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Sample records for surface-initiated living radical

  1. "Living" free radical photopolymerization initiated from surface-grafted iniferter monolayers

    NARCIS (Netherlands)

    de Boer, B.; Simon, H.K.; Werts, M.P L; van der Vegte, E.W.; Hadziioannou, G

    2000-01-01

    A method for chemically modifying a surface with grafted monolayers of initiator groups, which can be used for a "living" free radical photopolymerization, is described. By using "living" free radical polymerizations, we were able to control the length of the grafted polymer chains and therefore the

  2. Functionalized polymer film surfaces via surface-initiated atom transfer radical polymerization

    International Nuclear Information System (INIS)

    Hu, Y.; Li, J.S.; Yang, W.T.; Xu, F.J.

    2013-01-01

    The ability to manipulate and control the surface properties of polymer films, without altering the substrate properties, is crucial to their wide-spread applications. In this work, a simple one-step method for the direct immobilization of benzyl chloride groups (as the effective atom transfer radical polymerization (ATRP) initiators) on the polymer films was developed via benzophenone-induced coupling of 4-vinylbenzyl chloride (VBC). Polyethylene (PE) and nylon films were selected as examples of polymer films to illustrate the functionalization of film surfaces via surface-initiated ATRP. Functional polymer brushes of (2-dimethylamino)ethyl methacrylate, sodium 4-styrenesulfonate, 2-hydroxyethyl methacrylate and glycidyl methacrylate, as well as their block copolymer brushes, have been prepared via surface-initiated ATRP from the VBC-coupled PE or nylon film surfaces. With the development of a simple approach to the covalent immobilization of ATRP initiators on polymer film surfaces and the inherent versatility of surface-initiated ATRP, the surface functionality of polymer films can be precisely tailored. - Highlights: ► Atom transfer radical polymerization initiators were simply immobilized. ► Different functional polymer brushes were readily prepared. ► Their block copolymer brushes were also readily prepared

  3. Macromolecular Architectures Designed by Living Radical Polymerization with Organic Catalysts

    Directory of Open Access Journals (Sweden)

    Miho Tanishima

    2014-01-01

    Full Text Available Well-defined diblock and triblock copolymers, star polymers, and concentrated polymer brushes on solid surfaces were prepared using living radical polymerization with organic catalysts. Polymerizations of methyl methacrylate, butyl acrylate, and selected functional methacrylates were performed with a monofunctional initiator, a difunctional initiator, a trifunctional initiator, and a surface-immobilized initiator.

  4. Surface-initiated Atom Transfer Radical Polymerization - a Technique to Develop Biofunctional Coatings

    DEFF Research Database (Denmark)

    Fristrup, Charlotte Juel; Jankova Atanasova, Katja; Hvilsted, Søren

    2009-01-01

    The initial formation of initiating sites for atom transfer radical polymerization (ATRP) on various polymer surfaces and numerous inorganic and metallic surfaces is elaborated. The subsequent ATRP grafting of a multitude of monomers from such surfaces to generate thin covalently linked polymer...

  5. Radical Initiated Hydrosilylation on Silicon Nanocrystal Surfaces: An Evaluation of Functional Group Tolerance and Mechanistic Study.

    Science.gov (United States)

    Yang, Zhenyu; Gonzalez, Christina M; Purkait, Tapas K; Iqbal, Muhammad; Meldrum, Al; Veinot, Jonathan G C

    2015-09-29

    Hydrosilylation is among the most common methods used for modifying silicon surface chemistry. It provides a wide range of surface functionalities and effective passivation of surface sites. Herein, we report a systematic study of radical initiated hydrosilylation of silicon nanocrystal (SiNC) surfaces using two common radical initiators (i.e., 2,2'-azobis(2-methylpropionitrile) and benzoyl peroxide). Compared to other widely applied hydrosilylation methods (e.g., thermal, photochemical, and catalytic), the radical initiator based approach is particle size independent, requires comparatively low reaction temperatures, and yields monolayer surface passivation after short reaction times. The effects of differing functional groups (i.e., alkene, alkyne, carboxylic acid, and ester) on the radical initiated hydrosilylation are also explored. The results indicate functionalization occurs and results in the formation of monolayer passivated surfaces.

  6. “Living” Free Radical Photopolymerization Initiated from Surface-Grafted Iniferter Monolayers

    NARCIS (Netherlands)

    Boer, B. de; Simon, H.K.; Werts, M.P.L.; Vegte, E.W. van der; Hadziioannou, G.

    2000-01-01

    A method for chemically modifying a surface with grafted monolayers of initiator groups, which can be used for a “living” free radical photopolymerization, is described. By using “living” free radical polymerizations, we were able to control the length of the grafted polymer chains and therefore the

  7. On Surface-Initiated Atom Transfer Radical Polymerization Using Diazonium Chemistry To Introduce the Initiator Layer

    DEFF Research Database (Denmark)

    Iruthayaraj, Joseph; Chernyy, Sergey; Lillethorup, Mie

    2011-01-01

    This work features the controllability of surface-initiated atom transfer radical polymerization (SI-ATRP) of methyl methacrylate, initiated by a multilayered 2-bromoisobutyryl moiety formed via diazonium chemistry. The thickness as a function of polymerization time has been studied by varying di...

  8. Experimental study of living free radical polymerization using trifunctional initiator and polymerization mediated by nitroxide

    International Nuclear Information System (INIS)

    Galhardo, Eduardo; Lona, Liliane M.F.

    2009-01-01

    Controlled free radical polymerization or living free radical polymerization has received increasing attention as a technique for the production of polymers with microstructure highly controlled. In particular, narrow molecular weight distributions are obtained with polydispersity very close to one. In this research it was investigate the controlled polymerization mediated by nitroxide, using a cyclic trifunctional peroxide. As long as we know, there are only publications in literature dealing with NMRP using mono- and bi-functional initiators. It was believed that the trifunctional peroxide can increase the rate of polymerization, since more free radicals are generated, if compared with initiators with lower functionality. Furthermore, the fact of the initiator be cyclic means that branches are not generated in the chains, which theoretically prevents an increase in polydispersity of the polymer. The effect of the dissociation constant of the trifunctional initiator in the velocity of the reaction was analyzed. (author)

  9. In Situ Investigation of Electrochemically Mediated Surface-Initiated Atom Transfer Radical Polymerization by Electrochemical Surface Plasmon Resonance.

    Science.gov (United States)

    Chen, Daqun; Hu, Weihua

    2017-04-18

    Electrochemically mediated atom transfer radical polymerization (eATRP) initiates/controls the controlled/living ATRP chain propagation process by electrochemically generating (regenerating) the activator (lower-oxidation-state metal complex) from deactivator (higher-oxidation-state metal complex). Despite successful demonstrations in both of the homogeneous polymerization and heterogeneous systems (namely, surface-initiated ATRP, SI-ATRP), the eATRP process itself has never been in situ investigated, and important information regarding this process remains unrevealed. In this work, we report the first investigation of the electrochemically mediated SI-ATRP (eSI-ATRP) by rationally combining the electrochemical technique with real-time surface plasmon resonance (SPR). In the experiment, the potential of a SPR gold chip modified by the self-assembled monolayer of the ATRP initiator was controlled to electrochemically reduce the deactivator to activator to initiate the SI-ATRP, and the whole process was simultaneously monitored by SPR with a high time resolution of 0.1 s. It is found that it is feasible to electrochemically trigger/control the SI-ATRP and the polymerization rate is correlated to the potential applied to the gold chip. This work reveals important kinetic information for eSI-ATRP and offers a powerful platform for in situ investigation of such complicated processes.

  10. Fabrication of Robust and Antifouling Superhydrophobic Surfaces via Surface-Initiated Atom Transfer Radical Polymerization.

    Science.gov (United States)

    Xue, Chao-Hua; Guo, Xiao-Jing; Ma, Jian-Zhong; Jia, Shun-Tian

    2015-04-22

    Superhydrophobic surfaces were fabricated via surface-initiated atom transfer radical polymerization of fluorinated methacrylates on poly(ethylene terephthalate) (PET) fabrics. The hydrophobicity of the PET fabric was systematically tunable by controlling the polymerization time. The obtained superhydrophobic fabrics showed excellent chemical robustness even after exposure to different chemicals, such as acid, base, salt, acetone, and toluene. Importantly, the fabrics maintained superhydrophobicity after 2500 abrasion cycles, 100 laundering cycles, and long time exposure to UV irradiation. Also, the surface of the superhydrophobic fabrics showed excellent antifouling properties.

  11. Fast Resonance Raman Spectroscopy of Short-Lived Radicals

    DEFF Research Database (Denmark)

    Pagsberg, Palle Bjørn; Wilbrandt, Robert Walter; Hansen, Karina Benthin

    1976-01-01

    We report the first application of pulsed resonance Raman spectroscopy to the study of short-lived free radicals produced by pulse radiolysis. A single pulse from a flash-lamp pumped tunable dye laser is used to excite the resonance Raman spectrum of the p-terphenyl anion radical with an initial...

  12. Hydrophilization of poly(ether ether ketone) films by surface-initiated atom transfer radical polymerization

    DEFF Research Database (Denmark)

    Fristrup, Charlotte Juel; Jankova Atanasova, Katja; Hvilsted, Søren

    2010-01-01

    Surface-Initiated Atom Transfer Radical Polymerization (SI-ATRP) has been exploited to hydrophilize PEEK. The ketone groups on the PEEK surface were reduced to hydroxyl groups which were converted to bromoisobutyrate initiating sites for SI-ATRP. The modification steps were followed by contact...... angle measurements and XPS. Moreover, ATR FTIR has been used to confirm the formation of initiating groups. Grafting of PEGMA from PEEK was performed in aqueous solution. The presence of the PPEGMA grafts on PEEK was revealed by the thermograms from TGA whereas investigations with AFM rejected changes...

  13. Living atom transfer radical polymerization of 4-acetoxystyrene

    DEFF Research Database (Denmark)

    Gao, Bo; Chen, Xianyi; Ivan, Bela

    1997-01-01

    Living atom transfer radical polymerization (ATRP) of 4-acetoxystyrene (1), a protected 4-vinylphenol, leading to poly(4-acetoxystyrene) with well-defined molecular weight and narrow molecular weight distribution was carried out in bulk with a,a'-dibromoxylene(2)/CuBr/2,2-bipyridine(bpy) as initi......Living atom transfer radical polymerization (ATRP) of 4-acetoxystyrene (1), a protected 4-vinylphenol, leading to poly(4-acetoxystyrene) with well-defined molecular weight and narrow molecular weight distribution was carried out in bulk with a,a'-dibromoxylene(2)/CuBr/2,2-bipyridine......(bpy) as initiating system. A linear (M) over bar(n), versus monomer conversion plot was found in good accordance with the theoretical line, indicating 100% initiating efficiency. The polymerization is first order in respect to monomer up to about 70% monomer conversion. Deviations from linearity at higher conversion...

  14. Nitroxide-Mediated Radical Polymerization of Styrene Initiated from the Surface of Titanium Oxide Nanoparticles

    Directory of Open Access Journals (Sweden)

    M. Abbasian

    2016-01-01

    Full Text Available Titanium dioxide (TiO2 nanoparticles, with an average size of about 45 nm, were encapsulated by polystyrene using in situ nitroxide mediated radical polymerization   in the presence of 3-aminopropyl triethoxy silane (APTES as a coupling agent and 2, 2, 6, 6-tetramethylpiperidinyl-1-oxy  as a initiator. First, the initiator for NMRP was covalently bonded onto the surface of Titanium dioxide nanoparticles through our novel method. For this purpose, the surface of TiO2 nanoparticle was treated with 3-aminopropyl triethoxy silane, a silane coupling agent, and then these functionalized nanoparticles was reacted with ±-chloro phenyl acetyl chloride. The chlorine groups were converted to nitroxide mediated groups by coupling with 1-hydroxy-2, 2, 6, 6-tetramethyl piperidine. These modified TiO2 nanoparticles were then dispersed in styrene (St monomers to carry out the in situ free radical polymerization.

  15. Surface modification of thermoplastic poly(vinyl alcohol)/saponite nanocomposites via surface-initiated atom transfer radical polymerization enhanced by air dielectric discharges barrier plasma treatment

    International Nuclear Information System (INIS)

    Zhen Weijun; Lu Canhui

    2012-01-01

    To improve the water resistance of thermoplastic poly(vinyl alcohol)/saponite nanocomposites (TPVA), a simple two-step method was developed for the covalent immobilization of atom transfer radical polymerization (ATRP) initiators on the TPVA surfaces enhanced by air dielectric barrier discharges (DBD) plasma treatment, and hydrophobic poly(methyl methacrylate) (PMMA) brushes were then grafted onto the surface of TPVA via surface-initiated atom transfer radical polymerization (SI-ATRP). The chemical composition, morphology and hydrophobicity of the modified TPVA surfaces were characterized by X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM), respectively. The water resistance of the surface-functionalized PMMA was evaluated by the contact angle and water adsorption method. It was shown that air DBD plasma treatment activated the TPVA surface and accelerated the immobilization of ATRP initiator on the TPVA surface. Compared with TPVA control, TPVA modified by SI-ATRP can be grafted well-defined and covalently tethered network PMMA brushes onto the surface and the hydrophobicity of TPVA were significantly enhanced.

  16. Polymer coating comprising 2-methoxyethyl acrylate units synthesized by surface-initiated atom transfer radical polymerization

    DEFF Research Database (Denmark)

    2011-01-01

    Source: US2012184029A The present invention relates to preparation of a polymer coating comprising or consisting of polymer chains comprising or consisting of units of 2-methoxyethyl acrylate synthesized by Surface-Initiated Atom Transfer Radical Polymerization (SI ATRP) such as ARGET SI ATRP...

  17. Ternary hybrid polymeric nanocomposites through grafting of polystyrene on graphene oxide-TiO_2 by surface initiated atom transfer radical polymerization (SI-ATRP)

    International Nuclear Information System (INIS)

    Kumar, Arvind; Bansal, Ankushi; Behera, Babita; Jain, Suman L.; Ray, Siddharth S.

    2016-01-01

    A ternary hybrid of graphene oxide-titania-polystyrene (GO-TiO_2-PS) nanocomposite is developed where polystyrene composition is regulated by controlling growth of polymer chains and nanoarchitectonics is discussed. Graphene Oxide-TiO_2 (GO-TiO_2) nanocomposite is prepared by in-situ hydrothermal method and the surface is anchored with α-bromoisobutyryl bromide to activate GO-TiO_2 as initiator for polymerization. In-situ grafting of polystyrene through surface initiated atom transfer radical polymerization (SI- ATRP) on this Br-functionalized nano-composite initiator yields GO-TiO_2-PS ternary hybrid. Varying the monomer amount and keeping the concentration of initiator constant, polystyrene chain growth is regulated with narrow poly-dispersivity to achieve desired composition. This composite is well characterized by various analytical techniques like FTIR, XRD, DSC, SEM, TEM, and TGA. - Highlights: • Nanocomposite of ternary hybrid of GO-TiO_2 with polystyrene. • PS is surface grafted on GO-TiO_2. • Polymer chain lengths are well regulated by SI-ATRP living polymerization. • Thermal stability of this hybrid is relatively high.

  18. In situ AFM investigation of electrochemically induced surface-initiated atom-transfer radical polymerization.

    Science.gov (United States)

    Li, Bin; Yu, Bo; Zhou, Feng

    2013-02-12

    Electrochemically induced surface-initiated atom-transfer radical polymerization is traced by in situ AFM technology for the first time, which allows visualization of the polymer growth process. It affords a fundamental insight into the surface morphology and growth mechanism simultaneously. Using this technique, the polymerization kinetics of two model monomers were studied, namely the anionic 3-sulfopropyl methacrylate potassium salt (SPMA) and the cationic 2-(metharyloyloxy)ethyltrimethylammonium chloride (METAC). The growth of METAC is significantly improved by screening the ammonium cations by the addition of ionic liquid electrolyte in aqueous solution. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Surface-Initiated Graft Atom Transfer Radical Polymerization of Methyl Methacrylate from Chitin Nanofiber Macroinitiator under Dispersion Conditions

    Directory of Open Access Journals (Sweden)

    Ryo Endo

    2015-08-01

    Full Text Available Surface-initiated graft atom transfer radical polymerization (ATRP of methyl methacrylate (MMA from self-assembled chitin nanofibers (CNFs was performed under dispersion conditions. Self-assembled CNFs were initially prepared by regeneration from a chitin ion gel with 1-allyl-3-methylimidazolium bromide using methanol; the product was then converted into the chitin nanofiber macroinitiator by reaction with α-bromoisobutyryl bromide in a dispersion containing N,N-dimethylformamide. Surface-initiated graft ATRP of MMA from the initiating sites on the CNFs was subsequently carried out under dispersion conditions, followed by filtration to obtain the CNF-graft-polyMMA film. Analysis of the product confirmed the occurrence of the graft ATRP on the surface of the CNFs.

  20. Leghemoglobin-derived radicals. Evidence for multiple protein-derived radicals and the initiation of peribacteroid membrane damage

    DEFF Research Database (Denmark)

    Moreau, S; Davies, Michael Jonathan; Mathieu, C

    1996-01-01

    , with the consequent generation of lipid-derived radicals. The formation of such radicals may result in the depletion of membrane antioxidants and the initiation of lipid peroxidation. This transfer of damage from the heme center via the protein surface to neighboring membranes may be of considerable biological......-derived phenoxyl radical present at Tyr-133 in the soybean protein and Tyr-138 in the lupin protein. To obtain further information on these protein radicals and their potential interaction with the physiologically important peribacteroid membrane (which surrounds the microsymbiont in vivo), EPR spin trapping......); these radicals may be side chain- or alpha-carbon-derived, their exact sites have not been determined. Some of these radicals are on the protein surface and may be key intermediates in the formation of protein dimers. These radicals have been shown to be capable of reacting with peribacteroid membrane fractions...

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

    Science.gov (United States)

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

    2017-12-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2009-08-01

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

  3. Radiation-initiated free-radical fragmentation of biologically active glycerides

    International Nuclear Information System (INIS)

    Akhrem, A.A.; Kisel', M.A.; Shadyro, O.I.; Yurkova, I.L.

    1993-01-01

    Oxidation reactions of the free-radical type play a decisive role in the initial processes of radiation damage. The most suitable substrates for such reactions are lipids. Lipids are a basic structural element of biomembranes and are involved in the barrier function and biocatalytic activity of such membranes. Free-radical degradation of membrane lipids can lead to serious damage and ultimately to destruction of the living cell. A well-studied type of free-radical conversion of lipids is oxidation of polyunsaturated fatty acid residues, so-called peroxide oxidation of lipids. In this paper, using as examples dimyristoylphosphatidyl glycerol (DMPG), monoglycerides, and glycerophosphate, the authors investigated the possibility of free-radical degradation in compounds of a lipid nature containing the α,β-bifunctional group

  4. Ternary hybrid polymeric nanocomposites through grafting of polystyrene on graphene oxide-TiO{sub 2} by surface initiated atom transfer radical polymerization (SI-ATRP)

    Energy Technology Data Exchange (ETDEWEB)

    Kumar, Arvind; Bansal, Ankushi; Behera, Babita; Jain, Suman L.; Ray, Siddharth S., E-mail: ssray@iip.res.in

    2016-04-01

    A ternary hybrid of graphene oxide-titania-polystyrene (GO-TiO{sub 2}-PS) nanocomposite is developed where polystyrene composition is regulated by controlling growth of polymer chains and nanoarchitectonics is discussed. Graphene Oxide-TiO{sub 2} (GO-TiO{sub 2}) nanocomposite is prepared by in-situ hydrothermal method and the surface is anchored with α-bromoisobutyryl bromide to activate GO-TiO{sub 2} as initiator for polymerization. In-situ grafting of polystyrene through surface initiated atom transfer radical polymerization (SI- ATRP) on this Br-functionalized nano-composite initiator yields GO-TiO{sub 2}-PS ternary hybrid. Varying the monomer amount and keeping the concentration of initiator constant, polystyrene chain growth is regulated with narrow poly-dispersivity to achieve desired composition. This composite is well characterized by various analytical techniques like FTIR, XRD, DSC, SEM, TEM, and TGA. - Highlights: • Nanocomposite of ternary hybrid of GO-TiO{sub 2} with polystyrene. • PS is surface grafted on GO-TiO{sub 2}. • Polymer chain lengths are well regulated by SI-ATRP living polymerization. • Thermal stability of this hybrid is relatively high.

  5. Controlled Grafting of Poly(methyl methacrylate) Brushes on Poly(vinylidene fluoride) Powders by Surface-initiated Atom Transfer Radical Polymerization

    Institute of Scientific and Technical Information of China (English)

    TANG Zhaoqi; LI Wei; LIU Lanqin; HUANG Lei; ZHOU Jin; YU Haiyin

    2009-01-01

    Controlled grafting of well-defined polymer brushes of methyl methacrylate (MMA) on the poly(vinylidene fluoride) (PVDF) powders was carded out by the surface-initiated atom transfer radical polymerization (ATRP). The ATRP initiator was anchored on the PVDF surface by alkaline treatment, followed by UV-induced bromination; then methyl methacrylate (MMA) was grafted onto the brominated PVDF by the ATRP technique. The chemical composition changes of PVDF were characterized by Fourier transform-infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS). FT-IR and XPS results clearly indicated the successful graft of poly(methyl methacrylate) onto the PVDF surface.

  6. Surface-Initiated Atom Transfer Radical Polymerization and Electrografting Technique as a Means For Attaining Tailor-Made Polymer Coatings

    DEFF Research Database (Denmark)

    Chernyy, Sergey

    2012-01-01

    strategies for initiator grafting, physicochemical properties of polymer brushes and basic principles of quartz crystal microbalance technique (QCM) are discussed. In Chapter 2 various ATRP conditions are probed. The effects of solvent polarity, monomer concentration, initiator surface density, ligand nature......Atom transfer radical polymerization initiated from a surface of various substrates (SI-ATRP) has become a progressively popular technique for obtaining thin polymer films with predetermined properties. The present work addresses the main features of SI-ATRP with respect to the controllability...... and temperature on the kinetics of methyl methacrylate polymerization are elucidated. The strategy was based on the observation of dry polymer thickness versus time evolution by means of ellipsometry, profilometry and IR spectroscopy. An alternative approach, constituting Chapter 3, was based on optimization...

  7. Surface reactivity of Ge[111] for organic functionalization by means of a radical-initiated reaction: A DFT study

    Energy Technology Data Exchange (ETDEWEB)

    Rubio-Pereda, Pamela, E-mail: rubio.pereda@gmail.com [Centro de Investigación Científica y de Educación Superior de Ensenada 3918, Código Postal 22860, Ensenada, Baja California (Mexico); Takeuchi, Noboru, E-mail: takeuchi@cnyn.unam.mx [Centro de Nanociencias y Nanotecnología, Universidad Nacional Autónoma de México, Apartado Postal 14, Código Postal 22800, Ensenada, Baja California (Mexico)

    2016-08-30

    Highlights: • The surface reactivity of the Ge [111] surface is studied with DFT for the attachment of organic molecules by means of a radical-initiated reaction. • A hydrogen vacancy in the hydrogen terminated Ge [111] surface exhibits an accumulation of charge and electron pairing. • These characteristics make the hydrogen vacancy less reactive for the attachment of unsaturated organic molecules. • The adsorption of acetylene is probable to occur while the adsorption of ethylene and styrene is substantially less probable to occur. • The hydrogen terminated Ge [111] surface is found to be less reactive than its two-dimensional analogue, the hydrogen-terminated germanene. - Abstract: The study of interfacial chemistry at semiconductor surfaces has become an important area of research. Functionalities such as molecular recognition, biocompatibility of surfaces, and molecular computing, could be achieved by the combinations of organic chemistry with the semiconductor technology. One way to accomplish this goal is by means of organic functionalization of semiconductor surfaces such as the bulk-terminated germanium surfaces, more specifically the Ge[111]. In this work, we theoretically study, by applying density functional theory, the surface reactivity of the bulk-terminated Ge[111] surface for organic functionalization by means of a radical-initiated reaction of unsaturated molecules such as acetylene, ethylene and styrene with a hydrogen vacancy on a previously hydrogen-terminated Ge[111] surface. Results derived from this work are compared with those obtained in our previous calculations on the germanene surface, following the same chemical route. Our calculations show an accumulation of electronic charge at the H-vacancy having as a result electron pairing due to strong lattice-electron coupling and therefore a diminished surface reactivity. Calculation of the transition states for acetylene and ethylene indicates that the surface reactivity of the

  8. Crystalline TiO2 grafted with poly(2-methacryloyloxyethyl phosphorylcholine) via surface-initiated atom-transfer radical polymerization

    International Nuclear Information System (INIS)

    Zhao Yuancong; Tu Qiufen; Wang Jin; Huang Qiongjian; Huang Nan

    2010-01-01

    Crystalline TiO 2 films were prepared by unbalanced magnetron sputtering and the structure was confirmed by XRD. An organic layer of 11-hydroxyundecylphosphonic acid (HUPA) was prepared on the TiO 2 films by self-assembling, and the HUPA on TiO 2 films was confirmed by FTIR analysis. Simultaneously, hydroxyl groups were introduced in the phosphonic acid molecules to provide a functionality for further chemical modification. 2-Methacryloyloxyethyl phosphorylcholine (MPC), a biomimetic monomer, was chemically grafted on the HUPA surfaces at room temperature by surface-initiated atom-transfer radical polymerization. The surface characters of TiO 2 films modified by poly-MPC were confirmed by FTIR, XPS and SEM analysis. Platelet adhesion experiment revealed that poly-MPC modified surface was effective to inhibit platelet adhesion in vitro.

  9. Crystalline TiO 2 grafted with poly(2-methacryloyloxyethyl phosphorylcholine) via surface-initiated atom-transfer radical polymerization

    Science.gov (United States)

    Zhao, Yuancong; Tu, Qiufen; Wang, Jin; Huang, Qiongjian; Huang, Nan

    2010-12-01

    Crystalline TiO 2 films were prepared by unbalanced magnetron sputtering and the structure was confirmed by XRD. An organic layer of 11-hydroxyundecylphosphonic acid (HUPA) was prepared on the TiO 2 films by self-assembling, and the HUPA on TiO 2 films was confirmed by FTIR analysis. Simultaneously, hydroxyl groups were introduced in the phosphonic acid molecules to provide a functionality for further chemical modification. 2-Methacryloyloxyethyl phosphorylcholine (MPC), a biomimetic monomer, was chemically grafted on the HUPA surfaces at room temperature by surface-initiated atom-transfer radical polymerization. The surface characters of TiO 2 films modified by poly-MPC were confirmed by FTIR, XPS and SEM analysis. Platelet adhesion experiment revealed that poly-MPC modified surface was effective to inhibit platelet adhesion in vitro.

  10. Thermal and UV Hydrosilylation of Alcohol-Based Bifunctional Alkynes on Si (111) surfaces: How surface radicals influence surface bond formation.

    Science.gov (United States)

    Khung, Y L; Ngalim, S H; Scaccabarozi, A; Narducci, D

    2015-06-12

    Using two different hydrosilylation methods, low temperature thermal and UV initiation, silicon (111) hydrogenated surfaces were functionalized in presence of an OH-terminated alkyne, a CF3-terminated alkyne and a mixed equimolar ratio of the two alkynes. XPS studies revealed that in the absence of premeditated surface radical through low temperature hydrosilylation, the surface grafting proceeded to form a Si-O-C linkage via nucleophilic reaction through the OH group of the alkyne. This led to a small increase in surface roughness as well as an increase in hydrophobicity and this effect was attributed to the surficial etching of silicon to form nanosize pores (~1-3 nm) by residual water/oxygen as a result of changes to surface polarity from the grafting. Furthermore in the radical-free thermal environment, a mix in equimolar of these two short alkynes can achieve a high contact angle of ~102°, comparable to long alkyl chains grafting reported in literature although surface roughness was relatively mild (rms = ~1 nm). On the other hand, UV initiation on silicon totally reversed the chemical linkages to predominantly Si-C without further compromising the surface roughness, highlighting the importance of surface radicals determining the reactivity of the silicon surface to the selected alkynes.

  11. N-Chlorosuccinimide (NCS): A Novel Initiator for Atom Transfer Radical Polymerization of Methyl Methacrylate

    Institute of Scientific and Technical Information of China (English)

    WANG,Xia-Yan; CHANG,Li-Qun; ZHOU,Hong; ZHANG,Ke-Da

    2006-01-01

    Atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) was achieved, using N-chlorosuccinimide (NCS) as an initiator together with catalytic system CuCl/PMDETA (N,N,N',N',N"-pentamethyldiethyl-enetriamine), CuCl/MA5-DETA (N,N,N',N',N"-penta(methylacrylate)diethylenetriamine), and CuCl/bipy (bipy=2,2'-bipyridyl) respectively. The results indicated that the polymerization possessed typical controlled/living radical polymerization characteristics. The analysis for terminal group of obtained polymer by 1H NMR proved that NCS is an initiator for ATRP. In comparison with NBS, the polymerization rate was slower and the resulted polymer had narrower molecular weight distribution (MWD) when NCS was employed as the initiator.

  12. Hydrogel brushes grafted from stainless steel via surface-initiated atom transfer radical polymerization for marine antifouling

    Science.gov (United States)

    Wang, Jingjing; Wei, Jun

    2016-09-01

    Crosslinked hydrogel brushes were grafted from stainless steel (SS) surfaces for marine antifouling. The brushes were prepared by surface-initiated atom transfer radical polymerization (SI-ATRP) of 2-methacryloyloxyethyl phosphorylcholine (MPC) and poly(ethylene glycol) methyl ether methacrylate (PEGMA) respectively with different fractions of crosslinker in the feed. The grafted layers prepared with different thickness were characterized by X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), ellipsometry and water contact angle measurements. With the increase in the fraction of crosslinker in the feed, the thickness of the grafted layer increased and the surface became smooth. All the brush-coated SS surfaces could effectively reduce the adhesion of bacteria and microalgae and settlement of barnacle cyprids, as compared to the pristine SS surface. The antifouling efficacy of the PEGMA polymer (PPEGMA)-grafted surface was higher than that of the MPC polymer (PMPC)-grafted surfaces. Furthermore, the crosslinked hydrogel brush-grafted surfaces exhibited better fouling resistance than the non-crosslinked polymer brush-grafted surfaces, and the antifouling efficacy increased with the crosslinking density. These hydrogel coatings of low toxicity and excellent anti-adhesive characteristics suggested their useful applications as environmentally friendly antifouling coatings.

  13. Long-lived gas-phase radicals from combustion

    Energy Technology Data Exchange (ETDEWEB)

    Kaneko, Takashi; Furusawa, Koji; Amano, Toshiji; Okubo, Yoichi; Tsuchiya, Jun' ichi; Yoshizawa, Fujiroku; Akutsu, Yoshiaki; Tamura, Masamitsu; Yoshida, Tadao (Univ. of Tokyo (Japan))

    1989-04-20

    On indoor air pollution or fire, it is feared that the gas-phase radicals from the combustion of inflammables or fuel seriously exert an influence on the organisms as harmful matter. The gas-phase radicals were studied using the electron spin resonance (ESR) spin-trapping technique. For the spin trap solution, 0.1 mol solution of {alpha}-phenyl-N-t-butylnitron in benzene was used. As a result, apparently long-lived and highly reactive oxygen-centered radicals were detected in the smoke from polyethylene, polypropylene, polystyrene, polymethylmethacrylate, cellulose, kerosene, benzene, acetone, methanol and butylalcohol. It is suggested that the production mechanism for the radicals should be different from olefin-NOx-air system reaction, which is considered for the radicals from cigarette smoke. 11 refs., 6 figs., 2 tabs.

  14. Crystalline TiO{sub 2} grafted with poly(2-methacryloyloxyethyl phosphorylcholine) via surface-initiated atom-transfer radical polymerization

    Energy Technology Data Exchange (ETDEWEB)

    Zhao Yuancong; Tu Qiufen; Wang Jin; Huang Qiongjian [Key Lab. of Advanced Technology for Materials, Education Ministry, School of Material Science and Technology of Southwest Jiaotong University, Chengdu, Sichuan (China); Huang Nan, E-mail: zhaoyc7320@163.com [Key Lab. of Advanced Technology for Materials, Education Ministry, School of Material Science and Technology of Southwest Jiaotong University, Chengdu, Sichuan (China)

    2010-12-15

    Crystalline TiO{sub 2} films were prepared by unbalanced magnetron sputtering and the structure was confirmed by XRD. An organic layer of 11-hydroxyundecylphosphonic acid (HUPA) was prepared on the TiO{sub 2} films by self-assembling, and the HUPA on TiO{sub 2} films was confirmed by FTIR analysis. Simultaneously, hydroxyl groups were introduced in the phosphonic acid molecules to provide a functionality for further chemical modification. 2-Methacryloyloxyethyl phosphorylcholine (MPC), a biomimetic monomer, was chemically grafted on the HUPA surfaces at room temperature by surface-initiated atom-transfer radical polymerization. The surface characters of TiO{sub 2} films modified by poly-MPC were confirmed by FTIR, XPS and SEM analysis. Platelet adhesion experiment revealed that poly-MPC modified surface was effective to inhibit platelet adhesion in vitro.

  15. Grafting of antibacterial polymers on stainless steel via surface-initiated atom transfer radical polymerization for inhibiting biocorrosion by Desulfovibrio desulfuricans.

    Science.gov (United States)

    Yuan, S J; Xu, F J; Pehkonen, S O; Ting, Y P; Neoh, K G; Kang, E T

    2009-06-01

    To enhance the biocorrosion resistance of stainless steel (SS) and to impart its surface with bactericidal function for inhibiting bacterial adhesion and biofilm formation, well-defined functional polymer brushes were grafted via surface-initiated atom transfer radical polymerization (ATRP) from SS substrates. The trichlorosilane coupling agent, containing the alkyl halide ATRP initiator, was first immobilized on the hydroxylated SS (SS-OH) substrates for surface-initiated ATRP of (2-dimethylamino)ethyl methacrylate (DMAEMA). The tertiary amino groups of covalently immobilized DMAEMA polymer or P(DMAEMA), brushes on the SS substrates were quaternized with benzyl halide to produce the biocidal functionality. Alternatively, covalent coupling of viologen moieties to the tertiary amino groups of P(DMAEMA) brushes on the SS surface resulted in an increase in surface concentration of quaternary ammonium groups, accompanied by substantially enhanced antibacterial and anticorrosion capabilities against Desulfovibrio desulfuricans in anaerobic seawater, as revealed by antibacterial assay and electrochemical studies. With the inherent advantages of high corrosion resistance of SS, and the good antibacterial and anticorrosion capabilities of the viologen-quaternized P(DMAEMA) brushes, the functionalized SS is potentially useful in harsh seawater environments and for desalination plants. Copyright 2009 Wiley Periodicals, Inc.

  16. Visible Light-Induced Metal Free Surface Initiated Atom Transfer Radical Polymerization of Methyl Methacrylate on SBA-15

    Directory of Open Access Journals (Sweden)

    Liang Ma

    2017-02-01

    Full Text Available Surface-initiated atom transfer radical polymerization (SI-ATRP is one of the most versatile techniques to modify the surface properties of materials. Recent developed metal-free SI-ATRP makes such techniques more widely applicable. Herein photo-induced metal-free SI-ATRP of methacrylates, such as methyl methacrylate, N-isopropanyl acrylamide, and N,N-dimethylaminoethyl methacrylate, on the surface of SBA-15 was reported to fabricate organic-inorganic hybrid materials. A SBA-15-based polymeric composite with an adjustable graft ratio was obtained. The structure evolution during the SI-ATRP modification of SBA-15 was monitored and verified by FT-IR, XPS, TGA, BET, and TEM. The obtained polymeric composite showed enhanced adsorption ability for the model compound toluene in aqueous conditions. This procedure provides a low-cost, readily available, and easy modification method to synthesize polymeric composites without the contamination of metal.

  17. Hydrogel brushes grafted from stainless steel via surface-initiated atom transfer radical polymerization for marine antifouling

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Jingjing, E-mail: jjwang1@hotmail.com; Wei, Jun

    2016-09-30

    Highlights: • Crosslinked hydrogel brushes were grafted from SS surfaces for marine antifouling. • All brush-coated SS surfaces could effectively reduce the adhesion of biofouling. • The antifouling efficacy increased with the crosslinking density of hydrogels. - Abstract: Crosslinked hydrogel brushes were grafted from stainless steel (SS) surfaces for marine antifouling. The brushes were prepared by surface-initiated atom transfer radical polymerization (SI-ATRP) of 2-methacryloyloxyethyl phosphorylcholine (MPC) and poly(ethylene glycol) methyl ether methacrylate (PEGMA) respectively with different fractions of crosslinker in the feed. The grafted layers prepared with different thickness were characterized by X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), ellipsometry and water contact angle measurements. With the increase in the fraction of crosslinker in the feed, the thickness of the grafted layer increased and the surface became smooth. All the brush-coated SS surfaces could effectively reduce the adhesion of bacteria and microalgae and settlement of barnacle cyprids, as compared to the pristine SS surface. The antifouling efficacy of the PEGMA polymer (PPEGMA)-grafted surface was higher than that of the MPC polymer (PMPC)-grafted surfaces. Furthermore, the crosslinked hydrogel brush-grafted surfaces exhibited better fouling resistance than the non-crosslinked polymer brush-grafted surfaces, and the antifouling efficacy increased with the crosslinking density. These hydrogel coatings of low toxicity and excellent anti-adhesive characteristics suggested their useful applications as environmentally friendly antifouling coatings.

  18. Hydrogel brushes grafted from stainless steel via surface-initiated atom transfer radical polymerization for marine antifouling

    International Nuclear Information System (INIS)

    Wang, Jingjing; Wei, Jun

    2016-01-01

    Highlights: • Crosslinked hydrogel brushes were grafted from SS surfaces for marine antifouling. • All brush-coated SS surfaces could effectively reduce the adhesion of biofouling. • The antifouling efficacy increased with the crosslinking density of hydrogels. - Abstract: Crosslinked hydrogel brushes were grafted from stainless steel (SS) surfaces for marine antifouling. The brushes were prepared by surface-initiated atom transfer radical polymerization (SI-ATRP) of 2-methacryloyloxyethyl phosphorylcholine (MPC) and poly(ethylene glycol) methyl ether methacrylate (PEGMA) respectively with different fractions of crosslinker in the feed. The grafted layers prepared with different thickness were characterized by X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), ellipsometry and water contact angle measurements. With the increase in the fraction of crosslinker in the feed, the thickness of the grafted layer increased and the surface became smooth. All the brush-coated SS surfaces could effectively reduce the adhesion of bacteria and microalgae and settlement of barnacle cyprids, as compared to the pristine SS surface. The antifouling efficacy of the PEGMA polymer (PPEGMA)-grafted surface was higher than that of the MPC polymer (PMPC)-grafted surfaces. Furthermore, the crosslinked hydrogel brush-grafted surfaces exhibited better fouling resistance than the non-crosslinked polymer brush-grafted surfaces, and the antifouling efficacy increased with the crosslinking density. These hydrogel coatings of low toxicity and excellent anti-adhesive characteristics suggested their useful applications as environmentally friendly antifouling coatings.

  19. Comparison between Two Bromine Containing Free Radical Initiators in PRESAGE®

    Energy Technology Data Exchange (ETDEWEB)

    Park, Hyeonsuk; Ryu, Dongmin; Ye, Sung-Joon [Seoul National University, Seoul (Korea, Republic of)

    2016-10-15

    PRESAGE® is an optically clear 3-D polyurethane dosimeter which contains a halogenated carbon as a free radical initiator and leucomalachite dye. The change of the optical density is known to be linear with respect to the absorbed dose and the sensitivity is related to the carbon–halogen bond dissociation energy of the free radical initiator. Although there are some studies regarding free radical initiators and dye materials, there’s a lack of reports about the effect of other elements like LMG solvent which can be added when there’s a difficulty mixing materials. Also, there are some studies about comparison between free radicals with different kind of halogen atoms but there’s a lack of studies of comparison between initiators with the same halogen atom. In this experiments, two kinds of halocarbon free radical initiator with the same halogen atom (bromine) as well as the effect of the LMG solvent were studied to use the dosimeter as a therapeutic purpose. Effective atomic numbers were also calculated. The initiators with the same halogen atom, CBr{sub 4} and C{sub 2}H{sub 2}Br{sub 4}, reacted totally differently. CBr{sub 4} was more sensitive to the radiation and emitted maximum 4 times more free radicals upon irradiation with no additional effective atomic number but the absorbance after irradiation was highly variable with time. For stable measurement, C{sub 2}H{sub 2}Br{sub 4} would be more appropriate as a free radical initiator.

  20. Surface modification of hydroxyapatite with poly(methyl methacrylate) via surface-initiated ATRP

    Energy Technology Data Exchange (ETDEWEB)

    Wang Yan; Zhang Xi; Yan Jinliang; Xiao Yan [Shanghai Key Laboratory of Advanced Polymeric Materials, Key Laboratory for Ultrafine Materials of Ministry of Education, School of Materials Science and Engineering, East China University of Science and Technology, 130 Meilong Road, Shanghai 200237 (China); Lang Meidong, E-mail: mdlang@ecust.edu.cn [Shanghai Key Laboratory of Advanced Polymeric Materials, Key Laboratory for Ultrafine Materials of Ministry of Education, School of Materials Science and Engineering, East China University of Science and Technology, 130 Meilong Road, Shanghai 200237 (China)

    2011-05-01

    This article describes the fabrication of hydroxyapatite (HAP) nanocomposites grafted with poly(methyl methacrylate) (PMMA). Surface-initiated atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) was carried out from hydroxyapatite particles derivatized with ATRP initiators. The structure and properties of the nanocomposites were investigated by thermogravimetric analysis (TGA), transmission electron microscopy (TEM), differential scanning calorimeter (DSC) measurements, and contact angle analyses. TGA was used to estimate the grafting density of ATRP initiators (0.49 initiator/nm{sup 2}) and the amount of grafted PMMA on the HAP surface. The contact angle analyses indicated that grafting PMMA onto the HAP surface dramatically increased the hydrophobicity of the surface. Moreover, the HAP nanocomposites showed excellent dispersibility in both aqueous solution and organic solvent.

  1. Surface modification of hydroxyapatite with poly(methyl methacrylate) via surface-initiated ATRP

    International Nuclear Information System (INIS)

    Wang Yan; Zhang Xi; Yan Jinliang; Xiao Yan; Lang Meidong

    2011-01-01

    This article describes the fabrication of hydroxyapatite (HAP) nanocomposites grafted with poly(methyl methacrylate) (PMMA). Surface-initiated atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) was carried out from hydroxyapatite particles derivatized with ATRP initiators. The structure and properties of the nanocomposites were investigated by thermogravimetric analysis (TGA), transmission electron microscopy (TEM), differential scanning calorimeter (DSC) measurements, and contact angle analyses. TGA was used to estimate the grafting density of ATRP initiators (0.49 initiator/nm 2 ) and the amount of grafted PMMA on the HAP surface. The contact angle analyses indicated that grafting PMMA onto the HAP surface dramatically increased the hydrophobicity of the surface. Moreover, the HAP nanocomposites showed excellent dispersibility in both aqueous solution and organic solvent.

  2. Application of living radical polymerization to the synthesis of resist polymers for radiation lithography

    International Nuclear Information System (INIS)

    Shimizu, Takashi; Ichikawa, Tsuneki

    2005-01-01

    Poly(styrene) and poly(methyl acrylate) with benzyl ester of carboxylic acid at the center of the polymer skeletons were synthesized by living radical polymerization for developing a new type of radiation resist with high resistivity to plasma etching and high sensitivity and spatial resolution to ionizing radiations. The initiators were benzyl esters with two functional groups for living radical polymerization on the benzyl and the carboxylic sides. Introduction of benzyl ester to the polymer skeletons changed the polymers from cross-link type to scission type upon γ-irradiation. Irradiation of the polymers resulted in the binary change of the molecular weight, due to dissociative capture of secondary electrons by the benzyl ester, as M n R 1 COOCH(C 6 H 5 )R 2 M n +e - ->M n R 1 COO - + · CH(C 6 H 5 )R 2 M n . The generated polymer fragments were not decomposed by further irradiation, which suggests that the synthesized polymers have high resistivity to plasma etching

  3. Pentachlorophenol radical cations generated on Fe(III)-montmorillonite initiate octachlorodibenzo-p-dioxin formation in clays: DFT and FTIR studies

    Science.gov (United States)

    Gu, Cheng; Liu, Cun; Johnston, Cliff T.; Teppen, Brian J.; Li, Hui; Boyd, Stephen A.

    2011-01-01

    Octachlorodibenzodioxin (OCDD) forms spontaneously from pentachlorophenol (PCP) on the surfaces of Fe(III)-saturated smectite clay (1). Here, we used in situ FTIR methods and quantum mechanical calculations to determine the mechanism by which this reaction is initiated. As the clay was dehydrated, vibrational spectra showed new peaks that grew and then reversibly disappeared as the clay rehydrated. First principle DFT calculations of hydrated Fe-PCP clusters reproduced these transient FTIR peaks when inner-sphere complexation and concomitant electron transfer produced Fe(II) and PCP radical cations. Thus, our experimental (FTIR) and theoretical (quantum mechanical) results mutually support the hypothesis that OCDD formation on Fe-smectite surfaces is initiated by the reversible formation of metastable PCP radical cations via single electron transfer from PCP to Fe(III). The negatively charged clay surface apparently selects for this reaction mechanism by stabilizing PCP radical cations. PMID:21254769

  4. Formation of long-lived radicals on proteins by radical transfer from heme enzymes--a common process?

    DEFF Research Database (Denmark)

    Ostdal, H; Andersen, H J; Davies, Michael Jonathan

    1999-01-01

    concentrations were observed after limited digestion, although this effect was less marked with the HRP/H2O2/BSA system than with Fe(III)Mb/H2O2/BSA, consistent with different modes of radical transfer. More extensive digestion of BSA decreased the radical concentration to levels below those detected with native...... investigated using horseradish peroxidase (HRP)/H2O2, in the presence and absence of added tyrosine. Incubation of HRP with H2O2 and bovine or human serum albumins, in the presence and absence of tyrosine, gave long-lived albumin-derived radicals as detected by EPR spectroscopy. Evidence has been obtained...... for these albumin radicals being located on buried tyrosine residues on the basis of blocking experiments. The effect of protein conformation on radical transfer has been investigated using partial proteolytic digestion prior to protein oxidation. With HRP/H2O2/BSA and Fe(III)Mb/H2O2/BSA increased radical...

  5. Application of living radical polymerization to the synthesis of resist polymers for radiation lithography

    Energy Technology Data Exchange (ETDEWEB)

    Shimizu, Takashi [Nitto Denko Co. LTD., Shimohozumi 1-1-2, Ibaraki, Osaka 567-8680 (Japan); Ichikawa, Tsuneki [Division of Materials Chemistry, Graduate school of Engineering, Hokkaido University, Sapporo 060-8628 (Japan)]. E-mail: ichikawa@eng.hokudai.ac.jp

    2005-07-01

    Poly(styrene) and poly(methyl acrylate) with benzyl ester of carboxylic acid at the center of the polymer skeletons were synthesized by living radical polymerization for developing a new type of radiation resist with high resistivity to plasma etching and high sensitivity and spatial resolution to ionizing radiations. The initiators were benzyl esters with two functional groups for living radical polymerization on the benzyl and the carboxylic sides. Introduction of benzyl ester to the polymer skeletons changed the polymers from cross-link type to scission type upon {gamma}-irradiation. Irradiation of the polymers resulted in the binary change of the molecular weight, due to dissociative capture of secondary electrons by the benzyl ester, as M{sub n}R{sub 1}COOCH(C{sub 6}H{sub 5})R{sub 2}M{sub n}+e{sup -}->M{sub n}R{sub 1}COO{sup -}+{sup {center_dot}}CH(C{sub 6}H{sub 5})R{sub 2}M{sub n}. The generated polymer fragments were not decomposed by further irradiation, which suggests that the synthesized polymers have high resistivity to plasma etching.

  6. Enhanced protein retention on poly(caprolactone) via surface initiated polymerization of acrylamide

    International Nuclear Information System (INIS)

    Ma, Yuhao; Cai, Mengtan; He, Liu; Luo, Xianglin

    2016-01-01

    Graphical abstract: - Highlights: • Dense package of poly(acrylamide) on poly(caprolactone) surface was achieved by surface-initiated atom transfer radical polymerization. • Poly(acrylamide) grafted surface exhibited high protein retention ability. • Loaded protein was resistant to detachment and maintained its structure without denaturation. - Abstract: To enhance the biocompatibility or extend the biomedical application of poly(caprolactone) (PCL), protein retention on PCL surface is often required. In this study, poly(acrylamide) (PAAm) brushes were grown from PCL surface via surface-initiated atom transfer radical polymerization (SI-ATRP) and served as a protein-capturing platform. Grafted PAAm was densely packed on surface and exhibited superior protein retention ability. Captured protein was found to be resistant to washing under detergent environment. Furthermore, protein structure after being captured was investigated by circular dichroism (CD) spectroscopy, and the CD spectra verified that secondary structure of captured proteins was maintained, indicating no denaturation of protein happened for retention process.

  7. Inorganic-organic hybrid coatings on stainless steel by layer-by-layer deposition and surface-initiated atom-transfer-radical polymerization for combating biocorrosion.

    Science.gov (United States)

    Yuan, S J; Pehkonen, S O; Ting, Y P; Neoh, K G; Kang, E T

    2009-03-01

    To improve the biocorrosion resistance of stainless steel (SS) and to confer the bactericidal function on its surface for inhibiting bacterial adhesion and biofilm formation, well-defined inorganic-organic hybrid coatings, consisting of the inner compact titanium oxide multilayers and outer dense poly(vinyl-N-hexylpyridinium) brushes, were successfully developed. Nanostructured titanium oxide multilayer coatings were first built up on the SS substrates via the layer-by-layer sol-gel deposition process. The trichlorosilane coupling agent, containing the alkyl halide atom-transfer-radical polymerization (ATRP) initiator, was subsequently immobilized on the titanium oxide coatings for surface-initiated ATRP of 4-vinylpyridine (4VP). The pyridium nitrogen moieties of the covalently immobilized 4VP polymer, or P(4VP), brushes were quaternized with hexyl bromide to produce a high concentration of quaternary ammonium salt on the SS surfaces. The excellent antibacterial efficiency of the grafted polycations, poly(vinyl-N-pyridinium bromide), was revealed by viable cell counts and atomic force microscopy images of the surface. The effectiveness of the hybrid coatings in corrosion protection was verified by the Tafel plot and electrochemical impedance spectroscopy measurements.

  8. Test for antioxidant ability by scavenging long-lived mutagenic radicals in mammalian cells and by blood test with intentional radicals: an application of gallic acid

    International Nuclear Information System (INIS)

    Kumagai, Jun; Kawaura, Tomoko; Miyazaki, Tetsuo; Prost, Michel; Prost, Emmanuelle; Watanabe, Masami; Quetin-Leclercq, J.Joeelle

    2003-01-01

    Antioxidant ability of gallic acid (GA) are determined both by electron spin resonance measurement of long-lived radicals produced in γ-ray irradiated Syrian golden hamster embryo cells with GA and by hemolysis measurement with GA when blood cells are submitted to radicals. Scavenging properties of GA are determined by the reaction rate constant with long-lived mutagenic radicals in the cells while the blood test allows to analyze the global effects of this compound: radical scavenger+metal ion chelator+regeneration of intra- and extra-cellular antioxidant

  9. Antibacterial inorganic-organic hybrid coatings on stainless steel via consecutive surface-initiated atom transfer radical polymerization for biocorrosion prevention.

    Science.gov (United States)

    Yuan, S J; Pehkonen, S O; Ting, Y P; Neoh, K G; Kang, E T

    2010-05-04

    To enhance the corrosion resistance of stainless steel (SS) and to impart its surface with antibacterial functionality for inhibiting biofilm formation and biocorrosion, well-defined inorganic-organic hybrid coatings, consisting of a polysilsesquioxane inner layer and quaternized poly(2-(dimethyamino)ethyl methacrylate) (P(DMAEMA)) outer blocks, were prepared via successive surface-initiated atom transfer radical polymerization (ATRP) of 3-(trimethoxysilyl)propyl methacrylate (TMSPMA) and 2-(dimethylamino)ethyl methacrylate (DMAEMA). The cross-linked P(TMASPMA), or polysilsesquioxane, inner layer provided a durable and resistant coating to electrolytes. The pendant tertiary amino groups of the P(DMAEMA) outer block were quaternized with alkyl halide to produce a high concentration of quaternary ammonium groups with biocidal functionality. The so-synthesized inorganic-organic hybrid coatings on the SS substrates exhibited good anticorrosion and antibacterial effects and inhibited biocorrosion induced by sulfate-reducing bacteria (SRB) in seawater media, as revealed by antibacterial assay and electrochemical analyses, and they are potentially useful to steel-based equipment under harsh industrial and marine environments.

  10. Synthesis and characterization of TiO2/Ag/polymer ternary nanoparticles via surface-initiated atom transfer radical polymerization

    International Nuclear Information System (INIS)

    Park, Jung Tae; Koh, Joo Hwan; Seo, Jin Ah; Cho, Yong Soo; Kim, Jong Hak

    2011-01-01

    We report on the novel ternary hybrid materials consisting of semiconductor (TiO 2 ), metal (Ag) and polymer (poly(oxyethylene methacrylate) (POEM)). First, a hydrophilic polymer, i.e. POEM, was grafted from TiO 2 nanoparticles via the surface-initiated atom transfer radical polymerization (ATRP) technique. These TiO 2 -POEM brush nanoparticles were used to template the formation of Ag nanoparticles by introduction of a AgCF 3 SO 3 precursor and a NaBH 4 aqueous solution for reduction process. Successful grafting of polymeric chains from the surface of TiO 2 nanoparticles and the in situ formation of Ag nanoparticles within the polymeric chains were confirmed using transmission electron microscopy (TEM), UV-vis spectroscopy, X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). FT-IR spectroscopy also revealed the specific interaction of Ag nanoparticles with the C=O groups of POEM brushes. This study presents a simple route for the in situ synthesis of both metal and polymer confined within the semiconductor, producing ternary hybrid inorganic-organic nanomaterials.

  11. Protein adsorption resistance of PVP-modified polyurethane film prepared by surface-initiated atom transfer radical polymerization

    International Nuclear Information System (INIS)

    Yuan, Huihui; Qian, Bin; Zhang, Wei; Lan, Minbo

    2016-01-01

    Highlights: • Antifouling PVP brushes were successfully grafted on PU films by SI-ATRP. • The effect of polymerization time on surface property and topography was studied. • Hydrophilicity and protein fouling resistance of PVP–PU films were greatly promoted. • Competitive adsorption of three proteins on PVP–PU films was evaluated. - Abstract: An anti-fouling surface of polyurethane (PU) film grafted with Poly(N-vinylpyrrolidone) (PVP) was prepared through surface-initiated atom transfer radical polymerization (SI-ATRP). And the polymerization time was investigated to obtain PU films with PVP brushes of different lengths. The surface properties and protein adsorption of modified PU films were evaluated. The results showed that the hydrophilicity of PU–PVP films were improved with the increase of polymerization time, which was not positive correlation with the surface roughness due to the brush structure. Additionally, the protein resistance performance was promoted when prolonging the polymerization time. The best antifouling PU–PVP (6.0 h) film reduced the adsoption level of bovine serum albumin (BSA), lysozyme (LYS), and brovin serum fibrinogen (BFG) by 93.4%, 68.3%, 85.6%, respectively, compared to the unmodified PU film. The competitive adsorption of three proteins indicated that LYS preferentially adsorbed on the modified PU film, while BFG had the lowest adsorption selectivity. And the amount of BFG on PU–PVP (6.0 h) film reduced greatly to 0.08 μg/cm"2, which was almost one-tenth of its adsorption from the single-protein system. Presented results suggested that both hydrophilicity and surface roughness might be the important factors in all cases of protein adsorption, and the competitive or selective adsorption might be related to the size of the proteins, especially on the non-charged films.

  12. Protein adsorption resistance of PVP-modified polyurethane film prepared by surface-initiated atom transfer radical polymerization

    Energy Technology Data Exchange (ETDEWEB)

    Yuan, Huihui; Qian, Bin; Zhang, Wei [Shanghai Key Laboratory of Functional Materials Chemistry and Research Center of Analysis and Test, East China University of Science and Technology, Shanghai 200237 (China); Lan, Minbo, E-mail: minbolan@ecust.edu.cn [Shanghai Key Laboratory of Functional Materials Chemistry and Research Center of Analysis and Test, East China University of Science and Technology, Shanghai 200237 (China); State Key Laboratory of Bioreactor Engineering, East China University of Science and Technology, Shanghai 200237 (China)

    2016-02-15

    Highlights: • Antifouling PVP brushes were successfully grafted on PU films by SI-ATRP. • The effect of polymerization time on surface property and topography was studied. • Hydrophilicity and protein fouling resistance of PVP–PU films were greatly promoted. • Competitive adsorption of three proteins on PVP–PU films was evaluated. - Abstract: An anti-fouling surface of polyurethane (PU) film grafted with Poly(N-vinylpyrrolidone) (PVP) was prepared through surface-initiated atom transfer radical polymerization (SI-ATRP). And the polymerization time was investigated to obtain PU films with PVP brushes of different lengths. The surface properties and protein adsorption of modified PU films were evaluated. The results showed that the hydrophilicity of PU–PVP films were improved with the increase of polymerization time, which was not positive correlation with the surface roughness due to the brush structure. Additionally, the protein resistance performance was promoted when prolonging the polymerization time. The best antifouling PU–PVP (6.0 h) film reduced the adsoption level of bovine serum albumin (BSA), lysozyme (LYS), and brovin serum fibrinogen (BFG) by 93.4%, 68.3%, 85.6%, respectively, compared to the unmodified PU film. The competitive adsorption of three proteins indicated that LYS preferentially adsorbed on the modified PU film, while BFG had the lowest adsorption selectivity. And the amount of BFG on PU–PVP (6.0 h) film reduced greatly to 0.08 μg/cm{sup 2}, which was almost one-tenth of its adsorption from the single-protein system. Presented results suggested that both hydrophilicity and surface roughness might be the important factors in all cases of protein adsorption, and the competitive or selective adsorption might be related to the size of the proteins, especially on the non-charged films.

  13. Surface modification of nanodiamond through metal free atom transfer radical polymerization

    Energy Technology Data Exchange (ETDEWEB)

    Zeng, Guangjian; Liu, Meiying; Shi, Kexin; Heng, Chunning; Mao, Liucheng; Wan, Qing; Huang, Hongye [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Deng, Fengjie, E-mail: fengjiedeng@aliyun.com [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Zhang, Xiaoyong, E-mail: xiaoyongzhang1980@gmail.com [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Wei, Yen, E-mail: weiyen@tsinghua.edu.cn [Department of Chemistry and the Tsinghua Center for Frontier Polymer Research, Tsinghua University, Beijing, 100084 (China)

    2016-12-30

    Highlights: • Surface modification of ND with water soluble and biocompatible polymers. • Functionalized ND through metal free surface initiated ATRP. • The metal free surface initiated ATRP is rather simple and effective. • The ND-poly(MPC) showed high dispersibility and desirable biocompatibility. - Abstract: Surface modification of nanodiamond (ND) with poly(2-methacryloyloxyethyl phosphorylcholine) [poly(MPC)] has been achieved by using metal free surface initiated atom transfer radical polymerization (SI-ATRP). The ATRP initiator was first immobilized on the surface of ND through direct esterification reaction between hydroxyl group of ND and 2-bromoisobutyryl bromide. The initiator could be employed to obtain ND-poly(MPC) nanocomposites through SI-ATRP using an organic catalyst. The final functional materials were characterized by {sup 1}H nuclear magnetic resonance, transmission electron microscopy, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy and thermo gravimetric analysis in detailed. All of these characterization results demonstrated that ND-poly(MPC) have been successfully obtained via metal free photo-initiated SI-ATRP. The ND-poly(MPC) nanocomposites shown enhanced dispersibility in various solvents as well as excellent biocompatibility. As compared with traditional ATRP, the metal free ATRP is rather simple and effective. More importantly, this preparation method avoided the negative influence of metal catalysts. Therefore, the method described in this work should be a promising strategy for fabrication of polymeric nanocomposites with great potential for different applications especially in biomedical fields.

  14. Surface modification of nanodiamond through metal free atom transfer radical polymerization

    International Nuclear Information System (INIS)

    Zeng, Guangjian; Liu, Meiying; Shi, Kexin; Heng, Chunning; Mao, Liucheng; Wan, Qing; Huang, Hongye; Deng, Fengjie; Zhang, Xiaoyong; Wei, Yen

    2016-01-01

    Highlights: • Surface modification of ND with water soluble and biocompatible polymers. • Functionalized ND through metal free surface initiated ATRP. • The metal free surface initiated ATRP is rather simple and effective. • The ND-poly(MPC) showed high dispersibility and desirable biocompatibility. - Abstract: Surface modification of nanodiamond (ND) with poly(2-methacryloyloxyethyl phosphorylcholine) [poly(MPC)] has been achieved by using metal free surface initiated atom transfer radical polymerization (SI-ATRP). The ATRP initiator was first immobilized on the surface of ND through direct esterification reaction between hydroxyl group of ND and 2-bromoisobutyryl bromide. The initiator could be employed to obtain ND-poly(MPC) nanocomposites through SI-ATRP using an organic catalyst. The final functional materials were characterized by 1 H nuclear magnetic resonance, transmission electron microscopy, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy and thermo gravimetric analysis in detailed. All of these characterization results demonstrated that ND-poly(MPC) have been successfully obtained via metal free photo-initiated SI-ATRP. The ND-poly(MPC) nanocomposites shown enhanced dispersibility in various solvents as well as excellent biocompatibility. As compared with traditional ATRP, the metal free ATRP is rather simple and effective. More importantly, this preparation method avoided the negative influence of metal catalysts. Therefore, the method described in this work should be a promising strategy for fabrication of polymeric nanocomposites with great potential for different applications especially in biomedical fields.

  15. Atmospheric Oxidation Mechanism of Furfural Initiated by Hydroxyl Radicals.

    Science.gov (United States)

    Zhao, Xiaocan; Wang, Liming

    2017-05-04

    Furfural is emitted into the atmosphere because of its potential applications as an intermediate to alkane fuels from biomass, industrial usages, and biomass burning. The kinetic and mechanistic information on the furfural chemistry is necessary to assess the fate of furfural in the atmosphere and its impact on the air quality. Here we studied the atmospheric oxidation mechanisms of furfural initiated by the OH radicals using quantum chemistry and kinetic calculations. The reaction of OH and furfural was initiated mainly by OH additions to C 2 and C 5 positions, forming R2 and R5 adducts, which could undergo rapid ring-breakage to form R2B and R5B, respectively. Our calculations showed that these intermediate radicals reacted rather slowly with O 2 under the atmospheric conditions because the additions of O 2 to these radicals are only slightly exothermic and highly reversible. Alternatively, these radicals would react directly with O 3 , NO 2 , HO 2 /RO 2 , etc. Namely, the atmospheric oxidation of furfural would unlikely result in ozone formation. Under typical atmospheric conditions, the main products in OH-initiated furfural oxidation include 2-oxo-3-pentene-1,5-dialdehyde, 5-hydroxy-2(5H)-furanone, 4-oxo-2- butenoic acid, and 2,5-furandione. These compounds will likely stay in the gas phase and are subject to further photo-oxidation.

  16. Synthesis of Environmentally Responsive Polymers by Atom Transfer Radical Polymerization: Generation of Reversible Hydrophilic and Hydrophobic Surfaces

    Directory of Open Access Journals (Sweden)

    Vikas Mittal

    2010-05-01

    Full Text Available Environmentally responsive poly(N-isopropylacrylamide brushes were grafted from the surface of polymer particles or flat surfaces in order to generate reversible hydrophilic and hydrophobic surfaces. The use of atom transfer radical polymerization was demonstrated for the grafting of polymer brushes as it allows efficient control on the amount of grafted polymer. The polymer particles were generated with or without surfactant in the emulsion polymerization and their surface could be modified with the atom transfer radical polymerization (ATRP initiator. The uniform functionalization of the surface with ATRP initiator was responsible for the uniform grafting of polymer brushes. The grafted brushes responded reversibly with changes in temperature indicating that the reversible responsive behavior could be translated to the particle surfaces. The particles were observed to adsorb and desorb protein and virus molecules by changing the temperatures below or higher than 32 °C. The initiator functionalized particles could also be adsorbed on the flat surfaces. The adsorption process also required optimization of the heat treatment conditions to form a uniform layer of the particles on the substrate. The grafted polymer brushes also responded to the changes in temperatures similar to the spherical particles studied through water droplets placed on the flat substrates.

  17. Surface polyPEGylation of Eu3+ doped luminescent hydroxyapatite nanorods through the combination of ligand exchange and metal free surface initiated atom transfer radical polymerization

    Science.gov (United States)

    Zeng, Guangjian; Liu, Meiying; Heng, Chunning; Huang, Qiang; Mao, Liucheng; Huang, Hongye; Hui, Junfeng; Deng, Fengjie; Zhang, Xiaoyong; Wei, Yen

    2017-03-01

    The Eu3+ doped luminescent hydroxyapatite (HAp) nanorods with uniform size and morphology can be synthesized by hydrothermal route. However, these HAp nanorods are coated by hydrophobic oleylamine, which makes them difficult to be dispersed in aqueous solution and impede their biomedical applications. In this work, Eu3+ doped luminescent polymers functionalized HAp nanorods were prepared through the combination of ligand exchange reaction and metal free surface initiated atom transfer radical polymerization (ATRP) method. In this procedure, the amino group functionalized HAp nanorods were first prepared by ligand exchange reaction using adenosine monophosphate (AMP) as ligand. Then the Br-containing initiators (HAp-Br) were introduced onto the surface of HAp-AMP nanorods through the amidation reaction. Finally, polymers functionalized HAp nanorods were prepared by metal free ATRP method using poly(ethylene glycol) methacrylate (PEGMA) as monomer and 10-phenylphenothiazine (PTH) as organic photocatalyst. The properties of these obtained HAp nanocomposites (HAP-polyPEGMA nanorods) were characterized by means of transmission electron microscopy, Fourier transformed infrared spectroscopy, X-ray photoelectron spectroscopy and thermogravimetric analysis in detail. The cell imaging of these HAP-polyPEGMA nanorods was examined using laser scanning confocal microscope to evaluate their biomedical applications. We demonstrated for the first time that hydrophobic luminescent HAp nanorods can be functionalized with polyPEGMA through the combination of ligand exchange reaction and metal free surface initiated ATRP. As compared with the traditional ATRP, the metal free ATRP can overcome the toxic and fluorescence quenching effects of metal catalysts such as copper ions. More importantly, the strategy described in this work should also be utilized for fabrications of many other luminescent polymer nanocomposites due to its good monomer adoptability.

  18. Surface modification of nanodiamond through metal free atom transfer radical polymerization

    Science.gov (United States)

    Zeng, Guangjian; Liu, Meiying; Shi, Kexin; Heng, Chunning; Mao, Liucheng; Wan, Qing; Huang, Hongye; Deng, Fengjie; Zhang, Xiaoyong; Wei, Yen

    2016-12-01

    Surface modification of nanodiamond (ND) with poly(2-methacryloyloxyethyl phosphorylcholine) [poly(MPC)] has been achieved by using metal free surface initiated atom transfer radical polymerization (SI-ATRP). The ATRP initiator was first immobilized on the surface of ND through direct esterification reaction between hydroxyl group of ND and 2-bromoisobutyryl bromide. The initiator could be employed to obtain ND-poly(MPC) nanocomposites through SI-ATRP using an organic catalyst. The final functional materials were characterized by 1H nuclear magnetic resonance, transmission electron microscopy, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy and thermo gravimetric analysis in detailed. All of these characterization results demonstrated that ND-poly(MPC) have been successfully obtained via metal free photo-initiated SI-ATRP. The ND-poly(MPC) nanocomposites shown enhanced dispersibility in various solvents as well as excellent biocompatibility. As compared with traditional ATRP, the metal free ATRP is rather simple and effective. More importantly, this preparation method avoided the negative influence of metal catalysts. Therefore, the method described in this work should be a promising strategy for fabrication of polymeric nanocomposites with great potential for different applications especially in biomedical fields.

  19. Improving the drug delivery characteristics of graphene oxide based polymer nanocomposites through the “one-pot” synthetic approach of single-electron-transfer living radical polymerization

    Energy Technology Data Exchange (ETDEWEB)

    Gao, Peng; Liu, Meiying; Tian, Jianwen; Deng, Fengjie [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Wang, Ke [Department of Chemistry and the Tsinghua Center for Frontier Polymer Research, Tsinghua University, Beijing 100084 (China); Xu, Dazhuang [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Liu, Liangji [Affiliated Hospital of Jiangxi University of Traditional Chinese Medicine, Nanchang 330006 (China); Zhang, Xiaoyong, E-mail: xiaoyongzhang1980@gmail.com [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Wei, Yen, E-mail: weiyen@tsinghua.edu.cn [Department of Chemistry and the Tsinghua Center for Frontier Polymer Research, Tsinghua University, Beijing 100084 (China)

    2016-08-15

    Graphical abstract: The PEGylated graphene oxides with high water dispersibility, good biocompatibility as well as high drug loading capability were fabricated via “one-pot” SET-LRP. - Highlights: • Surface modification of graphene oxide with polymers. • One-pot single-electron-transfer living radical polymerization. • Improving drug delivery characteristics. • The synthetic approach is rather simple, universal and effective. - Abstract: Graphene oxide (GO) based polymer nanocomposites have attracted extensive research interest recently for their outstanding physicochemical properties and potential applications. However, surface modification of GO with synthetic polymers has demonstrated to be trouble for most polymerization procedures are occurred under non-aqueous solution, which will in turn lead to the restacking of GO. In this work, a facile and efficient “one-pot” strategy has been developed for surface modification of GO with synthetic polymers through single-electron-transfer living radical polymerization (SET-LRP). The GO based polymer nanocomposites were obtained via SET-LRP in aqueous solution using poly(ethylene glycol) methyl ether methacrylate (PEGMA) as the monomer and 11-bromoundecanoic acid as the initiator, which could be effectively adsorbed on GO through hydrophobic interaction. The successful preparation of GO based polymer nanocomposites was confirmed by a series of characterization techniques such as {sup 1}H nuclear magnetic resonance, Fourier transform infrared spectroscopy, thermogravimetric analysis, transmission electron microscopy and X-ray photoelectron spectroscopy. The resultant products exhibit high water disperisibility, excellent biocompatibility and high efficient drug loading capability, making these PEGylated GO nanocomposites promising candidates for biomedical applications.

  20. The free radical process for the polymer surface treated by radio frequency plasma

    International Nuclear Information System (INIS)

    Ma Yuguang; Yang Meiling; Shen Jiacong; Zheng Yingguang

    1992-01-01

    The formation and translation of the free radicals on the polymer surface treated by plasmas were studied and observed by ESR measurement. The results show that C-C bond split was main reaction in the process of the polymer irradiated by plasma, by which a stable alkyl free radical was formed. When alkyl free radical contacted with air, they translate into peroxide radical instantaneously. The peroxide radical was not as stable as radical in vacuum, they can react each other to form some polar-groups on polymer surface. The interaction between the peroxide free radical and polymer chain was correlative not only to the structure of polymer but also to the molecular motion of the polymer chain. The nature of plasma treating polymer surface was that the peroxide radicals were led onto polymer surface

  1. SYNTHESIS OF BLOCK COPOLYMER BY INTEGRATED LIVING ANIONIC POLYMERIZATION-ATOM TRANSFER RADICAL POLYMERIZATION (ATRP)

    Institute of Scientific and Technical Information of China (English)

    Bing Liu; Feng Liu; Ning Luo; Sheng-kang Ying; Qing Liu

    2000-01-01

    Alpha-trichloroacetoxy terminated polystyrene oligomer (PS-CH2CH2OCOCCl3) and poly-(styrene-b-butadiene)oligomer [P(S-b-B)-CH2CH2OCOCCl3)] were synthesized by living anionic polymeri-zation using n-butyllithium as initiator.Then the PS-CH2CH2OCOCCl3 (PS-Cl3) or P(S-b-B)-CH2CH2O-COCCl3 (PSB-Cl3) was used as the macroinitiator in the polymerization of (meth)acrylates in the presence of CuX/bpy. AB diblock and ABC triblock copolymers were prepared by the integrated living anionic polymerization (LAP)-atom transfer radical polymerization (ATRP). The structures of the PSB-Cl3 and the P(S-b-MMA) were identified by FTIR and 1H-NMR spectrum, respectively. A new way to design block copolymers (the combination of LAP and ATRP) was developed.

  2. Fabrication of ultrahydrophobic poly(lauryl acrylate) brushes on silicon wafer via surface-initiated atom transfer radical polymerization

    Energy Technology Data Exchange (ETDEWEB)

    Oztuerk, Esra; Turan, Eylem [Department of Chemistry, Faculty of Art and Science, Gazi University, 06500 Besevler, Ankara (Turkey); Caykara, Tuncer, E-mail: caykara@gazi.edu.tr [Department of Chemistry, Faculty of Art and Science, Gazi University, 06500 Besevler, Ankara (Turkey)

    2010-11-15

    In this report, ultrahydrophobic poly(lauryl acrylate) [poly(LA)] brushes were synthesized by surface-initiated atom transfer radical polymerization (SI-ATRP) of lauryl acrylate (LA) in N,N-dimethylformamide (DMF) at 90 deg. C. The formation of ultrahydrophobic poly(LA) films, whose thickness can be turned by changing polymerization time, is evidenced by using the combination of ellipsometry, X-ray photoelectron spectroscopy (XPS), grazing angle attenuated total reflectance-Fourier transform infrared spectroscopy (GATR-FTIR), atomic force microscopy (AFM), gel permeation chromatography (GPC), and water contact angle measurements. The SI-ATRP can be conducted in a well-controlled manner, as revealed by the linear kinetic plot, linear evolution of number-average molecular weights (M-bar{sub n}) versus monomer conversions, and the relatively narrow PDI (<1.28) of the grafted poly(LA) chains. The calculation of grafting parameters from experimental measurements indicated the synthesis of densely grafted poly(LA) films and allowed us to predict a 'brushlike' conformation for the chains in good solvent. The poly(LA) brushes exhibited high water contact angle of 163.3 {+-} 2.8{sup o}.

  3. Surface polyPEGylation of Eu"3"+ doped luminescent hydroxyapatite nanorods through the combination of ligand exchange and metal free surface initiated atom transfer radical polymerization

    International Nuclear Information System (INIS)

    Zeng, Guangjian; Liu, Meiying; Heng, Chunning; Huang, Qiang; Mao, Liucheng; Huang, Hongye; Hui, Junfeng; Deng, Fengjie; Zhang, Xiaoyong; Wei, Yen

    2017-01-01

    Highlights: • Surface modification of HAp nanorods through the combination of ligand exchange reaction and metal free SI-ATRP. • HAp-polyPEGMA displayed high water dispersibility, good biocompatibility and biological imaging capability. • Metal free ATRP can overcome the toxic and fluorescence quenching effects of metal catalysts of conventional ATRP. - Abstract: The Eu"3"+ doped luminescent hydroxyapatite (HAp) nanorods with uniform size and morphology can be synthesized by hydrothermal route. However, these HAp nanorods are coated by hydrophobic oleylamine, which makes them difficult to be dispersed in aqueous solution and impede their biomedical applications. In this work, Eu"3"+ doped luminescent polymers functionalized HAp nanorods were prepared through the combination of ligand exchange reaction and metal free surface initiated atom transfer radical polymerization (ATRP) method. In this procedure, the amino group functionalized HAp nanorods were first prepared by ligand exchange reaction using adenosine monophosphate (AMP) as ligand. Then the Br-containing initiators (HAp-Br) were introduced onto the surface of HAp-AMP nanorods through the amidation reaction. Finally, polymers functionalized HAp nanorods were prepared by metal free ATRP method using poly(ethylene glycol) methacrylate (PEGMA) as monomer and 10-phenylphenothiazine (PTH) as organic photocatalyst. The properties of these obtained HAp nanocomposites (HAP-polyPEGMA nanorods) were characterized by means of transmission electron microscopy, Fourier transformed infrared spectroscopy, X-ray photoelectron spectroscopy and thermogravimetric analysis in detail. The cell imaging of these HAP-polyPEGMA nanorods was examined using laser scanning confocal microscope to evaluate their biomedical applications. We demonstrated for the first time that hydrophobic luminescent HAp nanorods can be functionalized with polyPEGMA through the combination of ligand exchange reaction and metal free surface initiated

  4. Poly(glycidyl methacrylate) grafted CdSe quantum dots by surface-initiated atom transfer radical polymerization: Novel synthesis, characterization, properties, and cytotoxicity studies

    Energy Technology Data Exchange (ETDEWEB)

    Bach, Long Giang; Islam, Md. Rafiqul [Department of Imaging System Engineering, Pukyong National University, Busan 608-737 (Korea, Republic of); Lee, Doh Chang [Department of Chemical and Biomolecular Engineering, KAIST Institute for the Nanocentury (KINC), Korea Advanced Institute of Science and Technology (KAIST), Daejeon 305-701 (Korea, Republic of); Lim, Kwon Taek, E-mail: ktlim@pknu.ac.kr [Department of Imaging System Engineering, Pukyong National University, Busan 608-737 (Korea, Republic of)

    2013-10-15

    A novel approach for the synthesis of poly(glycidyl methacrylate) grafted CdSe quantum dot (QDs) (PGMA-g-CdSe) was developed. The PGMA-g-CdSe nanohybrids were synthesized by the surface-initiated atom transfer radical polymerization of glycidyl methacrylate from the surface of the strategic initiator, CdSe-BrIB QDs prepared by the interaction of 2-bromoisobutyryl bromide (BrIB) and CdSe-OH QDs. The structure, morphology, and optical property of the PGMA-g-CdSe nanohybrids were analyzed by FT-IR, XPS, TGA, XRD, TEM, and PL. The as-synthesized PGMA-g-CdSe nanohybrids having multi-epoxide groups were employed for the direct coupling of biotin via ring-opening reaction of the epoxide groups to afford the Biotin-f-PGMA-g-CdSe nanobioconjugate. The covalent immobilization of biotin onto PGMA-g-CdSe was confirmed by FT-IR, XPS, and EDX. Biocompatibility and imaging properties of the Biotin-f-PGMA-g-CdSe were investigated by MTT bioassay and PL analysis, respectively. The cell viability study suggested that the biocompatibility was significantly enhanced by the functionalization of CdSe QDs by biotin and PGMA.

  5. Poly(glycidyl methacrylate) grafted CdSe quantum dots by surface-initiated atom transfer radical polymerization: Novel synthesis, characterization, properties, and cytotoxicity studies

    International Nuclear Information System (INIS)

    Bach, Long Giang; Islam, Md. Rafiqul; Lee, Doh Chang; Lim, Kwon Taek

    2013-01-01

    A novel approach for the synthesis of poly(glycidyl methacrylate) grafted CdSe quantum dot (QDs) (PGMA-g-CdSe) was developed. The PGMA-g-CdSe nanohybrids were synthesized by the surface-initiated atom transfer radical polymerization of glycidyl methacrylate from the surface of the strategic initiator, CdSe-BrIB QDs prepared by the interaction of 2-bromoisobutyryl bromide (BrIB) and CdSe-OH QDs. The structure, morphology, and optical property of the PGMA-g-CdSe nanohybrids were analyzed by FT-IR, XPS, TGA, XRD, TEM, and PL. The as-synthesized PGMA-g-CdSe nanohybrids having multi-epoxide groups were employed for the direct coupling of biotin via ring-opening reaction of the epoxide groups to afford the Biotin-f-PGMA-g-CdSe nanobioconjugate. The covalent immobilization of biotin onto PGMA-g-CdSe was confirmed by FT-IR, XPS, and EDX. Biocompatibility and imaging properties of the Biotin-f-PGMA-g-CdSe were investigated by MTT bioassay and PL analysis, respectively. The cell viability study suggested that the biocompatibility was significantly enhanced by the functionalization of CdSe QDs by biotin and PGMA.

  6. INITIATION EFFICIENCY f OF METHYL METHACRYLATE BULK RADICAL POLYMERIZATION

    Institute of Scientific and Technical Information of China (English)

    沈家骢; 田元; 王国斌; 杨梅林

    1990-01-01

    The values of the initiation efficiency f at various conversions in the bulk polymerization of MMA initiated by AIBME have first been determined according to a strict unsteady-state formula and based on the data of radical concentration and the termination rate constant determined using ESR method. A model of diffusion control initiation is proposed. The theory is well in agreement with the experiments during the whole process of polymerization.

  7. Long-lived radicals produced by γ-irradiation or vital activity in plants, animals, cells, and protein solution: their observation and inhomogeneous decay dynamics

    International Nuclear Information System (INIS)

    Miyazaki, Tetsuo; Morikawa, Akiyuki; Kumagai, Jun; Ikehata, Masateru; Koana, Takao; Kikuchi, Shoshi

    2002-01-01

    Long-lived radicals produced by γ-irradiation or vital activity in plants, animals, cells, and protein (albumin) solution were studied by electron spin resonance spectroscopy. Long-lived radicals produced by vital activity exist in biological systems, such as plants, animals, and cells, in the range of 0.1-20 nmol g -1 . Since vital organs keep the radicals at a constant concentration, the radicals are probably related to life conservation. Long-lived radicals are also produced by γ-irradiation of cells or protein solution. The radicals decay after death of living things or after γ-irradiation. We found that the decay dynamics in all biological systems can be expressed by the same kinetic equation of an inhomogeneous reaction

  8. Surface polyPEGylation of Eu{sup 3+} doped luminescent hydroxyapatite nanorods through the combination of ligand exchange and metal free surface initiated atom transfer radical polymerization

    Energy Technology Data Exchange (ETDEWEB)

    Zeng, Guangjian; Liu, Meiying [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Heng, Chunning [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Shaanxi Key Laboratory of Degradable Biomedical Materials, Shaanxi R& D Center of Biomaterials and Fermentation Engineering, School of Chemical and Engineering, Northwest University, Xi’an 710069 (China); Huang, Qiang; Mao, Liucheng; Huang, Hongye [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Hui, Junfeng [Shaanxi Key Laboratory of Degradable Biomedical Materials, Shaanxi R& D Center of Biomaterials and Fermentation Engineering, School of Chemical and Engineering, Northwest University, Xi’an 710069 (China); Deng, Fengjie, E-mail: fengjiedeng@aliyun.com [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Zhang, Xiaoyong, E-mail: xiaoyongzhang1980@gmail.com [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Wei, Yen, E-mail: weiyen@tsinghua.edu.cn [Department of Chemistry and The Tsinghua Center for Frontier Polymer Research, Tsinghua University, Beijing 100084 (China)

    2017-03-31

    Highlights: • Surface modification of HAp nanorods through the combination of ligand exchange reaction and metal free SI-ATRP. • HAp-polyPEGMA displayed high water dispersibility, good biocompatibility and biological imaging capability. • Metal free ATRP can overcome the toxic and fluorescence quenching effects of metal catalysts of conventional ATRP. - Abstract: The Eu{sup 3+} doped luminescent hydroxyapatite (HAp) nanorods with uniform size and morphology can be synthesized by hydrothermal route. However, these HAp nanorods are coated by hydrophobic oleylamine, which makes them difficult to be dispersed in aqueous solution and impede their biomedical applications. In this work, Eu{sup 3+} doped luminescent polymers functionalized HAp nanorods were prepared through the combination of ligand exchange reaction and metal free surface initiated atom transfer radical polymerization (ATRP) method. In this procedure, the amino group functionalized HAp nanorods were first prepared by ligand exchange reaction using adenosine monophosphate (AMP) as ligand. Then the Br-containing initiators (HAp-Br) were introduced onto the surface of HAp-AMP nanorods through the amidation reaction. Finally, polymers functionalized HAp nanorods were prepared by metal free ATRP method using poly(ethylene glycol) methacrylate (PEGMA) as monomer and 10-phenylphenothiazine (PTH) as organic photocatalyst. The properties of these obtained HAp nanocomposites (HAP-polyPEGMA nanorods) were characterized by means of transmission electron microscopy, Fourier transformed infrared spectroscopy, X-ray photoelectron spectroscopy and thermogravimetric analysis in detail. The cell imaging of these HAP-polyPEGMA nanorods was examined using laser scanning confocal microscope to evaluate their biomedical applications. We demonstrated for the first time that hydrophobic luminescent HAp nanorods can be functionalized with polyPEGMA through the combination of ligand exchange reaction and metal free surface

  9. Thermal evolution of the morphology of Ni/Ag/Si(111)-{radical}3 Multiplication-Sign {radical}3 surface

    Energy Technology Data Exchange (ETDEWEB)

    Tomaszewska, Agnieszka; Huang, Xiao-Lan; Chang, Kuo-Wei; Fu, Tsu-Yi, E-mail: phtifu@phy.ntnu.edu.tw

    2012-08-31

    The temperature-driven changes in morphology of the interface formed by room temperature (RT) deposition of Ni atoms onto an Ag/Si(111)-{radical}3 Multiplication-Sign {radical}3 surface were investigated by scanning tunneling microscopy. Roughly 70% of Ni deposition diffused into bulk substrate within the temperature range between RT and 573 K. The images as obtained after annealing up to 670 K correspond to the formation of nano-sized islands of nickel silicides. Two types of islands, large triangular islands typical of the whole range of applied coverage, and smaller islands of different shapes, coexist at Ni coverage higher than 1 monolayer. Annealing above 870 K led to the formation of a 7 Multiplication-Sign 7 phase in coexistence with small 5 Multiplication-Sign 5 domains at the expense of a complete disappearance of the {radical}3 Multiplication-Sign {radical}3 phase. Also, formation of Ni,Si alloy was observed at the temperature, along with segregation of bulk-dissolved Ni species onto the surface. - Highlights: Black-Right-Pointing-Pointer We examine changes in morphology of Ni/Ag/Si(111)-{radical}3 Multiplication-Sign {radical}3 surface upon annealing. Black-Right-Pointing-Pointer 70% of deposited Ni atoms diffuse into the bulk after annealing at 570 K. Black-Right-Pointing-Pointer A variety of nano-sized Ni, Si islands develops after annealing at 670 K. Black-Right-Pointing-Pointer 5 Multiplication-Sign 5 reconstruction as an evidence for mass transport during the island growth.

  10. Observation of OH radicals produced by pulsed discharges on the surface of a liquid

    Science.gov (United States)

    Kanazawa, Seiji; Kawano, Hirokazu; Watanabe, Satoshi; Furuki, Takashi; Akamine, Shuichi; Ichiki, Ryuta; Ohkubo, Toshikazu; Kocik, Marek; Mizeraczyk, Jerzy

    2011-06-01

    The hydroxyl radical (OH) plays an important role in plasma chemistry at atmospheric pressure. OH radicals have a higher oxidation potential compared with other oxidative species such as free radical O, atomic oxygen, hydroperoxyl radical (HO2), hydrogen peroxide(H2O2) and ozone. In this study, surface discharges on liquids (water and its solutions) were investigated experimentally. A pulsed streamer discharge was generated on the liquid surface using a point-to-plane electrode geometry. The primary generation process of OH radicals is closely related to the streamer propagation, and the subsequent secondary process after the discharge has an influence on the chemical reaction. Taking into account the timescale of these processes, we investigated the behavior of OH radicals using two different diagnostic methods. Time evolution of the ground-state OH radicals above the liquid surface after the discharge was observed by a laser-induced fluorescence (LIF) technique. In order to observe the ground-state OH, an OH [A 2∑+(v' = 1) <-- X 2Π(v'' = 0)] system at 282 nm was used. As the secondary process, a portion of OH radicals diffused from gas phase to the liquid surface and dissolved in the liquid. These dissolved OH radicals were measured by a chemical probe method. Terephthalic acid was used as an OH radical trap and fluorescence of the resulting 2-hydroxyterephthalic acid was measured. This paper directly presents visualization of OH radicals over the liquid surface by means of LIF, and indirectly describes OH radicals dissolved in water by means of a chemical method.

  11. Stratified polymer brushes from microcontact printing of polydopamine initiator on polymer brush surfaces.

    Science.gov (United States)

    Wei, Qiangbing; Yu, Bo; Wang, Xiaolong; Zhou, Feng

    2014-06-01

    Stratified polymer brushes are fabricated using microcontact printing (μCP) of initiator integrated polydopamine (PDOPBr) on polymer brush surfaces and the following surface initiated atom transfer radical polymerization (SI-ATRP). It is found that the surface energy, chemically active groups, and the antifouling ability of the polymer brushes affect transfer efficiency and adhesive stability of the polydopamine film. The stickiness of the PDOPBr pattern on polymer brush surfaces is stable enough to perform continuous μCP and SI-ATRP to prepare stratified polymer brushes with a 3D topography, which have broad applications in cell and protein patterning, biosensors, and hybrid surfaces. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Uptake Coefficients of NO3 Radicals on Solid Surfaces of Sea-Salts

    Science.gov (United States)

    Gratpanche, F.; Sawerysyn, J.-P.

    1999-02-01

    Uptake coefficients of nitrate radicals (γ NO_3) have been measured by a technique involving a coated-wall flow tube with radical detection by E.P.R. spectrometry. The variation of NO3 concentration in the gas phase was followed indirectly by monitoring OH radicals produced by the titration reaction H + NO_3. The mean initial value of γ NO3 measured on solid NaCl surfaces was (1.7± 1.2)× 10-2) in the temperature range 258-301 K, while for solid NaBr surfaces the value was (0.11 ± 0.06) at 293 K. In each case, errors limits correspond to one standard deviation. For NaBr, a slight negative temperature dependence was observed over the investigated range, 243-293 K, which can be represented by γ_NO_3^NaBr = 1.6 ≤ft(begin{array}{l}+1.8 -0.9) × 10-3exp [(1210± 200)/T]. An analysis of the results shows that under some conditions the heterogeneous loss of nitrate radicals on sea-salt aerosol particles at ambient temperature could be competitive with their loss by homogeneous reaction in the marine troposphere at night. Les coefficients de capture des radicaux nitrate (γ NO_3) sur des surfaces de sels marins (NaCl et NaBr) ont été mesurés aux températures troposphériques en utilisant la technique du réacteur à écoulement à paroi recouverte couplée à un spectromètre de résonance paramagnétique électronique (R.P.E). La variation de la concentration en phase gazeuse des radicaux nitrate en présence des surfaces étudiées est suivie en mesurant le signal R.P.E des radicaux OH produits par la réaction de titrage H + NO3. Pour des températures comprises entre 258 et 301 K, la valeur moyenne du coefficient de capture initial (γ NO_3) sur des surfaces solides de NaCl est égal à (1.7± 1.2)× 10-2). Sur des surfaces solides de NaBr, (γ NO_3) est égal à (0.11 ± 0.06) à 293 K. L'incertitude correspond à une déviation standard. Par ailleurs, pour ce type de surfaces, une légère dépendance négative avec la température est observée dans la

  13. Rising from failure and learning from success: The role of past experience in radical initiative taking

    NARCIS (Netherlands)

    D. Deichmann (Dirk); J.C.M. van den Ende (Jan)

    2014-01-01

    markdownabstract__Abstract__ We investigate how the successes and failures of people who initiate radical ideas influence (a) the inclination to take new personal initiatives and (b) the outcome of those initiatives. Using the data of 1,792 radical ideas suggested by 908 employees in a

  14. Observation of OH radicals produced by pulsed discharges on the surface of a liquid

    Energy Technology Data Exchange (ETDEWEB)

    Kanazawa, Seiji; Kawano, Hirokazu; Watanabe, Satoshi; Furuki, Takashi; Akamine, Shuichi; Ichiki, Ryuta; Ohkubo, Toshikazu [Department of Electrical and Electronic Engineering, Oita University, 700 Dannoharu, Oita 870-1192 (Japan); Kocik, Marek; Mizeraczyk, Jerzy, E-mail: skana@cc.oita-u.ac.jp [Szewalski Institute of Fluid Flow Machinery, Polish Academy of Sciences Fiszera 14, 80-952, Gdansk (Poland)

    2011-06-15

    The hydroxyl radical (OH) plays an important role in plasma chemistry at atmospheric pressure. OH radicals have a higher oxidation potential compared with other oxidative species such as free radical O, atomic oxygen, hydroperoxyl radical (HO{sub 2}), hydrogen peroxide(H{sub 2}O{sub 2}) and ozone. In this study, surface discharges on liquids (water and its solutions) were investigated experimentally. A pulsed streamer discharge was generated on the liquid surface using a point-to-plane electrode geometry. The primary generation process of OH radicals is closely related to the streamer propagation, and the subsequent secondary process after the discharge has an influence on the chemical reaction. Taking into account the timescale of these processes, we investigated the behavior of OH radicals using two different diagnostic methods. Time evolution of the ground-state OH radicals above the liquid surface after the discharge was observed by a laser-induced fluorescence (LIF) technique. In order to observe the ground-state OH, an OH [A {sup 2}{Sigma}{sup +}(v' = 1) <- X {sup 2}{Pi}(v'' = 0)] system at 282 nm was used. As the secondary process, a portion of OH radicals diffused from gas phase to the liquid surface and dissolved in the liquid. These dissolved OH radicals were measured by a chemical probe method. Terephthalic acid was used as an OH radical trap and fluorescence of the resulting 2-hydroxyterephthalic acid was measured. This paper directly presents visualization of OH radicals over the liquid surface by means of LIF, and indirectly describes OH radicals dissolved in water by means of a chemical method.

  15. Rising from failure and learning from success: the role of past experience in radical initiative taking

    NARCIS (Netherlands)

    Deichmann, D.; van den Ende, J..

    2014-01-01

    We investigate how the successes and failures of people who initiate radical ideas influence (a) the inclination to take new personal initiatives and (b) the outcome of those initiatives. Using the data of 1,792 radical ideas suggested by 908 employees in a multinational firm's idea and innovation

  16. Preparation of Mg(OH)_2 hybrid pigment by direct precipitation and graft onto cellulose fiber via surface-initiated atom transfer radical polymerization

    International Nuclear Information System (INIS)

    Wang, Xiao; Zhang, Yue; Lv, Lihua; Cui, Yongzhu; Wei, Chunyan; Pang, Guibing

    2016-01-01

    Graphical abstract: - Highlights: • Adsorbed anionic dye molecules are conducive to preferential growth of (0 0 1) plane of Mg(OH)_2 crystal for Mg(OH)_2 pigments. • Uniform coverage of nanosized Mg(OH)_2 pigments on fiber surface is achieved via surface-initiated ATRP. • About 4 wt% of Mg(OH)_2 pigment on fiber surface shortens nearly half of burning time of cellulose. - Abstract: Mg(OH)_2 flame retardant hybrid pigment is synthesized through simultaneous solution precipitation and adsorption of anionic dyes (C.I. Acid Red 6). The Mg(OH)_2 hybrid pigment bearing vinyl groups after surface silane modification is immobilized onto the surface of bromo end-functional cellulose fiber by atom transfer radical polymerization (ATRP). The morphology and structure of Mg(OH)_2 pigments and cellulose fibers grafted with modified pigments are characterized. The thermal properties, flammability and color fastness of cellulose fibers grafted with modified pigments are measured. The results reveal that anionic dye molecules are adsorbed onto Mg(OH)_2 crystals and affect the formation of lamella-like Mg(OH)_2 crystals. The cellulose fiber grafted with modified Mg(OH)_2 hybrid pigment absorbs about four times heat more than original cellulose fiber with about 4% immobilization ratio of pigment, which shortens nearly half of afterflame time and afterglow time.

  17. Modification of dispersibility of nanodiamond by grafting of polyoxyethylene and by the introduction of ionic groups onto the surface via radical trapping

    International Nuclear Information System (INIS)

    Cha, I.; Hashimoto, K.; Fujiki, K.; Yamauchi, T.; Tsubokawa, N.

    2014-01-01

    To improve the dispersibility of polycrystalline nanodiamond (ND) in solvents, the grafting of polymers and introduction of ionic groups onto ND surface via radical trapping by ND surface were investigated. The grafting of polyoxyethylene (POE) onto ND surface by trapping of POE radicals formed by the thermal decomposition of POE macro azo-initiator (Azo-POE) was examined. The polymer radicals formed by the thermal decomposition of Azo-POE were successfully trapped by ND surface to give POE-grafted ND. The effect of temperature on the grafting of POE onto ND was discussed. In addition, the introduction of cationic protonated amidine groups onto ND was achieved by the trapping of radicals bearing protonated amidine groups formed by thermal decomposition of 2,2′-azobis(2-methylpropionamidine)dihydrochloride (AMPA). The anionic carboxylate groups was introduced onto ND surface by the trapping of the radicals bearing carboxyl groups formed by thermal decomposition of 4,4′-azobis(4-cyonovaleric acid) (ACVA) followed by the treatment with NaOH aqueous solution. The dispersibility of ND in water was remarkably improved by the grafting of POE, based on the steric hindrance of polymer chains and by the introduction of ionic groups, based on the ionic repulsion, onto ND surface. - Highlights: • Grafting of PEG onto nanodiamond was achieved by radical trapping. • Introduction of ionic groups onto nanodiamond was achieved by radical trapping. • Nanodiamond was dispersed by PEG grafting based on steric hindrance of PEG chains. • Nanodiamond was dispersed by introduction of ionic groups based on ionic repulsion

  18. Modification of dispersibility of nanodiamond by grafting of polyoxyethylene and by the introduction of ionic groups onto the surface via radical trapping

    Energy Technology Data Exchange (ETDEWEB)

    Cha, I. [Graduate School of Science and Technology, Niigata University, 8050, Ikarashi, 2-no-cho, Nishi-ku, Niigata 950-2181 (Japan); Hashimoto, K. [Department of Material Science and Technology, Faculty of Engineering, Niigata University, 8050, Ikarashi, 2-no-cho, Nishi-ku, Niigata 950-218 (Japan); Fujiki, K. [Department of Environmental Science, Niigata Institute of Technology, 1719, Fujihashi, Kashiwazaki, Niigata 945-1195 (Japan); Yamauchi, T. [Graduate School of Science and Technology, Niigata University, 8050, Ikarashi, 2-no-cho, Nishi-ku, Niigata 950-2181 (Japan); Department of Material Science and Technology, Faculty of Engineering, Niigata University, 8050, Ikarashi, 2-no-cho, Nishi-ku, Niigata 950-218 (Japan); Tsubokawa, N., E-mail: ntsuboka@eng.niigata-u.ac.jp [Graduate School of Science and Technology, Niigata University, 8050, Ikarashi, 2-no-cho, Nishi-ku, Niigata 950-2181 (Japan); Department of Material Science and Technology, Faculty of Engineering, Niigata University, 8050, Ikarashi, 2-no-cho, Nishi-ku, Niigata 950-218 (Japan)

    2014-02-14

    To improve the dispersibility of polycrystalline nanodiamond (ND) in solvents, the grafting of polymers and introduction of ionic groups onto ND surface via radical trapping by ND surface were investigated. The grafting of polyoxyethylene (POE) onto ND surface by trapping of POE radicals formed by the thermal decomposition of POE macro azo-initiator (Azo-POE) was examined. The polymer radicals formed by the thermal decomposition of Azo-POE were successfully trapped by ND surface to give POE-grafted ND. The effect of temperature on the grafting of POE onto ND was discussed. In addition, the introduction of cationic protonated amidine groups onto ND was achieved by the trapping of radicals bearing protonated amidine groups formed by thermal decomposition of 2,2′-azobis(2-methylpropionamidine)dihydrochloride (AMPA). The anionic carboxylate groups was introduced onto ND surface by the trapping of the radicals bearing carboxyl groups formed by thermal decomposition of 4,4′-azobis(4-cyonovaleric acid) (ACVA) followed by the treatment with NaOH aqueous solution. The dispersibility of ND in water was remarkably improved by the grafting of POE, based on the steric hindrance of polymer chains and by the introduction of ionic groups, based on the ionic repulsion, onto ND surface. - Highlights: • Grafting of PEG onto nanodiamond was achieved by radical trapping. • Introduction of ionic groups onto nanodiamond was achieved by radical trapping. • Nanodiamond was dispersed by PEG grafting based on steric hindrance of PEG chains. • Nanodiamond was dispersed by introduction of ionic groups based on ionic repulsion.

  19. Preparation of high-capacity, weak anion-exchange membranes by surface-initiated atom transfer radical polymerization of poly(glycidyl methacrylate) and subsequent derivatization with diethylamine

    International Nuclear Information System (INIS)

    Qian, Xiaolei; Fan, Hua; Wang, Chaozhan; Wei, Yinmao

    2013-01-01

    Ion-exchange membrane is of importance for the development of membrane chromatography. In this work, a high-capacity anion-exchange membrane was prepared by grafting of glycidyl methacrylate (GMA) onto the surface of regenerated cellulose (RC) membranes via surface-initiated atom transfer radical polymerization (SI-ATRP) and subsequent derivatization with diethylamine. Attenuated total reflectance Fourier-transform infrared (ATR-FTIR), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) were used to characterize changes in the chemical functionality, surface topography and pore morphology of the modified membranes. The static capacity of the prepared anion-exchange membrane was evaluated with bovine serum albumin (BSA) as a model protein. The results indicated that the anion-exchange membrane which could reach a maximum capacity of 96 mg/mL for static adsorption possesses a higher adsorption capacity, and the adsorption capacity increases with the polymerization time. The effect of pH and salt concentration confirmed that the adsorption of BSA followed ion-exchange mechanism. The established method would have potential application in the preparation of anion-exchange membrane.

  20. Modification of Ultra-High Vacuum Surfaces Using Free Radicals

    CERN Document Server

    Vorlaufer, G

    2002-01-01

    In ultra-high vacuum systems outgassing from vacuum chamber walls and desorption of surface adsorbates are usually the factors which determine pressure and residual gas composition. In particular in beam vacuum systems of accelerators like the LHC, where surfaces are exposed to intense synchrotron radiation and bombardment by energetic ions and electrons, surface properties like the molecular desorption yield or secondary electron yield can strongly influence the performance of the accelerator. Well-established treatment methods like vacuum bake-out or glow-discharge cleaning have been successfully applied in the past to condition ultra-high vacuum surfaces, but these methods are sometimes difficult to carry out, for example if the vacuum chambers are not accessible. In this work, an alternative treatment method is investigated. This method is based on the strong chemical reactivity of free radicals, electrically neutral fragments of molecules. Free radicals (in the case of this work, nitrogen and oxygen radi...

  1. Strong resistance of Arabidopsis thaliana and Raphanus sativus seeds for ionizing radiation as studied by ESR, ENDOR, ESE spectroscopy and germination measurement: Effect of long-lived and super-long-lived radicals

    Energy Technology Data Exchange (ETDEWEB)

    Kumagai, Jun E-mail: kumagai@apchem.nagoya-u.ac.jp; Katoh, Hiromi; Kumada, Takayuki; Tanaka, Atsushi; Tano, Shigemitsu; Miyazaki, Tetsuo

    2000-01-01

    Resistance of seeds for ionizing radiation effects on Arabidopsis thaliana and Raphanus sativus seeds were investigated by ESR, ENDOR, ESE spectroscopy and germination measurement. Two types of free radicals, such as long-lived (LL) and super-long-lived (SL) radicals, were produced by the {gamma}-irradiation in the seeds. More than 90% of the 1 kGy-irradiated-seeds can germinate probably by decreasing the LL radicals by absorbing water. 10 kGy-irradiated-seeds cannot germinate at all probably due to the existence of significant amounts of the SL radicals even after absorbing water. (author)

  2. Fluoropolymer materials and architectures prepared by controlled radical polymerizations

    DEFF Research Database (Denmark)

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

    2007-01-01

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

  3. Electronic structure of Co islands grown on the {radical}3 x {radical}3-Ag/Ge(111) surface

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Xiao-Lan; Chou, Chi-Hao; Lin, Chun-Liang; Tomaszewska, Agnieszka; Fu, Tsu-Yi, E-mail: phtifu@phy.ntnu.edu.tw

    2011-09-30

    By means of room temperature scanning tunneling spectroscopy (RT STS), we have studied the electronic structure of two different Ag/Ge(111) phases as well as Co islands grown on the {radical}3 x {radical}3-Ag/Ge (111) forming either {radical}13 x {radical}13 or 2 x 2 patterns. The spectrum obtained from 4 x 4-Ag/Ge(111) structure shows the existence of a shoulder at 0.7 V which is also present in the electronic structure of the Ge(111)-c2 x 8 and indicates donation of Ge electrons to electronic states of the Ag-driven phase. However, this fact is not supported by the electronic spectrum taken from the {radical}3 x {radical}3-Ag/Ge (111). The complexity of the Co-{radical}13 x {radical}13 islands bonding with the substrate is mirrored by a large number of peaks in their electronic spectra. The spectra obtained from the Co-2 x 2 islands which had grown on the step differ from those taken from Co-2 x 2 islands located along the edge of the terrace by a number of peaks at negative sample bias. This discrepancy is elucidated in terms of dissimilarities of Co-substrate interaction accompanying Co islands growth on different areas of the stepped surface.

  4. SIMULTANEOUS MEASUREMENT OF FREE RADICAL DECAY IN POLYMERIZATION OF MMA INITIATED BY AIBN USING ESR AND ITS KINETIC MODEL

    Institute of Scientific and Technical Information of China (English)

    Ping Xia; Qing-song Hu; Xiao-lan Qian; Xul-in Jiang; De-yue Yan

    2001-01-01

    The kinetics of free radical decay in the polymerization of MMA initiated by AIBN was studied by means of ESR spectroscopy. It was found that the curves of radical decay are strongly associated with the reaction temperature, the initiator concentration and the solvent. In the case of the radical polymerization carried out at high temperature or in solution, the radical concentration first reached a maximum, then declined monotonously with reaction time. It was also found that the greater the amount of initiator or the higher the temperature, the more rapidly the radicals decay. When the bulk polymerization was implemented at a relatively low temperature, the curves of radical decay became more complicated, i.e.,the radical concentration rapidly rose to a maximum, then dropped to a minimum, finally increased again with reaction time.Taking into account the diffusion effect, a semi-empirical equation is suggested to describe the kinetics of propagating radical decay.

  5. Initial consecutive 125 cases of robotic assisted laparoscopic radical prostatectomy performed in Ireland's first robotic radical prostatectomy centre.

    LENUS (Irish Health Repository)

    Bouchier-Hayes, D M

    2012-03-01

    We examined the patient characteristics, operative proceedings and the outcomes of the initial series of 125 cases of robot-assisted laparoscopic radical prostatectomy (RALRP) in an independent hospital in Ireland, performed by two surgeons using the da Vinci(®) surgical system.

  6. The impact of UV irradiation on the radical initiating capacity of dissolved dyes

    International Nuclear Information System (INIS)

    Vig, A.; Czilik, M.; Rusznak, I.

    2002-01-01

    Complete text of publication follows. Kinetics of photodecomposition of three model dyes dissolved in isopropanol-water mixture has been determined after exposure to UV radiation in the range from 360 through 400 nm and from 220 through 400 nm, respectively. It has been disclosed earlier that photodecomposition of the dissolved dyes was decelerated initially by the presence of the dissolved oxygen in the system. The presence of a radical initiator, AIBN was indispensable for arriving at the decomposition of the irradiated dye solution in the range from 360 through 400 nm. The equation of W i D = [O 2 ]/τ D was used for the calculation of radical initiating rate of the irradiated dye molecule on the isopropanol (W i D (mol/l x s)), where [O 2 ] (mol/l) is the dissolved oxygen concentration in the system and τ D (s) is duration of the induction period of the photodestruction of the dissolved dye. The equation is valid only for photodecomposition which are not chain reaction. The photodegradation of dissolved dyes was also other then chain reaction, consequently the above equation could be applied in the study too. The average radical initiating rate of the dyes applied in this study was in the order of magnitude equal to that of AIBN. The number of cycles between the first radical formation and the last regeneration of the dye molecule could be calculated in bath systems (in the presence and absence of oxygen, respectively): K = W i D /W D , where K is the number of cycles, W D (mol/l x s) is the initial rate of the decomposition of the dissolved dyed. The number of cycles in the oxygen containing systems significantly exceeded those obtained in the oxygen systems because W D was markedly higher in the latter system than in the former one

  7. Surface Initiated Polymerizations via e-ATRP in Pure Water

    Directory of Open Access Journals (Sweden)

    Seyed Schwan Hosseiny

    2013-10-01

    Full Text Available Here we describe the combined process of surface modification with electrochemical atom transfer radical polymerization (e-ATRP initiated from the surface of a modified gold-electrode in a pure aqueous solution without any additional supporting electrolyte. This approach allows for a very controlled growth of the polymer chains leading towards a steady increase in film thickness. Electrochemical quartz crystal microbalance displayed a highly regular increase in surface confined mass only after the addition of the pre-copper catalyst which is reduced in situ and transformed into the catalyst. Even after isolation and washing of the modified electrode surface, reinitiation was achieved with retention of the controlled electrochemical ATRP reaction. This reinitiation after isolation proves the livingness of the polymerization. This approach has interesting potential for smart thin film materials and offers also the possibility of post-modification via additional electrochemical induced reactions.

  8. Preparation of polystyrene-poly(ethylene glycol) diblock copolymer by "living" free radical polymerization

    DEFF Research Database (Denmark)

    Chen, Xianyi; Gao, Bo; Kops, Jørgen

    1998-01-01

    terminated with a TEMPO unit (MPEG-TEMPO), which was further used to prepare the diblock copolymer PS-b-PEG by 'living' free radical polymerisation of styrene. The product was purified and identified by H-1 n.m.r. and GPC. However, large amounts of homopolystyrene was also formed by simultaneous thermal...

  9. Constructing Functional Ionic Membrane Surface by Electrochemically Mediated Atom Transfer Radical Polymerization

    Directory of Open Access Journals (Sweden)

    Fen Ran

    2016-01-01

    Full Text Available The sodium polyacrylate (PAANa contained polyethersulfone membrane that was fabricated by preparation of PES-NH2 via nonsolvent phase separation method, the introduction of bromine groups as active sites by grafting α-Bromoisobutyryl bromide, and surface-initiated electrochemically atom transfer radical polymerization (SI-eATRP of sodium acrylate (AANa on the surface of PES membrane. The polymerization could be controlled by reaction condition, such as monomer concentration, electric potential, polymerization time, and modifier concentration. The membrane surface was uniform when the monomer concentration was 0.9 mol/L, the electric potential was −0.12 V, the polymerization time was 8 h, and the modifier concentration was 2 wt.%. The membrane showed excellent hydrophilicity and blood compatibility. The water contact angle decreased from 84° to 68° and activated partial thromboplastin increased from 51 s to 84 s after modification of the membranes.

  10. Preparing polymer brushes on polytetrafluoroethylene films by free radical polymerization

    International Nuclear Information System (INIS)

    Sun Wei; Chen Yiwang; Deng Qilan; Chen Lie; Zhou Lang

    2006-01-01

    Films of polytetrafluoroethylene (PTFE) were exposed to sodium naphthalenide (Na/naphtha) etchant so as to defluorinate the surface for obtaining hydroxyl functionality. Surface-initiators were immobilized on the PTFE films by esterification of 4,4'-azobis(4-cyanopentanoic acid) (ACP) and the hydroxyl groups covalently linked to the surface. Grafting of polymer brushes on the PTFE films was carried out by the surface-initiated free radical polymerization. Homopolymers brushes of methyl methacrylate (MMA) were prepared by free radical polymerization from the azo-functionalized PTFE surface. The chemical composition and topography of the graft-functionalized PTFE surfaces were characterized by X-ray photoelectron spectroscopy (XPS), attenuated total reflectance (ATR) FT-IR spectroscopy and atomic force microscopy (AFM). Water contact angles on PTFE films were reduced by surface grafting of MMA

  11. HPLC-ESR techniques for detection of complex trapped radicals

    International Nuclear Information System (INIS)

    Tu Tiecheng; Dong Jirong; Lin Nianyun; Xie Leidong; Liu Rengzhong

    1992-01-01

    High performance liquid chromatography (HPLC) and ESR combined examination of radical species is an advanced techniques for separation and identification of complex radical species. At SRCL, Waters 990 HPLC has been used to separate the complex trapped radicals and Varian E-112 ESR spectrometer to record the spectra of single trapped radicals after HPLC separation. The advantages of the combined techniques are described as bellow: HPLC is used to separate the long-lived complex trapped radicals derived from reaction of short-lived radicals with spin trap. ESR spectra from single trapped radicals, obtained following HPLC separation of complex trapped radicals, are recorded one by one and well resolved. The structures of short-lived radicals can be inferred from the ESR spectra of the long-lived trapped radicals

  12. Search for heavy long-lived charged particles with the ATLAS detector in pp collisions at {radical}(s)=7 TeV

    Energy Technology Data Exchange (ETDEWEB)

    Aad, G [Fakultaet fuer Mathematik und Physik, Albert-Ludwigs-Universitaet, Freiburg i.Br. (Germany); Abbott, B [Homer L. Dodge Department of Physics and Astronomy, University of Oklahoma, Norman, OK (United States); Abdallah, J [Institut de Fisica d' Altes Energies and Universitat Autonoma de Barcelona and ICREA, Barcelona (Spain); Abdelalim, A A [Section de Physique, Universite de Geneve, Geneva (Switzerland); Abdesselam, A [Department of Physics, Oxford University, Oxford (United Kingdom); Abdinov, O [Institute of Physics, Azerbaijan Academy of Sciences, Baku (Azerbaijan); Abi, B [Department of Physics, Oklahoma State University, Stillwater, OK (United States); Abolins, M [Department of Physics and Astronomy, Michigan State University, East Lansing, MI (United States); Abramowicz, H [Raymond and Beverly Sackler School of Physics and Astronomy, Tel Aviv University, Tel Aviv (Israel); Abreu, H [LAL, Univ. Paris-Sud and CNRS/IN2P3, Orsay (France); Acerbi, E [INFN Sezione di Milano (Italy); Dipartimento di Fisica, Universita di Milano, Milano (Italy); Acharya, B S [INFN Gruppo Collegato di Udine (Italy); ICTP, Trieste [Italy; Adams, D L [Physics Department, Brookhaven National Laboratory, Upton, NY (United States); Addy, T N [Department of Physics, Hampton University, Hampton, VA (United States); Adelman, J [Department of Physics, Yale University, New Haven, CT (United States); Aderholz, M [Max-Planck-Institut fuer Physik (Werner-Heisenberg-Institut), Muenchen (Germany); Adomeit, S [Fakultaet fuer Physik, Ludwig-Maximilians-Universitaet Muenchen, Muenchen (Germany); Adragna, P [Department of Physics, Queen Mary University of London, London (United Kingdom); Adye, T [Particle Physics Department, Rutherford Appleton Laboratory, Didcot (United Kingdom); Aefsky, S [Department of Physics, Brandeis University, Waltham, MA (United States)

    2011-09-20

    A search for long-lived charged particles reaching the muon spectrometer is performed using a data sample of 37 pb{sup -1} from pp collisions at {radical}(s)=7 TeV collected by the ATLAS detector at the LHC in 2010. No excess is observed above the estimated background. Stable {tau}{sup -tilde} sleptons are excluded at 95% CL up to a mass of 136 GeV, in GMSB models with N{sub 5}=3, m{sub messenger}=250 TeV, sign({mu})=1 and tan{beta}=5. Electroweak production of sleptons is excluded up to a mass of 110 GeV. Gluino R-hadrons in a generic interaction model are excluded up to masses of 530 GeV to 544 GeV depending on the fraction of R-hadrons produced as g{sup -tilde} -balls.

  13. Understanding the Role of Water on Electron-Initiated Processes and Radical Chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Garrett, Bruce C [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Colson, Steven D [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Dixon, David A. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Laufer, Allan H [US Department of Energy Office of Science Office of Basic Energy Sciences; Ray, Douglas [Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

    2003-06-10

    On September 26–28, 2002, a workshop entitled “Understanding the Role of Water on Electron-Initiated Processes and Radical Chemistry” was held to assess new research opportunities in electron-driven processes and radical chemistry in aqueous systems. Of particular interest was the unique and complex role that the structure of water plays in influencing these processes. Novel experimental and theoretical approaches to solving long-standing problems in the field were explored. A broad selection of participants from universities and the national laboratories contributed to the workshop, which included scientific and technical presentations and parallel sessions for discussions and report writing.

  14. Functional copolymer/organo-MMT nanoarchitectures. VI. Synthesis and characterization of novel nanocomposites by interlamellar controlled/living radical copolymerization via preintercalated RAFT-agent/organoclay complexes.

    Science.gov (United States)

    Rzayev, Zakir M O; Söylemez, A Ernur

    2011-04-01

    We have developed a new approach for the synthesis of polymer nanocomposites using a bifunctional reversible addition-fragmentation chain transfer (RAFT) agent, two types of organo-montmorillonites, such as a non-reactive dimethyldodecyl ammonium (DMDA)-MMT and a reactive octadecylamine (ODA)-MMT organoclays, and a radical initiator. The method includes the following stages: (1) synthesis of RAFT intercalated O-MMTs by a physical or chemical interaction of the RAFT agent having two pendant carboxylic groups [S,S-bis(alpha,alpha'-dimethyl-alpha"-acetic acid)trithiocarbonate] with surface alkyl amines of O-MMT containing tertiary ammonium cation or primary amine groups through strong H-bonding and complexing/amidization reactions, respectively, and (2) utilization of these well-dispersed and intercalated RAFT ... O-MMT complexes and their amide derivatives as new modified RAFT agents in radical-initiated interlamellar controlled/living copolymerization of itaconic acid (IA)-n-butylmethacrylate (BMA) monomer pair. The structure and compositions of the synthesized RAFT ... O-MMT complexes and functional copolymer/O-MMT hybrids were confirmed by FTIR, XRD, thermal (DSC-TGA), SEM and TEM morphology analyses. It was demonstrated that the degree of interaction/exfoliation, morphology and thermal behavior of nanocomposites significantly depended on the type of organoclay and in situ interaction, as well as on the content of flexible butyl-ester linkages as a internal plasticizer. The results of the comparative analysis of the nanocomposites structure-composition-property relations show that the functional copolymer-organoclay hybrids prepared with reactive RAFT ... ODA-MMT complex and containing a combination of partially intercalated and predominantly exfoliated nano-structures exhibit relatively higher thermal stability and fine dispersed morphology. These effects were explained by in situ interfacial chemical reactions through amidization of RAFT with surface alkyl amine

  15. Design of UV-absorbing PVDF membrane via surface-initiated AGET ATRP

    Science.gov (United States)

    Dong, Li; Liu, Xiangdong; Xiong, Zhengrong; Sheng, Dekun; Zhou, Yan; Lin, Changhong; Yang, Yuming

    2018-03-01

    Herein, PVDF membranes with excellent UV-absorbing property were first synthesized through grafting the polymerizable low-molecular-weight organic UV-absorber 2-hydroxy-4-(3-methacryloxy-2-hydroxylpropoxy) benzophenone (BPMA) onto α-bromoester-functionalized PVDF membranes via the surface-initiated activator generated by electron transfer atom transfer radical polymerization (SI-AGET ATRP). The surface initiators were immobilized by the reaction between 2-bromoisobutyryl bromide (BIBB) and the hydroxylated PVDF membranes. PVDF-g-PBPMA membranes with different grafting densities were obtained by tuning the polymerization time and the modified membranes were characterized by 1H-NMR, FT-IR, XPS, SEM, UV-vis Spectrophotometer, TGA and DSC. The experimental results indicated that PBPMA chains were successfully introduced onto PVDF membranes. Most importantly, the PVDF-g-PBPMA membranes exhibited outstanding UV-shielding property. UV-vis transmittance spectra showed that most UV light below 360 nm could be absorbed by PVDF-g-PBPMA membranes and the whole UV light region (200-400 nm) can be blocked with the reaction time increased.

  16. Surface modification of polystyrene with atomic oxygen radical anions-dissolved solution

    International Nuclear Information System (INIS)

    Wang Lian; Yan Lifeng; Zhao Peitao; Torimoto, Yoshifumi; Sadakata, Masayoshi; Li Quanxin

    2008-01-01

    A novel approach to surface modification of polystyrene (PS) polymer with atomic oxygen radical anions-dissolved solution (named as O - water) has been investigated. The O - water, generated by bubbling of the O - (atomic oxygen radical anion) flux into the deionized water, was characterized by UV-absorption spectroscopy and electron paramagnetic resonance (EPR) spectroscopy. The O - water treatments caused an obvious increase of the surface hydrophilicity, surface energy, surface roughness and also caused an alteration of the surface chemical composition for PS surfaces, which were indicated by the variety of contact angle and material characterization by atomic force microscope (AFM) imaging, field emission scanning electron microscopy (FESEM), X-ray photoelectron spectroscopy (XPS), and attenuated total-reflection Fourier transform infrared (ATR-FTIR) measurements. Particularly, it was found that some hydrophilic groups such as hydroxyl (OH) and carbonyl (C=O) groups were introduced onto the polystyrene surfaces via the O - water treatment, leading to the increases of surface hydrophilicity and surface energy. The active oxygen species would react with the aromatic ring molecules on the PS surfaces and decompose the aromatic compounds to produce hydrophilic hydroxyl and carbonyl compounds. In addition, the O - water is also considered as a 'clean solution' without adding any toxic chemicals and it is easy to be handled at room temperature. Present method may suit to the surface modification of polymers and other heat-sensitive materials potentially

  17. Bimolecular Excited-State Electron Transfer with Surprisingly Long-Lived Radical Ions

    KAUST Repository

    Alsam, Amani Abdu; Aly, Shawkat Mohammede; Usman, Anwar; Parida, Manas R.; Del Gobbo, Silvano; Alarousu, Erkki; Mohammed, Omar F.

    2015-01-01

    We explored the excited-state interactions of bimolecular, non-covalent systems consisting of cationic poly[(9,9-di(3,3’-N,N’-trimethyl-ammonium) propyl fluorenyl-2,7-diyl)-alt-co-(9,9-dioctyl-fluorenyl-2,7-diyl)] diiodide salt (PFN) and 1,4-dicyanobenzene (DCB) using steady-state and time-resolved techniques, including femto- and nanosecond transient absorption and femtosecond infrared spectroscopies with broadband capabilities. The experimental results demonstrated that photo-induced electron transfer from PFN to DCB occurs on the picosecond time scale, leading to the formation of PFN+• and DCB-• radical ions. Interestingly, real-time observations of the vibrational marker modes on the acceptor side provided direct evidence and insight into the electron transfer process indirectly inferred from UV-Vis experiments. The band narrowing on the picosecond time scale observed on the antisymmetric C-N stretching vibration of the DCB radical anion provides clear experimental evidence that a substantial part of the excess energy is channeled into vibrational modes of the electron transfer product and that the geminate ion pairs dissociate. More importantly, our nanosecond time-resolved data indicate that the charge-separated state is very long lived ( 30 ns) due to the dissociation of the contact radical ion pair into free ions. Finally, the fast electron transfer and slow charge recombination anticipate the current donor−acceptor system with potential applications in organic solar cells.

  18. Bimolecular Excited-State Electron Transfer with Surprisingly Long-Lived Radical Ions

    KAUST Repository

    Alsam, Amani Abdu

    2015-09-02

    We explored the excited-state interactions of bimolecular, non-covalent systems consisting of cationic poly[(9,9-di(3,3’-N,N’-trimethyl-ammonium) propyl fluorenyl-2,7-diyl)-alt-co-(9,9-dioctyl-fluorenyl-2,7-diyl)] diiodide salt (PFN) and 1,4-dicyanobenzene (DCB) using steady-state and time-resolved techniques, including femto- and nanosecond transient absorption and femtosecond infrared spectroscopies with broadband capabilities. The experimental results demonstrated that photo-induced electron transfer from PFN to DCB occurs on the picosecond time scale, leading to the formation of PFN+• and DCB-• radical ions. Interestingly, real-time observations of the vibrational marker modes on the acceptor side provided direct evidence and insight into the electron transfer process indirectly inferred from UV-Vis experiments. The band narrowing on the picosecond time scale observed on the antisymmetric C-N stretching vibration of the DCB radical anion provides clear experimental evidence that a substantial part of the excess energy is channeled into vibrational modes of the electron transfer product and that the geminate ion pairs dissociate. More importantly, our nanosecond time-resolved data indicate that the charge-separated state is very long lived ( 30 ns) due to the dissociation of the contact radical ion pair into free ions. Finally, the fast electron transfer and slow charge recombination anticipate the current donor−acceptor system with potential applications in organic solar cells.

  19. Surface-Initiated Atom Transfer Radical Polymerization of Magnetite Nanoparticles with Statistical Poly(tert-butyl acrylate-poly(poly(ethylene glycol methyl ether methacrylate Copolymers

    Directory of Open Access Journals (Sweden)

    Patcharin Kanhakeaw

    2015-01-01

    Full Text Available This work presented the surface modification of magnetite nanoparticle (MNP with poly[(t-butyl acrylate-stat-(poly(ethylene glycol methyl ether methacrylate] copolymers (P[(t-BA-stat-PEGMA] via a surface-initiated “grafting from” atom transfer radical polymerization (ATRP. Loading molar ratio of t-BA to PEGMA was systematically varied (100 : 0, 75 : 25, 50 : 50, and 25 : 75, resp. such that the degree of hydrophilicity of the copolymers, affecting the particle dispersibility in water, can be fine-tuned. The reaction progress in each step of the synthesis was monitored via Fourier transform infrared spectroscopy (FTIR. The studies in the reaction kinetics indicated that PEGMA had higher reactivity than that of t-BA in the copolymerizations. Gel permeation chromatography (GPC indicated that the molecular weights of the copolymers increased with the increase of the monomer conversion. Transmission electron microscopy (TEM revealed that the particles were spherical with averaged size of 8.1 nm in diameter. Dispersibility of the particles in water was apparently improved when the copolymers were coated as compared to P(t-BA homopolymer coating. The percentages of MNP and the copolymer in the composites were determined via thermogravimetric analysis (TGA and their magnetic properties were investigated via vibrating sample magnetometry (VSM.

  20. The LEGO toolbox: Supramolecular building blocks by nitroxide-mediated controlled radical polymerization

    NARCIS (Netherlands)

    Lohmeijer, B.G.G.; Schubert, U.S.

    2005-01-01

    A terpyridine-functionalized alkoxyamine unimolecular initiator was used for the nitroxide-mediated controlled living radical polymerization of n-butylacrylate, N,N-dimethylacrylamide, 4-vinylpyridine, 2-vinylpyridine, and isoprene. For the former three monomers, the kinetics were studied. All

  1. Reaction of long-lived radicals and vitamin C in γ-irradiated mammalian cells and their model system at 295 K. Tunneling reaction in biological system

    International Nuclear Information System (INIS)

    Matsumoto, Takuro; Kumada, Takayuki; Kodama, Seiji; Watanabe, Masami

    1997-01-01

    When golden hamster embryo (GHE) cells or concentrated albumin solution (0.1 kg dm -3 ), that is a model system of cells, is irradiated with γ-rays at 295 K, organic radicals produced can be observed by ESR. The organic radicals survive at both 295 and 310 K for as long as 20 h. The long-lived radicals in GHE cells and the albumin solution react with vitamin C by the rate constants of 0.007 dm 3 mol -1 s -1 and 0.014 dm 3 mol -1 s -1 , respectively. The long-lived radicals in human cells cause gene mutation, which is suppressed by the addition of vitamin C. The isotope effect on the rate constant (κ) for the reaction of the long-lived radicals and vitamin C has been studied in the albumin solution by use of protonated vitamin C and deuterated vitamin C. The isotope effect (κ H /κ D ) was more than 20 ∼ 50 and was interpreted in terms of tunnelling reaction. (author)

  2. COMPUTATIONAL STUDY OF INTERSTELLAR GLYCINE FORMATION OCCURRING AT RADICAL SURFACES OF WATER-ICE DUST PARTICLES

    International Nuclear Information System (INIS)

    Rimola, Albert; Sodupe, Mariona; Ugliengo, Piero

    2012-01-01

    Glycine is the simplest amino acid, and due to the significant astrobiological implications that suppose its detection, the search for it in the interstellar medium (ISM), meteorites, and comets is intensively investigated. In the present work, quantum mechanical calculations based on density functional theory have been used to model the glycine formation on water-ice clusters present in the ISM. The removal of either one H atom or one electron from the water-ice cluster has been considered to simulate the effect of photolytic radiation and of ionizing particles, respectively, which lead to the formation of OH . radical and H 3 O + surface defects. The coupling of incoming CO molecules with the surface OH . radicals on the ice clusters yields the formation of the COOH . radicals via ZPE-corrected energy barriers and reaction energies of about 4-5 kcal mol –1 and –22 kcal mol –1 , respectively. The COOH . radicals couple with incoming NH=CH 2 molecules (experimentally detected in the ISM) to form the NHCH 2 COOH . radical glycine through energy barriers of 12 kcal mol –1 , exceedingly high at ISM cryogenic temperatures. Nonetheless, when H 3 O + is present, one proton may be barrierless transferred to NH=CH 2 to give NH 2 =CH 2 + . This latter may react with the COOH . radical to give the NH 2 CH 2 COOH +. glycine radical cation which can then be transformed into the NH 2 CHC(OH) 2 +. species (the most stable form of glycine in its radical cation state) or into the NH 2 CHCOOH . neutral radical glycine. Estimated rate constants of these events suggest that they are kinetically feasible at temperatures of 100-200 K, which indicate that their occurrence may take place in hot molecular cores or in comets exposed to warmer regions of solar systems. Present results provide quantum chemical evidence that defects formed on water ices due to the harsh-physical conditions of the ISM may trigger reactions of cosmochemical interest. The relevance of surface H 3 O

  3. Computational Study of Interstellar Glycine Formation Occurring at Radical Surfaces of Water-ice Dust Particles

    Science.gov (United States)

    Rimola, Albert; Sodupe, Mariona; Ugliengo, Piero

    2012-07-01

    Glycine is the simplest amino acid, and due to the significant astrobiological implications that suppose its detection, the search for it in the interstellar medium (ISM), meteorites, and comets is intensively investigated. In the present work, quantum mechanical calculations based on density functional theory have been used to model the glycine formation on water-ice clusters present in the ISM. The removal of either one H atom or one electron from the water-ice cluster has been considered to simulate the effect of photolytic radiation and of ionizing particles, respectively, which lead to the formation of OH• radical and H3O+ surface defects. The coupling of incoming CO molecules with the surface OH• radicals on the ice clusters yields the formation of the COOH• radicals via ZPE-corrected energy barriers and reaction energies of about 4-5 kcal mol-1 and -22 kcal mol-1, respectively. The COOH• radicals couple with incoming NH=CH2 molecules (experimentally detected in the ISM) to form the NHCH2COOH• radical glycine through energy barriers of 12 kcal mol-1, exceedingly high at ISM cryogenic temperatures. Nonetheless, when H3O+ is present, one proton may be barrierless transferred to NH=CH2 to give NH2=CH2 +. This latter may react with the COOH• radical to give the NH2CH2COOH+• glycine radical cation which can then be transformed into the NH2CHC(OH)2 +• species (the most stable form of glycine in its radical cation state) or into the NH2CHCOOH• neutral radical glycine. Estimated rate constants of these events suggest that they are kinetically feasible at temperatures of 100-200 K, which indicate that their occurrence may take place in hot molecular cores or in comets exposed to warmer regions of solar systems. Present results provide quantum chemical evidence that defects formed on water ices due to the harsh-physical conditions of the ISM may trigger reactions of cosmochemical interest. The relevance of surface H3O+ ions to facilitate chemical

  4. A radical approach to radical innovation

    NARCIS (Netherlands)

    D. Deichmann (Dirk); J.C.M. van den Ende (Jan)

    2014-01-01

    textabstractInnovation pays. Amazon, Apple, Facebook, Google – nearly every one of today’s most successful companies has a talent for developing radical new ideas. But how best to encourage radical initiative taking from employees, and does their previous success or failure at it play a role?

  5. The games radicals play : special issue on free radicals and radical ions

    OpenAIRE

    Walton, J.C.; Williams, F.

    2015-01-01

    Chemistry and Physics have aptly been described as “most excellent children of Intellect and Art” [1]. Both these “children” engage with many playthings, and molecules rank as one of their first favorites, especially radicals, which are amongst the most lively and exciting. Checking out radicals dancing to the music of entropy round their potential energy ballrooms is surely both entertaining and enlightening. Radicals’ old favorite convolutions are noteworthy, but the new styles, modes and a...

  6. Synthesis of thermoresponsive poly(N-isopropylacrylamide) brush on silicon wafer surface via atom transfer radical polymerization

    Energy Technology Data Exchange (ETDEWEB)

    Turan, Eylem; Demirci, Serkan [Department of Chemistry, Faculty of Art and Science, Gazi University, 06500 Besevler, Ankara (Turkey); Caykara, Tuncer, E-mail: caykara@gazi.edu.t [Department of Chemistry, Faculty of Art and Science, Gazi University, 06500 Besevler, Ankara (Turkey)

    2010-08-31

    Thermoresponsive poly(N-isopropylacrylamide) [poly(NIPAM)] brush on silicon wafer surface was prepared by combining the self-assembled monolayer of initiator and atom transfer radical polymerization (ATRP). The resulting polymer brush was characterized by in situ reflectance Fourier transform infrared spectroscopy, atomic force microscopy and ellipsometry techniques. Gel permeation chromatography determination of the number-average molecular weight and polydispersity index of the brush detached from the silicon wafer surface suggested that the surface-initiated ATRP method can provide relatively homogeneous polymer brush. Contact angle measurements exhibited a two-stage increase upon heating over the board temperature range 25-45 {sup o}C, which is in contrast to the fact that free poly(NIPAM) homopolymer in aqueous solution exhibits a phase transition at ca. 34 {sup o}C within a narrow temperature range. The first de-wetting transition takes place at 27 {sup o}C, which can be tentatively attributed to the n-cluster induced collapse of the inner region of poly(NIPAM) brush close to the silicon surface; the second de-wetting transition occurs at 38 {sup o}C, which can be attributed to the outer region of poly(NIPAM) brush, possessing much lower chain density compared to that of the inner part.

  7. Surface modification of reverse osmosis desalination membranes by thin-film coatings deposited by initiated chemical vapor deposition

    Energy Technology Data Exchange (ETDEWEB)

    Ozaydin-Ince, Gozde, E-mail: gozdeince@sabanciuniv.edu [Department of Chemical Engineering, Massachusetts Institute of Technology, Cambridge, MA 02139 (United States); Matin, Asif, E-mail: amatin@mit.edu [Department of Mechanical Engineering, King Fahd University of Petroleum and Minerals, Dhahran 31261 (Saudi Arabia); Khan, Zafarullah, E-mail: zukhan@mit.edu [Department of Mechanical Engineering, King Fahd University of Petroleum and Minerals, Dhahran 31261 (Saudi Arabia); Zaidi, S.M. Javaid, E-mail: zaidismj@kfupm.edu.sa [Department of Mechanical Engineering, King Fahd University of Petroleum and Minerals, Dhahran 31261 (Saudi Arabia); Gleason, Karen K., E-mail: kkgleasn@mit.edu [Department of Chemical Engineering, Massachusetts Institute of Technology, Cambridge, MA 02139 (United States)

    2013-07-31

    Thin-film polymeric reverse osmosis membranes, due to their high permeation rates and good salt rejection capabilities, are widely used for seawater desalination. However, these membranes are prone to biofouling, which affects their performance and efficiency. In this work, we report a method to modify the membrane surface without damaging the active layer or significantly affecting the performance of the membrane. Amphiphilic copolymer films of hydrophilic hydroxyethylmethacrylate and hydrophobic perfluorodecylacrylate (PFA) were synthesized and deposited on commercial RO membranes using an initiated chemical vapor deposition technique which is a polymer deposition technique that involves free-radical polymerization initiated by gas-phase radicals. Relevant surface characteristics such as hydrophilicity and roughness could be systematically controlled by varying the polymer chemistry. Increasing the hydrophobic PFA content in the films leads to an increase in the surface roughness and hydrophobicity. Furthermore, the surface morphology studies performed using the atomic force microscopy show that as the thickness of the coating increases average surface roughness increases. Using this knowledge, the coating thickness and chemistry were optimized to achieve high permeate flux and to reduce cell attachment. Results of the static bacterial adhesion tests show that the attachment of bacterial cells is significantly reduced on the coated membranes. - Highlights: • Thin films are deposited on reverse osmosis membranes. • Amphiphilic thin films are resistant to protein attachment. • The permeation performance of the membranes is not affected by the coating. • The thin film coatings delayed the biofouling.

  8. COMPUTATIONAL STUDY OF INTERSTELLAR GLYCINE FORMATION OCCURRING AT RADICAL SURFACES OF WATER-ICE DUST PARTICLES

    Energy Technology Data Exchange (ETDEWEB)

    Rimola, Albert; Sodupe, Mariona [Departament de Quimica, Universitat Autonoma de Barcelona, 08193 Bellaterra (Spain); Ugliengo, Piero, E-mail: albert.rimola@uab.cat [Dipartimento di Chimica, NIS Centre of Excellence and INSTM (Materials and Technology National Consortium), UdR Torino, Universita di Torino, Via P. Giuria 7, 10125 Torino (Italy)

    2012-07-20

    Glycine is the simplest amino acid, and due to the significant astrobiological implications that suppose its detection, the search for it in the interstellar medium (ISM), meteorites, and comets is intensively investigated. In the present work, quantum mechanical calculations based on density functional theory have been used to model the glycine formation on water-ice clusters present in the ISM. The removal of either one H atom or one electron from the water-ice cluster has been considered to simulate the effect of photolytic radiation and of ionizing particles, respectively, which lead to the formation of OH{sup .} radical and H{sub 3}O{sup +} surface defects. The coupling of incoming CO molecules with the surface OH{sup .} radicals on the ice clusters yields the formation of the COOH{sup .} radicals via ZPE-corrected energy barriers and reaction energies of about 4-5 kcal mol{sup -1} and -22 kcal mol{sup -1}, respectively. The COOH{sup .} radicals couple with incoming NH=CH{sub 2} molecules (experimentally detected in the ISM) to form the NHCH{sub 2}COOH{sup .} radical glycine through energy barriers of 12 kcal mol{sup -1}, exceedingly high at ISM cryogenic temperatures. Nonetheless, when H{sub 3}O{sup +} is present, one proton may be barrierless transferred to NH=CH{sub 2} to give NH{sub 2}=CH{sub 2}{sup +}. This latter may react with the COOH{sup .} radical to give the NH{sub 2}CH{sub 2}COOH{sup +.} glycine radical cation which can then be transformed into the NH{sub 2}CHC(OH){sub 2}{sup +.} species (the most stable form of glycine in its radical cation state) or into the NH{sub 2}CHCOOH{sup .} neutral radical glycine. Estimated rate constants of these events suggest that they are kinetically feasible at temperatures of 100-200 K, which indicate that their occurrence may take place in hot molecular cores or in comets exposed to warmer regions of solar systems. Present results provide quantum chemical evidence that defects formed on water ices due to the harsh

  9. A novel heterogeneous system for sulfate radical generation through sulfite activation on a CoFe{sub 2}O{sub 4} nanocatalyst surface

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Zizheng [School of Civil Engineering, Wuhan University, Wuhan, 430072 (China); Yang, Shaojie; Yuan, Yanan; Xu, Jing; Zhu, Yifan [Department of Environmental Science, Hubei Key Lab of Biomass Resource Chemistry and Environmental Biotechnology, School of Resources and Environmental Science, Wuhan University, Wuhan, 430079 (China); Li, Jinjun, E-mail: ljj0410@163.com [Department of Environmental Science, Hubei Key Lab of Biomass Resource Chemistry and Environmental Biotechnology, School of Resources and Environmental Science, Wuhan University, Wuhan, 430079 (China); Wu, Feng, E-mail: fengwu@whu.edu.cn [Department of Environmental Science, Hubei Key Lab of Biomass Resource Chemistry and Environmental Biotechnology, School of Resources and Environmental Science, Wuhan University, Wuhan, 430079 (China)

    2017-02-15

    Highlights: • CoFe{sub 2}O{sub 4}−S(IV)−O{sub 2} system is proposed as a new system of sulfate radical based AOPs. • Alkaline pH favors the activation of sulfite on CoFe{sub 2}O{sub 4} surface to produce oxysulfur radicals. • Generation of Co−OH complexes on the surface of CoFe{sub 2}O{sub 4} is the main factor for sulfite activation. • Degradation of organic contaminants by CoFe{sub 2}O{sub 4}−S(IV)−O{sub 2} system were achieved. • Main intermediates and pathways for the degradation of metoprolol were identified. - Abstract: Heterogeneous catalytic activation is important for potential application of new sulfate-radical-based advanced oxidation process using sulfite as source of sulfate radical. We report herein a heterogeneous system for sulfite activation by CoFe{sub 2}O{sub 4} nanocatalyst for metoprolol removal. Factors that influence metoprolol removal were investigated, including pH and initial concentrations of components. The CoFe{sub 2}O{sub 4} nanocatalyst was characterized by X-ray diffractometry (XRD) and transmission electron microscopy (TEM), and the catalytic stability was tested by consecutive runs. Radicals generated in the CoFe{sub 2}O{sub 4}−S(IV)−O{sub 2} system were identified through radical quenching experiments and by electron spin resonance (ESR). The catalytic mechanism was elucidated further by X-ray photoelectron spectroscopy (XPS). The catalytic process was dependent on initial pH, and more than 80% of the metoprolol can be removed at pH 10.0 following the Langmubir-Hinshelwood equation. The generation of Co-OH complexes on the CoFe{sub 2}O{sub 4} surface was crucial for sulfite activation. SO{sub 4}{sup ·−} was verified to be the main oxidative species responsible for metoprolol degradation. Other organic pollutants, such as sulfanilamide, sulfasalazine, 2-nitroaniline, sulfapyridine, aniline, azo dye X-3B and 4-chloroaniline, could also be removed in this CoFe{sub 2}O{sub 4}−S(IV)−O{sub 2} system. The

  10. PNIPAAm-grafted thermoresponsive microcarriers: Surface-initiated ATRP synthesis and characterization

    Energy Technology Data Exchange (ETDEWEB)

    Çakmak, Soner [Nanotechnology and Nanomedicine Department, Hacettepe University, 06800, Beytepe, Ankara (Turkey); Çakmak, Anıl S. [Bioengineering Department, Hacettepe University, 06800, Beytepe, Ankara (Turkey); Gümüşderelioğlu, Menemşe, E-mail: menemse@hacettepe.edu.tr [Nanotechnology and Nanomedicine Department, Hacettepe University, 06800, Beytepe, Ankara (Turkey); Bioengineering Department, Hacettepe University, 06800, Beytepe, Ankara (Turkey); Chemical Engineering Department, Hacettepe University, 06800, Beytepe, Ankara (Turkey)

    2013-07-01

    In this study, we developed novel thermoresponsive microcarriers as a powerful tool for cell culture and tissue engineering applications. For this purpose, two types of commercially available spherical microparticles (approximately 100 μm in diameter), dextran-based Sephadex® and vinyl acetate-based VA-OH (Biosynth®), were used and themoresponsive poly(N-isopropylacrylamide) (PNIPAAm) was grafted to the beads' surfaces by surface-initiated atom transfer radical polymerization (SI-ATRP). Initially, hydroxyl groups of microbeads were reacted with 2-bromopropionyl bromide to form ATRP macroinitiator. Then, NIPAAm was successfully polymerized from the initiator attached microbeads by ATRP with CuBr/2,2′-dipyridyl, catalyst complex. Furthermore, grafted and ungrafted microbeads were characterized by attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy, scanning electron microscope (SEM), atomic force microscopy (AFM) and electron spectroscopy for chemical analysis (ESCA). The results of characterization studies confirmed that PNIPAAm was successfully grafted onto both dextran and vinyl acetate-based beads by means of ATRP reaction and thus, grafted microbeads gained thermoresponsive characteristics which will be evaluated for cell harvesting in further studies. Highlights: • PNIPAAm was grafted to the hydroxyl group carrying polymer beads by SI-ATRP. • Dex-g-PNIPAAm and VA-OH-g-PNIPAAm beads exhibited thermoresponsive characteristics. • They are appropriate candidates for microcarrier-facilitated cell cultures.

  11. PNIPAAm-grafted thermoresponsive microcarriers: Surface-initiated ATRP synthesis and characterization

    International Nuclear Information System (INIS)

    Çakmak, Soner; Çakmak, Anıl S.; Gümüşderelioğlu, Menemşe

    2013-01-01

    In this study, we developed novel thermoresponsive microcarriers as a powerful tool for cell culture and tissue engineering applications. For this purpose, two types of commercially available spherical microparticles (approximately 100 μm in diameter), dextran-based Sephadex® and vinyl acetate-based VA-OH (Biosynth®), were used and themoresponsive poly(N-isopropylacrylamide) (PNIPAAm) was grafted to the beads' surfaces by surface-initiated atom transfer radical polymerization (SI-ATRP). Initially, hydroxyl groups of microbeads were reacted with 2-bromopropionyl bromide to form ATRP macroinitiator. Then, NIPAAm was successfully polymerized from the initiator attached microbeads by ATRP with CuBr/2,2′-dipyridyl, catalyst complex. Furthermore, grafted and ungrafted microbeads were characterized by attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy, scanning electron microscope (SEM), atomic force microscopy (AFM) and electron spectroscopy for chemical analysis (ESCA). The results of characterization studies confirmed that PNIPAAm was successfully grafted onto both dextran and vinyl acetate-based beads by means of ATRP reaction and thus, grafted microbeads gained thermoresponsive characteristics which will be evaluated for cell harvesting in further studies. Highlights: • PNIPAAm was grafted to the hydroxyl group carrying polymer beads by SI-ATRP. • Dex-g-PNIPAAm and VA-OH-g-PNIPAAm beads exhibited thermoresponsive characteristics. • They are appropriate candidates for microcarrier-facilitated cell cultures

  12. Atmospheric Oxidation Mechanism and Kinetic Studies for OH and NO3 Radical-Initiated Reaction of Methyl Methacrylate

    Directory of Open Access Journals (Sweden)

    Rui Gao

    2014-03-01

    Full Text Available The mechanism for OH and NO3 radical-initiated oxidation reactions of methyl methacrylate (MMA was investigated by using density functional theory (DFT molecular orbital theory. Geometrical parameters of the reactants, intermediates, transition states, and products were fully optimized at the B3LYP/6-31G(d,p level. Detailed oxidation pathways were presented and discussed. The rate constants were deduced by the canonical variational transition-state (CVT theory with the small-curvature tunneling (SCT correction and the multichannel Rice-Ramspergere-Kassele-Marcus (RRKM theory, based on the potential energy surface profiles over the general atmospheric temperature range of 180–370 K. The calculated results were in reasonable agreement with experimental measurement.

  13. Oxidation of aromatic amines and diamines by OH radicals. Formation and ionization constants of amine cation radicals in water

    International Nuclear Information System (INIS)

    Hayon, E.; Rao, P.S.

    1975-01-01

    The one-electron oxidation by hydroxyl radicals of aromatic amines and diamines in water was studied using the fast-reaction technique of pulse radiolysis and kinetic absorption spectrophotometry. The following compounds were examined: N,N,N 1 ,N 1 - tetramethyl-p-phenylenediamine (TMPD), p-phenylenediamine (PD), N,N-dimethyl-p-phenylenediamene (DMPD), N,N,N 1 ,N 1 -tetramethylbenzidine (TMB), and diphenylamine (DPA). The main initial reaction of the OH radicals is suggested to be an addition to these compounds to give absorption spectra which absorb strongly in the visible and uv regions. These OH radical adducts decay by first-order kinetics and have lifetimes of approximately 5-50 μsec, dependent on the pH, buffer concentration, and the nature of the aromatic amines and diamines. They decay to give species with somewhat similar absorption spectra and extinction coefficients, which are very long lived in the absence of oxygen. The latter species are assigned to the cation radicals TMPD. + , PD. + , DMPD. + , TMB. + , and DPA. + . The OH radical adducts and the cation radicals have acid-base properties. The pK/sub a/ values of the cation radicals TMPDH. 2+ , PDH. 2+ , DMPDH. 2+ , TMBH. 2+ , and DPAH. 2+ were found to be 5.3, 5.9, 6.1, 5.1, and 4.2, respectively. The results indicate that these aromatic amines and diamines can be oxidized by free radicals to yield the corresponding cation radicals. (U.S.)

  14. A new face of phenalenyl-based radicals in the transition metal-free C-H arylation of heteroarenes at room temperature: trapping the radical initiator via C-C σ-bond formation.

    Science.gov (United States)

    Ahmed, Jasimuddin; P, Sreejyothi; Vijaykumar, Gonela; Jose, Anex; Raj, Manthan; Mandal, Swadhin K

    2017-11-01

    The radical-mediated transition metal-free approach for the direct C-H bond functionalization of arenes is considered as a cost effective alternative to transition metal-based catalysis. An organic ligand-based radical plays a key role by generating an aryl radical which undergoes a subsequent functionalization process. The design principle of the present study takes advantage of a relatively stable odd alternant hydrocarbon-based phenalenyl (PLY) radical. In this study, the first transition metal-free catalyzed direct C-H arylation of a variety of heteroarenes such as azoles, furan, thiophene and pyridine at room temperature has been reported using a phenalenyl-based radical without employing any photoactivation step. This protocol has been successfully applied to the gram scale synthesis of core moieties of bioactive molecules. The phenalenyl-based radical initiator has been characterized crystallographically by trapping it via the formation of a C-C σ-bond between the phenalenyl radical and solvent-based radical species.

  15. Red fluorescent chitosan nanoparticles grafted with poly(2-methacryloyloxyethyl phosphorylcholine) for live cell imaging.

    Science.gov (United States)

    Wang, Ke; Fan, Xingliang; Zhang, Xiaoyong; Zhang, Xiqi; Chen, Yi; Wei, Yen

    2016-08-01

    Poly(2-methacryloyloxyethyl phosphorylcholine) conjugated red fluorescent chitosan nanoparticles (GCC-pMPC) were facilely fabricated by "grafting from" method via surface initiated atom transfer radical polymerization (ATRP). Firstly, glutaraldehyde crosslinked red fluorescent chitosan nanoparticles (GCC NPs) with many amino groups and hydroxyl groups on their surface were prepared, which were then reacted with 2-bromoisobutyryl bromide to form GCC-Br; subsequently, poly(MPC) (pMPC) brushes were grafted onto GCC NPs surface using GCC-Br as initiator via ATRP. Compared with PEGylated nanoparticles, zwitterionic polymers modified nanoparticles demonstrated better performance in their cellular uptake. Moreover, the obtained GCC-pMPC demonstrated excellent water-dispersibility, biocompatibility, and photostability, which made them highly potential for long-term tracing applications. Importantly, the successful live cell imaging of GCC-pMPC would remarkably advance the research of their further bioapplications. Copyright © 2016 Elsevier B.V. All rights reserved.

  16. A novel heterogeneous system for sulfate radical generation through sulfite activation on a CoFe2O4 nanocatalyst surface.

    Science.gov (United States)

    Liu, Zizheng; Yang, Shaojie; Yuan, Yanan; Xu, Jing; Zhu, Yifan; Li, Jinjun; Wu, Feng

    2017-02-15

    Heterogeneous catalytic activation is important for potential application of new sulfate-radical-based advanced oxidation process using sulfite as source of sulfate radical. We report herein a heterogeneous system for sulfite activation by CoFe 2 O 4 nanocatalyst for metoprolol removal. Factors that influence metoprolol removal were investigated, including pH and initial concentrations of components. The CoFe 2 O 4 nanocatalyst was characterized by X-ray diffractometry (XRD) and transmission electron microscopy (TEM), and the catalytic stability was tested by consecutive runs. Radicals generated in the CoFe 2 O 4 S(IV)O 2 system were identified through radical quenching experiments and by electron spin resonance (ESR). The catalytic mechanism was elucidated further by X-ray photoelectron spectroscopy (XPS). The catalytic process was dependent on initial pH, and more than 80% of the metoprolol can be removed at pH 10.0 following the Langmubir-Hinshelwood equation. The generation of Co-OH complexes on the CoFe 2 O 4 surface was crucial for sulfite activation. SO 4 - was verified to be the main oxidative species responsible for metoprolol degradation. Other organic pollutants, such as sulfanilamide, sulfasalazine, 2-nitroaniline, sulfapyridine, aniline, azo dye X-3B and 4-chloroaniline, could also be removed in this CoFe 2 O 4 S(IV)O 2 system. The results suggest that the CoFe 2 O 4 S(IV)O 2 system has good application prospects in alkaline organic wastewater treatment. Copyright © 2016 Elsevier B.V. All rights reserved.

  17. Self-assembled organic radicals on Au(111) surfaces: a combined ToF-SIMS, STM, and ESR study.

    Science.gov (United States)

    Mannini, Matteo; Sorace, Lorenzo; Gorini, Lapo; Piras, Federica M; Caneschi, Andrea; Magnani, Agnese; Menichetti, Stefano; Gatteschi, Dante

    2007-02-27

    Electron spin resonance (ESR), time-of-flight secondary ion mass spectrometry (ToF-SIMS), and scanning tunneling microscopy (STM) have been used in parallel to characterize the deposition on gold surface of a series of nitronyl nitroxide radicals. These compounds have been specifically synthesized with methyl-thio linking groups suitable to interact with the gold surface to form self-assembled monolayers (SAMs), which can be considered relevant in the research for molecular-based spintronics devices, as suggested in recent papers. The degree of the expected ordering on the surface of these SAMs has been tuned by varying the chemical structure of synthesized radicals. ToF-SIMS has been used to support the evidence of the occurrence of the deposition process. STM has shown the different qualities of the obtained SAMs, with the degree of local order increasing as the degree of freedom of the molecules on the surface is decreased. Finally, ESR has confirmed that the deposition process does not affect the paramagnetic characteristics of radicals and that it affords a complete single-layered coverage of the surface. Further, the absence of angular dependence in the spectra indicates that the small regions of local ordering do not give rise to a long-range order and suggests a quite large mobility of the radical on the surface, probably due to the weak interaction with gold provided by the methyl-thio linking group.

  18. Polymethylene-based copolymers by polyhomologation or by its combination with controlled/living and living polymerizations

    KAUST Repository

    Zhang, Hefeng

    2014-01-20

    Polyhomologation, recently developed by Shea, is a borane-initiated living polymerization of ylides leading to linear polymethylenes (C1 polymerization) with controlled molecular weight, low polydispersity, and well-defined structures. In this Review, the copolyhomologation of different ylides as well as the combination of polyhomologation with controlled/living (nitroxide-mediated, atom transfer radical, reversible addition-fragmentation chain-transfer) and living (ring opening, anionic) polymerizations is discussed. Polyhomologation of ylides, in combination with living and controlled/living polymerizations, leads to a plethora novel well-defined polymethylene (polyethylene)-based polymeric materials, which are very important for understanding/improving the behavior of industrial polyethylenes. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. New insights into the aquatic photochemistry of fluoroquinolone antibiotics: Direct photodegradation, hydroxyl-radical oxidation, and antibacterial activity changes

    International Nuclear Information System (INIS)

    Ge, Linke; Na, Guangshui; Zhang, Siyu; Li, Kai; Zhang, Peng; Ren, Honglei; Yao, Ziwei

    2015-01-01

    The ubiquity and photoreactivity of fluoroquinolone antibiotics (FQs) in surface waters urge new insights into their aqueous photochemical behavior. This study concerns the photochemistry of 6 FQs: ciprofloxacin, danofloxacin, levofloxacin, sarafloxacin, difloxacin and enrofloxacin. Methods were developed to calculate their solar direct photodegradation half-lives (t d,E ) and hydroxyl-radical oxidation half-lives (t ·OH,E ) in sunlit surface waters. The t d,E values range from 0.56 min to 28.8 min at 45° N latitude, whereas t ·OH,E ranges from 3.24 h to 33.6 h, suggesting that most FQs tend to undergo fast direct photolysis rather than hydroxyl-radical oxidation in surface waters. However, a case study for levofloxacin and sarafloxacin indicated that the hydroxyl-radical oxidation induced risky photochlorination and resulted in multi-degradation pathways, such as piperazinyl hydroxylation and clearage. Changes in the antibacterial activity of FQs caused by photodegradation in various waters were further examined using Escherichia coli, and it was found that the activity evolution depended on primary photodegradation pathways and products. Primary intermediates with intact FQ nuclei retained significant antibacterial activity. These results are important for assessing the fate and risk of FQs in surface waters. - Highlights: • It is first reported on hydroxyl-radical oxidation of 6 fluoroquinolone antibiotics. • Methods were developed to assess photolysis and oxidation fate in surface waters. • The neutral form reacted faster with hydroxyl radical than protonated forms. • The main oxidation intermediates and transformation pathways were clarified. • The antibacterial activity changes depend on dominant photolysis pathways

  20. Copper-mediated homogeneous living radical polymerization of acrylamide with waxy potato starch-based macroinitiator.

    Science.gov (United States)

    Fan, Yifei; Cao, Huatang; van Mastrigt, Frank; Pei, Yutao; Picchioni, Francesco

    2018-07-15

    Cu 0 -mediated living radical polymerization (Cu 0 -mediated LRP) was employed in this research for the synthesis of starch-g-polyacrylamide (St-g-PAM). The use of a controlled radical grafting technique is necessary, as compared to the traditional free-radical polymerization methods, in order to obtain a well-defined structure of the final product. This is in turn essential for studying the relationship between such structure and the end-properties. Waxy potato starch-based water-soluble macroinitiator was first synthesized by esterification with 2-bromopropionyl bromide in the mixture of dimethylacetamide and lithium chloride. With the obtained macroinitiator, St-g-PAM was homogeneously synthesized by aqueous Cu 0 -mediated LRP using CuBr/hexamethylated tris(2-aminoethyl)amine (Me 6 Tren) as catalyst. The successful synthesis of the macroinitiator and St-g-PAM was proved by NMR, FT-IR, SEM, XRD and TGA analysis. The molecular weight and polydispersity of PAM chains were analyzed by gel permeation chromatography (GPC) after hydrolyzing the starch backbone. Monomer conversion was monitored by gas chromatography (GC), on the basis of which the kinetics were determined. A preliminarily rheological study was performed on aqueous solutions of the prepared materials. Copyright © 2018 Elsevier Ltd. All rights reserved.

  1. Surface modification of poly(dimethylsiloxane) for controlling biological cells' adhesion using a scanning radical microjet

    International Nuclear Information System (INIS)

    Tan, Helen M.L.; Fukuda, H.; Akagi, T.; Ichiki, T.

    2007-01-01

    A scanning radical microjet (SRMJ) equipment using oxygen microplasma has been developed and successfully applied for controlling biological cells' attachment on biocompatible polymer material, poly(dimethylsiloxane) (PDMS). The radical microjet has advantages in localized and high-rate surface treatment. Moreover, maskless hydrophilic patterning using SRMJ has been demonstrated to be applicable to patterned cell cultivation which is useful in emerging biotechnological field such as tissue engineering and cell-based biosensors. Since control of PDMS surface properties is an indispensable prerequisite for cells' attachment, effects of oxygen flow rates and treatment time on localized hydrophilic patterning of PDMS surfaces were first investigated for controlling HeLa cells' (human epitheloid carcinoma cell line) attachment. Relationships between surface conditions of treated PDMS films and attached cell density are also discussed based on surface properties analyzed using atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS)

  2. Reaction of long-lived radicals and vitamin C in γ-irradiated mammalian cells and their model system at 295 K. Tunneling reaction in biological system

    International Nuclear Information System (INIS)

    Matsumoto, Takuro; Miyazaki, Tetsuo; Kosugi, Yoshio; Kumada, Takayuki; Koyama, Sinji; Kodama, Seiji; Watanabe, Masami.

    1996-01-01

    When golden hamster embryo (GHE) cells or concentrated albumin solution (0.1 kg dm -3 ) that is a model system of cells is irradiated with γ-rays at 295 K, organic radicals produced can be observed by ESR. The organic radicals survive at both 295 K and 310 K for such a long time as 20 hr. The long-lived radicals in GHE cells and the albumin solution react with vitamin C by the rate constants of 0.007 dm 3 mol -1 s -1 and 0.014 dm 3 mol -1 s -1 , respectively. The long-lived radicals in human cells cause gene mutation, which is suppressed by addition of vitamin C. The isotope effect on the rate constant (k) for the reaction of the long-lived radicals and vitamin C has been studied in the albumin solution by use of protonated vitamin C and deuterated vitamin C. The isotope effect (k H /k D ) was more than 20-50 and was interpreted in terms of tunneling reaction. When GHE cells or the aqueous albumin solution (0.1 kg dm -3 ) is irradiated with γ-rays at 295 K, organic radicals produced survive for more than 24 hr at room temperature. Very recently we have found that vitamin C reacts with the long-lived organic radicals in the γ-irradiated albumin solution at high concentration of 0.1 kg dm -3 by the rate constant of 0.014 dm 3 mol -1 s -1 . Since most of reactions in biological systems including the reaction of vitamin C are a transfer of a hydrogen atom or a proton that has a large wave character, it is generally expected that the tunneling reaction may play an important role in biological systems at room temperature. The studies of isotope effects on reactions will give an information on the contribution of tunneling reaction. (J.P.N.)

  3. Synthesis of Well-defined Amphiphilic Block Copolymers by Organotellurium-Mediated Living Radical Polymerization (TERP).

    Science.gov (United States)

    Kumar, Santosh; Changez, Mohammad; Murthy, C N; Yamago, Shigeru; Lee, Jae-Suk

    2011-10-04

    Low-molecular weight amphiphilic diblock copolymers, polystyrene-block-poly (2-vinylpyridine) (PS-b-P2VP), and (P2VP-b-PS) with different block ratios were synthesized for the first time via organotellurium-mediated living radical polymerization (TERP). For both the homo- and block copolymerizations, good agreement between the theoretical, and experimental molecular weights was found with nearly 100% yield in every case. The molecular weight distribution for all the samples ranged between 1.10 and 1.24, which is well below the theoretical lower limit of 1.50 for a conventional free radical polymerization. Furthermore, a very simple approach to producing highly dense arrays of titania nanoparticles (TiO2 ) is presented using a site-selective reaction of titanium tetraisopropoxide within the P2VP domains of micellar film of P2VP-b-PS in toluene through the sol-gel method. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Facile surface glycosylation of PVDF microporous membrane via direct surface-initiated AGET ATRP and improvement of antifouling property and biocompatibility

    International Nuclear Information System (INIS)

    Yuan Jing; Meng Jianqiang; Kang Yinlin; Du Qiyun; Zhang Yufeng

    2012-01-01

    This paper describes a facile and novel approach for the surface glycosylation of poly(vinylidene difluoride) (PVDF) microporous membrane. A glycopolymer poly(D-gluconamidoethyl methacrylate) (PGAMA) was tethered onto the membrane surface via activators generated by electron transfer atom transfer radical polymerization (AGET ATRP) directly initiated from the PVDF surface. Chemical changes of membrane surface were characterized by Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS). It was revealed that PGAMA was successfully grafted onto the membrane surface and its grafting density can be modulated in a wide range up to 2.4 μmol/cm 2 . The effects of glycosylation on membrane morphology, flux and surface hydrophilicity were investigated. Field emission scanning electron microscopy (FESEM) results indicated shrinkage of the surface pore diameters and the growth of the glycopolymer layer on the membrane surface. The static water contact angle (WCA) of the membrane surface decreased from 110° to 30.4° with the increase of grafting density, indicating that the PGAMA grafts dramatically improved the surface hydrophilicity. The protein adsorption and platelets adhesion experiments indicated that the grafted PGAMA could effectively improve the membrane antifouling property and biocompatibility.

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

    Directory of Open Access Journals (Sweden)

    Khezrollah Khezri

    2014-04-01

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

  6. Functionalised Oximes: Emergent Precursors for Carbon-, Nitrogen- and Oxygen-Centred Radicals

    Directory of Open Access Journals (Sweden)

    John C. Walton

    2016-01-01

    Full Text Available Oxime derivatives are easily made, are non-hazardous and have long shelf lives. They contain weak N–O bonds that undergo homolytic scission, on appropriate thermal or photochemical stimulus, to initially release a pair of N- and O-centred radicals. This article reviews the use of these precursors for studying the structures, reactions and kinetics of the released radicals. Two classes have been exploited for radical generation; one comprises carbonyl oximes, principally oxime esters and amides, and the second comprises oxime ethers. Both classes release an iminyl radical together with an equal amount of a second oxygen-centred radical. The O-centred radicals derived from carbonyl oximes decarboxylate giving access to a variety of carbon-centred and nitrogen-centred species. Methods developed for homolytically dissociating the oxime derivatives include UV irradiation, conventional thermal and microwave heating. Photoredox catalytic methods succeed well with specially functionalised oximes and this aspect is also reviewed. Attention is also drawn to the key contributions made by EPR spectroscopy, aided by DFT computations, in elucidating the structures and dynamics of the transient intermediates.

  7. New insights into the aquatic photochemistry of fluoroquinolone antibiotics: Direct photodegradation, hydroxyl-radical oxidation, and antibacterial activity changes

    Energy Technology Data Exchange (ETDEWEB)

    Ge, Linke; Na, Guangshui [Key Laboratory for Ecological Environment in Coastal Areas (SOA), National Marine Environmental Monitoring Center, Dalian 116023 (China); Zhang, Siyu [Institute of Applied Ecology, Chinese Academy of Sciences, Shenyang 110016 (China); Li, Kai [Key Laboratory for Ecological Environment in Coastal Areas (SOA), National Marine Environmental Monitoring Center, Dalian 116023 (China); Zhang, Peng, E-mail: pzhang@nmemc.org.cn [Key Laboratory for Ecological Environment in Coastal Areas (SOA), National Marine Environmental Monitoring Center, Dalian 116023 (China); Ren, Honglei; Yao, Ziwei [Key Laboratory for Ecological Environment in Coastal Areas (SOA), National Marine Environmental Monitoring Center, Dalian 116023 (China)

    2015-09-15

    The ubiquity and photoreactivity of fluoroquinolone antibiotics (FQs) in surface waters urge new insights into their aqueous photochemical behavior. This study concerns the photochemistry of 6 FQs: ciprofloxacin, danofloxacin, levofloxacin, sarafloxacin, difloxacin and enrofloxacin. Methods were developed to calculate their solar direct photodegradation half-lives (t{sub d,E}) and hydroxyl-radical oxidation half-lives (t{sub ·OH,E}) in sunlit surface waters. The t{sub d,E} values range from 0.56 min to 28.8 min at 45° N latitude, whereas t{sub ·OH,E} ranges from 3.24 h to 33.6 h, suggesting that most FQs tend to undergo fast direct photolysis rather than hydroxyl-radical oxidation in surface waters. However, a case study for levofloxacin and sarafloxacin indicated that the hydroxyl-radical oxidation induced risky photochlorination and resulted in multi-degradation pathways, such as piperazinyl hydroxylation and clearage. Changes in the antibacterial activity of FQs caused by photodegradation in various waters were further examined using Escherichia coli, and it was found that the activity evolution depended on primary photodegradation pathways and products. Primary intermediates with intact FQ nuclei retained significant antibacterial activity. These results are important for assessing the fate and risk of FQs in surface waters. - Highlights: • It is first reported on hydroxyl-radical oxidation of 6 fluoroquinolone antibiotics. • Methods were developed to assess photolysis and oxidation fate in surface waters. • The neutral form reacted faster with hydroxyl radical than protonated forms. • The main oxidation intermediates and transformation pathways were clarified. • The antibacterial activity changes depend on dominant photolysis pathways.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2017-08-01

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

  9. Determination of the number of radicals in the initial chain reactions by mathematical methods

    Directory of Open Access Journals (Sweden)

    Pejović Branko B.

    2009-01-01

    Full Text Available Starting from the fact that the real mechanism in a chemical equation takes places through a certain number of radicals which participate in simultaneous reactions and initiate chain reactions according to a particular pattern, the aim of this study is to determine their number in the first couple of steps of the reaction. Based on this, the numbers of radicals were determined in the general case, in the form of linear difference equations, which, by certain mathematical transformations, were reduced to one equation that satisfies a particular numeric series, entirely defined if its first members are known. The equation obtained was solved by a common method developed in the theory of numeric series, in which its solutions represent the number of radicals in an arbitrary step of the reaction observed, in the analytical form. In the final part of the study, the method was tested and verified using two characteristic examples from general chemistry. The study also gives a suggestion of a more efficient procedure by reducing the difference equation to a lower order.

  10. Effects of radical initiators, polymerization inhibitors, and other agents on the sonochemical unzipping of double-walled carbon nanotubes

    Science.gov (United States)

    Fukumori, Minoru; Hara, Shinnosuke; Ogawa, Takuji; Tanaka, Hirofumi

    2018-03-01

    The mechanism of graphene nanoribbon synthesis by the sonication-assisted unzipping of carbon nanotubes (CNTs) was investigated utilizing 4-methoxyphenol and 1,4-dimethoxybenzene as moieties of poly[(m-phenylenevinylene)-co-(2,5-dioctoxy-p-phenylenevinylene)]. The obtained results revealed that unzipping was promoted by 4-methoxyphenol owing to the facile abstraction of its phenolic hydrogen by sonication-generated radicals on CNTs, whereas 1,4-dimethoxybenzene did not facilitate unzipping, since its methoxy hydrogens were hardly abstracted. Moreover, unzipping was also facilitated by trans-stilbene, the double bond of which reacts with CNT radicals. Furthermore, we succeeded in using a general radical initiator, namely, 2,2‧-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride to promote unzipping, confirming that it is promoted by radical donors/trapping agents.

  11. The role of proteins in damage induced by free radicals

    International Nuclear Information System (INIS)

    Gebicki, J.M.

    1996-01-01

    The initial consequence of oxidative stress in living organisms is chemical modification of cell components. Recently increasing attention in this area has been paid to the modification of proteins. A form of protein modification which has been studied in some detail only recently is peroxidation. In the last 8 years, we and our collaborators have shown that a range of isolated proteins acquire hydroperoxide groups when exposed to a range of biologically plausible oxidants. These include HO free radicals generated by radiation or in the Fenton reaction, peroxyl radicals, oxidants released by activated neutrophils, and peroxynitrite. In more complex systems, we also found protein peroxides in the apo B component of LDL treated with 20 μM Cu ++ , and in irradiated blood serum. These observations suggest that the formation of protein peroxides is a possible consequence of oxidative stress in vivo. A remarkable feature of the process of protein peroxidation is its high efficiency. This is most easily measured with proteins oxidized by radiation-generated free radicals. It was found that, for some proteins, peroxide yields reached 40% of the numbers of HO radicals generated. Thus in effect, almost half of these radicals can be converted to the much more long-lived protein peroxide groups. If they, in turn, have the capacity to damage other molecules, the major oxidative pathway in vivo may have the sequence: free radical ? protein peroxide ? another oxidized molecule. This hypothesis was tested by studying the ability of protein peroxides to react with selected molecules and the results are briefly discussed. Clearly, these effects are specific to individual proteins. More generally, amino acid and protein peroxides were found to be a potential source of a range of free radicals when reduced by Fe ++ . If this turns out to be a common phenomenon, protein peroxides may prove to be a major source of oxidative damage

  12. The role of proteins in damage induced by free radicals

    Energy Technology Data Exchange (ETDEWEB)

    Gebicki, J.M. [Macquarie Univ., North Ryde, NSW (Australia). School of Biological Sciences

    1996-12-31

    The initial consequence of oxidative stress in living organisms is chemical modification of cell components. Recently increasing attention in this area has been paid to the modification of proteins. A form of protein modification which has been studied in some detail only recently is peroxidation. In the last 8 years, we and our collaborators have shown that a range of isolated proteins acquire hydroperoxide groups when exposed to a range of biologically plausible oxidants. These include HO free radicals generated by radiation or in the Fenton reaction, peroxyl radicals, oxidants released by activated neutrophils, and peroxynitrite. In more complex systems, we also found protein peroxides in the apo B component of LDL treated with 20 {mu}M Cu{sup ++}, and in irradiated blood serum. These observations suggest that the formation of protein peroxides is a possible consequence of oxidative stress in vivo. A remarkable feature of the process of protein peroxidation is its high efficiency. This is most easily measured with proteins oxidized by radiation-generated free radicals. It was found that, for some proteins, peroxide yields reached 40% of the numbers of HO radicals generated. Thus in effect, almost half of these radicals can be converted to the much more long-lived protein peroxide groups. If they, in turn, have the capacity to damage other molecules, the major oxidative pathway in vivo may have the sequence: free radical ? protein peroxide ? another oxidized molecule. This hypothesis was tested by studying the ability of protein peroxides to react with selected molecules and the results are briefly discussed. Clearly, these effects are specific to individual proteins. More generally, amino acid and protein peroxides were found to be a potential source of a range of free radicals when reduced by Fe{sup ++}. If this turns out to be a common phenomenon, protein peroxides may prove to be a major source of oxidative damage.

  13. Surface modification of poly(dimethylsiloxane) for controlling biological cells' adhesion using a scanning radical microjet

    Energy Technology Data Exchange (ETDEWEB)

    Tan, Helen M.L. [Department of Materials Engineering, School of Engineering, University of Tokyo, 2-11-16 Yayoi, Bunkyo-ku, 113-8656 (Japan); Fukuda, H. [Department of Electrical and Electronics Engineering, Toyo University, 2100 Kujirai, Kawagoe, 350-8585 (Japan); Akagi, T. [Department of Bioengineering, School of Engineering, University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, 113-8656 (Japan); Center for NanoBio Integration, University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, 113-8656 (Japan); Ichiki, T. [Department of Bioengineering, School of Engineering, University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, 113-8656 (Japan) and Center for NanoBio Integration, University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, 113-8656 (Japan)]. E-mail: ichiki@sogo.t.u-tokyo.ac.jp

    2007-04-23

    A scanning radical microjet (SRMJ) equipment using oxygen microplasma has been developed and successfully applied for controlling biological cells' attachment on biocompatible polymer material, poly(dimethylsiloxane) (PDMS). The radical microjet has advantages in localized and high-rate surface treatment. Moreover, maskless hydrophilic patterning using SRMJ has been demonstrated to be applicable to patterned cell cultivation which is useful in emerging biotechnological field such as tissue engineering and cell-based biosensors. Since control of PDMS surface properties is an indispensable prerequisite for cells' attachment, effects of oxygen flow rates and treatment time on localized hydrophilic patterning of PDMS surfaces were first investigated for controlling HeLa cells' (human epitheloid carcinoma cell line) attachment. Relationships between surface conditions of treated PDMS films and attached cell density are also discussed based on surface properties analyzed using atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS)

  14. New insights into the aquatic photochemistry of fluoroquinolone antibiotics: Direct photodegradation, hydroxyl-radical oxidation, and antibacterial activity changes.

    Science.gov (United States)

    Ge, Linke; Na, Guangshui; Zhang, Siyu; Li, Kai; Zhang, Peng; Ren, Honglei; Yao, Ziwei

    2015-09-15

    The ubiquity and photoreactivity of fluoroquinolone antibiotics (FQs) in surface waters urge new insights into their aqueous photochemical behavior. This study concerns the photochemistry of 6 FQs: ciprofloxacin, danofloxacin, levofloxacin, sarafloxacin, difloxacin and enrofloxacin. Methods were developed to calculate their solar direct photodegradation half-lives (td,E) and hydroxyl-radical oxidation half-lives (tOH,E) in sunlit surface waters. The td,E values range from 0.56 min to 28.8 min at 45° N latitude, whereas tOH,E ranges from 3.24h to 33.6h, suggesting that most FQs tend to undergo fast direct photolysis rather than hydroxyl-radical oxidation in surface waters. However, a case study for levofloxacin and sarafloxacin indicated that the hydroxyl-radical oxidation induced risky photochlorination and resulted in multi-degradation pathways, such as piperazinyl hydroxylation and clearage. Changes in the antibacterial activity of FQs caused by photodegradation in various waters were further examined using Escherichia coli, and it was found that the activity evolution depended on primary photodegradation pathways and products. Primary intermediates with intact FQ nuclei retained significant antibacterial activity. These results are important for assessing the fate and risk of FQs in surface waters. Copyright © 2015. Published by Elsevier B.V.

  15. Initial decay process of radicals induced in irradiated food

    International Nuclear Information System (INIS)

    Kaimori, Yoshihiko; Sakamoto, Yuki; Nakamura, Hideo; Ukai, Mitsuko; Kikuchi, Masahiro; Shimoyama, Yuhei; Kobayashi, Yasuhiko; Kameya, Hiromi

    2011-01-01

    In order to determine radial decay behaviors of γ-irradiated food, we analyzed radicals in the food using ESR. We detected the ESR signal of specimens just several minutes after irradiation. The singlet signal intensity at g=2.0, originated from organic free radicals was increased as followed by the increasing radiation dose. Singlet signal intensity that increased by γ-irradiation was decreased with time. The phenomena of decay of the ESR singlet signal showed two phase that are rapid decay and slow decay. It was suggested that those two phase decay is due to at least the two radical species. Also we concluded that after three hours of radiation treatment long life radical as ESR signal intensity was detected in irradiated specimen; black pepper, green coffee bean and ginseng, showed the same decay phenomena. But the signal intensity of irradiated black pepper was three times larger than that of irradiated green coffee bean and irradiated ginseng. (author)

  16. Effects of Molecular Iodine and 4-tert-Butylcatechol Radical Inhibitor on the Radical Polymerization of Styrene

    Directory of Open Access Journals (Sweden)

    Mojtaba Bozorg

    2017-05-01

    Full Text Available The presence of molecular iodine was studied in relation the molecular weight and molecular weight distribution of polystyrene, produced by radical poly merization. Radical polymerization of styrene initiated by 2,2׳-azobisisobutyronitrile (AIBN was performed at 70°C in the presence of molecular iodine. The synthesized polymers were characterized by gel permeation chromatography (GPC and proton- nuclear magnetic resonance (1H NMR techniques. The results of these reactions including conversion data, number-average molecular weight and molecular weight distribution were compared with those obtained for styrene radical polymerization initiated by AIBN at the same temperature in the absence of molecular iodine. It was found that the presence of iodine had a profound effect on the molecular weight and its distribution in the produced polystyrene. This was attributed to the ability of iodine to control the polymerization of styrene initiated by AIBN via reverse iodine transfer polymerization (RITP mechanism. The polymer produced by this method had a molecular weight of 10600 g/mol with a molecular weight polydispersity index of 1.3. Due to the importance of induction period in reverse iodine transfer radical polymerization, increasing the temperature to 120°C during the induction period resulted in shorter induction periods and the produced species led to better control of the molecular weight. Also, due to the role of iodine molecules as a radical inhibitor, the presence of a secondary radical inhibitor, i.e. 4-tert-butylcatechol, along with the iodine was investigated in radical polymerization of polystyrene initiated by AIBN. It was observed that the secondary radical inhibitor prevented the consumption of the iodine molecules by the radicals produced from decomposition of the AIBN initiator; therefore, alkyl halides were not produced during the induction period.

  17. Examining the free radical bonding mechanism of benzoquinone– and hydroquinone–methanol passivation of silicon surfaces

    International Nuclear Information System (INIS)

    Kotulak, Nicole A.; Chen, Meixi; Schreiber, Nikolas; Jones, Kevin; Opila, Robert L.

    2015-01-01

    Highlights: • Photons are required for high levels of c-Si passivation by both BQ/ME and HQ/ME solutions. • Protons are required for high levels of c-Si passivation by both BQ/ME and HQ/ME solutions. • The free radical QH· is the likely passivating species for c-Si surfaces from BQ/ME and HQ/ME solutions. - Abstract: The surface passivation of p-benzoquinone (BQ) and hydroquinone (HQ) when dissolved in methanol (ME) has been examined through effective lifetime testing of crystalline silicon (c-Si) wafers treated with the aforementioned solutions. Changes in the availability of both photons and protons in the solutions were demonstrated to affect the level of passivation achieved. The requirement of both excess protons and ambient light exposure to maintain high effective lifetimes supports the presence of a free radical species that drives the surface passivation. Surface analysis suggests a 1:1 ratio of HQ-like bonds to methoxy bonds on the c-Si surface after treatment with a BQ/ME solution.

  18. The entry of free radicals into polystyrene latex particles

    International Nuclear Information System (INIS)

    Adams, M.E.; Trau, M.; Gilbert, R.C.; Napper, D.R.

    1988-01-01

    Mechanistic understanding of the processes governing the kinetics of emulsion polymerization has both scientific and technical interest. One component of this process that is poorly understood at present is that of free radical entry into latex particles. Measurements were made of the entry rate coefficient as a function of temperature for free radicals entering polystyrene latex particles in seeded emulsion polymerizations initiated by γ-rays. The activation energy for entry was found to be less than 24 ± 3 kJ mol -1 , consistent with entry being controlled by a physical (e.g. diffusional) rather than a chemical process. Measurement of the entry rate coefficient as a function of the γ-ray dose rate suggested that the factors that determine the entry rate when the primary free radicals are uncharged are similar to those that determine the entry rate for charged free radicals derived from chemical initiation by peroxydisulfate. This result was consistent with measurements of the entry rate coefficient of charged free radicals derived from peroxydisulfate; these data were found to be virtually independent of both the extent of the latex surface coverage by the anionic surfactant sodium dodecyl sulfate and the ionic strength of the continuous phase. The data refute several proposals given in the literature for the rate-determining step for entry, being inconsistent with control by collision of free radicals with the latex particles, surfactant desorption, and an electrostatic barrier arising from the colloidal nature of the entering free radical. The origin of the activation energy for entry remains obscure

  19. Conversion of alkyl radicals to allyl radicals in irradiated single crystal mats of polyethylene

    International Nuclear Information System (INIS)

    Fujimura, T.; Hayakawa, N.; Kuriyama, I.

    1978-01-01

    The decay of alkyl radicals, the conversion of alkyl radicals to allyl radicals and the trapping of allyl radicals in irradiated single crystal mats of polyethylene have been studied by electron spin resonance (e.s.r.). It has been suggested that in the crystal core alkyl radicals react with trans-vinylene double bonds and are converted into trans-vinylene allyl radicals; at the crystal surface, alkyl radicals react with vinyl end groups and are converted into allyl radicals with vinyl end groups. The decay of radical pairs and the formation of trans-vinylene double bonds are discussed. (author)

  20. Reactions of inorganic free radicals with liver protecting drugs

    International Nuclear Information System (INIS)

    Gyoergy, I.; Foeldiak, G.; Blazovics, A.; Feher, J.

    1990-01-01

    Liver protecting drugs, silibinin, a flavonolignane, and the dihydroquinoline derivatives, CH 402 and MTDQ-DA, were shown to inhibit processes in which enzymatically or non-enzymatically generated free radicals were involved. Inorganic free radicals (N 3 , (SCN) 2 - , OH, Trp, CO 2 - , O 2 - ) produced by pulse radiolysis readily react with the compounds, which transform into exceptionally long-lived, unreactive transients. Time evolution of the UV and visible spectra indicate that oxidising radicals form a phenoxyl type radical from silibinin, while OH forms an adduct by attacking, simultaneously, at various sites of the molecule. Superoxide radicals reduce silibinin and oxidise CH 402 and MTDQ-DA. It is concluded that the drugs might exhibit antioxidant behavior in living systems. (author)

  1. New cobalt-mediated radical polymerization (CMRP of methyl methacrylate initiated by two single-component dinuclear β-diketone cobalt (II catalysts.

    Directory of Open Access Journals (Sweden)

    Feng Bao

    Full Text Available Two dinuclear cobalt complexes based on bis-diketonate ligands (ligand 1: 3,3'-(1,3-phenylenebis(1-phenylpropane-1,3-dione; ligand 2: 3,3'-(1,4-phenylenebis(1-phenylpropane-1,3-dione were successfully synthesized. The two neutral catalysts all showed satisfactory activities in the cobalt-mediated radical polymerization (CMRP of methyl methacrylate (MMA with the common initiator of azodiisobutyronitrile (AIBN. The resulting polymerizations have all of the characteristics of a living polymerization and displayed linear semilogarithmic kinetic plots, a linear correlation between the number-average molecular weight and the monomer conversion, and low polydispersities. Mono- or dicomponent low polydispersity polymers could be obtained by using the two dinuclear catalysts under proper reaction conditions. All these improvements facilitate the implementation of the acrylate CMRP and open the door to the scale-up of the syntheses and applications of the multicomponent low polydispersity polymers.

  2. Time-resolved studies of free radicals and laser-initiated chain reactions: Final report, 1 April 1979-31 March 1988

    International Nuclear Information System (INIS)

    Leone, S.R.

    1988-03-01

    Pulsed lasers were used in this work to photofragment molecules or to initiate chain reactions. One of the major advances was the availability of high-powered rare gas halide excimer lasers. In addition, pulsed Nd:YAG lasers and dye lasers were used throughout. Results include: generalized kinetic formulations of the problem of laser-initiated chain reactions. Several studies were carried out to explore the details of chain combustion phenomena, slow chain reactions, chain branching behavior, and vibrational temperatures of combusting mixtures. A method to determine the rotational temperature of nitrogen molecules by laser multiphoton ionization was shown. The chain reaction methodology was applied to complex polyatomic systems, in which complete infrared spectra of the emitting species were obtained. Systems studied included, chlorine + HBr, HI, methane, hydrogen, ethane, propane, butane, cyclopropane, and cyclohexane. Photofragmentation studies involved the production and analysis of radical species, such as methyl, CH 2 I, and CCH. Molecules studied included methylene iodide, methyl iodide, dimethyl mercury, acetone, acetylene, vinyl chloride, dichloroethylene, and fluorochloroethylene. The first infrared characterization of a highly vibrationally excited radical was shown. Reactions of methyl radicals were studied in detail, in which a new method for obtaining absolute values of the methyl radical reaction rates were obtained

  3. Synthesis, Characterization and Bulk Properties of Amphiphilic Copolymers Containing Fluorinated Methacrylates from Sequential Copper-Mediated Radical Polymerization

    DEFF Research Database (Denmark)

    Hansen, Natanya Majbritt Louie; Gerstenberg, Michael; Haddleton, David M.

    2008-01-01

    acrylate (MEA), and poly(ethylene glycol) methyl ether methacrylate (PEGMA) by Atom Transfer Radical Polymerization. A kinetic study of the 3FM homopolymerization initiated with ethyl bromoisobutyrate and Cu(I)Br/N-(n-propyl)-2-pyridylmethanimine reveals a living/ controlled polymerization in the range 80...

  4. Surface functionalisation of polypyrrole films using UV light induced radical activation

    International Nuclear Information System (INIS)

    Lisboa, P.; Gilliland, D.; Ceccone, G.; Valsesia, A.; Rossi, F.

    2006-01-01

    Electrochemically deposited polypyrrole (PPy) films were functionalised with amine or carboxylic function. The functionalisation was done by grafting allylamine or acrylic acid (AAc) using UV light radical activation. The active groups of the surface were quantified by X-ray photoelectron spectroscopy (XPS) after chemical derivatisation with trifluoroethanol (TFE) or 4-trifluoromethylbenzaldehyde (TFBA), respectively. Grafting with AAc completely covered the PPy film introducing high levels of carboxylic function. In the case of allylamine grafting, a saturation point at low amine carbon level was achieved. Further characterisation of the surfaces was done by time of flight secondary ion mass spectroscopy (TOF-SIMS), atomic force microscope (AFM) and scanning electron microscope (SEM)

  5. Impact of OH Radical-Initiated H2CO3 Degradation in the Earth's Atmosphere via Proton-Coupled Electron Transfer Mechanism.

    Science.gov (United States)

    Ghoshal, Sourav; Hazra, Montu K

    2016-02-04

    The decomposition of isolated carbonic acid (H2CO3) molecule into CO2 and H2O (H2CO3 → CO2 + H2O) is prevented by a large activation barrier (>35 kcal/mol). Nevertheless, it is surprising that the detection of the H2CO3 molecule has not been possible yet, and the hunt for the free H2CO3 molecule has become challenging not only in the Earth's atmosphere but also on Mars. In view of this fact, we report here the high levels of quantum chemistry calculations investigating both the energetics and kinetics of the OH radical-initiated H2CO3 degradation reaction to interpret the loss of the H2CO3 molecule in the Earth's atmosphere. It is seen from our study that proton-coupled electron transfer (PCET) and hydrogen atom transfer (HAT) are the two mechanisms by which the OH radical initiates the degradation of the H2CO3 molecule. Moreover, the PCET mechanism is potentially the important one, as the effective barrier, defined as the difference between the zero point vibrational energy (ZPE) corrected energy of the transition state and the total energy of the isolated starting reactants in terms of bimolecular encounters, for the PCET mechanism at the CCSD(T)/6-311++G(3df,3pd) level of theory is ∼3 to 4 kcal/mol lower than the effective barrier height associated with the HAT mechanism. The CCSD(T)/6-311++G(3df,3pd) level predicted effective barrier heights for the degradations of the two most stable conformers of H2CO3 molecule via the PCET mechanism are only ∼2.7 and 4.3 kcal/mol. A comparative reaction rate analysis at the CCSD(T)/6-311++G(3df,3pd) level of theory has also been carried out to explore the potential impact of the OH radical-initiated H2CO3 degradation relative to that from water (H2O), formic acid (FA), acetic acid (AA) and sulfuric acid (SA) assisted H2CO3 → CO2 + H2O decomposition reactions in both the Earth's troposphere and stratosphere. The comparison of the reaction rates reveals that, although the atmospheric concentration of the OH radical is

  6. Free radical inactivation of trypsin

    International Nuclear Information System (INIS)

    Cudina, Ivana; Jovanovic, S.V.

    1988-01-01

    Reactivities of free radical oxidants, radical OH, Br2-anion radical and Cl 3 COO radical and a reductant, CO2-anion radical, with trypsin and reactive protein components were determined by pulse radiolysis of aqueous solutions at pH 7, 20 0 C. Highly reactive free radicals, radical OH, Br2-anion radical and CO2-anion radical, react with trypsin at diffusion controlled rates. Moderately reactive trichloroperoxy radical, k(Cl 3 COO radical + trypsin) preferentially oxidizes histidine residues. The efficiency of inactivation of trypsin by free radicals is inversely proportional to their reactivity. The yields of inactivation of trypsin by radical OH, Br2-anion radical and CO2-anion radical are low, G(inactivation) = 0.6-0.8, which corresponds to ∼ 10% of the initially produced radicals. In contrast, Cl 3 COO radical inactivates trypsin with ∼ 50% efficiency, i.e. G(inactivation) = 3.2. (author)

  7. Acrylonitrile-Butadiene Rubber (NBR) Prepared via Living/Controlled Radical Polymerization (RAFT).

    Science.gov (United States)

    Kaiser, Andreas; Brandau, Sven; Klimpel, Michael; Barner-Kowollik, Christopher

    2010-09-15

    In the current work we present results on the controlled/living radical copolymerization of acrylonitrile (AN) and 1,3-butadiene (BD) via reversible addition fragmentation chain transfer (RAFT) polymerization techniques. For the first time, a solution polymerization process for the synthesis of nitrile butadiene rubber (NBR) via the use of dithioacetate and trithiocarbonate RAFT agents is described. It is demonstrated that the number average molar mass, $\\overline M _{\\rm n} $, of the NBR can be varied between a few thousand and 60 000 g · mol(-1) with polydispersities between 1.2 and 2.0 (depending on the monomer to polymer conversion). Excellent agreement between the experimentally observed and the theoretically expected molar masses is found. Detailed information on the structure of the synthesized polymers is obtained by variable analytical techniques such as infrared spectroscopy (IR), nuclear magnetic resonance (NMR) spectroscopy, differential scanning calorimetry, and electrospray ionization-mass spectrometry (ESI-MS). Copyright © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Oxygen radical microscopy in living plant tissues

    DEFF Research Database (Denmark)

    Kristiansen, Kim Anker; Møller, Ian Max; Schulz, Alexander

    the ROS production stems from the mitochondria and peroxisomes as is seen in animal cells. At the Bioimaging Center at KVL we employ different techniques to induce, detect and monitor ROS production, distribution and in and among living plant cells. Both confocal laser scanning microscopy and 2-photon......Reactive oxygen species (ROS) play a crucial role in a wide variety of processes. Initiation of many different cellular pathways, crosstalk between cells, developmental signalling in planta, programmed cell death and hypersensitive response in connection with plant-pathogen interactions are among...... the different roles ROS play. On the other hand ROS also cause damage to cellular components at sub-lethal to lethal levels. In photosynthesizing plants the major production of ROS origin from the chloroplast. ROS is a by product from the Photosystem I/II handling of light energy. In nonphotosynthesizing plants...

  9. An Appreciation of Free Radical Chemistry

    Indian Academy of Sciences (India)

    ... Lecture Workshops · Refresher Courses · Symposia · Live Streaming. Home; Journals; Resonance – Journal of Science Education; Volume 10; Issue 9. An Appreciation of Free Radical Chemistry - 6. Experiments Involving Free Radicals. G Nagendrappa. Classroom Volume 10 Issue 9 September 2005 pp 79-84 ...

  10. Synthesis of triblock and random copolymers of 4- acetoxystyrene and styrene by living atom transfer radical polymerization

    DEFF Research Database (Denmark)

    Gao, Bo; Chen, Xianyi; Ivan, Bela

    1997-01-01

    Triblock copolymers containing polystyrene (PSt) and poly(4-acetoxystyrene) (PAcOSt) segments have been prepared by atom transfer radical polymerization (ATRP). In the first step one of the two monomers was polymerized in bulk using the initiating system alpha,alpha'-dibromo-p-xylene/CuBr/2,2'-bi...

  11. Live-cell imaging of conidial anastomosis tube fusion during colony initiation in Fusarium oxysporum.

    Directory of Open Access Journals (Sweden)

    Smija M Kurian

    Full Text Available Fusarium oxysporum exhibits conidial anastomosis tube (CAT fusion during colony initiation to form networks of conidial germlings. Here we determined the optimal culture conditions for this fungus to undergo CAT fusion between microconidia in liquid medium. Extensive high resolution, confocal live-cell imaging was performed to characterise the different stages of CAT fusion, using genetically encoded fluorescent labelling and vital fluorescent organelle stains. CAT homing and fusion were found to be dependent on adhesion to the surface, in contrast to germ tube development which occurs in the absence of adhesion. Staining with fluorescently labelled concanavalin A indicated that the cell wall composition of CATs differs from that of microconidia and germ tubes. The movement of nuclei, mitochondria, vacuoles and lipid droplets through fused germlings was observed by live-cell imaging.

  12. Studies of short-lived radicals in the. gamma. -irradiated aqueous solution of uridine-5'-monophosphate by the spin-trapping method and the liquid chromatography

    Energy Technology Data Exchange (ETDEWEB)

    Kominami, S [Hiroshima Univ. (Japan); Rokushika, S; Hatano, H

    1976-12-01

    An aerated aqueous solution of uridine-5'-monophosphate was ..gamma..-irradiated with 2-methyl-2-nitrosopropane as a spin-trapping reagent. Liquid chromatography was applied to separate the stable nitroxide radicals in the irradiated solution. The radicals were detected by U.V. and e.s.r. spectrometry. The e.s.r. detection showed four peaks in the chromatogram. The orcinol method for detection of the residual sugar moieties was applied before and after reduction of the base to determine the existence of the 5,6-double bond for the molecules in each fraction. From the combined results of the e.s.r. and orcinol methods, the short-lived radicals which were trapped by 2-methyl-2-nitrosopropane were identified as radicals of N-1 and C-6 positions of the base moiety and t-butyl radicals which was the radiolytic product of the trapping reagent.

  13. Kinetics of Waterborne Alkyd/Acrylic Hybrid Resin Free Radical Polymerization by Two Systems of Redox and Thermal Initiators

    OpenAIRE

    shirin Madadi; ali akbar Yousefi; elham Keshmirizadeh

    2012-01-01

    Kinetics of radical polymerizations of waterborne alkyd/acrylic hybrid resin via batch mini-emulsion technique was studied using redox initiators (TBHP/Fe2+/EDTA/AsAc  and  TBHP/Fe2+/EDTA/SFS) at relatively low temperatures and thermal initiators (BPO, KPS and AIBN) at higher temperatures to seek the most suitable initiator system. At the end of all reactions the unreacted monomer content was reduced using post-polymerization technique; consequently, leading to increased monomer conversion an...

  14. Bromine isotopic signature facilitates de novo sequencing of peptides in free-radical-initiated peptide sequencing (FRIPS) mass spectrometry.

    Science.gov (United States)

    Nam, Jungjoo; Kwon, Hyuksu; Jang, Inae; Jeon, Aeran; Moon, Jingyu; Lee, Sun Young; Kang, Dukjin; Han, Sang Yun; Moon, Bongjin; Oh, Han Bin

    2015-02-01

    We recently showed that free-radical-initiated peptide sequencing mass spectrometry (FRIPS MS) assisted by the remarkable thermochemical stability of (2,2,6,6-tetramethyl-piperidin-1-yl)oxyl (TEMPO) is another attractive radical-driven peptide fragmentation MS tool. Facile homolytic cleavage of the bond between the benzylic carbon and the oxygen of the TEMPO moiety in o-TEMPO-Bz-C(O)-peptide and the high reactivity of the benzylic radical species generated in •Bz-C(O)-peptide are key elements leading to extensive radical-driven peptide backbone fragmentation. In the present study, we demonstrate that the incorporation of bromine into the benzene ring, i.e. o-TEMPO-Bz(Br)-C(O)-peptide, allows unambiguous distinction of the N-terminal peptide fragments from the C-terminal fragments through the unique bromine doublet isotopic signature. Furthermore, bromine substitution does not alter the overall radical-driven peptide backbone dissociation pathways of o-TEMPO-Bz-C(O)-peptide. From a practical perspective, the presence of the bromine isotopic signature in the N-terminal peptide fragments in TEMPO-assisted FRIPS MS represents a useful and cost-effective opportunity for de novo peptide sequencing. Copyright © 2015 John Wiley & Sons, Ltd.

  15. Micrococcus radiodurans surface exonuclease. Dimer to monomer conversion by ionizing radiation-generated aqueous free radicals

    Energy Technology Data Exchange (ETDEWEB)

    Mitchel, R E.J.

    1980-01-01

    Micrococcus radiodurans possesses an exonuclease firmly bound to a middle cell wall membrane layer. Aqueous OH/sup -/ radicals generated chemically or by ionizing radiation cause the immediate release of this enzyme into the surrounding medium. The enzyme is located in a hydrophobic site and can also be released by aqueous n-butanol. When extracted by this solvent it is a non-covalently linked dimer and has a molecular weight of 260,000 as determined by gel filtration. When released by radiation generated OH/sup -/ radicals, the enzyme initially appears in solution as the dimer but is rapidly split by further aqueous radical attack into two 130,000 molecular weight subunits. Hydroxyl radicals are most effective but reducing radicals are also able to monomerize the enzyme. Only the released dimer enzyme is subject to free radical monomerization. Bound dimer enzyme is not split prior to release. No detectable loss of activity or change in catalytic properties accompanies the free radical cleavage of the enzyme. Both subunits of the dimer enzyme possess a tightly bound metal ion (probably Ca/sup 2 +/) required for activity. The monomer but not the dimer enzyme will bind to an anion exchanger. The monomer is susceptible to loss of its metal ion, and consequent inactivation, when exposed to the exchanger in the absence of Ca/sup 2 +/. Besides providing information on some of the immediate non-lethal effects of ionizing radiation, the behavior of this enzyme system demonstrates a potential cellular mechanism by which internally or externally generated free radicals could be utilized by the cell to control various enzymic reactions.

  16. Free radicals created by radiation and aging symptoms

    International Nuclear Information System (INIS)

    Ashry, O.M.

    2012-01-01

    The universality of aging implies that its cause is basically the same in all species. A free radical hypothesis of aging has been proposed that the free radicals produced during normal metabolism of the cell over time damage DNA and other macromolecules leading to degenerative diseases, malignancies, and eventual death of vital cells which in turn causes aging and death of the organism. This hypothesis is supported by several observations. Radiation produces its biologic effect through free radical formation and causes premature aging. Second, the age pigment lipo fuscin is associated with lipid peroxidation. The hypothesis that oxygen radicals play a role in aging is also supported by the observation that, in general, long-lived species produce less endogenous free oxygen radicals because of their lower metabolic rate. Long-lived animals also have more superoxide dismutase than do their short-lived counterparts, and animal species with the longest lifespan have the highest levels of superoxide dismutase. Oxidative DNA damage is rapidly and effectively repaired. It has been estimated that there are several thousand oxidative DNA damage sites in a human cell every day, and the majority of these are repaired. However, a small fraction of unrepaired lesions could cause permanent changes in DNA and might be a major contributor to aging and cancer. A consequence of the free radical hypothesis of aging is the idea that free radical scavenging agents might be used to prevent aging. (author)

  17. Theoretical perspectives on the mechanism and kinetics of the OH radical-initiated gas-phase oxidation of PCB126 in the atmosphere

    International Nuclear Information System (INIS)

    Dang, Juan; Shi, Xiangli; Zhang, Qingzhu; Wang, Wenxing

    2015-01-01

    Polychlorinated biphenyls (PCBs) primarily exist in the gas phase in air and may undergo atmospheric oxidation degradations, particularly the oxidation reaction initiated by OH radicals. In this work, the mechanism of the OH radical-initiated atmospheric oxidation of the most toxic PCB congener 3,3′,4,4′,5-pentachlorobiphenyl (PCB126) was investigated by using quantum chemistry methods. The rate constants of the crucial elementary reactions were estimated by the Rice–Ramsperger–Kassel–Marcus (RRKM) theory. The oxidation products of the reaction of PCB126 with OH radicals include 3,3′,4,4′,5-pentachlorobiphenyl-ols, chlorophenols, 2,3,4,7,8-pentachlorodibenzofuran, 2,3,4,6,7-pentachlorodibenzofuran, dialdehydes, 3,3′,4,4′,5-pentachloro-5′-nitro-biphenyl, and 4,5-dichloro-2-nitrophenol. Particularly, the formation of polychlorinated dibenzofurans (PCDFs) from the atmospheric oxidation of PCBs is revealed for the first time. The overall rate constant of the OH addition reaction is 2.52 × 10 −13 cm 3 molecule −1 s −1 at 298 K and 1 atm. The atmospheric lifetime of PCB126 determined by OH radicals is about 47.08 days which indicates that PCB126 can be transported long distances from local to global scales. - Highlights: • A comprehensive mechanism of OH-initiated oxidation of PCB126 was investigated. • The formation of PCDFs from the oxidation of PCBs is determined for the first time. • The rate constants for key elementary reactions were estimated by the RRKM theory. • The atmospheric lifetime of PCB126 determined by OH radicals is about 47.08 days

  18. Evidence of radicals created by plasma in bacteria in water

    International Nuclear Information System (INIS)

    Lee, Chae Bok; Na, Young Ho; Hong, Tae-Eun; Choi, Eun Ha; Uhm, Han S.; Baik, Ku Youn; Kwon, Gichung

    2014-01-01

    Heavy water (D 2 O) was introduced into a non-thermal plasma-jet (NTPJ) device to generate deuterium monoxide (OD) radicals at room temperature. Owing to the similar reactivity and low prevalence of deuterium in nature, OD radicals can be utilized to visualize the OH radical interactions with water and living cells. Escherichia coli in water were treated with OD radicals, and D atom incorporation into cells was visualized using time-of-flight SIMS and Nano-SIMS. The results show that D atoms from NTPJ reach the cytoplasm of E. coli in H 2 O, indicating the usefulness of this OD-tracking method for the study of radical interactions with living cells.

  19. Synergy between low and high energy radical femtochemistry

    International Nuclear Information System (INIS)

    Gauduel, Y A

    2011-01-01

    The deleterious effects of ionizing radiation on integrated biological targets being dependent on the spatio-temporal distribution of short-lived radical processes, a thorough knowledge of these early events requires a real-time probing in the range 10 -15 - 10 -10 s. This manuscript review is focused on the synergy that exists between low (1-10 eV) and high (MeV) energy radiation femtochemistry (LERF, HERF respectively). The synergy remains crucial for the investigation of primary radical processes that take place within the prethermal regime of low energy secondary electrons. The quantum character of very-short lived electron in a prehydrated configuration provides a unique sub-nanometric probe to spatially explore some early radiation-induced biomolecular damage. This approach would foreshadow the development of innovative applications for spatio-temporal radiation biology such as, i) a highly-selective pro-drug activation using well-defined quantum states of short-lived radicals, ii) the real-time nanodosimetry in biologically relevant environments, and iii) the ultrashort irradiation of living cells.

  20. Surface grafting of zwitterionic polymers onto dye doped AIE-active luminescent silica nanoparticles through surface-initiated ATRP for biological imaging applications

    Science.gov (United States)

    Mao, Liucheng; Liu, Xinhua; Liu, Meiying; Huang, Long; Xu, Dazhuang; Jiang, Ruming; Huang, Qiang; Wen, Yuanqing; Zhang, Xiaoyong; Wei, Yen

    2017-10-01

    Aggregation-induced emission (AIE) dyes have recently been intensively explored for biological imaging applications owing to their outstanding optical feature as compared with conventional organic dyes. The AIE-active luminescent silica nanoparticles (LSNPs) are expected to combine the advantages both of silica nanoparticles and AIE-active dyes. Although the AIE-active LSNPs have been prepared previously, surface modification of these AIE-active LSNPs with functional polymers has not been reported thus far. In this work, we reported a rather facile and general strategy for preparation of polymers functionalized AIE-active LSNPs through the surface-initiated atom transfer radical polymerization (ATRP). The AIE-active LSNPs were fabricated via direct encapsulation of AIE-active dye into silica nanoparticles through a non-covalent modified Stöber method. The ATRP initiator was subsequently immobilized onto these AIE-active LSNPs through amidation reaction between 3-aminopropyl-triethoxy-silane and 2-bromoisobutyryl bromide. Finally, the zwitterionic 2-(methacryloyloxy)ethyl phosphorylcholine (MPC) was selected as model monomer and grafted onto MSNs through ATRP. The characterization results suggested that LSNPs can be successfully modified with poly(MPC) through surface-initiated ATRP. The biological evaluation results demonstrated that the final SNPs-AIE-pMPC composites possess low cytotoxicity, desirable optical properties and great potential for biological imaging. Taken together, we demonstrated that AIE-active LSNPs can be fabricated and surface modified with functional polymers to endow novel functions and better performance for biomedical applications. More importantly, this strategy developed in this work could also be extended for fabrication of many other LSNPs polymer composites owing to the good monomer adoptability of ATRP.

  1. Interfacing biomembrane mimetic polymer surfaces with living cells - Surface modification for reliable bioartificial liver

    International Nuclear Information System (INIS)

    Iwasaki, Yasuhiko; Takami, Utae; Sawada, Shin-ichi; Akiyoshi, Kazunari

    2008-01-01

    The surface design used for reducing nonspecific biofouling is one of the most important issues for the fabrication of medical devices. We present here a newly synthesized a carbohydrate-immobilized phosphorylcholine polymer for surface modification of medical devices to control the interface with living cells. A random copolymer composed of 2-methacryloyloxyethyl phosphorylcholine (MPC), n-butyl methacrylate (BMA), and 2-lactobionamidoethyl methacrylate (LAMA) was synthesized by conventional radical polymerization. The monomer feeding ratio in the copolymer was adjusted to 24/75/1 (MPC/BMA/LAMA). The copolymer (PMBL1.0) could be coated by solvent evaporation from an ethanol solution. Cells of the human hepatocellular liver carcinoma cell line (HepG2) having asialoglycoprotein receptors (ASGPRs) were seeded on PMBL1.0 or poly(BMA) (PBMA)-coated PET plates. On PBMA, many adherent cells were observed and were well spread with monolayer adhesion. HepG2 adhesion was observed on PMBL1.0 because the cell has ASGPRs. Furthermore, some of the cells adhering to PMBL1.0 had a spheroid formation and similarly shaped spheroids were scattered on the surface. According to confocal laser microscopic observation after 96 h cultivation, it was found that albumin production preferentially occurred in the center of the spheroid. The albumin production of the cells that adhered to PBMA was sparse. The amount of albumin production per unit cell that adhered to PMBL1.0 was determined by ELISA and was significantly higher than that which adhered to PBMA. Long-term cultivation of HepG2 was also performed using hollow fiber mini-modules coated with PMBL1.0. The concentration of albumin produced from HepG2 increased continuously for one month. In the mini-module, the function of HepG2 was effectively preserved for that period. On the hollow fiber membrane, spheroid formation of HepG2 cells was also observed. In conclusion, PMBL1.0 can provide a suitable surface for the cultivation of

  2. Integrated in situ characterization of molten salt catalyst surface: Evidence of sodium peroxide and OH radical formation

    KAUST Repository

    Takanabe, Kazuhiro; Khan, Abdulaziz M.; Tang, Yu; Nguyen, Luan; Ziani, Ahmed; Jacobs, Benjamin W; Elbaz, Ayman M.; Sarathy, S Mani; Tao, Franklin Feng

    2017-01-01

    Na-based catalysts (i.e., Na2WO4) were proposed to selectively catalyze OH radical formation from H2O and O2 at high temperatures. This reaction may proceed on molten salt state surfaces due to the lower melting point of the used Na salts compared to the reaction temperature. This study provides direct evidence of the molten salt state of Na2WO4, which can form OH radicals, using in situ techniques including X-ray diffraction (XRD), scanning transmission electron microscopy (STEM), laser induced fluorescence (LIF) spectrometer, and ambient-pressure X-ray photoelectron spectroscopy (AP-XPS). As a result, Na2O2 species, which were hypothesized to be responsible for the formation of OH radicals, has been identified on the outer surfaces at temperatures ≥800°C, and these species are useful for various gas-phase hydrocarbon reactions including the selective transformation of methane to ethane.

  3. Integrated in situ characterization of molten salt catalyst surface: Evidence of sodium peroxide and OH radical formation

    KAUST Repository

    Takanabe, Kazuhiro

    2017-06-26

    Na-based catalysts (i.e., Na2WO4) were proposed to selectively catalyze OH radical formation from H2O and O2 at high temperatures. This reaction may proceed on molten salt state surfaces due to the lower melting point of the used Na salts compared to the reaction temperature. This study provides direct evidence of the molten salt state of Na2WO4, which can form OH radicals, using in situ techniques including X-ray diffraction (XRD), scanning transmission electron microscopy (STEM), laser induced fluorescence (LIF) spectrometer, and ambient-pressure X-ray photoelectron spectroscopy (AP-XPS). As a result, Na2O2 species, which were hypothesized to be responsible for the formation of OH radicals, has been identified on the outer surfaces at temperatures ≥800°C, and these species are useful for various gas-phase hydrocarbon reactions including the selective transformation of methane to ethane.

  4. Electric fields control the orientation of peptides irreversibly immobilized on radical-functionalized surfaces.

    Science.gov (United States)

    Martin, Lewis J; Akhavan, Behnam; Bilek, Marcela M M

    2018-01-24

    Surface functionalization of an implantable device with bioactive molecules can overcome adverse biological responses by promoting specific local tissue integration. Bioactive peptides have advantages over larger protein molecules due to their robustness and sterilizability. Their relatively small size presents opportunities to control the peptide orientation on approach to a surface to achieve favourable presentation of bioactive motifs. Here we demonstrate control of the orientation of surface-bound peptides by tuning electric fields at the surface during immobilization. Guided by computational simulations, a peptide with a linear conformation in solution is designed. Electric fields are used to control the peptide approach towards a radical-functionalized surface. Spontaneous, irreversible immobilization is achieved when the peptide makes contact with the surface. Our findings show that control of both peptide orientation and surface concentration is achieved simply by varying the solution pH or by applying an electric field as delivered by a small battery.

  5. Combination is the dominant free radical process initiated in DNA by ionizing radiation: an overview based on solid-state EPR studies

    International Nuclear Information System (INIS)

    Bernhard, W.A.; Mroczka, N.; Barnes, J.

    1994-01-01

    An overview of the early processes initiated in DNA by ionizing radiation is given from the perspective of studies done by solid-state EPR with the focus on radical combination. Comparisons with free radical formation and trapping in crystalline pyrimidines (1-methylcytosine, thymine, 1-methylthymine, 1-methyluracil, and cytosine monohydrate) provide insight into the processes occurring in DNA. Between 25 and 50% of low LET ionizations in fully hydrated DNA at 4 K lead to trapped free radicals, the remaining unobserved radicals are assumed to have combined. The majority of the radicals trapped in DNA at 4 K (G ∼ 0.3 μmol/J) are believed to be in clusters. Based on the value of G, it is argued that the range of holes and bound electrons in DNA at 4 K are, in the main, limited to within the cluster diameter, ∼ 4 nm. Proton transfer across hydrogen bonds promotes radical trapping and inhibits combination but is thermally reversible. Warming to room temperature mobilizes the reversibly trapped radicals and gives additional combination (50-80% of those trapped at 4 K). The yield of free radicals, after anneal, is sufficient to account for the yield of single-strand breaks produced by direct effects. (Author)

  6. Surface modification of carbon nanotubes via combination of mussel inspired chemistry and chain transfer free radical polymerization

    Energy Technology Data Exchange (ETDEWEB)

    Wan, Qing; Tian, Jianwen; Liu, Meiying; Zeng, Guangjian; Huang, Qiang [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang, 330031 (China); Wang, Ke; Zhang, Qingsong [Department of Chemistry and the Tsinghua Center for Frontier Polymer Research, Tsinghua University, Beijing, 100084 (China); Deng, Fengjie, E-mail: fengjiedeng@aliyun.com [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang, 330031 (China); Zhang, Xiaoyong, E-mail: xiaoyongzhang1980@gmail.com [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang, 330031 (China); Wei, Yen, E-mail: weiyen@tsinghua.edu.cn [Department of Chemistry and the Tsinghua Center for Frontier Polymer Research, Tsinghua University, Beijing, 100084 (China)

    2015-08-15

    Graphical abstract: A novel strategy combination of mussel inspired chemistry and chain transfer free radical polymerization has been developed for surface modification of carbon nanotubes with polymers for the first time. - Highlights: • Surface modification of CNTs via mussel inspired chemistry. • Preparation of aminated polymers through free radical polymerization. • Functionalized CNTs with aminated polymers via Michael addition reaction. • Highly dispersed CNTs in organic and aqueous solution. - Abstract: In this work, a novel strategy for surface modification of carbon nanotubes (CNTs) was developed via combination of mussel inspired chemistry and chain transfer free radical polymerization. First, pristine CNTs were functionalized with polydopamine (PDA), which is formed via self-polymerization of dopamine in alkaline conditions. These PDA functionalized CNTs can be further reacted with amino-terminated polymers (named as PDMC), which was synthesized through chain transfer free radical polymerization using cysteamine hydrochloride as chain transfer agent and methacryloxyethyltrimethyl ammonium chloride as the monomer. PDMC perfectly conjugated with CNT-PDA was ascertained by a series of characterization techniques including transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR), thermal gravimetric analysis (TGA) and X-ray photoelectron spectroscopy (XPS). The dispersibility of obtained CNT nanocomposites (named as CNT-PDA-PDMC) was further examined. Results showed that the dispersibility of CNT-PDA-PDMC in aqueous and organic solutions was obviously enhanced. Apart from PDMC, many other amino-terminated polymers can also be used to functionalization of CNTs via similar strategy. Therefore, the method described in this work should be a general strategy for fabrication various polymer nanocomposites.

  7. Oxidation of Cu(II) aminopolycarboxylates by carbonate radical. A flash photolysis study

    International Nuclear Information System (INIS)

    Mandal, P.C.; Bardhan, D.K.

    1999-01-01

    Reactions of carbonate radical (CO 3 -. ) generated by photolysis or by radiolysis of a carbonate solution, with Cu(II) complexes of aminopolycarboxylic acids viz., Cu(II)ethylenediamine tetraacetate [Cu II EDTA] 2- and Cu(II)-iminodiacetate [Cu II IDA] were studied at pH 10.5 and ionic strength 0.2 mol x dm -3 . Time-resolved spectroscopy and kinetics for the transients were studied using flash photolysis and stable products arising from the ligand degradation of the complex were ascertained by steady-state radiolysis experiments. From the kinetic data it is observed that CO 3 -. radical reacts initially with Cu II -complex to form a transient intermediate having maximum absorption at 335 nm and 430 nm. From the subsequent reactions of this intermediate it was assigned to be Cu III .species. This Cu(III) species undergoes intermolecular electron transfer with the Cu II -complex to give a radical intermediate which again slowly reacts with Cu II -complex to give a long lived species containing Cu-C bond. This long lived species, however, slowly decomposed to give glyoxalic reaction between Cu III -complex and a suitable donor, the one electron reduction potential for [Cu III EDTA] 1- /[Cu II EDTA] 2- and [Cu III IDA] +1 /Cu II IDA was determined. (author)

  8. Violent Radicalization in Europe

    DEFF Research Database (Denmark)

    Dalgaard-Nielsen, Anja

    2010-01-01

    When, why, and how do people living in a democracy become radicalized to the point of being willing to use or directly support the use of terrorist violence against fellow citizens? This question has been at the center of academic and public debate over the past years as terrorist attacks...... within this field and to answer the question: From an empirical point of view, what is known and what is not known about radicalization connected to militant Islamism in Europe?...

  9. Simple preparation of thiol-ene particles in glycerol and surface functionalization by thiol-ene chemistry (TEC) and surface chain transfer free radical polymerization (SCT-FRP)

    DEFF Research Database (Denmark)

    Hoffmann, Christian; Chiaula, Valeria; Yu, Liyun

    2018-01-01

    functionalization of excess thiol groups via photochemical thiol-ene chemistry (TEC) resulting in a functional monolayer. In addition, surface chain transfer free radical polymerization (SCT-FRP) was used for the first time to introduce a thicker polymer layer on the particle surface. The application potential...

  10. Involvement of hydroxyl radicals in the release by ionizing radiation of a cell surface nuclease from Micorcoccus radiodurans

    International Nuclear Information System (INIS)

    Mitchel, R.E.J.

    1975-01-01

    The ionizing radiation-induced release of a surface exonuclease from Micrococcus radiodurans is to a large extent inhibited by the removal of water. Irradiation of a cell suspension saturated with O 2 (an effective aqueous electron and hydrogen atom scavenger) allows the same release as irradiation in the presence of N 2 . Ethanol (a good hydroxyl radical scavenger) protects the enzyme from release. These data suggest that hydroxyl radicals produced by the radiolysis of water are important releasing agents. Hydroxyl radicals produced by the ultraviolet decomposition of H 2 O 2 were effective in releasing the enzyme

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

    International Nuclear Information System (INIS)

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

    2017-01-01

    In this study, we developed a new procedure to prepare monodispersed functionalized SiO_2 (SiO_2-PDA-PDMC) composites via mussel inspired chemistry and surface initiated atom transfer radical polymerization (SI-ATRP). Samples were characterized by transmission electron microscope (TEM), Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS) and thermal gravimetric analysis (TGA) measurements. TEM results showed that spherical morphology was unchanged after the functionalization. FT-IR results confirmed the successful modification with polydopamine (PDA) and the presence of poly-([2-(Methacryloyloxy) ethyl] trimethylammonium chloride) (PDMC) layer on the surface of SiO_2 spheres. TGA data showed that the PDMC account for about 12.12 wt% in the sample of SiO_2-PDA-PDMC composites. The XPS analysis further confirmed the existence of PDMC on the surface of SiO_2-PDA-PDMC composites. The obtained SiO_2-PDA-PDMC composites were used as adsorbent for the removal of Congo red (CR) from aqueous solution to evaluate the performance in environment application. The effect of contact time, solution pH, initial CR concentration and temperature on the adsorption of CR onto SiO_2-PDA-PDMC composites was investigated. Adsorption results demonstrated that adsorption of CR onto SiO_2-PDA-PDMC composites was a fast and efficient process. The adsorption equilibrium reached within 60 min, and the adsorption process followed the pseudo-second-order model. The experimental data of isotherms were better described by the Freundlich model. Thermodynamic study depicted the endothermic nature of adsorption and the process was spontaneous. Results from the effect of solution pH on the CR adsorption showed that the acidic condition favors the adsorption and provided evidence for the contribution of PDMC on the SiO_2-PDA-PDMC composites in the removal of CR. This study suggests SiO_2-PDA-PDMC composites can be developed as a new adsorbent for the removal of

  12. The Formation Time of Ti-O• and Ti-O•-Ti Radicals at the n-SrTiO3/Aqueous Interface during Photocatalytic Water Oxidation.

    Science.gov (United States)

    Chen, Xihan; Choing, Stephanie N; Aschaffenburg, Daniel J; Pemmaraju, C D; Prendergast, David; Cuk, Tanja

    2017-02-08

    The initial step of photocatalytic water oxidation reaction at the metal oxide/aqueous interface involves intermediates formed by trapping photogenerated, valence band holes on different reactive sites of the oxide surface. In SrTiO 3, these one-electron intermediates are radicals located in Ti-O • (oxyl) and Ti-O • -Ti (bridge) groups arranged perpendicular and parallel to the surface respectively, and form electronic states in the band gap of SrTiO 3 . Using an ultrafast sub band gap probe of 400 nm and white light, we excited transitions between these radical states and the conduction band. By measuring the time evolution of surface reflectivity following the pump pulse of 266 nm light, we determined an initial radical formation time of 1.3 ± 0.2 ps, which is identical to the time to populate the surface with titanium oxyl (Ti-O • ) radicals. The oxyl was separately observed by a subsurface vibration near 800 cm -1 from Ti-O located in the plane right below Ti-O • . Second, a polarized transition optical dipole allows us to assign the 1.3 ps time constant to the production of both O-site radicals. After a 4.5 ps delay, another distinct surface species forms with a time constant of 36 ± 10 ps with a yet undetermined structure. As would be expected, the radicals' decay, specifically probed by the oxyl's subsurface vibration, parallels that of the photocurrent. Our results led us to propose a nonadiabatic kinetic mechanism for generating radicals of the type Ti-O • and Ti-O • -Ti from valence band holes based on their solvation at aqueous interfaces.

  13. Pulse radiolysis of alkanes: a time-resolved EPR study - Part I. Alkyl radicals

    International Nuclear Information System (INIS)

    Shkrob, I.A.; Trifunac, A.D.

    1995-01-01

    Time-resolved EPR was applied to detect short-lived alkyl radicals in pulse radiolysis of liquid alkanes. Two problems were addressed: (i) the mechanism of radical formation and (ii) the mechanism of chemically-induced spin polarization in these radicals. (i) The ratio of yields of penultimate and interior radicals in n-alkanes at the instant of their generation was found to be ≅ 1.25 times greater than the statistical quantity. This higher-than-statistical production of penultimate radicals indicates that the proton transfer reaction involving excited radical cations must be a prevailing route of radical generation. The relative yields of hydrogen abstraction and fragmentation for various branched alkanes are estimated. It is concluded that the fragmentation occurs prior to the formation of radicals in an excited precursor species. (ii) The analysis of spin-echo kinetics in n-alkanes suggests that the alkyl radicals gain the emissive polarization in spur reactions. This initial polarization increases with shortening of the aliphatic chain. We suggest that the origin of this polarization is the ST mechanism operating in the pairs of alkyl radicals and hydrogen atoms generated in dissociation of excited alkane molecules. It is also found that a long-chain structure of alkyl radicals results in much higher rate of Heisenberg spin exchange relative to the recombination rate (up to 30 times). That suggests prominent steric effects in recombination or the occurrence of through-chain electron exchange. The significance of these results in the context of cross-linking in polyethylene and higher paraffins is discussed. (Author)

  14. STUDIES ON RADICAL POLYMERIZATION OF METHYL METHACRYLATE INITIATED WITH ORGANIC PEROXIDE-AMINE SYSTEMS

    Institute of Scientific and Technical Information of China (English)

    QIU Kunyuan; SHUI Li; FENG Xinde

    1984-01-01

    Radical polymerization of methyl methacrylate (MMA) initiated with various diacyl peroxideamine systems was studied. Benzoyl peroxide (BPO) and lauroyl peroxide (LPO) were used as diacyl peroxide component, N,N-dimethyl aniline (DMA) and its para substituted derivatives, i.e., N,N-dimethyl-p-toluidine (DMT), p-hydroxymethyl-N,N-dimethyl aniline (HDMA), p-nitro-N,N-dimethyl aniline (NDMA) and p-dimethylamino benzaldehyde (DMAB) were used as amine components. It was found that the peroxide-DMT systems give higher rates of bulk polymerization Rp of MMA than the organic hydroperoxide-DMT systems with the following descending order BPO-DMT>LPO-DMT>CHP (cumene hydroperoxide)-DMT>TBH (tert-butyl hydroperoxide)-DMT.The aromatic tertiary amines possess obvious structural effect on the Rp values in the diacyl peroxideamine system. The overall activation energy of MMA polymerization was determined and the kinetics of polymerization of MMA initiated with BPO-DMT system was investigated.

  15. Residual pathological stage at radical cystectomy significantly impacts outcomes for initial T2N0 bladder cancer.

    Science.gov (United States)

    Isbarn, Hendrik; Karakiewicz, Pierre I; Shariat, Shahrokh F; Capitanio, Umberto; Palapattu, Ganesh S; Sagalowsky, Arthur I; Lotan, Yair; Schoenberg, Mark P; Amiel, Gilad E; Lerner, Seth P; Sonpavde, Guru

    2009-08-01

    We hypothesized that in patients with T2N0 stage disease at transurethral bladder tumor resection a lower residual cancer stage (P1N0 or less) at radical cystectomy may correlate with improved outcomes relative to those with residual P2N0 disease. We analyzed 208 patients with T2N0 stage disease at transurethral bladder tumor resection whose tumors were organ confined at radical cystectomy (P2 or lower, pN0). None received perioperative chemotherapy. Kaplan-Meier as well as univariable and multivariable Cox regression models addressed the effect of residual pT stage at radical cystectomy on recurrence and cancer specific mortality rates. Covariates consisted of age, gender, grade, lymphovascular invasion, carcinoma in situ, number of lymph nodes removed and year of surgery. Residual pT stage at radical cystectomy was P0 in 24 (11.5%) patients, Pa in 9 (4.3%), PCIS in 22 (10.6%), P1 in 35 (16.8%) and P2 in 118 (56.7%). Median followup of censored patients was 55.7 months for recurrence and 52.1 months for cancer specific mortality analyses. The 5-year recurrence-free survival rates of patients with P0/Pa/PCIS, P1 and P2 stage disease were 100%, 85% and 75%, respectively. The 5-year cancer specific survival rates for the same cohorts were 100%, 93% and 81%, respectively. On multivariable analysis the effect of residual stage P1 or lower at radical cystectomy achieved independent predictor status for recurrence (adjusted HR 0.20, p = 0.002) and cancer specific mortality (adjusted HR 0.24, p = 0.02). Down staging from initial T2N0 bladder cancer at transurethral bladder tumor resection to lower stage at radical cystectomy significantly reduces recurrence and cancer specific mortality. Further validation of this finding is warranted.

  16. Facile graft polystyrene onto multi-walled carbon nanotubes via in situ thermo-induced radical polymerization

    International Nuclear Information System (INIS)

    Liu Peng

    2009-01-01

    A facile procedure was developed for the grafting of polystyrene onto the surfaces of multi-walled carbon nanotubes (MWNTs) via the in situ thermo-induced bulk radical polymerization of styrene at the different polymerizing temperatures, in the presence of MWNTs without any initiator added. The grafting products were validated by the dispersibility, TEM, TGA, FT-IR, and Raman analysis. The TGA results also showed the lower polymerizing temperature was propitious to the free radical addition reactions.

  17. Near-Infrared Free-Radical and Free-Radical-Promoted Cationic Photopolymerizations by In-Source Lighting Using Upconverting Glass.

    Science.gov (United States)

    Kocaarslan, Azra; Tabanli, Sevcan; Eryurek, Gonul; Yagci, Yusuf

    2017-11-13

    A method is presented for the initiation of free-radical and free-radical-promoted cationic photopolymerizations by in-source lighting in the near-infrared (NIR) region using upconverting glass (UCG). This approach utilizes laser irradiation of UCG at 975 nm in the presence of fluorescein (FL) and pentamethyldiethylene triamine (PMDETA). FL excited by light emitted from the UCG undergoes electron-transfer reactions with PMDETA to form free radicals capable of initiating polymerization of methyl methacrylate. To execute the corresponding free-radical-promoted cationic polymerization of cyclohexene oxide, isobutyl vinyl ether, and N-vinyl carbazole, it was necessary to use FL, dimethyl aniline (DMA), and diphenyliodonium hexafluorophosphate as sensitizer, coinitiator, and oxidant, respectively. Iodonium ions promptly oxidize DMA radicals formed to the corresponding cations. Thus, cationic polymerization with efficiency comparable to the conventional irradiation source was achieved. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. A novel property of gold nanoparticles: Free radical generation under microwave irradiation

    International Nuclear Information System (INIS)

    Paudel, Nava Raj; Shvydka, Diana; Parsai, E. Ishmael

    2016-01-01

    Purpose: Gold nanoparticles (GNPs) are known to be effective mediators in microwave hyperthermia. Interaction with an electromagnetic field, large surface to volume ratio, and size quantization of nanoparticles (NPs) can lead to increased cell killing beyond pure heating effects. The purpose of this study is to explore the possibility of free radical generation by GNPs in aqueous media when they are exposed to a microwave field. Methods: A number of samples with 500 mM 5,5-dimethyl-1-pyrroline N-oxide (DMPO) in 20 ppm GNP colloidal suspensions were scanned with an electron paramagnetic resonance (EPR)/electron spin resonance spectrometer to generate and detect free radicals. A fixed (9.68 GHz) frequency microwave from the spectrometer has served for both generation and detection of radicals. EPR spectra obtained as first derivatives of intensity with the spectrometer were double integrated to get the free radical signal intensities. Power dependence of radical intensity was studied by applying various levels of microwave power (12.5, 49.7, and 125 mW) while keeping all other scan parameters the same. Free radical signal intensities from initial and final scans, acquired at the same power levels, were compared. Results: Hydroxyl radical (OH⋅) signal was found to be generated due to the exposure of GNP–DMPO colloidal samples to a microwave field. Intensity of OH⋅ signal thus generated at 12.5 mW microwave power for 2.8 min was close to the intensity of OH⋅ signal obtained from a water–DMPO sample exposed to 1.5 Gy ionizing radiation dose. For repeated scans, higher OH⋅ intensities were observed in the final scan for higher power levels applied between the initial and the final scans. Final intensities were higher also for a shorter time interval between the initial and the final scans. Conclusions: Our results observed for the first time demonstrate that GNPs generate OH⋅ radicals in aqueous media when they are exposed to a microwave field. If OH

  19. A novel property of gold nanoparticles: Free radical generation under microwave irradiation.

    Science.gov (United States)

    Paudel, Nava Raj; Shvydka, Diana; Parsai, E Ishmael

    2016-04-01

    Gold nanoparticles (GNPs) are known to be effective mediators in microwave hyperthermia. Interaction with an electromagnetic field, large surface to volume ratio, and size quantization of nanoparticles (NPs) can lead to increased cell killing beyond pure heating effects. The purpose of this study is to explore the possibility of free radical generation by GNPs in aqueous media when they are exposed to a microwave field. A number of samples with 500 mM 5,5-dimethyl-1-pyrroline N-oxide (DMPO) in 20 ppm GNP colloidal suspensions were scanned with an electron paramagnetic resonance (EPR)/electron spin resonance spectrometer to generate and detect free radicals. A fixed (9.68 GHz) frequency microwave from the spectrometer has served for both generation and detection of radicals. EPR spectra obtained as first derivatives of intensity with the spectrometer were double integrated to get the free radical signal intensities. Power dependence of radical intensity was studied by applying various levels of microwave power (12.5, 49.7, and 125 mW) while keeping all other scan parameters the same. Free radical signal intensities from initial and final scans, acquired at the same power levels, were compared. Hydroxyl radical (OH⋅) signal was found to be generated due to the exposure of GNP-DMPO colloidal samples to a microwave field. Intensity of OH⋅ signal thus generated at 12.5 mW microwave power for 2.8 min was close to the intensity of OH⋅ signal obtained from a water-DMPO sample exposed to 1.5 Gy ionizing radiation dose. For repeated scans, higher OH⋅ intensities were observed in the final scan for higher power levels applied between the initial and the final scans. Final intensities were higher also for a shorter time interval between the initial and the final scans. Our results observed for the first time demonstrate that GNPs generate OH⋅ radicals in aqueous media when they are exposed to a microwave field. If OH⋅ radicals can be generated close to

  20. A novel property of gold nanoparticles: Free radical generation under microwave irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Paudel, Nava Raj, E-mail: nrpaudel@yahoo.com [Department of Radiation Oncology, The University of Toledo Medical Center, Toledo, Ohio 43614 and Department of Radiation Oncology, University of Arkansas for Medical Sciences, Little Rock, Arkansas 72205 (United States); Shvydka, Diana; Parsai, E. Ishmael [Department of Radiation Oncology, The University of Toledo Medical Center, Toledo, Ohio 43614 (United States)

    2016-04-15

    Purpose: Gold nanoparticles (GNPs) are known to be effective mediators in microwave hyperthermia. Interaction with an electromagnetic field, large surface to volume ratio, and size quantization of nanoparticles (NPs) can lead to increased cell killing beyond pure heating effects. The purpose of this study is to explore the possibility of free radical generation by GNPs in aqueous media when they are exposed to a microwave field. Methods: A number of samples with 500 mM 5,5-dimethyl-1-pyrroline N-oxide (DMPO) in 20 ppm GNP colloidal suspensions were scanned with an electron paramagnetic resonance (EPR)/electron spin resonance spectrometer to generate and detect free radicals. A fixed (9.68 GHz) frequency microwave from the spectrometer has served for both generation and detection of radicals. EPR spectra obtained as first derivatives of intensity with the spectrometer were double integrated to get the free radical signal intensities. Power dependence of radical intensity was studied by applying various levels of microwave power (12.5, 49.7, and 125 mW) while keeping all other scan parameters the same. Free radical signal intensities from initial and final scans, acquired at the same power levels, were compared. Results: Hydroxyl radical (OH⋅) signal was found to be generated due to the exposure of GNP–DMPO colloidal samples to a microwave field. Intensity of OH⋅ signal thus generated at 12.5 mW microwave power for 2.8 min was close to the intensity of OH⋅ signal obtained from a water–DMPO sample exposed to 1.5 Gy ionizing radiation dose. For repeated scans, higher OH⋅ intensities were observed in the final scan for higher power levels applied between the initial and the final scans. Final intensities were higher also for a shorter time interval between the initial and the final scans. Conclusions: Our results observed for the first time demonstrate that GNPs generate OH⋅ radicals in aqueous media when they are exposed to a microwave field. If OH

  1. Vinylcyclopropylacyl and polyeneacyl radicals. Intramolecular ketene alkyl radical additions in ring synthesis.

    Science.gov (United States)

    De Boeck, Benoit; Herbert, Nicola M A; Harrington-Frost, Nicole M; Pattenden, Gerald

    2005-01-21

    Treatment of a variety of substituted vinylcyclopropyl selenyl esters, e.g. 11, with Bu(3)SnH-AIBN in refluxing benzene leads to the corresponding acyl radical intermediates, which undergo rearrangement and intramolecular cyclisations via their ketene alkyl radical equivalents producing cyclohexenones in 50-60% yield. By contrast, treatment of conjugated triene selenyl esters, e.g. 32, with Bu(3)SnH-AIBN produces substituted 2-cyclopentenones via intramolecular cyclisations of their ketene alkyl radical intermediates. Under the same radical-initiating conditions the selenyl esters derived from o-vinylbenzoic acid and o-vinylcinnamic acid undergo intramolecular cyclisations producing 1-indanone and 5,6-dihydrobenzocyclohepten-7-one respectively in 60-70% yields. A tandem radical cyclisation from the alpha,beta,gamma,delta-diene selenyl ester 31 provides an expeditious synthesis of the diquinane 35 in 69% yield.

  2. Radical cations of quadricyclane and norbornadiene in polar ZSM-5 matrices: Radical cation photochemical transformations without photons

    International Nuclear Information System (INIS)

    Barnabas, M.V.; Trifunac, A.D.

    1994-01-01

    Radical cations of quadricyclane (Q) and norbornadiene (NBD) are produced by γ-radiolysis in zeolites. In polar ZSM-5, only one radical cation is initially observed below 100K. Increasing the temperature above 200K gives rise to the cyclopentadiene radical cation. Higher temperatures (>360K) give rise to the cyclopenten-4-yl radical. The observation of cyclopentadiene radical cation implies the occurrence of the reverse Diels-Alder reaction. This is a thermally forbidden, photochemically allowed, process, which is made possible by the interaction of the polar zeolite matrix sites with parent NBD and Q radical cations

  3. Radical-Mediated Enzymatic Polymerizations

    Science.gov (United States)

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

    2016-01-01

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

  4. Controlled/living surface-initiated ATRP of antifouling polymer brushes from gold in PBS and blood sera as a model study for polymer modifications in complex biological media

    Czech Academy of Sciences Publication Activity Database

    Rodriguez-Emmenegger, Cesar; Hasan, E.; Pop-Georgievski, Ognen; Houska, Milan; Brynda, Eduard; Bologna Alles, A.

    2012-01-01

    Roč. 12, č. 4 (2012), s. 525-532 ISSN 1616-5187 R&D Projects: GA AV ČR KAN200670701; GA ČR GAP503/10/0664 Institutional research plan: CEZ:AV0Z40500505 Keywords : antifouling surfaces * atom-transfer radical polymerization (ATRP) * biocompatibility Subject RIV: EE - Microbiology, Virology Impact factor: 3.742, year: 2012

  5. Preparation of Transparent Bulk TiO2/PMMA Hybrids with Improved Refractive Indices via an in Situ Polymerization Process Using TiO2 Nanoparticles Bearing PMMA Chains Grown by Surface-Initiated Atom Transfer Radical Polymerization.

    Science.gov (United States)

    Maeda, Satoshi; Fujita, Masato; Idota, Naokazu; Matsukawa, Kimihiro; Sugahara, Yoshiyuki

    2016-12-21

    Transparent TiO 2 /PMMA hybrids with a thickness of 5 mm and improved refractive indices were prepared by in situ polymerization of methyl methacrylate (MMA) in the presence of TiO 2 nanoparticles bearing poly(methyl methacrylate) (PMMA) chains grown using surface-initiated atom transfer radical polymerization (SI-ATRP), and the effect of the chain length of modified PMMA on the dispersibility of modified TiO 2 nanoparticles in the bulk hybrids was investigated. The surfaces of TiO 2 nanoparticles were modified with both m-(chloromethyl)phenylmethanoyloxymethylphosphonic acid bearing a terminal ATRP initiator and isodecyl phosphate with a high affinity for common organic solvents, leading to sufficient dispersibility of the surface-modified particles in toluene. Subsequently, SI-ATRP of MMA was achieved from the modified surfaces of the TiO 2 nanoparticles without aggregation of the nanoparticles in toluene. The molecular weights of the PMMA chains cleaved from the modified TiO 2 nanoparticles increased with increases in the prolonging of the polymerization period, and these exhibited a narrow distribution, indicating chain growth controlled by SI-ATRP. The nanoparticles bearing PMMA chains were well-dispersed in MMA regardless of the polymerization period. Bulk PMMA hybrids containing modified TiO 2 nanoparticles with a thickness of 5 mm were prepared by in situ polymerization of the MMA dispersion. The transparency of the hybrids depended significantly on the chain length of the modified PMMA on the nanoparticles, because the modified PMMA of low molecular weight induced aggregation of the TiO 2 nanoparticles during the in situ polymerization process. The refractive indices of the bulk hybrids could be controlled by adjusting the TiO 2 content and could be increased up to 1.566 for 6.3 vol % TiO 2 content (1.492 for pristine PMMA).

  6. Allylthioketone Mediated Free Radical Polymerization of Methacrylates

    Directory of Open Access Journals (Sweden)

    Feng Zhong

    2017-11-01

    Full Text Available By combination of high trapping free radical efficiency of the thioketone and resonance of the allylic radical, a new type of mediating agent, 1,3,3-triphenylprop-2-ene-1-thione (TPPT has been successfully synthesized, and then is used to study controlled free radical polymerization of methacrylates. Very stable TPPT radicals at the end of poly(methyl methacrylate (PMMA are detected in the polymerization of MMA using TPPT and AIBN as the control agent and initiator. The MALDI-TOF MS spectra are used to identify terminal groups of the resultant poly(glycidyl methacrylate (PGMA, and major component of the obtained polymer has the structure, (CH32(CNC-PGMA-C7H9O3. Chain extension reaction tests ascertain formation of the dead polymers during the polymer storage and purification process of the polymers. Owing to very slow fragmentation reaction of the TPPT-terminated polymethacrylate radical and addition reaction of this radical with a primary radical, the growing chain radicals are difficult to be regenerated, leading to an unobvious change of the molecular weight with monomer conversion. The molecular weights of polymers can be controlled by the ratios of monomer/initiator and TPPT/initiator. However, the first order kinetics of the polymerization and the polymers with narrow polydispersity are obtained, and these phenomena are discussed. This study provides useful information on how to design a better controlling agent.

  7. Concentration-dependent photodegradation kinetics and hydroxyl-radical oxidation of phenicol antibiotics.

    Science.gov (United States)

    Li, Kai; Zhang, Peng; Ge, Linke; Ren, Honglei; Yu, Chunyan; Chen, Xiaoyang; Zhao, Yuanfeng

    2014-09-01

    Thiamphenicol and florfenicol are two phenicol antibiotics widely used in aquaculture and are ubiquitous as micropollutants in surface waters. The present study investigated their photodegradation kinetics, hydroxyl-radical (OH) oxidation reactivities and products. Firstly, the photolytic kinetics of the phenicols in pure water was studied as a function of initial concentrations (C0) under UV-vis irradiation (λ>200nm). It was found that the kinetics was influenced by C0. A linear plot of the pseudo-first-order rate constant vs C0 was observed with a negative slope. Secondly, the reaction between the phenicol antibiotics and OH was examined with a competition kinetic method under simulated solar irradiation (λ>290nm), which quantified their bimolecular reaction rate constants of (2.13±0.02)×10(9)M(-1)s(-1) and (1.82±0.10)×10(9)M(-1)s(-1) for thiamphenicol and florfenicol, respectively. Then the corresponding OH oxidated half-lives in sunlit surface waters were calculated to be 90.5-106.1h. Some main intermediates were formed from the reaction, which suggested that the two phenicols underwent hydroxylation, oxygenation and dehydrogenation when OH existed. These results are of importance to assess the phenicol persistence in wastewater treatment and sunlit surface waters. Copyright © 2014 Elsevier Ltd. All rights reserved.

  8. Surface Warfare Officers Initial Training For Future Success

    Science.gov (United States)

    2018-03-01

    9 A school is initial rating specific technical training that is given to sailors. 14 Figure 4. Less...NAVAL POSTGRADUATE SCHOOL MONTEREY, CALIFORNIA MBA PROFESSIONAL REPORT SURFACE WARFARE OFFICERS— INITIAL TRAINING FOR FUTURE SUCCESS March 2018...professional report 4. TITLE AND SUBTITLE SURFACE WARFARE OFFICERS—INITIAL TRAINING FOR FUTURE SUCCESS 5. FUNDING NUMBERS 6. AUTHOR(S) Arron J

  9. Titanium, zirconium- and hafnium containing initiators in the polymerization of acrylic monomers to ''living'' polymers

    International Nuclear Information System (INIS)

    Farnham, W.B.; Hertler, W.R.

    1988-01-01

    This patent describes a process for preparing ''living'' polymer. The process comprises contacting one or more acrylic monomers under polymerizing conditions with a polymerization-initiating amount of a tetra-coordinate organotitanium, organozirconium or organo-hafnium polymerization initiator, and ''living'' polymers produced thereby

  10. The Games Radicals Play: Special Issue on Free Radicals and Radical Ions

    Directory of Open Access Journals (Sweden)

    John C. Walton

    2015-02-01

    Full Text Available Chemistry and Physics have aptly been described as “most excellent children of Intellect and Art” [1]. Both these “children” engage with many playthings, and molecules rank as one of their first favorites, especially radicals, which are amongst the most lively and exciting. Checking out radicals dancing to the music of entropy round their potential energy ballrooms is surely both entertaining and enlightening. Radicals’ old favorite convolutions are noteworthy, but the new styles, modes and arrangements appearing on the scene are even more interesting. Some of these are ephemeral and enjoy only a brief appearance, others are retro-types reappearing in new guises, still others are genuinely new and “go viral” in the scientific world. This Special Issue of Molecules contains the observations and reflections of a select group of chemists and physicists fascinated by this spectacle. It contains an eclectic mix reflecting on new modes and advances as well as on permutations and combinations that revive mature themes. [...

  11. Radical Cation Salt-initiated Aerobic C-H Phosphorylation of N-Benzylanilines: Synthesis of a-Aminophosphonates.

    Science.gov (United States)

    Jia, Xiao Dong; Liu, Xiaofei; Yuan, Yu; Li, Pengfei; Hou, Wentao; He, Kaixuan

    2018-06-03

    A radical cation salt-initiated phosphorylation of N-benzylanilines was realized through the aerobic oxidation of sp3 C-H bond, providing a series of α-aminophosphonates in high yields. The investigation of the reaction scope revealed that this mild catalyst system is superior in good functional group tolerance and high reaction efficiency. The mechanistic study implied that the cleavage of the sp3 C-H bond was involved in the rate-determining step. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. A model of extracellular enzymes in free-living microbes: which strategy pays off?

    Science.gov (United States)

    Traving, Sachia J; Thygesen, Uffe H; Riemann, Lasse; Stedmon, Colin A

    2015-11-01

    An initial modeling approach was applied to analyze how a single, nonmotile, free-living, heterotrophic bacterial cell may optimize the deployment of its extracellular enzymes. Free-living cells live in a dilute and complex substrate field, and to gain enough substrate, their extracellular enzymes must be utilized efficiently. The model revealed that surface-attached and free enzymes generate unique enzyme and substrate fields, and each deployment strategy has distinctive advantages. For a solitary cell, surface-attached enzymes are suggested to be the most cost-efficient strategy. This strategy entails potential substrates being reduced to very low concentrations. Free enzymes, on the other hand, generate a radically different substrate field, which suggests significant benefits for the strategy if free cells engage in social foraging or experience high substrate concentrations. Swimming has a slight positive effect for the attached-enzyme strategy, while the effect is negative for the free-enzyme strategy. The results of this study suggest that specific dissolved organic compounds in the ocean likely persist below a threshold concentration impervious to biological utilization. This could help explain the persistence and apparent refractory state of oceanic dissolved organic matter (DOM). Microbial extracellular enzyme strategies, therefore, have important implications for larger-scale processes, such as shaping the role of DOM in ocean carbon sequestration. Copyright © 2015, American Society for Microbiology. All Rights Reserved.

  13. Radical intermediates involved in the bleaching of the carotenoid crocin. Hydroxyl radicals, superoxide anions and hydrated electrons

    International Nuclear Information System (INIS)

    Bors, W.; Saran, M.; Michel, C.

    1982-01-01

    The participation of the primary radicals in the bleaching of aqueous solutions of the carotenoid crocin by ionizing radiation was investigated, employing both X-radiolysis and pulse radiolysis. The pulse-radiolytic data demonstrated a very rapid diffusion-controlled attack by both hydroxyl radicals (radicalsOH) and hydrated electrons (e - sub(aq)), while superoxide anions (O 2 - ) did not react at all. The site of the initial reaction of these radicals was not limited to the polyene chromophore. Slower secondary reactions involving crocin alkyl or peroxy radicals contribute mainly to the overall bleaching, in particular during steady-state irradiation. (author)

  14. Resonance Raman Spectroscopy of Free Radicals Produced by Ionizing Radiation

    DEFF Research Database (Denmark)

    Wilbrandt, Robert Walter

    1984-01-01

    Applications of time-resolved resonance Raman spectroscopy to the study of short-lived free radicals produced by ionizing radiation are briefly reviewed. Potential advantages and limitations of this technique are discussed in the light of given examples. The reduction of p-nitrobenzylchloride and......Applications of time-resolved resonance Raman spectroscopy to the study of short-lived free radicals produced by ionizing radiation are briefly reviewed. Potential advantages and limitations of this technique are discussed in the light of given examples. The reduction of p......-nitrobenzylchloride and subsequent formation of the p-nitrobenzyl radical and the reaction of p-nitrotoluene with O– are studied by resonance Raman and optical absorption spectroscopy....

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2017-06-01

    In this study, we developed a new procedure to prepare monodispersed functionalized SiO{sub 2} (SiO{sub 2}-PDA-PDMC) composites via mussel inspired chemistry and surface initiated atom transfer radical polymerization (SI-ATRP). Samples were characterized by transmission electron microscope (TEM), Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS) and thermal gravimetric analysis (TGA) measurements. TEM results showed that spherical morphology was unchanged after the functionalization. FT-IR results confirmed the successful modification with polydopamine (PDA) and the presence of poly-([2-(Methacryloyloxy) ethyl] trimethylammonium chloride) (PDMC) layer on the surface of SiO{sub 2} spheres. TGA data showed that the PDMC account for about 12.12 wt% in the sample of SiO{sub 2}-PDA-PDMC composites. The XPS analysis further confirmed the existence of PDMC on the surface of SiO{sub 2}-PDA-PDMC composites. The obtained SiO{sub 2}-PDA-PDMC composites were used as adsorbent for the removal of Congo red (CR) from aqueous solution to evaluate the performance in environment application. The effect of contact time, solution pH, initial CR concentration and temperature on the adsorption of CR onto SiO{sub 2}-PDA-PDMC composites was investigated. Adsorption results demonstrated that adsorption of CR onto SiO{sub 2}-PDA-PDMC composites was a fast and efficient process. The adsorption equilibrium reached within 60 min, and the adsorption process followed the pseudo-second-order model. The experimental data of isotherms were better described by the Freundlich model. Thermodynamic study depicted the endothermic nature of adsorption and the process was spontaneous. Results from the effect of solution pH on the CR adsorption showed that the acidic condition favors the adsorption and provided evidence for the contribution of PDMC on the SiO{sub 2}-PDA-PDMC composites in the removal of CR. This study suggests SiO{sub 2}-PDA-PDMC composites can be

  16. Biochemistry and pathology of radical-mediated protein oxidation

    DEFF Research Database (Denmark)

    Dean, R T; Fu, S; Stocker, R

    1997-01-01

    Radical-mediated damage to proteins may be initiated by electron leakage, metal-ion-dependent reactions and autoxidation of lipids and sugars. The consequent protein oxidation is O2-dependent, and involves several propagating radicals, notably alkoxyl radicals. Its products include several catego...

  17. Liquid-crystalline polyesters with end nitroxyl radical and their use in living free-radical polymerization

    Czech Academy of Sciences Publication Activity Database

    Razina, A B.; Sedláková, Zdeňka; Bouchal, Karel; Tenkovtsev, A. V.; Ilavský, Michal

    2002-01-01

    Roč. 44, č. 9 (2002), s. 924-930 ISSN 0965-545X R&D Projects: GA AV ČR KSK4050111 Institutional research plan: CEZ:AV0Z4050913 Keywords : liquid crystal * polyesters * nitroxyl radical Subject RIV: CD - Macromolecular Chemistry Impact factor: 0.627, year: 2002

  18. Diazonium salts as grafting agents and efficient radical-hydrosilylation initiators for freestanding photoluminescent silicon nanocrystals.

    Science.gov (United States)

    Höhlein, Ignaz M D; Kehrle, Julian; Helbich, Tobias; Yang, Zhenyu; Veinot, Jonathan G C; Rieger, Bernhard

    2014-04-07

    The reactivity of diazonium salts towards freestanding, photoluminescent silicon nanocrystals (SiNCs) is reported. It was found that SiNCs can be functionalized with aryl groups by direct reductive grafting of the diazonium salts. Furthermore, diazonium salts are efficient radical initiators for SiNC hydrosilylation. For this purpose, novel electron-deficient diazonium salts, highly soluble in nonpolar solvents were synthesized. The SiNCs were functionalized with a variety of alkenes and alkynes at room temperature with short reaction times. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Protonated o-semiquinone radical as a mimetic of the humic acids native radicals: A DFT approach to the molecular structure and EPR properties

    Science.gov (United States)

    Witwicki, Maciej; Jezierska, Julia

    2012-06-01

    Organic radicals are known to be an indispensable component of the humic acids (HA) structure. In HA two forms of radicals, stable (native) and short-lived (transient), are identified. Importantly, these radical forms can be easily differentiated by electron paramagnetic resonance (EPR) spectroscopy. This article provides a DFT-based insight into the electronic and molecular structure of the native radicals. The molecular models including an increase of the radical aromaticity and the hydrogen bonding between the radical and other functional groups of HA are taken under investigation. In consequence the interesting pieces of information on the structure of the native radical centers in HA are revealed and discussed, especially in terms of differences between the electronic structure of the native and transient forms.

  20. Photochemical Aryl Radical Cyclizations to Give (E-3-Ylideneoxindoles

    Directory of Open Access Journals (Sweden)

    Michael Gurry

    2014-09-01

    Full Text Available (E-3-Ylideneoxindoles are prepared in methanol in reasonable to good yields, as adducts of photochemical 5-exo-trig of aryl radicals, in contrast to previously reported analogous radical cyclizations initiated by tris(trimethylsilylsilane and azo-initiators that gave reduced oxindole adducts.

  1. Youth De-Radicalization: A Canadian Framework

    Directory of Open Access Journals (Sweden)

    Hafal (Haval Ahmad

    2017-09-01

    Full Text Available Youth radicalization leading to violence has become a growing fear among Canadians, as terrorist attacks are carried out in Western states. Although Canada has suffered relatively fewer acts of violence, this fear has intensified and a de-radicalization strategy is needed in the Canadian context. In a qualitative case study methodology, interviews were conducted with school counsellors, religious leaders, and academics to explore solutions to youth radicalization. Youth de-radicalization approaches from the United Kingdom were analyzed and found that community-based initiatives were missing from programming. Social identity theory is used to explain that youth join radicalized groups to feel a sense of belonging and have to be provided an alternative and moderate group identity to de-radicalize. This study found youth de-radicalization in Canada is best served through a community collaboration approach.

  2. A short review of radiation-induced raft-mediated graft copolymerization: A powerful combination for modifying the surface properties of polymers in a controlled manner

    Science.gov (United States)

    Barsbay, Murat; Güven, Olgun

    2009-12-01

    Surface grafting of polymeric materials is attracting increasing attention as it enables the preparation of new materials from known and commercially available polymers having desirable bulk properties such as thermal stability, elasticity, permeability, etc., in conjunction with advantageous newly tailored surface properties such as biocompatibility, biomimicry, adhesion, etc. Ionizing radiation, particularly γ radiation is one of the most powerful tools for preparing graft copolymers as it generates radicals on most substrates. With the advent of living free-radical polymerization techniques, application of γ radiation has been extended to a new era of grafting; grafting in a controlled manner to achieve surfaces with tailored and well-defined properties. This report presents the current use of γ radiation in living free-radical polymerization and highlights the use of both techniques together as a combination to present an advance in the ability to prepare surfaces with desired, tunable and well-defined properties.

  3. A short review of radiation-induced raft-mediated graft copolymerization: A powerful combination for modifying the surface properties of polymers in a controlled manner

    International Nuclear Information System (INIS)

    Barsbay, Murat; Gueven, Olgun

    2009-01-01

    Surface grafting of polymeric materials is attracting increasing attention as it enables the preparation of new materials from known and commercially available polymers having desirable bulk properties such as thermal stability, elasticity, permeability, etc., in conjunction with advantageous newly tailored surface properties such as biocompatibility, biomimicry, adhesion, etc. Ionizing radiation, particularly γ radiation is one of the most powerful tools for preparing graft copolymers as it generates radicals on most substrates. With the advent of living free-radical polymerization techniques, application of γ radiation has been extended to a new era of grafting; grafting in a controlled manner to achieve surfaces with tailored and well-defined properties. This report presents the current use of γ radiation in living free-radical polymerization and highlights the use of both techniques together as a combination to present an advance in the ability to prepare surfaces with desired, tunable and well-defined properties.

  4. A short review of radiation-induced raft-mediated graft copolymerization: A powerful combination for modifying the surface properties of polymers in a controlled manner

    Energy Technology Data Exchange (ETDEWEB)

    Barsbay, Murat [Department of Chemistry, Hacettepe University, 06800 Beytepe, Ankara (Turkey)], E-mail: mbarsbay@hacettepe.edu.tr; Gueven, Olgun [Department of Chemistry, Hacettepe University, 06800 Beytepe, Ankara (Turkey)], E-mail: guven@hacettepe.edu.tr

    2009-12-15

    Surface grafting of polymeric materials is attracting increasing attention as it enables the preparation of new materials from known and commercially available polymers having desirable bulk properties such as thermal stability, elasticity, permeability, etc., in conjunction with advantageous newly tailored surface properties such as biocompatibility, biomimicry, adhesion, etc. Ionizing radiation, particularly {gamma} radiation is one of the most powerful tools for preparing graft copolymers as it generates radicals on most substrates. With the advent of living free-radical polymerization techniques, application of {gamma} radiation has been extended to a new era of grafting; grafting in a controlled manner to achieve surfaces with tailored and well-defined properties. This report presents the current use of {gamma} radiation in living free-radical polymerization and highlights the use of both techniques together as a combination to present an advance in the ability to prepare surfaces with desired, tunable and well-defined properties.

  5. Modeling of laser damage initiated by surface contamination

    International Nuclear Information System (INIS)

    Feit, M.D.; Rubenchik, A.M.; Faux, D.R.; Riddle, R.A.; Shapiro, A.; Eder, D.C.; Penetrante, B.M.; Milam, D.; Genin, F.Y.; Kozlowski, M.R.

    1996-11-01

    The authors are engaged in a comprehensive effort to understand and model the initiation and growth of laser damage initiated by surface contaminants. This includes, for example, the initial absorption by the contaminant, heating and plasma generation, pressure and thermal loading of the transparent substrate, and subsequent shockwave propagation, 'splashing' of molten material and possible spallation, optical propagation and scattering, and treatment of material fracture. The integration use of large radiation hydrodynamics codes, optical propagation codes and material strength codes enables a comprehensive view of the damage process The following picture of surface contaminant initiated laser damage is emerging from our simulations

  6. Formation and Stabilization of Environmentally Persistent Free Radicals Induced by the Interaction of Anthracene with Fe(III)-Modified Clays.

    Science.gov (United States)

    Jia, Hanzhong; Nulaji, Gulimire; Gao, Hongwei; Wang, Fu; Zhu, Yunqing; Wang, Chuanyi

    2016-06-21

    Environmentally persistent free radicals (EPFRs) are occasionally detected in Superfund sites but the formation of EPFRs induced by polycyclic aromatic hydrocarbons (PAHs) is not well understood. In the present work, the formation of EPFRs on anthracene-contaminated clay minerals was quantitatively monitored via electron paramagnetic resonance (EPR) spectroscopy, and surface/interface-related environmental influential factors were systematically explored. The obtained results suggest that EPFRs are more readily formed on anthracene-contaminated Fe(III)-montmorillonite than in other tested systems. Depending on the reaction condition, more than one type of organic radicals including anthracene-based radical cations with g-factors of 2.0028-2.0030 and oxygenic carbon-centered radicals featured by g-factors of 2.0032-2.0038 were identified. The formed EPFRs are stabilized by their interaction with interlayer surfaces, and such surface-bound EPFRs exhibit slow decay with 1/e-lifetime of 38.46 days. Transformation pathway and possible mechanism are proposed on the basis of experimental results and quantum mechanical simulations. Overall, the formation of EPFRs involves single-electron-transfer from anthracene to Fe(III) initially, followed by H2O addition on formed aromatic radical cation. Because of their potential exposure in soil and atmosphere, such clay surface-associated EPFRs might induce more serious toxicity than PAHs and exerts significant impacts on human health.

  7. The Intersection of Black Lives Matter and Adult Education: One Community College Initiative

    Science.gov (United States)

    Miller, Brian; Schwartz, Joni

    2016-01-01

    This chapter is a call to action for adult educators to critically engage the Black Lives Matter Movement through pedagogy, community engagement and scholarly activism. It explores the intersection of the Black Lives Matter movement and adult education by highlighting the response of one community college initiative.

  8. Kinetics of Waterborne Alkyd/Acrylic Hybrid Resin Free Radical Polymerization by Two Systems of Redox and Thermal Initiators

    Directory of Open Access Journals (Sweden)

    shirin Madadi

    2012-12-01

    Full Text Available Kinetics of radical polymerizations of waterborne alkyd/acrylic hybrid resin via batch mini-emulsion technique was studied using redox initiators (TBHP/Fe2+/EDTA/AsAc  and  TBHP/Fe2+/EDTA/SFS at relatively low temperatures and thermal initiators (BPO, KPS and AIBN at higher temperatures to seek the most suitable initiator system. At the end of all reactions the unreacted monomer content was reduced using post-polymerization technique; consequently, leading to increased monomer conversion and flm formation with improved properties. The kinetics of mini-emulsion polymerization showed that in all redox initiator systems (Fe2+ catalyst + EDTA chelating agent, the radials are produced at relatively low temperature with more effcient control of the reactor temperature. It was found that at 45°C TBHP/Fe2+/EDTA/SFS redox initiator system leads to 98% monomer conversion, a much higher rate than that of systems involved thermal initiators.

  9. IRON AND FREE RADICAL OXIDATIONS IN CELL MEMBRANES

    Science.gov (United States)

    Schafer, Freya Q.; Yue Qian, Steven; Buettner, Garry R.

    2013-01-01

    Brain tissue being rich in polyunsaturated fatty acids, is very susceptible to lipid peroxidation. Iron is well known to be an important initiator of free radical oxidations. We propose that the principal route to iron-mediated lipid peroxidations is via iron-oxygen complexes rather than the reaction of iron with hydrogen peroxide, the Fenton reaction. To test this hypothesis, we enriched leukemia cells (K-562 and L1210 cells) with docosahexaenoic acid (DHA) as a model for brain tissue, increasing the amount of DHA from approximately 3 mole % to 32 mole %. These cells were then subjected to ferrous iron and dioxygen to initiate lipid peroxidation in the presence or absence of hydrogen peroxide. Lipid-derived radicals were detected using EPR spin trapping with α-(4-pyridyl-1-oxide)-N-t-butylnitrone (POBN). As expected, lipid-derived radical formation increases with increasing cellular lipid unsaturation. Experiments with Desferal demonstrate that iron is required for the formation of lipid radicals from these cells. Addition of iron to DHA-enriched L1210 cells resulted in significant amounts of radical formation; radical formation increased with increasing amount of iron. However, the exposure of cells to hydrogen peroxide before the addition of ferrous iron did not increase cellular radical formation, but actually decreased spin adduct formation. These data suggest that iron-oxygen complexes are the primary route to the initiation of biological free radical oxidations. This model proposes a mechanism to explain how catalytic iron in brain tissue can be so destructive. PMID:10872752

  10. Exploring the dynamics of hydrogen atom release from the radical-radical reaction of O(3P) with C3H5

    International Nuclear Information System (INIS)

    Joo, Sun-Kyu; Kwon, Lee-Kyoung; Lee, Hohjai; Choi, Jong-Ho

    2004-01-01

    The gas-phase radical-radical reaction dynamics of O( 3 P)+C 3 H 5 →H( 2 S)+C 3 H 4 O was studied at an average collision energy of 6.4 kcal/mol in a crossed beam configuration. The ground-state atomic oxygen [O( 3 P)] and allyl radicals (C 3 H 5 ) were generated by the photolysis of NO 2 and the supersonic flash pyrolysis of allyl iodide, respectively. Nascent hydrogen atom products were probed by the vacuum-ultraviolet-laser induced fluorescence spectroscopy in the Lyman-α region centered at 121.6 nm. With the aid of the CBS-QB3 level of ab initio theory, it has been found that the barrierless addition of O( 3 P) to C 3 H 5 forms the energy-rich addition complexes on the lowest doublet potential energy surface, which are predicted to undergo a subsequent direct decomposition step leading to the reaction products H+C 3 H 4 O. The major counterpart C 3 H 4 O of the probed hydrogen atom is calculated to be acrolein after taking into account the factors of barrier height, reaction enthalpy, and the number of intermediates involved along the reaction pathway. The nascent H-atom Doppler profile analysis shows that the average center-of-mass translational energy of the H+C 3 H 4 O products and the fraction of the total available energy released as the translational energy were determined to be 3.83 kcal/mol and 0.054, respectively. On the basis of comparison with statistical calculations, the reaction proceeds through the formation of short-lived addition complexes rather than statistical, long-lived intermediates, and the polyatomic acrolein product is significantly internally excited at the moment of the decomposition

  11. Exploring the dynamics of hydrogen atom release from the radical-radical reaction of O(3P) with C3H5

    Science.gov (United States)

    Joo, Sun-Kyu; Kwon, Lee-Kyoung; Lee, Hohjai; Choi, Jong-Ho

    2004-05-01

    The gas-phase radical-radical reaction dynamics of O(3P)+C3H5→H(2S)+C3H4O was studied at an average collision energy of 6.4 kcal/mol in a crossed beam configuration. The ground-state atomic oxygen [O(3P)] and allyl radicals (C3H5) were generated by the photolysis of NO2 and the supersonic flash pyrolysis of allyl iodide, respectively. Nascent hydrogen atom products were probed by the vacuum-ultraviolet-laser induced fluorescence spectroscopy in the Lyman-α region centered at 121.6 nm. With the aid of the CBS-QB3 level of ab initio theory, it has been found that the barrierless addition of O(3P) to C3H5 forms the energy-rich addition complexes on the lowest doublet potential energy surface, which are predicted to undergo a subsequent direct decomposition step leading to the reaction products H+C3H4O. The major counterpart C3H4O of the probed hydrogen atom is calculated to be acrolein after taking into account the factors of barrier height, reaction enthalpy, and the number of intermediates involved along the reaction pathway. The nascent H-atom Doppler profile analysis shows that the average center-of-mass translational energy of the H+C3H4O products and the fraction of the total available energy released as the translational energy were determined to be 3.83 kcal/mol and 0.054, respectively. On the basis of comparison with statistical calculations, the reaction proceeds through the formation of short-lived addition complexes rather than statistical, long-lived intermediates, and the polyatomic acrolein product is significantly internally excited at the moment of the decomposition.

  12. Study of the Radical Chain Mechanism of Hydrocarbon Oxidation for In Situ Combustion Process

    Directory of Open Access Journals (Sweden)

    Alexandra Ushakova

    2017-01-01

    Full Text Available Despite the abundance of in situ combustion models of oil oxidation, many of the effects are still beyond consideration. For example, until now, initial stages of oxidation were not considered from a position of radical chain process. This is a serious difficulty for the simulation of oil recovery process that involves air injection. To investigate the initial stages of oxidation, the paper considers the sequence of chemical reactions, including intermediate short-living compounds and radicals. We have attempted to correlate the main stages of the reaction with areas of heat release observed in the experiments. The system of differential equations based on the equations of oxidation reactions was solved. Time dependence of peroxides formation and start of heat release is analytically derived for the initial stages. We have considered the inhibition of initial oxidation stages by aromatic oil compounds and have studied the induction time in dependence on temperature. Chain ignition criteria for paraffins and crude oil in presence of core samples were obtained. The calculation results are compared with the stages of oxidation that arise by high-pressure differential scanning calorimetry. According to experimental observations we have determined which reactions are important for the process and which can be omitted or combined into one as insignificant.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-12-15

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

  14. Controlled radical polymerization of acrylates by {gamma}-irradiation in the presence of 1,1-diphenylethene

    Energy Technology Data Exchange (ETDEWEB)

    Wu Zongtao [Department of Polymer Science and Engineering, University of Science and Technology of China, Hefei, Anhui 230026 (China); Zhang Zhicheng [Department of Polymer Science and Engineering, University of Science and Technology of China, Hefei, Anhui 230026 (China)]. E-mail: zczhang@ustc.edu.cn

    2005-12-15

    Poly (butyl acrylate) and poly (methyl acrylate) were successfully prepared in the presence of 1,1-diphenylethene (DPE) by {gamma}-irradiation-induced polymerization in both bulk and solution. The influences of polymerization time, amounts of DPE in system on conversion, molecular weight (MW) and its distribution (M{sub w}/M{sub n}) were studied. The results indicate that the polymerization initiated by {gamma}-irradiation in the presence of DPE shows the character of living radical reaction.

  15. Free radicals trapped in polyethylene matrix

    International Nuclear Information System (INIS)

    Shimada, S.; Maeda, M.; Hori, Y.; Kashiwabara, H.

    1977-01-01

    Two types of alkyl radicals were found to be trapped in irradiated crystals grown from polyethylene solution. One of them corresponds to the broad sextet pattern of the e.s.r. spectrum and the other corresponds to the sharp sextet pattern. The free radicals attributed to the broad sextet began to disappear at a lower temperature than the temperature at which the free radicals attributed to the sharp sextet disappeared. When butadiene molecules were brought into contact with the specimen, the decay of the free radicals corresponding to the broad sextet was accelerated. When the specimen was subjected to fuming nitric acid treatment, no broad sextet was observed. The mat of the crystals was aligned so that the c-axes of its crystallites were perpendicular to its surface. The broad sextet showed no anisotropy when the angle between the direction of applied magnetic field and that of the c-axis of the crystallite was varied. On the other hand, the sharp component of the spectrum showed apparent anisotropy. It can be concluded that the broad component comes from the free radicals trapped in the lamellar surface and the sharp component is attributed to the free radicals trapped in the inner part of the crystallite. (author)

  16. Quenching of photoluminescence of colloidal ZnO nanocrystals by nitronyl nitroxide radicals

    Energy Technology Data Exchange (ETDEWEB)

    Stroyuk, Oleksandr L., E-mail: stroyuk@inphyschem-nas.kiev.ua [L.V. Pysarzhevsky Institute of Physical Chemistry of National Academy of Sciences of Ukraine, 31 Nauky avenue, 03028 Kyiv (Ukraine); Yakovenko, Anastasiya V.; Raevskaya, Oleksandra E. [L.V. Pysarzhevsky Institute of Physical Chemistry of National Academy of Sciences of Ukraine, 31 Nauky avenue, 03028 Kyiv (Ukraine); Plyusnin, Victor F. [Institute of Chemical Kinetics and Combustion of Siberian Branch of Russian Academy of Sciences, Novosibirsk (Russian Federation)

    2014-11-15

    Quenching of the photoluminescence of colloidal zinc oxide nanocrystals by a series of stable nitronyl nitroxide radicals was studied by means of stationary and time-resolved luminescence spectroscopy. Among the studied radicals the most efficient quenchers of the ZnO luminescence are the carboxyl-substituted species. The meta-substituted radical was found to be a more active quencher, than para-substituted one due to a closer proximity of the radical center to the nanocrystals surface. The PL quenching has a complex dynamic/static character. The dynamic quenching arises from photocatalytic radical reduction by ZnO conduction band electrons, while the static quenching is caused by adsorption of the photoreduction products on the nanocrystal surface. The non-substituted and OH-substituted radicals are inferior to the products of their photoreduction in capability of adsorption of the ZnO surface, and the quenching is dominated by interactions between the nanocrystals and photoreduced hydroxylamines. In case of COOH-substituted radicals, however, the radicals compete with the photoreduction products for the surface sites of ZnO nanocrystals resulting in a dynamic character of photoluminescence quenching.

  17. Abstracts of 2. symposium on free radicals in biology and medicine

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1994-12-31

    The abstracts presented in the booklet concern influence of free radicals (frequently generated by ionizing radiation) on DNA, proteins, lipids and chromatin of various living organisms. Works show, that free radicals cause serious damages in biological systems leading to carcinogenesis and many genetic diseases. Thus understanding of mechanisms of free radical action is important issue in medicine and life sciences.

  18. Abstracts of 2. symposium on free radicals in biology and medicine

    International Nuclear Information System (INIS)

    1994-01-01

    The abstracts presented in the booklet concern influence of free radicals (frequently generated by ionizing radiation) on DNA, proteins, lipids and chromatin of various living organisms. Works show, that free radicals cause serious damages in biological systems leading to carcinogenesis and many genetic diseases. Thus understanding of mechanisms of free radical action is important issue in medicine and life sciences

  19. Optimization of hydroxyl radical scavenging activity of exopolysaccharides from Inonotus obliquus in submerged fermentation using response surface methodology

    NARCIS (Netherlands)

    Chen, H.; Xu, X.; Zhu, Y.

    2010-01-01

    The objectives of this study were to investigate the effect of fermentation medium on the hydroxyl radical scavenging activity of exopolysaccharides from Inonotus obliquus by response surface methodology (RSM). A two-level fractional factorial design was used to evaluate the effect of different

  20. Synthesis of poly(2-ethyl-2-oxazoline)-b-poly(styrene) copolymers via a dual initiator route combining cationic ring-opening polymerization and atom transfer radical polymerization

    NARCIS (Netherlands)

    Becer, C.R.; Paulus, R.M.; ppener, S.; Hoogenboom, R.; Fustin, C.A.; Gohy, J.M.W.; Schubert, U.S.

    2008-01-01

    Block copolymers of 2-ethyl-2-oxazoline (EtOx) and styrene were synthesized by a combination of cationic ring-opening polymerization (CROP) and atom transfer radical polymerization (ATRP). Initially, a detailed kinetic investigation for the ?-bromoisobutyrylbromide (BrEBBr) initiated CROP of EtOx

  1. A New Initiator Cholesteryl Chloroformate for Cupper-Based Atom Transfer Radical Polymerization of Methyl Methacrylate

    Institute of Scientific and Technical Information of China (English)

    曹健; 楚娟; 张可达

    2004-01-01

    The polymerization of metyl methacrylate (MMA) was studied in detail by use of CuCl/L as a catalyst and cholesteryl chloroformate (CC) as an initiator. It was found that the atom transfer radical polymerization of MMA could proceed when L equals to a multidentate aliphatic amine ligand, N,N,N',N",N"-penta(methyl acrylate)diethylenetriamine (MA5-DETA), and no polymerization was occurred while L=2,2'-bipyridine and 1,10-phenanthroline. The linear proportionality of the molecular weights to the conversions and straight lines observed in ln[M]0/[M] versus time plots indicated that the present polymerization system had the typical controlled polymerization characteristics.

  2. Engineering a horseradish peroxidase C stable to radical attacks by mutating multiple radical coupling sites.

    Science.gov (United States)

    Kim, Su Jin; Joo, Jeong Chan; Song, Bong Keun; Yoo, Young Je; Kim, Yong Hwan

    2015-04-01

    Peroxidases have great potential as industrial biocatalysts. In particular, the oxidative polymerization of phenolic compounds catalyzed by peroxidases has been extensively examined because of the advantage of this method over other conventional chemical methods. However, the industrial application of peroxidases is often limited because of their rapid inactivation by phenoxyl radicals during oxidative polymerization. In this work, we report a novel protein engineering approach to improve the radical stability of horseradish peroxidase isozyme C (HRPC). Phenylalanine residues that are vulnerable to modification by the phenoxyl radicals were identified using mass spectrometry analysis. UV-Vis and CD spectra showed that radical coupling did not change the secondary structure or the active site of HRPC. Four phenylalanine (Phe) residues (F68, F142, F143, and F179) were each mutated to alanine residues to generate single mutants to examine the role of these sites in radical coupling. Despite marginal improvement of radical stability, each single mutant still exhibited rapid radical inactivation. To further reduce inactivation by radical coupling, the four substitution mutations were combined in F68A/F142A/F143A/F179A. This mutant demonstrated dramatic enhancement of radical stability by retaining 41% of its initial activity compared to the wild-type, which was completely inactivated. Structure and sequence alignment revealed that radical-vulnerable Phe residues of HPRC are conserved in homologous peroxidases, which showed the same rapid inactivation tendency as HRPC. Based on our site-directed mutagenesis and biochemical characterization, we have shown that engineering radical-vulnerable residues to eliminate multiple radical coupling can be a good strategy to improve the stability of peroxidases against radical attack. © 2014 Wiley Periodicals, Inc.

  3. Kinetics of free radical reactions in irradiated crystalline L-leucine

    International Nuclear Information System (INIS)

    Dole, M.; Mahdavi, M.

    1983-01-01

    Four aspects of the radiation chemistry of crystalline L-leucine are presented. They are as follows: the transformation of one type of free radical into another as observed by following the ESR spectrum of individual peaks in the initial stages of the free radical decay at room or higher temperatures after a gamma irradiation at 77K; the catalytic effect of hydrogen gas in significantly accelerating the free radical decay; the unexpected effect of argon gas in decreasing the rate of the free radical decay; and the accurate agreement of the decay data with the diffusion controlled second order Waite equation when the latter is expressed in the linear form. The major free radical which exists in irradiated L-leucine gives rise to a spectrum of 8 Doublets for a total of 16 lines. Numbering the peaks from the least intense to the strongest, peaks numbers 3, 4, 6, and 7, initially increase in intensity before decreasing while peak number 5 rapidly decreases. However, during this initial period the total free radical concentration as measured by the total moment of the ESR spectrum decreases. The kinetics of these effects are discussed. (author)

  4. Reverse atom transfer radical polymerization of methyl methacrylate initiated by AIBN/FeCl3/isophthalic acid system

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    The reverse ATRP of MMA using AIBN/FeCl3/ isophthalic acid as the initiating system was successfully performed. The new initiating system can be used to synthesize PMMA with high molecular weight and narrow polydis- persity index. The polymerization shows 'living'/controlled characteristics. Compared with other initiating system used in reverse ATRP, the easy availability and non-toxicity of isophthalic acid make it very attractive.

  5. Aminoxyl (nitroxyl) radicals in the early decomposition of the nitramine RDX.

    Science.gov (United States)

    Irikura, Karl K

    2013-03-14

    The explosive nitramine RDX (1,3,5-trinitrohexahydro-s-triazine) is thought to decompose largely by homolytic N-N bond cleavage, among other possible initiation reactions. Density-functional theory (DFT) calculations indicate that the resulting secondary aminyl (R2N·) radical can abstract an oxygen atom from NO2 or from a neighboring nitramine molecule, producing an aminoxyl (R2NO·) radical. Persistent aminoxyl radicals have been detected in electron-spin resonance (ESR) experiments and are consistent with autocatalytic "red oils" reported in the experimental literature. When the O-atom donor is a nitramine, a nitrosamine is formed along with the aminoxyl radical. Reactions of aminoxyl radicals can lead readily to the "oxy-s-triazine" product (as the s-triazine N-oxide) observed mass-spectrometrically by Behrens and co-workers. In addition to forming aminoxyl radicals, the initial aminyl radical can catalyze loss of HONO from RDX.

  6. A DFT Study of R-X Bond Dissociation Enthalpies of Relevance to the Initiation Process of Atom Transfer Radical Polymerization

    DEFF Research Database (Denmark)

    Gillies, Malcolm Bjørn; Matyjaszewski, Krzysztof; Norrby, Per-Ola

    2003-01-01

    DFT calculations at the B3P86/6-31G** level have been carried out to derive the bond dissociation energies (BDE) and free energies for a number of R-X systems (X ) Cl, Br, I, N3, and S2-CNMe2) that have been or can potentially be used as initiators for atom transfer radical polymerization (ATRP...

  7. Hydrophobic modification of wood via surface-initiated ARGET ATRP of MMA

    Energy Technology Data Exchange (ETDEWEB)

    Fu Yanchun; Li Gang [Material Science and Engineering College, Northeast Forestry University, Harbin 150040 (China); Yu Haipeng, E-mail: yuhaipeng20000@yahoo.com.cn [Key laboratory of Bio-based Material Science and Technology of Ministry of Education, Northeast Forestry University, Harbin 150040 (China); Material Science and Engineering College, Northeast Forestry University, Harbin 150040 (China); Liu Yixing, E-mail: yxl200488@sina.com [Key laboratory of Bio-based Material Science and Technology of Ministry of Education, Northeast Forestry University, Harbin 150040 (China); Material Science and Engineering College, Northeast Forestry University, Harbin 150040 (China)

    2012-01-15

    To convert the hydrophilic surface of wood into a hydrophobic surface, the present study investigated activators regenerated by electron transfer for atom transfer radical polymerization (ARGET ATRP) as a method of grafting methyl methacrylate (MMA) onto the wood surface. The wood treated with 2-bromoisobutyryl bromide and with the subsequently attached MMA via ARGET ATRP under different polymerization times (2 h, 4 h, 6 h, 8 h) were examined using scanning electron microscopy, Fourier transform infrared spectroscopy, and thermogravimetric analysis. All the analyses confirmed that PMMA had been grafted onto the wood surface. Water contact angle measurement proved that the covering layer of PMMA on wood made the surface hydrophobic. Polymerization time had a positive influence on the contact angle value and higher contact angle can be produced with the prolongation of the polymerization time. When the reaction time was extended to 8 h, the contact angle of treated wood surface reached 130 Degree-Sign in the beginning, and remained at 116 Degree-Sign after 60 s. The ARGET ATRP method may raise an alteration on the wood surface modification.

  8. Dimethylzinc-Initiated Radical Coupling of β-Bromostyrenes with Ethers and Amines

    DEFF Research Database (Denmark)

    Sølvhøj, Amanda Birgitte; Ahlburg, Andreas; Madsen, Robert

    2015-01-01

    A new coupling reaction has been developed in which β-bromostyrenes react with ethers and tertiary amines to introduce the styryl group in the α-position. The transformation is mediated by Me2Zn/O2 with 10 % MnCl2 and is believed to proceed by a radical addition-elimination mechanism. The ether...... and the amine are employed as solvent and the coupling takes place through the most stable α radical for unsymmetrical substrates. The products are obtained in moderate to good yields as the pure E isomers. The coupling can be achieved with a range of smaller cyclic and acyclic ethers/amines as well as various...

  9. Four-channel surface coil array for sequential CW-EPR image acquisition

    Science.gov (United States)

    Enomoto, Ayano; Emoto, Miho; Fujii, Hirotada; Hirata, Hiroshi

    2013-09-01

    This article describes a four-channel surface coil array to increase the area of visualization for continuous-wave electron paramagnetic resonance (CW-EPR) imaging. A 776-MHz surface coil array was constructed with four independent surface coil resonators and three kinds of switches. Control circuits for switching the resonators were also built to sequentially perform EPR image acquisition for each resonator. The resonance frequencies of the resonators were shifted using PIN diode switches to decouple the inductively coupled coils. To investigate the area of visualization with the surface coil array, three-dimensional EPR imaging was performed using a glass cell phantom filled with a solution of nitroxyl radicals. The area of visualization obtained with the surface coil array was increased approximately 3.5-fold in comparison to that with a single surface coil resonator. Furthermore, to demonstrate the applicability of this surface coil array to animal imaging, three-dimensional EPR imaging was performed in a living mouse with an exogenously injected nitroxyl radical imaging agent.

  10. Functionalization of lanthanum hydroxide nanowires by atom transfer radical polymerization

    International Nuclear Information System (INIS)

    Zhou Mi; Yuan Jinying; Yuan Weizhong; Yin Yingwu; Hong Xiaoyin

    2007-01-01

    Atom transfer radical polymerization (ATRP) has been used to prepare a core-shell hybrid nanostructure successfully: a hard core of single-crystalline lanthanum hydroxide nanowires and a soft shell of polystyrene (PS) brushes. Transmission electron microscopy (TEM) images indicated that the resulting products presented special structures and different thicknesses of polymer layers. The chemical components and grafted PS quantities of the samples were measured by Fourier transform infrared (FT-IR) spectroscopy and thermogravimetric analysis (TGA). The polymers showed narrow polydispersity, which proved that the lanthanum hydroxide nanowires initiated the 'living'/controlled polymerization of styrene. With the modifiability of lanthanum hydroxide nanowires, the solubility increased, which affords a new way to functionalize nanowires

  11. Optimization of free radical scavenging capacity and pH of Hylocereus polyrhizus peel by Response Surface Methodology

    Science.gov (United States)

    Putranto, A. W.; Dewi, S. R.; Puspitasari, Y.; Nuriah, F. A.

    2018-03-01

    Red dragon fruit (Hylocereus polyrhizus) peel, a by-product of juice processing, contains a high antioxidant that can be used for nutraceuticals. Hence, it is important to extract and investigate its antioxidant stability. The aim of this study was to optimize the free radical scavenging capacity and pH of H. polyrhizus peel extract using Central Composite Design (CCD) under Response Surface Methodology (RSM). The extraction of H. polyrhizus peel was done by using green-Pulsed Electric Field (PEF)-assisted extraction method. Factors optimized were electric field strength (kV/cm) and extraction time (seconds). The result showed that the correlation between responses (free radical-scavenging capacity and pH) and two factors was quadratic model. The optimum conditions was obtained at the electric field strength of 3.96 kV/cm, and treatment time of 31.9 seconds. Under these conditions, the actual free radical-scavenging capacity and pH were 75.86 ± 0.2 % and 4.8, respectively. The verification model showed that the actual values are in accordance with the predicted values, and have error rate values of free radical-scavenging capacity and pH responses were 0.1% and 3.98%, respectively. We suggest to extract the H. polyrhizus peel using a green and non-thermal extraction technology, PEF-assisted extraction, for research, food applications and nutraceuticals industry.

  12. Temperature Activated Diffusion of Radicals through Ion Implanted Polymers

    DEFF Research Database (Denmark)

    Wakelin, Edgar A.; Davies, Michael J.; Bilek, Marcela M. M.

    2015-01-01

    Plasma immersion ion implantation (PIII) is a promising technique for immobilizing biomolecules on the surface of polymers. Radicals generated in a subsurface layer by PIII treatment diffuse throughout the substrate, forming covalent bonds to molecules when they reach the surface. Understanding...... to the surface. The model makes useful predictions for the lifetime over which the surface is sufficiently active to covalently immobilize biomolecules and it can be used to determine radical fluence during biomolecule incubation for a range of storage and incubation temperatures so facilitating selection...

  13. Impact of high resolution land surface initialization in Indian summer ...

    Indian Academy of Sciences (India)

    The direct impact of high resolution land surface initialization on the forecast bias in a regional climate model in recent years ... surface initialization using a regional climate model. ...... ization of the snow field in a cloud model; J. Clim. Appl.

  14. Mechanisms of free radical-induced damage to DNA.

    Science.gov (United States)

    Dizdaroglu, Miral; Jaruga, Pawel

    2012-04-01

    Endogenous and exogenous sources cause free radical-induced DNA damage in living organisms by a variety of mechanisms. The highly reactive hydroxyl radical reacts with the heterocyclic DNA bases and the sugar moiety near or at diffusion-controlled rates. Hydrated electron and H atom also add to the heterocyclic bases. These reactions lead to adduct radicals, further reactions of which yield numerous products. These include DNA base and sugar products, single- and double-strand breaks, 8,5'-cyclopurine-2'-deoxynucleosides, tandem lesions, clustered sites and DNA-protein cross-links. Reaction conditions and the presence or absence of oxygen profoundly affect the types and yields of the products. There is mounting evidence for an important role of free radical-induced DNA damage in the etiology of numerous diseases including cancer. Further understanding of mechanisms of free radical-induced DNA damage, and cellular repair and biological consequences of DNA damage products will be of outmost importance for disease prevention and treatment.

  15. The international surface temperature initiative

    Science.gov (United States)

    Thorne, P. W.; Lawrimore, J. H.; Willett, K. M.; Allan, R.; Chandler, R. E.; Mhanda, A.; de Podesta, M.; Possolo, A.; Revadekar, J.; Rusticucci, M.; Stott, P. A.; Strouse, G. F.; Trewin, B.; Wang, X. L.; Yatagai, A.; Merchant, C.; Merlone, A.; Peterson, T. C.; Scott, E. M.

    2013-09-01

    The aim of International Surface Temperature Initiative is to create an end-to-end process for analysis of air temperature data taken over the land surface of the Earth. The foundation of any analysis is the source data. Land surface air temperature records have traditionally been stored in local, organizational, national and international holdings, some of which have been available digitally but many of which are available solely on paper or as imaged files. Further, economic and geopolitical realities have often precluded open sharing of these data. The necessary first step therefore is to collate readily available holdings and augment these over time either through gaining access to previously unavailable digital data or through data rescue and digitization activities. Next, it must be recognized that these historical measurements were made primarily in support of real-time weather applications where timeliness and coverage are key. At almost every long-term station it is virtually certain that changes in instrumentation, siting or observing practices have occurred. Because none of the historical measures were made in a metrologically traceable manner there is no unambiguous way to retrieve the true climate evolution from the heterogeneous raw data holdings. Therefore it is desirable for multiple independent groups to produce adjusted data sets (so-called homogenized data) to adequately understand the data characteristics and estimate uncertainties. Then it is necessary to benchmark the performance of the contributed algorithms (equivalent to metrological software validation) through development of realistic benchmark datasets. In support of this, a series of successive benchmarking and assessment cycles are envisaged, allowing continual improvement while avoiding over-tuning of algorithms. Finally, a portal is proposed giving access to related data-products, utilizing the assessment results to provide guidance to end-users on which product is the most suited to

  16. Catalytic surface radical in dye-decolorizing peroxidase: a computational, spectroscopic and site-directed mutagenesis study

    Science.gov (United States)

    Linde, Dolores; Pogni, Rebecca; Cañellas, Marina; Lucas, Fátima; Guallar, Victor; Baratto, Maria Camilla; Sinicropi, Adalgisa; Sáez-Jiménez, Verónica; Coscolín, Cristina; Romero, Antonio; Medrano, Francisco Javier; Ruiz-Dueñas, Francisco J.; Martínez, Angel T.

    2014-01-01

    Dye-decolorizing peroxidase (DyP) of Auricularia auricula-judae has been expressed in Escherichia coli as a representative of a new DyP family, and subjected to mutagenic, spectroscopic, crystallographic and computational studies. The crystal structure of DyP shows a buried haem cofactor, and surface tryptophan and tyrosine residues potentially involved in long-range electron transfer from bulky dyes. Simulations using PELE (Protein Energy Landscape Exploration) software provided several binding-energy optima for the anthraquinone-type RB19 (Reactive Blue 19) near the above aromatic residues and the haem access-channel. Subsequent QM/MM (quantum mechanics/molecular mechanics) calculations showed a higher tendency of Trp-377 than other exposed haem-neighbouring residues to harbour a catalytic protein radical, and identified the electron-transfer pathway. The existence of such a radical in H2O2-activated DyP was shown by low-temperature EPR, being identified as a mixed tryptophanyl/tyrosyl radical in multifrequency experiments. The signal was dominated by the Trp-377 neutral radical contribution, which disappeared in the W377S variant, and included a tyrosyl contribution assigned to Tyr-337 after analysing the W377S spectra. Kinetics of substrate oxidation by DyP suggests the existence of high- and low-turnover sites. The high-turnover site for oxidation of RB19 (kcat> 200 s−1) and other DyP substrates was assigned to Trp-377 since it was absent from the W377S variant. The low-turnover site/s (RB19 kcat ~20 s−1) could correspond to the haem access-channel, since activity was decreased when the haem channel was occluded by the G169L mutation. If a tyrosine residue is also involved, it will be different from Tyr-337 since all activities are largely unaffected in the Y337S variant. PMID:25495127

  17. Living the Utopia

    DEFF Research Database (Denmark)

    Davis, John; Warring, Anette Elisabeth

    2011-01-01

    This article examines experiments in communal living in Britain and Denmark in the early 1970s, using life-story interviews from seventeen members of two British and two Danish communes. It examines communal living as a fusion of radical political principles with the practice of experimental...... collective living. It concludes that the movement's egalitarian principles of resource-sharing, gender equality and the avoidance of hierarchies were broadly achieved, even if the movement obviously did not realize its more ambitious objective of undermining the bourgeois family. Though none...... of the interviewees lives communally now, most remain faithful to the principles behind the movement....

  18. A Surface Temperature Initiated Closure (STIC) for surface energy balance fluxes

    DEFF Research Database (Denmark)

    Mallick, Kaniska; Jarvis, Andrew J.; Boegh, Eva

    2014-01-01

    The use of Penman–Monteith (PM) equation in thermal remote sensing based surface energy balance modeling is not prevalent due to the unavailability of any direct method to integrate thermal data into the PM equation and due to the lack of physical models expressing the surface (or stomatal......) and boundary layer conductances (gS and gB) as a function of surface temperature. Here we demonstrate a new method that physically integrates the radiometric surface temperature (TS) into the PM equation for estimating the terrestrial surface energy balance fluxes (sensible heat, H and latent heat, λ......E). The method combines satellite TS data with standard energy balance closure models in order to derive a hybrid closure that does not require the specification of surface to atmosphere conductance terms. We call this the Surface Temperature Initiated Closure (STIC), which is formed by the simultaneous solution...

  19. Complex Macromolecular Architectures by Living Cationic Polymerization

    KAUST Repository

    Alghamdi, Reem D.

    2015-05-01

    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

  20. Living with risk. A global review of disaster reduction initiatives. Preliminary version

    International Nuclear Information System (INIS)

    2002-01-01

    In recent years the world has witnessed an interminable succession of disasters - floods, storms, earthquakes, landslides, volcanic eruptions and wildfires that have claimed many thousands of lives, caused material losses in the tens of billions of dollars, and inflicted a terrible toll on developing countries in particular, where disasters divert attention and resources needed desperately to escape poverty. Communities will always face natural hazards, but today's disasters are often generated by, or at least exacerbated by, human activities. At the most dramatic level, human activities are changing the natural balance of the earth, interfering as never before with the atmosphere, the oceans, the polar ice caps, the forest cover and the natural pillars that make our world a livable home. But we are also putting ourselves in harm's way in less visible ways. At no time in human history have so many people lived in cities clustered around seismically active areas. Destitution and demographic pressure have led more people than ever before to live in flood plains or in areas prone to landslides. Poor land-use planning; environmental mismanagement; and a lack of regulatory mechanisms both increase the risk and exacerbate the effects of disasters. Living with risk: a global review of disaster reduction is the first comprehensive effort by the United Nations system to take stock of disaster reduction initiatives throughout the world. Coordinated by the secretariat of the International Strategy for Disaster Reduction (ISDR), the report discusses current disaster trends, assesses policies aimed at mitigating the impact of disasters, and offers examples of successful initiatives. It also recommends that risk reduction be integrated into sustainable development at all levels - global, national and local. Most of all, Living with risk shows that we are far from helpless in the face of natural hazards. Early warning and risk reduction measures have been important factors in

  1. Heat-Initiated Chemical Functionalization of Graphene

    OpenAIRE

    Gao, Guodong; Liu, Dandan; Tang, Shangcheng; Huang, Can; He, Mengci; Guo, Yu; Sun, Xiudong; Gao, Bo

    2016-01-01

    A heat-initiated chemical reaction was developed to functionalize CVD-grown graphene at wafer scale and the reaction was universally extended to carbon nanotubes, and other precursors that could be thermally converted to active radicals. The chemical reaction can occur in absence of oxygen and water vapor when the temperature is above the decomposition temperature of the reactants. The chemical reaction was also found to be substrate-dependent due to surface doping and inhomogeneity. A large-...

  2. Oxidation of benzene by radiolytically produced OH radicals. [x rays

    Energy Technology Data Exchange (ETDEWEB)

    Klein, G W; Schuler, R H [Carnegie-Mellon Univ., Pittsburgh, Pa. (USA)

    1978-01-01

    The radiolysis of N/sub 2/O saturated-aqueous solutions of benzene-/sup 14/C has been examined using radio-liquid chromatographic methods to follow the quantitative aspects of the reactions of hydroxycyclohexadienyl radicals. In the absence of a radical oxidant, at least five important products are produced. The total yield of 5.8 observed for the incorporation of benzene into products accounts for essentially all of the radicals initially produced from the water. Dimeric products predominate with a total yield of 4.1. Phenol is produced with a yield of only 0.8 indicating a disproportionation/combination ratio for hydroxycyclohexadienyl radicals of < = 0.4. In the presence of 2mM ferricyanide the hydroxycyclohexadienyl radicals are quantitatively oxidized to phenol with no trace (< 1%) remaining of dimeric or other high molecular weight products. The initial yield for phenol formation (6.0 molecules/100 eV) provides a measure for OH production in N/sub 2/O saturated aqueous solutions.

  3. Identification of phosphoproteins coupled to initiation of motility in live epididymal mouse sperm

    Science.gov (United States)

    Tash, J. S.; Bracho, G. E.

    1998-01-01

    A method for collecting live immotile cauda epididymal mouse sperm that initiate motility by dilution into an activation buffer is described. Sperm in collection buffer showed low percent motility (MOT) and population progression (PRG) that increased 10-fold and 9-fold, respectively, during the first 2 min after dilution into activation buffer. Western phosphoserine (pS), phosphothreonine (pT), and phosphotyrosine (pY) analysis revealed a 120 kDa protein that markedly increased in pT content during initiation of motility and may be related to FP130, the motility-coupled axonemal protein of sea urchin sperm. A prominent 82 kDa protein that was pS and pT-phosphorylated in immotile and motile sperm is likely the fibrous sheath component AKAP82 that is phosphorylated during spermatogenesis. Analysis of live human sperm also identified a prominent 120 kDa pT protein. Thus it appears that phosphorylation of FP130 and related 120 kDa proteins in mouse, and perhaps human sperm, represent common targets during motility initiation in sperm. Copyright 1998 Academic Press.

  4. Preoperative radiochemotherapy and radical surgery in comparison with radical surgery alone

    International Nuclear Information System (INIS)

    Mohr, C.; Schettler, D.; Bohndorf, W.

    1994-01-01

    A multicentric, randomized study of squamous cell carcinoma (SCC) of the oral cavity and the oropharynx has been undertaken by DOeSAK. The results after radical surgery alone have been compared with the results of combined preoperative radiochemotherapy followed by radical surgery. Patients with primary (biopsy proven) SCC of the oral cavity or the oropharynx with tumor nodes metastasis (TNM) stages T2-4, N0-3, M0 were included in the study. A total of 141 patients were treated by radical surgery alone, whereas 127 patients were treated by radical surgery preceded by preoperative radiochemotherapy. The pre-operative treatment consisted of conventionally fractioned irradiation on the primary and the regional lymph nodes with a total dose of 36 Gy (5 x 2 Gy per week) and low-dose cisplatin chemotherapy with 5 x 12.5 mg cisplatin per m 2 of body surface during the first week of treatment. Radical surgery according to be DOeSAK definitions (DOeSAK, 1982) was performed after a delay of 10-14 days. During the follow-up period, 28.2% of all patients suffered from locoregional recurrence, and 27.2% of the patients died. The percentages were higher after radical surgery alone for locoregional recurrence (31% and 15.6%) and for death (28% and 18.6%). The life-table analysis showed improved survival rates of 4.5% after 1 year and 8.3% after 2 years in the group of patients treated with combined therapy. The demonstrated improvement appeared to be significant with the Gehan-Wilcoxon test as well as with the log rank test below a P value of 5%. (au) (29 refs.)

  5. Initial Bacterial Adhesion on Different Yttria-Stabilized Tetragonal Zirconia Implant Surfaces in Vitro

    Directory of Open Access Journals (Sweden)

    Lamprini Karygianni

    2013-12-01

    Full Text Available Bacterial adhesion to implant biomaterials constitutes a virulence factor leading to biofilm formation, infection and treatment failure. The aim of this study was to examine the initial bacterial adhesion on different implant materials in vitro. Four implant biomaterials were incubated with Enterococcus faecalis, Staphylococcus aureus and Candida albicans for 2 h: 3 mol % yttria-stabilized tetragonal zirconia polycrystal surface (B1a, B1a with zirconium oxide (ZrO2 coating (B2a, B1a with zirconia-based composite coating (B1b and B1a with zirconia-based composite and ZrO2 coatings (B2b. Bovine enamel slabs (BES served as control. The adherent microorganisms were quantified and visualized using scanning electron microscopy (SEM; DAPI and live/dead staining. The lowest bacterial count of E. faecalis was detected on BES and the highest on B1a. The fewest vital C. albicans strains (42.22% were detected on B2a surfaces, while most E. faecalis and S. aureus strains (approximately 80% were vital overall. Compared to BES; coated and uncoated zirconia substrata exhibited no anti-adhesive properties. Further improvement of the material surface characteristics is essential.

  6. Developments in laser-induced fluorescence spectroscopy for quantitative in situ measurements of free radicals in the troposphere

    Science.gov (United States)

    Heard, Dwayne

    2015-04-01

    Photo-oxidation in the troposphere is highly complex, being initiated by short lived free radical species, in the daytime dominated by the hydroxyl radical, OH. Chemical oxidation cycles, which also involve peroxy radicals (HO2 and RO2), remove natural or anthropogenic emissions (for example methane) and generate a range of secondary products, for example ozone, nitrogen dioxide, acidic and multifunctional organic species, and secondary organic aerosol, which impact on human health and climate. Owing to their short lifetime in the atmosphere, the abundance of radicals is determined solely by their rate of chemical production and loss, and not by transport. Field measurements of the concentrations of radicals and comparison with calculations using a numerical model therefore constitutes one of the very best ways to test whether the chemistry in each of these locations is understood and accurately represented in the model. Validation of the chemistry is important, as the predictions of climate and air quality models containing this chemistry are used to drive the formulation of policy and legislation. However, in situ measurements of radical species, owing to their very low abundance (often sub part per trillion) and short lifetimes (pulse repetition rate tunable laser systems, will be discussed, together with calibration methods to make signals absolute, and identification of potential interferences. LIF instruments have been operated on ground, ship and aircraft platforms at a number of locations worldwide, and examples from recent fieldwork involving the Leeds instruments will be presented.

  7. Radical fashion and radical fashion innovation

    NARCIS (Netherlands)

    Zhang, D.; Benedetto, Di A.C.

    2010-01-01

    This is a study of the related concepts of radical fashion and radical fashion innovation. Radical fashions are defined here as those that may never enter the market at all, and exist primarily on runway shows, in exhibitions and in publicity; by contrast, radical fashion innovations may be very

  8. The mitochondrial free radical theory of aging.

    Science.gov (United States)

    Barja, Gustavo

    2014-01-01

    The mitochondrial free radical theory of aging is reviewed. Only two parameters currently correlate with species longevity in the right sense: the mitochondrial rate of reactive oxygen species (mitROS) production and the degree of fatty acid unsaturation of tissue membranes. Both are low in long-lived animals. In addition, the best-known manipulation that extends longevity, dietary restriction, also decreases the rate of mitROS production and oxidative damage to mtDNA. The same occurs during protein restriction as well as during methionine restriction. These two manipulations also increase maximum longevity in rodents. The decrease in mitROS generation and oxidative stress that takes place in caloric restriction seems to be due to restriction of a single dietary substance: methionine. The information available supports a mitochondrial free radical theory of aging focused on low generation of endogenous damage and low sensitivity of membranes to oxidation in long-lived animals. © 2014 Elsevier Inc. All rights reserved.

  9. Changes in living arrangement, daily smoking, and risky drinking initiation among young Swiss men: a longitudinal cohort study.

    Science.gov (United States)

    Bähler, C; Foster, S; Estévez, N; Dey, M; Gmel, G; Mohler-Kuo, M

    2016-11-01

    The aim of this study was to assess the association between changes in living arrangement and the initiation of daily smoking and monthly risky single-occasion drinking (RSOD) in a cohort of young Swiss men. Longitudinal cohort study. The sample consisted of 4662 young men drawn from the Cohort Study on Substance Use Risk Factors who lived with their family at baseline. Follow-up assessments occurred 15 months later. Multiple regression models were adjusted for individual and family factors (family model), as well as for individual and peer-related factors (peer model). Relative to those still living with their parents at follow-up (n = 3845), those who had moved out (n = 817) were considerably more likely to have taken up smoking or RSOD after adjusting for several individual, family, and peer-related variables: OR (daily smoking) = 1.67 (95% CI 1.15-2.41) (P = 0.007) and OR (monthly RSOD) = 1.42 (95% CI 1.08-1.88) (P = 0.012). The strongest family-related predictors of smoking initiation were family structure and the lack of parental regulation and the strongest peer-related factors alcohol/drug problems in peers. Meanwhile, the strongest peer-related predictors of RSOD initiation were peer pressure (misconduct), perceived social support from friends, and perceived social support from a significant other, whereas family factors were not associated with RSOD initiation. Further subanalyses were conducted to examine the impact of different living arrangement changes on substance use initiation and revealed that living with peers at follow-up was associated with the greatest risk. We identified a strong association between moving out of one's parents' home and daily smoking and monthly RSOD initiation in young Swiss men. Moving out to live with peers was an especially strong predictor of substance use initiation. Campaigns that aim to prevent heavy smoking and drinking should be intensified at the end of obligatory school. Copyright © 2016 The Royal

  10. Introduction: Teaching Black Lives Matter

    OpenAIRE

    Paula Austin; Erica Cardwell; Christopher Kennedy; Robyn Spencer

    2016-01-01

    An introduction to Radical Teacher, Issue 106: Teaching Black Lives Matter. This issue brings together a diverse collection of articles exploring educator’s responses, strategies, and stories on how #BlackLivesMatter has informed their teaching practice, the content of their courses, and their personal relationship to colleagues, family, friends, and self.

  11. Hydrophilization of Poly(ether ether ketone) Films by Surface-initiated Atom Transfer Radical Polymerization

    DEFF Research Database (Denmark)

    Fristrup, Charlotte Juel; Eskimergen, Rüya; Burkrinsky, J.T.

    2008-01-01

    and confirmed by ATR FTIR, water contact ang;le, and Thermal Gravimetric Analysis (TGA). The surface topography was evaluated by "Atomic Force Microscopy (AFM). X-ray Photoelectron Spectroscopy (XPS) has been used to investigate the degree of functionalization. The performed modification allowed for successful...

  12. The initiation of environmentally-assisted cracking in semi-elliptical surface cracks

    International Nuclear Information System (INIS)

    James, L.A.

    1997-01-01

    A criterion to predict under what conditions EAC would Initiate In cracks In a high-sulfur steel in contact with low-oxygen water was recently proposed by Wire and U. This EAC Initiation Criterion was developed using transient analyses for the diffusion of sulfides plus experimental test results. The experiments were conducted mainly on compact tension-type specimens with initial crack depths of about 2.54 mm. The present paper expands upon the work of Wire and U by presenting results for significantly deeper initial semi-elliptical surface cracks. In addition, in one specimen, the surface crack penetrated weld-deposited cladding into the high-sulfur steel. The results for the semi-elliptical surface cracks agreed quite well with the EAC Initiation Criterion, and provide confirmation of the applicability of the criterion to crack configurations with more restricted access to water

  13. Radical polarization in double switching of external magnetic field

    International Nuclear Information System (INIS)

    Lukzen, N.N.; Morozov, V.A.; Sagdeev, R.Z.

    1999-01-01

    Theoretical treatment of radical spin evolution under the action of double switching of external magnetic field is proposed. Account is taken of evolution of the radical spin state during laser pulse which generates paramagnetic particles. It is shown that the most effective beats in the nuclear magnetization of diamagnetic products of recombination occur upon the jump into zero magnetic field after laser pulse. The phase of observed beats bears information about the type of the initial radical polarization. The frequency of the beats is determined by radical hyperfine structure. (Copyright (c) 1999 Elsevier Science B.V., Amsterdam. All rights reserved.)

  14. Initial Experience with ABO-incompatible Live Donor Renal Transplantation

    Directory of Open Access Journals (Sweden)

    Meng-Kun Tsai

    2006-01-01

    Full Text Available The serious shortage of cadaveric organs has prompted the development of ABO-incompatible live donor renal transplantation. We report our experience of the initial two live donor ABO incompatible renal transplants at our hospital. The first patient was a 55-year-old type A female who received a kidney from her AB type husband. The second patient was a 27-year-old type O male who received renal transplantation from his type A father. Preconditioning immunosuppressive therapy in the two patients with tacrolimus, mycophenolate mofetil and methylprednisolone was started 7 days before transplantation. During the period of preconditioning, double filtration plasmapheresis (DFPP was employed to remove anti-A and -B antibodies. Laparoscopic splenectomy and renal transplantation were performed after the anti-donor ABO antibodies were reduced to a titer of 1:4. Rituximab, a humanized monoclonal anti-CD20 antibody, was administered to the second patient due to a rebound in the anti-A antibody titer during the preconditioning period. Under a tacrolimus-based immunosuppressive regimen, both patients recovered very well without any evidence of rejection. Serum creatinine levels were 1.0 and 1.4 mg/dL at 6 and 3 months after transplantation, respectively. These cases illustrate that with new immunosuppressive agents, DFPP and splenectomy, ABO-incompatible renal transplantation can be successfully conducted in end-stage renal disease patients whose only available live donors are blood group incompatible.

  15. Homestake surface-underground scintillators: Initial results

    International Nuclear Information System (INIS)

    Cherry, M.L.; Corbato, S.; Daily, T.; Fenyves, E.J.; Kieda, D.; Lande, K.; Lee, C.K.

    1986-01-01

    The first 70 tons of the 140-ton Large Area Scintillation Detector (LASD) have been operating since Jan. 1985 at a depth of 4850 ft. (4200 m.w.e.) in the Homestake Gold Mine, Lead, S.D. A total of 4 x 10(4) high-energy muons (E sub mu is approx. 2.7 TeV at the surface) have been detected. The remainder of the detector is scheduled to be in operation by the Fall of 1985. In addition, a surface air shower array is under construction. The first 27 surface counters, spaced out over an area of 270' x 500', began running in June, 1985. The LASD performance, the potential of the combined shower array and underground muon experiment for detecting point sources, and the initial results of a search for periodic emission from Cygnus X-3 are discussed

  16. Impact of initial surface parameters on the final quality of laser micro-polished surfaces

    Science.gov (United States)

    Chow, Michael; Bordatchev, Evgueni V.; Knopf, George K.

    2012-03-01

    Laser micro-polishing (LμP) is a new laser-based microfabrication technology for improving surface quality during a finishing operation and for producing parts and surfaces with near-optical surface quality. The LμP process uses low power laser energy to melt a thin layer of material on the previously machined surface. The polishing effect is achieved as the molten material in the laser-material interaction zone flows from the elevated regions to the local minimum due to surface tension. This flow of molten material then forms a thin ultra-smooth layer on the top surface. The LμP is a complex thermo-dynamic process where the melting, flow and redistribution of molten material is significantly influenced by a variety of process parameters related to the laser, the travel motions and the material. The goal of this study is to analyze the impact of initial surface parameters on the final surface quality. Ball-end micromilling was used for preparing initial surface of samples from H13 tool steel that were polished using a Q-switched Nd:YAG laser. The height and width of micromilled scallops (waviness) were identified as dominant parameter affecting the quality of the LμPed surface. By adjusting process parameters, the Ra value of a surface, having a waviness period of 33 μm and a peak-to-valley value of 5.9 μm, was reduced from 499 nm to 301 nm, improving the final surface quality by 39.7%.

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

    International Nuclear Information System (INIS)

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

    2002-01-01

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

  18. Is there a link between blastomere contact surfaces of day 3 embryos and live birth rate?

    Directory of Open Access Journals (Sweden)

    Paternot Goedele

    2012-09-01

    Full Text Available Abstract Background Cell-cell communication and adhesion are essential for the compaction process of early stage embryos. The aim of this study was to develop a non-invasive objective calculation system of embryo compaction in order to test the hypothesis that embryos with a larger mean contact surface result in a higher live birth rate compared to embryos with a lower mean contact surface. Methods Multilevel images of 474 embryos transferred on day 3 were evaluated by the Cellify software. This software calculates the contact surfaces between the blastomeres. The primary outcome of this study was live birth. An ideal range of contact surface was determined and the positive and negative predictive value, the sensitivity, the specificity and the area under the curve for this new characteristic were calculated. Results In total, 115 (24% transferred embryos resulted in a live birth. Selection of an embryo for transfer on its mean contact surface could predict live birth with a high sensitivity (80% and high negative predicting value (83% but with a low positive predictive value (27%, a low specificity (31% and low area under the ROC curve (0.56. The mean contact surface of embryos cultured in a single medium was significantly higher compared to the mean contact surface of embryos cultured in a sequential medium (p = 0.0003. Conclusions Neither the mean contact surface nor the number of contact surfaces of a day 3 embryo had an additional value in the prediction of live birth. The type of culture medium, however, had an impact on the contact surface of an embryo. Embryos cultured in a single medium had a significant larger contact surface compared to embryos cultured in the sequential medium.

  19. Observations of Radical Precursors during TexAQS II: Findings and Implications

    Science.gov (United States)

    Olaguer, E. P.; Lefer, B. L.; Rappenglueck, B.; Pinto, J. P.

    2009-12-01

    The Texas Environmental Research Consortium (TERC) sponsored and helped organize significant components of the Second Texas Air Quality Study (TexAQS II). Some of the TERC-sponsored experiments, most notably those associated with the TexAQS II Radical and Aerosol Measurement Project (TRAMP) sited on top of the Moody Tower at the University of Houston, found evidence for the importance of short-lived radical sources such as formaldehyde (HCHO) and nitrous acid (HONO) in increasing ozone productivity. During TRAMP, daytime HCHO pulses as large as 32 ppb were observed and attributed to industrial activities upwind in the Houston Ship Channel (HSC), and HCHO peaks as large as 52 ppb were detected by in-situ surface monitors in the HSC. In addition, an instrumented Piper Aztec aircraft observed plumes of apparent primary formaldehyde in flares from petrochemical facilities in the HSC. In one such combustion plume, depleted of ozone by large NOx emissions, the Piper Aztec measured an HCHO-to-CO ratio three times that of mobile sources. HCHO from uncounted primary sources or ozonolysis of underestimated olefin emissions could significantly increase ozone productivity in Houston beyond previous expectations. Simulations with the CAMx model show that additional emissions of HCHO from industrial flares can increase peak ozone in Houston by up to 30 ppb, depending on conditions in the planetary boundary layer. Other findings from TexAQS II include significant concentrations of HONO throughout the day, well in excess of current air quality model predictions, with large nocturnal vertical gradients indicating a surface or near-surface source of HONO, and large concentrations of night-time radicals (~30 ppt HO2). Additional HONO sources could increase daytime ozone by more than 10 ppb. Improving the representation of primary and secondary HCHO and HONO in air quality models could enhance the effectiveness of simulated control strategies, and thus make ozone attainment

  20. Reaction kinetics of resveratrol with thiyl and alkoxyl radicals

    International Nuclear Information System (INIS)

    Dzeba, I.; Mihaljevic, B.

    2011-01-01

    Complete text of publication follows. Plant derived resveratrol (trans-3,5,4'-trihydroxystilbene) possesses a broad spectrum of biological activities, one of them are very well known its antioxidative properties. Our work aims to provide kinetic data with regard to the reactivity of resveratrol with uninvestigated short-lived bioradicals, identified as mediators in oxidative lipid degradation processes. Radicals of our interest are alkoxyl radicals, well known propagators of the chain free radical reactions in lipids, and thiyl radicals which protect lipids from their degradation pathway, but at the same time cause the isomerization of the double bonds. In order to investigate these reactions of resveratrol laser flash photolysis was used. On the basis of competitive kinetics the rate constants were determined under pseudo-first order conditions in acetonitrile solutions at room temperature. Thiyl radicals were generated indirectly in solution containing 1-octadecanthiol and photosensitive benzophenone in acetonitrile using the light pulses at 347 nm from ruby laser. Tert-butoxyl radicals were generated directly by peroxide bond cleavage from di-tert-butyl peroxide in acetonitrile by light pulses of Nd:YAG at 355 nm, and ruby at 347 nm. Obtained rate constants for the reactions of resveratrol and radicals generated by laser flash photolysis will be summarized and compared with rare literature data for the rate constants of investigated reactions of resveratrol and other radicals generated by pulse radiolysis.

  1. Introduction: Teaching Black Lives Matter

    Directory of Open Access Journals (Sweden)

    Paula Austin

    2016-11-01

    Full Text Available An introduction to Radical Teacher, Issue 106: Teaching Black Lives Matter. This issue brings together a diverse collection of articles exploring educator’s responses, strategies, and stories on how #BlackLivesMatter has informed their teaching practice, the content of their courses, and their personal relationship to colleagues, family, friends, and self.

  2. Chlorine as a primary radical: evaluation of methods to understand its role in initiation of oxidative cycles

    Science.gov (United States)

    Young, C. J.; Washenfelder, R. A.; Edwards, P. M.; Parrish, D. D.; Gilman, J. B.; Kuster, W. C.; Mielke, L. H.; Osthoff, H. D.; Tsai, C.; Pikelnaya, O.; Stutz, J.; Veres, P. R.; Roberts, J. M.; Griffith, S.; Dusanter, S.; Stevens, P. S.; Flynn, J.; Grossberg, N.; Lefer, B.; Holloway, J. S.; Peischl, J.; Ryerson, T. B.; Atlas, E. L.; Blake, D. R.; Brown, S. S.

    2014-04-01

    atoms do play an important role in photochemistry there, constituting 9% of the primary radical source. Furthermore, Cl-VOC reactivity differs from that of OH, being more than an order of magnitude larger and dominated by VOCs, such as alkanes, that are less reactive toward OH. Primary Cl is also slightly more effective as a radical source than primary OH due to its greater propensity to initiate radical propagation chains via VOC reactions relative to chain termination via reaction with nitrogen oxides.

  3. Polystyrene/magnesium hydroxide nanocomposite particles prepared by surface-initiated in-situ polymerization

    International Nuclear Information System (INIS)

    Liu Hui; Yi Jianhong

    2009-01-01

    In order to avoid their agglomeration and incompatibility with hydrophobic polystyrene substrate, magnesium hydroxide nanoparticles were encapsulated by surface-initiated in-situ polymerization of styrene. The process contained two steps: electrostatic adsorption of initiator and polymerization of monomer on the surface of magnesium hydroxide. It was found that high adsorption ratio in the electrostatic adsorption of initiator could be attained only in acidic region, and the adsorption belonged to typical physical process. Compared to traditional in-situ polymerization, higher grafting ratio was obtained in surface-initiated in-situ polymerization, which can be attributed to weaker steric hindrance. Both Fourier transform infrared spectroscopy (FTIR) and transmission electron microscopy (TEM) indicated that polystyrene/magnesium hydroxide nanocomposite particles had been successfully prepared by surface-initiated in-situ polymerization. The resulting samples were also analyzed and characterized by means of contact angle testing, dispersibility evaluation and thermogravimetric analysis

  4. Sulfate radical-based water treatment in presence of chloride: formation of chlorate, inter-conversion of sulfate radicals into hydroxyl radicals and influence of bicarbonate.

    Science.gov (United States)

    Lutze, Holger V; Kerlin, Nils; Schmidt, Torsten C

    2015-04-01

    Sulfate radical (SO4(-)) based oxidation is discussed as a potential water treatment option and is already used in ground water remediation. However, the complex SO4(-) chemistry in various matrices is poorly understood. In that regard, the fast reaction of SO4(-) with Cl(-) is of high importance since Cl(-) belongs to the main constituents in aqueous environments. This reaction yields chlorine atoms (Cl) as primary products. Cl initiate a cascade of subsequent reactions with a pH dependent product pattern. At low pH ( 5 Cl mainly react with water yielding hydroxyl radicals. Thus, at moderate Cl(-) concentrations (mM range) the SO4(-)-based process may be converted into a conventional (hydroxyl radical -based) advanced oxidation process. The conversion of SO4(-) into OH, however, is interrupted in presence of bicarbonate by scavenging of Cl. Copyright © 2014. Published by Elsevier Ltd.

  5. Hydroxyl radical reactivity at the air-ice interface

    Directory of Open Access Journals (Sweden)

    T. F. Kahan

    2010-01-01

    Full Text Available Hydroxyl radicals are important oxidants in the atmosphere and in natural waters. They are also expected to be important in snow and ice, but their reactivity has not been widely studied in frozen aqueous solution. We have developed a spectroscopic probe to monitor the formation and reactions of hydroxyl radicals in situ. Hydroxyl radicals are produced in aqueous solution via the photolysis of nitrite, nitrate, and hydrogen peroxide, and react rapidly with benzene to form phenol. Similar phenol formation rates were observed in aqueous solution and bulk ice. However, no reaction was observed at air-ice interfaces, or when bulk ice samples were crushed prior to photolysis to increase their surface area. We also monitored the heterogeneous reaction between benzene present at air-water and air-ice interfaces with gas-phase OH produced from HONO photolysis. Rapid phenol formation was observed on water surfaces, but no reaction was observed at the surface of ice. Under the same conditions, we observed rapid loss of the polycyclic aromatic hydrocarbon (PAH anthracene at air-water interfaces, but no loss was observed at air-ice interfaces. Our results suggest that the reactivity of hydroxyl radicals toward aromatic organics is similar in bulk ice samples and in aqueous solution, but is significantly suppressed in the quasi-liquid layer (QLL that exists at air-ice interfaces.

  6. Role of free radicals in radiation chemical aging

    Energy Technology Data Exchange (ETDEWEB)

    Greenstock, C L

    1986-01-01

    Ionizing radiation initiates chemical changes in DNA, phospholipid membranes and other critical cell targets, that, if allowed to accumulate unrepaired, may lead to aging and other chronic effects. The chemical effects are free radical mediated, the principal damaging species being radical OH and to a lesser extent O2-anion radical and the molecular product H/sub 2/O/sub 2/. Many compounds can act in combination with ionizing radiation, to amplify the potential oxidative stress. Chemicals, ultra-violet light, lipid peroxides and their breakdown products may increase the extent of acute and chronic radiobiological effects.

  7. Trichloroethylene Radicals: An EPR/SPIN Trapping Study

    National Research Council Canada - National Science Library

    Steel-Goodwin, Linda

    1995-01-01

    .... As part of the process to develop environmental and health effects criteria for base clean-up the initial radicals produced by TCE were studied by electron paramagnetic resonance spectroscopy (EPR...

  8. (2+1)-dimensional pure gravity for an arbitrary closed initial surface

    International Nuclear Information System (INIS)

    Hosoya, Akio; Nakao, Ken-ichi.

    1989-04-01

    The (2+1)-dimensional pure Einstein gravity is studied in the ADM formalism. We completely solve the initial value and the time evolution problems with a closed Riemann surface being an initial surface, choosing the time slicing so that the trace of the extrinsic curvature is independent of spatial coordinates. The possible topology of the two-surface is either a torus or a Riemann surface of genus g≥2. It is shown that the moduli parameters of the torus follow the geodesic curve in the moduli space, while the motion of the moduli is static for the case g≥2. (author)

  9. In situ development of self-reinforced cellulose nanocrystals based thermoplastic elastomers by atom transfer radical polymerization.

    Science.gov (United States)

    Yu, Juan; Wang, Chunpeng; Wang, Jifu; Chu, Fuxiang

    2016-05-05

    Recently, the utilization of cellulose nanocrystals (CNCs) as a reinforcing material has received a great attention due to its high elastic modulus. In this article, a novel strategy for the synthesis of self-reinforced CNCs based thermoplastic elastomers (CTPEs) is presented. CNCs were first surface functionalized with an initiator for surface-initiated atom transfer radical polymerization (SI-ATRP). Subsequently, SI-ATRP of methyl methacrylate (MMA) and butyl acrylate (BA) was carried out in the presence of sacrificial initiator to form CTPEs in situ. The CTPEs together with the simple blends of CNCs and linear poly(MMA-co-BA) copolymer (P(MMA-co-BA)) were characterized for comparative study. The results indicated that P(MMA-co-BA) was successfully grafted onto the surface of CNCs and the compatibility between CNCs and the polymer matrix in CTPEs was greatly enhanced. Specially, the CTPEs containing 2.15wt% CNCs increased Tg by 19.2°C and tensile strength by 100% as compared to the linear P(MMA-co-BA). Copyright © 2016 Elsevier Ltd. All rights reserved.

  10. Diffusion of 1,4-butanedithiol radicals on Au(111) and Au(100): A DFT-based comparison

    Energy Technology Data Exchange (ETDEWEB)

    Franke, Andreas; Pehlke, Eckhard [Institut fuer Theoretische Physik und Astrophysik, Universitaet Kiel, 24098 Kiel (Germany)

    2010-07-01

    Organic molecules chemisorbed on surfaces hold the perspective of surface functionalization. The 1,4-butanedithiol radical chemisorbed at the Au(111) or Au(100) surface serves as a model system for the S-Au molecule-substrate bond. Density functional total-energy calculations have been carried out for the chemisorption of the radical on the unreconstructed Au surfaces, which are both known to be stabilized under electrochemical conditions. Local minima with close-by energies indicate multi-valley potential-energy surfaces, which originate from the interplay between the two S-Au adsorbate-substrate bonds and the internal degrees of freedom of the butanedithiol radical. Diffusion paths of the radical on both Au surfaces have been calculated within DFT using VASP. The diffusion barriers for translation and rotation of the radical differ. They can be fine-tuned by varying the applied potential in the electrochemical cell. This is considered theoretically by inspecting the variation of the dipole moment along the reaction paths. Consequences for the dynamics of succeeding diffusion hops are discussed.

  11. Effect of Particulate Matter Mineral Composition on Environmentally Persistent Free Radical (EPFR) Formation.

    Science.gov (United States)

    Feld-Cook, Elisabeth E; Bovenkamp-Langlois, Lisa; Lomnicki, Slawo M

    2017-09-19

    Environmentally Persistent Free Radicals (EPFRs) are newly discovered, long-lived surface bound radicals that form on particulate matter and combustion borne particulates, such as fly ash. Human exposure to such particulates lead to translocation into the lungs and heart resulting in cardio-vascular and respiratory disease through the production of reactive oxygen species. Analysis of some waste incinerator fly ashes revealed a significant difference between their EPFR contents. Although EPFR formation occurs on the metal domains, these differences were correlated with the altering concentration of calcium and sulfur. To analyze these phenomena, surrogate fly ashes were synthesized to mimic the presence of their major mineral components, including metal oxides, calcium, and sulfur. The results of this study led to the conclusion that the presence of sulfates limits formation of EPFRs due to inhibition or poisoning of the transition metal active sites necessary for their formation. These findings provide a pathway toward understanding differences in EPFR presence on particulate matter and uncover the possibility of remediating EPFRs from incineration and hazardous waste sites.

  12. Acetone n-radical cation internal rotation spectrum: The torsional potential surface

    International Nuclear Information System (INIS)

    Shea, Dana A.; Goodman, Lionel; White, Michael G.

    2000-01-01

    The one color REMPI and two color ZEKE-PFI spectra of acetone-d 3 have been recorded. The 3p x Rydberg state of acetone-d 3 lies at 59 362.3 cm-1 and both of the torsional modes are visible in this spectrum. The antigearing Rydberg (a 2 ) mode, v 12 * , has a frequency of 62.5 cm-1, while the previously unobserved gearing (b 1 ) mode, v 17 * , is found at 119.1 cm-1. An ionization potential of 78 299.6 cm-1 for acetone-d 3 has been measured. In acetone-d 3 n-radical cation ground state, the fundamentals of both of the torsional modes have been observed, v 12 + at 51.0 cm-1 and v 17 + at 110.4 cm-1, while the first overtone of v 12 + has been measured at 122.4 cm-1. Deuterium shifts show that v 12 + behaves like a local C 3v rotor, but that v 17 + is canonical. Combining this data with that for acetone-d 0 and aacetone-d 6 has allowed us to fit the observed frequencies to a torsional potential energy surface based on an ab initio C 2v cation ground state geometry. This potential energy surface allows for prediction of the v 17 vibration in acetone-d 0 and acetone-d 6 . The barrier to synchronous rotation is higher in the cation ground state than in the neutral ground state, but significantly lower than in the 3s Rydberg state. The 3p x Rydberg and cation ground state potential energy surfaces are found to be very similar to each other, strongly supporting the contention that the 3p x Rydberg state has C 2v geometry and is a good model for the ion core. The altered 3s Rydberg state potential surface suggests this state has significant valence character. (c) 2000 American Institute of Physics

  13. Reactions of organic free radicals at colloidal silver in aqueous solution. Electron pool effect and water decomposition

    International Nuclear Information System (INIS)

    Henglein, A.

    1979-01-01

    Organic free radicals of high negative redox potential such as α-alcohol radicals were found to transfer electrons to colloidal silver particles stabilized by sodium dodecyl sulfate in aqueous solution. The colloidal particles thus became a pool of stored electrons that could reduce water to form hydrogen or react with suitable acceptors in solution. The organic radicals were produced by irradiation, using suitable scavengers for the primary radicals from the radiolysis of the aqueous solvent. The solutions initially contained silver ions at 1 x 10 -4 - 2 x 10 -3 M. At doses below 10 5 rd, the silver ions were completely reduced to form the colloidal catalyst. In this dose range, the corresponding hydrogen yield amounted to 1 molecule per 100 eV. It increased steeply at higher doses up to 3 molecules per 100 eV. The H 2 yield decreased with increasing dose rate and with increasing pH in alkaline solutions. It was highest at a concentration of sodium dodecyl sulfate of 1 x 10 -3 M, i.e., far below the critical micelle concentration of this surfactant. Changes in the absorption spectrum of the colloid are attributed to changes in the size of the silver particles upon charging up with electrons. The competition of radical-colloid reactions with radical-radical deactivation in the bulk of solution or at the surface of the colloidal particles is also discussed. 11 figures

  14. Radicals of DNA and DNA nucleotides generated by ionising radiation

    International Nuclear Information System (INIS)

    Przybytniak, G.

    2004-01-01

    A first stage of cell processes leading to DNA damage of initiated by radical reactions. In a model system such transformations were generated by ionising radiation which involves production of electron loss and electron gain centers of the substrate and radical formation. Using cryogenic ESR spectroscopy it was found that the DNA nucleotides, which convert to radical anions upon electron capture undergo the separation of unpaired spin and charge due to protonation. Circular and linear dichroism studies enabled to conclude that iron ions(III) induce strong changes in the DNA helical structure indicating their coordination with nitrogen bases. The repair of DNA radicals produced via radiolytic oxidation, i.e. the guanine radical cation and the allyl type radical of thymine, is possible at elevated temperatures due to the involvement of sulphydryl groups. The influence of the thiol charge is then limited

  15. Definitive pathology at radical prostatectomy is commonly favorable in men following initial active surveillance.

    Science.gov (United States)

    Hong, Sung Kyu; Sternberg, Itay A; Keren Paz, Gal E; Kim, Philip H; Touijer, Karim A; Scardino, Peter T; Eastham, James A

    2014-08-01

    Limited data are currently available regarding the outcomes of radical prostatectomy (RP) in men with low-risk prostate cancer who were initially managed by active surveillance (AS). To evaluate the pathologic outcomes of patients who underwent RP following initial AS. We analyzed the records of 67 patients who underwent RP following initial AS begun between 1993 and 2011. All patients underwent confirmatory biopsy to reassess eligibility for AS. RP was recommended for disease progression suggested by follow-up biopsies or imaging. Unfavorable disease was defined as having at least one of the following pathologic findings: Gleason score (GS) ≥4+3, extracapsular extension of tumor, seminal vesicle invasion, or lymph node involvement. A descriptive analysis was performed to assess pathologic features. Median time from confirmatory biopsy to RP was 1.7 yr (range: 0.3-7.8). Reasons for discontinuing AS to undergo RP included evidence of increased tumor volume or grade on follow-up biopsy, patient preference/anxiety, and findings on follow-up imaging in 46 patients (68.7%), 17 patients (25.3%), and 4 patients (6.0%), respectively. Pathologic analyses revealed organ-confined disease in 55 patients (82.1%), and GS was ≥4+3 in 9 (13.4%). Positive nodes were observed in three patients (4.4%) and positive surgical margin in two (3.0%). Overall, 19 patients (28.4%) had unfavorable disease. Of the biopsy criteria for triggering RP, Gleason patterns >3 were the most frequently associated with unfavorable disease (43.3%). One patient (1.5%) experienced biochemical recurrence during postoperative follow-up (median: 3.2 yr). Our study may be limited by its retrospective and single-institution nature. Most patients who started initially on AS after undergoing confirmatory biopsy showed pathologically organ-confined disease with a low GS at RP. Such findings provide further evidence that, overall, AS is a safe treatment approach. Copyright © 2013. Published by Elsevier B.V.

  16. Atom transfer radical polymerization of styrene under pulsed microwave irradiation

    International Nuclear Information System (INIS)

    Cheng Zhenping; Zhu Xiulin; Zhou Nianchen; Zhu Jian; Zhang Zhengbiao

    2005-01-01

    A homogeneous solution atom transfer radical polymerization (ATRP) and reverse atom transfer radical polymerization (RATRP) of styrene (St) in N,N-dimethylformamide (DMF) were successfully carried out under pulsed microwave irradiation (PMI), using 1-bromo-1-phenylethane (1-PEBr)/CuCl/N,N,N',N'',N''-pentamethyldiethylenetriamine (PMDETA) as an initiating system at 85 deg. C and 2,2'-azo-bis-isobutyrontrile (AIBN)/CuCl 2 /PMDETA as an initiating system at 95 deg. C, respectively. The polymerization rates under PMI were greatly increased in comparison with those under identical conventional heating (CH)

  17. Encapsulation of Gibbsite platelets with free radical and controlled radical emulsion polymerization approaches, a small review

    NARCIS (Netherlands)

    Loiko, O.P.; Spoelstra, A.B.; van Herk, A.M.; Meuldijk, J.; Heuts, J.P.A.

    2016-01-01

    Water-borne anisotropic polymer-Gibbsite latex particles were prepared by a conventional and an atom transfer radical polymerisation (ATRP) based starved-feed emulsion polymerisation without any chemical modification of the platelet surface. Anionic co-oligomers, synthesised via ATRP, were used in

  18. Resveratrol products resulting by free radical attack

    Energy Technology Data Exchange (ETDEWEB)

    Bader, Yvonne; Quint, R.M. [Section Radiation Biology, Department of Nutritional Sciences, Faculty of Life Sciences, University of Vienna, UZAII, Althanstrasse 14, A-1090 Vienna (Austria); Getoff, Nikola [Section Radiation Biology, Department of Nutritional Sciences, Faculty of Life Sciences, University of Vienna, UZAII, Althanstrasse 14, A-1090 Vienna (Austria)], E-mail: nikola.getoff@univie.ac.at

    2008-06-15

    Trans-resveratrol (trans-3,4',5-trihydroxystilbene; RES), which is contained in red wine and many plants, is one of the most relevant and extensively investigated stilbenes with a broad spectrum of biological activities. Among other duties, RES has been reported to have anti-carcinogenetic activities, which could be attributed to its antioxidant properties. The degradation of RES was studied under various conditions. The products (aldehydes, carboxylic acids, etc.) generated from RES by the attack of free radicals were registered as a function of the radical concentration (absorbed radiation dose). Based on the obtained data it appears that the OH radicals are initiating the rather complicated process, which involves of the numerous consecutive reactions. A possible starting reaction mechanism is presented.

  19. Probing cytochrome c in living mitochondria with surface-enhanced Raman spectroscopy

    DEFF Research Database (Denmark)

    Brazhe, Nadezda A.; Evlyukhin, Andrey B.; Goodilin, Eugene A.

    2015-01-01

    Selective study of the electron transport chain components in living mitochondria is essential for fundamental biophysical research and for the development of new medical diagnostic methods. However, many important details of inter- and intramembrane mitochondrial processes have remained in shadow...... due to the lack of non-invasive techniques. Here we suggest a novel label-free approach based on the surface-enhanced Raman spectroscopy (SERS) to monitor the redox state and conformation of cytochrome c in the electron transport chain in living mitochondria. We demonstrate that SERS spectra of living...... mitochondria placed on hierarchically structured silver-ring substrates provide exclusive information about cytochrome c behavior under modulation of inner mitochondrial membrane potential, proton gradient and the activity of ATP-synthetase. Mathematical simulation explains the observed enhancement of Raman...

  20. Radiation-induced polymerisation of 2,3-dihydrofuran: free-radical or cationic mechanism?

    International Nuclear Information System (INIS)

    Janovsky, Igor; Naumov, Sergej; Knolle, Wolfgang; Mehnert, Reiner

    2005-01-01

    Concentrated (10 mol%) solutions of 2,3-dihydrofuran in CFCl 2 CF 2 Cl matrix were irradiated at 77 K and several intermediates (dimer radical cation, dihydrofuryl radical, and polymer radicals) were observed by low-temperature EPR spectroscopy. The irradiated solutions yielded after melting a polymeric product, which was characterised by IR spectroscopy and gel permeation chromatography. The polydisperse polymer is assumed to be formed mainly by a cationic process initiated by a dimer carbocation. The free-radical mechanism via the dihydrofuryl radical leads to low molecular weight oligomers only. Quantum chemical calculations support the interpretation of the experimental results

  1. Why Nature Uses Radical SAM Enzymes so Widely: Electron Nuclear Double Resonance Studies of Lysine 2,3-Aminomutase Show the 5'-dAdo• "Free Radical" Is Never Free.

    Science.gov (United States)

    Horitani, Masaki; Byer, Amanda S; Shisler, Krista A; Chandra, Tilak; Broderick, Joan B; Hoffman, Brian M

    2015-06-10

    Lysine 2,3-aminomutase (LAM) is a radical S-adenosyl-L-methionine (SAM) enzyme and, like other members of this superfamily, LAM utilizes radical-generating machinery comprising SAM anchored to the unique Fe of a [4Fe-4S] cluster via a classical five-membered N,O chelate ring. Catalysis is initiated by reductive cleavage of the SAM S-C5' bond, which creates the highly reactive 5'-deoxyadenosyl radical (5'-dAdo•), the same radical generated by homolytic Co-C bond cleavage in B12 radical enzymes. The SAM surrogate S-3',4'-anhydroadenosyl-L-methionine (anSAM) can replace SAM as a cofactor in the isomerization of L-α-lysine to L-β-lysine by LAM, via the stable allylic anhydroadenosyl radical (anAdo•). Here electron nuclear double resonance (ENDOR) spectroscopy of the anAdo• radical in the presence of (13)C, (2)H, and (15)N-labeled lysine completes the picture of how the active site of LAM from Clostridium subterminale SB4 "tames" the 5'-dAdo• radical, preventing it from carrying out harmful side reactions: this "free radical" in LAM is never free. The low steric demands of the radical-generating [4Fe-4S]/SAM construct allow the substrate target to bind adjacent to the S-C5' bond, thereby enabling the 5'-dAdo• radical created by cleavage of this bond to react with its partners by undergoing small motions, ∼0.6 Å toward the target and ∼1.5 Å overall, that are controlled by tight van der Waals contact with its partners. We suggest that the accessibility to substrate and ready control of the reactive C5' radical, with "van der Waals control" of small motions throughout the catalytic cycle, is common within the radical SAM enzyme superfamily and is a major reason why these enzymes are the preferred means of initiating radical reactions in nature.

  2. Interaction of radiation-generated radicals with myoglobin in aqueous solution

    International Nuclear Information System (INIS)

    Whitburn, K.D.; Hoffman, M.Z.

    1985-01-01

    The γ-radiolysis of aqueous solutions of ferrimyoglobin in the presence of N 2 O at pH 7.3 has been examined as a function of added catalase and oxygen. Changes in the nature of the heme group have been monitored by visible absorption spectrophotometry and analysed quantitatively by a multiple wavelength method based on Beer's Law. Simple chemical analyses have been used to confirm qualitative identification of the product derivatives. As observed previously, the ferriheme is reduced by indirect globin-mediated action initiated by radical OH/H radical. The yield of reduced product decreases as [O 2 ] derived from irradiated water and from protein-mediated processes in oxygenated solution, is eliminated by the presence of catalase. Formation of a hemichrome form of ferrimyoglobin is apparent at higher doses in the presence of O 2 . These results demonstrate that oxygen plays an important role in controlling the nature and extent of redox that manifests ultimately on the heme group of ferrimyoglobin as a result of the initial interaction of radical OH/H radical. (author)

  3. The effect of surface modification on initial ice formation on aluminum surfaces

    DEFF Research Database (Denmark)

    Rahimi, Maral; Afshari, Alireza; Fojan, Peter

    2015-01-01

    material of heat exchanger fins is aluminum, this paper focuses on the effect of aluminum wettability on the initial stages of ice formation. The ice growth was studied on bare as well as hydrophilically and hydrophobically modified surfaces of aluminum (8011A) sheets, commonly used in heat exchangers...

  4. Facile surface modification of silicone rubber with zwitterionic polymers for improving blood compatibility

    International Nuclear Information System (INIS)

    Liu, Pingsheng; Chen, Qiang; Yuan, Bo; Chen, Mengzhou; Wu, Shishan; Lin, Sicong; Shen, Jian

    2013-01-01

    A facile approach to modify silicone rubber (SR) membrane for improving the blood compatibility was investigated. The hydrophobic SR surface was firstly activated by air plasma, after which an initiator was immobilized on the activated surface for atom transfer radical polymerization (ATRP). Three zwitterionic polymers were then grafted from SR membrane via surface-initiated atom transfer radical polymerization (SI-ATRP). The surface composition, wettability, and morphology of the membranes before and after modification were characterized by X-ray photoelectron spectroscopy (XPS), static water contact angle (WCA) measurement, and atomic force microscopy (AFM). Results showed that zwitterionic polymers were successfully grafted from SR surfaces, which remarkably improved the wettability of the SR surface. The blood compatibility of the membranes was evaluated by protein adsorption and platelet adhesion tests in vitro. As observed, all the zwitterionic polymer modified surfaces have improved resistance to nonspecific protein adsorption and have excellent resistance to platelet adhesion, showing significantly improved blood compatibility. This work should inspire many creative uses of SR based materials for biomedical applications such as vessel, catheter, and microfluidics. Highlights: • Facile surface modification of silicone rubber with functional brushes • Modified SR surfaces have improved resistance to nonspecific protein adsorption. • Modified SR surfaces have excellent resistance to platelet adhesion. • Zwitteironic surface significant improvement in blood compatibility • Could inspire many creative uses of SR based materials for biomedical

  5. Facile surface modification of silicone rubber with zwitterionic polymers for improving blood compatibility

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Pingsheng [School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093 (China); Chen, Qiang, E-mail: chem100@nju.edu.cn [School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093 (China); High Technology Research Institute of Nanjing University, Changzhou 213164 (China); Yuan, Bo; Chen, Mengzhou; Wu, Shishan; Lin, Sicong [School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093 (China); Shen, Jian, E-mail: shenj1957@yahoo.com.cn [School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093 (China)

    2013-10-15

    A facile approach to modify silicone rubber (SR) membrane for improving the blood compatibility was investigated. The hydrophobic SR surface was firstly activated by air plasma, after which an initiator was immobilized on the activated surface for atom transfer radical polymerization (ATRP). Three zwitterionic polymers were then grafted from SR membrane via surface-initiated atom transfer radical polymerization (SI-ATRP). The surface composition, wettability, and morphology of the membranes before and after modification were characterized by X-ray photoelectron spectroscopy (XPS), static water contact angle (WCA) measurement, and atomic force microscopy (AFM). Results showed that zwitterionic polymers were successfully grafted from SR surfaces, which remarkably improved the wettability of the SR surface. The blood compatibility of the membranes was evaluated by protein adsorption and platelet adhesion tests in vitro. As observed, all the zwitterionic polymer modified surfaces have improved resistance to nonspecific protein adsorption and have excellent resistance to platelet adhesion, showing significantly improved blood compatibility. This work should inspire many creative uses of SR based materials for biomedical applications such as vessel, catheter, and microfluidics. Highlights: • Facile surface modification of silicone rubber with functional brushes • Modified SR surfaces have improved resistance to nonspecific protein adsorption. • Modified SR surfaces have excellent resistance to platelet adhesion. • Zwitteironic surface significant improvement in blood compatibility • Could inspire many creative uses of SR based materials for biomedical.

  6. Structure and dynamics of olefin radical cation aggregates. Time-resolved fluorescence detected magnetic resonance

    International Nuclear Information System (INIS)

    Desrosiers, M.F.; Trifunac, A.D.

    1986-01-01

    The time-resolved EPR spectra and thus the structure and dynamics of transient hydrocarbon radical cations are obtained by the pulse radiolysis-fluorescence detected magnetic resonance (FDMR) technique. Here the authors report the observation of short-lived radical cations from olefins. FDMR-EPR spectra of radical cations from tetramethylethylene and cyclohexadiene are illustrated. The olefin radical cations, FDMR spectra are concentration-dependent, since dimerization with neutral molecules takes place at higher (>10 -2 M) olefin concentration. Rate constants for the dimerization reaction are derived and the effect of solvent viscosity on aggregate formation is demonstrated. By monitoring the further reactions of dimer cations the authors have obtained EPR evidence for previously unobserved higher-order (multimer) radical cation aggregates of olefins. 16 references, 5 figures

  7. A/r/tographic Collaboration as Radical Relatedness

    Directory of Open Access Journals (Sweden)

    Barbara Bickel PhD

    2011-03-01

    Full Text Available In this paper the authors examine a/r/tographical collaboration in a community-engaged research study investigating immigrant understandings of home and place. The study, The City of Richgate, involves a complex collaboration between community members, community organizations, educational institutions, and a research team comprising artist-educators. The study crosses border zones of cultural, ethnic, geographic, institutional, public, private, and disciplinary boundaries, reflecting the ever-changing character of postmodern reality. In this paper the authors reflect critically and theoretically on the lived experience of radical relatedness found within the complex collaboration, particularly within the a/r/tographic research team. This offers a qualitative methodology of radical collaboration applicable to many fields of inquiry in the academy, art world, and community.

  8. Exploring the Leishmania Hydrophilic Acylated Surface Protein B (HASPB) Export Pathway by Live Cell Imaging Methods.

    Science.gov (United States)

    MacLean, Lorna; Price, Helen; O'Toole, Peter

    2016-01-01

    Leishmania major is a human-infective protozoan parasite transmitted by the bite of the female phlebotomine sand fly. The L. major hydrophilic acylated surface protein B (HASPB) is only expressed in infective parasite stages suggesting a role in parasite virulence. HASPB is a "nonclassically" secreted protein that lacks a conventional signal peptide, reaching the cell surface by an alternative route to the classical ER-Golgi pathway. Instead HASPB trafficking to and exposure on the parasite plasma membrane requires dual N-terminal acylation. Here, we use live cell imaging methods to further explore this pathway allowing visualization of key events in real time at the individual cell level. These methods include live cell imaging using fluorescent reporters to determine the subcellular localization of wild type and acylation site mutation HASPB18-GFP fusion proteins, fluorescence recovery after photobleaching (FRAP) to analyze the dynamics of HASPB in live cells, and live antibody staining to detect surface exposure of HASPB by confocal microscopy.

  9. Photoisomerization and photodissociation dynamics of reactive free radicals

    Energy Technology Data Exchange (ETDEWEB)

    Bise, Ryan T. [Univ. of California, Berkeley, CA (United States)

    2000-08-01

    The photofragmentation pathways of chemically reactive free radicals have been examined using the technique of fast beam photofragment translational spectroscopy. Measurements of the photodissociation cross-sections, product branching ratios, product state energy distributions, and angular distributions provide insight into the excited state potential energy surfaces and nonadiabatic processes involved in the dissociation mechanisms. Photodissociation spectroscopy and dynamics of the predissociative $\\tilde{A}$2A1 and $\\tilde{B}$2A2 states of CH3S have been investigated. At all photon energies, CH3 + S(3Pj), was the main reaction channel. The translational energy distributions reveal resolved structure corresponding to vibrational excitation of the CH3 umbrella mode and the S(3Pj) fine-structure distribution from which the nature of the coupled repulsive surfaces is inferred. Dissociation rates are deduced from the photofragment angular distributions, which depend intimately on the degree of vibrational excitation in the C-S stretch. Nitrogen combustion radicals, NCN, CNN and HNCN have also been studied. For all three radicals, the elimination of molecular nitrogen is the primary reaction channel. Excitation to linear excited triplet and singlet electronic states of the NCN radical generates resolved vibrational structure of the N2 photofragment. The relatively low fragment rotational excitation suggests dissociation via a symmetric C2V transition state. Resolved vibrational structure of the N2 photofragment is also observed in the photodissociation of the HNCN radical. The fragment vibrational and rotational distributions broaden with increased excitation energy. Simple dissociation models suggest that the HNCN radical isomerizes to a cyclic intermediate (c-HCNN) which then dissociates via a tight cyclic

  10. Exploring how lead users develop radical innovation

    DEFF Research Database (Denmark)

    Lettl, Christopher; Gemuenden, Hans Georg; Hienerth, C.

    2008-01-01

    in order to transform their radically new solutions into functional prototypes and then to convince established manufacturers of the technological and market potential of their innovations. Using a comparative case study design in the high-tech field of medical equipment technology, we find that individual...... the supply of diversified knowledge, the development and coordination of a network for further development of the innovation, and initial tests of technical or market feasibility. Our findings have implications for manufacturing firms that wish to design radical innovation projects with (individual) lead...

  11. Early events following radiolytic and photogeneration of radical cations in hydrocarbons

    International Nuclear Information System (INIS)

    Werst, D.W.; Trifunac, A.D.

    1992-01-01

    Real-time studies in hydrocarbons have revealed a richness of chemistry involving the initial ionic species produced in radiolysis and photoionization. A modified radical cation mechanism patterned after the core mechanism for alkane radiolysis-formation of radical cations and their disappearance via ion-molecule reactions - is capable of explaining a wide range of observations in high-energy photochemistry, and thus unifies two high-energy regimes. Fundamental studies of radical cations suggest strategies for mitigating radiation effects in materials

  12. Free Radical Imaging Using In Vivo Dynamic Nuclear Polarization-MRI.

    Science.gov (United States)

    Utsumi, Hideo; Hyodo, Fuminori

    2015-01-01

    Redox reactions that generate free radical intermediates are essential to metabolic processes, and their intermediates can produce reactive oxygen species, which may promote diseases related to oxidative stress. The development of an in vivo electron spin resonance (ESR) spectrometer and its imaging enables us noninvasive and direct measurement of in vivo free radical reactions in living organisms. The dynamic nuclear polarization magnetic resonance imaging (DNP-MRI), also called PEDRI or OMRI, is also a new imaging method for observing free radical species in vivo. The spatiotemporal resolution of free radical imaging with DNP-MRI is comparable with that in MRI, and each of the radical species can be distinguished in the spectroscopic images by changing the frequency or magnetic field of ESR irradiation. Several kinds of stable nitroxyl radicals were used as spin probes to detect in vivo redox reactions. The signal decay of nitroxyl probes, which is determined with in vivo DNP-MRI, reflects the redox status under oxidative stress, and the signal decay is suppressed by prior administration of antioxidants. In addition, DNP-MRI can also visualize various intermediate free radicals from the intrinsic redox molecules. This noninvasive method, in vivo DNP-MRI, could become a useful tool for investigating the mechanism of oxidative injuries in animal disease models and the in vivo effects of antioxidant drugs. © 2015 Elsevier Inc. All rights reserved.

  13. Transmission of Free Radicals through and Damage to Freestanding Single and Multilayer Dielectric Film

    Science.gov (United States)

    Choudhury, Faraz Anwar

    A high concentration of free radicals is present in many processing plasmas, which affects the processing conditions and the properties of materials exposed to the plasma. Measuring the types and concentrations of free radicals present in the plasma is critical in order to determine their effects on the materials being processed. Current methods for detecting free radicals in a plasma require multiple expensive and bulky instruments, complex setups and often modifications to the plasma reactor. In this work, we present a simple technique that detects reactive-oxygen radicals incident on a surface from a plasma. The measurements are made using a fluorophore dye that is commonly used in biological and cellular systems for assay labeling in liquids. Using fluorometric analysis, it was found that the fluorophore reacts with oxygen radicals incident from the plasma, which is indicated by degradation of its fluorescence. As plasma power was increased, the quenching of the fluorescence significantly increased. Both immobilized and non-immobilized fluorophore dyes were used and the results indicate that both states function effectively under vacuum conditions. Using radical-sensitive dyes and free-standing films, the transmission of oxygen radicals through silicon nitride and silicon dioxide dielectric films is measured and their absorption lengths are determined. The absorption lengths were found to be 33, 37 and 40 nm for 15, 30 and 45-minute oxygen plasma exposures respectively. FTIR and XRR measurements show that a silicon oxynitride-like layer forms on the surface of the film which has a lower density than silicon nitride. The increase in absorption length with plasma-exposure time is attributed to the formation of the surface layer. In silicon dioxide films, the absorption length of oxygen radicals was found to be 70 nm after 20 minutes of plasma exposure. After 30 minutes of plasma exposure under the same conditions, the absorption length was reduced to 66 nm. XRR

  14. Impacts of model initialization on an integrated surface water - groundwater model

    KAUST Repository

    Ajami, Hoori

    2015-04-01

    Integrated hydrologic models characterize catchment responses by coupling the subsurface flow with land surface processes. One of the major areas of uncertainty in such models is the specification of the initial condition and its influence on subsequent simulations. A key challenge in model initialization is that it requires spatially distributed information on model states, groundwater levels and soil moisture, even when such data are not routinely available. Here, the impact of uncertainty in initial condition was explored across a 208 km2 catchment in Denmark using the ParFlow.CLM model. The initialization impact was assessed under two meteorological conditions (wet vs dry) using five depth to water table and soil moisture distributions obtained from various equilibrium states (thermal, root zone, discharge, saturated and unsaturated zone equilibrium) during the model spin-up. Each of these equilibrium states correspond to varying computation times to achieve stability in a particular aspect of the system state. Results identified particular sensitivity in modelled recharge and stream flow to the different initializations, but reduced sensitivity in modelled energy fluxes. Analysis also suggests that to simulate a year that is wetter than the spin-up period, an initialization based on discharge equilibrium is adequate to capture the direction and magnitude of surface water–groundwater exchanges. For a drier or hydrologically similar year to the spin-up period, an initialization based on groundwater equilibrium is required. Variability of monthly subsurface storage changes and discharge bias at the scale of a hydrological event show that the initialization impacts do not diminish as the simulations progress, highlighting the importance of robust and accurate initialization in capturing surface water–groundwater dynamics.

  15. Relationships between substrate, surface characteristics, and vegetation in an initial ecosystem

    Science.gov (United States)

    Biber, P.; Seifert, S.; Zaplata, M. K.; Schaaf, W.; Pretzsch, H.; Fischer, A.

    2013-12-01

    We investigated surface and vegetation dynamics in the artificial initial ecosystem "Chicken Creek" (Lusatia, Germany) in the years 2006-2011 across a wide spectrum of empirical data. We scrutinized three overarching hypotheses concerning (1) the relations between initial geomorphological and substrate characteristics with surface structure and terrain properties, (2) the effects of the latter on the occurrence of grouped plant species, and (3) vegetation density effects on terrain surface change. Our data comprise and conflate annual vegetation monitoring results, biennial terrestrial laser scans (starting in 2008), annual groundwater levels, and initially measured soil characteristics. The empirical evidence mostly confirms the hypotheses, revealing statistically significant relations for several goal variables: (1) the surface structure properties, local rill density, local relief energy and terrain surface height change; (2) the cover of different plant groups (annual, herbaceous, grass-like, woody, Fabaceae), and local vegetation height; and (3) terrain surface height change showed significant time-dependent relations with a variable that proxies local plant biomass. Additionally, period specific effects (like a calendar-year optimum effect for the occurrence of Fabaceae) were proven. Further and beyond the hypotheses, our findings on the spatiotemporal dynamics during the system's early development grasp processes which generally mark the transition from a geo-hydro-system towards a bio-geo-hydro system (weakening geomorphology effects on substrate surface dynamics, while vegetation effects intensify with time), where pure geomorphology or substrate feedbacks are changing into vegetation-substrate feedback processes.

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

    Science.gov (United States)

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

    2017-08-01

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

  17. Identification of Surface-Exposed Protein Radicals and A Substrate Oxidation Site in A-Class Dye-Decolorizing Peroxidase from Thermomonospora curvata

    Energy Technology Data Exchange (ETDEWEB)

    Shrestha, Ruben; Chen, Xuejie; Ramyar, Kasra X.; Hayati, Zahra; Carlson, Eric A.; Bossmann, Stefan H.; Song, Likai; Geisbrecht, Brian V.; Li, Ping (FSU); (KSU)

    2016-12-12

    Dye-decolorizing peroxidases (DyPs) are a family of heme peroxidases in which a catalytic distal aspartate is involved in H2O2 activation to catalyze oxidations under acidic conditions. They have received much attention due to their potential applications in lignin compound degradation and biofuel production from biomass. However, the mode of oxidation in bacterial DyPs remains unknown. We have recently reported that the bacterial TcDyP from Thermomonospora curvata is among the most active DyPs and shows activity toward phenolic lignin model compounds. On the basis of the X-ray crystal structure solved at 1.75 Å, sigmoidal steady-state kinetics with Reactive Blue 19 (RB19), and formation of compound II like product in the absence of reducing substrates observed with stopped-flow spectroscopy and electron paramagnetic resonance (EPR), we hypothesized that the TcDyP catalyzes oxidation of large-size substrates via multiple surface-exposed protein radicals. Among 7 tryptophans and 3 tyrosines in TcDyP consisting of 376 residues for the matured protein, W263, W376, and Y332 were identified as surface-exposed protein radicals. Only the W263 was also characterized as one of the surface-exposed oxidation sites. SDS-PAGE and size-exclusion chromatography demonstrated that W376 represents an off-pathway destination for electron transfer, resulting in the cross-linking of proteins in the absence of substrates. Mutation of W376 improved compound I stability and overall catalytic efficiency toward RB19. While Y332 is highly conserved across all four classes of DyPs, its catalytic function in A-class TcDyP is minimal, possibly due to its extremely small solvent-accessible areas. Identification of surface-exposed protein radicals and substrate oxidation sites is important for understanding the DyP mechanism and modulating its catalytic functions for improved activity on phenolic lignin.

  18. Notes on free radicals in the field of human and environmental protection against ionizing radiations

    International Nuclear Information System (INIS)

    Bittel, R.

    It is well known that ionizing radiations, in vitro and in vivo produce, free radicals which may be considered as mediators between physical agents and biological targets. Some aspects of this vast problem are accentuated. Ionizing radiations act either directly on the organic molecules of tissues or indirectly by creating, in the surroundings and in tissular water, inorganic free radicals which act on biochemical molecules to gives new radicals. Analysis of the free radical initiation phenomenon in vivo shows that many initiating agents exist, ionizing radiations representing only one group. The role of oxydants, especially oxydising polluants, and the part played by various enzyme systems (super-oxide dismutase, oxydases etc...) are emphasized. After propagation the chain reactions end in combinations between radicals are stopped by certain organic molecules (radical scavengers). Examples are given (free radical formation from compounds of great biological importance: puric and pyrimidic bases, nucleic acids in particular). These aspects are discussed from the viewpoint of their effects on human and environmental protection against both ionizing radiations and certain chemical pollution [fr

  19. Bioconjugate functionalization of thermally carbonized porous silicon using a radical coupling reaction†

    Science.gov (United States)

    Sciacca, Beniamino; Alvarez, Sara D.; Geobaldo, Francesco; Sailor, Michael J.

    2011-01-01

    The high stability of Salonen’s thermally carbonized porous silicon (TCPSi) has attracted attention for environmental and biochemical sensing applications, where corrosion-induced zero point drift of porous silicon-based sensor elements has historically been a significant problem. Prepared by the high temperature reaction of porous silicon with acetylene gas, the stability of this silicon carbide-like material also poses a challenge—many sensor applications require a functionalized surface, and the low reactivity of TCPSi has limited the ability to chemically modify its surface. This work presents a simple reaction to modify the surface of TCPSi with an alkyl carboxylate. The method involves radical coupling of a dicarboxylic acid (sebacic acid) to the TCPSi surface using a benzoyl peroxide initiator. The grafted carboxylic acid species provides a route for bioconjugate chemical modification, demonstrated in this work by coupling propylamine to the surface carboxylic acid group through the intermediacy of pentafluorophenol and 1-ethyl-3-[3-dimethylaminopropyl]carbodiimide hydrochloride (EDC). The stability of the carbonized porous Si surface, both before and after chemical modification, is tested in phosphate buffered saline solution and found to be superior to either hydrosilylated (with undecylenic acid) or thermally oxidized porous Si surfaces. PMID:20967329

  20. Inactivation of catalase by free radicals derived from oxygen via gamma radiolysis

    International Nuclear Information System (INIS)

    Malhaire, J.P.; Gardes-Albert, M.; Ferradini, C.; Sabourault, D.; Ribiere, C.

    1991-01-01

    The inactivation of catalase (10 -5 mol/l) by OH· or OH·/O 2 - · free radicals, at pH 7.4, has been investigated using γ radiolysis with doses up to 9000 Gy. Maxima initial G-values of catalase inactivation have been determined. These values are inferior to those of the free radicals OH· and O 2 - · produced by water radiolysis. Nevertheless, the presence of O 2 /O 2 - · enhances the inactivation due to OH· radicals. The general shape of the inactivation curves as a function of the radiation dose is biphasic: an initial rapid phase (from 0 to ∼ 500 Gy) followed by a slow phase (from ∼ 500 to 9000 Gy). The addition of H 2 O 2 at the beginning of irradiation decreases the inactivation yield by OH· radicals. This phenomenon could be due to the formation of compound-I (catalase-H 2 O 2 ) which would be less sensitive towards OH· radicals than catalase. In the presence of 0.1 mol/l ethanol, catalase (5 x 10 -6 mol/l) is not inactived by O 2 - · and RO 2 · (from ethanol) radicals for an irradiation dose of 2000 Gy, implying a complete protecting effect by ethanol [fr

  1. beta-Scission of C-3 (beta-carbon) alkoxyl radicals on peptides and proteins

    DEFF Research Database (Denmark)

    Headlam, H A; Mortimer, A; Easton, C J

    2000-01-01

    Exposure of proteins to radicals in the presence of O(2) brings about multiple changes in the target molecules. These alterations include oxidation of side chains, fragmentation, cross-linking, changes in hydrophobicity and conformation, altered susceptibility to proteolytic enzymes, and formation...... of methanal (formaldehyde). This product has been quantified with a number of oxidized peptides and proteins, and can account for up to 64% of the initial attacking radicals with some Ala peptides. When quantified together with the hydroperoxide precursors, these species account for up to 80% of the initial...... radicals, confirming that this is a major process. Methanal causes cell toxicity and DNA damage and is an animal carcinogen and a genotoxic agent in human cells. Thus, the formation and subsequent reaction of alkoxyl radicals formed at the C-3 position on aliphatic amino acid side chains on peptides...

  2. "'And They Lived Happily Ever After": The Fairy Tale of Radical Constructivism and Von Glasersfeld's Ethical Disengagement

    Science.gov (United States)

    d'Agnese, Vasco

    2015-01-01

    Is von Glasersfeld's constructivism actually radical? In this article, I respond to this question by analyzing von Glasersfeld's main works. I argue that the essential theoretical move of radical constructivism--namely the assertion that reality is the construction of a human mind that only responds to the subjective perception of "what…

  3. Preparation of poly(methyl methacrylate) grafted titanate nanotubes by in situ atom transfer radical polymerization

    International Nuclear Information System (INIS)

    Gao Yuan; Zhou Yongfeng; Yan Deyue; Gao Xueping

    2008-01-01

    This paper reports the successful preparation of core-shell hybrid nanocomposites by a 'grafting from' approach based on in situ atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) from titanate nanotubes (TNTs). Transmission electron microscope (TEM) images of the products provide direct evidence for the formation of a core-shell structure, possessing a hard core of TNTs and a soft shell of poly-MMA (PMMA). Fourier-transform infrared spectroscopy (FT-IR), hydrogen nuclear magnetic resonance ( 1 H NMR), scanning electron microscopy (SEM), and thermal gravimetric analysis (TGA) were used to determine the chemical structure, morphology, and the grafted PMMA quantities of the resulting products. The grafted PMMA content was well controlled and increased with increasing monomer/initiator ratio. Further copolymerization of hydroxyethyl methacrylate (HEMA) with PMMA-coated TNTs as initiators was realized, illustrating the 'living' characteristics of the ATRP method used in this paper.

  4. Direct plasma interaction with living tissue

    Science.gov (United States)

    Fridman, Gregory

    For some time, plasma has been used in medicine to cauterize or cut tissue using heat and mechanical energy. In the recent decade, some researchers around the world have started to investigate how gas jets that pass through thermal plasma can be employed in medicine. This thesis presents the first investigation of biomedical uses of non-thermal plasma discharge which comes in direct contact with living tissue. It is demonstrated that the direct application of non-thermal plasma in air can cause rapid deactivation of bacteria on surfaces of tissues without causing any visible tissue damage. Medical need for such a device is discussed. Construction and operation of various types of non-thermal plasma power supplies and many types of treatment electrodes are presented as well. Application of this plasma to living organisms is shown to be safe from both the electrical perspective and from the biological perspective. Biological safety is revealed through a series of differential skin toxicity trials on human cadaver tissue, live hairless mouse skin tissue, live pig skin tissue, and finally in an open wound model on pigs. Direct non-thermal plasma in air is shown to deactivate bacteria about 100 times faster than indirect application using jets. A series of experiments reveal that this effectiveness is due to the ability of direct discharge to bring charges to tissue surfaces. It is demonstrated that neither ultraviolet (UV) radiation nor neutral active species such as hydroxyl radicals or ozone produced in plasma are responsible for the main effect on bacteria. Although much additional work remains on establishing detailed mechanism by which charges from plasma achieve this effect, the work carried out in this thesis clearly demonstrates that direct application of non-thermal plasma in air can be a very useful tool in medicine.

  5. Measurements of hydroxyl and hydroperoxy radicals during CalNex-LA: Model comparisons and radical budgets

    Science.gov (United States)

    Griffith, S. M.; Hansen, R. F.; Dusanter, S.; Michoud, V.; Gilman, J. B.; Kuster, W. C.; Veres, P. R.; Graus, M.; de Gouw, J. A.; Roberts, J.; Young, C.; Washenfelder, R.; Brown, S. S.; Thalman, R.; Waxman, E.; Volkamer, R.; Tsai, C.; Stutz, J.; Flynn, J. H.; Grossberg, N.; Lefer, B.; Alvarez, S. L.; Rappenglueck, B.; Mielke, L. H.; Osthoff, H. D.; Stevens, P. S.

    2016-04-01

    Measurements of hydroxyl (OH) and hydroperoxy (HO2*) radical concentrations were made at the Pasadena ground site during the CalNex-LA 2010 campaign using the laser-induced fluorescence-fluorescence assay by gas expansion technique. The measured concentrations of OH and HO2* exhibited a distinct weekend effect, with higher radical concentrations observed on the weekends corresponding to lower levels of nitrogen oxides (NOx). The radical measurements were compared to results from a zero-dimensional model using the Regional Atmospheric Chemical Mechanism-2 constrained by NOx and other measured trace gases. The chemical model overpredicted measured OH concentrations during the weekends by a factor of approximately 1.4 ± 0.3 (1σ), but the agreement was better during the weekdays (ratio of 1.0 ± 0.2). Model predicted HO2* concentrations underpredicted by a factor of 1.3 ± 0.2 on the weekends, while measured weekday concentrations were underpredicted by a factor of 3.0 ± 0.5. However, increasing the modeled OH reactivity to match the measured total OH reactivity improved the overall agreement for both OH and HO2* on all days. A radical budget analysis suggests that photolysis of carbonyls and formaldehyde together accounted for approximately 40% of radical initiation with photolysis of nitrous acid accounting for 30% at the measurement height and ozone photolysis contributing less than 20%. An analysis of the ozone production sensitivity reveals that during the week, ozone production was limited by volatile organic compounds throughout the day during the campaign but NOx limited during the afternoon on the weekends.

  6. A Community-Level Initiative to Prevent Obesity: Results From Kaiser Permanente's Healthy Eating Active Living Zones Initiative in California.

    Science.gov (United States)

    Cheadle, Allen; Atiedu, Akpene; Rauzon, Suzanne; Schwartz, Pamela M; Keene, Laura; Davoudi, Mehrnaz; Spring, Rebecca; Molina, Michelle; Lee, Lynda; Boyle, Kathryn; Williamson, Dana; Steimberg, Clara; Tinajero, Roberta; Ravel, Jodi; Nudelman, Jean; Azuma, Andrea Misako; Kuo, Elena S; Solomon, Loel

    2018-05-01

    A growing number of health systems are leading health promotion efforts in their wider communities. What impact are these efforts having on health behaviors and ultimately health status? This paper presents evaluation results from the place-based Kaiser Permanente Healthy Eating Active Living Zones obesity prevention initiative, implemented in 2011-2015 in 12 low-income communities in Kaiser Permanente's Northern and Southern California Regions. The Healthy Eating Active Living Zones design targeted places and people through policy, environmental, and programmatic strategies. Each Healthy Eating Active Living Zone is a small, low-income community of 10,000 to 20,000 residents with high obesity rates and other health disparities. Community coalitions planned and implemented strategies in each community. A population-dose approach and pre and post surveys were used to assess impact of policy, program, and environmental change strategies; the analysis was conducted in 2016. Population dose is the product of reach (number of people affected by a strategy divided by target population size) and strength (the effect size or relative change in behavior for each person exposed to the strategy). More than 230 community change strategies were implemented over 3 years, encompassing policy, environmental, and programmatic changes as well as efforts to build community capacity to sustain strategies and make changes in the future. Positive population-level results were seen for higher-dose strategies, particularly those targeting youth physical activity. Higher-dose strategies were more likely to be found in communities with the longest duration of investment. These results demonstrate that strong (high-dose), community-based obesity prevention strategies can lead to improved health behaviors, particularly among youth in school settings. This article is part of a supplement entitled Building Thriving Communities Through Comprehensive Community Health Initiatives, which is

  7. Getting to know patients’ lived space

    DEFF Research Database (Denmark)

    Norlyk, Annelise; Martinsen, Bente; Dahlberg, Karen

    2013-01-01

    .g. the role of the good patient and the ambiance of hospitals. Home, on the other hand, offers familiar lived space in which patients feel protected and safe. Further, the paper relates patients’ experience of lived space to a phenomenological view of lived space in order to illustrate the radical influence...... as a theoretical framework for an excursive analysis. The paper demonstrates that existential dimensions of lived space at the hospital and at home differ significantly. For the patients, the hospital space means alien territory as opposed to the familiar territory of home. To some extent the experienced...

  8. Neuroprotection by Radical Avoidance: Search for Suitable Agents

    Directory of Open Access Journals (Sweden)

    Rüdiger Hardeland

    2009-12-01

    Full Text Available Neurodegeneration is frequently associated with damage by free radicals. However, increases in reactive oxygen and nitrogen species, which may ultimately lead to neuronal cell death, do not necessarily reflect its primary cause, but can be a consequence of otherwise induced cellular dysfunction. Detrimental processes which promote free radical formation are initiated, e.g., by disturbances in calcium homeostasis, mitochondrial malfunction, and an age-related decline in the circadian oscillator system. Free radicals generated at high rates under pathophysiological conditions are insufficiently detoxified by scavengers. Interventions at the primary causes of dysfunction, which avoid secondary rises in radical formation, may be more efficient. The aim of such approaches should be to prevent calcium overload, to reduce mitochondrial electron dissipation, to support electron transport capacity, and to avoid circadian perturbations. l-Theanine and several amphiphilic nitrones are capable of counteracting excitotoxicity and/or mitochondrial radical formation. Resveratrol seems to promote mitochondrial biogenesis. Mitochondrial effects of leptin include attenuation of electron leakage. Melatonin combines all the requirements mentioned, additionally regulates anti- and pro-oxidant enzymes and is, with few exceptions, very well tolerated. In this review, the perspectives, problems and limits of drugs are compared which may be suitable for reducing the formation of free radicals.

  9. Spin relaxation of radicals in cryptochrome and its role in avian magnetoreception

    Energy Technology Data Exchange (ETDEWEB)

    Worster, Susannah; Kattnig, Daniel R.; Hore, P. J., E-mail: peter.hore@chem.ox.ac.uk [Department of Chemistry, Physical and Theoretical Chemistry Laboratory, University of Oxford, South Parks Road, Oxford OX1 3QZ (United Kingdom)

    2016-07-21

    Long-lived spin coherence and rotationally ordered radical pairs have previously been identified as key requirements for the radical pair mechanism of the avian magnetic compass sense. Both criteria are hard to meet in a biological environment, where thermal motion of the radicals creates dynamic disorder and drives efficient spin relaxation. This has long been cited as a major stumbling block of the radical pair hypothesis. Here we combine Redfield relaxation theory with analytical solutions to a rotational diffusion equation to assess the impact of restricted rotational motion of the radicals on the operation of the compass. The effects of such motions are first investigated generally in small, model systems and are then critically examined in the magnetically sensitive flavin-tryptophan radical pair that is formed photochemically in the proposed magnetoreceptor protein, cryptochrome. We conclude that relaxation is slowest when rotational motion of the radicals within the protein is fast and highly constrained; that in a regime of slow relaxation, the motional averaging of hyperfine interactions has the potential to improve the sensitivity of the compass; and that consideration of motional effects can significantly alter the design criteria for an optimal compass. In addition, we demonstrate that motion of the flavin radical is likely to be compatible with its role as a component of a functioning radical-pair compass, whereas the motion of the tryptophan radical is less ideal, unless it is particularly fast.

  10. Radiation-induced radical ions in calcium sulfite

    Science.gov (United States)

    Bogushevich, S. E.

    2006-07-01

    We have used EPR to study the effect of γ radiation on calcium sulfite. We have observed and identified the radiation-induced radical ions SO 2 - (iso) with g = 2.0055 and SO 2 - (orth-1) with g1 = 2.0093, g2 = 2.0051, g3 = 2.0020, identical to the initial and thermally induced SO 2 - respectively, SO 3 - (iso) with g = 2.0031 and SO 3 - (axial) with g⊥ = 2.0040, g∥ = 2.0023, identical to mechanically induced SO 3 - . We have established the participation of radiation-induced radical ions SO 3 - in formation of post-radiation SO 2 - .

  11. Bacterial resistance of self-assembled surfaces using PPOm-b-PSBMAn zwitterionic copolymer - concomitant effects of surface topography and surface chemistry on attachment of live bacteria.

    Science.gov (United States)

    Hsiao, Sheng-Wen; Venault, Antoine; Yang, Hui-Shan; Chang, Yung

    2014-06-01

    Three well-defined diblock copolymers made of poly(sulfobetaine methacrylate) (poly(SBMA)) and poly(propylene oxide) (PPO) groups were synthesized by atom transfer radical polymerization (ATRP) method. They were physically adsorbed onto three types of surfaces having different topography, including smooth flat surface, convex surface, and indented surface. Chemical state of surfaces was characterized by XPS while the various topographies were examined by SEM and AFM. Hydrophilicity of surfaces was dependent on both the surface chemistry and the surface topography, suggesting that orientation of copolymer brushes can be tuned in the design of surfaces aimed at resisting bacterial attachment. Escherichia coli, Staphylococcus epidermidis, Streptococcus mutans and Escherichia coli with green fluorescent protein (E. coli GFP) were used in bacterial tests to assess the resistance to bacterial attachment of poly(SBMA)-covered surfaces. Results highlighted a drastic improvement of resistance to bacterial adhesion with the increasing of poly(SBMA) to PPO ratio, as well as an important effect of surface topography. The chemical effect was directly related to the length of the hydrophilic moieties. When longer, more water could be entrapped, leading to improved anti-bacterial properties. The physical effect impacted on the orientation of the copolymer brushes, as well as on the surface contact area available. Convex surfaces as well as indented surfaces wafer presented the best resistance to bacterial adhesion. Indeed, bacterial attachment was more importantly reduced on these surfaces compared with smooth surfaces. It was explained by the non-orthogonal orientation of copolymer brushes, resulting in a more efficient surface coverage of zwitterionic molecules. This work suggests that not only the control of surface chemistry is essential in the preparation of surfaces resisting bacterial attachment, but also the control of surface topography and orientation of antifouling

  12. Delocalization model of regioselectivity and reactivity of free radicals in reactions of addition to olefins

    International Nuclear Information System (INIS)

    Volovik, S.V.; Dyadyusha, G.G.; Staninets, V.I.

    1987-01-01

    On the basis of the concept of polarity (philicity) of free radicals as proposed by the authors, within the framework of methods of qualitative surfaces of potential energy (linear combinations of configurations of fragments) and stabilization energy, an effective model has been developed for the regioselectivity and reactivity of radicals in processes of addition. A critical examination is made of certain key aspects of the change in regiochemistry and reactivity with changes in the electronic structure of the free radical and substrate. The dominant trends in regioselectivity and reactivity in processes of free-radical addition to olefins are controlled by electronic effects and can be predicted by analyzing interactions of diabatic potential energy surfaces or orbital interactions for a system consisting of a free radical and an unsaturated substrate

  13. Free radical scavenging injectable hydrogels for regenerative therapy.

    Science.gov (United States)

    Komeri, Remya; Thankam, Finosh Gnanaprakasam; Muthu, Jayabalan

    2017-02-01

    Pathological free radicals generated from inflamed and infarcted cardiac tissues interferes natural tissue repair mechanisms. Hypoxic microenvironment at the injured zone of non-regenerating cardiac tissues hinders the therapeutic attempts including cell therapy. Here we report an injectable, cytocompatible, free radical scavenging synthetic hydrogel formulation for regenerative therapy. New hydrogel (PEAX-P) is prepared with D-xylitol-co-fumarate-co-poly ethylene adipate-co-PEG comaromer (PEAX) and PEGDiacrylate. PEAX-P hydrogel swells 4.9 times the initial weight and retains 100.07kPa Young modulus at equilibrium swelling, which is suitable for cardiac applications. PEAX-P hydrogel retains elastic nature even at 60% compressive strain, which is favorable to fit with the dynamic and elastic natural tissue counterparts. PEAX-P hydrogel scavenges 51% DPPH radical, 40% hydroxyl radicals 41% nitrate radicals with 31% reducing power. The presence of hydrogel protects 62% cardiomyoblast cells treated with stress inducing media at LD 50 concentration. The free hydroxyl groups in sugar alcohols of the comacromer influence the free radical scavenging. Comparatively, PEAX-P hydrogel based on xylitol evinces slightly lower scavenging characteristics than with previously reported PEAM-P hydrogel containing mannitol having more hydroxyl groups. The possible free radical scavenging mechanism of the present hydrogel relies on the free π electrons associated with uncrosslinked fumarate bonds, hydrogen atoms associated with sugar alcohols/PEG and radical dilution by free water in the matrix. Briefly, the present PEAX-P hydrogel is a potential injectable system for combined antioxidant and regenerative therapy. Copyright © 2016 Elsevier B.V. All rights reserved.

  14. Nitroxide free radical clearance in the live rat monitored by radio-frequency CW-EPR and PEDRI

    International Nuclear Information System (INIS)

    Alecci, Marcello; Seimenis, Ioannis; McCallum, Stephen J.; Lurie, David J.; Foster, Margaret A.

    1998-01-01

    The use of RF (100 to 300 MHz) PEDRI and CW-EPR techniques allows the in vivo study of large animals such as whole rats and rabbits. Recently a PEDRI instrument was modified to also allow CW-EPR spectroscopy with samples of similar size and under the same experimental conditions. In the present study, this CW-EPR and PEDRI apparatus was used to assess the feasibility of the detection of a pyrrolidine nitroxide free radical (2,2,5,5,-tetramethylpyrrolidine-1-oxyl-3-carboxylic acid, PCA) in the abdomen of rats. In particular, we have shown that after the PCA administration (4 mmol kg -1 b.w.): (i) the PCA EPR linewidth does not show line broadening due to concentration effects; (ii) a similar PCA up-take phase is observed by EPR and PEDRI; and (iii) the PCA half-lives in the whole abdomen of rats measured with the CW-EPR (T 1/2 =26±4 min, mean±sd, n=10) and PEDRI (T 1/2 =29±4 min, mean±sd, n=4) techniques were not significantly different (p>0.05). These results show, for the first time, that information about PCA pharmacokinetics obtained by CW-EPR is the same as that from PEDRI under the same experimental conditions. (author)

  15. Radicals in DNA as seen by ESR spectroscopy

    International Nuclear Information System (INIS)

    Symons, M.C.R.

    1997-01-01

    This is a review of ESR studies, mainly of DNA systems, after exposure to ionising radiation at low temperatures. Under this conditions 'direct' damage is of major significance, and ESR evidence for the concept of the initial formation of electron-gain and electron-loss centers localised within DNA bases, and deeply trapped by proton-gain and loss, will be discussed. It is stressed that 'negative' evidence, showing that various phosphate and sugar centred radicals are not detected, is of major importance since the ESR 'fingerprints' of base-radicals are relatively ill defined. (author)

  16. Investigation on the recombination kinetics of the pyrolytic free-radicals in the irradiated polyimide

    International Nuclear Information System (INIS)

    Sun Chengyue; Wu Yiyong; Yue Long; Shi Yaping; Xiao Jingdong

    2012-01-01

    Highlights: ► Free radicals behavior was exposure during the irradiation and anneal during the post storage. ► Both of the recombination and oxygen reaction affect the post-annealing evolution of free radicals. ► The activation energy and the surface reaction rate were calculated by the analysis of the free radical anneal process. - Abstract: The free radical behavior of 60 and 110 keV proton-irradiated polyimide were investigated using electron paramagnetic resonance measurements. The results indicate that during proton irradiation, a type of pyrolytic carbon free radical was formed with a g value of 2.0025. The radical population was found, after proton irradiation to decrease in a combination of an exponential and linear modes with an annealing time in the range of 50–120 °C. The exponential part indicated a radical recombination process while the linear part is due to the reaction of the radical with the ambient. Using the annealing results, the recombination activation energy of the radicals was determined as 12.4 ± 0.2 and 17.6 ± 0.2 kJ/mol for 60 and 110 keV irradiated polyimide, respectively, with a surface reaction rate of about 0.02/h. It is possible that the kinetic study presented here is used as one of the criteria for predicting the optical properties of polyimide material in spacecraft. The mechanism of the free radical evolution will be discussed in this paper.

  17. Investigation of the role of bicyclic peroxy radicals in the oxidation mechanism of toluene.

    Science.gov (United States)

    Birdsall, Adam W; Andreoni, John F; Elrod, Matthew J

    2010-10-07

    The products of the primary OH-initiated oxidation of toluene were investigated using the turbulent flow chemical ionization mass spectrometry technique under different oxygen, NO, and initial OH radical concentrations as well as a range of total pressures. The bicyclic peroxy radical intermediate, a key proposed intermediate species in the Master Chemical Mechanism (MCM) for the atmospheric oxidation of toluene, was detected for the first time. The toluene oxidation mechanism was shown to have a strong oxygen concentration dependence, presumably due to the central role of the bicyclic peroxy radical in determining the stable product distribution at atmospheric oxygen concentrations. The results also suggest a potential role for bicyclic peroxy radical + HO(2) reactions at high HO(2)/NO ratios. These reactions are postulated to be a source of the inconsistencies between environmental chamber results and predictions from the MCM.

  18. Surface treatment of glass substrates for the preparation of long-lived carbon stripper foils

    International Nuclear Information System (INIS)

    Takeuchi, Suehiro; Takekoshi, Eiko

    1981-02-01

    Glass substrates having uniformly distributed microscopic grains on the surfaces are useful to make long-lived carbon stripper foils for heavy ions. A method of surface treatment of glass substrates to form the surface structure is described. This method consists of precipitation of glass components, such as soda, onto the surfaces in a hot and humid atmosphere and a fogging treatment of forming microscopic grains of the precipitated substances. Some results of studies on the treatment conditions are also presented. (author)

  19. Radical fragmentation of six-membered oxygen-containing heterocycles

    International Nuclear Information System (INIS)

    Petryaev, E.P.; Kosobutskij, V.S.; Shadyro, O.I.

    1982-01-01

    Using chromatography, the composition and radiation-chemical yields of final products of desctruction of six-member saturated oxygen-containing heterocycles (the effect of #betta#-radiation on aqueous solutions of tetrahydropyran, 1,3-dioxane, 2,2 dimethyl-1,3 dioxane, 1,4-dioxane, paraldehyde) have been determined. It is established that the identified products are formed at the expense of decomposition of primary radicals of the initial compounds and point to the realization of the following fragmentation ways: 1) #betta#-scattering, 2) #betta#-scattering with a subsequent 1,5 migration of an H atom, 3) simultaneous rupture of two vicinal, relative to the radical center, bonds. A formation mechanism of the substances desctruction products is suggested. Material balance of the product yields of 1,3-dioxane radical synchronous decomposition is presented

  20. Free radical scavenging injectable hydrogels for regenerative therapy

    Energy Technology Data Exchange (ETDEWEB)

    Komeri, Remya [Sree Chitra Tirunal Institute for Medical Sciences and Technology, Polymer Science Division, BMT Wing, Thiruvananthapuram 695 012, Kerala State (India); Thankam, Finosh Gnanaprakasam [Dept. of Biomedical Sciences, Creighton University, 2500 California Plaza, Omaha NE68178 (United States); Muthu, Jayabalan, E-mail: mjayabalan52@gmail.com [Sree Chitra Tirunal Institute for Medical Sciences and Technology, Polymer Science Division, BMT Wing, Thiruvananthapuram 695 012, Kerala State (India)

    2017-02-01

    Pathological free radicals generated from inflamed and infarcted cardiac tissues interferes natural tissue repair mechanisms. Hypoxic microenvironment at the injured zone of non-regenerating cardiac tissues hinders the therapeutic attempts including cell therapy. Here we report an injectable, cytocompatible, free radical scavenging synthetic hydrogel formulation for regenerative therapy. New hydrogel (PEAX-P) is prepared with D-xylitol-co-fumarate-co-poly ethylene adipate-co-PEG comaromer (PEAX) and PEGDiacrylate. PEAX-P hydrogel swells 4.9 times the initial weight and retains 100.07 kPa Young modulus at equilibrium swelling, which is suitable for cardiac applications. PEAX-P hydrogel retains elastic nature even at 60% compressive strain, which is favorable to fit with the dynamic and elastic natural tissue counterparts. PEAX-P hydrogel scavenges 51% DPPH radical, 40% hydroxyl radicals 41% nitrate radicals with 31% reducing power. The presence of hydrogel protects 62% cardiomyoblast cells treated with stress inducing media at LD 50 concentration. The free hydroxyl groups in sugar alcohols of the comacromer influence the free radical scavenging. Comparatively, PEAX-P hydrogel based on xylitol evinces slightly lower scavenging characteristics than with previously reported PEAM-P hydrogel containing mannitol having more hydroxyl groups. The possible free radical scavenging mechanism of the present hydrogel relies on the free π electrons associated with uncrosslinked fumarate bonds, hydrogen atoms associated with sugar alcohols/PEG and radical dilution by free water in the matrix. Briefly, the present PEAX-P hydrogel is a potential injectable system for combined antioxidant and regenerative therapy. - Graphical abstract: Injectable hydrogel with inherent free radical scavenging property for regenerative tissue engineering application. - Highlights: • Novel injectable hydrogel (PEAX-P) is prepared using D-xylitol-co-fumarate-co-poly ethylene adipate-co-PEG comaromer

  1. Free radical scavenging injectable hydrogels for regenerative therapy

    International Nuclear Information System (INIS)

    Komeri, Remya; Thankam, Finosh Gnanaprakasam; Muthu, Jayabalan

    2017-01-01

    Pathological free radicals generated from inflamed and infarcted cardiac tissues interferes natural tissue repair mechanisms. Hypoxic microenvironment at the injured zone of non-regenerating cardiac tissues hinders the therapeutic attempts including cell therapy. Here we report an injectable, cytocompatible, free radical scavenging synthetic hydrogel formulation for regenerative therapy. New hydrogel (PEAX-P) is prepared with D-xylitol-co-fumarate-co-poly ethylene adipate-co-PEG comaromer (PEAX) and PEGDiacrylate. PEAX-P hydrogel swells 4.9 times the initial weight and retains 100.07 kPa Young modulus at equilibrium swelling, which is suitable for cardiac applications. PEAX-P hydrogel retains elastic nature even at 60% compressive strain, which is favorable to fit with the dynamic and elastic natural tissue counterparts. PEAX-P hydrogel scavenges 51% DPPH radical, 40% hydroxyl radicals 41% nitrate radicals with 31% reducing power. The presence of hydrogel protects 62% cardiomyoblast cells treated with stress inducing media at LD 50 concentration. The free hydroxyl groups in sugar alcohols of the comacromer influence the free radical scavenging. Comparatively, PEAX-P hydrogel based on xylitol evinces slightly lower scavenging characteristics than with previously reported PEAM-P hydrogel containing mannitol having more hydroxyl groups. The possible free radical scavenging mechanism of the present hydrogel relies on the free π electrons associated with uncrosslinked fumarate bonds, hydrogen atoms associated with sugar alcohols/PEG and radical dilution by free water in the matrix. Briefly, the present PEAX-P hydrogel is a potential injectable system for combined antioxidant and regenerative therapy. - Graphical abstract: Injectable hydrogel with inherent free radical scavenging property for regenerative tissue engineering application. - Highlights: • Novel injectable hydrogel (PEAX-P) is prepared using D-xylitol-co-fumarate-co-poly ethylene adipate-co-PEG comaromer

  2. Hydroxyl-radical-induced oxidation of cyclic dipeptides: Reactions of free peptide radicals and their peroxyl radicals

    International Nuclear Information System (INIS)

    Mieden, O.J.

    1989-01-01

    In the course of this study investigations were carried out into the reactions of hydroxyl radicals and hydrogen atoms with cyclic dipeptides as well as the subsequent reactions of peptide radicals and their peroxyl radicals in aqueous solution. The radiolysis products formed in the absence and presence of oxygen or transient metal complexes were characterized and determined on a quantitative basis. The linking of information from product analyses to the kinetic data for transient species obtained by time-resolving UV/VIS and conductivity measurements (pulse radiolysis) as well as computer-assisted simulations of individual events during the reaction permitted an evaluation of the mechanisms underlying the various processes and an identification of interim products with short life-times, which did or did not belong to the group of radicals. Through the characterization of key reactions of radicals and peroxyl radicals of this substance class a major advance has been made towards a better understanding of the role of radicals in the peptide compound and the mechanisms involved in indirect radiation effects on long-chain peptides and proteins. (orig.) [de

  3. Lateral Trunk Surface as a new parameter to estimate live body weight by Visual Image Analysis

    Directory of Open Access Journals (Sweden)

    S. Terramoccia

    2010-02-01

    Full Text Available Live weight of 74 milking Mediterranean buffaloes (Bubalus bubalis L. have been estimated by Visual Image Analysis. The total surface of lateral profile, tested in previous researches with viable result, was substituted by the measurement of the Lateral Trunk Surface (LTrS. The measurements were recorded by a camera equipped by a laser distance recorder and data were elaborated by a specific software. This parameter, eliminating the surface of neck, head and legs, that are less easily measurable, simplified and accelerated the procedure. Correlation between LTrS and live weight was r = 0.90 (P < 0.01. A significant equation (P < 0.01 was obtained from the recorded data of a random sample of 38 buffaloes. When the validation of the equation was tested on the other 36 subjects, the estimated live weight had a mean of 691.74 kg ± 68.55. This was corresponding to a 1.08% overestimation of the real weight.

  4. Quantification of Radicals Generated in a Sonicator

    Directory of Open Access Journals (Sweden)

    Kassim Badmus

    2016-06-01

    Full Text Available The hydroxyl radical (OH• is a powerful oxidant produced as a consequence of cavitation in water. It can react nonspecifically in breaking down persistent organic pollutants in water into their mineral form. It can also recombine to form hydrogen peroxide which is very useful in water treatment. In this study, terephthalic acid (TA and potassium iodide dosimetry were used to quantify and investigate the behaviour of the generated OH radical in a laboratory scale sonicator. The 2-hydroxyl terephthalic acid (HTA formed during terephthalic acid dosimetry was determined by optical fibre spectrometer. The production rate of HTA served as a means of evaluating and characterizing the OH• generated over given time in a sonicator. The influence of sonicator power intensity, solution pH and irradiation time upon OH• generation were investigated. Approximately 2.2 ´ 10-9 M s-1 of OH radical was generated during the sonication process. The rate of generation of the OH radicals was established to be independent of the concentration of the initial reactant. Thus, the rate of generation of OH• can be predicted by zero order kinetics in a sonicator.

  5. Radicalization In Pakistan And The Spread Of Radical Islam In Pakistan

    Directory of Open Access Journals (Sweden)

    Bahir ahmad

    2015-08-01

    Full Text Available ABSTRACT It is pertinent to mention that radicalism is not intrinsic to Islam and radical interpretations of the religion or for that matter may occur within any way of life and religion Saikal 2003 and yet the question remains as to why Muslims in certain geographical regions have more radical approaches towards their religion and also that what are the causes of such radicalization. Becoming a radical Muslim is not even a matter of a day nor is it a sudden process. There are several reasons behind making a person radical peaceful angry smiling or tolerant. For knowing the reason behind radicalization or radicals persons one has to understand the causes. Tracing these causes is one of the ways to eliminate such behavior. The first step in the elimination of the radical sentiments in a person is to develop peace in his personality Fair Malhotra amp Shapiro 2010. The chapter which has been addressed here is going to shed light on the roots and symptoms of the radicalism. There will be a brief discussion on how the roots of radicalism can be traced and can be eliminated. The assessment and discussion will be conducted on the parameters of the economy media politics and theology from social cultural point of view. According to the analysis of Ahrari 2000 political factor is one of the major and direct factors which have resulted in causing of the radicalism. These factors however intertwine with one another. Radical actions cannot take place only because of the political factors.

  6. Patterning of gold substrates by surface-initiated polymerization

    Energy Technology Data Exchange (ETDEWEB)

    Dyer, D.J. [Department of Chemistry and Biochemistry, Southern Illinois University, Carbondale, IL 62901-4409 (United States)

    2003-09-01

    The design and synthesis of durable and functional organic coatings is an important topic in contemporary polymer science. The well-defined patterning of inorganic substrates is highlighted with an emphasis on planar gold. New advances in contact printing and surface initiated polymerization promise unprecedented control of the polymer architecture in the micrometer and nanometer range. (Abstract Copyright [2003], Wiley Periodicals, Inc.)

  7. Chemical determination of free radical-induced damage to DNA.

    Science.gov (United States)

    Dizdaroglu, M

    1991-01-01

    Free radical-induced damage to DNA in vivo can result in deleterious biological consequences such as the initiation and promotion of cancer. Chemical characterization and quantitation of such DNA damage is essential for an understanding of its biological consequences and cellular repair. Methodologies incorporating the technique of gas chromatography/mass spectrometry (GC/MS) have been developed in recent years for measurement of free radical-induced DNA damage. The use of GC/MS with selected-ion monitoring (SIM) facilitates unequivocal identification and quantitation of a large number of products of all four DNA bases produced in DNA by reactions with hydroxyl radical, hydrated electron, and H atom. Hydroxyl radical-induced DNA-protein cross-links in mammalian chromatin, and products of the sugar moiety in DNA are also unequivocally identified and quantitated. The sensitivity and selectivity of the GC/MS-SIM technique enables the measurement of DNA base products even in isolated mammalian chromatin without the necessity of first isolating DNA, and despite the presence of histones. Recent results reviewed in this article demonstrate the usefulness of the GC/MS technique for chemical determination of free radical-induced DNA damage in DNA as well as in mammalian chromatin under a vast variety of conditions of free radical production.

  8. In vitro free radical scavenging activity of platinum nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Watanabe, Aki; Kajita, Masashi; Kim, Juewon; Kanayama, Atsuhiro; Miyamoto, Yusei [Department of Integrated Biosciences, Graduate School of Frontier Sciences, University of Tokyo, Bioscience Building 402, 5-1-5 Kashiwanoha, Kashiwa, Chiba 277-8562 (Japan); Takahashi, Kyoko; Mashino, Tadahiko, E-mail: yusei74@k.u-tokyo.ac.j [Department of Pharmaceutical Sciences, Faculty of Pharmacy, Keio University, 1-5-30 Shibakoen, Minato, Tokyo 105-8512 (Japan)

    2009-11-11

    A polyacrylic acid (PAA)-protected platinum nanoparticle species (PAA-Pt) was prepared by alcohol reduction of hexachloroplatinate. The PAA-Pt nanoparticles were well dispersed and homogeneous in size with an average diameter of 2.0 {+-} 0.4 nm (n = 200). We used electron spin resonance to quantify the residual peroxyl radical AOO. generated from 2,2-azobis (2-aminopropane) dihydrochloride (AAPH) by thermal decomposition in the presence of O{sub 2} and a spectrophotometric method to quantify the residual 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical. PAA-Pt scavenged these two radicals in a dose-dependent manner. Platinum was the functional component. PAA-Pt reduced the rate of oxygen consumption required for linoleic acid peroxidation initiated by AOO. generated from AAPH, indicating inhibition of the propagation of linolate peroxidation. A thiobarbituric acid test also revealed dose-dependent inhibition of the linolate peroxidation by PAA-Pt. Fifty micromolar platinum, as PAA-Pt, completely quenched 250 {mu}M DPPH radical for 5 min. Even when twice diluted in half, the PAA-Pt still quenched 100% of the 250 {mu}M DPPH radical. The scavenging activity of PAA-Pt is durable. These observations suggest that PAA-Pt is an efficient scavenger of free radicals.

  9. Social determinants of health in Canada: Are healthy living initiatives there yet? A policy analysis

    Directory of Open Access Journals (Sweden)

    Gore Dana

    2012-08-01

    Full Text Available Abstract Introduction Preventative strategies that focus on addressing the social determinants of health to improve healthy eating and physical activity have become an important strategy in British Columbia and Ontario for combating chronic diseases. What has not yet been examined is the extent to which healthy living initiatives implemented under these new policy frameworks successfully engage with and change the social determinants of health. Methods Initiatives active between January 1, 2006 and September 1, 2011 were found using provincial policy documents, web searches, health organization and government websites, and databases of initiatives that attempted to influence to nutrition and physical activity in order to prevent chronic diseases or improve overall health. Initiatives were reviewed, analyzed and grouped using the descriptive codes: lifestyle-based, environment-based or structure-based. Initiatives were also classified according to the mechanism by which they were administered: as direct programs (e.g. directly delivered, blueprints (or frameworks to tailor developed programs, and building blocks (resources to develop programs. Results 60 initiatives were identified in Ontario and 61 were identified in British Columbia. In British Columbia, 11.5% of initiatives were structure-based. In Ontario, of 60 provincial initiatives identified, 15% were structure-based. Ontario had a higher proportion of direct interventions than British Columbia for all intervention types. However, in both provinces, as the intervention became more upstream and attempted to target the social determinants of health more directly, the level of direct support for the intervention lessened. Conclusions The paucity of initiatives in British Columbia and Ontario that address healthy eating and active living through action on the social determinants of health is problematic. In the context of Canada's increasingly neoliberal political and economic policy, the

  10. Catalase expression is modulated by vancomycin and ciprofloxacin and influences the formation of free radicals in Staphylococcus aureus cultures

    DEFF Research Database (Denmark)

    Wang, Ying; Hougaard, Anni Bygvrå; Paulander, Wilhelm Erik Axel

    2015-01-01

    Detection of free radicals in biological systems is challenging due to their short half-lives. We have applied electron spin resonance (ESR) spectroscopy combined with spin traps using the probes PBN (N-tert-butyl-α-phenylnitrone) and DMPO (5,5-dimethyl-1-pyrroline N-oxide) to assess free radical...... that in S. aureus, bactericidal antibiotics modulate catalase expression, which in turn influences the formation of free radicals in the surrounding broth medium. If similar regulation is found in other bacterial species, it might explain why bactericidal antibiotics are perceived as inducing formation...... of free radicals....

  11. Triplet state and semiquinone free radical of 5-methoxyquinizarin : a laser flash photolysis and pulse radiolysis study

    International Nuclear Information System (INIS)

    Pal, H.; Patil, D.K.; Mukherjee, T.; Mittal, J.P.

    1992-01-01

    The triplet(T) state properties like T-T absorption spectra, quantum yield, energy level and decay kinetics of 5-methoxyquinizarin (5-methoxy-1, 4-dihydroxy-9, 10-anthraquinone; MQZ) have been investigated in cyclohexane, acetonitrile and isopropyl alcohol using nanosecond laser flash photolysis technique. In isopropylalcohol, a neutral semiquinone radical is also formed which has been characterised by comparing the long lived transient spectra with the MQZ-semiquinone spectra obtained by pulse radiolysis of MQZ in the same solvent. A relatively small amount of a long lived transient formed in cyclohexane and acetonitrile, along with the triplet state of MQZ, could not be characterised unambiguously, but has been attributed to the semiquinone radical of MQZ, produced by the reaction of the excited states of the quinone with the solvent. The quantum yield of the semiquinone radical in isopropyl alcohol is considerably higher than the triplet quantum yield, showing that both the excited singlet and the triplet states of the quinone probably react with the solvent molecules to form the semiquinone radical. The photophysical properties of the triplet and the semiquinone radical of MQZ have been compared with those of simple 1,4-disubstituted anthraquinones. (author). 23 refs., 5 figs., 1 tab

  12. Fluorophore-based sensor for oxygen radicals in processing plasmas

    International Nuclear Information System (INIS)

    Choudhury, Faraz A.; Shohet, J. Leon; Sabat, Grzegorz; Sussman, Michael R.; Nishi, Yoshio

    2015-01-01

    A high concentration of radicals is present in many processing plasmas, which affects the processing conditions and the properties of materials exposed to the plasma. Determining the types and concentrations of free radicals present in the plasma is critical in order to determine their effects on the materials being processed. Current methods for detecting free radicals in a plasma require multiple expensive and bulky instruments, complex setups, and often, modifications to the plasma reactor. This work presents a simple technique that detects reactive-oxygen radicals incident on a surface from a plasma. The measurements are made using a fluorophore dye that is commonly used in biological and cellular systems for assay labeling in liquids. Using fluorometric analysis, it was found that the fluorophore reacts with oxygen radicals incident from the plasma, which is indicated by degradation of its fluorescence. As plasma power was increased, the quenching of the fluorescence significantly increased. Both immobilized and nonimmobilized fluorophore dyes were used and the results indicate that both states function effectively under vacuum conditions. The reaction mechanism is very similar to that of the liquid dye

  13. Fluorophore-based sensor for oxygen radicals in processing plasmas

    Energy Technology Data Exchange (ETDEWEB)

    Choudhury, Faraz A.; Shohet, J. Leon, E-mail: shohet@engr.wisc.edu [Plasma Processing and Technology Laboratory and Department of Electrical and Computer Engineering, University of Wisconsin-Madison, Madison, Wisconsin 53706 (United States); Sabat, Grzegorz; Sussman, Michael R. [Department of Biochemistry, University of Wisconsin-Madison, Madison, Wisconsin 53706 (United States); Nishi, Yoshio [Department of Electrical Engineering, Stanford University, Stanford, California 94305 (United States)

    2015-11-15

    A high concentration of radicals is present in many processing plasmas, which affects the processing conditions and the properties of materials exposed to the plasma. Determining the types and concentrations of free radicals present in the plasma is critical in order to determine their effects on the materials being processed. Current methods for detecting free radicals in a plasma require multiple expensive and bulky instruments, complex setups, and often, modifications to the plasma reactor. This work presents a simple technique that detects reactive-oxygen radicals incident on a surface from a plasma. The measurements are made using a fluorophore dye that is commonly used in biological and cellular systems for assay labeling in liquids. Using fluorometric analysis, it was found that the fluorophore reacts with oxygen radicals incident from the plasma, which is indicated by degradation of its fluorescence. As plasma power was increased, the quenching of the fluorescence significantly increased. Both immobilized and nonimmobilized fluorophore dyes were used and the results indicate that both states function effectively under vacuum conditions. The reaction mechanism is very similar to that of the liquid dye.

  14. Predicting tropospheric ozone and hydroxyl radical in a global, three-dimensional, chemistry, transport, and deposition model

    Energy Technology Data Exchange (ETDEWEB)

    Atherton, C.S.

    1995-01-05

    Two of the most important chemically reactive tropospheric gases are ozone (O{sub 3}) and the hydroxyl radical (OH). Although ozone in the stratosphere is a necessary protector against the sun`s radiation, tropospheric ozone is actually a pollutant which damages materials and vegetation, acts as a respiratory irritant, and is a greenhouse gas. One of the two main sources of ozone in the troposphere is photochemical production. The photochemistry is initiated when hydrocarbons and carbon monoxide (CO) react with nitrogen oxides (NO{sub x} = NO + NO{sub 2}) in the presence of sunlight. Reaction with the hydroxyl radical, OH, is the main sink for many tropospheric gases. The hydroxyl radical is highly reactive and has a lifetime on the order of seconds. Its formation is initiated by the photolysis of tropospheric ozone. Tropospheric chemistry involves a complex, non-linear set of chemical reactions between atmospheric species that vary substantially in time and space. To model these and other species on a global scale requires the use of a global, three-dimensional chemistry, transport, and deposition (CTD) model. In this work, I developed two such three dimensional CTD models. The first model incorporated the chemistry necessary to model tropospheric ozone production from the reactions of nitrogen oxides with carbon monoxide (CO) and methane (CH{sub 4}). The second also included longer-lived alkane species and the biogenic hydrocarbon isoprene, which is emitted by growing plants and trees. The models` ability to predict a number of key variables (including the concentration of O{sub 3}, OH, and other species) were evaluated. Then, several scenarios were simulated to understand the change in the chemistry of the troposphere since preindustrial times and the role of anthropogenic NO{sub x} on present day conditions.

  15. Iodine-catalyzed diazo activation to access radical reactivity.

    Science.gov (United States)

    Li, Pan; Zhao, Jingjing; Shi, Lijun; Wang, Jin; Shi, Xiaodong; Li, Fuwei

    2018-05-17

    Transition-metal-catalyzed diazo activation is a classical way to generate metal carbene, which are valuable intermediates in synthetic organic chemistry. An alternative iodine-catalyzed diazo activation is disclosed herein under either photo-initiated or thermal-initiated conditions, which represents an approach to enable carbene radical reactivity. This metal-free diazo activation strategy were successfully applied into olefin cyclopropanation and epoxidation, and applying this method to pyrrole synthesis under thermal-initiated conditions further demonstrates the unique reactivity using this method over typical metal-catalyzed conditions.

  16. Insight into the Reaction Mechanism of Graphene Oxide with Oxidative Free Radical

    Institute of Scientific and Technical Information of China (English)

    ZHOU Xuejiao; XU Liangyou

    2017-01-01

    Graphene oxide(GO),as an important derivative of graphene,could be considered as a super aromatic molecule decorated with a range of reactive oxygen-containing groups on its surface,which endows graphene high reactivity with other molecules.In our previous work,we demonstrated that GO sheets were cut into small pieces(graphene quantum dots,GQDs) by oxidative free radicals(hydroxyl radical HO or oxygen radical [O]) under UV irradiation.It is notable that reactions involving free radicals are influenced by reaction conditions pronouncedly.However,researches on details about reactions of GO with free radicals have not been reported thus far.In this work,the effects of different factors on the photo-Fenton reaction of GO were studied.It is demonstrated that the reaction rate is closely related to the concentration of free radicals.It is speculated that through the optimization of reaction conditions,the reaction of graphene with free radicals could carry out efficiently for further applications.

  17. Radiation-curing of acrylate composites including carbon fibres: A customized surface modification for improving mechanical performances

    International Nuclear Information System (INIS)

    Martin, Arnaud; Pietras-Ozga, Dorota; Ponsaud, Philippe; Kowandy, Christelle; Barczak, Mariusz; Defoort, Brigitte; Coqueret, Xavier

    2014-01-01

    The lower transverse mechanical properties of radiation-cured acrylate-based composites reinforced with carbon-fibre with respect to the thermosettable analogues was investigated from the viewpoint of chemical interactions at the interface between the matrix and the carbon material. XPS analysis of representative commercial carbon fibres revealed the presence of a significant amount of chemical functions potentially exerting an adverse effect on the initiation and propagation of the free radical polymerization initiated under high energy radiation. The EB-induced polymerization of n-butyl acrylate as a simple model monomer was conducted in the presence of various aromatic additives exhibiting a strong inhibiting effect, whereas thiols efficiently sensitize the initiation mechanism and undergo transfer reactions. A method based on the surface modification of sized fibres by thiomalic acid is proposed for overcoming the localized inhibition phenomenon and for improving the mechanical properties of the resulting acrylate-based composites. - Highlights: • Surface functions of C-fibres are analyzed for their effect on radical reaction. • Irradiation of nBu-acrylate in presence of aromatic additives reveals inhibition. • Thiol groups sensitize the radiation-initiated polymerization of nBu-acrylate. • Modification of C-fibres with thiomalic acid enhances composite properties

  18. Enzymatic shaving of the tegument surface of live schistosomes for proteomic analysis: a rational approach to select vaccine candidates.

    Directory of Open Access Journals (Sweden)

    William Castro-Borges

    2011-03-01

    Full Text Available The membrane-associated and membrane-spanning constituents of the Schistosoma mansoni tegument surface, the parasite's principal interface with the host bloodstream, have recently been characterized using proteomic techniques. Biotinylation of live worms using membrane-impermeant probes revealed that only a small subset of the proteins was accessible to the reagents. Their position within the multilayered architecture of the surface has not been ascertained.An enzymatic shaving approach on live worms has now been used to release the most accessible components, for analysis by MS/MS. Treatment with trypsin, or phosphatidylinositol-specific phospholipase C (PiPLC, only minimally impaired membrane integrity. PiPLC-enriched proteins were distinguished from those released in parasite vomitus or by handling damage, using isobaric tagging. Trypsin released five membrane proteins, Sm200, Sm25 and three annexins, plus host CD44 and the complement factors C3 and C4. Nutrient transporters and ion channels were absent from the trypsin fraction, suggesting a deeper location in the surface complex; surprisingly, two BAR-domain containing proteins were released. Seven parasite and two host proteins were enriched by PiPLC treatment, the vaccine candidate Sm29 being the most prominent along with two orthologues of human CD59, potentially inhibitors of complement fixation. The enzymes carbonic anhydrase and APD-ribosyl cyclase were also enriched, plus Sm200 and alkaline phosphatase. Host GPI-anchored proteins CD48 and CD90, suggest 'surface painting' during worm peregrination in the portal system.Our findings suggest that the membranocalyx secreted over the tegument surface is not the inert barrier previously proposed, some tegument proteins being externally accessible to enzymes and thus potentially located within it. Furthermore, the detection of C3 and C4 indicates that the complement cascade is initiated, while two CD59 orthologues suggest a potential

  19. Effect of irregularity on torsional surface waves in an initially ...

    Indian Academy of Sciences (India)

    initially stressed anisotropic porous layer sandwiched between ... layer under a rigid boundary and lying over an ..... surface is flat, the above boundary condition reduces to ..... Gubbins D 1990 Seismology and plate tectonics; Cambridge.

  20. Oxidation of free, peptide and protein tryptophan residues mediated by AAPH-derived free radicals: role of alkoxyl and peroxyl radicals

    DEFF Research Database (Denmark)

    Fuentes-Lemus, E.; Dorta, E.; Escobar, E.

    2016-01-01

    The oxidation of tryptophan (Trp) residues, mediated by peroxyl radicals (ROOc), follows a complex mechanism involving free radical intermediates, and short chain reactions. The reactivity of Trp towards ROOc should be strongly affected by its inclusion in peptides and proteins. To examine...... the latter, we investigated (by fluorescence) the kinetic of the consumption of free, peptide- and protein-Trp residues towards AAPH (2,20 -azobis(2-amidinopropane)dihydrochloride)-derived free radicals. Interestingly, the initial consumption rates (Ri ) were only slightly influenced by the inclusion of Trp...... concentrations (10–50 mM), the values of Ri were nearly constant; and at high Trp concentrations (50 mM to 1 mM), a slower increase of Ri than expected for chain reactions. Similar behavior was detected for all three systems (free Trp, and Trp in peptides and proteins). For the first time we are showing...

  1. Aerosol Fragmentation Driven by Coupling of Acid-Base and Free-Radical Chemistry in the Heterogeneous Oxidation of Aqueous Citric Acid by OH Radicals.

    Science.gov (United States)

    Liu, Matthew J; Wiegel, Aaron A; Wilson, Kevin R; Houle, Frances A

    2017-08-10

    A key uncertainty in the heterogeneous oxidation of carboxylic acids by hydroxyl radicals (OH) in aqueous-phase aerosol is how the free-radical reaction pathways might be altered by acid-base chemistry. In particular, if acid-base reactions occur concurrently with acyloxy radical formation and unimolecular decomposition of alkoxy radicals, there is a possibility that differences in reaction pathways impact the partitioning of organic carbon between the gas and aqueous phases. To examine these questions, a kinetic model is developed for the OH-initiated oxidation of citric acid aerosol at high relative humidity. The reaction scheme, containing both free-radical and acid-base elementary reaction steps with physically validated rate coefficients, accurately predicts the experimentally observed molecular composition, particle size, and average elemental composition of the aerosol upon oxidation. The difference between the two reaction channels centers on the reactivity of carboxylic acid groups. Free-radical reactions mainly add functional groups to the carbon skeleton of neutral citric acid, because carboxylic acid moieties deactivate the unimolecular fragmentation of alkoxy radicals. In contrast, the conjugate carboxylate groups originating from acid-base equilibria activate both acyloxy radical formation and carbon-carbon bond scission of alkoxy radicals, leading to the formation of low molecular weight, highly oxidized products such as oxalic and mesoxalic acid. Subsequent hydration of carbonyl groups in the oxidized products increases the aerosol hygroscopicity and accelerates the substantial water uptake and volume growth that accompany oxidation. These results frame the oxidative lifecycle of atmospheric aerosol: it is governed by feedbacks between reactions that first increase the particle oxidation state, then eventually promote water uptake and acid-base chemistry. When coupled to free-radical reactions, acid-base channels lead to formation of low molecular

  2. Effects of natural water constituents on the photo-decomposition of methylmercury and the role of hydroxyl radical

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Moon-Kyung; Zoh, Kyung-Duk, E-mail: zohkd@snu.ac.kr

    2013-04-01

    Photo-decomposition of methylmercury (MeHg) in surface water is thought to be an important process that reduces the bioavailability of mercury (Hg) to aquatic organisms. In this study, photo-initiated decomposition of MeHg was investigated under UVA irradiation in the presence of natural water constituents including NO{sub 3}{sup −}, Fe{sup 3+}, and HCO{sub 3}{sup −} ions, and dissolved organic matter such as humic and fulvic acid. MeHg degradation followed the pseudo-first-order kinetics; the rate constant increased with increasing UVA intensity (0.3 to 3.0 mW cm{sup −2}). In the presence of NO{sub 3}{sup −}, Fe{sup 3+}, and fulvic acid, the decomposition rate of MeHg increased significantly due to photosensitization by reactive species such as hydroxyl radical. The presence of humic acid and HCO{sub 3}{sup −} ions lowered the degradation rate through a radical scavenging effect. Increasing the pH of the solution increased the degradation rate constant by enhancing the generation of hydroxyl radicals. Hydroxyl radicals play an important role in the photo-decomposition of MeHg in water, and natural constituents in water can affect the photo-decomposition of MeHg by changing radical production and inhibition. - Highlights: ► The abiotic photodecomposition of methylmercury (MeHg) in water was examined. ► UVA light is a primary factor inducing MeHg photodecomposition in water. ► Fulvic acid, NO{sub 3}{sup −}, and Fe{sup 3+} ion increased MeHg photo-decomposition rate significantly. ► Humic acid and HCO{sub 3}{sup −} ions inhibited photodecomposition through radical scavenging. ► OH radical is an important compound affecting photodecomposition of MeHg in water.

  3. Allergy, living and learning

    DEFF Research Database (Denmark)

    Chivato, T; Valovirta, E; Dahl, R

    2012-01-01

    Allergy Living and Learning (ALL) is a European initiative designed to increase knowledge and understanding of people living with allergies in order to improve respiratory allergy care.......Allergy Living and Learning (ALL) is a European initiative designed to increase knowledge and understanding of people living with allergies in order to improve respiratory allergy care....

  4. Manipulating radicals: Using cobalt to steer radical reactions

    OpenAIRE

    Chirilă, A.

    2017-01-01

    This thesis describes research aimed at understanding and exploiting metallo-radical reactivity and explores reactions mediated by square planar, low-spin cobalt(II) complexes. A primary goal was to uncover novel reactivity of discrete cobalt(III)-bound carbene radicals generated upon reaction of the cobalt(II) catalysts with carbene precursors. Another important goal was to replace cobalt(II)-porphyrin catalysts with cheaper and easier to prepare metallo-radical analogues. Therefore the cata...

  5. Polarized proton spin density images the tyrosyl radical locations in bovine liver catalase

    Directory of Open Access Journals (Sweden)

    Oliver Zimmer

    2016-09-01

    Full Text Available A tyrosyl radical, as part of the amino acid chain of bovine liver catalase, supports dynamic proton spin polarization (DNP. Finding the position of the tyrosyl radical within the macromolecule relies on the accumulation of proton polarization close to it, which is readily observed by polarized neutron scattering. The nuclear scattering amplitude due to the polarization of protons less than 10 Å distant from the tyrosyl radical is ten times larger than the amplitude of magnetic neutron scattering from an unpaired polarized electron of the same radical. The direction of DNP was inverted every 5 s, and the initial evolution of the intensity of polarized neutron scattering after each inversion was used to identify those tyrosines which have assumed a radical state. Three radical sites, all of them close to the molecular centre and the haem, appear to be equally possible. Among these is tyr-369, the radical state of which had previously been proven by electron paramagnetic resonance.

  6. The Nanoconfined Free Radical Polymerization: Reaction Kinetics and Thermodynamics

    Science.gov (United States)

    Zhao, Haoyu; Simon, Sindee

    The reaction kinetics and thermodynamics of nanoconfined free radical polymerizations are investigated for methyl methacrylate (MMA) and ethyl methacrylate (EMA) monomers using differential scanning calorimetry. Controlled pore glass is used as the confinement medium with pore diameters as small as 7.5 nm; the influence of both hydrophobic (silanized such that trimethylsilyl groups cover the surface) and hydrophilic (native silanol) surfaces is investigated. Propagation rates increase when monomers are reacted in the hydrophilic pores presumably due to the specific interactions between the carbonyl and silanol groups; however, the more flexible EMA monomer shows weaker effects. On the other hand, initial rates of polymerization in hydrophobic pores are unchanged from the bulk. In both pores, the onset of autoacceleration occurs earlier due to the reduced diffusivity of confined chains, which may be compensated at high temperatures. In addition to changes in kinetics, the reaction thermodynamics can be affected under nanoconfinement. Specifically, the ceiling temperature (Tc) is shifted to lower temperatures in nanopores, with pore surface chemistry showing no significant effects; the equilibrium conversion is also reduced at high temperatures below Tc. These observations are attributed to a larger negative change in entropy on propagation for the confined system, with the MMA system again showing greater effects. Funding from ACS PRF is gratefully acknowledged.

  7. Watson-Crick Base Pair Radical Cation as a Model for Oxidative Damage in DNA.

    Science.gov (United States)

    Feketeová, Linda; Chan, Bun; Khairallah, George N; Steinmetz, Vincent; Maitre, Philippe; Radom, Leo; O'Hair, Richard A J

    2017-07-06

    The deleterious cellular effects of ionizing radiation are well-known, but the mechanisms causing DNA damage are poorly understood. The accepted molecular events involve initial oxidation and deprotonation at guanine sites, triggering hydrogen atom abstraction reactions from the sugar moieties, causing DNA strand breaks. Probing the chemistry of the initially formed radical cation has been challenging. Here, we generate, spectroscopically characterize, and examine the reactivity of the Watson-Crick nucleobase pair radical cation in the gas phase. We observe rich chemistry, including proton transfer between the bases and propagation of the radical site in deoxyguanosine from the base to the sugar, thus rupturing the sugar. This first example of a gas-phase model system providing molecular-level details on the chemistry of an ionized DNA base pair paves the way toward a more complete understanding of molecular processes induced by radiation. It also highlights the role of radical propagation in chemistry, biology, and nanotechnology.

  8. Effect of metal complexation to anti-inflammatory over the action against oxidative and free radicals: ketoprofen action

    International Nuclear Information System (INIS)

    Manente, Francine Alessandra; Mello, Lucas Rosolen de Almeida; Vellosa, Jose Carlos Rebuglio; Khalil, Omar Arafat Kdudsi; Carvalho, Claudio Teodoro de; Bannach, Gilbert

    2011-01-01

    Free radicals are highly reactive species generated in living organisms for the purpose of protection. However, in some circumstances, they are responsible for the occurrence or aggravation of tissue damage. Many anti-inflammatory drugs have a direct effect on free radicals and not radical reactive species, which contributes to its actions against inflammation. Ketoprofen is a nonsteroidal anti-inflammatory agent that generates free radicals by photo irradiation and has an important hemolytic effect with that. The complexation of metals to different drugs has been used as a strategy to improve the pharmacological action of different molecules and reduce their side effects. This paper presents the results of ketoprofen and their metallic complexes action on erythrocytes and free radicals. It was observed that the cerium enhances the scavenger properties of ketoprofen on free radicals, while copper enhances its action over non-radical oxidants. Copper also reduced the hemolytic effect presented by ketoprofen meanwhile its cerium derivative maintained it. (author)

  9. Immobilizing live Escherichia coli for AFM studies of surface dynamics

    International Nuclear Information System (INIS)

    Lonergan, N.E.; Britt, L.D.; Sullivan, C.J.

    2014-01-01

    Atomic force microscopy (AFM) is a probe-based technique that permits high resolution imaging of live bacterial cells. However, stably immobilizing cells to withstand the probe-based lateral forces remains an obstacle in AFM mediated studies, especially those of live, rod shaped bacteria in nutrient media. Consequently, AFM has been under-utilized in the research of bacterial surface dynamics. The aim of the current study was to immobilize a less adherent Escherichia coli strain in a method that both facilitates AFM imaging in nutrient broth and preserves overall cell viability. Immobilization reagents and buffers were systematically evaluated and the cell membrane integrity was monitored in all sample preparations. As expected, the biocompatible gelatin coated surfaces facilitated stable cell attachment in lower ionic strength buffers, yet poorly immobilized cells in higher ionic strength buffers. In comparison, poly-L-lysine surfaces bound cells in both low and high ionic strength buffers. The benefit of the poly-L-lysine binding capacity was offset by the compromised membrane integrity exhibited by cells on poly-L-lysine surfaces. However, the addition of divalent cations and glucose to the immobilization buffer was found to mitigate this unfavorable effect. Ultimately, immobilization of E. coli cells on poly-L-lysine surfaces in a lower ionic strength buffer supplemented with Mg 2+ and Ca 2+ was determined to provide optimal cell attachment without compromising the overall cell viability. Cells immobilized in this method were stably imaged in media through multiple division cycles. Furthermore, permeability assays indicated that E. coli cells recover from the hypoosmotic stress caused by immobilization in low ionic strength buffers. Taken together, this data suggests that stable immobilization of viable cells on poly-L-lysine surfaces can be accomplished in lower ionic strength buffers that are supplemented with divalent cations for membrane stabilization while

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

    NARCIS (Netherlands)

    Zhang, H.; Linde, van der R.

    2002-01-01

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

  11. Investigations by the surface photo-E. M. F. method of the effect of low temperature vacuum baking of an Si(111) surface

    Energy Technology Data Exchange (ETDEWEB)

    Dlugosz, B.; Kochowski, S.

    1982-02-26

    Investigations of the effect of low temperature vacuum baking on the surface potential of silicon are reported. The surface potential Vsub(s0) was measured by the surface photo-e.m.f. method. No noticeable changes in Vsub(s0) occurred after baking of samples which had been freshly etched in HF for 2 h in a vacuum of 6.6 x 10/sup -3/ Pa (5 x 10/sup -5/ Torr) at temperatures of 573, 623 and 723 K. Radical changes were observed when the samples had been aged in air for 2 months before vacuum baking. These results suggest that the direction and the value of the surface potential changes during vacuum baking are determined by the initial surface state.

  12. Single-electron transfer living radical copolymerization of SWCNT-g-PMMA via graft from approach

    Czech Academy of Sciences Publication Activity Database

    Jaisankar, S. N.; Haridharan, N.; Murali, A.; Ponyrko, Sergii; Špírková, Milena; Mandal, A. B.; Matějka, Libor

    2014-01-01

    Roč. 55, č. 13 (2014), s. 2959-2966 ISSN 0032-3861 R&D Projects: GA ČR GAP108/12/1459 Institutional support: RVO:61389013 Keywords : single electron transfer * single-walled carbon nanotubes * controlled radical polymerization Subject RIV: CD - Macromolecular Chemistry Impact factor: 3.562, year: 2014

  13. Study on distribution and behavior of long-lived radionuclides in surface soil environment

    International Nuclear Information System (INIS)

    Morita, Shigemitsu; Watanabe, Hitoshi; Katagiri, Hiromi; Akatsu, Yasuo; Ishiguro, Hideharu

    1996-01-01

    Technetium-99 ( 99 Tc) and Neptunium-237 ( 237 Np) are important radionuclides for environmental assessment around nuclear fuel cycle facilities, because these have long-lives and relatively high mobility in the environment. Therefore, we have been studied the determination, distribution and behavior of such long-lived radionuclides in surface soil environment. A new analytical technique using Inductively Coupled Plasma Mass Spectrometry (ICP-MS) was applied to the determination of long-lived radionuclides in environmental samples. The determination method consists of dry ashing, anion exchange and solvent extraction to eliminate the interfering elements and ICP-MS measurement. The sensitivity of this method was 10 to 100,000 times higher, and the counting time was 300 to 100,000 times shorter than the conventional radioanalytical methods. The soil samples were collected at nine points and core soil sample was collected by an electric core sampler at one point. The core soil sample was divided into eight layers. The depth profiles showed that more than 90% of 99 Tc and 237 Np were retained in the surface layer up to 10cm in depth which contained much amount of organic materials. The results suggest that content of organic materials in soil is related to adsorption of 99 Tc and 237 Np onto soil. (author)

  14. Fabrication of nonfouling, bactericidal, and bacteria corpse release multifunctional surface through surface-initiated RAFT polymerization.

    Science.gov (United States)

    Wang, Bailiang; Ye, Zi; Tang, Yihong; Han, Yuemei; Lin, Quankui; Liu, Huihua; Chen, Hao; Nan, Kaihui

    Infections after surgery or endophthalmitis are potentially blinding complications caused by bacterial adhesion and subsequent biofilm formation on the intraocular lens. Neither single-function anti-adhesion surface nor contacting killing surface can exhibit ideal antibacterial function. In this work, a novel (2-(dimethylamino)-ethyl methacrylate- co -2-methacryloyloxyethyl phosphorylcholine) (p (DMAEMA- co -MPC)) brush was synthesized by "grafting from" method through reversible-addition fragmentation chain transfer polymerization. 1-Bromoheptane was used to quaternize the p (DMAEMA- co -MPC) brush coating and to endow the surface with bactericidal function. The success of the surface functionalization was confirmed by atomic force microscopy, water contact angle, and spectroscopic ellipsometry. The quaternary ammonium salt units were employed as efficient disinfection that can eliminate bacteria through contact killing, whereas the 2-methacryloyloxyethyl phosphorylcholine units were introduced to suppress unwanted nonspecific adsorption. The functionalized poly(dimethyl siloxane) surfaces showed efficiency in reducing bovine serum albumin adsorption and in inhibiting bacteria adhesion and biofilm formation. The copolymer brushes also demonstrated excellent bactericidal function against gram-positive ( Staphylococcus aureus ) bacteria measured by bacteria live/dead staining and shake-flask culture methods. The surface biocompatibility was evaluated by morphology and activity measurement with human lens epithelial cells in vitro. The achievement of the p (DMAEMA + - co -MPC) copolymer brush coating with nonfouling, bactericidal, and bacteria corpse release properties can be used to modify intraocular lenses.

  15. How Hume's Philosophy Informed Radical Behaviorism.

    Science.gov (United States)

    Nuzzolilli, Andrew E; Diller, James W

    2015-05-01

    The present paper analyzes consistencies between the philosophical systems of David Hume and B. F. Skinner, focusing on their conceptualization of causality and attitudes about scientific behavior. The ideas that Hume initially advanced were further developed in Skinner's writings and shaped the behavior-analytic approach to scientific behavior. Tracing Skinner's logical antecedents allows for additional historical and philosophical clarity when examining the development of radical behaviorism.

  16. Reactive surface organometallic complexes observed using dynamic nuclear polarization surface enhanced NMR spectroscopy

    KAUST Repository

    Pump, Eva; Viger-Gravel, Jasmine; Abou-Hamad, Edy; Samantaray, Manoja; Hamzaoui, Bilel; Gurinov, Andrei; Anjum, Dalaver H.; Gajan, David; Lesage, Anne; Bendjeriou-Sedjerari, Anissa; Emsley, Lyndon; Basset, Jean-Marie

    2016-01-01

    Dynamic Nuclear Polarization Surface Enhanced NMR Spectroscopy (DNP SENS) is an emerging technique that allows access to high-sensitivity NMR spectra from surfaces. However, DNP SENS usually requires the use of radicals as an exogenous source of polarization, which has so far limited applications for organometallic surface species to those that do not react with the radicals. Here we show that reactive surface species can be studied if they are immobilized inside porous materials with suitably small windows, and if bulky nitroxide bi-radicals (here TEKPol) are used as the polarization source and which cannot enter the pores. The method is demonstrated by obtaining significant DNP enhancements from highly reactive complelxes [(equivalent to Si-O-)W(Me)(5)] supported on MCM-41, and effects of pore size (6.0, 3.0 and 2.5 nm) on the performance are discussed.

  17. Reactive surface organometallic complexes observed using dynamic nuclear polarization surface enhanced NMR spectroscopy

    KAUST Repository

    Pump, Eva

    2016-08-15

    Dynamic Nuclear Polarization Surface Enhanced NMR Spectroscopy (DNP SENS) is an emerging technique that allows access to high-sensitivity NMR spectra from surfaces. However, DNP SENS usually requires the use of radicals as an exogenous source of polarization, which has so far limited applications for organometallic surface species to those that do not react with the radicals. Here we show that reactive surface species can be studied if they are immobilized inside porous materials with suitably small windows, and if bulky nitroxide bi-radicals (here TEKPol) are used as the polarization source and which cannot enter the pores. The method is demonstrated by obtaining significant DNP enhancements from highly reactive complelxes [(equivalent to Si-O-)W(Me)(5)] supported on MCM-41, and effects of pore size (6.0, 3.0 and 2.5 nm) on the performance are discussed.

  18. Airborne measurement of peroxy radicals in the lower troposphere

    Science.gov (United States)

    Andrés Hernández, Maria Dolores; Horstjann, Markus; Kartal, Deniz; Krebsbach, Marc; Linke, Christian; Lichtenstern, Michael; Andrey, Javier; Burrows, John P.

    2013-04-01

    The importance of peroxy radicals in the tropospheric chemistry is well recognized in the scientific literature. Hydroxy- and organic peroxy radicals (HO2 and RO2, R being an organic chain) are key intermediates in the OH radical initiated oxidation of CO and SO2, of volatile organic compounds (VOC), in the ozonolysis of alkenes and photo-oxidation of carbonyl species. Peroxy radicals are responsible for the ozone production in the troposphere, the formation of peroxides and other oxidants. Although radical chemistry in the troposphere has been subject of intensive research in the past three decades, it is still very few known about the vertical distribution of peroxy radicals. Airborne observations are scarce in spite of their particular importance to improve the understanding of the tropospheric chemistry and the oxidising capacity of the atmosphere at different altitudes. In situ trace gas measurements were carried out in summer 2010 on board of the INTA (Instituto Nacional de Técnicas Aeroespaciales) C212 aircraft over Spain in the frame of the EUFAR project VERDRILLT (VERtical Distribution of Radicals In the Lower Layers of the Troposphere), and in cooperation with the DLR (Deutsches Zentrum für Luft- und Raumfahrt), the University of Wuppertal, the CEAM (Centro de Estudios Ambientales del Mediterráneo) and the UPV-EHU University in Bilbao. VERDRILLT aimed at getting a deeper understanding of the vertical distribution of peroxy radicals in the lower layers of the troposphere. Measurements were taken over urban areas and extensions of different vegetation under meteorological conditions favouring active photochemistry and convection from the ground into close atmospheric layers. Results and main findings will be presented and discussed.

  19. Wayfinding the Live 5-2-1-0 Initiative-At the Intersection between Systems Thinking and Community-Based Childhood Obesity Prevention.

    Science.gov (United States)

    Amed, Shazhan; Shea, Stephanie; Pinkney, Susan; Wharf Higgins, Joan; Naylor, Patti-Jean

    2016-06-21

    Childhood obesity is complex and requires a 'systems approach' that collectively engages across multiple community settings. Sustainable Childhood Obesity Prevention through Community Engagement (SCOPE) has implemented Live 5-2-1-0-a multi-sector, multi-component childhood obesity prevention initiative informed by systems thinking and participatory research via an innovative knowledge translation (KT) model (RE-FRAME). This paper describes the protocol for implementing and evaluating RE-FRAME in two 'existing' (>2 years of implementation) and two 'new' Live 5-2-1-0 communities to understand how to facilitate and sustain systems/community-level change. In this mixed-methods study, RE-FRAME was implemented via online resources, webinars, a backbone organization (SCOPE) coordinating the initiative, and a linking system supporting KT. Qualitative and quantitative data were collected using surveys and stakeholder interviews, analyzed using thematic analysis and descriptive statistics, respectively. Existing communities described the consistency of Live 5-2-1-0 and extensive local partnerships/champions as catalysts for synergistic community-wide action; new communities felt that the simplicity of the message combined with the transfer of experiential learning would inform their own strategies and policies/programs to broadly disseminate Live 5-2-1-0. RE-FRAME effectively guided the refinement of the initiative and provided a framework upon which evaluation results described how to implement a community-based systems approach to childhood obesity prevention.

  20. The Prospects of Radical Change Today

    Directory of Open Access Journals (Sweden)

    Slavoj Žižek

    2018-05-01

    Full Text Available In this contribution, Slavoj Žižek takes the occasion of Marx’s bicentenary for reflecting on the prospects of radical change today. First, it is shown that under Stalinism, Lenin’s works were quoted out of context in an arbitrary way in order to legitimise arbitrary political measures. Marxism thereby became an ideology that justified brutal subjective interventions. Second, this contribution poses the question of the revolutionary subject and democracy today. It stresses the role of both contingency and strategy in revolutions. In political assemblages taking place on public squares, the inert mass of ordinary people is transubstantiated into a politically engaged united force. The basic political problem today is how to best reconfigure democracy. Third, this contribution analyses the “interesting times” we live in. These are times that feature multiple crises, right-wing populism à la Donald Trump and Marine Le Pen, the lower classes’ opposition to immigration, and the refugee crisis. Questions about human rights and their violation and about radical change need to be asked in this context.

  1. Cell-mediated reduction of protein and peptide hydroperoxides to reactive free radicals

    DEFF Research Database (Denmark)

    Headlam, Henrietta A; Davies, Michael Jonathan

    2003-01-01

    Radical attack on proteins in the presence of O(2) gives protein hydroperoxides in high yields. These peroxides are decomposed by transition metal ions, reducing agents, UV light and heat, with the formation of a range of reactive radicals that are capable of initiating further damage. Evidence has...... been presented for the formation of alcohols as stable products of peroxide decomposition, and these have been employed as markers of oxidative damage in vivo. The mechanism of formation of these alcohols is unclear, with both radical and nonradical pathways capable of generating these products....... In this study we have investigated the reduction of peptide and protein hydroperoxides by THP-1 (human monocyte-like) cells and it is shown that this process is accompanied by radical formation as detected by EPR spin trapping. The radicals detected, which are similar to those detected from metal-ion catalyzed...

  2. Radical clashes : what tangible interaction is made of

    NARCIS (Netherlands)

    Dijk, van J.; Mousette, C.; Kuenen, C.D.; Hummels, C.C.M.

    2013-01-01

    Driven by a critique of Ishii et al's recent vision of Radical Atoms we call for a debate on the different conceptual paradigms underlying the TEI community and its activities. TEI was initiated to share and connect different perspectives, but we feel conceptual debate is lacking. To fuel this

  3. Guest Editorial: Processes of Radicalization and De-Radicalization

    Directory of Open Access Journals (Sweden)

    Donatella Della Porta

    2012-05-01

    Full Text Available The study of radicalization and de-radicalization, understood as processes leading towards the increased or decreased use of political violence, is central to the question of how political violence emerges, how it can be prevented, and how it can be contained. The focus section of this issue of the International Journal of Conflict and Violence addresses radicalization and de-radicalization, seeking to develop a more comprehensive understanding of the processes, dynamics, and mechanisms involved and taking an interdisciplinary approach to overcome the fragmentation into separate disciplines and focus areas. Contributions by Pénélope Larzillière, Felix Heiduk, Bill Kissane, Hank Johnston, Christian Davenport and Cyanne Loyle, Veronique Dudouet, and Lasse Lindekilde address repressive settings, legitimacy, institutional aspects, organizational outcomes, and dynamics in Europe, Asia, Africa, and North and South America.

  4. The kinetics of free radical metathetical and addition reactions in silane solutions

    International Nuclear Information System (INIS)

    Aloni, R.

    1976-12-01

    In this work radiolytic technique was employed for the initiation of free radical chainreactions in silane solution. The kinetic analysis of the chain mechanism in various solutions enabled the determination of the Arrhenius parameters for metathesis, addition and unimolecular decomposition reactions which make up the chainpropagation sequence in the systems studied. The following radical reactions were investigated: chlorine atom abstraction from chloromethanes by SiCl 3 and Et 3 Si radicals, and chlorine atom abstraction from chloroethanes by Et 3 Si radicals; unimolecular decomposition reactions and hydrogen atom abstraction, *from the solvent, of chloroethyl radicals in triethylsilane solutions; addition and abstraction reactions of Et 3 Si radicals with chloroolefins. Arrhenius parameters were determined for abstraction of chlorine atom from CH 3 Cl, CH 2 Cl 2 , CHCl 3 and CCl 4 , by SiCl 3 radicals and from CCl 4 , CHCl 3 , CH 2 Cl 2 , CCl 3 CN, C 2 Cl 5 H, sym-C 2 Cl 4 H 2 , asym-C 2 Cl 4 H 2 , 1.1.1-C 2 Cl 3 H 3 , 1.1.1-C 2 Dl 3 F 3 and 1.1-C 2 Cl 2 H 4 by Et 3 Si radicals. (author)

  5. Modelling of the initial stage of the surface discharge development

    International Nuclear Information System (INIS)

    Gibalov, V.; Pietsch, G.

    1998-01-01

    Computer modelling of the initial stage of the surface discharge was performed by solving numerically the coupled continuity, the Poisson and Townsend ionization equations and taking into account the ionization, attachment and detachment processes. The potential distribution at the dielectric surface and at the boundaries which surround the integration region have been calculated with the charge-image method in a 3D approach. In order to eliminate numerical diffusion effects, the solution of the continuity equation was corrected using a flux correction transport routine. At the positive voltage the development of the discharge channel is determined mainly by the shape of the electrode tip. At the negative voltage the following phases of the discharge may be distinguished: the initial phase, the cathode directed streamer phase resulting in the cathode layer formation, and the propagating phase. The physical processes governing each discharge phase are described in detail. (J.U.)

  6. Live Imaging of Kv7.2/7.3 Cell Surface Dynamics at the Axon Initial Segment: High Steady-State Stability and Calpain-Dependent Excitotoxic Downregulation Revealed

    DEFF Research Database (Denmark)

    Benned-Jensen, Tau; Christensen, Rasmus Kordt; Denti, Federico

    2016-01-01

    The voltage-gated K(+) channels Kv7.2 and Kv7.3 are located at the axon initial segment (AIS) and exert strong control over action potential generation. Therefore, changes in their localization or cell surface numbers are likely to influence neuronal signaling. However, nothing is known about......7.3. This seven transmembrane chimera, named super ecliptic phluorin (SEP)-TAC-7.3, functions and traffics as a wild-type (WT) channel. We expressed SEP-TAC-7.3 in dissociated rat hippocampal neurons to examine the lateral mobility, surface numbers, and localization of AIS Kv7.2/7.3 heteromers using...

  7. Excimer laser corneal surgery and free oxygen radicals.

    Science.gov (United States)

    Bilgihan, K; Bilgihan, A; Akata, F; Hasanreisoğlu, B; Türközkan, N

    1996-01-01

    Corneal photoablation with 193 nm argon fluoride excimer laser is a new technique for the treatment of refractive errors and for removing corneal opacities and irregularities. Ultraviolet radiation and thermal injury induce free radical formation in the tissues. The aim of this study was to confirm the production of free radicals by excimer laser photoablation in rabbits. The thermal changes of the posterior corneal surface were recorded during excimer laser photoablation. The lipid peroxide (LPO) levels and superoxide dismutase (SOD) activities of aqueous humour were measured after excimer laser keratectomy. The aqueous LPO levels were not changed after excimer laser ablation, but both the thermal increase in the cornea during the photoablation and the decreased aqueous SOD activities suggest that free radicals are formed in the cornea during excimer laser keratectomy, and that they may be responsible for some of the complications of excimer laser corneal surgery.

  8. Formation and fragmentation of radical peptide anions: insights from vacuum ultra violet spectroscopy.

    Science.gov (United States)

    Brunet, Claire; Antoine, Rodolphe; Dugourd, Philippe; Canon, Francis; Giuliani, Alexandre; Nahon, Laurent

    2012-02-01

    We have studied the photodissociation of gas-phase deprotonated caerulein anions by vacuum ultraviolet (VUV) photons in the 4.5 to 20 eV range, as provided by the DESIRS beamline at the synchrotron radiation facility SOLEIL (France). Caerulein is a sulphated peptide with three aromatic residues and nine amide bonds. Electron loss is found to be the major relaxation channel at every photon energy. However, an increase in the fragmentation efficiency (neutral losses and peptide backbone cleavages) as a function of the energy is also observed. The oxidized ions, generated by electron photodetachment were further isolated and activated by collision (CID) in a MS(3) scheme. The branching ratios of the different fragments observed by CID as a function of the initial VUV photon energy are found to be independent of the initial photon energy. Thus, there is no memory effect of the initial excitation energy on the fragmentation channels of the oxidized species on the time scale of our tandem MS experiment. We also report photofragment yields as a function of photon energy for doubly deprotonated caerulein ions, for both closed-shell ([M-2H](2-)) non-radical ions and open-shell ([M-3H](2-•)) radical ions. These latter ions are generated by electron photodetachment from [M-3H](3-) precursor ions. The detachment yield increases monotonically with the energy with the appearance of several absorption bands. Spectra for radical and non-radical ions are quite similar in terms of observed bands; however, the VUV fragmentation yield is enhanced by the presence of a radical in caerulein peptides. © American Society for Mass Spectrometry, 2011

  9. Radical SAM Enzymes in the Biosynthesis of Ribosomally Synthesized and Post-translationally Modified Peptides (RiPPs

    Directory of Open Access Journals (Sweden)

    Alhosna Benjdia

    2017-11-01

    Full Text Available Ribosomally-synthesized and post-translationally modified peptides (RiPPs are a large and diverse family of natural products. They possess interesting biological properties such as antibiotic or anticancer activities, making them attractive for therapeutic applications. In contrast to polyketides and non-ribosomal peptides, RiPPs derive from ribosomal peptides and are post-translationally modified by diverse enzyme families. Among them, the emerging superfamily of radical SAM enzymes has been shown to play a major role. These enzymes catalyze the formation of a wide range of post-translational modifications some of them having no counterparts in living systems or synthetic chemistry. The investigation of radical SAM enzymes has not only illuminated unprecedented strategies used by living systems to tailor peptides into complex natural products but has also allowed to uncover novel RiPP families. In this review, we summarize the current knowledge on radical SAM enzymes catalyzing RiPP post-translational modifications and discuss their mechanisms and growing importance notably in the context of the human microbiota.

  10. A novel plasma source for sterilization of living tissues

    International Nuclear Information System (INIS)

    Martines, E; Zuin, M; Cavazzana, R; Gazza, E; Serianni, G; Spagnolo, S; Spolaore, M; Leonardi, A; Deligianni, V; Brun, P; Aragona, M; Castagliuolo, I; Brun, P

    2009-01-01

    A source for the production of low-power plasmas at atmospheric pressure, to be used for the nondamaging sterilization of living tissues, is presented. The source, powered by radiofrequency and working with a helium flow, has a specific configuration, studied to prevent the formation of electric arcs dangerous to living matter. It is capable of killing different types of bacteria with a decimal reduction time of 1-2 min; on the contrary, human cells such as conjunctival fibroblasts were found to be almost unharmed by the plasma. A high concentration of OH radicals, likely to be the origin of the sterilizing effect, is detected through their UV emission lines. The effect of the UV and the OH radicals on the fibroblasts was analysed and no significant effects were detected.

  11. Manipulation of radicals and ions in LFICP-aided fabrication of high efficiency solar cells

    International Nuclear Information System (INIS)

    Xu, S.

    2013-01-01

    In this talk, we report on the development and diagnostics of low frequency inductively coupled plasma (LFICP) reactor for fabrication of high efficiency silicon solar cells. Chemically active, thermally non-equilibrium plasma possess unique advantages for manipulation of plasma-generated radicals/ions and overall control of growth and self-organization processes that are crucial for fabrication of photovoltaic materials and solar cells. In low frequency inductively coupled plasmas, generation, selection and control of densities and fluxes of the radicals and ions can easily be controlled by the electron energy distributions and other plasma parameters. The electric field and thermal forces guide selective delivery of the radicals to the surface. Specific substrate activation and temperature determine the ion/heat fluxes from the gas phase to the charged surfaces. Detailed discussion includes the inter-connection between in-situ plasma diagnostics (Optical Emission Spectroscopy, Langmuir Probe diagnostics, and Quadruple Mass Spectrometry) and ex-situ material characterization (XRD, Raman, FTIR EDX, UV/Vis, SEM, Hall-effect and others). Special emphasis is paid to the identification and control strategies of the plasma-generated radicals/ions existed in both the ionized gas phase and on the deposition surfaces. We will show how radicals and ions can be manipulated to meet the structural, optical and electronic requirements for high efficiency photovoltaic cells. Solar cell fabricated by the LFICP plasma exhibits an extraordinarily photovoltaic performance with energy conversion efficiency exceeding 18%. (author)

  12. Ion microbeam irradiation for radiobiology and radical chemistry: status and prospect

    Energy Technology Data Exchange (ETDEWEB)

    Khodja, H, E-mail: hicham.khodja@cea.fr [CEA, IRAMIS, SIS2M, LEEL, 91191 Gif-sur-Yvette (France); CNRS, UMR 3299, SIS2M, LEEL, 91191 Gif-sur-Yvette (France)

    2011-01-01

    Ion microbeams are commonly used to study local irradiation effects in living cells, as it has been established that ion beam irradiations can lead to deleterious changes in cells that are not struck directly by the microbeam. Such changes, which take place over distances long compared to the size of the irradiation spot and for times long compared to the time of irradiation, are collectively termed radiation-induced bystander effect or RIBE. Free-radical chemistry is frequently invoked to explain the RIBE but no unified model is available at present. Ion microbeams when coupled with advanced methods for observing free radicals are the tools of choice for investigating the chemistry and biological processes governing RIBE.

  13. Engaging unactivated alkyl, alkenyl and aryl iodides in visible-light-mediated free radical reactions

    Science.gov (United States)

    Nguyen, John D.; D'Amato, Erica M.; Narayanam, Jagan M. R.; Stephenson, Corey R. J.

    2012-10-01

    Radical reactions are a powerful class of chemical transformations. However, the formation of radical species to initiate these reactions has often required the use of stoichiometric amounts of toxic reagents, such as tributyltin hydride. Recently, the use of visible-light-mediated photoredox catalysis to generate radical species has become popular, but the scope of these radical precursors has been limited. Here, we describe the identification of reaction conditions under which photocatalysts such as fac-Ir(ppy)3 can be utilized to form radicals from unactivated alkyl, alkenyl and aryl iodides. The generated radicals undergo reduction via hydrogen atom abstraction or reductive cyclization. The reaction protocol utilizes only inexpensive reagents, occurs under mild reaction conditions, and shows exceptional functional group tolerance. Reaction efficiency is maintained upon scale-up and decreased catalyst loading, and the reaction time can be significantly shortened when the reaction is performed in a flow reactor.

  14. Atmospheric implications of simultaneous nighttime measurements of NO3 radicals and hono

    International Nuclear Information System (INIS)

    Pitts, J.N. Jr.; Biermann, H.W.; Atkinson, R.; Winer, A.M.

    1984-01-01

    Atmospheric concentrations of gaseous HONO and the NO 3 radical were measured simultaneously for the first time using long path differential optical absorption spectroscopy. Diurnal profiles are reported for two successive nights following days of moderate pollution at Riverside, California, together with concurrent measurements of NO 2 , O 3 and NO concentrations and an upper limit for HCHO levels. These measurements permit an examination of selected aspects of the nighttime atmospheric chemistry of HONO and the NO 3 radical and related species. Our data do not support a recently proposed homogeneous gas phase mechanism for HONO formation initiated by the reaction of the NO 3 radical with HCHO

  15. Formation of nitro products from the gas-phase OH radical-initiated reactions of toluene, naphthalene, and biphenyl: effect of NO2 concentration.

    Science.gov (United States)

    Nishino, Noriko; Atkinson, Roger; Arey, Janet

    2008-12-15

    Aromatic hydrocarbons, including polycyclic aromatic hydrocarbons (PAHs), are released into the atmosphere principally during incomplete combustion and account for approximately 20% of nonmethane organic compounds in urban air. Reaction with OH radicals is the dominant atmospheric chemical loss process for aromatic hydrocarbons, leading mainly to the formation of an OH-aromatic or OH-PAH adduct which then reacts with O2 and/or NO2. For OH-monocyclic aromatic adducts, reaction with O2 dominates under atmospheric conditions; however, no data are available concerning the relative importance of reactions of OH-PAH adducts with O2 and NO2. We have measured formation yields of 3-nitrotoluene, 1- and 2-nitronaphthalene, and 3-nitrobiphenyl from the OH radical-initiated reactions of toluene, naphthalene, and biphenyl as a function of NO2 concentration. Our data showthatthe OH-aromatic adduct reactions with O2 and NO2 are of equal importance in the atmosphere at NO2 mixing ratios of approximately 3.3 ppmV for toluene, approximately 0.06 ppmV for naphthalene, and approximately 0.6 ppmV for biphenyl. Ambient concentrations of toluene, naphthalene, and biphenyl and their nitrated products measured at a site in the Los Angeles air basin are consistent with our laboratory measurements.

  16. Pulsed EPR studies of small reactive radicals produced by ionizing radiation

    International Nuclear Information System (INIS)

    Lawler, R.G.

    1985-01-01

    For several years we have participated in a collaborative research effort to apply the pulsed EPR-pulse radiolysis technique to several problems associated with the dynamics of small reactive radicals formed during radiolysis of aqueous solutions using 3 MeV electrons from a Van de Graaff accelerator. We will discuss experimental techniques and applications arising from this work, with particular emphasis on problems requiring high initial radical concentrations and EPR time resolution of one microsecond or better. 2 figs., 2 tabs

  17. Surface-Initiated Polymerization by Means of Novel, Stable, Non-Ester-Based Radical Initiator

    Czech Academy of Sciences Publication Activity Database

    Bain, E. D.; Dawes, K.; Ozcam, A. E.; Hu, X.; Gorman, C. B.; Šrogl, Jiří; Genzer, J.

    2012-01-01

    Roč. 45, č. 9 (2012), s. 3802-3815 ISSN 0024-9297 Institutional support: RVO:61388963 Keywords : self-assembled monolayers * poly(acrylic acid) brushes * thermoresponsive polymer Subject RIV: CC - Organic Chemistry Impact factor: 5.521, year: 2012

  18. Spontaneous Isomerization of Peptide Cation Radicals Following Electron Transfer Dissociation Revealed by UV-Vis Photodissociation Action Spectroscopy.

    Science.gov (United States)

    Imaoka, Naruaki; Houferak, Camille; Murphy, Megan P; Nguyen, Huong T H; Dang, Andy; Tureček, František

    2018-01-16

    Peptide cation radicals of the z-type were produced by electron transfer dissociation (ETD) of peptide dications and studied by UV-Vis photodissociation (UVPD) action spectroscopy. Cation radicals containing the Asp (D), Asn (N), Glu (E), and Gln (Q) residues were found to spontaneously isomerize by hydrogen atom migrations upon ETD. Canonical N-terminal [z 4 + H] +● fragment ion-radicals of the R-C ● H-CONH- type, initially formed by N-C α bond cleavage, were found to be minor components of the stable ion fraction. Vibronically broadened UV-Vis absorption spectra were calculated by time-dependent density functional theory for several [ ● DAAR + H] + isomers and used to assign structures to the action spectra. The potential energy surface of [ ● DAAR + H] + isomers was mapped by ab initio and density functional theory calculations that revealed multiple isomerization pathways by hydrogen atom migrations. The transition-state energies for the isomerizations were found to be lower than the dissociation thresholds, accounting for the isomerization in non-dissociating ions. The facile isomerization in [ ● XAAR + H] + ions (X = D, N, E, and Q) was attributed to low-energy intermediates having the radical defect in the side chain that can promote hydrogen migration along backbone C α positions. A similar side-chain mediated mechanism is suggested for the facile intermolecular hydrogen migration between the c- and [z + H] ● -ETD fragments containing Asp, Asn, Glu, and Gln residues. Graphical Abstract ᅟ.

  19. Spontaneous Isomerization of Peptide Cation Radicals Following Electron Transfer Dissociation Revealed by UV-Vis Photodissociation Action Spectroscopy

    Science.gov (United States)

    Imaoka, Naruaki; Houferak, Camille; Murphy, Megan P.; Nguyen, Huong T. H.; Dang, Andy; Tureček, František

    2018-01-01

    Peptide cation radicals of the z-type were produced by electron transfer dissociation (ETD) of peptide dications and studied by UV-Vis photodissociation (UVPD) action spectroscopy. Cation radicals containing the Asp (D), Asn (N), Glu (E), and Gln (Q) residues were found to spontaneously isomerize by hydrogen atom migrations upon ETD. Canonical N-terminal [z4 + H]+● fragment ion-radicals of the R-C●H-CONH- type, initially formed by N-Cα bond cleavage, were found to be minor components of the stable ion fraction. Vibronically broadened UV-Vis absorption spectra were calculated by time-dependent density functional theory for several [●DAAR + H]+ isomers and used to assign structures to the action spectra. The potential energy surface of [●DAAR + H]+ isomers was mapped by ab initio and density functional theory calculations that revealed multiple isomerization pathways by hydrogen atom migrations. The transition-state energies for the isomerizations were found to be lower than the dissociation thresholds, accounting for the isomerization in non-dissociating ions. The facile isomerization in [●XAAR + H]+ ions (X = D, N, E, and Q) was attributed to low-energy intermediates having the radical defect in the side chain that can promote hydrogen migration along backbone Cα positions. A similar side-chain mediated mechanism is suggested for the facile intermolecular hydrogen migration between the c- and [z + H]●-ETD fragments containing Asp, Asn, Glu, and Gln residues. [Figure not available: see fulltext.

  20. Macromolecular surface design: photopatterning of functional stable nitrile oxides.

    Science.gov (United States)

    Altintas, Ozcan; Glassner, Mathias; Rodriguez-Emmenegger, Cesar; Welle, Alexander; Trouillet, Vanessa; Barner-Kowollik, Christopher

    2015-05-04

    The efficient trapping of photogenerated thioaldehydes with functional shelf-stable nitrile oxides in a 1,3-dipolar cycloaddition is a novel and versatile photochemical strategy for polymer end-group functionalization and surface modification under mild and equimolar conditions. The modular ligation in solution was followed in detail by electrospray ionization mass spectrometry (ESI-MS). X-ray photoelectron spectroscopy (XPS) was employed to analyze the functionalized surfaces, whereas time-of-flight secondary-ion mass spectrometry (ToF-SIMS) confirmed the spatial control of the surface functionalization using a micropatterned shadow mask. Polymer brushes were grown from the surface in a spatially confined regime by surface-initiated atom transfer radical polymerization (SI-ATRP) as confirmed by TOF-SIMS, XPS as well as ellipsometry. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Electron curing of surface coatings

    International Nuclear Information System (INIS)

    Nablo, S.V.

    1974-01-01

    The technical development of electron curing of surface coatings has received great impetus since 1970 from dramatic changes in the economics of the conventional thermal process. The most important of these changes are reviewed, including: the Clear Air Act, increasing cost and restrictive allocation of energy, decreased availability and increased costs of solvents, competitive pressure for higher line productivity. The principles of free-radical initiated curing as they pertain to industrial coatings are reviewed. Although such electron initiated processes have been under active development for at least two decades, high volume production applications on an industrial scale have only recently appeared. These installations are surveyed with emphasis on the developments in machinery and coatings which have made this possible. The most significant economic advantages of electron curing are presented. In particular, the ability of electron curing to eliminate substrate damage and to eliminate the curing station (oven) as the pacing element for most industrial surface coating curing applications is discussed. Examples of several new processes of particular interest in the textile industry are reviewed, including the curing of transfer cast urethane films, flock adhesives, and graftable surface finishes

  2. Radical Change by Entrepreneurial Design

    National Research Council Canada - National Science Library

    Roberts, Nancy C

    1998-01-01

    .... How radical change in public policy has occurred in the past is then documented. We find examples of radical change by chance, radical change by consensus, radical change by learning, and radical change by entrepreneurial design...

  3. Impacts of model initialization on an integrated surface water - groundwater model

    KAUST Repository

    Ajami, Hoori; McCabe, Matthew; Evans, Jason P.

    2015-01-01

    Integrated hydrologic models characterize catchment responses by coupling the subsurface flow with land surface processes. One of the major areas of uncertainty in such models is the specification of the initial condition and its influence

  4. Free radical generation from an aniline derivative in HepG2 cells: a possible captodative effect.

    Science.gov (United States)

    Horinouchi, Yuya; Summers, Fiona A; Ehrenshaft, Marilyn; Mason, Ronald P

    2015-01-01

    Xenobiotic metabolism can induce the generation of protein radicals, which are believed to play an important role in the toxicity of chemicals and drugs. It is therefore important to identify chemical structures capable of inducing macromolecular free radical formation in living cells. In this study, we evaluated the ability of four structurally related environmental chemicals, aniline, nitrosobenzene, N,N-dimethylaniline, and N,N-dimethyl-4-nitrosoaniline (DMNA), to induce free radicals and cellular damage in the hepatoma cell line HepG2. Cytotoxicity was assessed using lactate dehydrogenase assays, and morphological changes were observed using phase contrast microscopy. Protein free radicals were detected by immuno-spin trapping using in-cell western experiments and confocal microscopy to determine the subcellular locale of free radical generation. DMNA induced free radical generation, lactate dehydrogenase release, and morphological changes in HepG2 cells, whereas aniline, nitrosobenzene, N,N-dimethylaniline did not. Confocal microscopy showed that DMNA induced free radical generation mainly in the cytosol. Preincubation of HepG2 cells with N-acetylcysteine and 2,2'-dipyridyl significantly prevented free radical generation on subsequent incubation with DMNA, whereas preincubation with apocynin and dimethyl sulfoxide had no effect. These results suggest that DMNA is metabolized to reactive free radicals capable of generating protein radicals which may play a critical role in DMNA toxicity. We propose that the captodative effect, the combined action of the electron-releasing dimethylamine substituent, and the electron-withdrawing nitroso substituent, leads to a thermodynamically stabilized radical, facilitating enhanced protein radical formation by DMNA. Copyright © 2014 Elsevier Inc. All rights reserved.

  5. p53 Mutagenesis by Benzo[a]pyrene derived Radical Cations

    Science.gov (United States)

    Sen, Sushmita; Bhojnagarwala, Pratik; Francey, Lauren; Lu, Ding; Jeffrey Field, Trevor M. Penning

    2013-01-01

    Benzo[a]pyrene (B[a]P), a major human carcinogen in combustion products such as cigarette smoke and diesel exhaust, is metabolically activated into DNA-reactive metabolites via three different enzymatic pathways. The pathways are the anti-(+)-benzo[a]pyrene 7,8-diol 9, 10-epoxide pathway (P450/ epoxide hydrolase catalyzed) (B[a]PDE), the benzo[a]pyrene o-quinone pathway (aldo ketose reductase (AKR) catalyzed) and the B[a]P radical cation pathway (P450 peroxidase catalyzed). We used a yeast p53 mutagenesis system to assess mutagenesis by B[a]P radical cations. Because radical cations are short-lived, they were generated in situ by reacting B[a]P with cumene hydroperoxide (CuOOH) and horse radish peroxidase (HRP) and then monitoring the generation of the more stable downstream products, B[a]P-1,6-dione and B[a]P-3,6-dione. Based on the B[a]P-1,6 and 3,6-dione formation, approximately 4µM of radical cation was generated. In the mutagenesis assays, the radical cations produced in situ showed a dose-dependent increase in mutagenicity from 0.25 µM to 10 µM B[a]P with no significant increase seen with further escalation to 50 µM B[a]P. However, mutagenesis was 200-fold less than with the AKR pathway derived B[a]P, 7–8 dione. Mutant p53 plasmids, which yield red colonies, were recovered from the yeast to study the pattern and spectrum of mutations. The mutation pattern observed was G to T (31%) > G to C (29%) > G to A (14%). The frequency of codons mutated by the B[a]P radical cations was essentially random and not enriched at known cancer hotspots. The quinone products of radical cations, B[a]P-1,6-dione and B[a]P-3,6-dione were more mutagenic than the radical cation reactions, but still less mutagenic than AKR derived B[a]P-7,8-dione. We conclude that B[a]P radical cations and their quinone products are weakly mutagenic in this yeast-based system compared to redox cycling PAH o-quinones. PMID:22768918

  6. WRF Simulation over the Eastern Africa by use of Land Surface Initialization

    Science.gov (United States)

    Sakwa, V. N.; Case, J.; Limaye, A. S.; Zavodsky, B.; Kabuchanga, E. S.; Mungai, J.

    2014-12-01

    The East Africa region experiences severe weather events associated with hazards of varying magnitude. It receives heavy precipitation which leads to wide spread flooding and lack of sufficient rainfall in some parts results into drought. Cases of flooding and drought are two key forecasting challenges for the Kenya Meteorological Service (KMS). The source of heat and moisture depends on the state of the land surface which interacts with the boundary layer of the atmosphere to produce excessive precipitation or lack of it that leads to severe drought. The development and evolution of precipitation systems are affected by heat and moisture fluxes from the land surface within weakly-sheared environments, such as in the tropics and sub-tropics. These heat and moisture fluxes during the day can be strongly influenced by land cover, vegetation, and soil moisture content. Therefore, it is important to represent the land surface state as accurately as possible in numerical weather prediction models. Improved modeling capabilities within the region have the potential to enhance forecast guidance in support of daily operations and high-impact weather over East Africa. KMS currently runs a configuration of the Weather Research and Forecasting (WRF) model in real time to support its daily forecasting operations, invoking the Non-hydrostatic Mesoscale Model (NMM) dynamical core. They make use of the National Oceanic and Atmospheric Administration / National Weather Service Science and Training Resource Center's Environmental Modeling System (EMS) to manage and produce the WRF-NMM model runs on a 7-km regional grid over Eastern Africa.SPoRT and SERVIR provide land surface initialization datasets and model verification tool. The NASA Land Information System (LIS) provide real-time, daily soil initialization data in place of interpolated Global Forecast System soil moisture and temperature data. Model verification is done using the Model Evaluation Tools (MET) package, in order

  7. Formation of hydroxyl radical (sm-bulletOH) in illuminated surface waters contaminated with acidic mine drainage

    International Nuclear Information System (INIS)

    Allen, J.M.; Lucas, S.; Allen, S.K.

    1996-01-01

    Formation rates and steady-state concentrations of hydroxyl radical ( sm-bullet OH) in illuminated surface water samples collected in west-central Indiana that receive acidic mine drainage runoff are reported. Formation rates for sm-bullet OH in samples were measured by the addition of 1 x 10 -3 M benzene prior to illuminate in order to effectively scavenge all of the sm-bullet OH formed, thereby yielding phenol. The sm-bullet OH formation rates were calculated from the measured phenol formation rates. Steady-state concentrations of sm-bullet OH were measured by the addition of 5 x 10 -7 M nitrobenzene to the samples prior to illumination. Estimated sunlight sm-bullet OH formation rates range from 16 microM h -1 to 265 microM h -1 . Estimated sunlight steady-state sm-bullet OH concentrations range from 6.7 x 10 -15 to 4.0 x 10 -12 M. Both the formation rates and steady-state concentrations for sm-bullet OH are thus two to three orders of magnitude higher than values reported in the literature for other sunlit surface water samples. Due to the very high rates of formation and steady-state concentrations for sm-bullet OH in these samples, the authors conclude that aqueous-phase reactions involving sm-bullet OH represent a significant pathway by which organic pollutants in illuminated surface waters receiving acidic mine drainage runoff may be consumed

  8. Structure, stability, and properties of the trans peroxo nitrate radical: the importance of nondynamic correlation.

    Science.gov (United States)

    Dutta, Achintya Kumar; Dar, Manzoor; Vaval, Nayana; Pal, Sourav

    2014-02-27

    We report a comparative single-reference and multireference coupled-cluster investigation on the structure, potential energy surface, and IR spectroscopic properties of the trans peroxo nitrate radical, one of the key intermediates in stratospheric NOX chemistry. The previous single-reference ab initio studies predicted an unbound structure for the trans peroxo nitrate radical. However, our Fock space multireference coupled-cluster calculation confirms a bound structure for the trans peroxo nitrate radical, in accordance with the experimental results reported earlier. Further, the analysis of the potential energy surface in FSMRCC method indicates a well-behaved minima, contrary to the shallow minima predicted by the single-reference coupled-cluster method. The harmonic force field analysis, of various possible isomers of peroxo nitrate also reveals that only the trans structure leads to the experimentally observed IR peak at 1840 cm(-1). The present study highlights the critical importance of nondynamic correlation in predicting the structure and properties of high-energy stratospheric NOx radicals.

  9. Radical Transparency in Journalism: Digital Evolutions from Historical Precedents

    Directory of Open Access Journals (Sweden)

    Luke Justin Heemsbergen

    2013-06-01

    Full Text Available This paper argues that transparency projects retain a political hue from the social-technological context from which they are created. Thus, radical transparency is considered as an opportunity to evolve both journalistic and democratic practices. Transparency in practice reveals diverse expectations of how journalists reporting should be used, and these expectations in turn, seem dependent on specific worldviews. This paper presents a comparative analysis of the effects of the current exemplar of radical journalism, WikiLeaks. It compares Wikileaks to its historical equivalents, including Hansard in the 18th century, and the reporting of open diplomacy in the early 20th century. This analysis shows how journalism evolves along with radical transparency projects, and how the current context of networked radical transparency can, and will, be made into news with specific political effects. In conclusion, this paper argues that practitioners should be aware of the political hues that new transparency mechanisms afford. Being cognizant of context and design choices can increase the degree to which new initiatives can have a deep systemic impact—as well as acknowledge the qualities and repercussions of that impact.

  10. Some biochemical consequences of the spatial distribution of ionizing radiation-produced free radicals

    International Nuclear Information System (INIS)

    Ward, J.F.

    1981-01-01

    Ionizing radiation deposits energy nonhomogeneously in the medium through which it passes. Mozumder and Magee (Radiat. Res. 28, 203-214(1966)) have classified the events as spurs, blobs, and short tracks. These are defined by size and amount of energy deposited. Thus the initial chemically reactive species are distributed in an inhomogeneous manner. In these volumes of high radical concentration, radical-radical reactions can occur which can only be scavenged by solutes at high concentration. Making the reasonable assumption that similar events occur intracellularly, the consequences of such events must be considered. In the case of DNA, several authors have shown that OH radicals diffuse only tens of angstroms prior to reaction. In the volume from which these radicals originate, DNA is necessarily at high concentration and consequently will interact with the radicals formed in the spur, etc. Such events are probably the source of radiation-production double-strand breaks in cellular DNA. However, the radicals cause other types of damage than strand breaks-potential strand breaks and base damage. An attempt is made to present the interrelation of multiply damaged sites - their constitution, the problems they present to cell repair mechanisms, and their possible relationship to cell survival

  11. A Brief Review on Electro-generated Hydroxyl Radical for Organic Wastewater Mineralization

    Directory of Open Access Journals (Sweden)

    Ervin Nurhayati

    2016-05-01

    Full Text Available Hydroxyl radical is a highly reactive oxidizing agent that can be electrochemically generated on the surface of Boron doped diamond (BDD anode. Once generated, this radical will non-selectively mineralize organic pollutants to carbon dioxide, water and organic anions as the oxidation products. Its application in Advanced Oxidation Process (AOP to degrade nonbiodegradable even the recalcitrant pollutants in wastewater has been increasingly studied and even applied.

  12. Time resolved resonance Raman spectra of anilino radical and aniline radical cation

    International Nuclear Information System (INIS)

    Tripathi, G.N.R.; Schuler, R.H.

    1987-01-01

    We report, in this paper, submicrosecond time resolved resonance Raman spectra of anilino radical and its radical cation as observed in pulse radiolytic studies of the oxidation of aniline in aqueous solution. By excitation in resonance with the broad and weak electronic transition of anilino radical at 400 nm (ε--1250 M -1 cm -1 ) we have observed, for the first time, the vibrational features of this radical. The Wilson ν 8 /sub a/ ring stretching mode at 1560 cm -1 is most strongly resonance enhanced. The ν 7 /sub a/ CN stretching band at 1505 cm -1 , which is shifted to higher frequency by 231 cm -1 with respect to aniline, is also prominent. The frequency of this latter mode indicates that the CN bond in the radical has considerable double bond character. The Raman spectrum of aniline radical cation, excited in resonance with the --425 nm electronic absorption (ε--4000 M -1 cm -1 ), shows features which are similar to phenoxyl radical. Most of the observed frequencies of this radical in solution are in good agreement with vibrational energies determined by recent laser photoelectron spectroscopic studies in the vapor phase. The bands most strongly enhanced in the resonance Raman spectrum are, however, weak in the photoelectron spectrum. While the vibrational frequencies observed for anilino radical and its isoelectronic cation are quite similar, the resonance enhancement patterns are very different. In particular the ν 14 b 2 mode of anilino radical observed at 1324 cm -1 is highly resonance enhanced because of strong vibronic coupling between the 400 nm 2 A 2 -- 2 B 1 and the higher 2 B 1 -- 2 B 1 electronic transitions

  13. Learning curve of robot-assisted laparoscopic radical prostatectomy for a single experienced surgeon: comparison with simultaneous laparoscopic radical prostatectomy.

    Science.gov (United States)

    Ku, Ja Yoon; Ha, Hong Koo

    2015-04-01

    Despite the large number of analytical reports regarding the learning curve in the transition from open to robot-assisted radical prostatectomy (RARP), few comparative results with laparoscopic radical prostatectomy (LRP) have been reported. Thus, we evaluated operative and postoperative outcomes in RARP versus 100 simultaneously performed LRPs. A single surgeon had performed more than 1,000 laparoscopic operations, including 415 cases of radical nephrectomy, 85 radical cystectomies, 369 radical prostatectomies, and treatment of 212 other urological tumors, since 2009. We evaluated operative (operation time, intraoperative transfusion, complications, hospital stay, margin status, pathological stage, Gleason score) and postoperative (continence and erectile function) parameters in initial cases of RARP without tutoring compared with 100 recently performed LRPs. Mean operation time and length of hospital stay for RARP and LRP were 145.5±43.6 minutes and 118.1±39.1 minutes, and 6.4±0.9 days and 6.6±1.1 days, respectively (p=0.003 and p=0.721). After 17 cases, the mean operation time for RARP was similar to LRP (less than 2 hours). Positive surgical margins in localized cancer were seen in 11.1% and 8.9% of cases in RARP and LRP, respectively (p=0.733). At postoperative 3 months, sexual intercourse was reported in 14.0% and 12.0%, and pad-free continence in 96.0% and 81.0% in patients with RARP and LRP, respectively (p=0.796 and p=0.012). Previous large-volume experience of LRPs may shorten the learning curve for RARP in terms of oncological outcome. Additionally, previous experience with laparoscopy may improve the functional outcomes of RARP.

  14. Antioxidant and free radical scavenging activities of plant extracts ...

    African Journals Online (AJOL)

    Twenty-two species of medicinal plants collected in the Mexican state of Morelos were selected to evaluate their free radical scavenging and antioxidant activities. The extracts from the aerial parts of the plants were obtained using hexane, acetone and methanol (66 extracts). The initial qualitative screening of antioxidants ...

  15. Radical-scavenging Activity of Natural Methoxyphenols vs. Synthetic Ones using the Induction Period Method

    Directory of Open Access Journals (Sweden)

    Seiichiro Fujisawa

    2007-02-01

    Full Text Available The radical-scavenging activities of the synthetic antioxidants 2-allyl-4-X-phenol (X=NO2, Cl, Br, OCH3, COCH3, CH3, t-(CH33, C6H5 and 2,4-dimethoxyphenol, and the natural antioxidants eugenol and isoeugenol, were investigated using differential scanning calorimetry (DSC by measuring their anti-1,1-diphenyl-2-picrylhydrazyl (DPPH radical activity and the induction period for polymerization of methyl methacrylate (MMA initiated by thermal decomposition of 2,2'-azobisisobutyronitrile (AIBN and benzoyl peroxide (BPO. 2-Allyl-4-methoxyphenol and 2,4-dimethoxy-phenol scavenged not only oxygen-centered radicals (PhCOO. derived from BPO, but also carbon-centered radicals (R. derived from the AIBN and DPPH radical much more efficiently, in comparison with eugenol and isoeugenol. 2-Allyl-4-methoxyphenol may be useful for its lower prooxidative activity.

  16. Efficient peroxydisulfate activation process not relying on sulfate radical generation for water pollutant degradation.

    Science.gov (United States)

    Zhang, Tao; Chen, Yin; Wang, Yuru; Le Roux, Julien; Yang, Yang; Croué, Jean-Philippe

    2014-05-20

    Peroxydisulfate (PDS) is an appealing oxidant for contaminated groundwater and toxic industrial wastewaters. Activation of PDS is necessary for application because of its low reactivity. Present activation processes always generate sulfate radicals as actual oxidants which unselectively oxidize organics and halide anions reducing oxidation capacity of PDS and producing toxic halogenated products. Here we report that copper oxide (CuO) can efficiently activate PDS under mild conditions without producing sulfate radicals. The PDS/CuO coupled process is most efficient at neutral pH for decomposing a model compound, 2,4-dichlorophenol (2,4-DCP). In a continuous-flow reaction with an empty-bed contact time of 0.55 min, over 90% of 2,4-DCP (initially 20 μM) and 90% of adsorbable organic chlorine (AOCl) can be removed at the PDS/2,4-DCP molar ratio of 1 and 4, respectively. Based on kinetic study and surface characterization, PDS is proposed to be first activated by CuO through outer-sphere interaction, the rate-limiting step, followed by a rapid reaction with 2,4-DCP present in the solution. In the presence of ubiquitous chloride ions in groundwater/industrial wastewater, the PDS/CuO oxidation shows significant advantages over sulfate radical oxidation by achieving much higher 2,4-DCP degradation capacity and avoiding the formation of highly chlorinated degradation products. This work provides a new way of PDS activation for contaminant removal.

  17. Efficient peroxydisulfate activation process not relying on sulfate radical generation for water pollutant degradation

    KAUST Repository

    Zhang, Tao

    2014-05-20

    Peroxydisulfate (PDS) is an appealing oxidant for contaminated groundwater and toxic industrial wastewaters. Activation of PDS is necessary for application because of its low reactivity. Present activation processes always generate sulfate radicals as actual oxidants which unselectively oxidize organics and halide anions reducing oxidation capacity of PDS and producing toxic halogenated products. Here we report that copper oxide (CuO) can efficiently activate PDS under mild conditions without producing sulfate radicals. The PDS/CuO coupled process is most efficient at neutral pH for decomposing a model compound, 2,4-dichlorophenol (2,4-DCP). In a continuous-flow reaction with an empty-bed contact time of 0.55 min, over 90% of 2,4-DCP (initially 20 μM) and 90% of adsorbable organic chlorine (AOCl) can be removed at the PDS/2,4-DCP molar ratio of 1 and 4, respectively. Based on kinetic study and surface characterization, PDS is proposed to be first activated by CuO through outer-sphere interaction, the rate-limiting step, followed by a rapid reaction with 2,4-DCP present in the solution. In the presence of ubiquitous chloride ions in groundwater/industrial wastewater, the PDS/CuO oxidation shows significant advantages over sulfate radical oxidation by achieving much higher 2,4-DCP degradation capacity and avoiding the formation of highly chlorinated degradation products. This work provides a new way of PDS activation for contaminant removal. © 2014 American Chemical Society.

  18. Complex-radical copolymerization of vinyl monomers on organoelemental initiators

    International Nuclear Information System (INIS)

    Grishin, D.F.

    1993-01-01

    Data on regularities of the initiation and growth of the (co)polymerization of polar vinyl series monomers on organo-elemental initiator, organo-boron in particular, are generalized. The effect of organo-metallic compounds and some phenol type inhibitors on the rate of acrylate (co)polymerization is analyzed from view of the change of electroacceptor properties (electrophilicity) of macroradicals

  19. Measurement of glucose utilization by Pseudomonas fluorescens that are free-living and that are attached to surfaces

    International Nuclear Information System (INIS)

    Fletcher, M.

    1986-01-01

    The assimilation and respiration of glucose by attached and free-living Pseudomonas fluorescens were compared. The attachment surfaces were polyvinylidene fluoride, polyethylene, and glass. Specific uptake of [ 1 C]glucose was determined after bacterial biomass was measured by (1) microscopic counts or (2) prelabelling of cells by providing [ 3 H]leucine as substrate, followed by dual-labelling scintillation counting. The glucose concentration was 1.4, 3.5, 5.5, 7.6, or 9.7 μM. Glucose assimilation by cells which became detached from the surfaces during incubation with glucose was also measured after the detached cells were collected by filtration. The composition of the substratum had no effect on the amount of glucose assimilated by attached cells. Glucose assimilation by attached cells exceeded that by free-living cells by a factor of between 2 and 5 or more, and respiration of glucose by surface-associated cells was greater than that by free-living bacteria. Glucose assimilation by detached cells was greater than that by attached bacteria. Measurements of biomass by microscopic counts gave more consistent results than those obtained with dual-labelling, but in general, results obtained by both methods were corroborative

  20. Intramolecular transformation of thiyl radicals to α-aminoalkyl radicals: 'ab initio' calculations on homocystein

    International Nuclear Information System (INIS)

    Chhun, S.; Berges, J.; Bleton, V.; Abedinzadeh, Z.

    2000-01-01

    One-electron oxidation of thiols by oxidizing radicals leads to the formation of thiyl radical and carbon-centered radicals. It has been shown experimentally that in the absence of oxygen, the thiyl radicals derived from certain thiols of biological interest such as glutathion, cysteine and homocysteine decay rapidly by intramolecular rearrangement reactions into the carbon-centered radical. In the present work we have investigated theoretically the structure and the stability of thiyl and carbon-centered radicals of homocysteine in order to check the possibility of this rearrangement. (author)

  1. Free radical transfer in polymers

    International Nuclear Information System (INIS)

    Sonntag, C. von; Bothe, E.; Ulanski, P.

    1998-01-01

    For the present study of free-radical transfer in polymers pulse radiolysis and product studies have been carried out in aqueous solutions using thus far only the water-soluble polymers polyacrylic acid, polymethacrylic acid and polyvinyl alcohol. When OH radicals, generated in the radiolysis of N 2 O-saturated aqueous solutions, react with polymers the lifetime of the polymer radical thus created very much depends on the number of radicals per polymer chain. When there are a large number of radicals per chain their bimolecular decay may be faster than the corresponding (diffusion controlled) decay of monomeric radicals, but when the macromolecule contains only few or even just one radical their lifetime is considerably prolonged. Highly charged polymers such as polyacrylic acid at high pH attain a rod-like conformation which again favors a long lifetime of the radicals. Under such conditions, radical transfer reactions can occur. For example, in polyacrylic acid OH radicals generate two kinds of radicals side by side. The radical in β-position to the carboxylate group converts into the thermodynamically more stable α-radicals by an H-transfer reaction as can be followed by spectrophotometry. Besides radical transfer reactions β-fragmentation reactions occur causing chain scission. Such reactions can be followed in a pulse radiolysis experiment by conductometry, because counter ions are released upon chain scission. Such a process is especially effective in the case of polymethacrylic acid, where it results in a chain depolymerization. An intramolecular H-abstraction is also observed in the γ-radiolysis of polyacrylic acid with the corresponding peroxyl radicals. This causes a chain reaction to occur. The resulting hydroperoxides are unstable and decarboxylate given rise to acetylacetone-like products. In polyvinyl alcohol the peroxyl radicals in α-position to the alcohol function undergo HO 2 -elimination. This prevents a scission of the polymer chain in the

  2. Absolute photoionization cross-section of the methyl radical.

    Science.gov (United States)

    Taatjes, Craig A; Osborn, David L; Selby, Talitha M; Meloni, Giovanni; Fan, Haiyan; Pratt, Stephen T

    2008-10-02

    The absolute photoionization cross-section of the methyl radical has been measured using two completely independent methods. The CH3 photoionization cross-section was determined relative to that of acetone and methyl vinyl ketone at photon energies of 10.2 and 11.0 eV by using a pulsed laser-photolysis/time-resolved synchrotron photoionization mass spectrometry method. The time-resolved depletion of the acetone or methyl vinyl ketone precursor and the production of methyl radicals following 193 nm photolysis are monitored simultaneously by using time-resolved synchrotron photoionization mass spectrometry. Comparison of the initial methyl signal with the decrease in precursor signal, in combination with previously measured absolute photoionization cross-sections of the precursors, yields the absolute photoionization cross-section of the methyl radical; sigma(CH3)(10.2 eV) = (5.7 +/- 0.9) x 10(-18) cm(2) and sigma(CH3)(11.0 eV) = (6.0 +/- 2.0) x 10(-18) cm(2). The photoionization cross-section for vinyl radical determined by photolysis of methyl vinyl ketone is in good agreement with previous measurements. The methyl radical photoionization cross-section was also independently measured relative to that of the iodine atom by comparison of ionization signals from CH3 and I fragments following 266 nm photolysis of methyl iodide in a molecular-beam ion-imaging apparatus. These measurements gave a cross-section of (5.4 +/- 2.0) x 10(-18) cm(2) at 10.460 eV, (5.5 +/- 2.0) x 10(-18) cm(2) at 10.466 eV, and (4.9 +/- 2.0) x 10(-18) cm(2) at 10.471 eV. The measurements allow relative photoionization efficiency spectra of methyl radical to be placed on an absolute scale and will facilitate quantitative measurements of methyl concentrations by photoionization mass spectrometry.

  3. Air-spun PLA nanofibers modified with reductively sheddable hydrophilic surfaces for vascular tissue engineering: synthesis and surface modification.

    Science.gov (United States)

    Ko, Na Re; Sabbatier, Gad; Cunningham, Alexander; Laroche, Gaétan; Oh, Jung Kwon

    2014-02-01

    Polylactide (PLA) is a class of promising biomaterials that hold great promise for various biological and biomedical applications, particularly in the field of vascular tissue engineering where it can be used as a fibrous mesh to coat the inside of vascular prostheses. However, its hydrophobic surface providing nonspecific interactions and its limited ability to further modifications are challenges that need to be overcome. Here, the development of new air-spun PLA nanofibers modified with hydrophilic surfaces exhibiting reduction response is reported. Surface-initiated atom transfer radical polymerization allows for grafting pendant oligo(ethylene oxide)-containing polymethacrylate (POEOMA) from PLA air-spun fibers labeled with disulfide linkages. The resulting PLA-ss-POEOMA fibers exhibit enhanced thermal stability and improved surface properties, as well as thiol-responsive shedding of hydrophilic POEOMA by the cleavage of its disulfide linkages in response to reductive reactions, thus tuning the surface properties. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Comparative analysis between clinical outcomes of primary radical resection and second completion radical resection for T2 gallbladder cancer: single-center experience.

    Science.gov (United States)

    Cho, Seong Yeon; Park, Sang-Jae; Kim, Seong Hoon; Han, Sung-Sik; Kim, Young-Kyu; Lee, Kwang-Woong

    2010-07-01

    Gallbladder (GB) cancer may be discovered incidentally by histopathologic examination following simple cholecystectomy. Incidental GB cancer > or =T2 or > or =N1 needs a second radical resection. It is a matter of concern whether the prognosis may be worse in patients with T2GB cancer who undergo a second radical resection than in those who undergo primary radical resection. Between March 2001 and March 2009, 21 patients underwent a one-step operation (OSO group), and 17 patients underwent a two-step operation (TSO group) for T2GB cancer. We compared clinicopathologic factors and survival between patients in the OSO group (n = 9) and those in the TSO group (n = 9) with T2N0M0 GB cancer and between patients in the OSO group (n = 12) and those in the TSO group (n = 8) with T2N1M0 GB cancer. Except for patient age, clinicopathologic factors as well as disease-free survival were not significantly different between the OSO group and the TSO group in the aforementioned cancer stages. Patient age was significantly higher in the OSO group than in the TSO group. Second completion radical resection following initial simple cholecystectomy (TSO) provided a survival benefit similar to that of primary radical surgery (OSO) for patients with both T2N0M0 and T2N1M0 GB cancers in our study.

  5. Influence of various scavengers of •OH radicals on the radiation sensitivity of yeast and bacteria.

    Science.gov (United States)

    Múčka, Viliam; Bláha, Pavel; Čuba, Václav; Červenák, Jaroslav

    2013-12-01

    To quantitatively investigate the influence of various •OH (hydroxyl radical) scavengers on the radiation sensitivity of yeast and bacteria, particularly to define the relationship between the protective effect of a scavenger and its •OH scavenging efficiency. In order to study the protective effect of •OH scavengers we used various concentrations of four scavengers (methanol, potassium formate, ethanol and ascorbic acid) in isotonic salt solutions. These solutions containing live yeast (Saccharomyces cerevisiae) or bacteria (Escherichia coli) were irradiated with (60)Co isotope γ -radiation using two different doses and dose rates. The number of surviving cells was determined prior to and after irradiation both in suspension with and without scavengers. The surviving fractions after irradiation with and without the scavenger were evaluated. The main results of the paper were: The surviving fraction increased approximately linearly within the measured interval with increasing concentration of the scavenger. The same dependences were found for the protecting effect depending on the scavenging efficiency. The slopes of these dependences (k) were found to be characteristic for each scavenger. The k value determined the degree in which the scavenging of •OH radicals participated in the protection of living cells. The protective effects of scavengers at the same scavenging efficiency were different and unique for each scavenger. No simple relation was found between the efficiency of scavenger k and the rate constant kOH of the reactions between scavengers and •OH radicals. Our results suggest that the studied scavengers effectively protected yeast and bacteria against ionizing radiation. Although the scavenging of •OH radicals seems to be important for protection of living cells, it is clearly not the only process on which the protection is based.

  6. Microwave plasma initiated graft copolymerization modification of monomers onto PTFE surface

    International Nuclear Information System (INIS)

    Guan Weishu; Wen Yunjian; Fang Yan; Yin Yongxiang

    1996-02-01

    A graft copolymerization modification technique of monomers onto polytetrafluoroethylene (PTFE) surface initiated by a 2.45 GHz non-equilibrium microwave plasma has been investigated. Standard X-Ray Photoelectron Spectroscopy (XPS), Attenuated Total Reflectance-Fourier Transform Infrared Spectroscopy (ATR-FTIR), Scanning Electron Microscopy (sEM) and wetting techniques were used for examination and analysis of samples. Considerable changes in chemical structure, composition and in morphology of grafted surface of PTFE were found. Results showed the occurrence of noticeable defluorination and cross-linked structure on grafted surface, and indicated that different kinds and contents of oxygen-containing functional groups were introduced into the surface of PTFE. Wetting and adhesion experiment of the sample proved that significant improvements in hydrophilicity and adhesion of surface were exhibited. These results confirmed the success of grafting. (8 refs., 7 figs., 1 tab.)

  7. Learning in Different Modes: The Interaction Between Incremental and Radical Change

    DEFF Research Database (Denmark)

    Petersen, Anders Hedegaard; Boer, Harry; Gertsen, Frank

    2004-01-01

    The objective of the study presented in this article is to contribute to the development of theory on continuous innovation, i.e. the combination of operationally effective exploitation and strategically flexible exploration. A longitudinal case study is presented of the interaction between...... incremental and radical change in Danish company, observed through the lens of organizational learning. The radical change process is described in five phases, each of which had its own effects on incremental change initiatives in the company. The research identified four factors explaining these effects, all...

  8. Importance of initial buoyancy field on evolution of mantle thermal structure: Implications of surface boundary conditions

    Directory of Open Access Journals (Sweden)

    Petar Glišović

    2015-01-01

    Full Text Available Although there has been significant progress in the seismic imaging of mantle heterogeneity, the outstanding issue that remains to be resolved is the unknown distribution of mantle temperature anomalies in the distant geological past that give rise to the present-day anomalies inferred by global tomography models. To address this question, we present 3-D convection models in compressible and self-gravitating mantle initialised by different hypothetical temperature patterns. A notable feature of our forward convection modelling is the use of self-consistent coupling of the motion of surface tectonic plates to the underlying mantle flow, without imposing prescribed surface velocities (i.e., plate-like boundary condition. As an approximation for the surface mechanical conditions before plate tectonics began to operate we employ the no-slip (rigid boundary condition. A rigid boundary condition demonstrates that the initial thermally-dominated structure is preserved, and its geographical location is fixed during the evolution of mantle flow. Considering the impact of different assumed surface boundary conditions (rigid and plate-like on the evolution of thermal heterogeneity in the mantle we suggest that the intrinsic buoyancy of seven superplumes is most-likely resolved in the tomographic images of present-day mantle thermal structure. Our convection simulations with a plate-like boundary condition reveal that the evolution of an initial cold anomaly beneath the Java-Indonesian trench system yields a long-term, stable pattern of thermal heterogeneity in the lowermost mantle that resembles the present-day Large Low Shear Velocity Provinces (LLSVPs, especially below the Pacific. The evolution of subduction zones may be, however, influenced by the mantle-wide flow driven by deeply-rooted and long-lived superplumes since Archean times. These convection models also detect the intrinsic buoyancy of the Perm Anomaly that has been identified as a unique

  9. Theoretical investigation of radical species formed from L-α-alanine under gamma-irradiation

    International Nuclear Information System (INIS)

    Simion, C.

    2008-01-01

    Gamma-irradiated L-α-alanine used in EPR-coupled dosimetry has a complex EPR spectrum at room temperature. Changing the temperature or other conditions of the irradiated samples leads to varied EPR spectrum, i.e., some components disappear and/or new ones are formed. We used both molecular mechanics (MM+) and semiempirical (AM1) methods to perform a theoretical investigation of the seven radical species that have been experimentally detected. We established their order of priority in the given simulation conditions (at 0 K, in vacuo). The formation stages advanced for these long-lived radical species were characterized by a theoretical determination of the reaction enthalpies. (author)

  10. Voting for the populist radical right in Switzerland: A panel data analysis

    OpenAIRE

    Orsholits, Dan

    2017-01-01

    Working-class voters no longer systematically support left-wing political parties. This finding was initially viewed as signalling the end of class voting and the decline of the class cleavage's salience. Yet, in Western Europe, it would seem to be turning to a new party family: the populist radical right. This realignment is thought to be linked to globalization and the societal and economic changes that it brings. Populist radical right parties are thought to channel the frustrations of wor...

  11. Origin and evolution of the free radical theory of aging: a brief personal history, 1954–2009.

    Science.gov (United States)

    Harman, Denham

    2009-12-01

    Aging is the progressive accumulation in an organism of diverse, deleterious changes with time that increase the chance of disease and death. The basic chemical process underlying aging was first advanced by the free radical theory of aging (FRTA) in 1954: the reaction of active free radicals, normally produced in the organisms, with cellular constituents initiates the changes associated with aging. The involvement of free radicals in aging is related to their key role in the origin and evolution of life. The initial low acceptance of the FRTA by the scientific community, its slow growth, manifested by meetings and occasional papers based on the theory, prompted this account of the intermittent growth of acceptance of the theory over the past nearly 55 years.

  12. Surface functionalization of solid state ultra-high molecular weight polyethylene through chemical grafting

    Science.gov (United States)

    Sherazi, Tauqir A.; Rehman, Tayyiba; Naqvi, Syed Ali Raza; Shaikh, Ahson Jabbar; Shahzad, Sohail Anjum; Abbas, Ghazanfar; Raza, Rizwan; Waseem, Amir

    2015-12-01

    The surface of ultra-high molecular weight polyethylene (UHMWPE) powder was functionalized with styrene using chemical grafting technique. The grafting process was initiated through radical generation on base polymer matrix in the solid state by sodium thiosulfate, while peroxides formed at radical sites during this process were dissociated by ceric ammonium nitrate. Various factors were optimized and reasonably high level of monomer grafting was achieved, i.e., 15.6%. The effect of different acids as additive and divinyl benzene (DVB) as a cross-linking agent was also studied. Post-grafting sulfonation was conducted to introduce the ionic moieties to the grafted polymer. Ion-exchange capacity (IEC) was measured experimentally and is found to be 1.04 meq g-1, which is in close agreement with the theoretical IEC values. The chemical structure of grafted and functionalized polymer was characterized by attenuated total reflection infrared spectroscopy (ATR-FTIR) and thermal properties were investigated by thermo gravimetric analysis (TGA) and differential scanning calorimetry (DSC). Thermal analysis depicts that the presence of radicals on the polymer chain accelerates the thermal decomposition process. The results signify that the chemical grafting is an effective tool for substantial surface modification and subsequent functionalization of polyethylene.

  13. Surface grafting of a dense and rigid coordination polymer based on tri-para-carboxy-polychlorotriphenylmethyl radical and copper acetate

    KAUST Repository

    Mugnaini, Veró nica; Paradinas, Markos; Shekhah, Osama; Roques, Nans; Ocal, Carmen; Wö ll, Christof H.; Veciana, Jaume

    2013-01-01

    The step-by-step method is here presented as suitable to anchor on appropriately functionalized gold surfaces a metal-organic coordination polymer based on a non-planar trigonal tri-para-carboxy-polychlorotriphenylmethyl radical derivative and copper acetate. The structural characteristics of the grafted coordination polymer are derived during the step-wise growth from the real time changes in refractive index and oscillation frequency. The film thickness, as measured by scanning force microscopy, combined with the mass uptake value from the quartz crystal microbalance, are used to estimate an average density of the grafted metal-organic coordination polymer that suggests the formation of a dense and rather rigid thin film. This journal is © 2013 The Royal Society of Chemistry.

  14. On fatigue crack growth mechanisms of MMC: Reflection on analysis of 'multi surface initiations'

    International Nuclear Information System (INIS)

    Mkaddem, A.; El Mansori, M.

    2009-01-01

    This work attempts to examine the mechanisms of fatigue when cracks synergetically initiate in more than one site at the specimen surface. The metal matrix composites (MMC) i.e. silicon carbide particles reinforced aluminium matrix composites (Al/SiC p -MMC), seem to be good candidates to accelerate fatigue failures following multi surface initiations (MSI). Closure effects of MSI mechanisms on the variation of fatigue behaviour are explored for various stress states. Experiments were carried out using non pre-treated and pre-treated specimens. Using an Equivalent Ellipse Method (EEM), it is shown that the aspect of surface finish of specimen plays an important role on crack growth. Scanning Electron Microscope (SEM) inspections have lead to distinguishing the initiation regions from propagation regions and final separation regions. It is also revealed that the total lifetime of specimens is sensitive to heat treatment. Moreover, it is found that the appearance of MSI in cycled materials is more probable at high level of fatigue loads.

  15. Increased recombination of CH3 radicals on stainless steel

    International Nuclear Information System (INIS)

    Gorodetsky, A.E.; Zalavutdinov, R.Kh.; Zakharov, A.P.; Vnukov, S.P.; Varshavskaya, I.G.; Makhankov, A.N.; Mazul, I.V.; Federici, G.

    2005-01-01

    By using a so-called 'stream technique', which consists of flowing gas in laminar regime along a quartz tube, we determine that CH 3 radicals are completely removed from the pumped mixture (CH 4 /C X H Y /H 2 /H/CH 3 ) after several hundred collisions with the inner surface of a stainless steel insert (T = 380-470 K). The methyl sticking coefficient decreased to ∼10 -6 and the recombination coefficient increased up to ∼0.01 at impingement with the metal surface. After passing through the heated zone no hydrocarbon deposition occurred at 300 K. However, unsaturated hydrocarbons, which formed in discharge zone and appeared as a result of interaction of radicals with stainless steel, condensed in a liquid phase at a temperature of ∼130 K and partial pressure of 0.01-0.1 Pa. Liquid films underwent partial polymerization and formed island deposits, which were stable at 300 K

  16. Constraining storm-scale forecasts of deep convective initiation with surface weather observations

    Science.gov (United States)

    Madaus, Luke

    Successfully forecasting when and where individual convective storms will form remains an elusive goal for short-term numerical weather prediction. In this dissertation, the convective initiation (CI) challenge is considered as a problem of insufficiently resolved initial conditions and dense surface weather observations are explored as a possible solution. To better quantify convective-scale surface variability in numerical simulations of discrete convective initiation, idealized ensemble simulations of a variety of environments where CI occurs in response to boundary-layer processes are examined. Coherent features 1-2 hours prior to CI are found in all surface fields examined. While some features were broadly expected, such as positive temperature anomalies and convergent winds, negative temperature anomalies due to cloud shadowing are the largest surface anomaly seen prior to CI. Based on these simulations, several hypotheses about the required characteristics of a surface observing network to constrain CI forecasts are developed. Principally, these suggest that observation spacings of less than 4---5 km would be required, based on correlation length scales. Furthermore, it is anticipated that 2-m temperature and 10-m wind observations would likely be more relevant for effectively constraining variability than surface pressure or 2-m moisture observations based on the magnitudes of observed anomalies relative to observation error. These hypotheses are tested with a series of observing system simulation experiments (OSSEs) using a single CI-capable environment. The OSSE results largely confirm the hypotheses, and with 4-km and particularly 1-km surface observation spacing, skillful forecasts of CI are possible, but only within two hours of CI time. Several facets of convective-scale assimilation, including the need for properly-calibrated localization and problems from non-Gaussian ensemble estimates of the cloud field are discussed. Finally, the characteristics

  17. Sulfate radical-induced degradation of Acid Orange 7 by a new magnetic composite catalyzed peroxymonosulfate oxidation process

    International Nuclear Information System (INIS)

    Chen, Dan; Ma, Xiaolong; Zhou, Jizhi; Chen, Xi; Qian, Guangren

    2014-01-01

    Graphical abstract: Organic dyes could be absorbed on the surface of the composite or dispersed in the solution. Sulfate radicals (SO 4 · − ) generated by the synergistic reaction between peroxymonosulfate (PMS) and the composite, attacked the organic functional groups of the dyes molecules both adsorbed on the composite surface and dispersed in the solution, which resulted in the degradation of AO7 dye. - Highlights: • A new composite was synthesized successfully via microwave hydrothermal method. • The complete degradation in the system of FLCN and PMS can be achieved. • The catalytic behavior of FLCN can be reused at least for five times. • The AO7 degradation mechanism in the system of FLCN and PMS was demonstrated. - Abstract: We synthesized a novel magnetic composite, Fe 3 O 4 /Cu(Ni)Cr-LDH, as a heterogeneous catalyst for the degradation of organic dyes in the solution using sulfate radical-based advanced oxidation processes. The physicochemical properties of the composite synthesized via two-step microwave hydrothermal method were characterized by several techniques, such as X-ray diffraction (XRD), inductively coupled plasma (ICP), transmission electron microscopy (TEM) and vibrating sample magnetometer (VSM). The degradation tests were performed at 25 °C with Acid Orange 7 (AO7) initial concentration of 25 mg/L and AO7/peroxymonosulfate (PMS) molar ratio of 1:10, which showed that the complete degradation by Fe 3 O 4 /Cu 1.5 Ni 0.5 Cr-LDH could be achieved and the mineralization rate could reach 46%. PMS was activated by Cu (II) and Fe (II/III) of Fe 3 O 4 /Cu(Ni)Cr-LDH to generate sulfate radicals (SO 4 · − ). Subsequently, the organic functional groups of AO7 molecules were destroyed by sulfate radicals (SO 4 · − ), inducing the degradation of AO7. Moreover, the catalytic behavior of the catalysts could be reused five times. Therefore, our work suggested that the Fe 3 O 4 /Cu(Ni)Cr-LDH composite could be applied widely for the

  18. Glutathione--hydroxyl radical interaction: a theoretical study on radical recognition process.

    Directory of Open Access Journals (Sweden)

    Béla Fiser

    Full Text Available Non-reactive, comparative (2 × 1.2 μs molecular dynamics simulations were carried out to characterize the interactions between glutathione (GSH, host molecule and hydroxyl radical (OH(•, guest molecule. From this analysis, two distinct steps were identified in the recognition process of hydroxyl radical by glutathione: catching and steering, based on the interactions between the host-guest molecules. Over 78% of all interactions are related to the catching mechanism via complex formation between anionic carboxyl groups and the OH radical, hence both terminal residues of GSH serve as recognition sites. The glycine residue has an additional role in the recognition of OH radical, namely the steering. The flexibility of the Gly residue enables the formation of further interactions of other parts of glutathione (e.g. thiol, α- and β-carbons with the lone electron pair of the hydroxyl radical. Moreover, quantum chemical calculations were carried out on selected GSH/OH(• complexes and on appropriate GSH conformers to describe the energy profile of the recognition process. The relative enthalpy and the free energy changes of the radical recognition of the strongest complexes varied from -42.4 to -27.8 kJ/mol and from -21.3 to 9.8 kJ/mol, respectively. These complexes, containing two or more intermolecular interactions, would be the starting configurations for the hydrogen atom migration to quench the hydroxyl radical via different reaction channels.

  19. Analysis of surface properties of fixed and live cells using derivatized agarose beads.

    Science.gov (United States)

    Navarro, Vanessa M; Walker, Sherri L; Badali, Oliver; Abundis, Maria I; Ngo, Lylla L; Weerasinghe, Gayani; Barajas, Marcela; Zem, Gregory; Oppenheimer, Steven B

    2002-01-01

    A novel assay has been developed for the histochemical characterization of surface properties of cells based on their adhesion to agarose beads derivatized with more than 100 types of molecules, including sugars, lectins and other proteins, and amino acids. The assay simply involves mixing small quantities of washed cells and beads in droplets on glass microscope slides and determining to which beads various cell types adhere. Distilled water was found to be the best medium for this assay because added ions or molecules in other media inhibit adhesion in some cases. Many cells, however, cannot tolerate distilled water. Here we show that cells fixed with either of two fixatives (1% formaldehyde or Prefer fixative) displayed similar bead-binding properties as did live cells. Specificity of cell-bead binding was tested by including specific free molecules in the test suspensions in hapten-type inhibition experiments. If a hapten compound inhibited live-cell adhesion to a specific bead, it also inhibited fixed-cell adhesion to a specific bead. The results of these experiments suggest that fixed cells display authentic surface properties, opening the door for the use of this assay with many cell types that cannot tolerate distilled water.

  20. Surface modification of an epoxy resin with polyamines and polydopamine: The effect on the initial electroless copper deposition

    Energy Technology Data Exchange (ETDEWEB)

    Schaubroeck, David, E-mail: David.Schaubroeck@elis.ugent.be [Center for Microsystems Technology (CMST), imec and Ghent University, Technologiepark 914A, B-9052 Ghent (Belgium); Mader, Lothar [Center for Microsystems Technology (CMST), imec and Ghent University, Technologiepark 914A, B-9052 Ghent (Belgium); De Geyter, Nathalie; Morent, Rino [Research Unit Plasma Technology (RUPT), Department of Applied Physics, Faculty of Engineering, Ghent University, Sint-Pietersnieuwstraat 41, B-9000 Ghent (Belgium); Dubruel, Peter [Polymer Chemistry and Biomaterials Research Group, Ghent University, Krijgslaan 281 S4 bis, B-9000 Ghent (Belgium); Vanfleteren, Jan [Center for Microsystems Technology (CMST), imec and Ghent University, Technologiepark 914A, B-9052 Ghent (Belgium)

    2014-06-01

    This paper describes the influence of polydopamine and polyamine surface modifications of an etched epoxy cresol novolak (ECN) resin on the initial electroless copper deposition. Three different strategies to introduce polyamines on a surface in aqueous environment are applied: via polyethyleneimine adsorption (PEI), via polydopamine and via polyamines grafted to polydopamine. Next, the influence of these surface modifications on the catalytic palladium activation is investigated through X-ray photoelectron spectroscopy (XPS) analysis. Finally, the initial electroless copper deposition on modified epoxy surfaces is evaluated using SEM and Energy Dispersive Spectroscopy (EDS). Grafted polyamines on polydopamine surface modifications result in a large increase of the initial deposited copper.

  1. Quantification of the number of EP3 receptors on a living CHO cell surface by the AFM

    International Nuclear Information System (INIS)

    Kim, Hyonchol; Arakawa, Hideo; Hatae, Noriyuki; Sugimoto, Yukihiko; Matsumoto, Osamu; Osada, Toshiya; Ichikawa, Atsushi; Ikai, Atsushi

    2006-01-01

    The distribution of EP3 receptors on a living cell surface was quantitatively studied by atomic force microscopy (AFM). Green fluorescent protein (GFP) was introduced to the extracellular region of the EP3 receptor on a CHO cell. A microbead was used as a probe to ensure certain contact area, whose surface was coated with anti-GFP antibody. The interactions between the antibodies and GFP molecules on the cell surface were recorded to observe the distribution of the receptors. The result indicated that EP3 receptors were distributed on the CHO cell surface not uniformly but in small patches coincident with immunohistochemical observation. Repeated measurements on the same area of cell surface gave confirmation that it was unlikely that the receptors were extracted from the cell membrane during the experiments. The measurement of single molecular interaction between GFP and the anti-GFP antibody was succeeded on the cell surface using compression-free force spectroscopy. The value of separation work required to break a single molecular pair was estimated to be about 1.5x10 -18 J. The number of EP3 receptor on the CHO cell surface was estimated using this value to be about 1x10 4 under the assumption that the area of the cell surface was about 5000 μm 2 . These results indicated that the number of receptors on a living cell surface could be quantified through the force measurement by the AFM

  2. Development of a new free radical absorption capacity assay method for antioxidants: aroxyl radical absorption capacity (ARAC).

    Science.gov (United States)

    Nagaoka, Shin-ichi; Nagai, Kanae; Fujii, Yuko; Ouchi, Aya; Mukai, Kazuo

    2013-10-23

    A new free radical absorption capacity assay method is proposed with use of an aroxyl radical (2,6-di-tert-butyl-4-(4'-methoxyphenyl)phenoxyl radical) and stopped-flow spectroscopy and is named the aroxyl radical absorption capacity (ARAC) assay method. The free radical absorption capacity (ARAC value) of each tocopherol was determined through measurement of the radical-scavenging rate constant in ethanol. The ARAC value could also be evaluated through measurement of the half-life of the aroxyl radical during the scavenging reaction. For the estimation of the free radical absorption capacity, the aroxyl radical was more suitable than the DPPH radical, galvinoxyl, and p-nitrophenyl nitronyl nitroxide. The ARAC value in tocopherols showed the same tendency as the free radical absorption capacities reported previously, and the tendency was independent of an oxygen radical participating in the scavenging reaction and of a medium surrounding the tocopherol and oxygen radical. The ARAC value can be directly connected to the free radical-scavenging rate constant, and the ARAC method has the advantage of treating a stable and isolable radical (aroxyl radical) in a user-friendly organic solvent (ethanol). The ARAC method was also successfully applied to a palm oil extract. Accordingly, the ARAC method would be useful in free radical absorption capacity assay of antioxidative reagents and foods.

  3. TEMPO addition into pre-irradiated fluoropolymers and living-radical graft polymerization of styrene for preparation of polymer electrolyte membranes

    Energy Technology Data Exchange (ETDEWEB)

    Sawada, Shin-ichi, E-mail: sawada.shinnichi@jaea.go.j [Conducting Polymer Materials Research Group, Quantum Beam Science Directorate, Japan Atomic Energy Agency (JAEA), 1233 Watanuki, Takasaki, Gunma 370-1292 (Japan); Department of Nuclear Engineering and Management, Graduate School of Engineering, University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656 (Japan); Suzuki, Akihiro; Terai, Takayuki [Department of Nuclear Engineering and Management, Graduate School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656 (Japan); Maekawa, Yasunari, E-mail: maekawa.yasunari@jaea.go.j [Conducting Polymer Materials Research Group, Quantum Beam Science Directorate, Japan Atomic Energy Agency (JAEA), 1233 Watanuki, Takasaki, Gunma 370-1292 (Japan)

    2010-04-15

    We prepared proton exchange membranes (PEMs) by 2,2,6,6-tetramethylpiperidinyl-1-oxy (TEMPO)-mediated living-radical graft polymerization (LRGP) of styrene into fluoropolymer films and subsequent sulfonation. Poly(vinylidene fluoride) (PVDF) and poly(ethylene-co-tetrafluoroethylene) (ETFE) films were first irradiated and then treated with TEMPO solutions in various solvents. TEMPO addition was confirmed by the test of styrene grafting into TEMPO-treated films at 60 deg. C, at which the LRGP never proceeds. This test enabled us to differentiate the LRGP from the conventional graft polymerization. In order to gain a deep insight about TEMPO-addition reaction, the TEMPO-penetration behavior into the base polymer films was examined by a permeation experiment and computer simulation. Xylene and dioxane were appropriate solvents for the complete introduction of TEMPO into PVDF and ETFE films, respectively. Then, the LRGP of styrene was performed based on the fully TEMPO-capped films at 125 deg. C with various solvents. By using an alcoholic solvent, the degree of grafting was enhanced and it reached a maximum of 38%. This grafted film was sulfonated to prepare a PEM showing an ion exchange capacity of 2.2 meq/g and proton conductivity of 1.6x10{sup -1} S/cm.

  4. Formation of Hydroxylamine from Ammonia and Hydroxyl Radicals

    Science.gov (United States)

    Krim, Lahouari; Zins, Emilie-Laure

    2014-06-01

    In the interstellar medium, as well as in icy comets, ammonia may be a crucial species in the first step toward the formation of amino-acids and other prebiotic molecules such as hydroxylamine (NH2OH). It is worth to notice that the NH3/H2 ratio in the ISM is 3 10-5 compared the H2O/H2 one which is only 7 10-5. Using either electron-UV irradiations of water-ammonia ices or successive hydrogenation of solid nitric oxide, laboratory experiments have already shown the feasibility of reactions that may take place on the surface of ice grains in molecular clouds, and may lead to the formation of this precursor. Herein is proposed a new reaction pathway involving ammonia and hydroxyl radicals generated in a microwave discharge. Experimental studies, at 3 and 10 K, in solid phase as well as in neon matrix have shown that this reaction proceed via a hydrogen abstraction, leading to the formation of NH2 radical, that further recombine with hydroxyl radical to form hydroxylamine, under non-energetic conditions.

  5. Free radical reaction characteristics of coal low-temperature oxidation and its inhibition method.

    Science.gov (United States)

    Li, Zenghua; Kong, Biao; Wei, Aizhu; Yang, Yongliang; Zhou, Yinbo; Zhang, Lanzhun

    2016-12-01

    Study on the mechanism of coal spontaneous combustion is significant for controlling fire disasters due to coal spontaneous combustion. The free radical reactions can explain the chemical process of coal at low-temperature oxidation. Electron spin resonance (ESR) spectroscopy was used to measure the change rules of the different sorts and different granularity of coal directly; ESR spectroscopy chart of free radicals following the changes of temperatures was compared by the coal samples applying air and blowing nitrogen, original coal samples, dry coal samples, and demineralized coal samples. The fragmentation process was the key factor of producing and initiating free radical reactions. Oxygen, moisture, and mineral accelerated the free radical reactions. Combination of the free radical reaction mechanism, the mechanical fragmentation leaded to the elevated CO concentration, fracturing of coal pillar was more prone to spontaneous combustion, and spontaneous combustion in goaf accounted for a large proportion of the fire in the mine were explained. The method of added diphenylamine can inhibit the self-oxidation of coal effectively, the action mechanism of diphenylamine was analyzed by free radical chain reaction, and this research can offer new method for the development of new flame retardant.

  6. National Enforcement Initiative: Preventing Animal Waste from Contaminating Surface and Ground Water

    Science.gov (United States)

    This page describes EPA's goal in preventing animal waste from contaminating surface and ground Water. It is an EPA National Enforcement Initiative. Both enforcement cases, and a map of enforcement actions are provided.

  7. Crosslinking of fibrinogen and fibronectin by free radicals : A possible initial step in adhesion formation in osteoarthritis of the temporomandibular joint

    NARCIS (Netherlands)

    Dijkgraaf, LC; Zardeneta, G; Cordewener, FW; Liem, RSB; Schmitz, JP; de Bont, LGM; Milam, SB

    Purpose: Adhesion formation in osteoarthritis (OA) of the temporomandibular joint (TMJ) typically results in a sustained limitation of joint movement. We propose the hypothesis that free-radical-mediated crosslinking of proteins underlies this adhesion formation in affected joints. Free radicals may

  8. Improving Hemocompatibility of Membranes for Extracorporeal Membrane Oxygenators by Grafting Nonthrombogenic Polymer Brushes.

    Science.gov (United States)

    Obstals, Fabian; Vorobii, Mariia; Riedel, Tomáš; de Los Santos Pereira, Andres; Bruns, Michael; Singh, Smriti; Rodriguez-Emmenegger, Cesar

    2018-03-01

    Nonthrombogenic modifications of membranes for extracorporeal membrane oxygenators (ECMOs) are of key interest. The absence of hemocompatibility of these membranes and the need of anticoagulation of patients result in severe and potentially life-threatening complications during ECMO treatment. To address the lack of hemocompatibility of the membrane, surface modifications are developed, which act as barriers to protein adsorption on the membrane and, in this way, prevent activation of the coagulation cascade. The modifications are based on nonionic and zwitterionic polymer brushes grafted directly from poly(4-methyl-1-pentene) (TPX) membranes via single electron transfer-living radical polymerization. Notably, this work introduces the first example of well-controlled surface-initiated radical polymerization of zwitterionic brushes. The antifouling layers markedly increase the recalcification time (a proxy of initiation of coagulation) compared to bare TPX membranes. Furthermore, platelet and leukocyte adhesion is drastically decreased, rendering the ECMO membranes hemocompatible. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Physiology of free radicals

    Directory of Open Access Journals (Sweden)

    Stevanović Jelka

    2011-01-01

    Full Text Available Free radicals imply that every atom, molecule, ion, group of atoms, or molecules with one or several non-paired electrons in outer orbital. Among these are: nitrogenoxide (NO•, superoxide-anion-radical (O2•-, hydroxyl radical (OH•, peroxyl radical (ROO•, alcoxyl radical (RO• and hydroperoxyl radical (HO2•. However, reactive oxygen species also include components without non-paired electrons in outer orbital (so-called reactive non-radical agents, such as: singlet oxygen (1O2, peroxynitrite (ONOO-, hydrogen-peroxide (H2O2, hypochloric acid (eg. HOCl and ozone (O3. High concentrations of free radicals lead to the development of oxidative stress which is a precondition for numerous pathological effects. However, low and moderate concentrations of these matter, which occur quite normally during cell metabolic activity, play multiple significant roles in many reactions. Some of these are: regulation of signal pathways within the cell and between cells, the role of chemoattractors and leukocyte activators, the role in phagocytosis, participation in maintaining, changes in the position and shape of the cell, assisting the cell during adaption and recovery from damage (e.g.caused by physical effort, the role in normal cell growth, programmed cell death (apoptosis and cell ageing, in the synthesis of essential biological compounds and energy production, as well as the contribution to the regulation of the vascular tone, actually, tissue vascularization.

  10. Influence of surface defects on the fatigue crack initiation in pearlitic steel

    Directory of Open Access Journals (Sweden)

    Toribio Jesús

    2014-06-01

    Full Text Available Tensile fatigue tests were performed under load control, with constant stress range Δσ on pearlitic steel wires, from the hot rolled bar to the commercial prestressing steel wire (which has undergone seven cold drawing steps. Results show that fatigue cracks in pearlitic steels initiate at the wire surface starting from small defects, whose size decreases with the drawing process. Fatigue cracks created from defects (initiation phase exhibit a fractographic appearance consisting of ductile microtearing events which can be classified as tearing topography surface or TTS, and exhibit a remarkably lower spacing in the prestressing steel wire than in the hot rolled bar. In addition, some S-N tests were performed in both material forms under a stress range of about half the yield strength. In these tests, the main part of the fatigue life corresponds to the propagation stage in the hot rolled bar whereas such a main part of the life is associated with the initiation stage in the case of the prestressing steel wire.

  11. Contemporary open and robotic radical prostatectomy practice patterns among urologists in the United States.

    Science.gov (United States)

    Lowrance, William T; Eastham, James A; Savage, Caroline; Maschino, A C; Laudone, Vincent P; Dechet, Christopher B; Stephenson, Robert A; Scardino, Peter T; Sandhu, Jaspreet S

    2012-06-01

    We describe current trends in robotic and open radical prostatectomy in the United States after examining case logs for American Board of Urology certification. American urologists submit case logs for initial board certification and recertification. We analyzed logs from 2004 to 2010 for trends and used logistic regression to assess the impact of urologist age on robotic radical prostatectomy use. A total of 4,709 urologists submitted case logs for certification between 2004 and 2010. Of these logs 3,374 included 1 or more radical prostatectomy cases. Of the urologists 2,413 (72%) reported performing open radical prostatectomy only while 961 (28%) reported 1 or more robotic radical prostatectomies and 308 (9%) reported robotic radical prostatectomy only. During this 7-year period we observed a large increase in the number of urologists who performed robotic radical prostatectomy and a smaller corresponding decrease in those who performed open radical prostatectomy. Only 8% of patients were treated with robotic radical prostatectomy by urologists who were certified in 2004 while 67% underwent that procedure in 2010. Median age of urologists who exclusively performed open radical prostatectomy was 43 years (IQR 38-51) vs 41 (IQR 35-46) for those who performed only robotic radical prostatectomy. While the rate was not as high as the greater than 85% industry estimate, 67% of radical prostatectomies were done robotically among urologists who underwent board certification or recertification in 2010. Total radical prostatectomy volume almost doubled during the study period. These data provide nonindustry based estimates of current radical prostatectomy practice patterns and further our understanding of the evolving surgical treatment of prostate cancer. Copyright © 2012 American Urological Association Education and Research, Inc. Published by Elsevier Inc. All rights reserved.

  12. Raydet non-electric blast initiation system for efficient and environment-friendly surface blasts

    Energy Technology Data Exchange (ETDEWEB)

    Sarathy, M.O. [IDL Chemicals Ltd., Hyderabad (India). Technical Services Cell

    1995-08-01

    This paper discusses the advantages of using the Raydet shock tube based blast initiation system and reviews research work carried out on release of explosive energy in the drillhole, effect of stemming retention (stemming effectiveness) and advantages of `true bottom hole initiation` of drillholes in surface blasting. Some case studies are presented. 6 refs., 5 figs., 1 tab.

  13. Fabrication of nonfouling, bactericidal, and bacteria corpse release multifunctional surface through surface-initiated RAFT polymerization

    Directory of Open Access Journals (Sweden)

    Wang B

    2016-12-01

    Full Text Available Bailiang Wang,1,2 Zi Ye,1 Yihong Tang,1 Yuemei Han,1 Quankui Lin,1,2 Huihua Liu,2 Hao Chen,1,2 Kaihui Nan1,2 1School of Ophthalmology and Optometry, Eye Hospital, Wenzhou Medical University, Wenzhou, 2Wenzhou Institute of Biomaterials and Engineering, Chinese Academy of Sciences, Wenzhou, People’s Republic of China Abstract: Infections after surgery or endophthalmitis are potentially blinding complications caused by bacterial adhesion and subsequent biofilm formation on the intraocular lens. Neither single-function anti-adhesion surface nor contacting killing surface can exhibit ideal antibacterial function. In this work, a novel (2-(dimethylamino-ethyl methacrylate-co-2-methacryloyloxyethyl phosphorylcholine (p (DMAEMA-co-MPC brush was synthesized by “grafting from” method through reversible–addition fragmentation chain transfer polymerization. 1-Bromoheptane was used to quaternize the p (DMAEMA-co-MPC brush coating and to endow the surface with bactericidal function. The success of the surface functionalization was confirmed by atomic force microscopy, water contact angle, and spectroscopic ellipsometry. The quaternary ammonium salt units were employed as efficient disinfection that can eliminate bacteria through contact killing, whereas the 2-methacryloyloxyethyl phosphorylcholine units were introduced to suppress unwanted nonspecific adsorption. The functionalized poly(dimethyl siloxane surfaces showed efficiency in reducing bovine serum albumin adsorption and in inhibiting bacteria adhesion and biofilm formation. The copolymer brushes also demonstrated excellent bactericidal function against gram-positive (Staphylococcus aureus bacteria measured by bacteria live/dead staining and shake-flask culture methods. The surface biocompatibility was evaluated by morphology and activity measurement with human lens epithelial cells in vitro. The achievement of the p (DMAEMA+-co-MPC copolymer brush coating with nonfouling, bactericidal, and

  14. Personalization, Self-Advocacy and Inclusion: An Evaluation of Parent-Initiated Supported Living Schemes for People with Intellectual and Developmental Disabilities in the Netherlands

    Science.gov (United States)

    Reindl, Marie-Sol; Waltz, Mitzi; Schippers, Alice

    2016-01-01

    This study focused on parent-initiated supported living schemes in the South of the Netherlands and the ability of these living schemes to enhance participation, choice, autonomy and self-advocacy for people with intellectual or developmental disabilities through personalized planning, support and care. Based on in-depth interviews with tenants,…

  15. Evaluation of the LiveWell@School Food Initiative Shows Increases in Scratch Cooking and Improvement in Nutritional Content

    Science.gov (United States)

    Schober, Daniel J.; Carpenter, Leah; Currie, Venita; Yaroch, Amy L.

    2016-01-01

    Background: The purpose of this evaluation was to examine the effects of the LiveWell@School Food Initiative (LW@SFI), a Colorado-based childhood obesity prevention program that partners with school districts to enable them to serve more scratch cooked foods through culinary training, action planning, and equipment grants. Methods: This evaluation…

  16. Resonance Raman Spectra of the Transient Cl2 and Br2 Radical Anions

    DEFF Research Database (Denmark)

    Wilbrandt, Robert Walter; Jensen, Niels-Henrik; Sillesen, Alfred Hegaard

    1984-01-01

    The resonance Raman spectra of the short-lived radical anions ClImage 2− and BrImage − in aqueous solution are reported. The observed wavenumbers of 279 cm−1 for ClImage − and 177 cm−1 for BrImage − are about 10% higher than those published for the corresponding species isolated in solid argon ma...

  17. Serum Hydroxyl Radical Scavenging Capacity as Quantified with Iron-Free Hydroxyl Radical Source

    Science.gov (United States)

    Endo, Nobuyuki; Oowada, Shigeru; Sueishi, Yoshimi; Shimmei, Masashi; Makino, Keisuke; Fujii, Hirotada; Kotake, Yashige

    2009-01-01

    We have developed a simple ESR spin trapping based method for hydroxyl (OH) radical scavenging-capacity determination, using iron-free OH radical source. Instead of the widely used Fenton reaction, a short (typically 5 seconds) in situ UV-photolysis of a dilute hydrogen peroxide aqueous solution was employed to generate reproducible amounts of OH radicals. ESR spin trapping was applied to quantify OH radicals; the decrease in the OH radical level due to the specimen’s scavenging activity was converted into the OH radical scavenging capacity (rate). The validity of the method was confirmed in pure antioxidants, and the agreement with the previous data was satisfactory. In the second half of this work, the new method was applied to the sera of chronic renal failure (CRF) patients. We show for the first time that after hemodialysis, OH radical scavenging capacity of the CRF serum was restored to the level of healthy control. This method is simple and rapid, and the low concentration hydrogen peroxide is the only chemical added to the system, that could eliminate the complexity of iron-involved Fenton reactions or the use of the pulse-radiolysis system. PMID:19794928

  18. Ports Initiative

    Science.gov (United States)

    EPA's Ports Initiative works in collaboration with the port industry, communities, and government to improve environmental performance and increase economic prosperity. This effort helps people near ports breath cleaner air and live better lives.

  19. Initial stages of Pt(111) electrooxidation: dynamic and structural studies by surface X-ray diffraction

    International Nuclear Information System (INIS)

    Drnec, Jakub; Ruge, Martin; Reikowski, Finn; Rahn, Björn; Carlà, Francesco; Felici, Roberto; Stettner, Jochim; Magnussen, Olaf M.; Harrington, David A.

    2017-01-01

    In-situ surface X-ray diffraction is used to characterize the surface oxides on a Pt(111) surface in 0.1 M HClO 4 . Detailed analysis at two potentials confirms that the surface restructuring in the initial oxidation stages is consistent with a place exchange process between Pt and O atoms, and the exchanged Pt atoms are located above their original positions in the Pt(111) lattice. The (1,1,1.5) reflection is used to dynamically study the surface during cyclic voltammetry. The restructuring associated with the place exchange initiates with the CV peak at 1.05 V, even though multiple cycles to 1.17 V lead to no changes in the CV. The restructuring is reversible below a critical coverage of place exchanged Pt atoms, which we estimate to be between 0.07 and 0.15 ML. Extensive cycling to potentials higher or equal to 1.17 V leads to progressive disordering of the surface.

  20. Monte Carlo simulation of non-linear free radical polymerization using a percolation kinetic gelation model (I): free radical homo polymerization

    International Nuclear Information System (INIS)

    Ghiass, M.; Dabir, B.; Nikazar, M.; Rey, A.D.; Mirzadeh, H.

    2001-01-01

    A kinetic gelation model that incorporates the kinetics of free radical homo polymerization is implemented to determine the effects of kinetics on polymerization statistics and microstructures. The simulation is performed on a simple cubic lattice that has 100 sites in each direction. A new algorithm for random selecting of the next step in a self-avoiding random walk and very efficient mechanisms of mobility of components are introduced to improve the generality of the predictions by removing commonly accruing deficiencies due to early trapping of radicals. A first order kinetics is considered for decomposition of initiator that enables us to consider the effect of temperature on polymerization reaction. Better understanding of microstructural evolution during polymerization and providing a framework to produce a realistic system of highly packed random chains within polymer network are among the benefits of model

  1. Radical transfer between proteins: role of tyrosine, tryptophan and protein peroxyl radicals

    International Nuclear Information System (INIS)

    Irwin, J.A.; Ostdal, H.; Davies, M.J.

    1998-01-01

    Reaction of the Fe(III) forms of the heme proteins myoglobin (Mb) and horseradish peroxidase (HRP) with H 2 O 2 gives rise to high-oxidation-state heme-derived species which can be described as a Fe(IV)-oxo porphyrin radical-cation ('Compound 1'). In the case of Mb, the Fe(IV)-oxo porphyrin radical-cation undergoes rapid electron transfer with the surrounding protein to give protein (globin)-derived radicals and an Fe(lV)-oxo species ('Compound 2'). The globin-derived radicals have been shown to be located at two (or more) sites: Tyr-103 or Trp-14, with the latter radical known to react with oxygen to give a Trp-derived peroxyl radical (Mb-Trp-OO*). With HRP, the Fe(lV)-oxo porphyrin radical-cation carries out two successive one-electron oxidation reactions at the exposed heme edge to give firstly 'Compound 2' [the Fe(lV)oxo species] and then the resting Fe(III) state of the enzyme. n this study we have investigated whether the Trp-14 peroxyl radical from Mb and the Compound 1 and 2 species from HRP (in the absence and presence of free Tyr) can oxidise amino acids, peptides and proteins. Such reactions constitute intermolecular protein-to-protein radical transfer reactions and hence protein chain-oxidation. We have also examined whether these oxidants react with antioxidants. Reaction of these heme-protein derived oxidants with amino acids, proteins and antioxidants has been carried out at room temperature for defined periods of time before freeze-quenching to 77K to halt reaction. The radical species present in the reaction system at the time of freezing were subsequently examined by EPR spectroscopy at 77K. Three free amino acids, Tyr, Trp and Cys (with Cys the least efficient) have been shown to react rapidly with Mb-Trp-OO*, as evidenced by the loss of the characteristic EPR features of Mb-Trp-OO* on inclusion of increasing concentrations of the amino acids. All other amino acids are much less reactive. Evidence has also been obtained for (inefficient) hydrogen

  2. Mechanism of fatigue crack initiation in austenitic stainless steels in light water reactor environments

    International Nuclear Information System (INIS)

    Chopra, O.K.; Shack, W.J.; Muscara, J.

    2003-01-01

    This paper examines the mechanism of fatigue crack initiation in austenitic stainless steels (SSs) in light water reactor (LWR) coolant environments. The effects of key material and loading variables on the fatigue lives of wrought and cast austenitic SSs in air and LWR environments have been evaluated. The influence of reactor coolant environments on the formation and growth of fatigue cracks in polished smooth SS specimens is discussed. The results indicate that the fatigue lives of these steels are decreased primarily by the effects of the environment on the growth of cracks <200 μm and, to a lesser extent, on enhanced growth rates of longer cracks. The fracture morphology in the specimens has been characterized. Exploratory fatigue tests were conducted to study the effects of surface micropits or minor differences in the surface oxide on fatigue crack initiation. (author)

  3. Surface modification of polysulfone membranes applied for a membrane reactor with immobilized alcohol dehydrogenase

    DEFF Research Database (Denmark)

    Hoffmann, Christian; Silau, Harald; Pinelo, Manuel

    2018-01-01

    activated by lithiation followed by functionalization with acid chlorides at 0 °C, permitting modification of commercial PSf membranes without compromising the mechanical integrity of the membrane. Post-functionalization polymer grafting was illustrated through both, a “grafting from” approach by surface...... initiated atom transfer radical polymerization (SI-ATRP) and by a “grafting to” approach exploiting Cu(I) catalyzed 1,3-cycloadditions of alkynes with azides (CuAAC) introducing hydrophilic polymers onto the membrane surface. Poly(1-vinyl imidazole) (pVim) grafted membranes were exploited as support...

  4. Homegrown religious radicalization

    DEFF Research Database (Denmark)

    Khawaja, Iram

    It has been reported that a growing number of youngsters from Western Europe are engaging in conflicts motivated by religious and political conflicts in the Middle East. This paper explores the reasons behind this seemingly religious radicalization from the point of view of the youngsters...... youngsters and parents of youngsters who have chosen a radicalized path in life. The paper will shed light on how the sense of and yearning for belonging and recognition have to be taken into account in our understanding of homegrown religious radicalization...

  5. GLYCOLALDEHYDE FORMATION VIA THE DIMERIZATION OF THE FORMYL RADICAL

    Energy Technology Data Exchange (ETDEWEB)

    Woods, Paul M.; Viti, Serena [Department of Physics and Astronomy, University College London, Gower Street, London WC1E 6BT (United Kingdom); Slater, Ben; Raza, Zamaan; Brown, Wendy A.; Burke, Daren J., E-mail: p.woods@qub.ac.uk [Department of Chemistry, University College London, 20 Gordon Street, London WC1H 0AJ (United Kingdom)

    2013-11-10

    Glycolaldehyde, the simplest monosaccharide sugar, has recently been detected in low- and high-mass star-forming cores. Following our previous investigation into glycolaldehyde formation, we now consider a further mechanism for the formation of glycolaldehyde that involves the dimerization of the formyl radical, HCO. Quantum mechanical investigation of the HCO dimerization process upon an ice surface is predicted to be barrierless and therefore fast. In an astrophysical context, we show that this mechanism can be very efficient in star-forming cores. It is limited by the availability of the formyl radical, but models suggest that only very small amounts of CO are required to be converted to HCO to meet the observational constraints.

  6. GLYCOLALDEHYDE FORMATION VIA THE DIMERIZATION OF THE FORMYL RADICAL

    International Nuclear Information System (INIS)

    Woods, Paul M.; Viti, Serena; Slater, Ben; Raza, Zamaan; Brown, Wendy A.; Burke, Daren J.

    2013-01-01

    Glycolaldehyde, the simplest monosaccharide sugar, has recently been detected in low- and high-mass star-forming cores. Following our previous investigation into glycolaldehyde formation, we now consider a further mechanism for the formation of glycolaldehyde that involves the dimerization of the formyl radical, HCO. Quantum mechanical investigation of the HCO dimerization process upon an ice surface is predicted to be barrierless and therefore fast. In an astrophysical context, we show that this mechanism can be very efficient in star-forming cores. It is limited by the availability of the formyl radical, but models suggest that only very small amounts of CO are required to be converted to HCO to meet the observational constraints

  7. Intrinsically secure fast reactors for long-lived waste free and proliferation resistant nuclear power

    International Nuclear Information System (INIS)

    Slessarev, Igor

    2008-01-01

    This paper provides description of a nuclear reactor concept aimed towards a radical safety enhancement, an increased proliferation resistance, as well as a realisation of a 'long-lived waste free' NP development. It emphasizes the achievement of considerable reduction ('by design') of residual actinides in the waste streams and of the most hazardous long-lived fission products. It allows to implement only small volume of repositories for the radioactive waste (mostly fission products) and to postpone the technically arduous problems of a large scale disposal of the long-lived wastes until the next millennium, i.e. up to the exhaustion of the fertile natural resources and/or the emergence of more effective technologies of nuclide separation/transmutation. A thorough incineration/transmutation of the wastes (residual actinides in the mixture with lanthanides as well as of the most hazardous fission products) under reactor neutron flux is proposed for their mass reduction. A gradual growth of NP park is necessary for increasing the NP park capacity for waste irradiation. This 'constraint' is not really limiting because it coincides with the permanently growing demands in energy production. The potential of long-lived waste reduction depends on the total fertile fuel resources and on NP growth rate. It was shown that the accumulated actinide long-lived radioactive masses will be reduced significantly: by factor in the range of 10 4 -10 8 in magnitude (compared with LWR once-through cycle) and by 10 2 -10 6 (compared with the ordinary fast reactor park). Thus, the total long-lived waste toxicity pollution source might be comparable with the 'burnt away' toxicity of the natural fertile feed stream. This is quite realistic taking into account the large fertile fuel (U/Th) world-wide resources which provide the NP growth for a sustained time. Along side with the radical intrinsic safety improvement, a further enhancement of core physics ('neutronics') is one of the

  8. Personalization, self-advocacy and inclusion: An evaluation of parent-initiated supported living schemes for people with intellectual and developmental disabilities in the Netherlands.

    Science.gov (United States)

    Reindl, Marie-Sol; Waltz, Mitzi; Schippers, Alice

    2016-06-01

    This study focused on parent-initiated supported living schemes in the South of the Netherlands and the ability of these living schemes to enhance participation, choice, autonomy and self-advocacy for people with intellectual or developmental disabilities through personalized planning, support and care. Based on in-depth interviews with tenants, parents and caregivers, findings included that parent-initiated supported housing schemes made steps towards stimulating self-advocacy and autonomy for tenants. However, overprotective and paternalistic attitudes expressed by a significant number of parents, as well as structural constraints affecting the living schemes, created obstacles to tenants' personal development. The study calls for consideration of interdependence as a model for the relationship of parents and adult offspring with disabilities. The benefits and tensions inherent within this relationship must be taken into consideration during inclusive community building. © The Author(s) 2016.

  9. Ascorbic Acid-Initiated Tandem Radical Cyclization of N-Arylacrylamides to Give 3,3-Disubstituted Oxindoles

    Directory of Open Access Journals (Sweden)

    Sheng Liu

    2015-08-01

    Full Text Available An ascorbic acid-promoted and metal-free tandem room temperature cyclization of N-arylacrylamides with 4-nitrobenzenediazonium generated in situ was developed. This reaction proceeds smoothly through a radical mechanism and provides an environmentally friendly alternative approach to biologically active 3-alkyl-3-benzyloxindoles, avoiding the use of excess oxidants and light irradiation.

  10. Free radical behaviours during methylene blue degradation in the Fe2+/H2O2 system.

    Science.gov (United States)

    Wang, Zhonghua; Zhao, Haiqian; Qi, Hanbing; Liu, Xiaoyan; Liu, Yang

    2017-12-22

    Behaviours of the free radicals during the methylene blue (MB) oxidation process in the Fe 2+ /H 2 O 2 system were studied to reveal the reason for the low utilization efficiency of H 2 O 2 . The roles of [Formula: see text], [Formula: see text] and [Formula: see text] radicals were proven to be different in the MB oxidation process. The results showed that [Formula: see text] radicals had a strong ability to oxidize MB; however, they were not the main active substances for MB degradation due to the low concentration in the traditional Fe 2+ /H 2 O 2 system. [Formula: see text] radicals could not oxidize MB. [Formula: see text] radicals were the main active substances for MB oxidation. In the short initial stage, the utilization efficiency of H 2 O 2 was high, because the generation rate of [Formula: see text] was much higher than that of [Formula: see text]. More [Formula: see text] radicals were involved in the MB oxidation reaction. In the long deceleration stage (after the short initial stage), a large amount of H 2 O 2 was consumed, but the amount of oxidized MB was very small. Most of the [Formula: see text] radicals were consumed via the rapid useless reaction between [Formula: see text] and [Formula: see text] in this stage, resulting in the serious useless consumption of H 2 O 2 . It is a feasible method to improve the utilization efficiency of H 2 O 2 by adding suitable additives into the Fe 2+ /H 2 O 2 system to weaken the useless reaction between [Formula: see text] and [Formula: see text].

  11. Transport mechanism of an initially spherical droplet on a combined hydrophilic/hydrophobic surface

    Energy Technology Data Exchange (ETDEWEB)

    Myong, Hyon Kook; Kwon, Young Hoo [Dept. of Mechanical Engineering, Kookmin University, Seoul (Korea, Republic of)

    2015-11-15

    Fluid transport is a key issue in the development of microfluidic systems. Recently, Myong (2014) has proposed a new concept for droplet transport without external power sources, and numerically validated the results for a hypothetical 2D shape, initially having a hemicylindrical droplet shape. Myong and Kwon (2015) have also examined the transport mechanism for an actual water droplet, initially having a 3D hemispherical shape, on a horizontal hydrophilic/hydrophobic surface, based on the numerical results of the time evolution of the droplet shape, as well as the total kinetic, gravitational, pressure and surface free energies inside the droplet. In this study, a 3D numerical analysis of an initially spherical droplet is carried out to establish a new concept for droplet transport. Further, the transport mechanism of an actual water droplet is examined in detail from the viewpoint of the capillarity force imbalance through the numerical results of droplet shape and various energies inside the droplet.

  12. Laparoscopic radical trachelectomy.

    Science.gov (United States)

    Rendón, Gabriel J; Ramirez, Pedro T; Frumovitz, Michael; Schmeler, Kathleen M; Pareja, Rene

    2012-01-01

    The standard treatment for patients with early-stage cervical cancer has been radical hysterectomy. However, for women interested in future fertility, radical trachelectomy is now considered a safe and feasible option. The use of minimally invasive surgical techniques to perform this procedure has recently been reported. We report the first case of a laparoscopic radical trachelectomy performed in a developing country. The patient is a nulligravid, 30-y-old female with stage IB1 adenocarcinoma of the cervix who desired future fertility. She underwent a laparoscopic radical trachelectomy and bilateral pelvic lymph node dissection. The operative time was 340 min, and the estimated blood loss was 100mL. There were no intraoperative or postoperative complications. The final pathology showed no evidence of residual disease, and all pelvic lymph nodes were negative. At 20 mo of follow-up, the patient is having regular menses but has not yet attempted to become pregnant. There is no evidence of recurrence. Laparoscopic radical trachelectomy with pelvic lymphadenectomy in a young woman who desires future fertility may also be an alternative technique in the treatment of early cervical cancer in developing countries.

  13. Scavenging performance and antioxidant activity of γ-alumina nanoparticles towards DPPH free radical: Spectroscopic and DFT-D studies.

    Science.gov (United States)

    Zamani, Mehdi; Moradi Delfani, Ali; Jabbari, Morteza

    2018-05-03

    The radical scavenging performance and antioxidant activity of γ-alumina nanoparticles towards 2,2-diphenyl-1-picrylhydrazyl (DPPH) free radical were investigated by spectroscopic and computational methods. The radical scavenging ability of γ-alumina nanoparticles in the media with different polarity (i.e. i-propanol and n-hexane) was evaluated by measuring the DPPH absorbance in UV-Vis absorption spectra. The structure and morphology of γ-alumina nanoparticles before and after adsorption of DPPH were studied using XRD, FT-IR and UV-Vis spectroscopic techniques. The adsorption of DPPH free radical on the clean and hydrated γ-alumina (1 1 0) surface was examined by dispersion corrected density functional theory (DFT-D) and natural bond orbital (NBO) calculations. Also, time-dependent density functional theory (TD-DFT) was used to predict the absorption spectra. The adsorption was occurred through the interaction of radical nitrogen N and NO 2 groups of DPPH with the acidic and basic sites of γ-alumina surface. The high potential for the adsorption of DPPH radical on γ-alumina nanoparticles was investigated. Interaction of DPPH with Brønsted and Lewis acidic sites of γ-alumina was more favored than Brønsted basic sites. The following order for the adsorption of DPPH over the different active sites of γ-alumina was predicted: Brønsted base free radicals. Copyright © 2018. Published by Elsevier B.V.

  14. Simultaneous electrochemical-electron spin resonance studies of carotenoid cation radicals and dications

    International Nuclear Information System (INIS)

    Khaled, M.; Hadjipetrou, A.; Xinhai Chen; Kispert, L.

    1989-01-01

    Carotenoids are present in the chloroplasts of photosynthetic green plants and serve as photoprotect devices and antenna pigments, and active role in the photosynthetic electron-transport chain with the carotenoid cation radical as an integral part of the electron-transfer process. The research reported herein has confirmed that carotenoid cation radicals have a lifetime that is sensitive to solvent, being longest in CH 2 Cl 2 and are best prepared electrochemically. Semiempirical AM1 and INDO calculations of the trans and cis isomers of β-carotene, canthaxanthin and β-apo-8'-carotenal cation radicals predicted the unresolved EPR line whose linewidth varies to a measurable degree with carotenoid, which subsequent experimental observations affirmed. Simultaneous electrochemical - electron spin resonance studies of carotenoid cation radicals and dications have shown the radicals detected by EPR are formed by the one electron oxidation of the carotenoid, that dimers are not formed upon decay of the radical cations and an estimate of the rate of comproportionation as a function of carotenoid can be given. The formal rate constant K' for heterogenous electron transfer rate at the electrode surface has been deduced from rotating disc experiments. Upon deuteration, and in the presence of excess β-carotene, the half-life for decay of the carotenoid radical cation increased an order of magnitude due to the reaction between diffusion carotenoid dications and carotenoids to form additional radical cations. The carotenoid diffusion coefficients deduced by chronocoulometry substantiates this measurement. The produces formed upon electrochemical studies are being studied by HPLC and the isomers formed thermally are being separated. Additional radical reactions are currently being studied by EPR and electrochemical methods

  15. Influence of the irradiation temperature on the free-radical response of alanine

    International Nuclear Information System (INIS)

    Wieser, A.; Siegele, R.; Regulla, D.F.

    1989-01-01

    GSF operates the only IAEA high-level dosimetry reference laboratory and, as a joint project with the IAEA, the International Dose Assurance Service (IDAS). Dosimetry is based on long-lived free radicals in organic alanine induced by ionizing radiation and readout by ESR spectroscopy. The thermal time response of the radical concentration in alanine is fairly constant after irradiation provided that the alanine samples are stored at temperatures below 50 0 C. By contrast, a positive temperature coefficient had earlier been found at GSF for the production rate of alanine radicals, for irradiation temperatures between 0 and 50 0 C. This effect has to be considered for reference dosimetry in radiation processing. Radiation processing is also of interest at irradiation temperatures below 0 0 C. The present study describes experiments on the influence of irradiation temperatures between +50 and -100 0 C. Comparison is made between the present and earlier results, in the overlapping temperature range. An empirical function is proposed for the temperature coefficient based on the experimental data. (author)

  16. Theoretical Investigation of Kinetic Processes in Small Radicals of Importance in Combustion

    Energy Technology Data Exchange (ETDEWEB)

    Alexander, Millard [Univ. of Maryland, College Park, MD (United States). Dept. of Chemistry and Biochemistry; Dagdigian, Paul J. [Johns Hopkins Univ., Baltimore, MD (United States). Dept. of Chemistry

    2017-12-12

    Our group studies inelastic and reactive collisions of small molecules, focusing on radicals important in combustion environments. The goal is the better understanding of kinetic processes that may be difficult to access experimentally. An essential component is the accurate determination and fitting of potential energy surfaces (PESs). After fitting the ab initio points to obtain global PESs, we treat the dynamics using time-independent (close-coupling) methods. Cross sections and rate constants for collisions of are determined with our Hibridon program suite . We have studied energy transfer (rotationally, vibrationally, and/or electronically inelastic) in small hydrocarbon radicals (CH2 and CH3) and the CN radical. We have made a comparison with experimental measurements of relevant rate constants for collisions of these radicals. Also, we have calculated accurate transport properties using state-of-the-art PESs and to investigate the sensitivity to these parameters in 1-dimensional flame simulations. Of particular interest are collision pairs involving the light H atom.

  17. A preliminary oncologic outcome and postoperative complications in patients undergoing robot-assisted radical cystectomy: Initial experience

    Directory of Open Access Journals (Sweden)

    Satoru Muto

    2017-05-01

    Full Text Available Purpose: Robot-assisted radical cystectomy (RARC was originally intended to replace open radical cystectomy (ORC as a minimally invasive surgery for patients with invasive bladder cancer. The purpose of this study was to evaluate the advantages of robotic surgery, comparing perioperative and oncologic outcomes between RARC and ORC. Materials and Methods: Between June 2012 and August 2016, 49 bladder cancer patients were given a radical cystectomy, 21 robotically and 28 by open procedure. We compared the clinical variables between the RARC and ORC groups. Results: In the RARC group, the median estimated blood loss (EBL during cystectomy, total EBL, operative time during cystectomy, and total operative time were 0 mL, 457.5 mL, 199 minutes, and 561 minutes, respectively. EBL during cystectomy (p<0.001, total EBL (p<0.001, and operative time during cystectomy (p=0.003 in the RARC group were significantly lower compared with the ORC group. Time to resumption of a regular diet (p<0.001 and length of stay (p=0.017 were also significantly shorter compared with the ORC group. However, total operative time in the RARC group (median, 561 minutes was significantly longer compared with the ORC group (median, 492.5 minutes; p=0.015. Conclusions: This Japanese study presented evidence that RARC yields benefits in terms of BL and time to regular diet, while consuming greater total operative time. RARC may be a minimally invasive surgical alternative to ORC with less EBL and shorter length of stay.

  18. Radical Evil

    Directory of Open Access Journals (Sweden)

    Carlos Manrique

    2007-12-01

    Full Text Available There is an aporia in Kant’s analysis of evil: he defines radical evilas an invisible disposition of the will, but he also demands an inferential connection between visible evil actions and this invisible disposition. This inference,however, undermines the radical invisibility of radical evil according to Kant’s own definition of the latter. Noting how this invisibility of moral worth is a distinctive feature of Kant’s approach to the moral problem, the paper then asks why, in the Groundwork, he nonetheless forecloses a question about evil that seems to be consistent with this approach. It is argued that to account for this aporia and this foreclosure, one has to interrogate the way in which the category of religion orients Kant’s incipient philosophy of history in Die Religion.

  19. A ‘NanoSuit’ surface shield successfully protects organisms in high vacuum: observations on living organisms in an FE-SEM

    Science.gov (United States)

    Takaku, Yasuharu; Suzuki, Hiroshi; Ohta, Isao; Tsutsui, Takami; Matsumoto, Haruko; Shimomura, Masatsugu; Hariyama, Takahiko

    2015-01-01

    Although extremely useful for a wide range of investigations, the field emission scanning electron microscope (FE-SEM) has not allowed researchers to observe living organisms. However, we have recently reported that a simple surface modification consisting of a thin extra layer, termed ‘NanoSuit’, can keep organisms alive in the high vacuum (10−5 to 10−7 Pa) of the SEM. This paper further explores the protective properties of the NanoSuit surface-shield. We found that a NanoSuit formed with the optimum concentration of Tween 20 faithfully preserves the integrity of an organism's surface without interfering with SEM imaging. We also found that electrostatic charging was absent as long as the organisms were alive, even if they had not been coated with electrically conducting materials. This result suggests that living organisms possess their own electrical conductors and/or rely on certain properties of the surface to inhibit charging. The NanoSuit seems to prolong the charge-free condition and increase survival time under vacuum. These findings should encourage the development of more sophisticated observation methods for studying living organisms in an FE-SEM. PMID:25631998

  20. Addressing Emerging Risks: Scientific and Regulatory Challenges Associated with Environmentally Persistent Free Radicals.

    Science.gov (United States)

    Dugas, Tammy R; Lomnicki, Slawomir; Cormier, Stephania A; Dellinger, Barry; Reams, Margaret

    2016-06-08

    Airborne fine and ultrafine particulate matter (PM) are often generated through widely-used thermal processes such as the combustion of fuels or the thermal decomposition of waste. Residents near Superfund sites are exposed to PM through the inhalation of windblown dust, ingestion of soil and sediments, and inhalation of emissions from the on-site thermal treatment of contaminated soils. Epidemiological evidence supports a link between exposure to airborne PM and an increased risk of cardiovascular and pulmonary diseases. It is well-known that during combustion processes, incomplete combustion can lead to the production of organic pollutants that can adsorb to the surface of PM. Recent studies have demonstrated that their interaction with metal centers can lead to the generation of a surface stabilized metal-radical complex capable of redox cycling to produce ROS. Moreover, these free radicals can persist in the environment, hence their designation as Environmentally Persistent Free Radicals (EPFR). EPFR has been demonstrated in both ambient air PM2.5 (diameter challenges associated with regulating this new, emerging contaminant.

  1. New era of silicon technologies due to radical reaction based semiconductor manufacturing

    International Nuclear Information System (INIS)

    Ohmi, Tadahiro; Hirayama, Masaki; Teramoto, Akinobu

    2006-01-01

    Current semiconductor technology, the so-called the molecule reaction based semiconductor manufacturing, now faces a very severe standstill due to the drastic increase of gate leakage currents and drain leakage currents. Radical reaction based semiconductor manufacturing has been developed to completely overcome the current standstill by introducing microwave excited high density plasma with very low electron temperatures and without accompanying charge-up damage. The introduction of radical reaction based semiconductor manufacturing has made it possible to fabricate LSI devices on any crystal orientation Si substrate surface as well as (100) Si substrate surfaces, and to eliminate a very severe limitation to the antenna ratio in the circuit layout patterns, which is strictly limited to less than 100-200 in order to obtain a relatively high production yield. (topical review)

  2. An Investigation of the Influence of Initial Roughness on the Friction and Wear Behavior of Ground Surfaces

    Science.gov (United States)

    Liang, Guoxing; Schmauder, Siegfried; Lyu, Ming; Schneider, Yanling; Zhang, Cheng; Han, Yang

    2018-01-01

    Friction and wear tests were performed on AISI 1045 steel specimens with different initial roughness parameters, machined by a creep-feed dry grinding process, to study the friction and wear behavior on a pin-on-disc tester in dry sliding conditions. Average surface roughness (Ra), root mean square (Rq), skewness (Rsk) and kurtosis (Rku) were involved in order to analyse the influence of the friction and wear behavior. The observations reveal that a surface with initial roughness parameters of higher Ra, Rq and Rku will lead to a longer initial-steady transition period in the sliding tests. The plastic deformation mainly concentrates in the depth of 20–50 μm under the worn surface and the critical plastic deformation is generated on the rough surface. For surfaces with large Ra, Rq, low Rsk and high Rku values, it is easy to lose the C element in, the reciprocating extrusion. PMID:29401703

  3. Robotic radical perineal cystectomy and extended pelvic lymphadenectomy: initial investigation using a purpose-built single-port robotic system.

    Science.gov (United States)

    Maurice, Matthew J; Kaouk, Jihad H

    2017-12-01

    To assess the feasibility of radical perineal cystoprostatectomy using the latest generation purpose-built single-port robotic surgical system. In two male cadavers the da Vinci ® SP1098 Surgical System (Intuitive Surgical, Sunnyvale, CA, USA) was used to perform radical perineal cystoprostatectomy and bilateral extended pelvic lymph node dissection (ePLND). New features in this model include enhanced high-definition three-dimensional optics, improved instrument manoeuvrability, and a real-time instrument tracking and guidance system. The surgery was accomplished through a 3-cm perineal incision via a novel robotic single-port system, which accommodates three double-jointed articulating robotic instruments, an articulating camera, and an accessory laparoscopic instrument. The primary outcomes were technical feasibility, intraoperative complications, and total robotic operative time. The cases were completed successfully without conversion. There were no accidental punctures or lacerations. The robotic operative times were 197 and 202 min. In this preclinical model, robotic radical perineal cystoprostatectomy and ePLND was feasible using the SP1098 robotic platform. Further investigation is needed to assess the feasibility of urinary diversion using this novel approach and new technology. © 2017 The Authors BJU International © 2017 BJU International Published by John Wiley & Sons Ltd.

  4. Ability of nitrones of various structures to control the radical polymerization of styrene mediated by in situ formed nitroxides.

    NARCIS (Netherlands)

    Sciannamea, V.; Guerrero-Sanchez, C.A.; Schubert, U.S.; Catala, J.-M.; Jerome, R.; Detrembleur, C.

    2005-01-01

    The ability of several nitrones to control the radical polymerization of styrene at 110 °C has been investigated by high-throughput experimentation. The nitrone/free radical initiator pair dictates the structure of the nitroxide and the alkoxyamine formed in situ, which determines the position of

  5. Toll-Like Receptor-Mediated Free Radical Generation in Clonorchis sinensis Excretory-Secretory Product-Treated Cholangiocarcinoma Cells.

    Science.gov (United States)

    Bahk, Young Yil; Pak, Jhang Ho

    2016-10-01

    Clonorchiasis, caused by direct contact with Clonorchis sinensis worms and their excretory-secretory products (ESPs), is associated with chronic inflammation, malignant changes in bile ducts, and even cholangiocarcinogenesis. Our previous report revealed that intracellular free radicals enzymatically generated by C. sinensis ESPs cause NF-κB-mediated inflammation in human cholangiocarcinoma cells (HuCCT1). Therefore, the present study was conducted to examine the role of upstream Toll-like receptors (TLRs) on the initial host innate immune responses to infection. We found that treatment of HuCCT1 cells with native ESPs induced changes in TLR mRNA levels in a time-dependent manner, concomitant with the generation of free radicals. ESP-mediated free radical generation was markedly attenuated by preincubation of the cells with TLR1-4-neutralizing antibodies, indicating that at least TLR1 through 4 participate in stimulation of the host innate immune responses. These findings indicate that free radicals triggered by ESPs are critically involved in TLR signal transduction. Continuous signaling by this pathway may function in initiating C. sinensis infection-associated inflammation cascades, a detrimental event leading to progression to more severe hepatobiliary diseases.

  6. Radical radiotherapy for T3 laryngeal cancers

    International Nuclear Information System (INIS)

    Uno, T.; Itami, J.; Kotaka, K.; Toriyama, M.

    1996-01-01

    From 1974 through 1992, 37 previously untreated patients with T3 laryngeal cancer (supraglottic 15, glottic 22) were treated with initial radical radiotherapy and surgery for salvage. Two-year local control rate with radiotherapy alone, ultimate voice preservation rate, and ultimate local control rate for T3 supraglottic cancer were 33%, 33%, and 60%, respectively. Corresponding figures for T3 glottic cancer were 32%, 23%, and 77%, respecitvely. Five-year cause-specific survival rate for T3 supraglottic cancer and glottic cancer were 47% and 77%, respectively. In T3 supraglottic cancer, none of the 4 patients with subglottic tumor extension attained local control by radiotherapy alone, and local-regional recurrence-free time were significantly shorter in patients with subglottic tumor extension or tracheostomy before radiotherapy. There were no serious late complications such as chondronecrosis, rupture of carotid artery attributed to radical radiotherapy, while 3 patients had severe laryngeal edema requiring total laryngectomy. (orig.) [de

  7. N-tert-butylmethanimine N-oxide is an efficient spin-trapping probe for EPR analysis of glutathione thiyl radical

    Science.gov (United States)

    Scott, Melanie J.; Billiar, Timothy R.; Stoyanovsky, Detcho A.

    2016-01-01

    The electron spin resonance (EPR) spin-trapping technique allows detection of radical species with nanosecond half-lives. This technique is based on the high rates of addition of radicals to nitrones or nitroso compounds (spin traps; STs). The paramagnetic nitroxides (spin-adducts) formed as a result of reactions between STs and radical species are relatively stable compounds whose EPR spectra represent “structural fingerprints” of the parent radical species. Herein we report a novel protocol for the synthesis of N-tert-butylmethanimine N-oxide (EBN), which is the simplest nitrone containing an α-H and a tertiary α′-C atom. We present EPR spin-trapping proof that: (i) EBN is an efficient probe for the analysis of glutathione thiyl radical (GS•); (ii) β-cyclodextrins increase the kinetic stability of the spin-adduct EBN/•SG; and (iii) in aqueous solutions, EBN does not react with superoxide anion radical (O2−•) to form EBN/•OOH to any significant extent. The data presented complement previous studies within the context of synthetic accessibility to EBN and efficient spin-trapping analysis of GS•. PMID:27941944

  8. Radical constructivism: Between realism and solipsism

    Science.gov (United States)

    Martínez-Delgado, Alberto

    2002-11-01

    This paper criticizes radical constructivism of the Glasersfeld type, pointing out some contradictions between the declared radical principles and their theoretical and practical development. These contradictions manifest themselves in a frequent oscillation between solipsism and realism, despite constructivist claims to be an anti-realist theory. The paper also points out the contradiction between the relativism of the radical constructivist principles and the constructivist exclusion of other epistemological or educational paradigms. It also disputes the originality and importance of the radical constructivist paradigm, suggesting the idea of an isomorphism between radical constructivist theory and contemplative realism. In addition, some pedagogical and scientific methodological aspects of the radical constructivist model are examined. Although radical constructivism claims to be a rational theory and advocates deductive thinking, it is argued that there is no logical deductive connection between the radical principles of constructivism and the radical constructivist ideas about scientific research and learning. The paper suggests the possibility of an ideological substratum in the construction and hegemonic success of subjective constructivism and, finally, briefly advances an alternative realist model to epistemological and educational radical constructivism.

  9. A Derivative Method with Free Radical Oxidation to Predict Resveratrol Metabolites by Tandem Mass Spectrometry.

    Science.gov (United States)

    Liu, Wangta; Shiue, Yow-Ling; Lin, Yi-Reng; Lin, Hugo You-Hsien; Liang, Shih-Shin

    2015-10-01

    In this study, we demonstrated an oxidative method with free radical to generate 3,5,4'-trihydroxy- trans -stilbene ( trans -resveratrol) metabolites and detect sequentially by an autosampler coupling with liquid chromatography electrospray ionization tandem mass spectrometer (LC-ESI-MS/MS). In this oxidative method, the free radical initiator, ammonium persulfate (APS), was placed in a sample bottle containing resveratrol to produce oxidative derivatives, and the reaction progress was tracked by autosampler sequencing. Resveratrol, a natural product with purported cancer preventative qualities, produces metabolites including dihydroresveratrol, 3,4'-dihydroxy- trans -stilbene, lunularin, resveratrol monosulfate, and dihydroresveratrol monosulfate by free radical oxidation. Using APS free radical, the concentrations of resveratrol derivatives differ as a function of time. Besides simple, convenient and time- and labor saving, the advantages of free radical oxidative method of its in situ generation of oxidative derivatives followed by LC-ESI-MS/MS can be utilized to evaluate different metabolites in various conditions.

  10. Light ions and ozone - generation and interactions with living organisms

    International Nuclear Information System (INIS)

    Kriha, V.; Aubrecht, L.

    2005-01-01

    With directly in the living organism born ions exception, LNI coming through three phases: ionisation, attachment by the electronegative molecules and the clusters formation due to local electrostatic interactions. The quantitative analysis of physical parameters leads to conclusion that we cannot find any physical property (till known) explaining the positive affect of LNI on living organisms. Analysis of possible mechanism produces several hypotheses of LNI-organism interaction. A simplified semi-quantitative model of respiratory tract was developed for estimation of ions and ozone interaction with living organisms. A formation of oxygen radicals and products of their chain-reactions in intrinsic conditions is discussed

  11. Bureaucratic Activism and Radical School Change in Tamil Nadu, India

    Science.gov (United States)

    Niesz, Tricia; Krishnamurthy, Ramchandar

    2013-01-01

    In 2007, Activity Based Learning (ABL), a child-centered, activity-based method of pedagogical practice, transformed classrooms in all of the over 37,000 primary-level government schools in Tamil Nadu, India. The large scale, rapid pace, and radical nature of educational change sets the ABL initiative apart from most school reform efforts.…

  12. Initialization of high resolution surface wind simulations using NWS gridded data

    Science.gov (United States)

    J. Forthofer; K. Shannon; Bret Butler

    2010-01-01

    WindNinja is a standalone computer model designed to provide the user with simulations of surface wind flow. It is deterministic and steady state. It is currently being modified to allow the user to initialize the flow calculation using National Digital Forecast Database. It essentially allows the user to downscale the coarse scale simulations from meso-scale models to...

  13. Salvage robotic radical prostatectomy

    Directory of Open Access Journals (Sweden)

    Samuel D Kaffenberger

    2014-01-01

    Full Text Available Failure of non-surgical primary treatment for localized prostate cancer is a common occurrence, with rates of disease recurrence ranging from 20% to 60%. In a large proportion of patients, disease recurrence is clinically localized and therefore potentially curable. Unfortunately, due to the complex and potentially morbid nature of salvage treatment, radical salvage surgery is uncommonly performed. In an attempt to decrease the morbidity of salvage therapy without sacrificing oncologic efficacy, a number of experienced centers have utilized robotic assistance to perform minimally invasive salvage radical prostatectomy. Herein, we critically evaluate the existing literature on salvage robotic radical prostatectomy with a focus on patient selection, perioperative complications and functional and early oncologic outcomes. These results are compared with contemporary and historical open salvage radical prostatectomy series and supplemented with insights we have gained from our experience with salvage robotic radical prostatectomy. The body of evidence by which conclusions regarding the efficacy and safety of robotic salvage radical prostatectomy can be drawn comprises fewer than 200 patients with limited follow-up. Preliminary results are promising and some outcomes have been favorable when compared with contemporary open salvage prostatectomy series. Advantages of the robotic platform in the performance of salvage radical prostatectomy include decreased blood loss, short length of stay and improved visualization. Greater experience is required to confirm the long-term oncologic efficacy and functional outcomes as well as the generalizability of results achieved at experienced centers.

  14. Solution Exchange Lithography: A Versatile Tool for Sequential Surface Engineering

    Science.gov (United States)

    Pester, Christian; Mattson, Kaila; Bothman, David; Klinger, Daniel; Lee, Kenneth; Discekici, Emre; Narupai, Benjaporn; Hawker, Craig

    The covalent attachment of polymers has emerged as a viable strategy for the preparation of multi-functional surfaces. Patterned, surface-grafted polymer brushes provide spatial control over wetting, mechanical, biological or electronic properties, and allow fabrication of `intelligent' substrates which selectively adapt to their environment. However, the route towards patterned polymer brush surfaces often remains challenging, creating a demand for more efficient and less complicated fabrication strategies. We describe the design and application of a novel experimental setup to combine light-mediated and flow chemistry for the fabrication of hierarchical surface-grafted polymer brushes. Using light-mediated, surface initiated controlled radical polymerization and post-functionalization via well-established, and highly efficient chemistries, polymer brush films of previously unimaginable complexity are now shown to be accessible. This methodology allows full flexibility to exchange both lithographic photomasks and chemical environments in-situ, readily affording multidimensional thin film architectures, all from uniformly functionalized substrates.

  15. Electrografting of alkyl films at low driving force by diverting the reactivity of aryl radicals derived from diazonium salts.

    Science.gov (United States)

    Hetemi, Dardan; Kanoufi, Frédéric; Combellas, Catherine; Pinson, Jean; Podvorica, Fetah I

    2014-11-25

    Alkyl and partial perfluoroalkyl groups are strongly attached to carbon surfaces through (i) the abstraction of the iodine atom from an iodoalkane by the sterically hindered 2,6-dimethylphenyl radical and (ii) the reaction of the ensuing alkyl radical with the carbon surface. Since the 2,6-dimethylphenyl radical is obtained at -0.25 V/Ag/AgCl by reducing the corresponding diazonium salt, the electrografting reaction is facilitated by ∼1.7 V by comparison with the direct electrografting of the iodo compounds. Layers of various thicknesses, including monolayers, are obtained by controlling the time duration of the electrolysis. The grafted films are characterized by electrochemistry, IR, XPS, ellipsometry, and water contact angles.

  16. Muoniated acyl and thioacyl radicals

    International Nuclear Information System (INIS)

    McKenzie, Iain; Brodovitch, Jean-Claude; Ghandi, Khashayar; Percival, Paul W.

    2006-01-01

    The product of the reaction of muonium with tert-butylisocyanate was previously assigned as the muoniated tert-butylaminyl radical (I. McKenzie, J.-C. Brodovitch, K. Ghandi, S. Kecman, P. W. Percival, Physica B 326 (2003) 76). This assignment is incorrect since the muon and 14 N hyperfine-coupling constants (hfcc) of this radical would have the opposite sign, which is in conflict with the experimental results. The radical is now reassigned as the muoniated N-tert-butylcarbamoyl radical, based on the similarities between the experimental muon and 14 N hfcc and hfcc calculated at the UB3LYP/6-311G(d,p)//UB3LYP/EPR-III level. The large zero-point energy in the N-Mu bond results in the dissociation barrier of the muoniated N-tert-butylcarbamoyl radical being above the combined energy of the reactants, in contrast to the N-tert-butylcarbamoyl radical where the dissociation barrier lies below the combined energy of the reactants. The reaction of muonium with tert-butylisothiocyanate produced both conformers of the muoniated N-tert-butylthiocarbamoyl radical and their assignment was based on the similarities between the experimental and calculated muon hfcc. These are the first acyl and thioacyl radicals to be directly detected by muon spin spectroscopy

  17. Muoniated acyl and thioacyl radicals

    Energy Technology Data Exchange (ETDEWEB)

    McKenzie, Iain [TRIUMF and Department of Chemistry, 8888 University Drive, Simon Fraser University, Burnaby B.C., V5A 1S6 (Canada); Brodovitch, Jean-Claude [TRIUMF and Department of Chemistry, 8888 University Drive, Simon Fraser University, Burnaby B.C., V5A 1S6 (Canada); Ghandi, Khashayar [TRIUMF and Department of Chemistry, 8888 University Drive, Simon Fraser University, Burnaby B.C., V5A 1S6 (Canada); Percival, Paul W. [TRIUMF and Department of Chemistry, 8888 University Drive, Simon Fraser University, Burnaby B.C., V5A 1S6 (Canada)]. E-mail: percival@sfu.ca

    2006-03-31

    The product of the reaction of muonium with tert-butylisocyanate was previously assigned as the muoniated tert-butylaminyl radical (I. McKenzie, J.-C. Brodovitch, K. Ghandi, S. Kecman, P. W. Percival, Physica B 326 (2003) 76). This assignment is incorrect since the muon and {sup 14}N hyperfine-coupling constants (hfcc) of this radical would have the opposite sign, which is in conflict with the experimental results. The radical is now reassigned as the muoniated N-tert-butylcarbamoyl radical, based on the similarities between the experimental muon and {sup 14}N hfcc and hfcc calculated at the UB3LYP/6-311G(d,p)//UB3LYP/EPR-III level. The large zero-point energy in the N-Mu bond results in the dissociation barrier of the muoniated N-tert-butylcarbamoyl radical being above the combined energy of the reactants, in contrast to the N-tert-butylcarbamoyl radical where the dissociation barrier lies below the combined energy of the reactants. The reaction of muonium with tert-butylisothiocyanate produced both conformers of the muoniated N-tert-butylthiocarbamoyl radical and their assignment was based on the similarities between the experimental and calculated muon hfcc. These are the first acyl and thioacyl radicals to be directly detected by muon spin spectroscopy.

  18. Genetic diversity of free-living Symbiodinium in surface water and sediment of Hawai`i and Florida

    Science.gov (United States)

    Takabayashi, M.; Adams, L. M.; Pochon, X.; Gates, R. D.

    2012-03-01

    Marine dinoflagellates in the genus Symbiodinium are primarily known for their symbiotic associations with invertebrates and protists, although they are also found free-living in nanoplankton and microphytobenthic communities. Free-living Symbiodinium are necessary for hosts that must acquire their symbionts anew each generation and for the possible reestablishment of endosymbiosis in bleached adults. The diversity and ecology of free-living Symbiodinium are not well studied by comparison with their endosymbiotic counterparts, and as a result, our understanding of the linkages between free-living and endosymbiotic Symbiodinium is poor. Here, we begin to address this knowledge gap by describing the genetic diversity of Symbiodinium in the surface water and reef sediments of Hawai`i and Florida using Symbiodinium-specific primers for the hypervariable region of the chloroplast 23S domain V (cp23S-HVR). In total, 29 Symbiodinium sequence types were detected, 16 of which were novel. The majority of Symbiodinium sequence types in free-living environments belonged to clades A and B, but smaller numbers of sequence types belonging to clades C, D, and G were also detected. The majority of sequences recovered from Hawai`i belonged to clades A and C and those from Florida to clade B. Such distribution patterns are consistent with the endosymbiotic diversity previously reported for these two regions. The ancestral sequence types in each clade were typically recovered from surface water and sediments both in Hawai`i and Florida and have been previously reported as endosymbionts of a range of invertebrates, suggesting that these types have the capacity to exploit a range of very different habitats. More derived sequence types in clades A, B, C, and G were not recovered here, suggesting they are potentially restricted to endosymbiotic environments.

  19. Rational preparation of dibenzothiophene-imprinted polymers by surface imprinting technique combined with atom transfer radical polymerization

    International Nuclear Information System (INIS)

    Yang, Wenming; Liu, Lukuan; Zhou, Zhiping; Liu, Hong; Xie, Binze; Xu, Wanzhen

    2013-01-01

    A computational simulation method is introduced to simulate the dibenzothiophene-monomer pre-assembly system of molecular imprinted polymers. The interaction type and intensity between dibenzothiophene and monomer are discussed from the binding energy and spatial position distribution. The simulation and analysis results indicate that the amount of the function monomer is not the more the better in preparing molecular imprinted polymers. Based on the above results, a novel dibenzothiophene-imprinted polymers with the favorable specific adsorption effect was prepared by surface imprinting technique combined with atom transfer radical polymerization. This combined technologies are used for preparing a desulfurization adsorbent for the first time. Various measures were selected to characterize the structure and morphology of the prepared adsorbent. The characterization results show that the adsorbent has suitable features for further adsorption process. A series of static adsorption experiments were conducted to analyze its adsorption performance. The adsorption process follows Elovich model by the kinetic analysis and Sips equation by the isothermal analysis. The approach we described will provide another opportunity in the deep desulfurization field.

  20. Development of linear free energy relationships for aqueous phase radical-involved chemical reactions.

    Science.gov (United States)

    Minakata, Daisuke; Mezyk, Stephen P; Jones, Jace W; Daws, Brittany R; Crittenden, John C

    2014-12-02

    Aqueous phase advanced oxidation processes (AOPs) produce hydroxyl radicals (HO•) which can completely oxidize electron rich organic compounds. The proper design and operation of AOPs require that we predict the formation and fate of the byproducts and their associated toxicity. Accordingly, there is a need to develop a first-principles kinetic model that can predict the dominant reaction pathways that potentially produce toxic byproducts. We have published some of our efforts on predicting the elementary reaction pathways and the HO• rate constants. Here we develop linear free energy relationships (LFERs) that predict the rate constants for aqueous phase radical reactions. The LFERs relate experimentally obtained kinetic rate constants to quantum mechanically calculated aqueous phase free energies of activation. The LFERs have been applied to 101 reactions, including (1) HO• addition to 15 aromatic compounds; (2) addition of molecular oxygen to 65 carbon-centered aliphatic and cyclohexadienyl radicals; (3) disproportionation of 10 peroxyl radicals, and (4) unimolecular decay of nine peroxyl radicals. The LFERs correlations predict the rate constants within a factor of 2 from the experimental values for HO• reactions and molecular oxygen addition, and a factor of 5 for peroxyl radical reactions. The LFERs and the elementary reaction pathways will enable us to predict the formation and initial fate of the byproducts in AOPs. Furthermore, our methodology can be applied to other environmental processes in which aqueous phase radical-involved reactions occur.

  1. Muonium and muonic radicals

    International Nuclear Information System (INIS)

    Burkhard, P.; Fischer, H.; Roduner, E.; Strub, W.; Geeson, D.; Symons, M.C.R.

    1985-01-01

    An energetic positive muon which is injected in a liquid sample of substrate molecules (S) creates an ionization track consisting of substrate cations (S + ) and electrons. Near the end of this track the muon may combine with an electron to form muonium (Mu) which is observable in inert liquids, but which reacts by addition to form a radical. Alternatively, the electron can add to S to form S - , which then combines with the muon to form the radical. Furthermore, instead of ending up in Mu or in a radical the muon may stay in a diamagnetic environment as a solvated muon, or as a muon substituting a proton in a molecule. Of interest in these schemes are the mechanisms and rates of formation of muonated radicals and in particular the rate constants for their reactions to products. Investigations are based on the observation of Mu and the radical by means of the μSR technique in transverse magnetic fields. (Auth.)

  2. Radiolysis of water in the vicinity of passive surfaces

    International Nuclear Information System (INIS)

    Moreau, S.; Fenart, M.; Renault, J.P.

    2014-01-01

    Highlights: • HO° production through water radiolysis is enhanced near metal surfaces. • Hastelloy and Stainless steel surfaces can also produce HO° radicals through hydrogen peroxide activation. • There is a deficit in solvated electron production compared to hydroxyl radicals near metal surfaces. - Abstract: Porous metals were used to describe the water radiolysis in the vicinity of metal surfaces. The hydroxyl radical production under gamma irradiation was measured by benzoate scavenging in water confined in a 200 nm porous Ni base alloy or in Stainless steel. The presence of the metallic surfaces changed drastically the HO° production level and lifetime. The solvated electron production was measured via glycylglycine scavenging for Stainless steel and was found to be significantly smaller than hydroxyl production. These observations imply that interfacial radiolysis may deeply impact the corrosion behavior of the SS and Ni based alloys

  3. Studies of radiation-produced radicals and radical ions. Progress report, June 1, 1981-August 31, 1982

    International Nuclear Information System (INIS)

    Williams, T.F.

    1982-01-01

    The discovery and characterization of novel radical ions produced by the γ irradiation of solids continues to be a fertile field for investigation. This Progress Report describes the generation and ESR identification of several new paramagnetic species, some of which have long been sought as important intermediates in radiation chemistry. We have also contributed to a general theoretical problem in ESR spectroscopy. Solid-state studies of electron attachment reactions, both non-dissociative and dissociative, reveal interesting structural and chemical information about the molecular nature of these processes for simple compounds. In particular, ESR measurements of the spin distribution in the products allow a fairly sharp distinction to be drawn between radical anions and radical-anion pairs or adducts. Dimer radical anion formation can also take place but the crystal structure plays a role in this process, as expected. Some radical anions undergo photolysis to give radical-anion pairs which may then revert back to the original radical anion by a thermal reaction. The chemistry of these reversible processes is made more intricate by a competing reaction in which the radical abstracts a hydrogen atom from a neighboring molecule. However, the unraveling of this complication has also served to extend our knowledge of the role of quantum tunneling in chemical reactions. The results of this investigation testify to the potential of solid-state techniques for the study of novel and frangible radical ions. Progress in this field shows no sign of abating, as witness the recent discovery of perfluorocycloalkane radical anions and alkane radical cations

  4. Study on initial stage of hetero-epitaxial growth by glancing angle scattering of fast ions from surfaces

    International Nuclear Information System (INIS)

    Fujii, Yoshikazu; Toba, Kazuaki; Narumi, Kazumasa; Kimura, Kenji; Mannami, Michihiko

    1993-01-01

    Initial stages of epitaxial growth of lead chalcogenides on the (100) surface of SnTe under UHV conditions are studied from the angular distribution of scattered ions at glancing angle incidence of 0.7 MeV He ions on the growing surfaces. Real time measurement of the angular distribution is performed during the growth. Anomalous broadening of the angular distribution is observed at the initial stage of the growth. The broadening is attributed to the surface wrinkles induced by a square network of misfit edge dislocations. (author)

  5. Effect of Surface Tension Anisotropy and Welding Parameters on Initial Instability Dynamics During Solidification: A Phase-Field Study

    Science.gov (United States)

    Yu, Fengyi; Wei, Yanhong

    2018-05-01

    The effects of surface tension anisotropy and welding parameters on initial instability dynamics during gas tungsten arc welding of an Al-alloy are investigated by a quantitative phase-field model. The results show that the surface tension anisotropy and welding parameters affect the initial instability dynamics in different ways during welding. The surface tension anisotropy does not influence the solute diffusion process but does affect the stability of the solid/liquid interface during solidification. The welding parameters affect the initial instability dynamics by varying the growth rate and thermal gradient. The incubation time decreases, and the initial wavelength remains stable as the welding speed increases. When welding power increases, the incubation time increases and the initial wavelength slightly increases. Experiments were performed for the same set of welding parameters used in modeling, and the results of the experiments and simulations were in good agreement.

  6. Muonium-containing vinyl radicals

    International Nuclear Information System (INIS)

    Rhodes, C.J.; Symons, M.C.R.; Roduner, E.; Heming, M.

    1987-01-01

    Exposure of trimethylsilylacetylene and bis(trimethylsilyl)acetylene to positive muons gave radicals whose muon-electron hyperfine coupling constants establish that the corresponding vinyl radicals were formed. (author)

  7. Biomimetic surface modification of polypropylene by surface chain transfer reaction based on mussel-inspired adhesion technology and thiol chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Niu, Zhijun; Zhao, Yang; Sun, Wei; Shi, Suqing, E-mail: shisq@nwu.edu.cn; Gong, Yongkuan

    2016-11-15

    Highlights: • Biomimetic surface modification of PP was successfully conducted by integrating mussel-inspired technology, thiol chemistry and cell outer membranes-like structures. • The resultant biomimetic surface exhibits good interface and surface stability. • The obvious suppression of protein adsorption and platelet adhesion is also achieved. • The residue thoil groups on the surface could be further functionalized. - Abstract: Biomimetic surface modification of polypropylene (PP) is conducted by surface chain transfer reaction based on the mussel-inspired versatile adhesion technology and thiol chemistry, using 2-methacryloyloxyethylphosphorylcholine (MPC) as a hydrophilic monomer mimicking the cell outer membrane structure and 2,2-azobisisobutyronitrile (AIBN) as initiator in ethanol. A layer of polydopamine (PDA) is firstly deposited onto PP surface, which not only offers good interfacial adhesion with PP, but also supplies secondary reaction sites (-NH{sub 2}) to covalently anchor thiol groups onto PP surface. Then the radical chain transfer to surface-bonded thiol groups and surface re-initiated polymerization of MPC lead to the formation of a thin layer of polymer brush (PMPC) with cell outer membrane mimetic structure on PP surface. X-ray photoelectron spectrophotometer (XPS), atomic force microscopy (AFM) and water contact angle measurements are used to characterize the PP surfaces before and after modification. The protein adsorption and platelet adhesion experiments are also employed to evaluate the interactions of PP surface with biomolecules. The results show that PMPC is successfully grafted onto PP surface. In comparison with bare PP, the resultant PP-PMPC surface exhibits greatly improved protein and platelet resistance performance, which is the contribution of both increased surface hydrophilicity and zwitterionic structure. More importantly, the residue thiol groups on PP-PMPC surface create a new pathway to further functionalize such

  8. Biomimetic surface modification of polypropylene by surface chain transfer reaction based on mussel-inspired adhesion technology and thiol chemistry

    International Nuclear Information System (INIS)

    Niu, Zhijun; Zhao, Yang; Sun, Wei; Shi, Suqing; Gong, Yongkuan

    2016-01-01

    Highlights: • Biomimetic surface modification of PP was successfully conducted by integrating mussel-inspired technology, thiol chemistry and cell outer membranes-like structures. • The resultant biomimetic surface exhibits good interface and surface stability. • The obvious suppression of protein adsorption and platelet adhesion is also achieved. • The residue thoil groups on the surface could be further functionalized. - Abstract: Biomimetic surface modification of polypropylene (PP) is conducted by surface chain transfer reaction based on the mussel-inspired versatile adhesion technology and thiol chemistry, using 2-methacryloyloxyethylphosphorylcholine (MPC) as a hydrophilic monomer mimicking the cell outer membrane structure and 2,2-azobisisobutyronitrile (AIBN) as initiator in ethanol. A layer of polydopamine (PDA) is firstly deposited onto PP surface, which not only offers good interfacial adhesion with PP, but also supplies secondary reaction sites (-NH 2 ) to covalently anchor thiol groups onto PP surface. Then the radical chain transfer to surface-bonded thiol groups and surface re-initiated polymerization of MPC lead to the formation of a thin layer of polymer brush (PMPC) with cell outer membrane mimetic structure on PP surface. X-ray photoelectron spectrophotometer (XPS), atomic force microscopy (AFM) and water contact angle measurements are used to characterize the PP surfaces before and after modification. The protein adsorption and platelet adhesion experiments are also employed to evaluate the interactions of PP surface with biomolecules. The results show that PMPC is successfully grafted onto PP surface. In comparison with bare PP, the resultant PP-PMPC surface exhibits greatly improved protein and platelet resistance performance, which is the contribution of both increased surface hydrophilicity and zwitterionic structure. More importantly, the residue thiol groups on PP-PMPC surface create a new pathway to further functionalize such

  9. Radicals in arithmetic

    NARCIS (Netherlands)

    W.J. Palenstijn (Willem Jan)

    2014-01-01

    htmlabstractLet K be a field. A radical is an element of the algebraic closure of K of which a power is contained in K. In this thesis we develop a method for determining what we call entanglement. This describes unexpected additive relations between radicals, and is encoded in an entanglement

  10. Correlation of Gear Surface Fatigue Lives to Lambda Ratio (Specific Film Thickness)

    Science.gov (United States)

    Krantz, Timothy Lewis

    2013-01-01

    The effect of the lubrication regime on gear performance has been recognized, qualitatively, for decades. Often the lubrication regime is characterized by the specific film thickness being the ratio of lubricant film thickness to the composite surface roughness. Three studies done at NASA to investigate gearing pitting life are revisited in this work. All tests were done at a common load. In one study, ground gears were tested using a variety of lubricants that included a range of viscosities, and therefore the gears operated with differing film thicknesses. In a second and third study, the performance of gears with ground teeth and superfinished teeth were assessed. Thicker oil films provided longer lives as did improved surface finish. These datasets were combined into a common dataset using the concept of specific film thickness. This unique dataset of more 258 tests provides gear designers with some qualitative information to make gear design decisions.

  11. On the initial condition problem of the time domain PMCHWT surface integral equation

    KAUST Repository

    Uysal, Ismail Enes; Bagci, Hakan; Ergin, A. Arif; Ulku, H. Arda

    2017-01-01

    Non-physical, linearly increasing and constant current components are induced in marching on-in-time solution of time domain surface integral equations when initial conditions on time derivatives of (unknown) equivalent currents are not enforced

  12. Initial adhesion of Listeria monocytogenes to solid surfaces under liquid flow

    DEFF Research Database (Denmark)

    Szlavik, Julie; Soares Paiva, Dionísio; Mørk, Nils

    2012-01-01

    .001) was observed but not of interactions between surface-shear stress. No correlation between surface hydrophobicity and IAR was observed. Addition of 5% NaCl during propagation resulted in a decrease in IAR whilst propagation in low nutrient media caused an increase indicating a general change in surface......Some strains of the food borne pathogen Listeria monocytogenes persist in food processing environments. The exact reason behind this phenomenon is not known, but strain differences in the ability to adhere to solid surfaces could offer an explanation. In the present work, initial adhesion of nine...... strains of L. monocytogenes was investigated under liquid flow at two levels of shear stress on six different surfaces using a flow chamber set-up with microscopy measurements. The surfaces tested were glass and PVC, and glass coated with beef extract, casein, and homogenised and unhomogenised milk...

  13. Multiple free-radical scavenging capacity in serum

    Science.gov (United States)

    Oowada, Shigeru; Endo, Nobuyuki; Kameya, Hiromi; Shimmei, Masashi; Kotake, Yashige

    2012-01-01

    We have developed a method to determine serum scavenging-capacity profile against multiple free radical species, namely hydroxyl radical, superoxide radical, alkoxyl radical, alkylperoxyl radical, alkyl radical, and singlet oxygen. This method was applied to a cohort of chronic kidney disease patients. Each free radical species was produced with a common experimental procedure; i.e., uv/visible-light photolysis of free-radical precursor/sensitizer. The decrease in free-radical concentration by the presence of serum was quantified with electron spin resonance spin trapping method, from which the scavenging capacity was calculated. There was a significant capacity change in the disease group (n = 45) as compared with the healthy control group (n = 30). The percent values of disease’s scavenging capacity with respect to control group indicated statistically significant differences in all free-radical species except alkylperoxyl radical, i.e., hydroxyl radical, 73 ± 12% (p = 0.001); superoxide radical, 158 ± 50% (p = 0.001); alkoxyl radical, 121 ± 30% (p = 0.005); alkylperoxyl radical, 123 ± 32% (p>0.1); alkyl radical, 26 ± 14% (p = 0.001); and singlet oxygen, 57 ± 18% (p = 0.001). The scavenging capacity profile was illustrated using a radar chart, clearly demonstrating the characteristic change in the disease group. Although the cause of the scavenging capacity change by the disease state is not completely understood, the profile of multiple radical scavenging capacities may become a useful diagnostic tool. PMID:22962529

  14. Radicals in arithmetic

    NARCIS (Netherlands)

    Palenstijn, Willem Jan

    2014-01-01

    Let K be a field. A radical is an element of the algebraic closure of K of which a power is contained in K. In this thesis we develop a method for determining what we call entanglement. This describes unexpected additive relations between radicals, and is encoded in an entanglement group. We give

  15. Modelling On Photogeneration Of Hydroxyl Radical In Surface Waters And Its Reactivity Towards Pharmaceutical Wastes

    International Nuclear Information System (INIS)

    Das, Radha; Vione, Davide; Rubertelli, Francesca; Maurino, Valter; Minero, Claudio; Barbati, Stephane; Chiron, Serge

    2010-01-01

    This paper reports a simple model to describe the formation and reactivity of hydroxyl radicals in the whole column of freshwater lakes. It is based on empirical irradiation data and is a function of the water chemical composition (the photochemically significant parameters NPOC, nitrate, nitrite, carbonate and bicarbonate), the lake conformation best expressed as the average depth, and the water absorption spectrum in a simplified Lambert-Beer approach. The purpose is to derive the lifetime of dissolved molecules, due to reaction with OH, on the basis of their second-order rate constants with the hydroxyl radical. The model was applied to two compounds of pharmaceutical wastes ibuprofen and carbamazepine, for which the second-order rate constants for reaction with the hydroxyl radical were measured by means of the competition kinetics with 2-propanol. The measured values of the rate constants are 1.0x10 10 and 1.6x10 10 M -1 s -1 for ibuprofen and carbamazepine, respectively. The model suggests that the lifetime of a given compound can be very variable in different lakes, even more than the lifetime of different compounds in the same lake. It can be concluded that as far as the reaction with OH, is concerned the concepts of photolability and photostability, traditionally attached to definite compounds, are ecosystem-dependent at least as much as they depend on the molecule under consideration.

  16. Radicalization as a Vector: Exploring Non-Violent and Benevolent Processes of Radicalization.

    Directory of Open Access Journals (Sweden)

    Ken Reidy

    2018-03-01

    Full Text Available Successful radicalization posits three outcomes: extremism, terrorism or both. As these are undesirable, radicalization is understood as wholly malevolent and governments work to prevent and/or stop it. Nonetheless, a handful of scholars have recognized that the same radicalization process which results in either outcome may, theoretically at least, also have beneficial outcomes such as environmental awareness or human rights. This article explores one such outcome. Based on interviews with British Muslim aid workers (n=6 operating in Jihadist conflict zones post Arab spring and using constructivist grounded theory, it illustrates how the research participants radicalized to humanitarianism which resulted in them assisting the most plighted of Muslims by deploying to the most wanton of areas: ones commonly referred to as Jihadist conflict zones. Evidently, these destinations are shared with Jihadists and given the array of other observable similarities (socio-demographics and [pre-]mobilization behaviours, these morally opposed groups become conflated by the security services. This is further compounded by the fact that Jihadists manipulate and/or impersonate aid workers so as to funnel people and funds. To distinguish both, this article documents the benevolent pathway of the research participants and juxtaposes it to scholarly knowledge on Jihadist pathways. Socialization was revealed to be the key distinguishing feature rather than descriptive risk factors (such as ideology or moral outrage because the process of radicalization was not found to be the start of the radicalized pathway. It concludes that benevolently radicalized Islamic groups constitute an effective means of pathway divergence for particular typologies by offering an attractive and prosocial alternative to Jihadism. This strengths-based preventative approach (“what’s right” takes the form of a community-centric market competitor to Jihadism rather than a problem

  17. Oxidation of alpha-tocopherol in micelles and liposomes by the hydroxyl, perhydroxyl, and superoxide free radicals

    International Nuclear Information System (INIS)

    Fukuzawa, K.; Gebicki, J.M.

    1983-01-01

    Rates of oxidation of alpha-tocopherol by the hydroxyl- and superoxide free radicals were measured. The radicals were produced in known yields by radiolysis of aqueous solutions with gamma rays. Two main systems were used to dissolve the tocopherol; micelles, made up from charged and uncharged amphiphiles, and membranes made from dimyristyl phosphatidylcholine which could be charged by addition of stearyl amine or dicetyl phosphate. The HO. radicals were efficient oxidants of alpha-tocopherol in all systems, with up to 83% of radicals generated in micelle and 32% in membrane suspensions initiating the oxidation. The HO 2 radical was an even more effective oxidant, but when most of it was in the O 2 form at neutral or alkaline pH, the oxidation rates became low. Tocopherol held in positively charged micelles or membranes was oxidized at a higher rate by the O 2 than in uncharged or negative particles. Possible biological significance of these results is discussed

  18. Ethanol attracts scolytid beetles to Phytophthora ramorum cankers on coast live oak [Abstract

    Science.gov (United States)

    Rick G. Kelsey; Maia Beh; Dave Shaw; Daniel K. Manter

    2013-01-01

    Successful infection of coast live oak (Quercus agrifolia Née) stems by Phytophthora ramorum results in the formation of a canker visible initially at the bark surface by the release of a dark red to black colored exudate referred to as "bleeding." Bark and ambrosia beetles are often attracted to diseased trees within...

  19. Halloysite nanotubes grafted hyperbranched (co)polymers via surface-initiated self-condensing vinyl (co)polymerization

    International Nuclear Information System (INIS)

    Mu Bin; Zhao Mingfei; Liu Peng

    2008-01-01

    Halloysite nanotubes (HNTs) grafted hyperbranched polymers were prepared by the self-condensing vinyl polymerization (SCVP) of 2-((bromoacetyl)oxy)ethyl acrylate (BAEA) and the self-condensing vinyl copolymerization of n-butyl acrylate (BA) and BAEA with BAEA as inimer (AB*) respectively, from the surfaces of the 2-bromoisobutyric acid modified halloysite nanotubes (HNTs-Br) via atom transfer radical polymerization (ATRP) technique. The halloysite nanotubes grafted hyperbranched polymer (HNTs-HP) and the halloysite nanotubes grafted hyperbranched copolymer (HNTs-HCP) were characterized by elemental analysis (EA), Fourier transform infrared (FTIR), thermogravimetric analysis (TGA), X-ray diffraction (XRD), and transmission electron microscope (TEM). The grafted hyperbranched polymers were characterized with Nuclear magnetic resonance (NMR) and the molecular ratio between the inimer AB* and BA in the grafted hyperbranched copolymers was found to be 3:2, calculated from the TGA and EA results

  20. Halloysite nanotubes grafted hyperbranched (co)polymers via surface-initiated self-condensing vinyl (co)polymerization

    Energy Technology Data Exchange (ETDEWEB)

    Mu Bin; Zhao Mingfei; Liu Peng [Lanzhou University, State Key Laboratory of Applied Organic Chemistry and Institute of Polymer Science and Engineering, College of Chemistry and Chemical Engineering (China)], E-mail: pliu@lzu.edu.cn

    2008-05-15

    Halloysite nanotubes (HNTs) grafted hyperbranched polymers were prepared by the self-condensing vinyl polymerization (SCVP) of 2-((bromoacetyl)oxy)ethyl acrylate (BAEA) and the self-condensing vinyl copolymerization of n-butyl acrylate (BA) and BAEA with BAEA as inimer (AB*) respectively, from the surfaces of the 2-bromoisobutyric acid modified halloysite nanotubes (HNTs-Br) via atom transfer radical polymerization (ATRP) technique. The halloysite nanotubes grafted hyperbranched polymer (HNTs-HP) and the halloysite nanotubes grafted hyperbranched copolymer (HNTs-HCP) were characterized by elemental analysis (EA), Fourier transform infrared (FTIR), thermogravimetric analysis (TGA), X-ray diffraction (XRD), and transmission electron microscope (TEM). The grafted hyperbranched polymers were characterized with Nuclear magnetic resonance (NMR) and the molecular ratio between the inimer AB* and BA in the grafted hyperbranched copolymers was found to be 3:2, calculated from the TGA and EA results.