WorldWideScience

Sample records for copper-mediated radical polymerization

  1. 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...

  2. Aqueous copper-mediated living polymerization: exploiting rapid disproportionation of CuBr with Me6TREN.

    Science.gov (United States)

    Zhang, Qiang; Wilson, Paul; Li, Zaidong; McHale, Ronan; Godfrey, Jamie; Anastasaki, Athina; Waldron, Christopher; Haddleton, David M

    2013-05-15

    A new approach to perform single-electron transfer living radical polymerization (SET-LRP) in water is described. The key step in this process is to allow full disproportionation of CuBr/Me6TREN (TREN = tris(dimethylamino)ethyl amine to Cu(0) powder and CuBr2 in water prior to addition of both monomer and initiator. This provides an extremely powerful tool for the synthesis of functional water-soluble polymers with controlled chain length and narrow molecular weight distributions (polydispersity index approximately 1.10), including poly(N-isopropylacrylamide), N,N-dimethylacrylamide, poly(ethylene glycol) acrylate, 2-hydroxyethyl acrylate (HEA), and an acrylamido glyco monomer. The polymerizations are performed at or below ambient temperature with quantitative conversions attained in minutes. Polymers have high chain end fidelity capable of undergoing chain extensions to full conversion or multiblock copolymerization via iterative monomer addition after full conversion. Activator generated by electron transfer atom transfer radical polymerization of N-isopropylacrylamide in water was also conducted as a comparison with the SET-LRP system. This shows that the addition sequence of l-ascorbic acid is crucial in determining the onset of disproportionation, or otherwise. Finally, this robust technique was applied to polymerizations under biologically relevant conditions (PBS buffer) and a complex ethanol/water mixture (tequila).

  3. Mechanically controlled radical polymerization initiated by ultrasound

    Science.gov (United States)

    Mohapatra, Hemakesh; Kleiman, Maya; Esser-Kahn, Aaron Palmer

    2017-02-01

    In polymer chemistry, mechanical energy degrades polymeric chains. In contrast, in nature, mechanical energy is often used to create new polymers. This mechanically stimulated growth is a key component of the robustness of biological materials. A synthetic system in which mechanical force initiates polymerization will provide similar robustness in polymeric materials. Here we show a polymerization of acrylate monomers initiated and controlled by mechanical energy provided by ultrasonic agitation. The activator for an atom-transfer radical polymerization is generated using piezochemical reduction of a Cu(II) precursor complex, which thus converts a mechanical activation of piezoelectric particles to the synthesis of a new material. This polymerization reaction has some characteristics of controlled radical polymerization, such as narrow molecular-weight distribution and linear dependence of the polymeric chain length on the time of mechanical activation. This new method of controlled radical polymerization complements the existing methods to synthesize commercially useful well-defined polymers.

  4. AQUEOUS STABLE FREE RADICAL POLYMERIZATION PROCESSES

    Institute of Scientific and Technical Information of China (English)

    Andrea R. Szkurhan; Michael K. Georges

    2004-01-01

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

  5. Synthesis and characterization of poly(2-ethylhexyl acrylate) prepared via atom transfer radical polymerization, reverse atom transfer radical polymerization and radical polymerization

    Indian Academy of Sciences (India)

    Dhruba Jyoti Haloi; Bishnu Prasad Koiry; Prithwiraj Mandal; Nikhil Kumar Singha

    2013-07-01

    This investigation reports a comparative study of poly(2-ethylhexyl acrylate) (PEHA) prepared via atom transfer radical polymerization (ATRP), reverse atom transfer radical polymerization (RATRP) and conventional free radical polymerization (FRP). The molecular weights and the molecular weight distributions of the polymers were measured by gel permeation chromatography (GPC) analysis. Structural characterization of the polymers was carried out by 1H NMR and MALDI-TOF-MS analyses. Thermal properties of the polymers were evaluated by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The polymerization results and the thermal properties of PEHAs prepared via ATRP, RATRP and FRP were compared.

  6. Synthesis of Glycopolymer Architectures by Reversible-Deactivation Radical Polymerization

    Directory of Open Access Journals (Sweden)

    Ali Ghadban

    2013-05-01

    Full Text Available This review summarizes the state of the art in the synthesis of well-defined glycopolymers by Reversible-Deactivation Radical Polymerization (RDRP from its inception in 1998 until August 2012. Glycopolymers architectures have been successfully synthesized with four major RDRP techniques: Nitroxide-mediated radical polymerization (NMP, cyanoxyl-mediated radical polymerization (CMRP, atom transfer radical polymerization (ATRP and reversible addition-fragmentation chain transfer (RAFT polymerization. Over 140 publications were analyzed and their results summarized according to the technique used and the type of monomer(s and carbohydrates involved. Particular emphasis was placed on the experimental conditions used, the structure obtained (comonomer distribution, topology, the degree of control achieved and the (potential applications sought. A list of representative examples for each polymerization process can be found in tables placed at the beginning of each section covering a particular RDRP technique.

  7. Origins and Development of Initiation of Free Radical Polymerization Processes

    Directory of Open Access Journals (Sweden)

    Dietrich Braun

    2009-01-01

    Full Text Available At present worldwide about 45% of the manufactured plastic materials and 40% of synthetic rubber are obtained by free radical polymerization processes. The first free radically synthesized polymers were produced between 1910 and 1930 by initiation with peroxy compounds. In the 1940s the polymerization by redox processes was found independently and simultaneously at IG Farben in Germany and ICI in Great Britain. In the 1950s the systematic investigation of azo compounds as free radical initiators followed. Compounds with labile C–C-bonds were investigated as initiators only in the period from the end of the 1960s until the early 1980s. At about the same time, iniferters with cleavable S–S-bonds were studied in detail. Both these initiator classes can be designated as predecessors for “living” or controlled free radical polymerizations with nitroxyl-mediated polymerizations, reversible addition fragmentation chain transfer processes (RAFT, and atom transfer radical polymerizations (ATRP.

  8. [Study of "living" radical polymerization by FTIR in situ].

    Science.gov (United States)

    Chen, J; Hua, F; Qiu, J; Yang, Y

    2001-02-01

    Three types of living radical polymerization processes were monitored by means of FTIR spectrometer with handful diamond detector called as Dicomp in situ. It was found that both styrene and styrene/hydroxylpropyl methyacrylate (HPMA) could polymerize according to stable free radical polymerization (SFRP) mechanism in presence of 4-hydroxyl tetramethypiperidiyl-1-oxy(HTEMPO). For styrene/HPMA system, the styrene and HPMA conversion monitored by FTIR were linear with increase of molecular weight, but it gave longer induction period compared with that for St bulk polymerization. It was related to the hydrogen-transfer reaction between the propagating radicals with the end HPMA unit and HTEMPO. Furthermore, This following method in situ could be introduced into monitoring heterogeneous polymerization of styrene during atom transfer radical polymerization (ATRP). The apparent kinetics was found to be about zero order and not 1.0 order, due to propagating on the complex including radicals, CuX and bpy in heterogeneous interface. The polymerization rate will be not related to the St in bulk St phase.

  9. Novel Complex Polymers with Carbazole Functionality by Controlled Radical Polymerization

    Directory of Open Access Journals (Sweden)

    Kazuhiro Nakabayashi

    2012-01-01

    Full Text Available This review summarizes recent advances in the design and synthesis of novel complex polymers with carbazole moieties using controlled radical polymerization techniques. We focus on the polymeric architectures of block copolymers, star polymers, including star block copolymers and miktoarm star copolymers, comb-shaped copolymers, and hybrids. Controlled radical polymerization of N-vinylcarbazole (NVC and styrene and (methacrylate derivatives having carbazole moieties is well advanced, leading to the well-controlled synthesis of complex macromolecules. Characteristic optoelectronic properties, assembled structures, and three-dimensional architectures are briefly introduced.

  10. Radicals contributing to preirradiation graft polymerization onto porous polyethylene

    Science.gov (United States)

    Uezu, Kazuya; Saito, Kyoichi; Furusaki, Shintaro; Sugo, Takanobu; Ishigaki, Isao

    Porous polyethylene hollow fiber was irradiated by an electron beam at 160 kGy and 8 kGy/min. The concentrations of the radicals such as alkyl, allyl and peroxy were determined by analyzing an integral form of ESR spectra. The comparison of the decay of the radicals with and without contact with air demonstrated that the key radical contributing to the preirradiation graft polymerization is the alkyl radical. The decay of the alkyl radical was simulated by the diffusion-controlled model in the spherical crystallites of polyethylene.

  11. 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...

  12. COPPER(0)-MEDIATED RADICAL POLYMERIZATION OF STYRENE AT ROOM TEMPERATURE

    Institute of Scientific and Technical Information of China (English)

    Xiao-fei Zhang; Yang Wu; Jun Huang; Xue-lang Miao; Zheng-biao Zhang; Xiu-lin Zhu

    2013-01-01

    The "living'/controlled radical polymerization (LRP) of styrene (St) at room temperature is rarely reported.In this work,copper(0) (Cu(0))-mediated radical polymerization of St at room temperature was investigated in detail.Dimethyl sulfoxide (DMSO),N,N-dimethylformamide (DMF) as well as a binary solvent,tetrahydrofuran/1,1,1,3,3,3-hexafluoro-2-propanol were used as the solvents,respectively.Methyl-2-bromopropionate and ethyl 2-bromoisobutyrate were used as the initiators,respectively.The polymerization proceeded smoothly with moderate conversions at room temperature.It was found that DMF was a good solvent with the essential features of LRP,while DMSO was a poor solvent with uncontrollable molecular weights.Besides,the match among the initiator,solvent and molar ratios of reactants can modulate the livingness of the polymerization,and the proper selection of ligand was also crucial to a controlled process.This work provided a first example of Cu(0)-mediated radical polymerization of St at room temperature,which would enrich and strength the LRP technique.

  13. Controlled/"Living" Radical Polymerization of (-)-Menthyl Methacrylate

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    The atom transfer radical polymerization(ATRP) of (-)-menthyl methacrylate((-)-MnMA) mediated by CuCl/bipyridine and ethyl 2-bromopropionate or 1-phenylethyl bromide in THF system has been studied. The dependence of the specific rotation on molecular weight and the CD of Poly((-)-MnMA) thus obtained was investigated.

  14. Reverse Atom Transfer Radical Polymerization of (-)-Menthyl Methacrylate

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    The reverse atom transfer radical polymerization(RATRP) of (-)-menthyl methacrylate ((-)-MnMA) with AIBN(AIBN/CuCl2/bipyridine(bipy) or (-)sparteine((-)Sp) =1/2/4) initiating system in THF has been studied. The dependence of the specific rotation on molecular weight was investigated.

  15. Mechanism and Kinetics of Nitroxide-Controlled Free Radical Polymerization (ORGANIC MATERIALS CHEMISTRY-Polymeric Materials)

    OpenAIRE

    1997-01-01

    In the nitroxide-mediated free radical polymerization, the rate of polymerization is determined by the balance of the rates of thermal initiation and bialkyl termination, just like in the conventional system, while the polydispersity is determined by the dissociation-combination frequency of the polymer-nitroxyl adduct and the rate of decomposition of the adduct. These mechanisms were quantitatively confirmed by both experiments and computer simulations.

  16. Synthesis and Characterization of Tailored Macromolecules via Stable Free Radical Polymerization Methodologies

    OpenAIRE

    2003-01-01

    The stable free radical polymerization methodology for production of controlled macromolecules was investigated using a novel monomer, 2-vinylnaphthalene. Initial polymerizations resulted in molecular weight distributions typical of conventional free radical polymerization techniques (>2.0). Manipulation of the initiator concentration and the molar ratio of initiator to nitroxide demonstrated no significant control over the resulting polymer products. Analysis of the polymerization kinetics...

  17. Controlled free radical polymerization of vinyl acetate with cobalt acetoacetonate

    Indian Academy of Sciences (India)

    Mohammad Ali Semsarzadeh; Sahar Amiri

    2012-03-01

    The polymerization of vinyl acetate with the complex catalyst of cobalt acetoacetonate [Co (acac)2] and DMF ligand with benzoyl peroxide initiator has been successfully carried out in bulk and in solution. The bulk polymerization has been used in a new route consisting of a one-step polymer formation in a fine capillary tube. In this process, the high rate of propagation was used to carry out the reaction in a microcapillary tube. Under 60°C, the colour-free reaction without solid catalyst impurity was 95% complete within a few hours. The high molecular weight of polyvinyl acetate (PVAc) with its relatively low molecular distribution without unreacted monomer provided a new method in microprocessing of the controlled radical polymerization of vinyl acetate in a one-step polymerization process. PVAc polymerization systems showed induction time, which was reduced in this reaction with using complex of DMF/ Co(acac)2. The kinetics of the reaction with a smaller degree of branching from this catalyst indicated that the electronegativity of the transition metal and diffusion of the homogeneous catalyst with DMF are important factors of fast polymerization in the bulk. Thermal properties of the polymer indicated a lower glass transition state. The easily reformed or stretched microsolid polymer demonstrated 20% crystallinity.

  18. Utilization of Nitrones in Radical Polymerizations and Polymer Conjugations

    OpenAIRE

    Ranieri Lynn, Kayte

    2015-01-01

    Much research has been performed in the last 10 years on the use of nitrones in synthetic polymer chemistry. Nitrone polymer chemistry represents an additional tool to the “polymer toolbox”, which contributes to the advancement of modern polymer science and technology. In this present thesis, four interconnecting themes centered on the use of nitrones in radical polymerizations and coupling have been investigated. (1) Synthesize nitrones with various functionalities. (2) Utilize controlled ra...

  19. 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.

  20. Pickering emulsion templated interfacial atom transfer radical polymerization for microencapsulation.

    Science.gov (United States)

    Li, Jian; Hitchcock, Adam P; Stöver, Harald D H

    2010-12-01

    This Article describes a new microencapsulation method based on a Pickering emulsion templated interfacial atom transfer radical polymerization (PETI-ATRP). Cationic LUDOX CL nanoparticles were coated electrostatically with an anionic polymeric ATRP initiator, poly(sodium styrene sulfonate-co-2-(2-bromoisobutyryloxy)ethyl methacrylate) (PSB), prepared by radical copolymerization of sodium styrene sulfonate and 2-(2-bromoisobutyryloxy)ethyl methacrylate (BIEM). The resulting PSB-modified CL particles were surface active and could be used to stabilize oil-in-water Pickering emulsions. ATRP of water-soluble cross-linking monomers, confined to the oil-water interface by the surface-bound PSB, then led to nanoparticle/polymer composite shells. This method allowed encapsulation of core solvents (xylene, hexadecane, perfluoroheptane) with different solubility parameters. The microcapsule (MC) wall chemistry could accommodate different monomers, demonstrating the versatility of this method. Double-walled MCs were formed by sequentially carrying out PETI-ATRP and in situ polymerization of encapsulated monomers. The double-walled structure was verified by both transmission electron microscopy (TEM) and scanning transmission X-ray microscopy (STXM).

  1. Application of living free radical polymerization for nucleic acid delivery.

    Science.gov (United States)

    Chu, David S H; Schellinger, Joan G; Shi, Julie; Convertine, Anthony J; Stayton, Patrick S; Pun, Suzie H

    2012-07-17

    Therapeutic gene delivery can alter protein function either through the replacement of nonfunctional genes to restore cellular health or through RNA interference (RNAi) to mask mutated and harmful genes. Researchers have investigated a range of nucleic acid-based therapeutics as potential treatments for hereditary, acquired, and infectious diseases. Candidate drugs include plasmids that induce gene expression and small, interfering RNAs (siRNAs) that silence target genes. Because of their self-assembly with nucleic acids into virus-sized nanoparticles and high transfection efficiency in vitro, cationic polymers have been extensively studied for nucleic acid delivery applications, but toxicity and particle stability have limited the clinical applications of these systems. The advent of living free radical polymerization has improved the quality, control, and reproducibility of these synthesized materials. This process yields well-defined, narrowly disperse materials with designed architectures and molecular weights. As a result, researchers can study the effects of polymer architecture and molecular weight on transfection efficiency and cytotoxicity, which will improve the design of next-generation vectors. In this Account, we review findings from structure-function studies that have elucidated key design motifs necessary for the development of effective nucleic acid vectors. Researchers have used robust methods such as atom transfer radical polymerization (ATRP), reverse addition-fragmentation chain transfer polymerization (RAFT), and ring-opening metastasis polymerization (ROMP) to engineer materials that enhance extracellular stability and cellular specificity and decrease toxicity. In addition, we discuss polymers that are biodegradable, form supramolecular structures, target specific cells, or facilitate endosomal release. Finally, we describe promising materials with a range of in vivo applications from pulmonary gene delivery to DNA vaccines.

  2. Cobalt-mediated radical polymerization of vinyl monomers: investigation of cobalt-coordination

    OpenAIRE

    2009-01-01

    Controlled Radical Polymerization techniques have been developed to obtain well-defined architectures and to control polymer parameters. Among these systems is Cobalt-Mediated Radical Polymerization (CMRP), which is based on the reversible deactivation of the growing radical chains with a cobalt complex, the cobalt (II) bis(acetylacetonate). The interest of this system is not only due to its ability to control the polymerization of very reactive monomers such as vinyl acetate (VAc) and N-viny...

  3. Diffusion-regulated phase-transfer catalysis for atom transfer radical polymerization of methyl methacrylate in an aqueous/organic biphasic system.

    Science.gov (United States)

    Ding, Mingqiang; Jiang, Xiaowu; Peng, Jinying; Zhang, Lifen; Cheng, Zhenping; Zhu, Xiulin

    2015-03-01

    A concept based on diffusion-regulated phase-transfer catalysis (DRPTC) in an aqueous-organic biphasic system with copper-mediated initiators for continuous activator regeneration is successfully developed for atom transfer radical polymerization (ICAR ATRP) (termed DRPTC-based ICAR ATRP here), using methyl methacrylate (MMA) as a model monomer, ethyl α-bromophenylacetate (EBrPA) as an initiator, and tris(2-pyridylmethyl)amine (TPMA) as a ligand. In this system, the monomer and initiating species in toluene (organic phase) and the catalyst complexes in water (aqueous phase) are simply mixed under stirring at room temperature. The trace catalyst complexes transfer into the organic phase via diffusion to trigger ICAR ATRP of MMA with ppm level catalyst content once the system is heated to the polymerization temperature (75 °C). It is found that well-defined PMMA with controlled molecular weights and narrow molecular weight distributions can be obtained easily. Furthermore, the polymerization can be conducted in the presence of limited amounts of air without using tedious degassed procedures. After cooling to room temperature, the upper organic phase is decanted and the lower aqueous phase is reused for another 10 recycling turnovers with ultra low loss of catalyst and ligand loading. At the same time, all the recycled catalyst complexes retain nearly perfect catalytic activity and controllability, indicating a facile and economical strategy for catalyst removal and recycling.

  4. Studies on the Self-condensing Vinyl Living Radical Polymerization of a Novel Acrylate Inimer

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    A novel acrylate inimer, 2-(2-chloroacetyloxy) ethyl acrylate, was prepared by the reaction of 2-hydroxyethyl acrylate with chloroacetyl chloride in the presence of triethylamine. The self-condensing vinyl living radical polymerization of the inimer was studied and the hyperbranched macromolecules containing ester linkages on their backbone were prepared. All the polymerization products were characterized by 1H NMR. The polymerization degree and the branching parameter were calculated based on the 1H NMR spectra. It has been shown that this inimer exhibits a very distinctive polymerization behavior. Similar to step-growth polymerization, the polymerization degree of the products formed increased exponentially during the early stage of the polymerization, and then the increasing rate slowed down. However, the inimer remained present throughout the polymerization consistent with conventional free radical polymerization. Also, if much longer polymerization time was used, the polymerization system would become gel due to the crosslinking reaction derived from radical-radical recombination. As a result of the unequal reactivity of -CH2Cl and >CHCl, an almost linear product was obtained at a molar ratio of bipy to inimer=0.05, while a relatively high ratio of bipy to inimer 1 favored the formation of the branched structure. The macromolecules formed at a high ratio of bipy to inimer 1 exhibited an excellent solubility in organic solvents such as acetone.

  5. INTERACTIONS BETWEEN KETONES AND AMINES IN PHOTOINITIATING SYSTEMS USED FOR RADICAL POLYMERIZATION

    Institute of Scientific and Technical Information of China (English)

    WU Shikang; FOUASSIER ,J. P.

    1990-01-01

    Time resolved laser spectroscopy and GC/MS were used to investigate the primary processes and the side reactions occurring in benzophenone and chlorothioxanthone/amine systems used as photoinitiators of radical polymerization. The discrepancy observed between the experimental data and the expected behaviour is accounted for by detrimental chemicalreaction involving the ketone triplet state, the ketyl radical and the amine - derived radical.

  6. Biodegradable and radically polymerized elastomers with enhanced processing capabilities.

    Science.gov (United States)

    Ifkovits, Jamie L; Padera, Robert F; Burdick, Jason A

    2008-09-01

    The development of biodegradable materials with elastomeric properties is beneficial for a variety of applications, including for use in the engineering of soft tissues. Although others have developed biodegradable elastomers, they are restricted by their processing at high temperatures and under vacuum, which limits their fabrication into complex scaffolds. To overcome this, we have modified precursors to a tough biodegradable elastomer, poly(glycerol sebacate) (PGS) with acrylates to impart control over the crosslinking process and allow for more processing options. The acrylated-PGS (Acr-PGS) macromers are capable of crosslinking through free radical initiation mechanisms (e.g., redox and photo-initiated polymerizations). Alterations in the molecular weight and % acrylation of the Acr-PGS led to changes in formed network mechanical properties. In general, Young's modulus increased with % acrylation and the % strain at break increased with molecular weight when the % acrylation was held constant. Based on the mechanical properties, one macromer was further investigated for in vitro and in vivo degradation and biocompatibility. A mild to moderate inflammatory response typical of implantable biodegradable polymers was observed, even when formed as an injectable system with redox initiation. Moreover, fibrous scaffolds of Acr-PGS and a carrier polymer, poly(ethylene oxide), were prepared via an electrospinning and photopolymerization technique and the fiber morphology was dependent on the ratio of these components. This system provides biodegradable polymers with tunable properties and enhanced processing capabilities towards the advancement of approaches in engineering soft tissues.

  7. Simulating Controlled Radical Polymerizations with mcPolymer—A Monte Carlo Approach

    Directory of Open Access Journals (Sweden)

    Georg Drache

    2012-07-01

    Full Text Available Utilizing model calculations may lead to a better understanding of the complex kinetics of the controlled radical polymerization. We developed a universal simulation tool (mcPolymer, which is based on the widely used Monte Carlo simulation technique. This article focuses on the software architecture of the program, including its data management and optimization approaches. We were able to simulate polymer chains as individual objects, allowing us to gain more detailed microstructural information of the polymeric products. For all given examples of controlled radical polymerization (nitroxide mediated radical polymerization (NMRP homo- and copolymerization, atom transfer radical polymerization (ATRP, reversible addition fragmentation chain transfer polymerization (RAFT, we present detailed performance analyses demonstrating the influence of the system size, concentrations of reactants, and the peculiarities of data. Different possibilities were exemplarily illustrated for finding an adequate balance between precision, memory consumption, and computation time of the simulation. Due to its flexible software architecture, the application of mcPolymer is not limited to the controlled radical polymerization, but can be adjusted in a straightforward manner to further polymerization models.

  8. Synthesis of glycopolymers by controlled radical polymerization techniques and their applications.

    Science.gov (United States)

    Vázquez-Dorbatt, Vimary; Lee, Juneyoung; Lin, En-Wei; Maynard, Heather D

    2012-11-26

    Natural saccharides are involved in numerous biological processes. It has been shown that these carbohydrates play a role in cell adhesion and proliferation, as well as protein stabilization, organization, and recognition. Certain carbohydrates also serve as receptors for viruses and bacteria. They are over expressed in diseases such as cancer. Hence, a lot of effort has been focused on mimicking these sugars. Polymers with pendent saccharide groups, also known as glycopolymers, are studied as oligo- and polysaccharide mimics. Controlled radical polymerization (CRP) techniques such as atom transfer radical polymerization (ATRP), reversible addition-fragmentation chain transfer (RAFT) polymerization, and nitroxide-mediated polymerization (NMP), as well as cyanoxyl-mediated free radical polymerization have allowed chemists to synthesize well-defined glycopolymers that, in some cases, have particular end-group functionalities. This review focuses on the synthesis of glycopolymers by these methods and the applications of glycopolymers as natural saccharide mimics.

  9. The influence of cobalt-coordination on cobalt-mediated radical polymerization of vinyl monomers

    OpenAIRE

    2009-01-01

    Nowadays, polymers are a part of everyday life. Researchers encouraged by growing need in high performance polymers develop new synthesis tools to manage the molecular architecture and thus the polymer properties. In this context, CRP (Controlled Radical Polymerization) techniques have been developed to obtain well-defined architectures and to control polymer parameters. Among these systems is Cobalt-Mediated Radical Polymerization (CMRP), which is based on the reversible deactivation of the ...

  10. Interfacial/free radical polymerization microencapsulation: kinetics of particle formation.

    Science.gov (United States)

    Mahabadi, H K; Ng, T H; Tan, H S

    1996-01-01

    Microcapsules containing pigment and polymer were prepared by dispersing a viscous mixture of pigment, core monomers, initiators and oil-soluble shell monomer in an aqueous solution of surfactants, forming oil-in-water droplets. Subsequently, a water-soluble shell monomer was added to these droplets, encapsulating them via interfacial (IF) polycondensation. These microcapsules were then heated for free radical (FR) polymerization of the core monomers. Effects of primary variables, such as the shearing time during particle formation, surfactant concentration, organic phase concentration, and mode of water-soluble shell monomer addition, were studied. The results indicated that polyvinylalcohol (PVOH), used as the surfactant/stabilizer, reacted with the oil-soluble shell monomers. The depletion of PVOH, especially when PVOH concentration was low, resulted in rapid growth of particle size and, eventually, suspension failure. The kinetic data revealed a particle formation mechanism which consists of two processes. The first process is the formation of an equilibrium particle size by the equilibrium process of particle breakage due to the mechanical shearing force and coalescence due to collisions among particles and surface tension forces. The second process is the reaction between PVOH and oil-soluble shell monomer which leads to the depletion of PVOH and consequently causes more coalescence of particles and a significant increase in the equilibrium particle size. The net effect of these two processes shows an optimum shearing time where the smallest particle size can be attained, and this optimum time is a function of several primary variables. Methods to prevent the reaction and therefore the depletion of PVOH are proposed.

  11. Synthesis of Dendritic-Linear Block Copolymers by Atom Transfer Radical Polymerization

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    The dendritic polyarylether 2-bromoisobutyrate as the macromolecular initiator for the controlled free radical polymerization of styrene was investigated. The polymerization was carried out with CuBr/2,2′-bipyridine catalyst at 110℃. It is found that the hybrid dendritic-linear block copolymers possess well-defined molecular weights and low polydispersities.

  12. ATOM TRANSFER RADICAL POLYMERIZATION OF 2,5-BIS[(4-HEXYLOXYPHENYL)OXYCARBONYL]STYRENE

    Institute of Scientific and Technical Information of China (English)

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

    2005-01-01

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

  13. Twin screw extruders as polymerization reactors for a free radical homo polymerization

    NARCIS (Netherlands)

    Ganzeveld, K.J.; Janssen, L.P.B.M.

    1993-01-01

    The bulk polymerization of n-butylmethacrylate was investigated in a counter-rotating twin screw extruder. It appeared that the gel effect, occurring with bulk polymerizations, affected the polymerization progress very strongly. Due to this effect the conversion of the reaction is independent of the

  14. Free-radical solution-polymerization of trifluoronitrosomethane with tetrafluoroethylene

    Science.gov (United States)

    Gdickman, S. A.

    1972-01-01

    Heavy-walled glass reactor, equipped with aerosol-compatible couplings and needle valve and charged with solvent and initiator, is utilized for polymerization. Polymer conversions and reactor/vessel operation are discussed.

  15. Monte Carlo simulation on kinetics of batch and semi-batch free radical polymerization

    KAUST Repository

    Shao, Jing

    2015-10-27

    Based on Monte Carlo simulation technology, we proposed a hybrid routine which combines reaction mechanism together with coarse-grained molecular simulation to study the kinetics of free radical polymerization. By comparing with previous experimental and simulation studies, we showed the capability of our Monte Carlo scheme on representing polymerization kinetics in batch and semi-batch processes. Various kinetics information, such as instant monomer conversion, molecular weight, and polydispersity etc. are readily calculated from Monte Carlo simulation. The kinetic constants such as polymerization rate k p is determined in the simulation without of “steady-state” hypothesis. We explored the mechanism for the variation of polymerization kinetics those observed in previous studies, as well as polymerization-induced phase separation. Our Monte Carlo simulation scheme is versatile on studying polymerization kinetics in batch and semi-batch processes.

  16. Free radical (co)polymerization of methyl methacrylate and styrene in room temperature ionic liquids

    Science.gov (United States)

    Zhang, Hongwei

    Conventional free radical polymerizations were carried out in a variety of room temperature ionic liquids (RTILs). Generally, methyl methacrylate (MMA) and styrene (St) were used as typical monomers to compare the polymerization behavior both in RTILs and in common volatile organic compound solvents (VOCs). In most cases, it was observed that both yields and molecular weights are enhanced in the RTIL. While we believe the "diffusion-controlled termination" mechanism makes the termination of the radical propagating chains difficult due to the highly viscous nature of RTIL, other researchers have suggested that the rapid polymerization rates are due to the high polarity of these reaction media. By employing more than a dozen RTILs with a wide range of anions and cations, we attempted to correlate the viscosity and polarity of the RTILs with the molecular weights and polymerization rates. This correlation was not successful, suggesting that other parameters may also play a role in affecting the polymerization behavior. Other kinds of polymerizations have also been attempted including nitroxide-mediated living radical polymerizations of St and MMA in 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM]PF6), and redox initiation system initiated polymerization of MMA through redox pair formed by cation of trihexyl-tetradecyl-phosphonium bis(2,4,4-trimethylpentyl) phosphinate ([H3TDP] [(PM3) 2P]) and BPO. The formation of PSt-b-PMMA by sequential monomer addition through the standard free radical polymerization mechanism, using BPO as initiator, can be realized in [BMIM]PF6 due to the insolubility of polymerized first block---PSt in [BMIM]PF6. The macroradicals wrapped inside the chain coils have prolonged lifetimes because of the diminished termination, which allow some of these radicals to initiate polymerization of MMA at room temperature to form diblock copolymer. Solvents effects on reactivity ratios for free radical statistical copolymerization have been

  17. Polar, Functional Diene-Based Materials: Free Radical Polymerization of 2-Cyanomethyl-1,3-Butadiene

    Energy Technology Data Exchange (ETDEWEB)

    Jing, Y [Iowa State Univ., Ames, IA (United States)

    2000-09-12

    This thesis presented here focuses on the synthesis of 2-cyanomethyl-l ,3-butadiene and the free-radical polymerization of this monomer. In addition to the bulk, solution and emulsion polymerizations,, copolymerization with styrene and acrylonitrile will also be discussed. The comonomers were chosen due to the potential applications mentioned above. Furthermore, the thermal properties and rnicrostructures of the homopolymers and the copolymers are examined.

  18. Probing the reactivity of photoinitiators for free radical polymerization: time-resolved infrared spectroscopic study of benzoyl radicals.

    Science.gov (United States)

    Colley, Christopher S; Grills, David C; Besley, Nicholas A; Jockusch, Steffen; Matousek, Pavel; Parker, Anthony W; Towrie, Michael; Turro, Nicholas J; Gill, Peter M W; George, Michael W

    2002-12-18

    A series of substituted benzoyl radicals has been generated by laser flash photolysis of alpha-hydroxy ketones, alpha-amino ketones, and acyl and bis(acyl)phosphine oxides, all of which are used commercially as photoinitiators in free radical polymerizations. The benzoyl radicals have been studied by fast time-resolved infrared spectroscopy. The absolute rate constants for their reaction with n-butylacrylate, thiophenol, bromotrichloromethane and oxygen were measured in acetonitrile solution. The rate constants of benzoyl radical addition to n-butylacrylate range from 1.3 x 10(5) to 5.5 x 10(5) M(-1) s(-1) and are about 2 orders of magnitude lower than for the n-butylacrylate addition to the counterradicals that are produced by alpha-cleavage of the investigated ketones. Density functional theoretical calculations have been performed in order to rationalize the observed reactivities of the initiating radicals. Calculations of the phosphorus-centered radicals generated by photolysis of an acyl and bis(acyl)phosphine oxide suggest that P atom Mulliken spin populations are an indicator of the relative reactivities of the phosphorus-centered radicals. The alpha-cleavage of (2,4,6-trimethylbenzoyl)phosphine oxide was studied by picosecond pump-probe and nanosecond step-scan time-resolved infrared spectroscopy. The results support a mechanism in which the alpha-cleavage occurs from the triplet excited state that has a lifetime less than or equal to the singlet excited state.

  19. Reverse atom transfer radical polymerization of styrene in emulsion initiated by AIBN or V50

    Institute of Scientific and Technical Information of China (English)

    ZHANG Kai; ZHANG Hongwen; LI Hongtu; WANG Jingyuan

    2005-01-01

    Reverse atom transfer radical polymerization of styrene was conducted in emulsion by using Cu(II)/2,2′- bipydine or Cu(II)/phen complexes, AIBN or V50 as the initiator, Brij-98 or OP-10 as the surfactant. The results of GPC showed that both polymerization processes exhibit living characters when using AIBN as the initiator. However, when V50 was used, the monomer conversion was fairly low and the whole polymerization was not controlled well. The measurement of particle size and its distribution told us that the latex particles were mean and stable when using Brij-98 as the surfactant.

  20. Mechanism study and molecular design in controlled/“living” radical polymerization

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    This tutorial review summarizes recent progress in the research field of controlled/"living" radical polymerization (CLRP) from Soochow University.The present paper gives a broad overview of the mechanism study and molecular design in CLRP.The mechanism study in CLRP aided by microwave,initiated by γ-radiation at low temperature,mediated by iron,in reversible addition-fragmentation chain transfer (RAFT) polymerization and the mechanism transfer between different CLRP processes are reviewed and summarized.The molecular design in CLRP,especially in RAFT polymerization for mechanism study,and in achieving tailor-made functional polymers is studied and discussed in the later part.

  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. VINYL RADICAL POLYMERIZATION INITIATED WITH CERIC ION AND ETHYL N,N-DIETHYLDITHIOCARBAMYL ACETATE SYSTEM

    Institute of Scientific and Technical Information of China (English)

    XU Shoujun; QIU Kunyuan

    1997-01-01

    Acrylamide polymerization initiated with a redox initiation system consisting of ceric ion and ethyl N, N-diethyldithiocarbamyl acetate (EDCA) has been studied. It was found that the polymerization rate equation is in good agreement with that of a redox initiated polymerization, and the overall activation energy of the polymerization was determined to be 25.2 kJ·mol-1. Accordingly, the system belongs to a redox initiator. The initiation mechanism was proposed based on the end group analysis using FT-IR, UV spectroscopies.Analysis results revealed that the N, N-diethyldithiocarbamyl radical produced from the redox reaction of EDCA with ceric ion can initiate acrylonitrile (AN) polymerization and form the end group on PAN. The resulting PAN was photopolymerized with butyl acrylate (BA) to form PAN-b-PBA block copolymer.

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

    Directory of Open Access Journals (Sweden)

    Takashi Morinaga

    2016-04-01

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

  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. 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...... or AGET SI ATRP and uses of said polymer coating....

  6. 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...

  7. Novel fluorinated block copolymer architectures fuelled by atom transfer radical polymerization

    DEFF Research Database (Denmark)

    Jankova, Katja; Hvilsted, Søren

    2005-01-01

    Block copolymers based on poly(pentafluorostyrene), PFS, in various numbers and of different lengths, and polystyrene are prepared by atom transfer radical polymerization (ATRP). Di- and triblock copolymers with varying amounts of PFS were synthesized employing either I phenylethylbromide or 1,4-...

  8. Acrylamide Homopolymers and Acrylamide-N-Isopropylacrylamide Block Copolymers by Atomic Transfer Radical Polymerization in Water

    NARCIS (Netherlands)

    Wever, D. A. Z.; Raffa, P.; Picchioni, F.; Broekhuis, A. A.

    2012-01-01

    Atomic transfer radical polymerization (ATRP) of acrylamide has been accomplished in aqueous media at room temperature. By using methyl 2-chloropropionate (MeClPr) as the initiator and tris[2-(dimethylamino)ethyl]-amine (Me6TREN)/copper halogenide (CuX) as the catalyst system, different linear

  9. Surface-Initiated Atom Transfer Radical Polymerization from Electrospun Mats: An Alternative to Nafion

    DEFF Research Database (Denmark)

    Javakhishvili, Irakli; Dimitrov, Ivaylo; Tynelius, Oskar

    2017-01-01

    Proton exchange membranes for fuel cell applications are synthesized by surface-initiated(SI) atom transfer radical polymerization (ATRP). Poly(vinylidene fluoride-co-chlorotrifluoroethylene)is electrospun into 50 μm thick mat, which is then employed as multifunctionalinitiator for copper...

  10. Acrylamide Homopolymers and Acrylamide-N-Isopropylacrylamide Block Copolymers by Atomic Transfer Radical Polymerization in Water

    NARCIS (Netherlands)

    Wever, D. A. Z.; Raffa, P.; Picchioni, F.; Broekhuis, A. A.

    2012-01-01

    Atomic transfer radical polymerization (ATRP) of acrylamide has been accomplished in aqueous media at room temperature. By using methyl 2-chloropropionate (MeClPr) as the initiator and tris[2-(dimethylamino)ethyl]-amine (Me6TREN)/copper halogenide (CuX) as the catalyst system, different linear polya

  11. Proton-Conducting Sulfonated Ionomers by Chemical Modification and Atom Transfer Radical Polymerization

    DEFF Research Database (Denmark)

    Nielsen, Mads Møller

    of hydrocarbon macromolecular architectures, PSU with postsulfonated polystyrene (PS) grafts are investigated. Here, IEC is controlled through the degree of substitution, the graft length and DS. The grafting is performed with atom transfer radical polymerization (ATRP). The third assessment is dedicated...

  12. Hydrolysis of 4-Acetoxystyrene Polymers Prepared by Atom Transfer Radical Polymerization

    DEFF Research Database (Denmark)

    Chen, Xianyi; Jankova, Katja; Kops, Jørgen

    1999-01-01

    Hydrolysis of 4-acetoxystyrene polymers prepared by atom transfer radical polymerization was carried out under various reaction conditions. It was found that hydrazinolysis of 4-acetoxystyrene homopolymers, random and block copolymers with styrene in 1,4-dioxane, afforded the corresponding narrow...

  13. Protein repellent hydrophilic grafts prepared by surface-initiated atom transfer radical polymerization from polypropylene

    DEFF Research Database (Denmark)

    Fristrup, Charlotte Juel; Jankova Atanasova, Katja; Eskimergen, Rüya

    2012-01-01

    Grafting of poly(ethylene glycol)methacrylate (PEGMA) and N,N-dimethylacrylamide (DMAAm) from UV-initiator modified polypropylene (PP) was performed by Surface-Initiated Atom Transfer Radical Polymerization (SI-ATRP). The modification and hydrophilization of the PP substrates were confirmed...

  14. 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...

  15. AMPHIPHILIC STAR-BLOCK COPOLYMERS BY IODIDE-MEDIATED RADICAL POLYMERIZATION

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    Amphiphilic star-block copolymers composed of polystyrene and poly(acrylic acid) were synthesized by iodidemediated radical polymerization. Firstly, free radical polymerization of styrene was carried out with AIBN as initiator and 1,1,1-trimethyolpropane tri(2-iodoisobutyrate) as chain transfer agent, giving iodine atom ended star-shaped polystyrene with three arm chains, R(polystyrene)3. Secondly, tert-butyl acrylate was polymerization using polystyrene obtained as macro-chain transfer agent, and star-block copolymer, R(polystyrene-b-poly(tert-butyl acrylate))3 with controlled molecular weight was obtained. Finally, amphiphilic star-block copolymer, R(polystyrene-b-poly(acrylic acid))3 was obtained by hydrolysis of R(polystyrene-b-poly(tert-butyl acrylate))3 under acidic condition.

  16. Ionic Liquids as Catalysts for the Radical Acrylate Polymerization Co-initiated by Imine Bases

    Science.gov (United States)

    Polenz, I.; Spange, S.

    2014-08-01

    The catalysis of the imine base acrylate (IBA) polymerization by Ionic Liquids (ILs) is reported. Addition of IL traces (~10-50 mM) to an imine base / acrylate mixture leads to both a significant decrease of the activation temperature (40 °C) required for the IBA polymerization process and an increase in the polymerization rate by a factor of 5-40 depending on the IL species. The radical character of the polymerization is proved by copolymerization experiments using methyl methacrylate (MMA) and methacrylonitrile (MAN) and comparison with literature known values of copolymerization parameters rMMA and rMAN of these co-monomers. The influence of the IL on the polymerization kinetics is quantified by the polymerization rate law; the order referring to the IL is 1 indicating its crucial impact on the monomer activation. The IBA activation properties are strongly dependent on the IL interaction strengths with the IBA components verified by the KAMELT-TAFT hydrogen bond donating ability α. The stronger the interaction (higher α) is, the less the IBA polymerization activation. The temperature dependence of four different IL catalysed IBA polymerization is investigated, allows a classification and anomalous non-ARRHENIUS regimes are discussed. Activation energies EA,P span over 20 and 50 kJ·mol-1, which is between the values of thermal- (~80 kJ·mol-1) and photo-initiation (~20 kJ·mol-1).

  17. Cytocompatible Polymer Grafting from Individual Living Cells by Atom-Transfer Radical Polymerization.

    Science.gov (United States)

    Kim, Ji Yup; Lee, Bong Soo; Choi, Jinsu; Kim, Beom Jin; Choi, Ji Yu; Kang, Sung Min; Yang, Sung Ho; Choi, Insung S

    2016-12-05

    A cytocompatible method of surface-initiated, activator regenerated by electron transfer, atom transfer radical polymerization (SI-ARGET ATRP) is developed for engineering cell surfaces with synthetic polymers. Dopamine-based ATRP initiators are used for both introducing the ATRP initiator onto chemically complex cell surfaces uniformly (by the material-independent coating property of polydopamine) and protecting the cells from radical attack during polymerization (by the radical-scavenging property of polydopamine). Synthetic polymers are grafted onto the surface of individual yeast cells without significant loss of cell viability, and the uniform and dense grafting is confirmed by various characterization methods including agglutination assay and cell-division studies. This work will provide a strategic approach to the generation of living cell-polymer hybrid structures and open the door to their application in multitude of areas, such as sensor technology, catalysis, theranostics, and cell therapy. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Advancing Polymer-Supported Ionogel Electrolytes Formed via Radical Polymerization

    Science.gov (United States)

    Visentin, Adam F.

    fabricated. In addition to developing an understanding of UV-polymerized systems, a rapid 10 to 20 second, microwave-assisted polymerization method was developed as a novel means to create ionogels. These ionogels exhibited comparable mechanical response and ionic conductivity levels to those gels fabricated by the UV method. Lastly, an EDLC prototype was fabricated using a UV-polymerized ionogel formed in situ between two high-surface area carbon electrodes. The device performance metrics were comparable to commercial EDLCs, and functioned for several thousand cycles with limited loss in capacitance.

  19. Surface-initiated atom transfer radical polymerization of methyl methacrylate from magnetite nanoparticles at ambient temperature.

    Science.gov (United States)

    Raghuraman, G K; Dhamodharan, R

    2006-07-01

    The synthesis of methyl methacrylate (MMA) brush from the surface of magnetite nanoparticles (core-shell structure), from initiator moieties anchored covalently to the nanoparticles, via room temperature atom transfer radical polymerization (ATRP) is described. The surface-initiated polymerization was carried out from a surface-confined initiator containing a 2-bromoisobutyrate moiety with Cu(I)Br/PMDETA catalytic system. The initiator moiety was covalently anchored to the nanoparticles via a two step modification reaction scheme. Controlled polymerization was observed if ethyl-2-bromoisobutyrate (2-EiBrB) was added as a free/sacrificial initiator. A linear increase of molecular weight and a narrow molecular weight distribution of the PMMA formed in solution, provide evidence for a controlled surface-initiated polymerization, leading to surface-attached polymer brushes under mild conditions. The grafted PMMA provides good stability and dispersibility for the nanoparticles in organic solvents.

  20. 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.

  1. Novel Polymers Based on Atom Transfer Radical Polymerization of 2-Methoxyethyl Acrylate

    DEFF Research Database (Denmark)

    Bednarek, Melania; Jankova Atanasova, Katja; Hvilsted, Søren

    2007-01-01

    Atom transfer radical polymerization (ATRP) has been employed in the polymerization of 2-methoxyethyl acrylate (MEA) initiated by ethyl 2-bromoisobutyrate in bulk or in toluene solution at 90– 95 C with the catalytic systems Cu(I)Br/PMDETA or HMTETA. Kinetics investigations revealed that ATRP...... macroinitiators, however, for the latter the controlled conditions were somehow difficult to maintain. The amphiphilic behavior of the diblock copolymers lead to phase separation resulting in two glass transition temperatures as detected by DSC. Contact angle (Y) investigations with water on PMEA, PMMA...

  2. Facile Soap-Free Miniemulsion Polymerization of Methyl Methacrylate via Reverse Atom Transfer Radical Polymerization.

    Science.gov (United States)

    Zhu, Gaohua; Zhang, Lifen; Pan, Xiangqiang; Zhang, Wei; Cheng, Zhenping; Zhu, Xiulin

    2012-12-21

    A facile soap-free miniemulsion polymerization of methyl methacrylate (MMA) was successfully carried out via a reverse ATRP technique, using a water-soluble potassium persulfate (KPS) or 2,2'-azobis(2-methylpropionamidine) dihydrochloride (V-50) both as the initiator and the stabilizer, and using an oil-soluble N,N-n-butyldithiocarbamate copper (Cu(S2CN(C4H9)2)2) as the catalyst without adding any additional ligand. Polymerization results demonstrated the "living"/controlled characteristics of ATRP and the resultant latexes showed good colloidal stability with average particle size around 300-700 nm in diameter. The monomer droplet nucleation mechanism was proposed. NMR spectroscopy and chain-extension experiments under UV light irradiation confirmed the attachment and livingness of UV light sensitive -S-C(=S)-N(C4H9)2 group in the chain end.

  3. 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.

  4. Radical polymerization of vinyl acetate with bis(tetramethylheptadionato)cobalt(II): coexistence of three different mechanisms.

    Science.gov (United States)

    Santhosh, Kumar; Gnanou, Yves; Champouret, Yohan; Daran, Jean-Claude; Poli, Rinaldo

    2009-01-01

    The complex [Co(II)(tmhd)(2)] (4; tmhd = 2,2,6,6-tetramethylhepta-3,5-dionato) has been investigated as a mediator for controlled radical polymerization of vinyl acetate (VAc) and compared with the analogue [Co(II)(acac)(2)] (1; acac = acetylacetonato). A relatively well controlled process occurs, after an induction time, with 2,2'-azobis(4-methoxyl-2,4-dimethylvaleronitrile) (V-70) as radical initiator at 30 degrees C. However, whereas the polymerization essentially stops after about six initiator half-lives in the presence of 1, it continues with a first-order rate law in the presence of 4. The successful simulation of the kinetic data shows that 4 operates simultaneously by associative (degenerative transfer, DT) and dissociative (organometallic radical polymerization, OMRP) mechanisms. The occurrence of OMRP was confirmed by an independent polymerization experiment starting from an isolated and purified [Co(tmhd)(2)](PVAc) macroinitiator. The polymer molecular weight evolves linearly with conversion in accordance with the expected values for one chain per Co atom when DT is the predominant mechanism and also during the pure OMRP process; however, observation of stagnating molecular weights at long reaction times with concomitant breakdown of the first-order rate law for monomer consumption indicates a competitive chain-transfer process catalyzed by an increasing amount of Co(II). In the presence of external donors L (water, pyridine, triethylamine) the DT pathway is blocked and the OMRP pathway is accelerated, and polymerization with complex 4 is then about five times slower than with complex 1. The reversal of relative effective OMRP rate constants k(eff) (4>1 in the absence of external donors, 4<1 in their presence) is rationalized through competitive steric effects on Co(III)-C and Co(II)-L bond strengths. These propositions are supported by (1)H NMR studies and by DFT calculations.

  5. Seawater uranium sorbents: preparation from a mesoporous copolymer initiator by atom-transfer radical polymerization

    Energy Technology Data Exchange (ETDEWEB)

    Yue, Yanfeng; Mayes, Richard T.; Fulvio, Pasquale F.; Sun, Xiao-Guang [Chemical Sciences Division, Oak Ridge National Laboratory, Oak Ridge, TN (United States); Kim, Jungseung; Tsouris, Costas [Energy and Transportation Science Division, Oak Ridge National Laboratory, Oak Ridge, TN (United States); Chen, Jihua [Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge, TN (United States); Brown, Suree [Department of Chemistry, University of Tennessee, Knoxville, TN (United States); Dai, Sheng [Chemical Sciences Division, Oak Ridge National Laboratory, Oak Ridge, TN (United States); Department of Chemistry, University of Tennessee, Knoxville, TN (United States)

    2013-12-09

    Nanoporous template-free initiators for atom-transfer radical polymerization (ATRP) were synthesized with surface and framework initiator sites and tailorable pore structures. Polyacrylonitrile grown on one initiator was converted into polyamidoxime to generate a uranium sorbent for seawater extraction with a high uptake rate and capacity relative to those of nonwoven irradiation-grafted polyethylene-fiber composites. (Copyright copyright 2013 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  6. A NOVEL PHOTO-INITIATING SYSTEM FOR ATOM TRANSFER RADICAL POLYMERIZATION OF STYRENE

    Institute of Scientific and Technical Information of China (English)

    Shu-hui Qin; Dong-qi Qin; Kun-yuan Qiu

    2001-01-01

    A novel photo-induced initiating system, 2,2-dimethoxy-2-phenylacetophenone (DMPA)/ferric tri(N,N-diethyldithiocarbamate) [Fe(DC)3], was developed and used for the atom transfer radical polymerization (ATRP) of styrene in toluene. The polymerization proceeds with DMPA as photo-initiator, Fe(DC)3 as catalyst and DC as a reversible transfer group, while the halogen and ligands are free. Well-defined PSt was prepared and the polymerization mechanism revealed by end group analysis belongs to a reverse ATRP. Block copolymer was prepared by using thus obtained PSt as macroinitiator and Fe(DC)2 as catalyst under UV light irradiation via a conventional ATRP process.``

  7. Surface modification of electrospun fibres for biomedical applications: A focus on radical polymerization methods.

    Science.gov (United States)

    Duque Sánchez, Lina; Brack, Narelle; Postma, Almar; Pigram, Paul J; Meagher, Laurence

    2016-11-01

    The development of electrospun ultrafine fibres from biodegradable and biocompatible polymers has created exciting opportunities for biomedical applications. Fibre meshes with high surface area, suitable porosity and stiffness have been produced. Despite desirable structural and topographical properties, for most synthetic and some naturally occurring materials, the nature of the fibre surface chemistry has inhibited development. Hydrophobicity, undesirable non-specific protein adsorption and bacterial attachment and growth, coupled with a lack of surface functionality in many cases and an incomplete understanding of the myriad of interactions between cells and extracellular matrix (ECM) proteins have impeded the application of these systems. Chemical and physical treatments have been applied in order to modify or control the surface properties of electrospun fibres, with some success. Chemical modification using controlled radical polymerization, referred to here as reversible-deactivation radical polymerization (RDRP), has successfully introduced advanced surface functionality in some fibre systems. Atom transfer radical polymerization (ATRP) and reversible addition fragmentation chain transfer (RAFT) are the most widely investigated techniques. This review analyses the practical applications of electrospinning for the fabrication of high quality ultrafine fibres and evaluates the techniques available for the surface modification of electrospun ultrafine fibres and includes a detailed focus on RDRP approaches.

  8. Synthesis of a functional polymer with pendent luminescent phenylenevinylene units through nitroxide-mediated free-radical polymerization

    NARCIS (Netherlands)

    Moroni, M.; Hilberer, A; Hadziioannou, G

    1996-01-01

    In this communication we report the synthesis and the efficient polymerization of a PPV trimer, 4-tert-butyl-4'-(4-vinylstyryl)-trans-stilbene. By using the TEMPO (2,2,6,6-tetramethylpiperidin-1-yloxy)-mediated free-radical polymerization method, the corresponding polymer was obtained in high yields

  9. Nitroxide mediated and atom transfer radical graft polymerization of atactic polymers onto syndiotactic polystyrene

    Directory of Open Access Journals (Sweden)

    M. Abbasian

    2012-06-01

    Full Text Available 'Living' radical graft polymerization was employed to prepare graft copolymers with nitroxide-mediated arylated syndiotactic polystyrene as the backbone and polystyrene (PS, poly(p-methylstyrene (PMS and poly(methylmethacrylate (PMMA as branches. A two-stage process has been developed to synthesize the macroinitiator. First, syndiotactic polystyrene (sPS was modified by the Friedel-Crafts reaction to introduce chlorine; second, the chlorine groups were converted to nitroxide mediated groups by coupling with 1-hydroxy-2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO-OH. The resulting macroinitiator (sPS-TEMPO for 'living' free radical polymerization was then heated in the presence of styrene and p-methylstyrene to form graft and block copolymers. We used the obtained copolymer and N-bromosuccinimide as brominating agent to achieve polymers with bromine groups. This brominated copolymer was used as a macroinitiator for polymerizing methyl methacrylate in the presence of the CuBr/bpy catalyst system. The formation of the graft and block copolymers was confirmed by DSC, ¹H NMR and FTIR spectroscopy. This approach using macroinitiators is an effective method for the preparation of new materials.

  10. Nitroxide mediated and atom transfer radical graft polymerization of atactic polymers onto syndiotactic polystyrene

    Energy Technology Data Exchange (ETDEWEB)

    Abbasian, M. [Department of Basic Science, Payame Noor University, Tehran (Iran, Islamic Republic of); Shoja, S. Esmaeily [Lab. of Materials, Faculty of Engineering, Islamic Azad University, Bonab (Iran, Islamic Republic of)

    2012-04-15

    'Living' radical graft polymerization was employed to prepare graft copolymers with nitroxide mediated arylated syndiotactic polystyrene as the backbone and polystyrene (PS), poly(p-methylstyrene) (PMS) and poly(methylmethacrylate) (PMMA) as branches. A two-stage process has been developed to synthesize the macroinitiator. First, syndiotactic polystyrene (sPS) was modified by the Friedel-Crafts reaction to introduce chlorine; second, the chlorine groups were converted to nitroxide mediated groups by coupling with 1-hydroxy-2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO-OH). The resulting macroinitiator (sPSTEMPO) for 'living' free radical polymerization was then heated in the presence of styrene and pmethylstyrene to form graft and block copolymers. We used the obtained copolymer and N-bromosuccinimide as brominating agent to achieve polymers with bromine groups. This brominated copolymer was used as a macroinitiator for polymerizing methyl methacrylate in the presence of the CuBr/bpy catalyst system. The formation of the graft and block copolymers was confirmed by DSC, {sup 1}H NMR and FTIR spectroscopy. This approach using macroinitiators is an effective method for the preparation of new materials. (author)

  11. Improvement in Liquid Chromatographic Performance of Organic Polymer Monolithic Capillary Columns with Controlled Free-Radical Polymerization.

    Science.gov (United States)

    Gama, Mariana R; Aggarwal, Pankaj; Liu, Kun; Lee, Milton L; Bottoli, Carla B G

    2016-12-19

    Capillary columns containing butyl or lauryl methacrylate monoliths were prepared using two different free-radical polymerization methods: conventional free-radical polymerization and controlled/living free-radical polymerization, both initiated thermally, and these methods were compared for the first time. Both monolith morphology and chromatographic efficiency were compared for the synthesized stationary phases using scanning electronic microscopy (SEM) and capillary liquid chromatography, respectively. Columns prepared using controlled method gave better chromatographic performance for both monomers tested. The lauryl-based monolith showed 7-fold improvement in chromatographic efficiency with a plate count of 42,000 plates/m (corrected for dead volume) for a non-retained compound. Columns fabricated using controlled polymerization appeared more homogenous radially with fused small globular morphologies, evaluated by SEM, and lower column permeability. The columns were compared with respect to resolving power of a series of alkylbenzenes under isocratic and gradient elution conditions.

  12. Liquid-core capsules via interfacial polymerization: a free-radical analogy of the nylon rope trick.

    Science.gov (United States)

    Scott, Charles; Wu, Dan; Ho, Chia-Chi; Co, Carlos C

    2005-03-30

    Liquid-core capsules have wide-ranging applications in the high-efficiency encapsulation and controlled release of drugs, dyes, enzymes, and other substrates. Their great utility has driven the rapid development of various preparation techniques. However, there remains no convenient technique for the preparation of submicrometer liquid-core capsules with shell thicknesses less than 100 nm. Here, we demonstrate a new interfacial free-radical polymerization approach for the straightforward preparation of liquid-core polymer capsules. Conceptually, this interfacial free-radical polymerization is analogous to the classical "nylon rope trick" wherein hydrophobic and hydrophilic monomers alternately copolymerize to constrain the polymerization at interfaces, but its free-radical mechanism allows precise control of initiation, which makes it possible to finely disperse the immiscible phases prior to polymerization.

  13. Radical polymerization by a supramolecular catalyst: cyclodextrin with a RAFT reagent

    Directory of Open Access Journals (Sweden)

    Kohei Koyanagi

    2016-11-01

    Full Text Available Supramolecular catalysts have received a great deal of attention because they improve the selectivity and efficiency of reactions. Catalysts with host molecules exhibit specific reaction properties and recognize substrates via host–guest interactions. Here, we examined radical polymerization reactions with a chain transfer agent (CTA that has α-cyclodextrin (α-CD as a host molecule (α-CD-CTA. Prior to the polymerization of N,N-dimethylacrylamide (DMA, we investigated the complex formation of α-CD with DMA. Single X-ray analysis demonstrated that α-CD includes DMA inside its cavity. When DMA was polymerized in the presence of α-CD-CTA using 2,2'-azobis[2-(2-imidazolin-2-ylpropane dihydrochloride (VA-044 as an initiator in an aqueous solution, poly(DMA was obtained in good yield and with narrow molecular weight distribution. In contrast, the polymerization of DMA without α-CD-CTA produced more widely distributed polymers. In the presence of 1,6-hexanediol (C6 diol which works as a competitive molecule by being included in the α-CD cavity, the reaction yield was lower than that without C6 diol.

  14. Kinetics of Atom Transfer Radical Polymerization of Methyl Methacrylate Initiated by Cellulose Chloroacetate in BMIMCI

    Institute of Scientific and Technical Information of China (English)

    LIN Chun-xiang; ZHAN Huai-yu; LIU Ming-hua; FU Shi-yu; LUCIA Lucian

    2013-01-01

    The kinetics of atom transfer radical polymerization(ATRP) of methyl methacrylate(MMA) initiated by cellulose based macroinitator,cellulose chloroacetate,performed in ionic liquid(1-N-butyl-3-methylimidazolium chloride,BMIMCl),dimethyl sulfoxide(DMSO) and dimethyl formamide(DMF) were respectively studied in detail.The polymerizations were carried out under homogeneous conditions with CuBr as catalyst and 2,2'-bipyridine(bpy)as ligand.The dependences of the rate of polymerization on solvent,temperature,monomer/initiator ratio and catalyst/ligand ratio were presented.Plots of ln([M]0/[M]t) vs.time and molecular weight vs.conversion showed a linear dependence,indicating a constant number of propagating species throughout the polymerization as well as a negligible contribution of termination or transfer reactions.On the basis of an Arrhenius plot,the apparent energy of activation(△Eaapp) for ATRP of MMA in BMIMC1 was 16.6 kJ/mol which is much lower than that in diphenyl ether.

  15. 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.

  16. Cobalt-Mediated Radical Polymerization of Vinyl Acetate and Acrylonitrile in Supercritical Carbon Dioxide.

    Science.gov (United States)

    Kermagoret, Anthony; Chau, Ngoc Do Quyen; Grignard, Bruno; Cordella, Daniela; Debuigne, Antoine; Jérôme, Christine; Detrembleur, Christophe

    2016-03-01

    Cobalt-mediated radical polymerization (CMRP) of vinyl acetate (VAc) is successfully achieved in supercritical carbon dioxide (scCO2). CMRP of VAc is conducted using an alkyl-cobalt(III) adduct that is soluble in scCO2. Kinetics studies coupled to visual observations of the polymerization medium highlight that the melt viscosity and PVAc molar mass (Mn) are key parameters that affect the CMRP in scCO2. It is noticed that CMRP is controlled for Mn up to 10 000 g mol(-1), but loss of control is progressively observed for higher molar masses when PVAc precipitates in the polymerization medium. Low molar mass PVAc macroinitiator, prepared by CMRP in scCO2, is then successfully used to initiate the acrylonitrile polymerization. PVAc-b-PAN block copolymer is collected as a free flowing powder at the end of the process although the dispersity of the copolymer increases with the reaction time. Although optimization is required to decrease the dispersity of the polymer formed, this CMRP process opens new perspectives for macromolecular engineering in scCO2 without the utilization of fluorinated comonomers or organic solvents.

  17. Organometallic mediated radical polymerization of vinyl acetate using bis(imino)pyridine vanadium trichloride complexes.

    Science.gov (United States)

    Perry, Mitchell R; Allan, Laura E N; Decken, Andreas; Shaver, Michael P

    2013-07-07

    The synthesis and characterization of one novel proligand and six novel vanadium(III) trichloride complexes is described. The controlled radical polymerization activity towards vinyl acetate of these, and eight other bis(imino)pyridine vanadium trichloride complexes previously reported, is investigated. Those complexes possessing variation at the N-aryl para-position with no steric protection offered by ortho-substituents (4 examples) result in poor control over poly(vinyl acetate) polymerization. Control is improved with increasing steric bulk at the ortho-position of the N-aryl substituent (4 examples) although attempts to increase steric bulk past isopropyl were unsuccessful. Synthesizing bis(imino)pyridine vanadium trichloride complexes with substituted imine backbones restores polymerization control when aliphatic substituents are used (4 examples) but ceases to make any drastic improvements on catalyst lifetime. Modification of the polymerization conditions is also investigated, in an attempt to improve the catalyst lifetime. Expansion of the monomer scope to include other vinyl esters, particularly those derived from renewable resources, shows promising results.

  18. THERMOSENSITIVITY OF NARROW-DISPERSED POLY(N-N-PROPYLACRYLAMIDE) PREPARED BY ATOM TRANSFER RADICAL POLYMERIZATION

    Institute of Scientific and Technical Information of China (English)

    Hua-yong Hu; Jing Du; Qing-bin Meng; Zhan-yong Li; Xiao-xia Zhu

    2008-01-01

    Controlled polymerization of N-n-propylacrylamide was achieved by atom transfer radical polymerization (ATRP)in a N,N-dimethylformamide-water mixture (50 vol%) at room temperature with methyl 2-chloropropinonate as initiator andCuCl/tris(2-dimethylaminoethyl)amine as the catalytic system in a ratio of 1:1:1. High molecular weight homopolymers (upto 3.7×104) with narrow molecular weight distribution (less than 1.2) were obtained. The living character of thepolymerization was further demonstrated by self-blocking experiment. An inverse molecular weight dependence of the cloudpoint of narrow-dispersed poly(N-n-propylacrylamide) aqueous solution was determined by turbidimetry and differentialscanning calorimetry, especially for the low molecular weight samples.

  19. Engineering live cell surfaces with functional polymers via cytocompatible controlled radical polymerization

    Science.gov (United States)

    Niu, Jia; Lunn, David J.; Pusuluri, Anusha; Yoo, Justin I.; O'Malley, Michelle A.; Mitragotri, Samir; Soh, H. Tom; Hawker, Craig J.

    2017-06-01

    The capability to graft synthetic polymers onto the surfaces of live cells offers the potential to manipulate and control their phenotype and underlying cellular processes. Conventional grafting-to strategies for conjugating preformed polymers to cell surfaces are limited by low polymer grafting efficiency. Here we report an alternative grafting-from strategy for directly engineering the surfaces of live yeast and mammalian cells through cell surface-initiated controlled radical polymerization. By developing cytocompatible PET-RAFT (photoinduced electron transfer-reversible addition-fragmentation chain-transfer polymerization), synthetic polymers with narrow polydispersity (Mw/Mn cells using either covalent attachment or non-covalent insertion, while maintaining high cell viability. Compared with conventional grafting-to approaches, these methods significantly improve the efficiency of grafting polymer chains and enable the active manipulation of cellular phenotypes.

  20. Thermosensitive Nanocables Prepared by Surface-Initiated Atom Transfer Radical Polymerization

    Directory of Open Access Journals (Sweden)

    Wei Qingshan

    2008-01-01

    Full Text Available Abstract Thermosensitive nanocables consisting of Au nanowire cores and poly(N-isopropylacrylamide sheaths (denoted as Au/PNIPAAm were synthesized by surface-initiated atom transfer radical polymerization (SI-ATRP. The formation of PNIPAAm sheath was verified by Fourier transform infrared (FTIR and hydrogen nuclear magnetic resonance (1H NMR spectroscopy. Transmission electron microscope (TEM results confirmed the core/shell structure of nanohybrids. The thickness and density of PNIPAAm sheaths can be adjusted by controlling the amount of cross-linker during the polymerization. Signature temperature response was observed from Au/cross-linked-PNIPAAm nanocables. Such smart nanocables show immense potentials as building blocks for novel thermosensitive nanodevices in future.

  1. 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

    -modified PEEK using Surface-Initiated Atom Transfer Radical Polymerization (SI ATRP). Surface reduction of PEEK to form hydroxyl groups [1, 2, 3] was .performed prior to the attachment of 2-bromoisobutyrate initiating groups. Each modification step of PEEK as well as the polymer grafting was followed...... 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...

  2. Organic thin film transistors with polymer brush gate dielectrics synthesized by atom transfer radical polymerization

    DEFF Research Database (Denmark)

    Pinto, J.C.; Whiting, G.L.; Khodabakhsh, S.

    2008-01-01

    , synthesized by atom transfer radical polymerization (ATRP), were used to fabricate low voltage OFETs with both evaporated pentacene and solution deposited poly(3-hexylthiophene). The semiconductor-dielectric interfaces in these systems were studied with a variety of methods including scanning force microscopy......Low operating voltage is an important requirement that must be met for industrial adoption of organic field-effect transistors (OFETs). We report here solution fabricated polymer brush gate insulators with good uniformity, low surface roughness and high capacitance. These ultra thin polymer films...

  3. 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

    -modified PEEK using Surface-Initiated Atom Transfer Radical Polymerization (SI ATRP). Surface reduction of PEEK to form hydroxyl groups [1, 2, 3] was .performed prior to the attachment of 2-bromoisobutyrate initiating groups. Each modification step of PEEK as well as the polymer grafting was followed...... 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...

  4. RECENT ADVANCES IN THE PREPARATION OF MOLECULARLY IMPRINTED POLYMERS VIA CONTROLLED RADICAL POLYMERIZATION TECHNIQUES

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    Molecular imprinting technique is a simple and efficient method for the preparation of polymer materials (i.e., molecularly imprinted polymers, MIPs) with tailor-made recognition sites for certain target molecules. The resulting MIPs have proven to be versatile synthetic receptors due to their high specific recognition ability, favorable mechanical, thermal and chemical stability, and ease of preparation. Recent years have witnessed significant progress in the synthesis and applications of MIPs. This review focus on the recent developments and advances in the preparation of MIPs via various controlled radical polymerization techniques.

  5. RECENT ADVANCES IN THE PREPARATION OF MOLECULARLY IMPRINTED POLYMERS VIA CONTROLLED RADICAL POLYMERIZATION TECHNIQUES

    Institute of Scientific and Technical Information of China (English)

    ZHANG Ying; ZHANG Huiqi

    2008-01-01

    Molecular imprinting technique is a simple and efficient method for the preparation of polymer materials (i.e., molecularly imprinted polymers, MIPs) with tailor-made recognition sites for certain target molecules.The resulting MIPs have proven to be versatile synthetic receptors due to their high specific recognition ability, favorable mechanical, thermal and chemical stability, and ease of preparation.Recent years have witnessed signifwant progress in the synthesis and applications of MIPs.This review focus on the recent developments and advances in the preparation of MIPs via various controlled radical polymerization techniques.

  6. CONTROLLED/"LIVING" RADICAL POLYMERIZATION OF STYRENE IN AN AQUEOUS DISPERSION SYSTEM

    Institute of Scientific and Technical Information of China (English)

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

    2002-01-01

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

  7. Functional Interfaces Constructed by Controlled/Living Radical Polymerization for Analytical Chemistry.

    Science.gov (United States)

    Wang, Huai-Song; Song, Min; Hang, Tai-Jun

    2016-02-10

    The high-value applications of functional polymers in analytical science generally require well-defined interfaces, including precisely synthesized molecular architectures and compositions. Controlled/living radical polymerization (CRP) has been developed as a versatile and powerful tool for the preparation of polymers with narrow molecular weight distributions and predetermined molecular weights. Among the CRP system, atom transfer radical polymerization (ATRP) and reversible addition-fragmentation chain transfer (RAFT) are well-used to develop new materials for analytical science, such as surface-modified core-shell particles, monoliths, MIP micro- or nanospheres, fluorescent nanoparticles, and multifunctional materials. In this review, we summarize the emerging functional interfaces constructed by RAFT and ATRP for applications in analytical science. Various polymers with precisely controlled architectures including homopolymers, block copolymers, molecular imprinted copolymers, and grafted copolymers were synthesized by CRP methods for molecular separation, retention, or sensing. We expect that the CRP methods will become the most popular technique for preparing functional polymers that can be broadly applied in analytical chemistry.

  8. Optically active helical vinylterphenyl polymers: chiral teleinduction in radical polymerization and tunable stereomutation.

    Science.gov (United States)

    Wang, Rong; Zhang, Jie; Wan, Xinhua

    2015-04-01

    Helical vinyl aromatic polymers are emerging as interesting chiral materials due to their dynamic tailorability, synthetic simplicity, and outstanding chemical and physical stabilities. This Personal Account discusses long-range chirality transfer in the radical polymerization of vinylterphenyl monomers and tunable stereomutation of the resultant polymers. It begins with a general introduction to the design, synthesis, and characterization of helical poly{(+)-2,5-bis[4'-((S)-2-methylbutyloxy)phenyl]styrene}, the first one of this series of polymers. Then, long-range chirality transfer during radical polymerization of terphenyl-based vinyl monomers is explained. After that, the chiroptical property control of the resultant polymers by means of the transition from kinetically controlled conformation to thermodynamically controlled conformation and external stimulus is described. This Personal Account concludes by discussing the advantages and disadvantages of the strategy of using vinylterphenyls to obtain optically active helical polymers and providing a short outlook, especially emphasizing the importance of tacticity on the chiroptical properties of polymers. Copyright © 2015 The Chemical Society of Japan and Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. 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.

  10. Sequence-regulated copolymers via tandem catalysis of living radical polymerization and in situ transesterification.

    Science.gov (United States)

    Nakatani, Kazuhiro; Ogura, Yusuke; Koda, Yuta; Terashima, Takaya; Sawamoto, Mitsuo

    2012-03-07

    Sequence regulation of monomers is undoubtedly a challenging issue as an ultimate goal in polymer science. To efficiently produce sequence-controlled copolymers, we herein developed the versatile tandem catalysis, which concurrently and/or sequentially involved ruthenium-catalyzed living radical polymerization and in situ transesterification of methacrylates (monomers: RMA) with metal alkoxides (catalysts) and alcohols (ROH). Typically, gradient copolymers were directly obtained from the synchronization of the two reactions: the instantaneous monomer composition in feed gradually changed via the transesterification of R(1)MA into R(2)MA in the presence of R(2)OH during living polymerization to give R(1)MA/R(2)MA gradient copolymers. The gradient sequence of monomers along a chain was catalytically controlled by the reaction conditions such as temperature, concentration and/or species of catalysts, alcohols, and monomers. The sequence regulation of multimonomer units was also successfully achieved in one-pot by monomer-selective transesterification in concurrent tandem catalysis and iterative tandem catalysis, providing random-gradient copolymers and gradient-block counterparts, respectively. In contrast, sequential tandem catalysis via the variable initiation of either polymerization or in situ transesterification led to random or block copolymers. Due to the versatile adaptability of common and commercially available reagents (monomers, alcohols, catalysts), this tandem catalysis is one of the most efficient, convenient, and powerful tools to design tailor-made sequence-regulated copolymers.

  11. Controlled synthesis of photochromic polymer brushes by atom transfer radical polymerization.

    Energy Technology Data Exchange (ETDEWEB)

    Piech, Marcin; Bell, Nelson Simmons; Long, Timothy Michael

    2005-06-01

    This work reports on the grafting of methyl methacrylate polymer brushes containing spirobenzopyran pendant groups from flat silica surfaces and colloidal particles utilizing atom transfer radical polymerization (ATRP). The reaction conditions were optimized with respect to the kind of surface bound initiator, the type of halide and ligand used in the catalytic complex, the presence/absence of untethered initiator, and solvent type. This enabled synthesis of coatings up to 80 {+-} 3 nm thick with controlled spirobenzopyran content. While polymerization kinetics indicate the presence of chain termination reactions, the 'living' character of the process is confirmed by controlled formation of block copolymer brushes. UV/vis spectroscopy was used to characterize the UV-induced isomerization of spirobenzopyran to zwitterionic merocyanine and the thermal back-reaction. Spectral and kinetic analyses of this latter bleaching process points to the existence of free and associated merocyanines in the polymeric brush in both tetrahydrofuran and toluene. However, stabilization of merocyanine species by the polymer matrix is considerably greater in toluene with thermal back-reaction rates approaching those determined for solid dry films.

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

    Institute of Scientific and Technical Information of China (English)

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

    2006-01-01

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

  13. RADICAL POLYMERIZATION OF N, N-DI(2-2 '-METHYL-ACRYLOYLOXY-PROPYL) -PARA-TOLUIDINE FUNCTIONAL MONOMER

    Institute of Scientific and Technical Information of China (English)

    QIU Kunyuan; FU Jie

    1989-01-01

    Functional monomer ( MP )2PT having tertiary aromatic amino group was systhesized from the reaction of N, N-di ( 2 -hydroxypropyl )-p-toluidine with 2-methyl acryloyl chloride. In the presence of organic peroxide, the radical polymerization of ( MP )2PT in toluene took place. The kinetics of ( MP )2PT polymerization and the ESR spectra ofLPO-( MP )2PT-MNP systems were determined respectively.

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

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

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

  15. Mechanism of Photoinduced Metal-Free Atom Transfer Radical Polymerization: Experimental and Computational Studies.

    Science.gov (United States)

    Pan, Xiangcheng; Fang, Cheng; Fantin, Marco; Malhotra, Nikhil; So, Woong Young; Peteanu, Linda A; Isse, Abdirisak A; Gennaro, Armando; Liu, Peng; Matyjaszewski, Krzysztof

    2016-02-24

    Photoinduced metal-free atom transfer radical polymerization (ATRP) of methyl methacrylate was investigated using several phenothiazine derivatives and other related compounds as photoredox catalysts. The experiments show that all selected catalysts can be involved in the activation step, but not all of them participated efficiently in the deactivation step. The redox properties and the stability of radical cations derived from the catalysts were evaluated by cyclic voltammetry. Laser flash photolysis (LFP) was used to determine the lifetime and activity of photoexcited catalysts. Kinetic analysis of the activation reaction according to dissociative electron-transfer (DET) theory suggests that the activation occurs only with an excited state of catalyst. Density functional theory (DFT) calculations revealed the structures and stabilities of the radical cation intermediates as well as the reaction energy profiles of deactivation pathways with different photoredox catalysts. Both experiments and calculations suggest that the activation process undergoes a DET mechanism, while an associative electron transfer involving a termolecular encounter (the exact reverse of DET pathway) is favored in the deactivation process. This detailed study provides a deeper understanding of the chemical processes of metal-free ATRP that can aid the design of better catalytic systems. Additionally, this work elucidates several important common pathways involved in synthetically useful organic reactions catalyzed by photoredox catalysts.

  16. Synthesis of Poly(styrene-b-isoprene-b-styrene) via Nitroxide-mediated Radical Polymerization by a Novel Alkoxyamine

    Institute of Scientific and Technical Information of China (English)

    GAO Long-cheng; PAN Qi-wei; FAN Xing-he; CHEN Xiao-fang; WAN Xin-hua; ZHOU Qi-feng

    2005-01-01

    Bifunctional alkoxyamine bis-TIPNO derived from 2,2,5-trimethyl-4-phenyl-3-azahexane-3-oxyl(TIPNO) and α, ω-alkyl bromide by atom transfer radical addition(ATRA) was employed as "biradical initiator" for nitroxide-mediated radical polymerization(NMRP) of isoprene and styrene. The kinetics study for the polymerization of styrene at different time showed living features. The poly(styrene-b-isoprene-b-styrene)(SIS) copolymers have two glass transition temperatures, indicating the immiscibility of the corresponding blocks.

  17. DESIGN AND SYNTHESIS OF NOVEL CHIRAL IONIC LIQUIDS AND THEIR APPLICATION IN FREE RADICAL POLYMERIZATION OF METHYL METHACRYLATE

    Institute of Scientific and Technical Information of China (English)

    Hong-yang Ma; Xin-hua Wan; Xiao-fang Chen; Qi-feng Zhou

    2003-01-01

    Two new chiral ionic liquids, 1-((-)-menthoxycarbonylmethylene)-3-methylimidazolium hexafluorophosphate and l-((-)-menthoxycarbonylmethylene)-3-hexadecylimidazolium hexafluorophosphate, were designed and prepared. Their chemical structures were characterized by 1H-NMR. Reverse atom transfer radical polymerization of methyl methacrylate(MMA) in these two ionic liquids was carried out using AIBN/CuC12/bipy as the initiating system. The resultant well-defined polymethyl methacrylate (PMMA) was employed as a macroinitiator to induce the atom transfer radical polymerization of menthyl methacrylate (MnMA) in chlorobenzene, which yielded a PMMA-b-PMnMA diblock copolymer with narrow polydispersity.

  18. Influence of ultrasonic condition on phase transfer catalyzed radical polymerization of methyl methacrylate in two phase system - A kinetic study.

    Science.gov (United States)

    Marimuthu, Elumalai; Murugesan, Vajjiravel

    2017-09-01

    An ultrasonic condition assisted phase transfer catalyzed radical polymerization of methyl methacrylate was investigated in an ethyl acetate/water two phase system at 60±1°C and 25kHz, 300W under inert atmosphere. The influence of monomer, initiator, catalyst and temperature, volume fraction of aqueous phase on the rate of polymerization was examined in detail. The reaction order was found to be unity for monomer, initiator and catalyst. Generally, the reaction rate was relatively fast in two phase system, when a catalytic amount of phase transfer catalyst was used. The combined approach, use of ultrasonic and PTC condition was significantly enhances the rate of polymerization. An ultrasonic and phase transfer catalyzed radical polymerization of methyl methacrylate has shown about three fold enhancements in the rate compared with silent polymerization of MMA using cetyltrimethylammonium bromide as PTC. The resultant kinetics was evaluated with silent polymerization and an important feature was discussed. The activation energy and other thermodynamic parameters were computed. Based on the obtained results an appropriate radical mechanism has been derived. TGA showed the polymer was stable up to 150°C. The FT-IR and DSC analysis validates the atactic nature of the obtained polymer. The XRD pattern reveals the amorphous nature of polymer was dominated. Copyright © 2016 Elsevier B.V. All rights reserved.

  19. Radical polymerization of styrene controlled by half-sandwich Mo(III)/Mo(IV) couples: all basic mechanisms are possible.

    Science.gov (United States)

    Le Grognec, E; Claverie, J; Poli, R

    2001-10-03

    Density functional calculations of bond dissociation energies (BDEs) have been used as a guide to the choice of metal system suitable for controlling styrene polymerization by either the stable free radical polymerization (SFRP) or the atom transfer radical polymerization (ATRP) mechanism. In accord with the theoretical prediction, CpMo(eta(4)-C(4)H(6))(CH(2)SiMe(3))(2), 2, is not capable of yielding SFRP of styrene. Still in accord with theoretical prediction, CpMo(eta(4)-C(4)H(6))Cl(2), 1, CpMo(PMe(3))(2)Cl(2), 3, and CpMo(dppe)Cl(2) (dppe = 1,2-bis(diphenylphosphino)ethane), 4, yield controlled styrene polymerization by the SFRP mechanism in the presence of 2,2'-azobisisobutyronitrile (AIBN). This arises from the generation of a putative Mo(IV) alkyl species from the AIBN-generated radical addition to the Mo(III) compound. The controlled nature of the polymerizations is indicated by linear M(n) progression with the conversion in all cases and moderate polydispersity indices (PDIs). Controlled polymerization of styrene is also given by compounds 3 and 4 in combination with alkyl bromides. These complexes then operate by the ATRP mechanism, again in accord with the theoretical predictions. Controlled character is revealed by linear increase of M(n) versus conversion, low PDIs, a stop-and-go experiment, and (1)H NMR and MALDI-TOF analyses of the polymer end groups. The same controlled polymerization is given by a "reverse" ATRP experiment, starting from AIBN and CpMo(PMe(3))(2)Cl(2)Br, 5. On the other hand, when compound 1 or 2 is used in combination with an alkyl bromide (as for an ATRP experiment), the isolated polystyrene shows by M(n), (1)H NMR, and MALDI-TOF analyses that catalytic chain transfer (CCT) radical polymerization takes place in this case. Kinetics simulations underscore the conditions regulating the radical polymerization mechanism and the living character of the polymerization. The complexes herein described are ineffective at controlling the

  20. THE EFFECTS OF N-2-HYDROXYETHYL-N-METHYL-P-TOLUIDINE ON METHYL METHACRYLATE RADICAL POLYMERIZATION AND ACRYLONITRILE PHOTOINDUCED POLYMERIZATION

    Institute of Scientific and Technical Information of China (English)

    QIU Kunyuan; ZHANG Zhanghua; FENG Xinde

    1992-01-01

    The effects of N-2-hydroxyethyl-N-methyl-p-toluidine (HMT) on MMA polymerization using organic peroxide as an initiator and on AN photoinduced polymerization have been investigated respectively. The kinetics of polymerization and the overall activation energy of polymerization were determined. Based on kinetics study and the end group analysis of the polymer obtained by UV spectrum method, the initiation mechanism is proposed.

  1. 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

    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......, the kinetics of polymerization was analyzed in-situ and in real time by QCM. For the first time the specific adsorption of monovalent copper to the surface tethered initiator was detected by observation of an activation period preceding the onset of polymerization. The driving force for high affinity of copper...

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

    Directory of Open Access Journals (Sweden)

    Mu Bin

    2009-01-01

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

  3. Reversible-Deactivation Radical Polymerization of Methyl Methacrylate Induced by Photochemical Reduction of Various Copper Catalysts

    Directory of Open Access Journals (Sweden)

    Jaroslav Mosnáček

    2014-11-01

    Full Text Available Photochemically mediated reversible-deactivation radical polymerization of methyl methacrylate was successfully performed using 50–400 ppm of various copper compounds such as CuSO4·5H2O, copper acetate, copper triflate and copper acetylacetonate as catalysts. The copper catalysts were reduced in situ by irradiation at wavelengths of 366–546 nm, without using any additional reducing agent. Bromopropionitrile was used as an initiator. The effects of various solvents and the concentration and structure of ligands were investigated. Well-defined polymers were obtained when at least 100 or 200 ppm of any catalyst complexed with excess tris(2-pyridylmethylamine as a ligand was used in dimethyl sulfoxide as a solvent.

  4. Modification of Jute Fibers with Polystyrene via Atom Transfer Radical Polymerization

    DEFF Research Database (Denmark)

    Plackett, David; Jankova, Katja Atanassova; Egsgaard, Helge

    2005-01-01

    Atom transfer radical polymerization (ATRP) was investigated as a method of covalently bonding polystyrene to jute (Corchorus capsularis) and as a possible approach to fiber composites with enhanced properties. Jute fibers were modified with a brominated initiator and subsequently ATRP modified...... to attach polystyrene and then examined using SEM, DSC, TGA, FTIR, XPS, elemental analysis, and Py-GC-MS. These techniques confirmed that polystyrene had been covalently bound to the fibers and consequently ATRP-modified jute fiber mats were used to prepare hot-pressed polystyrene composites. Composite...... applications, we conclude that further optimization of the ATRP method is required, possibly targeting higher and more uniform loading of polystyrene on the fibers....

  5. Preparation of polystyrene-grafted titanate nanotubes by in situ atom transfer radical polymerization

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    This work successfully prepared nanohybrids by in situ atom transfer radical polymerization (ATRP) of styrene from titanate nanotubes (TNTs). Fourier-transform infrared (FT-IR), pronton nuclear magnetic resonance spectroscopy (1H NMR), and thermal gravimetric analysis (TGA) were used to verify the successful graft of polystyrene (PS) chains from TNTs. Transmission electron microscopy (TEM) dis-played that the obtained PS-g-TNTs nanohybrids had a core-shell structure of TNT core and PS shell. The grafted PS content was well controlled and increased with increasing of the monomer/initiator ratio. Further copolymerization of tert-butyl acrylate (tBA) from the surface of PS-g-TNTs was studied, illus-trating the "living" characteristics of the surface-induced ATRP method used in this work.

  6. Modification of jute fibers with polystyrene via atom transfer radical polymerization.

    Science.gov (United States)

    Plackett, David; Jankova, Katja; Egsgaard, Helge; Hvilsted, Søren

    2005-01-01

    Atom transfer radical polymerization (ATRP) was investigated as a method of covalently bonding polystyrene to jute (Corchorus capsularis) and as a possible approach to fiber composites with enhanced properties. Jute fibers were modified with a brominated initiator and subsequently ATRP modified to attach polystyrene and then examined using SEM, DSC, TGA, FTIR, XPS, elemental analysis, and Py-GC-MS. These techniques confirmed that polystyrene had been covalently bound to the fibers and consequently ATRP-modified jute fiber mats were used to prepare hot-pressed polystyrene composites. Composite specimens were tensile tested and fracture surfaces examined using SEM. Although SEM examination suggested different fracture modes between unmodified fiber and ATRP-modified samples, the tensile strength of modified samples was slightly lower on average than that of unmodified samples. For fiber composite applications, we conclude that further optimization of the ATRP method is required, possibly targeting higher and more uniform loading of polystyrene on the fibers.

  7. SYNTHESIS OF POLY(METHYL METHACRYLATE)-graft-POLYSTYRENE BY ATOM TRANSFER RADICAL POLYMERIZATION

    Institute of Scientific and Technical Information of China (English)

    Sheng-min Gong; Qun-sheng Li; Yan Shi; Zhi-feng Fu; Shu-ke Jiao; Wan-tai Yang

    2003-01-01

    The radical copolymerization of methyl methacrylate and 2-hydroxyethyl methacrylate was carried out via atom complex. This polymerization proceeds in a living fashion with controlled molecular weight and low polydispersity. The obtained copolymer was esterified with 2-bromoisobutylryl bromide yielding a macroinitiator, poly(methyl methacrylate-co-2-hydroxyethyl methacrylate-co-2-(2-bromoisobutyryloxy)ethyl methacrylate), and its structure was characterized by 1HNMR. This macroinitiator was used for ATRP of styrene to synthesize poly(methyl methacrylate)-grafi-polystyrene. The molecular weight of graft copolymer increased with the monomer conversion, and the polydispersity remained relatively low.The individual grafted polystyrene chains were cleaved from the macroinitiator backbone by hydrolysis and the hydrolyzed product was characterized by 1H-NMR and GPC.

  8. Synthesis of End Functional Polymers via Atom Transfer Radical Polymerization in Immobilized Catalytic System

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    Cross-linked polystyrene with azo-crown ether functional side chain (PSt-1, 10-dicarbonyl-3,6,9-trizaocylcodecane) was prepared under microwave irradiation and the structure was characterized through FT-IR and element analysis. The functionalized cross-linked polystyrene (cross-link degree, 3.5%) combining with immobilized catalyst system (CuBr and ethyl α-bromo-isobutyrate) can catalyze atom transfer radical polymerization of Styrene. Neat polymer products can be obtained then. Complex of La and the polymer end group (EBiB) was synthesized. The third order nonlinear optical property of the polymer-La complex was investigated and the structure was also characterized by FT-IR and XPS.

  9. Mechanism study of copper-mediated one-pot reductive amination of aryl halides using trimethylsilyl azide.

    Science.gov (United States)

    Maejima, Toshihide; Ueda, Moriatsu; Nakano, Jun; Sawama, Yoshinari; Monguchi, Yasunari; Sajiki, Hironao

    2013-09-20

    Reaction mechanisms of the copper-mediated amination of aryl halides with trimethylsilyl azide (TMSN3) were analyzed on the basis of the time-course study using reaction monitoring FT-IR, trapping an intermediary aryl azide by the Huisgen reaction, and the analysis of the generated N2 gas during the reaction. This amination would proceed through multiple pathways via aryl radicals and copper(I) azide.

  10. A novel solid state photocatalyst for living radical polymerization under UV irradiation

    Science.gov (United States)

    Fu, Qiang; McKenzie, Thomas G.; Ren, Jing M.; Tan, Shereen; Nam, Eunhyung; Qiao, Greg G.

    2016-01-01

    This study presents the development of a novel solid state photocatalyst for the photoinduced controlled radical polymerization of methacrylates under mild UV irradiation (λmax ≈ 365 nm) in the absence of conventional photoinitiators, metal-catalysts or dye sensitizers. The photocatalyst design was based on our previous finding that organic amines can act in a synergistic photochemical reaction with thiocarbonylthio compounds to afford well controlled polymethacrylates under UV irradiation. Therefore, in the current contribution an amine-rich polymer was covalently grafted onto a solid substrate, thus creating a heterogeneous catalyst that would allow for facile removal, recovery and recyclability when employed for such photopolymerization reactions. Importantly, the polymethacrylates synthesized using the solid state photocatalyst (ssPC) show similarly excellent chemical and structural integrity as those catalysed by free amines. Moreover, the ssPC could be readily recovered and re-used, with multiple cycles of polymerization showing minimal effect on the integrity of the catalyst. Finally, the ssPC was employed in various photo-“click” reactions, permitting high yielding conjugations under photochemical control. PMID:26863939

  11. Efficient Functionalization of Polyethylene Fibers for the Uranium Extraction from Seawater through Atom Transfer Radical Polymerization

    Energy Technology Data Exchange (ETDEWEB)

    Neti, Venkata S.; Das, Sadananda; Brown, Suree; Janke, Christopher J.; Kuo, Li-Jung; Gill, Gary A.; Dai, Sheng; Mayes, Richard T.

    2017-08-29

    Brush-on-brush structures are proposed as one method to overcome support effects in grafted polymers. Utilizing glycidyl methacrylate (GMA) grafted on polyethylene (PE) fibers using radiation-induced graft polymerization (RIGP) provides a hydrophilic surface on the hydrophobic PE. When integrated with atom transfer radical polymerization (ATRP), the grafting of acrylonitrile (AN) and hydroxyethyl acrylate (HEA) can be controlled and manipulated more easily than with RIGP. Poly(acrylonitrile)-co-poly(hydroxyethyl acrylate) chains were grown via ATRP on PE-GMA fibers to generate an adsorbent for the extraction of uranium from seawater. The prepared adsorbents in this study demonstrated promise (159.9 g- U/kg of adsorbent) in laboratory screening tests using a high uranium concentration brine and 1.24 g-U/Kg of adsorbent in the filtered natural seawater in 21-days. The modest capacity in 21- days exceeds previous efforts to generate brush-on-brush adsorbents by ATRP while manipulating the apparent surface hydrophilicity of the trunk material (PE).

  12. 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.

  13. Methyleneation of peptides by N, N, N, N -tetramethylethylenediamine (TEMED) under conditions used for free radical polymerization : A mechanistic study

    NARCIS (Netherlands)

    Shirangi, Mehrnoosh; Sastre Toraño, Javier; Sellergren, Börje; Hennink, Wim E.; Somsen, Govert W.; Van Nostrum, Cornelus F.

    2015-01-01

    Free radical polymerization is often used to prepare protein and peptide-loaded hydrogels for the design of controlled release systems and molecular imprinting materials. Peroxodisulfates (ammonium peroxodisulfates (APS) or potassium peroxodisulfates (KPS)) with N,N,N,N-tetramethylethylenediamine (T

  14. Conditional Monte Carlo sampling to find branching architectures of polymers from radical polymerizations with transfer to polymer and recombination termination

    NARCIS (Netherlands)

    Iedema, P.D.; Wulkow, M.; Hoefsloot, H.C.J.

    2007-01-01

    A model is developed that predicts branching architectures of polymers from radical polymerization with transfer to polymer and termination by disproportionation and recombination, in a continuously stirred tank reactor (CSTR). It is a so-called conditional Monte Carlo (MC) method generating archite

  15. Versatile procedure for site-specific grafting of polymer brushes on patchy particles via atom transfer radical polymerization (ATRP)

    NARCIS (Netherlands)

    Van Ravensteijn, Bas G P; Kegel, Willem K.

    2016-01-01

    We report the preparation of chemically anisotropic colloidal dumbbells of which one lobe is functionalized with chemical handles in the form of chlorine groups. The chlorines are easily converted to azides and subsequently to active initiators for Atom Transfer Radical Polymerization (ATRP) by Clic

  16. Multifunctional Giant Amphiphiles via simultaneous copper(I)-catalyzed azide-alkyne cycloaddition and living radical polymerization.

    Science.gov (United States)

    Daskalaki, Eleftheria; Le Droumaguet, Benjamin; Gérard, David; Velonia, Kelly

    2012-02-01

    A novel class of chemically addressable, multifunctional Giant Amphiphiles was synthesized in excellent yields and polydispersity following simultaneous or sequential living radical polymerization and the click, copper(I)-catalysed azide-alkyne cycloaddition (CuAAC). This new approach allows chemical tailoring of the biomacromolecules and in situ formation of nanocontainers. This journal is © The Royal Society of Chemistry 2012

  17. Ion conducting solid polymer electrolytes based on polypentafluorostyrene-b-polyether-b-polypentafluorostyrene prepared by atom transfer radical polymerization

    DEFF Research Database (Denmark)

    Jankova, Katja; Jannasch, P.; Hvilsted, Søren

    2004-01-01

    Novel triblock copolymers based on central poly( ethylene glycol) ( PEG) or poly( ethylene glycol-co-propylene glycol) (PEGPG) blocks with poly( pentafluorostyrene) (PFS) outer blocks were prepared by Atom Transfer Radical Polymerization (ATRP) with polydispersities on the order of 1.2 - 1...

  18. THE EFFECTS OF MONOMER STRUCTURE OF CYCLIC KETENE ACETALS ON THE BEHAVIOR OF CONTROLLED RADICAL RING-OPENING POLYMERIZATION

    Institute of Scientific and Technical Information of China (English)

    Jin-ying Yuan; Cai-yuan Pana

    2002-01-01

    Polymerization of three cyclic ketene acetals: i.e., 5,6-benzo-2-methylene-1,3-dioxepane (BMDO), 2-methylene-4-phenyl-1,3-dioxolane (MPDO) and 4,7-dimethyl-2-methylene-1,3-dioxepane (DMMDO) were carried out in the presence of ethyl α-bromobutyrate/CuBr/2,2'-bipyridine respectively. The structures ofpoly(BMDO), poly(MPDO) and poly(DMMDO)were characterized by 1H and 13C-NMR spectra. The effects of monomer structure on the behavior of atom transfer free radical ring-opening polymerization were investigated and the mechanism of controlled free radical ring-opening polymerization was discussed.

  19. Quantitative investigation of free radicals in bio-oil and their potential role in condensed-phase polymerization.

    Science.gov (United States)

    Kim, Kwang Ho; Bai, Xianglan; Cady, Sarah; Gable, Preston; Brown, Robert C

    2015-03-01

    We report on the quantitative analysis of free radicals in bio-oils produced from pyrolysis of cellulose, organosolv lignin, and corn stover by EPR spectroscopy. Also, we investigated their potential role in condensed-phase polymerization. Bio-oils produced from lignin and cellulose show clear evidence of homolytic cleavage reactions during pyrolysis that produce free radicals. The concentration of free radicals in lignin bio-oil was 7.5×10(20)  spin g(-1), which was 375 and 138 times higher than free-radical concentrations in bio-oil from cellulose and corn stover. Pyrolytic lignin had the highest concentration in free radicals, which could be a combination of carbon-centered (benzyl radicals) and oxygen-centered (phenoxy radicals) organic species because they are delocalized in a π system. Free-radical concentrations did not change during accelerated aging tests despite increases in molecular weight of bio-oils, suggesting that free radicals in condensed bio-oils are stable.

  20. NARROW-DISPERSED CROSSLINKED CORE-SHELL POLYMER MICROSPHERES PREPARED BY SURFACE-INITIATED ATOM TRANSFER RADICAL POLYMERIZATION

    Institute of Scientific and Technical Information of China (English)

    Yu-zeng Zhao; Xin-lin Yang; Feng Bai; Wen-qiang Huang

    2005-01-01

    Grafting of polystyrene with narrowly dispersed polymer microspheres through surface-initiated atom transfer radical polymerization (ATRP) was investigated. Polydivinylbenzene (PDVB) microspheres were prepared by dispersion polymerization with poly(N-vinyl pyrrolidone) (PVP) as stabilizer. The surfaces of PDVB microspheres were chloromethylated by chloromethyl methyl ether in the presence of zinc chloride as catalyst to form chloromethylbenzene initiating core sites for subsequent ATRP grafting of styrene using CuC1/bpy as catalytic system. Polystyrene was found to be grafted not only from the particle surfaces but also from within a thin shell layer, resulting in the formation of particles size increased from 2.38-2.58 μm, which can further grow to 2.93 μm during secondary grafting polymerization of styrene. This demonstrates that grafting polymerization proceeds through a typical ATRP procedure with living nature. All of the prepared microspheres have narrow particle size distribution with coefficient of variation around 10%.

  1. 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.

  2. Metal-catalyzed simultaneous chain- and step-growth radical polymerization: marriage of vinyl polymers and polyesters.

    Science.gov (United States)

    Mizutani, Masato; Satoh, Kotaro; Kamigaito, Masami

    2010-06-02

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

  3. 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.

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

    Indian Academy of Sciences (India)

    M A Semsarzadeh; S Amiri; M Azadeh

    2012-10-01

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

  5. Removal of cefalexin using yeast surface-imprinted polymer prepared by atom transfer radical polymerization.

    Science.gov (United States)

    Li, Xiuxiu; Pan, Jianming; Dai, Jiangdong; Dai, Xiaohui; Ou, Hongxiang; Xu, Longcheng; Li, Chunxiang; Zhang, Rongxian

    2012-10-01

    The first use of yeast as a support in the molecular imprinting field combined with atom transfer radical polymerization was described. Then, the as-prepared molecularly imprinted polymers were characterized by Fourier transmission infrared spectrometry, scanning electron microscope, thermogravimetric analysis, and elemental analysis. The obtained imprinted polymers demonstrated elliptical-shaped particles with the thickness of imprinting layer of 0.63 μm. The batch mode experiments were adopted to investigate the adsorption equilibrium, kinetics, and selectivity. The kinetic properties of imprinted polymers were well described by the pseudo-second-order kinetic equation, indicating the chemical process was the rate-limiting step for the adsorption of cefalexin (CFX). The equilibrium data were well fitted by the Freundlich isotherm, and the multimolecular layers adsorption capacity of imprinted polymers was 34.07 mg g(-1) at 298 K. The selectivity analysis suggested that the imprinted polymers exhibited excellent selective recognition for CFX in the presence of other compounds with related structure. Finally, the analytical method based on the imprinted polymers extraction coupled with high-performance liquid chromatograph was successfully used for CFX analysis in spiked pork and water samples.

  6. Characterization of silver/polystyrene nanocomposites prepared by in situ bulk radical polymerization

    Energy Technology Data Exchange (ETDEWEB)

    Vukoje, Ivana D., E-mail: ivanav@vinca.rs [Vinča Institute of Nuclear Sciences, University of Belgrade, P.O. Box 522, 11001 Belgrade (Serbia); Vodnik, Vesna V., E-mail: vodves@vinca.rs [Vinča Institute of Nuclear Sciences, University of Belgrade, P.O. Box 522, 11001 Belgrade (Serbia); Džunuzović, Jasna V., E-mail: jasnav2002@googlemail.com [Institute of Chemistry, Technology and Metallurgy (ICTM)-Center of Chemistry, University of Belgrade, Studentski trg 12-16, 11000 Belgrade (Serbia); Džunuzović, Enis S., E-mail: edzunuzovic@tmf.bg.ac.rs [Faculty of Technology and Metallurgy, University of Belgrade, Karnegijeva 4, 11120 Belgrade (Serbia); Marinović-Cincović, Milena T., E-mail: milena@vinca.rs [Vinča Institute of Nuclear Sciences, University of Belgrade, P.O. Box 522, 11001 Belgrade (Serbia); Jeremić, Katarina, E-mail: kjeremic@tmf.bg.ac.rs [Faculty of Technology and Metallurgy, University of Belgrade, Karnegijeva 4, 11120 Belgrade (Serbia); Nedeljković, Jovan M., E-mail: jovned@vinca.rs [Vinča Institute of Nuclear Sciences, University of Belgrade, P.O. Box 522, 11001 Belgrade (Serbia)

    2014-01-01

    Graphical abstract: - Highlights: • Synthesis and characterization of polystyrene nanocomposites based on Ag nanoparticles. • The glass transition temperature decreased in nanocomposites with respect to the pure polymer. • Resistance of the polymer to thermal degradation enhanced with Ag nanoparticles content. - Abstract: Nanocomposites (NCs) with different content of silver nanoparticles (Ag NPs) embeded in polystyrene (PS) matrix were prepared by in situ bulk radical polymerization. The nearly monodisperse Ag NPs protected with oleylamine were synthesized via organic solvo-thermal method and further used as a filler. The as-prepared spherical Ag NPs with diameter of 7.0 ± 1.5 nm were well dispersed in the PS matrix. The structural properties of the resulting Ag/PS NCs were characterized by transmission electron microscope (TEM) and Fourier transform infrared (FTIR) spectroscopy, while optical properties were characterized using optical absorption measurements. The gel permeation chromatography (GPC) measurements showed that the presence of Ag NPs stabilized with oleylamine has no influence on the molecular weight and polydispersity of the PS matrix. The influence of silver content on the thermal properties of Ag/PS NCs was investigated by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The results indicated that resistance of PS to thermal degradation was improved upon incorporation of Ag NPs. The Ag/PS NCs have lower glass transition temperatures than neat PS because loosely packed oleylamine molecules at the interface caused the increase of free volume and chain segments mobility near the surface of Ag NPs.

  7. Rapid cellular internalization of multifunctional star polymers prepared by atom transfer radical polymerization.

    Science.gov (United States)

    Cho, Hong Y; Gao, Haifeng; Srinivasan, Abiraman; Hong, Joanna; Bencherif, Sidi A; Siegwart, Daniel J; Paik, Hyun-Jong; Hollinger, Jeffrey O; Matyjaszewski, Krzysztof

    2010-09-13

    Poly(ethylene glycol) (PEG) star polymers containing GRGDS (Gly-Arg-Gly-Asp-Ser) peptide sequences on the star periphery were synthesized by atom transfer radical polymerization (ATRP) of poly(ethylene glycol) methyl ether methacrylate (PEGMA), GRGDS modified poly(ethylene glycol) acrylate (GRGDS-PEG-Acryl), fluorescein o-methacrylate (FMA), and ethylene glycol dimethacrylate (EGDMA) via an "arm-first" method. Star polymers were approximately 20 nm in diameter, as measured by dynamic light scattering and atomic force microscopy. Conjugation of FMA to the stars was confirmed by fluorescence microscopy, and successful attachment of GRGDS segments to the star periphery was confirmed by (1)H NMR spectroscopy. Both fluorescent PEG star polymers with and without peripheral GRGDS peptide segments were cultured with MC3T3-E1.4 cells. These star polymers were biocompatible with ≥ 90% cell viability after 24 h of incubation. Cellular uptake of PEG star polymers in MC3T3-E1.4 cells was observed by confocal microscopy. Rapid uptake of PEG star polymers with GRGDS peptides (∼ 100% of FITC-positive cells in 15 min measured by flow cytometry) was observed, suggesting enhanced delivery potential of these functional star polymers.

  8. Functionalization of nylon membranes via surface-initiated atom-transfer radical polymerization.

    Science.gov (United States)

    Xu, F J; Zhao, J P; Kang, E T; Neoh, K G; Li, J

    2007-07-31

    The ability to manipulate and control the surface properties of nylons is of crucial importance to their widespread applications. In this work, surface-initiated atom-transfer radical polymerization (ATRP) is employed to tailor the functionality of the nylon membrane and pore surfaces in a well-controlled manner. A simple two-step method, involving the activation of surface amide groups with formaldehyde and the reaction of the resulting N-methylol polyamide with 2-bromoisobutyryl bromide, was first developed for the covalent immobilization of ATRP initiators on the nylon membrane and its pore surfaces. Functional polymer brushes of 2-hydroxyethyl methacrylate (HEMA) and poly(ethylene glycol)monomethacrylate (PEGMA) were prepared via surface-initiated ATRP from the nylon membranes. A kinetics study revealed that the chain growth from the membranes was consistent with a "controlled" process. The dormant chain ends of the grafted HEMA polymer (P(HEMA)) and PEGMA polymer (P(PEGMA)) on the nylon membranes could be reactivated for the consecutive surface-initiated ATRP to produce the corresponding nylon membranes functionalized by P(HEMA)-b-P(PEGMA) and P(PEGMA)-b-P(HEMA) diblock copolymer brushes. In addition, membranes with grafted P(HEMA) and P(PEGMA) brushes exhibited good resistance to protein adsorption and fouling under continuous-flow conditions.

  9. Removal of dye by carboxymethyl cellulose, acrylamide and graphene oxide via a free radical polymerization process.

    Science.gov (United States)

    Varaprasad, Kokkarachedu; Jayaramudu, Tippabattini; Sadiku, Emmanuel Rotimi

    2017-05-15

    Carboxymethyl cellulose has been used for the design of novel engineered hydrogels in order to obtain effective three-dimensional structures for industrial applications. In this work, dye removal carboxymethyl cellulose-acrylamide-graphene oxide (CMC-AM-GO) hydrogels were prepared by a free-radical polymerization method. The GO was developed by the modified Hummers method. The CMC-AM-GO and GO were characterized by FTIR, XRD and SEM. The swelling and swelling kinetics were calculated using gravimetric process. The kinetic parameter, swelling exponent values [n=0.59-0.7507] explained the fact that the CMC-AM-GO hydrogles have super Case II diffusion transport mechanism. CMCx-AM-GO (x=1-4) and CMC-AM hydrogels were used for removal of Acid Blue-133. The result explains that composite hydrogels significantly removed the acid blue when compared to the neat hydrogel. The maximum AB absorption (185.45mg/g) capacity was found in the case of CMC2-AM-GO hydrogel. Therefore, cellulose-based GO hydrogels can be termed as smart systems for the abstraction of dye in water purification applications. Copyright © 2017 Elsevier Ltd. All rights reserved.

  10. HYDROPHILIC MODIFICATION OF PPESK POROUS MEMBRANES VIA AQUEOUS SURFACE-INITIATED ATOM TRANSFER RADICAL POLYMERIZATION

    Institute of Scientific and Technical Information of China (English)

    Zhuan Yi; You-yi Xu; Li-ping Zhu; Han-bang Dong; Bao-ku Zhu

    2009-01-01

    Hydrophilic surface modification of poly(phthalazinone ether sulfone ketone)(PPESK)porous membranes was achieved via surface-initiated atom transfer radical polymerization(ATRP)in aqueous medium.Prior to ATRP,chloromethyl groups were introduced onto PPESK main chains by chloromethylation.Chloromethylated PPESK(CMPPESK)was fabricated into porous membrane through phase inversion technique.Hydrophilic poly(poly(ethylene glycol)methyl ether methacrylate)(P(PEGMA))brushes were grafted from CMPPESK membrane under the initiation of benzyl chloride groups on membrane surface.The results of Fourier transform infrared(FT-IR)spectroscopy and X-ray photoelectron spectroscopy (XPS)confirmed the grafting of P(PEGMA)chains.Water contact angle measurements and protein adsorption experiments suggested that the hydrophilicity and anti-fouling ability of PPESK membrane were remarkably improved after the grafting of P(PEGMA)brushes.The addition of small amount of water in the reaction solvent apparently accelerated the progress of the grafting reaction.The use of CuCl2 in the catalyst system promoted the controllability of the ATRP reaction.

  11. Colorful Polyelectrolytes: An Atom Transfer Radical Polymerization Route to Fluorescent Polystyrene Sulfonate.

    Science.gov (United States)

    Huberty, Wayne; Tong, Xiaowei; Balamurugan, Sreelatha; Deville, Kyle; Russo, Paul S; Zhang, Donghui

    2016-03-01

    A labeled green fluorescent polystyrene sulfonate (LNaPSS) has been synthesized using atom transfer radical polymerization of a styrene sulfonate monomer with a fluorescent co-monomer, fluorescein thiocyanate-vinyl aniline. As a result this 100 % sulfonated polymer contains no hydrophobic patches along the chain backbone besides the fluorescent marker itself. The concentration of the fluorescent monomer was kept low to maintain the characteristic properties of the anionic polyelectrolyte, LNaPSS. ATRP conditions facilitated the production of polymers spanning a range of molecular weights from 35,000 to 175,000 in gram-scale batches with polydispersity indices of 1.01-1.24. Molecular weight increased with the monomer to initiator ratio. Gel permeation chromatography results show a unimodal distribution, and the polymer structure was also confirmed by (1)H NMR and FT-IR spectroscopy. Fluorescence spectroscopy confirmed covalent bonding of fluorescein isothiocyanate to the polymer, indicating that the polymer is suitable as a probe in fluorescence microscopy. To demonstrate this ability, the polymer was used to locate structural features in salt crystals formed during drying, as in the evaporation of sea mist. A second application to probe diffusion studies is also demonstrated.

  12. Controlled fabrication of theophylline imprinted polymers on multiwalled carbon nanotubes via atom transfer radical polymerization.

    Science.gov (United States)

    Xu, Jianxiong; Gao, Yong; Li, Huaming

    2011-02-01

    Theophylline imprinted polymers were synthesized on the surface of multiwalled carbon nanotubes via atom transfer radical polymerization using brominated multiwalled carbon nanotubes as an initiator. The nanotube-based initiator was prepared by directly reacting acyl chloride-modified multiwalled carbon nanotubes with 2-hydroxylethyl-2'-bromoisobutyrate. The grafting copolymerization of 2-hydroxyethyl-2-methyl-2-propenoate and ethylene glycol dimethacrylate in the presence of template theophylline led to thin molecularly imprinted polymer films coating multiwalled carbon nanotubes. The thickness of molecularly imprinted polymer films prepared in this study was about 5 nm as determined by transmission electron microscopy. Fourier-transform infrared spectroscopy was utilized to follow the introduction of initiator groups as well as polymers on the carbon nanotube surfaces. Thermogravimetric analysis indicated that the molecularly imprinted polymers were successfully grown from the carbon nanotube surfaces, with the final products having a polymer weight percentage of ca. 50 wt%. The adsorption properties, such as adsorption dynamics, special binding and selective recognition capacity, of the as-prepared molecularly imprinted polymer films were evaluated. The results demonstrated that the composite of molecularly imprinted polymers and multiwalled carbon nanotubes not only possessed a rapid dynamics but also exhibited a good selectivity toward theophylline, compared to caffeine.

  13. Efficient copper-mediated reactions of nitrenes derived from sulfonimidamides.

    Science.gov (United States)

    Leca, Dominique; Toussaint, Aurélie; Mareau, Camille; Fensterbank, Louis; Lacôte, Emmanuel; Malacria, Max

    2004-09-30

    [reaction: see text] Sulfonimidamides lead efficiently to nitrenes and have been converted to sulfimides, sulfoximines, and aziridines in good yields, through a copper-mediated multicomponent reaction. The stereogenic sulfur atom and the trivalent nitrogen atom present in the molecules open the way to asymmetric synthesis, whose first results are presented.

  14. Synthesis of Thermo-Responsive Polymer via Radical (Co)polymerization of N,N-Dimethyl-α-(hydroxymethyl)acrylamide with N,N-Diethylacrylamide

    National Research Council Canada - National Science Library

    Kohsaka, Yasuhiro; Tanimoto, Yoshiaki

    2016-01-01

    .... In this article, we report the first example of radical polymerization of α-functionalized N,N-disubstituted acrylamide affording thermo-responsive hydrophilic polymers. N,N-dimethyl-α-(hydroxymethyl)acrylamide (DMαHAA) was (co...

  15. Influence of cure via network structure on mechanical properties of a free-radical polymerizing thermoset

    Science.gov (United States)

    Ganglani, Manisha Sachin

    The matrix of a composite material exerts influence over composite properties. The hypothesis is that control of molecular architecture of the matrix allows for the control of resin properties and therefore impacts composite properties. The objective of this research is to define the relationship between cure chemistry, network structure, and final physical properties of vinyl ester-styrene (VE/S) resin, a free-radical polymerizing thermoset polymer often used as the matrix of fiber reinforced polymers. Tensile and fracture properties of the polymer are found to depend on both cure schedule and cure formulation. The possibilities of phase separation and microgel formation being the cause for the differences in mechanical properties are examined. This research shows that the VE/S system does not phase separate under the conditions studied. This proven, the research examines changes in network architecture under different cure conditions. It is found that though bulk properties of the resin are unaffected by the details of the cure, the microscopic morphology, in particular the type of crosslink formed (intermolecular bond or intramolecular bond), is sensitive to both cure temperature and initiation mechanism as determined by cure formulation. Thus, the molecular architecture of the network is responsible for the bulk mechanical properties of the resin. A kinetic analysis shows that both temperature and initiation mechanism affect the apparent "reaction order" of the VE/S system as determined by the autoacceleration equation. This apparent reaction order is interpreted as being an indication of the degree of heterogeneity in the resin. By controlling cure temperature and cure formulation, it is possible to minimize the apparent reaction order and thereby optimize physical properties. Finally, a theory is adapted from other non-network polymer systems to describe qualitatively how cure temperature and initiation mechanism may alter the heterogeneity in network

  16. Surface modification of glycidyl-containing poly(methyl methacrylate) microchips using surface-initiated atom-transfer radical polymerization.

    Science.gov (United States)

    Sun, Xuefei; Liu, Jikun; Lee, Milton L

    2008-02-01

    Fabrication of microfluidic systems from polymeric materials is attractive because of simplicity and low cost. Unfortunately, the surfaces of many polymeric materials can adsorb biological samples. Therefore, it is necessary to modify their surfaces before these polymeric materials can be used for separation and analysis. Oftentimes it is difficult to modify polymeric surfaces because of their resistance to chemical reaction. Recently, we introduced a surface-reactive acrylic polymer, poly(glycidyl methacrylate-co-methyl methacrylate) (PGMAMMA), which can be modified easily and is suitable for fabrication of microfluidic devices. Epoxy groups on the surface can be activated by air plasma treatment, hydrolysis, or aminolysis. In this work, the resulting hydroxyl or amino groups were reacted with 2-bromoisobutylryl bromide to introduce an initiator for surface-initiated atom-transfer radical polymerization (SI-ATRP). Polyethylene glycol (PEG) layers grown on the surface using this method were uniform, hydrophilic, stable, and resistant to protein adsorption. Contact angle measurement and X-ray photoelectron spectroscopy (XPS) were used to characterize activated polymer surfaces, initiator-bound surfaces, and PEG-grafted surfaces. We obtained excellent capillary electrophoresis (CE) separations of proteins and peptides with the PEG-modified microchips. A separation efficiency of 4.4 x 10(4) plates for a 3.5 cm long separation channel was obtained.

  17. Facile synthesis of thermally stable poly(N-vinylpyrrolidone)-modified gold surfaces by surface-initiated atom transfer radical polymerization.

    Science.gov (United States)

    Liu, Xiaoli; Sun, Kai; Wu, Zhaoqiang; Lu, Jianhong; Song, Bo; Tong, Weifang; Shi, Xiujuan; Chen, Hong

    2012-06-26

    Well-controlled polymerization of N-vinylpyrrolidone (NVP) on Au surfaces by surface-initiated atom transfer radical polymerization (SI-ATRP) was carried out at room temperature by a silanization method. Initial attempts to graft poly(N-vinylpyrrolidone) (PVP) layers from initiators attached to alkanethiol monolayers yielded PVP films with thicknesses less than 5 nm. The combined factors of the difficulty in the controllable polymerization of NVP and the instability of alkanethiol monolayers led to the difficulty in the controlled polymerization of NVP on Au surfaces. Therefore, the silanization method was employed to form an adhesion layer for initiator attachment. This method allowed well-defined ATRP polymerization to occur on Au surfaces. Water contact angle, X-ray photoelectron spectroscopy (XPS), and reflectance Fourier transform infrared (reflectance FTIR) spectroscopy were used to characterize the modified surfaces. The PVP-modified gold surface remained stable at 130 °C for 3 h, showing excellent thermal stability. Thus, postfunctionalization of polymer brushes at elevated temperatures is made possible. The silanization method was also applied to modify SPR chips and showed potential applications in biosensors and biochips.

  18. SYNTHESIS AND FREE RADICAL RING-OPENING POLYMERIZATION OF 2 - METHYL-AND 2- METHYL- 9- n- BUTYL- (- 7- METHYLENE- 1,4,6 - TRIOXASPIRO (4, 4 )NONANE )

    Institute of Scientific and Technical Information of China (English)

    PAN Caiyuan; WANG Yin

    1989-01-01

    This paper describes the synthesis and free radical ring- opening polymerization of 2 - methyl-and2 - methyl - 9 - n - butyl ( - 7 - methylene - 1,4, 6 - trioxaspiro (4, 4 ) nonane ). The structures of the two polymers were verified by IR, 1H and 13C NMR spectra. The substituent on 9-position of 7-methylene- trioxaspiro (4, 4 ) nona ne affects the structure of polymer and polymerization activity. The polymerization mechanism is discussed .

  19. 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.

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

    Science.gov (United States)

    Wan, Qing; Tian, Jianwen; Liu, Meiying; Zeng, Guangjian; Huang, Qiang; Wang, Ke; Zhang, Qingsong; Deng, Fengjie; Zhang, Xiaoyong; Wei, Yen

    2015-08-01

    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.

  1. Preparation of end-grafted polymer brushes by nitroxide-mediated free radical polymerization of vaporized vinyl monomers.

    Science.gov (United States)

    Li, Jun; Chen, Xiaoru; Chang, Ying-Chih

    2005-10-11

    In this work, we report a gas-phase polymerization approach to create end-grafted vinyl based polymer films on silicon oxide based substrates. The "surface-initiated vapor deposition polymerization" (SI-VDP) of vaporized vinyl monomers, via the nitroxide-mediated free radical polymerization mechanism, was developed to fabricate various homo- and block copolymer brushes from surface-bound initiators, 1-(4'-oxa-2'-phenyl-12'-trimethoxysilyldodecyloxy)-2,2,6,6-tetra-methylpiperidine ("TEMPO"). The resulting polymer thin films were characterized by the Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, ellipsometry, and contact angle goniometry, respectively, to identify the surface composition, film thickness, surface coverage, and water contact angles. Through the SI-VDP, end-grafted polymer films of polystyrene (PSt), poly(acrylic acid) (PAAc), poly(N-(2-hydroxypropyl) methacrylamide) (PHPMA), and poly(N-isopropylacrylamide) (PNIPAAm) with 10-200 nm thicknesses were fabricated. Furthermore, the block copolymer films of PAAc (1st block)-b-PSt (2nd block), PSt (1st block)-b-PAAc (2nd block), and a triblock copolymer film of PAAc (1st)-b-PSt (2nd)-b-PHPMA (3rd), were also fabricated, suggesting the "renewability" of the TEMPO-initiated polymerization in the SI-VDP scheme. It is also noticed that the SI-VDP is more efficient than the conventional solution phase polymerization in producing functional polymer brushes such as PNIPAAm, PAAc, or PAAc-b-PSt end-grafted films. In summary, our studies have shown clear advantages of the SI-VDP setup for the nitroxide-mediated polymerization scheme in controlling synthesis of end-grafted homo- and copolymer thin films.

  2. Controlled Radical Polymerization as an Enabling Approach for the Next Generation of Protein-Polymer Conjugates.

    Science.gov (United States)

    Pelegri-O'Day, Emma M; Maynard, Heather D

    2016-09-20

    Protein-polymer conjugates are unique constructs that combine the chemical properties of a synthetic polymer chain with the biological properties of a biomacromolecule. This often leads to improved stabilities, solubilities, and in vivo half-lives of the resulting conjugates, and expands the range of applications for the proteins. However, early chemical methods for protein-polymer conjugation often required multiple polymer modifications, which were tedious and low yielding. To solve these issues, work in our laboratory has focused on the development of controlled radical polymerization (CRP) techniques to improve synthesis of protein-polymer conjugates. Initial efforts focused on the one-step syntheses of protein-reactive polymers through the use of functionalized initiators and chain transfer agents. A variety of functional groups such as maleimide and pyridyl disulfide could be installed with high end-group retention, which could then react with protein functional groups through mild and biocompatible chemistries. While this grafting to method represented a significant advance in conjugation technique, purification and steric hindrance between large biomacromolecules and polymer chains often led to low conjugation yields. Therefore, a grafting from approach was developed, wherein a polymer chain is grown from an initiating site on a functionalized protein. These conjugates have demonstrated improved homogeneity, characterization, and easier purification, while maintaining protein activity. Much of this early work utilizing CRP techniques focused on polymers made up of biocompatible but nonfunctional monomer units, often containing oligoethylene glycol meth(acrylate) or N-isopropylacrylamide. These branched polymers have significant advantages compared to the historically used linear poly(ethylene glycols) including decreased viscosities and thermally responsive behavior, respectively. Recently, we were motivated to use CRP techniques to develop polymers with

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

    Science.gov (United States)

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

    2016-02-01

    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/cm2, 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.

  4. Bottom-Up Fabrication of Nanopatterned Polymers on DNA Origami by In Situ Atom-Transfer Radical Polymerization.

    Science.gov (United States)

    Tokura, Yu; Jiang, Yanyan; Welle, Alexander; Stenzel, Martina H; Krzemien, Katarzyna M; Michaelis, Jens; Berger, Rüdiger; Barner-Kowollik, Christopher; Wu, Yuzhou; Weil, Tanja

    2016-05-04

    Bottom-up strategies to fabricate patterned polymers at the nanoscale represent an emerging field in the development of advanced nanodevices, such as biosensors, nanofluidics, and nanophotonics. DNA origami techniques provide access to distinct architectures of various sizes and shapes and present manifold opportunities for functionalization at the nanoscale with the highest precision. Herein, we conduct in situ atom-transfer radical polymerization (ATRP) on DNA origami, yielding differently nanopatterned polymers of various heights. After cross-linking, the grafted polymeric nanostructures can even stably exist in solution without the DNA origami template. This straightforward approach allows for the fabrication of patterned polymers with low nanometer resolution, which provides access to unique DNA-based functional hybrid materials.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-11-15

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

  6. Preparation of Polystryenylphosphonous Acid of Low Polymerization Degree and Influence of Initiators upon the Free Radical Reaction Mechanism

    Institute of Scientific and Technical Information of China (English)

    XiangKaiFU; YanSUI; 等

    2002-01-01

    The polystyrenylphosphonous acid (PSPA) of low polymerization degress was prepared with one step reaction. The reaction mechanism was changed with different initiators. For the reaction with AIBN or BPO as the initiator, therer are 2 or 3 serives of radical reaction chains and 5 or 9 series of polystyrenyl products. The main products are PSPA without or with the fragment of the initiator H[CH(C6H5)-CH2]n-PO2H2 and C6H5CO2-[CH2CH(C6H5)]n-PO2H2 respectively.

  7. Preparation of Polystyrenylphosphonous Acid of Low Polymerization Degree and Influence of Initiators upon the Free Radical Reaction Mechanism

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    The polystyrenylphosphonous acid (PSPA) of low polymerization degree was prepared with one step reaction. The reaction mechanism was changed with different initiators. For the reaction with AIBN or BPO as the initiator, there are 2 or 3 series of radical reaction chains and 5 or 9 series of polystyrenyl products. The main products are PSPA without or with the fragment of the initiator H[CH(C6H5)-CH2]n-PO2H2 and C6H5CO2-[CH2CH (C6H5)]n-PO2H2 respectively.

  8. Preparation of water-soluble multi-walled carbon nanotubes by Ce(Ⅳ)-induced redox radical polymerization

    Institute of Scientific and Technical Information of China (English)

    Dong Yang; Xiaohong Zhang; Changchun Wang; Yuechao Tang; Junjun Li; Jianhua Hu

    2009-01-01

    Poly(acrylic acid), poly(N-isopropylacrylamide) and polyacrylamide functionalized MWNTs were prepared by Ce(IV)-induced redox radical polymerization. The reaction can be conducted in aqueous media at room temperature, and the polymer graft ratio increased with the increase of monomer feed ratio. MWNTs anchored with PAA on the surface are pH sensitive and exhibit a reversible assembly-deas-sembly response in aqueous solution, whereas those coated with PNIPAM are thermally sensitive. All the polymer-functionalized MWNTs are highly soluble in water to give robust stable black solutions. Such water-soluble MWNTs are promising for biological and biomedical applications.

  9. Formation of Core-Shell Particles by Interfacial Radical Polymerization Initiated by a Glucose Oxidase-Mediated Redox System.

    Science.gov (United States)

    Shenoy, Raveesh; Tibbitt, Mark W; Anseth, Kristi S; Bowman, Christopher N

    2013-03-12

    A unique design paradigm to form core-shell particles based on interfacial radical polymerization is described. The interfacial initiation system is comprised of an enzymatic reaction between glucose and glucose oxidase (GOx) to generate hydrogen peroxide, which, in the presence of iron (Fe(2+)), generates hydroxyl radicals that initiate polymerization. Shell formation on prefabricated polymeric cores is achieved by localizing the initiation reaction to the interface of the core and a surrounding aqueous monomer formulation into which it is immersed. The interfacially confined initiation reaction is accomplished by incorporating one or more of the initiating species in the particle core and the remainder of the complementary initiating components in the surrounding media such that interactions and the resulting initiation reaction occur at the interface. This work is focused on engineering the reaction behavior and mass transport processes to promote interfacially confined polymerization, controlling the rate of shell formation, and manipulating the structure of the core-shell particle. Specifically, incorporating GOx in the precursor solution used to fabricate cores ranging from 100 to 200 μm, and the remainder of the complementary initiating components and monomer in the bulk solution prior to interfacial polymerization yielded shells whose average thickness was 20 μm after 4 min of immersion and at a bulk iron concentration of 12.5 mM. When the locations of glucose and GOx are interchanged, the average thickness of the shell was 15 or 100 μm for bulk iron concentrations of 45 and 12.5 mM, respectively. The initial locations of glucose and GOx also determine the degree of interpenetration of the core and the shell. Specifically, for a bulk iron concentration of 45 mM, the thickness of the interpenetrating layer averaged 12 μm when GOx was initially within the core, whereas no interpenetrating layer was observed when glucose was incorporated in the core. The

  10. The radical trap in atom transfer radical polymerization need not be thermodynamically stable. A study of the MoX(3)(PMe(3))(3) catalysts.

    Science.gov (United States)

    Maria, Sébastien; Stoffelbach, François; Mata, José; Daran, Jean-Claude; Richard, Philippe; Poli, Rinaldo

    2005-04-27

    The molybdenum(III) coordination complexes MoX(3)(PMe(3))(3) (X = Cl, Br, and I) are capable of controlling styrene polymerization under typical atom transfer radical polymerization (ATRP) conditions, in conjunction with 2-bromoethylbenzene (BEB) as an initiator. The process is accelerated by the presence of Al(OPr(i))(3) as a cocatalyst. Electrochemical and synthetic studies aimed at identifying the nature of the spin trap have been carried out. The cyclic voltammogram of MoX(3)(PMe(3))(3) (X = Cl, Br, I) shows partial reversibility (increasing in the order Cl MoX(4)(PMe(3))(3) for X = Cl and Br. On the other hand, I(-) is more easily oxidized than the MoI(3)(PMe(3))(3) complex; thus, the putative MoI(4)(PMe(3))(3) complex is redox unstable. Electrochemical studies of MoI(3)(PMe(3))(3) in the presence of X(-) (X = Cl or Br) reveal the occurrence of facile halide-exchange processes, leading to the conclusion that the MoI(3)X(PMe(3))(3) products are also redox unstable. The oxidation of MoX(3)(PMe(3))(3) with (1)/(2)Br(2) yields MoX(3)Br(PMe(3))(3) (X = Cl, Br), whose molecular nature is confirmed by single-crystal X-ray analyses. On the other hand, the oxidation of MoI(3)(PMe(3))(3) by I(2) slowly yields a tetraiodomolybdate(III) salt of iodotrimethylphosphonium, [Me(3)PI][MoI(4)(PMe(3))(3)], as confirmed by an X-ray study. This product has no controlling ability in radical polymerization. The redox instability of MoI(3)X(PMe(3))(3) can be reconciled with its involvement as a radical trapping species in the MoI(3)(PMe(3))(3)-catalyzed ATRP, given the second-order nature of its decomposition rate.

  11. On the Teaching of Free Radical Polymerization%关于自由基聚合几个值得关注的问题

    Institute of Scientific and Technical Information of China (English)

    王峰; 张红亚; 周海鸥

    2011-01-01

    Some issues related the free radical polymerization should be focused on during the course of being educated and have been discussed in detail in this paper.These issues included the selection of initiator,polymerization temperature,time of polymerization and used solvent when free radical polymerization mechanism was applied.Meanwhile,it also expressed the inreaction between these above factors when the free radical polymerization route and technologies were designed.It aims at to improve students understanding and application of free radical polymerization systemly and develop the ability of design.%总结了自由基聚合教学中的几个值得关注的问题,包括自由基聚合时不同引发剂类型的选择和确定、聚合温度及其区间选择及确定、聚合时间的确定、溶剂选择等。同时阐述了这些相关因素在自由基聚合研究方案设计时的相互关系。旨在使学生对自由基聚合的认识更为深刻和系统,培养学生独立进行自由基聚合研究方案设计的能力。

  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. Hydrophilic Modification of Microporous Polysulfone Membrane via Surface-Initiated Atom Transfer Radical Polymerization and Hydrolysis of Poly(glycidylmethacrylate)%Hydrophilic Modification of Microporous Polysulfone Membrane via Surface-Initiated Atom Transfer Radical Polymerization and Hydrolysis of Poly(glycidylmethacrylate)

    Institute of Scientific and Technical Information of China (English)

    王超展; 赵飒; 卫引茂

    2012-01-01

    Poly(glycidylmethacrylate) (PGMA) brushes were grafted from chloromethylated polysulfone (CMPSF) mem- brane surface by surface-initiated atom transfer radical polymerization (S1-ATRP), and the grafting was followed by hydrolysis of epoxy groups in the grafting chains to improve the membrane's hydrophilie property. Fourier trans- form infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS) measurements confirmed the suc- cessful grafting and hydrolysis of PGMA. The grafting degree of the monomer, measured by periodic acid titration and gravimetric analysis, increased linearly with the polymerization time, while the static water contact angle of the membrane grafted with PGMA or hydrolyzed PGMA linearly decreased. In comparison with the PGMA-grafted membranes, the hydrolyzed PGMA-grafted membranes possess stronger hydrophilicity as indicated by their contact angle and hydration capacity, and as a result they have an improved antifouling property. Therefore, the control of the hydrophilicity of PSF membrane could be realized through adjusting the polymerization time and transforming the functional groups in the grafting chain.

  14. The influence of water on visible-light initiated free-radical/cationic ring-opening hybrid polymerization of methacrylate/epoxy: Polymerization kinetics, crosslinking structure and dynamic mechanical properties

    OpenAIRE

    2015-01-01

    The objective of this study was to determine the influence of water on the polymerization kinetics, crosslinking structure and dynamic mechanical properties of methacrylate/epoxy polymers cured by visible-light initiated free-radical/cationic ring-opening hybrid polymerization. Water-containing formulations were prepared by adding ~4–7 wt% D2O depending on the water miscibility of monomer resins. The water-containing adhesives were compared with the adhesives photo-cured in the absence of wat...

  15. A new approach to network heterogeneity: Polymerization Induced Phase Separation in photo-initiated, free-radical methacrylic systems.

    Science.gov (United States)

    Szczepanski, Caroline R; Pfeifer, Carmem S; Stansbury, Jeffrey W

    2012-09-28

    Non-reactive, thermoplastic prepolymers (poly- methyl, ethyl and butyl methacrylate) were added to a model homopolymer matrix composed of triethylene glycol dimethacrylate (TEGDMA) to form heterogeneous networks via polymerization induced phase separation (PIPS). PIPS creates networks with distinct phase structure that can partially compensate for volumetric shrinkage during polymerization through localized internal volume expansion. This investigation utilizes purely photo-initiated, free-radical systems, broadening the scope of applications for PIPS since these processing conditions have not been studied previously.The introduction of prepolymer into TEGDMA monomer resulted in stable, homogeneous monomer formulations, most of which underwent PIPS upon photo-irradiation, creating heterogeneous networks. During polymerization the presence of prepolymer enhanced autoacceleration, allowing for a more extensive ambient cure of the material. Phase separation, as characterized by dynamic changes in sample turbidity, was monitored simultaneously with monomer conversion and either preceded or was coincident with network gelation. Dynamic mechanical analysis shows a broadening of the tan delta peak and secondary peak formation, characteristic of phase-separated materials, indicating one phase rich in prepolymer and another depleted form upon phase separation. In certain cases, PIPS leads to an enhanced physical reduction of volumetric shrinkage, which is attractive for many applications including dental composite materials.

  16. On the Use of Quantum Chemistry for the Determination of Propagation, Copolymerization, and Secondary Reaction Kinetics in Free Radical Polymerization

    Directory of Open Access Journals (Sweden)

    Evangelos Mavroudakis

    2015-09-01

    Full Text Available Throughout the last 25 years, computational chemistry based on quantum mechanics has been applied to the investigation of reaction kinetics in free radical polymerization (FRP with growing interest. Nowadays, quantum chemistry (QC can be considered a powerful and cost-effective tool for the kinetic characterization of many individual reactions in FRP, especially those that cannot yet be fully analyzed through experiments. The recent focus on copolymers and systems where secondary reactions play a major role has emphasized this feature due to the increased complexity of these kinetic schemes. QC calculations are well-suited to support and guide the experimental investigation of FRP kinetics as well as to deepen the understanding of polymerization mechanisms. This paper is intended to provide an overview of the most relevant QC results obtained so far from the investigation of FRP. A comparison between computational results and experimental data is given, whenever possible, to emphasize the performances of the two approaches in the prediction of kinetic data. This work provides a comprehensive database of reaction rate parameters of FRP to assist in the development of advanced models of polymerization and experimental studies on the topic.

  17. Recent Developments in the Synthesis of Biomacromolecules and their Conjugates by Single Electron Transfer-Living Radical Polymerization.

    Science.gov (United States)

    Lligadas, Gerard; Grama, Silvia; Percec, Virgil

    2017-04-10

    Single electron transfer-living radical polymerization (SET-LRP) represents a robust and versatile tool for the synthesis of vinyl polymers with well-defined topology and chain end functionality. The crucial step in SET-LRP is the disproportionation of the Cu(I)X generated by activation with Cu(0) wire, powder, or nascent Cu(0) generated in situ into nascent, extremely reactive Cu(0) atoms and nanoparticles and Cu(II)X2. Nascent Cu(0) activates the initiator and dormant chains via a homogeneous or heterogeneous outer-sphere single-electron transfer mechanism (SET-LRP). SET-LRP provides an ultrafast polymerization of a plethora of monomers (e.g., (meth)-acrylates, (meth)-acrylamides, styrene, and vinyl chloride) including hydrophobic and water insoluble to hydrophilic and water soluble. Some advantageous features of SET-LRP are (i) the use of Cu(0) wire or powder as readily available catalysts under mild reaction conditions, (ii) their excellent control over molecular weight evolution and distribution as well as polymer chain ends, (iii) their high functional group tolerance allowing the polymerization of commercial-grade monomers, and (iv) the limited purification required for the resulting polymers. In this Perspective, we highlight the recent advancements of SET-LRP in the synthesis of biomacromolecules and of their conjugates.

  18. A review of our development of dental adhesives--effects of radical polymerization initiators and adhesive monomers on adhesion.

    Science.gov (United States)

    Ikemura, Kunio; Endo, Takeshi

    2010-03-01

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

  19. Kinetics of interfacial radical polymerization initiated by a glucose-oxidase mediated redox system.

    Science.gov (United States)

    Shenoy, Raveesh; Bowman, Christopher N

    2012-10-01

    The reaction and coating kinetics for the glucose oxidase initiated interfacial polymerization are elaborated. The interfacial film grows rapidly and linearly with time, producing time-dependent controllable conformal coating thicknesses of up to a millimeter in less than 4 min. Bulk polymerization was only observed when the immersing media was stirred to induce higher mass transport rates. The dramatically different film thicknesses observed between different concentrations of glucose in the hydrogel and iron in the bulk media are demonstrated to be a result of an initial rapid growth phase following which the film grows at the same rate nearly independent of either the glucose or iron concentration. The polymerization rate and hence the thickness growth rate in this initial phase saturate at glucose and iron concentrations above 0.8 M and 0.63 mM, respectively. At iron concentrations above 0.05 mM, the film thickness at the end of 3 h of reaction monotonically decreased with increasing iron concentration from 5.7 mm to 4.2 mm. The glucose oxidase is trapped by the growing polymerization front and can be used as the sole enzymatic precursor to coat a second polymeric layer. However, the rate of film growth of the second layer is 14-fold lower than the rate of film growth when bulk enzyme is present during the second stage coating process.

  20. SYNTHESIS OF HETEROARM STAR-SHAPED POLYMER BY THE USE OF POLYFUNCTIONAL CHAIN-TRANSFER AGENT via CONVENTIONAL FREE RADICAL POLYMERIZATION

    Institute of Scientific and Technical Information of China (English)

    Zhi-hua Luo; Zhi-feng Fu; Yan Shi

    2008-01-01

    Heteroarm star-shaped polymers were synthesized by conventional free radical polymerization in two steps by the use of polyfunctional chain transfer agent. In the first step, free radical polymerization of methyl methacrylate was carried out in the presence of a polyfunctional chain transfer agent, pentaerythritol tetrakis(3-mercaptopropinate). At appropriate monomer conversions, two-arm PMMA having two residual thiol groups at the chain center or three-arm PMMA having one residual thiol group at the core were obtained. In the second step, free radical polymerization of styrene was carried out using PMMAs obtained above as macro-chain transfer agent. When styrene conversion was lower than 30%, heteroarm star-shaped polymers, (PMMA)2(PS)a and (PMMA)3(PS), were obtained successfully.

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

    Science.gov (United States)

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

    2015-10-04

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

  2. QSRR correlation of free-radical polymerization chain-transfer constants for styrene.

    Science.gov (United States)

    Ignatz-Hoover, F; Petrukhin, R; Karelson, M; Katritzky, A R

    2001-01-01

    Quantitative structure-reactivity relationships (QSRR) are deduced for kinetic chain-transfer constants for 90 agents on styrene polymerization at 60 degrees C. Three- and five-parameter correlations were obtained with R2 of 0.725 and 0.818, respectively. The descriptors involved in the correlations are consistent with the proposed mechanism of the chain-transfer reactions.

  3. Free radical suspension polymerization kinetics of styrene up to high conversion

    NARCIS (Netherlands)

    Tefera, Nurelegne; Weickert, Günter; Bloodworth, Robert; Schweer, Johannes

    1994-01-01

    Styrene was polymerized using different amounts of azoisobutyronitrile as initiator at temperatures of 70°C, 75°C and 80°C in suspension. The course of reaction up to almost complete conversion was modeled within a classical kinetic framework. Optimal simultaneous descriptions of both conversion and

  4. 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...

  5. Ultrasound assisted free radical polymerization of glycidyl methacrylate by a new disite phase-transfer catalyst system: A kinetic study.

    Science.gov (United States)

    Sankar, Kavitha; Rajendran, Venugopal

    2012-11-01

    The kinetics of multi-site phase-transfer catalyzed free radical polymerisation of glycidyl methacrylate (GMA) using potassium peroxy disulphate (PDS) as water soluble initiator and newly synthesized 1,4-dihexadecylpyrazine-1,4-diium dibromide as multi-site phase-transfer catalyst (MPTC) has been investigated in ethyl acetate/water two phase system at constant temperature 65±1°C under nitrogen atmosphere and ultrasound irradiation conditions. The rate of polymerization increases with an increase in concentrations of GMA, PDS and MPTC. The order with respect to monomer, initiator and MPTC were found to be 1.0, 0.5 and 1.0, respectively. The comparative study reveals that the Rp of GMA determined in the presence of PTC combined with ultrasound has shown more enhancements in the activity than PTC alone. Based on the observed results a suitable mechanism has been proposed to account for the experimental observations and its significance was discussed.

  6. Ferroferric oxide/polystyrene (Fe3O4/PS superparamagnetic nanocomposite via facile in situ bulk radical polymerization

    Directory of Open Access Journals (Sweden)

    2010-03-01

    Full Text Available Organo-modified ferroferric oxide superparamagnetic nanoparticles, synthesized by the coprecipitation of superparamagnetic nanoparticles in presence of oleic acid (OA, were incorporated in polystyrene (PS by the facile in situ bulk radical polymerization by using 2,2-azobisisobutyronitrile (AIBN as initiator. The transmission electron microscopy (TEM analysis of the resultant uniform ferroferric oxide/polystyrene superparamagnetic nanocomposite (Fe3O4/PS showed that the superparamagnetic nanoparticles had been dispersed homogeneously in the polymer matrix due to the surface grafted polystyrene, confirmed by Fourier transform infrared (FT-IR spectroscopy and thermogravimetric analysis (TGA. The superparamagnetic property of the Fe3O4/PS nanocomposite was testified by the vibrating sample magnetometer (VSM analysis. The strategy developed is expected to be applied for the large-scale industrial manufacturing of the superparamagnetic polymer nanocomposite.

  7. Highly selective capture of nucleosides with boronic acid functionalized polymer brushes prepared by atom transfer radical polymerization.

    Science.gov (United States)

    Cheng, Ting; Zhu, Shuqiang; Zhu, Bin; Liu, Xiaoyan; Zhang, Haixia

    2016-04-01

    The nucleoside or modified nucleoside level in biological fluids reflects the pathological or physiological state of the body. Boronate affinity absorbents are widely used to selectively extract nucleosides from complex samples. In this work, a novel functionalized absorbent was synthesized by attaching 4-mercaptophenylboronic acid to gold nanoparticles on modified attapulgite. The surface of the attapulgite was modified by poly(acryloyloxyethyltrimethyl ammonium chloride) by atom transfer radical polymerization, creating many polymer brushes on the surface. The resultant material exhibited superior binding capacity (30.83 mg/g) for adenosine and was able to capture cis-diol nucleosides from 1000-fold interferences. Finally, to demonstrate its potential for biomolecule extraction, this boronate affinity material was used to preconcentrate nucleosides from human urine and plasma.

  8. Synthesis and characterization of styrene-co-divinylbenzene-graft-linseed oil by free radical polymerization

    Directory of Open Access Journals (Sweden)

    2008-04-01

    Full Text Available A variety of opaque white to light yellow polymeric material have been prepared by two methods, one copolymerization of styrene (ST, divinylbenzene (DVB, and grafting of linseed oil (LIN, and the second involves the copolymerization of the same comonomers with pre-reacted (with initiator linseed oil. All of the reactant mixtures in different concentrations start to solidify at 100°C and give rise to a solid crosslinked polymer at 130°C. These polymeric materials contain approximately 30 to 74% of crosslinked materials. Their 1H NMR spectra indicate that the polymeric samples contain both soft oily and hard aromatic segments. The insoluble material left after soxhlet extraction contains finely distributed micropores. The heat deflection temperatures (HDT of the polymer samples range from 26 to 44°C. The glass transition temperature for different linseed oil polymer samples ranges from 66 to 147°C (from dynamic mechanical analysis and 158 to 182°C (from differential scanning calorimetry. The crosslinking density of samples ranges from 35.0 to 6.01•104 mol/m3. Irrespective of methods, the storage modulus decreases with increasing oil content in the copolymers. The polymers prepared by the first method show minimum swelling in saline water and maximum swelling in tetrahydrofuran. On the other hand, the polymers from the second method show maximum swelling in alkaline solution and a minimum in acidic solution.

  9. Controlled grafting of comb copolymer brushes on poly(tetrafluoroethylene) films by surface-initiated living radical polymerizations.

    Science.gov (United States)

    Yu, W H; Kang, E T; Neoh, K G

    2005-01-04

    Surface modification of poly(tetrafluoroethylene) (PTFE) films by well-defined comb copolymer brushes was carried out. Peroxide initiators were generated directly on the PTFE film surface via radio frequency Ar plasma pretreatment, followed by air exposure. Poly(glycidyl methacrylate) (PGMA) brushes were first prepared by surface-initiated reversible addition-fragmentation chain transfer polymerization from the peroxide initiators on the PTFE surface in the presence of a chain transfer agent. Kinetics study revealed a linear increase in the graft concentration of PGMA with the reaction time, indicating that the chain growth from the surface was consistent with a "controlled" or "living" process. alpha-Bromoester moieties were attached to the grafted PGMA by reaction of the epoxide groups with 2-bromo-2-methylpropionic acid. The comb copolymer brushes were subsequently prepared via surface-initiated atom transfer radical polymerization of two hydrophilic vinyl monomers, including poly(ethylene glycol) methyl ether methacrylate and sodium salt of 4-styrenesulfonic acid. The chemical composition of the modified PTFE surfaces was characterized by X-ray photoelectron spectroscopy.

  10. 3D scaffolds from vertically aligned carbon nanotubes/poly(methyl methacrylate) composites via atom transfer radical polymerization

    Energy Technology Data Exchange (ETDEWEB)

    Tebikachew, Behabtu; Magina, Sandra [CICECO, Department of Chemistry, University of Aveiro (Portugal); Mata, Diogo; Oliveira, Filipe J.; Silva, Rui F. [CICECO, Department of Materials and Ceramic Engineering, University of Aveiro (Portugal); Barros-Timmons, Ana, E-mail: anabarros@ua.pt [CICECO, Department of Chemistry, University of Aveiro (Portugal)

    2015-01-15

    Vertically aligned carbon nanotubes (VACNTs) synthesized by Thermal Chemical Vapour Deposition (TCVD) were modified using an Ar:O{sub 2} (97:3) plasma to generate oxygen-containing functional groups on the surface for subsequent modification. X-ray photo-emission spectroscopy (XPS) and micro-Raman analyses confirmed the grafting of those functional groups onto the surface of the nanotubes as well as the removal of amorphous carbon produced and deposited on the VACNT forests during the CVD process. The plasma treated VACNT forests were further modified with 2-bromo-2-methylpropionyl bromide, an atom transfer radical polymerization (ATRP) initiator, to grow poly(methyl methacrylate) (PMMA) chains from the forests via ATRP. Scanning transmission electron microscopy (STEM) of the ensuing VACNT/PMMA composites confirmed the coating of the nanotube forests with the PMMA polymer. 3D scaffolds of polymeric composites with honeycomb like structure were then obtained. Compressive tests have shown that the VACNT/PMMA composite has higher compressive strength than the pristine forest. - Highlights: • Vertically aligned carbon nanotubes (VACNTs) were synthesized and plasma modified. • X-ray photo-emission and Raman spectroscopies confirmed the VACNTs modification. • Poly(methyl methacrylate) chains were grown via ATRP from the VACNTs. • STEM of the VACNT/PMMA composites confirmed that PMMA surrounds the nanotubes. • VACNT/PMMA composite has higher compressive strength compared to the pristine forest.

  11. Comb-Type Grafted Hydrogels of PNIPAM and PDMAEMA with Reversed Network-Graft Architectures from Controlled Radical Polymerizations

    Directory of Open Access Journals (Sweden)

    Sheng-Qi Chen

    2016-02-01

    Full Text Available Dual thermo- and pH-responsive comb-type grafted hydrogels of poly(N,N-dimethylaminoethyl methacrylate (PDMAEMA and poly(N-isopropylacrylamide (PNIPAM with reversed network-graft architectures were synthesized by the combination of atom transfer radical polymerization (ATRP, reversible addition-fragmentation chain transfer (RAFT polymerization and click chemistry. Two kinds of macro-cross-linkers with two azido groups at one chain-end and different chain length [PNIPAM–(N32 and PDMAEMA–(N32] were prepared with N,N-di(β-azidoethyl 2-halocarboxylamide as the ATRP initiator. Through RAFT copolymerization of DMAEMA or NIPAM with propargyl acrylate (ProA using dibenzyltrithiocarbonate as a chain transfer agent, two network precursors with different content of alkynyl side-groups [P(DMAEMA-co-ProA and P(NIPAM-co-ProA] were obtained. The subsequent azido-alkynyl click reaction of macro-cross-linkers and network precursors led to the formation of the network-graft hydrogels. These dual stimulus-sensitive hydrogels exhibited rapid response, high swelling ratio and reproducible swelling/de-swelling cycles under different temperatures and pH values. The influences of cross-linkage density and network-graft architecture on the properties of the hydrogels were investigated. The release of ceftriaxone sodium from these hydrogels showed both thermal- and pH-dependence, suggesting the feasibility of these hydrogels as thermo- and pH-dependent drug release devices.

  12. Effect of Surface Charge on Surface-Initiated Atom Transfer Radical Polymerization from Cellulose Nanocrystals in Aqueous Media.

    Science.gov (United States)

    Zoppe, Justin O; Xu, Xingyu; Känel, Cindy; Orsolini, Paola; Siqueira, Gilberto; Tingaut, Philippe; Zimmermann, Tanja; Klok, Harm-Anton

    2016-04-11

    Cellulose nanocrystals (CNCs) with different charge densities were utilized to examine the role of electrostatic interactions on surface-initiated atom transfer radical polymerization (SI-ATRP) in aqueous media. To this end, growth of hydrophilic uncharged poly(N,N-dimethylacrylamide) (PDMAM) brushes was monitored by electrophoresis, (1)H NMR spectroscopy, and dynamic light scattering (DLS). Molecular weight and polydispersity of PDMAM brushes was determined by GPC analysis of hydrolytically cleaved polymers. Initiator and polymer brush grafting densities, and thus, initiator efficiencies were derived from elemental analysis. Higher initiator efficiency of polymer brush growth was observed for CNCs with higher anionic surface sulfate half-ester group density, but at the expense of high polydispersity caused by inefficient deactivation. PDMAM grafts with number-average molecular weights up to 530 kDa and polydispersity indices interfacial region at the onset of polymerization is proposed. The results presented here could have implications for other substrates that present surface charges and for the assumption that the kinetics of Cu-mediated SI-CRP are analogous to those conducted in solution.

  13. Free Radical Addition Polymerization Kinetics without Steady-State Approximations: A Numerical Analysis for the Polymer, Physical, or Advanced Organic Chemistry Course

    Science.gov (United States)

    Iler, H. Darrell; Brown, Amber; Landis, Amanda; Schimke, Greg; Peters, George

    2014-01-01

    A numerical analysis of the free radical addition polymerization system is described that provides those teaching polymer, physical, or advanced organic chemistry courses the opportunity to introduce students to numerical methods in the context of a simple but mathematically stiff chemical kinetic system. Numerical analysis can lead students to an…

  14. Acrylamide-b-N-isopropylacrylamide block copolymers : Synthesis by atomic transfer radical polymerization in water and the effect of the hydrophilic-hydrophobic ratio on the solution properties

    NARCIS (Netherlands)

    Wever, Diego Armando Z.; Ramalho, Graham; Picchioni, Francesco; Broekhuis, Antonius Augustinus

    2014-01-01

    A series of block copolymers of acrylamide and N-isopropylacrylamide (NIPAM) characterized by different ratios between the length of the two blocks have been prepared through atomic transfer radical polymerization in water at room temperature. The solution properties of the block copolymers were cor

  15. Magnetic iron oxide nanoparticles as long wavelength photoinitiators for free radical polymerization

    OpenAIRE

    2015-01-01

    Polymer Chemistry COMMUNICATION Cite this: Polym. Chem., 2015, 6, 1918 Received 1st December 2014, Accepted 7th January 2015 DOI: 10.1039/c4py01658k www.rsc.org/polymers Magnetic iron oxide nanoparticles as long wavelength photoinitiators for free radical polymerization† Sajjad Dadashi-Silab,a Yasemin Yar,b Havva Yagci Acarb and Yusuf Yagci*a,c Iron oxide nanoparticles (Fe3O4 NPs) capped with lauric acid agents were synthesized and their photocatalyti...

  16. Key role of intramolecular metal chelation and hydrogen bonding in the cobalt-mediated radical polymerization of N-vinyl amides.

    Science.gov (United States)

    Debuigne, Antoine; Morin, Aurélie N; Kermagoret, Anthony; Piette, Yasmine; Detrembleur, Christophe; Jérôme, Christine; Poli, Rinaldo

    2012-10-01

    This work reveals the preponderance of an intramolecular metal chelation phenomenon in a controlled radical polymerization system involving the reversible trapping of the radical chains by a cobalt complex bis(acetylacetonato)cobalt(II). The cobalt-mediated radical polymerization (CMRP) of a series of N-vinyl amides was considered with the aim of studying the effect of the cobalt chelation by the amide moiety of the last monomer unit of the chain. The latter reinforces the cobalt-polymer bond in the order N-vinylpyrrolidonepolymerizations observed for the last two monomers. Such a double linkage between the controlling agent and the polymer, through a covalent bond and a dative bond, is unique in the field of controlled radical polymerization and represents a powerful opportunity to fine tune the equilibrium between latent and free radicals. Possible hydrogen bond formation is also taken into account in the case of N-vinyl acetamide and N-vinyl formamide. These results are essential for understanding the factors influencing Co-C bond strength in general, and the CMRP mechanism in particular, but also for developing a powerful platform for the synthesis of new precision poly(N-vinyl amide) materials, which are an important class of polymers that sustain numerous applications today.

  17. Facile "living" radical polymerization of methyl methacrylate in the presence of iniferter agents: homogeneous and highly efficient catalysis from copper(II) acetate.

    Science.gov (United States)

    Jiang, Hongjuan; Zhang, Lifen; Jiang, Xiaowu; Bao, Xiaoguang; Cheng, Zhenping; Zhu, Xiulin

    2014-08-01

    A facile homogeneous polymerization system involving the iniferter agent 1-cyano-1-methylethyl diethyldithiocarbamate (MANDC) and copper(II) acetate (Cu(OAc)2 ) is successfully developed in bulk using methyl methacylate (MMA) as a model monomer. The detailed polymerization kinetics with different molar ratios (e.g., [MMA]0 /[MANDC]0 /[Cu(OAc)2 ]0 = 500/1/x (x = 0.1, 0.2, 0.5, 1.0)) demonstrate that this system has the typical "living"/controlled features of "living" radical polymerization, even with ppm level catalyst Cu(OAc)2 , first order polymerization kinetics, a linear increase in molecular weight with monomer conversion and narrow molecular weight distributions for the resultant PMMA. (1) H NMR spectra and chain-extension experiments further confirm the "living" characteristics of this process. A plausible mechanism is discussed.

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

    Science.gov (United States)

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

    2006-11-01

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

  19. NMR, ESI/MS, and MALDI-TOF/MS analysis of pear juice polymeric proanthocyanidins with potent free radical scavenging activity.

    Science.gov (United States)

    Es-Safi, Nour-Eddine; Guyot, Sylvain; Ducrot, Paul-Henri

    2006-09-20

    The structure of a polymeric proanthocyanidin fraction isolated from pear juice was characterized by NMR, ESI/MS, and MALDI-TOF/MS analyses, and its antioxidant activity was investigated using the DPPH free radical scavenging method. The results obtained from 13C NMR analysis showed the predominance of signals representative of procyanidins. Typical signals in the chemical shift region between 70 and 90 ppm demonstrated the exclusive presence of epicatechin units. The results obtained through negative ESI/MS analysis showed singly and doubly charged ions corresponding to the molecular mass of procyanidins with a degree of polymerization up to 22. The spectra obtained through MALDI-TOF/MS analysis revealed the presence of two series of tannin oligomers. Supporting the observations from NMR spectroscopy, the first series consists of well-resolved tannin identified as procyanidin polymers units with chain lengths of up to 25. A second series of monogalloyl flavan-3-ols polymers with polymerization degree up to 25 were also detected. This is the first mass spectrometric evidence confirming the existence of galloylated procyanidin oligomers in pear fruits. Within each of these oligomers, various signals exist suggesting the presence of several oligomeric tannins. The antioxidant properties of the polymeric fraction were investigated through reduction of the DPPH free radical, and the results obtained showed that the polymeric fraction exhibited a higher antioxidant power compared to those of (+)-catechin and B3 procyanidin dimer.

  20. Micropatterned Surfaces for Atmospheric Water Condensation via Controlled Radical Polymerization and Thin Film Dewetting.

    Science.gov (United States)

    Wong, Ian; Teo, Guo Hui; Neto, Chiara; Thickett, Stuart C

    2015-09-30

    Inspired by an example found in nature, the design of patterned surfaces with chemical and topographical contrast for the collection of water from the atmosphere has been of intense interest in recent years. Herein we report the synthesis of such materials via a combination of macromolecular design and polymer thin film dewetting to yield surfaces consisting of raised hydrophilic bumps on a hydrophobic background. RAFT polymerization was used to synthesize poly(2-hydroxypropyl methacrylate) (PHPMA) of targeted molecular weight and low dispersity; spin-coating of PHPMA onto polystyrene films produced stable polymer bilayers under appropriate conditions. Thermal annealing of these bilayers above the glass transition temperature of the PHPMA layer led to complete dewetting of the top layer and the formation of isolated PHPMA domains atop the PS film. Due to the vastly different rates of water nucleation on the two phases, preferential dropwise nucleation of water occurred on the PHPMA domains, as demonstrated by optical microscopy. The simplicity of the preparation method and ability to target polymers of specific molecular weight demonstrate the value of these materials with respect to large-scale water collection devices or other materials science applications where patterning is required.

  1. 新引发体系引发MMA活性自由基聚合%Living Radical Polymerization of Methyl Methacrylate with a New Initiation System

    Institute of Scientific and Technical Information of China (English)

    秦东奇; 钦曙辉; 丘坤元

    2001-01-01

    Living radical polymerization of methyl methacrylate was investigated using a new initiation system, i. e. DCDPS/Fe(DC)3, in which diethyl 2,3-dicyano-2,3-diphenyl-succinate(DCDPS) is a hexa-substituted ethane thermal iniferter and ferric tri(diethyldithiocarbamate)(Fe(DC)3) is a ligand-free catalyst. The polymerization was successfully controlled in bulk at 95 ℃, PMMA with high molecular weight and quite narrow polydispersities(Mw/Mn=1.20~1.29) were obtained. End group analysis by 1H NMR spectroscopy shows that the resulting PMMA is ω-functionalized by a DC group.

  2. Curing theory of A_f-A_g type free radical polymerization (Ⅲ)——The evaluation of network defects

    Institute of Scientific and Technical Information of China (English)

    王海军; 巴信武; 赵敏; 李泽生

    2000-01-01

    Evaluation of defects in the polymer network is important to characterize the polymer materials, in which there always exist the defects that affect the physical and chemical properties of polymer network. Taking Af-Ag type nonlinear free radical polymerization as an example, one type of defects called dangling loops in the gel network is investigated by means of the statistical theory of polymeric reactions. The number of dangling loops and the probability of its formation are obtained by analyzing the polymer network structure in detail.

  3. Radical graft polymerization of an allyl monomer onto hydrophilic polymers and their antibacterial nanofibrous membranes.

    Science.gov (United States)

    Wang, Dong; Xu, Weilin; Sun, Gang; Chiou, Bor-Sen

    2011-08-01

    Hydrophilic poly (vinyl alcohol-co-ethylene) (PVA-co-PE) copolymers with 27 mol %, 32 mol % and 44 mol % ethylene were functionalized by melt radical graft copolymerization with 2,4-diamino-6-diallylamino-1,3,5-triazine (NDAM) using reactive extrusion. This functionalization imparts antibacterial properties. The covalent attachments of the NDAM as side chains onto the PVA-co-PE polymer backbones were confirmed. The effects of initiator concentrations and ethylene contents in PVA-co-PE polymers on grafting of NDAM were studied. The chain scissions of PVA-co-PE polymers during reactive extrusion were investigated by monitoring changes in the melt torque and FTIR spectra. The NDAM grafted PVA-co-PE polymers were successfully fabricated into hydrophilic nanofibers and nanofibrous membranes with sufficient surface exposure of the grafted NDAM. The hydrophilicity of the PVA-co-PE polymers and the large specific surface area offered by the nanofiber membranes significantly facilitated the chlorine activation process, enhanced the active chlorine contents of the grafted PVA-co-PE nanofiber membranes, and therefore led to their superior antibacterial properties.

  4. Copper-mediated amidation of alkenylzirconocenes with acyl azides: formation of enamides.

    Science.gov (United States)

    Liu, Hailan; Zhou, Yiqing; Yan, Xiaoyu; Chen, Chao; Liu, Qingbin; Xi, Chanjuan

    2013-10-18

    Copper-mediated amidation of alkenylzirconocenes generated in situ from alkynes and zirconocenes with acyl azides is accomplished under mild conditions. The reaction can be used to prepare various enamides.

  5. Copper-mediated electrophilic imination of alkenylzirconocenes with O-benzoyl ketoximes and aldoximes.

    Science.gov (United States)

    Liu, Hailan; Yan, Xiaoyu; Chen, Chao; Liu, Qingbin; Xi, Chanjuan

    2013-06-18

    Copper-mediated electrophilic imination of alkenylzirconocenes generated in situ from alkynes and zirconocenes is accomplished under mild reaction conditions. The reaction can be used to prepare various 2-azadienes.

  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......). For selected systems, a conformational search was carried out for R-X and R by using semiempirical (PM3) and molecular mechanics (MM+ augmented with appropriately optimized parameters for the radical systems) methods. The MM+ technique is more suited to search for the most stable conformations. The computed...

  7. UV-Induced Radical Photo-Polymerization: A Smart Tool for Preparing Polymer Electrolyte Membranes for Energy Storage Devices

    Directory of Open Access Journals (Sweden)

    Claudio Gerbaldi

    2012-06-01

    Full Text Available In the present work, the preparation and characterization of quasi-solid polymer electrolyte membranes based on methacrylic monomers and oligomers, with the addition of organic plasticizers and lithium salt, are described. Noticeable improvements in the mechanical properties by reinforcement with natural cellulose hand-sheets or nanoscale microfibrillated cellulose fibers are also demonstrated. The ionic conductivity of the various prepared membranes is very high, with average values approaching 10-3 S cm-1 at ambient temperature. The electrochemical stability window is wide (anodic breakdown voltages > 4.5 V vs. Li in all the cases along with good cyclability in lithium cells at ambient temperature. The galvanostatic cycling tests are conducted by constructing laboratory-scale lithium cells using LiFePO4 as cathode and lithium metal as anode with the selected polymer electrolyte membrane as the electrolyte separator. The results obtained demonstrate that UV induced radical photo-polymerization is a well suited method for an easy and rapid preparation of easy tunable quasi-solid polymer electrolyte membranes for energy storage devices.

  8. Rational preparation of dibenzothiophene-imprinted polymers by surface imprinting technique combined with atom transfer radical polymerization

    Science.gov (United States)

    Yang, Wenming; Liu, Lukuan; Zhou, Zhiping; Liu, Hong; Xie, Binze; Xu, Wanzhen

    2013-10-01

    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.

  9. Grafting of thermoresponsive polymer from the surface of functionalized multiwalled carbon nanotubes via atom transfer radical polymerization

    Institute of Scientific and Technical Information of China (English)

    XU GuoYong; XIA Ru; WANG Hu; MENG XiangChun; ZHU QingRen

    2008-01-01

    Multiwalled carbon nanotubes were oxidized with concentrated HNOz and H2SO4 to introduce carboxylic groups onto carbon nanotubes surfaces. The oxidized carbon nanotubes were reacted subsequently with thionyl chloride and 2-Hydroxylethyl-2'-bromoisobutyrate, producing MWNT-based macroinitiators, MWNT-Br, for the atom transfer radical polymerization of (N-isopropylacrylamide). FTIR, XPS, 1H NMR, Raman and TGA were used to characterize the resulting products and to determine the content of the water-soluble poly (N-isopropylacrylamide) chains in the product. The MWNTs grafted with PNIPAM chains have good solubility in distilled water; THF and CHCl3. TEM images of the samples provide direct evidence for the formation of a nanostructure that MWNTs coated with polymer layer. The produced MWNT-g-PNIPAM has a PNIPAM shell, which is very sensitive to the change of temperature.This method would open a door for the fabrication of novel functional carbon nanotube-based nanomaterials or nanodevices with designable structure and tailor-made properties.

  10. Protein-resistant polyurethane via surface-initiated atom transfer radical polymerization of oligo(ethylene glycol) methacrylate.

    Science.gov (United States)

    Jin, Zhilin; Feng, Wei; Zhu, Shiping; Sheardown, Heather; Brash, John L

    2009-12-15

    Protein-resistant polyurethane (PU) surfaces were prepared by surface-initiated simultaneous normal and reverse atom transfer radical polymerization (s-ATRP) of poly(oligo(ethylene glycol) methacrylate) (poly (OEGMA)). Oxygen plasma treatment was employed for initial activation of the PU surface. The grafted polymer chain length was adjusted by varying the molar ratio of monomer to sacrificial initiator in solution from 5:1 to 200:1. The modified PU surfaces were characterized by water contact angle, X-ray photoelectron spectroscopy (XPS), and atomic force microscopy (AFM). Protein adsorption experiments from tris-buffered saline (TBS) and plasma were carried out to evaluate the protein-resistance of the surfaces. Adsorption from single and binary protein solutions as well as from plasma was significantly reduced after modification. Adsorption decreased with increasing poly(OEGMA) chain length. Fibrinogen (Fg) adsorption on the 200:1 monomer/initiator surface was in the range of 3-33 ng/cm(2) representing 96-99% reduction compared with the unmodified PU. Fg adsorption from 0.01-10% plasma was as low as 1-5 ng/cm(2). Moreover, binary protein adsorption experiments using Fg and lysozyme (Lys) showed that protein size is a factor in the protein resistance of these surfaces.

  11. 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.

  12. Thermoresponsive Melamine Sponges with Switchable Wettability by Interface-Initiated Atom Transfer Radical Polymerization for Oil/Water Separation.

    Science.gov (United States)

    Lei, Zhiwen; Zhang, Guangzhao; Deng, Yonghong; Wang, Chaoyang

    2017-03-15

    Here we have obtained a temperature responsive melamine sponge with a controllable wettability between superhydrophilicity and superhydrophobicity by grafting the octadecyltrichlorosilane and thermoresponsive poly(N-isopropylacrylamide) (PNIPAAm) onto the surface of melamine sponge skeletons. The whole process included the silanization in which step the rough surface with low surface energy and the NH2 were provided, and the atom transfer radical polymerization which ensured the successful grafting of PNIPAAm onto the skeleton's surface. The product exhibits a good reversible switch between superhydrophilicity and superhydrophobicity by changing the temperature below or above the lower critical solution temperature (LCST, about 32 °C) of PNIPAAm, and the modified sponge still retains a good responsiveness after undergoing two temperature switches for 20 cycles. Simultaneously, the functionalized sponges could be used to absorb the oil under water at 37 °C, and they released the absorbed oil in various ways under water at 20 °C, showing wide potential applications including oil/water separation.

  13. UV-Induced Radical Photo-Polymerization: A Smart Tool for Preparing Polymer Electrolyte Membranes for Energy Storage Devices

    Directory of Open Access Journals (Sweden)

    Claudio Gerbaldi

    2012-10-01

    Full Text Available In the present work, the preparation and characterization of quasi-solid polymer electrolyte membranes based on methacrylic monomers and oligomers, with the addition of organic plasticizers and lithium salt, are described. Noticeable improvements in the mechanical properties by reinforcement with natural cellulose hand-sheets or nanoscale microfibrillated cellulose fibers are also demonstrated. The ionic conductivity of the various prepared membranes is very high, with average values approaching 10-3 S cm-1 at ambient temperature. The electrochemical stability window is wide (anodic breakdown voltages > 4.5 V vs. Li in all the cases along with good cyclability in lithium cells at ambient temperature. The galvanostatic cycling tests are conducted by constructing laboratory-scale lithium cells using LiFePO4 as cathode and lithium metal as anode with the selected polymer electrolyte membrane as the electrolyte separator. The results obtained demonstrate that UV induced radical photo-polymerization is a well suited method for an easy and rapid preparation of easy tunable quasi-solid polymer electrolyte membranes for energy storage devices.

  14. 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.

  15. Joint theoretical experimental investigation of the electron spin resonance spectra of nitroxyl radicals: application to intermediates in in situ nitroxide mediated polymerization (in situ NMP) of vinyl monomers.

    Science.gov (United States)

    Zarycz, Natalia; Botek, Edith; Champagne, Benoît; Sciannaméa, Valérie; Jérôme, Christine; Detrembleur, Christophe

    2008-08-28

    Density functional theory (DFT) calculations have been performed to address the structure of nitroxide intermediates in controlled radical polymerization. In a preliminary step, the reliability of different theoretical methods has been substantiated by comparing calculated hyperfine coupling constants (HFCCs) to experimental data for a set of linear and cyclic alkylnitroxyl radicals. Considering this tested approach, the nature of different nitroxides has been predicted or confirmed for (a) the reaction of C-phenyl- N- tert-butylnitrone and AIBN, (b) N- tert-butyl-alpha-isopropylnitrone and benzoyl peroxide, (c) tert-butyl methacrylate polymerization in the presence of sodium nitrite as mediator, and (d) for the reaction of a nitroso compound with AIBN. Values of HFCC experimentally determined have been confirmed by DFT calculations.

  16. Facile Synthesis of Well-Defined MDMO-PPV Containing (TriBlock—Copolymers via Controlled Radical Polymerization and CuAAC Conjugation

    Directory of Open Access Journals (Sweden)

    Neomy Zaquen

    2015-02-01

    Full Text Available A systematic investigation into the chain transfer polymerization of the so-called radical precursor polymerization of poly(p-phenylene vinylene (PPV materials is presented. Polymerizations are characterized by systematic variation of chain transfer agent (CTA concentration and reaction temperature. For the chain transfer constant, a negative activation energy of −12.8 kJ·mol−1 was deduced. Good control over molecular weight is achieved for both the sulfinyl and the dithiocarbamate route (DTC. PPVs with molecular weights ranging from thousands to ten thousands g·mol−1 were obtained. To allow for a meaningful analysis of the CTA influence, Mark–Houwink–Kuhn–Sakurada (MHKS parameters were determined for conjugated MDMO-PPV ([2-methoxy-5-(3',7'-dimethyloctyloxy]-1,4-phenylenevinylene to α = 0.809 and k = 0.00002 mL·g−1. Further, high-endgroup fidelity of the CBr4-derived PPVs was proven via chain extension experiments. MDMO-PPV-Br was successfully used as macroinitiator in atom transfer radical polymerization (ATRP with acrylates and styrene. A more polar PPV counterpart was chain extended by an acrylate in single-electron transfer living radical polymerization (SET-LRP. In a last step, copper-catalyzed azide alkyne cycloaddition (CuAAC was used to synthesize block copolymer structures. Direct azidation followed by macromolecular conjugation showed only partial success, while the successive chain extension via ATRP followed by CuAAC afforded triblock copolymers of the poly(p-phenylene vinylene-block-poly(tert-butyl acrylate-block-poly(ethylene glycol (PPV-b-PtBuA-b-PEG.

  17. Curing theory of A_f-A_g type free radical polymerization (Ⅱ)——Characterization of network structural parameters

    Institute of Scientific and Technical Information of China (English)

    王海军; 吕中元; 黄旭日; 李泽生; 唐敖庆

    1999-01-01

    By means of the polymer statistical theory, the A_f-A_g type nonlinear free radical polymerization is investigated to give the number of effective elastic chains, the number of effective elastic mers and the average length for the elastic chains. The corresponding quantities for the dangling chains, the number of effective cross-linkage and the modulus are also obtained. Furthermore, the number- and weight-fractions of elastic chains are deduced.

  18. New Cobalt-Mediated Radical Polymerization (CMRP) of Methyl Methacrylate Initiated by Two Single-Component Dinuclear β-Diketone Cobalt (II) Catalysts

    Science.gov (United States)

    Bao, Feng; Feng, Lingling; Gao, Jie; Tan, Zhifang; Xing, Bin; Ma, Rui; Yan, Chunjie

    2010-01-01

    Two dinuclear cobalt complexes based on bis-diketonate ligands (ligand 1: 3,3′-(1,3-phenylene)bis(1-phenylpropane-1,3-dione); ligand 2: 3,3′-(1,4-phenylene)bis(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. PMID:21049027

  19. Hydroxy- and silyloxy-substituted TEMPO derivatives for the living free-radical polymerization of styrene and n-butyl acrylate: synthesis, kinetics, and mechanistic studies.

    Science.gov (United States)

    Knoop, Christoph Alexander; Studer, Armido

    2003-12-31

    The synthesis of new 2,2,6,6-tetramethylpiperidin-1-oxyl (TEMPO) styryl derivatives as mediators for the living free-radical polymerization is described. Two of the alpha-methyl groups at the 2- and 6-position of the parent TEMPO styryl alkoxyamine have been replaced by hydroxymethyl and silyloxymethyl groups. To further increase the steric hindrance around the alkoxyamine oxygen atom, the remaining two methyl groups have been substituted with larger ethyl groups. Styrene polymerizations using hydroxy-substituted TEMPO derivatives are fast, but are not well-controlled. As previously shown for other OH-substituted alkoxyamines, intramolecular H-bonding leads to an acceleration of the C-O bond homolysis and, hence, to an acceleration of the polymerization process. However, the OH groups also increase the alkoxyamine decomposition rate constant. The kinetics of the C-O bond homolysis have been determined using EPR spectroscopy. Decomposition studies have been conducted with the aid of 1H NMR spectroscopy. In contrast to the OH-substituted alkoxyamines, highly hindered silyloxy-substituted TEMPO alkoxyamines turned out to be excellent mediator/initiators for the controlled styrene polymerization. Polystyrene with M(n) of up to 80 000 g/mol and narrow polydispersities (PDI) has been prepared using the new alkoxyamines. Reactions have been conducted at 105 degrees C; however, even at 90 degrees C controlled but slow polymerizations can be achieved. Furthermore, and more importantly, poly(n-butyl acrylates) with narrow PDIs (acrylate polymerization can be conducted at temperatures as low as 90 degrees C. The silylated alkoxyamines presented belong to the most efficient initiator/mediators for the controlled acrylate polymerization known to date. The effect of the addition of free nitroxide on the acrylate polymerization is discussed. Moreover, the synthesis of diblock copolymers with narrow PDIs is described.

  20. Combination of electrografting and atom-transfer radical polymerization for making the stainless steel surface antibacterial and protein antiadhesive.

    Science.gov (United States)

    Ignatova, Milena; Voccia, Samuel; Gilbert, Bernard; Markova, Nadya; Cossement, Damien; Gouttebaron, Rachel; Jérôme, Robert; Jérôme, Christine

    2006-01-03

    A two-step "grafting from" method has been successfully carried out, which is based on the electrografting of polyacrylate chains containing an initiator for the atom transfer radical polymerization (ATRP) of 2-(tert-butylamino)ethyl methacrylate (TBAEMA) or copolymerization of TBAEMA with either monomethyl ether of poly(ethylene oxide) methacrylate (PEOMA) or acrylic acid (AA) or styrene. The chemisorption of this type of polymer brushes onto stainless steel surfaces has potential in orthopaedic surgery. These films have been characterized by ATR-FTIR, Raman spectroscopy, atomic force microscopy (AFM), and measurement of contact angles of water. The polymer formed in solution by ATRP and that one detached on purpose from the surface have been analyzed by size exclusion chromathography (SEC) and (1)H NMR spectroscopy. The strong adherence of the films onto stainless steel has been assessed by peeling tests. AFM analysis has shown that addition of hydrophilic comonomers to the grafted chains decreases the surface roughness. According to dynamic quartz crystal microbalance experiments, proteins (e.g., fibrinogen) are more effectively repelled whenever copolymer brushes contain neutral hydrophilic (PEOMA) co-units rather than negatively charged groups (PAA salt). Moreover, a 2- to 3-fold decrease in the fibrinogen adsorption is observed when TBAEMA is copolymerized with either PEOMA or AA rather than homopolymerized or copolymerized with styrene. Compared to the bare stainless steel surface, brushes of polyTBAEMA, poly(TBAEMA-co-PEOMA) and poly(TBAEMA-co-AA) decrease the bacteria adhesion by 3 to 4 orders of magnitude as revealed by Gram-positive bacteria S. aureus adhesion tests.

  1. Methyleneation of peptides by N,N,N,N-tetramethylethylenediamine (TEMED) under conditions used for free radical polymerization: a mechanistic study.

    Science.gov (United States)

    Shirangi, Mehrnoosh; Sastre Toraño, Javier; Sellergren, Börje; Hennink, Wim E; Somsen, Govert W; van Nostrum, Cornelus F

    2015-01-21

    Free radical polymerization is often used to prepare protein and peptide-loaded hydrogels for the design of controlled release systems and molecular imprinting materials. Peroxodisulfates (ammonium peroxodisulfates (APS) or potassium peroxodisulfates (KPS)) with N,N,N,N-tetramethylethylenediamine (TEMED) are frequently used as initiator and catalyst. However, exposure to these free radical polymerization reagents may lead to modification of the protein and peptide. In this work, we show the modification of lysine residues by ammonium peroxodisulfate (APS)/TEMED of the immunostimulant thymopentin (TP5). Parallel studies on a decapeptide and a library of 15 dipeptides were performed to reveal the mechanism of modification. LC-MS of APS/TEMED-exposed TP5 revealed a major reaction product with an increased mass (+12 Da) with respect to TP5. LC-MS(2) and LC-MS(3) were performed to obtain structural information on the modified peptide and localize the actual modification site. Interpretation of the obtained data demonstrates the formation of a methylene bridge between the lysine and arginine residue in the presence of TEMED, while replacing TEMED with a sodium bisulfite catalyst did not show this modification. Studies with the other peptides showed that the TEMED radical can induce methyleneation on peptides when lysine is next to arginine, proline, cysteine, aspargine, glutamine, histidine, tyrosine, tryptophan, and aspartic acid residues. Stability of peptides and protein needs to be considered when using APS/TEMED in in situ polymerization systems. The use of an alternative catalyst such as sodium bisulfite may preserve the chemical integrity of peptides during in situ polymerization.

  2. 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 TiO2/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 TiO2 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 TiO2 nanoparticles in the bulk hybrids was investigated. The surfaces of TiO2 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 TiO2 nanoparticles without aggregation of the nanoparticles in toluene. The molecular weights of the PMMA chains cleaved from the modified TiO2 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 TiO2 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 TiO2 nanoparticles during the in situ polymerization process. The refractive indices of the bulk hybrids could be controlled by adjusting the TiO2 content and could be increased up to 1.566 for 6.3 vol % TiO2 content (1.492 for pristine PMMA).

  3. Synthesis of Novel μ-Star Copolymers with Poly(N-Octyl Benzamide) and Poly(ε-Caprolactone) Miktoarms through Chain-Growth Condensation Polymerization, Styrenics-Assisted Atom Transfer Radical Coupling, and Ring-Opening Polymerization.

    Science.gov (United States)

    Huang, Chih-Feng; Aimi, Junko; Lai, Kuan-Yu

    2017-02-01

    Star copolymers are known to phase separate on the nanoscale, providing useful self-assembled morphologies. In this study, the authors investigate synthesis and assembly behavior of miktoarm star (μ-star) copolymers. The authors employ a new strategy for the synthesis of unprecedented μ-star copolymers presenting poly(N-octyl benzamide) (PBA) and poly(ε-caprolactone) (PCL) arms: a combination of chain-growth condensation polymerization, styrenics-assisted atom transfer radical coupling, and ring-opening polymerization. Gel permeation chromatography, mass-analyzed laser desorption/ionization mass spectrometry, and (1) H NMR spectroscopy reveal the successful synthesis of a well-defined (PBA11 )2 -(PCL15 )4 μ-star copolymer (Mn,NMR ≈ 12 620; Đ = 1.22). Preliminary examination of the PBA2 PCL4 μ-star copolymer reveals assembled nanofibers having a uniform diameter of ≈20 nm.

  4. Progress of the Non-free Radical Polymerizations in the Channel of Mesoporous Molecular Sieve%介孔材料孔道内进行的非自由基聚合反应研究进展

    Institute of Scientific and Technical Information of China (English)

    张发爱; 宋程; 余彩莉

    2011-01-01

    介孔材料在催化、吸附、分离等领域有潜在的应用价值.近来,研究人员将介孔材料的有序孔道作为聚合微反应器,在其内部进行了许多类型的聚合反应,如自由基聚合反应和非自由基聚合反应.本文综述了近二十年来在介孔材料孔道内各类单体进行的非自由基聚合反应,包括氧化聚合反应、配位聚合反应、缩合聚合反应、开环聚合反应和阳离子聚合反应,阐述了各种因素对聚合反应及其聚合产物性能的影响,初步探讨其应用领域,对其应用前景进行了展望.%Mesoporous materials are potentially used in catalysis, absorption and separation. Lately, researchers applied the order channel of the material as microreaetor for monomer polymerization. Many polymerizations were carried out within the channel, including free radical polymerization and non-free radical polymerization. The latest 20 year's progress of the non-free radical polymerizations in the channel of mesoporous molecular sieve was reviewed. These polymerizations included the oxidative polymerization, coordination polymerization, condensation polymerization, ring-opening polymerization and ionic polymerization. Some effects on the polymerization and polymer composite were discussed. The application fields of the obtained polymer/mesoporous composites were overlooked.

  5. 梯度引发自由基聚合体系(Ⅰ)——基原法合成超高分子量聚合物%Graduation Initiating Radical Polymerization(Ⅰ) ——Synthesis of Hyper-high Molecular Weight Polymers by Free Radical Sources

    Institute of Scientific and Technical Information of China (English)

    杨万泰; 刘涛; 尹梅贞

    2001-01-01

    There are presently two ways to realize “controlled/living radical polymerization”: one is by a reversible termination or reversible chain transfer to make active polymer chains continuously propagate; the other is by a physical method to suppress chain termination and to prolong radical lifetime. Here we report a new method called Graduation Initiating Radical Polymerization System for realizing “controlled/living radical polymerization”. Its principle and experimental setup are as follows: firstly, initiatable groups(i.e. peroxide groups) were introduced onto the polymer substrates like LDPE film by photo-oxidation reaction; secondly, the films carried peroxide groups were put and fixed to the bottom of polymerization bottle containing monomer and solvent. Afterwards, they were made to produce radicals(by heating or reductive agent), and finally the system polymerization was initiated. Once these radicals are produced on the surface of these films, they will undergo three different processes: terminating by combination, diffusing to monomer solution and taking in monomers(polymerizing). The reactive diffusion makes this system produce “two graduation”: one is the graduation of radical concentration(i.e. the farther away from the surface of the film, the lower radical concentration); the other is the length-graduation of living chains, \\{i.e.\\} the farther away from the surface of the film the longer the propagating chains. By this way, we could obtain a polymerization field where the radical concentration is very low and there are no primary free radicals approximately, which are benefit to realize “controlled/living radical polymerization”. This communication reports the first experimental results based on the above idea: with benzophenone(BP) as photo-catalyst and peroxide groups introduced on the LDPE surface in a concentration 10-8 mol/cm2; by these peroxided films as the sources of free radicals, polyacrylamide and polyacrylic acid were

  6. Localized surface plasmon resonance nanosensing of C-reactive protein with poly(2-methacryloyloxyethyl phosphorylcholine)-grafted gold nanoparticles prepared by surface-initiated atom transfer radical polymerization.

    Science.gov (United States)

    Kitayama, Yukiya; Takeuchi, Toshifumi

    2014-06-03

    Highly sensitive and selective protein nanosensing based on localized surface plasmon resonance (LSPR) of gold nanoparticles (AuNPs) on which polymerized specific ligands were grafted as an artificial protein recognition layer for the target protein were demonstrated. As a model, optical nanosensing for C-reactive protein (CRP), a known biomarker for chronic inflammation that predicts the risk of arteriosclerosis or heart attacks, was achieved by measuring the shift of LSPR spectra derived from the change of permittivity of poly(2-methacryloyloxyethyl phosphorylcholine)-grafted AuNPs (PMPC-g-AuNPs) upon interacting with CRP, in which the PMPC-g-AuNPs layer were grafted on AuNPs by surface-initiated atom transfer radical polymerization (ATRP). This nanosensing system was effective even for detecting CRP concentrations in a human serum solution diluted to 1% (w/w), at which point a limit of detection was ~50 ng/mL and nonspecific adsorption of other proteins was negligible. The nanosensing system using specific ligand-grafted AuNPs has several strengths, such as low preparation cost, avoiding the need for expensive instruments, no necessary complex pretreatments, and high stability, because it does not contain biobased molecules. We believe this novel synthetic route for protein nanosensors, composed of AuNPs and a polymerized specific ligand utilizing surface-initiated controlled/living radical polymerization, will provide a foundation for the design and synthesis of nanosensors targeting various other biomarker proteins, paving the way for future advances in the field of biosensing.

  7. DISPERSION PRODUCTION BY SEMI-CONTINUOUS RADICAL VINYL ACETATE EMULSION POLYMERIZATION WITH SILANE CO-MONOMER AND CHARACTERIZATION OF FINAL PRODUCTS

    Institute of Scientific and Technical Information of China (English)

    Mindaugas Dubininkas; Gintaras Buika

    2013-01-01

    Vinyl acetate radical emulsion polymerization in water with GF51 silane co-monomer was performed by semi continuous way.The GF51 impacts on dispersion rheology as well on films and bonding strength properties were determined.It should be stated that even low quantities of GF51 (up to 6% from VAc) determined high viscosity of dispersions.The GF51 modified films have low water absorption and high affinity to glass.Molecular mass and thermal properties of GF51 modified polymers were determined accordingly.

  8. Visible-light organic photocatalysis for latent radical-initiated polymerization via 2e⁻/1H⁺ transfers: initiation with parallels to photosynthesis.

    Science.gov (United States)

    Aguirre-Soto, Alan; Lim, Chern-Hooi; Hwang, Albert T; Musgrave, Charles B; Stansbury, Jeffrey W

    2014-05-21

    We report the latent production of free radicals from energy stored in a redox potential through a 2e(-)/1H(+) transfer process, analogous to energy harvesting in photosynthesis, using visible-light organic photoredox catalysis (photocatalysis) of methylene blue chromophore with a sacrificial sterically hindered amine reductant and an onium salt oxidant. This enables light-initiated free-radical polymerization to continue over extended time intervals (hours) in the dark after brief (seconds) low-intensity illumination and beyond the spatial reach of light by diffusion of the metastable leuco-methylene blue photoproduct. The present organic photoredox catalysis system functions via a 2e(-)/1H(+) shuttle mechanism, as opposed to the 1e(-) transfer process typical of organometallic-based and conventional organic multicomponent photoinitiator formulations. This prevents immediate formation of open-shell (radical) intermediates from the amine upon light absorption and enables the "storage" of light-energy without spontaneous initiation of the polymerization. Latent energy release and radical production are then controlled by the subsequent light-independent reaction (analogous to the Calvin cycle) between leuco-methylene blue and the onium salt oxidant that is responsible for regeneration of the organic methylene blue photocatalyst. This robust approach for photocatalysis-based energy harvesting and extended release in the dark enables temporally controlled redox initiation of polymer syntheses under low-intensity short exposure conditions and permits visible-light-mediated synthesis of polymers at least 1 order of magnitude thicker than achievable with conventional photoinitiated formulations and irradiation regimes.

  9. Visible-Light Organic Photocatalysis for Latent Radical-Initiated Polymerization via 2e–/1H+ Transfers: Initiation with Parallels to Photosynthesis

    Science.gov (United States)

    2015-01-01

    We report the latent production of free radicals from energy stored in a redox potential through a 2e–/1H+ transfer process, analogous to energy harvesting in photosynthesis, using visible-light organic photoredox catalysis (photocatalysis) of methylene blue chromophore with a sacrificial sterically hindered amine reductant and an onium salt oxidant. This enables light-initiated free-radical polymerization to continue over extended time intervals (hours) in the dark after brief (seconds) low-intensity illumination and beyond the spatial reach of light by diffusion of the metastable leuco-methylene blue photoproduct. The present organic photoredox catalysis system functions via a 2e–/1H+ shuttle mechanism, as opposed to the 1e– transfer process typical of organometallic-based and conventional organic multicomponent photoinitiator formulations. This prevents immediate formation of open-shell (radical) intermediates from the amine upon light absorption and enables the “storage” of light-energy without spontaneous initiation of the polymerization. Latent energy release and radical production are then controlled by the subsequent light-independent reaction (analogous to the Calvin cycle) between leuco-methylene blue and the onium salt oxidant that is responsible for regeneration of the organic methylene blue photocatalyst. This robust approach for photocatalysis-based energy harvesting and extended release in the dark enables temporally controlled redox initiation of polymer syntheses under low-intensity short exposure conditions and permits visible-light-mediated synthesis of polymers at least 1 order of magnitude thicker than achievable with conventional photoinitiated formulations and irradiation regimes. PMID:24786755

  10. Kinetic Modeling of Atom Transfer Radical Polymerization%原子转移自由基聚合的动力学模型化研究

    Institute of Scientific and Technical Information of China (English)

    周寅宁; 罗正鸿

    2013-01-01

    Atom transfer radical polymerization (ATRP) is one of the most extensively studied "living"/controlled radical polymerization (CRP) methods,not only owing to its simple,mild reaction conditions and broad applicability,but also it can be easily applied to produce polymeric materials with well-defined structure.In order to well understand and control the polymerization process,it is necessary to develop a comprehensive kinetic model for ATRP and coupling it with different reactor models,which can be useful for researchers to control over chain microstructure with predetermined molecular weight and narrow polydispersity,as well as copolymer composition and its composition distribution,and also optimize the polymerization conditions.This review illustrates the establishment of the appropriate ATRP kinetic model based on the theory of conventional free radical polymerization.Moreover,it also makes a comparison of the mechanism between "living"/controlled and conventional free radical polymerization examples in order to reveal the similarities and differences of the two methods within this field.In addition,we detail the research work concerning the kinetic modeling of ATRP,and more attention has been paid to analyze and summarize on the kinetic models from the point of different mathematical processing methods (method of moment,Monte Carlo simulation,and commercial software-PREDICI,GEPASI etc.).%原子转移自由基聚合(ATRP)是“活性”/可控自由基聚合方法中研究最为广泛的一种,它不仅适用单体广泛、反应条件温和,而且可以方便地对聚合物进行结构设计.为了能够更深入地了解和控制聚合过程,通过ATRP动力学模型化并耦合不同操作方式下的反应器模型已成为必然,它可以更精确地控制大分子链结构,如分子量及其分布、共聚组成及组成分布,同时还能优化聚合条件.从传统自由基聚合理论入手并结合ATRP与传统 自由基聚合的异同,本文首先论

  11. Enlightening the Mechanism of Copper Mediated PhotoRDRP via High-Resolution Mass Spectrometry.

    Science.gov (United States)

    Frick, Elena; Anastasaki, Athina; Haddleton, David M; Barner-Kowollik, Christopher

    2015-06-03

    The initiation mechanism of photochemically mediated Cu-based reversible-deactivation radical polymerization (photoRDRP) was investigated using pulsed-laser polymerization (PLP) and high-resolution mass spectrometry. The variation of the catalyst composition and ESI-MS analysis of the resulting products provided information on how initiator, ligand, copper species, and monomer are interacting upon irradiation with UV light. A discussion of the results allows for a new postulation of the mechanism of photoRDRP and-for the first time-the unambiguous identification of the initiating species and their interactions within the reaction mixture. One pathway for radical generation proceeds via UV light-induced C-Br bond scission of the initiator, giving rise to propagating radicals. The generation of copper(I) species from copper(II) can occur via several pathways, including, among others, via reduction by free amine ligand in its excited as well as from its ground state via the irradiation with UV light. The amine ligand serves as a strong reducing agent and is likely the main participant in the generation of copper(I) species.

  12. Copper-mediated pyrazole synthesis from 2,3-allenoates or 2-alkynoates, amines and nitriles.

    Science.gov (United States)

    Chen, Bo; Zhu, Can; Tang, Yang; Ma, Shengming

    2014-07-21

    An efficient copper-mediated three-component reaction of 2,3-allenoates or 2-alkynoates, amines, and nitriles affording fully substituted pyrazoles with a very nice diversity has been developed. A tandem conjugate addition, 1,2-addition, and N-N bond formation mechanism has been proposed for this diverse synthesis of pyrazoles based on mechanistic studies.

  13. Well-defined polyethylene-based graft terpolymers by combining nitroxide-mediated radical polymerization, polyhomologation and azide/alkyne “click” chemistry†

    KAUST Repository

    Alkayal, Nazeeha

    2016-03-30

    Novel well–defined polyethylene–based graft terpolymers were synthesized via the “grafting onto” strategy by combining nitroxide-mediated radical polymerization (NMP), polyhomologation and copper (I)-catalyzed azide-alkyne cycloaddition (CuAAC) “click” chemistry. Three steps were involved in this approach: (i) synthesis of alkyne-terminated polyethylene-b-poly(ε-caprolactone) (PE-b-PCL-alkyne) block copolymers (branches) by esterification of PE-b-PCL-OH with 4-pentynoic acid; the PE-b-PCL-OH was obtained by polyhomologation of dimethylsulfoxonium methylide to afford PE-OH, followed by ring opening polymerization of ε-caprolactone using the PE-OH as macroinitiator, (ii) synthesis of random copolymers of styrene (St) and 4-chloromethylstyrene (4-CMS) with various CMS contents, by nitroxide-mediated radical copolymerization (NMP), and conversion of chloride to azide groups by reaction with sodium azide (NaN3) (backbone) and (iii) “click” linking reaction to afford the PE-based graft terpolymers. All intermediates and final products were characterized by high-temperature size exclusion chromatography (HT-SEC), Fourier transform infrared spectroscopy (FTIR), proton nuclear magnetic resonance spectroscopy (1H NMR) and differential scanning calorimetry (DSC).

  14. Synthesis and characterization of TiO{sub 2}/Ag/polymer ternary nanoparticles via surface-initiated atom transfer radical polymerization

    Energy Technology Data Exchange (ETDEWEB)

    Park, Jung Tae; Koh, Joo Hwan; Seo, Jin Ah [Department of Chemical and Biomolecular Engineering, Yonsei University, 262 Seongsanno, Seodaemun-gu, Seoul 120-749 (Korea, Republic of); Cho, Yong Soo [Department of Materials Science and Engineering, Yonsei University, 262 Seongsanno, Seodaemun-gu, Seoul 120-749 (Korea, Republic of); Kim, Jong Hak, E-mail: jonghak@yonsei.ac.kr [Department of Chemical and Biomolecular Engineering, Yonsei University, 262 Seongsanno, Seodaemun-gu, Seoul 120-749 (Korea, Republic of)

    2011-08-01

    We report on the novel ternary hybrid materials consisting of semiconductor (TiO{sub 2}), metal (Ag) and polymer (poly(oxyethylene methacrylate) (POEM)). First, a hydrophilic polymer, i.e. POEM, was grafted from TiO{sub 2} nanoparticles via the surface-initiated atom transfer radical polymerization (ATRP) technique. These TiO{sub 2}-POEM brush nanoparticles were used to template the formation of Ag nanoparticles by introduction of a AgCF{sub 3}SO{sub 3} precursor and a NaBH{sub 4} aqueous solution for reduction process. Successful grafting of polymeric chains from the surface of TiO{sub 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.

  15. 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.

  16. Extra Copper-mediated Enhancement of the DNA Cleavage Activity Supported with Wild-type Cu, Zn Superoxide Dismutase

    Institute of Scientific and Technical Information of China (English)

    ZHOU Ruo-Yu; JIANG Wei; ZHANG Li-Na; WANG Li; LIU Chang-Lin

    2008-01-01

    It is well known that the primary function of wild type Cu, Zn superoxide dismutase (holo SOD) is to catalyze the conversion of the superoxide anion to H2O2 and O2 as an antioxidant enzyme. However, the aberrant copper-mediated oxidation chemistry in the enzyme (including its mutation forms) that damages nucleic acids, proteins including itself and cell membrane has attracted extensive attention in the past decade. The present study examined the hydrogen peroxide-dependent DNA cleavage activity supported with the combinations between holo SOD and extra copper (holo SOD+nCu(Ⅱ)). The results indicate that the presence of extra copper can enhance the DNA cleavage activity and a cooperative effect between holo SOD and the extra Cu(Ⅱ) occurs in DNA cleavage. The relative activity and kinetic assay showed that the DNA cleavage activity of holo SOD+nCu(Ⅱ) was enhanced upon addition of extra Cu(Ⅱ). The favorable pH regions for the DNA cleavage were observed to be 3.6-5.6 and 9.0-10, suggesting the species responsible for the DNA cleavage are different in different pH regions. In addition,to obtain an insight into DNA cleavage pathways, the effect of free radical scavengers and inhibitors on the DNA cleavage activity was probed.

  17. Radical routes to interstellar glycolaldehyde. The possibility of stereoselectivity in gas-phase polymerization reactions involving CH(2)O and ˙CH(2)OH.

    Science.gov (United States)

    Wang, Tianfang; Bowie, John H

    2010-10-21

    A previous report that the interstellar molecule glycolaldehyde (HOCH(2)CHO) can be made from hydroxymethylene (HOCH:) and formaldehyde has been revisited at the CCSD(T)/6-311++G(3df,2p)//MP2/6-311++G(3df,2p) level of theory. This reaction competes with the formation of acetic acid and methylformate, molecules which have also been detected in interstellar clouds. Other possible modes of formation of glycolaldehyde by radical/radical reactions have been shown to be viable theoretically as follows: HO˙+˙CH2CHO -->HOCH2CHO [ΔG(Γ)(298K)=-303kJ mol⁻¹] HOCH2˙+˙CHO-->HOCH2CHO (-259kJ mol⁻¹). The species in these two processes are known interstellar molecules. Key radicals ˙CH(2)CHO and ˙CH(2)OH in these sequences have been shown to be stable for the microsecond duration of neutralization/reionization experiments in the dual collision cells of a VG ZAB 2HF mass spectrometer. The polymerization reaction HOCH(2)CH˙OH + nCH(2)O → HOCH(2)[CH(OH)](n)˙CHOH (n = 1 to 3) has been studied theoretically and shown to be energetically feasible, as is the cyclization reaction of HOCH(2)[(CH(2)OH)(4)]˙CHOH (in the presence of one molecule of water at the reacting centre) to form glucose. The probability of such a reaction sequence is small even if polymerization were to occur in interstellar ice containing a significant concentration of CH(2)O. The large number of stereoisomers produced by such a reaction sequence makes the formation of a particular sugar, again for example glucose, an inefficient synthesis. The possibility of stereoselectivity occurring during the polymerization was investigated for two diastereoisomers of HOCH(2)[(CHOH)](2)˙CHOH. No significant difference was found in the transition state energies for addition of CH(2)O to these two diastereoisomers, but a barrier difference of 12 kJ mol(-1) was found for the H transfer reactions ˙OCH(2)[(CHOH)](2)CH(2)OH → HOCH(2)[(CHOH)(2)˙CHOH of the two diastereoisomers.

  18. Two-cationic 2-methylbenzothiazole derivatives as green light absorbed sensitizers in initiation of free radical polymerization

    OpenAIRE

    2015-01-01

    N-Methylpyridinium esters derivatives of 2-methylbenzothiazole hemicyanine dyes photoinitiators/photosensitizers derived from N-propyl-3-[N-2-methylbenzothiazolo]-4-pyridyno phenylacetic acid ester diiodide and N-propyl-3-[N-2-me]thylbenzothiazolo]-4-pyridino diphenylacetic acid ester diiodide were synthesized and proposed as new photoinitiators of polymerization of 2-ethyl-(2-hydroxymethyl)-1,3-propanediol triacrylate under argon laser exposure at 514 nm. These compounds exhibit a strong abs...

  19. Polymer@MOF@MOF: "grafting from" atom transfer radical polymerization for the synthesis of hybrid porous solids.

    Science.gov (United States)

    McDonald, Kyle A; Feldblyum, Jeremy I; Koh, Kyoungmoo; Wong-Foy, Antek G; Matzger, Adam J

    2015-08-04

    The application of a core-shell architecture allows the formation of a polymer-coated metal-organic framework (MOF) maintaining high surface area (2289-2857 m(2) g(-1)). The growth of a MOF shell from a MOF core was used to spatially localize initiators by post-synthetic modification. The confinement of initiators ensures that polymerization is restricted to the outer shell of the MOF.

  20. Synthesis of biomimetic poly[2-(methacryloyloxy)ethyl phosphorycholine]-coated magnetite nanoparticles via surface-initiated atom transfer radical polymerization.

    Science.gov (United States)

    Sui, Jie-He; Cao, Chang-Yan; Cai, Wei

    2011-10-01

    Modification of magnetite nanoparticles with biomimetic poly[2-(methacryloyloxy)ethyl phosphorycholine] (poly(MPC)) via surface-initiated atom transfer radical polymerization (ATRP) was carried out. Fourier transform infrared (FT-IR) spectroscopy, thermogravimetric analyses (TGA) and zeta potential studies indicated that well defined poly (MPC) was successfully grafted on the surface of magnetite nanoparticles. X-ray diffraction results showed the structure of magnetite nanoparticles after surface modification was not changed. The poly (MPC)-coated magnetite nanoparticles had a mean transmission electron microscopy (TEM) diameter of 11 +/- 1.5 nm. The resulting nanomaterials were superparamagnetic at room temperature, exhibited good colloidal stability in aqueous media and good responsibility to magnetic field. Such magnetite nanoparticles with biomimetic surface have potential application in prolonging circulation time in vivo.

  1. SYNTHESIS OF BLOCK COPOLYMER FROM 5,6-BENZO-2-METHYLENE-1,3-DIOXEPANE AND METHYL ACRYLATE VIA ATOM TRANSFER RADICAL POLYMERIZATION

    Institute of Scientific and Technical Information of China (English)

    Jin-ying Yuan; Cai-yuan Pan

    2002-01-01

    Poly(methyl acrylate)-b-poly(5,6-benzo-2-methylene-1,3-dioxepane) (PMA-b-PBMDO) was synthesized by twostep atom transfer radical polymerization (ATRP). Firstly, ATRP of methyl acrylate (MA) was realized using ethyl α-bromobutyrate (EBrB) as initiator in the presence of CuBr/2,2'-bipyridine. After isolation, poly(methyl acrylate) with terminal bromine (PMA-Br) was synthesized. Secondly, the resulting PMA-Br was used as a macromolecular initiator in the ATRP of BMDO. The structure of block copolymer was characterized by 1H-NMR spectroscopy. Molecular weight and molecular weight distribution were determined on a gel permeation chromatograph (GPC).

  2. Preparation of Mg(OH)2 hybrid pigment by direct precipitation and graft onto cellulose fiber via surface-initiated atom transfer radical polymerization

    Science.gov (United States)

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

    2016-02-01

    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.

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

    Science.gov (United States)

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

    2017-02-01

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

  4. Synthesis and characterization of TiO2/poly(methyl methacrylate) nanocomposites via surface thiol-lactam initiated radical polymerization.

    Science.gov (United States)

    Bach, Long Giang; Islam, M Rafiqul; Gal, Yeong Soon; Lim, Kwon Taek

    2012-07-01

    An approach to the surface modification of TiO2 nanoparticles was described based on the thiol functionalization of TiO2 followed by thiol-lactam initiated radical polymerization (TLIRP) of methyl methacrylate (MMA). FT-IR, XRD and XPS analyses confirmed the grafting of the polymer on the TiO2 surface. TGA analysis revealed superior thermal stability of PMMA-g-TiO2 compared with PMMA. TEM measurements and time-dependent phase monitoring suggested much higher colloidal stability of PMMA-g-TiO2 than TiO2 in toluene. The controlled nature of the TLIRP of MMA from the surface of TiO2 was determined by GPC analysis.

  5. 自由基聚合反应的新介质--离子液体的新应用%The Novel Applications of Ionic Liquids Used as Radical Polymerization Media

    Institute of Scientific and Technical Information of China (English)

    游倩倩; 张普玉; 张怀敏

    2012-01-01

      离子液体具有独特的理化性能,作为一种环境友好、“可设计性”的溶剂,近年来成为化学领域的热点和前沿。离子液体作为自由基聚合反应的溶剂,对聚合速率、聚合产物结构及性能都有一定的影响。离子液体已经被较为广泛地应用于不同介质、不同物相中的自由基聚合反应,但是并不完全。近两年来已有研究工作者将离子液体应用于微乳液和气相中的自由基聚合反应,并和其他有机溶剂及水溶液共同调控自由基聚合反应。离子液体也首次应用于有机碲调控的自由基聚合反应和氮氧稳定的自由基聚合反应。同时离子液体也可以调控自由基聚合反应后聚合物的结构和形貌,是一种很好的进行聚合物自组装的溶剂。本文主要综述了近年来离子液体对自由基聚合反应的影响,特别是对聚合产物结构及性能的影响,最后展望了离子液体在聚合反应中的应用前景。%  With many unique physical and chemical characteristics, ionic liquids are the novel green and“designable” solvents, and they have become the frontier of chemistry research in recent years. Ionic liquids have an effect on the polymerization rate, the structure and properties of polymerization products as the solvents of radical polymerization. Ionic liquids have been somewhat widely used in the different media, different physical phases of radical polymerization. But there are other media and physical phases, in which ionic liquids have not been used. In the past two years, some researchers have firstly used ionic liquids in the microemulsion radical polymerization and gas phase radical polymerization, and then to control the radical polymerization with other organic solvents and aqueous solutions in common. Ionic liquids have also been used in the Organotellurium-Mediated living radical polymerization (TERP) and Nitroxide-Mediated controlled/living radical

  6. The Novel Applications of Ionic Liquids Used as Radical Polymerization Media%自由基聚合反应的新介质——离子液体的新应用

    Institute of Scientific and Technical Information of China (English)

    游倩倩; 张普玉; 张怀敏

    2012-01-01

    离子液体具有独特的理化性能,作为一种环境友好、"可设计性"的溶剂,近年来成为化学领域的热点和前沿。离子液体作为自由基聚合反应的溶剂,对聚合速率、聚合产物结构及性能都有一定的影响。离子液体已经被较为广泛地应用于不同介质、不同物相中的自由基聚合反应,但是并不完全。近两年来已有研究工作者将离子液体应用于微乳液和气相中的自由基聚合反应,并和其他有机溶剂及水溶液共同调控自由基聚合反应。离子液体也首次应用于有机碲调控的自由基聚合反应和氮氧稳定的自由基聚合反应。同时离子液体也可以调控自由基聚合反应后聚合物的结构和形貌,是一种很好的进行聚合物自组装的溶剂。本文主要综述了近年来离子液体对自由基聚合反应的影响,特别是对聚合产物结构及性能的影响,最后展望了离子液体在聚合反应中的应用前景。%With many unique physical and chemical characteristics,ionic liquids are the novel green and "designable" solvents,and they have become the frontier of chemistry research in recent years.Ionic liquids have an effect on the polymerization rate,the structure and properties of polymerization products as the solvents of radical polymerization.Ionic liquids have been somewhat widely used in the different media,different physical phases of radical polymerization.But there are other media and physical phases,in which ionic liquids have not been used.In the past two years,some researchers have firstly used ionic liquids in the microemulsion radical polymerization and gas phase radical polymerization,and then to control the radical polymerization with other organic solvents and aqueous solutions in common.Ionic liquids have also been used in the Organotellurium-Mediated living radical polymerization(TERP) and Nitroxide-Mediated controlled/living radical copolymerization(NMP) firstly

  7. Encapsulation of Fe 3O 4 magnetic nanoparticles with poly(methyl methacrylate) via surface functionalized thiol-lactam initiated radical polymerization

    Science.gov (United States)

    Bach, Long Giang; Islam, Md. Rafiqul; Kim, Jong Tae; Seo, SungYong; Lim, Kwon Taek

    2012-01-01

    Poly(methyl methacrylate) (PMMA) was grafted onto Fe3O4 magnetic nanoparticles (MNPs) by using a thiol-lactam initiated radical polymerization (TLIRP) via grafting from approach. The surface of the MNPs was treated with the (3-mercaptopropyl)trimethoxysilane coupling agent to give thiol functionalized MNPs (MNPs-SH). Subsequently, the polymerization of MMA performed in the presence of the MNPs-SH and butyrolactam efficiently afforded PMMA-g-MNPs. The grafting of PMMA on the surface of the MNPs was investigated by FT-IR, 1H NMR, TGA, XPS, and EDX analyses. The morphology of the core/shell type PMMA-g-MNPs was confirmed by HR-TEM. GPC analysis showed that the molecular weight of PMMA and monomer conversion increased with the reaction time. The amount of the grafted polymer on the surface of the MNPs was found to be ca. 82.5% as estimated from TGA analysis. The MNPs and PMMA-g-MNPs were subjected to magnetic property investigation by SQUID, and the PMMA-g-MNPs showed relatively high saturated magnetization (53.3 emu/g) without any remanence or coercivity, which made the nanocomposites easily separable from solid-liquid phases suggesting their superparamagnetic character. The magnetic nanocomposites had an exceptionally good dispersibility in organic solvents as demonstrated by UV-Vis spectroscopy as well as time-dependent digital photographic monitoring.

  8. Surface grafting of Eu(3+) doped luminescent hydroxyapatite nanomaterials through metal free light initiated atom transfer radical polymerization for theranostic applications.

    Science.gov (United States)

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

    2017-08-01

    We reported a simple and efficient method to prepare the hydrophilic luminescent HAp polymer nanocomposites through the combination of ligand exchange and metal free light initiated surface-initiated atom transfer radical polymerization (SI-ATRP) using 10-phenylphenothiazine (PTH) as organic catalyst and 2-methacryloyloxyethyl phosphorylcholine (MPC) and itaconic acid (IA) as monomers. The biological imaging and drug delivery performance of HAp-poly(MPC-IA) nanorods were examined to evaluate their potential for biomedical applications. Results suggested that hydrophilic HAp-poly(MPC-IA) nanorods can be successfully prepared. More importantly, the HAp-poly(MPC-IA) exhibited excellent water dispersibility, desirable biocompatibility and good performance for biological imaging and controlled drug delivery applications. As compared with other controlled living polymerization reactions, the metal free light initiated SI-ATRP displayed many advantages such as easy for handle, mild reaction conditions, toxicity and fluorescence quenching from metal catalysts. Therefore, we believe that this strategy should be a useful and effective strategy for preparation of HAp nanomaterials for biomedical applications. Copyright © 2017 Elsevier B.V. All rights reserved.

  9. Synthesis of poly(poly(ethylene glycol) methacrylate)-polyisobutylene ABA block copolymers by the combination of quasiliving carbocationic and atom transfer radical polymerizations.

    Science.gov (United States)

    Szabó, Ákos; Szarka, Györgyi; Iván, Béla

    2015-01-01

    Systematic investigations are carried out on the synthesis of a series of new, unique ABA-type triblock copolymers consisting of the hydrophobic and chemically inert polyisobutylene (PIB) inner and the hydrophilic comb-shaped poly(poly(ethylene glycol) methacrylate) (PPEGMA) polymacromonomer as an outer block. Telechelic PIB macroinitiators with narrow molecular weight distributions (MWD) are synthesized by quasiliving carbocationic polymerization of isobutylene with a bifunctional initiator followed by quantitative chain end derivatizations. Atom transfer radical polymerization (ATRP) of PEGMAs with various molecular weights is investigated by using these macroinitiators. It is found that CuBr is an inefficient ATRP catalyst, while CuCl leads to high, nearly complete conversions of the PEGMA macromonomers. Gel permeation chromatography (GPC) analyses reveal slow initiation of PEGMA at relatively high PIB/PEGMA ratios or with PEGMAs of higher molecular weights due to steric hindrance between the macroinitiator and macromonomer. The occurrence of slow initiation, and not permanent termination, is proven by highly efficient ATRP of a low-molecular-weight monomer, methyl methacrylate, with the block copolymers as macroinitiators. Successful synthesis of PPEGMA-PIB-PPEGMA ABA block copolymers is obtained by using either low-molecular-weight PEGMA or relatively low macroinitiator/macromonomer ratios. Differential scanning calorimetry (DSC) indicates phase separation and significant suppression of the crystallinity of the pendant poly(ethylene glycol) (PEG) chains in these new block copolymers. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    Science.gov (United States)

    Gao, Peng; Liu, Meiying; Tian, Jianwen; Deng, Fengjie; Wang, Ke; Xu, Dazhuang; Liu, Liangji; Zhang, Xiaoyong; Wei, Yen

    2016-08-01

    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 1H 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.

  11. 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.

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

    Science.gov (United States)

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

    2013-04-01

    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.

  13. Preparation of a thick polymer brush layer composed of poly(2-methacryloyloxyethyl phosphorylcholine) by surface-initiated atom transfer radical polymerization and analysis of protein adsorption resistance.

    Science.gov (United States)

    Inoue, Yuuki; Onodera, Yuya; Ishihara, Kazuhiko

    2016-05-01

    The purpose of this study was to prepare a thick polymer brush layer composed of poly(2-methacryloyloxyethyl phosphorylcholine (MPC)) and assess its resistance to protein adsorption from the dissolved state of poly(MPC) chains in an aqueous condition. The thick poly(MPC) brush layer was prepared through the surface-initiated atom transfer radical polymerization (SI-ATRP) of MPC with a free initiator from an initiator-immobilized substrate at given [Monomer]/[Free initiator] ratios. The ellipsometric thickness of the poly(MPC) brush layers could be controlled by the polymerization degree of the poly(MPC) chains. The thickness of the poly(MPC) brush layer in an aqueous medium was larger than that in air, and this tendency became clearer when the polymerization degree of the poly(MPC) increased. The maximum thickness of the poly(MPC) brush layer in an aqueous medium was around 110 nm. The static air contact angle of the poly(MPC) brush layer in water indicated a reasonably hydrophilic nature, which was independent of the thickness of the poly(MPC) brush layer at the surface. This result occurred because the hydrated state of the poly(MPC) chains is not influenced by the environment surrounding them. Finally, as measured with a quartz crystal microbalance, the amount of protein adsorbed from a fetal bovine serum solution (10% in phosphate-buffered saline) on the original substrate was 420 ng/cm(2). However, the poly(MPC) brush layer reduced this value dramatically to less than 50 ng/cm(2). This effect was independent of the thickness of the poly(MPC) brush layer for thicknesses between 20 nm and about 110 nm. These results indicated that the surface covered with a poly(MPC) brush layer is a promising platform to avoid biofouling and could also be applied to analyze the reactions of biological molecules with a high signal/noise ratio.

  14. Synthesis of novel well-defined poly(vinyl acetate)-b-poly(acrylonitrile) and derivatized water-soluble poly(vinyl alcohol)-b-poly(acrylic acid) block copolymers by cobalt-mediated radical polymerization

    NARCIS (Netherlands)

    Debuigne, A.; Warnant, J.; Jerome, R.; Voets, I.K.; Keizer, de A.; Cohen Stuart, M.A.; Detrembleur, C.

    2008-01-01

    Poly(vinyl acetate)¿Co(acac)2 macroinitiators, prepared by cobalt-mediated radical polymerization of vinyl acetate (VAc), were used to synthesize well-defined poly(vinyl acetate)-b-poly(acrylonitrile) (PVAc-b-PAN) block copolymers. Different solvents and temperatures were tested for the polymerizati

  15. A rare example of the formation of polystyrene-grafted aliphatic polyester in one-pot by radical polymerization.

    Science.gov (United States)

    Shi, Yinfeng; Zheng, Zhicheng; Agarwal, Seema

    2014-06-10

    The radical copolymerization of cyclic ester β-propiolactone (β-PL) with styrene (St) at 120 °C, with a complete range of monomer ratios, is a rare example of a system providing graft copolymers (PSt-g-β-PL) in one pot. The structure of the resulting β-PL-St copolymers was proven by using a combination of different characterization techniques, such as 1D and 2D NMR spectroscopy and gel permeation chromatography (GPC), before and after alkaline hydrolysis of the polymers. The number of grafting points increased with an increasing amount of β-PL in the feed. A significant difference in the reactivity of St and β-PL and radical chain-transfer reactions at the polystyrene (PSt) backbone, followed by combination with the active growing poly(β-PL) chains, led to the formation of graft copolymers by a grafting-onto mechanism.

  16. TERMINATION AND TRANSFER OF THE CHAIN RADICALS IN THE POLYMERIZATION OF ACRYLONITRILE INITIATED BY VANADIUM(V)-THIOUREA REDOX SYSTEM

    Institute of Scientific and Technical Information of China (English)

    WU Jinyuan; YANG Chaoxiong; WU Yuxian

    1990-01-01

    The dependence of the molecular weights on the concentration of reactants in the polymerization of acrylonitrile initiated by vanadium (V)-thiourea red ox system has been investigated. It was found that the molecular weights of the polymer change nonlinearly with increasing concentrations of nitric acid and thiourea. Probably, the composition of the complexes exert a great influence on the chain initiation and termination. The reaction of "complextermination " gives rise to the decrease of the molecular weights markedly while the concentrations of thiourea and vanadium (V)in the range from one to three molar ratios.

  17. Chromatographic assessment of two hybrid monoliths prepared via epoxy-amine ring-opening polymerization and methacrylate-based free radical polymerization using methacrylate epoxy cyclosiloxane as functional monomer.

    Science.gov (United States)

    Wang, Hongwei; Ou, Junjie; Lin, Hui; Liu, Zhongshan; Huang, Guang; Dong, Jing; Zou, Hanfa

    2014-11-07

    Two kinds of hybrid monolithic columns were prepared by using methacrylate epoxy cyclosiloxane (epoxy-MA) as functional monomer, containing three epoxy moieties and one methacrylate group. One column was in situ fabricated by ring-opening polymerization of epoxy-MA and 1,10-diaminodecane (DAD) using a porogenic system consisting of isopropanol (IPA), H2O and ethanol at 65°C for 12h. The other was prepared by free radical polymerization of epoxy-MA and ethylene dimethacrylate (EDMA) using 1-propanol and 1,4-butanediol as the porogenic solvents at 60°C for 12h. Two hybrid monoliths were investigated on the morphology and chromatographic assessment. Although two kinds of monolithic columns were prepared with epoxy-MA, their morphologies looked rather different. It could be found that the epoxy-MA-DAD monolith possessed higher column efficiencies (25,000-34,000plates/m) for the separation of alkylbenzenes than the epoxy-MA-EDMA monolith (12,000-13,000plates/m) in reversed-phase nano-liquid chromatography (nano-LC). Depending on the remaining epoxy or methacrylate groups on the surface of two pristine monoliths, the epoxy-MA-EDMA monolith could be easily modified with 1-octadecylamine (ODA) via ring-opening reaction, while the epoxy-MA-DAD monolith could be modified with stearyl methacrylate (SMA) via free radical reaction. The chromatographic performance for the separation of alkylbenzenes on SMA-modified epoxy-MA-DAD monolith was remarkably improved (42,000-54,000 plates/m) when compared with that on pristine epoxy-MA-DAD monolith, while it was not obviously enhanced on ODA-modified epoxy-MA-EDMA monolith when compared with that on pristine epoxy-MA-EDMA monolith. The enhancement of the column efficiency of epoxy-MA-DAD monolith after modification might be ascribed to the decreased mass-transfer resistence. The two kinds of hybrid monoliths were also applied for separations of six phenols and seven basic compounds in nano-LC. Copyright © 2014 Elsevier B.V. All

  18. Photolysis of alpha-xylyl chlorides: an efficient deep-UV photoinitiating system for radical and cationic polymerization.

    Science.gov (United States)

    Ponce, Patricia; Catalani, Luiz Henrique

    2004-07-01

    Photoacid generators (PAG) are chemical systems where light absorption renders strong acid formation, typically with quantum yields greater than one. Many compounds bearing halogen atoms are reported to produce hydrogen halides upon photolysis. Here, alpha-chloroxylene derivatives (ortho, meta and para) were subject of a photolysis study in order to: (i) determine the operative mechanism, (ii) identify the products formed and (iii) quantify the amount of HCl formed. Product structure and quantum yields of HCl formation where determined for the photolysis of alpha-chloro-o-xylene (1), alpha-chloro-m-xylene (2), alpha-chloro-p-xylene (3), alpha, alpha'-dichloro-o-xylene (4), alpha, alpha'-dichloro-m-xylene (5) and alpha, alpha'-dichloro-p-xylene (6) in apolar (benzene, cumene, ethylbenzene, toluene and isooctane) and polar (methanol, n-propanol, isopropyl alcohol) solvents. Some of these compounds were analysed by laser flash photolysis in argon-purged isooctane as solvent to examine the possible reaction intermediates involved. The observed products are derived from typical radical reactions like recombination, dimerization and hydrogen abstraction from the starting compound or from solvents. The formation of HCl is expected as the result of C-Cl homolysis followed by hydrogen abstraction by chlorine atom. The results showed yields ranging from 1.2 to 18, depending on the conditions used. These numbers indicate the potential use of these compounds as PAG systems for the deep UV region.

  19. Facile synthesis of dendrimer-like star-branched poly(isopropylacrylamide) via combination of click chemistry and atom transfer radical polymerization

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    We report a facile synthesis method of dendrimer-like star-branched poly(N-isopropylacrylamide) (PNIPAM) via the combination of click chemistry and atom transfer radical polymerization (ATRP) by employing the arm-first approach.First,the α-azido-ω-chloro-heterodifunctionalized building block,N3-PNIPAM-Cl (G0-Cl),was synthesized via ATRP by 3-azidopropyl 2-chloropropionate as the initiator.Taking advantage of click chemistry,the first generation (G1) of dendrimer-like star-branched PNIPAM,G1-(Cl)3,was facilely prepared via the click coupling reaction between G0-Cl and tripropargylamine.For the construction of second generation (G2) dendrimer-like star-branched PNIPAM,G2-(Cl)6,terminal chloride moieties of G1-(Cl)3 were first converted to azide,and then reacted with excess tripropargylamine to give G1-(alkynyl)6 ;G2-(Cl)6 was subsequently prepared via click reaction between G1-(alkynyl) 6 and G0-Cl.Gel permeation chromatography (GPC) and matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) mass spectrometry were employed to confirm the successful construction of dendrimer-like star-branched polymers.The unique thermal phase transition behavior of this dendrimer-like star-branched polymer in aqueous solutions was further investigated by turbidimetry and micro-differential scanning calorimetry (Micro-DSC).

  20. 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.

  1. Synthesis of well-defined structurally silica-nonlinear polymer core-shell nanoparticles via the surface-initiated atom transfer radical polymerization

    Science.gov (United States)

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

    2011-05-01

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

  2. 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.

  3. Enhanced and selective adsorption of mercury ions on chitosan beads grafted with polyacrylamide via surface-initiated atom transfer radical polymerization.

    Science.gov (United States)

    Li, Nan; Bai, Renbi; Liu, Changkun

    2005-12-06

    Enhanced and selective removal of mercury ions was achieved with chitosan beads grafted with polyacrylamide (chitosan-g-polyacrylamide) via surface-initiated atom transfer radical polymerization (ATRP). The chitosan-g-polyacrylamide beads were found to have significantly greater adsorption capacities and faster adsorption kinetics for mercury ions than the chitosan beads. At pH 4 and with initial mercury concentrations of 10-200 mg/L, the chitosan-g-polyacrylamide beads can achieve a maximum adsorption capacity of up to 322.6 mg/g (in comparison with 181.8 mg/g for the chitosan beads) and displayed a short adsorption equilibrium time of less than 60 min (compared to more than 15 h for the chitosan beads). Coadsorption experiments with both mercury and lead ions showed that the chitosan-g-polyacrylamide beads had excellent selectivity in the adsorption of mercury ions over lead ions at pH mercury adsorption was due to the many amide groups grafted onto the surfaces of the beads, and the selectivity in mercury adsorption can be attributed to the ability of mercury ions to form covalent bonds with the amide. It was found that adsorbed mercury ions on the chitosan-g-polyacrylamide beads can be effectively desorbed in a perchloric acid solution, and the regenerated beads can be reused almost without any loss of adsorption capacity.

  4. End-Functionalized Poly(N-isopropylacrylamide with d-Glucosamine through Different Initiator from C-1 and C-2 Positions via Atom Transfer Radical Polymerization

    Directory of Open Access Journals (Sweden)

    Guihua Cui

    2016-11-01

    Full Text Available Regioselective modification of d-glucosamine (2-amino-2-deoxy-d-glucopyranose, GA through C-1 and C-2 positions to synthesized thermo-responsive D-Glucosamine-poly(N-iso-propylacrylamide (PNIPAM via atom transfer radical polymerization (ATRP was investigated for the first time. Two different schemes of the synthesis for GA derivatives (GA-PNIPAM (i and (ii with well-defined structures using 3,4,6-tri-o-acetyl-2-deoxy-2-phthalimido-β-d-glucopyranose and 1,3,4,6-tetra-o-acetyl-2-amino-2-deoxy-β-d-glucopyranose intermediates were examined. The GA-PNIPAM (ii had an amino at C-2 position, while there was a hydroxyl in GA-PNIPAM (i at this position. Both the resulting oligomers (i and (ii had a narrow dispersity, and no significant cytotoxic response of copolymers (i and (ii was observed in the cell line over the concentration range from 0.1 μg/mL to 1000 μg/mL at any of the exposure times. In addition, it was discovered that GA-PNIPAM (i and (ii inhibited the proliferation of Human Hepatocellular Carcinoma Cells HepG2 as the concentration and the time changed, and the inhibitory activity of polymer (ii was higher than that of he (i. The results suggest that the GA-PNIPAM polymers show excellent biocompatibility in vitro.

  5. Grafting N-Isopropyl Acrylamide) from Poly(vinylidene Fluoride) Mirofiltration, Membranes via Direct Surface-Initiated Atom Transfer Radical Polymerization, and Temperature Sensitivity

    Science.gov (United States)

    Chen, Yiwang; Xiao, Jichun; Zhou, Weihua; Deng, Qilan; Nie, Huarong; Wan, Meixiang; Bai, Fenglian

    Well-defined poly(N-isopropyl acrylamide) (PNIPAAm) brushes on commercial hydrophobic poly(vinylidene fluoride) (PVDF) microfiltration membrane surfaces were prepared, via direct atom transfer radical polymerization (ATRP) with the secondary fluorinated site of PVDF as initiator and water as solvent at 80°C. The effect of solvents on the ATRP was studied in detail. The water as reaction solvent was in favor of surface-initiated ATRP of N-isopropyl acrylamide (NIPAAm) from secondary fluoride of PVDF membranes. The chemical composition and structure of the modified PVDF membrane surfaces were determined by attenuated total reflectance (ATR) Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy. The surface and cross-section morphology of membranes were studied by scanning electron microscopy (SEM). The pore sizes of the pristine PVDF membrane and the PNIPAAm-grafted PVDF membranes were measured using micro-image analysis and process software. The introduction of the well-defined PNIPAAm on the PVDF membrane gave rise to hydrophilicity. Water contact angles of PVDF membranes reduced after the surface grafting of PNIPAAm. Water fluxes and protein solution permeation experiments revealed that the PNIPAAm-grafted PVDF membranes exhibited temperature-responsive permeability. The unique microstructure of PNIPAAm brushes facilitated hydrophilicity below the lower critical solution temperature.

  6. Self-assemblies of γ-CDs with pentablock copolymers PMA-PPO-PEO-PPO-PMA and endcapping via atom transfer radical polymerization of 2-methacryloyloxyethyl phosphorylcholine

    Directory of Open Access Journals (Sweden)

    Jing Lin

    2015-11-01

    Full Text Available Pentablock copolymers PMA-PPO-PEO-PPO-PMA synthesized via atom transfer radical polymerization (ATRP were self-assembled with varying amounts of γ-CDs to prepare poly(pseudorotaxanes (PPRs. When the concentration of γ-CDs was lower, the central PEO segment served as a shell of the micelles and was preferentially bent to pass through the γ-CD cavity to construct double-chain-stranded tight-fit PPRs characterized by a channel-like crystal structure. With an increase in the amount of γ-CDs added, they began to accommodate the poly(methyl acrylate (PMA segments dissociated from the core of the micelles. When more γ-CDs were threaded and slipped over the segments, the γ-CDs were randomly distributed along the pentablock copolymer chain to generate single-chain-stranded loose-fit PPRs and showed no characteristic channel-like crystal structure. All the self-assembly processes of the pentablock copolymers resulted in the formation of hydrogels. After endcapping via in situ ATRP of 2-methacryloyloxyethyl phosphorylcholine (MPC, these single-chain-stranded loose-fit PPRs were transformed into conformational identical polyrotaxanes (PRs. The structures of the PPRs and PRs were characterized by means of 1H NMR, GPC, 13C CP/MAS NMR, 2D 1H NOESY NMR, FTIR, WXRD, TGA and DSC analyses.

  7. 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.

  8. Green polymer chemistry: investigating the mechanism of radical ring-opening redox polymerization (R3P) of 3,6-dioxa-1,8-octanedithiol (DODT).

    Science.gov (United States)

    Rosenthal-Kim, Emily Q; Puskas, Judit E

    2015-04-13

    The mechanism of the new Radical Ring-opening Redox Polymerization (R3P) of 3,6-dioxa-1,8-octanedithiol (DODT) by triethylamine (TEA) and dilute H2O2 was investigated. Scouting studies showed that the formation of high molecular weight polymers required a 1:2 molar ratio of DODT to TEA and of DODT to H2O2. Further investigation into the chemical composition of the organic and aqueous phases by 1H-NMR spectroscopy and mass spectrometry demonstrated that DODT is ionized by two TEA molecules (one for each thiol group) and thus transferred into the aqueous phase. The organic phase was found to have cyclic disulfide dimers, trimers and tetramers. Dissolving DODT and TEA in water before the addition of H2O2 yielded a polymer with Mn = 55,000 g/mol, in comparison with Mn = 92,000 g/mol when aqueous H2O2 was added to a DODT/TEA mixture. After polymer removal, MALDI-ToF MS analysis of the residual reaction mixtures showed only cyclic oligomers remaining. Below the LCST for TEA in water, 18.7 °C, the system yielded a stable emulsion, and only cyclic oligomers were found. Below DODT/TEA and H2O2 1:2 molar ratio mostly linear oligomers were formed, with <20% cyclic oligomers. The findings support the proposed mechanism of R3P.

  9. Preparation of Mg(OH){sub 2} hybrid pigment by direct precipitation and graft onto cellulose fiber via surface-initiated atom transfer radical polymerization

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Xiao, E-mail: wangxiao@dlpu.edu.cn [School of Textile and Materials Engineering, Dalian Polytechnic University, Dalian, Liaoning Province (China); Zhang, Yue; Lv, Lihua; Cui, Yongzhu; Wei, Chunyan [School of Textile and Materials Engineering, Dalian Polytechnic University, Dalian, Liaoning Province (China); Pang, Guibing [School of Mechanical Engineering and Automation, Dalian Polytechnic University, Dalian, Liaoning Province (China)

    2016-02-15

    Graphical abstract: - Highlights: • Adsorbed anionic dye molecules are conducive to preferential growth of (0 0 1) plane of Mg(OH){sub 2} crystal for Mg(OH){sub 2} pigments. • Uniform coverage of nanosized Mg(OH){sub 2} pigments on fiber surface is achieved via surface-initiated ATRP. • About 4 wt% of Mg(OH){sub 2} pigment on fiber surface shortens nearly half of burning time of cellulose. - Abstract: Mg(OH){sub 2} flame retardant hybrid pigment is synthesized through simultaneous solution precipitation and adsorption of anionic dyes (C.I. Acid Red 6). The Mg(OH){sub 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){sub 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){sub 2} crystals and affect the formation of lamella-like Mg(OH){sub 2} crystals. The cellulose fiber grafted with modified Mg(OH){sub 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.

  10. Kilohertz Pulsed-Laser-Polymerization: Simultaneous Determination of Backbiting, Secondary, and Tertiary Radical Propagation Rate Coefficients for tert-Butyl Acrylate.

    Science.gov (United States)

    Wenn, Benjamin; Junkers, Thomas

    2016-05-01

    For the first time, a 1000 Hz pulse laser has been applied to determine detailed kinetic rate coefficients from pulsed laser polymerization-size exclusion chromatography experiments. For the monomer tert-butyl acrylate, apparent propagation rate coefficients kp (app) have been determined in the temperature range of 0-80 °C. kp (app) in the range of few hundreds to close to 50 000 L·mol(-1) ·s(-1) are determined for low and high pulse frequencies, respectively. The apparent propagation coefficients show a distinct pulse-frequency dependency, which follows an S-shape curve. From these curves, rate coefficients for secondary radial propagation (kp (SPR) ), backbiting (kbb ), midchain radical propagation (kp (tert) ), and the (residual) effective propagation rate (kp (eff) ) can be deduced via a herein proposed simple Predici fitting procedure. For kp (SPR) , the activation energy is determined to be (17.9 ± 0.6) kJ·mol(-1) in excellent agreement with literature data. For kbb , an activation energy of (25.9 ± 2.2) kJ·mol(-1) is deduced.

  11. Green Polymer Chemistry: Investigating the Mechanism of Radical Ring-Opening Redox Polymerization (R3P of 3,6-Dioxa-1,8-octanedithiol (DODT

    Directory of Open Access Journals (Sweden)

    Emily Q. Rosenthal-Kim

    2015-04-01

    Full Text Available The mechanism of the new Radical Ring-opening Redox Polymerization (R3P of 3,6-dioxa-1,8-octanedithiol (DODT by triethylamine (TEA and dilute H2O2 was investigated. Scouting studies showed that the formation of high molecular weight polymers required a 1:2 molar ratio of DODT to TEA and of DODT to H2O2. Further investigation into the chemical composition of the organic and aqueous phases by 1H-NMR spectroscopy and mass spectrometry demonstrated that DODT is ionized by two TEA molecules (one for each thiol group and thus transferred into the aqueous phase. The organic phase was found to have cyclic disulfide dimers, trimers and tetramers. Dissolving DODT and TEA in water before the addition of H2O2 yielded a polymer with Mn = 55,000 g/mol, in comparison with Mn = 92,000 g/mol when aqueous H2O2 was added to a DODT/TEA mixture. After polymer removal, MALDI-ToF MS analysis of the residual reaction mixtures showed only cyclic oligomers remaining. Below the LCST for TEA in water, 18.7 °C, the system yielded a stable emulsion, and only cyclic oligomers were found. Below DODT/TEA and H2O2 1:2 molar ratio mostly linear oligomers were formed, with <20% cyclic oligomers. The findings support the proposed mechanism of R3P.

  12. 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.

  13. Synthesis and Characterization of a Novel Addition-Fragmentation Reactive Surfactant (TRANSURF) for Use in Free-Radical Emulsion Polymerizations.

    Science.gov (United States)

    Wilkinson, Terence S.; Boonstra, Armin; Montoya-Goñi, Amaia; van Es, Steven; Monteiro, Michael J.; German, Anton L.

    2001-05-01

    The synthesis and characterization of a new type of chain-transfer-active surfactant (i.e., TRANSURF) is reported. The compound was designed on the basis of the chemistry of macromers, which undergo free-radical chain-transfer addition-fragmentation reactions. In effect this allows incorporation of the surfactant molecule into the polymer backbone, and thus reduces the influence of surfactant migration during film formation. Surfactants of this type, containing two hydrophilic head groups, can have a marked influence on the polymer and latex properties (e.g., molecular weight distributions and particle size). Characterization of the physical properties of this surfactant was therefore carried out using surface tension, conductivity, and fluorescence techniques. Because of the surfactant's unusual "bolaform" (alpha, omega) (Zana, R., in "Structure-Performance Relationships in Surfactants" (K. Esumi and M. Ueno, Eds.), Surfactant Science Series 70, Dekker, New York, 1997) structure the micelle formation process has been found to be quite different from that of the conventional surfactant, sodium dodecyl sulfate (SDS). From the surface tension data a flat molecular conformation was evident at 1x10(-3) mol dm(-3) (131 Å(2) surface area), which we assumed to correspond to the low aggregation number of premicellar aggregates. There is evidence to suggest formation of a larger volume of the microdomains in these micelles compared to that in SDS. At higher TRANSURF concentrations, however, we find no clear indication of a switch to a "wicket"-type conformation, although such conformational changes cannot be ruled out. Copyright 2001 Academic Press.

  14. The Progress of the Free Radical Polymerizations in the Channelof Mesoporous Molecular Sieve%介孔材料孔道内进行的自由基聚合反应研究进展

    Institute of Scientific and Technical Information of China (English)

    张发爱; 宋程; 余彩莉

    2011-01-01

    介孔材料具有孔道大小均匀、排列有序、高比表面积、孔径连续可调的特性,主要应用在催化、吸附、分离、传感器以及光、电、磁等许多领域.近年来,研究人员利用其空旷的孔道作为聚合"微反应器",在其内部进行了许多类型的聚合反应.综述了近二十年来在介孔材料孔道内烯类单体进行的自由基聚合反应,包括常规的自由基聚合反应和活性聚合反应,讨论了所得聚合物和介孔材料/聚合物复合材料的性能,认为对其聚合反应机理和应用值得进一步研究.%Mesoporous molecular sieves (MMS) have been used in many fields such as catalysis,absorption, separation and sensor along with optical, electrical and magnetic science, due to their uniform and order channel, large specific surface area and adjustable pore size. Recently, a lot of polymerizations were carried out in the channel of MMS, taking the advantage of their empty channels as the microreactor. The latest 20 years progress of the free radical polymerizations in the channel of MMS,including the regular free radical polymerization and active free radical polymerization were reviewed.The properties of the polymer and polymer/MMS composite were discussed.The polymerization mechanism and application need further investigated.

  15. Architecture of Star-block Copolymers Consisting of Triblock Arms via a N,N-diethyldi-thiocarbamate-mediated Living Radical Photo-polymerization and Application for Nanocomposites by Using as Fillers

    Institute of Scientific and Technical Information of China (English)

    K.Ishizu

    2007-01-01

    1 Results Highly branched poly(methyl methacrylate) (PMMA) stars were prepared by one-pot approach based on N,N-diethyldithiocarbamate-(DC) mediated living radical photo-polymerization.Soluble alternating hyperbranched microgel formation was initiated fast with preferential consumption of inimer 4-vinylbenzyl N,N-diethyldithiocarbamate (VBDC) and 4,4′-bismaleimidediphenylmethane (BMIM) in the presence of an excess of methyl methacrylate (MMA),PMMA arms could then grow from DC groups of microgel as macro...

  16. Influences of environment on the free radical polymerization in pStHblhoto-thermal sensitive microcapsules%环境对光热敏微胶囊自由基聚合的影响

    Institute of Scientific and Technical Information of China (English)

    李新政; 李晓苇; 赖伟东; 安文

    2012-01-01

    采用界面聚合技术获得了新型信息记录材料光热敏微胶囊,利用红外光谱技术研究了外部环境因素对包裹聚合体系自由基聚合的影响.实验结果表明:聚合体系经包裹后曝光瞬间聚合速度与程度迅速增大,氧对微胶囊内部自由基聚合抑制作用不明显,但单体不饱和双键最终转化率降低;囊芯单体的聚合速度与程度随曝光强度的增加而增大,不饱和C=C双键转化率与曝光能量的平方根[Ⅰ]1/2具有很好的线性关系;温度对微胶囊内部自由基聚合影响明显.%The light-thermal sensitive microcapsule is synthesized with interfacial polymerization method , which is a new type of optical information recording function material. The influences of environmental factors on the free radical polymerization in microcapsule are studied with infrared spectroscopy technology. The results show that the speed and degree of polymerization increase rapidly at the moment of exposure, and the inhibitory effect of oxygen on free radical polymerization is not obvious in microcapsule, but the final conversion ratio of unsaturated C = C bond decreases. The speed and degree of polymerization of monomer in microcapsule increase rapidly with the light intensity, and the conversion ratio of unsaturated C = C double bond has a good linear relation with the [I]1/2. The temperature has obvious effect on the polymerizing process in microcapsule.

  17. Preparation and self-assembly behavior of polystyrene-block-poly (dimethylaminoethyl methacrylate amphiphilic block copolymer using atom transfer radical polymerization

    Directory of Open Access Journals (Sweden)

    2008-03-01

    Full Text Available Asymmetric and semi-symmetric amphiphilic diblock copolymers polystyrene-block-poly (dimethylaminoethyl methacrylate (PS-b-PDMAEMA with the same PS block length of 62 repeat units and quite short (3 repeat units or equivalent (47 repeat units length of PDMAEMA have been prepared simply by varying the ratio of the bromine-terminated macroinitiator polystyrene (PS-Br to DMAEMA using atom transfer radical polymerization (ATRP. The chemical structures and compositions of the PS-b-PDMAEMA block copolymers are studied by nuclear magnetic resonance (NMR spectroscopy, gel permeation chromatography (GPC, and elementary analysis (EA. The self-assembly behaviors of copolymers in N,N-dimethyl formamide (DMF with different pH and dioxane/water binary solvent mixture by direct dissolution method (DD, are studied by transmission electron microscopy (TEM, electron diffracting analysis (EDA, and energy-dispersive analysis of X-rays (EDAX techniques. Transmission electron microscopy results suggest that asymmetric block copolymer PS62-b-PDMAEMA3 (the numbers in the form of footnotes represent repeated units of each monomer in the copolymer can form spherical core-shell micelles, large compound reverse micelles (LCRMs, hexagonal/rhombic phases, reverse hexagonal/rhombic phases, vesicles, reverse vesicles and necklace-like reverse micelles, controlled by common or selective solvent and pH, while most of the aggregates of semi-symmetric PS62-b-PDMAEMA47 are simply spherical, such as spherical core-shell micelles and reverse spherical core-shell micelles, besides hexagonal/rhombic phases. All above structures are controlled by three components of the free energy of aggregation: core-chain stretching, interfacial energy and intercoronal chain interaction.

  18. 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.

  19. Vinylimidazole-Based Asymmetric Ion Pair Comonomers: Synthesis, Polymerization Studies and Formation of Ionically Crosslinked PMMA

    NARCIS (Netherlands)

    Jana, S.; Vasantha, V.A.; Stubbs, L.P.; Parthiban, A.; Vancso, G.J.

    2013-01-01

    Vinylimidazole-based asymmetric ion pair comonomers (IPCs) which are free from nonpolymerizable counter ions have been synthesized, characterized and polymerized by free radical polymerization (FRP), atom transfer radical polymerization (ATRP), and reversible addition-fragmentation chain transfer (R

  20. Clickable Polymeric Coating for Oriented Peptide Immobilization.

    Science.gov (United States)

    Sola, Laura; Gori, Alessandro; Cretich, Marina; Finetti, Chiara; Zilio, Caterina; Chiari, Marcella

    2016-01-01

    A new methodology for the fabrication of an high-performance peptide microarray is reported, combining the higher sensitivity of a layered Si-SiO2 substrate with the oriented immobilization of peptides using a N,N-dimethylacrylamide-based polymeric coating that contains alkyne monomers as functional groups. This clickable polymer allows the oriented attachment of azido-modified peptides via a copper-mediated azide/alkyne cycloaddition. A similar coating that does not contain the alkyne functionality has been used as comparison, to demonstrate the importance of a proper orientation for facilitating the probe recognition and interaction with the target antibody.

  1. Electrospun regenerated cellulose nanofibrous membranes surface-grafted with polymer chains/brushes via the atom transfer radical polymerization method for catalase immobilization.

    Science.gov (United States)

    Feng, Quan; Hou, Dayin; Zhao, Yong; Xu, Tao; Menkhaus, Todd J; Fong, Hao

    2014-12-10

    In this study, an electrospun regenerated cellulose (RC) nanofibrous membrane with fiber diameters of ∼200-400 nm was prepared first; subsequently, 2-hydroxyethyl methacrylate (HEMA), 2-dimethylaminoethyl methacrylate (DMAEMA), and acrylic acid (AA) were selected as the monomers for surface grafting of polymer chains/brushes via the atom transfer radical polymerization (ATRP) method. Thereafter, four nanofibrous membranes (i.e., RC, RC-poly(HEMA), RC-poly(DMAEMA), and RC-poly(AA)) were explored as innovative supports for immobilization of an enzyme of bovine liver catalase (CAT). The amount/capacity, activity, stability, and reusability of immobilized catalase were evaluated, and the kinetic parameters (Vmax and Km) for immobilized and free catalase were determined. The results indicated that the respective amounts/capacities of immobilized catalase on RC-poly(HEMA) and RC-poly(DMAEMA) nanofibrous membranes reached 78 ± 3.5 and 67 ± 2.7 mg g(-1), which were considerably higher than the previously reported values. Meanwhile, compared to that of free CAT (i.e., 18 days), the half-life periods of RC-CAT, RC-poly(HEMA)-CAT, RC-poly(DMAEMA)-CAT, and RC-poly(AA)-CAT were 49, 58, 56, and 60 days, respectively, indicating that the storage stability of immobilized catalase was also significantly improved. Furthermore, the immobilized catalase exhibited substantially higher resistance to temperature variation (tested from 5 to 70 °C) and lower degree of sensitivity to pH value (tested from 4.0 and 10.0) than the free catalase. In particular, according to the kinetic parameters of Vmax and Km, the nanofibrous membranes of RC-poly(HEMA) (i.e., 5102 μmol mg(-1) min(-1) and 44.89 mM) and RC-poly(DMAEMA) (i.e., 4651 μmol mg(-1) min(-1) and 46.98 mM) had the most satisfactory biocompatibility with immobilized catalase. It was therefore concluded that the electrospun RC nanofibrous membranes surface-grafted with 3-dimensional nanolayers of polymer chains/brushes would be

  2. Carborane complexes of ruthenium(III): studies on thermal reaction chemistry and the catalyst design for atom transfer radical polymerization of methyl methacrylate.

    Science.gov (United States)

    Grishin, Ivan D; D'yachihin, Dmitrii I; Piskunov, Alexander V; Dolgushin, Fedor M; Smol'yakov, Alexander F; Il'in, Mikhail M; Davankov, Vadim A; Chizhevsky, Igor T; Grishin, Dmitry F

    2011-08-15

    The heating of the 18-electron complex [3,3-(dppb)-3-H-3-Cl-closo-3,1,2-RuC(2)B(9)H(11)] (3) in benzene at 80 °C in the presence of a small amount of CCl(4) as initiator afforded paramagnetic 17-electron species [3,3-(dppb)-3-Cl-closo-3,1,2-RuC(2)B(9)H(11)] (4) along with minor amounts of two P-phenylene ortho-cycloboronated derivatives [3-Cl-3,3,8-{Ph(2)P(CH(2))(4)PPh-μ-(C(6)H(4)-ortho)}-closo-3,1,2-RuC(2)B(9)H(10)] (5) and [3,7-Cl(2)-3,3,8-{Ph(2)P(CH(2))(4)PPh-μ-(C(6)H(4)-ortho)}-closo-3,1,2-RuC(2)B(9)H(10)] (6) in total yield of ca. 80%. The heating of either 3 or 4 in toluene at 95 °C in the absence of CCl(4) led to the selective formation of 5, which was isolated in 64% and 46% yield, respectively. Thermolysis of 3 at higher temperatures (boiling toluene, 110 °C) gives novel paramagnetic species [3-Cl-3,3,7,8-{Ph(2)P(CH(2))(4)P-μ-(C(6)H(4)-ortho)(2)}-closo-3,1,2-RuC(2)B(9)H(9)] (7) featuring bis(ortho-cycloboronation) of both P-phenyl groups at the same phosphorus atom of the ruthenium-bound dppb ligand. All new paramagnetic complexes 4-7, as well as starting diamagnetic species 3, were characterized by single-crystal X-ray diffraction and, in addition, by EPR spectroscopic studies of odd-electron complexes. Ruthenacarboranes 3-5 and 7 all display high efficiency as catalysts for the atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA). Complex 5 gave the best catalyst performance in terms of polydispersity; the PDI (M(w)/M(n)) of the polymer samples is as low as 1.15.

  3. Study of ″Living″ Radical Polymerization by FTIR in Situ%红外光谱原位跟踪活性自由基聚合反应过程研究

    Institute of Scientific and Technical Information of China (English)

    陈靖民; 华峰君; 邱江; 杨玉良

    2001-01-01

    使用新型可插入式红外光谱仪原位检测在4-羟基2,2,6,6-四甲基氧化哌啶醇(HTEMPO)存在下苯乙烯稳定自由基活性均聚合反应和苯乙烯/甲基丙烯酸羟丙酯的共聚合反应以及苯乙烯原子转移活性自由基聚合(ATRP)反应三个过程,分别考虑了它们的反应动力学,并给出了可能的聚合反应机理。研究结果表明,对于均相的苯乙烯(St)均聚合反应和苯乙烯(St)/甲基丙烯酸羟丙酯(HPMA)的自由基共聚合反应体系,聚合反应动力学为一级,聚合物分子量随着转化率逐步增加,显示出典型的活性自由基聚合特征。但是这两个聚合反应显示一定的诱导期,与反应体系中存在的HTEMPO捕捉自由基有关。而对于St/HPMA共聚合体系,诱导期更长,这是因为HPMA易和HTEMPO捕捉自由基有关。而对于St/HPMA共聚合体系,诱导期更长,这是因为HPMA易和HTEMPO自由基发生氢转移反应,导致游离的HTEMPO浓度升高。最后用红外光谱实时跟踪苯乙烯非均相ATRP过程,发现苯乙烯聚合反应动力学接近于表现零级,因为单体分子在由增长自由基、卤化铜和联二吡啶形成的络合物的界面增长,与单体相内St浓度无关。%Three types of living radical polymerization processes were monitored by means of FTIR spectrometer with handful diamond detector called as Dicomp in situ.It was found that both styrene and styrene/hydroxylpropyl methyacrylate (HPMA) could polymerize according to stable free radical polymerization (SFRP) mechanism in presence of 4-hydroxyl tetramethypiperidiyl-1-oxy(HTEMPO).For styrene/HPMA system,the styrene and HPMA conversion monitored by FTIR were linear with increase of molecular weight,but it gave longer induction period compared with that for St bulk polymerization.It was related to the hydrogen-transfer reaction between the propagating radicals with the end HPMA unit and HTEMPO.Furthermore,This following

  4. Synthesis of [18F]Arenes via the Copper-Mediated [18F]Fluorination of Boronic Acids.

    Science.gov (United States)

    Mossine, Andrew V; Brooks, Allen F; Makaravage, Katarina J; Miller, Jason M; Ichiishi, Naoko; Sanford, Melanie S; Scott, Peter J H

    2015-12-04

    A copper-mediated radiofluorination of aryl- and vinylboronic acids with K(18)F is described. This method exhibits high functional group tolerance and is effective for the radiofluorination of a range of electron-deficient, -neutral, and -rich aryl-, heteroaryl-, and vinylboronic acids. This method has been applied to the synthesis of [(18)F]FPEB, a PET radiotracer for quantifying metabotropic glutamate 5 receptors.

  5. 自由基聚合法合成天然橡胶接枝共聚物的研究综述%Review on Synthesis of Graft Copolymer of Natural Rubber by Free-radical Polymerization

    Institute of Scientific and Technical Information of China (English)

    廖禄生; 廖建和; 李一民; 陈永平; 黄桂春; 陈桂雄

    2011-01-01

    Natural rubber (NR) modification by polymer grafting is an important way to improve the properties of NR and to expand its application. Currently, graft copolymers of natural rubber are mainly synthesized by free-radical polymerization (FRP). The reaction mechanism and processing conditions are summarized. An outlook to the synthesis method of NR graft copolymer is made from the perspective of structural controllability of the copolymer and controlled/"living" radical polymerization.%通过聚合物接枝改性天然橡胶(NR)是改善NR性能和扩展其应用范围的重要方法之一.目前,人们主要通过自由基聚合(freeradical po1ymerization,FRP)法合成NR接枝共聚物,本文就其反应机理和反应工艺进行了综述,并从接枝共聚物的结构可控性和可控/"活性"自由基聚合的角度对NR接枝共聚物的合成方法进行了展望.

  6. Polymers based on stable phenoxyl radicals for the use in organic radical batteries.

    Science.gov (United States)

    Jähnert, Thomas; Häupler, Bernhard; Janoschka, Tobias; Hager, Martin D; Schubert, Ulrich S

    2014-05-01

    Polymers with pendant phenoxyl radicals are synthesized and the electrochemical properties are investigated in detail. The monomers are polymerized using ring-opening metathesis polymerization (ROMP) or free-radical polymerization methods. The monomers and polymers, respectively, are oxidized to the radical either before or after the polymerization. These phenoxyl radicals containing polymers reveal a reversible redox behavior at a potential of -0.6 V (vs Ag/AgCl). Such materials can be used as anode-active material in organic radical batteries (ORBs).

  7. Syntheses and structures of closely related copper(I) complexes of tridentate (2-pyridylmethyl)imine and (2-pyridylmethyl)amine ligands and their use in mediating atom transfer radical polymerizations.

    Science.gov (United States)

    Turner, Sara A; Remillard, Zachary D; Gijima, Desire T; Gao, Emily; Pike, Robert D; Goh, Christopher

    2012-10-15

    A series of five copper(I) bromide complexes of tridentate (N,N,L) pyridine-imine and pyridine-amine ligands with a third amine, ether, or thioether neutral donor was synthesized and utilized in the atom transfer radical polymerization of styrene. The ligand design illustrated a systematic approach to the development of copper complexes for use in ATRP. Variations in the nature of the ligand impacted the solid state structures of the complexes. A mononuclear [CuBr(L)] complex was observed for L = pyridine-amine-amine, whereas complexes of L = pyridine-imine-amine and -thioether formed dinuclear [CuBr(L)](2) structures with a central 10-membered ring. A doubly-bromide-bridged dimer was revealed for the [CuBr(L)] complex of L = pyridine-imine-ether and a polymeric species for [CuBr(L)], where L = pyridine-imine-amine and the imine-amine spacer was extended from two to three carbon atoms. In the application of these complexes to the ATRP of styrene, the redox potentials of the complexes were found to be one indicator of ATRP efficiency. Of the series presented, two complexes in particular provided fast polymerization rates and good to excellent molecular weight control. In both of these complexes, the ligand contained all nitrogen-based donor moieties.

  8. Progress of Atom Transfer Radical Polymerization in Aqueous Dispersion Systems%水分散体系中原子转移自由基聚合研究进展

    Institute of Scientific and Technical Information of China (English)

    王思瑶; 雷良才; 张俊; 郭磊; 李海英

    2011-01-01

    In aqueous dispersion system, atom transfer radical polymerization (ATRP) has the advantages of free radical process, emulsion polymerization and controlled/living polymerization.So in recent years,development of ATRP in aqueous dispersion system has received more attention.In this paper, recent developments of ATRP in aqueous dispersion system, such as emulsion, miniemulsion, microemulsion, have been introduced.Several mechanism for ATRP in aqueous dispersion system have been summarized, including normal ATRP, reverse ATRP.SR&NI (simultaneous reverse and normal initiation)ATRP and AGET (activator generated by electron transfer) ATRP.Advantages and disadvantages of ATRP, RATRP, SR&NI ATRP, AGET ATRP have been summarized.%水分散体系中原子转移自由基聚合(ATRP)具有自由基聚合、乳液聚合和活性/可控聚合的优点,因此近年来关于水分散体系中ATRP的研究日益增多.本文综述了近年来水分散体系(包括乳液体系、细乳液体系、微乳液体系)中原子转移自由基聚合的研究进展,对应用在水分散体系中的几种ATRP反应机理做了简要介绍,包括正向AT-RP、反向ATRP(RATRP)、正向/反向同时进行的(SR&NI)ATRP、电子转移活化剂(AGET)ATRP,并对RATRP、SR&NI、ATRPAGET ATRP的优缺点进行了总结.

  9. Inhibition of copper-mediated aggregation of human γD-crystallin by Schiff bases.

    Science.gov (United States)

    Chauhan, Priyanka; Muralidharan, Sai Brinda; Velappan, Anand Babu; Datta, Dhrubajyoti; Pratihar, Sanjay; Debnath, Joy; Ghosh, Kalyan Sundar

    2017-01-05

    Protein aggregation, due to the imbalance in the concentration of Cu(2+) and Zn(2+) ions is found to be allied with various physiological disorders. Copper is known to promote the oxidative damage of β/γ-crystallins in aged eye lens and causes their aggregation leading to cataract. Therefore, synthesis of a small-molecule 'chelator' for Cu(2+) with complementary antioxidant effect will find potential applications against aggregation of β/γ-crystallins. In this paper, we have reported the synthesis of different Schiff bases and studied their Cu(2+) complexation ability (using UV-Vis, FT-IR and ESI-MS) and antioxidant activity. Further based on their copper complexation efficiency, Schiff bases were used to inhibit Cu(2+)-mediated aggregation of recombinant human γD-crystallin (HGD) and β/γ-crystallins (isolated from cataractous human eye lens). Among these synthesized molecules, compound 8 at a concentration of 100 μM had shown ~95% inhibition of copper (100 μM)-induced aggregation. Compound 8 also showed a positive cooperative effect at a concentration of 5-15 μM on the inhibitory activity of human αA-crystallin (HAA) during Cu(2+)-induced aggregation of HGD. It eventually inhibited the aggregation process by additional ~20%. However, ~50% inhibition of copper-mediated aggregation of β/γ-crystallins (isolated from cataractous human eye lens) was recorded by compound 8 (100 μM). Although the reductive aminated products of the imines showed better antioxidant activity due to their lower copper complexing ability, they were found to be non-effective against Cu(2+)-mediated aggregation of HGD.

  10. Molecular study on copper-mediated tumor proteasome inhibition and cell death.

    Science.gov (United States)

    Xiao, Yan; Chen, Di; Zhang, Xia; Cui, Qiuzhi; Fan, Yuhua; Bi, Caifeng; Dou, Q Ping

    2010-07-01

    The metal ion copper is a cofactor essential for maintaining normal biological and physical functions in human beings. High copper levels have been found in variety of tumor tissues and are involved in tumor angiogenesis processes. The ubiquitin-proteasome system plays an important role in cell growth and apoptosis and has been shown as a novel target for cancer therapy. We previously reported that some organic copper complexes can inhibit the proteasomal chymotrypsin-like activity and induce apoptosis in human cancer cells and xenograft models. In the current study, we investigated the effect of oxidation status of copper, Cu(I) or Cu(II), on inhibition of proteasome activity, induction of apoptosis, and induction of reactive oxygen species (ROS) in human cancer cells. We report four major findings here: i) both Cu(I) and Cu(II) could inhibit the chymotrypsin-like activity of purified 20S proteasome, but Cu(I) was more potent than Cu(II), ii) purified 20S proteasome protein was able to reduce Cu(II) to Cu(I), suggesting that Cu(I) is the oxidation status of copper that directly reacts with the proteasome, iii) when complexed with the copper ligand neocuproine, Cu(I) showed higher ability to induce ROS production in cancer cells, compared with Cu(II), iv) addition of a ROS scavenger in the cancer cell culture-blocked copper-induced ROS generation, but did not overcome copper-mediated proteasome-inhibitory and cell death-inducing events, demonstrating the ROS-independent proteasome-inhibitory property of copper complexes.

  11. Novel UV Initiator for Functionalization of Multiwalled Carbon Nanotubes by Atom Transfer Radical Polymerization Applied on Two Different Grades of Nanotubes

    DEFF Research Database (Denmark)

    Daugaard, Anders Egede; Jankova Atanasova, Katja; Bøgelund, J.

    2010-01-01

    differences in reactivity and polymer loading, underlining the importance of the choice of MWCNT starting material. In addition to styrene, also poly(ethylene glycol) methacrylate (PEGMA) was shown to polymerize from the surface of the MWCNT. Finally, initial results from composites of polystyrene...

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

    OpenAIRE

    2009-01-01

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

  13. Effect of ultrasound in the free radical polymerization of acrylonitrile under a new multi-site phase-transfer catalyst - a kinetic study.

    Science.gov (United States)

    Selvaraj, Varathan; Sakthivel, Perumal; Rajendran, Venugopal

    2015-01-01

    The kinetics of polymerization of acrylonitrile (AN) was carried out under heterogeneous condition using a new multi-site phase-transfer catalyst (MPTC), viz., N,N'-dihexyl-4,4'-bipyridinium dibromide in the presence of water soluble initiator, potassium peroxydisulphate (PDS) under chlorobenzene/water two phase system assisted by ultrasound irradiation at constant temperature 60+1°C under nitrogen atmosphere. The rate of polymerization increases with an increasing the concentrations of AN, MPTC and PDS. The order with respect to [AN], [MPTC], and [PDS] were found to be 1.01, 1.03 and 0.52, respectively. Based on the observed results a suitable mechanism has been proposed to account for the experimental observations followed by a discussion on its significance.

  14. Cu(II)-mediated atom transfer radical polymerization of methyl methacrylate via a strategy of thermo-regulated phase-separable catalysis in a liquid/liquid biphasic system: homogeneous catalysis, facile heterogeneous separation, and recycling.

    Science.gov (United States)

    Pan, Jinlong; Zhang, Bingjie; Jiang, Xiaowu; Zhang, Lifen; Cheng, Zhenping; Zhu, Xiulin

    2014-09-01

    A strategy of thermo-regulated phase-separable catalysis (TPSC) is applied to the Cu(II)-mediated atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) in a p-xylene/PEG-200 biphasic system. Initiators for continuous activator regeneration ATRP (ICAR ATRP) are used to establish the TPSC-based ICAR ATRP system using water-soluble TPMA as a ligand, EBPA as an initiator, CuBr2 as a catalyst, and AIBN as a reducing agent. By heating to 70 °C, unlimited miscibility of both solvents is achieved and the polymerization can be carried out under homogeneous conditions; then on cooling to 25 °C, the mixture separates into two phases again. As a result, the catalyst complex remains in the PEG-200 phase while the obtained polymers stay in the p-xylene phase. The catalyst can therefore be removed from the resultant polymers by easily separating the two different layers and can be reused again. It is important that well-defined PMMA with a controlled molecular weight and narrow molecular weight distribution could be obtained using this TPSC-based ICAR ATRP system.

  15. Polymerization rate and mechanism of ultrasonically initiated emulsion polymerization of n-butyl acrylate.

    Science.gov (United States)

    Xia, Hesheng; Wang, Qi; Liao, Yongqin; Xu, Xi; Baxter, Steven M; Slone, Robert V; Wu, Shuguang; Swift, Graham; Westmoreland, David G

    2002-07-01

    The factors affecting the induction period and polymerization rate in ultrasonically initiated emulsion polymerization of n-butyl acrylate (BA) were investigated. The induction period takes only an instant in ultrasonically initiated emulsion polymerization of BA without any added initiator by enhancing the N2 flow rate. Increasing temperature, power output and SDS concentration, decreasing the monomer concentration results in further decreasing induction period and enhanced polymerization rate. Under optimized reaction conditions the conversion of BA reaches 92% in 11 min. The polymerization rate can be controlled by varying reaction parameters. The apparatus of ultrasonically initiated semi-continuous and continuous emulsion polymerization were set up and the feasibility was first studied. Based on the experimental results, a free radical polymerization mechanism for ultrasonically initiated emulsion polymerization was proposed, including the sources of the radicals, the process of radical formation, the locus of polymerization and the polymerization process. Compared with conventional emulsion polymerization, where the radicals come from thermal decomposition of a chemical initiator, ultrasonically initiated emulsion polymerization has attractive features such as no need for a chemical initiator, lower reaction temperature, faster polymerization rate, and higher molecular weight of the polymer prepared.

  16. 甲基丙烯酸-N,N-2-甲基乙胺酯原子转移自由基聚合动力学研究%Kinetic Study of Atom Transfer Radical Polymerization of 2- (N,N- Dimethylamino)ethyl Methacrylate

    Institute of Scientific and Technical Information of China (English)

    江成发; 张允湘

    2004-01-01

    A kinetic model was developed to describe the atom transfer radical polymerization (ATRP) of 2-(N,N-dimethylamino) ethyl methacrylate (DMAEMA). The model was based on a polymerization mechanism,which included the atom transfer equilibrium for primary radical, the propagation of growing polymer radical, and the atom transfer equilibrium for the growing polymer radical. An experiment was carried out to measure the conversion of monomer, the number-average molecular weight of polymer and molecular weight distribution for the ATRP process of DMAEMA. The experimental data were used to correlate the kinetic model and rate constants were obtained. The rate constants of activation and deactivation in the atom transfer equilibrium for primary radical are 1.0 x 104 L·mol-1.s-1 and 0.04 L·mol-1.s-1, respectively. The rate constant of the propagation of growing polymer radical is 8.50 L·mol-1.s-1, and the rate constants of activation and deactivation in the atom transfer equilibrium for growing polymer radical are 0.045 L.mol-1.s-1 and 1.2 × 105 L·mol-1.s- 1, respectively. The values of the rate constants represent the features of the ATRP process. The kinetic model was used to calculate the ATRP process of DMAEMA. The results show that the calculations agree well with the measurements.

  17. Polymerization Initiated at the Sidewalls of Carbon Nanotubes

    Science.gov (United States)

    Tour, James M.; Hudson, Jared L.

    2011-01-01

    A process has been developed for growing polymer chains via anionic, cationic, or radical polymerization from the side walls of functionalized carbon nanotubes, which will facilitate greater dispersion in polymer matrices, and will greatly enhance reinforcement ability in polymeric material.

  18. 活性/可控自由基聚合制备奎宁分子印迹微球及识别性能研究%Study on the preparation for quinine imprinted polymeric microsphere by living/controlled radical polymerization and its recognition properties

    Institute of Scientific and Technical Information of China (English)

    何建峰; 杨万里; 黄少梅

    2014-01-01

    以奎宁分子为模板,甲基丙烯酸( MAA)为功能单体,乙二醇二甲基丙烯酸酯( EDMA)为交联剂,二硫代四乙基秋兰姆( TED)为活性/可控引发剂,将可逆加成-断裂链转移自由基聚合与沉淀聚合相结合,制备微米级的球形奎宁分子印迹聚合物。并用扫描电镜和激光粒度扫描对聚合物粒子进行表征,结果显示,活性/可控聚合制备的分子印迹聚合物呈均匀的球形,其平均粒径最大可达2.3μm。对不同底物的结合实验表明,与传统沉淀聚合物相比,该分子印迹聚合物表现出更高的络合容量和分子选择性。%The spherical molecularly imprinted polymers with micron-size were prepared by using quinine as template,methylacrylic acid( MAA) as functional monomer,ethylene glycol dimethacrylate( EDMA) as cross-linker and dithiotetraethylthiuram( TED) as the living/controlled initiator by combining reversible addition-fragmentation chain transfer radical polymerization with precipitation pol-ymerization. The polymeric particles were characterized by scanning electron microscopy and laser particle size analysis. The results show that the polymeric particles prepared by living/controlled polymerization present uniform spherical shape and its maximum av-erage diameter reach 2. 3 μm. The binding experiment towards different substrates indicates that the living/controlled molecularly imprinted polymer shows higher binding capacity and molecular selectivity than the traditional precipitation polymers.

  19. 光照射下丙烯腈活性自由基聚合的研究%Photo-induced Living Radical Polymerization of Acrylonitrile

    Institute of Scientific and Technical Information of China (English)

    何斌鸿

    2015-01-01

    Acrylonitrile as monomer, azobisisobutyronitrile as initiator, hexamethylenetetramine as ligand, copper chloride dihydrate as catalyst and Vitamin C as reducing agent, polyacrylonitrile was synthesized in N,N-dimethylformamide under the light irradiation. The effects of the amount of monomer, initiator, catalyst, hexamethylenetetramine and Vitamin C on the photo-induced polymerization of acrylonitrile have been invetigated. On the basis of experiments, it is concluded that the best polymerization conditions were that the amount of monomer is 0.2 mol and the usage of azobisisobutyronitrile, copper chloride dihydrate, hexamethylenetetramine and vitamin C was 1%, 0.75%, 1%, 4 % of the mole of monomer, respectively. The best reaction time is 11 h.%以丙烯腈作为单体,偶氮二异丁腈为引发剂,六次亚甲基四胺为配体,二水氯化铜为催化剂,维生素C为还原剂,在光的照射下,于溶剂 N,N-二甲基甲酰胺中采用自由基聚合的原理制得聚丙烯腈,并探究改变单一反应物的用量时对该聚合反应的影响,最后得出最佳的聚合条件为:在室温20℃下反应时,最佳单体用量为0.2mol,引发剂偶氮二异丁腈、催化剂二水氯化铜、配体六次亚甲基四胺、还原剂维生素C分别为单体摩尔总量的1%、0.75%、1%、4%,最佳反应时间为11 h.

  20. Uranium Adsorbent Fibers Prepared by Atom-Transfer Radical Polymerization (ATRP) from Poly(vinyl chloride)- co -chlorinated Poly(vinyl chloride) (PVC- co -CPVC) Fiber

    Energy Technology Data Exchange (ETDEWEB)

    Brown, Suree; Yue, Yanfeng; Kuo, Li-Jung; Mehio, Nada; Li, Meijun; Gill, Gary; Tsouris, Costas; Mayes, Richard T.; Saito, Tomonori; Dai, Sheng

    2016-04-20

    The need to secure future supplies of energy attracts researchers in several countries to a vast resource of nuclear energy fuel: uranium in seawater (estimated at 4.5 billion tons in seawater). In this study, we developed effective adsorbent fibers for the recovery of uranium from seawater via atom-transfer radical polymerization (ATRP) from a poly- (vinyl chloride)-co-chlorinated poly(vinyl chloride) (PVC-co-CPVC) fiber. ATRP was employed in the surface graft polymerization of acrylonitrile (AN) and tert-butyl acrylate (tBA), precursors for uranium-interacting functional groups, from PVC-co-CPVC fiber. The [tBA]/[AN] was systematically varied to identify the optimal ratio between hydrophilic groups (from tBA) and uranyl-binding ligands (from AN). The best performing adsorbent fiber, the one with the optimal [tBA]/[AN] ratio and a high degree of grafting (1390%), demonstrated uranium adsorption capacities that are significantly greater than those of the Japan Atomic Energy Agency (JAEA) reference fiber in natural seawater tests (2.42-3.24 g/kg in 42 days of seawater exposure and 5.22 g/kg in 49 days of seawater exposure, versus 1.66 g/kg in 42 days of seawater exposure and 1.71 g/kg in 49 days of seawater exposure for JAEA). Adsorption of other metal ions from seawater and their corresponding kinetics were also studied. The grafting of alternative monomers for the recovery of uranium from seawater is now under development by this versatile technique of ATRP.

  1. Tuning the Solubility of Copper Complex in Atom Transfer Radical Self-Condensing Vinyl Polymerizations to Control Polymer Topology via One-Pot to the Synthesis of Hyperbranched Core Star Polymers

    Directory of Open Access Journals (Sweden)

    Zong-Cheng Chen

    2014-09-01

    Full Text Available In this paper, we propose a simple one-pot methodology for proceeding from atom transfer reaction-induced conventional free radical polymerization (AT-FRP to atom transfer self-condensing vinyl polymerization (AT-SCVP through manipulation of the catalyst phase homogeneity (i.e., CuBr/2,2'-bipyridine (CuBr/Bpy in a mixture of styrene (St, 4-vinyl benzyl chloride (VBC, and ethyl 2-bromoisobutyrate. Tests of the solubilities of CuBr/Bpy and CuBr2/Bpy under various conditions revealed that both temperature and solvent polarity were factors affecting the solubility of these copper complexes. Accordingly, we obtained different polymer topologies when performing AT-SCVP in different single solvents. We investigated two different strategies to control the polymer topology in one-pot: varying temperature and varying solvent polarity. In both cases, different fractions of branching revealed the efficacy of varying the polymer topology. To diversify the functionality of the peripheral space, we performed chain extensions of the resulting hyperbranched poly(St-co-VBC macroinitiator (name as: hbPSt MI with either St or tBA (tert-butyl acrylate. The resulting hyperbranched core star polymer had high molecular weights (hbPSt-g-PSt: Mn = 25,000, Đ = 1.77; hbPSt-g-PtBA: Mn = 27,000, Đ = 1.98; hydrolysis of the tert-butyl groups of the later provided a hyperbranched core star polymer featuring hydrophilic poly(acrylic acid segments.

  2. Synthesis and optimization of fluorescent poly(N-isopropyl acrylamide)-coated surfaces by atom transfer radical polymerization for cell culture and detachment.

    Science.gov (United States)

    Cooperstein, Marta A; Bluestein, Blake M; Canavan, Heather E

    2014-03-16

    Although there are many stimulus-responsive polymers, poly(N-isopropyl acrylamide) (pNIPAM) is of special interest due to the phase change it undergoes in a physiologically relevant temperature range that leads to the release of cells and proteins. The nondestructive release of cells opens up a wide range of applications, including the use of pNIPAM for cell sheet and tissue engineering. In this work, pNIPAM surfaces were generated that can be distinguished from the extracellular matrix. A polymerization technique was adapted that was previously used by Mendez, and the existing protocol was optimized for the culture of mammalian cells. The resulting surfaces were characterized with X-ray photoelectron spectroscopy and goniometry. The developed pNIPAM surfaces were further adapted by incorporation of 5-acrylamidofluorescein to generate fluorescent pNIPAM-coated surfaces. Both types of surfaces (fluorescent and nonfluorescent) sustained cellular attachment and produced cellular detachment of ∼90%, and are therefore suitable for the generation of cell sheets for engineered tissues and other purposes. These surfaces will be useful tools for experiments investigating cellular detachment from pNIPAM and the pNIPAM/cell interface.

  3. Development and characterization of a novel, antimicrobial, sterile hydrogel dressing for burn wounds: single-step production with gamma irradiation creates silver nanoparticles and radical polymerization.

    Science.gov (United States)

    Boonkaew, Benjawan; Barber, Philip M; Rengpipat, Sirirat; Supaphol, Pitt; Kempf, Margit; He, Jibao; John, Vijay T; Cuttle, Leila

    2014-10-01

    Patients with burn wounds are susceptible to wound infection and sepsis. This research introduces a novel burn wound dressing that contains silver nanoparticles (SNPs) to treat infection in a 2-acrylamido-2-methylpropane sulfonic acid sodium salt (AMPS-Na(+) ) hydrogel. Silver nitrate was dissolved in AMPS-Na(+) solution and then exposed to gamma irradiation to form SNP-infused hydrogels. The gamma irradiation results in a cross-linked polymeric network of sterile hydrogel dressing and a reduction of silver ions to form SNPs infused in the hydrogel in a one-step process. About 80% of the total silver was released from the hydrogels after 72 h immersion in simulated body fluid solution; therefore, they could be used on wounds for up to 3 days. All the hydrogels were found to be nontoxic to normal human dermal fibroblast cells. The silver-loaded hydrogels had good inhibitory action against Pseudomonas aeruginosa and methicillin-resistant Staphylococcus aureus. Results from a pilot study on a porcine burn model showed that the 5-mM silver hydrogel was efficient at preventing bacterial colonization of wounds, and the results were comparable to the commercially available silver dressings (Acticoat(TM) , PolyMem Silver(®) ). These results support its use as a potential burn wound dressing.

  4. Ultrahigh Molecular Weight Linear Block Copolymers: Rapid Access by Reversible-Deactivation Radical Polymerization and Self- Assembly into Large Domain Nanostructures

    Energy Technology Data Exchange (ETDEWEB)

    Mapas, Jose Kenneth D.; Thomay, Tim; Cartwright, Alexander N.; Ilavsky, Jan; Rzayev, Javid

    2016-05-05

    Block copolymer (BCP) derived periodic nanostructures with domain sizes larger than 150 nm present a versatile platform for the fabrication of photonic materials. So far, the access to such materials has been limited to highly synthetically involved protocols. Herein, we report a simple, “user-friendly” method for the preparation of ultrahigh molecular weight linear poly(solketal methacrylate-b-styrene) block copolymers by a combination of Cu-wire-mediated ATRP and RAFT polymerizations. The synthesized copolymers with molecular weights up to 1.6 million g/mol and moderate dispersities readily assemble into highly ordered cylindrical or lamella microstructures with domain sizes as large as 292 nm, as determined by ultra-small-angle x-ray scattering and scanning electron microscopy analyses. Solvent cast films of the synthesized block copolymers exhibit stop bands in the visible spectrum correlated to their domain spacings. The described method opens new avenues for facilitated fabrication and the advancement of fundamental understanding of BCP-derived photonic nanomaterials for a variety of applications.

  5. Studies on the synthesis of peptides containing dehydrovaline and dehydroisoleucine based on copper-mediated enamide formation

    Directory of Open Access Journals (Sweden)

    Franziska Gille

    2016-03-01

    Full Text Available The preparation of peptide fragments containing dehydrovaline and dehydroisoleucine moieties present in the antibiotic myxovalargin is reported. Peptide formation is based on a copper-mediated C–N cross-coupling protocol between an acyl amide and a peptidic vinyl iodide. The presence of a neighboring arginine in the vinyl iodide posed a challenge with respect to the choice of the protecting group and the reaction conditions. It was found that ornithine – a suitable precursor – is better suited than arginine for achieving good yields for the C–N cross-coupling reaction. The optimized conditions were utilized for the synthesis of peptides 32, 33, 39 and 40 containing a neighboring ornithine as well as for the tripeptide 44 containing dehydroisoleucine with the correct stereochemistry.

  6. Polymeric microspheres

    Science.gov (United States)

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

    2004-04-13

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

  7. SYNTHESIS OF BRANCHED POLY( METHYL ACRYLATE) VIA SINGLE ELECTRON TRANSFER LIVING RADICAL POLYMERIZATION%单电子转移活性自由基聚合制备支化聚丙烯酸甲酯的研究

    Institute of Scientific and Technical Information of China (English)

    郑逸良; 薛小强; 黄文艳; 朱剑; 蒋必彪

    2012-01-01

    The branched poly ( methyl acrylate) was prepared by using 2-( 2-bromoisobutyryloxy) ethyl acrylate as inimer agent, methyl acrylate as monomer and Cu /CuBr2/PMDETA as catalyst system via single electron transfer living radical polymerization (SET-LRP) in DMSO polar solvent at room temperature. In the polymerization process, gas chromatography ( GC ), nuclear magnetic resonance spectroscopy ( H-NMR) and triple detection size exclusion chromatography ( TD-SEC ) were used to analyse and characterize the polymerization and the resulting polymers. The results showed that the polymerization rate was significantly fast at room temperature, when the polymerization time was 130 min,the conversion of monomer methyl acrylate was over 99% . The degree of branching for the branched polymer increased gradually with monomer conversion, and the viscosity of branched polymer was low compared to that of the linear polymer at the same molecular weight. Therefore,the characteristic constant α of Mark-Houwink would be minimized to 0. 290. In addition,the primary chains with low molecular weight ( component 1) in the branched polymers were decreasing during the whole reaction. In the late stages of the reaction, the high branched poly ( methyl acrylate) component was mainly obtained.%以丙烯酸2-(2-溴异丁酰氧基)乙酯( BIEA)为引发剂单体(inimer),丙烯酸甲酯(MA)为单体,Cu0/CuBr2和N,N,N′,N″,N"-五甲基二亚乙基三胺(PMDETA)为催化体系,二甲亚砜(DMSO)为溶剂,在常温(25℃)下通过单电子转移活性自由基聚合(SET-LRP)合成支化聚丙烯酸甲酯.聚合反应过程中,采用气相色谱(GC)、核磁共振(1 H-NMR)和三检测体积排除色谱(TD-SEC)等测试手段跟踪分析和表征支化聚合物的结构.研究结果表明,采用SET-LRP方法,铜粉作为催化剂,常温下聚合反应就能快速进行,130 min之内MA的转化率已达99%以上,制备出高分子量支化聚合物.随着反应的不断进行,聚合物支化程度

  8. Surface functionalized SiO2 nanoparticles with cationic polymers via the combination of mussel inspired chemistry and surface initiated atom transfer radical polymerization: Characterization and enhanced removal of organic dye.

    Science.gov (United States)

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

    2017-03-28

    Monodispersed SiO2 particles functionalized with cationic polymers poly-((3-acrylamidopropyl)trimethylammonium chloride) (PAPTCl) were prepared using mussel inspired surface modification strategy and surface initiated atom transfer radical polymerization (SI-ATRP). Fourier transform infrared spectroscopy, transmission electron microscope, thermogravimetric analysis, X-ray photoelectron spectroscopy, and zeta potential were employed to characterize these SiO2 samples. The adsorption performance of the functionalized SiO2 (donated as SiO2-PDA-PAPTCl) towards anionic organic dye Congo red (CR) was investigated to evaluate their potential environmental applications. We demonstrated that the surface of SiO2 particles can be successfully functionalized with cationic PAPTCl. The adsorption capability of as-prepared SiO2 was found to increases from 28.70 and 106.65mg/g after surface grafted with cationic polymers. The significant enhancement in the adsorption capability of SiO2-PDA-PAPTCl is mainly attributed to the introduction of cationic polymers. More importantly, this strategy is expected to be promising for fabrication of many other functional polymer nanocomposites for environmental applications due to the universality of mussel inspired chemistry and well designability and good monomer adaptability of SI-ATRP.

  9. Induction heating vs conventional heating for the hydrothermal treatment of nitinol and its subsequent 2-(methacryloyloxy)ethyl 2-(trimethylammonio)ethyl phosphate coating by surface-initiated atom transfer radical polymerization.

    Science.gov (United States)

    Devillers, S; Barthélémy, B; Delhalle, J; Mekhalif, Z

    2011-10-01

    Nitinol is an alloy of great interest in general and especially in the biomedical field where many researches are aimed to improve both its corrosion resistance and its biocompatibility. In this work, we report on the advantage of an induction heating treatment in pure water compared to a conventional hydrothermal procedure. Both treatments lead to a hydroxylation of the surface, a decrease of the nickel amount in the outer part of the oxide layer, and a drastically decreased corrosion current density. However, the amount of surface hydroxyl groups is higher in the case of the induction heating treatment, which in turn leads to a denser grafting of atom transfer radical polymerization initiators and ultimately to a thicker 2-(methacryloyloxy)ethyl 2-(trimethylammonio)ethyl phosphate (MPC) polymer layer than in the case of conventional heating treatments. X-ray photoelectron spectroscopy (XPS), static contact angle, and polarization curves measurements as well as scanning electron microscopy (SEM) have been used to characterize the obtained modified surfaces.

  10. Magnetic properties of polymerized diphenyloctatetrayne

    Energy Technology Data Exchange (ETDEWEB)

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

    2012-10-15

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

  11. Polymerization as a Model Chain Reaction

    Science.gov (United States)

    Morton, Maurice

    1973-01-01

    Describes the features of the free radical, anionic, and cationic mechanisms of chain addition polymerization. Indicates that the nature of chain reactions can be best taught through the study of macromolecules. (CC)

  12. 间歇自由基聚合反应器的Pareto蚁群优化%Pareto ant colony optimization to batch free-radical polymerization reactors

    Institute of Scientific and Technical Information of China (English)

    郭相坤; 王晓静; 许德平; 王晓玲

    2009-01-01

    Optimization technologies are widely used in chemical industry for chemical engineers to select the "best" manipulating profile out of a given set of technological conditions. The engineers must consider multiple objectives and can improve their opportunities by determining and exploring the solution space of all efficient solutions interactively with little a priori preference information available. However, the enumerative method only works on small instances and the underlying complex optimization problems become increasingly demanding as the number of projects grow. The recently developed meta-heuristics, Ant Colony Optimization Algorithms, provide a useful compromise between the computation time and the quality of the approximated solution space. In this study, a Pareto Ant Colony Optimization Algorithm was applied to a real world batch polymerization process of multi-objective optimization. The results indicate that the algorithm is robust and useful for the chemical process optimization.%优化技术广泛用于化工生产中"最佳"工艺条件的确定,工程师常需在无先验信息情况下,从若干工艺条件中确定同时能满足多方需求的最佳方案,实现效益最大化.枚举法只能在较简单的情况下使用,随着生产实际复杂程度的增加,枚举法显得无能为力.近来提出的元启发式蚁群优化算法无论计算时间,还是优化质量,都能满足复杂体系的优化.本研究采用Pareto蚁群算法,对间歇自由基聚合反应器进行了多目标优化,结果表明,该算法具有较强的鲁棒性,可用于间歇自由基聚合反应器的设计.

  13. Functionalization and Polymerization on the CNT Surfaces

    KAUST Repository

    Albuerne, Julio

    2013-07-01

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

  14. Study on Light-induced Atom Transfer Radical Precipatation Polymerization of Methyl Methacrylate%光诱导活性沉淀聚合法合成聚甲基丙烯酸甲酯的研究

    Institute of Scientific and Technical Information of China (English)

    王国祥; 王雪娜

    2015-01-01

    本文以2-羟基-2-甲基-1-苯基-1-丙酮(1173)为光引发剂,FeCl3·6H2O作为催化剂,六次甲基四胺作为配体,维生素C作为还原剂,在无水乙醇溶剂中进行聚合反应。通过光诱导原子转移自由基沉淀聚合法合成了聚甲基丙烯酸甲酯。研究了反应时间、光引发剂用量、还原剂用量、配体用量、催化剂用量等因素对聚合反应收率的影响。聚合物的红外谱图证实得到目标产物聚甲基丙烯酸甲酯。热分析结果表明该种方法得到的聚甲基丙烯酸甲酯金属残留量较低。并通过改变实验参数得到了甲基丙烯酸甲酯均聚的最佳反应条件:反应时间12 h,引发剂1173与单体总量的摩尔比为1:25,还原剂维生素C与单体总量的摩尔比为3:4,催化剂FeCl3·6H2O与单体总量的摩尔比为3:250,配体六次甲基四胺与单体总量的摩尔比为3:100。%In this paper, 1173 as the initiator, FeCl3·6H2O as a catalyst , hexamethylenetetramine as a ligand, vitamin C as a reducing agent, the polymerization reaction was carried out in ethanol solvent. Poly(methyl methacrylate)s were prepared via atom transfer radical polymerization precipitation polymerization. The effects of reaction temperature, the amount of initiator, reducing, ligand, catalyst on the polymerization have been investigated. The Poly(methyl methacrylate)s were characterized by FT-IR and differential thermal analysis of polymers. The optimal reaction conditions of synthesis of Poly(methyl methacrylate) were obtained by changing the experimental factor: the reaction time was 12 h, 1173 was 4.0% of the total monomers (molar ratio) , Vitamin C was 7.5% of the total monomers (molar ratio), catalyst was 1.2% of the total amount of the monomers (molar ratio), hexamethylenetetramine ligand was 3.0% of the total monomers (molar ratio) .

  15. Preparation of a poly(3'-azido-3'-deoxythymidine-co-propargyl methacrylate-co-pentaerythritol triacrylate) monolithic column by in situ polymerization and a click reaction for capillary liquid chromatography of small molecules and proteins.

    Science.gov (United States)

    Lin, Zian; Yu, Ruifang; Hu, Wenli; Zheng, Jiangnan; Tong, Ping; Zhao, Hongzhi; Cai, Zongwei

    2015-07-01

    Combining free radical polymerization with click chemistry via a copper-mediated azide/alkyne cycloaddition (CuAAC) reaction in a "one-pot" process, a facile approach was developed for the preparation of a poly(3'-azido-3'-deoxythymidine-co-propargyl methacrylate-co-pentaerythritol triacrylate) (AZT-co-PMA-co-PETA) monolithic column. The resulting poly(AZT-co-PMA-co-PETA) monolith showed a relatively homogeneous monolithic structure, good permeability and mechanical stability. Different ratios of monomers and porogens were used for optimizing the properties of a monolithic column. A series of alkylbenzenes, amides, anilines, and benzoic acids were used to evaluate the chromatographic properties of the polymer monolith in terms of hydrophobic, hydrophilic and cation-exchange interactions, and the results showed that the poly(AZT-co-PMA-co-PETA) monolith exhibited more flexible adjustment in chromatographic selectivity than that of the parent poly(PMA-co-PETA) and AZT-modified poly(PMA-co-PETA) monoliths. Column efficiencies for toluene, DMF, and formamide with 35,000-48,000 theoretical plates per m could be obtained at a linear velocity of 0.17 mm s(-1). The run-to-run, column-to-column, and batch-to-batch repeatabilities of the retention factors were less than 4.2%. In addition, the proposed monolith was also applied to efficient separation of sulfonamides, nucleobases and nucleosides, anesthetics and proteins for demonstrating its potential.

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

    Directory of Open Access Journals (Sweden)

    Cai Xialing

    2009-08-01

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

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

    Science.gov (United States)

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

    2015-07-30

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

  18. Biocompatible Polymeric Materials Intended for Drug Delivery and Therapeutic Applications

    DEFF Research Database (Denmark)

    Hvilsted, Søren; Javakhishvili, Irakli; Bednarek, Melania

    2007-01-01

    water soluble polymers, polyethylene glycol (PEG), and poly(acrylic acid) (PAA) with good mycoadhesive properties, are all prepared by living/controlled polymerization techniques. These techniques, atom transfer radical polymerization (ATRP) and ring opening polymerization (ROP), ensure at the same time...

  19. Copper-mediated oxidative degradation of catecholamines and oxidative damage of protein

    Energy Technology Data Exchange (ETDEWEB)

    Goncalves, P.R.; Harria, M.I.N.; Felix, J.M.; Hoffmann, M.E. [Universidade Estadual de Campinas, SP (Brazil). Inst. de Biologia

    1997-12-31

    Full text. Degradative oxidation of catecholamines has been a matter of large interest in recent years due to the evidences associating their autoxidation with the etiology of neurotoxic and cardiotoxic processes. In this work we present data on the degradative oxidation of catecholamines of physiological importance: isoproterenol (IP), epinephrine (EP), norepinephrine (NEP), deoxyepinephrine (DEP) and dopamine (DA). The degradative oxidation of the catecholamines was followed by measurement of spectral changes and oxygen consumption by neutral aqueous solutions. The data show that Cu{sup 2+} strongly accelerated the rate of catecholamine oxidation, following the decreasing order; EP>DEP>IP>NEP>DA. The production of superoxide anion radical during catecholamine oxidation was very slow, even in the presence of Cu{sup 2+}. The ability of IP to induce damages on bovine serum albumin (BSA) was determined by measuring the formation of carbonyl-groups in the protein, detected by reduction with tritiated Na BH{sub 4}. The incubation of BSA with IP (50-500{mu}M), in the presence of 100{mu}M Cu{sup 2+} leaded to an increased and dose dependent {sup 3} H-incorporation by the oxidized protein. The production of oxidative damage by IP/Cu{sup 2+} was accompanied by marked BSA fragmentation, detected by SDS-polyacrylamide gel dependent (25-400{mu}M IP) des appearance of the original BSA band and appearance of smaller fragments spread in the gel, when incubation has been done in the presence of 100{mu}M Cu{sup 2+}. These results suggest that copper-catalysed oxidative degradation of proteins induced by catecholamines might be critically involved in the toxic action of these molecules

  20. Palladium- and copper-mediated N-aryl bond formation reactions for the synthesis of biological active compounds

    Directory of Open Access Journals (Sweden)

    Burkhard Koenig

    2011-01-01

    Full Text Available N-Arylated aliphatic and aromatic amines are important substituents in many biologically active compounds. In the last few years, transition-metal-mediated N-aryl bond formation has become a standard procedure for the introduction of amines into aromatic systems. While N-arylation of simple aromatic halides by simple amines works with many of the described methods in high yield, the reactions may require detailed optimization if applied to the synthesis of complex molecules with additional functional groups, such as natural products or drugs. We discuss and compare in this review the three main N-arylation methods in their application to the synthesis of biologically active compounds: Palladium-catalysed Buchwald–Hartwig-type reactions, copper-mediated Ullmann-type and Chan–Lam-type N-arylation reactions. The discussed examples show that palladium-catalysed reactions are favoured for large-scale applications and tolerate sterically demanding substituents on the coupling partners better than Chan–Lam reactions. Chan–Lam N-arylations are particularly mild and do not require additional ligands, which facilitates the work-up. However, reaction times can be very long. Ullmann- and Buchwald–Hartwig-type methods have been used in intramolecular reactions, giving access to complex ring structures. All three N-arylation methods have specific advantages and disadvantages that should be considered when selecting the reaction conditions for a desired C–N bond formation in the course of a total synthesis or drug synthesis.

  1. Copper-mediated C-H activation/C-S cross-coupling of heterocycles with thiols

    KAUST Repository

    Ranjit, Sadananda

    2011-11-04

    We report the synthesis of a series of aryl- or alkyl-substituted 2-mercaptobenzothiazoles by direct thiolation of benzothiazoles with aryl or alkyl thiols via copper-mediated aerobic C-H bond activation in the presence of stoichiometric CuI, 2,2′-bipyridine and Na 2CO 3. We also show that the approach can be extended to thiazole, benzimidazole, and indole substrates. In addition, we present detailed mechanistic investigations on the Cu(I)-mediated direct thiolation reactions. Both computational studies and experimental results reveal that the copper-thiolate complex [(L)Cu(SR)] (L: nitrogen-based bidentate ligand such as 2,2′-bipyridine; R: aryl or alkyl group) is the first reactive intermediate responsible for the observed organic transformation. Furthermore, our computational studies suggest a stepwise reaction mechanism based on a hydrogen atom abstraction pathway, which is more energetically feasible than many other possible pathways including β-hydride elimination, single electron transfer, hydrogen atom transfer, oxidative addition/reductive elimination, and σ-bond metathesis. © 2011 American Chemical Society.

  2. Fundamentals of Atom Transfer Radical Polymerization

    Science.gov (United States)

    Coessens, Veerle M. C.; Matyjaszewski, Krzysztof

    2010-01-01

    Today's market increasingly demands sophisticated materials for advanced technologies and high-value applications, such as nanocomposites, optoelectronic, or biomedical materials. Therefore, the demand for well-defined polymers with very specific molecular architecture and properties increases. Until recently, these kinds of polymers could only be…

  3. Advances in fabrication of polymer UF membrane by atom transfer radical polymerization%原子转移自由基聚合制备高分子超滤膜技术进展

    Institute of Scientific and Technical Information of China (English)

    隋燕; 高从堦; 王志宁; 徐佳

    2011-01-01

    Atom transfer radical polymerization(ATRP) is the "Controlled/Living" new technology developed for the past two decades. ATRP reactions, where metal catalysts are utilized in combination with Uganda yielding well-controlled structures and narrow molecular weight distributions, has been carried out since 1995. This review summarizes such recent research activities. The synthesis strategies of anti-fouling and/or anti-bacterial surfaces and materials via ATRP are described in detail. The highly robust and versatile ATRP technique is particularly suited for the preparation of functional surfaces including high-capacity exchange membranes for chromatographic bioseparations. This contribution describes the method that hydrophilic polymer is grafted or blocked on surface or material by ATRP to prepare well-structured functional materials or membranes. The ATRP reaction can control the graft or block chain length and density with polymerization time or monomer and initiator concentration in a linear fashion, which makes the hydrophilic material bonding stably on the hydrophobic membrane materials,and also effectively controls pore sizes and pore distributions of the membrane surface without changing the properties of base membrane. The separation performance of resulting membrane is improved considerably. The research activities in the last decade indicate that ATRP has become an essential tool for the design and synthesis of advanced, noble and novel materials and membranes.%原子转移自由基聚合(ATRP)是近十几年来发展起来的高效“可控/活性”聚合新技术.ATRP技术自1995年发现后,将金属催化剂与配位基结合可以控制结构,获得窄分子质量分布.通过ATRP技术在膜表面和膜材料上接枝或嵌段亲水高聚物来制备抗污染、抗菌超滤膜,包括用于生物分离色谱的高效离子交换膜.由于ATRP随反应时间、反应单体和引发剂浓度可以线性控制接枝或嵌段链密度和长度,这使亲

  4. Bioinorganic chemistry of Parkinson's disease: structural determinants for the copper-mediated amyloid formation of alpha-synuclein.

    Science.gov (United States)

    Binolfi, Andrés; Rodriguez, Esaú E; Valensin, Daniela; D'Amelio, Nicola; Ippoliti, Emiliano; Obal, Gonzalo; Duran, Rosario; Magistrato, Alessandra; Pritsch, Otto; Zweckstetter, Markus; Valensin, Gianni; Carloni, Paolo; Quintanar, Liliana; Griesinger, Christian; Fernández, Claudio O

    2010-11-15

    The aggregation of alpha-synuclein (AS) is a critical step in the etiology of Parkinson's disease (PD). A central, unresolved question in the pathophysiology of PD relates to the role of AS-metal interactions in amyloid fibril formation and neurodegeneration. Our previous works established a hierarchy in alpha-synuclein-metal ion interactions, where Cu(II) binds specifically to the protein and triggers its aggregation under conditions that might be relevant for the development of PD. Two independent, non-interacting copper-binding sites were identified at the N-terminal region of AS, with significant difference in their affinities for the metal ion. In this work we have solved unknown details related to the structural binding specificity and aggregation enhancement mediated by Cu(II). The high-resolution structural characterization of the highest affinity N-terminus AS-Cu(II) complex is reported here. Through the measurement of AS aggregation kinetics we proved conclusively that the copper-enhanced AS amyloid formation is a direct consequence of the formation of the AS-Cu(II) complex at the highest affinity binding site. The kinetic behavior was not influenced by the His residue at position 50, arguing against an active role for this residue in the structural and biological events involved in the mechanism of copper-mediated AS aggregation. These new findings are central to elucidate the mechanism through which the metal ion participates in the fibrillization of AS and represent relevant progress in the understanding of the bioinorganic chemistry of PD.

  5. The human septin7 and the yeast CDC10 septin prevent Bax and copper mediated cell death in yeast.

    Science.gov (United States)

    Horowitz, Avital; Lapointe, Jason F; Eid, Rawan; Sheibani, Sara; Gharib, Nada; Jones, Natalie K; Vali, Hojatollah; Mandato, Craig A; Greenwood, Michael T

    2013-12-01

    The mechanisms of programmed cell death activate genetically encoded intracellular programs in a controlled manner, the most common form being apoptosis. Apoptosis is carried out through a cascade of caspase mediated proteolytic cleavages initiated by the oligomerization of Bax, a cardinal regulator of mitochondrial-mediated apoptosis. Heterologous expression of Bax in yeast causes cell death that shares a number of similarities to processes that occur in mammalian apoptosis. A screen of a cardiac cDNA library for suppressors of Bax-mediated apoptosis identified human septin7, a protein that belongs to the septin superfamily of conserved GTP-binding proteins that share a conserved cdc/septin domain. Analysis of the amino acid sequence deduced from the septin7 clone as well as the corresponding human septin7 gene revealed that a novel alternatively spliced transcript called septin7 variant4 (v4) was uncovered. Yeast cells overexpressing the human septin7 v4 cDNA were also capable of resisting copper-mediated cell death suggesting that it is not only a Bax suppressor but also an anti-apoptotic sequence. Analysis of septin7 function in a MCA1Δ yeast strain suggests that septin7 inhibits apoptosis in a caspase independent pathway. Overexpression of the yeast septin7 ortholog CDC10 also conferred resistance to the negative effects of copper as well as protecting cells from the overexpression of Bax. In contrast, septin7 was unable to prevent the increase in cell size associated with mutants lacking the endogenous yeast CDC10 gene. Taken together, our analysis suggests that anti-apoptosis is a novel yet evolutionarily conserved property of the septin7 sub-family of septins.

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

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Wei; He, Maofang; Wang, Chaozhan; Wei, Yinmao, E-mail: ymwei@nwu.edu.cn

    2015-07-30

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

  7. 光学活性(甲基)丙烯酰胺的立体定向自由基聚合——立体控制机理探讨%STEREOSPECIFIC RADICAL POLYMERIZATION OF OPTICALLY ACTIVE (METH) ACRYLAMIDE——STUDY ON THE MECHANISM OF STEREOCONTROL

    Institute of Scientific and Technical Information of China (English)

    徐晓冬; 朱元棋; 李晗; 冯四伟; 代海存; 沈贤德; 白建伟; 张丽丽; 岡本佳男

    2013-01-01

    Optically active poly (meth) acrylamides were synthesized by the stereospecific radical polymerization of (S)-N-( 2-hydroxy-l-phenylethyl)methacrylamide ((S)-HPEMA) and ( S) -N-(2-hydroxy-1 -phenylethyl) acrylamide ( ( S ) -HPEA ) in the absence and presence of Lewis acid ytterbium trifluoromethanesulfonate (Yb( OTf)3). The effect of the Lewis acid on the radical polymerization of (S)-HPEMA and (S)-HPEA was investigated. In the presence of a catalytic amount of the Lewis acid,the isotactic specificity of the polymers remarkably increased when the radical polymerization proceeded in methanol and n-butanol. However,the isotactic selectivity disappeared when the radical polymerization proceeded in DMSO. The interaction between the Lewis acid and monomers (S)-HPEMA and (S)-HPEA was investigated by 'H-NMR. It was found that the monomers strongly interacted with the Lewis acid in methanol-d4 , which included the coordination of the amide group to the rare earth metal ion and the hydrogen bond between the hydroxyl group of the monomers and the trifluoromethanesulfonate ion of the Lewis acid. The plausible mechanism of stereocontrol in the radical polymerization of (S)-HPEMA and (S)-HPEA was analyzed. The monomers are activated by the interaction with the Lewis acid, and the activated monomer is preferentially polymerized. Therefore, the Lewis acid is incorporated into the propagating chain end. The Lewis acid could interact with two or more structural units, because of its high coordination numbers and more than one triflate ions, and control the stereochemistry of the polymerization to an isotactic-selective manner. The Lewis acid might weakly interact with the polymer chain to be readily transferred to another monomer and activate it.%利用Lewis酸三氟甲磺酸镱(Yb(OTf)3)调控(S)-N-(2-羟基-1-苯乙基)甲基丙烯酰胺((S)-HPEMA)和(S)-N-(2-羟基-1-苯乙基)丙烯酰胺((S)-HPEA)的自由基聚合,得到相应的光学活性聚合物;研究了

  8. Condensation Polymerization

    Indian Academy of Sciences (India)

    S Ramakrishnan

    2017-04-01

    The very idea that large polymer molecules can indeed existwas hotly debated during the early part of the 20th century.As highlighted by Sivaram in his articles on Carothersand Flory, Staudinger’s macromolecular hypothesis was finallyaccepted, and the study of polymers gained momentumbecause of the remarkable efforts of the these two individualswho laid down the foundations concerning the processes thatled to the formation of large polymer molecules, and to thosethat led to an understanding of many of their extraordinaryphysical properties. Condensation polymerizations, as thename suggests, utilizes bond-forming reactions that generatea small molecule condensate, which often needs to be continuouslyremoved to facilitate the formation of the polymer. Inthis article, I shall describe some of the essential principles ofcondensation polymerizations or more appropriately calledstep-growth polymerizations; and I will also describe someinteresting extensions that lead to the formation of polymernetworks and highly branched polymers.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1996-02-01

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

  10. Functionalized polymer networks: synthesis of microporous polymers by frontal polymerization

    Indian Academy of Sciences (India)

    N S Pujari; A R Vishwakarma; T S Pathak; A M Kotha; S Ponrathnam

    2004-12-01

    A series of glycidyl methacrylate (GMA)–ethylene dimethacrylate (EGDM) copolymers of varying compositions were synthesized by free-radically triggered thermal frontal polymerization (FP) as well as by suspension polymerization (SP) using azobisisobutyronitrile [AIBN] as initiator. The two sets of copolymers were characterized by IR spectroscopy and mercury intrusion porosimetry, for determination of epoxy number and specific surface area. Frontal polymerization was more efficient, yielding greater conversions at much shorter reaction times. The self-propagating frontal polymerization also generates microporous material with narrow pore size distribution. It yields higher internal pore volume and surface area than suspension polymerization, surface morphologies are, however, inferior.

  11. Polymerization Simulator for Introductory Polymer and Material Science Courses

    Science.gov (United States)

    Chirdon, William M.

    2010-01-01

    This work describes how molecular simulation of polymerization reactions can be used to enrich introductory polymer or material science courses to give students a deeper understanding of free-radical chain and stepwise growth polymerization reactions. These simulations have proven to be effective media for instruction that do not require material…

  12. 表面引发原子转移自由基聚合制备聚电解质修饰的碳纳米管%Preparation of Polyelectrolyte Functionalized Multiwalled Carbon Nanotubes via Surface-Initiated Atom Transfer Radical Polymerization

    Institute of Scientific and Technical Information of China (English)

    孙庆文; 于颖; 张南; 张法永

    2012-01-01

    Surface modification of multiwalled carbon nanotubes (MWNT) by polyelectrolyte can enhance the dispersibility of carbon nanotubes in various solvents. Hydroxyl groups were firstly introduced onto the surface of carbon nanotubes (CNT) via esterification of glycol with MWNT which previously treated by concentrated HNO3 and then excess thionyl chloride. Initiating sites (MWNT-Br or MWNT-C1) for atom transfer radical polymerization (ATRP) were formed by reacting MWNT-OH with 2-bromoisobutyryl bromide or 2-chloropropionyl chloride. Grafting polymerization of poly(terf-butyl acry-late) (PtBA) or poly(4-vinylpyridine) (P4VP) from MWNT-Br or MWNT-C1 was carried out by surface-initiated ATRP polymerization. The content of grafted polymer, determined by thermal gravimetric analysis (TGA), was tuned through the feed ratio of monomer to the initiating-sites on MWNT. After hydrolysis (or quaternary amination) of the polymers, different types of polyelectrolyte-functionalized MWNT with good dispersibility in water were prepared successfully. All the materials were well characterized by TGA and infer-red spectrum (IR).%利用聚电解质对多壁碳纳米管(MWNT的表面进行修饰,能有效改善碳纳米管在溶剂中的分散性.首先将经硝酸氧化的碳纳米管与二甲亚砜和乙二醇反应,得到羟基修饰的碳纳米管.然后利用羟基与α-溴异丁酰溴(或α-氯丙酰氯)的酯化反应,在碳纳米管的表面引入了原子转移自由基聚合(atom transfer radical polymerization,ATRP)引发基团,引发丙烯酸叔丁酯(tBA)或4-乙烯基吡啶(4VP)聚合,通过投料比的改变,得到接入量不同的聚合物修饰的碳纳米管.利用热重分析(TGA)和红外对聚合物修饰的碳纳米管进行表征.将聚合物修饰的碳纳米管进行水解(或季胺化),制备得到在水溶液中良好分散的聚电解质修饰的碳纳米管.

  13. Biokompatible Polymere

    Science.gov (United States)

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

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

  14. Core functionalization of semi-crystalline polymeric cylindrical nanoparticles using photo-initiated thiol–ene radical reactions† †Electronic supplementary information (ESI) available: Further methods, polymer and nanostructure characterization. See DOI: 10.1039/c5py01970b Click here for additional data file.

    Science.gov (United States)

    Sun, Liang; Pitto-Barry, Anaïs; Thomas, Anthony W.; Inam, Maria; Doncom, Kay

    2016-01-01

    Sequential ring-opening and reversible addition–fragmentation chain transfer (RAFT) polymerization was used to form a triblock copolymer of tetrahydropyran acrylate (THPA), 5-methyl-5-allyloxycarbonyl-1,3-dioxan-2-one (MAC) and l-lactide. Concurrent deprotection of the THPA block and crystallization-driven self-assembly (CDSA) was undertaken and allowed for the formation of cylindrical micelles bearing allyl handles in a short outer core segment. These handles were further functionalized by different thiols using photo-initiated thiol–ene radical reactions to demonstrate that the incorporation of an amorphous PMAC block within the core does not disrupt CDSA and can be used to load the cylindrical nanoparticles with cargo. PMID:27478513

  15. STUDIES ON THE INITIATION MECHANISM OF CERIC ION AND ACETYLACETONE REDOX SYSTEM IN VINYL POLYMERIZATION

    Institute of Scientific and Technical Information of China (English)

    QIU Kunyuan; GUO Xinqiu; ZHANG Dong; FENG Xinde

    1991-01-01

    The initiation mechanism of acrylamide (AAM)polymerization using ceric ion/acetylacetone system as an initiator has been studied. The redox polymerization was revealed by the low value of overall activation energy ofAAm polymerization. The structure of free radicals formed from above-mentioned initiation sytem were detected by radical trapping and ESR spectra techniques and the end groups of polymers obtained were determined by FT-IR spectra analysis method. Based on these results the initiation mechanism is proposed.

  16. (2,6-DIPHENYL) PHENYL METHACRYLATE .2. RADICAL COPOLYMERIZATION WITH METHYL-METHACRYLATE - THE T(G)S OF ITS COPOLYMERS WITH AN ADDENDUM ON THE POLYMERIZATION OF (2,6-DIPHENYL) PHENYL ACRYLATE

    NARCIS (Netherlands)

    TAN, YY; VANEKENSTEIN, GORA

    1994-01-01

    The radical copolymerization of (2,6-diphenyl) phenyl methacrylate (1) with methyl methacrylate in DMF with AIBN at 70-degrees-C has the reactivity rators r1 = 0.071 and r2 = 1.42, from which Q1 = 1.45 and e(l) = 1.20. The copolymers had M(n) s in the range of 10,000-40,000 and T(g) s ranging from 4

  17. Biocompatible Polymeric Materials Intended for Drug Delivery and Therapeutic Applications

    DEFF Research Database (Denmark)

    Hvilsted, Søren; Javakhishvili, Irakli; Bednarek, Melania

    2007-01-01

    water soluble polymers, polyethylene glycol (PEG), and poly(acrylic acid) (PAA) with good mycoadhesive properties, are all prepared by living/controlled polymerization techniques. These techniques, atom transfer radical polymerization (ATRP) and ring opening polymerization (ROP), ensure at the same time...... both good molecular weight control and well defined, manageable structural end groups that sets the scene for combination of the different polymer blocks. With this tool box at hand the choice becomes to decide between all polymerization strategies or build in chemical functionalities allowing coupling...

  18. 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.

  19. A Novel RAFT Polymerization under UV Radiation at Ambient Temperature

    Institute of Scientific and Technical Information of China (English)

    Nianfa Yang; Lican Lu; Yuanli Cai

    2005-01-01

    @@ 1Introduction Reversible Addition Fragmentation chain Transfer (RAFT) polymerization has become a highly versatile technique for the controlled/"living" radical polymerization of a wide range of monomers under various conditions[1,2]. The RAFT polymerization was carried out using a dithiocarboxylate or trithiocarbonate as a Chain Transfer Agent (CTA), which mediates the growing chain radicals via an equilibrium[1,2]. From both academic and industrial standpoints, it is clearly desirable to develop a RAFT process under mild conditions. Rizzardo, et al [3] and McCormick's group[4] have respectively reported RAFT polymerization using conventional radical initiators at ambient temperature by adjusting the structure of CTA. The RAFT Polymerization initiated by γ-radiation has also reported recently[5]. Quinn, et al [6] have reported the RAFT polymerization under UV radiation using CTA as the source of primary radicals at 42 ℃, which was well controlled at low conversions (below 20% ) but less controlled at higher conversions (over 20% ) due to the photolysis of CTA residues under UV radiation.

  20. Mechanism and kinetics of addition polymerizations

    CERN Document Server

    Kucera, M

    1991-01-01

    This volume presents an up-to-date survey of knowledge concerning addition type polymerizations. It contains nine chapters, each of which covers a particular basic term. Whenever necessary, the phenomena are discussed from the viewpoint of both stationary and non-stationary state of radical, ionic (i.e. anionic and cationic) and coordination polymerization. Special attention has been paid to the propagation process. It provides not only a general overview but also information on important special cases (theoretical conditions of propagation, influence of external factors, controlled propagatio

  1. Radical prostatectomy

    DEFF Research Database (Denmark)

    Fode, Mikkel; Sønksen, Jens; Jakobsen, Henrik

    2014-01-01

    OBJECTIVE: The aim of this study was to compare oncological and functional outcomes between robot-assisted laparoscopic radical prostatectomy (RALP) and retropubic radical prostatectomy (RRP) during the initial phase with RALP at a large university hospital. MATERIAL AND METHODS: Patient and tumour...... surgery and at follow-up and they were asked to report their use of pads/diapers. Potency was defined as an IIEF-5 score of at least 17 with or without phosphodiesterase-5 inhibitors. Patients using up to one pad daily for security reasons only were considered continent. Positive surgical margins, blood...... loss and functional outcomes were compared between groups. RESULTS: Overall, 453 patients were treated with RRP and 585 with RALP. On multivariate logistic regression analyses, the type of surgery did not affect surgical margins (p = 0.96) or potency at 12 months (p = 0.7). Patients who had undergone...

  2. Conducting Polymeric Materials

    DEFF Research Database (Denmark)

    Hvilsted, Søren

    2016-01-01

    The overall objective of this collection is to provide the most recent developments within the various areas of conducting polymeric materials. The conductivity of polymeric materials is caused by electrically charged particles, ions, protons and electrons. Materials in which electrons...

  3. First example of a reversible single-crystal-to-single-crystal polymerization-depolymerization accompanied by a magnetic anomaly for a transition-metal complex with an organic radical.

    Science.gov (United States)

    Ovcharenko, Victor I; Fokin, Sergey V; Kostina, Elvina T; Romanenko, Galina V; Bogomyakov, Artem S; Tretyakov, Eugene V

    2012-11-19

    The reaction of copper(II) hexafluoroacetylacetonate [Cu(hfac)2] with the stable nitronyl nitroxide 2-(1-ethyl-3-methyl-1H-pyrazol-4-yl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-3-oxide-1-oxyl (L(a)) resulted in a paired heterospin complex [[Cu(hfac)2]3(μ-O,N-L(a))2][Cu(hfac)2(O-L(a))2]. The crystals of the compound were found to be capable of a reversible single-crystal-to-single-crystal (SC-SC) transformation initiated by the variation of temperature. At room temperature, the molecular structure of [[Cu(hfac)2]3(μ-O,N-L(a))2][Cu(hfac)2(O-L(a))2] is formed by the alternating fragments of the pair complex. Cooling the crystals of the complex below 225 K caused considerable mutual displacements of adjacent molecules, which ended in a transformation of the molecular structure into a polymer chain structure. A reversible topotactic polymerization-depolymerization coordination reaction actually takes place in the solid during repeated cooling-heating cycles: [[Cu(hfac)2]3(μ-O,N-L(a))2][Cu(hfac)2(O-L(a))2] ⇌ Cu(hfac)2(μ-O,N-L(a))]∞. Polymerization during cooling is the result of the anomalously great shortening of intermolecular distances (from 4.403 Å at 295 K to 2.460 Å at 150 K; Δd = 1.943 Å) between the terminal Cu atoms of the trinuclear fragments {[[Cu(hfac)2]3(μ-O,N-L(a))2]} and the noncoordinated N atoms of the pyrazole rings of the mononuclear {[Cu(hfac)2(O-L(a))2]} fragments. When the low-temperature phase was heated above 270 K, the polymer chain structure was destroyed and the compound was again converted to the pair molecular complex. The specifics of the given SC-SC transformation lies in the fact that the process is accompanied by a magnetic anomaly, because the intracrystalline displacements of molecules lead to a considerable change in the mutual orientation of the paramagnetic centers, which, in turn, causes modulation of the exchange interaction between the odd electrons of the Cu(2+) ion and nitroxide. On the temperature curve of

  4. Irradiation modes' impact on radical entrapment in photoactive resins.

    Science.gov (United States)

    Leprince, J G; Lamblin, G; Devaux, J; Dewaele, M; Mestdagh, M; Palin, W M; Gallez, B; Leloup, G

    2010-12-01

    Different irradiation protocols are proposed to polymerize dental resins, and discordances remain concerning their impact on the material. To improve this knowledge, we studied entrapment of free radicals in unfilled Bis-GMA/TEGDMA (50:50 wt%) resin after light cure. The tested hypothesis was that various irradiation parameters (curing time, irradiance, and radiant exposure) and different irradiation modes (continuous and pulse-delay) led to different amounts of trapped free radicals. The analysis of cured samples (n = 3) by electron paramagnetic resonance (EPR) revealed that the concentrations of trapped free radicals significantly differed according to the curing protocol. When continuous modes with similar radiant exposure were compared, higher concentrations of trapped free radicals were measured for longer times with lower irradiance. Concerning pulse modes, the delay had no influence on trapped radical concentration. These results give new insights into the understanding of the photopolymerization process and highlight the relevance of using EPR when studying polymerization of dimethacrylate-based materials.

  5. Dyes as Photoinitiators or Photosensitizers of Polymerization Reactions

    Directory of Open Access Journals (Sweden)

    Christian Ley

    2010-12-01

    Full Text Available A short but up-to-date review on the role of dyes in the photoinitiation processes of polymerization reactions is presented. Radical and cationic reactions are largely encountered in the radiation curing and the imaging areas for use in traditional coating applications as well as in high tech sectors such as nanofabrication, computer-to-plate processing, laser direct imaging, manufacture of optical elements, etc. Recent promising developments concerned with the introduction of the silyl radical chemistry that enhances the polymerization efficiency are also discussed.

  6. Theoretical Study of 1,8-Diaminonaphthalene Polymerization

    Science.gov (United States)

    Nateghi, Mohammad R.; Kalantari, F.

    2007-12-01

    The polymerization of 1,8-diaminonaphthalene (1,8-DAN) was studied by a theoretical approach based on Hartree-Fock calculations. Investigation of relative stability of most possible dimers, trimers and tetramers yields very useful data concerning the regioselectivity of the coupling reaction as well as the final structures of the polymeric chains. The mechanism is more likely to occur via a radical-radical pathway and leads to mixture of compounds through ortho-C-C and para-C-N linkages.

  7. 离子液体中单电子转移活性自由基聚合法制备星形聚丙烯酰胺%Synthesis of Star Polyacrylamide by Single Electron Transfer Living Radical Polymerization in Ionic Liquid System

    Institute of Scientific and Technical Information of China (English)

    丁伟; 孙颖; 吕崇福; 景慧; 于涛; 曲广淼

    2011-01-01

    A single electron transfer living radical polymerization (SET-LRP) is able to rapidly achieve high molecular mass, with excellent control of molecular mass distribution, represents a robust and versatile method for the rapid synthesis of macromolecules with defined architecture. The SET-LRP of acryl amide( AM) was investigated at 40℃ in 1-butyl, 3-methyl tetrafluoroborate ([ Bmim] BF4 ) ionic liquid, using Cu0 power/ tris(2-dimethylamin ethyl) amine( Me6-TREN) as catalyst, 2,2-dibromomethyl-l ,3-dibromopropane( PEBr4) as initiator. The polymerization showed some "living" features; the conversion and In ([M]0/[M]) increased linearly with- time as well as the number-average molecular mass increased linearly with conversion. The star polyacrylamide(sPAM) prepared via SET-LRP was characterized by GPC and 'H NMR to identify its polymerization mechanism, and the results showed that the polymer had the perfect functional chain ends and relatively low molecular mass distribution Mw/Mn ≈ 1. 26 (HnGPC = 14. 1 x 103 , conversion rate is 43. 4% ) , indicating a controlled polymerization. The effects of water, catalyst and initiator on polymerization were studied, and the dynamic experiments were carried out. A small amount of water added could accerlerate the polymerization, the apparent rate constants of propagation (kPapp) were 0.04248 h-1 and 0. 14869 h-1 for adding free water and 0. 5 mL H2 0 respectively; the control of polymerization could be improved with the presence of catalyst and increasing the concentration of initiator. The polymerization rate of SET-LRP increased with the amount of catalyst and initiator. In addition, Mn increased with the amount of catalyst or decreasing the amount of initiator and was closed to the theoretical molecular mass. The molecular mass distribution showed a decreasing trend, the minimum was about 1.26. The [Bmim]BF4 ionic liquid was a good solvent to PEBr4 and acryl amide, and the polymers were easily separated from the catalyst.%

  8. PHOTOINDUCED CHARGE TRANSFER POLYMERIZATION OF STYRENE INITIATED BY ELECTRON ACCEPTOR

    Institute of Scientific and Technical Information of China (English)

    CAO Weixiao; ZHANG Peng; FENG Xinde

    1995-01-01

    Photoinduced charge transfer polymerization of styrene(St) with electron acceptor as initiator was investigated. In case of fumaronitrile (FN) or maleic anhydride (MA) as initiator the polymerization takes place regularly, whereas the tetrachloro-1, 4-benzenequinone (TCQ), 2, 3-dichloro-5, 6-dicyano-1, 4-benzenequinone (DDQ) . or tetracyano ethylene (TCNE) as initiator the polymerization proceeds reluctantly only after the photoaddition reaction. A mechanism was proposed that free radicals would be formed following the charge and proton transfer in the exciplex formed between St and electron acceptors.

  9. STUDIES ON VINYL POLYMERIZATION WITH INITIATION SYSTEM CONTAINING AMINE DERIVATIVES

    Institute of Scientific and Technical Information of China (English)

    QIU Kunyuan; ZHANG Jingyi; FENG Xinde(S. T. Voong)

    1983-01-01

    Two main types of amine-containing initiation systems were studied in this work. In the case of MMA polymerization initiated by BPO-amine (DMT, DHET, DMA) redox systems, it was found that the polymerization rate and colour stability of the polymer for different amine systems were in the following order: DMT≈DHET>DMA. Accordingly, BPO-DMT and BPO-DHET are effective initiators. In the case of MEMA polymerization by amine (DMT, DHET, DMA) alone, it was found that the polymerization rate and the percentage of conversion for these different amine systems were in the following order: DMT≥DHET>DMA. The polymerization rate and the percentage of conversion also increased with the increase of DMT concentration. From the kinetic investigation the rate equation of Rp=K [DMT]1/2 [MEMA]3/2 was obtained, and the overall activation energy of polymerization was calculated to be 34.3 KJ/mol (8.2 Kcal/mol). Moreover, the polymerization of MEMA in the presence of DMT was strongly inhibited by hydroquinone, indicating the polymerization being free radical in nature. From these results, the mechanism of MEMA polymerization initiated by amine was proposed.

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

    Institute of Scientific and Technical Information of China (English)

    WAN; Xiaolong

    2001-01-01

    [1]Ewen, J. A., Novel method for plastic production, Science (in Chinese), 1997, 9: 34.[2]Brintzinger, H. H., Fischer, D., Waymouth, R. M. et al., Stereospecific olefin polymerization with chiral metallocene catalysts, Angewandte Chemie International Edition in English, 1995, 34(11): 1143.[3]Matyjaszewski, K., Atom transfer radical polymerization, role of various components and reaction conditions, Polym. Prep., 1997, 38(2): 736.[4]Wang, J. S., Matyjaszewski, K., Controlled/"living" radical polymerization, atom transfer radical polymerization in the presence of transition-metal complex, J. Am. Soc., 1995, 117: 5614.[5]Wang, J. S., Matyjaszewski, K., Controlled/"living" radical polymerization, halogen atom transfer radical polymerization promoted by a Cu(I)/Cu(II) redox process, Macromolecules, 1995, 28: 7901.[6]Koto, M., Kamigaito, M., Sawamoto, M. et al., Polymerization of methyl methacrylate with the carbon tetrachloride/dichloro-tris(triphenyphosphine) ruthenium(II)/methylaluminum bis(2,6-di-tert-butylphenoxide) initiating system: possible of living radical polymerization, Macromolecules, 1995, 28: 1721.[7]Ando, T., Kato, M., Living radical polymerization of methyl methacrylate with Ruthenium complex: formation of polymers with controlled molecular weights and very narrow distributions, Macromolecules, 1996, 29: 1070.[8]Granel, C., Dubios, P., Jerome, R. et al., Controlled radical polymerization of methacrylic monomers in the presence of a bis(ortho-chelated) arylnickel(II) complex and different activated alkyl halides, Macromolecules, 1996, 29: 8576.[9]Granel, C., Moineau, G., Lecome, P. et al., (Meth)acrylates pseudo-living radical polymerization in the presence of transition metal complexes: the kharasch reaction revisited, Polym. Prep., 1997, 38(1): 450.[10]Ando, T., Kamigaito, M., Sawamoto, M., Iron(II) chloride complex for living radical polymerization of methyl methacrylate, Macromolecules, 1997, 30: 4507.[11

  11. Ignorance Radicalized

    Directory of Open Access Journals (Sweden)

    Gergo Somodi

    2009-12-01

    Full Text Available The aim of this paper is twofold. I criticize Michael Devitt's linguistic---as opposed to Chomsky's psychological---conception of linguistics on the one hand, and I modify his related view on linguistic intuitions on the other. I argue that Devitt's argument for the linguistic conception is in conflict with one of the main theses of that very conception, according to which linguistics should be about physical sentence tokens of a given language rather than about the psychologically real competence of native speakers. The basis of this conflict is that Devitt's view on language, as I will show, inherits too much from the criticized Chomskian view. This is also the basis of Devitt's strange claim that it is the linguist, and not the ordinary speaker, whose linguistic intuition should have an evidential role in linguistics. I will argue for the opposite by sketching a view on language that is more appropriate to the linguistic conception. That is, in criticizing Devitt, I am not defending the Chomskian approach. My aim is to radicalize Devitt's claims.

  12. Terrorism, radicalization, and de-radicalization

    NARCIS (Netherlands)

    Doosje, B.; Moghaddam, F.M.; Kruglanski, A.W.; de Wolf, A.; Mann, L.; Feddes, A.R.

    2016-01-01

    In this article, we review the literature and present a model of radicalization and de-radicalization. In this model, we distinguish three phases in radicalization: (1) a sensitivity phase, (2) a group membership phase and (3) an action phase. We describe the micro-level, meso-level and macro-level

  13. Signal amplification strategies for DNA and protein detection based on polymeric nanocomposites and polymerization: A review

    Energy Technology Data Exchange (ETDEWEB)

    Zhou, Shaohong; Yuan, Liang; Hua, Xin; Xu, Lingling; Liu, Songqin, E-mail: liusq@seu.edu.cn

    2015-06-02

    Highlights: • We review the innovative advances in polymer-based signal amplification. • Conceptual connectivity between different amplified methodologies is illustrated. • Examples explain the mechanisms of polymers/polymerizations-based amplification. • Several elegant applications are summarized that illustrate underlying concept. - Abstract: Demand is increasing for ultrasensitive bioassays for disease diagnosis, environmental monitoring and other research areas. This requires novel signal amplification strategies to maximize the signal output. In this review, we focus on a series of significant signal amplification strategies based on polymeric nanocomposites and polymerization. Some common polymers are used as carriers to increase the local concentration of signal probes and/or biomolecules on their surfaces or in their interiors. Some polymers with special fluorescence and optical properties can efficiently transfer the excitation energy from a single site to the whole polymer backbone. This results in superior fluorescence signal amplification due to the resulting collective effort (integration of signal). Recent polymerization-based signal amplification strategies that employ atom transfer radical polymerization (ATRP) and photo-initiated polymerization are also summarized. Several distinctive applications of polymers in ultrasensitive bioanalysis are highlighted.

  14. KINETIC STUDIES ON THE POLYMERIZATION OF ACRYLONITRILE INITIATED BY METALLIC MAGNESIUM-NITRIC ACID SYSTEM

    Institute of Scientific and Technical Information of China (English)

    WU Chinyung

    1983-01-01

    This article reports the polymerization kinetics of acrylonitrile initiated by metallic magnesiumnitric acid system. The rate of polymerization is independent of the amount of magnesium used; when the concentration of nitric acid is higher than acrylonitrile, the equation of polymerization kinetics may be expressed as Rp=1.91 × 105e-15000/RT[Mg]0 [AN]2·2 [HNO3]0·46 The result of copolymerization of acyrlonitrile and methyl acrylate supports a free-radical mechanism.

  15. Sterically and electrosterically stabilized emulsion polymerization. Kinetics and preparation.

    Science.gov (United States)

    Capek, Ignác

    2002-10-21

    The principal subject discussed in the current paper is the radical polymerization in the aqueous emulsions of unsaturated monomers (styrene, alkyl (meth)acrylates, etc.) stabilized by non-ionic and ionic/non-ionic emulsifiers. The sterically and electrosterically stabilized emulsion polymerization is a classical method which allows to prepare polymer lattices with large particles and a narrow particle size distribution. In spite of the similarities between electrostatically and sterically stabilized emulsion polymerizations, there are large differences in the polymerization rate, particle size and nucleation mode due to varying solubility of emulsifiers in oil and water phases, micelle sizes and thickness of the interfacial layer at the particle surface. The well-known Smith-Ewart theory mostly applicable for ionic emulsifier, predicts that the number of particles nucleated is proportional to the concentration of emulsifier up to 0.6. The thin interfacial layer at the particle surface, the large surface area of relatively small polymer particles and high stability of small particles lead to rapid polymerization. In the sterically stabilized emulsion polymerization the reaction order is significantly above 0.6. This was ascribed to limited flocculation of polymer particles at low concentration of emulsifier, due to preferential location of emulsifier in the monomer phase. Polymerization in the large particles deviates from the zero-one approach but the pseudo-bulk kinetics can be operative. The thick interfacial layer can act as a barrier for entering radicals due to which the radical entry efficiency and also the rate of polymerization are depressed. The high oil-solubility of non-ionic emulsifier decreases the initial micellar amount of emulsifier available for particle nucleation, which induces non-stationary state polymerization. The continuous release of emulsifier from the monomer phase and dismantling of the non-micellar aggregates maintained a high level of

  16. Polymerization Using Phosphazene Bases

    KAUST Repository

    Zhao, Junpeng

    2015-09-01

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

  17. Síntese de copolímeros em bloco de p-acetoxiestireno com isopreno através de polimerização "viva" via radical livre Synthesis of block copolymers from p-acetoxystyrene and isoprene by "living" free radical polymerization

    Directory of Open Access Journals (Sweden)

    José Carlos Moreira

    2004-09-01

    Full Text Available Neste trabalho, é mostrada a síntese de homopolímeros de p-acetoxiestireno e copolímeros diblocos de p-acetoxiestireno com isopreno, utilizando um iniciador TEMPO-modificado, por um processo de polimerização "viva" via radical livre. As análises de GPC indicaram a formação de copolímeros em bloco com massas molares e polidispersão mais altas quando comparadas aos dos homopolímeros correspondentes. Os copolímeros em bloco poli(p-acetoxiestireno-b-isopreno foram preparados com controle de composição e massa molar até 94500 u.m.a. As análises de DSC mostraram que a transição vítrea do bloco de p-acetoxiestireno foi de 5 a 18 °C mais baixa que aquelas obtidas para os homopolímeros correspondentes. A transição vítrea do bloco de isopreno apresentou valores similares àqueles dos homopolímeros de poliisopreno (-67 a -55 °C.In this work we show the synthesis of homopolymers and diblock copolymers of p-acetoxystyrene and isoprene by using TEMPO-modified free radical initiator. The GPC analyses have shown an increase in the molar masses and in the polydispersity of the copolymers in comparison with their corresponding homopolymer. Poly(p-acetoxystyrene-b-isoprene were prepared with good control of composition and molar mass up to 94,500 a.m.u. DSC analyses have shown a glass transition temperature decrease of 5-18 °C for the poly(p-acetoxystyrene segment in copolymers compared to that observed for the parent homopolymer. The glass transition temperature of polyisoprene segment in copolymers remained similar to those observed for the homopolymers (-67 to -55 °C.

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

    Institute of Scientific and Technical Information of China (English)

    王凇旸; 郭冠南; 杨东; 胡建华

    2014-01-01

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

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

    NARCIS (Netherlands)

    Hosseiny, Seyed Schwan; van Rijn, Patrick

    2013-01-01

    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 controlle

  20. Homogeneous catalysts for stereoregular olefin polymerization

    Science.gov (United States)

    Marks, T.J.; Eisen, M.S.; Giardello, M.A.

    1995-10-03

    The synthesis, and use as precatalysts of chiral organozirconium complexes for olefin polymerization are disclosed, having the structure (C{sub 5}R{prime}{sub 4{minus}x}R*{sub x})A(C{sub 5}R{double_prime}{sub 4{minus}y}R{double_prime}{prime}{sub y})MQ{sub p}, where x and y represent the number of unsubstituted locations on the cyclopentadienyl ring; R{prime}, R{double_prime}, R{double_prime}{prime}, and R* represent substituted and unsubstituted alkyl groups having 1--30 carbon atoms and R* is a chiral ligand; A is a fragment containing a Group 13, 14, 15, or 16 element of the Periodic Table; M is a Group 3, 4, or 5 metal of the Periodic Table; and Q is a hydrocarbyl radical, or halogen radical, with 3{>=}p{>=}0. Related complexes may be prepared by alkylation of the corresponding dichlorides. In the presence of methylalumoxane or triarylborane cocatalysts, these complexes form ``cation-like`` species which are highly active for olefin polymerization. In combination with a Lewis acid cocatalyst, propylene or other {alpha}-olefin polymerization can be effected with very high efficiency and isospecificity. 1 fig.

  1. Homogeneous catalysts for stereoregular olefin polymerization

    Science.gov (United States)

    Marks, Tobin J.; Eisen, Moris S.; Giardello, Michael A.

    1994-01-01

    The synthesis, and use as precatalysts of chiral organozirconium complexes for olefin polymerization are disclosed, having the structure (C.sub.5 R'.sub.4-x R*.sub.x) A (C.sub.5 R".sub.4-y R'".sub.y) M Q.sub.p, where x and y represent the number of unsubstituted locations on the cyclopentadienyl ring; R', R", R'", and R* represent substituted and unsubstituted alkyl groups having 1-30 carbon atoms and R* is a chiral ligand; A is a fragment containing a Group 13, 14, 15, or 16 element of the Periodic Table; M is a Group 3, 4, or 5 metal of the Periodic Table; and Q is a hydrocarbyl radical, or halogen radical, with 3.ltoreq.p.ltoreq.o. Related complexes may be prepared by alkylation of the corresponding dichorides. In the presence of methylalumoxane or triarylborane cocatalysts, these complexes form "cation-like" species which are highly active for olefin polymerization. In combination with a Lewis acid cocatalyst, propylene or other .alpha.-olefin polymerization can be effected with very high efficiency and isospecificity.

  2. STUDY ON THE KINETICS OF POLYMERIZATION OF MMA BY COPPER(Ⅱ) CHELATING RESINS

    Institute of Scientific and Technical Information of China (English)

    WangHongzuo; JiangYuanzhang; 等

    1993-01-01

    The polymerization of MMA initiated by copper(Ⅱ) chelating resins/CCl4 system was studied.From the kinetic data,the kinetic equation of polymerization can be expressed as Rp=Ke-56400/RT[MMA]1.57[CCl4]m[RESIN-Cu]0.18 where m:3-4.5,when[CCl4] 0.1-6.93M.The free radical polymerization mechanism is proposed.The primary radicals are formed by the process of complexation-chlorine transformation among the copper(Ⅱ) chelating resin,CCl4 and methacrylate.

  3. Making Polymeric Microspheres

    Science.gov (United States)

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

    1989-01-01

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

  4. Stereospecific olefin polymerization catalysts

    Science.gov (United States)

    Bercaw, John E.; Herzog, Timothy A.

    1998-01-01

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

  5. Influence of Cyclodextrin on the Styrene Polymerization

    Institute of Scientific and Technical Information of China (English)

    HU Jie; LIU Bai-ling

    2004-01-01

    Cyclodextrin (CD) are oligosaccharides consisting of 6( α ), 7( β ), 8( γ ) units of1,4-linked glucose. Due to their polar hydrophilic outer shell and relatively hydrophobic cavity, theyare able to build up host-guest complexes by inclusion of suitable hydrophobic molecules. Theformation of these complexes leads to significant changes of the solubility and reactivity of the guestmolecules, but without any chemical modification. Thus, water insoluble molecules may becomecompletely water soluble simply by mixing with an aqueous solution of native CD or CD-derivatives.Hydrogen bonds or hydrophobic interactions are responsible for the stability of the complexes and itturned out that the complexed monomers could be successfully polymerized by free radicalpolymerization in water.In our present work, using styrene as monomer, potassium peroxodisulfate as radical initiator thatreacted in water in the presence ofβ-CD but without any additional surfactant, the effect ofcyclodextrin on the polymerization was described. Additionally, the acceleration mechanism ofcyclodextrin in the polymerization was also explained based on dynamic study.Table 1 Effect of CD on the monomer reactivityIt is found that β -CD could greatly accelerate the polymerization, enhance the final conversion ofmonomer. And the more the amount of β-CD was introduced, the faster the polymerization wasobtained. From Figure 1, after 5 hours reaction at 80℃, the monomer conversion in the presence of1.0g cyclodextrin reached to 95%. However, that in absence of cyclodextrin was only 60%. And themonomer conversion was not to exceed 75% even reacted for 8 hours when no CD in reactionsystem.In order to describe the acceleration of CD in the polymerization quantitatively, based onCD and without CD. As shown in Table 1, CD produced significant effect on the monomer reactivity.The relative relativities of monomer were greatly increased with the increase of the amount of CD.

  6. Applied bioactive polymeric materials

    CERN Document Server

    Carraher, Charles; Foster, Van

    1988-01-01

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

  7. Dynamic Monte Carlo simulation of chain growth polymerization and its concentration effect

    Institute of Scientific and Technical Information of China (English)

    L(U) Wenqi; DING Jiandong

    2005-01-01

    Free radical polymerization and living ion polymerization have been simulated via the dynamic Monte Carlo method with the bond-fluctuation model in this paper. The polymerization-related parameters such as conversion of monomers, degree of polymerization, average molecular weight and its distribution are obtained by statistics. The simulation outputs are consistent with the corresponding theoretical predictions. The scaling relationships of the coil size versus chain length are also confirmed at different volume fractions. Furthermore, the effect of diffusion on polymerization is revealed preliminarily in our simulation. Hence the simulation approach has been proven to be feasible to investigate polymerization reactions with the advantages that configuration and diffusion of polymer chains can be examined together with polymerization kinetics.

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

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

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

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

    Science.gov (United States)

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

  10. ATOM TRANSFER RADICAL POLYMERIZATION IN SUPERCRITICAL CARBON DIOXIDE. (R826735)

    Science.gov (United States)

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

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

    Science.gov (United States)

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

  12. Synthesis of Amphiphilic Copolymwers by Atom Transfer Radical Polymerization

    DEFF Research Database (Denmark)

    Hansen, Natanya Majbritt Louie

    2007-01-01

    atom transfer radikal polymerisation (ATRP) blev anvendt til alle polymerisationerne. De reaktionskinetiske forhold samt de opnåelige materialestrukturer viste, at næsten alle anvendte monomer-kombinationer kan håndteres til fremstilling af fluorholdige polymermaterialer med velkontrolleret struktur...

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

    Science.gov (United States)

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

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

    Science.gov (United States)

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

  15. ATOM TRANSFER RADICAL POLYMERIZATION IN SUPERCRITICAL CARBON DIOXIDE. (R826735)

    Science.gov (United States)

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

  16. The pentafluorostyrene endeavours with atom transfer radical polymerization - quo vadis?

    DEFF Research Database (Denmark)

    Hvilsted, Søren

    2014-01-01

    by exploitation of the very labile para-fluorine demonstrates new material architecture possibilities through very mild reaction conditions. Finally the utility of PFS in various conducting materials is elaborated. The amphiphilic nature of PFS in triblock copolymers with polyethers has been exploited for Li+ ion...... electrolytes. The convenient grafting of PFS through ‘click’ chemistry to a polysulfone and subsequent phosphonation of the PFS grafts seem very beneficial for the fabrication of proton conducting materials with high conductivity...

  17. "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

  18. Tuning the Properties of Functional Pyrrolidinium Polymers by (Co)polymerization of Diallyldimethylammonium Ionic Liquids.

    Science.gov (United States)

    Jovanovski, V; Marcilla, R; Mecerreyes, David

    2010-09-15

    The synthesis and polymerization of novel diallyldimethylammonium ionic liquid monomers is described. A free-radical polymerization follows a ring-closing cyclopolymerization mechanism similar to the one observed previously for diallyldimethylammonium halides that leads to pyrrolidinium functional polymers. As previously observed in other families of polymeric ionic liquids, their physico-chemical properties are seriously affected by the nature of the counter-anion. As an example, the thermal stability increases following the trend SCN(-)  polymerization route may lead to the synthesis of a new family of random copolymers that have a similar poly(diallyldimethylammonium) backbone and a mixture of counter-anions determined by the comonomer selection.

  19. 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?

  20. A radical approach to radical innovation

    OpenAIRE

    Deichmann, Dirk; van der 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?

  1. Polymeric bicontinuous microemulsions

    DEFF Research Database (Denmark)

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

    1997-01-01

    High molecular weight block copolymers can be viewed as macromolecular surfactants when blended with thermodynamically incompatible homopolymers. This Letter describes the formation of polymeric bicontinuous microemulsions in nurtures containing a model diblock copolymer and two homopolymers...

  2. Modeling the chemistry of plasma polymerization using mass spectrometry.

    Science.gov (United States)

    Ihrig, D F; Stockhaus, J; Scheide, F; Winkelhake, Oliver; Streuber, Oliver

    2003-04-01

    The goal of the project is a solvent free painting shop. The environmental technologies laboratory is developing processes of plasma etching and polymerization. Polymerized thin films are first-order corrosion protection and primer for painting. Using pure acetylene we get very nice thin films which were not bonded very well. By using air as bulk gas it is possible to polymerize, in an acetylene plasma, well bonded thin films which are stable first-order corrosion protections and good primers. UV/Vis spectroscopy shows nitrogen oxide radicals in the emission spectra of pure nitrogen and air. But nitrogen oxide is fully suppressed in the presence of acetylene. IR spectroscopy shows only C=O, CH(2) and CH(3) groups but no nitrogen species. With the aid of UV/Vis spectra and the chemistry of ozone formation it is possible to define reactive traps and steps, molecule depletion and processes of proton scavenging and proton loss. Using a numerical model it is possible to evaluate these processes and to calculate theoretical mass spectra. Adjustment of theoretical mass spectra to real measurements leads to specific channels of polymerization which are driven by radicals especially the acetyl radical. The estimated theoretical mass spectra show the specific channels of these chemical processes. It is possible to quantify these channels. This quantification represents the mass flow through this chemical system. With respect to these chemical processes it is possible to have an idea of pollutant production processes.

  3. Chelating polymeric membranes

    KAUST Repository

    Peinemann, Klaus-Viktor

    2015-01-22

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

  4. Radical and Atom Transfer Halogenation (RATH): A Facile Route for Chemical and Polymer Functionalization.

    Science.gov (United States)

    Han, Yi-Jen; Lin, Chia-Yu; Liang, Mong; Liu, Ying-Ling

    2016-05-01

    This work demonstrates a new halogenation reaction through sequential radical and halogen transfer reactions, named as "radical and atom transfer halogenation" (RATH). Both benzoxazine compounds and poly(2,6-dimethyl-1,4-phenylene oxide) have been demonstrated as active species for RATH. Consequently, the halogenated compound becomes an active initiator of atom transfer radical polymerization. Combination of RATH and sequential ATRP provides an convenient and effective approach to prepare reactive and crosslinkable polymers. The RATH reaction opens a new window both to chemical synthesis and molecular design and preparation of polymeric materials.

  5. Radical theory of rings

    CERN Document Server

    Gardner, JW

    2003-01-01

    Radical Theory of Rings distills the most noteworthy present-day theoretical topics, gives a unified account of the classical structure theorems for rings, and deepens understanding of key aspects of ring theory via ring and radical constructions. Assimilating radical theory's evolution in the decades since the last major work on rings and radicals was published, the authors deal with some distinctive features of the radical theory of nonassociative rings, associative rings with involution, and near-rings. Written in clear algebraic terms by globally acknowledged authorities, the presentation

  6. Rhodium-Catalyzed/Copper-Mediated Tandem C(sp(2))-H Alkynylation and Annulation: Synthesis of 11-Acylated Imidazo[1,2-a:3,4-a']dipyridin-5-ium-4-olates from 2H-[1,2'-Bipyridin]-2-ones and Propargyl Alcohols.

    Science.gov (United States)

    Li, Ting; Wang, Zhiqiang; Xu, Kun; Liu, Wenmin; Zhang, Xu; Mao, Wutao; Guo, Yongming; Ge, Xiaolin; Pan, Fei

    2016-03-01

    A rhodium-catalyzed/copper-mediated tandem C(sp(2))-H alkynylation and intramolecular annulation of 2H-[1,2'-bipyridin]-2-ones with propargyl alcohols for the synthesis of 11-acylated imidazo[1,2-a:3,4-a']dipyridin-5-ium-4-olates is described.

  7. [Lavoisier and radicals].

    Science.gov (United States)

    Lafont, Olivier

    2007-01-01

    Lavoisier and his co-workers (Guyton de Morveau, Bertholet, Fourcroy) considered that acids were constituted of oxygen and of something else that they called radicals. These radicals were known in some cases, i.e. nitrogen for nitrous acid, carbon for carbonic acid, phosphorus for phosphoric acid. In the case of sulfur, the sulfuric radical could be associated with different quantities of oxigen leading to sulfuric or sulfurous acids. In other cases radicals remained unknown at the time i.e. muriatic radical for muriatic acid, or benzoyl radical for benzoic acid. It is interesting to notice that Lavoisier evoked the case of compound radicals constituted of different substances such as carbon and hydrogen.

  8. Localized Polymerization Using Single Photon Photoinitiators in Two-photon process for Fabricating Subwavelength Structures

    CERN Document Server

    Ummethala, Govind; Chaudhary, Raghvendra P; Hawal, Suyog; Saxena, Sumit; Shukla, Shobha

    2016-01-01

    Localized polymerization in subwavelength volumes using two photon dyes has now become a well-established method for fabrication of subwavelength structures. Unfortunately, the two photon absorption dyes used in such process are not only expensive but also proprietary. LTPO-L is an inexpensive, easily available single photon photoinitiator and has been used extensively for single photon absorption of UV light for polymerization. These polymerization volumes however are not localized and extend to micron size resolution having limited applications. We have exploited high quantum yield of radicals of LTPO-Lfor absorption of two photons to achieve localized polymerization in subwavelength volumes, much below the diffraction limit. Critical concentration (10wt%) of LTPO-Lin acrylate (Sartomer) was found optimal to achieve subwavelength localized polymerization and has been demonstrated by fabricating 2D/3D complex nanostructures and functional devices such as variable polymeric gratings with nanoscaled subwavelen...

  9. How are radicals (re)generated in photochemical ATRP?

    Science.gov (United States)

    Ribelli, Thomas G; Konkolewicz, Dominik; Bernhard, Stefan; Matyjaszewski, Krzysztof

    2014-09-24

    The polymerization mechanism of photochemically mediated Cu-based atom-transfer radical polymerization (ATRP) was investigated using both experimental and kinetic modeling techniques. There are several distinct pathways that can lead to photochemical (re)generation of Cu(I) activator species or formation of radicals. These (re)generation pathways include direct photochemical reduction of the Cu(II) complexes by excess free amine moieties and unimolecular reduction of the Cu(II) complex, similar to activators regenerated by electron-transfer (ARGET) ATRP processes. Another pathway is photochemical radical generation either directly from the alkyl halide, ligand, or via interaction of ligand with either monomer or with alkyl halides. These photochemical radical generation processes are similar to initiators for continuous activator regeneration (ICAR) ATRP processes. A series of model experiments, ATRP reactions, and kinetic simulations were performed to evaluate the contribution of these reactions to the photochemical ATRP process. The results of these studies indicate that the dominant radical (re)generation reaction is the photochemical reduction of Cu(II) complexes by free amines moieties (from amine containing ligands). The unimolecular reduction of the Cu(II) deactivator complex is not significant, however, there is some contribution from ICAR ATRP reactions involving the interaction of alkyl halides and ligand, ligand with monomer, and the photochemical cleavage of the alkyl halide. Therefore, the mechanism of photochemically mediated ATRP is consistent with a photochemical ARGET ATRP reaction dominating the radical (re)generation.

  10. 不同聚合机理的聚合反应速率串讲%Explain of Polymerization Reaction Rate of Different Polymerization Mechanism

    Institute of Scientific and Technical Information of China (English)

    赵文杰; 张会轩

    2013-01-01

    In the polymerization reaction engineering course,the polymerization reaction rate directly influences average polymerization degree of the polymerization products,and has the important position in the teaching material.The polymerization rate of different polymerization mechanisms is different,but they have high correlation.In this paper,The polymerization rate in the course of “polymerization reaction engineering” was detailed based on the clue of different mechanism of free radical polymerization,ion polymerization,coordination polymerization and the condensation polymerization.The similarities and differences among different polymerization rate were pointed out,aimed at improving students to understand and grasp the definition of the polymerizationrate.%在《聚合反应工程》课程中,聚合反应速率直接影响聚合产物的平均聚合度,是课程的一个核心内容,在教材中占有重要地位.不同聚合反应机理所对应的聚合反应速率不同,但它们具有很强的关联性.文中以自由基聚合、离子聚合、配位聚合以及缩聚的聚合机理为主线,把不同聚合机理中的聚合反应速率这一重要知识点做了串讲;指出了不同聚合反应速率之间的相同之处和不同之处.旨在使学生对聚合反应速率能有一个系统的认识和把握.

  11. Plasma polymerization by Softplasma

    DEFF Research Database (Denmark)

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

    2008-01-01

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

  12. Contemporary Radical Prostatectomy

    Directory of Open Access Journals (Sweden)

    Qiang Fu

    2011-01-01

    Full Text Available Purpose. Patients diagnosed with clinically localized prostate cancer have more surgical treatment options than in the past. This paper focuses on the procedures' oncological or functional outcomes and perioperative morbidities of radical retropubic prostatectomy, radical perineal prostatectomy, and robotic-assisted laparoscopic radical prostatectomy. Materials and Methods. A MEDLINE/PubMed search of the literature on radical prostatectomy and other new management options was performed. Results. Compared to the open procedures, robotic-assisted radical prostatectomy has no confirmed significant difference in most literatures besides less blood loss and blood transfusion. Nerve sparing is a safe means of preserving potency on well-selected patients undergoing radical prostatectomy. Positive surgical margin rates of radical prostatectomy affect the recurrence and survival of prostate cancer. The urinary and sexual function outcomes have been vastly improved. Neoadjuvant treatment only affects the rate of positive surgical margin. Adjuvant therapy can delay and reduce the risk of recurrence and improve the survival of the high risk prostate cancer. Conclusions. For the majority of patients with organ-confined prostate cancer, radical prostatectomy remains a most effective approach. Radical perineal prostatectomy remains a viable approach for patients with morbid obesity, prior pelvic surgery, or prior pelvic radiation. Robot-assisted laparoscopic prostatectomy (RALP has become popular among surgeons but has not yet become the firmly established standard of care. Long-term data have confirmed the efficacy of radical retropubic prostatectomy with disease control rates and cancer-specific survival rates.

  13. POLYMERIC SURFACTANT STRUCTURE

    Institute of Scientific and Technical Information of China (English)

    P.M. Saville; J.W. White

    2001-01-01

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

  14. Perfluorocyclobutyl-containing Amphiphilic Block Copolymers Synthesized by RAFT Polymerization

    Institute of Scientific and Technical Information of China (English)

    LI, Yongjun; ZHANG, Sen; FENG, Chun; ZHANG, Yaqin; LI, Qingnuan; LI, Wenxin; HUANG, Xiaoyu

    2009-01-01

    Amphiphilic block copolymers containing hydrophobic perfluorocyclobutyl-based (PFCB) polyacrylate and hydrophilic poly(ethylene glycol) (PEG) segments were prepared via reversible addition-fragmentation chain transfer (RAP-T) polymerization. The PFCB-containing acrylate monomer, p-(2-(p-tolyloxy)perfluorocyclobutoxy)phenyl acrylate, was first synthesized from commercially available compounds in good yields, and this kind of acrylate monomer can be homopolymerized by free radical polymerization or RAFT polymerization. Kinetic study showed the 2,2'-azobis(isobutyronitrile) (AIBN) initiated and cumyl dithiobenzoate (CDB) mediated RAFT polymerization was in a living fashion, as suggested by the fact that the number-average molecular weights (M_n) increased linearly with the conversions of the monomer, while the polydispersity indices kept less than 1.10. The block polymers with narrow molecular weight distributions (M_w/M_n≤1.21) were prepared through RAFT polymerization using PEG monomethyl ether capped with 4-cyanopentanoic acid dithiobenzoate end group as the macro chain transfer agent (mPEG-CTA). The length of the hydrophobic segment can be tuned by the feed ratio of the PFCB-based acrylate monomer and the extending of the polymerization time. The micellization behavior of the block copolymers in aqueous media was investigated by the fluorescence probe technique.

  15. Protein Compatible Polymer Brushes on Polymeric Substrates Prepared by Surface-Initiated Transfer Radica Polymerization

    DEFF Research Database (Denmark)

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

    2008-01-01

    limited. Therefore, a polymer coating containing some of the required properties may expand the use ofpolymers in medical devices. 'The approach was to graft polymer brushes from initiator-functionalized substrates using Surface-Initiated Atom TnlJlsfer Radical Polymerization (SI ATRP). Initial studies......Materials for insulin containers and delivery systems should comply with requirements like compatibility with proteins, sterilisability, 'good barrier properties towards preservatives, and no toxic leachables. The number of commercially available polymer materials which can be u sed is rather...

  16. FROM ATOM TRANSFER RADICAL ADDITION TO ATOM TRANSFER RADICAL POLYMERIZATION. (R829580)

    Science.gov (United States)

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

  17. FROM ATOM TRANSFER RADICAL ADDITION TO ATOM TRANSFER RADICAL POLYMERIZATION. (R829580)

    Science.gov (United States)

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

  18. Forgotten Radicals in Biology

    OpenAIRE

    2008-01-01

    Redox reactions play key roles in intra- and inter-cellular signaling, and in adaptative processes of tissues towards stress. Among the major free radicals with essential functions in cells are reactive oxygen species (ROS) including superoxide anion (O2 •-), hydroxyl radical (•OH) and reactive nitrogen species (RNS) such as nitric oxide (•NO). In this article, we review the forgotten and new radicals with potential relevance to cardiovascular pathophysiology. Approximately 0.3% of O2 •- pres...

  19. 卟啉锌末端功能化的PMMA活性自由基聚合与非线性吸收性能研究%Atom Transfer Radical Polymerization and Nonlinear Absorption Properties of Zincporphyrin-end-functionalized Polymethacrylate

    Institute of Scientific and Technical Information of China (English)

    谷彩莲; 刘大军

    2014-01-01

    Used α-bromo-isobutyryIbromide end-caped 5,10,15,20-tetra(p-hydroxyethylphenyl) zincporphyrin tripropio-nate as indicator,zincporphyrin-end-functionalized polymethacrylate (PMMA) was synthesized by atom transfer radical polymerization (ATRP) method. The structure of the prepared polymer was determined by infrared spectrum and nucle-ar magnetic resonance hydrogen spectrum techniques. The molecular weight and molecular weight distribution of the polymer samples were measured by gel permeation chromatograph (GPC) technique. Polymerziation reaction kinetics of the synthesized polymer was also studied by GPC. The rusults showed that polymerziation process followed a first-or-der reaction kinetics. By z-scan method, nonlinear optical properties of the polymer sample were tested using ns and ps pulsed laser. By fitting the experimental results, nonlinear absorption coefficient of the polymer sample,β is 4.5 × 10-10 m/W and 6.0×10-12 m/W,respectively. The results displayed that the prepared polymer sample has nonlinear ab-sorption characteristic for ns and ps pulsed laser. Furthermore,β value under ns-laser pulse is bigger than that under ps-laser pulse,showing that the triplet excited state absorption cross-section of the sample is larger than singlet excit-ed state absorption cross-section.%以α-溴代异丁酰溴封端的5,10,15,20-四对羟乙基苯基卟啉锌三丙酸酯为引发剂,通过原子转移自由基聚合方法(ATRP)合成卟啉锌末端功能化的PMMA高分子聚合物。通过红外光谱仪和氢核磁共振波谱对聚合物的结构进行了确定。利用GPC测试了聚合物分子量、分子量分布,研究了其聚合过程动力学,结果表明聚合过程符合一级反应动力学。通过Z-扫描技术测试了ns和ps脉冲激光下的非线性特性,拟合结果样品的非线性吸收系数β分别为4.5×10-10m/W和6.0×10-12m/W。样品对ns和ps激光均有非线性吸收特性,且ns脉冲下β值大于ps,说

  20. Polymerized and functionalized triglycerides

    Science.gov (United States)

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

  1. Waterborne Polymeric Films.

    Science.gov (United States)

    1981-02-01

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

  2. Polymeric peptide pigments with sequence-encoded properties

    Energy Technology Data Exchange (ETDEWEB)

    Lampel, Ayala; McPhee, Scott A.; Park, Hang-Ah; Scott, Gary G.; Humagain, Sunita; Hekstra, Doeke R.; Yoo, Barney; Frederix, Pim W. J. M.; Li, Tai-De; Abzalimov, Rinat R.; Greenbaum, Steven G.; Tuttle, Tell; Hu, Chunhua; Bettinger, Christopher J.; Ulijn, Rein V.

    2017-06-08

    Melanins are a family of heterogeneous polymeric pigments that provide ultraviolet (UV) light protection, structural support, coloration, and free radical scavenging. Formed by oxidative oligomerization of catecholic small molecules, the physical properties of melanins are influenced by covalent and noncovalent disorder. We report the use of tyrosine-containing tripeptides as tunable precursors for polymeric pigments. In these structures, phenols are presented in a (supra-)molecular context dictated by the positions of the amino acids in the peptide sequence. Oxidative polymerization can be tuned in a sequence-dependent manner, resulting in peptide sequence–encoded properties such as UV absorbance, morphology, coloration, and electrochemical properties over a considerable range. Short peptides have low barriers to application and can be easily scaled, suggesting near-term applications in cosmetics and biomedicine.

  3. Simulation of styrene polymerization reactors: kinetic and thermodynamic modeling

    Directory of Open Access Journals (Sweden)

    A. S. Almeida

    2008-06-01

    Full Text Available A mathematical model for the free radical polymerization of styrene is developed to predict the steady-state and dynamic behavior of a continuous process. Special emphasis is given for the kinetic and thermodynamic models, where the most sensitive parameters were estimated using data from an industrial plant. The thermodynamic model is based on a cubic equation of state and a mixing rule applied to the low-pressure vapor-liquid equilibrium of polymeric solutions, suitable for modeling the auto-refrigerated polymerization reactors, which use the vaporization rate to remove the reaction heat from the exothermic reactions. The simulation results show the high predictive capability of the proposed model when compared with plant data for conversion, average molecular weights, polydispersity, melt flow index, and thermal properties for different polymer grades.

  4. 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

  5. Synthesis and Characterization of the in Situ Bulk Polymerization of PMMA Containing Graphene Sheets Using Microwave Irradiation

    Directory of Open Access Journals (Sweden)

    Mohammad A. Aldosari

    2013-03-01

    Full Text Available Polymethylmethacrylate–graphene (PMMA/RGO nanocomposites were prepared via in situ bulk polymerization using two different preparation techniques. In the first approach, a mixture of graphite oxide (GO and methylmethacrylate monomers (MMA were polymerized using a bulk polymerization method with a free radical initiator. After the addition of the reducing agent hydrazine hydrate (HH, the product was reduced via microwave irradiation (MWI to obtain R-(GO-PMMA composites. In the second approach, a mixture of graphite sheets (RGO and MMA monomers were polymerized using a bulk polymerization method with a free radical initiator to obtain RGO-(PMMA composites. The composites were characterized by FTIR, 1H-NMR and Raman spectroscopy and XRD, SEM, TEM, TGA and DSC. The results indicate that the composite obtained using the first approach, which involved MWI, had a better morphology and dispersion with enhanced thermal stability compared with the composites prepared without MWI.

  6. The Radicalization Puzzle [video

    OpenAIRE

    Mohammed Hafez; Center for Homeland Defense and Security Naval Postgraduate School

    2015-01-01

    This 20 minute lecture, by Dr. Mohammad Hafez of the Naval Postgraduate School examines the driving factors behind the process of radicalization, turning seemingly ordinary men and women into potential terrorists. The lecture is based on the article "The Radicalization Puzzle: A Theoretical Synthesis of Empirical Approaches to Homegrown Extremism" in Studies in Conflict and Terrorism, by Mohammad Hafez and Creighton Mullins.

  7. Orgasm after radical prostatectomy

    NARCIS (Netherlands)

    Koeman, M; VanDriel, MF; Schultz, WCMW; Mensink, HJA

    1996-01-01

    Objective To evaluate the ability to obtain and the quality of orgasm after radical prostatectomy, Patients and methods The orgasms experienced after undergoing radical prostatectomy were evaluated in 20 men (median age 65 years, range 56-76) using a semi-structured interview and a self-administered

  8. Mixing in polymeric microfluidic devices.

    Energy Technology Data Exchange (ETDEWEB)

    Schunk, Peter Randall; Sun, Amy Cha-Tien; Davis, Robert H. (University of Colorado at Boulder, Boulder, CO); Brotherton, Christopher M. (University of Colorado at Boulder, Boulder, CO)

    2006-04-01

    This SAND report describes progress made during a Sandia National Laboratories sponsored graduate fellowship. The fellowship was funded through an LDRD proposal. The goal of this project is development and characterization of mixing strategies for polymeric microfluidic devices. The mixing strategies under investigation include electroosmotic flow focusing, hydrodynamic focusing, physical constrictions and porous polymer monoliths. For electroosmotic flow focusing, simulations were performed to determine the effect of electroosmotic flow in a microchannel with heterogeneous surface potential. The heterogeneous surface potential caused recirculations to form within the microchannel. These recirculations could then be used to restrict two mixing streams and reduce the characteristic diffusion length. Maximum mixing occurred when the ratio of the mixing region surface potential to the average channel surface potential was made large in magnitude and negative in sign, and when the ratio of the characteristic convection time to the characteristic diffusion time was minimized. Based on these results, experiments were performed to evaluate the manipulation of surface potential using living-radical photopolymerization. The material chosen to manipulate typically exhibits a negative surface potential. Using living-radical surface grafting, a positive surface potential was produced using 2-(Dimethylamino)ethyl methacrylate and a neutral surface was produced using a poly(ethylene glycol) surface graft. Simulations investigating hydrodynamic focusing were also performed. For this technique, mixing is enhanced by using a tertiary fluid stream to constrict the two mixing streams and reduce the characteristic diffusion length. Maximum mixing occurred when the ratio of the tertiary flow stream flow-rate to the mixing streams flow-rate was maximized. Also, like the electroosmotic focusing mixer, mixing was also maximized when the ratio of the characteristic convection time to the

  9. Polystyrene-based Hollow Microsphere Synthesized by [gamma]-ray Irradiation-assisted Polymerization and Self-Assembly and Its Application in Detection of Ionizing Radiation

    National Research Council Canada - National Science Library

    Wenhui Fan; Qing Li; Liang Hu; Siqi Yan; Wanxin Wen; Zhifang Chai; Hanzhou Liu

    2017-01-01

    .... Here, a simple and novel one-pot synthetic strategy to prepare polystyrene (PS) hollow microspheres via irradiation-assisted free-radical polymerizing and self-assembly (IFPS) approach under γ...

  10. STUDIES ON THE POLYMERIZATION OF ACRYLONITRILE INITIATED BY METAVANADATE- CONTAINING ANION EXCHANGER-THIOUREA REDOX SYSTEM

    Institute of Scientific and Technical Information of China (English)

    YANG Chaoxiong; WU Jinyuan; WU Yuxian

    1991-01-01

    The polymerization of acrylonitrile (AN) in aqueous nitric acid initiated by metavanadate-containing anion exchange resin (PV)-thiourea (TU) redox system at 20- 40 ℃. has been investigated. The overall rate of polymerization (Rp) is given by Rp= 1.92 × 104 e -6,860/RT [AN]1.2[PV]0.44[TU]1.0[HNO3]1.0 The kinetic parameters differed from those of V5+-TU system indicated that the generation of the primary radicals is mainly a difffusion-controlled reaction . The effect of macromolecular field arisen from the polymer matrix exerts a great influence on the polymerization process.

  11. Sulfur and selenium antioxidants: challenging radical scavenging mechanisms and developing structure-activity relationships based on metal binding.

    Science.gov (United States)

    Zimmerman, Matthew T; Bayse, Craig A; Ramoutar, Ria R; Brumaghim, Julia L

    2015-04-01

    Because sulfur and selenium antioxidants can prevent oxidative damage, numerous animal and clinical trials have investigated the ability of these compounds to prevent the oxidative stress that is an underlying cause of cardiovascular disease, Alzheimer's disease, and cancer, among others. One of the most common sources of oxidative damage is metal-generated hydroxyl radical; however, very little research has focused on determining the metal-binding abilities and structural attributes that affect oxidative damage prevention by sulfur and selenium compounds. In this review, we describe our ongoing investigations into sulfur and selenium antioxidant prevention of iron- and copper-mediated oxidative DNA damage. We determined that many sulfur and selenium compounds inhibit Cu(I)-mediated DNA damage and that DNA damage prevention varies dramatically when Fe(II) is used in place of Cu(I) to generate hydroxyl radical. Oxidation potentials of the sulfur or selenium compounds do not correlate with their ability to prevent DNA damage, highlighting the importance of metal coordination rather than reactive oxygen species scavenging as an antioxidant mechanism. Additional gel electrophoresis, mass spectrometry, and UV-visible studies confirmed sulfur and selenium antioxidant binding to Cu(I) and Fe(II). Ultimately, our studies established that both the hydroxyl-radical-generating metal ion and the chemical environment of the sulfur or selenium significantly affect DNA damage prevention and that metal coordination is an essential mechanism for these antioxidants. Copyright © 2015 Elsevier Inc. All rights reserved.

  12. Relationship between bilirubin free radical and formation of pigment gallstone

    Institute of Scientific and Technical Information of China (English)

    Xiang-Tao Liu; Jian Hu

    2002-01-01

    In this paper, we summarize the main progresses made inour group in the field of the mechanism of pigment gallstoneformation. It was found that after treetment with freeradicals, bilirubin (BR) was changed into free radical itself,and a semiquinone free radical and a superoxide free radicalbound with metal were recognized, which was detected byESR (electron spin resonance). By the meana of NMR(nuclear magnetic resonance) and IR (Infra-red spectra), itwas postulated that bilirubin polymerized through thereaction between the vinyl group and the hydroxyl groupunder the attack of free radicals. It was also found thatbilirubin free radical were liable to calcify in a kinetic study.Because of its chemical properties, bilirubin free radical wasshown to be cytotoxic to hepetocyte, which wasdemonstrated based on the following facts: induction ofphospholipid peroxidation (LPO), leakage of lactatedehydrogenase (LDH) and decrease of glutathione. As tothe mechanism of bilirubin-induced cytotoxicity, it waspostulated that the main target of bilirubin free radical wasthe cell membrane, including phospholipid and membranebound proteins, especially spectrin, a content ofcytoskeleton. Based on the results mentioned above, it wasdeduced that bilirubin free radical is the key factor thatinitiates and promotes the formation of pigment gallstone,which is consistent with other researches in recent years.

  13. Nucleobase-templated polymerization: copying the chain length and polydispersity of living polymers into conjugated polymers.

    Science.gov (United States)

    Lo, Pik Kwan; Sleiman, Hanadi F

    2009-04-01

    Conjugated polymers synthesized by step polymerization mechanisms typically suffer from poor molecular weight control and broad molecular weight distributions. We report a new method which uses nucleobase recognition to read out and efficiently copy the controlled chain length and narrow molecular weight distribution of a polymer template generated by living polymerization, into a daughter conjugated polymer. Aligning nucleobase-containing monomers on their complementary parent template using hydrogen-bonding interactions, and subsequently carrying out a Sonogashira polymerization, leads to the templated synthesis of a conjugated polymer. Remarkably, this daughter strand is found to possess a narrow molecular weight distribution and a chain length nearly equivalent to that of the parent template. On the other hand, nontemplated polymerization or polymerization with the incorrect template generates a short conjugated oligomer with a significantly broader molecular weight distribution. Hence, nucleobase-templated polymerization is a useful tool in polymer synthesis, in this case allowing the use of a large number of polymers generated by living methods, such as anionic polymerization, controlled radical polymerizations (NMP, ATRP, and RAFT) and other mechanisms to program the structure, length, and molecular weight distribution of polymers normally generated by step polymerization methods and significantly enhance their properties.

  14. 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.

  15. Pickering miniemulsion polymerization using Laponite clay as a stabilizer.

    Science.gov (United States)

    Bon, Stefan A F; Colver, Patrick J

    2007-07-31

    Solid-stabilized, or Pickering, miniemulsion polymerizations using Laponite clay discs as stabilizer are investigated. Free radical polymerizations are carried out using a variety of hydrophobic monomers (i.e., styrene, lauryl (meth)acrylate, butyl (meth)acrylate, octyl acrylate, and 2-ethyl hexyl acrylate). Armored latexes, of which the surfaces of the particles are covered with clay discs, are obtained, as confirmed by scanning electron microscopy (FE-SEM) and atomic force microscopy (AFM). Overall polymerization kinetics of the Pickering miniemulsion polymerizations of styrene were investigated via gravimetry. Comparison with the bulk polymerization analogue clearly shows compartmentalization. Moreover, retardation effects up to intermediate monomer conversions are observed; they are more prominent for the smaller particles and are ascribed to the Laponite clay. A model is presented that allows for the prediction of the average particle size of the latexes produced as a function of the amounts of monomer and Pickering stabilizers used. It shows that under specific generic conditions the number of clay discs used correlates in a linear fashion with the total surface area of the latex particles. This is a direct result of the reversibility of the Laponite clay disc adhesion process under the emulsification conditions (i.e., sonication) used.

  16. Gnosticism and Radical Feminism

    DEFF Research Database (Denmark)

    Cahana, Jonathan

    2016-01-01

    and radical feminism would easily fall under this definition. There is, however, one major difference: since radical feminism is a relatively recent phenomenon which also benefited from modern modes of text production and preservation, almost all of the sources are still with us. This, in turn, may allow us...... to use radical feminism to make certain aspects of ancient Gnosticism re-emerge from their long submersion, provided that enough similarities can be independently drawn between the two phenomena to merit such a comparison. This paper therefore presents a comparison between concepts and positions...

  17. Radical aminomethylation of imines.

    Science.gov (United States)

    Fujii, Shintaro; Konishi, Takehito; Matsumoto, Yusuke; Yamaoka, Yousuke; Takasu, Kiyosei; Yamada, Ken-Ichi

    2014-09-05

    Taking advantage of the high level of performance of N-alkoxycarbonyl-imines, we achieved the first example of addition of the aminomethyl radical to imine. The reaction efficiency depended on the structure of the radical precursor, whether it is an iodide or a xanthate, and an electron-withdrawing group on the nitrogen atom of the radical. This reaction allows direct introduction of an N-substituted aminomethyl group onto imine to provide 1,2-diamine as well as the short-step synthesis of ICI-199,441.

  18. Radical chemistry of artemisinin

    Energy Technology Data Exchange (ETDEWEB)

    Denisov, Evgenii T; Solodova, S L; Denisova, Taisa G [Institute of Problems of Chemical Physics, Russian Academy of Sciences, Chernogolovka, Moscow Region (Russian Federation)

    2010-12-29

    The review summarizes physicochemical characteristics of the natural sesquiterpene peroxide artemisinin. The kinetic schemes of transformations of artemisinin radicals under anaerobic conditions are presented and analyzed. The sequence of radical reactions of artemisinin in the presence of oxygen is considered in detail. Special emphasis is given to the intramolecular chain oxidation resulting in the transformation of artemisinin into polyatomic hydroperoxide. The kinetic characteristics of elementary reaction steps involving alkyl, alkoxyl, and peroxyl radicals generated from artemisinin are discussed. The results of testing of artemisinin and its derivatives for the antimalarial activity and the scheme of the biochemical synthesis of artemisinin in nature are considered.

  19. Radical chemistry of artemisinin

    Science.gov (United States)

    Denisov, Evgenii T.; Solodova, S. L.; Denisova, Taisa G.

    2010-12-01

    The review summarizes physicochemical characteristics of the natural sesquiterpene peroxide artemisinin. The kinetic schemes of transformations of artemisinin radicals under anaerobic conditions are presented and analyzed. The sequence of radical reactions of artemisinin in the presence of oxygen is considered in detail. Special emphasis is given to the intramolecular chain oxidation resulting in the transformation of artemisinin into polyatomic hydroperoxide. The kinetic characteristics of elementary reaction steps involving alkyl, alkoxyl, and peroxyl radicals generated from artemisinin are discussed. The results of testing of artemisinin and its derivatives for the antimalarial activity and the scheme of the biochemical synthesis of artemisinin in nature are considered.

  20. Space environmental effects on polymeric materials

    Science.gov (United States)

    Kiefer, Richard L.; Orwoll, Robert A.

    1987-01-01

    Polymeric materials that may be exposed on spacecraft to the hostile environment beyond Earth's atmosphere were subjected to atomic oxygen, electron bombardment, and ultraviolet radiation in terrestrial experiments. Evidence is presented for the utility of an inexpensive asher for determining the relative susceptibility of organic polymers to atomic oxygen. Kapton, Ultem, P1700 polysulfone, and m-CBB/BIS-A (a specially formulated polymer prepared at NASA Langley) all eroded at high rates, just as was observed in shuttle experiments. Films of Ultem, P1700 polysulfone, and m-CBB/BIS-A were irradiated with 85 keV electrons. The UV/VIS absorbance of Ultem was found to decay with time after irradiation, indicating free radical decay. The tensile properties of Ultem began to change only after it had been exposed to 100 Mrads. The effects of dose rate, temperature, and simultaneous vs. sequential electron and UV irradiation were also studied.

  1. Radical prostatectomy - discharge

    Science.gov (United States)

    ... to 6 months. You will learn exercises (called Kegel exercises) that strengthen the muscles in your pelvis. ... Radical prostatectomy Retrograde ejaculation Urinary incontinence Patient Instructions Kegel exercises - self-care Suprapubic catheter care Urinary catheters - ...

  2. Recent Developments of Versatile Photoinitiating Systems for Cationic Ring Opening Polymerization Operating at Any Wavelengths and under Low Light Intensity Sources.

    Science.gov (United States)

    Lalevée, Jacques; Mokbel, Haifaa; Fouassier, Jean-Pierre

    2015-04-20

    Photoinitiators (PI) or photoinitiating systems (PIS) usable in light induced cationic polymerization (CP) and free radical promoted cationic polymerization (FRPCP) reactions (more specifically for cationic ring opening polymerization (ROP)) together with the involved mechanisms are briefly reviewed. The recent developments of novel two- and three-component PISs for CP and FRPCP upon exposure to low intensity blue to red lights is emphasized in details. Examples of such reactions under various experimental conditions are provided.

  3. Synthesis of photolabile fluorescent polymeric micelles.

    Science.gov (United States)

    Park, Teahoon; You, Jungmok; Oikawa, Hidetoshi; Kim, Eunkyoung

    2014-11-01

    A new amphiphilic block copolymers were synthesized with the atom transfer radical polymerization (ATRP) method. Then, the micelle structures were fabricated with a self-assembly method for application in nanocarriers and sensing. The fluorescent intensity was increased by a factor of 4 in the micelle solution due to more stacked pyrene moieties. The core-shell structure of the micelle was confirmed by HR-TEM images. The pyrene moieties were positioned in the core of the micelle, and the surface consisted of hydrophilic PMMA blocks. The ester bond of the polymer backbone was breakable by irradiation with UV light. Therefore, the micelle structure was deformed after UV irradiation, and the excimer peak was drastically reduced as the monomer peak appeared. The deformation of micelle structures was clearly confirmed by FE-SEM and NMR analysis. These photolabile polymeric micelles may be widely useful for photo-stimulative nanocarriers as well as for the design of new functional micelles with many other chromophores.

  4. Living olefin polymerization processes

    Science.gov (United States)

    Schrock, Richard R.; Baumann, Robert

    1999-01-01

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

  5. Phosphazene-promoted anionic polymerization

    KAUST Repository

    Zhao, Junpeng

    2014-01-01

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

  6. Free-radical concentrations and other properties of pile-irradiated coals

    Science.gov (United States)

    Friedel, R.A.; Breger, I.A.

    1959-01-01

    Five coals reacted quite differently when they were exposed to pile-irradiation. Little or no change was found in free-radical content for the three coals of lowest carbon content, whereas the two coals of highest carbon content were found to have a considerable increase in free-radical content. The infrared spectra and the apparent hardness of the irradiated coals of higher carbon content indicate that polymerization occurred. Radiation of these coals in chemical reagents may promote reactivity.

  7. Free Radical Reactions in Food.

    Science.gov (United States)

    Taub, Irwin A.

    1984-01-01

    Discusses reactions of free radicals that determine the chemistry of many fresh, processed, and stored foods. Focuses on reactions involving ascorbic acid, myoglobin, and palmitate radicals as representative radicals derived from a vitamin, metallo-protein, and saturated lipid. Basic concepts related to free radical structure, formation, and…

  8. Reversible Addition Fragmentation Chain Transfer (RAFT) Polymerization in Undergraduate Polymer Science Lab

    Science.gov (United States)

    Nguyen, T. L. U.; Bennet, Francesca; Stenzel, Martina H.; Barner-Kowollik, Christopher

    2008-01-01

    This 8-hour experiment (spread over two 4-hour sessions) is designed to equip students with essential skills in polymer synthesis, particularly in synthesizing polymers of well-defined molecular weight. The experiment involves the synthesis and characterization of poly(vinyl neodecanoate) via living free radical polymerization, specifically the…

  9. Gratings in polymeric waveguides

    Science.gov (United States)

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

    2007-04-01

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

  10. 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.

  11. Fire-Retardant Polymeric Additives

    Science.gov (United States)

    Williams, Martha K.; Smith, Trent M.

    2011-01-01

    Polyhydroxyamide (PHA) and polymethoxyamide (PMeOA) are fire-retardant (FR) thermoplastic polymers and have been found to be useful as an additive for imparting fire retardant properties to other compatible, thermoplastic polymers (including some elastomers). Examples of compatible flammable polymers include nylons, polyesters, and acrylics. Unlike most prior additives, PHA and PMeOA do not appreciably degrade the mechanical properties of the matrix polymer; indeed, in some cases, mechanical properties are enhanced. Also, unlike some prior additives, PHA and PMeOA do not decompose into large amounts of corrosive or toxic compounds during combustion and can be processed at elevated temperatures. PMeOA derivative formulations were synthesized and used as an FR additive in the fabrication of polyamide (PA) and polystyrene (PS) composites with notable reduction (>30 percent for PS) in peak heat release rates compared to the neat polymer as measured by a Cone Calorimeter (ASTM E1354). Synergistic effects were noted with nanosilica composites. These nanosilica composites had more than 50-percent reduction in peak heat release rates. In a typical application, a flammable thermoplastic, thermoplastic blend, or elastomer that one seeks to render flame-retardant is first dry-mixed with PHA or PMeOA or derivative thereof. The proportion of PHA or PMeOA or derivative in the mixture is typically chosen to lie between 1 and 20 weight percent. The dry blend can then be melt-extruded. The extruded polymer blend can further be extruded and/or molded into fibers, pipes, or any other of a variety of objects that may be required to be fire-retardant. The physical and chemical mechanisms which impart flame retardancy of the additive include inhibiting free-radical oxidation in the vapor phase, preventing vaporization of fuel (the polymer), and cooling through the formation of chemical bonds in either the vapor or the condensed phase. Under thermal stress, the cyclic hydroxyl/ methoxy

  12. Novel hybrid polymeric materials for barrier coatings

    Science.gov (United States)

    Pavlacky, Erin Christine

    . The novel preparation of hybrid films coupling the advantageous properties of organic-inorganic hybrids formed through sol-gel chemistry with polymer-clay nanocomposite technology was also explored. Alkoxysilane-functional copolymer-clay nanocomposites were first synthesized, followed by crosslinking via simultaneous hydrolysis and condensation reactions to create the novel hybrid barrier films. By dispersing organomodified clay throughout the hybrid network, dramatic improvements in several film properties were observed, particularly regarding the viscoelastic properties. Additional studies with the same organic-inorganic preparation technique were performed to incorporate amine-functionality into the hybrid film for potential applications as protective membranes in carbon dioxide capture and separation technologies. Finally, controlled free-radical polymerization techniques were combined with the preparation of the organic-inorganic hybrids.

  13. Sexuality Following Radical Prostatectomy

    DEFF Research Database (Denmark)

    Fode, Mikkel; Serefoglu, Ege C; Albersen, Maarten;

    2017-01-01

    INTRODUCTION: Radical prostatectomies can result in urinary incontinence and sexual dysfunction. Traditionally, these issues have been studied separately, and the sexual problem that has received the most focus has been erectile dysfunction. AIM: To summarize the literature on sexually related side...... effects and their consequences after radical prostatectomy and focus on the occurrence and management of problems beyond erectile dysfunction. METHODS: The literature on sexuality after radical prostatectomy was reviewed through a Medline search. Original research using quantitative and qualitative...... methodologies was considered. Priority was given to studies exploring aspects of sexuality other than erectile function. MAIN OUTCOME MEASURES: The prevalence, predictive factors, and management of post-prostatectomy sexual problems beyond erectile dysfunction. RESULTS: Most patients will develop urinary...

  14. Laparoscopic radical prostatectomy

    Directory of Open Access Journals (Sweden)

    Lipke Michael

    2005-01-01

    Full Text Available Millions of men are diagnosed annually with prostate cancer worldwide. With the advent of PSA screening, there has been a shift in the detection of early prostate cancer, and there are increased numbers of men with asymptomatic, organ confined disease. Laparoscopic radical prostatectomy is the latest, well accepted treatment that patients can select. We review the surgical technique, and oncologic and functional outcomes of the most current, large series of laparoscopic radical prostatectomy published in English. Positive margin rates range from 2.1-6.9% for pT2a, 9.9-20.6% for pT2b, 24.5-42.3% for pT3a, and 22.6-54.5% for pT3b. Potency rates after bilateral nerve sparing laparoscopic radical prostatectomy range from 47.1 to 67%. Continence rates at 12 months range from 83.6 to 92%.

  15. Gangs, Terrorism, and Radicalization

    Directory of Open Access Journals (Sweden)

    Scott Decker

    2011-01-01

    Full Text Available What can street gangs tell us about radicalization and extremist groups? At first glance, these two groups seem to push the boundaries of comparison. In this article, we examine the important similarities and differences across criminal, deviant, and extremist groups. Drawing from research on street gangs, this article explores issues such as levels of explanation,organizational structure, group process, and the increasingly important role of technology and the Internet in the context of radicalization. There are points of convergence across these groups, but it is important to understand the differences between these groups. This review finds little evidence to support the contention that American street gangs are becoming increasingly radicalized. This conclusion is based largely on organizational differences between gangs and terror groups.

  16. Radical Nature of C-Lignin

    Energy Technology Data Exchange (ETDEWEB)

    Berstis, Laura; Elder, Thomas; Crowley, Michael; Beckham, Gregg T.

    2016-10-03

    The recently discovered lignin composed of caffeoyl alcohol monolignols or C-lignin is particularly intriguing given its homogeneous, linear polymeric structure and exclusive benzodioxane linkage between monomers. By virtue of this simplified chemistry, the potential emerges for improved valorization strategies with C-lignin relative to other natural heterogeneous lignins. To better understand caffeoyl alcohol polymers, we characterize the thermodynamics of the radical recombination dimerization reactions forming the benzodioxane linkage and the bond dissociation into radical monolignol products. These properties are also predicted for the cross-coupling of caffeoyl alcohol with the natural monolignols, coniferyl alcohol, sinapyl alcohol, and p-coumaryl alcohol, in anticipation of polymers potentially enabled by genetic modification. The average BDEs for the C-lignin benzodioxane ..alpha..- and ..beta..-bonds are 56.5 and 63.4 kcal/mol, respectively, with similar enthalpies for heterodimers. The BDE of the ..alpha..-bond within the benzodioxane linkage is consistently greater than that of the ..beta..-bond in all dimers of each stereochemical arrangement, explained by the ability the ..alpha..-carbon radical generated to delocalize onto the adjacent phenyl ring. Relative thermodynamics of the heterodimers demonstrates that the substituents on the phenyl ring directly neighboring the bond coupling the monolignols more strongly impact the dimer bond strengths and product stability, compared to the substituents present on the terminal phenyl ring. Enthalpy comparisons furthermore demonstrate that the erythro stereochemical configurations of the benzodioxane bond are slightly less thermodynamically stable than the threo configurations. The overall differences in strength of bonds and reaction enthalpies between stereoisomers are generally found to be insignificant, supporting that postcoupling rearomatization is under kinetic control. Projecting the lowest

  17. Radical dematerialization and degrowth

    Science.gov (United States)

    Kallis, Giorgos

    2017-05-01

    The emission targets agreed in Paris require a radical reduction of material extraction, use and disposal. The core claim of this article is that a radical dematerialization can only be part and parcel of degrowth. Given that capitalist economies are designed to grow, this raises the question of whether, and under what circumstances, the inevitable `degrowth' can become socially sustainable. Three economic policies are discussed in this direction: work-sharing, green taxes and public money. This article is part of the themed issue 'Material demand reduction'.

  18. Collaborative Research: Polymeric Multiferroics

    Energy Technology Data Exchange (ETDEWEB)

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

    2017-04-20

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

  19. Pigment encapsulation by emulsion polymerization using macro-RAFT copolymers.

    Science.gov (United States)

    Nguyen, Duc; Zondanos, Hollie S; Farrugia, Jason M; Serelis, Algirdas K; Such, Chris H; Hawkett, Brian S

    2008-03-04

    A new method is described, based on living amphipathic random macro-RAFT copolymers, which enables the efficient polymeric encapsulation of both inorganic and organic particulate materials via free-radical polymerization. The mechanism for this new approach is examined in the context of the polymer coating of zirconia- and alumina-coated titanium dioxide particles and its breadth of application demonstrated by the coating of organic phthalocyanine blue pigment particles. The particulate materials were first dispersed in water using a macro-RAFT copolymer as a stabilizer. Monomer and water-soluble initiator were then added to the system, and the monomer polymerized to form the coating. If nucleation of new polymer particles in the aqueous phase was to be avoided, it was found necessary to use a macro-RAFT copolymer that did not form micelles; within this constraint, a broad range of RAFT agents could be used. The macro-RAFT agents used in this work were found not to transfer competitively in the aqueous phase and therefore did not support growth of aqueous-phase polymer. Successful encapsulation of particles was demonstrated by TEM. The process described enables 100% of the particles to be encapsulated with greater than 95% of the polymer finishing up in the polymeric shells around the particles. Moreover, the coating reaction can be carried out at greater than 50% solids in many cases and avoids the agglomeration of particles during the coating step.

  20. Multilayered composite microgels synthesized by surfactant-free seeded polymerization.

    Science.gov (United States)

    Suzuki, Daisuke; Yamagata, Tomoyo; Murai, Masaki

    2013-08-20

    We report on a simple and rapid method to produce multilayered composite microgels. Thermosensitive microgels were synthesized by aqueous free radical precipitation polymerization using N-isopropylacrylamide (NIPAm) as a monomer. Using the microgels as cores, surfactant-free seeded polymerization of an oil-soluble monomer, glycidyl methacrylate (GMA), was carried out at 70 °C, where the microgels were highly deswollen in water. All of the oil-soluble monomers were polymerized, and the resultant polymers were attached on the pre-existing microgel cores, resulting in hard shell formation. It is worth mentioning that secondary particles of oil-soluble monomers have never been formed during the polymerization. The composite microgels were characterized by electron microscopy and dynamic light scattering. In particular, X-ray photoelectron spectroscopy (XPS) measurements revealed that the surface of the composite microgels was composed of a hydrogel layer, although microgel cores were covered by polyGMA shell. The mechanism of the trilayered composite microgel formation will be discussed.

  1. Patterned hydrogel layers produced by electrochemically triggered polymerization.

    Science.gov (United States)

    Bünsow, Johanna; Johannsmann, Diethelm

    2009-05-19

    We report on a lithographic mode of electrochemically triggered free radical polymerization. The polymerization is initiated by the reduction of an electrochemically active initiator. Hydrogel patterns can be written by employing a small insulated counter electrode. The investigations show that the "pen" actually is a small oxygen bubble between the counter electrode and the sample surface. The spot size corresponds to the size of the bubble produced between the counter electrode and the substrate. The gas/liquid interface traps the growing chains and guides the growth of a gel layer at the bubble surface. Since bubbles can be created and controlled in many different ways, this mechanism constitutes an easy route for the formation of structured, surface-bound polymer layers.

  2. 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.

  3. Highly Defined Multiblock Copolypeptoids: Pushing the Limits of Living Nucleophilic Ring-Opening Polymerization

    KAUST Repository

    Fetsch, Corinna

    2012-06-05

    Advanced macromolecular engineering requires excellent control over the polymerization reaction. Living polymerization methods are notoriously sensitive to impurities, which makes a practical realization of such control very challenging. Reversible-deactivation radical polymerization methods are typically more robust, but have other limitations. Here, we demonstrate by repeated (ge;10 times) chain extension the extraordinary robustness of the living nucleophilic ring-opening polymerization of N-substituted glycine N-carboxyanhydrides, which yields polypeptoids. We observe essentially quantitative end-group fidelity under experimental conditions that are comparatively easily managed. This is employed to synthesize a pentablock quinquiespolymer with high definition. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Enzyme- and affinity biomolecule-mediated polymerization systems for biological signal amplification and cell screening.

    Science.gov (United States)

    Malinowska, Klara H; Nash, Michael A

    2016-06-01

    Enzyme-mediated polymerization and polymerization-based signal amplification have emerged as two closely related techniques that are broadly applicable in the nanobio sciences. We review recent progress on polymerization systems mediated by biological molecules (e.g., affinity molecules and enzymes), and highlight newly developed formats and configurations of these systems to perform such tasks as non-instrumented biodetection, synthesis of core-shell nanomaterials, isolation of rare cells, and high-throughput screening. We discuss useful features of biologically mediated polymerization systems, such as multiple mechanisms of amplification (e.g., enzymatic, radical chain propagation), and the ability to localize structures at interfaces and at cell surfaces with microscopic spatial confinement. We close with a perspective on desirable improvements that need to be addressed to adapt these molecular systems to future applications.

  5. Combining On-Line Characterization Tools with Modern Software Environments for Optimal Operation of Polymerization Processes

    Directory of Open Access Journals (Sweden)

    Navid Ghadipasha

    2016-02-01

    Full Text Available This paper discusses the initial steps towards the formulation and implementation of a generic and flexible model centric framework for integrated simulation, estimation, optimization and feedback control of polymerization processes. For the first time it combines the powerful capabilities of the automatic continuous on-line monitoring of polymerization system (ACOMP, with a modern simulation, estimation and optimization software environment towards an integrated scheme for the optimal operation of polymeric processes. An initial validation of the framework was performed for modelling and optimization using literature data, illustrating the flexibility of the method to apply under different systems and conditions. Subsequently, off-line capabilities of the system were fully tested experimentally for model validations, parameter estimation and process optimization using ACOMP data. Experimental results are provided for free radical solution polymerization of methyl methacrylate.

  6. Radical School Reform.

    Science.gov (United States)

    Gross, Beatrice, Ed.; Gross, Ronald, Ed.

    This book provides a comprehensive examination of the nature of the school crisis and the ways in which radical thinkers and educators are dealing with it. Excerpts from the writings of Jonathan Kozol, John Holt, Kenneth Clark, and others are concerned with the realities of education in ghettos and suburbs. Paul Goodman, Marshall McLuhan, Sylvia…

  7. 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 and the...

  8. Radically enhanced molecular recognition

    KAUST Repository

    Trabolsi, Ali

    2009-12-17

    The tendency for viologen radical cations to dimerize has been harnessed to establish a recognition motif based on their ability to form extremely strong inclusion complexes with cyclobis(paraquat-p-phenylene) in its diradical dicationic redox state. This previously unreported complex involving three bipyridinium cation radicals increases the versatility of host-guest chemistry, extending its practice beyond the traditional reliance on neutral and charged guests and hosts. In particular, transporting the concept of radical dimerization into the field of mechanically interlocked molecules introduces a higher level of control within molecular switches and machines. Herein, we report that bistable and tristable [2]rotaxanes can be switched by altering electrochemical potentials. In a tristable [2]rotaxane composed of a cyclobis(paraquat-p-phenylene) ring and a dumbbell with tetrathiafulvalene, dioxynaphthalene and bipyridinium recognition sites, the position of the ring can be switched. On oxidation, it moves from the tetrathiafulvalene to the dioxynaphthalene, and on reduction, to the bipyridinium radical cation, provided the ring is also reduced simultaneously to the diradical dication. © 2010 Macmillan Publishers Limited. All rights reserved.

  9. 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...

  10. Beyond Radical Educational Cynicism.

    Science.gov (United States)

    Wood, George H.

    1982-01-01

    An alternative is presented to counter current radical arguments that the schools cannot bring about social change because they are instruments of capitalism. The works of Samuel Bowles, Herbert Gintis, and Louis Althusser are discussed. Henry Giroux's "Ideology, Culture and the Process of Schooling" provides an alternative to cynicism.…

  11. Electromeric rhodium radical complexes

    NARCIS (Netherlands)

    Puschmann, F.F.; Harmer, J.; Stein, D.; Rüegger, H.; de Bruin, B.; Grützmacher, H.

    2010-01-01

    Radical changes: One single P-Rh-P angle determines whether the odd electron in the paramagnetic complex [Rh(trop2PPh)(PPh3)] is delocalized over the whole molecule (see picture, blue) or is localized on the P—Rh unit (red). The two energetically almost degenerate electromers exist in a fast equilib

  12. Homegrown religious radicalization

    DEFF Research Database (Denmark)

    Khawaja, Iram

    and their families. Existing literature and ways of thinking about the social psychological process of radicalization will be reviewed, such as social identity theory and transformative learning theory, and a theoretical framework based on a focus on belonging, recognition and the sense of community will be proposed...

  13. On Radical Feminism

    Institute of Scientific and Technical Information of China (English)

    翟良锴

    2015-01-01

    <正>All men are created equal.For centuries,human have been struggling for their rights.Women,as a special social force,are fighting vigorously for their equal rights with men.According to an introduction to feminism,there are three main types of feminism:socialist,reformist and radical(Feminism 101).In order

  14. Analysis of beer volatiles by polymeric imidazolium-solid phase microextraction coatings: Synthesis and characterization of polymeric imidazolium ionic liquids.

    Science.gov (United States)

    González-Álvarez, Jaime; Blanco-Gomis, Domingo; Arias-Abrodo, Pilar; Pello-Palma, Jairo; Ríos-Lombardía, Nicolás; Busto, Eduardo; Gotor-Fernández, Vicente; Gutiérrez-Álvarez, María Dolores

    2013-08-30

    Two polymeric ionic liquids, 3-(but-3″-en-1″-yl)-1-[2'-hydroxycyclohexyl]-1H-imidazol-3-ium bis(trifluoromethanesulfonyl)imide (IL-1) and 1-(2'-hydroxycyclohexyl)-3-(4″-vinylbenzyl)-1H-imidazol-3-ium bis(trifluoromethylsulfonyl)imide (IL-2), have been synthesized by a free radical polymerization reaction and used as coatings for solid-phase microextraction (SPME). These new fibers exhibit good film stability, high thermal stability (270-290°C) and long lifetimes, and are used for the extraction of volatile compounds in lemon beer using gas chromatography separation and flame ionization detection. The scanning electron micrographs of the fiber surface revealed a polymeric ionic liquid (PIL) film, which is distributed homogeneously on the fiber. The developed PIL fiber showed good linearity between 50 and 2000μg/L with regression coefficients in the range of 0.996-0.999. The relative standard deviations (RSD) obtained in the peak area were found to vary between 1% and 12%, which assured that adequate repeatability was achieved. The spiked recoveries for three beer samples ranged from 78.4% to 123.6%. Experimental design has been employed in the optimization of extraction factors and robustness assessment. The polymeric IL-1 butenyl fiber showed a greater efficiency compared to the PDMS-DVB (65μm) and CAR-PDMS (75μm) for the extraction of all of the analytes studied.

  15. Organometallic Polymeric Conductors

    Science.gov (United States)

    Youngs, Wiley J.

    1997-01-01

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

  16. Radical-scavenging Activity of Natural Methoxyphenols vs. Synthetic Ones using the Induction Period Method

    Directory of Open Access Journals (Sweden)

    Ichiro Yokoe

    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.

  17. Scavenging of free-radical metabolites of aniline xenobiotics and drugs by amino acid derivatives: toxicological implications of radical-transfer reactions.

    Science.gov (United States)

    Michail, Karim; Baghdasarian, Argishti; Narwaley, Malyaj; Aljuhani, Naif; Siraki, Arno G

    2013-12-16

    We investigated a novel scavenging mechanism of arylamine free radicals by poly- and monoaminocarboxylates. Free radicals of arylamine xenobiotics and drugs did not react with oxygen in peroxidase-catalyzed reactions; however, they showed marked oxygen uptake in the presence of an aminocarboxylate. These free-radical intermediates were identified using the spin trap 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) and electron paramagnetic resonance (EPR) spectrometry. Diethylenetriaminepentaacetic acid (DTPA), a polyaminocarboxylate, caused a concentration-dependent attenuation of N-centered radicals produced by the peroxidative metabolism of arylamines with the subsequent formation of secondary aliphatic carbon-centered radicals stemming from the cosubstrate molecule. Analogously, N,N-dimethylglycine (DMG) and N-methyliminodiacetate (MIDA), but not iminodiacetic acid (IDA), demonstrated a similar scavenging effect of arylamine-derived free radicals in a horseradish peroxidase/H2O2 system. Using human promyelocytic leukemia (HL-60) cell lysate as a model of human neutrophils, DTPA, MIDA, and DMG readily reduced anilinium cation radicals derived from the arylamines and gave rise to the corresponding carbon radicals. The rate of peroxidase-triggered polymerization of aniline was studied as a measure of nitrogen-radical scavenging. Although, IDA had no effect on the rate of aniline polymerization, this was almost nullified in the presence of DTPA and MIDA at half of the molar concentration of the aniline substrate, whereas a 20 molar excess of DMPO caused only a partial inhibition. Furthermore, the yield of formaldehyde, a specific reaction endproduct of the oxidation of aminocarboxylates by aniline free-radical metabolites, was quantitatively determined. Azobenzene, a specific reaction product of peroxidase-catalyzed free-radical dimerization of aniline, was fully abrogated in the presence of DTPA, as confirmed by GC/MS. Under aerobic conditions, a radical-transfer reaction

  18. Electroactivity in Polymeric Materials

    CERN Document Server

    2012-01-01

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

  19. Kinetics of silica polymerization

    Energy Technology Data Exchange (ETDEWEB)

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

    1980-05-01

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

  20. Studies in reactive extrusion processing of biodegradable polymeric materials

    Science.gov (United States)

    Balakrishnan, Sunder

    Various reaction chemistries such as Polymerization, Polymer cross-linking and Reactive grafting were investigated in twin-screw extruders. Poly (1,4-dioxan-2-one) (PPDX) was manufactured in melt by the continuous polymerization of 1,4-dioxan-2-one (PDX) monomer in a twin-screw extruder using Aluminum tri-sec butoxide (ATSB) initiator. Good and accurate control over molecular weight was obtained by controlling the ratio of monomer to initiator. A screw configuration consisting of only conveying elements was used for the polymerization. The polymerization reaction was characterized by a monomer-polymer dynamic equilibrium, above the melting temperature of the polymer, limiting the equilibrium conversion to 78-percent. Near complete (˜100-percent) conversion was obtained on co-polymerizing PDX monomer with a few mol-percent (around 8-percent) Caprolactone (CL) monomer in a twin-screw extruder using ATSB initiator. The co-polymers exhibited improved thermal stability with reduction in glass transition temperature. The extruder was modeled as an Axial Dispersed Plug Flow Reactor for the polymerization of CL monomer using Residence Time Distribution (RTD) Analysis. The model provided a good fit to the experimental RTD and conversion data. Aliphatic and aliphatic-aromatic co-polyesters, namely Polycaprolactone (PCL) and Poly butylenes (adipate-co-terephthalate) (Ecoflex) were cross-linked in a twin-screw extruder using radical initiator to form micro-gel reinforced biodegradable polyesters. Cross-linked Ecoflex was further extrusion blended with talc to form blends suitable to be blown into films. A screw configuration consisting of conveying and kneading elements was found to be effective in dispersion of the talc particles (5--10 microns) in the polyester matrix. While the rates of crystallization increased for the talc filled polyester blends, overall crystallinity reduced. Mechanical, tear and puncture properties of films made using the talc filled polyester blends

  1. Polymerization of anionic wormlike micelles.

    Science.gov (United States)

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

    2006-01-31

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

  2. 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.

  3. Assorted Phenoxyl-Radical Polymers and Their Application in Lithium-Organic Batteries.

    Science.gov (United States)

    Jähnert, Thomas; Hager, Martin D; Schubert, Ulrich S

    2016-04-01

    The synthesis and electrochemical characterization of novel polymers bearing phenoxyl-radicals as redox-active side chains is described. The monomers are synthesized from the corresponding phenols and quinones, respectively. These compounds are subsequently poly-merized via ring-opening metathesis polymerization. The electrochemical properties of the phenoxyl-radical polymers are characterized using cyclic voltammetry and the most promising polymer is investigated as active material in a lithium coin-cell, creating the first phenoxyl-lithium battery. These phenoxyl-containing polymers represent interesting anode materials for organic radical and lithium batteries due to their suitable redox-potentials and possibility to create batteries with higher potentials as well as straightforward synthesis procedures.

  4. Surface glycosylation of polymeric membranes

    Institute of Scientific and Technical Information of China (English)

    DAI ZhengWei; WAN LingShu; XU ZhiKang

    2008-01-01

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

  5. Women and radicalization

    OpenAIRE

    Badran, Margot

    2006-01-01

    The paper focuses on women and radicalization within the context of Muslim societies (majority, minority, and half Muslim) societies and groups, mainly in Asia and Africa. The basic argument advanced in this paper is that Islamic feminism with its gender-egalitarian discourse and practices has a major role to play in the empowerment of Muslim women—and of men and society as a whole—and should be brought to bear in devising policy, strategy, and tools.

  6. Probability and radical behaviorism

    Science.gov (United States)

    Espinosa, James M.

    1992-01-01

    The concept of probability appears to be very important in the radical behaviorism of Skinner. Yet, it seems that this probability has not been accurately defined and is still ambiguous. I give a strict, relative frequency interpretation of probability and its applicability to the data from the science of behavior as supplied by cumulative records. Two examples of stochastic processes are given that may model the data from cumulative records that result under conditions of continuous reinforcement and extinction, respectively. PMID:22478114

  7. Probability and radical behaviorism

    OpenAIRE

    Espinosa, James M.

    1992-01-01

    The concept of probability appears to be very important in the radical behaviorism of Skinner. Yet, it seems that this probability has not been accurately defined and is still ambiguous. I give a strict, relative frequency interpretation of probability and its applicability to the data from the science of behavior as supplied by cumulative records. Two examples of stochastic processes are given that may model the data from cumulative records that result under conditions of continuous reinforc...

  8. Radical chic, javisst!

    NARCIS (Netherlands)

    Hartle, J.F.

    2012-01-01

    Det är lätt att raljera över engagerade människor, i synnerhet när engagemanget framstår som ytligt och chict snarare än grundläggande och autentiskt. Men vad ligger bakom ett sådant avfärdande? Johan Frederik Hartle läser om Tom Wolfes klassiska essä "Radical Chic" och visar hur Wolfe −− genom att

  9. Radical substitution with azide

    DEFF Research Database (Denmark)

    Pedersen, Christian Marcus; Marinescu, Lavinia Georgeta; Bols, Mikael

    2005-01-01

    and the substrate. A primary deuterium kinetic isotope effect was found for the azidonation of benzyl ethers both with TMSN3-PhI(OAc)2 and with IN3. Also a Hammett free energy relationship study of this reaction showed good correlation with sigma+ constants giving with rho-values of -0.47 for TMSN3-PhI(OAc)2 and -0.......39 for IN3. On this basis a radical mechanism of the reaction was proposed....

  10. Biomimetic polymeric superhydrophobic surfaces and nanostructures: from fabrication to applications.

    Science.gov (United States)

    Wen, Gang; Guo, ZhiGuang; Liu, Weimin

    2017-03-09

    Numerous research studies have contributed to the development of mature superhydrophobic systems. The fabrication and applications of polymeric superhydrophobic surfaces have been discussed and these have attracted tremendous attention over the past few years due to their excellent properties. In general, roughness and chemical composition, the two most crucial factors with respect to surface wetting, provide the basic criteria for yielding polymeric superhydrophobic materials. Furthermore, with their unique properties and flexible configurations, polymers have been one of the most efficient materials for fabricating superhydrophobic materials. This review aims to summarize the most recent progress in polymeric superhydrophobic surfaces. Significantly, the fundamental theories for designing these materials will be presented, and the original methods will be introduced, followed by a summary of multifunctional superhydrophobic polymers and their applications. The principles of these methods can be divided into two categories: the first involves adding nanoparticles to a low surface energy polymer, and the other involves combining a low surface energy material with a textured surface, followed by chemical modification. Notably, surface-initiated radical polymerization is a versatile method for a variety of vinyl monomers, resulting in controlled molecular weights and low polydispersities. The surfaces produced by these methods not only possess superhydrophobicity but also have many applications, such as self-cleaning, self-healing, anti-icing, anti-bioadhesion, oil-water separation, and even superamphiphobic surfaces. Interestingly, the combination of responsive materials and roughness enhances the responsiveness, which allows the achievement of intelligent transformation between superhydrophobicity and superhydrophilicity. Nevertheless, surfaces with poor physical and chemical properties are generally unable to withstand the severe conditions of the outside world

  11. THERMOCHEMISTRY OF HYDROCARBON RADICALS

    Energy Technology Data Exchange (ETDEWEB)

    Kent M. Ervin, Principal Investigator

    2004-08-17

    Gas phase negative ion chemistry methods are employed to determine enthalpies of formation of hydrocarbon radicals that are important in combustion processes and to investigate the dynamics of ion-molecule reactions. Using guided ion beam tandem mass spectrometry, we measure collisional threshold energies of endoergic proton transfer and hydrogen atom transfer reactions of hydrocarbon molecules with negative reagent ions. The measured reaction threshold energies for proton transfer yield the relative gas phase acidities. In an alternative methodology, competitive collision-induced dissociation of proton-bound ion-molecule complexes provides accurate gas phase acidities relative to a reference acid. Combined with the electron affinity of the R {center_dot} radical, the gas phase acidity yields the RH bond dissociation energy of the corresponding neutral molecule, or equivalently the enthalpy of formation of the R{center_dot} organic radical, using equation: D(R-H) = {Delta}{sub acid}H(RH) + EA(R) - IE(H). The threshold energy for hydrogen abstraction from a hydrocarbon molecule yields its hydrogen atom affinity relative to the reagent anion, providing the RH bond dissociation energy directly. Electronic structure calculations are used to evaluate the possibility of potential energy barriers or dynamical constrictions along the reaction path, and as input for RRKM and phase space theory calculations. In newer experiments, we have measured the product velocity distributions to obtain additional information on the energetics and dynamics of the reactions.

  12. [Radical prostatectomy - pro robotic].

    Science.gov (United States)

    Gillitzer, R

    2012-05-01

    Anatomical radical prostatectomy was introduced in the early 1980s by Walsh and Donker. Elucidation of key anatomical structures led to a significant reduction in the morbidity of this procedure. The strive to achieve similar oncological and functional results to this gold standard open procedure but with further reduction of morbidity through a minimally invasive access led to the establishment of laparoscopic prostatectomy. However, this procedure is complex and difficult and is associated with a long learning curve. The technical advantages of robotically assisted surgery coupled with the intuitive handling of the device led to increased precision and shortening of the learning curve. These main advantages, together with a massive internet presence and aggressive marketing, have resulted in a rapid dissemination of robotic radical prostatectomy and an increasing patient demand. However, superiority of robotic radical prostatectomy in comparison to the other surgical therapeutic options has not yet been proven on a scientific basis. Currently robotic-assisted surgery is an established technique and future technical improvements will certainly further define its role in urological surgery. In the end this technical innovation will have to be balanced against the very high purchase and running costs, which remain the main limitation of this technology.

  13. Emulsion Polymerization of Tung Oil-Based Latexes with Asolectin as a Biorenewable Surfactant

    Directory of Open Access Journals (Sweden)

    Ashley Johns

    2016-11-01

    Full Text Available Bio-based vesicles, with potential application in drug delivery and/or catalyst encapsulation, have been prepared by the free radical emulsion co-polymerization of tung oil, divinylbenzene (DVB, n-butyl methacrylate (BMA, and asolectin in a xylene/water mixture. The free radical polymerization was initiated by di-tert-butyl peroxide (DTBP at 100 °C in a convection oven. Molecular weights of approximately 11,000 Da were measured by Matrix-assisted Laser Desorption/Ionization-Time of Flight (Maldi-TOF for tung oil-asolectin copolymers, verifying that significant polymerization occurs under the cure conditions employed. The cure of the co-monomer mixture employed in this work was monitored by Dielectric Analysis (DEA, while changes in the Raman spectrum of all co-monomers before and after the cure, along with differential scanning calorimetry (DSC analysis, have been used to verify the need of a post-cure step and completion of the polymerization reaction. Scanning Transmission Electron Microscopy (STEM images of the emulsion after polymerization indicate that vesicles were formed, and vesicle size distribution of samples prepared with different amounts of tung oil were determined using a Zetasizer.

  14. Polymeric materials for neovascularization

    Science.gov (United States)

    DeVolder, Ross John

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

  15. Photoinitiated chemical vapor deposition of polymeric thin films using a volatile photoinitiator.

    Science.gov (United States)

    Chan, Kelvin; Gleason, Karen K

    2005-12-06

    Photoinitiated chemical vapor deposition (piCVD) is an evolutionary CVD technique for depositing polymeric thin films in one step without using any solvents. The technique requires no pre- or post-treatment and uses a volatile photoinitiator to initiate free-radical polymerization of gaseous monomers under UV irradiation. Glycidyl methacrylate (GMA) was used as a test monomer for its ability to undergo free-radical polymerization, and 2,2'-azobis(2-methylpropane) (ABMP) was used as the photoinitiator, as it is known to produce radicals when excited by photons. GMA and ABMP vapors were fed into a vacuum chamber in which film growth was observed on a substrate exposed to UV irradiation. The resulting poly(glycidyl methacrylate) (PGMA) thin films were comprised of linear chains and had high structural resemblance to conventionally polymerized PGMA, as shown by the high solubility in tetrahydrofuran and the infrared and X-ray photoelectron spectroscopy measurements. The introduction of ABMP into the vacuum chamber significantly increased growth rates. The maximum growth rate achieved was approximately 140 nm/min and represents a 7-fold enhancement over the case without ABMP. The molecular weight was found to increase with increasing monomer-to-initiator (M/I) feed ratio, and the polydispersity indexes (PDIs) of the samples were between 1.8 and 2.2, lower than the values obtained in conventional batch polymerization but in agreement with the theoretical expressions developed for low-conversion solution-phase polymerization, which are applicable to continuous processes such as piCVD. Molecular-weight distributions can be narrowed by filtering out wavelengths shorter than 300 nm, which induce branching and/or cross-linking. The strong dependence of the molecular weight on the M/I ratio, the rate enhancement due to the use of a radical photoinitiator, the good agreement between the experimental, and the theoretical PDIs provide evidence of a free-radical mechanism in pi

  16. Improved Mechanical Performance Fracture Properties and Reliability of Radical-Cured Thermosets.

    Energy Technology Data Exchange (ETDEWEB)

    Redline, Erica Marie; Bolintineanu, Dan; Lane, J. Matthew; Stevens, Mark J.; Alam, Todd M.; Celina, Mathias C.

    2016-10-01

    The aim of this study was to alter polymerization chemistry to improve network homogeneity in free-radical crosslinked systems. It was hypothesized that a reduction in heterogeneity of the network would lead to improved mechanical performance. Experiments and simulations were carried out to investigate the connection between polymerization chemistry, network structure and mechanical properties. Experiments were conducted on two different monomer systems - the first is a single monomer system, urethane dimethacrylate (UDMA), and the second is a two-monomer system consisting of bisphenol A glycidyl dimethacrylate (BisGMA) and triethylene glycol dimethacrylate (TEGDMA) in a ratio of 70/30 BisGMA/TEGDMA by weight. The methacrylate systems were crosslinked using traditional radical polymeriza- tion (TRP) with azobisisobutyronitrile (AIBN) or benzoyl peroxide (BPO) as an initiator; TRP systems were used as the control. The monomers were also cross-linked using activator regenerated by electron transfer atom transfer radical polymerization (ARGET ATRP) as a type of controlled radical polymerization (CRP). FTIR and DSC were used to monitor reac- tion kinetics of the systems. The networks were analyzed using NMR, DSC, X-ray diffraction (XRD), atomic force microscopy (AFM), and small angle X-ray scattering (SAXS). These techniques were employed in an attempt to quantify differences between the traditional and controlled radical polymerizations. While a quantitative methodology for characterizing net- work morphology was not established, SAXS and AFM have shown some promising initial results. Additionally, differences in mechanical behavior were observed between traditional and controlled radical polymerized thermosets in the BisGMA/TEGDMA system but not in the UDMA materials; this finding may be the result of network ductility variations between the two materials. Coarse-grained molecular dynamics simulations employing a novel model of the CRP reaction were carried out for

  17. Purification of inkjet ink from water using liquid phase, electric discharge polymerization and cellulosic membrane filtration.

    Science.gov (United States)

    Jordan, Alexander T; Hsieh, Jeffery S; Lee, Daniel T

    2013-01-01

    A method to separate inkjet ink from water was developed using a liquid phase, electric discharge process. The liquid phase, electric discharge process with filtration or sedimentation was shown to remove 97% of inkjet ink from solutions containing between 0.1-0.8 g/L and was consistent over a range of treatment conditions. Additionally, particle size analysis of treated allyl alcohol and treated propanol confirmed the electric discharge treatment has a polymerization mechanism, and small molecule analysis of treated methanol using gas chromatography and mass spectroscopy confirmed the mechanism was free radical initiated polymerization.

  18. Olefin Metathesis Polymerization: The Unexpected Role of Carbenoid Species in Formation of Macromolecules

    Science.gov (United States)

    Snyder, Donald M.

    1996-02-01

    Today most undergraduate organic chemistry texts present some material on polymers, but the coverage in these texts is necessarily quite limited. Step-growth and free-radical chain growth systems, along with some mention of coordination polymerization, usually constitute the bulk of introductory material. Very little of the advances in polymer chemistry since the 1960's is reflected in the undergraduate curriculum. One particularly interesting topic still rarely seen outside of the research literature is the subject of metathesis polymerization. This article is intended to present the interested reader with a brief introduction to the mechanism of this unique process, its historical background, and some recent developments in the field.

  19. DEPENDENCE OF ACRYLONITRILE POLYMERIZATION KINETICS ON THE COMPOSITION OF POLYAMID OXIME -THIOUREA SYSTEM

    Institute of Scientific and Technical Information of China (English)

    WU Jinyuan; YANG Chaoxiong; ZHANG Guangzhao

    1993-01-01

    The polymerization of acrylonitrile (AN) initiated by polypropylene based-polyamidoxime (PPAO)- thiourea (TU) system was investigated at [ TU]/[ PPAO] > 0.5 molar ratio. It shows that the variation of the concentrations of PPAO, thiourea and nitric acid does not exert an observable influence on the reaction rate. The overall rate of polymerization (Rp) is Rp = 2.07e - 7,800/RT[AN] 2.0The zero order dependence on PPAO and thiourea concentrations and the lowest value of the collision frequence factor were considered to be a feature of the primary radical termination.

  20. INFLUENCES OF WATER-SOLUBLE CATIONIC MONOMERS ON THE POLYMERIZATION RATE IN THE INVERSE EMULSION

    Institute of Scientific and Technical Information of China (English)

    HOU Sijian; HA Runhua

    1996-01-01

    This investigation deals with the free radical polymerization both of (2-methacryloyloxyethyl) trimethyl ammonium chloride (QACEMA) and of diallyldimethyl ammonium chloride (DADMAC) in inverse emulsion. The influences of some factors, such as the concentration of monomers, initiator and emulsifier are discussed. The polymerization rate equations of above two monomers can be written as follows:Rp = k[M]1.21[I]0.82[E]0.57 (for QACEMA)Rp = k′[M]1.34[I]0.90[E]0.62 (for DADMAC)

  1. A Mechanistic and Kinetic Study of the Photoinitiated Cationic Double Ring-opening Polymerization of 2-Methylene-7-phenyl-1,4,6,9-tetraoxa-spiro[4.4]nonane

    OpenAIRE

    2006-01-01

    Efficient photopolymerization of a potentially expandable monomer is of practical importance for a variety of polymeric applications demanding dimensional stability, particularly if the polymerization process is well controlled based on a detailed investigation of the reaction. In the current study, photoinitiated polymerization kinetics of 2-methylene-7-phenyl-1,4,6,9-tetraoxaspiro[4.4]nonane (MPN) either with cationic initiation alone or with combined cationic/free radical initiation was ex...

  2. Catalysis of Radical Reactions: A Radical Chemistry Perspective.

    Science.gov (United States)

    Studer, Armido; Curran, Dennis P

    2016-01-04

    The area of catalysis of radical reactions has recently flourished. Various reaction conditions have been discovered and explained in terms of catalytic cycles. These cycles rarely stand alone as unique paths from substrates to products. Instead, most radical reactions have innate chains which form products without any catalyst. How do we know if a species added in "catalytic amounts" is a catalyst, an initiator, or something else? Herein we critically address both catalyst-free and catalytic radical reactions through the lens of radical chemistry. Basic principles of kinetics and thermodynamics are used to address problems of initiation, propagation, and inhibition of radical chains. The catalysis of radical reactions differs from other areas of catalysis. Whereas efficient innate chain reactions are difficult to catalyze because individual steps are fast, both inefficient chain processes and non-chain processes afford diverse opportunities for catalysis, as illustrated with selected examples.

  3. A Mechanistic and Kinetic Study of the Photoinitiated Cationic Double Ring-opening Polymerization of 2-Methylene-7-phenyl-1,4,6,9-tetraoxa-spiro[4.4]nonane.

    Science.gov (United States)

    Ge, Junhao; Trujillo-Lemon, Marianela; Stansbury, Jeffrey W

    2006-12-26

    Efficient photopolymerization of a potentially expandable monomer is of practical importance for a variety of polymeric applications demanding dimensional stability, particularly if the polymerization process is well controlled based on a detailed investigation of the reaction. In the current study, photoinitiated polymerization kinetics of 2-methylene-7-phenyl-1,4,6,9-tetraoxaspiro[4.4]nonane (MPN) either with cationic initiation alone or with combined cationic/free radical initiation was examined using real-time FT-IR. A proposed mechanism based on the simplified propagation steps of the cationic double ring-opening polymerization of MPN was confirmed by both computer modeling and NMR spectroscopic analysis of resulting polymers as well as the experimentally observed apparent activation energy. According to this mechanism, alpha-position attack is the predominant mode for the second ring opening during cationic polymerization of MPN. Further, cationic photopolymerization was performed along with a free radical co-initiator or with exposure to moisture to get an improved understanding of the complex cationic double ring-opening polymerization. As a result, free radical-promoted cationic polymerization helps increase the polymerization rate of MPN while even a trace amount of moisture was found to significantly impact both the reaction kinetics and the polymerization course.

  4. Role of nanoclay shape and surface characteristics on the morphology and thermal properties of polystyrene nanocomposites synthesized via emulsion polymerization

    CSIR Research Space (South Africa)

    Greesh, N

    2013-10-01

    Full Text Available This work evaluates the role of the surface properties and shape of clay type on the morphology, thermal, and thermo-mechanical properties of the polystyrene (PS)/clay nanocomposites prepared via free-radical emulsion polymerization. Attapulgite...

  5. Photocatalysed (Methacrylate Polymerization by (Antimony-Doped Tin Oxide Nanoparticles and Photoconduction of Their Crosslinked Polymer Nanoparticle Composites

    Directory of Open Access Journals (Sweden)

    J. C. M. Brokken-Zijp

    2010-01-01

    Full Text Available In the absence of another (photoradical initiator Sb:SnO2 nanoparticles (0≤Sb≤13 at % photocatalyze during irradiation with UV light the radical polymerization of (methacrylate monomers. When cured hard and transparent (>98% films with a low haze (0 at % nanoparticles can be attractive fillers for other photocatalytic applications photorefractive materials, optoelectronic devices and sensors.

  6. Nanometer scale vacuum lithography using plasma polymerization and plasma etching

    CERN Document Server

    Kim, S O

    1998-01-01

    Thin films of plasma polymerization were fabricated through plasma polymerization of interelectrode capacitively coupled gas flow system. After delineating the pattern with an accelerating voltage of 30kV, ranging the dose of 1 approx 500 mu C/cm sup 2 , the pattern was developed with a dry type and formed by plasma etching. By analyzing the molecule structure using FT-IR ( Fourier Transform-Infrared Spectrometry), it was confirmed that the thin films of PPMST (Plasma Polymerized Methylmethacrylate+Styrene+Tetramethyltin) contained the functional radicals of the MST (Methylmethacrylate sub S tyrene+Tetramethyltin) monomer. The Thin films of PPMST had a highly cross-linked structure resulting in a higher molecule weight than the conventional resist. The deposition rate of the PPMST thin films was 230 approx 600 A/min as a function of 50 approx 200 W power and 200 approx 60 A/min as a function 0.1 approx 0.7 Torr pressure. The etching rate of the thin films of PPMST was 875 approx 3520 A/min as a function of 50...

  7. Powering up the future: radical polymers for battery applications.

    Science.gov (United States)

    Janoschka, Tobias; Hager, Martin D; Schubert, Ulrich S

    2012-12-18

    Our society's dependency on portable electric energy, i.e., rechargeable batteries, which permit power consumption at any place and in any time, will eventually culminate in resource wars on limited commodities like lithium, cobalt, and rare earth metals. The substitution of conventional metals as means of electric charge storage by organic and polymeric materials, which may ultimately be derived from renewable resources, appears to be the only feasible way out. In this context, the novel class of organic radical batteries (ORBs) excelling in rate capability (i.e., charging speed) and cycling stability (>1000 cycles) sets new standards in battery research. This review examines stable nitroxide radical bearing polymers, their processing to battery systems, and their promising performance.

  8. 基于RAFT聚合策略合成功能化聚烯烃嵌段聚合物的研究进展%Progress of synthesis of functional polyolefin block copolymers via strategy based on RAFT polymerization

    Institute of Scientific and Technical Information of China (English)

    毛国梁; 王欣; 宁英男; 马志

    2012-01-01

    首先介绍了可逆加成-断裂链转移聚合(RAFT)的聚合机理及其常用的RAFT试剂,并与其它两种活性可控自由基聚合[氮氧化合物媒介的自由基聚合(NMP)和原子转移自由基聚合(ATRP)]进行了简单的优缺点对比。其次,介绍了近些年在基于RAFT聚合制备功能化聚烯烃嵌段聚合物研究中取得的进展,重点综述了制备功能化聚烯烃嵌段聚合物时所采用的6种方法,包括①烯烃配位聚合与RAFT聚合相结合;②阴离子聚合与RAFT聚合相结合;③阳离子聚合与RAFT聚合相结合;④Click反应与RAFT聚合相结合;⑤开环聚合与RAFT聚合相结合;⑥叶立德活性聚合与RAFT聚合相结合。最后,对基于RAFT聚合策略设计合成功能化聚烯烃嵌段聚合物的研究前景与实际应用进行了展望。%The paper briefly describes the general polymerization mechanism of reversible addition-fragmentation chain transfer(RAFT) polymerization and some common RAFT agents.The RAFT polymerization is compared with other two kinds of active controlled radical polymerizations [nitrogen oxide mediated free radical polymerization(NMP) and atom transfer radical polymerization(ATRP)].The recent progress of synthesis of functional polyolefin block copolymers on the basis of RAFT polymerization is reviewed.Six kinds of combined methodologies based on RAFT polymerization aiming at the synthesis of functional polyolefin block copolymers are introduced:① Combination of olefin coordination polymerization and RAFT polymerization,②Combination of living anionic polymerization and RAFT polymerization,③Combination of cationic polymerization and RAFT polymerization,④ Combination of Click chemistry and RAFT polymerization,⑤ Combination of ring-opening polymerization and RAFT polymerization,⑥Combination of living polymerization of Ylides and RAFT polymerization.Finally,the prospect of the design and synthesis of functional polyolefin block copolymers via

  9. Supramolecular Polymeric Materials Containing Cyclodextrins.

    Science.gov (United States)

    Nakahata, Masaki; Takashima, Yoshinori; Harada, Akira

    2017-01-01

    Smart design of polymeric materials may lead to intelligent materials exhibiting unique functional properties. Looking at nature, living systems use specific and reversible intermolecular interactions in realizing complex functions. Hence reversible bonds based on selective molecular recognition can impart artificial materials with unique functional properties. This review mainly focuses on supramolecular polymeric materials based on cyclodextrin-based host-guest interactions. Polymeric materials using molecular recognition at polymer main chain, side chain, and termini are described. Polymers carrying host and guest residues exhibit unique properties such as: 1) formation of macroscopic self-assembly of polymer gels carrying host and guest residues; 2) stimuli-responsive self-healing properties due to the reversible nature of host-guest interactions; and 3) macroscopic motion of artificial muscle cross-linked by host-guest interaction controlled by external stimuli. An overview of recent developments in this new frontier between materials science and life science is given.

  10. Radically innovative steelmaking technologies

    Science.gov (United States)

    Szekely, Julian

    1980-09-01

    The steel industry is faced with serious problems caused by the increasing cost of energy, labor and capital and by tough overseas competition, employing new highly efficient process plants. The very high cost of capital and of capital equipment renders the construction of new green field site plants, exemplifying the best available technology economically unattractive. For this reason, over the long term the development radically innovative steelmaking technologies appears to be the only satisfactory resolution of this dilemma. The purpose of this article is to present a critical review of some of the radically innovative steelmaking technologies that have been proposed during the past few years and to develop the argument that these indeed do deserve serious consideration at the present time. It should be stressed, however, that these innovative technologies can be implemented only as part of a carefully conceived long range plan, which contains as a subset short term solutions, such as trigger prices improved investment credits, and so forth and intermediate term solutions, such as more extensive use of continuous casting, external desulfurization and selective modernization in general.

  11. Bursectomy at radical gastrectomy

    Institute of Scientific and Technical Information of China (English)

    Cuneyt; Kayaalp

    2015-01-01

    Radical gastrectomy with extended lymph node dissec tion and prophylactic resection of the omentum, peri toneum over the posterior lesser sac, pancreas and/o spleen was advocated at the beginning of the 1960 s in Japan. In time, prophylactic routine resections of the pancreas and/or spleen were abandoned because of the high incidence of postoperative complications. However omentectomy and bursectomy continued to be standard parts of traditional radical gastrectomy. The bursaomentalis was thought to be a natural barrier against invasion of cancer cells into the posterior part of the stomach. The theoretical rationale for bursectomy was to reduce the risk of peritoneal recurrences by eliminating the peritoneum over the lesser sac, which might include free cancer cells or micrometastases. Over time, the indication for bursectomy was gradually reduced to only patients with posterior gastric wall tumors penetrating the serosa. Despite its theoretical advantages, its benefit for recurrence or survival has not been proven yet. The possible reasons for this inconsistency are discussed in this review. In conclusion, the value of bursectomy in the treatment of gastric cancer is still under debate and large-scale randomized studies are necessary. Until clear evidence of patient benefit is obtained, its routine use cannot be recommended.

  12. SENSITIVITY ANALYSIS OF KINETIC CONSTANTS AS A TOOL FOR ELUCIDATING THE POLYMERIZATION MECHANISM OF ACRYL-FURANIC COMPOUNDS

    Directory of Open Access Journals (Sweden)

    Jurgen Lange

    2013-12-01

    Full Text Available By means of the sensitivity analysis of kinetics constants in a proposed mechanism for radical polymerization of acrylfuranic compounds [Furfuryl Acrylate (FA and Methacrylate (FM],it is elucidated which elementary steps are relevant in the phenomenology. In this analysis, the application of Come's methodology allows to classify the elementary steps of a mechanism in three categories: Non-sensible, Non-determinant, Sensible. The results obtained with this tool in modeling of experimental data in free radical polymerization of FA and FM suggest that kinetic mechanism consists mainly on five elementary steps: 1 Primary initiation, 2 propagation, 3 degradative transfers (which include intermolecular and primary, 4 re-initiation and 5 cross-termination. Thus, taking into account these elementary steps in mathematical modeling, the polymerization of FA and FM in different experimental conditions was successfully simulated.

  13. STUDIES OF THE INITIATION MECHANISM OF VINYL POLYMERIZATION WITH THE SYSTEM PERSULFATE/N-ALKYL SUBSTITUTED ETHYLENEDIAMINE DERIVATIVES

    Institute of Scientific and Technical Information of China (English)

    GUO Xinqiu; QIU Kunyuan; FENG Xinde

    1989-01-01

    Effects of N-alkyl substituted ethylenediamine derivatives on vinyl polymerization using persulfate as initiator were studied. The apparent kinetic equations and overall activation energies of acrylamide polymerization were determined using the above mentioned system as initiator. The promoting activities of diamine > primary diamine. Diamines having methyl groups as the substituent on their nitrogen atom possess higher promoting activity than that of having larger alkyl groups.The initialfree radicals produced through the redox reaction of persulfate and diamines were studied by spin strapping technique and ESR spectroscopy. The results obtained confirm the fact that the initial free radicals of the diamine species can initiate vinyl polymerization and become the amino end group of the resulting polymers.

  14. Surface glycosylation of polymeric membranes

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

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

  15. On-demand photoinitiated polymerization

    Science.gov (United States)

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

    2013-12-10

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

  16. Effect of tamoxifen in RAFT miniemulsion polymerization during the synthesis of polymer nanoparticles

    Directory of Open Access Journals (Sweden)

    Tailane Sant'Anna Moreira

    2014-01-01

    Full Text Available Tamoxifen (TXF is currently the only hormonal agent used for treatment of breast cancer. Although very effective, TXF presents low solubility in water, which affects its absorption and bioavailability. A common strategy to overcome this barrier is the formulation of a drug delivery system (DDS in order to increase the drug stability and improve the treatment effectiveness. Reversible addition-fragmentation chain transfer (RAFT polymerization is the most versatile method of controlled/living radical polymerization (CLRP, allowing for synthesis of well-defined polymers and being adapted to a wide range of polymerization systems. Miniemulsion polymerization is a dispersed system that is commonly used to prepare nanoparticles (NP with 50 to 500 nm of diameter. The aim of this work was to evaluate the effect of the in situ incorporation of TXF during miniemulsion conventional and RAFT polymerizations, using methyl methacrylate (MMA as monomer. Although the in situ addition of TXF promoted a slight reduction of the reaction rate, it did not affect the final particle size distribution of the latex or the molecular weight control exerted by the RAFT agent. The obtained results suggest that in situ incorporation of TXF during the synthesis of polymer NP via RAFT polymerization allows for production of a polymer DDS for different uses, such as the breast cancer treatment.

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

    Science.gov (United States)

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

    2016-06-21

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

  18. Measurement of the Relative Free Radical Content of Insulating Oils of Petroleum Origin

    Directory of Open Access Journals (Sweden)

    Issouf Fofana

    2015-07-01

    Full Text Available Oil/paper insulation degradation in transformers involves chemical and physical changes in the materials. Some of the chemical reactions involve very reactive intermediates called free radicals. Free radicals play a major role in a wide variety of ageing processes. The detection of these reactive species in oil may, in principle, provide useful information for monitoring oil degradation. This manuscript details a laboratory technique, which determines the relative content of free radicals in insulating oils of petroleum origin by a spectrophotometric method. Free radicals may be formed in oils under operating or test conditions. The procedure enables the determination of the relative concentration of free radicals, which can act as the precursors of decay products such as charge carriers, oxidized molecules, as well as polymerization products. The technique involves using a reactive free radical reagent, 2,2-diphenyl-1-picrylhydrazyl (DPPH, added to oil to assess free radical concentration. This method is applicable to new, reclaimed, or used oils as well as naturally or artificially oxidized oil (the cause of aging can be chemical, physical, or electrical. In this contribution, free radicals were assessed following electrical discharge application in oil.

  19. Morphological control of conductive polymers utilized electrolysis polymerization technique: trial of fabricating biocircuit.

    Science.gov (United States)

    Onoda, Mitsuyoshi

    2014-10-01

    Conductive polymers are a strong contender for making electronic circuits. The growth pattern in conductive polymer synthesis by the electrolysis polymerization method was examined. The growth pattern is deeply related to the coupling reaction of the radical cation and the deprotonation reaction following it and changes suddenly depending on the kind and concentration of the supporting electrolyte and the solvent used. That is, when the electrophilic substitution coupling reaction becomes predominant, the three-dimensional growth form is observed, and when the radical coupling reaction becomes predominant, the two-dimensional growth morphology is observed. In addition, the growth pattern can be comparatively easily controlled by changing the value of the polymerization constant current, and it is considered that the indicator and development for biocircuit research with neuron-type devices made of conjugated polymers was obtained.

  20. SYNTHESIS AND POLYMERIZATION OF 2-OXO-3-METHYLENE-5,6-DIPHENYL-1,4-DIOXAN

    Institute of Scientific and Technical Information of China (English)

    FENG Pinzhen; LU Jiantao

    1994-01-01

    A new cyclic monomer, 2-oxo-3-methylene-5, 6-diphenyl-1,4-dioxan, was synthesized. The structure of the intermediates and the monomer were determined by IR,1H NMR,13C NMR and elemental analysis. This new monomer is different from other cyclic monomers in this series,it is a solid (mp 108-109℃)and not very reactive,but still can undergo free radical ring-opening polymerization. The free radical polymerization was carried out at 130℃. The structure of the resulting polymer was discussed and charaterized by IR, 1H NMR, 13C NMR and elemental analysis. The molecular weight of the polymer was estimated by viscosity determination.

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

    Institute of Scientific and Technical Information of China (English)

    Dong Jinyong

    2006-01-01

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

  2. The absorption of polymeric composites

    Science.gov (United States)

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

    2016-06-01

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

  3. The Viscosity of Polymeric Fluids.

    Science.gov (United States)

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

    1983-01-01

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

  4. Biodegradable polymeric prodrugs of naltrexone

    NARCIS (Netherlands)

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

    1991-01-01

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

  5. Buckling of polymerized monomolecular films

    Science.gov (United States)

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

    1994-03-01

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

  6. Novel polymeric materials from triglycerides

    Science.gov (United States)

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

  7. Radicals in Berkeley?

    Science.gov (United States)

    Linn, Stuart

    2015-04-03

    In a previous autobiographical sketch for DNA Repair (Linn, S. (2012) Life in the serendipitous lane: excitement and gratification in studying DNA repair. DNA Repair 11, 595-605), I wrote about my involvement in research on mechanisms of DNA repair. In this Reflections, I look back at how I became interested in free radical chemistry and biology and outline some of our bizarre (at the time) observations. Of course, these studies could never have succeeded without the exceptional aid of my mentors: my teachers; the undergraduate and graduate students, postdoctoral fellows, and senior lab visitors in my laboratory; and my faculty and staff colleagues here at Berkeley. I am so indebted to each and every one of these individuals for their efforts to overcome my ignorance and set me on the straight and narrow path to success in research. I regret that I cannot mention and thank each of these mentors individually.

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

    Science.gov (United States)

    Hong, Miao; Chen, Eugene Y-X

    2014-10-27

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

  9. Effect of reactor's positions on polymerization and degradation in an ultrasonic field.

    Science.gov (United States)

    Kobayashi, Daisuke; Matsumoto, Hideyuki; Kuroda, Chiaki

    2008-03-01

    Ultrasonic generators are used as emulsifiers and efficient alternative initiators in polymerization processes. In this study, the effects of reactor's position on the emulsion polymerization of styrene under indirect ultrasonic irradiation were investigated, along with the effects of reactor's position on chemical and physical degradation. Both polymer yield and molecular weight were influenced by the position of the reactor. The ultrasonic irradiation could be divided into three stages, and the molecular weight of the polymer was influenced by polymerization and degradation processes. It was found that the extent of radical generation estimated by KI oxidation dosimetry and the shock wave index obtained from studies of degradation of standard polymer were useful for controlling the characteristics of the polymer generated.

  10. Polymeric amines and biomedical uses thereof

    NARCIS (Netherlands)

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

    2010-01-01

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

  11. THE POLYMERIZATION OF AROMATIC AND HETEROCYCLIC DINITRILES

    Institute of Scientific and Technical Information of China (English)

    HUANG Zhitang

    1988-01-01

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

  12. Glycine Polymerization on Oxide Minerals

    Science.gov (United States)

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

    2016-07-01

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

  13. RADICAL GRAFTING OF POLY(METHYL METHACRYLATE) ONTO SILICON-WAFERS, GLASS SLIDES AND GLASS-BEADS

    NARCIS (Netherlands)

    FOLKERSMA, R; CHALLA, G; SCHOUTEN, AJ

    1991-01-01

    Poly(methyl methacrylate) was grafted onto glass beads, glass slides and silicon wafers using an immobilized radical initiator. The polymeric monolayers had thicknesses varying from a few hundred to 4000 angstrom, being up to 10 times larger than the radii of gyration of comparable free polymers. Du

  14. 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.

  15. Radical chic? Yes we are!

    OpenAIRE

    Hartle, J.F.

    2012-01-01

    Ever since Tom Wolfe in a classical 1970 essay coined the term "radical chic", upper-class flirtation with radical causes has been ridiculed. But by separating aesthetics from politics Wolfe was actually more reactionary than the people he criticized, writes Johan Frederik Hartle.

  16. Melatonin scavenges phenylglyoxylic ketyl radicals.

    Science.gov (United States)

    Sersen, F; Vencel, T; Annus, J

    2004-12-01

    The antioxidant properties of melatonin were tested in this work by EPR technique. It was found that melatonin scavenges phenylglyoxylic ketyl radicals. Its effectiveness was 10-times lower than that of vitamin C. A new method of generation of phenylglyoxylic ketyl radicals by spontaneous decomposition of D,L-2,3-diphenyltartaric acid in propan-2-ol was used.

  17. Synthesis and Characterization of Novel Polymethylene-Based 3-Miktoarm Star Copolymers by Combining Polyhomologation with Other Living Polymerizations

    KAUST Repository

    Altaher, Maryam

    2015-05-01

    Polyethylene (PE) is produced in a huge scale globally and has plenty of desirable properties. It is used in coating, packaging, and artificial joint replacements. The growing need for high performance polyethylene led to the development of new catalysts, monomers and polymerizations. The synthesis of polymethylene (equivalent to polyethylene) by living polyhomologation opened the way to well-defined polymethylenes-based polymeric materials with controlled structure, molecular weight and narrow polydispersity. Such model polymers are substantial to study the structure-properties relationships. This research presents a new strategy based on the in situ formation of B-thexyl-silaboracyclic serving as initiating sites for the polyhomologation of dimethylsulfoxonium methylide. Combination with metal-free ring-opening polymerization (ROP) of ɛ-caprolactone (CL) and atom transfer radical polymerization (ATRP) of styrene led to three polymethylene-based 3-miktoarm stars copolymers PCL(PM-OH)2, Br-PCL(PM-OH)2 and PS(PM-OH)2.

  18. N-Vinylcarbazole: As an Additive for Thermal Polymerization at Room Temperature with in situ Formation of Ag(0 Nanoparticules

    Directory of Open Access Journals (Sweden)

    Mohamad-Ali Tehfe

    2015-08-01

    Full Text Available N-vinylcarbazole (NVK is proposed as an additive for acrylates thermal free radical polymerization (FRP and epoxy thermal ring opening polymerization (ROP at room temperature. The new initiating systems are based on a silane/silver salt/N-vinylcarbazole interaction, which ensures good to excellent polymerization. Moreover, the polymerization is much more efficient under air than under argon. The effects of the N-vinylcarbazole, silane, silver salt and monomer structures are investigated. Interestingly, silver nanoparticles Ag(0 are formed in situ. The as-synthesized nanocomposite materials contained spherical nanoparticles homogeneously dispersed in the polymer matrices. Polymers and nanoparticles were characterized by Differential Scanning Calorimetry (DSC, Transmission Electron Microscopy (TEM, Energy-Dispersive X-ray Spectrometry (EDS, Fourier Transform Infrared Spectroscopy (FTIR, and UV-vis spectroscopy. A coherent picture of the involved chemical mechanisms is presented.

  19. Synthesis of Novel Chiral Stationary Phase Based on Atom Transfer Radical Polymerization and Click Chemistry%基于原子转移自由基聚合和“Click”化学方法制备手性色谱固定相

    Institute of Scientific and Technical Information of China (English)

    王怀松; 彭江涛; 魏纪平; 姜安

    2012-01-01

    应用原子转移自由基聚合(ATRP)法和“Click”化学方法,以含叠氮基的烯类化合物为单体,在硅胶表面引发聚合,制备了“梳状”手性固定相.该固定相的合成采用“接出”方法接枝聚合物链,使接枝层更为均匀,并且避免了传统合成方法(如物理吸附等)稳定性差的缺点.所得到的“梳状”手性固定相实现了对一些手性药物的分离;并考察了该固定相中聚合物链的密度和长度对其手性分离能力的影响.%A novel chiral stationary phase was synthesized via the combination of atom transfer radical po- lymerization (ATRP) and click chemistry. In the synthesis, the silane coupling agent 3-(2-bromoisobutyryl)- propyl triethoxysilane (BPE) was chosen as the ATRP initiator and immobized on the porous silica gel. The polymer chains of poly(2-methyl-3-butyn-2-ol methacrylate) (pMBMA) were grafted on the silica substrates by surface-initiated ATRP. This "grafting-from" technique was used to synthesize polymers with controlla- ble molecular weight and narrow molecular weight distributions. For immobilizing the chiral selector, azide-modified β-cyclodextrin (β-CD) was synthesized and bounded on the pMBMA by click chemistry, which can avoid the side-reactions in the preparation. The materials with different pMBMA chain density and length on the silica gel surface were prepared. Several pharmaceuticals were used to evaluate the enantioseparation ability of the materials under reversed-phase high performance liquid chromatography. The results demonstrate that ATRP can well design the polymer structure, and click chemistry can provide an ef- fective route in the β-CD immobilization for chiral discrimination. It was found that the retention and separation factors of chiral compounds could be improved by adjusting the pMBMA chain density and length on the surface of silica gel.

  20. Free radical homopolymerization of a vinylferrocene/cyclodextrin complex in water

    Directory of Open Access Journals (Sweden)

    Helmut Ritter

    2010-06-01

    Full Text Available We report the radical initiated homopolymerization of a soluble vinylferrocene cyclodextrin-complex in water. Uncomplexed vinylferrocene 1 and the corresponding homopolymer are hydrophobic and completely insoluble in water. Complexation of 1 with methyl-β-cyclodextrin 2 results in clearly water-soluble structures due to incorporation of the ferrocene moiety into the cyclodextrin cavity. After free radical polymerization of the water-soluble complexed monomer, corresponding to polyvinylferrocene (PVFc, the water-soluble polymer is obtained due to the host guest interactions. Those polymeric complexes are stable in water up to about 90 °C. Above this temperature the polymer precipitates due to decomplexation. The complex was investigated by 1H NMR spectrometry, dynamic light scattering (DLS, differential scanning calorimetry (DSC, and lower critical solution temperature (LCST measurements.