences of the incorporation of differently sized cations in the cavities of various crown ethers and the characterization of the resulting compounds. The coordination preferences of crown ethers with different cavities have long been known, and the impact of other effects on the structure formation have increasingly become the focus of attention. In this work a comparative overview of the coordination preferences depending on various factors was undertaken. The focus was mainly on the variation of the cavity of the crown ether in the presence of differently sized cations. In addition, the effects of the solvent and differently coordinating anions have been investigated. Within the framework of this work, basic coordination preferences could be detected with rare earth nitrates, which are affected particularly by the choice of the solvent. The formation of different types of structures could be controlled by varying the conditions such that the incorporation of the cation in the cavity of the crown ether was influenced and the formation of a particular type of structure can be influenced partly by the choice of solvent. In this case no direct preferences for the incorporation into the cavity of the crown ether in relation to the cation size were observed for rare earth cations. However, the coordination of the crown ether leads in each case - for lanthanides - to rather high coordination numbers. A total of five new rare earth complexes and two structural variants could be observed with crown ethers. In the study of the selectivity of the incorporation into the cavity, known structures were also reproduced and further structures were characterized but the crystal structures not entirely solved. With the use of monovalent cations such as potassium, lithium or silver a total of nine new compounds could be synthesized, while no clear preferences for the incorporation of certain cations were detected. The

  7. Spectroscopy of electronic transitions in Polycyclic Aromatic Hydrocarbon cations and their clusters

    International Nuclear Information System (INIS)

    Friha, Hela


    This thesis is an experimental study of the electronic spectroscopy of cations of Polycyclic Aromatic Hydrocarbons (PAHs) and their aggregates in conditions close to those of the interstellar medium (ISM), i.e. cold and totally isolated in the gas phase. It is related to the astrophysical context of the interstellar medium (ISM), in particular on the question of the possible link between interstellar PAHs and Diffuse Interstellar Bands (DIBs). The purpose of this thesis is to provide laboratory spectra which can be directly compared to the spectra of DIBs. Indeed these bands are the oldest spectroscopy riddle in astrophysics which remained unanswered for nearly 100 years and whose key is still looked for. A special attention is given to the methylated derivatives of PAHs species detected in many interstellar environments, cationic PAH dimers (the simplest PAH clusters). These clusters have been proposed as a model of the very small grains, which contribute to the formation of interstellar PAHs and whose chemical composition remains uncertain. This thesis has been mainly devoted to the determination of the electronic spectra of naphthalene cation monomer (Np + ) and its methylated derivative (2-MeN p + ), as well as the associated homogeneous dimers. The experimental method used is based on the photodissociation of van der Waals complexes PAH + m -Ar n (argon atoms spectators), prepared by UV laser photoionization in a supersonic jet. This technique combines different experimental tools, namely: molecular beam mass spectrometry and laser spectroscopy as well as physical tools such as the handling of clusters VdW PAH + m -Ar n , the detection of photo-fragments, the measurement of photodissociation efficiency. The identification of the fragments by the photodissociation of VdW clusters allowed us to determine the different possible fragmentation channels and especially to obtain the spectra the charge resonance transition and the first allowed transition to locally

  8. The difference of acrylic resin residual monomer levels with various polymerization method

    Directory of Open Access Journals (Sweden)

    Sherman Salim


    Full Text Available Background: After polymerization process, heat cured acrylic resin denture base actually still contains residual monomers that can become potential irritants later in oral cavity. Polymerization process is essential to obtain acrylic resin which can meet the requirements of the biocompatible and good physical properties. To meet the requirements, there are several methods of polymerization process used. Purpose: The purpose of this study was to determine the differences of the residual monomer levels of acrylic resin processed by various polymerization methods. Methods: Acrylic resin powder and liquid were mixed based on the rules of factory, and sample was made with size of 30 mm × 50 mm × 3 mm and then polymerized by using microwave at 70° C for 24 hours based on the methods of Japan Industrial Standard (JIS. Each group of samples was cut with weight of ± 0.2 g, dissolved in 5 ml of methyl ethyl ketone in test tubes, and then stored at ± 5° C for four days. Residual monomer level was conducted by using gas chromatograph mass spectrometer. Data obtained were then analyzed by using One-Way ANOVA test with p < 0.05. Results: After the level of polymerizing residual monomer with JIS method was compared to that at 70° C for 24 hours using microwave, it is known that there were significant differences (p < 0.05. Conclusion: The highest level of residual monomer of acrylic resin was that polymerized at 70° C for 24 hours.Latar belakang: Basis gigi tiruan yang berbahan dasar resin akrilik jenis heat cured setelah proses polimerisasi selesai masih mengandung monomer sisa yang berpotensi sebagai bahan iritan dalam rongga mulut. Proses polimerisasi sangat penting untuk mendapatkan resin akrilik yang memenuhi persyaratan biokompatibilitas dan fisik yang baik. Untuk persyaratan tersebut digunakan berbagai macam proses polimerisasi. Tujuan: Penelitian ini bertujuan untuk menentukan kadar monomer sisa resin akrilik yang diproses dengan metode

  9. Variation in array size, monomer composition and expression of the macrosatellite DXZ4.

    Directory of Open Access Journals (Sweden)

    Deanna C Tremblay

    Full Text Available Macrosatellites are some of the most polymorphic regions of the human genome, yet many remain uncharacterized despite the association of some arrays with disease susceptibility. This study sought to explore the polymorphic nature of the X-linked macrosatellite DXZ4. Four aspects of DXZ4 were explored in detail, including tandem repeat copy number variation, array instability, monomer sequence polymorphism and array expression. DXZ4 arrays contained between 12 and 100 3.0 kb repeat units with an average array containing 57. Monomers were confirmed to be arranged in uninterrupted tandem arrays by restriction digest analysis and extended fiber FISH, and therefore DXZ4 encompasses 36-288 kb of Xq23. Transmission of DXZ4 through three generations in three families displayed a high degree of meiotic instability (8.3%, consistent with other macrosatellite arrays, further highlighting the unstable nature of these sequences in the human genome. Subcloning and sequencing of complete DXZ4 monomers identified numerous single nucleotide polymorphisms and alleles for the three microsatellite repeats located within each monomer. Pairwise comparisons of DXZ4 monomer sequences revealed that repeat units from an array are more similar to one another than those originating from different arrays. RNA fluorescence in situ hybridization revealed significant variation in DXZ4 expression both within and between cell lines. DXZ4 transcripts could be detected originiating from both the active and inactive X chromosome. Expression levels of DXZ4 varied significantly between males, but did not relate to the size of the array, nor did inheritance of the same array result in similar expression levels. Collectively, these studies provide considerable insight into the polymorphic nature of DXZ4, further highlighting the instability and variation potential of macrosatellites in the human genome.

  10. Monomer priming of denture teeth and its effects on the bond strength of composite resin. (United States)

    Perea, Leila; Matinlinna, Jukka P; Tolvanen, Mimmi; Lassila, Lippo V; Vallittu, Pekka K


    The bond strength of acrylic resin denture teeth used as pontics in fiber-reinforced composite fixed dental prostheses needs to be improved. The purpose of this study was to assess the influence of various chemical surface-conditioning monomers on the ridge-lap surface of acrylic resin denture teeth by determining the strength of their bonding to a composite resin and changes in surface hardness. Acrylic resin denture teeth of 2 different brands (Artic 8 and Vitapan Cuspiform) (n=120) were tested. Four monomer systems were used as surface primers (conditioning): a flowable composite resin, methylmethacrylate 99%, composite primer, and a photopolymerizable dimethacrylate resin. Five surface-conditioning exposure times were used: no conditioning, 1, 5, 15, and 60 minutes. Surface microhardness measurements were made after the application of the monomer systems. Shear bond strength tests were subsequently performed, followed by a new surface microhardness indentation after the application of the load. The evaluation of the changes on specimen surfaces was performed with a scanning electron microscope. The differences between the shear bond strength and the surface hardness were evaluated for statistical significance by using a 3-way ANOVA. Tooth brand, monomer used, exposure time, and their 2- and 3-way interactions had a significant effect on the shear bond strength and hardness before and after testing, except for the 3-way interaction effect on hardness before testing. The chemical pretreatment of the ridge-lap surface of acrylic resin denture teeth increased the shear bond strength and influenced the surface hardness. The monomer systems caused dissolution on the denture surfaces. Copyright © 2014 Editorial Council for the Journal of Prosthetic Dentistry. Published by Elsevier Inc. All rights reserved.

  11. Organic - Inorganic Hybrids made from Polymerizable Precursors

    NARCIS (Netherlands)

    Uricanu, V.I.; Donescu, D.; Banu, A.G.; Serban, S.; Olteanu, M.; Dudau, M.


    Organic–inorganic hybrid films were prepared based on a recipe using organoalkoxysilanes’ ability to create an inorganic network combined with polymer network formation via radical polymerization of the organic groups. The starting mixtures included different triethoxysilanes (RTES), where the

  12. Printing continuously graded interpenetrating polymer networks of acrylate/epoxy by manipulating cationic network formation during stereolithography

    Directory of Open Access Journals (Sweden)

    W. Li


    Full Text Available Ultra-violet (UV laser assisted stereolithography is used to print graded interpenetrating polymer networks (IPNs by controlling network formation. Unlike the traditional process where structural change in IPNs is achieved by varying the feeding ratio of monomers or polymer precursors, in this demonstration property is changed by controlled termination of network formation. A photo-initiated process is used to construct IPNs by a combination of radical and cationic network formation in an acrylate/epoxy system. The extent of the cationic network formation is used to control the final properties of the system. Rapid-Scan Fourier Transformation Infrared Spectroscopy (RS-FTIR is used to track the curing kinetics of the two networks and identify key parameters to control the final properties. Atomic force microscopy (AFM and differential scanning calorimetry (DSC confirm the formation of homogenous IPNs, whereas nano-indentation indicates that properties vary with the extent of cationic network formation. The curing characteristics are used to design and demonstrate printing of graded IPNs that show two orders of magnitude variation in mechanical properties in the millimeter scale.

  13. The Use of Commercial Non-Hazardous Air Pollutant Monomers to Optimize the Properties of Fatty Acid-Based Resins (United States)


    It was found that cyclohexyl methacrylate (CHMA) was the most effective reactive diluent in replacing methacrylated lauric acid (MLau) because it...The reaction of glycidyl methacrylate and lauric acid to produce the MLau monomer... acid -based monomers to be used as the reactive diluent in VE resins (9, 10). Figure 1 depicts the synthetic route used to form methacrylated lauric

  14. Guidelines To Select the N-Heterocyclic Carbene for the Organopolymerization of Monomers with a Polar Group

    KAUST Repository

    Falivene, Laura


    We report on the DFT stability of zwitterion and spirocycle adducts of five polar monomers with nine N-heterocyclic carbenes (NHC), covering the most typical classes of monomers and NHCs used in organopolymerization. Results indicate that the relative stability of the two adducts is dominated by the singlet-triplet energy gap of the free NHC, with low energy gaps favoring the spirocycle adduct, while high energy gaps favor the zwitterionic adduct. This basic structure/property relationship can be tuned by the hindrance of the NHC and the nature of the monomer. In addition to rationalize existing systems, the 45 NHC/monomer combinations we examined can be used as a guideline to predict the behavior of a new NHC/monomer combination.

  15. The adjuvant mechanism of cationic dimethyldioctadecylammonium liposomes

    DEFF Research Database (Denmark)

    Korsholm, Karen Smith; Agger, Else Marie; Foged, Camilla


    Cationic liposomes are being used increasingly as efficient adjuvants for subunit vaccines but their precise mechanism of action is still unknown. Here, we investigated the adjuvant mechanism of cationic liposomes based on the synthetic amphiphile dimethyldioctadecylammonium (DDA). The liposomes...... concentrations. This efficient adsorption onto the liposomes led to an enhanced uptake of OVA by BM-DCs as assessed by flow cytometry and confocal fluorescence laser-scanning microscopy. This was an active process, which was arrested at 4 degrees and by an inhibitor of actin-dependent endocytosis, cytochalasin D....... In vivo studies confirmed the observed effect because adsorption of OVA onto DDA liposomes enhanced the uptake of the antigen by peritoneal exudate cells after intraperitoneal injection. The liposomes targeted antigen preferentially to antigen-presenting cells because we only observed a minimal uptake...

  16. Regulation of Cation Balance in Saccharomyces cerevisiae (United States)

    Cyert, Martha S.; Philpott, Caroline C.


    All living organisms require nutrient minerals for growth and have developed mechanisms to acquire, utilize, and store nutrient minerals effectively. In the aqueous cellular environment, these elements exist as charged ions that, together with protons and hydroxide ions, facilitate biochemical reactions and establish the electrochemical gradients across membranes that drive cellular processes such as transport and ATP synthesis. Metal ions serve as essential enzyme cofactors and perform both structural and signaling roles within cells. However, because these ions can also be toxic, cells have developed sophisticated homeostatic mechanisms to regulate their levels and avoid toxicity. Studies in Saccharomyces cerevisiae have characterized many of the gene products and processes responsible for acquiring, utilizing, storing, and regulating levels of these ions. Findings in this model organism have often allowed the corresponding machinery in humans to be identified and have provided insights into diseases that result from defects in ion homeostasis. This review summarizes our current understanding of how cation balance is achieved and modulated in baker’s yeast. Control of intracellular pH is discussed, as well as uptake, storage, and efflux mechanisms for the alkali metal cations, Na+ and K+, the divalent cations, Ca2+ and Mg2+, and the trace metal ions, Fe2+, Zn2+, Cu2+, and Mn2+. Signal transduction pathways that are regulated by pH and Ca2+ are reviewed, as well as the mechanisms that allow cells to maintain appropriate intracellular cation concentrations when challenged by extreme conditions, i.e., either limited availability or toxic levels in the environment. PMID:23463800

  17. Mechanism of metal cationization in organic SIMS

    International Nuclear Information System (INIS)

    Wojciechowski, I.; Delcorte, A.; Gonze, X.; Bertrand, P.


    A scenario of metal cationization in which the organic molecule combines with a neutral excited metal atom is proposed. Ionization of the nascent complex occurs via ejection of an electron during the association process. Electron structure calculations for the model systems C 6 H 6 +Me (Me=Ag, Cu, Au) using the density functional theory give a strong argument in favor of the proposed mechanism

  18. Proton dynamics investigation for dimethyl ammonium cation

    International Nuclear Information System (INIS)

    Pislewski, N.; Tritt-Goc, J.; Jakubas, R.


    Proton dynamics in dimethyl ammonium cation has been investigated by means of NMR and spin echo methods in polycrystalline salts [NH 2 (CH 3 ) 2 ] + Bi 2 J 9 - and [NH 2 (CH 3 ) 2 ] + SbJ 9 - . Spin-lattice relaxation time as well as second moment of NMR line have been measured for influence study of crystal structure changes on proton dynamics

  19. Reducible cationic lipids for gene transfer. (United States)

    Wetzer, B; Byk, G; Frederic, M; Airiau, M; Blanche, F; Pitard, B; Scherman, D


    One of the main challenges of gene therapy remains the increase of gene delivery into eukaryotic cells. We tested whether intracellular DNA release, an essential step for gene transfer, could be facilitated by using reducible cationic DNA-delivery vectors. For this purpose, plasmid DNA was complexed with cationic lipids bearing a disulphide bond. This reduction-sensitive linker is expected to be reduced and cleaved in the reducing milieu of the cytoplasm, thus potentially improving DNA release and consequently transfection. The DNA--disulphide-lipid complexation was monitored by ethidium bromide exclusion, and the size of complexes was determined by dynamic light scattering. It was found that the reduction kinetics of disulphide groups in DNA--lipid complexes depended on the position of the disulphide linker within the lipid molecule. Furthermore, the internal structure of DNA--lipid particles was examined by small-angle X-ray scattering before and after lipid reduction. DNA release from lipid complexes was observed after the reduction of disulphide bonds of several lipids. Cell-transfection experiments suggested that complexes formed with selected reducible lipids resulted in up to 1000-fold higher reporter-gene activity, when compared with their analogues without disulphide bonds. In conclusion, reduction-sensitive groups introduced into cationic lipid backbones potentially allow enhanced DNA release from DNA--lipid complexes after intracellular reduction and represent a tool for improved vectorization. PMID:11389682

  20. GPCR homomers and heteromers: a better choice as targets for drug development than GPCR monomers? (United States)

    Casadó, Vicent; Cortés, Antoni; Mallol, Josefa; Pérez-Capote, Kamil; Ferré, Sergi; Lluis, Carmen; Franco, Rafael; Canela, Enric I


    G protein-coupled receptors (GPCR) are targeted by many therapeutic drugs marketed to fight against a variety of diseases. Selection of novel lead compounds are based on pharmacological parameters obtained assuming that GPCR are monomers. However, many GPCR are expressed as dimers/oligomers. Therefore, drug development may consider GPCR as homo- and hetero-oligomers. A two-state dimer receptor model is now available to understand GPCR operation and to interpret data obtained from drugs interacting with dimers, and even from mixtures of monomers and dimers. Heteromers are distinct entities and therefore a given drug is expected to have different affinities and different efficacies depending on the heteromer. All these concepts would lead to broaden the therapeutic potential of drugs targeting GPCRs, including receptor heteromer-selective drugs with a lower incidence of side effects, or to identify novel pharmacological profiles using cell models expressing receptor heteromers.

  1. Direct Arylation Strategies in the Synthesis of π-Extended Monomers for Organic Polymeric Solar Cells

    Directory of Open Access Journals (Sweden)

    Andrea Nitti


    Full Text Available π-conjugated macromolecules for organic polymeric solar cells can be rationally engineered at the molecular level in order to tune the optical, electrochemical and solid-state morphology characteristics, and thus to address requirements for the efficient solid state device implementation. The synthetic accessibility of monomers and polymers required for the device is getting increasing attention. Direct arylation reactions for the production of the π-extended scaffolds are gaining importance, bearing clear advantages over traditional carbon-carbon forming methodologies. Although their use in the final polymerization step is already established, there is a need for improving synthetic accessibility to implement them also in the monomer synthesis. In this review, we discuss recent examples highlighting this useful strategy.

  2. Mangrove tannins and their flavanoid monomers as alternative steel corrosion inhibitors in acidic medium

    International Nuclear Information System (INIS)

    Rahim, Afidah A.; Rocca, E.; Steinmetz, J.; Kassim, M.J.; Adnan, R.; Sani Ibrahim, M.


    The inhibitive behaviour on steel of flavanoid monomers that constitute mangrove tannins namely catechin, epicatechin, epigallocatechin and epicatechingallate was investigated in an aerated HCl solution via electrochemical methods. The monomers were found to be mainly cathodic inhibitors and the inhibition efficiency was dependent on concentration. To explain the adsorptive behaviour of the molecules on the steel surface, a semiempirical approach involving quantum chemical calculations using HyperChem 6.0 was undertaken. The HOMO electronic density of the molecule was used to explain the inhibiting mechanism. The most probable adsorption centers were found in the vicinity of the phenolic groups. In a second part, the use of mangrove tannin, extracted from the mangrove barks as steel corrosion inhibitors in acidic media was investigated and its inhibitive efficiency was compared with that of commercial mimosa, quebracho and chestnut tannins. The inhibitive performance of mangrove tannins was comparable to the other tannins investigated, indicating their potential in corrosion protection

  3. Structural characterization of the alpha-hemolysin monomer from Staphylococcus aureus. (United States)

    Meesters, Christian; Brack, Antje; Hellmann, Nadja; Decker, Heinz


    Alpha-hemolysin from Staphylococcus aureus is secreted as a water-soluble monomer and assembles on membranes to oligomerize into a homo-heptameric, water-filled pore. These pores lead to lysis and cell death. Although the structure of the heptameric pore is solved by means of X-ray crystallography, structures of intermediate states-from the soluble monomer to all potential "pre-pore" structures-are yet unknown. Here, we propose a model of the monomeric alpha-hemolysin in solution based on molecular modeling, verified by small angle X-ray scattering data. This structure reveals details of the monomeric conformation of the alpha-hemolysin, for example inherent flexibility, along with definite differences in comparison to the structures used as templates. (c) 2008 Wiley-Liss, Inc.

  4. Penelitian penggunaan monomer n-butil akrilat untuk peningkatan mutu kulit secara iradiasi

    Directory of Open Access Journals (Sweden)

    Dwi Wahini Nurhajati


    Full Text Available Research on the utilization of n-butyl acrylate monomer for quality improvement leather by irradiation cobalt-60 gamma-rays is carried out as follows: Javanese crust hide was impregnated with water emulsions of n-butyl acrylate monomer for 2 hours, packed in to poly ethylene bags, sealed, then irradiated by cobalt-60 gamma rays (doses : 5 to 25 kGy. The irradiated leather was washed by water, dried and then physical tested. The results of physical test of leather modified with n-butyl acrylate showed the increasing of tensile strength and elongation, decreasing of water absorption, resistance against the flexing test of 20,000 times, and PH was constant. Organoleptic test showed that the softly of the modified leather was no different with unmodified leather.

  5. Direct Arylation Strategies in the Synthesis of π-Extended Monomers for Organic Polymeric Solar Cells. (United States)

    Nitti, Andrea; Po, Riccardo; Bianchi, Gabriele; Pasini, Dario


    π-conjugated macromolecules for organic polymeric solar cells can be rationally engineered at the molecular level in order to tune the optical, electrochemical and solid-state morphology characteristics, and thus to address requirements for the efficient solid state device implementation. The synthetic accessibility of monomers and polymers required for the device is getting increasing attention. Direct arylation reactions for the production of the π-extended scaffolds are gaining importance, bearing clear advantages over traditional carbon-carbon forming methodologies. Although their use in the final polymerization step is already established, there is a need for improving synthetic accessibility to implement them also in the monomer synthesis. In this review, we discuss recent examples highlighting this useful strategy.

  6. Mangrove tannins and their flavanoid monomers as alternative steel corrosion inhibitors in acidic medium

    Energy Technology Data Exchange (ETDEWEB)

    Rahim, Afidah A. [School of Chemical Sciences, University Sains Malaysia, 11800 Penang (Malaysia)]. E-mail:; Rocca, E. [Laboratoire de Chimie du Solide Mineral, Universite Henri Poincare, Nancy I BP 239, 54506 Vandoeuvre Les Nancy (France); Steinmetz, J. [Laboratoire de Chimie du Solide Mineral, Universite Henri Poincare, Nancy I BP 239, 54506 Vandoeuvre Les Nancy (France); Kassim, M.J. [School of Chemical Sciences, University Sains Malaysia, 11800 Penang (Malaysia); Adnan, R. [School of Chemical Sciences, University Sains Malaysia, 11800 Penang (Malaysia); Sani Ibrahim, M. [School of Chemical Sciences, University Sains Malaysia, 11800 Penang (Malaysia)


    The inhibitive behaviour on steel of flavanoid monomers that constitute mangrove tannins namely catechin, epicatechin, epigallocatechin and epicatechingallate was investigated in an aerated HCl solution via electrochemical methods. The monomers were found to be mainly cathodic inhibitors and the inhibition efficiency was dependent on concentration. To explain the adsorptive behaviour of the molecules on the steel surface, a semiempirical approach involving quantum chemical calculations using HyperChem 6.0 was undertaken. The HOMO electronic density of the molecule was used to explain the inhibiting mechanism. The most probable adsorption centers were found in the vicinity of the phenolic groups. In a second part, the use of mangrove tannin, extracted from the mangrove barks as steel corrosion inhibitors in acidic media was investigated and its inhibitive efficiency was compared with that of commercial mimosa, quebracho and chestnut tannins. The inhibitive performance of mangrove tannins was comparable to the other tannins investigated, indicating their potential in corrosion protection.

  7. Radiation initiated grafting of hydrophilic and reactive monomers on polyetherurethane for biomedical application

    International Nuclear Information System (INIS)

    Jansen, B.; Ellinghorst, G.


    Hydrogels such poly(hydroxyethylmethacrylate), poly (acrylamide) and poly(2,3-dihydroxypropylmethacrylate) are a class of well-known materials with good to excellent biomedical properties. Unfortunately the mechanical behaviour of the water-swollen gels is poor, and thus their application in pure state is limited. Much work has been done, especially by the grafting technique, on supporting the hydrogels by several techniques in order to improve their mechanical properties. In this work grafting of hydrogel forming or reactive monomers (which can be made hydrophilic by a following chemical process) onto a polyetherurethane was performed by a technique in which the trunk polymer is swollen in the graft monomer before irradiation. (author)

  8. Immobilization of enzymes by radiation-induced polymerization of glass-forming monomers

    International Nuclear Information System (INIS)

    Yoshida, M.; Kumakura, M.; Kaetsu, I.


    The effect of cooling rate of a monomeric system on the porosity and activity of an immobilized enzyme prepared by radiation-induced polymerization of 2-hydroxyethyl methacrylate at low temperatures has been studied. Slow cooling gave the same effect on porosity of the polymer as decreasing the monomer concentration. A glass-forming solvent such as diethylene glycol was added to water to study the effect of the supercooling tendency of the solvent. Addition of diethylene glycol decreased porosity and also enzymic activity. Water was replaced by the miscible solvent p-dioxane and the immiscible solvent n-decane in order to clarify the effect of solvent. p-Dioxane had a similar effect to water on the relation between the monomer concentration, porosity and activity. On the other hand, polymer prepared from the system containing n-decane showed different immobilization properties owing to the presence of independent pores in the matrix. (author)

  9. Modeling the structure and vibrational spectra for oxouranium dichloride monomer and dimer (United States)

    Umreiko, D. S.; Shundalau, M. B.; Trubina, O. V.


    Structural models are designed and spectral characteristics are computed for the monomer and dimer of the oxouranium dichloride (UOCl2) molecule based on ab initio calculations. The calculations were carried out in the LANL2DZ effective core potential approximation for the uranium atom and all-electron basis sets using DFT methods for oxygen and chlorine atoms (B3LYP/cc-pVDZ). A close-to-planar Y-shaped equilibrium configuration with Cs symmetry is obtained for the UOCl2 monomer. The formation of the dimer is accompanied by both significant changes in the structure of the monomeric fragments and the actual loss of their identities. The obtained spectral characteristics are analyzed and compared with experimental data. The adequacy of the proposed models and qualitative agreement between calculation and experiment are demonstrated.

  10. [Antioxidant activity of cationic whey protein isolate]. (United States)

    titova, M E; Komolov, S A; Tikhomirova, N A


    The process of lipid peroxidation (LPO) in biological membranes of cells is carried out by free radical mechanism, a feature of which is the interaction of radicals with other molecules. In this work we investigated the antioxidant activity of cationic whey protein isolate, obtained by the cation-exchange chromatography on KM-cellulose from raw cow's milk, in vitro and in vivo. In biological liquids, which are milk, blood serum, fetal fluids, contains a complex of biologically active substances with a unique multifunctional properties, and which are carrying out a protective, antimicrobial, regenerating, antioxidant, immunomodulatory, regulatory and others functions. Contents of the isolate were determined electrophoretically and by its biological activity. Cationic whey protein isolate included lactoperoxidase, lactoferrin, pancreatic RNase, lysozyme and angeogenin. The given isolate significantly has an antioxidant effect in model experimental systems in vitro and therefore may be considered as a factor that can adjust the intensity of lipid oxidation. In model solutions products of lipid oxidation were obtained by oxidation of phosphatidylcholine by hydrogen peroxide in the presence of a source of iron. The composition of the reaction mixture: 0,4 mM H2O2; 50 mcM of hemin; 2 mg/ml L-alpha-phosphatidylcholine from soybean (Sigma, German). Lipid peroxidation products were formed during the incubation of the reaction mixture for two hours at 37 degrees C. In our studies rats in the adaptation period immediately after isolation from the nest obtained from food given orally native cationic whey protein isolate at the concentration three times higher than in fresh cow's milk. On the manifestation of the antioxidant activity of cationic whey protein isolate in vivo evidence decrease of lipid peroxidation products concentration in the blood of rats from the experimental group receipt whey protein isolate in dos 0,6 mg/g for more than 20% (pisolate has an antioxidant

  11. Surface Induced Dissociations and Reactions of Acetonitrile Monomer, Dimer and Trimer Ions

    Czech Academy of Sciences Publication Activity Database

    Mair, C.; Herman, Zdeněk; Fedor, J.; Lezius, M.; Märk, T. D.


    Roč. 118, č. 3 (2003), s. 1479-1486 ISSN 0021-9606 R&D Projects: GA ČR GA203/00/0632 Grant - others:Cooperation PST(AT) 2000-06 Institutional research plan: CEZ:AV0Z4040901 Keywords : surface-induced * acetonitrile monomer * trimer ions Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.950, year: 2003

  12. Benzylpyrazinium Salts as Photo-Initiators in the Polymerization of Epoxide Monomers


    Kim, Moon Suk; Lee, Sang Bong


    In order to study the capability of pyrazinium salt derivatives to act as photo-initiators of epoxide monomers, benzyl pyrazinium hexafluoroantimonate (BPH), benzyl 3,5-dimethyl pyrazine hexafluoroantimonate (BDH) and benzyl quinoxalinium hexafluoroantimonate (BQH) were synthesized by the Menschutkin reaction of benzyl bromide with pyrazine, 2,6-dimethyl pyrazine, and quinoxaline, followed by exchanging with hexafluoroantimonate (SbF6). BPH, BDH, and BQH exhibited characteristic ultraviolet ...

  13. Synthesis of new antibacterial quaternary ammonium monomer for incorporation into CaP nanocomposite (United States)

    Zhou, Chenchen; Weir, Michael D.; Zhang, Ke; Deng, Dongmei; Cheng, Lei; Xu, Hockin H. K.


    Objectives Composites are the principal material for tooth cavity restorations due to their esthetics and direct-filling capabilities. However, composites accumulate biofilms in vivo, and secondary caries due to biofilm acids is the main cause of restoration failure. The objectives of this study were to: (1) synthesize new antibacterial monomers; and (2) develop nanocomposite containing nanoparticles of amorphous calcium phosphate (NACP) and antibacterial monomer. Methods Two new antibacterial monomers were synthesized: dimethylaminohexane methacrylate (DMAHM) with a carbon chain length of 6, and dimethylaminododecyl methacrylate (DMADDM) with a chain length of 12. A spray-drying technique was used to make NACP. DMADDM was incorporated into NACP nanocomposite at mass fractions of 0%, 0.75%, 1.5%, 2.25% and 3%. A flexural test was used to measure composite strength and elastic modulus. A dental plaque microcosm biofilm model with human saliva as inoculum was used to measure viability, metabolic activity, and lactic acid production of biofilms on composites. Results The new DMAHM was more potent than a previous quaternary ammonium dimethacrylate (QADM). DMADDM was much more strongly antibacterial than DMAHM. The new DMADDM-NACP nanocomposite had strength similar to that of composite control (p > 0.1). At 3% DMADDM in the composite, the metabolic activity of adherent biofilms was reduced to 5% of that on composite control. Lactic acid production by biofilms on composite containing 3% DMADDM was reduced to only 1% of that on composite control. Biofilm colony-forming unit (CFU) counts on composite with 3% DMADDM were reduced by 2-3 orders of magnitude. Significance New antibacterial monomers were synthesized, and the carbon chain length had a strong effect on antibacterial efficacy. The new DMADDM-NACP nanocomposite possessed potent anti-biofilm activity without compromising load-bearing properties, and is promising for antibacterial and remineralizing dental

  14. Synthesis of functional polylactide : Monomer synthesis scale-up and poly(ethylene glycol) functionalization


    Lindman, Jonas


    This master’s degree project optimized the synthesis route to a functional lactide by increasing the total yield from 25 to 33 % and reducing the number of unit operations from 17 to 10. This was done by optimizing an existing synthetic pathway to better fit larger scale manufacturing. The monomer was also successfully copolymerized with ʟ-lactide and functionalized by attaching poly(ethylene glycol) units of varying chain lengths to the polylactide chain, which gives some antifouling propert...

  15. Self-assembly of actin monomers into long filaments: Brownian dynamics simulations (United States)

    Guo, Kunkun; Shillcock, Julian; Lipowsky, Reinhard


    Brownian dynamics simulations are used to study the dynamical process of self-assembly of actin monomers into long filaments containing up to 1000 actin protomers. In order to overcome the large separation of time scales between the diffusive motion of the free monomers and the relatively slow attachment and detachment processes at the two ends of the filaments, we introduce a novel rescaling procedure by which we speed all dynamical processes related to actin polymerization and depolymerization up by the same factor. In general, the actin protomers within a filament can attain three different states corresponding to a bound adenosine triphosphate (ATP), adenosine diphosphate with inorganic phosphate (ADP/P), and ADP molecule. The simplest situation that has been studied experimentally is provided by the polymerization of ADP-actin, for which all protomers are identical. This case is used to unravel certain relations between the filament's physical properties and the model parameters such as the attachment rate constant and the size of the capture zone, the detachment rate and the probability of the detached event, as well as the growth rate and waiting times between two successive attachment/detachment events. When a single filament is allowed to grow in a bath of constant concentration of free ADP-actin monomers, its growth rate increases linearly with the free monomer concentration in quantitative agreement with in vitro experiments. The results also show that the waiting time is governed by exponential distributions and that the two ends of a filament undergo biased random walks. The filament length fluctuations are described by a length diffusion constant that is found to attain a constant value at low ADP-actin concentration and to increase linearly with this concentration. It is straightforward to apply our simulation code to more complex processes such as polymerization of ATP-actin coupled to ATP hydrolysis, force generation by filaments, formation of

  16. Enhanced lignin monomer production caused by cinnamic Acid and its hydroxylated derivatives inhibits soybean root growth.

    Directory of Open Access Journals (Sweden)

    Rogério Barbosa Lima

    Full Text Available Cinnamic acid and its hydroxylated derivatives (p-coumaric, caffeic, ferulic and sinapic acids are known allelochemicals that affect the seed germination and root growth of many plant species. Recent studies have indicated that the reduction of root growth by these allelochemicals is associated with premature cell wall lignification. We hypothesized that an influx of these compounds into the phenylpropanoid pathway increases the lignin monomer content and reduces the root growth. To confirm this hypothesis, we evaluated the effects of cinnamic, p-coumaric, caffeic, ferulic and sinapic acids on soybean root growth, lignin and the composition of p-hydroxyphenyl (H, guaiacyl (G and syringyl (S monomers. To this end, three-day-old seedlings were cultivated in nutrient solution with or without allelochemical (or selective enzymatic inhibitors of the phenylpropanoid pathway in a growth chamber for 24 h. In general, the results showed that 1 cinnamic, p-coumaric, caffeic and ferulic acids reduced root growth and increased lignin content; 2 cinnamic and p-coumaric acids increased p-hydroxyphenyl (H monomer content, whereas p-coumaric, caffeic and ferulic acids increased guaiacyl (G content, and sinapic acid increased sinapyl (S content; 3 when applied in conjunction with piperonylic acid (PIP, an inhibitor of the cinnamate 4-hydroxylase, C4H, cinnamic acid reduced H, G and S contents; and 4 when applied in conjunction with 3,4-(methylenedioxycinnamic acid (MDCA, an inhibitor of the 4-coumarate:CoA ligase, 4CL, p-coumaric acid reduced H, G and S contents, whereas caffeic, ferulic and sinapic acids reduced G and S contents. These results confirm our hypothesis that exogenously applied allelochemicals are channeled into the phenylpropanoid pathway causing excessive production of lignin and its main monomers. By consequence, an enhanced stiffening of the cell wall restricts soybean root growth.

  17. Interactions between resin monomers and commercial composite resins with human saliva derived esterases. (United States)

    Jaffer, F; Finer, Y; Santerre, J P


    Cholesterol esterase (CE) and pseudocholinesterase (PCE) have been reported to degrade commercial and model composite resins containing bisphenylglycidyl dimethacrylate (BisGMA), triethylene glycol dimethacrylate (TEGDMA) or the latter in combination with urethane modified BisGMA monomer systems. In addition, human saliva has been shown to contain esterase like activities similar to CE and PCE. Hence, it was the aim of the current study to determine to what extent human saliva could degrade two common commercial composite resins (Z250 from 3M Inc. and Spectrum TPH from L.D. Caulk) which contain the above monomer systems. Saliva samples from different volunteers were collected, processed, pooled, and freeze-dried. TEGDMA and BisGMA monomers were incubated with human saliva derived esterase activity (HSDEA) and their respective hydrolysis was monitored using high performance liquid chromatography (HPLC). Both monomers were completely hydrolyzed within 25 h by HSDEA. Photopolymerized composites were incubated with buffer or human saliva (pH 7.0 and 37 C) for 2, 8 and 16 days. The incubation solutions were analyzed using HPLC and mass spectrometry. Surface morphology characterization was carried out using scanning electron microscopy. Upon biodegradation, the Z250 composite yielded higher amounts of BisGMA and TEGDMA related products relative to the TPH composite. However, there were higher amounts of ethoxylated bis-phenol A released from the TPH material. In terms of total mass of products released, human saliva demonstrated a greater ability to degrade Z250. In summary, HSDEA has been shown to contain esterase activities that can readily catalyze the biodegradation of current commercial composite resins.

  18. Effect of radiation combined with Chinese medicinal monomers on Me180 cells

    International Nuclear Information System (INIS)

    Geng Chuanying; Xu Bo; Li Hongyan; Chen Zhihua; Xia Qisheng; Xu Mei; Liu Xuan; Xiang Qing; Liu Yufeng


    Objective: To observe the effect of radiation treatment combined with Chinese medicinal monomers on the proliferation function, telomerase activity, expressions of apoptosis- and proliferation-related genes of Me180 cells. Methods: Me180 cells were cultured in the medium with oleanolic acid, curcumin and allicin. The survival rates of cells were detected by the methods of MTT, the telomerase activity by the method of telomeric repeat amplification protocol (TRAP) and the apoptosis -and proliferation-related genes by the method of reverse transeriptase-PCR. Me180 cells were cultured in the medium with Chinese medicinal monomers, and exposed to X-ray irradiation and the survival rates were detected. Results: The results of MTY showed that survival rates of tumor cells exposed to X rays in combination with oleanolic acid, curcumin and allicin were decreased significantly(t=2.81, 4.16, and 3.42, P<0.05). Chinese medicinal monomers inhibited the telomerase activity of MelS0 cells and the inhibiting function changed with time. At 16 h, the telomerase activities of MelS0 cells administered with oleanolic acid and allicin were reduced markedly (t=5.11 and 5.29, P<0.05). After 48 h, the telomerase activities returned to the normal level. The gene expressions of p21 and p16 in Me180 cells treated with oleanolic acid were 2.43 and 2.78 times higher than the control, respectively, while those of cyclin D1 and CDK4 were 56% and 41% of the control, respectively. Conclusions: Chinese medicinal monomers could effectively kill tumor cells, inhibit the telomerase activity and the expression of proliferation-related genes, and enhance the radiosensitivity of tumor cells. (authors)

  19. Photocuring of multifunctional monomers initiated by camphorquinone/amine systems for application in dental restorative resins


    Jun, Nie


    This thesis deals with the photopolymerization of mono-, di- and trifunctional monomers initiated by carnphorquinone (CQ) alone and/or with different amines (AMH) as coinitiators in air as well in nitrogen. The kinetics of photopolymerization was measured by photoisothermal calorimetry (photo-DSC), which allowed the measurement of the rate of polymerization (Rp), maximum rate of polymerization (Rpmax), time of inhibition (tinh), time at which Rpmax was obtained (tmax), doubl...

  20. Chemical analysis of monomers in epoxy resins based on bisphenols F and A. (United States)

    Pontén, A; Zimerson, E; Sörensen, O; Bruze, M


    Diglycidyl ether of bisphenol A (DGEBA) is the monomer and most important contact allergen in epoxy resin(s) based on bisphenol A (DGEBA-R). Both thin-layer chromatography (TLC) and high-pressure liquid chromatography (HPLC) methods are available for the analysis of products containing DGEBA-R. With respect to detection and quantification, epoxy resins of the bisphenol F-type, i.e. epoxy resins containing the isomers of diglycidyl ethers of bisphenol F (DGEBF), are not as well investigated as DGEBA-R. The isomers of DGEBF are p,p'-DGEBF, o,p'-DGEBF and o,o'-DGEBF. Both p,p'-DGEBF and o,p'-DGEBF have been shown to be contact allergens in humans, and all 3 isomers are sensitizers in the guinea pig maximization test. We aimed (i). to develop HPLC methods for separation and purification of the individual DGEBF isomers, (ii). to detect and quantify the DGEBF isomers in epoxy resins of the bisphenol F-type and (iii). to evaluate and develop the TLC as a method for the detection of the DGEBF monomers. We found the total content of the DGEBF isomers in the investigated epoxy resins of the bisphenol F-type to vary from 17.0 to 81.7% w/w. Some of them also contained 0.1-2.4% w/w DGEBA. The HPLC method showed a sensitivity that was 2000-20 000x higher than that obtained with the TLC method for the DGEBF monomers. We concluded that the range of the DGEBF isomer content in epoxy resins of the bisphenol F-type is approximately the same as the monomer content in liquid compared to solid DGEBA-R. The relevance of contact allergy to DGEBA-R can remain unrecognized if the suspected product is an epoxy resin of the bisphenol F-type, which is analysed with the TLC method.

  1. Hydrophobic Coatings on Cotton Obtained by in Situ Plasma Polymerization of a Fluorinated Monomer in Ethanol Solutions. (United States)

    Molina, Ricardo; Teixidó, Josep Maria; Kan, Chi-Wai; Jovančić, Petar


    Plasma polymerization using hydrophobic monomers in the gas phase is a well-known technology to generate hydrophobic coatings. However, synthesis of functional hydrophobic coatings using plasma technology in liquids has not yet been accomplished. This work is consequently focused on polymerization of a liquid fluorinated monomer on cotton fabric initiated by atmospheric plasma in a dielectric barrier discharge configuration. Functional hydrophobic coatings on cotton were successfully achieved using in situ atmospheric plasma-initiated polymerization of fluorinated monomer dissolved in ethanol. Gravimetric measurements reveal that the amount of polymer deposited on cotton substrates can be modulated with the concentration of monomer in ethanol solution, and cross-linking reactions occur during plasma polymerization of a fluorinated monomer even without the presence of a cross-linking agent. FTIR and XPS analysis were used to study the chemical composition of hydrophobic coatings and to get insights into the physicochemical processes involved in plasma treatment. SEM analysis reveals that at high monomer concentration, coatings possess a three-dimensional pattern with a characteristic interconnected porous network structure. EDX analysis reveals that plasma polymerization of fluorinated monomers takes place preferentially at the surface of cotton fabric and negligible polymerization takes place inside the cotton fabric. Wetting time measurements confirm the hydrophobicity of cotton coatings obtained although equilibrium moisture content was slightly decreased. Additionally, the abrasion behavior and resistance to washing of plasma-coated cotton has been evaluated.

  2. Comparative analysis of cation/proton antiporter superfamily in plants

    Energy Technology Data Exchange (ETDEWEB)

    Ye, Chuyu [ORNL; Yang, Xiaohan [ORNL; Xia, Xinli [Beijing Forestry University, China; Yin, Weilun [Beijing Forestry University, China


    The cation/proton antiporter superfamily is associated with the transport of monovalent cations across membranes. This superfamily was annotated in the Arabidopsis genome and some members were functionally characterized. In the present study, a systematic analysis of the cation/proton antiporter genes in diverse plant specieswas reported.We identified 240 cation/proton antiporters in alga, moss, and angiosperm. A phylogenetic tree was constructed showing these 240members are separated into three families, i.e., Na+/H+ exchangers, K+ efflux antiporters, and cation/H+ exchangers. Our analysis revealed that tandem and/or segmental duplications contribute to the expansion of cation/H+ exchangers in the examined angiospermspecies. Sliding windowanalysis of the nonsynonymous/synonymous substitution ratios showed some differences in the evolutionary fate of cation/proton antiporter paralogs. Furthermore, we identified over-represented motifs among these 240 proteins and foundmostmotifs are family specific, demonstrating diverse evolution of the cation/proton antiporters among three families. In addition, we investigated the co-expressed genes of the cation/proton antiporters in Arabidopsis thaliana. The results showed some biological processes are enriched in the co-expressed genes, suggesting the cation/proton antiporters may be involved in these biological processes. Taken together, this study furthers our knowledge on cation/proton antiporters in plants.

  3. Modification of polyethersulfone films by grafting hydrophilic monomers with 60Co γ-rays

    International Nuclear Information System (INIS)

    Hou Zhengchi; Deng Bo; Li Jing


    Polyethersulfone (PES), with its high strength, high temperature resistance, corrosion- resistance, oxidation resistance and applicability under wide pH range, is used extensively as ultrafiltration and nanofiltration membrane. However, PES membranes foul easily in such an application because of hydrophobic nature of PES raw materials. Improving the hydrophilicity of PES by grafting hydrophilic monomers onto it is of potential to solve the problem. At present, common approaches to improve hydrophilicity of PES membranes are UV grafting modification, plasma modification, and chemical modification, whereas grafting and modifying PES films by 60 Co γ-rays has rarely been reported. Studies have been carried out in our laboratory to graft hydrophilic monomers onto PES membranes directly or PES powders via simultaneous radiation grafting with the rays. Acrylic acid, methyl acrylic acid or acrylamide was used to study effects of the monomer concentration, irradiation dose and dose rate, solvent, inhibitor and pH of the grafting solution on the degree of grafting. The results showed that hydrophilicity of all the PES membranes could be improved, with the extent of improvement being dependent on the grafting conditions. (authors)

  4. Effects of calcium salts of acidic monomers on mineral induction of phosphoprotein immobilized to agarose beads. (United States)

    Ito, Shuichi; Iijima, Masahiro; Motai, Fumiko; Mizoguchi, Itaru; Saito, Takashi


    The aim of this study is to evaluate the mineralizing potential of acidic monomers and their calcium salts for mineralization, using an in vitro mineral induction model. Phosvitin (PV) was used as a model phosphoprotein in this study. PV was immobilized on agarose beads with divinyl sulfone. Five aliquots of agarose-immobilized PV, acidic monomers, and their calcium salts were incubated in mineralizing solution at various concentrations. The PV beads and acidic monomers were incubated at 37°C. Samples were taken at several time points during the incubation. Then, the agarose beads were analyzed for bound calcium by atomic absorption spectrometry. The mineral formed on the agarose beads was identified as an apatite by microarea X-ray diffraction. Additionally, the specimens were observed using scanning electron microscopy (SEM). Mineral induction time decreased with increasing solution saturation. 4-METCa salt [calcium salt of 4-methacryloxyethyl trimellitate (CMET)] significantly reduced the mineral induction time. Using these data, the interfacial tension for mineral induction of PV and CMET was determined to be 90.1 and 92.7 ergs/cm(2), respectively. The mineral induced in each specimen after incubation for 24 h was identified by its X-ray diffraction pattern as apatite. SEM observation showed that lath-shaped crystals were formed on the surfaces of the CMET. We conclude that CMET could play a role in dentin remineralization. Copyright © 2012 Wiley Periodicals, Inc.

  5. Effect of low-shrinkage monomers on the physicochemical properties of experimental composite resin. (United States)

    He, Jingwei; Garoushi, Sufyan; Vallittu, Pekka K; Lassila, Lippo


    This study was conducted to determine whether novel experimental low-shrinkage dimethacrylate co-monomers could provide low polymerization shrinkage composites without sacrifice to degree of conversion, and mechanical properties of the composites. Experimental composites were prepared by mixing 28.6 wt% of bisphenol-A-glycidyl dimethacrylate based resin matrix ( bis -GMA) with various weight-fractions of co-monomers; tricyclo decanedimethanol dacrylate (SR833s) and isobornyl acrylate (IBOA) to 71.4 wt% of particulate-fillers. A composite based on bis -GMA/TEGDMA (triethylene glycol dimethacrylate) was used as a control. Fracture toughness and flexural strength were determined for each experimental material following international standards. Degree of monomer-conversion (DC%) was determined by FTIR spectrometry. The volumetric shrinkage in percent was calculated as a buoyancy change in distilled water by means of the Archimedes' principle. Polymerization shrinkage-strain and -stress of the specimens were measured using the strain-gage technique and tensilometer, respectively with respect to time. Statistical analysis revealed that control group had the highest double-bond conversion ( p   .05). Volumetric shrinkage and shrinkage stress decreased with increasing IBOA concentration. Replacing TEGDMA with SR833s and IBOA can decrease the volumetric shrinkage, shrinkage strain, and shrinkage stress of composite resins without affecting the mechanical properties. However, the degree of conversion was also decreased.

  6. Antibacterial Activity of Silver Nanoparticle-Loaded Soft Contact Lens Materials: The Effect of Monomer Composition. (United States)

    Shayani Rad, Maryam; Khameneh, Bahman; Sabeti, Zahra; Mohajeri, Seyed Ahmad; Fazly Bazzaz, Bibi Sedigheh


    In the present work, the effect of monomer composition on silver nanoparticles' (SNPs) binding capacity of hydrogels was investigated and their antibacterial efficacy was evaluated. Three series of poly-hydroxyethyl methacrylate (HEMA) hydrogels were prepared using methacrylic acid (MAA), methacrylamide (MAAM), and 4-vinylpyridine (4VP) as co-monomers, and ethylene glycol dimethacrylate (EGDMA) as cross-linker. SNPs binding capacity of hydrogels was evaluated in different concentrations (2, 10, and 20 ppm). In vitro antibacterial activity of SNP-loaded hydrogels was studied against Pseudomonas aeruginosa (P. aeruginosa) isolated from patients' eyes. Then, inhibitory effect of hydrogels in biofilm formation was evaluated in the presence of Staphylococcus epidermidis (S. epidermidis) (DSMZ 3270). Our data indicated that poly(HEMA-co-MAA-co-EGDMA) had superior binding affinity for SNPs in comparison with other hydrogels. All SNP-loaded hydrogels demonstrated excellent antimicrobial effects at all times against P. aeruginosa and S. epidermidis after soaking in 10 and 20 ppm SNP suspensions. Scanning electron microscope (SEM) images revealed excellent inhibitory effect of SNPs against biofilm formation on the surface of the hydrogels. This study indicated the effect of monomer compositions in SNP loading capacity of poly(HEMA) hydrogels and antibacterial efficacy of SNP-loaded hydrogels against P. aeruginosa and S. epidermidis, but further in vivo evaluation is necessary.

  7. Do the monomers release from the composite resins after artificial aging? (United States)

    Tokay, Ugur; Koyuturk, Alp Erdin; Aksoy, Abdurrahman; Ozmen, Bilal


    The aim of this study is to measure the effect of thermal cycling on the amount of monomer released from three different composite materials by HPLC analysis method. Three different composite materials, inlay composite, posterior composite and micro-hybrid composite were used. Sixty cylinder specimens each with a dimension of approximately 1 cm width and 3 mm depth, were prepared before experiments were carried out. Inlay composite material was polymerized according to manufacturers' instructions. Thermal cycling device was used to simulate thermal differences which occur in the mouth media. Monomers were analyzed using HPLC technic after thermal cycling process. The amount of ethoxylated Bis-GMA and urethane dimethacrylate (UDMA) in inlay composite material, the amount of ethoxylated Bis-GMA in posterior composite material, the amount of ethoxylated Bis-GMA and triethyleneglycol dimethacrylate (TEGDMA) in micro-hybrid composite material were investigated. Monomer release of thermal cycles levels showed a linear increase in UDMA and TEGDMA (P composite showed a cubic change (P composite resins have more outstanding features than direct composite resins in terms of biocompatibility. © 2015 Wiley Periodicals, Inc.

  8. HEMA inhibits interfacial nano-layering of the functional monomer MDP. (United States)

    Yoshida, Y; Yoshihara, K; Hayakawa, S; Nagaoka, N; Okihara, T; Matsumoto, T; Minagi, S; Osaka, A; Van Landuyt, K; Van Meerbeek, B


    Previous research showed that the functional monomer 10-methacryloxydecyl dihydrogen phosphate (MDP) ionically bonds to hydroxyapatite (HAp) and forms a nano-layered structure at the interface with HAp-based substrates. Such hydrophobic nano-layering is considered to contribute to the long-term durability of the bond to tooth tissue. However, dental adhesives are complex mixtures usually containing different monomers. This study investigated the effect of the monomer 2-hydroxyethylmethacrylate (HEMA) on the chemical interaction of MDP with HAp by x-ray diffraction (XRD), nuclear magnetic resonance (NMR), and quartz crystal microbalance (QCM). We examined the chemical interaction of 5 experimental MDP solutions with increasing concentrations of HEMA. XRD revealed that addition of HEMA inhibits nano-layering at the interface, while NMR confirmed that MDP remained adsorbed onto the HAp surface. QCM confirmed this adsorption of MDP to HAp, as well as revealed that the demineralization rate of HAp by MDP was reduced by HEMA. It was concluded that even though the adsorption of MDP to HAp was not hindered, addition of HEMA inhibited interfacial nano-layering. Potential consequences with regard to bond durability necessitate further research.

  9. Synthesis and characterization of copolymers from hindered amines and vinyl monomers

    Directory of Open Access Journals (Sweden)

    Marcelo Aparecido Chinelatto


    Full Text Available New copolymers from hindered amines and vinyl monomers were synthesized by radical chain polymerization. To obtain polymeric HALS, acrylamide-(1ATP and acrylate-(4ATP monomers, derivatives from 2,2,6,6-tetramethylpiperidine and 2,2,6,6-tetramethyl-4-piperidinol were synthesized. The radical chain polymerization of 1ATP with styrene (Sty using 1-butanethiol (BTN resulted in a copolymer with 95 units of Sty and 15 units of 1ATP. The radical chain polymerization of 1ATP and vinyl acetate (VAc has produced only 1ATP homopolymer. In the chain polymerization of 4ATP with Sty or VAc, the hydrogen atom bonded to the nitrogen of 4ATP is labile enough to originate another radical at this site. The steric hindrance imposed by methyl groups on this bonding site hampers its reaction with other propagating species and the formation of a copolymer or network structure will be dependent on the size of the pendent group in the vinyl monomer.

  10. [Lipid-lowering effect of seven traditional Chinese medicine monomers in zebrafish system]. (United States)

    Chen, Kan; Wang, Chang-Qian; Fan, Yu-Qi; Han, Zhi-Hua; Wang, Yue; Gao, Lin; Zeng, Hua-Su


    The present study aimed to study lipid-lowering effect of seven traditional Chinese medicine monomers in zebrafish system. Zebrafish were fed with high fat diet to establish a hyperlipemia model, then fasted and bathed with seven traditional Chinese medicine monomers stigmasterol, triacontanol, chrysophanol, vanillic acid, shikimic acid, polydatin and oleanolic acid respectively. The oil red O staining was used to detect the blood lipids of zebrafish. Serum total cholesterol and triglyceride levels were detected to validate the lipid-lowering effect. The result showed that a zebrafish model of hyperlipemia could be established by feeding larvae zebrafish with high fat diet. Among the seven traditional Chinese medicine monomers, chrysophanol had lipid-lowering effect. Chrysophanol significantly reduced serum total cholesterol and triglyceride levels in adult zebrafish fed with high fat diet. Chrysophanol accelerated peristalsis frequency of zebrafish intestine and the excretion of high fat food. It is concluded that chrysophanol has lipid- lowering effect in zebrafish, and the mechanism of the effect may be due to the roles of chrysophanol in reducing lipid absorption from gastrointestinal tract and accelerating the excretion of food.

  11. Flexural properties of repaired heat-polymerising acrylic resin after wetting with monomer and acetone. (United States)

    Bural, Canan; Bayraktar, Gülsen; Aydin, Ismail; Yusufoğlu, Ibrahim; Uyumaz, Natuk; Hanzade, Mete


    Repair strength can be improved by treating fractured surfaces of a denture. This study investigated flexural properties of heat-polymerised acrylic resin specimens repaired with auto-polymerising and visible light curing (VLC) resins after the repair surfaces were wetted with monomers or acetone. Fifty-four specimens (65 x 10 x 2.5 mm) were prepared and 48 of them were sectioned to simulate denture fracture. Butt-joint designed repair surfaces were wetted with heat-, auto-polymerising monomers and acetone for 180 s and repaired with auto-polymerising and VLC resins. After repairs, specimens were subjected to three-point bending test and flexural strength, strain, fracture load, modulus of elasticity and deflection values were recorded. Data were analysed with Student t and LSD tests (p properties, while wetting with acetone did not provide superior effect over both monomers. In clinical use, wetting the repair surfaces may result in stronger repairs. The use of bonding agent in VLC resin repairs in combination with wetting agent results in improved flexural properties.

  12. Molecularly imprinted microspheres prepared by precipitation polymerization at high monomer concentrations

    Directory of Open Access Journals (Sweden)

    Renkecz Tibor


    Full Text Available Highly crosslinked polymer microparticles have been prepared by precipitation polymerization using high monomer loadings (≥25 v/v % which generally would lead to bulk monoliths. The microparticle format was achieved by the use of non-solvating diluents either alone or in combination with co-solvents. Two distinct morphologies were observed. Monodisperse smooth microspheres were obtained using a thermodynamically good co-solvent whereas segmented irregular particles were formed with poorer co-solvents. It has been found that during polymerization the forming polymer particles were enriched in the co-solvent and this effect was more pronounced when good co-solvents were used. The type of functional monomer, crosslinker and co-solvent, and the non-solvent/co-solvent ratio were identified as influential parameters on the microparticle morphology. With the proposed methodology molecularly imprinted microparticles have been prepared successfully for three different templates, naproxen, diclofenac and toltrazuril using various functional monomers, crosslinkers and polymerization solvent mixtures.

  13. Two Functionally Distinct Sources of Actin Monomers Supply the Leading Edge of Lamellipodia

    Directory of Open Access Journals (Sweden)

    Eric A. Vitriol


    Full Text Available Lamellipodia, the sheet-like protrusions of motile cells, consist of networks of actin filaments (F-actin regulated by the ordered assembly from and disassembly into actin monomers (G-actin. Traditionally, G-actin is thought to exist as a homogeneous pool. Here, we show that there are two functionally and molecularly distinct sources of G-actin that supply lamellipodial actin networks. G-actin originating from the cytosolic pool requires the monomer-binding protein thymosin β4 (Tβ4 for optimal leading-edge localization, is targeted to formins, and is responsible for creating an elevated G/F-actin ratio that promotes membrane protrusion. The second source of G-actin comes from recycled lamellipodia F-actin. Recycling occurs independently of Tβ4 and appears to regulate lamellipodia homeostasis. Tβ4-bound G-actin specifically localizes to the leading edge because it does not interact with Arp2/3-mediated polymerization sites found throughout the lamellipodia. These findings demonstrate that actin networks can be constructed from multiple sources of monomers with discrete spatiotemporal functions.

  14. Permeability of different types of medical protective gloves to acrylic monomers. (United States)

    Lönnroth, Emma-Christin; Wellendorf, Hanne; Ruyter, Eystein


    Dental personnel and orthopedic surgeons are at risk when manually handling products containing methyl methacrylate (MMA). Dental products may also contain cross-linking agents such as ethylene glycol dimethacrylate (EGDMA) or 1,4-butanediol dimethacrylate (1,4-BDMA). Skin contact with monomers can cause hand eczema, and the protection given by gloves manufactured from different types of material is not well known. The aim of this study was to determine the breakthrough time (BTT, min) as a measure of protection (according to the EU standard EN-374-3) for a mixture consisting of MMA, EGDMA and 1,4-BDMA. Fifteen different gloves representing natural rubber latex material, synthetic rubber material (e.g. nitrile rubbers), and synthetic polymer material were tested. The smallest monomer MMA permeated within 3 min through all glove materials. A polyethylene examination glove provided the longest protection period to EGDMA and 1, 4-BDMA (> 120 min and 25.0 min), followed by the surgical glove Tactylon (6.0 min and 8.7 min) and the nitrile glove Nitra Touch (5.0 min and 8.7 min). This study showed that the breakthrough time (based on permeation rate) cannot be regarded as a 'safe limit'. When the permeation rate is low, monomers may have permeated before BTT can be determined. Using double gloves with a synthetic rubber inner glove and a natural rubber outer glove provided longer protection when the inner glove was rinsed in water before placing the outer glove on top.

  15. A Simple and Rapid Method for Quality Control of Major Histocompatibility Complex–Peptide Monomers by Flow Cytometry (United States)

    Chandran, P. Anoop; Heidu, Sonja; Zelba, Henning; Schmid-Horch, Barbara; Rammensee, Hans-Georg; Pascolo, Steve; Gouttefangeas, Cécile


    Major histocompatibility complex (MHC) multimers are essential tools in T cell immunomonitoring, which are employed both in basic and clinical research, as well as for assessing clinical samples during therapy. The generation of MHC monomers loaded with synthetic peptides is an elaborate and time-consuming process. It would be beneficial to assess the quality of these monomers prior to downstream applications. In this technical note, we describe a novel flow cytometry-based, cell-free, quick, and robust assay to check the quality of MHC monomers directly after refolding or after long-term storage. PMID:28228758

  16. A Simple and Rapid Method for Quality Control of Major Histocompatibility Complex-Peptide Monomers by Flow Cytometry. (United States)

    Chandran, P Anoop; Heidu, Sonja; Zelba, Henning; Schmid-Horch, Barbara; Rammensee, Hans-Georg; Pascolo, Steve; Gouttefangeas, Cécile


    Major histocompatibility complex (MHC) multimers are essential tools in T cell immunomonitoring, which are employed both in basic and clinical research, as well as for assessing clinical samples during therapy. The generation of MHC monomers loaded with synthetic peptides is an elaborate and time-consuming process. It would be beneficial to assess the quality of these monomers prior to downstream applications. In this technical note, we describe a novel flow cytometry-based, cell-free, quick, and robust assay to check the quality of MHC monomers directly after refolding or after long-term storage.

  17. On the relationship between the local segmental dynamics and the tagged monomer dynamics in lamellar phases of diblock copolymers (United States)

    Sethuraman, Vaidyanathan; Ganesan, Venkat


    In this brief article, we present results from coarse-grained molecular dynamics simulations which probed the relationship between the local segmental dynamics and the tagged monomer dynamics in lamellar phases of diblock copolymers. Our results demonstrate that monomer relaxation times do not provide directly a quantitatively accurate measure of the spatial variations in segmental dynamics. However, a convolution of the monomer density distributions with their corresponding relaxation times is shown to provide an approximate, but accurate, quantitative characterization of the average local segmental dynamics.

  18. Bioaccumulation study of acrylate monomers in algae (Chlorella Kessleri) by PY-GC and PY-GC/MS

    International Nuclear Information System (INIS)

    Halas, L.; Orinak, A.; Adamova, M.; Ladomersky, J.


    Acrylate monomers methylmethacrylate (MMA) and cyclohexylmethacrylate (CHMA) bioaccumulation has been determined in aquatic organism, algae (Chlorella kessleri). Algae were collected in amount of 0.4 mg and directly injected to the paralytic cell. In algae bodies accumulated monomers were analysed by pyrolysis gas chromatography (Py-GC) and pyrolysis gas chromatography coupled with mass spectrometry (Py-GC/MS). Traces of the accumulated monomers in algae body can be determined after 1-, 2 -, 3-weeks of incubation. Maximum content of MMA was determined after 3-week of experiment, contrariwise in the case of CHMA after 2-week exposition. Relationship with pyrolysis temperature has also been studied. (authors)

  19. Michael Addition Polymerization of Trifunctional Amine and Acrylic Monomer: A Versatile Platform for Development of Biomaterials. (United States)

    Cheng, Weiren; Wu, Decheng; Liu, Ye


    Michael addition polymerizations of amines and acrylic monomers are versatile approaches to biomaterials for various applications. A combinatorial library of poly(β-amino ester)s and diverse poly(amido amine)s from diamines and diacrylates or bis(acrylamide)s have been reported, respectively. Furthermore, novel linear and hyperbranched polymers from Michael addition polymerizations of trifunctional amines and acrylic monomers significantly enrich this category of biomaterials. In this Review, we focus on the biomaterials from Michael addition polymerizations of trifunctional amines and acrylic monomers. First we discuss how the polymerization mechanisms, which are determined by the reactivity sequence of the three types of amines of trifunctional amines, i.e., secondary (2°) amines (original), primary (1°) amines, and 2° amines (formed), are affected by the chemistry of monomers, reaction temperature, and solvent. Then we update how to design and synthesize linear and hyperbranched polymers based on the understanding of polymerization mechanisms. Linear polymers containing 2° amines in the backbones can be obtained from polymerizations of diacrylates or bis(acrylamide)s with equimolar trifunctional amine, and several approaches, e.g., 2A 2 +BB'B″, A 3 +2BB'B', A 2 +BB'B″, to hyperbranched polymers are developed. Further through molecular design of monomers, conjugation of functional species to 2° amines in the backbones of linear polymers and the abundant terminal groups of hyperbranched polymers, the amphiphilicity of polymers can be adjusted, and additional stimuli, e.g., thermal, redox, reactive oxidation species (ROS), and light, responses can be integrated with the intrinsic pH response. Finally we discuss the applications of the polymers for gene/drug delivery and bioimaging through exploring their self-assemblies in various motifs, e.g., micelles, polyplexes particles/nanorings and hydrogels. Redox-responsive hyperbranched polymers can display 300

  20. Cationic niosomes an effective gene carrier composed of novel spermine-derivative cationic lipids: effect of central core structures. (United States)

    Opanasopit, Praneet; Leksantikul, Lalita; Niyomtham, Nattisa; Rojanarata, Theerasak; Ngawhirunpat, Tanasait; Yingyongnarongkul, Boon-Ek


    Cationic niosomes formulated from Span 20, cholesterol (Chol) and novel spermine-based cationic lipids of multiple central core structures (di(oxyethyl)amino, di(oxyethyl)amino carboxy, 3-amino-1,2-dioxypropyl and 2-amino-1,3-dioxypropyl) were successfully prepared for improving transfection efficiency in vitro. The niosomes composed of spermine cationic lipid with central core structure of di(oxyethyl)amino revealed the highest gene transfection efficiency. To investigate the factors affecting gene transfection and cell viability including differences in the central core structures of cationic lipids, the composition of vesicles, molar ratio of cationic lipids in formulations and the weight ratio of niosomes to DNA. Cationic niosomes composed of nonionic surfactants (Span20), cholesterol and spermine-based cationic lipids of multiple central core structures were formulated. Gene transfection and cell viability were evaluated on a human cervical carcinoma cell line (HeLa cells) using pDNA encoding green fluorescent protein (pEGFP-C2). The morphology, size and charge were also characterized. High transfection efficiency was obtained from cationic niosomes composed of Span20:Chol:cationic lipid at the molar ratio of 2.5:2.5:0.5 mM. Cationic lipids with di(oxyethyl)amino as a central core structure exhibited highest transfection efficiency. In addition, there was also no serum effect on transfection efficiency. These novel cationic niosomes may constitute a good alternative carrier for gene transfection.

  1. Complexes of natural carbohydrates with metal cations

    International Nuclear Information System (INIS)

    Alekseev, Yurii E; Garnovskii, Alexander D; Zhdanov, Yu A


    Data on the interaction of natural carbohydrates (mono-, oligo-, and poly-saccharides, amino sugars, and natural organic acids of carbohydrate origin) with metal cations are surveyed and described systematically. The structural diversity of carbohydrate metal complexes, caused by some specific features of carbohydrates as ligands, is demonstrated. The influence of complex formation on the chemical properties of carbohydrates is discussed. It is shown that the formation of metal complexes plays an important role in the configurational and conformational analysis of carbohydrates. The practical significance of the coordination interaction in the series of carbohydrate ligands is demonstrated. The bibliography includes 571 references.

  2. Homogeneous cation exchange membrane by radiation grafting

    International Nuclear Information System (INIS)

    Kolhe, Shailesh M.; G, Agathian; Ashok Kumar


    Preparation of a strong cation exchange membrane by radiation grafting of styrene on to polyethylene (LDPE) film by mutual irradiation technique in the presence of air followed by sulfonation is described. The grafting has been carried out in the presence of air and without any additive. Low dose rate has been seen to facilitate the grafting. Further higher the grafting percentage more is the exchange capacity. The addition of a swelling agent during the sulfonation helped in achieving the high exchange capacity. The TGA-MASS analysis confirmed the grafting and the sulfonation. (author)

  3. New biosourced AA and AB monomers from 1,4:3,6-dianhydrohexitols, Isosorbide, Isomannide, and Isoidide. (United States)

    Saadaoui, Asma; Medimagh, Raouf; Marque, Sylvain; Prim, Damien; Chatti, Saber; Casabianca, Herve; Said Zina, Mongia


    In the present work, we propose the synthesis of a new family of sugar derived 1,4:3,6-dianhydrohexitol based AA/AB-type monomers. Unprecedented diacids based on Isomannide and Isoidide were elaborated with high yields and showed interestingly high melting point ranges (240-375 °C). Optimization of reaction conditions (temperature, time of reaction, and reactant ratios) has been investigated to synthesize the key intermediate of a set of AB monomers with acid, ester, and acid chloride functionalities. Isosorbide based ether benzoic acid AB monomer was polymerized and characterized by NMR and DSC techniques. The results show a semicrystalline behavior of the obtained polymer thanks to the controlled stereoregular arrangement of the AB starting monomer.

  4. LF-NMR study of effect the octadecylamine addition in the copolymerization process between acrylic acid and styrene monomers

    International Nuclear Information System (INIS)

    Pedroza, Oscar J.O.; Tavares, Maria I.B.


    The copolymer content at least two monomer units that are the repetitive unities in the polymeric chains. The use of Low Field Nuclear Magnetic Resonance (LF-NMR), MARAN ultra 23, was applied to measure the proton spin-lattice relaxation time values. The process of copolymerization between the acrylic acid (A) and the styrene (S) monomers was studied with the addition of the octadecylamine (D) in the acrylic acid monomer. These materials were submitted at reflux by 24 hours. After this process the polymerization was carried out at room temperature. The values of the relaxation parameter are showed in Table 1. The co polymerizations between acrylic acid and styrene monomers were influenced by the octadecylamine addition. The results showed that an increase in the amine concentration promotes flexibility in the final material. This can be explained in terms of chains size after amine addition, which promotes an increasing in the free space among the polymer chains. (author)

  5. Influence of Monomer Concentration on the Morphologies and Electrochemical Properties of PEDOT, PANI, and PPy Prepared from Aqueous Solution

    Directory of Open Access Journals (Sweden)

    Shalini Kulandaivalu


    Full Text Available Poly(3,4-ethylenedioxyhiophene (PEDOT, polyaniline (PANI, and polypyrrole (PPy were prepared on indium tin oxide (ITO substrate via potentiostatic from aqueous solutions containing monomer and lithium perchlorate. The concentration of monomers was varied between 1 and 10 mM. The effects of monomer concentration on the polymers formation were investigated and compared by using Fourier transform infrared spectroscopy (FTIR, Raman spectroscopy, scanning electron microscopy (SEM, cyclic voltammetry (CV, and electrochemical impedance spectroscopy (EIS measurements. FTIR and Raman spectra showed no changes in the peaks upon the increment of the concentration. Based on the SEM images, the increment in monomer concentration gives significant effect on morphologies and eventually affects the electrochemical properties. PEDOT electrodeposited from 10 mM solution showed excellent electrochemical properties with the highest specific capacitance value of 12.8 mF/cm2.

  6. Determination of migration monomer styrene from GPPS (general purpose polystyrene) and HIPS (high impact polystyrene) cups to hot drinks. (United States)

    Khaksar, Mohammad-Reza; Ghazi-Khansari, Mahmoud


    In this study, 162 samples were analysed for monomer styrene content with using high performance liquid chromatography (HPLC) method in hot tea, milk, cocoa milk. The monomer styrene content, expressed in microg/l of drink and the level of migration of styrene monomer were varied from 0.61 to 8.15 for hot tea, from 0.65 to 8.30 for hot milk, from 0.71 to 8.65 for hot cocoa milk in GPPS (general purpose polystyrene), from 0.48 to 6.85 for hot tea, from 0.61 to 7.65 for hot milk, from 0.72 to 7.78 for hot cocoa milk in HIPS (high performance polystyrene) cups in different temperatures and times. The estimated limit of detection of (HPLC) method for all samples was 0.001 mg/kg. There is linear regression for styrene monomer from 1 to 10 ng/ml. Several samples spiked with a known amount of styrene monomer. The results of the recovery in study for styrene monomer were determinate to be mean, 96.1 +/- 1.92 to 99.7 +/- 1.15%. The results of this study indicate that styrene monomer from polystyrene disposable into hot and fat drinks was migrated and this migration was highly dependent on fat content and temperature of drinks. The derived concentration of styrene monomer in this study was above the EPA (Environmental protection agency) recommended level, especially in MCLG (Maximum contaminant level goal) standard. More study is needed to further elucidate this finding.

  7. Alkali Metal Cation versus Proton and Methyl Cation Affinities: Structure and Bonding Mechanism. (United States)

    Boughlala, Zakaria; Fonseca Guerra, Célia; Bickelhaupt, F Matthias


    We have analyzed the structure and bonding of gas-phase Cl-X and [HCl-X](+) complexes for X(+)= H(+), CH3 (+), Li(+), and Na(+), using relativistic density functional theory (DFT). We wish to establish a quantitative trend in affinities of the anionic and neutral Lewis bases Cl(-) and HCl for the various cations. The Cl-X bond becomes longer and weaker along X(+) = H(+), CH3 (+), Li(+), and Na(+). Our main purpose is to understand the heterolytic bonding mechanism behind the intrinsic (i.e., in the absence of solvent) alkali metal cation affinities (AMCA) and how this compares with and differs from those of the proton affinity (PA) and methyl cation affinity (MCA). Our analyses are based on Kohn-Sham molecular orbital (KS-MO) theory in combination with a quantitative energy decomposition analysis (EDA) that pinpoints the importance of the different features in the bonding mechanism. Orbital overlap appears to play an important role in determining the trend in cation affinities.

  8. Cationic Antimicrobial Polymers and Their Assemblies (United States)

    Carmona-Ribeiro, Ana Maria; de Melo Carrasco, Letícia Dias


    Cationic compounds are promising candidates for development of antimicrobial agents. Positive charges attached to surfaces, particles, polymers, peptides or bilayers have been used as antimicrobial agents by themselves or in sophisticated formulations. The main positively charged moieties in these natural or synthetic structures are quaternary ammonium groups, resulting in quaternary ammonium compounds (QACs). The advantage of amphiphilic cationic polymers when compared to small amphiphilic molecules is their enhanced microbicidal activity. Besides, many of these polymeric structures also show low toxicity to human cells; a major requirement for biomedical applications. Determination of the specific elements in polymers, which affect their antimicrobial activity, has been previously difficult due to broad molecular weight distributions and random sequences characteristic of radical polymerization. With the advances in polymerization control, selection of well defined polymers and structures are allowing greater insight into their structure-antimicrobial activity relationship. On the other hand, antimicrobial polymers grafted or self-assembled to inert or non inert vehicles can yield hybrid antimicrobial nanostructures or films, which can act as antimicrobials by themselves or deliver bioactive molecules for a variety of applications, such as wound dressing, photodynamic antimicrobial therapy, food packing and preservation and antifouling applications. PMID:23665898

  9. Cobalt 60 cation exchange with mexican clays

    International Nuclear Information System (INIS)

    Nava Galve, R.G.


    Mexican clays can be used to remove radioactive elements from contaminated aqueous solutions. Cation exchange experiments were performed with 60 Co radioactive solution. In the present work the effect of contact time on the sorption of Co 2+ was studied. The contact time in hydrated montmorillonite was from 5 to 120 minutes and in dehydrated montmorillonite 5 to 1400 minutes. The Co 2+ uptake value was, in hydrated montmorillonite, between 0.3 to 0.85 m eq/g and in dehydrated montmorillonite, between 0.6 to 1.40 m eq/g. The experiments were done in a pH 5.1 to 5.7 and normal conditions. XRD patterns were used to characterize the samples. The crystallinity was determined by X-ray Diffraction and it was maintained before and after the cation exchange. DTA thermo grams showed the temperatures of the lost humidity and crystallization water. Finally, was observed that dehydrated montmorillonite adsorb more cobalt than hydrated montmorillonite. (Author)

  10. Cationic Antimicrobial Polymers and Their Assemblies

    Directory of Open Access Journals (Sweden)

    Ana Maria Carmona-Ribeiro


    Full Text Available Cationic compounds are promising candidates for development of antimicrobial agents. Positive charges attached to surfaces, particles, polymers, peptides or bilayers have been used as antimicrobial agents by themselves or in sophisticated formulations. The main positively charged moieties in these natural or synthetic structures are quaternary ammonium groups, resulting in quaternary ammonium compounds (QACs. The advantage of amphiphilic cationic polymers when compared to small amphiphilic molecules is their enhanced microbicidal activity. Besides, many of these polymeric structures also show low toxicity to human cells; a major requirement for biomedical applications. Determination of the specific elements in polymers, which affect their antimicrobial activity, has been previously difficult due to broad molecular weight distributions and random sequences characteristic of radical polymerization. With the advances in polymerization control, selection of well defined polymers and structures are allowing greater insight into their structure-antimicrobial activity relationship. On the other hand, antimicrobial polymers grafted or self-assembled to inert or non inert vehicles can yield hybrid antimicrobial nanostructures or films, which can act as antimicrobials by themselves or deliver bioactive molecules for a variety of applications, such as wound dressing, photodynamic antimicrobial therapy, food packing and preservation and antifouling applications.

  11. Conformationally locked aryl C-nucleosides: synthesis of phosphoramidite monomers and incorporation into single-stranded DNA and LNA (locked nucleic acid)

    DEFF Research Database (Denmark)

    Babu, B. Ravindra; Prasad, Ashok K.; Trikha, Smriti


    . The phosphoramidite approach was used for automated incorporation of the LNA-type beta-configured C-aryl monomers 17a-17e into short DNA and 2'-OMe-RNA/LNA strands. It is shown that universal hybridization can be obtained with a conformationally restricted monomer as demonstrated most convincingly for the pyrene LNA...... monomer 17d, both in a DNA context and in an RNA-like context. Increased binding affinity of oligonucleotide probes for universal hybridization can be induced by combining the pyrene LNA monomer 17d with affinity-enhancing 2'-OMe-RNA/LNA monomers....

  12. Computational Modeling and Theoretical Calculations on the Interactions between Spermidine and Functional Monomer (Methacrylic Acid in a Molecularly Imprinted Polymer

    Directory of Open Access Journals (Sweden)

    Yujie Huang


    Full Text Available This paper theoretically investigates interactions between a template and functional monomer required for synthesizing an efficient molecularly imprinted polymer (MIP. We employed density functional theory (DFT to compute geometry, single-point energy, and binding energy (ΔE of an MIP system, where spermidine (SPD and methacrylic acid (MAA were selected as template and functional monomer, respectively. The geometry was calculated by using B3LYP method with 6-31+(d basis set. Furthermore, 6-311++(d, p basis set was used to compute the single-point energy of the above geometry. The optimized geometries at different template to functional monomer molar ratios, mode of bonding between template and functional monomer, changes in charge on natural bond orbital (NBO, and binding energy were analyzed. The simulation results show that SPD and MAA form a stable complex via hydrogen bonding. At 1 : 5 SPD to MAA ratio, the binding energy is minimum, while the amount of transferred charge between the molecules is maximum; SPD and MAA form a stable complex at 1 : 5 molar ratio through six hydrogen bonds. Optimizing structure of template-functional monomer complex, through computational modeling prior synthesis, significantly contributes towards choosing a suitable pair of template-functional monomer that yields an efficient MIP with high specificity and selectivity.

  13. A review of our development of dental adhesives--effects of radical polymerization initiators and adhesive monomers on adhesion. (United States)

    Ikemura, Kunio; Endo, Takeshi


    This paper reviews the development of dental adhesives by collating information of related studies from original scientific papers, reviews, and patent literatures. Through our development, novel radical polymerization initiators, adhesive monomers, and microcapsules were synthesized, and their effects on adhesion were investigated. It was found that 5-monosubstituted barbituric acid (5-MSBA)-containing ternary initiators in conjunction with adhesive monomers contributed to effective adhesion with good polymerization reactivity. Several kinds of novel adhesive monomers bearing carboxyl group, phosphonic acid group or sulfur-containing group were synthesized, and investigated their multi-purpose bonding functions. It was suggested that the flexible methylene chain in the structure of adhesive monomers played a pivotal role in their enhanced bonding durability. It was found that the combination of acidic monomers with sulfur-containing monomer markedly improved adhesion to enamel, dentin, porcelain, alumina, zirconia, non-precious metals and precious metals. A new poly(methyl methacrylate) (PMMA)-type adhesive resin comprising microencapsulated polymerization initiators was also found to exhibit both good formulation stability and excellent adhesive property.

  14. Noncovalent cation-π interactions – their role in nature

    Directory of Open Access Journals (Sweden)

    Krzysztof Fink


    Full Text Available Non-covalent interactions play an extremely important role in organisms. The main non-covalent interactions in nature are: ion-ion interactions, dipole-dipole interactions, hydrogen bonds, and van der Waals interactions. A new kind of intermolecular interactions – cation-π interactions – is gaining increasing attention. These interactions occur between a cation and a π system. The main contributors to cation-π interactions are electrostatic, polarization and, to a lesser extent, dispersion interactions. At first, cation-π interactions were studied in a gas phase, with metal cation–aromatic system complexes. The characteristics of these complexes are as follows: an increase of cation atomic number leads to a decrease of interaction energy, and an increase of cation charge leads to an increase of interaction energy. Aromatic amino acids bind with metal cations mainly through interactions with their main chain. Nevertheless, cation-π interaction with a hydrophobic side chain significantly enhances binding energy. In water solutions most cations preferentially interact with water molecules rather than aromatic systems. Cation-π interactions occur in environments with lower accessibility to a polar solvent. Cation-π interactions can have a stabilizing role on the secondary, tertiary and quaternary structure of proteins. These interactions play an important role in substrate or ligand binding sites in many proteins, which should be taken into consideration when the screening of effective inhibitors for these proteins is carried out. Cation-π interactions are abundant and play an important role in many biological processes.

  15. Stability and recovery of DNA origami structure with cation concentration (United States)

    Chen, Yi; Wang, Ping; Liu, Yang; Liu, Ting; Xu, Yan; Zhu, Shanshan; Zhu, Jun; Ye, Kai; Huang, Guang; Dannong, He


    We synthesized triangular and rectangular DNA origami nanostructures and investigated the stability and recovery of them under low cation concentration. Our results demonstrated that the origami nanostructures would melt when incubated in low cation concentration, and recover whilst kept in the concentration for less than 10 min. However, extending the incubation time would lead to irreversible melting. Our results show the possibility of application of DNA origami nanostructures for things such as a sensor for cation concentration response, etc.

  16. High-resolution structure of a retroviral protease folded as a monomer

    International Nuclear Information System (INIS)

    Gilski, Miroslaw; Kazmierczyk, Maciej; Krzywda, Szymon; Zábranská, Helena; Cooper, Seth; Popović, Zoran; Khatib, Firas; DiMaio, Frank; Thompson, James; Baker, David; Pichová, Iva; Jaskolski, Mariusz


    The crystal structure of Mason–Pfizer monkey virus protease folded as a monomer has been solved by molecular replacement using a model generated by players of the online game Foldit. The structure shows at high resolution the details of a retroviral protease folded as a monomer which can guide rational design of protease dimerization inhibitors as retroviral drugs. Mason–Pfizer monkey virus (M-PMV), a D-type retrovirus assembling in the cytoplasm, causes simian acquired immunodeficiency syndrome (SAIDS) in rhesus monkeys. Its pepsin-like aspartic protease (retropepsin) is an integral part of the expressed retroviral polyproteins. As in all retroviral life cycles, release and dimerization of the protease (PR) is strictly required for polyprotein processing and virion maturation. Biophysical and NMR studies have indicated that in the absence of substrates or inhibitors M-PMV PR should fold into a stable monomer, but the crystal structure of this protein could not be solved by molecular replacement despite countless attempts. Ultimately, a solution was obtained in mr-rosetta using a model constructed by players of the online protein-folding game Foldit. The structure indeed shows a monomeric protein, with the N- and C-termini completely disordered. On the other hand, the flap loop, which normally gates access to the active site of homodimeric retropepsins, is clearly traceable in the electron density. The flap has an unusual curled shape and a different orientation from both the open and closed states known from dimeric retropepsins. The overall fold of the protein follows the retropepsin canon, but the C α deviations are large and the active-site ‘DTG’ loop (here NTG) deviates up to 2.7 Å from the standard conformation. This structure of a monomeric retropepsin determined at high resolution (1.6 Å) provides important extra information for the design of dimerization inhibitors that might be developed as drugs for the treatment of retroviral infections

  17. Effect of Magnetic Field on the Type and Amount of Monomers in Polyhydroxyalkanoate Copolymer

    Directory of Open Access Journals (Sweden)

    Marzie Fatehi


    Full Text Available Many studies have been conducted on production of biodegradable polymers such as polyhydroxyalkanoates (PHAs in overcoming the environmental problems due to the accumulation of synthetic plastics as waste materials and excessive activated sludge produced in municipal waste water treatment plants. In this study; the effect of magnetic field intensity of 5, 10, 15, 20, 25 and 50 milliTesla (mT was investigated on the type and amount of monomers produced in the copolymer and PHA production in activated sludge and the results were compared simultaneously with the results of PHA production without the magnetic field (0 mT. The experimental procedure included the transfer of the activated sludge into the batch reactor, addition of sodium acetate, magnetic field generation by magnets, aeration for 30 h, sampling at definite timing, measurement of PHA by gas chromatography. In summary, this research indicated that, the maximum PHA content was produced at 20 mT which was equal to 0.75 g/L, whereas the lowest PHA content was observed at 50 mT (0.55 g/L. In addition, the magnetic field was influenced by the type and amount of monomer produced in PHA. The highest amount of valerate was observed at 50 mT, while this magnetic field decreased the amount of PHA (8.33% compared to the control sample. Also, the maximum amount of butyrate monomer in the copolymer was observed at 5 and 20 mT, which were equal to 81% and 74 %. According to the results obtained, the mass percentage of valerate in the control sample and those exposed to magnetic field with negative effects was more than the mass percentage of butyrate; an indication of better copolymers on the basis of their mechanical properties.

  18. Graft copolymers of polyurethane with various vinyl monomers via radiation-induced miniemulsion polymerization: Influential factors to grafting efficiency and particle morphology

    Energy Technology Data Exchange (ETDEWEB)

    Wang Hua [CAS Key Laboratory of Soft Matter Chemistry, Department of Polymer Science and Engineering, University of Science and Technology of China (USTC), Hefei, Anhui 230026 (China); Wang Mozhen [CAS Key Laboratory of Soft Matter Chemistry, Department of Polymer Science and Engineering, University of Science and Technology of China (USTC), Hefei, Anhui 230026 (China)], E-mail:; Ge Xuewu [CAS Key Laboratory of Soft Matter Chemistry, Department of Polymer Science and Engineering, University of Science and Technology of China (USTC), Hefei, Anhui 230026 (China)], E-mail:


    Graft copolymers of polyurethane (PU) with various vinyl monomers were synthesized through a one-pot but two-step miniemulsion polymerization process. Firstly, the polycondensation of isophorone diisocyanate (IPDI) with hydroxyl-terminated polybutadiene (HTPB) had been performed in aqueous miniemulsion at 40 deg. C in order to obtain PU dispersions. Consecutively, an in-situ graft copolymerization of the vinyl monomers with the synthesized PU was initiated by {gamma}-ray radiation at room temperature. The grafting efficiency of PU with vinyl monomer (G{sub PU/monomer}) was calculated from {sup 1}H NMR spectra and the particle morphology of the final hybrid latex was observed by transmission electron microscopy (TEM). As there was no monomer transferring in miniemulsion system, homogenous hybrid particles would be synthesized provided that the monomer was miscible with PU, such as styrene. With the increase of the polarity of the monomer, the compatibility of PU with monomer decreased. G{sub PU/monomer} varied as G{sub PU/styrene}(37%)>G{sub PU/butyl} {sub acrylate} {sub (BA)}(21%)>G{sub PU/methyl} {sub methacrylate} {sub (MMA)}(12%). The proportion of homogeneous nucleation would increase as the hydrophilicity of the monomer increased. High temperature would destabilize the miniemulsion so as to result in a less grafting efficiency. Compared to the phase separation during the seeded emulsion polymerization, the miniemulsion polymerization method facilitated the preparation of homogeneous materials owing to its monomer droplet nucleation mechanism.

  19. Synthesis and Characterization of Oligodeoxyribonucleotides Modified with 2'-Amino-α-l-LNA Adenine Monomers

    DEFF Research Database (Denmark)

    Andersen, Nicolai K; Anderson, Brooke A; Wengel, Jesper


    thereof. Oligonucleotides modified with these units display greatly increased affinity toward nucleic acid targets, improved binding specificity, and enhanced enzymatic stability relative to unmodified strands. Here we present the synthesis and biophysical characterization of oligodeoxyribonucleotides....... ONs modified with pyrene-functionalized 2'-amino-α-l-LNA adenine monomers X-Z display greatly increased affinity toward DNA targets (ΔTm/modification up to +14 °C). Results from absorption and fluorescence spectroscopy suggest that the duplex stabilization is a result of pyrene intercalation....... These characteristics render N2'-pyrene-functionalized 2'-amino-α-l-LNAs of considerable interest for DNA-targeting applications....

  20. Non-Toxic Multifunctional Silsesquioxane Diamine Monomer for Use in Aerospace Polyimides (United States)


    previous studies of 6-FDA-ODA-POSS-PE systems [22] that with higher degrees of POSS in oligomer chains, the more thermal energy was required to render what...of co-oligomerization of a POSS dianiline monomer designed to be highly thermally stable was successfully proven in SERDP project WP-2403. This...ELEMENT NUMBER 6. AUTHOR(S) 5d. PROJECT NUMBER SERDP WP-2403 Gregory Yandek 5e. TASK NUMBER 5f. WORK UNIT NUMBER Q16J 7. PERFORMING ORGANIZATION

  1. Inverse problem for the mean-field monomer-dimer model with attractive interaction

    International Nuclear Information System (INIS)

    Contucci, Pierluigi; Luzi, Rachele; Vernia, Cecilia


    The inverse problem method is tested for a class of monomer-dimer statistical mechanics models that contain also an attractive potential and display a mean-field critical point at a boundary of a coexistence line. The inversion is obtained by analytically identifying the parameters in terms of the correlation functions and via the maximum-likelihood method. The precision is tested in the whole phase space and, when close to the coexistence line, the algorithm is used together with a clustering method to take care of the underlying possible ambiguity of the inversion. (paper)

  2. Metal nanoparticle ensembles: tunable laser pulses distinguish monomer from dimer vibrations. (United States)

    Jais, Pablo M; Murray, Daniel B; Merlin, Roberto; Bragas, Andrea V


    Resonant interaction of laser pulses with plasmons is used to identify vibrations associated with isolated spheres and pairs of contacting spheres in a system of gold nanoparticles. The optical pulses generate coherent mechanical oscillations of both monomers and dimers in the 5-150 GHz range, the amplitudes of which exhibit a strong enhancement when the laser central wavelength is tuned to resonate with the corresponding plasmon. Because of the resonant selection in the excitation process, the widths of the acoustic modes are significantly smaller than broadening caused by the spread in radii in the ensemble.

  3. Pseudomonas syringae evades host Immunity by degrading flagellin monomers with alkaline protease AprA


    Pel, M.J.C.; Van Dijken, A.J.H.; Bardoel, B.W.; Seidl, M.F; Van der Ent, S.; Van Strijp, J.A.G.


    Bacterial flagellin molecules are strong inducers of innate immune responses in both mammals and plants. The opportunistic pathogen Pseudomonas aeruginosa secretes an alkaline protease called AprA that degrades flagellin monomers. Here, we show that AprA is widespread among a wide variety of bacterial species. In addition, we investigated the role of AprA in virulence of the bacterial plant athogen P. syringae pv. tomato DC3000. The AprA-deficient DC3000 ΔaprA knockout mutant was significantl...

  4. Effect of the fluorinated groups on nematic liquid crystal alignment on monomer crosslinked film

    International Nuclear Information System (INIS)

    Yu Tao; Peng Zenghui; Ruan Shengping; Xuan Li


    It was found in this work that photosensitive monomers, bisphenol A dicinnamate ester and hexafluorobiphenol a dicinnamate ester were crosslinked under irradiation of linearly polarized ultraviolet light. The exposed films induced homogeneous and homeotropic alignment of liquid crystals (LC), respectively. We verified through experiments that it was fluorinated groups that caused the generation of LC homeotropic alignment on the crosslinked film. Photoreaction process was revealed by Fourier transform infrared spectra. There was no clear morphological anisotropy on these aligned films observed through atomic force microscope analysis. The surface energies were measured and homeotropic alignment reason was discussed in this work

  5. Inverse problem for the mean-field monomer-dimer model with attractive interaction (United States)

    Contucci, Pierluigi; Luzi, Rachele; Vernia, Cecilia


    The inverse problem method is tested for a class of monomer-dimer statistical mechanics models that contain also an attractive potential and display a mean-field critical point at a boundary of a coexistence line. The inversion is obtained by analytically identifying the parameters in terms of the correlation functions and via the maximum-likelihood method. The precision is tested in the whole phase space and, when close to the coexistence line, the algorithm is used together with a clustering method to take care of the underlying possible ambiguity of the inversion.

  6. Communication: Remarkable electrophilicity of the oxalic acid monomer: An anion photoelectron spectroscopy and theoretical study

    International Nuclear Information System (INIS)

    Buonaugurio, Angela; Graham, Jacob; Buytendyk, Allyson; Bowen, Kit H.; Ryder, Matthew R.; Gutowski, Maciej; Keolopile, Zibo G.; Haranczyk, Maciej


    Our experimental and computational results demonstrate an unusual electrophilicity of oxalic acid, the simplest dicarboxylic acid. The monomer is characterized by an adiabatic electron affinity and electron vertical detachment energy of 0.72 and 1.08 eV (±0.05 eV), respectively. The electrophilicity results primarily from the bonding carbon-carbon interaction in the singly occupied molecular orbital of the anion, but it is further enhanced by intramolecular hydrogen bonds. The well-resolved structure in the photoelectron spectrum is reproduced theoretically, based on Franck-Condon factors for the vibronic anion → neutral transitions

  7. Erosion characteristics of ethylene propylene diene monomer composite insulation by high-temperature dense particles (United States)

    Li, Jiang; Guo, Meng-fei; Lv, Xiang; Liu, Yang; Xi, Kun; Guan, Yi-wen


    In this study, a dense particles erosion test motor which can simulate the erosion state of a solid rocket motor under high acceleration was developed. Subsequently, erosion experiments were carried out for the ethylene propylene diene monomer composite insulation and the microstructure of the char layer analysed. A turning point effect was found from the influence of the particle impact velocity on the ablation rate, and three erosion modes were determined according to the micro-morphology of the char layer. A reasonable explanation for the different structures of the char layer in the three modes was presented based on the formation mechanism of the compact/loose structure of the char layer.

  8. The formation of singly and doubly cationized oligomers in SIMS

    International Nuclear Information System (INIS)

    Delcorte, A.; Wojciechowski, I.; Gonze, X.; Garrison, B.J.; Bertrand, P.


    The cationization of sputtered organic species via metal particle adduction is investigated using poly-4-methylstyrene molecules in combination with Cu, Pd, Ag and Au substrates. Metal-cationization occurs for these four substrates. The cationized molecule yields vary with the considered substrate and they are not correlated with the metal ion yields. In addition, double cationization with two metal particles is observed with a very significant intensity for Cu, Ag and Au supports. We interpret the results with an emission scheme in which excited molecules and metal atoms recombine above the surface and decay via electron emission, thereby locking the complex in the ionic state

  9. Tailoring Macromolecular Structure of Cationic Polymers towards Efficient Contact Active Antimicrobial Surfaces

    Directory of Open Access Journals (Sweden)

    Rubén Tejero


    Full Text Available The aim of this work is the preparation of contact active antimicrobial films by blending copolymers with quaternary ammonium salts and polyacrylonitrile as matrix material. A series of copolymers based on acrylonitrile and methacrylic monomers with quaternizable groups were designed with the purpose of investigating the influence of their chemical and structural characteristics on the antimicrobial activity of these surfaces. The biocide activity of these systems was studied against different microorganisms, such as the Gram-positive bacteria Staphylococcus aureus and the Gram-negative bacteria Pseudomona aeruginosa and the yeast Candida parapsilosis. The results confirmed that parameters such as flexibility and polarity of the antimicrobial polymers immobilized on the surfaces strongly affect the efficiency against microorganisms. In contrast to the behavior of copolymers in water solution, when they are tethered to the surface, the active cationic groups are less accessible and then, the mobility of the side chain is critical for a good contact with the microorganism. Blend films composed of copolymers with high positive charge density and chain mobility present up to a more than 99.999% killing efficiency against the studied microorganisms.

  10. Steady-state electrophoresis of RNA against a gradient of cationic charges in a polyacrylamide matrix. (United States)

    Zilberstein, Gleb; Shlar, Ilya; Baskin, Emmanuil; Korol, Leonid; Righetti, Pier Giorgio; Bukshpan, Shmuel


    A novel method for separation of RNA fragments is reported here, based on migrating the polyanionic RNA fragments in a polycationic polyacrylamide gel, made by incorporating positively charged monomers (the Immobilines used for creating immobilized pH gradients) into the neutral polyacrylamide backbone. Separations are typically performed in a 0-10 mM, pK 10.3 Immobiline gradient under denaturing conditions (6 M urea). In the 100-1000 bp length, it is shown that separations of RNA are optimal and very sharp bands can be obtained, in comparison with conventional electrophoresis, due to the "focusing" effect originated by the charge balancing between the positively charged gel matrix and the negatively charged RNA species. Excellent separations are also obtained from micro-RNAs, single-stranded RNA molecules of 21-23 nucleotides in length, which appear to regulate gene expression in animal and plant tissues. As a third example, 2-D runs in control and polycationic gels are shown. Under native conditions, RNAs are not aligned in a diagonal, suggesting that molecular shape has a strong influence on the interaction between RNA and the charged gel matrix. Thus, 2-D runs in cationic matrices might be exploited for structural studies of RNA molecules.

  11. A Spectroscopic and Electrochemical Investigation of Interactions of Anticancer Uracil Derivatives with Cationic and Anionic Surfactants

    International Nuclear Information System (INIS)

    Zafar, F.; Shah, A.; Ahmad, Z.; Siddiq, M.; Ali, S.; Asad Muhammad Khan, A. M.; Rana, U. A.


    Interactions of 5-fluorouracil (5-FU), a commercially available anti-cancer drug and two other possibly anti-cancer actives, 2-thiouracil (2-TU) and 2,4-dithiouracil (DTU), with anionic sodium dodecyl sulphate (SDS) and cationic cetlytrimethyl ammonium bromide (CTAB) surfactants were studied using cyclic voltammetry and UV-Visible spectroscopic techniques. The results from both techniques asserted the formation of complex between the drugs and surfactants. In the pre-micellar concentrations, the binding was mainly due to the interactions between the surfactants monomers (electrostatic) and the drug molecules, while in the post-micellar region, drug was encapsulated within the micelle due to electrostatic as well as hydrophobic interactions. The UV-Visible spectroscopic data of the interaction between 5-fluorouracil and the surfactants exhibited an isobestic point which indicated the presence of equilibrium species in bulk and the micellar phase. Binding constant, partition coefficient between bulk and miceller phase, and the number of drug molecules incorporated per micelle were calculated. (author)

  12. Removal of acidic indigo carmine textile dye from aqueous solutions using radiation induced cationic hydrogels. (United States)

    Sari, Müfrettin Murat


    This study examined the removal of acidic indigo carmine dyes from aqueous solutions using cationic hydrogels. Irradiated hydrogels were investigated as a new sorbent for dye removal from aqueous solution. Poly(N,N-Diethylamino ethyl methacrylate) [poly(DEAEMA)] hydrogels were prepared by radiation polymerisation of N,N-diethylamino ethyl methacrylate [DEAEMA] monomer in the presence of cross-linking agent, ethylene glycol dimethacrylate [EGDMA], and used for the removal of acidic indigo carmine textile dye. The adsorption of dyes was examined using a batch sorption technique. The effects of pH, time and initial dye concentration on the adsorption capacity of hydrogels were investigated. Maximum gelation ratio was 98.2% at irradiation dose of 5.3 kGy. Maximum equilibrium volume swelling, V/V(0), value was 21.3 at pH 2.8. Maximum amount of adsorbed indigo carmine onto hydrogels was 96.7 mg dye/g gel at pH 2.8, 21 h of adsorption time and 120 mg/L initial dye solution. Swelling and adsorption capacity increased with decreasing of pH. Compared with Congo red, amounts of adsorbed indigo carmine are much higher than those of Congo red. Langmuir isotherm model was the best fit for these poly(DEAEMA) hydrogels-indigo carmine systems.

  13. Hydration Structure of the Quaternary Ammonium Cations

    KAUST Repository

    Babiaczyk, Wojtek Iwo


    Two indicators of the hydropathicity of small solutes are introduced and tested by molecular dynamics simulations. These indicators are defined as probabilities of the orientation of water molecules\\' dipoles and hydrogen bond vectors, conditional on a generalized distance from the solute suitable for arbitrarily shaped molecules. Using conditional probabilities, it is possible to distinguish features of the distributions in close proximity of the solute. These regions contain the most significant information on the hydration structure but cannot be adequately represented by using, as is usually done, joint distance-angle probability densities. Our calculations show that using our indicators a relative hydropathicity scale for the interesting test set of the quaternary ammonium cations can be roughly determined. © 2010 American Chemical Society.

  14. Use of a material conducting hydrogen cations

    International Nuclear Information System (INIS)

    Howe, A.T.; Shilton, M.G.


    The invention concerns a separator conducting hydrogenous for electrical devices, which contains at least one compound with the formula H(UO 2 )PO 4 x nH 2 O, H(UO 2 )AsO 4 x nH 2 O or H(UO 2 )IO 4 (OH) 2 x nH 2 O, where not more than 50% by weight of the H + is replaced by one or more cations, such as Li + , Na + , K + , NH 4 + , Cu 2+ , Mg 2+ , Ca 2+ , Ba 2+ , Sr 2+ , Pb 2+ , Fe 2+ , Co 2+ , Ni 2+ , Mn 2+ or Al 3+ . The electrical device having the separator can be an electrolysis cell, for example, an electro chromium cell. (H x WO 3 ), a hydrogen isotope enrichment device, a proton-sensitive electrode (eg for a pH meter), a battery or a fuel cell. (orig./MM) [de

  15. An investigation of mixed cation oxide glasses

    International Nuclear Information System (INIS)

    Brook, H.C.


    This study has been undertaken with several purposes in mind. Firstly, the author wished to ascertain whether EXAFS would show the mixed alkali (MAE) in a mixed alkali glass in shell parameters other than those for the first shell, as well as being a structural probe. Secondly, it was desired to see whether borate glasses show the MAE in EXAFS. Thirdly, the author attempted to ascertain whether cations of different charges would show an effect similar to the MAE. Fourthly, to use NMR as a second structure probe in an attempt to gain a better understanding of the structure. Fifthly, to perform electrical conductivity experiments to try to link the conductivity behaviour with structural changes. Finally, to attempt to develop a generalised explanation of the origins of the MAE and the variations in physical properties in glasses. (author)

  16. Retention of Cationic Starch onto Cellulose Fibres (United States)

    Missaoui, Mohamed; Mauret, Evelyne; Belgacem, Mohamed Naceur


    Three methods of cationic starch titration were used to quantify its retention on cellulose fibres, namely: (i) the complexation of CS with iodine and measurement of the absorbency of the ensuing blue solution by UV-vis spectroscopy; (ii) hydrolysis of the starch macromolecules followed by the conversion of the resulting sugars to furan-based molecules and quantifying the ensuing mixture by measuring their absorbance at a Ι of 490 nm, using the same technique as previous one and; finally (iii) hydrolysis of starch macromolecules by trifluoro-acetic acid and quantification of the sugars in the resulting hydrolysates by high performance liquid chromatography. The three methods were found to give similar results within the range of CS addition from 0 to 50 mg per g of cellulose fibres.

  17. Altered erythrocyte cation permeability in familial pseudohyperkalaemia. (United States)

    Dagher, G; Vantyghem, M C; Doise, B; Lallau, G; Racadot, A; Lefebvre, J


    1. Erythrocyte cation transport pathways have been investigated in a family with pseudohyperkalaemia. 2. Ouabain- and bumetanide-resistant Na+ and K+ effluxes in three pseudohyperkalaemic patients were not different from those of control subjects when assessed at 37 degrees C. 3. When the temperature was decreased to 20 degrees C and 9 degrees C, K+ passive permeability markedly increased and Na+ permeability remained unchanged in these patients. In contrast, in control subjects a reduction in temperature caused a marked reduction in Na+ and K+ passive permeability. 4. These findings could account for the marked increase in plasma K+ concentration observed at subphysiological temperatures. 5. The Na+-K+ co-transport pathway was reduced in all members of the family, but the Na+-K+ pump was reduced in only two of them. These alterations were independent from the pseudohyperkalaemic state.

  18. A Cationic Smart Copolymer for DNA Binding

    Directory of Open Access Journals (Sweden)

    Tânia Ribeiro


    Full Text Available A new block copolymer with a temperature-responsive block and a cationic block was prepared by reversible addition-fragmentation chain transfer (RAFT polymerization, with good control of its size and composition. The first block is composed by di(ethylene glycol methyl ether methacrylate (DEGMA and oligo(ethylene glycol methyl ether methacrylate (OEGMA, with the ratio DEGMA/OEGMA being used to choose the volume phase transition temperature of the polymer in water, tunable from ca. 25 to above 90 °C. The second block, of trimethyl-2-methacroyloxyethylammonium chloride (TMEC, is positively charged at physiological pH values and is used for DNA binding. The coacervate complexes between the block copolymer and a model single strand DNA are characterized by fluorescence correlation spectroscopy and fluorescence spectroscopy. The new materials offer good prospects for biomedical application, for example in controlled gene delivery.

  19. Cell Penetrating Peptides and Cationic Antibacterial Peptides (United States)

    Rodriguez Plaza, Jonathan G.; Morales-Nava, Rosmarbel; Diener, Christian; Schreiber, Gabriele; Gonzalez, Zyanya D.; Lara Ortiz, Maria Teresa; Ortega Blake, Ivan; Pantoja, Omar; Volkmer, Rudolf; Klipp, Edda; Herrmann, Andreas; Del Rio, Gabriel


    Cell penetrating peptides (CPP) and cationic antibacterial peptides (CAP) have similar physicochemical properties and yet it is not understood how such similar peptides display different activities. To address this question, we used Iztli peptide 1 (IP-1) because it has both CPP and CAP activities. Combining experimental and computational modeling of the internalization of IP-1, we show it is not internalized by receptor-mediated endocytosis, yet it permeates into many different cell types, including fungi and human cells. We also show that IP-1 makes pores in the presence of high electrical potential at the membrane, such as those found in bacteria and mitochondria. These results provide the basis to understand the functional redundancy of CPPs and CAPs. PMID:24706763

  20. Silver Nanocube and Nanobar Growth via Anisotropic Monomer Addition and Particle Attachment Processes. (United States)

    Xiao, Dongdong; Wu, Zhigang; Song, Miao; Chun, Jaehun; Schenter, Gregory K; Li, Dongsheng


    Understanding the growth mechanism of noble metal nanocrystals during solution synthesis is of significant importance for shape and property control. However, much remains unknown about the growth pathways of metal nanoparticles due to the lack of direct observation. Using an in situ transmission electron microscopy technique, we directly observed Ag nanocube and nanobar growth in an aqueous solution through both classical monomer-by-monomer addition and nonclassical particle attachment processes. During the particle attachment process, Ag nanocubes and nanobars were formed via both oriented and nonoriented attachment. Our calculations, along with the dynamics of the observed attachment, showed that the van der Waals force overcomes hydrodynamic and friction forces and drives the particles toward each other at separations of 10-100 nm in our experiments. During classical growth, anisotropic growth was also revealed, and the resulting unsymmetrical shape constituted an intermediate state for Ag nanocube growth. We hypothesized that the temporary symmetry breaking resulted from different growth rates on (001) surfaces due to a local surface concentration variation caused by the imbalance between the consumption of Ag + near the surface and the diffusion of Ag + from the bulk to the surface.

  1. Benzylpyrazinium Salts as Photo-Initiators in the Polymerization of Epoxide Monomers

    Directory of Open Access Journals (Sweden)

    Moon Suk Kim


    Full Text Available In order to study the capability of pyrazinium salt derivatives to act as photo-initiators of epoxide monomers, benzyl pyrazinium hexafluoroantimonate (BPH, benzyl 3,5-dimethyl pyrazine hexafluoroantimonate (BDH and benzyl quinoxalinium hexafluoroantimonate (BQH were synthesized by the Menschutkin reaction of benzyl bromide with pyrazine, 2,6-dimethyl pyrazine, and quinoxaline, followed by exchanging with hexafluoroantimonate (SbF6. BPH, BDH, and BQH exhibited characteristic ultraviolet (UV absorbance as well as exothermic peaks as a function of irradiation time in a differential photo-calorimeter (DPC. In the absence of photo-irradiation, cyclohexene oxide (CHO underwent slow polymerization at 25 °C using BPH derivatives, but quantitative conversion was achieved even after a 5-min photo-irradiation. In addition, photo-irradiation was required for the photo-polymerization of CHO and styrene oxide (STO, which was characterized by a short induction period followed by a very rapid and exothermic polymerization. While glycidyl methyl ether (GME required long induction periods, glycidyl phenyl ether (GPE underwent rather slow and/or no photo-polymerization. The reactivity order of the monomers was CHO > STO >> GME >>> GPE, and the reactivity order for the photo-polymerization of CHO was BPH > BQH > BDH. It was found that BPH, BDH, and BQH could serve as photo-latent initiators for CHO, STO and GME, respectively.

  2. Silver Nanocube and Nanobar Growth via Anisotropic Monomer Addition and Particle Attachment Processes

    Energy Technology Data Exchange (ETDEWEB)

    Xiao, Dongdong [Physical; Wu, Zhigang [School; Song, Miao [Physical; Chun, Jaehun [Physical; Schenter, Gregory K. [Physical; Li, Dongsheng [Physical


    Understanding the growth mechanism of noble metal nanocrystals during solution synthesis is of significant importance for shape and property control. However, much remains unknown about the growth pathways of metal nanoparticles due to lack of direct observation. Using an in-situ transmission electron microscopy technique, we directly observed Ag nanocube and nanobar growth in aqueous solution through both classical monomer-by-monomer addition and non-classical particle attachment processes. During the particle attachment process, Ag nanocubes and nanobars formed via both oriented and non-oriented attachment. Our calculations, along with dynamics of the observed attachment, showed that van der Waals force overcame hydrodynamic and friction forces and drove the particles toward each other. During classical growth, an anisotropic growth was also revealed, and the resulting unsymmetrical shape constituted an intermediate state for Ag nanocube growth. We hypothesized that the temporary symmetry breaking resulted from different growth rates on {001} surfaces due to a local surface concentration variation caused by the imbalance between the consumption of Ag+ near the surface and the diffusion of Ag+ from bulk to surface.

  3. Bifunctional monomer magnetic imprinted nanomaterials for selective separation of tetracyclines directly from milk samples. (United States)

    Xu, Yuan; Tang, Yuhai; Zhao, Yayun; Gao, Ruixia; Zhang, Junjie; Fu, Delai; Li, Zhaolun; Li, Hecheng; Tang, Xiaoshuang


    Novel magnetic molecularly imprinted nanomaterials (DA + BSA-MMIPs) were prepared adopting bovine serum albumin (BSA) and dopamine as bifunctional monomers for the first time. Besides the role of assistant functional monomer, BSA can exclude the proteins with like charges and promote low molecular weight tetracyclines to be adsorbed. Thus, the DA + BSA-MMIPs could fulfil the selective separation of tetracyclines directly from milk samples. The characteristics, polymerization conditions, and adsorption performances of the resultant nanomaterials were investigated in detail. In addition of uniform imprinting layers, stable crystalline phase, and good magnetism of the DA + BSA-MMIPs, they have rapid binding kinetic, high adsorption capacity, and favorable reusability. The imprinted nanomaterials were coupled with HPLC to selectively extract and determine trace tetracyclines from untreated milk samples. The recoveries of tetracyclines are in the range of 84.1-95.8% with relative standard deviations of less than 6.7%. The developed method is especially suitable for the selective enrichment and detection of target compounds directly from a complex sample with proteins. Copyright © 2018 Elsevier Inc. All rights reserved.

  4. Self-assembly of actin monomers into long filaments: Brownian Dynamics simulations

    DEFF Research Database (Denmark)

    Shillcock, Julian C.


    states corresponding to a bound adenosine triphosphate (ATP), adenosine diphosphate with inorganic phosphate (ADP/P), and ADP molecule. The simplest situation that has been studied experimentally is provided by the polymerization of ADP-actin, for which all protomers are identical. This case is used...... attachment and detachment processes at the two ends of the filaments, we introduce a novel rescaling procedure by which we speed all dynamical processes related to actin polymerization and depolymerization up by the same factor. In general, the actin protomers within a filament can attain three different....../detachment events. When a single filament is allowed to grow in a bath of constant concentration of free ADP-actin monomers, its growth rate increases linearly with the free monomer concentration in quantitative agreement with in vitro experiments. Theresults also show that the waiting time is governed by...

  5. 13C Kinetic isotopic effect of polymerization on monomers with multiple bond

    International Nuclear Information System (INIS)

    Berman, E.L.; Polyakov, V.B.; Makovetskij, K.L.; Golenko, T.G.; Galimov, Eh.M.; AN SSSR, Moscow. Inst. Organicheskoj Khimii; AN SSSR, Moscow. Inst. Geokhimii i Analiticheskoj Khimii)


    13 C kinetic isotopic effect (KIE) of anionic and radical polymerization and metathesis reaction of monomers with multiple bonds are studied and correlation between the found KIE values of polymerization and the structure of transition state is established. 13 C KIE of polymerization reactions are investigated using monomers with natural content of the isotope. Polymerization was carried out using high-vacuum equipment: radical polymerization of methyl acrylate (MA) and vinyl acetate in benzene solution under the effect of benzoyl peroxide (60 deg C); anionic polymerization of MA, initiated by potassium butyl cellosolvolate, was realized in mass at 25 deg C; cyclopentene metathesis reaction was conducted in benzene under the effect of initiating system WCl 6 - (C 3 H 5 ) 2 Si(CH 3 ) 2 at -30 deg C; phenylacetylene polymers were prepared by polymerization in benzene solution at 20 deg C under the effect of WCl 6 . It is ascertained that 13 C KIE of radical and anionic polymerization of olefins and cycloolefin metathesis constitutes 2.0 -2.4%. Polymerization of compound with ternary bond is accompanied by a lower value of 13 C KIE (<1%), which is explained by double bond of reacting bond in transition state

  6. Highly Efficient and Facile Photocatalytic Recycling System Suitable for ICAR ATRP of Hydrophilic Monomers. (United States)

    Jiang, Xiaowu; Zhang, Lifen; Cheng, Zhenping; Zhu, Xiulin


    Photoinduced initiators for continuous activator regeneration atom transfer radical polymerization (ATRP) of hydrophilic monomers in heptane/ethanol latent-biphasic system for copper catalyst separation and recycling have been realized for the first time at room temperature with different wavelengths of visible light LED (green, blue, purple, and white LED) as external stimulus, using 2-bromophenylacetate as the ATRP initiator and camphorquinone/triethylamine as the photoinitiator. In this system, hybrid catalyst complex (HCc) is synthesized as a novel nonpolar catalyst, which is preferentially dissolved in heptane. The hydrophilic polymers obtained catalyzed by HCc in heptane/ethanol mixture solvent show typical "living" features, for example, the values of Mn,GPC increase linearly with monomer conversion up to quantitative level (>96%) and the molecular weight distributions were kept narrow (Mw /Mn < 1.20) throughout the polymerization process. It should be noted that the excellent controllability of this novel polymerization system can be achieved even after 5 catalyst recycling experiments under LED irradiation. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. An investigation of the chemical stability of a monomer/polymer gel dosimeter

    International Nuclear Information System (INIS)

    De Deene, Y.; De Wagter, C.; De Neve, W.; Achten, E.


    The aim of this work is to investigate the temporal stability of a polyacrylamide gelatin hydrogel used for 3D monomer/polymer gel dosimetry techniques involving different methods of analysis. Long-term instabilities for a similar gel have recently been reported, but differ markedly from those described in this work. Two kinds of long-term instabilities are described. One affects the slope of the dose-R 2 plot and is related to post-irradiation polymerization of the comonomer/polymer aggregates. It is observed that post-irradiation polymerization only lasts 12 hours after irradiation. The other instability affects the intercept of the dose-R 2 plot, lasts for up to 30 days and is related to the gelation process of gelatin. Further studies were performed on gelatin gels of varying compositions to obtain a better understanding of the molecular mechanism that causes the instability due to gelation. The studies included observations of the spin-spin and spin-lattice relaxation rates in combination with diffusion measurements and optical measurements. It is shown that the heating history during the manufacture of the gel affects the absolute R 2 value of the gel but not its variation. The findings presented in this study may help in producing more stable and reproducible monomer/polymer gel dosimeters. (author)

  8. Analysis of lignocellulose derived phenolic monomers by headspace solid-phase microextraction and gas chromatography. (United States)

    Kolb, Michaela; Schieder, Doris; Faulstich, Martin; Sieber, Volker


    A headspace solid-phase microextraction method with subsequent GC-MS (HS-SPME/GC-MS) was established for the quantitative analysis of volatile lignin derived phenolic monomers in complex aqueous solutions. Extraction was done using a polyacrylate fiber. The optimization of HS-SPME - parameters was performed using a multi component model solution of six representative phenolic monomers identified in liquid hot water (LHW) supernatants of hydrothermally treated lignocellulosic biomass: p-coumaric acid, guaiacol, vanillin, acetosyringone, 4-hydroxy-3-methoxyphenylacetone, and acetophenone. Plackett-Burman design was applied for pre-evaluation and 2(3) central composite designs with star points for parameter optimization. LOQ (S/N>10) and LOD (S/N>3) were determined for 12 phenols yielding LOQ of <0.005-618nM and LOD of <0.005-412nM. Within-day and between-day tests (n=6) showed different results for the tested phenols. RSD ranged from 2% to 30% and recovery rates from 99% to 160% in LHW matrix. Tests on storage of LHW supernatants for several weeks indicated a considerable influence of temperature on the stability of the solutions which may even have to be taken into account for auto sampler handling. All in all the method allows a fast and solvent free analysis requiring low sample volumes making it a powerful tool for screening or high-throughput analysis of aqueous solutions of lignin derived aromatics. Copyright © 2013. Published by Elsevier B.V.

  9. Macromolecules with amphiphilic monomer units at interface of two immiscible liquids (United States)

    Glagoleva, A. A.; Vasilevskaya, V. V.


    The adsorption of macromolecules with amphiphilic monomer units at the liquid-liquid interface was studied. The amphiphilic structure of monomer units with groups selectively interacting with α and β liquids was described by the A-graft-B dumbbell model. The calculations were performed for the symmetrical interaction of A and B groups with liquids, different selectivity parameters ξ and degree of polymerization N. The simulations indicate a three-step adsorption scenario, including non-adsorbed, weak and strong localization states. It was shown that the adsorption of (A-graft-B)N macromolecules obeys scaling laws developed to describe the adsorption of the alternating (AB)N copolymer at the liquid-liquid interface with critical selectivity parameter ξc of transition into the weak localization state depending on the degree of polymerization as N-1/5; critical selectivity parameter ξ∞ of transition to the strong localization regime non-depending on the degree of polymerization; and relative change of perpendicular Rz radius of gyration varying as a power function of ξN1/5: Rz(ξ)/Rz(0) ˜ (ξN1/5)ρ and ρ = -2ν/(1 - v). Meanwhile, (A-graft-B)N macromolecules have much lower ξc and ξ∞ values and thus are more prospective for practical applications.

  10. Noise-and delay-induced phase transitions of the dimer–monomer surface reaction model

    International Nuclear Information System (INIS)

    Zeng Chunhua; Wang Hua


    Highlights: ► We study the dimer–monomer surface reaction model. ► We show that noise induces first-order irreversible phase transition (IPT). ► Combination of noise and time-delayed feedback induce first- and second-order IPT. ► First- and second-order IPT is viewed as noise-and delay-induced phase transitions. - Abstract: The effects of noise and time-delayed feedback in the dimer–monomer (DM) surface reaction model are investigated. Applying small delay approximation, we construct a stochastic delayed differential equation and its Fokker–Planck equation to describe the state evolution of the DM reaction model. We show that the noise can only induce first-order irreversible phase transition (IPT) characteristic of the DM model, however the combination of the noise and time-delayed feedback can simultaneously induce first- and second-order IPT characteristics of the DM model. Therefore, it is shown that the well-known first- and second-order IPT characteristics of the DM model may be viewed as noise-and delay-induced phase transitions.

  11. Redesign of the monomer–monomer interface of Cre recombinase yields an obligate heterotetrameric complex (United States)

    Zhang, Chi; Myers, Connie A.; Qi, Zongtai; Mitra, Robi D.; Corbo, Joseph C.; Havranek, James J.


    Cre recombinase catalyzes the cleavage and religation of DNA at loxP sites. The enzyme is a homotetramer in its functional state, and the symmetry of the protein complex enforces a pseudo-palindromic symmetry upon the loxP sequence. The Cre-lox system is a powerful tool for many researchers. However, broader application of the system is limited by the fixed sequence preferences of Cre, which are determined by both the direct DNA contacts and the homotetrameric arrangement of the Cre monomers. As a first step toward achieving recombination at arbitrary asymmetric target sites, we have broken the symmetry of the Cre tetramer assembly. Using a combination of computational and rational protein design, we have engineered an alternative interface between Cre monomers that is functional yet incompatible with the wild-type interface. Wild-type and engineered interface halves can be mixed to create two distinct Cre mutants, neither of which are functional in isolation, but which can form an active heterotetramer when combined. When these distinct mutants possess different DNA specificities, control over complex assembly directly discourages recombination at unwanted half-site combinations, enhancing the specificity of asymmetric site recombination. The engineered Cre mutants exhibit this assembly pattern in a variety of contexts, including mammalian cells. PMID:26365240

  12. Multiple routes and milestones in the folding of HIV-1 protease monomer.

    Directory of Open Access Journals (Sweden)

    Massimiliano Bonomi

    Full Text Available Proteins fold on a time scale incompatible with a mechanism of random search in conformational space thus indicating that somehow they are guided to the native state through a funneled energetic landscape. At the same time the heterogeneous kinetics suggests the existence of several different folding routes. Here we propose a scenario for the folding mechanism of the monomer of HIV-1 protease in which multiple pathways and milestone events coexist. A variety of computational approaches supports this picture. These include very long all-atom molecular dynamics simulations in explicit solvent, an analysis of the network of clusters found in multiple high-temperature unfolding simulations and a complete characterization of free-energy surfaces carried out using a structure-based potential at atomistic resolution and a combination of metadynamics and parallel tempering. Our results confirm that the monomer in solution is stable toward unfolding and show that at least two unfolding pathways exist. In our scenario, the formation of a hydrophobic core is a milestone in the folding process which must occur along all the routes that lead this protein towards its native state. Furthermore, the ensemble of folding pathways proposed here substantiates a rational drug design strategy based on inhibiting the folding of HIV-1 protease.

  13. Radiation-induced crosslinking of polyethylene in the presence of bifunctional vinyl monomers

    Energy Technology Data Exchange (ETDEWEB)

    Joshi, M.S.


    The apparent crosslinking produced by the radiation grafting of two monomers to polyethylene, acrylic acid and acrylonitrile, was investigated. Evidence is presented to show that covalent crosslinks are not produced during the radiation grafting step; covalent crosslinks are produced by the post-irradiation heat treatment associated with measurements of gel; the enhancement in gel fraction and physical properties arises from true crosslinks rather than chain entanglements; and there may be practical value associated with the sensitization of crosslinking produced by the methods employed in this work. The effect of monomer-solvent composition on the graft and gel yield was studied. Viscoelastic properties of grafted films were determined above the melting point of pure polyethylene. The kinetic data, infrared spectra, and viscoelastic properties are the bases for the following mechanism: (1) Acrylic acid-g-PE: Acrylic acid enters the film in the form of a hydrogen bonded dimer and undergoes a grafting reaction that produces hydrogen-bond crosslinks. The heat treatment during the conventional methods for determining of crosslinks convert them into intermolecular anhydride bonds. (2) Acrylonitrile-g-PE: In this, the post-grafting crosslinking is the result of a thermally induced chain reaction leading to an uninterrupted conjugated sequence. The length of the ring structure increases with time and temperature, and the intensity of color increases with the length of the ring structure.

  14. Improved i-motif thermal stability by insertion of anthraquinone monomers

    DEFF Research Database (Denmark)

    Gouda, Alaa S; Amine, Mahasen S.; Pedersen, Erik Bjerregaard


    In order to gain insight into how to improve thermal stability of i-motifs when used in the context of biomedical and nanotechnological applications, novel anthraquinone-modified i-motifs were synthesized by insertion of 1,8-, 1,4-, 1,5- and 2,6-disubstituted anthraquinone monomers into the TAA...... loops of a 22mer cytosine-rich human telomeric DNA sequence. The influence of the four anthraquinone linkers on the i-motif thermal stability was investigated at 295 nm and pH 5.5. Anthraquinone monomers modulate the i-motif stability in a position-depending manner and the modulation also depends...... on the substitution pattern of the anthraquinone. The insertion of anthraquinone was found to stabilize the i-motif structure when replacing any one of the positions of the central TAA loop and the thermal stabilities were typically higher than those previously found for i-motifs containing pyrene-modified uracilyl...

  15. Restriction endonuclease AgeI is a monomer which dimerizes to cleave DNA. (United States)

    Tamulaitiene, Giedre; Jovaisaite, Virginija; Tamulaitis, Gintautas; Songailiene, Inga; Manakova, Elena; Zaremba, Mindaugas; Grazulis, Saulius; Xu, Shuang-Yong; Siksnys, Virginijus


    Although all Type II restriction endonucleases catalyze phosphodiester bond hydrolysis within or close to their DNA target sites, they form different oligomeric assemblies ranging from monomers, dimers, tetramers to higher order oligomers to generate a double strand break in DNA. Type IIP restriction endonuclease AgeI recognizes a palindromic sequence 5΄-A/CCGGT-3΄ and cuts it ('/' denotes the cleavage site) producing staggered DNA ends. Here, we present crystal structures of AgeI in apo and DNA-bound forms. The structure of AgeI is similar to the restriction enzymes that share in their target sites a conserved CCGG tetranucleotide and a cleavage pattern. Structure analysis and biochemical data indicate, that AgeI is a monomer in the apo-form both in the crystal and in solution, however, it binds and cleaves the palindromic target site as a dimer. DNA cleavage mechanism of AgeI is novel among Type IIP restriction endonucleases. © The Author(s) 2016. Published by Oxford University Press on behalf of Nucleic Acids Research.

  16. Recovery and Utilization of Lignin Monomers as Part of the Biorefinery Approach

    Directory of Open Access Journals (Sweden)

    Kirsten M. Davis


    Full Text Available Lignin is a substantial component of lignocellulosic biomass but is under-utilized relative to the cellulose and hemicellulose components. Historically, lignin has been burned as a source of process heat, but this heat is usually in excess of the process energy demands. Current models indicate that development of an economically competitive biorefinery system requires adding value to lignin beyond process heat. This addition of value, also known as lignin valorization, requires economically viable processes for separating the lignin from the other biomass components, depolymerizing the lignin into monomeric subunits, and then upgrading these monomers to a value-added product. The fact that lignin’s biological role is to provide biomass with structural integrity means that this heteropolymer can be difficult to depolymerize. However, there are chemical and biological routes to upgrade lignin from its native form to compounds of industrial value. Here we review the historical background and current technology of (thermo chemical depolymerization of lignin; the natural ability of microbial enzymes and pathways to utilize lignin, the current prospecting work to find novel microbial routes to lignin degradation, and some applications of these microbial enzymes and pathways; and the current chemical and biological technologies to upgrade lignin-derived monomers.

  17. Analytic solution of two-density integral equations for sticky Janus dumbbells with arbitrary monomer diameters. (United States)

    Gazzillo, Domenico; Munaò, Gianmarco; Prestipino, Santi


    We study a pure fluid of heteronuclear sticky Janus dumbbells, considered to be the result of complete chemical association between unlike species in an initially equimolar mixture of hard spheres (species A) and sticky hard spheres (species B) with different diameters. The B spheres are particles whose attractive surface layer is infinitely thin. Wertheim's two-density integral equations are employed to describe the mixture of AB dumbbells together with unbound A and B monomers. After Baxter factorization, these equations are solved analytically within the associative Percus-Yevick approximation. The limit of complete association is taken at the end. The present paper extends to the more general, heteronuclear case of A and B species with size asymmetry a previous study by Wu and Chiew [J. Chem. Phys. 115, 6641 (2001)], which was restricted to dumbbells with equal monomer diameters. Furthermore, the solution for the Baxter factor correlation functions qij (αβ)(r) is determined here in a fully analytic way, since we have been able to find explicit analytic expressions for all the intervening parameters.

  18. Preliminary study of acrylamide monomer decomposition during methane fermentation of dairy waste sludge. (United States)

    Mroczek, Ewelina; Konieczny, Piotr; Lewicki, Andrzej; Waśkiewicz, Agnieszka; Dach, Jacek


    Polyacrylamide (PAM) used in sludge dewatering exists widely in high-solid anaerobic digestion. Acrylamide is registered in the list of chemicals demonstrating toxic, carcinogenic and mutagenic properties. Therefore, it is reasonable to ask about the mobility of such residual substances in the environment. The study was carried out to assess the impact of the mesophilic (39±1°C) and thermophilic (54±1°C) fermentation process on the level of acrylamide monomer (AMD) content in the dairy sludge. The material was analysed using high-performance liquid chromatography (HPLC) for quantification of AMD. The results indicate that the process of methane fermentation continues regardless of the temperature effects on the degradation of AMD in dairy sludge. The degree of reduction of acrylamide monomer for thermophilic fermentation is 100%, while for mesophilic fermentation it is 91%. In practice, this means that biogas technology eliminates the risk of AMD migration to plant tissue. Moreover, it should be stressed that 90% of cumulative biogas and methane production was reached one week earlier under thermophilic conditions - the dynamics of the methanisation process were over 20% faster. Copyright © 2016. Published by Elsevier B.V.

  19. Structural and Vibrational Study on Monomer and Dimer Forms and Water Clusters of Acetazolamide

    Directory of Open Access Journals (Sweden)

    Aysen E. Ozel


    Full Text Available Experimental IR and Raman spectra of solid acetazolamide have been analysed by computing the molecular structures and vibrational spectra of monomer and dimer forms and water clusters of acetazolamide. The possible stable conformers of free acetazolamide molecule in the ground state were obtained by scanning the potential energy surface through the dihedral angles, D1 (1S-2C-6S-9N, D2 (4N-5C-12N-14C, and D3 (5C-12N-14C-16C. The final geometry parameters for the obtained stable conformers were determined by means of geometry optimization, carried out at DFT/B3LYP/6-31G++(d,p theory level. Afterwards the possible dimer forms of the molecule and acetazolamide-H2O clusters were formed and their energetically preferred conformations were investigated using the same method and the same level of theory. The effect of BSSE on the structure and energy of acetazolamide dimer has been investigated. The assignment of the vibrational modes was performed based on the potential energy distribution of the vibrational modes, calculated by using GAR2PED program. The experimental vibrational wavenumbers of solid acetazolamide are found to be in better agreement with the calculated wavenumbers of dimer form of acetazolamide than those of its monomeric form. NBO analysis has been performed on both monomer and dimer geometries.

  20. Dental primer and adhesive containing a new antibacterial quaternary ammonium monomer dimethylaminododecyl methacrylate (United States)

    Cheng, Lei; Weir, Michael D.; Zhang, Ke; Arola, Dwayne D.; Zhou, Xuedong; Xu, Hockin H. K.


    Objectives The main reason for restoration failure is secondary caries caused by biofilm acids. Replacing the failed restorations accounts for 50–70% of all operative work. The objectives of this study were to incorporate a new quaternary ammonium monomer (dimethylaminododecyl methacrylate, DMADDM) and nanoparticles of silver (NAg) into a primer and an adhesive, and to investigate their effects on antibacterial and dentin bonding properties. Methods Scotchbond Multi-Purpose (SBMP) served as control. DMADDM was synthesized and incorporated with NAg into primer/adhesive. A dental plaque microcosm biofilm model with human saliva was used to investigate metabolic activity, colony-forming units (CFU), and lactic acid. Dentin shear bond strengths were measured. Results Minimum inhibitory concentration (MIC) and minimum bactericidal concentration (MBC) of the new DMADDM were orders of magnitude lower than those of a previous quaternary ammonium dimethacrylate (QADM). Uncured primer with DMADDM had much larger inhibition zones than QADM (pcontrol. Incorporation of DMADDM and NAg into primer/adhesive did not adversely affect dentin bond strength. Conclusions A new antibacterial monomer DMADDM was synthesized and incorporated into primer/adhesive for the first time. The bonding agents are promising to combat residual bacteria in tooth cavity and invading bacteria at tooth-restoration margins to inhibit caries. DMADDM and NAg are promising for use into a wide range of dental adhesive systems and restoratives. PMID:23353068

  1. Therapeutic TNF Inhibitors can Differentially Stabilize Trimeric TNF by Inhibiting Monomer Exchange (United States)

    van Schie, Karin A.; Ooijevaar-de Heer, Pleuni; Dijk, Lisanne; Kruithof, Simone; Wolbink, Gertjan; Rispens, Theo


    Tumor necrosis factor (TNF) is a homotrimeric cytokine that is a key mediator of inflammation. It is unstable at physiological concentrations and slowly converts into an inactive form. Here, we investigated the mechanism of this process by using a Förster resonance energy transfer (FRET) assay that allowed monitoring of monomeric subunit exchange in time. We observed continuous exchange of monomeric subunits even at concentrations of TNF high enough to maintain its bioactivity. The kinetics of this process closely corresponds with the appearance of monomeric subunits and disappearance of trimeric TNF in time at ng/ml concentrations as monitored by high-performance size-exclusion chromatography (HP-SEC). Furthermore, of the five therapeutic TNF inhibitors that are currently used in the clinic, three (adalimumab, infliximab, etanercept) were found to completely inhibit the monomer exchange reaction and stabilize TNF trimers, whereas golimumab and certolizumab could not prevent monomer exchange, but did slow down the exchange process. These differences were not correlated with the affinities of the TNF inhibitors, measured with both surface plasmon resonance (SPR) and in fluid phase using fluorescence-assisted HP-SEC. The stabilizing effect of these TNF inhibitors might result in prolonged residual TNF bioactivity under conditions of incomplete blocking, as observed in vitro for adalimumab. PMID:27605058

  2. Synthesis of Molecularly Imprinted Polymers for Amino Acid Derivates by Using Different Functional Monomers

    Directory of Open Access Journals (Sweden)

    Sonia Scorrano


    Full Text Available Fmoc-3-nitrotyrosine (Fmoc-3-NT molecularly imprinted polymers (MIPs were synthesized to understand the influence of several functional monomers on the efficiency of the molecular imprinting process. Acidic, neutral and basic functional monomers, such as acrylic acid (AA, methacrylic acid (MAA, methacrylamide (MAM, 2-vinylpyridine (2-VP, 4-vinylpyridine (4-VP, have been used to synthesize five different polymers. In this study, the MIPs were tested in batch experiments by UV-visible spectroscopy in order to evaluate their binding properties. The MIP prepared with 2-VP exhibited the highest binding affinity for Fmoc-3NT, for which Scatchard analysis the highest association constant (2.49 × 104 M−1 was obtained. Furthermore, titration experiments of Fmoc-3NT into acetonitrile solutions of 2-VP revealed a stronger bond to the template, such that a total interaction is observed. Non-imprinted polymers as control were prepared and showed no binding affinities for Fmoc-3NT. The results are indicative of the importance of ionic bonds formed between the –OH residues of the template molecule and the pyridinyl groups of the polymer matrix. In conclusion, 2-VP assists to create a cavity which allows better access to the analytes.

  3. The Tec family kinase Itk exists as a folded monomer in vivo. (United States)

    Qi, Qian; August, Avery


    Tec family tyrosine kinases transduce signals from antigen and other receptors. In particular, Itk plays an important role in T-cell development and activation. Itk has an N-terminal pleckstrin homology domain, a Tec Homology domain with a proline-rich region, SH3 and SH2 domains and a kinase domain, the structure each of which has been determined. However, the full structure of Itk and other Tec kinases remain elusive. Models of Itk suggest either a head to tail dimer, with the SH2 domain interacting with the SH3 domain, or a folded monomer with the SH3 domain interacting with the proline-rich region. We show here that in vivo Itk exists as a monomer, with the pleckstrin homology domain less than 80 A from the C terminus. Zn2+ coordinating residues in the Tec Homology domain, not the proline-rich region, are critical for this intramolecular interaction. These data have implications for our understanding of Tec family kinase structure.

  4. Synthesis and characterization of a novel resin monomer with low viscosity. (United States)

    Hong, Lihua; Wang, Yu; Wang, Lin; Zhang, Hong; Na, Hui; Zhang, Zhimin


    In this study, we designed and synthesized a novel macromolecule (tetramethyl bisphenol F acrylate, TMBPF-Ac) with low viscosity, excellent mechanical properties, and good biocompatibility. It could be used as a monomer for dental resin composites, which could reduce the risk of human exposure to bisphenol A derivatives in the oral environment. In addition, the monomer could be used without diluent, thereby avoiding the negative effect of a diluent METHODS: TMBPF-Ac was synthesized by a multistep condensation reaction. Its structure was confirmed by 1 H NMR spectra. Different resin mixtures were prepared, and then a number of performance and cytotoxicity tests were performed on these specimens. 1 H NMR spectra showed that the structure of TMBPF-Ac was in accordance with the design. The viscosity of TMBPF-Ac was obviously lower than that of bisphenol-A diglycidyl methacrylate. The three kinds of resins used in this study were in line with ISO 4049:2009 and ISO 10993-5:2009. TMBPF-Ac-based resin had better physical and biological properties. Copyright © 2017 Elsevier Ltd. All rights reserved.

  5. Radical Copolymerization Kinetics of Bio-Renewable Butyrolactone Monomer in Aqueous Solution

    Directory of Open Access Journals (Sweden)

    Sharmaine B. Luk


    Full Text Available The radical copolymerization kinetics of acrylamide (AM and the water-soluble monomer sodium 4-hydroxy-4-methyl-2-methylene butanoate (SHMeMB, formed by saponification of the bio-sourced monomer γ-methyl-α-methylene-γ-butyrolactone (MeMBL, are investigated to explain the previously reported slow rates of reaction during synthesis of superabsorbent hydrogels. Limiting conversions were observed to decrease with increased temperature during SHMeMB homopolymerization, suggesting that polymerization rate is limited by depropagation. Comonomer composition drift also increased with temperature, with more AM incorporated into the copolymer due to SHMeMB depropagation. Using previous estimates for the SHMeMB propagation rate coefficient, the conversion profiles were used to estimate rate coefficients for depropagation and termination (kt. The estimate for kt,SHMeMB was found to be of the same order of magnitude as that recently reported for sodium methacrylate, with the averaged copolymerization termination rate coefficient dominated by the presence of SHMeMB in the system. In addition, it was found that depropagation still controlled the SHMeMB polymerization rate at elevated temperatures in the presence of added salt.

  6. Fed-Batch Control and Visualization of Monomer Sequences of Individual ICAR ATRP Gradient Copolymer Chains

    Directory of Open Access Journals (Sweden)

    Dagmar R. D'hooge


    Full Text Available Based on kinetic Monte Carlo simulations of the monomer sequences of a representative number of copolymer chains (≈ 150,000, optimal synthesis procedures for linear gradient copolymers are proposed, using bulk Initiators for Continuous Activator Regeneration Atom Transfer Radical Polymerization (ICAR ATRP. Methyl methacrylate and n-butyl acrylate are considered as comonomers with CuBr2/PMDETA (N,N,N′,N′′,N′′-pentamethyldiethylenetriamine as deactivator at 80 °C. The linear gradient quality is determined in silico using the recently introduced gradient deviation ( polymer property. Careful selection or fed-batch addition of the conventional radical initiator I2 allows a reduction of the polymerization time with ca. a factor 2 compared to the corresponding batch case, while preserving control over polymer properties ( ≈ 0.30; dispersity ≈ 1.1. Fed-batch addition of not only I2, but also comonomer and deactivator (50 ppm under starved conditions yields a below 0.25 and, hence, an excellent linear gradient quality for the dormant polymer molecules, albeit at the expense of an increase of the overall polymerization time. The excellent control is confirmed by the visualization of the monomer sequences of ca. 1000 copolymer chains.

  7. How mobile are sorbed cations in clays and clay rocks? (United States)

    Gimmi, T; Kosakowski, G


    Diffusion of cations and other contaminants through clays is of central interest, because clays and clay rocks are widely considered as barrier materials for waste disposal sites. An intriguing experimental observation has been made in this context: Often, the diffusive flux of cations at trace concentrations is much larger and the retardation smaller than expected based on their sorption coefficients. So-called surface diffusion of sorbed cations has been invoked to explain the observations but remains a controversial issue. Moreover, the corresponding surface diffusion coefficients are largely unknown. Here we show that, by an appropriate scaling, published diffusion data covering a broad range of cations, clays, and chemical conditions can all be modeled satisfactorily by a surface diffusion model. The average mobility of sorbed cations seems to be primarily an intrinsic property of each cation that follows inversely its sorption affinity. With these surface mobilities, cation diffusion coefficients can now be estimated from those of water tracers. In pure clays at low salinities, surface diffusion can reduce the cation retardation by a factor of more than 1000.

  8. In vivo toxicity of cationic micelles and liposomes

    DEFF Research Database (Denmark)

    Knudsen, Kristina Bram; Northeved, Helle; Ek, Pramod Kumar


    This study investigated toxicity of nanocarriers comprised of cationic polymer and lipid components often used in gene and drug delivery, formulated as cationic micelles and liposomes. Rats were injected intravenously with 10, 25 or 100 mg/kg and sacrificed after 24 or 48 h, or 24 h after the las...

  9. Effects of metallic cations in the beryl flotation

    International Nuclear Information System (INIS)

    Lima Leonel, C.M. de; Peres, A.E.C.


    The beryl zeta potential in microelectrophoretic cell is studied in the presence of neutral electrolyte, cations of calcium, magnesium and iron. The petroleum sulfonate is used how collector in Hallimond tube. Hydroxy complex of metallic cations seems activate the ore and precipitates of colloidal metallic hidroxies seems lower him when added to the mixture. (M.A.C.) [pt

  10. Does alkali cation binding to aromatic ring retard the fluxional ...

    Indian Academy of Sciences (India)

    A Kalpana


    Nov 10, 2017 ... the role of cation on haptotropic migration. Cation binding not only enhances the complex interaction energy but also delicately affects the fluxionality in the molecule by increasing the barrier to haptotropic shift of Cr(CO)3. The competing nature of the bifacial acids with sandwiched aromatic ring is ...

  11. Membrane potential change effects on cationic and neutral drug ...

    African Journals Online (AJOL)

    Membrane potential change effects on cationic and neutral drug - induced erythrocyte shape change and cellular uptake of drugs. A Nwafor, WT Coakley. Abstract. The effect of membrane potential change of the human erythrocytes on cationic drugs tetracaine and chlorpromazine and neutral drug benzyl alcohol induced ...

  12. Cation substitution induced blue-shift of optical band gap

    Indian Academy of Sciences (India)

    Cation substitution induced blue-shift of optical band gap in nanocrystalline Zn ( 1 − x ) Ca x O thin films deposited by sol–gel dip coating technique ... thin films giving 13.03% enhancement in theenergy gap value due to the electronic perturbation caused by cation substitution as well as deterioration in crystallinity.

  13. Base Cation Leaching From the Canopy of a Rubber ( Hevea ...

    African Journals Online (AJOL)

    Base cations are essential to the sustainability of forest ecosystems. They are important for neutralizing the acidifying effects of atmospheric deposition. There is the need for in-depth understanding of base cation depletion and leaching from forest canopy. This is important particularly due to the increasing acidification and ...

  14. Cationic Antimicrobial Peptides Inactivate Shiga Toxin-Encoding Bacteriophages

    Directory of Open Access Journals (Sweden)

    Manuel E. Del Cogliano


    Full Text Available Shiga toxin (Stx is the principal virulence factor during Shiga toxin-producing Escherichia coli (STEC infections. We have previously reported the inactivation of bacteriophage encoding Stx after treatment with chitosan, a linear polysaccharide polymer with cationic properties. Cationic antimicrobial peptides (cAMPs are short linear aminoacidic sequences, with a positive net charge, which display bactericidal or bacteriostatic activity against a wide range of bacterial species. They are promising novel antibiotics since they have shown bactericidal effects against multiresistant bacteria. To evaluate whether cationic properties are responsible for bacteriophage inactivation, we tested seven cationic peptides with proven antimicrobial activity as anti-bacteriophage agents, and one random sequence cationic peptide with no antimicrobial activity as a control. We observed bacteriophage inactivation after incubation with five cAMPs, but no inactivating activity was observed with the random sequence cationic peptide or with the non-alpha helical cAMP Omiganan. Finally, to confirm peptide-bacteriophage interaction, zeta potential was analyzed by following changes on bacteriophage surface charges after peptide incubation. According to our results we could propose that: (1 direct interaction of peptides with phage is a necessary step for bacteriophage inactivation, (2 cationic properties are necessary but not sufficient for bacteriophage inactivation, and (3 inactivation by cationic peptides could be sequence (or structure specific. Overall our data suggest that these peptides could be considered a new family of molecules potentially useful to decrease bacteriophage replication and Stx expression.

  15. Cation-cation "attraction": when London dispersion attraction wins over Coulomb repulsion. (United States)

    Grimme, Stefan; Djukic, Jean-Pierre


    London forces are omnipresent in nature and relevant to molecular engineering. Proper tuning of their energetic contribution may stabilize molecular aggregates, which would be otherwise highly unstable by virtue of other overwhelming repulsive terms. The literature contains a number of such noncovalently bonded molecular aggregates, of which the "binding mode" has never been thoroughly settled. Among those are the emblematic cationic complexes of tetrakis(isonitrile)rhodium(I) studied by a number of researchers. The propensity of these complexes to spontaneously produce oligomers has been an "open case" for years. For the dimer [(PhNC)(4)Rh](2)(2+), one of the archetypes of such oligomers, density functional theory methods (DFT-D3) and wave function based spin-component-scaled second-order Møller-Plesset perturbation theory (SCS-MP2) quantum chemical calculations indicate that when the eight isonitrile ligands arrange spatially in an optimal π-stacked fashion, the energy due to dispersion not only overcomes coulombic repulsion but also the entropy penalty of complex formation. This central role of long-range electron correlation explains such cation-cation attractive interactions. Furthermore, the present findings relativize the role of the metal-metal "d(8)-d(8)" interactions, which are present on a relatively small scale compared to the effects of the ligands; d(8)-d(8) interactions represent about 10-15% of the total dispersion contribution to the binding energy.

  16. pKa value and buffering capacity of acidic monomers commonly used in self-etching primers. (United States)

    Salz, Ulrich; Mücke, Angela; Zimmermann, Jörg; Tay, Franklin R; Pashley, David H


    The aim of this investigation was to characterize acidic monomers used in self-etching primers/adhesives by determination of their pKa values and by calculation of their calcium dissolving capacity in comparison with phosphoric and hydrochloric acid. The following acidic monomers were included in this study: 4-methacryloyloxyethyl trimellitate anhydride (4-META), 10-methacryloyloxydecyl dihydrogen phosphate (MDP), dimethacryloyloxyethyl hydrogen phosphate (di-HEMA-phosphate), ethyl 2-[4-(dihydroxyphosphoryl)-2-oxabutyl]acrylate (EAEPA), 2-[4-(dihydroxyphosphoryl)-2-ox-abutyl]acrylic acid (HAEPA), and 2,4,6 trimethylphenyl 2-[4-(dihydroxyphosphoryl)-2-oxabutyl]acrylate (MAEPA). The pKa values were obtained by titration with 0.1 mol/l NaOH in aqueous solution. The inflection points of the resulting potentiometric titration curve were determined as pKa values. In the case of the sparingly water-soluble acidic monomers MAEPA and 4-META, the co-solvent method using different water/ethanol ratios for MAEPA or water/acetone ratios for 4-META was used. The dissolving capacity of each acidic monomer is defined as the amount of hydroxyapatite (HA) dissolved by 1 g of acid. For each monomer, the HA dissolving capacity was calculated bythe corresponding pKa value and the molecular weight. To confirm the calculated dissolving capacities, increasing amounts of HA powder (100 mg portions) were slowly added to 15 mmol/l aqueous solutions of the monomers to determine how much HA could be dissolved in the acidic solutions. For all the investigated acidic monomers, pKal values between 1.7 to 2.5 were observed. The pKa2 values for the phosphate/phosphonate derivatives are between 7.0 and 7.3, and are comparable to phosphoric acid. For dicarboxylic acid derivatives, the pKa2 values are in the range of 4.2 to 4.5. Due to their comparable molecular weights and pKal values, the three tested acids di-HEMA phosphate, MDP and 4-META all possess comparable dissolving capacities for HA (ie, 0

  17. Cooling of PAH cations studied with an electrostatic storage ring (United States)

    Bernard, Jérôme; Chen, Li; Brédy, Richard; Ji, Mingchao; Ortéga, Céline; Matsumoto, Jun; Martin, Serge


    In this paper we discuss the production of molecular PAH cations using an ECR ion source and their subsequent cooling studied with an electrostatic storage ring, the Mini-Ring on a time range up to 10 ms. We show that the ECR ion source can produce high currents of small PAH cation, here naphthalene and anthracene cations. Then, we report experimental result for the cooling of three PAH cations (anthracene, naphthalene and pyrene) stored in our compact electrostatic storage ring (the Mini-Ring). We show that the Poincaré recurrent fluorescence plays a major role in the cooling process of those PAH cations. We show that for a given internal energy, the cooling rate is much smaller for pyrene than for anthracene and naphthalene. We conclude that the Poincaré recurrent fluorescence is less efficient due to smaller oscillator strength of the D2-D0 electronic transition for pyrene.

  18. Thermochemical stability of Soviet macroporous sulfonated cation-exchangers

    Energy Technology Data Exchange (ETDEWEB)

    Rukhlyada, N.N.; Plotnikova, V.P.; Roginskaya, B.S.; Znamenskii, Yu.P.; Zavodovskaya, A.S.; Dobrova, E.I.


    The purpose of this work was to study the influence of macroporosity on the thermochemical stability of sulfonated cation-exchangers. The investigations were carried out on commercial macroporous sulfonated cation-exchangers based on styrene-divinylbenzene copolymers. Study of the thermochemical stability of macroporous sulfonated cation-exchangers in dilute hydrogen peroxide solutions showed that the type of macroporosity has virtually no influence on their stability. The determining factor in thermal stability of macroporous cation-exchangers, as of the gel type, is the degree of cross-linking of the polymer matrix. The capacity loss of macroporous cation-exchangers during oxidative thermolysis is caused by destruction of the macromolecular skeleton and elution of fragments of polar chains containing sulfo groups into the solution.

  19. Structural Basis of Native CXCL7 Monomer Binding to CXCR2 Receptor N-Domain and Glycosaminoglycan Heparin

    Directory of Open Access Journals (Sweden)

    Aaron J. Brown


    Full Text Available CXCL7, a chemokine highly expressed in platelets, orchestrates neutrophil recruitment during thrombosis and related pathophysiological processes by interacting with CXCR2 receptor and sulfated glycosaminoglycans (GAG. CXCL7 exists as monomers and dimers, and dimerization (~50 μM and CXCR2 binding (~10 nM constants indicate that CXCL7 is a potent agonist as a monomer. Currently, nothing is known regarding the structural basis by which receptor and GAG interactions mediate CXCL7 function. Using solution nuclear magnetic resonance (NMR spectroscopy, we characterized the binding of CXCL7 monomer to the CXCR2 N-terminal domain (CXCR2Nd that constitutes a critical docking site and to GAG heparin. We found that CXCR2Nd binds a hydrophobic groove and that ionic interactions also play a role in mediating binding. Heparin binds a set of contiguous basic residues indicating a prominent role for ionic interactions. Modeling studies reveal that the binding interface is dynamic and that GAG adopts different binding geometries. Most importantly, several residues involved in GAG binding are also involved in receptor interactions, suggesting that GAG-bound monomer cannot activate the receptor. Further, this is the first study that describes the structural basis of receptor and GAG interactions of a native monomer of the neutrophil-activating chemokine family.

  20. Synthesis of three different galactose-based methacrylate monomers for the production of sugar-based polymers. (United States)

    Desport, Jessica S; Mantione, Daniele; Moreno, Mónica; Sardón, Haritz; Barandiaran, María J; Mecerreyes, David


    Glycopolymers, synthetic sugar-containing macromolecules, are attracting ever-increasing interest from the chemistry community. Glycidyl methacrylate (GMA) is an important building block for the synthesis of sugar based methacrylate monomers and polymers. Normally, glycidyl methacrylate shows some advantages such as reactivity against nucleophiles or milder synthetic conditions such as other reactive methacrylate monomers. However, condensation reactions of glycidyl methacrylate with for instance protected galactose monomer leads to a mixture of two products due to a strong competition between the two possible pathways: epoxide ring opening or transesterification. In this paper, we propose two alternative routes to synthesize regiospecific galactose-based methacrylate monomers using the epoxy-ring opening reaction. In the first alternative route, the protected galactose is first oxidized to the acid in order to make it more reactive against the epoxide of GMA. In the second route, the protected sugar was first treated with epichlorohydrin followed by the epoxy ring opening reaction with methacrylic acid, to create an identical analogue of the ring-opening product of GMA. These two monomers were polymerized using conventional radical polymerization and were compared to the previously known galactose-methacrylate one. The new polymers show similar thermal stability but lower glass transition temperature (Tg) with respect to the known galactose methacrylate polymer. Copyright © 2016 Elsevier Ltd. All rights reserved.

  1. Dimethacrylate network formation and polymer property evolution as determined by the selection of monomers and curing conditions. (United States)

    Stansbury, Jeffrey W


    This overview is intended to highlight connections between monomer structure and the development of highly crosslinked photopolymer networks including the conversion dependent properties of shrinkage, modulus and stress. A review is provided that combines the polymer science and dental materials literature along with examples of relevant experimental results, which include measurements of reaction kinetics, photorheology as well as polymerization shrinkage and stress. While new monomers are continually under development for dental materials applications, mixtures of dimethacrylate monomers persist as the most common form of dental resins used on composite restorative materials. Monomer viscosity and reaction potential is derived from molecular structure and by employing real-time near-infrared spectroscopic techniques, the development of macromolecular networks is linked to the evolution of polymerization shrinkage (measured by linometer), modulus (measured by photorheometer), and stress (measured by tensometer). Relationships between the respective polymer properties are examined. Through a better understanding of the polymer network formation and property development processes using conventional dimethacrylate monomer formulations, the rational design of improved materials is facilitated with the ultimate goal of achieving dental polymers that deliver enhanced clinical outcomes. Copyright © 2011 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

  2. Assessment of cross-reactivity of new less sensitizing epoxy resin monomers in epoxy resin-allergic individuals. (United States)

    Hagvall, Lina; Niklasson, Ida B; Rudbäck, Johanna; O'Boyle, Niamh M; Niklasson, Eva; Luthman, Kristina; Karlberg, Ann-Therese


    Measures to prevent occupational exposure to epoxy resins, including education, medical examination, and voluntary agreements between employers and workers, have not been effective enough to protect against skin sensitization. Therefore, alternatives to the major epoxy resin haptens that have been found to be less sensitizing in the local lymph node assay have been developed. To study the cross-reactivity of two newly designed epoxy resin monomers, with decreased skin-sensitizing potency and good technical properties as compared with diglycidyl ether of bisphenol A (DGEBA), in subjects with known contact allergy to epoxy resin of DGEBA type. Eleven individuals with previous positive patch test reactions to epoxy resin of DGEBA participated in the study. The two alternative epoxy resin monomers were synthesized and patch tested in dilution series in parallel with epoxy resin of DGEBA from the baseline series (containing 92% DGEBA). All participants reacted to epoxy resin of DGEBA on retesting. Three participants reacted to monomer 1. No reactions were seen to monomer 2. The alternative monomers studied showed little or no cross-reactivity with epoxy resin of DGEBA. Decreasing the risk of sensitization by using less sensitizing compounds is important, as contact allergy to epoxy resins is common in spite of thorough preventive measures. © 2016 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

  3. Increasing Base Cations in Streams: Another Legacy of Deicing Salts? (United States)

    Helton, A. M.; Barclay, J. R.; Bellucci, C.; Rittenhouse, C.


    Elevated use of deicing salts directly increases sodium chloride inputs to watersheds. Sodium can accumulate in soils over time and has the potential to leach other cations (e.g., calcium, magnesium, and potassium) from the soil through cation exchange. We hypothesize that increased use of deicing salts results in a legacy of soils depleted in non-sodium base cations with loss of cations to receiving waters. The goal of this project is to quantify temporal trends in base cations and chloride in streams and rivers across the United States. We used Weighted Regressions on Time, Discharge, and Season (WRTDS) to analyze trends in base cations. Our preliminary analysis of 10 rivers in Connecticut with chemical periods of record ranging from 24 - 64 years (median = 55 years), shows that the flux of base cations is increasing in all sites (25 - 366 103 meq ha-1 yr-1 yr-1), driven largely by increases in sodium (23 - 222 103 meq ha-1 yr-1 yr-1), the dominant cation in 7 of the sites. Chloride is also increasing at all sites (26 - 261 103 meq ha-1 yr-1 yr-1), which, in combination with salt use trends, suggests a road salt source for the increased sodium. Non-sodium cations are also increasing in 9 of the sites (8 - 54 103 meq ha-1 yr-1 yr-1), though they are not directly added with most deicing salts. We will compare these trends to other long-term sites across the United States, and quantify relationships between cation trends and land cover, road density, and snowfall.

  4. IRMPD Action Spectroscopy of Alkali Metal Cation-Cytosine Complexes: Effects of Alkali Metal Cation Size on Gas Phase Conformation

    NARCIS (Netherlands)

    Yang, B.; Wu, R.R.; Polfer, N.C.; Berden, G.; Oomens, J.; Rodgers, M.T.


    The gas-phase structures of alkali metal cation-cytosine complexes generated by electrospray ionization are probed via infrared multiple photon dissociation (IRMPD) action spectroscopy and theoretical calculations. IRMPD action spectra of five alkali metal cation-cytosine complexes exhibit both

  5. Thermal and Optical Properties of CdS Nanoparticles in Thermotropic Liquid Crystal Monomers

    Directory of Open Access Journals (Sweden)

    Marc Alnot


    Full Text Available Two new mesogenic monomers, namely 3,3’-dimethoxy-4,4’-di(hydroxyhexoxy-N-benzylidene-o-Tolidine (Ia and 4,4’-di(6-hydroxyhexoxy-N-benzylidene-o-Tolidine (IIa, were reacted with cadmium sulfide (CdS via an in situ chemical precipitation method in ethanol to produce CdS nanocomposites. A series of different mass compositions of CdS with Ia and IIa ranging from 0.1:1.0 to 1.0:1.0 (w/w were prepared and characterized using X-ray Diffraction (XRD, Raman spectroscopy, Fourier Transform Infrared Spectroscopy (FT-IR, Transmission Electron Microscopy (TEM, Polarizing Optical Microscopy (POM and Differential Scanning Calorimetry (DSC, X-ray Photoelectron Spectroscopy (XPS and Photoluminescence Spectroscopy (PL. XRD showed that the broad peaks are ascribed to the formation of cubic CdS nanoparticles in both Ia and IIa. The average particle size for both nanocomposites was less than 5 nm with a narrower size distribution when compared with pure CdS nanoparticles. The analyses from POM and DSC demonstrated that mass composition from 0.1:1.0 up to 0.5:1.0 of CdS:Ia nanocomposites showed their enantiotropic nematic phase. On the other hand, polarizing optical microscopy (POM for IIa nanocomposites showed that the liquid crystal property vanished completely when the mass composition was at 0.2:1.0. PL emissions for CdS: Ia or IIa nanocomposites indicated deep trap defects occurred in these both samples. The PL results revealed that addition of CdS to Ia monomers suppressed the photoluminescence intensity of Ia. However, the introduction of CdS to IIa monomers increased the photoluminescence and was at a maximum when the mass composition was 0.3:1.0, then decreased in intensity as more CdS was added. The XPS results also showed that the stoichiometric ratios of S/Cd were close to 1.0:1.0 for both types of nanocomposites for a mass composition of 1.0:1.0 (CdS:matrix.

  6. Anaerobic toxicity of cationic silver nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Gitipour, Alireza; Thiel, Stephen W. [Biomedical, Chemical, and Environmental Engineering, University of Cincinnati, Cincinnati, OH (United States); Scheckel, Kirk G. [USEPA, Office of Research and Development, Cincinnati, OH (United States); Tolaymat, Thabet, E-mail: [USEPA, Office of Research and Development, Cincinnati, OH (United States)


    The microbial toxicity of silver nanoparticles (AgNPs) stabilized with different capping agents was compared to that of Ag{sup +} under anaerobic conditions. Three AgNPs were investigated: (1) negatively charged citrate-coated AgNPs (citrate-AgNPs), (2) minimally charged polyvinylpyrrolidone coated AgNPs (PVP-AgNPs) and (3) positively charged branched polyethyleneimine coated AgNPs (BPEI-AgNPs). The AgNPs investigated in this experiment were similar in size (10–15 nm), spherical in shape, but varied in surface charge which ranged from highly negative to highly positive. While, at AgNPs concentrations lower than 5 mg L{sup −1}, the anaerobic decomposition process was not influenced by the presence of the nanoparticles, there was an observed impact on the diversity of the microbial community. At elevated concentrations (100 mg L{sup −1} as silver), only the cationic BPEI-AgNPs demonstrated toxicity similar in magnitude to that of Ag{sup +}. Both citrate and PVP-AgNPs did not exhibit toxicity at the 100 mg L{sup −1} as measured by biogas evolution. These findings further indicate the varying modes of action for nanoparticle toxicity and represent one of the few studies that evaluate end-of-life management concerns with regards to the increasing use of nanomaterials in our everyday life. These findings also highlight some of the concerns with a one size fits all approach to the evaluation of environmental health and safety concerns associated with the use of nanoparticles. - Highlights: • At concentrations -1 the anaerobic decomposition process was not impacted. • An impact on the microbial community at concentrations -1 were observed. • At high concentrations (100 mg L{sup −1}), the cationic BPEI-AgNPs demonstrated toxicity. • Toxicity was demonstrated without the presence of oxidative dissolution of silver. • A one size fits all approach for the evaluation of NPs may not be accurate.

  7. Cycling performance of lithium polymer cells assembled by in situ polymerization of a non-flammable ionic liquid monomer

    International Nuclear Information System (INIS)

    Lee, Yoon-Sung; Kim, Dong-Won


    Highlights: • Gel polymer electrolytes were synthesized by in situ polymerization of ionic liquid in the lithium polymer cells. • Flammability of the electrolyte was significantly reduced by polymerizing electrolyte containing a non-flammable ionic liquid monomer. • The cells assembled with polymeric ionic liquid-based electrolytes exhibited reversible cycling behavior with good capacity retention. -- Abstract: Lithium polymer cells composed of a lithium negative electrode and a LiCoO 2 positive electrode were assembled with a gel polymer electrolyte obtained by in situ polymerization of an electrolyte solution containing an ionic liquid monomer with vinyl groups. The polymerization of the electrolyte solution containing the non-flammable ionic liquid monomer resulted in a significant reduction of the flammability of the gel polymer electrolytes. The lithium polymer cell assembled with the stable gel polymer electrolyte delivered a discharge capacity of 134.3 mAh g −1 at ambient temperature and exhibited good capacity retention

  8. The role of monomer fraction data in association theories—Can we improve the performance for phase equilibrium calculations?

    DEFF Research Database (Denmark)

    Tsivintzelis, Ioannis; Bøgh, David; Karakatsani, Eirini


    with different ethanol content as inhibitor. There are some differences in the performance of CPA with the two sets but on average the results are similar. This may indicate that monomer fraction data are not very useful in this case or that ethanol monomer fraction data are not accurate and both possibilities...... accurate and how useful are such data today and how successful is their use in the context of association models? In this work we attempt to answer these questions in the case of the CPA model and for ethanol. CPA has been already successfully used to describe thermodynamic properties of many ethanol...... containing mixtures, using an ethanol parameter set that was adjusted to experimental vapor pressure and liquid density data. We present in this work a new parameter set for ethanol which is estimated using experimental vapor pressure, liquid density data as well as the experimental monomer fractions...

  9. Ordered, microphase-separated, noncharged-charged diblock copolymers via the sequential ATRP of styrene and styrenic imidazolium monomers

    Energy Technology Data Exchange (ETDEWEB)

    Shi, ZX; Newell, BS; Bailey, TS; Gin, DL


    A series of imidazolium-based noncharged-charged diblock copolymers (1) was synthesized by the direct, sequential ATRP of styrene and styrenic imidazolium bis(trifluoromethyl)sulfonamide monomers with methyl, n-butyl, and n-decyl side-chains. Small-angle X-ray scattering studies on initial examples of 1 with a total of 50 repeat units and styrene:imidazolium-styrene repeat unit ratios of 25:25, 20:30, and 15:35 showed that their ability to form ordered nanostructures (i.e., sphere and cylinder phases) in their neat states depends on both the block ratio and the length of the alkyl side-chain on the imidazolium monomer. To our knowledge, the synthesis of imidazolium-based BCPs that form ordered, phase-separated nanostructures via direct ATRP of immiscible co-monomers is unprecedented. (C) 2014 Elsevier Ltd. All rights reserved.

  10. Efficient method for polymerization of diallycarbonate and hexa(allylcarbonate) monomers and their thermal properties

    International Nuclear Information System (INIS)

    Herrera-González, A M; García-Serrano, J; Pelaez-Cid, A A; Montalvo-Sierra, I


    Polymers have had a significant increase in the industrial field, and polycarbonates (PCs) are an example. PCs have important properties such as high impact resistance, high heat capability, hardness, toughness, optical clarity, heat resistance, abrasion resistance and high refractive index. PCs with these properties have a variety of applications, for example, astronaut helmets, CDs/ DVDs, automobile parts, bulletproof windows, ophthalmic lenses and welding masks. In the present work we report the synthesis and characterization of network polycarbonates, based (1,1'-biphenyl)-4,4'-diyldiallylcarbonate (I) and hexa(4-allylcarbonatephenoxy) cyclotriphosphazene (III). The polycarbonates were obtained by bulk polymerization technique. The polymers obtained with thermal initiators showed degrees of cross-linking greater than 80%. The PCs obtained have thermal stability to 250 °C. The polycarbonate obtained from the monomer III showed a limiting oxygen index of 46.3%, therefore this polymer can be considered potentially useful as flame-retardant.

  11. Monte Carlo simulation of star/linear and star/star blends with chemically identical monomers

    Energy Technology Data Exchange (ETDEWEB)

    Theodorakis, P E [Department of Materials Science and Engineering, University of Ioannina, 45110 Ioannina (Greece); Avgeropoulos, A [Department of Materials Science and Engineering, University of Ioannina, 45110 Ioannina (Greece); Freire, J J [Departamento de Ciencias y Tecnicas FisicoquImicas, Universidad Nacional de Educacion a Distancia, Facultad de Ciencias, Senda del Rey 9, 28040 Madrid (Spain); Kosmas, M [Department of Chemistry, University of Ioannina, 45110 Ioannina (Greece); Vlahos, C [Department of Chemistry, University of Ioannina, 45110 Ioannina (Greece)


    The effects of chain size and architectural asymmetry on the miscibility of blends with chemically identical monomers, differing only in their molecular weight and architecture, are studied via Monte Carlo simulation by using the bond fluctuation model. Namely, we consider blends composed of linear/linear, star/linear and star/star chains. We found that linear/linear blends are more miscible than the corresponding star/star mixtures. In star/linear blends, the increase in the volume fraction of the star chains increases the miscibility. For both star/linear and star/star blends, the miscibility decreases with the increase in star functionality. When we increase the molecular weight of linear chains of star/linear mixtures the miscibility decreases. Our findings are compared with recent analytical and experimental results.

  12. Radiation curing of mixture of diallylphthalate prepolymer and vinyl monomer, 11

    International Nuclear Information System (INIS)

    Gotoda, Masao; Yagi, Toshiaki; Yoshizawa, Iwao; Okugawa, Hideo.


    Preparation of Wood-Polymer Composite (WPC) piled plywood for flooring, was attempted by electron beam irradiation of American Hemlock veneer, impregnated with low molecular weight diallylphthalate prepolymer (DAPsub(p).L)/vinyl monomer mixtures, in comparison with that by thermal curing reported previously. For the improvement of the mechanical properties of WPC piled plywood, 5-15 parts of low molecular weight polyvinylacetate (PVAc) was added to DAPsub(p).L/methyl acrylate/hydroxyethyl acrylate/benzoyl peroxide (50/40/10/2) mixture. The addition of PVAc did not give much influence to the degree of impregnation in the veneer and to the curability by electron beam irradiation. As to the resistance to hot and cold cycle test, WPC piled plywood, prepared by the resin containing 5 parts of PVAc gave the best results. As a general conclusion, due to the superior mechanical properties, the WPC piled plywood processed by electron beam irradiation is suitable for flooring use. (author)

  13. Lurgi MegaMethanol technology. Delivering the building blocks for the future fuel and monomer demand

    Energy Technology Data Exchange (ETDEWEB)

    Wurzel, T. [Lurgi AG, Frankfurt/Main (Germany)


    The paper describes the central role of methanol within a changing environment with respect to feedstock availability as well as steadily growing demand in fuel and monomer demand. The current large-scale production facilities are described with respect to the technological challenges in order to ensure the availability of sufficient methanol for down-stream applications. Different down-stream applications are described which clearly confirm that methanol is the dominant C1-building block due to its chemical flexibility. It is concluded that by means of the implementation of two MTP (Methanol to Propylene) projects in China initiated the era of ''down-stream methanol'' has begun in the industry. (orig.)

  14. Design of Spin-Frustrated Monomer-Type C60•− Mott Insulator

    Directory of Open Access Journals (Sweden)

    Akihiro Otsuka


    Full Text Available Spin-frustrated monomer-type Mott insulator C60•− solids are discussed in this review article. For the C60•− solids, the interfullerene center-to-center distance (r is the key parameter that controls the competition between covalent bond-formation, itinerancy, and spin frustration. Eight C60•− salts with various compositions and dimensionalities are reviewed. In all of these C60•− salts except one, neither bond-formation nor long-range magnetic ordering was observed down to low temperatures. A plot of Weiss temperature (|ΘCW| against r shows that |ΘCW| grows rapidly below r = 10.0 Å.

  15. Compensated Arrhenius formalism applied to a conductivity study in poly(propylene glycol) diacrylate monomers (United States)

    Dubois, F.; Derouiche, Y.; Leblond, J. M.; Maschke, U.; Douali, R.


    The temperature dependence of the ionic conductivity is studied in a series of poly(propylene glycol) diacrylate monomers. The experimental data are analyzed by means of the approach recently proposed by Petrowsky et al. [J. Phys. Chem. B. 113, 5996 (2009), 10.1021/jp810095g]. This so-called compensated Arrhenius formalism (CAF) approach takes into account the influence of the dielectric permittivity on the exponential prefactor in the classical Arrhenius equation. The experimental data presented in this paper show a good agreement with the CAF; this means that the exponential prefactor is principally dielectric permittivity dependent. The compensated data revealed two conduction processes with different activation energies; they correspond to low and high temperature ranges, respectively.

  16. Role of Monomer Sequence, Hydrogen Bonding and Mesoscale Architecture in Marine Antifouling Coatings (United States)

    Segalman, Rachel

    Polypeptoids are non-natural, sequence specific polymers that offer the opportunity to probe the effect of monomer sequence, chirality, and chain shape on self-assembly and surface properties. Additionally, polypeptoid synthesis is more scaleable than traditional polypeptides suggesting their utility in large area applications. We have designed efficient marine anti-fouling coatings by using triblock copolymer scaffolds to which polypeptoids are tethered in order to tune both the modulus and surface energies with great precision. Surprisingly, when short sequences are tethered to a polymer backbone, polypeptoids consistently outperform analogous polypeptides in antifouling properties. We hypothesize that the hydrogen bonding inherent to the polypeptide backbone drives the observed differences in performance. We also find that the polymer scaffold housing the polypeptoids also plays a crucial role in directing surface presentation and therefore the overall coating properties.

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

    DEFF Research Database (Denmark)

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

    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...... 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...... systems will be discussed in relation to alkyd coatings. By combination with longer chain water soluble polymers such as PEGs it is also possible to prepare water soluble polyesters with some control over the endgroup structure. In combination with different carboxylic acids, functional polyesters based...

  18. Effect of microwave postpolymerization treatment on residual monomer content and the flexural strength of autopolymerizing reline resin. (United States)

    Patil, Padmakar S; Chowdhary, Ramesh; Mandokar, Rashmi B


    Microwave postpolymerization has been suggested as a method to improve the flexural strength of an autopolymerizing denture reline resin. However, the effect of microwave postpolymerization on the residual monomer content and its influence on flexural strength have not been investigated. This study analyzed the effect of microwave postpolymerization on the residual monomer content and its influence on the flexural strength of an autopolymerizing reline resin (Denture Liner). A total of 70 specimens (64 Chi 10 Chi 3.3 mm) were polymerized according to the manufacturer's instructions and divided into 7 groups (n = 10). Control group specimens were not subjected to any further processing. Before testing, the specimens were subjected to postpolymerization in a microwave oven using different power (550 and 650 W) and time (3, 4, and 5 min) settings. Two specimens of each group were then manually ground into fine powder and samples extracted from the specimens using reflux method. The samples were then subjected to gas chromatography for residual monomer determination in area%. Eight specimens were subjected to a three-point bending device with a span of 50 mm and crosshead speed of 5 mm/min, and the flexural strength was determined in MPa. Data analyses included Student's t-test and one-way analysis of variance. For the Denture Liner reline resin, the residual monomer content decreased and the flexural strength increased significantly with the application of microwave irradiation using different time/power combinations. The specimens with the lowest residual monomer content were the similar specimens which presented with the highest flexural strength. Microwave postpolymerization irradiation can be an effective method for increasing the flexural strength of denture liner (at 650 W for 5 min) by reducing the residual monomer content by further polymerization at free radical sites.

  19. Effect of microwave postpolymerization treatment on residual monomer content and the flexural strength of autopolymerizing reline resin

    Directory of Open Access Journals (Sweden)

    Patil Padmakar


    Full Text Available Background : Microwave postpolymerization has been suggested as a method to improve the flexural strength of an autopolymerizing denture reline resin. However, the effect of microwave postpolymerization on the residual monomer content and its influence on flexural strength have not been investigated. Objectives : This study analyzed the effect of microwave postpolymerization on the residual monomer content and its influence on the flexural strength of an autopolymerizing reline resin (Denture Liner. Materials and Methods : A total of 70 specimens (64 Χ 10 Χ 3.3 mm were polymerized according to the manufacturer′s instructions and divided into 7 groups (n = 10. Control group specimens were not subjectedto any further processing. Before testing, the specimens were subjected to postpolymerization in a microwave oven using different power (550 and 650 W and time (3, 4, and 5 min settings. Two specimens of each group were then manually ground into fine powder and samples extracted from the specimens using reflux method. The samples were then subjected to gas chromatography for residual monomer determination in area%. Eight specimens were subjected to a three-point bending device with a span of 50 mm and crosshead speed of 5 mm/min, and the flexural strength was determined in MPa. Data analyses included Student′s t-test and one-way analysis of variance. Results : For the Denture Liner reline resin, the residual monomer content decreased and the flexural strength increased significantly with the application of microwave irradiation using different time/power combinations. The specimens with the lowest residual monomer content were the similar specimens which presented with the highest flexural strength. Conclusion : Microwave postpolymerization irradiation can be an effective method for increasing the flexural strength of denture liner (at 650 W for 5 min by reducing the residual monomer content by further polymerization at free radical sites.

  20. Computational studies at the density functional theory (DFT) level about the surface functionalization of hexagonal monolayers by chitosan monomer (United States)

    Ebrahimi, Javad; Ahangari, Morteza Ghorbanzadeh; Jahanshahi, Mohsen


    Theoretical investigations based on density functional theory have been carried out to understand the underlying interactions between the chitosan monomer and several types of hexagonal monolayers consisting of pristine and defected graphene and boron-nitride nanosheets. Based on the obtained results, it was found that the type of the interaction for all the systems is of non-covalent nature and the chitosan monomer physically interacts with the surface of mentioned nanostructures. The interaction strength was evaluated by calculating the adsorption energies for the considered systems and it was found that the adsorption of chitosan monomer accompanies by the release of about -0.67 and -0.66 eV energy for pristine graphene and h-BN monolayer, respectively. The role of structural defect has also been considered by embedding a Stone-Wales defect within the structure of mentioned monolayers and it was found that the introduced defect enhances the interactions between the chitosan monomer and nanostructures. The role of dispersion interactions has also been taken into account and it was found that these long-range interactions play the dominating role in the attachment of chitosan monomer onto the graphene sheet, while having strong contribution together with the electrostatic interactions for the stabilization of chitosan onto the surface of h-BN monolayer. For all the cases, the adsorption of chitosan monomer did not change the inherent electronic properties of the nanostructures based on the results of charge transfer analysis and energy gap calculations. The findings of the present work would be very useful in future investigations to explore the potential applications of these hybrid materials in materials science and bio-related fields.

  1. Electron collisions with α-D-glucose and β-D-glucose monomers (United States)

    da Costa, Romarly F.; Bettega, Márcio H. F.; Varella, Márcio T. do N.; Lima, Marco A. P.


    The development of new alternative routes for production of second generation ethanol from sugarcane biomass poses a challenge to the scientific community. Current research in this field addresses the use of a plasma-based pretreatment of the lignocellulosic raw material. With the aim to provide a theoretical background for this experimental technique we investigate the role of low-energy electrons from the plasma in the rupture of the matrix of cellulosic chains. In this paper, we report calculated cross sections for elastic scattering of low-energy electrons by the α- and β-D-glucose monomers. The calculations employed the Schwinger multichannel method with pseudopotentials and were carried out at the static-exchange and static-exchange plus polarization levels of approximation. Through the comparison of the results obtained with inclusion of polarization effects we discuss the influence of the different conformations of the hydroxyl group linked to the anomeric carbon on the resonance spectra of these molecules. Resonant structures appearing at different energies for α- and β-glucose at the low-energy regime of impact energies can be understood as a fingerprint of an "isomeric effect" and suggest that distinct fragmentation mechanisms proceeding via σ∗ shape resonances may become operative depending on the glucose anomer under consideration. For energies above 15 eV the integral elastic cross sections are very similar for both monomers. Differential cross sections for the glucopyranose anomers considered in this work are typically dominated by a strong forward scattering due to the molecules' large electric dipole moments and, for energies close to the resonances' positions, they display particular features at the intermediate angular region, notably a pronounced f-wave scattering pattern, that are probably associated with the presence of those structures.

  2. Synthesis, characterization and evaluation of a fluorinated resin monomer with low water sorption. (United States)

    Liu, Xue; Wang, Zengyao; Zhao, Chengji; Bu, Wenhuan; Zhang, Yurong; Na, Hui


    A fluorinated acrylate monomer (4-TF-PQEA) without BPA (bisphenol-A) structure was synthesized and mixed with triethylene glycol dimethacrylate (TEGDMA) to used as dental resin system in order to achieve lower water sorption and reduce human exposure to BPA derivatives. Double bond conversion (DC) was measured using Fourier transform infrared spectroscopy (FTIR). Water sorption (WS), water solution (WL) and depth of cure (DOC) were evaluated according to ISO 4049:2009. Water contact angle (CA) was measured using contact angle analyzer. Polymerization shrinkage (PS) was evaluated according to the Archimedes' principle and ISO 17304:2013. Flexural strength (FS) and flexural modulus (FM) were measured by three-point bending test with a universal testing machine according to ISO 4049:2009. Comprehensive strength (CS) and vickers microhardness (VM) were also investigated. Thermal stability test was measure by Thermogravimetric analyzer. Cytotoxicity of three resin systems was tested through MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazoliumbromid) cytotoxicity method according to the ISO 10993-5:2009. Bisphenol-A glycidyl dimethacrylate (Bis-GMA)/ TEGDMA resin system was used as a control. The results show that 4-TF-PQEA/TEGDMA resin system had lower PS, lower WS and higher DC values than those of Bis-GMA/TEGDMA resin system except some mechanical properties, such as FS, FM and CS. Moreover, properties of other 4-TF-PQEA-containing resin systems were also comparable with those of Bis-GMA/TEGDMA resin system. In particular, the overall performance of resin system consisted of 4-TF-PQEA/Bis-GMA/TEGDMA is optimized when the mixture ratio is 30/40/30(wt/wt/wt). Therefore, the 4-TF-PQEA has potential to be used as resin monomer for dental resin composites to achieve lower water sorption. Copyright © 2017 Elsevier Ltd. All rights reserved.

  3. Prediction of monomer reactivity in radical copolymerizations from transition state quantum chemical descriptors

    Directory of Open Access Journals (Sweden)

    Zhengde Tan


    Full Text Available In comparison with the Q-e scheme, the Revised Patterns Scheme: the U, V Version (the U-V scheme has greatly improved both its accessibility and its accuracy in interpreting and predicting the reactivity of a monomer in free-radical copolymerizations. Quantitative structure-activity relationship (QSAR models were developed to predict the reactivity parameters u and v of the U-V scheme, by applying genetic algorithm (GA and support vector machine (SVM techniques. Quantum chemical descriptors used for QSAR models were calculated from transition state species with structures C¹H3 - C²HR³• or •C¹H2 - C²H2R³ (formed from vinyl monomers C¹H²=C²HR³ + H•, using density functional theory (DFT, at the UB3LYP level of theory with 6-31G(d basis set. The optimum support vector regression (SVR model of the reactivity parameter u based on Gaussian radial basis function (RBF kernel (C = 10, ε = 10- 5 and γ = 1.0 produced root-mean-square (rms errors for the training, validation and prediction sets being 0.220, 0.326 and 0.345, respectively. The optimal SVR model for v with the RBF kernel (C = 20, ε = 10- 4 and γ = 1.2 produced rms errors for the training set of 0.123, the validation set of 0.206 and the prediction set of 0.238. The feasibility of applying the transition state quantum chemical descriptors to develop SVM models for reactivity parameters u and v in the U-V scheme has been demonstrated.

  4. Lignin monomer composition affects Arabidopsis cell-wall degradability after liquid hot water pretreatment

    Directory of Open Access Journals (Sweden)

    Ladisch Michael


    Full Text Available Abstract Background Lignin is embedded in the plant cell wall matrix, and impedes the enzymatic saccharification of lignocellulosic feedstocks. To investigate whether enzymatic digestibility of cell wall materials can be improved by altering the relative abundance of the two major lignin monomers, guaiacyl (G and syringyl (S subunits, we compared the degradability of cell wall material from wild-type Arabidopsis thaliana with a mutant line and a genetically modified line, the lignins of which are enriched in G and S subunits, respectively. Results Arabidopsis tissue containing G- and S-rich lignins had the same saccharification performance as the wild type when subjected to enzyme hydrolysis without pretreatment. After a 24-hour incubation period, less than 30% of the total glucan was hydrolyzed. By contrast, when liquid hot water (LHW pretreatment was included before enzyme hydrolysis, the S-lignin-rich tissue gave a much higher glucose yield than either the wild-type or G-lignin-rich tissue. Applying a hot-water washing step after the pretreatment did not lead to a further increase in final glucose yield, but the initial hydrolytic rate was doubled. Conclusions Our analyses using the model plant A. thaliana revealed that lignin composition affects the enzymatic digestibility of LHW pretreated plant material. Pretreatment is more effective in enhancing the saccharification of A. thaliana cell walls that contain S-rich lignin. Increasing lignin S monomer content through genetic engineering may be a promising approach to increase the efficiency and reduce the cost of biomass to biofuel conversion.

  5. Pseudomonas syringae evades host immunity by degrading flagellin monomers with alkaline protease AprA. (United States)

    Pel, Michiel J C; van Dijken, Anja J H; Bardoel, Bart W; Seidl, Michael F; van der Ent, Sjoerd; van Strijp, Jos A G; Pieterse, Corné M J


    Bacterial flagellin molecules are strong inducers of innate immune responses in both mammals and plants. The opportunistic pathogen Pseudomonas aeruginosa secretes an alkaline protease called AprA that degrades flagellin monomers. Here, we show that AprA is widespread among a wide variety of bacterial species. In addition, we investigated the role of AprA in virulence of the bacterial plant pathogen P. syringae pv. tomato DC3000. The AprA-deficient DC3000 ΔaprA knockout mutant was significantly less virulent on both tomato and Arabidopsis thaliana. Moreover, infiltration of A. thaliana Col-0 leaves with DC3000 ΔaprA evoked a significantly higher level of expression of the defense-related genes FRK1 and PR-1 than did wild-type DC3000. In the flagellin receptor mutant fls2, pathogen virulence and defense-related gene activation did not differ between DC3000 and DC3000 ΔaprA. Together, these results suggest that AprA of DC3000 is important for evasion of recognition by the FLS2 receptor, allowing wild-type DC3000 to be more virulent on its host plant than AprA-deficient DC3000 ΔaprA. To provide further evidence for the role of DC3000 AprA in host immune evasion, we overexpressed the AprA inhibitory peptide AprI of DC3000 in A. thaliana to counteract the immune evasive capacity of DC3000 AprA. Ectopic expression of aprI in A. thaliana resulted in an enhanced level of resistance against wild-type DC3000, while the already elevated level of resistance against DC3000 ΔaprA remained unchanged. Together, these results indicate that evasion of host immunity by the alkaline protease AprA is important for full virulence of strain DC3000 and likely acts by preventing flagellin monomers from being recognized by its cognate immune receptor.

  6. Structural effect of monomer type on properties of copolyimides and copolyimide-silica hybrid materials

    Directory of Open Access Journals (Sweden)

    Kizilkaya Canan


    Full Text Available In this work, the effect of two different diamine monomers, containing phosphine oxide, on thermal, mechanical and morphological properties of copolyimides and their hybrid materials was investigated. Gas separation properties of the synthesized copolyimides were also analysed. Two different diamine monomers with phosphine oxide were bis(3-aminophenyl phenylphosphine oxide (BAPPO and bis(3-aminophenoxy-4-phenyl phenylphosphine oxide (m-BAPPO. In the synthesis of copolyimides 3,3’-diamino-diphenyl sulfone (DDS was also used as the diamine, as well as 2,2’-bis(3,4-dicarboxyphenylhexafluoropropane dianhydride (6FDA. Copolyimide films were prepared by thermal imidization. Hybrid materials containing 5 % SiO2 were synthesised further by sol-gel technique. The Fourier-transform infrared spectroscopy (FTIR, Nuclear magnetic resonance spectroscopy (NMR confirmed the expected structure. Dynamic mechanical analysis (DMA demonstrated that m-BAPPO based copolyimides had lower glass transition temperatures (Tg than BAPPO based copolyimides. m-BAPPO containing copolyimide without silica shifted the thermal decomposition temperature to a higher value. The moduli and strength values of BAPPO diamine containing copolyimide and its hybrid were higher than those of m-BAPPO containing materials. The contact angle measurements showed the hydrophobicity. Scanning electron microscope (SEM analysis exhibited the silica particles dispersion in the copolyimides. These copolyimides may be used in the coating industry. The CO2 permeability and the permselectivity were the highest among the other values in this study, when m-BAPPO containing copolyimide in the absence of silica was used. The gas permeabilities obtained from this work were in this decreasing order: PCO2 > PO2 > PN2.

  7. Vulcanization Kinetics and Mechanical Properties of Ethylene Propylene Diene Monomer Thermal Insulation

    Directory of Open Access Journals (Sweden)

    Mohamad Irfan Fathurrohman


    Full Text Available The vulcanization kinetics of Ethylene-propylene diene monomer (EPDM rubber thermal insulation was studied by using rheometer under isothermal condition at different temperatures. The rheometry analysis was used to determining the cure kinetic parameters and predicting the cure time of EPDM thermal insulation. The experimental results revealed that the curing curves of EPDM thermal insulation were marching and the optimum curing time decreased with increasing the temperature. The kinetic parameters were determined from the autocatalytic model showed close fitting with the experimental results, indicating suitability of autocatalytic model in characterizing the cure kinetics. The activation energy was determined from the autocatalytic model is 46.3661 kJ mol-1. The cure time were predicted from autocatalytic model and the obtained kinetic parameter by using the relationship among degree of conversion, cure temperature, and cure time. The predictions of cure time provide information for the actual curing characteristic of EPDM thermal insulation. The mechanical properties of EPDM thermal insulation with different vulcanization temperatures showed the same hardness, tensile strength and modulus at 300%, except at temperature 70 °C, while the elongation at breaking point decreased with increasing temperature of vulcanization. © 2015 BCREC UNDIP. All rights reservedReceived: 8th April 2014; Revised: 7th January 2015; Accepted: 16th January 2015How to Cite: Fathurrohman, M.I., Maspanger, D.R., Sutrisno, S. (2015. Vulcanization Kinetics and Mechanical Properties of Ethylene Propylene Diene Monomer Thermal Insulation. Bulletin of Chemi-cal Reaction Engineering & Catalysis, 10 (2, 104-110. (doi:10.9767/bcrec.10.2.6682.104-110Permalink/DOI: 

  8. Monomer-dimer equilibrium and oxygen binding properties of ferrous Vitreoscilla hemoglobin. (United States)

    Giangiacomo, L; Mattu, M; Arcovito, A; Bellenchi, G; Bolognesi, M; Ascenzi, P; Boffi, A


    The monomer-dimer equilibrium and the oxygen binding properties of ferrous recombinant Vitreoscilla hemoglobin (Vitreoscilla Hb) have been investigated. Sedimentation equilibrium data indicate that the ferrous deoxygenated and carbonylated derivatives display low values of equilibrium dimerization constants, 6 x 10(2) and 1 x 10(2) M(-1), respectively, at pH 7.0 and 10 degrees C. The behavior of the oxygenated species, as measured in sedimentation velocity experiments, is superimposable to that of the carbonylated derivative. The kinetics of O(2) combination, measured by laser photolysis at pH 7.0 and 20 degrees C, is characterized by a second-order rate constant of 2 x 10(8) M(-1) s(-1) whereas the kinetics of O(2) release at pH 7.0 is biphasic between 10 and 40 degrees C, becoming essentially monophasic below 10 degrees C. Values of the first-order rate constants (at 20 degrees C) and of the activation energies for the fast and slow phases of the Vitreoscilla Hb deoxygenation process are 4.2 s(-1) and 19.2 kcal mol(-1) and 0.15 s(-1) and 24.8 kcal mol(-1), respectively. Thus the biphasic kinetics of Vitreoscilla Hb deoxygenation is unrelated to the association state of the protein. The observed biphasic oxygen release may be accounted for by the presence of two different conformers in thermal equilibrium within the monomer. The two conformers may be assigned to a structure in which the heme-iron-bound ligand is stabilized by direct hydrogen bonding to TyrB10 and a structure in which such interaction is absent. The slow interconversion between the two conformers may reflect a very large conformational rearrangement in the disordered distal pocket segment connecting helices C and E.

  9. Radical Cations and Acid Protection during Radiolysis

    International Nuclear Information System (INIS)

    Mincher, Bruce J.; Zarzana, Christopher A.; Mezyk, Stephen P.


    Ligand molecules for used nuclear fuel separation schemes are exposed to high radiation fields and high concentrations of acid. Thus, an understanding of the complex interactions between extraction ligands, diluent, and acid is critical to understanding the performance of a separation process. The diglycolamides are ligands with important structural similarities to CMPO; however, previous work has shown that their radiolytic degradation has important mechanistic differences from CMPO. The DGAs do not enjoy radioprotection by HNO3 and the kinetics of DGA radiolytic degradation are different. CMPO degrades with pseudo-zero-order kinetics in linear fashion with absorbed dose while the DGAs degrade in pseudo-first-order, exponential fashion. This suggests that the DGAs degrade by simple reaction with some product of direct diluent radiolysis, while CMPO degradation is probably multi-step, with a slow step that is not dependent on the CMPO concentration, and mitigated by HNO 3 . It is thus believed that radio-protection and the zero-order radiolytic degradation kinetics are related, and that these phenomena are a function of either the formation of strong acid complexes with CMPO and/or to the presence of the CMPO phenyl ring. Experiments to test both these hypotheses have been designed and partially conducted. This report summarizes findings related to these phenomena for FY16, in satisfaction of milestone M3FT-16IN030104053. It also reports continued kinetic measurements for the reactions of the dodecane radical cation with solvent extraction ligands.

  10. Antiviral activity of cationic amphiphilic drugs. (United States)

    Salata, Cristiano; Calistri, Arianna; Parolin, Cristina; Baritussio, Aldo; Palù, Giorgio


    Emerging and reemerging viral infections represent a major concern for human and veterinary public health and there is an urgent need for the development of broad-spectrum antivirals. Areas covered: A recent strategy in antiviral research is based on the identification of molecules targeting host functions required for infection of multiple viruses. A number of FDA-approved drugs used to treat several human diseases are cationic amphiphilic drugs (CADs) that have the ability to accumulate inside cells affecting several structures/functions hijacked by viruses during infection. In this review we summarized the CADs' chemical properties and effects on the cells and reported the main FDA-approved CADs that have been identified so far as potential antivirals in drug repurposing studies. Expert commentary: Although there have been concerns regarding the efficacy and the possible side effects of the off-label use of CADs as antivirals, they seem to represent a promising starting point for the development of broad-spectrum antiviral strategies. Further knowledge about their mechanism of action is required to improve their antiviral activity and to reduce the risk of side effects.

  11. Radical Cations and Acid Protection during Radiolysis

    Energy Technology Data Exchange (ETDEWEB)

    Mincher, Bruce J. [Idaho National Lab. (INL), Idaho Falls, ID (United States); Zarzana, Christopher A. [Idaho National Lab. (INL), Idaho Falls, ID (United States); Mezyk, Stephen P. [Idaho National Lab. (INL), Idaho Falls, ID (United States)


    Ligand molecules for used nuclear fuel separation schemes are exposed to high radiation fields and high concentrations of acid. Thus, an understanding of the complex interactions between extraction ligands, diluent, and acid is critical to understanding the performance of a separation process. The diglycolamides are ligands with important structural similarities to CMPO; however, previous work has shown that their radiolytic degradation has important mechanistic differences from CMPO. The DGAs do not enjoy radioprotection by HNO3 and the kinetics of DGA radiolytic degradation are different. CMPO degrades with pseudo-zero-order kinetics in linear fashion with absorbed dose while the DGAs degrade in pseudo-first-order, exponential fashion. This suggests that the DGAs degrade by simple reaction with some product of direct diluent radiolysis, while CMPO degradation is probably multi-step, with a slow step that is not dependent on the CMPO concentration, and mitigated by HNO3. It is thus believed that radio-protection and the zero-order radiolytic degradation kinetics are related, and that these phenomena are a function of either the formation of strong acid complexes with CMPO and/or to the presence of the CMPO phenyl ring. Experiments to test both these hypotheses have been designed and partially conducted. This report summarizes findings related to these phenomena for FY16, in satisfaction of milestone M3FT-16IN030104053. It also reports continued kinetic measurements for the reactions of the dodecane radical cation with solvent extraction ligands.

  12. Interaction of cationic drugs with liposomes. (United States)

    Howell, Brett A; Chauhan, Anuj


    Interactions between cationic drugs and anionic liposomes were studied by measuring binding of drugs and the effect of binding on liposome permeability. The measurements were analyzed in the context of a continuum model based on electrostatic interactions and a Langmuir isotherm. Experiments and modeling indicate that, although electrostatic interactions are important, the fraction of drug sequestered in the double-layer is negligible. The majority of drug enters the bilayer with the charged regions interacting with the charged lipid head groups and the lipophilic regions associated with the bilayer. The partitioning of the drug can be described by a Langmuir isotherm with the electrostatic interactions increasing the sublayer concentration of the drug. The binding isotherms are similar for all tricyclic antidepressants (TCA). Bupivacaine (BUP) binds significantly less compared to TCA because its structure is such that the charged region has minimal interactions with the lipid heads once the BUP molecule partitions inside the bilayer. Conversely, the TCAs are linear with distinct hydrophilic and lipophilic regions, allowing the lipophilic regions to lie inside the bilayer and the hydrophilic regions to protrude out. This conformation maximizes the permeability of the bilayer, leading to an increased release of a hydrophilic fluorescent dye from liposomes.

  13. Water Adsorption on Free Cobalt Cluster Cations. (United States)

    Kiawi, Denis M; Bakker, Joost M; Oomens, Jos; Buma, Wybren Jan; Jamshidi, Zahra; Visscher, Lucas; Waters, L B F M


    Cationic cobalt clusters complexed with water Con(+)-H2O (n = 6-20) are produced through laser ablation and investigated via infrared multiple photon dissociation (IR-MPD) spectroscopy in the 200-1700 cm(-1) spectral range. All spectra exhibit a resonance close to the 1595 cm(-1) frequency of the free water bending vibration, indicating that the water molecule remains intact upon adsorption. For n = 6, the frequency of this band is blue-shifted, but it gradually converges to the free water value with increasing cluster size. In the lower-frequency range (200-650 cm(-1)) the spectra contain several bands which show a very regular frequency evolution, suggesting that the exact cluster geometry has little effect on the water-surface interaction. Density functional theory (DFT) calculations are carried out at the OPBE/TZP level for three representative sizes (n = 6, 9, 13) and indicate that the vibrations responsible for the resonances correspond to bending and torsional modes between the cluster and water moieties. The potential energy surfaces describing these interactions are very shallow, making the calculated harmonic frequencies and IR intensities very sensitive to small geometrical perturbations. We conclude that harmonic frequency calculations on (local) minima structures provide insufficient information for these types of cluster complexes and need to be complemented with calculations that provide a more extensive sampling of the potential energy surface.

  14. Repurposing Cationic Amphiphilic Antihistamines for Cancer Treatment

    Directory of Open Access Journals (Sweden)

    Anne-Marie Ellegaard


    Full Text Available Non-small cell lung cancer (NSCLC is one of the deadliest cancers worldwide. In search for new NSCLC treatment options, we screened a cationic amphiphilic drug (CAD library for cytotoxicity against NSCLC cells and identified several CAD antihistamines as inducers of lysosomal cell death. We then performed a cohort study on the effect of CAD antihistamine use on mortality of patients diagnosed with non-localized cancer in Denmark between 1995 and 2011. The use of the most commonly prescribed CAD antihistamine, loratadine, was associated with significantly reduced all-cause mortality among patients with non-localized NSCLC or any non-localized cancer when compared with use of non-CAD antihistamines and adjusted for potential confounders. Of the less frequently described CAD antihistamines, astemizole showed a similar significant association with reduced mortality as loratadine among patients with any non-localized cancer, and ebastine use showed a similar tendency. The association between CAD antihistamine use and reduced mortality was stronger among patients with records of concurrent chemotherapy than among those without such records. In line with this, sub-micromolar concentrations of loratadine, astemizole and ebastine sensitized NSCLC cells to chemotherapy and reverted multidrug resistance in NSCLC, breast and prostate cancer cells. Thus, CAD antihistamines may improve the efficacy of cancer chemotherapy.

  15. Repurposing Cationic Amphiphilic Antihistamines for Cancer Treatment. (United States)

    Ellegaard, Anne-Marie; Dehlendorff, Christian; Vind, Anna C; Anand, Atul; Cederkvist, Luise; Petersen, Nikolaj H T; Nylandsted, Jesper; Stenvang, Jan; Mellemgaard, Anders; Østerlind, Kell; Friis, Søren; Jäättelä, Marja


    Non-small cell lung cancer (NSCLC) is one of the deadliest cancers worldwide. In search for new NSCLC treatment options, we screened a cationic amphiphilic drug (CAD) library for cytotoxicity against NSCLC cells and identified several CAD antihistamines as inducers of lysosomal cell death. We then performed a cohort study on the effect of CAD antihistamine use on mortality of patients diagnosed with non-localized cancer in Denmark between 1995 and 2011. The use of the most commonly prescribed CAD antihistamine, loratadine, was associated with significantly reduced all-cause mortality among patients with non-localized NSCLC or any non-localized cancer when compared with use of non-CAD antihistamines and adjusted for potential confounders. Of the less frequently described CAD antihistamines, astemizole showed a similar significant association with reduced mortality as loratadine among patients with any non-localized cancer, and ebastine use showed a similar tendency. The association between CAD antihistamine use and reduced mortality was stronger among patients with records of concurrent chemotherapy than among those without such records. In line with this, sub-micromolar concentrations of loratadine, astemizole and ebastine sensitized NSCLC cells to chemotherapy and reverted multidrug resistance in NSCLC, breast and prostate cancer cells. Thus, CAD antihistamines may improve the efficacy of cancer chemotherapy. Copyright © 2016 The Authors. Published by Elsevier B.V. All rights reserved.

  16. Preparation, characterization, and efficient transfection of cationic liposomes and nanomagnetic cationic liposomes

    Directory of Open Access Journals (Sweden)

    Samadikhah HR


    Full Text Available Hamid Reza Samadikhah1,*, Asia Majidi2,*, Maryam Nikkhah2, Saman Hosseinkhani11Department of Biochemistry, 2Department of Nanobiotechnology, Faculty of Biological Sciences, Tarbiat Modares University, Tehran, Iran *These authors contributed equally to this work Purpose: Cationic liposomes (CLs are composed of phospholipid bilayers. One of the most important applications of these particles is in drug and gene delivery. However, using CLs to deliver therapeutic nucleic acids and drugs to target organs has some problems, including low transfection efficiency in vivo. The aim of this study was to develop novel CLs containing magnetite to overcome the deficiencies. Patients and methods: CLs and magnetic cationic liposomes (MCLs were prepared using the freeze-dried empty liposome method. Luciferase-harboring vectors (pGL3 were transferred into liposomes and the transfection efficiencies were determined by luciferase assay. Firefly luciferase is one of most popular reporter genes often used to measure the efficiency of gene transfer in vivo and in vitro. Different formulations of liposomes have been used for delivery of different kinds of gene reporters. Lipoplex (liposome–plasmid DNA complexes formation was monitored by gel retardation assay. Size and charge of lipoplexes were determined using particle size analysis. Chinese hamster ovary cells were transfected by lipoplexes (liposome-pGL3; transfection efficiency and gene expression level was evaluated by luciferase assay. Results: High transfection efficiency of plasmid by CLs and novel nanomagnetic CLs was achieved. Moreover, lipoplexes showed less cytotoxicity than polyethyleneimine and Lipofectamine™. Conclusion: Novel liposome compositions (1,2-dipalmitoyl-sn-glycero-3-phosphocholine [DPPC]/dioctadecyldimethylammonium bromide [DOAB] and DPPC/cholesterol/DOAB with high transfection efficiency can be useful in gene delivery in vitro. MCLs can also be used for targeted gene delivery, due to

  17. Evaluation of phenomena affecting diffusion of cations in compacted bentonite

    International Nuclear Information System (INIS)

    Muurinen, A.; Lehikoinen, J.


    In a number of diffusion studies, contradictions between the apparent diffusivities of cations and their distribution coefficients in bentonite have been found. Two principal reasons have been offered as explanations for this discrepancy; diffusion of the sorbed cations, often called surface diffusion, and the decrease of sorption in compacted clay compared to a sorption value obtained from a batch experiment. In the study the information available from the literature on sorption-diffusion mechanisms of cations in bentonite has been compiled and re-interpreted in order to improve the understanding of the diffusion process. (103 refs., 23 figs., 8 tabs.)

  18. Triblock and pentablock terpolymers by sequential base-assisted living cationic copolymerization of functionalized vinyl ethers

    KAUST Repository

    Bouchekif, Hassen


    A series of novel, well-defined triblock (PnBVE-b-PCEVE-b-PSiDEGVE) and pentablock (PSiDEGVE-b-PCEVE-b-PnBVE-b-PCEVE-b-PSiDEGVE) terpolymers of n-butyl vinyl ether (nBVE), 2-chloroethyl vinyl ether (CEVE) and tert-butyldimethylsilyl ethylene glycol vinyl ether (SiEGVE) were synthesized by sequential base-assisted living cationic polymerization. The living character of the homopolymerization of the three VE monomers and the crossover reaction resulting in the formation of well-defined block copolymers were investigated in various solvents (toluene, dichloromethane and n-hexane) using either a monofunctional [nBVE-acetic acid adduct (nBEA), CEVE-acetic acid adduct (CEEA) and SiDEGVE-acetic acid adduct (SiDEGEA)] or a difunctional [1,4-cyclohexane-1,4-diyl bis(2-methoxyethyl acetate) (cHDMEA)] initiator. All initiators are structurally equivalent to the dormant species of the corresponding monomers in order to achieve fast initiation. The optimal conditions of polymerization were achieved in n-hexane at -20 °C, in the presence of 1 M AcOEt (base). Good control over the number average molecular weight (Mn) and the polydispersity index (PDI) was obtained only at [Et3Al2Cl3]0 = [Chain-end]0 ≤ 10 mM. 2,6-Di-tert-butylpyridine (DtBP) was used as a non-nucleophilic proton trap to suppress any protonic initiation from moisture (i.e., Et3Al2Cl3·H2O). Well-defined PnBVEn-b-PCEVEp-b-PSiDEGVEq and PSiDEGVEq-b-PCEVEp-b-PnBVEn-b-PCEVEp-b-PSiDEGVEq terpolymers with a high crossover efficiency, no PCEVE-induced physical gelation, and predictable Mn and PDI < 1.15 were synthesized successfully provided that the targeted DPCEVE/DPnBVE ratio (i.e., p/n) did not exceed 2 and 0.2, respectively. The quantitative desilylation of the PSiEGVE by n-Bu4N+F- in THF at 0 °C led to triblock and pentablock terpolymers in which the PCEVE is the central block and the polyalcohol is the outer block. The thermal properties of the synthesized materials were examined by differential scanning

  19. Alkali Metal Cation versus Proton and Methyl Cation Affinities: Structure and Bonding Mechanism


    Boughlala, Z.; Guerra, C.F.; Bickelhaupt, F.M.


    Abstract We have analyzed the structure and bonding of gas?phase Cl?X and [HCl?X]+ complexes for X+=?H+, CH3 +, Li+, and Na+, using relativistic density functional theory (DFT). We wish to establish a quantitative trend in affinities of the anionic and neutral Lewis bases Cl? and HCl for the various cations. The Cl?X bond becomes longer and weaker along X+?=?H+, CH3 +, Li+, and Na+. Our main purpose is to understand the heterolytic bonding mechanism behind the intrinsic (i.e., in the absence ...

  20. Design of a metal primer containing a dithiooctanoate monomer and a phosphonic acid monomer for bonding of prosthetic light-curing resin composite to gold, dental precious and non-precious metal alloys. (United States)

    Ikemura, Kunio; Fujii, Toshihide; Negoro, Noriyuki; Endo, Takeshi; Kadoma, Yoshinori


    The effect of metal primers on adhesion of a resin composite to dental metal alloys was investigated. Experimental primers containing a dithiooctanoate monomer [10-methacryloyloxydecyl 6,8-dithiooctanoate (10-MDDT) or 6-methacryloyloxyhexyl 6,8-dithiooctanoate (6-MHDT)] and a phosphonic acid monomer [6-methacryloyloxyhexyl phosphonoacetate (6-MHPA) or 6-methacryloyloxyhexyl 3-phosphonopropionate (6-MHPP)] were prepared. After treating Au, Au alloy, Ag alloy, Au-Ag-Pd alloy, and Ni-Cr alloy with the experimental primers, their shear bond strengths (SBSs) with a prosthetic light-curing resin composite (Solidex, Shofu Inc., Japan) were measured after 1-day storage followed by 5,000 thermal cycles. The SBSs between Solidex and the primer-treated metals which were incubated in air at 50°C for 2 months were further measured. Results showed that the SBSs [mean (SD)] of all metal adherends treated with primer DT-PA-1 (5.0 wt% 10-MDDT, 1.0 wt% 6-MHPA) ranged between 31.2 (5.2) and 34.5 (5.8) MPa. The SBSs of the primer-treated metals did not degrade after 2-month incubation at 50°C. Therefore, a combined primer application consisting of a dithiooctanoate monomer and a phosphonic acid monomer provided efficacious bonding to Au as well as precious and non-precious metal alloys.

  1. Converting Hg-1212 to Tl-2212 via Tl-Hg cation exchange in combination with Tl cation intercalation

    International Nuclear Information System (INIS)

    Zhao Hua; Wu, Judy Z


    In a cation exchange process developed recently for epitaxy of HgBa 2 CaCu 2 O 6 (Hg-1212) thin films, TlBa 2 CaCu 2 O 7 (Tl-1212) or Tl 2 Ba 2 CaCu 2 O 9 (Tl-2212) precursor films were employed as the precursor matrices and Hg-1212 was obtained by replacing Tl cations on the precursor lattice with Hg cations. The reversibility of the cation exchange dictates directly the underlying mechanism. Following our recent success in demonstrating a complete reversibility within '1212' structure, we show the conversion from Hg-1212 to Tl-2212 can be achieved via two steps: conversion from Hg-1212 to Tl-1212 followed by Tl intercalation to form double Tl-O plans in each unit cell. The demonstrated reversibility of the cation exchange process has confirmed the process is a thermal perturbation of weakly bonded cations on the lattice and the direction of the process is determined by the population ratio between the replacing cations and that to be replaced

  2. Endomembrane Cation Transporters and Membrane Trafficking

    Energy Technology Data Exchange (ETDEWEB)

    Sze, Heven [Univ. of Maryland, College Park, MD (United States). Dept. of Cell Biology & Molecular Genetics


    Multicellular, as well as unicellular, organisms have evolved mechanisms to regulate ion and pH homeostasis in response to developmental cues and to a changing environment. The working hypothesis is that the balance of fluxes mediated by diverse transporters at the plasma membrane and in subcellular organelles determines ionic cellular distribution, which is critical for maintenance of membrane potential, pH control, osmolality, transport of nutrients, and protein activity. An emerging theme in plant cell biology is that cells respond and adapt to diverse cues through changes of the dynamic endomembrane system. Yet we know very little about the transporters that might influence the operation of the secretory system in plants. Here we focus on transporters that influence alkali cation and pH homeostasis, mainly in the endomembrane/ secretory system. The endomembrane system of eukaryote cells serves several major functions: i) sort cargo (e.g. enzymes, transporters or receptors) to specific destinations, ii) modulate the protein and lipid composition of membrane domains through remodeling, and iii) determine and alter the properties of the cell wall through synthesis and remodeling. We had uncovered a novel family of predicted cation/H+ exchangers (CHX) and K+ efflux antiporters (KEA) that are prevalent in higher plants, but rare in metazoans. We combined phylogenetic and transcriptomic analyses with molecular genetic, cell biological and biochemical studies, and have published the first reports on functions of plant CHXs and KEAs. CHX studied to date act at the endomembrane system where their actions are distinct from the better-studied NHX (Na/K-H+ exchangers). Arabidopsis thaliana CHX20 in guard cells modulate stomatal opening, and thus is significant for vegetative survival. Other CHXs ensure reproductive success on dry land, as they participate in organizing pollen walls, targeting of pollen tubes to the ovule or promoting

  3. Opposing effects of cationic antimicrobial peptides and divalent cations on bacterial lipopolysaccharides (United States)

    Smart, Matthew; Rajagopal, Aruna; Liu, Wing-Ki; Ha, Bae-Yeun


    The permeability of the bacterial outer membrane, enclosing Gram-negative bacteria, depends on the interactions of the outer, lipopolysaccharide (LPS) layer, with surrounding ions and molecules. We present a coarse-grained model for describing how cationic amphiphilic molecules (e.g., antimicrobial peptides) interact with and perturb the LPS layer in a biologically relevant medium, containing monovalent and divalent salt ions (e.g., Mg2+). In our approach, peptide binding is driven by electrostatic and hydrophobic interactions and is assumed to expand the LPS layer, eventually priming it for disruption. Our results suggest that in parameter ranges of biological relevance (e.g., at micromolar concentrations) the antimicrobial peptide magainin 2 effectively disrupts the LPS layer, even though it has to compete with Mg2+ for the layer. They also show how the integrity of LPS is restored with an increasing concentration of Mg2+. Using the approach, we make a number of predictions relevant for optimizing peptide parameters against Gram-negative bacteria and for understanding bacterial strategies to develop resistance against cationic peptides.

  4. Removal of cesium ions from clays by cationic surfactant intercalation. (United States)

    Park, Chan Woo; Kim, Bo Hyun; Yang, Hee-Man; Seo, Bum-Kyoung; Moon, Jei-Kwon; Lee, Kune-Woo


    We propose a new approach to remediate cesium-contaminated clays based on intercalation of the cationic surfactant dodecyltrimethylammonium bromide (DTAB) into clay interlayers. Intercalation of DTAB was found to occur very rapidly and involved exchanging interlayer cations. The reaction yielded efficient cesium desorption (∼97%), including of a large amount of otherwise non-desorbable cesium ions by cation exchange with ammonium ions. In addition, the intercalation of DTAB afforded an expansion of the interlayers, and an enhanced desorption of Cs by cation exchange with ammonium ions even at low concentrations of DTAB. Finally, the residual intercalated surfactants were easily removed by a decomposition reaction with hydrogen peroxide in the presence of Cu 2+ /Fe 2+ catalysts. Copyright © 2016 Elsevier Ltd. All rights reserved.

  5. Chemical bonding and structural ordering of cations in silicate glasses

    International Nuclear Information System (INIS)

    Calas, G.; Cormier, L.; Galoisy, L.; Ramos, A.; Rossano, St.


    The specific surrounding of cations in multicomponent silicate glasses is briefly presented. Information about interatomic distances and site geometry may be gained by using spectroscopic methods among which x-ray absorption spectroscopy may be used for the largest number of glass components. Scattering of x-rays and neutrons may also be used to determine the importance of medium range order around specific cations. All the existing data show that cations occur in sites with a well-defined geometry, which are in most cases connected to the silicate polymeric network. Medium range order has been detected around cations such as Ti, Ca and Ni, indicating that these elements have an heterogeneous distribution within the glassy matrix. (authors)

  6. Significant role of cationic polymers in drug delivery systems. (United States)

    Farshbaf, Masoud; Davaran, Soodabeh; Zarebkohan, Amir; Annabi, Nasim; Akbarzadeh, Abolfazl; Salehi, Roya


    Cationic polymers are characterized as the macromolecules that possess positive charges, which can be either inherently in the polymer side chains and/or its backbone. Based on their origins, cationic polymers are divided in two category including natural and synthetic, in which the possessed positive charges are as result of primary, secondary or tertiary amine functional groups that could be protonated in particular situations. Cationic polymers have been employed commonly as drug delivery agents due to their superior encapsulation efficacy, enhanced bioavailability, low toxicity and improved release profile. In this paper, we focus on the most prominent examples of cationic polymers which have been revealed to be applicable in drug delivery systems and we also discuss their general synthesis and surface modification methods as well as their controlled release profile in drug delivery.

  7. Pseudomonas putida KT2442 as a platform for the biosynthesis of polyhydroxyalkanoates with adjustable monomer contents and compositions

    DEFF Research Database (Denmark)

    Tripathi, Lakshmi; Wu, Lin-Ping; Dechuan, Meng


    The β-oxidation weakened Pseudomonas putida were established as a platform for the production of polyhydroxyalkanoates (PHA) with adjustable monomer compositions and micro-structures. When mutant P. putida KTOYO6ΔC (phaPCJA.c) was cultivated on mixtures of sodium butyrate and sodium hexanoate (C4...

  8. Production of medium-chain, a, omega-bifunctional monomers from fatty acids and n-alkanes

    NARCIS (Netherlands)

    Nuland, Youri M.


    In chapter 1, we give an introduction to bifunctional monomers that play an important role in the chemical industry. Briefly, the conventional production processes of α,ω-dicarboxylic acids and α,ω-diols are discussed. Strategies for more sustainable

  9. Comparative effect of different polymerization techniques on residual monomer and hardness properties of PMMA-based denture resins. (United States)

    Ayaz, Elif Aydogan; Durkan, Rukiye; Koroglu, Ayşegul; Bagis, Bora


    The aim of this study was to compare the residual monomer and microhardness of poly(methyl methacrylate) (PMMA)-based denture resins processed by using autoclave and conventional water bath techniques. To determine the amount of residual methyl methacrylate (MMA) monomer, disk-shaped specimens (n=5) were prepared from 3 different acrylic resins (Meliodent, Paladent and Qc-20). Control groups were polymerized in water bath for 30 minutes at 100°C. The study groups were prepared in an autoclave device for 60°C/30 min followed 130°C/10 min and the other group for 60°C/30 min followed by 130°C/20 min. According to standard calibration curves, ultraviolet spectrophotometry at 230 nm was used to determine the residual monomer. For the Vickers hardness measurements, disk-shaped specimens (n=5) were prepared for each test group. Hardness measurements were performed with a Vickers hardness tester under a 4.91-N press load for a 30 seconds, after immersion in distilled water at 37ºC for 48 hours. The data were analyzed by ANOVA and Tukey HSD test (phardness for all resin groups (p0.05). The autoclave polymerization technique exhibited significantly lower residual monomer content and greater hardness than conventional heat polymerization.

  10. Oligonucleotides containing a piperazino-modified 2'-amino-LNA monomer exhibit very high duplex stability and remarkable nuclease resistance

    DEFF Research Database (Denmark)

    Lou, Chenguang; Vester, Birte; Wengel, Jesper


    Incorporation of a piperazino-modified 2'-amino-LNA monomer (PipLNA-T) into oligonucleotides conferred very high affinity and base-pairing selectivity towards complementary DNA and RNA strands. Furthermore, one PipLNA-T modification provided a robust nuclease resistance that safeguarded three...

  11. Preparation of polyurethane foams using liquefied oil palm mesocarp fibre (OPMF) and renewable monomer from waste cooking oil (United States)

    Kormin, Shaharuddin; Rus, Anika Zafiah M.; Azahari, M. Shafiq M.


    The aim of this research is the production of polyurethane (PU) foams with biopolyols from liquefied oil palm mesocarp fibre (OPMF) and renewable monomer. Liquefaction of OPMF was studied using polyhydric alcohol (PA) which is PEG-400 as liquefaction solvents in conventional glass flask. In the second part of this paper was obtained the PU foams which presented good results when compared with commercial foams and include polyols from of fossil fuels. PU foams were prepared by mixing liquefied OPMF biopolyol, renewable monomer from waste cooking, additives and methylene diphenyl diisocyanate (MDI). Water was used as an environmental friendly blowing agent. The factors that influence the cell structure of foams (i.e., catalyst, surfactant, dosage of blowing agent, and mass ratio of biopolyol to renewable monomer were studied. The synthesized PU foams were characterized by FTIR and SEM. The formulation of the PU foams should be improved, but the results show that is possible the use biopolyols and renewable monomer to produce industrial foams with lower cost.

  12. Computer simulation based selection of optimal monomer for imprinting of tri-O-acetiladenosine in polymer matrix: vacuum calculations. (United States)

    Barkaline, Viatcheslav V; Douhaya, Yana V; Tsakalof, Andreas


    Molecularly imprinted polymers can be anticipated as synthetic imitation of natural antibodies, receptors and enzymes. In case of successful imprinting the selectivity and affinity of the imprint for substrate molecules are comparable with those of natural counterparts. The selection of the optimal functional monomer, monomer/template ratio as well as choosing of polymerization solvent is crucial determinants of the successful imprinting. In the present study the simulation approach to the development of molecular imprinting polymers for the extraction of new protein kinase ATP-competitive inhibitors is presented. By imprinting tri-O-acetyladenosine into polymer matrix the synthetic reproduction of adenosine triphosphate binding site to protein kinases can be fabricated and further used for adenosine triphosphate analogs screening in different sources. The optimized geometrical structure and energy of the pre-polymerization complexes of tri-O-acetyladenosine (template) with three different monomers-methacrylic acid, 3-vinyl benzoic acid and acrylamide in vacuum were calculated using hybrid quantum mechanical/molecular mechanical (QM/MM) approach. These calculations demonstrate that methacrylic acid forms the most stable complex with template, the next is 3-vinyl benzoic acid complex and the third-acrylamide one. The bond energies of the complexes are shown to increase monotonically as more monomers are linked to the template. The same conclusions are made from purely quantum self-consistent field calculations of pre-polymerization complex energy and structure. Hybrid calculation is shown to be effective and can substantially accelerate the development of the imprinting technology.

  13. Novel polymer composites from waste ethylene-propylene-diene-monomer rubber by supercritical CO2 foaming technology. (United States)

    Jeong, Keuk Min; Hong, Yeo Joo; Saha, Prosenjit; Park, Seong Ho; Kim, Jin Kuk


    In this study, a composite has been prepared by mixing waste rubber, such as ethylene-propylene-diene-monomer and low-density poly ethylene foaming, with supercritical carbon dioxide. In order to optimise the foaming process of the waste ethylene-propylene-diene-monomer-low-density poly ethylene composite, the variations of pressure and temperature on the foamed Microcell formation were studied. As indicated in scanning electron microscope photographs, the most uniform microcellular pattern was found at 200 bar and 100 °C using 30% by weight of waste ethylene-propylene-diene-monomer. Carbon dioxide could not be dissolved uniformly during foaming owing to extensive cross-linking of the waste ethylene-propylene-diene-monomer used for the composite. As a result the presence of un-uniform microcells after foaming were observed in the composite matrix to impart inferior mechanical properties of the composite. This problem was solved with uniform foaming by increasing the cross-link density of low-density poly ethylene using 1.5 parts per hundred dicumyl peroxide that enhances composite tensile and compressive strength up to 57% and 15%, respectively. The composite has the potential to be used as a foaming mat for artificial turf. © The Author(s) 2014.

  14. Effect of increased exposure times on amount of residual monomer released from single-step self-etch adhesives. (United States)

    Altunsoy, Mustafa; Botsali, Murat Selim; Tosun, Gonca; Yasar, Ahmet


    The aim of this study was to evaluate the effect of increased exposure times on the amount of residual Bis-GMA, TEGDMA, HEMA and UDMA released from single-step self-etch adhesive systems. Two adhesive systems were used. The adhesives were applied to bovine dentin surface according to the manufacturer's instructions and were polymerized using an LED curing unit for 10, 20 and 40 seconds (n = 5). After polymerization, the specimens were stored in 75% ethanol-water solution (6 mL). Residual monomers (Bis-GMA, TEGDMA, UDMA and HEMA) that were eluted from the adhesives (after 10 minutes, 1 hour, 1 day, 7 days and 30 days) were analyzed by high-performance liquid chromatography (HPLC). The data were analyzed using 1-way analysis of variance and Tukey HSD tests. Among the time periods, the highest amount of released residual monomers from adhesives was observed in the 10th minute. There were statistically significant differences regarding released Bis-GMA, UDMA, HEMA and TEGDMA between the adhesive systems (p<0.05). There were no significant differences among the 10, 20 and 40 second polymerization times according to their effect on residual monomer release from adhesives (p>0.05). Increasing the polymerization time did not have an effect on residual monomer release from single-step self-etch adhesives.

  15. Selective adsorption of carbohydrates and glycoproteins via molecularly imprinted hydrogels: application to visible detection by a boronic acid monomer. (United States)

    Kubo, Takuya; Furuta, Hayato; Naito, Toyohiro; Sano, Tomoharu; Otsuka, Koji


    Selective adsorption of carbohydrates and glycoproteins was effectively achieved by molecularly imprinted hydrogels (MIHs) with a poly(ethylene glycol) (PEG)-based crosslinker and 4-vinylphenylboronic acid. In addition, an MIH with a novel boronic acid monomer provided selective adsorption and enabled visible detection of fructose.

  16. Accuracy of the blob model for single flexible polymers inside nanoslits that are a few monomer sizes wide (United States)

    Nikoofard, Narges; Hoseinpoor, S. Mohammad; Zahedifar, Mostafa


    The de Gennes' blob model is extensively used in different problems of polymer physics. This model is theoretically applicable when the number of monomers inside each blob is large enough. For confined flexible polymers, this requires the confining geometry to be much larger than the monomer size. In this paper, the opposite limit of polymer in nanoslits with one to several monomers width is studied, using molecular dynamics simulations. Extension of the polymer inside nanoslits, confinement force on the plates, and the effective spring constant of the confined polymer are investigated. Despite the theoretical limitations of the blob model, the simulation results are explained with the blob model very well. The agreement is observed for the static properties and the dynamic spring constant of the polymer. A theoretical description of the conditions under which the dynamic spring constant of the polymer is independent of the small number of monomers inside blobs is given. Our results on the limit of applicability of the blob model can be useful in the design of nanotechnology devices.

  17. Comparison of residual monomer loss from cold-cure orthodontic acrylic resins processed by different polymerization techniques. (United States)

    Nik, Tahereh Hosseinzadeh; Shahroudi, Atefe Saffar; Eraghihzadeh, Zeinab; Aghajani, Farzaneh


    This investigation aimed to assess and compare the amount of residual monomer (RM) released from removable orthodontic appliances constructed by sprinkle-on and dough techniques. One hundred and twenty acrylic samples were prepared from orthodontic autopolymerized acrylic resins and divided into three groups, according to the processing method: sprinkle-on with polyclave, sprinkle-on without polyclave and dough technique. After polymerization, the specimens of each group were immersed in distilled water for 24 h, 48 h, 72 h and 1 week. High-performances liquid chromatography (HPLC) was utilized to measure residual monomer content. Maximum observed RM was 1284·91±129·07 ppm measured for sprinkle-on technique without polyclave after 24 h of water immersion. At this time, the level of RM was significantly different among the three applied techniques (Psprinkle-on technique with polyclave released the least amount of RM. Within each group, the maximum monomer releasing was observed after the first 24 h and decreases were observed in subsequent time groups. The reduction over the time was not significant in the polyclave groups (P>0·05). The sprinkle-on technique with polyclave and longer water immersion reduced residual monomer released from acrylic orthodontic appliances.

  18. Protective effect of divalent cations against aluminum toxicity in soybean


    Silva,Ivo Ribeiro da; Corrêa,Tarcísio Fernando Côrtes; Novais,Roberto Ferreira; Gebrim,Fabrício de Oliveira; Nunes,Flancer Novais; Silva,Eulene Francisco da; Smyth,Thomas Jot


    A large proportion of soybean fields in Brazil are currently cultivated in the Cerrado region, where the area planted with this crop is growing considerably every year. Soybean cultivation in acid soils is also increasing worldwide. Since the levels of toxic aluminum (Al) in these acid soils is usually high it is important to understand how cations can reduce Al rhizotoxicity in soybean. In the present study we evaluated the ameliorative effect of nine divalent cations (Ca, Mg, Mn, Sr, Sn, Cu...

  19. Isomerizations of the Nitromethane Radical Cation in the Gas Phase

    DEFF Research Database (Denmark)

    Egsgaard, Helge; Carlsen, Lars; Elbel, Susanne


    The concurrent isomerizations of the nitromethane radical cation to its aci-nitromethane and methylnitrite isomers, respectively, has been established based on metastable ion studies and collision activation mass spectrometry. The energy diagram for the ionized nitromethane/aci-nitromethane tauto......The concurrent isomerizations of the nitromethane radical cation to its aci-nitromethane and methylnitrite isomers, respectively, has been established based on metastable ion studies and collision activation mass spectrometry. The energy diagram for the ionized nitromethane...

  20. Bithiophene radical cation: Resonance Raman spectroscopy and molecular orbital calculations

    DEFF Research Database (Denmark)

    Grage, M.M.-L.; Keszthelyi, T.; Offersgaard, J.F.


    The resonance Raman spectrum of the photogenerated radical cation of bithiophene is reported. The bithiophene radical cation was produced via a photoinduced electron transfer reaction between excited bithiophene and the electron acceptor fumaronitrile in a room temperature acetonitrile solution...... and the Raman spectrum excited in resonance with the absorption band at 425 nm. The spectrum was interpreted with the help of density functional theory calculations. (C) 1998 Elsevier Science B.V....

  1. Mercury release from deforested soils triggered by base cation enrichment

    International Nuclear Information System (INIS)

    Farella, N.; Lucotte, M.; Davidson, R.; Daigle, S.


    The Brazilian Amazon has experienced considerable colonization in the last few decades. Family agriculture based on slash-and-burn enables millions of people to live in that region. However, the poor nutrient content of most Amazonian soils requires cation-rich ashes from the burning of the vegetation biomass for cultivation to be successful, which leads to forest ecosystem degradation, soil erosion and mercury contamination. While recent studies have suggested that mercury present in soils was transferred towards rivers upon deforestation, little is known about the dynamics between agricultural land-use and mercury leaching. In this context, the present study proposes an explanation that illustrates how agricultural land-use triggers mercury loss from soils. This explanation lies in the competition between base cations and mercury in soils which are characterized by a low adsorption capacity. Since these soils are naturally very poor in base cations, the burning of the forest biomass suddenly brings high quantities of base cations to soils, destabilizing the previous equilibrium amongst cations. Base cation enrichment triggers mobility in soil cations, rapidly dislocating mercury atoms. This conclusion comes from principal component analyses illustrating that agricultural land-use was associated with base cation enrichment and mercury depletion. The overall conclusions highlight a pernicious cycle: while soil nutrient enrichment actually occurs through biomass burning, although on a temporary basis, there is a loss in Hg content, which is leached to rivers, entering the aquatic chain, and posing a potential health threat to local populations. Data presented here reflects three decades of deforestation activities, but little is known about the long-term impact of such a disequilibrium. These findings may have repercussions on our understanding of the complex dynamics of deforestation and agriculture worldwide

  2. Fabrication of Mn3O4-carbon nanotube composites with high areal capacitance using cationic and anionic dispersants. (United States)

    Ata, M S; Milne, J; Zhitomirsky, I


    Mn 3 O 4 -multiwalled carbon nanotube (MWCNT) electrodes for supercapacitors with high active mass loadings have been fabricated with the goal of achieving a high area normalized capacitance (C S ) and enhanced capacitance retention at high charge-discharge rates. Poly(4-styrenesulfonic acid-co-maleic acid) sodium salt P(SSA-MA) was used as a charging and dispersing agent for the fabrication of Mn 3 O 4 . The unique bonding properties of the MA monomers allowed efficient P(SSA-MA) adsorption on Mn 3 O 4 , whereas SSA monomers imparted a negative charge. Cationic ethyl violet (EV) and pyronin Y (PY) dyes were used for dispersion and charging of MWCNT. Good dispersion of the individual components and their electrostatic heterocoagulation facilitated efficient mixing, which allowed enhanced capacitive behavior at mass loadings of 28.4 mg cm -2 , which meet requirements for practical applications. The highest capacitance of 2.8 F cm -2 was obtained at a scan rate of 2 mV s -1 for the composites, prepared using PY. However, the composites, prepared using EV showed better capacitance retention of 88% in the scan rate range of 2-100 mV s -1 and the capacitance of 2.1 F cm -2 was obtained at a scan rate of 100 mV s -1 . The composites showed activation behavior during cycling, which resulted in a capacitance increase and electrical resistance reduction. The results of this investigation showed that Mn 3 O 4 -MWCNT composites, prepared by new colloidal methods are promising materials for practical applications in electrochemical supercapacitors. Copyright © 2017 Elsevier Inc. All rights reserved.

  3. Sorption phenomena of modification of clinoptilolite tuffs by surfactant cations. (United States)

    Rozić, M; Ivanec Sipusić, D; Sekovanić, L; Miljanić, S; Curković, L; Hrenović, J


    The sorption of cationic surfactant hexadecyltrimethylammonium (HDTMA) onto the solid/liquid interfaces of different clinoptilolite rich tuffs (CT) is examined. Examined were CT from Serbia with 75% clinoptilolite, CT from Turkey with 70% clinoptilolite, and CT from Croatia with 60% clinoptilolite. The sorption of HDTMA cations increased in the following order: CT from Serbia>CT from Turkey>CT from Croatia. The maximum amounts of sorbed HDTMA cations, normalized with regard to external cation exchange capacities of tuffs, were 1.79, 1.70, and 1.14 for Serbian, Turkish, and Croatian CT. FTIR analysis of samples with the maximum amount of sorbed HDTMA cations showed that HDTMA chains on Serbian CT adopt mainly a stretched all-trans conformation, while at the surfaces of CT from Turkey and Croatia the amount of gauche conformations increased. The zeta potentials of CT samples with the maximum amount of sorbed HDTMA cations and the sorption of benzoate anions on these samples increased in the following order: CT from Turkey>CT from Serbia>CT from Croatia. It can be assumed that on the surface of CT from Turkey iron (hydr)oxide clusters or nanoparticles with positive surface sites are present, due to which the isoelectric point is sifted toward lower and the zeta potential toward higher values. Therefore, the sorption of benzoate anions on modified CT from Turkey is also higher.

  4. On the mobility of exchangeable cations on clay surfaces

    International Nuclear Information System (INIS)

    Gimmi, T.; Kosakowski, G.; Glaus, M.A.


    Document available in extended abstract form only. The diffusive mobility of radionuclides in buffer materials and potential host rocks is an important topic in the safety analysis for underground waste repositories. Many of the radionuclides are cations. Accordingly, the diffusion and retention of cations in compacted clay minerals and clay rocks is of central interest. The retention properties of the clay minerals originate from their negative surface charges. These are compensated by un-specifically sorbed cations that are located on planar surfaces or in interlayers (exchangeable cations) and by cations that are more specifically sorbed for instance to edge sites. In general, sorbed cations are considered as immobile with respect to diffusive transport. Whereas this may be correct for specifically sorbed cations, this is probably not the case for un-specifically sorbed exchangeable cations. They can easily exchange with cations in the pore solution, even if they are located- at low hydration states-in very narrow interlayers. For such exchange a certain mobility in the sorbed state is required. This is in line with the observations that many experimentally derived cation diffusion coefficients are larger than expected when compared with those of water tracers. This and the dependence of effective diffusion coefficients on the external salt concentration can be explained with so-called surface diffusion, that is, a movement of sorbed cations. Unfortunately, no direct proof of this phenomenon is available, and parameters like surface diffusion coefficients or surface mobilities are largely unknown. We compiled a large number of published cation diffusion coefficients for various clay minerals and clay rocks. We showed that by an appropriate scaling of the cation diffusion coefficients, it is possible to estimate the average surface mobility of the cation in each experiment. We define the surface mobility as the surface diffusion coefficient of a cation on a flat

  5. Tunable states of interlayer cations in two-dimensional materials

    Energy Technology Data Exchange (ETDEWEB)

    Sato, K.; Numata, K. [Department of Environmental Sciences, Tokyo Gakugei University, Koganei, Tokyo 184-8501 (Japan); Dai, W. [Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), College of Chemistry, Nankai University, Tianjin 300071 (China); Hunger, M. [Institute of Chemical Technology, University of Stuttgart, 70550 Stuttgart (Germany)


    The local state of cations inside the Ångstrom-scale interlayer spaces is one of the controlling factors for designing sophisticated two-dimensional (2D) materials consisting of 2D nanosheets. In the present work, the molecular mechanism on how the interlayer cation states are induced by the local structures of the 2D nanosheets is highlighted. For this purpose, the local states of Na cations in inorganic 2D materials, in which the compositional fluctuations of a few percent are introduced in the tetrahedral and octahedral units of the 2D nanosheets, were systematically studied by means of {sup 23}Na magic-angle-spinning (MAS) nuclear magnetic resonance (NMR) and {sup 23}Na multiple-quantum MAS (MQMAS) NMR spectroscopy. In contrast with an uniform distribution of Na cations expected so far, various well-defined cation states sensitive to the local structures of the 2D nanosheets were identified. The tunability of the interlayer cation states along with the local structure of the 2D nanosheets, as the smallest structural unit of the 2D material, is discussed.

  6. Surface functionalized SiO2nanoparticles with cationic polymers via the combination of mussel inspired chemistry and surface initiated atom transfer radical polymerization: Characterization and enhanced removal of organic dye. (United States)

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


    Monodispersed SiO 2 particles functionalized with cationic polymers poly-((3-acrylamidopropyl)trimethylammonium chloride) (PAPTCl) were prepared using mussel inspired surface modification strategy and surface initiated atom transfer radical polymerization (SI-ATRP). Fourier transform infrared spectroscopy, transmission electron microscope, thermogravimetric analysis, X-ray photoelectron spectroscopy, and zeta potential were employed to characterize these SiO 2 samples. The adsorption performance of the functionalized SiO 2 (donated as SiO 2 -PDA-PAPTCl) towards anionic organic dye Congo red (CR) was investigated to evaluate their potential environmental applications. We demonstrated that the surface of SiO 2 particles can be successfully functionalized with cationic PAPTCl. The adsorption capability of as-prepared SiO 2 was found to increases from 28.70 and 106.65mg/g after surface grafted with cationic polymers. The significant enhancement in the adsorption capability of SiO 2 -PDA-PAPTCl is mainly attributed to the introduction of cationic polymers. More importantly, this strategy is expected to be promising for fabrication of many other functional polymer nanocomposites for environmental applications due to the universality of mussel inspired chemistry and well designability and good monomer adaptability of SI-ATRP. Copyright © 2017 Elsevier Inc. All rights reserved.

  7. Novel Galvanic Corrosion Inhibitors: Synthesis, Characterization, Fabrication and Testing

    National Research Council Canada - National Science Library

    Harruna, Issifu I


    ...). The copolymers of the polymerizable methacrylate-type monomer with styrene, methyl methacrylate, and butyl methacrylate have strong blue-light- emitting properties. Amphiphilic tris(2,2'-bipyridine...

  8. Folding Landscape of Mutant Huntingtin Exon1: Diffusible Multimers, Oligomers and Fibrils, and No Detectable Monomer.

    Directory of Open Access Journals (Sweden)

    Bankanidhi Sahoo

    Full Text Available Expansion of the polyglutamine (polyQ track of the Huntingtin (HTT protein above 36 is associated with a sharply enhanced risk of Huntington's disease (HD. Although there is general agreement that HTT toxicity resides primarily in N-terminal fragments such as the HTT exon1 protein, there is no consensus on the nature of the physical states of HTT exon1 that are induced by polyQ expansion, nor on which of these states might be responsible for toxicity. One hypothesis is that polyQ expansion induces an alternative, toxic conformation in the HTT exon1 monomer. Alternative hypotheses posit that the toxic species is one of several possible aggregated states. Defining the nature of the toxic species is particularly challenging because of facile interconversion between physical states as well as challenges to identifying these states, especially in vivo. Here we describe the use of fluorescence correlation spectroscopy (FCS to characterize the detailed time and repeat length dependent self-association of HTT exon1-like fragments both with chemically synthesized peptides in vitro and with cell-produced proteins in extracts and in living cells. We find that, in vitro, mutant HTT exon1 peptides engage in polyQ repeat length dependent dimer and tetramer formation, followed by time dependent formation of diffusible spherical and fibrillar oligomers and finally by larger, sedimentable amyloid fibrils. For expanded polyQ HTT exon1 expressed in PC12 cells, monomers are absent, with tetramers being the smallest molecular form detected, followed in the incubation time course by small, diffusible aggregates at 6-9 hours and larger, sedimentable aggregates that begin to build up at 12 hrs. In these cell cultures, significant nuclear DNA damage appears by 6 hours, followed at later times by caspase 3 induction, mitochondrial dysfunction, and cell death. Our data thus defines limits on the sizes and concentrations of different physical states of HTT exon1 along the

  9. Investigation of the Hydantoin Monomer and its Interaction with Water Molecules (United States)

    Gruet, Sébastien; Perez, Cristobal; Schnell, Melanie


    Hydantoin (Imidazolidine-2,4-dione, C_3H_4N_2O_2) is a five-membered heterocyclic compound of astrobiological interest. This molecule has been detected in carbonaceous chondrites [1], and its formation can rise from the presence of glycolic acid and urea, two prebiotic molecules [2]. The hydrolysis of hydantoin under acidic conditions can also produce glycine [3], an amino acid actively searched for in the interstellar medium. Spectroscopic data of hydantoin is very limited and mostly dedicated to the solid phase. The high resolution study in gas phase is restricted to the work recently published by Ozeki et al. reporting the pure rotational spectra of the ground state and two vibrational states of the molecule in the millimeter-wave region (90-370 GHz)[4]. Using chirped-pulse Fourier-transform microwave (CP-FTMW) spectroscopy, we recorded the jet-cooled rotational spectra of hydantoin with water between 2 to 8 GHz. We observed the ground state of hydantoin monomer and several water complexes with one or two water molecules. All the observed species exhibit a hyperfine structure due to the two nitrogen atoms present in the molecule, which were fully resolved and analyzed. Additional experiments with a ^{18}O enriched water sample were realized to determine the oxygen-atom positions of the water monomers. These experiments yielded accurate structural information on the preferred water binding sites. The observed complexes and the interactions that hold them together, mainly strong directional hydrogen bonds, will be presented and discussed. [1] Shimoyama, A. and Ogasawara, R., Orig. Life Evol. Biosph., 32, 165-179, 2002. DOI:10.1023/A:1016015319112. [2] Menor-Salván, C. and Marín-Yaseli, M.R., Chem. Soc. Rev., 41(16), 5404-5415, 2012. DOI:10.1039/c2cs35060b. [3] De Marcellus P., Bertrand M., Nuevo M., Westall F. and Le Sergeant d'Hendecourt L., Astrobiology. 11(9), 847-854, 2011. DOI:10.1089/ast.2011.0677. [4] Ozeki, H., Miyahara R., Ihara H., Todaka S., Kobayashi

  10. Novel Reactivity Of The Cationic Complex

    International Nuclear Information System (INIS)

    Wang, J.; Dash, A.K.; Eisen, AM.; Berthet, J.C.; Ephritikhine, M.


    The catalytic chemistry of electrophilic d 0 /f organometallic complexes is nowadays under intense investigation, reaching a high level of sophistication. General aspects concerning these complexes are concentrated for most studies to the functionalization of unsaturated organic molecules. To cite an instance, the actinide-promoted oligomerization of terminal alkynes is of essential present concern since it may introduce to a diversity of organic enynes and oligoacetylene products that are valuable synthons for the synthesis of natural products. Enynes are the simplest oligomerization products of alkynes. We have demonstrated that organoactinides complexes of the type [Cp* 2 AnMe 2 AnMe 2 ] (Cp* = C 5 Me 5 ; An = U, Th) are active catalysts for the linear oligomerization of terminal alkynes and the extent of oligomerization was found to be strongly dependent on the electronic and steric properties of the alkyne substituents. Bulky alkynes were reacted with high regioselectivity toward dimer and/or trimers whereas for non-bulky alkynes, these compounds were transformed into oligomers with a total deficiency of regioselectivity. The addition of primary amines to the catalytic cycle, for An = Th, granted the chemoselective formation of dimers, chemoselectively, whereas for An = U, this control was not succeeded. In distinction to the neutral organoactinide complexes, homogeneous cationic d 0 /f n actinide complexes have been used as in the homogeneous polymerization of olefins as extremely active catalysts. Hence, the catalytic alkyne oligomerization is a opportune route to explore insertions and σ-bond metathesis reactivity of complexes. We have recently shown that the reaction of terminal alkynes (RC≡CH), promoted by [(Et 2 N) 3 U][BPh 4 ], in toluene, produces efficiently mostly the gem dimers (for R = Me, i Pr and n Bu) as the major products, whereas for bulky alkynes (R = t MS or t Bu) small amounts of the cis dimer was concomitantly obtained. A plausible

  11. N-Acetyl Cysteine Depletes Reactive Oxygen Species and Prevents Dental Monomer-Induced Intrinsic Mitochondrial Apoptosis In Vitro in Human Dental Pulp Cells.

    Directory of Open Access Journals (Sweden)

    Yang Jiao

    Full Text Available To investigate the involvement of intrinsic mitochondrial apoptosis in dental monomer-induced cytotoxicity and the influences of N-acetyl cysteine (NAC on this process.Human dental pulp cells (hDPCs were exposed to several dental monomers in the absence or presence of NAC, and cell viability, intracellular redox balance, morphology and function of mitochondria and key indicators of intrinsic mitochondrial apoptosis were evaluated using various commercial kits.Dental monomers exerted dose-dependent cytotoxic effects on hDPCs. Concomitant to the over-production of reactive oxygen species (ROS and depletion of glutathione (GSH, differential changes in activities of superoxide dismutase, glutathione peroxidase, and catalase were detected. Apoptosis, as indicated by positive Annexin V/propidium iodide (PI staining and activation of caspase-3, was observed after dental monomer treatment. Dental monomers impaired the morphology and function of mitochondria, and induced intrinsic mitochondrial apoptosis in hDPCs via up-regulation of p53, Bax and cleaved caspase-3, and down-regulation of Bcl-2. NAC restored cell viability, relieved oxidative stress and blocked the apoptotic effects of dental monomers.Dental monomers induced oxidative stress and mitochondrial intrinsic apoptosis in hDPCs. NAC could reduce the oxidative stress and thus protect hDPCs against dental monomer-induced apoptosis.

  12. New photoresponsive (meth)acrylate (co)polymers containing azobenzene pendant sidegroups with carboxylic and dimethylamino substituents .1. Synthesis and characterization of the monomers

    NARCIS (Netherlands)

    Haitjema, HJ; Buruma, R; VanEkenstein, GORA; Tan, YY; Challa, G


    New azobenzene-based (az.b.) monomers with CO2H (acid) or N(CH3)(2) (basic) substituents were synthesized. For some of these compounds new synthetic routes had to be developed, especially for the az.b. monomers with a CO2H substituent (azoacids) where their synthesis, purification and (thermal)

  13. Synthesis and spectroscopy of clay intercalated Cu(II) bio-monomer complexes: coordination of Cu(II) with purines and nucleotides

    NARCIS (Netherlands)

    Weckhuysen, B.M.; Leeman, H.; Schoonheydt, R.A.


    The spectroscopic properties of Cu(bio-monomer)nm+ complexes [BM=bio-monomer (purine, adenine, guanine, hypoxanthine, 5-ADP and 5-GMP)] in saponite clays have been investigated by diffuse reflectance spectroscopy (DRS) in the UV-Vis-NIR region and electron paramagnetic resonance (EPR) at X-band.

  14. A Low Protein Binding Cationic Poly(2-oxazoline) as Non-Viral Vector

    KAUST Repository

    He, Zhijian


    © 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. Developing safe and efficient non-viral gene delivery systems remains a major challenge. We present a new cationic poly(2-oxazoline) (CPOx) block copolymer for gene therapy that was synthesized by sequential polymerization of non-ionic 2-methyl-2-oxazoline and a new 2-oxazoline monomer, 2-(N-methyl, N-Boc-amino)-methyl-2-oxazoline, followed by deprotection of the pendant secondary amine groups. Upon mixing with plasmid DNA (pDNA), CPOx forms small (diameter ≈80 nm) and narrowly dispersed polyplexes (PDI <0.2), which are stable upon dilution in saline and against thermal challenge. These polyplexes exhibited low plasma protein binding and very low cytotoxicity in vitro compared to the polyplexes of pDNA and poly(ethylene glycol)-b-poly(L-lysine) (PEG-b-PLL). CPOx/pDNA polyplexes at N/P = 5 bound considerably less plasma protein compared to polyplexes of PEG-b-PLL at the same N/P ratio. This is a unique aspect of the developed polyplexes emphasizing their potential for systemic delivery in vivo. The transfection efficiency of the polyplexes in B16 murine melanoma cells was low after 4 h, but increased significantly for 10 h exposure time, indicative of slow internalization of polyplexes. Addition of Pluronic P85 boosted the transfection using CPOx/pDNA polyplexes considerably. The low protein binding of CPOx/pDNA polyplexes is particularly interesting for the future development of targeted gene delivery.

  15. A systematic coarse-graining strategy for semi-dilute copolymer solutions: from monomers to micelles

    Energy Technology Data Exchange (ETDEWEB)

    Capone, Barbara [Computational Physics, University of Vienna, Sensengasse 8, A-1090 Wien (Austria); Coluzza, Ivan [Computational Physics, University of Vienna, Boltzmanngasse 5, A-1090 Wien (Austria); Hansen, Jean-Pierre [University Chemical Laboratory, Lensfield Road, Cambridge CB2 1EW (United Kingdom)


    A systematic coarse-graining procedure is proposed for the description and simulation of AB diblock copolymers in selective solvents. Each block is represented by a small number, n{sub A} or n{sub B}, of effective segments or blobs, containing a large number of microscopic monomers. n{sub A} and n{sub B} are unequivocally determined by imposing that blobs do not, on average, overlap, even if complete copolymer coils interpenetrate (semi-dilute regime). Ultra-soft effective interactions between blobs are determined by a rigorous inversion procedure in the low concentration limit. The methodology is applied to an athermal copolymer model where A blocks are ideal (theta solvent), B blocks self-avoiding (good solvent), while A and B blocks are mutually avoiding. The model leads to aggregation into polydisperse spherical micelles beyond a critical micellar concentration determined by Monte Carlo simulations for several size ratios f of the two blocks. The simulations also provide accurate estimates of the osmotic pressure and of the free energy of the copolymer solutions over a wide range of concentrations. The mean micellar aggregation numbers are found to be significantly lower than those predicted by an earlier, minimal two-blob representation (Capone et al 2009 J. Phys. Chem. B 113 3629).

  16. A systematic coarse-graining strategy for semi-dilute copolymer solutions: from monomers to micelles

    International Nuclear Information System (INIS)

    Capone, Barbara; Coluzza, Ivan; Hansen, Jean-Pierre


    A systematic coarse-graining procedure is proposed for the description and simulation of AB diblock copolymers in selective solvents. Each block is represented by a small number, n A or n B , of effective segments or blobs, containing a large number of microscopic monomers. n A and n B are unequivocally determined by imposing that blobs do not, on average, overlap, even if complete copolymer coils interpenetrate (semi-dilute regime). Ultra-soft effective interactions between blobs are determined by a rigorous inversion procedure in the low concentration limit. The methodology is applied to an athermal copolymer model where A blocks are ideal (theta solvent), B blocks self-avoiding (good solvent), while A and B blocks are mutually avoiding. The model leads to aggregation into polydisperse spherical micelles beyond a critical micellar concentration determined by Monte Carlo simulations for several size ratios f of the two blocks. The simulations also provide accurate estimates of the osmotic pressure and of the free energy of the copolymer solutions over a wide range of concentrations. The mean micellar aggregation numbers are found to be significantly lower than those predicted by an earlier, minimal two-blob representation (Capone et al 2009 J. Phys. Chem. B 113 3629).

  17. A systematic coarse-graining strategy for semi-dilute copolymer solutions: from monomers to micelles (United States)

    Capone, Barbara; Coluzza, Ivan; Hansen, Jean-Pierre


    A systematic coarse-graining procedure is proposed for the description and simulation of AB diblock copolymers in selective solvents. Each block is represented by a small number, nA or nB, of effective segments or blobs, containing a large number of microscopic monomers. nA and nB are unequivocally determined by imposing that blobs do not, on average, overlap, even if complete copolymer coils interpenetrate (semi-dilute regime). Ultra-soft effective interactions between blobs are determined by a rigorous inversion procedure in the low concentration limit. The methodology is applied to an athermal copolymer model where A blocks are ideal (theta solvent), B blocks self-avoiding (good solvent), while A and B blocks are mutually avoiding. The model leads to aggregation into polydisperse spherical micelles beyond a critical micellar concentration determined by Monte Carlo simulations for several size ratios f of the two blocks. The simulations also provide accurate estimates of the osmotic pressure and of the free energy of the copolymer solutions over a wide range of concentrations. The mean micellar aggregation numbers are found to be significantly lower than those predicted by an earlier, minimal two-blob representation (Capone et al 2009 J. Phys. Chem. B 113 3629).

  18. Determination of residual monomers released from soft lining materials with the use of HPLC

    International Nuclear Information System (INIS)

    Sofou, A.; Tsoupi, I.; Karayannia, M.


    A study was carried out to examine the post polymerized leachability of three non phthalic and four phthalic residual monomers, from twelve commercially available soft lining materials, using HPLC. Specimens of equal: dimensions were constructed from each brand of material following a standardized procedure and were stored in three different conditions of storage i.e. distilled water, artificial saliva and a binary mixture of ethanol-water with the resulting liquids providing samples for analysis in the HPLC apparatus. Three different experiments were performed for each brand of material and each condition of storage, in order to examine the parameters time and temperature. The results obtained from this study suggest that a wide spectrum of residues is diffusing out of the twelve examined soft lining materials. The non phthalic compounds were leaching at high concentrations while all the phthalates examined exhibited different degrees of elusion commensurate with the storage condition, brand of material and type of experiment. The main non phthalic component extracted from all the materials was methyl methacrylate, while the mainly extracted phthalic compound was different from each material. The level of elusion seems to be increasing dependent on time, medium of storage and temperature as well. (author)

  19. A novel hydroxyl epoxy phosphate monomer enhancing the anticorrosive performance of waterborne Graphene/Epoxy coatings (United States)

    Ding, Jiheng; Rahman, Obaid ur; Peng, Wanjun; Dou, Huimin; Yu, Haibin


    Herein, we report the synthesis of a novel hydroxyl epoxy phosphate monomer (PGHEP) as an efficient dispersant for graphene to enhance the compatibility of the graphene in epoxy resin. Raman spectroscopy, Ultraviolet-visible spectroscopy (UV-vis) and X-ray photoelectron spectroscopy (XPS) studies were confirmed the π-π interactions between PGHEP and graphene. Well-dispersed states of PGHEP functionalized graphene (G) sheets in water were analyzed by transmission electron microscopy (TEM), atomic force microscopy (AFM) and scanning electron microscopy (SEM). Further, microstructure of prepared G/waterborne epoxy coatings containing 0.5-1.0 wt.% of PGHEP functionalized G sheets were also observed with the help of SEM and TEM. The PGHEP functionalized G sheets dispersed composite coatings displayed enhanced corrosion resistance compared with pure epoxy resin, these coatings have higher contact angle, lower water absorption as evident from the results of electrochemical impedance spectroscopy (EIS) and salt spray tests. The superior corrosion protection performances of G/epoxy coatings were mainly attributed to the formed passive film from uniformly dispersed PGHEP functionalized G sheets which act as physical barrier on the steel surface. Therefore, this work provides a novel bio-based efficient dispersant for G sheets and an important method for preparing G/waterborne epoxy coatings with superior corrosion resistance properties.

  20. Mortality from liver disease among Italian vinyl chloride monomer/polyvinyl chloride manufacturers. (United States)

    Pirastu, R; Comba, P; Reggiani, A; Foa, V; Masina, A; Maltoni, C


    The possible association in humans between nonangiosarcoma primary liver tumors (PLC-non-A), particularly hepatocellular carcinoma (HCC), and exposure to vinyl chloride monomer (VCM) is supported by both experimental and human data. This article presents a review of the information regarding 253 deaths that occurred in seven plants manufacturing VCM/PVC and one plant extruding PVC. The retrieval of clinical and pathological data, in addition to the information from death certificate, is referred to as "best evidence" (BE). BE has been carried out for 63 deaths. A total of 14 primary liver cancer (PLC) were detected: seven were angiosarcoma (PLC-A), and two of the remaining seven were hepatocellular carcinoma (HCC). In our series of 14 PLC cases, there was no significant difference between PLC-A and PLC-non-A as to length of exposure and latency. There was no noticeable difference in terms of job title between ASL and non-ASL cases. The list of longest held jobs shows the presence of various job titles, different from autoclave cleaner, for primary liver cancer, PLC-A and PLC-non-A. In conclusion, our observations show that VCM may have a broader carcinogenicity action on the liver and that exposure lower than that occurring in autoclave cleaning can cause primary liver cancer, both angiosarcoma and nonangiosarcoma.

  1. Alternate fuels and chemicals from synthesis gas: Vinyl acetate monomer. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Richard D. Colberg; Nick A. Collins; Edwin F. Holcombe; Gerald C. Tustin; Joseph R. Zoeller


    There has been a long-standing desire on the part of industry and the U.S. Department of Energy to replace the existing ethylene-based vinyl acetate monomer (VAM) process with an entirely synthesis gas-based process. Although there are a large number of process options for the conversion of synthesis gas to VAM, Eastman Chemical Company undertook an analytical approach, based on known chemical and economic principles, to reduce the potential candidate processes to a select group of eight processes. The critical technologies that would be required for these routes were: (1) the esterification of acetaldehyde (AcH) with ketene to generate VAM, (2) the hydrogenation of ketene to acetaldehyde, (3) the hydrogenation of acetic acid to acetaldehyde, and (4) the reductive carbonylation of methanol to acetaldehyde. This report describes the selection process for the candidate processes, the successful development of the key technologies, and the economic assessments for the preferred routes. In addition, improvements in the conversion of acetic anhydride and acetaldehyde to VAM are discussed. The conclusion from this study is that, with the technology developed in this study, VAM may be produced from synthesis gas, but the cost of production is about 15% higher than the conventional oxidative acetoxylation of ethylene, primarily due to higher capital associated with the synthesis gas-based processes.

  2. Bond strength and monomer conversion of indirect composite resin restorations, Part 1: Light vs heat polymerization. (United States)

    Malta, Daniel Alexandre Menezes Pedrosa; Magne, Pascal; Monteiro-Junior, Sylvio


    To assess the resin microtensile bond strength (MTBS) and the monomer conversion (MC) of indirect composite resin restorations made of three different materials. Two light-polymerized direct materials (Filtek Z100 and Premise) and one light- and heat-polymerized indirect material (Premise Indirect) were used. For MTBS testing, 42 cylindrical samples were fabricated (7 pairs per material). Surface conditioning included airborne-particle abrasion, cleaning, and application of a silane. Cylinders were bonded to each other using adhesive resin (Optibond FL). Specimens were stored in water for 24 h. Another 15 cylinders (5 per material) were fabricated for MC measurements (FT-IR) immediately and at 24 h. The MTBS data were submitted to one-way ANOVA and the MC to two-way ANOVA (material and storage time) (α=0.05), followed by post-hoc comparisons with the Tukey test. The MTBS to Z100 was 72.2 MPa, significantly higher than that to Premise (48.4 MPa) and Premise Indirect (52.7 MPa). The immediate MC was similar for all materials (range 51% to 56%) and significantly increased at 24 h (range 57% to 66%), except for Z100. Premise Indirect showed the highest MC (66% at 24 h). Z100 showed better "bondability" than Premise and Premise Indirect. Premise Indirect, with its heat initiator, did not present a higher MC.

  3. A convenient and highly efficient synthesis of one kind of peptide nucleic acid monomer

    Directory of Open Access Journals (Sweden)

    Xuemei Tang


    Full Text Available S-Thyminyl-L-cysteine methyl ester hydrochloride (compound 1, a non-classical peptide nucleic acid monomer, was synthesized through the key intermediate, N-tert- butoxycarbonyl-S-thyminyl-L-cysteine (compound 3, which afforded from the reaction of S-thyminyl-L-cysteine hydrochloride (compound 2 with di-tert-butyl dicarbonate (Boc2O. This was followed by the esterification and deprotection of compound 3 at an overall yield of 82%. The mixture of thionyl chloride and methanol was found as an efficient reagent for simultaneous deprotection of tert-butoxycarbonyl (Boc group and esterification of carboxy group of compound 3. This high-yield two-step method was also applied to other analogues of compound 1 successfully. The chemical structures of four new compounds (5a-5d were confirmed by 1H NMR and 13C NMR.DOI:

  4. Determination of Residual Monomers Released from Soft Lining Materials with the use of HPLC

    Directory of Open Access Journals (Sweden)

    Afrodite Sofou


    Full Text Available A study was carried out to examine the post polymerized leachability of three non phthalic and four phthalic residual monomers, from twelve commercially available soft lining materials, using HPLC. Specimens of equal dimensions were constructed from each brand of material following a standardized procedure and were stored in three different conditions of storage i.e. distilled water, artificial saliva and a binary mixture of ethanol-water, with the resulting liquids providing samples for analysis in the HPLC apparatus. Three different experiments were performed for each brand of material and each condition of storage, in order to examine the parameters time and temperature. The results obtained from this study suggest that a wide spectrum of residues is diffusing out of the twelve examined soft lining materials. The non phthalic compounds were leaching at high concentrations while all the phthalates examined exhibited different degrees of elusion commensurate with the storage condition, brand of material and type of experiment. The main non phthalic component extracted from all the materials was methyl methacrylate, while the mainly extracted phthalic compound was different from each material. The level of elusion seems to be increasing dependent on time, medium of storage, and temperature as well.

  5. The value of quantitative fibrin monomer determination in the early diagnosis of postoperative deep vein thrombosis. (United States)

    Vogel, G; Dempfle, C E; Spannagl, M; Leskopf, W


    A new test for the determination of fibrin monomer in plasma was clinically evaluated in comparison to the plasma concentration of D-D, TAT and F1,2 for the early diagnosis of prethrombotic conditions. For this purpose 129 patients who underwent abdominal surgery were followed longitudinally. 12 patients developed DVT postoperatively, proved by phlebography. The identical specificity level 73.2% was chosen for all 4 tests. At this specificity, FM had the highest sensitivity (91.7%), followed by D-D (75.0%), TAT (41.7%) and F1,2 (33.3%). All FM-positive DVT-patients had pathological FM-values at least one day prior to the clinical manifestation of thrombosis. In a group of 255 obviously healthy persons the cut-off value for the new FM test was determined at 3.6 mg/l (95th percentile). No clinically relevant influence of gender, age, smoking habits or oral anticonception could be observed. It is concluded that FM is a valuable diagnostic tool for the early diagnosis of prethrombotic conditions.

  6. Properties of PHA bi-, ter-, and quarter-polymers containing 4-hydroxybutyrate monomer units. (United States)

    Zhila, Natalia; Shishatskaya, Ekaterina


    The present study investigates physicochemical, mechanical, and biological properties of polyhydroxyalkanoate (PHA) copolymers containing 4-hydroxybutyrate (4HB) synthesized in Cupriavidus eutrophus B10646 culture. In poly(3-hydroxybutyrate/4-hydroxybutyrate) [P(3HB/4HB)] bipolymers, 4HB varied between 10.4 and 75.0 mol%; in poly(3-hydroxybutyrate/3-hydroxyvalerate/4-hydroxybutyrate) terpolymers, 4HB constituted 28.7-55.6 mol%; and in poly(3-hydroxybutyrate/3-hydroxyvalerate/4-hydroxybutyrate/3-hydroxyhexanoate) quaterpolymers, 4HB varied between 9.3 and 13.3 mol%. The degree of crystallinity of P(3HB/4HB) copolymers decreased consistently with an increase in 4HB content, reaching 38%. The incorporation of 3-hydroxyvalerate and 3-hydroxyhexanoate into copolymers enhanced that effect. The effect of 4HB monomer units on temperature properties of copolymers was exhibited as lowering of the melting temperature and crystallization temperature, which improved the processing-related properties of the copolymers. All copolymers containing 4HB showed enhanced elongation at break compared to poly(3-hydroxybutyrate). Polymer films prepared from PHAs with different chemical composition had similar microstructure and porosity and had no toxic effect on mouse fibroblast NIH 3 T3 cells, proving their high biocompatibility. Copyright © 2018 Elsevier B.V. All rights reserved.

  7. HPLC analysis of monomers eluted from self-adhesive resin cements

    Directory of Open Access Journals (Sweden)

    Özgür Genç Şen


    Full Text Available OBJECTIVE: The aim of this study was to determine the residual monomer leaching from two self-adhesive resin cements polymerized with Light Emitting Diode (LED or halogen light curing unit. MATERIALS AND METHOD: Clearfil SA (group A, n = 48 and BisCem (group B, n = 48 cements were inserted in plastic moulds. Each group was further divided into two subgroups. Specimens were light cured with LED light curing unit (LCU in group A1 and group B1 and halogen LCU in group A2 and group B2 for 20 seconds. The following compounds released from the samples stored in distilled water were analyzed: triethylene glycol-dimethacrylate (TEGDMA and bisphenol A glycidyl methacrylate (Bis-GMA. Analysis of substances was performed with the use of high performance liquid chromatography, after 1 hour and 24 hour incubation periods. Factorial experimental design and independent t-test was used for statistical analyses. RESULTS: Self-adhesive resin cements released more Bis-GMA and TEGDMA when they were polymerized with LED LCUs (p0.05. Clearfil SA cement released more Bis-GMA than BisCem (p<0.05. BisCem released more TEGDMA than Clearfil SA (p<0.05. CONCLUSION: The results of this study showed that the quantity of Bis-GMA and TEGDMA leached from self-adhesive resin cements was influenced by the type of LCU and by the type of self-adhesive resin cement.

  8. Response of ethylene propylene diene monomer rubber (EPDM) to simulant Hanford tank waste

    Energy Technology Data Exchange (ETDEWEB)



    This report presents the findings of the Chemical Compatibility Program developed to evaluate plastic packaging components that may be incorporated in packaging mixed-waste forms for transportation. Consistent with the methodology outlined in this report, the author performed the second phase of this experimental program to determine the effects of simulant Hanford tank mixed wastes on packaging seal materials. That effort involved the comprehensive testing of five plastic liner materials in an aqueous mixed-waste simulant. The testing protocol involved exposing the materials to {approximately}143, 286, 571, and 3,670 krad of gamma radiation and was followed by 7-, 14-, 28-, 180-day exposures to the waste simulant at 18, 50, and 60 C. Ethylene propylene diene monomer (EPDM) rubber samples subjected to the same protocol were then evaluated by measuring seven material properties: specific gravity, dimensional changes, mass changes, hardness, compression set, vapor transport rates, and tensile properties. The author has determined that EPDM rubber has excellent resistance to radiation, this simulant, and a combination of these factors. These results suggest that EPDM is an excellent seal material to withstand aqueous mixed wastes having similar composition to the one used in this study.

  9. Large scale nonproton ion release and bacteriorhodopsin's state of aggregation in lipid vesicles. I. Monomers. (United States)

    Marinetti, T


    Light-induced conductivity transients have been observed in preparations of bacteriorhodopsin (bR) in phospholipid vesicles at high lipid/protein molar ratios. Under these conditions, bR is known to be dissolved as monomers in the lipid bilayer. The conductivity transients are due mostly to proton movements, including a trans-membrane component. Kinetic resolution of the conductance change due to proton ionophore-induced leakage through the vesicle membrane provides a novel method to quantitate the number of protons pumped, even in heavily buffered solutions. Some of the transient signal seen on the timescale of the bR photocycle is due to nonproton ions but is smaller than that observed in native purple membranes at pH 7 in low salt. Furthermore, when the pH is raised to 8, the very large transient nonproton ion release seen in purple membranes is not seen in the vesicles. This correlates well with previous results (Marinetti, T., and D. Mauzerall, 1986, Biophys. J., 50:405-415), in which the nonproton ion movements observed with native purple membranes were abolished by solubilization in Triton X-100. Thus, the nonproton ion release appears to be a property of bR in the native aggregated state.

  10. Efficient exploration of large combinatorial chemistry spaces by monomer-based similarity searching. (United States)

    Yu, Ning; Bakken, Gregory A


    In modern drug discovery, 2-D similarity searching is widely employed as a cost-effective way to screen large compound collections and select subsets of molecules that may have interesting biological activity prior to experimental screening. Nowadays, there is a growing interest in applying the existing 2-D similarity searching methods to combinatorial chemistry libraries to search for novel hits or to evolve lead series. A dilemma thus arises when many identical substructures recur in library products and they have to be considered repeatedly in descriptor calculations. The dilemma is exacerbated by the astronomical number of combinatorial products. This problem imposes a major barrier to similarity searching of large combinatorial chemistry spaces. An efficient approach, termed Monomer-based Similarity Searching (MoBSS), is proposed to remedy the problem. MoBSS calculates atom pair (AP) descriptors based on interatomic topological distances, which lend themselves to pair additivity. A fast algorithm is employed in MoBSS to rapidly compute product atom pairs from those of the constituent fragments. The details of the algorithm are presented along with a series of proof-of-concept studies, which demonstrate the speed, accuracy, and utility of the MoBSS approach.

  11. Aβ peptide fibrillar architectures controlled by conformational constraints of the monomer.

    Directory of Open Access Journals (Sweden)

    Kristoffer Brännström

    Full Text Available Anomalous self-assembly of the Aβ peptide into fibrillar amyloid deposits is strongly correlated with the development of Alzheimer's disease. Aβ fibril extension follows a template guided "dock and lock" mechanism where polymerisation is catalysed by the fibrillar ends. Using surface plasmon resonance (SPR and quenched hydrogen-deuterium exchange NMR (H/D-exchange NMR, we have analysed the fibrillar structure and polymerisation properties of both the highly aggregation prone Aβ1-40 Glu22Gly (Aβ(40Arc and wild type Aβ1-40 (Aβ(40WT. The solvent protection patterns from H/D exchange experiments suggest very similar structures of the fibrillar forms. However, through cross-seeding experiments monitored by SPR, we found that the monomeric form of Aβ(40WT is significantly impaired to acquire the fibrillar architecture of Aβ(40Arc. A detailed characterisation demonstrated that Aβ(40WT has a restricted ability to dock and isomerise with high binding affinity onto Aβ(40Arc fibrils. These results have general implications for the process of fibril assembly, where the rate of polymerisation, and consequently the architecture of the formed fibrils, is restricted by conformational constraints of the monomers. Interestingly, we also found that the kinetic rate of fibril formation rather than the thermodynamically lowest energy state determines the overall fibrillar structure.

  12. Phosphorus limitation strategy to increase propionic acid flux towards 3-hydroxyvaleric acid monomers in Cupriavidus necator. (United States)

    Grousseau, Estelle; Blanchet, Elise; Déléris, Stéphane; Albuquerque, Maria G E; Paul, Etienne; Uribelarrea, Jean-Louis


    Properties of polyhydroxybutyrate-co-hydroxyvalerate (P(3HB-co-3HV)) depend on their 3HV content. 3HV can be produced by Cupriavidus necator from propionic acid. Few studies explored carbon distribution and dynamics of 3HV and 3HB monomers production, and none of them have been done with phosphorus as limiting nutrient. In this study, fed-batch cultures of C. necator with propionic acid, as sole carbon source or mixed with butyric acid, were performed. Phosphorus deficiency allowed sustaining 3HV production rate and decreasing 3HB production rate, leading to an instant production of up to 100% of 3HV. When a residual growth is sustained by a phosphorus feeding, the maximum 3HV percentage produced from propionic acid is limited to 33% (Mole.Mole(-1)). The association of a second carbon source like butyric acid lead to higher conversion of propionic acid into 3HV. This study showed the importance of the limiting nutrient and of the culture strategy to get the appropriate product. Copyright © 2013 Elsevier Ltd. All rights reserved.

  13. Water-resistive humidity sensor prepared by printing process using polyelectrolyte ink derived from new monomer. (United States)

    Kim, Min-Ji; Gong, Myoung-Seon


    A simple strategy was developed based on a new monomer containing both photocurable function and ammonium salt, N-(2-cinnamoyloxy)ethyl-N-(2-(methacryloyloxy)ethyl)-N,N-dimethyl ammonium bromide (CMDAB) to obtain photocurable polyelectrolyte ink and stable humidity-sensitive membranes by printing process. Humidity-sensitive membranes are photocrosslinked polyelectrolytes obtained from copolymers of [2-(methacryloyloxy)ethyl] dimethyl propyl ammonium bromide (MEPAB), CMDAB and MMA. A flexible gold electrode/polyimide was pretreated with 2-(mercaptoethyl) cinnamamide (MEC) containing a thiol-coupling agent for the purpose of anchoring the humidity-sensitive polyelectrolyte to the gold electrode. The sensors using screen printing methods reduced the deflection of sensor characteristics showing humidity precision ±1%RH. The photocured copolymer MEPAB/CMDAB/MMA = 63/7/30 show good sensitivity (0.0586 logΩ/%RH) changing resistance approximately four orders of magnitude with relative humidity varying from 20% to 95% and fast response and recovery time. The resultant sensors showed acceptable linearity (Y = -0.04X + 7.0, R(2) = -0.9900) and small hysteresis. The reliability including water resistance and a long-term stability were estimated for the application of the flexible humidity sensor prepared by screen printing process.

  14. 1-O-vinyl glycosides via Tebbe olefination, their use as chiral auxiliaries and monomers. (United States)

    Yuan, Jialong; Lindner, Kristof; Frauenrath, Holger


    A series of anomerically pure 1-O-formyl glycosides 1 was prepared and converted into the corresponding 1-O-vinyl glycosides 2 by Tebbe olefination. The unsubstituted vinyl glycosides were obtained as anomerically pure compounds in good yields, and the method of preparation was compatible with the presence of a variety of functional groups. Remarkably, the anomeric formate group was regioselectively converted into the corresponding olefin in the presence of acetate and benzoate protecting groups. With the perspective to use the 1-O-vinyl glycosides as monomers for the preparation of glycosylated poly(vinyl alcohol) derivatives with controlled tacticity, their scope as chiral auxiliaries for a stereodifferentiation in addition reactions to the olefin function was investigated by using the [2+2] cycloaddition to dichloroketene as a model reaction. In particular, vinyl 2,3,4,6-tetra-O-benzoyl-alpha-d-mannopyranoside (2i) exhibited excellent diastereoselectivity. Finally, the 1-O-vinyl glycosides were successfully subjected to radical homopolymerization in bulk or used as electron-rich comonomers in radical copolymerizations with maleic anhydride, yielding alternating, glycosylated poly(vinyl alcohol-alt-maleic anhydride).

  15. Synergistic inhibition of Haemonchus contortus exsheathment by flavonoid monomers and condensed tannins (United States)

    Klongsiriwet, Chaweewan; Quijada, Jessica; Williams, Andrew R.; Mueller-Harvey, Irene; Williamson, Elizabeth M.; Hoste, Hervé


    This study investigated the separate and combined anthelmintic (AH) effects of different phenolic compounds, including condensed tannins and flavonoids, all of which are known to occur in willow leaves, a potentially valuable dry season feed. A range of contrasting model tannins, which span the whole range of willow tannins, were isolated from tilia flowers, goat willow leaves, black currant leaves and red currant leaves. All together, the tested compounds represented the major tannin types (procyanidins and prodelphinidins) and flavonoid types (flavonols, flavones and flavanones). The larval exsheathment inhibition assay (LEIA) was used to assess their in vitro effects on Haemonchus contortus third stage larvae. Arbutin, vanillic acid, and taxifolin proved to be ineffective whereas naringenin, quercetin and luteolin were highly effective at 250 μM concentrations. Procyanidin (PC) tannins tended to be less active than prodelphinidin tannins (PD). Experiments with combinations of tannins and quercetin or luteolin revealed for the first time the existence of synergistic AH effects between tannins and flavonoid monomers. They also provided evidence that synergistic effects appear to occur at slightly lower concentrations of PC than PD. This suggests that the AH activity of condensed tannins can be significantly enhanced by the addition of quercetin or luteolin. This information may prove useful for plant breeding or selection and for designing optimal feed mixtures. PMID:26199861

  16. Production of bone cement composites: effect of fillers, co-monomer and particles properties

    Energy Technology Data Exchange (ETDEWEB)

    Santos Junior, J.G.F.; Melo, P.A.; Pinto, J.C., E-mail: jjunior@peq.coppe.ufrj.b, E-mail: melo@peq.coppe.ufrj.b, E-mail: pinto@peq.coppe.ufrj.b [Coordenacao dos Programas de Pos-Graduacao de Engenharia. (PEQ/COPPE/UFRJ), RJ (Brazil). Programa de Engenharia Quimica; Pita, V.J.R.R., E-mail: vjpita@ima.ufrj.b [Universidade Federal do Rio de Janeiro (IMA/UFRJ), RJ (Brazil). Inst. de Macromoleculas Eloisa Mano; Nele, M. [Universidade Federal do Rio de Janeiro (EQ/UFRJ), RJ (Brazil). Escola de Quimica


    Artificial bone cements (BCs) based on poly(methyl methacrylate) (PMMA) powders and methyl methacrylate (MMA) liquid monomer also present in their formulation small amounts of other substances, including a chemical initiator compound and radiopaque agents. Because inadequate mixing of the recipe components during the manufacture of the bone cement may compromise the mechanical properties of the final pieces, new techniques to incorporate the fillers into the BC and their effect upon the mechanical properties of BC pieces were investigated in the present study. PMMA powder composites were produced in situ in the reaction vessel by addition of X-ray contrasts to the reacting MMA mixture. It is shown that this can lead to much better mechanical properties of test pieces, when compared to standard bone cement formulations, because enhanced dispersion of the radiopaque agents can be achieved. Moreover, it is shown that the addition of hydroxyapatite (HA) and acrylic acid (AA) to the bone cement recipe can be beneficial for the mechanical performance of the final material. It is also shown that particle morphology can exert a tremendous effect upon the performance of test pieces, indicating that the suspension polymerization step should be carefully controlled when optimization of the bone cement formulation is desired. (author)

  17. Production of bone cement composites: effect of fillers, co-monomer and particles properties

    Directory of Open Access Journals (Sweden)

    J. G. F. Santos Jr.


    Full Text Available Artificial bone cements (BCs based on poly(methyl methacrylate (PMMA powders and methyl methacrylate (MMA liquid monomer also present in their formulation small amounts of other substances, including a chemical initiator compound and radiopaque agents. Because inadequate mixing of the recipe components during the manufacture of the bone cement may compromise the mechanical properties of the final pieces, new techniques to incorporate the fillers into the BC and their effect upon the mechanical properties of BC pieces were investigated in the present study. PMMA powder composites were produced in-situ in the reaction vessel by addition of X-ray contrasts to the reacting MMA mixture. It is shown that this can lead to much better mechanical properties of test pieces, when compared to standard bone cement formulations, because enhanced dispersion of the radiopaque agents can be achieved. Moreover, it is shown that the addition of hydroxyapatite (HA and acrylic acid (AA to the bone cement recipe can be beneficial for the mechanical performance of the final material. It is also shown that particle morphology can exert a tremendous effect upon the performance of test pieces, indicating that the suspension polymerization step should be carefully controlled when optimization of the bone cement formulation is desired.

  18. Copolymers of Vinyl-Containing Benzoxazine with Vinyl Monomers as Precursors for High Performance Thermosets

    Directory of Open Access Journals (Sweden)

    Tsutomu Takeichi


    Full Text Available A benzoxazine containing a vinyl group (P-4va was prepared by the reaction of phenol, 4-vinylaniline, and paraformaldehyde. A differential scanning calorimetry (DSC study revealed that ring-opening polymerization of the benzoxazine and chain polymerization of the vinyl group occurred in the same temperature range. When 2,2'-azobisisobutyronitrile was added as a radical initiator to P-4va, however, only the vinyl groups were polymerized at lower temperature, giving oligo(P-4va that contains pendent benzoxazine units. Radical copolymerization of P-4va with various vinyl monomers such as styrene, methyl methacrylate (MMA, and n-butyl acrylate (BuA was examined. The chemical structure of the copolymers was confirmed by FT-IR and 1H-NMR to be one of polyolefins bearing benzoxazine units as the pendant groups. The weight-average molecular weights of the copolymers determined by size exclusion chromatography were to be in the range of 1900–51,500 depending on the comonomers. DSC of the copolymers showed that the maxima of the exothermic peaks corresponding to the ring-opening polymerization of the pendent benzoxazine units were observed in the temperature range of 229–250 °C. Thermal cure up to 240 °C of the copolymer films afforded homogenous transparent films with improved thermal properties. Tough cured film was obtained by the copolymerization with MMA, while a tough and flexible film was obtained by the copolymerization with BuA.

  19. Monitoring Conformational Landscape of Ovine Prion Protein Monomer Using Ion Mobility Coupled to Mass Spectrometry (United States)

    Van der Rest, Guillaume; Rezaei, Human; Halgand, Frédéric


    Prion protein is involved in deadly neurodegenerative diseases. Its pathogenicity is linked to its structural conversion (α-helix to β-strand transition). However, recent studies suggest that prion protein can follow a plurality of conversion pathways, which hints towards different conformers that might coexist in solution. To gain insights on the plasticity of the ovine prion protein (PrP) monomer, wild type (A136, R154, Q171), mutants and deletions of ARQ were studied by traveling wave ion mobility experiments coupled to mass spectrometry. In order to perform the analysis of a large body of data sets, we designed and evaluated the performance of a processing pipeline based on Driftscope peak detection and a homemade script for automated peak assignment, annotation, and quantification on specific multiply charged protein data. Using this approach, we showed that in the gas phase, PrPs are represented by at least three conformer families differing in both charge state distribution and collisional cross-section, in agreement with the work of Hilton et al. (2010). We also showed that this plasticity is borne both by the N- and C-terminal domains. Effect of protein concentration, pH and temperature were also assessed, showing that (1) pH does not affect conformer distributions, (2) protein concentration modifies the conformational landscape of one mutant (I208M) only, and (3) heating leads to other unfolded species and to a modification of the conformer intensity ratios.

  20. Vegetable oil-derived epoxy monomers and polymer blends: A comparative study with review

    Directory of Open Access Journals (Sweden)

    T. P. Schuman


    Full Text Available Glycidyl esters of epoxidized fatty acids derived from soybean oil (EGS and linseed oil (EGL have been synthesized to have higher oxirane content, more reactivity and lower viscosity than epoxidized soybean oil (ESO or epoxidized linseed oil (ELO. The EGS and ESO, for comparison, were used neat and in blends with diglycidyl ether of bisphenol A (DGEBA. Thermosetting resins were fabricated with the epoxy monomers and either BF3 catalyst or anhydride. The curing behaviors, glass transition temperatures, crosslink densities and mechanical properties were tested. The results indicated that polymer glass transition temperatures were mostly a function of oxirane content with additional influence of glycidyl versus internal oxirane reactivity, pendant chain content, and chemical structure and presence of saturated components. EGS provided better compatibility with DGEBA, improved intermolecular crosslinking and glass transition temperature, and yielded mechanically stronger polymerized materials than materials obtained using ESO. Other benefits of the EGS resin blend systems were significantly reduced viscosities compared to either DGEBA or ESO-blended DGEBA counterparts. Therefore, EGS that is derived from renewable sources has improved potential for fabrication of structural and structurally complex epoxy composites, e.g., by vacuum-assisted resin transfer molding.

  1. Kinetics of the H 2O 2-dependent ligninase-catalyzed oxidation of veratryl alcohol in the presence of cationic surfactant studied by spectrophotometric technique (United States)

    Liu, Airong; Huang, Xirong; Song, Shaofang; Wang, Dan; Lu, Xuemei; Qu, Yinbo; Gao, Peiji


    The kinetics of ligninase-catalyzed oxidation of veratryl alcohol (VA) by H 2O 2 in the aqueous medium containing cationic surfactant cetyltrimethylammonium bromide (CTAB) has been investigated using spectrophotometric technique. Steady-state kinetic studies at different concentrations of CTAB indicate that the reaction follows a ping pong mechanism and the mechanism always holds but the kinetic parameters vary with CTAB concentrations. CTAB is a weak inhibitor for ligninase; it lowers the maximum initial velocity. CTAB also causes the Michaelis constant of H 2O 2 to decrease dramatically and that of VA to increase markedly. Based on the changes in kinetic parameters of the enzyme-catalyzed reaction at different CTAB concentrations (lower than, near to and larger than its critical micelle concentration) and the effects of the CTAB monomer and the micelles on the spectra of VA and its corresponding aldehyde, a conclusion could be made that modification of the enzymatic protein by the surfactant monomer should be responsible for the above-mentioned results.

  2. Langmuir-Blodgett monolayers of cationic dyes in the presence and absence of clay mineral layers: N,N'-dioctadecyl thiacyanine, octadecyl rhodamine B and laponite. (United States)

    Hussain, Syed Arshad; Schoonheydt, Robert A


    Langmuir-Blodgett (LB) films of N,N'-dioctadecyl thiacyanine perchlorate (TC18) and octadecyl rhodamine B chloride (RhB18) and their mixtures in the presence and absence of clay mineral layers were investigated by recording surface pressure-area (pi-A) isotherms and by UV-vis and fluorescence spectroscopies. The pi-A isotherms of TC18, RhB18, and their mixtures are characteristic of liquid expanded state behavior with repulsive interactions between the two cationic dyes. In the presence of laponite, the pi-A isotherms show liquid expanded and condensed-state behavior. In laponite dispersions and in monolayers, TC18 has a strong tendency to aggregate with formation of H- and J- aggregates. The absorption and fluorescence maxima of the monomers in the films are at 435 nm and at 480 nm; H-dimers have an absorption maximum around 410 nm and do not fluoresce. J-dimers are present in all the films with absorption maximum at 461 nm and fluorescence at 463 nm. RhB18 is mainly present as monomers in the LB films with an absorption maximum at 576 nm and fluorescence at 595 nm. Fluorescence resonance energy transfer from TC18 to RhB18 has been observed in clay dispersions and in films with and without laponite. The optimum condition for TC18 --> RhB18 fluorescence energy transfer in the films is 90 mol % TC18 + 10 mol % RhB18.

  3. Conformational alteration in alpha-toxin from Staphylococcus aureus concomitant with the transformation of the water-soluble monomer to the membrane oligomer. (United States)

    Ikigai, H; Nakae, T


    The membrane-damaging alpha-toxin aggregate of Staphylococcus aureus was characterized physicochemically. The aggregate weight of the toxin formed by various methods appeared to be 6 times higher than the molecular weight of the monomer as determined by the laser light scattering technique, suggesting the presence of a hexamer in the membrane. The aggregates fluoresced 20 to 50% more than the monomer at 336 nm. Circular dichroism measurements revealed that both the monomer and the oligomer showed essentially beta-sheet structure with the maximum ellipticity about -8,400 deg.cm2.dmol-1 at 215 nm. Circular dichroism spectrum of the oligomers showed ellipticity difference of -6,600, -44 and +84 deg.cm2.dmol-1, at 200, 250 and 280 nm, respectively, compared with the monomer. All these results suggest that the conformational change in the toxin molecule occurs concomitant with the transformation of the water-soluble monomer to the membrane-embedded hexamer.

  4. The Continuation Study of the Measurement of Residual Monomer from theDenture Base After Three Month Worn by Gas Chromatography on the Radiationand Non Radiation Worker

    International Nuclear Information System (INIS)

    Isyuniarto; Winoto


    Residual monomer measurement on the radiation and non radiation workerafter three month worn the denture has been done. The aim of the research isto investigated residual monomer concentration on after three month worn. Thedenture base material, made of resin acrylic, sometimes is cause mucosairritation in the mouth, and dental irritation or allergic reaction, becauseof residual monomer that left on the mouth cavity. In this research two groupwere needed there are the radiation and non radiation worker, the level ofthe residual monomer count by gas chromatography analysis. The result of thisresearch showed that the level of residual monomer of two group are same orthere have same level of the limit value. The measurement result is in therange of 0.1783 ± 0.011 mg/l to 0.1790 ± 0.004 mg/l. (author)

  5. Cation Exchange in the Presence of Oil in Porous Media. (United States)

    Farajzadeh, R; Guo, H; van Winden, J; Bruining, J


    Cation exchange is an interfacial process during which cations on a clay surface are replaced by other cations. This study investigates the effect of oil type and composition on cation exchange on rock surfaces, relevant for a variety of oil-recovery processes. We perform experiments in which brine with a different composition than that of the in situ brine is injected into cores with and without remaining oil saturation. The cation-exchange capacity (CEC) of the rocks was calculated using PHREEQC software (coupled to a multipurpose transport simulator) with the ionic composition of the effluent histories as input parameters. We observe that in the presence of crude oil, ion exchange is a kinetically controlled process and its rate depends on residence time of the oil in the pore, the temperature, and kinetic rate of adsorption of the polar groups on the rock surface. The cation-exchange process occurs in two stages during two phase flow in porous media. Initially, the charged sites of the internal surface of the clays establish a new equilibrium by exchanging cations with the aqueous phase. At later stages, the components of the aqueous and oleic phases compete for the charged sites on the external surface or edges of the clays. When there is sufficient time for crude oil to interact with the rock (i.e., when the core is aged with crude oil), a fraction of the charged sites are neutralized by the charged components stemming from crude oil. Moreover, the positively charged calcite and dolomite surfaces (at the prevailing pH environment of our experiments) are covered with the negatively charged components of the crude oil and therefore less mineral dissolution takes place when oil is present in porous media.

  6. Radiation-induced cationic polymerization of vinyl ethers in solution

    International Nuclear Information System (INIS)

    Deffieux, A.; Young, J.A.; Hsieh, W.C.; Squire, D.R.; Stannett, V.


    The influences of the polymerization media, the monomer and solvent concentrations and the temperature on the radiation-induced polymerization of isopropyl vinyl ether (IPVE) have been studied in detail under super-dry conditions. Rates of polymerization were measured and estimates of the rate constants of polymerization were calculated according to the simplified Hayashi-Williams equation. A comparison of the results with those previously reported for ethyl vinyl ether (EVE) is made. The much higher reactivity of IPVC in low polar solvents is interpreted by a drastic reduction of the polymer intramolecular solvation of the growing chain ends. This is ascribed to the bulkiness of the isopropyl side-chain groups. The radiation-induced polymerization of IPVE in bulk and in various solvents with different physical and solvating properties was studied. This was to obtain further information on the kinetics and the mechanisms involved with this monomer and also the role of the polymerization media. The influence of the monomer and solvent concentrations and of the polymerization temperature on the rate of polymerization have also been investigated. (author)


    Directory of Open Access Journals (Sweden)

    R. E. Khoma


    Full Text Available The literature data on the thermodynamics of ethanolamines onium cations dissociation have been systematized and generalized. The correlation between these cations dissociation thermodynamic functions (DH and DS and physicochemical properties (Tmp., Tbp, Pp, lgPow et al. has been revealed. There was a correlation between lipophilicity determined experimentally and calculated by QSAR. For monoethanolammonium, diethanolammonium, and their N-methyl and N-ethyl derivatives it was found dissociation thermodynamic functions to depend on bases lgPow. Acid-base dissociation of TRIS and triethanolamine onium cations does not correspond to said relationship because TRIS (primary amine, TEA (tertiary amine act differently on aqueous solutions of SO2. TEA, unlike MEA, DEA and MMEA, has a salting out effect towards sulfur dioxide because of competing hydration that promotes sulfite «onium» salts hydrolysis. TRIS promotes S(IV → S(VI sulphooxidation, in contrast to another ethanolamines. Enthalpy–enthropy compensation with isothermodynamic temperature 303 K has been recorded. The revealed correlations may be useful in developing of procedures for air sanitary cleaning from acidic gases; chemisorbents immobilized for gas and ion exchange chromatography; potentiometric methods for fluorocomplex acids determinations. The use of monoethanolamine is most promising to obtain chemisorbents because the thermodynamic functions of its onium cation acid-base dissociation are least dependent on temperature compared to other etanolammonium cations.

  8. Solid phase graft copolymerization of acrylic monomers onto thermoplastics and their use as blend compatibilizers (United States)

    Subramanian, Srinivas

    This research work is an extension of some of the earlier work done on the development of solid phase grafting technique to graft various monomers onto polymers as well as postulation of the usefulness of the graft copolymers thus synthesized. Polystyrene grafted with acrylic acid, previously developed in bench scale, was synthesized in pilot-plant scale batches. Process parameter studies on the grafting of acrylic acid onto polypropylene and developmental studies on the grafting of maleic anhydride onto polystyrene were also done. Polymers grafted with polar molecules such as maleic anhydride and acrylic acid have been used to compatibilize immiscible blends of polar and non-polar polymers. On the same note, the applicability of the solid phase graft copolymers as blend compatibilizers were investigated and their performance was compared to commercially available compatibilizers. Solid phase graft copolymerization process is a technique to synthesize graft copolymers. Some of its salient features are use of minimal solvent to conduct the reaction and easy equipment modification. It is a low pressure and low temperature process. This technique provides a viable alternative to the environmentally hazardous, and time consuming conventional process currently in use. Hence, development of this technique could be beneficial not only to the plastics industry, but also to mankind. Also, this technique provides a low-cost and extremely easy method to develop graft copolymers such as acrylic acid functionalized polymers that are rapidly gaining popularity as blend compatibilizers and polymer reinforcing agents. A study that proves the potential of these solid phase graft copolymers as good blend compatibilizers for industrially important immiscible polymers will develop interest in the industries about this grafting process. The free radical solid phase graft copolymerization process was carried in a modified Brabender-type mixer fitted with specially designed blades to

  9. Immobilized enzymes in organic media: Chiral monomer production in organic media. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Zemel, H.; Bedwell, B.W.; Kasper, M.; Marinelli, G.


    The overall goals of this project were to investigate the critical factors that limit commercial scale applications of enzymes in organic solvents, and to scale-up a process for the production of a precursor to a specialty polymer. In the last phase of the project, we focused on optimizing and scaling up a trans-esterification reaction catalyzed by Subtilisin Carlsberg in very dry organic solvent. The reaction system we have employed has been reported. It involves the trans-esterification of vinyl acrylate with (R,S)-sec-(2-naphthyl)ethyl alcohol catalyzed by Subtilisin Carlsberg in tert-amyl-alcohol as a solvent. Only the S ester is produced. The other product, vinyl alcohol, converts spontaneously to acetaldehyde, thus shifting the equilibrium towards production of the desired product. The scaled up reaction was run under various conditions in order to identify the controlling factors. We have been able to scale up successfully the trans-esterification reaction from 5ml to 75ml. By varying the immobilization and reaction conditions, we increased the initial rate of the reaction by two orders of magnitude and the conversion from 20% to 100%. We have isolated several grams of the S-sec-(2-naphthyl)ethyl acrylate product. It contains two minor impurities, none of which is the R enantiomer. This and other chiral acrylic monomers could be polymerized to form polymers with special optical properties. In our dry enzymatic trans-esterification system, we found that two factors dominate the observed Subtilisin activity: Iyoprotection and water control. This is in agreement with other reports. Our results are consistent with the observed initial rate affected mostly by changes in the amount of active protease rather than in the enzyme`s intrinsic catalytic rate.

  10. Characterization of γ-radiation induced polymerization in ethyl methacrylate and methyl acrylate monomers solutions (United States)

    Baccaro, Stefania; Casieri, Cinzia; Cemmi, Alessia; Chiarini, Marco; D'Aiuto, Virginia; Tortora, Mariagrazia


    The present work is focused on the γ-radiation induced polymerization of ethyl methacrylate (EMA) and methyl acrylate (MA) monomers mixture to obtain a co-polymer with specific features. The effect of the irradiation parameters (radiation absorbed dose, dose rate) and of the environmental atmosphere on the features of the final products was investigated. Attenuated Total Reflectance - Fourier Transform Infrared Spectroscopy (ATR-FTIR) and Nuclear Magnetic Resonance high-resolution analyses of hydrogen and carbon nuclei (1H and 13C NMR) were applied to follow the γ-induced modifications by monitoring the co-polymerization process and allowed the irradiation parameters optimization. Diffusion-Ordered NMR (DOSY-NMR) data were used to evaluate the co-polymers polydispersity and polymerization degree. Since the last parameter is strongly influenced by the γ radiation and environmental conditions, a comparison among samples prepared and irradiated in air and under nitrogen atmosphere was carried out. In presence of oxygen, higher radiation was required to obtain a full solid co-polymer since a partial amount of energy released to the samples was involved in competitive processes, i.e. oxygen-containing free radicals formation and primary radicals recombination. Irrespectively to the environmental atmosphere, more homogeneous samples in term of polymerization degree dispersion was achieved at lower dose rates. At radiation absorbed doses higher than those needed for the formation of the co-polymer, while in case of samples irradiated in air heavy depolymerization was verified, a sensible increase of the samples stability was attained if the irradiation was performed under nitrogen atmosphere.

  11. Enhanced resin-composite bonding to zirconia framework after pretreatment with selected silane monomers. (United States)

    Matinlinna, Jukka P; Lassila, Lippo V


    To evaluate the effect of five experimental silane monomer primers in vitro on the shear bond strength of a phosphate ester resin-composite cement bonded to a silicatized zirconia framework. A total of 144 planar zirconia (Procera AllZircon) specimens were subjected to tribochemical silica treatment, randomly divided into 12 sub-groups (n=12), and silanized with 1.0%(v/v) activated solutions of 3-acryloxypropyltrimethoxysilane, 3 glycidoxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, styrylethyltrimethoxysilane, and 3-isocyanatopropyltriethoxysilane, which had been prepared in 95% ethanol (pH 4.5). A ready-to-use 3-methacryloxypropyltrimethoxysilane (RelyX™ Ceramic Primer) was used as the control. One resincomposite cement (RelyX™ Unicem) stub was bonded to each silicatized and silanized zirconia specimen. Half of the specimen groups were dry-tested and half were thermo-cycled at 6000 cycles between 5°C and 55°C, with a constant dwelling time of 30s. The shear bond strengths of the cement stubs bonded to zirconia were measured using a universal testing machine using a constant cross-head speed of 1mm/min. The silane primer activation was evaluated using Fourier-transform infrared spectroscopy. The highest shear bond strength was obtained for 3-acryloxypropyltrimethoxysilane in dry storage, 11.7 MPa (SD, 2.3 MPa) and after thermo-cycling 17.6 (4.1) MPa for glycidoxypropyltrimethoxysilane. The lowest shear bond strength values were obtained with control silane: in dry storage, 4.5 (1.3) MPa, after thermo-cycling 6.5 (2.6) MPa. Thermo-cycling increased the bond strengths significantly (ANOVA, psilane (ANOVA, pSilanization with five experimental silane primers in vitro produced significantly greater shear bond strengths than the ready-to-use control silane. Copyright © 2010 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

  12. Generation and characterization of a transgenic pig carrying a DsRed-monomer reporter gene.

    Directory of Open Access Journals (Sweden)

    Chih-Jen Chou

    Full Text Available Pigs are an optimal animal for conducting biomedical research because of their anatomical and physiological resemblance to humans. In contrast to the abundant resources available in the study of mice, few fluorescent protein-harboring porcine models are available for preclinical studies. In this paper, we report the successful generation and characterization of a transgenic DsRed-Monomer porcine model.The transgene comprised a CMV enhancer/chicken-beta actin promoter and DsRed monomeric cDNA. Transgenic pigs were produced by using pronuclear microinjection. PCR and Southern blot analyses were applied for identification of the transgene. Histology, blood examinations and computed tomography were performed to study the health conditions. The pig amniotic fluid progenitor/stem cells were also isolated to examine the existence of red fluorescence and differentiation ability.Transgenic pigs were successfully generated and transmitted to offspring at a germ-line transmission rate of 43.59% (17/39. Ubiquitous expression of red fluorescence was detected in the brain, eye, tongue, heart, lung, liver, pancreas, spleen, stomach, small intestine, large intestine, kidney, testis, and muscle; this was confirmed by histology and western blot analyses. In addition, we confirmed the differentiation potential of amniotic fluid progenitor stem cells isolated from the transgenic pig.This red fluorescent pig can serve as a host for other fluorescent-labeled cells in order to study cell-microenvironment interactions, and can provide optimal red-fluorescent-labeled cells and tissues for research in developmental biology, regenerative medicine, and xenotransplantation.

  13. Final Report: Investigation of Catalytic Pathways for Lignin Breakdown into Monomers and Fuels

    Energy Technology Data Exchange (ETDEWEB)

    Gluckstein, Jeffrey A [ORNL; Hu, Michael Z. [ORNL; Kidder, Michelle [ORNL; McFarlane, Joanna [ORNL; Narula, Chaitanya Kumar [ORNL; Sturgeon, Matthew R [ORNL


    Lignin is a biopolymer that comprises up to 35% of woody biomass by dry weight. It is currently underutilized compared to cellulose and hemicellulose, the other two primary components of woody biomass. Lignin has an irregular structure of methoxylated aromatic groups linked by a suite of ether and alkyl bonds which makes it difficult to degrade selectively. However, the aromatic components of lignin also make it promising as a base material for the production of aromatic fuel additives and cyclic chemical feed stocks such as styrene, benzene, and cyclohexanol. Our laboratory research focused on three methods to selectively cleave and deoxygenate purified lignin under mild conditions: acidolysis, hydrogenation and electrocatalysis. (1) Acidolysis was undertaken in CH2Cl2 at room temperature. (2) Hydrogenation was carried out by dissolving lignin and a rhodium catalyst in 1:1 water:methoxyethanol under a 1 atm H2 environment. (3) Electrocatalysis of lignin involved reacting electrically generated hydrogen atoms at a catalytic palladium cathode with lignin dissolved in a solution of aqueous methanol. In all of the experiments, the lignin degradation products were identified and quantified by gas chromatography mass spectroscopy and flame ionization detection. Yields were low, but this may have reflected the difficulty in recovering the various fractions after conversion. The homogeneous hydrogenation of lignin showed fragmentation into monomers, while the electrocatalytic hydrogenation showed production of polyaromatic hydrocarbons and substituted benzenes. In addition to the experiments, promising pathways for the conversion of lignin were assessed. Three conversion methods were compared based on their material and energy inputs and proposed improvements using better catalyst and process technology. A variety of areas were noted as needing further experimental and theoretical effort to increase the feasibility of lignin conversion to fuels.

  14. Cyclic fatty acid monomers from dietary heated fats affect rat liver enzyme activity. (United States)

    Lamboni, C; Sébédio, J L; Perkins, E G


    This study was conducted to investigate the effects of dietary cyclic fatty acid monomers (CFAM), contained in heated fat from a commercial deep-fat frying operation, on rat liver enzyme activity. A partially hydrogenated soybean oil (PHSBO) used 7 d (7-DH) for frying foodstuffs, or 0.15% methylated CFAM diets was fed to male weanling rats in comparison to a control group fed a nonheated PHSBO (NH) diet in a 10-wk experiment. All diets were isocaloric with 15% fat. Animals fed either CFAM or 7-DH diets showed increased hepatic content of cytochrome (cyt.) b5 and P450 and increased activity of (E.C. NADPH-cyt. P450 reductase in comparison to the control rats. In addition, the activities of (E.C. carnitine palmitoyltransferase-I and (E.C. isocitrate dehydrogenase were significantly decreased when compared to that of rats fed the NH diet. A significantly depressed activity of (E.C. glucose 6-phosphate dehydrogenase was also observed for these animals compared to the control rats fed NH diet. Moreover, liver and microsomal proteins were significantly increased when CFAM or 7-DH diets were fed to animals in comparison to controls while liver glycogen was decreased significantly in experimental groups of rats. The results obtained in this study indicate that the CFAM in the diet from either synthetic sources or used fats increase the activity of liver enzyme systems that detoxify them.

  15. Coxibs interfere with the action of aspirin by binding tightly to one monomer of cyclooxygenase-1

    Energy Technology Data Exchange (ETDEWEB)

    Rimon, Gilad; Sidhu, Ranjinder S.; Lauver, D. Adam; Lee, Jullia Y.; Sharma, Narayan P.; Yuan, Chong; Frieler, Ryan A.; Trievel, Raymond C.; Lucchesi, Benedict R.; Smith, William L. (Michigan)


    Pain associated with inflammation involves prostaglandins synthesized from arachidonic acid (AA) through cyclooxygenase-2 (COX-2) pathways while thromboxane A{sub 2} formed by platelets from AA via cyclooxygenase-1 (COX-1) mediates thrombosis. COX-1 and COX-2 are both targets of nonselective nonsteroidal antiinflammatory drugs (nsNSAIDs) including aspirin whereas COX-2 activity is preferentially blocked by COX-2 inhibitors called coxibs. COXs are homodimers composed of identical subunits, but we have shown that only one subunit is active at a time during catalysis; moreover, many nsNSAIDS bind to a single subunit of a COX dimer to inhibit the COX activity of the entire dimer. Here, we report the surprising observation that celecoxib and other coxibs bind tightly to a subunit of COX-1. Although celecoxib binding to one monomer of COX-1 does not affect the normal catalytic processing of AA by the second, partner subunit, celecoxib does interfere with the inhibition of COX-1 by aspirin in vitro. X-ray crystallographic results obtained with a celecoxib/COX-1 complex show how celecoxib can bind to one of the two available COX sites of the COX-1 dimer. Finally, we find that administration of celecoxib to dogs interferes with the ability of a low dose of aspirin to inhibit AA-induced ex vivo platelet aggregation. COX-2 inhibitors such as celecoxib are widely used for pain relief. Because coxibs exhibit cardiovascular side effects, they are often prescribed in combination with low-dose aspirin to prevent thrombosis. Our studies predict that the cardioprotective effect of low-dose aspirin on COX-1 may be blunted when taken with coxibs.

  16. Colorimetric Detection of Some Highly Hydrophobic Flavonoids Using Polydiacetylene Liposomes Containing Pentacosa-10,12-diynoyl Succinoglycan Monomers (United States)

    Yun, Deokgyu; Jeong, Daham; Cho, Eunae; Jung, Seunho


    Flavonoids are a group of plant secondary metabolites including polyphenolic molecules, and they are well known for antioxidant, anti-allergic, anti-inflammatory and anti-viral propertied. In general, flavonoids are detected with various non-colorimetric detection methods such as column liquid chromatography, thin-layer chromatography, and electrochemical analysis. For the first time, we developed a straightforward colorimetric detection system allowing recognition of some highly hydrophobic flavonoids such as alpha-naphthoflavone and beta-naphthoflavone, visually using 10,12-pentacosadiynoic acid (PCDA) derivatized with succinoglycan monomers isolated from Sinorhizobium meliloti. Besides changes in visible spectrum, we also demonstrate fluorescence changes using our detection system in the presence of those flavonoids. The succinoglycan monomers attached to PCDA molecules may function as an unstructured molecular capturer for some highly hydrophobic flavonoids by hydrophobic interactions, and transmit their molecular interactions as a color change throughout the PCDA liposome. PMID:26600071

  17. Effect of the hardener to epoxy monomer ratio on the water absorption behavior of the DGEBA/TETA epoxy system

    Directory of Open Access Journals (Sweden)

    Ayrton Alef Castanheira Pereira


    Full Text Available Abstract The water absorption behavior of the DGEBA/TETA epoxy system was evaluated as a function of the epoxy monomer to amine hardener ratio. Weight gain versus immersion time curves were obtained and the experimental points were fitted using Fickian and Non-Fickian diffusion models. The results obtained showed that for all epoxy monomer to hardener ratios analyzed water diffusion followed non-Fickian behavior. It was possible to correlate the water absorption behavior to the macromolecular structure developed when the epoxy/ hardener ratio was varied. All epoxy/hardener ratios present a two-phase macromolecular structure, composed of regions with high crosslink density and regions with lower crosslinking. Epoxy rich systems have a more open macromolecular structure with a lower fraction of the dense phase than the amine rich systems, which present a more compact two-phase structure.

  18. Luminescent molecular hybrid system derived from 2-furancarboxylic acid and silylated monomer coordinated to rare earth ions

    International Nuclear Information System (INIS)

    Sui Yulong; Yan Bing


    In this study, silica-based organic-inorganic hybrids were prepared by the sol-gel method. Tetraethoxysilane (abbreviated as TEOS) and a kind of monomer (abbreviated as FA-APES) derived from modified 2-furancarboxylic acid (abbreviated as FA) with (3-aminopropyl)triethoxysilane (abbreviated as APES) were used as the inorganic and organic fragments, respectively. Coordination reaction between lanthanides (europium and terbium ions) and -C=O group of the monomer happened simultaneously. And after days of aging process the resultant materials showed characteristic luminescence of lanthanides. The enhancement of luminescence can be seen by the comparison with simply doped lanthanide hybrid systems. And it can be explained by the coordination ability of the organic counterpart. IR, NMR, UV-vis absorption, low-temperature phosphorescence spectroscopy and fluorescence spectroscopy were applied to characterize and the above spectroscopic data revealed that the triplet state energy of organic ligand matches with the emissive energy level of lanthanides (especially of Tb 3+ )

  19. Development of PNTDs synthesized from monomers with different molecular length and analysis of molecular damages by heavy ion

    International Nuclear Information System (INIS)

    Kawashima, Hajime; Kodaira, Satoshi; Ihara, Daisuke; Yasuda, Nakahiro; Kusumoto, Tamon; Mori, Yutaka; Yamauchi, Tomoya; Kobayashi, Keiichi; Benton, Eric


    Our interests for years lay to investigate the reason why CR-39 polymer has such high sensitivity as plastic nuclear track detector (PNTD) on chemical structural aspects. We developed three PNTDs from three diacrylate compounds as monomers bearing different molecular length as well as different numbers of internal ether bonds. The polymer products obtained were colorless and transparent with 3-D molecular structures as CR-39 and different lattice structures each other. Our purpose of the current study was to investigate structural damages caused in newly prepared PNTDs and CR-39 by irradiation of Nitrogen ion (6 MeV/n, fluence of 5 x 10 11 cm -2 ). The structural damage by irradiation was analyzed by the magnitude of the relative absorbance of specific functional groups such as ester, C=O, ether and C-H bonds by means of FT-IR (ATR) method. The correlation between the relative absorbance and the molecular length of the monomers were discussed. (author)

  20. Comparison contemporary methods of regeneration sodium-cationic filters (United States)

    Burakov, I. A.; Burakov, A. Y.; Nikitina, I. S.; Verkhovsky, A. E.; Ilyushin, A. S.; Aladushkin, S. V.


    Regeneration plays a crucial role in the field of efficient application sodium-cationic filters for softening the water. Traditionally used as regenerant saline NaCl. However, due to the modern development of the energy industry and its close relationship with other industrial and academic sectors the opportunity to use in the regeneration of other solutions. The report estimated data and application possibilities as regenerant solution sodium-cationic filters brine wells a high mineral content, as both primary application and after balneotherapeutic use reverse osmosis and concentrates especially recycled regenerant water repeated. Comparison of the effectiveness of these solutions with the traditional use of NaCl. Developed and tested system for the processing of highly mineralized brines wells after balneological use. Recommendations for use as regeneration solutions for the sodium-cationic unit considered solutions and defined rules of brine for regeneration costs.