Gamma-radiation induced polymerization of methyl methacrylate in aliphatic hydrocarbons: kinetics and evidence for incorporation of hydrocarbon in the polymer chain

International Nuclear Information System (INIS)

Mohan, H.; Iyer, R.M.

1989-01-01

On γ-radiolysis, the rate of polymerization of methyl methacrylate in hydrocarbon solvents is observed to decrease. It is explained by hydrocarbon entry into the polymer chains. The hydrocarbon entry into the polymer chains is observed to take place at later stages of polymerization and increases with hydrocarbon chain length. The extent of hydrocarbon entry into the polymer chains is estimated by NMR and GLC analysis. It is observed to be equal to ∼ 12% corresponding to ∼ 97 hexadecane molecules in each polymer chain. The IR, DSC, MW determination and radiation effects on the polymer showed evidences for hydrocarbon entry into the polymer. It is explained by chain transfer from the growing polymer radical to the hydrocarbon molecules. The chain transfer constant is determined to be equal to 1 x 10 -2 . (author)

Non-local spatial frequency response of photopolymer materials containing chain transfer agents: I. Theoretical modelling

International Nuclear Information System (INIS)

Guo, Jinxin; Gleeson, Michael R; Liu, Shui; Sheridan, John T

2011-01-01

The non-local photopolymerization driven diffusion (NPDD) model predicts that a reduction in the non-local response length within a photopolymer material will improve its high spatial frequency response. The introduction of a chain transfer agent reduces the average molecular weight of polymer chains formed during free radical polymerization. Therefore a chain transfer agent (CTA) provides a practical method to reduce the non-local response length. An extended NPDD model is presented, which includes the chain transfer reaction and most major photochemical processes. The addition of a chain transfer agent into an acrylamide/polyvinyl alcohol photopolymer material is simulated and the predictions of the model are examined. The predictions of the model are experimentally examined in part II of this paper

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

International Nuclear Information System (INIS)

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

2016-01-01

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

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...

prepared via atom transfer radical polymerization, reverse atom

Indian Academy of Sciences (India)

Synthesis and characterization of poly(2-ethylhexyl acrylate) prepared via atom transfer radical polymerization, reverse atom transfer radical polymerization and ... Zydex Industries, 25-A Gandhi Oil Mill Compound, Gorwa, Vadodara 390 016, India; Rubber Technology Centre, Indian Institute of Technology Kharagpur, ...

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.

Noncovalent assembly. A rational strategy for the realization of chain-growth supramolecular polymerization.

Science.gov (United States)

Kang, Jiheong; Miyajima, Daigo; Mori, Tadashi; Inoue, Yoshihisa; Itoh, Yoshimitsu; Aida, Takuzo

2015-02-06

Over the past decade, major progress in supramolecular polymerization has had a substantial effect on the design of functional soft materials. However, despite recent advances, most studies are still based on a preconceived notion that supramolecular polymerization follows a step-growth mechanism, which precludes control over chain length, sequence, and stereochemical structure. Here we report the realization of chain-growth polymerization by designing metastable monomers with a shape-promoted intramolecular hydrogen-bonding network. The monomers are conformationally restricted from spontaneous polymerization at ambient temperatures but begin to polymerize with characteristics typical of a living mechanism upon mixing with tailored initiators. The chain growth occurs stereoselectively and therefore enables optical resolution of a racemic monomer. Copyright © 2015, American Association for the Advancement of Science.

Living catalyzed-chain-growth polymerization and block copolymerization of isoprene by rare-earth metal allyl precursors bearing a constrained-geometry-conformation ligand.

Science.gov (United States)

Jian, Zhongbao; Cui, Dongmei; Hou, Zhaomin; Li, Xiaofang

2010-05-07

Aminophenyl functionalized cyclopentadienyl ligated rare-earth metal allyl mediated cationic systems display high cis-1,4 selectivity for the polymerization of isoprene, and living reversible and rapid chain transfer to aluminium additives.

Ethylene homo- and copolymerization chain-transfers: A perspective from supported (n BuCp) 2 ZrCl 2 catalyst active centre distribution

KAUST Repository

Atiqullah, Muhammad

2015-04-01

Polymerization chain termination reactions and unsaturation of the polymer backbone end are related. Therefore, in this study, the parameters resulting from the modelling of the active centre distribution of the supported catalyst - silica/MAO/(nBuCp)2ZrCl2 - were applied to evaluate the active-centre-dependent ethylene homo- and copolymerization rates, as well as the corresponding chain termination rates. This approach, from a microkinetic mechanistic viewpoint, elucidates better the 1-hexene-induced positive comonomer effect and chain transfer phenomenon. The kinetic expressions, developed on the basis of the proposed polymerization mechanisms, illustrate how the active site type-dependent chain transfer phenomenon is influenced by the different apparent termination rate constants and momoner concentrations. The active centre-specific molecular weight M ni (for the above homo- and copolymer), as a function of chain transfer probability, p CTi, varied as follows: log (p C Ti) = log (mwru) - log (Mn i), where mw ru is the molecular weight of the repeat unit. The physical significance of this finding has been explained. The homo- and copolymer backbones showed all the three chain end unsaturations (vinyl, vinylidene, and trans-vinylene). The postulated polymerization mechanisms reveal the underlying polymer chemistry. The results of the present study will contribute to develop in future supported metallocene catalysts that will be useful to synthesize polyethylene precursors having varying chain end unsaturations, which can be eventually used to prepare functional polyethylenes. [Figure not available: see fulltext.] © 2015 Indian Academy of Sciences.

Gamma radiation-initiated polymerization of styrene at high pressure. II. Chain termination

International Nuclear Information System (INIS)

Moore, P.W.; Clouston, J.G.; Chaplin, R.P.

1981-01-01

The pressure dependence of the termination rate constant k/sub t/ for the free radical polymerization of monomers such as styrene is a function of polymer chain length, chain stiffness, and monomer viscosity, all of which influence the rate of segmental diffusion of an active radical chain end out of the coiled polymer chain to a position in which it can react with a proximate radical. Although k/sub t/ is not sensitive to changes in chain length, the large increase in molecular weight is responsible for a significant reduction in k/sub t/ at high pressures. For most of the common vinyl polymers, which exhibit some degree of chain stiffness, k/sub t/is inversely proportional to a fractional power of the monomer viscosity because it depends in part on the resistance of chain segments to movement and in part on the influence of viscosity in controlling diffusion of the chain ends. The fractional exponent appears to increase with pressure and this is interpreted as evidence that the polymer chains become more flexible in a more viscous solvent. Because the fractional exponent is higher for more flexible chains, the value of the activation volume for chain termination is an indication of the degree of flexibility of the polymer chains, provided that the monomer is a good solvent for the polymer and that chain transfer is negligible

RAFT polymerization mediated bioconjugation strategies

OpenAIRE

Bulmuş, Volga

2011-01-01

This review aims to highlight the use of RAFT polymerization in the synthesis of polymer bioconjugates. It covers two main bioconjugation strategies using the RAFT process: (i) post-polymerization bioconjugations using pre-synthesized reactive polymers, and (ii) bioconjugations via in situ polymerization using biomolecule-modified monomers or chain transfer agents. © 2011 The Royal Society of Chemistry.

Synthesis of Well-Defined Three-Arm Star-Branched Polystyrene through Arm-First Coupling Approach by Atom Transfer Radical Polymerization

OpenAIRE

Shahabuddin, Syed; Hamime Ismail, Fatem; Mohamad, Sharifah; Muhamad Sarih, Norazilawati

2015-01-01

Here we describe a simple route to synthesize three-arm star-branched polystyrene. Atom transfer radical polymerization technique has been utilized to yield branched polystyrene involving Williamson coupling strategy. Initially a linear polymeric chain of predetermined molecular weight has been synthesized which is further end-functionalized into a primary alkyl bromide moiety, a prime requisition for Williamson reaction. The end-functionalized polymer is then coupled using 1,1,1-tris(4-hydro...

Chain-growth cycloaddition polymerization via a catalytic alkyne [2 + 2 + 2] cyclotrimerization reaction and its application to one-shot spontaneous block copolymerization.

Science.gov (United States)

Sugiyama, Yu-ki; Kato, Rei; Sakurada, Tetsuya; Okamoto, Sentaro

2011-06-29

A cobalt-catalyzed alkyne [2 + 2 + 2] cycloaddition reaction has been applied to polymerizations yielding linear polymers via selective cross-cyclotrimerization of yne-diyne monomers, which occurs in a chain-growth manner. Additionally, through control of the alkyne reactivity of the two monomers, this method was efficiently applied to the spontaneous block copolymerization of their mixture. Here we present the proposed mechanism of the catalyst transfer process of this cycloaddition polymerization.

Synthesis of Main-Chain Chiral Quaternary Ammonium Polymers for Asymmetric Catalysis Using Quaternization Polymerization

Directory of Open Access Journals (Sweden)

Md. Masud Parvez

2012-06-01

Full Text Available Main-chain chiral quaternary ammonium polymers were successfully synthesized by the quaternization polymerization of cinchonidine dimer with dihalides. The polymerization occurred smoothly under optimized conditions to give novel type of main-chain chiral quaternary ammonium polymers. The catalytic activity of the polymeric chiral organocatalysts was investigated on the asymmetric benzylation of N-(diphenylmethylideneglycine tert-butyl ester.

Self assembled linear polymeric chains with tuneable semiflexibility using isotropic interactions

Science.gov (United States)

Abraham, Alex; Chatterji, Apratim

2018-04-01

We propose a two-body spherically symmetric (isotropic) potential such that particles interacting by the potential self-assemble into linear semiflexible polymeric chains without branching. By suitable control of the potential parameters, we can control the persistence length of the polymer and can even introduce a controlled number of branches. Thus we show how to achieve effective directional interactions starting from spherically symmetric potentials. The self-assembled polymers have an exponential distribution of chain lengths akin to what is observed for worm-like micellar systems. On increasing particle density, the polymeric chains self-organize to an ordered line-hexagonal phase where every chain is surrounded by six parallel chains, the transition is first order. On further increase in monomer density, the order is destroyed and we get a branched gel-like phase. This potential can be used to model semi-flexible equilibrium polymers with tunable semiflexibility and excluded volume. The use of the potential is computationally cheap and hence can be used to simulate and probe equilibrium polymer dynamics with long chains. The potential also gives a plausible method of tuning colloidal interactions in experiments such that one can obtain self-assembling polymeric chains made up of colloids and probe polymer dynamics using an optical microscope. Furthermore, we show how a modified potential leads to the observation of an intermediate nematic phase of self-assembled chains in between the low density disordered phase and the line-ordered hexagonal phase.

Direct surface PEGylation of nanodiamond via RAFT polymerization

International Nuclear Information System (INIS)

Shi, Yingge; Liu, Meiying; Wang, Ke; Huang, Hongye; Wan, Qing; Tao, Lei; Fu, Lihua; Zhang, Xiaoyong; Wei, Yen

2015-01-01

Graphical abstract: In this paper, we describe an efficient, practical and novel method to modify ND via direct immobilization of chain transfer agent for RAFT polymerization. - Highlights: • Surface PEGylation of ND via RAFT polymerization. • ND with high water dispersibility and excellent biocompatibility. • Controlled living polymerization. - Abstract: Nanodiamond (ND) is a novel class of carbon nanomaterials, which has been extensively investigated for biomedical applications because of its small size, high surface area and excellent biocompatibility. However, the biomedical applications of unmodified ND are still largely restricted because of their poor dispersibility in both aqueous and organic medium. In this work, we reported a novel strategy for the surface modification of ND via reversible addition fragmentation chain transfer (RAFT) polymerization. For preparation of the PEGylated ND (pPEGMA-ND), chain transfer agent (CTA) was immobilized onto ND through reaction between the hydroxyl group of ND and the carboxyl group of CTA, which was used as the initiator for surface-initiated RAFT polymerization. The successful preparation of pPEGMA-ND was characterized by nuclear magnetic resonance spectroscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectra and thermal gravimetric analysis in detail. Results demonstrated that pPEGMA-ND exhibited enhanced water dispersibility and desirable biocompatibility, making it promising for biomedical applications.

Direct surface PEGylation of nanodiamond via RAFT polymerization

Energy Technology Data Exchange (ETDEWEB)

Shi, Yingge [Department of Chemistry and Jiangxi Provincial Key Laboratory of New Energy Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); School of Chemistry and Chemical Engineering, Guangxi University, Nanning 530004 (China); Liu, Meiying [Department of Chemistry and Jiangxi Provincial Key Laboratory of New Energy 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); Huang, Hongye; Wan, Qing [Department of Chemistry and Jiangxi Provincial Key Laboratory of New Energy Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Tao, Lei [Department of Chemistry and the Tsinghua Center for Frontier Polymer Research, Tsinghua University, Beijing 100084 (China); Fu, Lihua [School of Chemistry and Chemical Engineering, Guangxi University, Nanning 530004 (China); Zhang, Xiaoyong, E-mail: xiaoyongzhang1980@gmail.com [Department of Chemistry and Jiangxi Provincial Key Laboratory of New Energy 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)

2015-12-01

Graphical abstract: In this paper, we describe an efficient, practical and novel method to modify ND via direct immobilization of chain transfer agent for RAFT polymerization. - Highlights: • Surface PEGylation of ND via RAFT polymerization. • ND with high water dispersibility and excellent biocompatibility. • Controlled living polymerization. - Abstract: Nanodiamond (ND) is a novel class of carbon nanomaterials, which has been extensively investigated for biomedical applications because of its small size, high surface area and excellent biocompatibility. However, the biomedical applications of unmodified ND are still largely restricted because of their poor dispersibility in both aqueous and organic medium. In this work, we reported a novel strategy for the surface modification of ND via reversible addition fragmentation chain transfer (RAFT) polymerization. For preparation of the PEGylated ND (pPEGMA-ND), chain transfer agent (CTA) was immobilized onto ND through reaction between the hydroxyl group of ND and the carboxyl group of CTA, which was used as the initiator for surface-initiated RAFT polymerization. The successful preparation of pPEGMA-ND was characterized by nuclear magnetic resonance spectroscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectra and thermal gravimetric analysis in detail. Results demonstrated that pPEGMA-ND exhibited enhanced water dispersibility and desirable biocompatibility, making it promising for biomedical applications.

Effect of homopolymer in polymerization-induced microphase separation process

Energy Technology Data Exchange (ETDEWEB)

Park, Jongmin; Saba, Stacey A.; Hillmyer, Marc A.; Kang, Dong-Chang; Seo, Myungeun (IBS-Korea); (KAIST); (UMMN)

2017-09-01

We report on the phase separation behaviors of polymerization mixtures containing a polylactide macro-chain transfer agent (PLA-CTA), styrene, divinylbenzene, hydroxyl-terminated PLA (PLA-OH), and a molecular chain transfer agent which enable the ability to tune the pore size of a cross-linked polymer monolith in a facile manner. Cross-linked monoliths were produced from the mixtures via reversible addition-fragmentation chain transfer (RAFT) polymerization and converted into cross-linked porous polymers by selective removal of PLA while retaining the parent morphology. We demonstrate that pore sizes are tunable over a wide range of length scales from the meso- to macroporous regimes by adjusting the ratio of PLA-CTA to PLA-OH in the reaction mixture which causes the phase separation mechanism to change from polymerization-induced microphase separation to polymerization-induced phase separation. The possibility of increasing porosity and inducing simultaneous micro- and macrophase separation was also realized by adjustments in the molar mass of PLA which enabled the synthesis of hierarchically meso- and macroporous polymers.

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, Gyula 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

Synthesis of butyl acrylate-styrene block copolymers in emulsion by reversible addition-fragmentation chain transfer : effect of surfactant migration upon film formation

NARCIS (Netherlands)

Monteiro, M.J.; Sjöberg, M.; Göttgens, C.M.; Vlist, van der J.

2000-01-01

The synthesis of block copolymers in an environmentally friendly medium was carried out in emulsion polymerizations through the reversible addition-fragmentation chain transfer process, using a transfer active xanthate (MADIX) agent, under batch and starved-feed conditions. First, ab initio

Atom transfer radical polymerization of styrene under pulsed microwave irradiation

International Nuclear Information System (INIS)

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

2005-01-01

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

Effect of the different chain transfer agents on molecular weight and optical properties of poly(methyl methacrylate)

Science.gov (United States)

Çetinkaya, Onur; Demirci, Gökhan; Mergo, Paweł

2017-08-01

Investigation of molecular weight and optical properties of poly(methyl metacrylate) (PMMA) polymerized in house with different chain transfer agents was studied. Isopropyl alcohol (IPA), n-butyl mercaptan (nBMC) and pentamethyl disilane (PMDS) were used as chain transfer agents. The molecular weight (Mw) of PMMA samples were measured by Ostwald viscometer. Mw of bulk polymer samples were decreased with increase the concentration of chain transfer agents (CTA). Since reactivity of used CTAs is not same, molecular weights of samples which were produced with different type of CTA but same concentration of CTA was varied. Higher concentration of n-BMC showed higher scattering. Transmission of samples could not be correlated with different concentration of CTA. Refractive index of samples was not affected by concentration of CTA nevertheless higher molecular weight of CTA showed higher refractive index.

Radical-Mediated Enzymatic Polymerizations

Science.gov (United States)

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

2016-01-01

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

All solid-state polymer electrolytes prepared from a hyper-branched graft polymer using atom transfer radical polymerization

International Nuclear Information System (INIS)

Higa, Mitsuru; Fujino, Yukiko; Koumoto, Taihei; Kitani, Ryousuke; Egashira, Satsuki

2005-01-01

We propose an all solid-state (liquid free) polymer electrolyte (SPE) prepared from a hyper-branched graft copolymer. The graft copolymer consisting of a poly(methyl methacrylate) main chain and poly(ethylene glycol) methyl ether methacrylate side chains was synthesized by atom transfer radical polymerization changing the average chain distance between side chains, side chain length and branched chain length of the proposed structure of the graft copolymer. The ionic conductivity of the SPEs increases with increasing the side chain length, branched chain length and/or average distance between the side chains. The ionic conductivity of the SPE prepared from POEM 9 whose POEM content = 51 wt% shows 2 x 10 -5 S/cm at 30 deg. C. The tensile strength of the SPEs decreases with increases the side chain length, branched chain length and/or average distance between the side chains. These results indicate that a SPE prepared from the hyper-branched graft copolymer has potential to be applied to an all-solid polymer electrolyte

Synthesis of Well-Defined Three-Arm Star-Branched Polystyrene through Arm-First Coupling Approach by Atom Transfer Radical Polymerization

Directory of Open Access Journals (Sweden)

Syed Shahabuddin

2015-01-01

Full Text Available Here we describe a simple route to synthesize three-arm star-branched polystyrene. Atom transfer radical polymerization technique has been utilized to yield branched polystyrene involving Williamson coupling strategy. Initially a linear polymeric chain of predetermined molecular weight has been synthesized which is further end-functionalized into a primary alkyl bromide moiety, a prime requisition for Williamson reaction. The end-functionalized polymer is then coupled using 1,1,1-tris(4-hydroxyphenylethane, a trifunctional core molecule, to give well-defined triple-arm star-branched polystyrene.

Living atom transfer radical polymerization of 4-acetoxystyrene

DEFF Research Database (Denmark)

Gao, Bo; Chen, Xianyi; Ivan, Bela

1997-01-01

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

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

International Nuclear Information System (INIS)

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

2011-01-01

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

In situ stabilizer formation from methacrylic acid macromonomers in emulsion polymerization

NARCIS (Netherlands)

Schreur-Piet, Ingeborg; Heuts, Johan P.A.

2017-01-01

Oligomers of methacrylic acid containing a propenyl ω-endgroup (i.e. MAA-macromonomers) were synthesized by cobalt-mediated catalytic chain transfer polymerization and used as precursors to stabilizers in emulsion polymerization. It was found that only in those polymerizations in which these

Self-catalyzed photo-initiated RAFT polymerization for fabrication of fluorescent polymeric nanoparticles with aggregation-induced emission feature.

Science.gov (United States)

Zeng, Guangjian; Liu, Meiying; Jiang, Ruming; Huang, Qiang; Huang, Long; Wan, Qing; Dai, Yanfeng; Wen, Yuanqing; Zhang, Xiaoyong; Wei, Yen

2018-02-01

In recent years, the fluorescent polymeric nanoparticles (FPNs) with aggregation-induced emission (AIE) feature have been extensively exploited in various biomedical fields owing to their advantages, such as low toxicity, biodegradation, excellent biocompatibility, good designability and optical properties. Therefore, development of a facile, efficient and well designable strategy should be of great importance for the biomedical applications of these AIE-active FPNs. In this work, a novel method for the fabrication of AIE-active FPNs has been developed through the self-catalyzed photo-initiated reversible addition fragmentation chain transfer (RAFT) polymerization using an AIE dye containing chain transfer agent (CTA), which could initiate the RAFT polymerization under light irradiation. The results suggested that the final AIE-active FPNs (named as TPE-poly(St-PEGMA)) showed great potential for biomedical applications owing to their optical and biological properties. More importantly, the method described in the work is rather simple and effective and can be further extended to prepare many other different AIE-active FPNs owing to the good monomer adoptability of RAFT polymerization. Copyright © 2017 Elsevier B.V. All rights reserved.

Quasi-Block Copolymers Based on a General Polymeric Chain Stopper.

Science.gov (United States)

Sanguramath, Rajashekharayya A; Nealey, Paul F; Shenhar, Roy

2016-07-11

Quasi-block copolymers (q-BCPs) are block copolymers consisting of conventional and supramolecular blocks, in which the conventional block is end-terminated by a functionality that interacts with the supramolecular monomer (a "chain stopper" functionality). A new design of q-BCPs based on a general polymeric chain stopper, which consists of polystyrene end-terminated with a sulfonate group (PS-SO3 Li), is described. Through viscosity measurements and a detailed diffusion-ordered NMR spectroscopy study, it is shown that PS-SO3 Li can effectively cap two types of model supramolecular monomers to form q-BCPs in solution. Furthermore, differential scanning calorimetry data and structural characterization of thin films by scanning force microscopy suggests the existence of the q-BCP architecture in the melt. The new design considerably simplifies the synthesis of polymeric chain stoppers; thus promoting the utilization of q-BCPs as smart, nanostructured materials. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Peptide block copolymers by N-carboxyanhydride ring-opening polymerization and atom transfer radical polymerization: The effect of amide macroinitiators

NARCIS (Netherlands)

Habraken, G.J.M.; Koning, C.E.; Heise, A.

2009-01-01

The synthesis of polypeptide-containing block copolymers combining N-carboxyanhydride (NCA) ring-opening polymerization and atom transfer radical polymerization (ATRP) was investigated. An amide initiator comprising an amine function for the NCA polymerization and an activated bromide for ATRP was

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.

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.

Fluoropolymer materials and architectures prepared by controlled radical polymerizations

DEFF Research Database (Denmark)

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

2007-01-01

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

Facile Synthesis of Worm-like Micelles by Visible Light Mediated Dispersion Polymerization Using Photoredox Catalyst.

Science.gov (United States)

Yeow, Jonathan; Xu, Jiangtao; Boyer, Cyrille

2016-06-08

Presented herein is a protocol for the facile synthesis of worm-like micelles by visible light mediated dispersion polymerization. This approach begins with the synthesis of a hydrophilic poly(oligo(ethylene glycol) methyl ether methacrylate) (POEGMA) homopolymer using reversible addition-fragmentation chain-transfer (RAFT) polymerization. Under mild visible light irradiation (λ = 460 nm, 0.7 mW/cm(2)), this macro-chain transfer agent (macro-CTA) in the presence of a ruthenium based photoredox catalyst, Ru(bpy)3Cl2 can be chain extended with a second monomer to form a well-defined block copolymer in a process known as Photoinduced Electron Transfer RAFT (PET-RAFT). When PET-RAFT is used to chain extend POEGMA with benzyl methacrylate (BzMA) in ethanol (EtOH), polymeric nanoparticles with different morphologies are formed in situ according to a polymerization-induced self-assembly (PISA) mechanism. Self-assembly into nanoparticles presenting POEGMA chains at the corona and poly(benzyl methacrylate) (PBzMA) chains in the core occurs in situ due to the growing insolubility of the PBzMA block in ethanol. Interestingly, the formation of highly pure worm-like micelles can be readily monitored by observing the onset of a highly viscous gel in situ due to nanoparticle entanglements occurring during the polymerization. This process thereby allows for a more reproducible synthesis of worm-like micelles simply by monitoring the solution viscosity during the course of the polymerization. In addition, the light stimulus can be intermittently applied in an ON/OFF manner demonstrating temporal control over the nanoparticle morphology.

Monomode microwave-assisted atom transfer radical polymerization

NARCIS (Netherlands)

Zhang, H.; Schubert, U.S.

2004-01-01

The first monomode microwave-assisted atom transfer radical polymerization (ATRP) is reported. The ATRP of methyl methacrylate was successfully performed with microwave heating, which was well controlled and provided almost the same results as experiments with conventional heating, demonstrating the

TRANSITION METAL CATALYSIS IN CONTROLLED RADICAL POLYMERIZATION: ATOM TRANSFER RADICAL POLYMERIZATION. (R826735)

Science.gov (United States)

Novel and diversified macromolecular structures, which include polymers with designed topologies (top), compostions (middle), and functionalities (bottom), can be prepared by atom transfer radical polymerization processes. These polymers can be synthesized from a large variety of...

Conjugation of diisocyanate side chains to dimethacrylate reduces polymerization shrinkage and increases the hardness of composite resins.

Science.gov (United States)

Jan, Yih-Dean; Lee, Bor-Shiunn; Lin, Chun-Pin; Tseng, Wan-Yu

2014-04-01

Polymerization shrinkage is one of the main causes of dental restoration failure. This study tried to conjugate two diisocyanate side chains to dimethacrylate resins in order to reduce polymerization shrinkage and increase the hardness of composite resins. Diisocyanate, 2-hydroxyethyl methacrylate, and bisphenol A dimethacrylate were reacted in different ratios to form urethane-modified new resin matrices, and then mixed with 50 wt.% silica fillers. The viscosities of matrices, polymerization shrinkage, surface hardness, and degrees of conversion of experimental composite resins were then evaluated and compared with a non-modified control group. The viscosities of resin matrices increased with increasing diisocyanate side chain density. Polymerization shrinkage and degree of conversion, however, decreased with increasing diisocyanate side chain density. The surface hardness of all diisocyanate-modified groups was equal to or significantly higher than that of the control group. Conjugation of diisocyanate side chains to dimethacrylate represents an effective means of reducing polymerization shrinkage and increasing the surface hardness of dental composite resins. Copyright © 2012. Published by Elsevier B.V.

Thermally conductive, electrically insulating and melt-processable polystyrene/boron nitride nanocomposites prepared by in situ reversible addition fragmentation chain transfer polymerization

International Nuclear Information System (INIS)

Huang, Xingyi; Wang, Shen; Zhu, Ming; Yang, Ke; Jiang, Pingkai; Bando, Yoshio; Golberg, Dmitri; Zhi, Chunyi

2015-01-01

Thermally conductive and electrically insulating polymer/boron nitride (BN) nanocomposites are highly attractive for various applications in many thermal management fields. However, so far most of the preparation methods for polymer/BN nanocomposites have usually caused difficulties in the material post processing. Here, an in situ grafting approach is designed to fabricate thermally conductive, electrically insulating and post-melt processable polystyrene (PS)/BN nanosphere (BNNS) nanocomposites by initiating styrene (St) on the surface functionalized BNNSs via reversible addition fragmentation chain transfer polymerization. The nanocomposites exhibit significantly enhanced thermal conductivity. For example, at a St/BN feeding ratio of 5:1, an enhancement ratio of 1375% is achieved in comparison with pure PS. Moreover, the dielectric properties of the nanocomposites show a desirable weak dependence on frequency, and the dielectric loss tangent of the nanocomposites remains at a very low level. More importantly, the nanocomposites can be subjected to multiple melt processing to form different shapes. Our method can become a universal approach to prepare thermally conductive, electrically insulating and melt-processable polymer nanocomposites with diverse monomers and nanofillers. (paper)

Surface molecular imprinting onto fluorescein-coated magnetic nanoparticlesvia reversible addition fragmentation chain transfer polymerization: A facile three-in-one system for recognition and separation of endocrine disrupting chemicals

Science.gov (United States)

Li, Ying; Dong, Cunku; Chu, Jia; Qi, Jingyao; Li, Xin

2011-01-01

In this study, we present a general protocol for the making of surface-imprinted magnetic fluorescence beads viareversible addition-fragmentation chain transfer polymerization. The resulting composites were characterized by X-ray diffraction analysis, transmission electron microscopy, scanning electron microscopy, fluorescence spectroscopy, Fourier transform infrared spectroscopy, and energy dispersive spectroscopy. The as-synthesized beads exhibited homogeneous polymer films (thickness of about 5.7 nm), spherical shape, high fluorescence intensity and magnetic property (Magnetization (Ms) = 3.67 emu g-1). The hybrids bind the original template 17β-estradiol with an appreciable selectivity over structurally related compounds. In addition, the resulting hybrids performed without obvious deterioration after five repeated cycles. This study therefore demonstrates the potential of molecularly imprinted polymers for the recognition and separation of endocrine disrupting chemicals.In this study, we present a general protocol for the making of surface-imprinted magnetic fluorescence beads viareversible addition-fragmentation chain transfer polymerization. The resulting composites were characterized by X-ray diffraction analysis, transmission electron microscopy, scanning electron microscopy, fluorescence spectroscopy, Fourier transform infrared spectroscopy, and energy dispersive spectroscopy. The as-synthesized beads exhibited homogeneous polymer films (thickness of about 5.7 nm), spherical shape, high fluorescence intensity and magnetic property (Magnetization (Ms) = 3.67 emu g-1). The hybrids bind the original template 17β-estradiol with an appreciable selectivity over structurally related compounds. In addition, the resulting hybrids performed without obvious deterioration after five repeated cycles. This study therefore demonstrates the potential of molecularly imprinted polymers for the recognition and separation of endocrine disrupting chemicals. Electronic

Organocatalytic conjugate-addition polymerization of linear and cyclic acrylic monomers by N-heterocyclic carbenes: Mechanisms of chain initiation, propagation, and termination

KAUST Repository

Zhang, Yuetao

2013-11-27

formation/dimerization through proton transfer vs polymerization through conjugate addition, and mapped out extensive energy profiles for chain initiation, propagation, and termination steps, thereby satisfactorily explaining the experimental observations. © 2013 American Chemical Society.

Organocatalytic conjugate-addition polymerization of linear and cyclic acrylic monomers by N-heterocyclic carbenes: Mechanisms of chain initiation, propagation, and termination

KAUST Repository

Zhang, Yuetao; Schmitt, Meghan L.; Falivene, Laura; Caporaso, Lucia; Cavallo, Luigi; Chen, Eugene You Xian

2013-01-01

formation/dimerization through proton transfer vs polymerization through conjugate addition, and mapped out extensive energy profiles for chain initiation, propagation, and termination steps, thereby satisfactorily explaining the experimental observations. © 2013 American Chemical Society.

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.

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.

Chain propagation and termination mechanisms for polymerization of conjugated polar alkenes by [Al]-based frustrated Lewis pairs

KAUST Repository

He, Jianghua

2014-11-25

A combined experimental and theoretical study on mechanistic aspects of polymerization of conjugated polar alkenes by frustrated Lewis pairs (FLPs) based on N-heterocyclic carbene (NHC) and Al(C6F5)3 pairs is reported. This study consists of three key parts: structural characterization of active propagating intermediates, propagation kinetics, and chain-termination pathways. Zwitterionic intermediates that simulate the active propagating species in such polymerization have been generated or isolated from the FLP activation of monomers such as 2-vinylpyridine and 2-isopropenyl-2-oxazoline-one of which, IMes+-CH2C(Me)=(C3H2NO)Al(C6F5)3 - (2), has been structurally characterized. Kinetics performed on the polymerization of 2-vinylpyridine by ItBu/Al(C6F5)3 revealed that the polymerization follows a zero-order dependence on monomer concentration and a first-order dependence on initiator (ItBu) and activator [Al(C6F5)3] concentrations, indicating a bimolecular, activated monomer propagation mechanism. The Lewis pair polymerization of conjugate polar alkenes such as methacrylates is accompanied by competing chain-termination side reactions; between the two possible chain-termination pathways, the one that proceeds via intramolecular backbiting cyclization involving nucleophilic attack of the activated ester group of the growing polymer chain by the O-ester enolate active chain end to generate a six-membered lactone (δ-valerolactone)-terminated polymer chain is kinetically favored, but thermodynamically disfavored, over the pathway leading to the -ketoester-terminated chain, as revealed by computational studies.

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

Energy Technology Data Exchange (ETDEWEB)

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

2010-11-15

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

Carboxyl-Functionalized Polymeric Microspheres Prepared by One-Stage Photoinitiated RAFT Dispersion Polymerization

Directory of Open Access Journals (Sweden)

Jianbo Tan

2017-12-01

Full Text Available Herein, we report a photoinitiated reversible addition-fragmentation chain transfer (RAFT dispersion copolymerization of methyl methacrylate (MMA and methyl methacrylic (MAA for the preparation of highly monodisperse carboxyl-functionalized polymeric microspheres. High rates of polymerization were observed, with more than 90% particle yields being achieved within 3 h of UV irradiation. Effects of reaction parameters (e.g., MAA concentration, RAFT agent concentration, photoinitiator concentration, and solvent composition were studied in detail, and highly monodisperse polymeric microspheres were obtained in most cases. Finally, silver (Ag composite microspheres were prepared by in situ reduction of AgNO3 using the carboxyl-functionalized polymeric microspheres as the template. The obtained Ag composite microspheres were able to catalyze the reduction of methylene blue (MB with NaBH4 as a reductant.

High temperature initiator-free RAFT polymerization of methyl methacrylate in a microwave reactor

NARCIS (Netherlands)

Paulus, R.M.; Becer, C.R.; Hoogenboom, R.; Schubert, U.S.

2009-01-01

The reversible additionfragmentation chain transfer (RAFT) polymerization of methyl methacrylate (MMA) was investigated under microwave irradiation. At first, a comparison was made between microwave and thermal heating for the RAFT polymerization of MMA with azobis(isobutyronitrile) (AIBN) as

Selective polymerization catalysis: controlling the metal chain end group to prepare block copolyesters.

Science.gov (United States)

Zhu, Yunqing; Romain, Charles; Williams, Charlotte K

2015-09-30

Selective catalysis is used to prepare block copolyesters by combining ring-opening polymerization of lactones and ring-opening copolymerization of epoxides/anhydrides. By using a dizinc complex with mixtures of up to three different monomers and controlling the chemistry of the Zn-O(polymer chain) it is possible to select for a particular polymerization route and thereby control the composition of block copolyesters.

A method for the computation of turbulent polymeric liquids including hydrodynamic interactions and chain entanglements

Energy Technology Data Exchange (ETDEWEB)

Kivotides, Demosthenes, E-mail: demosthenes.kivotides@strath.ac.uk

2017-02-12

An asymptotically exact method for the direct computation of turbulent polymeric liquids that includes (a) fully resolved, creeping microflow fields due to hydrodynamic interactions between chains, (b) exact account of (subfilter) residual stresses, (c) polymer Brownian motion, and (d) direct calculation of chain entanglements, is formulated. Although developed in the context of polymeric fluids, the method is equally applicable to turbulent colloidal dispersions and aerosols. - Highlights: • An asymptotically exact method for the computation of polymer and colloidal fluids is developed. • The method is valid for all flow inertia and all polymer volume fractions. • The method models entanglements and hydrodynamic interactions between polymer chains.

A Green Platform for Preparation of the Well-Defined Polyacrylonitrile: 60Co γ-ray Irradiation-Initiated RAFT Polymerization at Room Temperature

Directory of Open Access Journals (Sweden)

Shuangshuang Zhang

2017-01-01

Full Text Available 60Co γ-ray irradiation-initiated reversible addition–fragmentation chain transfer (RAFT polymerization at room temperature with 2-cyanoprop-2-yl 1-dithionaphthalate (CPDN as the chain transfer agent was first applied to acrylonitrile (AN polymerization, providing a “green” platform for preparing polyacrylonitrile (PAN-based carbon fibers using an environment-friendly energy source. Various effects of dose rate, molar ratio of the monomer to the chain transfer agent, monomer concentration and reaction time on the AN polymerization behaviors were performed to improve the controllability of molecular the weight and molecular weight distribution of the obtained PAN. The feature of the controlled polymerization was proven by the first-order kinetics, linear increase of the molecular weight with the monomer conversion and a successful chain-extension experiment. The molecular weight and molecular weight distribution of PAN were characterized by size exclusion chromatography (SEC. 1H NMR and Matrix assisted laser desorption ionization/time of flight mass spectra (MALDI-TOF-MS confirmed the chain-end functionality of PAN, which also was supported by the successful chain-extension experiments of original PANs with acrylonitrile and styrene as the second monomers respectively.

Chain-end modification of living anionic polybutadiene with diphenylethylenes and styrenes

NARCIS (Netherlands)

Donkers, E.H.D.; Willemse, R.X.E.; Klumperman, B.

2005-01-01

The first step in the transformation of poly(butadienyl)lithium into a macromolecular atom transfer radical polymerization initiator or reversible addition-fragmentation chain transfer agent is the modification of the anionic chain end into a suitable leaving/reinitiating group. We have investigated

Transfer coating by electron initiated polymerization

International Nuclear Information System (INIS)

Nablo, S.V.

1985-01-01

The high speed and depth of cure possible with electron initiated monomer/oligomer coating systems provide many new opportunities for approaches to product finishing. Moreover, the use of transfer or cast coating using films or metallic surfaces offers the ability to precisely control the surface topology of liquid film surfaces during polymerization. Transfer coating such as with textiles has been a commercial process for many years and the synergistic addition of EB technology permits the manufacture of unusual new products. One of these, the casting paper used in the manufacture of vinyl and urethane fabrics, is the first EB application to use a drum surface for pattern replication in the coating. In this case the coated paper is cured against, and then released from, an engraved drum surface. Recent developments in the use of plastic films for transfer have been applied to the manufacture of transfer metallized and coated paper and paperboard products for packaging. Details of these and related processes will be presented as well as a discussion of the typical product areas using this high speed transfer technology. (author)

Atom transfer radical polymerization of n-butyl acrylate catalyzed by atom transfer radical polymerization of n-butyl acrylate catalyzed by

NARCIS (Netherlands)

Zhang, H.; Linde, van der R.

2002-01-01

The homogeneous atom transfer radical polymerization (ATRP) of n-butyl acrylate with CuBr/N-(n-hexyl)-2-pyridylmethanimine as a catalyst and ethyl 2-bromoisobutyrate as an initiator was investigated. The kinetic plots of ln([M]0/[M]) versus the reaction time for the ATRP systems in different

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

Energy Technology Data Exchange (ETDEWEB)

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

2009-08-01

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

Computational study of chain transfer to monomer reactions in high-temperature polymerization of alkyl acrylates.

Science.gov (United States)

Moghadam, Nazanin; Liu, Shi; Srinivasan, Sriraj; Grady, Michael C; Soroush, Masoud; Rappe, Andrew M

2013-03-28

This article presents a computational study of chain transfer to monomer (CTM) reactions in self-initiated high-temperature homopolymerization of alkyl acrylates (methyl, ethyl, and n-butyl acrylate). Several mechanisms of CTM are studied. The effects of the length of live polymer chains and the type of monoradical that initiated the live polymer chains on the energy barriers and rate constants of the involved reaction steps are investigated theoretically. All calculations are carried out using density functional theory. Three types of hybrid functionals (B3LYP, X3LYP, and M06-2X) and four basis sets (6-31G(d), 6-31G(d,p), 6-311G(d), and 6-311G(d,p)) are applied to predict the molecular geometries of the reactants, products and transition sates, and energy barriers. Transition state theory is used to estimate rate constants. The results indicate that abstraction of a hydrogen atom (by live polymer chains) from the methyl group in methyl acrylate, the methylene group in ethyl acrylate, and methylene groups in n-butyl acrylate are the most likely mechanisms of CTM. Also, the rate constants of CTM reactions calculated using M06-2X are in good agreement with those estimated from polymer sample measurements using macroscopic mechanistic models. The rate constant values do not change significantly with the length of live polymer chains. Abstraction of a hydrogen atom by a tertiary radical has a higher energy barrier than abstraction by a secondary radical, which agrees with experimental findings. The calculated and experimental NMR spectra of dead polymer chains produced by CTM reactions are comparable. This theoretical/computational study reveals that CTM occurs most likely via hydrogen abstraction by live polymer chains from the methyl group of methyl acrylate and methylene group(s) of ethyl (n-butyl) acrylate.

Control of in vivo disposition and immunogenicity of polymeric micelles by adjusting poly(sarcosine) chain lengths on surface

Science.gov (United States)

Kurihara, Kensuke; Ueda, Motoki; Hara, Isao; Ozeki, Eiichi; Togashi, Kaori; Kimura, Shunsaku

2017-07-01

Four kinds of A3B-type amphiphilic polydepsipeptides, (poly(sarcosine))3- b-poly( l-lactic acid) (the degree of polymerization of poly(sarcosine) are 10, 33, 55, and 85; S10 3 , S33 3 , S55 3 , and S85 3 ) were synthesized to prepare core-shell type polymeric micelles. Their in vivo dispositions and stimulations to trigger immune system to produce IgM upon multiple administrations to mice were examined. With increasing poly(sarcosine) chain lengths, the hydrophilic shell became thicker and the surface density at the most outer surface decreased on the basis of dynamic and static light scattering measurements. These two physical elements of polymeric micelles elicited opposite effects on the immune response in light of the chain length therefore to show an optimized poly(sarcosine) chain length existing between 33mer and 55mer to suppress the accelerated blood clearance phenomenon associated with polymeric micelles.

Transfer coating by electron initiated polymerization

International Nuclear Information System (INIS)

Nablo, S.V.

1984-01-01

The high speed and depth of cure possible with electron initiated monomer/oligomer coating systems provide many new opportunities for approaches to product finishing. Moreover, the use of transfer or cast coating using films or metallic surfaces offers the ability to precisely control the surface topology of liquid film surfaces during polymerization. Transfer coating such as with textiles has been a commercial process for many years and the synergistic addition of EB technology permits the manufacture of unusual new products. One of these, the casting paper used in the manufacture of vinyl and urethane fabrics, is the first EB application to use a drum surface for pattern replication in the coating. In this case the coated paper is cured against, and then released from, an engraved drum surface. Recent developments in the use of plastic films for transfer have been applied to the manufacture of transfer metallized and coated paper and paperboard products for packaging. Details of these and related processes are presented as well as a discussion of the typical product areas (e.g. photographic papers, release papers, magnetic media) using this high speed transfer technology

Silyl Ketene Acetals/B(C6F53 Lewis Pair-Catalyzed Living Group Transfer Polymerization of Renewable Cyclic Acrylic Monomers

Directory of Open Access Journals (Sweden)

Lu Hu

2018-03-01

Full Text Available This work reveals the silyl ketene acetal (SKA/B(C6F53 Lewis pair-catalyzed room-temperature group transfer polymerization (GTP of polar acrylic monomers, including methyl linear methacrylate (MMA, and the biorenewable cyclic monomers γ-methyl-α-methylene-γ-butyrolactone (MMBL and α-methylene-γ-butyrolactone (MBL as well. The in situ NMR monitored reaction of SKA with B(C6F53 indicated the formation of Frustrated Lewis Pairs (FLPs, although it is sluggish for MMA polymerization, such a FLP system exhibits highly activity and living GTP of MMBL and MBL. Detailed investigations, including the characterization of key reaction intermediates, polymerization kinetics and polymer structures have led to a polymerization mechanism, in which the polymerization is initiated with an intermolecular Michael addition of the ester enolate group of SKA to the vinyl group of B(C6F53-activated monomer, while the silyl group is transferred to the carbonyl group of the B(C6F53-activated monomer to generate the single-monomer-addition species or the active propagating species; the coordinated B(C6F53 is released to the incoming monomer, followed by repeated intermolecular Michael additions in the subsequent propagation cycle. Such neutral SKA analogues are the real active species for the polymerization and are retained in the whole process as confirmed by experimental data and the chain-end analysis by matrix-assisted laser desorption/ionization time of flight mass spectroscopy (MALDI-TOF MS. Moreover, using this method, we have successfully synthesized well-defined PMMBL-b-PMBL, PMMBL-b-PMBL-b-PMMBL and random copolymers with the predicated molecular weights (Mn and narrow molecular weight distribution (MWD.

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

Energy Technology Data Exchange (ETDEWEB)

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

2017-09-14

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).

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.

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.

Chain polymerization of diacetylene compound multilayer films on the topmost surface initiated by a scanning tunneling microscope tip.

Science.gov (United States)

Takajo, Daisuke; Okawa, Yuji; Hasegawa, Tsuyoshi; Aono, Masakazu

2007-05-08

Chain polymerizations of diacetylene compound multilayer films on graphite substrates were examined with a scanning tunneling microscope (STM) at the liquid/solid interface of the phenyloctane solution. The first layer grew very quickly into many small domains. This was followed by the slow formation of the piled up layers into much larger domains. Chain polymerization on the topmost surface layer could be initiated by applying a pulsed voltage between the STM tip and the substrate, usually producing a long polymer of submicrometer length. In contrast, polymerizations on the underlying layer were never observed. This can be explained by a conformation model in which the polymer backbone is lifted up.

Synthesis of Thermally Switchable Chromatographic Materials with Immobilized Ti4+ for Enrichment of Phosphopeptides by Reversible Addition Fragmentation Chain Transfer Polymerization

Science.gov (United States)

Wang, Di; Cao, Zhihan; Pang, Xinzhu; Deng, Yulin; Li, Bo; Dai, Rongji

2018-01-01

Reversible phosphorylation of proteins is one of the most crucial types of post-translational modifications (PTMs). And it shows significant work in diversified biological processes. However, the separation technology of phosphorylated peptides is still an analytical challenge in phosphoproteomics, because phosphopeptides are alway in low stoichiometry. Thus, enrichment of phosphopeptides before detection is indispensable. In this study, a novel temperature regulated separation protocol was developed. Silica@p (NIPAAm-co-IPPA)-Ti4+, a new Ti(IV)-IMAC (Immobilized Metal Affinity chromatography) materials was synthesized by reversible addition fragmentation chain transfer polymerization (RAFT). By the unique thermally responsive properties of poly(N-isopropylacrylamide) (PNIPAAm), the captured phosphorylated peptides could be released by changing temperature only without applying any other eluant which could damage the phosphopeptides. We employed isopropanol phosphonic acid (IPPA) as an IMAC ligand for the immobilization of Ti(IV) which could increase the specific adsorption of phosphopeptides. The enrichment and release properties were examined by treatment with pyridoxal 5’-phosphate (PLP) and casein phosphopeptides (CPP). Two phosphorylated compounds above have temperature-stimulated binding to Ti4+. Finally, silica@p (NIPAAm-co-IPPA)-Ti4+ was successfully employed in pretreatment of phosphopeptides in a tryptic digest of a-casein and human serum albumin (HSA). The results indicated a great potential of this new temperature-responsive material in phosphoproteomics study.

Tunable, Quantitative Fenton-RAFT Polymerization via Metered Reagent Addition.

Science.gov (United States)

Nothling, Mitchell D; McKenzie, Thomas G; Reyhani, Amin; Qiao, Greg G

2018-05-10

A continuous supply of radical species is a key requirement for activating chain growth and accessing quantitative monomer conversions in reversible addition-fragmentation chain transfer (RAFT) polymerization. In Fenton-RAFT, activation is provided by hydroxyl radicals, whose indiscriminate reactivity and short-lived nature poses a challenge to accessing extended polymerization times and quantitative monomer conversions. Here, an alternative Fenton-RAFT procedure is presented, whereby radical generation can be finely controlled via metered dosing of a component of the Fenton redox reaction (H 2 O 2 ) using an external pumping system. By limiting the instantaneous flux of radicals and ensuring sustained radical generation over tunable time periods, metered reagent addition reduces unwanted radical "wasting" reactions and provides access to consistent quantitative monomer conversions with high chain-end fidelity. Fine tuning of radical concentration during polymerization is achieved simply via adjustment of reagent dose rate, offering significant potential for automation. This modular strategy holds promise for extending traditional RAFT initiation toward more tightly regulated radical concentration profiles and affords excellent prospects for the automation of Fenton-RAFT polymerization. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

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

International Nuclear Information System (INIS)

Tebikachew, Behabtu; Magina, Sandra; Mata, Diogo; Oliveira, Filipe J.; Silva, Rui F.; Barros-Timmons, Ana

2015-01-01

Vertically aligned carbon nanotubes (VACNTs) synthesized by Thermal Chemical Vapour Deposition (TCVD) were modified using an Ar:O 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

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

Science.gov (United States)

Chen, Daqun; Hu, Weihua

2017-04-18

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

Side-chain amino-acid-based pH-responsive self-assembled block copolymers for drug delivery and gene transfer.

Science.gov (United States)

Kumar, Sonu; Acharya, Rituparna; Chatterji, Urmi; De, Priyadarsi

2013-12-10

Developing safe and effective nanocarriers for multitype of delivery system is advantageous for several kinds of successful biomedicinal therapy with the same carrier. In the present study, we have designed amino acid biomolecules derived hybrid block copolymers which can act as a promising vehicle for both drug delivery and gene transfer. Two representative natural chiral amino acid-containing (l-phenylalanine and l-alanine) vinyl monomers were polymerized via reversible addition-fragmentation chain transfer (RAFT) process in the presence of monomethoxy poly(ethylene glycol) based macro-chain transfer agents (mPEGn-CTA) for the synthesis of well-defined side-chain amino-acid-based amphiphilic block copolymers, monomethoxy poly(ethylene glycol)-b-poly(Boc-amino acid methacryloyloxyethyl ester) (mPEGn-b-P(Boc-AA-EMA)). The self-assembled micellar aggregation of these amphiphilic block copolymers were studied by fluorescence spectroscopy, atomic force microscopy (AFM) and scanning electron microscopy (SEM). Potential applications of these hybrid polymers as drug carrier have been demonstrated in vitro by encapsulation of nile red dye or doxorubicin drug into the core of the micellar nanoaggregates. Deprotection of side-chain Boc- groups in the amphiphilic block copolymers subsequently transformed them into double hydrophilic pH-responsive cationic block copolymers having primary amino groups in the side-chain terminal. The DNA binding ability of these cationic block copolymers were further investigated by using agarose gel retardation assay and AFM. The in vitro cytotoxicity assay demonstrated their biocompatible nature and these polymers can serve as "smart" materials for promising bioapplications.

Quantum communication and state transfer in spin chains

International Nuclear Information System (INIS)

Van der Jeugt, Joris

2011-01-01

We investigate the time evolution of a single spin excitation state in certain linear spin chains, as a model for quantum communication. We consider first the simplest possible spin chain, where the spin chain data (the nearest neighbour interaction strengths and the magnetic field strengths) are constant throughout the chain. The time evolution of a single spin state is determined, and this time evolution is illustrated by means of an animation. Some years ago it was discovered that when the spin chain data are of a special form so-called perfect state transfer takes place. These special spin chain data can be linked to the Jacobi matrix entries of Krawtchouk polynomials or dual Hahn polynomials. We discuss here the case related to Krawtchouk polynomials, and illustrate the possibility of perfect state transfer by an animation showing the time evolution of the spin chain from an initial single spin state. Very recently, these ideas were extended to discrete orthogonal polynomials of q-hypergeometric type. Here, a remarkable result is a new analytic model where perfect state transfer is achieved: this is when the spin chain data are related to the Jacobi matrix of q-Krawtchouk polynomials. This case is discussed here, and again illustrated by means of an animation.

Surface water retardation around single-chain polymeric nanoparticles: critical for catalytic function?

Science.gov (United States)

Stals, Patrick J M; Cheng, Chi-Yuan; van Beek, Lotte; Wauters, Annelies C; Palmans, Anja R A; Han, Songi; Meijer, E W

2016-03-01

A library of water-soluble dynamic single-chain polymeric nanoparticles (SCPN) was prepared using a controlled radical polymerisation technique followed by the introduction of functional groups, including probes at targeted positions. The combined tools of electron paramagnetic resonance (EPR) and Overhauser dynamic nuclear polarization (ODNP) reveal that these SCPNs have structural and surface hydration properties resembling that of enzymes.

The effect of reducing monosaccharides on the atom transfer radical polymerization of butyl methacrylate

NARCIS (Netherlands)

Vries, de Andrew; Klumperman, B.; Wet-Roos, de D.; Sanderson, R.D.

2001-01-01

The effect of various reducing monosaccharides on the rate of atom transfer radical polymerization (ATRP) of butyl methacrylate is reported in this study. The addition of reducing sugars affects the rate of ATRP positively with a 100% increase in the rate of polymerization in some cases. In

Mechanism and kinetics of dithiobenzoate-mediated RAFT polymerization. I. The current situation

NARCIS (Netherlands)

Barner-Kowollik, C.; Buback, M.; Charleux, B.; Coote, M.L.; Drache, M.; Fukuda, T.; Goto, A.; Klumperman, B.; Lowe, A.B.; McLeary, J.B.; Moad, G.; Monteiro, M.J.; Sanderson, R.D.; Tonge, M.P.; Vana, P.

2006-01-01

Investigations into the kinetics and mechanism of dithiobenzoate-mediated Reversible Addition-Fragmentation Chain Transfer (RAFT) polymerizations, which exhibit nonideal kinetic behavior, such as induction periods and rate retardation, are comprehensively reviewed. The appreciable uncertainty in the

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

Directory of Open Access Journals (Sweden)

Li Hua-Rong

2014-01-01

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

Aqueous dispersion polymerization: a new paradigm for in situ block copolymer self-assembly in concentrated solution.

Science.gov (United States)

Sugihara, Shinji; Blanazs, Adam; Armes, Steven P; Ryan, Anthony J; Lewis, Andrew L

2011-10-05

Reversible addition-fragmentation chain transfer polymerization has been utilized to polymerize 2-hydroxypropyl methacrylate (HPMA) using a water-soluble macromolecular chain transfer agent based on poly(2-(methacryloyloxy)ethylphosphorylcholine) (PMPC). A detailed phase diagram has been elucidated for this aqueous dispersion polymerization formulation that reliably predicts the precise block compositions associated with well-defined particle morphologies (i.e., pure phases). Unlike the ad hoc approaches described in the literature, this strategy enables the facile, efficient, and reproducible preparation of diblock copolymer spheres, worms, or vesicles directly in concentrated aqueous solution. Chain extension of the highly hydrated zwitterionic PMPC block with HPMA in water at 70 °C produces a hydrophobic poly(2-hydroxypropyl methacrylate) (PHPMA) block, which drives in situ self-assembly to form well-defined diblock copolymer spheres, worms, or vesicles. The final particle morphology obtained at full monomer conversion is dictated by (i) the target degree of polymerization of the PHPMA block and (ii) the total solids concentration at which the HPMA polymerization is conducted. Moreover, if the targeted diblock copolymer composition corresponds to vesicle phase space at full monomer conversion, the in situ particle morphology evolves from spheres to worms to vesicles during the in situ polymerization of HPMA. In the case of PMPC(25)-PHPMA(400) particles, this systematic approach allows the direct, reproducible, and highly efficient preparation of either block copolymer vesicles at up to 25% solids or well-defined worms at 16-25% solids in aqueous solution.

Atom-transfer radical polymerization of methyl methacrylate (MMA) using CuSCN as the catalyst

NARCIS (Netherlands)

Singha, N.K.; Klumperman, B.

2000-01-01

The effect of CuSCN as a catalyst in atom-transfer radical polymerization (ATRP) was investigated. CuSCN can successfully be used for the ATRP of MMA. Substituted bipyridines as well as imines can be used to stabilize the copper complex in solution. CuSCN induces faster polymerization compared to

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

International Nuclear Information System (INIS)

Aikins, J.A.; Williams, F.

1984-01-01

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

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

DEFF Research Database (Denmark)

Iruthayaraj, Joseph; Chernyy, Sergey; Lillethorup, Mie

2011-01-01

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

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

Emulsion polymerization with high energy radiation

International Nuclear Information System (INIS)

Stannett, V.T.; Stahel, E.P.

1992-01-01

High energy radiation, particularly that of cobalt-60 or caesium-137 gamma-rays, provides in principle an ideal initiator for emulsion polymerization. The high free radical yields from the radiolysis of the aqueous phase combined with the high kinetic chain lengths associated with emulsion polymerization lead to a highly effective utilization of the radiation. There are other important advantages compared with the use of chemical initiators such as potassium persulfate. These are outlined in the chapter, together with some attendant disadvantages. Radiation-induced initiation is temperature independent, and low temperature polymerizations can be conducted with ease. Monomers that mainly terminate their growing chains by chain transfer to monomer give higher molecular weights at lower temperatures. Industrially, vinyl acetate is an important example of such a monomer, and it has been studied using radiation initiation. Both laboratory and pilot plant studies have been carried out and reported. The results are summarized in this chapter. Styrene is the classical example of a material that under a number of conditions closely obeys the so-called ideal Smith-Ewart kinetics. It has been found that under similar conditions but substituting radiation for potassium persulfate as the initiator, ideal kinetics were closely followed. Most of the conventional and some non-standard vinyl and diene monomers have been studied to some extent with radiation-initiated polymerizations in emulsion. To conserve space however, this chapter presents and discusses the results obtained only with styrene and vinyl acetate, both in laboratory and pilot plant investigations. Other monomers and special situations are referenced either directly or to the other available reviews. (orig.)

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...

Simultaneous Contact Sensing and Characterizing of Mechanical and Dynamic Heat Transfer Properties of Porous Polymeric Materials

Directory of Open Access Journals (Sweden)

Bao-guo Yao

2017-10-01

Full Text Available Porous polymeric materials, such as textile fabrics, are elastic and widely used in our daily life for garment and household products. The mechanical and dynamic heat transfer properties of porous polymeric materials, which describe the sensations during the contact process between porous polymeric materials and parts of the human body, such as the hand, primarily influence comfort sensations and aesthetic qualities of clothing. A multi-sensory measurement system and a new method were proposed to simultaneously sense the contact and characterize the mechanical and dynamic heat transfer properties of porous polymeric materials, such as textile fabrics in one instrument, with consideration of the interactions between different aspects of contact feels. The multi-sensory measurement system was developed for simulating the dynamic contact and psychological judgment processes during human hand contact with porous polymeric materials, and measuring the surface smoothness, compression resilience, bending and twisting, and dynamic heat transfer signals simultaneously. The contact sensing principle and the evaluation methods were presented. Twelve typical sample materials with different structural parameters were measured. The results of the experiments and the interpretation of the test results were described. An analysis of the variance and a capacity study were investigated to determine the significance of differences among the test materials and to assess the gage repeatability and reproducibility. A correlation analysis was conducted by comparing the test results of this measurement system with the results of Kawabata Evaluation System (KES in separate instruments. This multi-sensory measurement system provides a new method for simultaneous contact sensing and characterizing of mechanical and dynamic heat transfer properties of porous polymeric materials.

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-...

Thermoresponsive Poly(2-oxazoline) Molecular Brushes by Living Ionic Polymerization: Kinetic Investigations of Pendant Chain Grafting and Cloud Point Modulation by Backbone and Side Chain Length Variation

KAUST Repository

Zhang, Ning

2012-04-17

Molecular brushes of poly(2-oxazoline)s were prepared by living anionic polymerization of 2-iso-propenyl-2-oxazoline to form the backbone and subsequent living cationic ring-opening polymerization of 2-n- or 2-iso-propyl-2-oxazoline for pendant chain grafting. In situ kinetic studies indicate that the initiation efficiency and polymerization rates are independent from the number of initiator functions per initiator molecule. This was attributed to the high efficiency of oxazolinium salt and the stretched conformation of the backbone, which is caused by the electrostatic repulsion of the oxazolinium moieties along the macroinitiator. The resulting molecular brushes showed thermoresponsive properties, that is, having a defined cloud point (CP). The dependence of the CP as a function of backbone and side chain length as well as concentration was studied. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Conjugation of diisocyanate side chains to dimethacrylate reduces polymerization shrinkage and increases the hardness of composite resins

Directory of Open Access Journals (Sweden)

Yih-Dean Jan

2014-04-01

Conclusion: Conjugation of diisocyanate side chains to dimethacrylate represents an effective means of reducing polymerization shrinkage and increasing the surface hardness of dental composite resins.

The Effect of the Chain Length on MMA Free Radicl Polymerization

Institute of Scientific and Technical Information of China (English)

无

2001-01-01

In the polymerization process of methyl methacrylate (MMA), the Arrhenius parameters (activation energy and frequency factor) of propagating reaction monotonically decrease with increasing monomer conversion. At the beginning and middle stage of the propagating reaction, the increase of radical chain length is the main reason of above mentioned change. And at the end stage, the sharp decrease of kp indicates that the activation energy is approximately incline to zero and the propagating reaction is controlled by molecular diffusion motion.

Radiation-induced controlled polymerization of acrylic acid by RAFT and RAFT-MADIX methods in protic solvents

Science.gov (United States)

Sütekin, S. Duygu; Güven, Olgun

2018-01-01

The kinetic investigation of one-pot synthesis of poly(acrylic acid) (PAA) prepared via gamma radiation induced controlled polymerization was reported. PAA homopolymers were prepared by Reversible Addition-Fragmentation Chain Transfer (RAFT) polymerization in the presence of trithiocarbonate-based chain transfer agent (CTA) 2-(Dodecylthiocarbonothioylthio)-2-methylpropionic acid (DDMAT) and also by Reversible Addition-Fragmentation/Macromolecular Design by Inter-change of Xanthates (RAFT/MADIX) polymerization in the presence of a xanthate based CTA O-ethyl-S-(1-methoxycarbonyl) ethyl dithiocarbonate (RA1). The polymerizations were performed at room temperature by the virtue of ionizing radiation. Protic solvents were used for the RAFT polymerization of AA considering environmental profits. The linear first-order kinetic plot, close control of molecular weight by the monomer/CTA molar ratio supported that the polymerization proceeds in a living fashion. The linear increase in molecular weight with conversion monitored by Size Exclusion Chromatography (SEC) is another proof of controlling of polymerization. [Monomer]/[RAFT] ratio and conversion was controlled to obtain PAA in the molecular weight range of 6900-35,800 with narrow molecular weight distributions. Reaction kinetics and effect of the amount of RAFT agent were investigated in detail. Between two different types of CTA, trithiocarbonate based DDMAT was found to be more efficient in terms of low dispersity (Đ) and linear first-order kinetic behavior for the radiation induced controlled synthesis of PAA homopolymers.

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.

Role of β-h elimination in rhodium-mediated carbene insertion polymerization

NARCIS (Netherlands)

Finger, M.; Reek, J.N.H.; de Bruin, B.

2011-01-01

The importance of β-H elimination as a possible mechanism to induce chain termination/transfer and/or the formation of stereodefects in the Rh(diene)-mediated oligomerization and polymerization of carbenes has been studied by means of different approaches. As a remarkable feature, this reaction is

Functionalization of lanthanum hydroxide nanowires by atom transfer radical polymerization

International Nuclear Information System (INIS)

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

2007-01-01

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

Effect of Inhibitors on Atom Transfer Radical Polymerization of MMA

Institute of Scientific and Technical Information of China (English)

张鸿; 徐冬梅; 张可达

2005-01-01

Effect of a series of inhibitors as additives on atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) with FeCl2/PPh3 as catalyst system was studied, including 2,4,6-trinitrophenol (TNP), 4-methoxyphenol (4-MP), hydroquinone (HQ) and nitrobenzene (NB). It was found that TNP was the only. efficient additive for ATRP among these inhibitors. In the presence of small amounts of TNP, the polymerization proceeded rapidly after induction period to yield the polymers with controlled molecular weights and narrow molecular weight distributions (MWD). The initiating efficiency of the modified catalyst system with TNP was increased. The mechanism was proposed and confirmed by the end group analysis of the polymer.

Roles of N-glycans in the polymerization-dependent aggregation of mutant Ig-μ chains in the early secretory pathway.

Science.gov (United States)

Giannone, Chiara; Fagioli, Claudio; Valetti, Caterina; Sitia, Roberto; Anelli, Tiziana

2017-02-03

The polymeric structure of secretory IgM allows efficient antigen binding and complement fixation. The available structural models place the N-glycans bound to asparagines 402 and 563 of Ig-μ chains within a densely packed core of native IgM. These glycans are found in the high mannose state also in secreted IgM, suggesting that polymerization hinders them to Golgi processing enzymes. Their absence alters polymerization. Here we investigate their role following the fate of aggregation-prone mutant μ chains lacking the Cμ1 domain (μ∆). Our data reveal that μ∆ lacking 563 glycans (μ∆5) form larger intracellular aggregates than μ∆ and are not secreted. Like μ∆, they sequester ERGIC-53, a lectin previously shown to promote polymerization. In contrast, μ∆ lacking 402 glycans (μ∆4) remain detergent soluble and accumulate in the ER, as does a double mutant devoid of both (μ∆4-5). These results suggest that the two C-terminal Ig-μ glycans shape the polymerization-dependent aggregation by engaging lectins and acting as spacers in the alignment of individual IgM subunits in native polymers.

Studies on atom transfer radical polymerization of acrylates and styrenes with controlled polymeric block structures

OpenAIRE

Ibrahim, Khalid

2006-01-01

Atom transfer radical polymerization (ATRP) was applied to homo and block copolymerization of vinyl monomers methacrylates, acrylates, and styrene with iron (FeCl2.4H2O) as the transition metal in most cases. As complexing ligand either a commercially available ligand (triphenyl phosphine) (PPh3) or synthetic aliphatic amines were used. As initiators, methyl 2-bromopropionate, ethyl 2-bromoisobutyrate, α,α-dichloroacetophenone, and poly(ethylene oxide) macroinitiator were employed. Block ...

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

NARCIS (Netherlands)

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

2008-01-01

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

CONCERNING CHAIN GROWTH SPECIFIC REACTION RATE AS A PART OF THE PROCESS OF METHYL METHACRYLATE MASS RADICAL POLYMERIZATION

Directory of Open Access Journals (Sweden)

A. A. Sultanova

2017-02-01

Full Text Available It is the chain growth specific reaction rate that was determined for the process of methyl methacrylate mass radical polymerization within the temperature range of 40–900 С in quasi-steady approximation by means of Monte Carlo method. The theoretical model of radical polymerization was developed taking the gel effect into account. Computer software was developed that enables to imitate radical polymerization process taking gel effect into account within the minimum run time. The programme was tested on asymptotic examples as well as was applied for methyl methacrylate mass radical polymerization. The programme makes it possible to calculate monomer conversion, molecular mass variation, molecular-mass distribution, etc.

Chain propagation and termination mechanisms for polymerization of conjugated polar alkenes by [Al]-based frustrated Lewis pairs

KAUST Repository

He, Jianghua; Zhang, Yuetao; Falivene, Laura; Caporaso, Lucia; Cavallo, Luigi; Chen, Eugene You Xian

2014-01-01

key parts: structural characterization of active propagating intermediates, propagation kinetics, and chain-termination pathways. Zwitterionic intermediates that simulate the active propagating species in such polymerization have been generated

Construction of Hierarchical Polymer Brushes on Upconversion Nanoparticles via NIR-Light-Initiated RAFT Polymerization.

Science.gov (United States)

Xie, Zhongxi; Deng, Xiaoran; Liu, Bei; Huang, Shanshan; Ma, Pingan; Hou, Zhiyao; Cheng, Ziyong; Lin, Jun; Luan, Shifang

2017-09-13

Photoinduced reversible addition-fragmentation chain transfer (RAFT) polymerization generally adopts high-energy ultraviolet (UV) or blue light. In combination with photoredox catalyst, the excitation light wavelength was extended to the visible and even near-infrared (NIR) region for photoinduced electron transfer RAFT polymerization. In this report, we introduce for the first time a surface NIR-light-initiated RAFT polymerization on upconversion nanoparticles (UCNPs) without adding any photocatalyst and construct a functional inorganic core/polymer shell nanohybrid for application in cancer theranostics. The multilayer core-shell UCNPs (NaYF 4 :Yb/Tm@NaYbF 4 :Gd@NaNdF 4 :Yb@NaYF 4 ), with surface anchorings of chain transfer agents, can serve as efficient NIR-to-UV light transducers for initiating the RAFT polymerization. A hierarchical double block copolymer brush, consisting of poly(acrylic acid) (PAA) and poly(oligo(ethylene oxide)methacrylate-co-2-(2-methoxy-ethoxy)ethyl methacrylate) (PEG for short), was grafted from the surface in sequence. The targeting arginine-glycine-aspartic (RGD) peptide was modified at the end of the copolymer through the trithiolcarbonate end group. After loading of doxorubicin, the UCNPs@PAA-b-PEG-RGD exhibited an enhanced U87MG cancer cell uptake efficiency and cytotoxicity. Besides, the unique upconversion luminescence of the nanohybrids was used for the autofluoresence-free cell imaging and labeling. Therefore, our strategy verified that UCNPs could efficiently activate RAFT polymerization by NIR photoirradiation and construct the complex nanohybrids, exhibiting prospective biomedical applications due to the low phototoxicity and deep penetration of NIR light.

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

Institute of Scientific and Technical Information of China (English)

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

2006-01-01

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

Chemical vapor deposition graphene transfer process to a polymeric substrate assisted by a spin coater

International Nuclear Information System (INIS)

Kessler, Felipe; Da Rocha, Caique O C; Medeiros, Gabriela S; Fechine, Guilhermino J M

2016-01-01

A new method to transfer chemical vapor deposition graphene to polymeric substrates is demonstrated here, it is called direct dry transfer assisted by a spin coater (DDT-SC). Compared to the conventional method DDT, the improvement of the contact between graphene-polymer due to a very thin polymeric film deposited by spin coater before the transfer process prevented air bubbles and/or moisture and avoided molecular expansion on the graphene-polymer interface. An acrylonitrile-butadiene-styrene copolymer, a high impact polystyrene, polybutadiene adipate-co-terephthalate, polylactide acid, and a styrene-butadiene-styrene copolymer are the polymers used for the transfers since they did not work very well by using the DDT process. Raman spectroscopy and optical microscopy were used to identify, to quantify, and to qualify graphene transferred to the polymer substrates. The quantity of graphene transferred was substantially increased for all polymers by using the DDT-SC method when compared with the DDT standard method. After the transfer, the intensity of the D band remained low, indicating low defect density and good quality of the transfer. The DDT-SC transfer process expands the number of graphene applications since the polymer substrate candidates are increased. (paper)

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.

Effect of side chain length and degree of polymerization on the decomposition and crystallization behaviour of chlorinated poly(vinyl ester) oligomers

International Nuclear Information System (INIS)

Heinze, D.; Mang, Th.; Popescu, C.; Weichold, O.

2016-01-01

Highlights: • Thermal behaviour of telomerized polyvinyl esters is investigated. • Thermal stability relies mainly on the contribution of side chains. • At equal molecular weights thermal stability is dictated by length of side chain. • Increasing the length of side chains improves also the packing degree of polymer. - Abstract: Four members of a homologous series of chlorinated poly(vinyl ester) oligomers CCl_3–(CH_2CH (OCO(CH_2)_mCH_3))_n–Cl with degrees of polymerization of 10 and 20 were prepared by telomerisation using carbon tetrachloride. The number of side chain carbon atoms ranges from 2 (poly(vinyl acetate) to 18 (poly(vinyl stearate)). The effect of the n-alkyl side chain length and of the degree of polymerization on the thermal stability and crystallization behaviour of the synthesized compounds was investigated. All oligomers degrade in two major steps by first losing HCl and side chains with subsequent breakdown of the backbone. The members with short side chains, up to poly(vinyl octanoate), are amorphous and show internal plasticization, whereas those with high number of side chain carbon atoms are semi-crystalline due to side-chain crystallization. A better packing for poly(vinyl stearate) is also noticeable. The glass transition and melting temperatures as well as the onset temperature of decomposition are influenced to a larger extent by the side chain length than by the degree of polymerization. Thermal stability is improved if both the size and number of side chains increase, but only a long side chain causes a significant increase of the resistance to degradation. This results in a stabilization of PVAc so that oligomers from poly(vinyl octanoate) on are stable under atmospheric conditions. Thus, the way to design stable, chlorinated PVEs oligomers is to use a long n-alkyl side chain.

Effect of side chain length and degree of polymerization on the decomposition and crystallization behaviour of chlorinated poly(vinyl ester) oligomers

Energy Technology Data Exchange (ETDEWEB)

Heinze, D.; Mang, Th. [Aachen University of Applied Sciences, Heinrich-Mussmann-Str. 1, 52428 Jülich (Germany); Popescu, C., E-mail: crisan.popescu@kao.com [KAO Germany GmbH, Pfungstädterstr. 98-100, 64297 Darmstadt (Germany); Weichold, O., E-mail: weichold@ibac.rwth-aachen.de [Institute of Building Materials Research, Schinkelstr. 3, 52062 Aachen (Germany)

2016-08-10

Highlights: • Thermal behaviour of telomerized polyvinyl esters is investigated. • Thermal stability relies mainly on the contribution of side chains. • At equal molecular weights thermal stability is dictated by length of side chain. • Increasing the length of side chains improves also the packing degree of polymer. - Abstract: Four members of a homologous series of chlorinated poly(vinyl ester) oligomers CCl{sub 3}–(CH{sub 2}CH (OCO(CH{sub 2}){sub m}CH{sub 3})){sub n}–Cl with degrees of polymerization of 10 and 20 were prepared by telomerisation using carbon tetrachloride. The number of side chain carbon atoms ranges from 2 (poly(vinyl acetate) to 18 (poly(vinyl stearate)). The effect of the n-alkyl side chain length and of the degree of polymerization on the thermal stability and crystallization behaviour of the synthesized compounds was investigated. All oligomers degrade in two major steps by first losing HCl and side chains with subsequent breakdown of the backbone. The members with short side chains, up to poly(vinyl octanoate), are amorphous and show internal plasticization, whereas those with high number of side chain carbon atoms are semi-crystalline due to side-chain crystallization. A better packing for poly(vinyl stearate) is also noticeable. The glass transition and melting temperatures as well as the onset temperature of decomposition are influenced to a larger extent by the side chain length than by the degree of polymerization. Thermal stability is improved if both the size and number of side chains increase, but only a long side chain causes a significant increase of the resistance to degradation. This results in a stabilization of PVAc so that oligomers from poly(vinyl octanoate) on are stable under atmospheric conditions. Thus, the way to design stable, chlorinated PVEs oligomers is to use a long n-alkyl side chain.

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

Extraction or adsorption? Voltammetric assessment of protamine transfer at ionophore-based polymeric membranes.

Science.gov (United States)

Garada, Mohammed B; Kabagambe, Benjamin; Amemiya, Shigeru

2015-01-01

Cation-exchange extraction of polypeptide protamine from water into an ionophore-based polymeric membrane has been hypothesized as the origin of a potentiometric sensor response to this important heparin antidote. Here, we apply ion-transfer voltammetry not only to confirm protamine extraction into ionophore-doped polymeric membranes but also to reveal protamine adsorption at the membrane/water interface. Protamine adsorption is thermodynamically more favorable than protamine extraction as shown by cyclic voltammetry at plasticized poly(vinyl chloride) membranes containing dinonylnaphthalenesulfonate as a protamine-selective ionophore. Reversible adsorption of protamine at low concentrations down to 0.038 μg/mL is demonstrated by stripping voltammetry. Adsorptive preconcentration of protamine at the membrane/water interface is quantitatively modeled by using the Frumkin adsorption isotherm. We apply this model to ensure that stripping voltammograms are based on desorption of all protamine molecules that are transferred across the interface during a preconcentration step. In comparison to adsorption, voltammetric extraction of protamine requires ∼0.2 V more negative potentials, where a potentiometric super-Nernstian response to protamine is also observed. This agreement confirms that the potentiometric protamine response is based on protamine extraction. The voltammetrically reversible protamine extraction results in an apparently irreversible potentiometric response to protamine because back-extraction of protamine from the membrane extremely slows down at the mixed potential based on cation-exchange extraction of protamine. Significantly, this study demonstrates the advantages of ion-transfer voltammetry over potentiometry to quantitatively and mechanistically assess protamine transfer at ionophore-based polymeric membranes as foundation for reversible, selective, and sensitive detection of protamine.

Improved performance and stability of field-effect transistors with polymeric residue-free graphene channel transferred by gold layer.

Science.gov (United States)

Jang, Mi; Trung, Tran Quang; Jung, Jin-Heak; Kim, Bo-Yeong; Lee, Nae-Eung

2014-03-07

One of the most significant issues that occurs when applying chemical-vapor deposited (CVD) graphene (Gr) to various high-performance device applications is the result of polymeric residues. Polymeric residues remain on the Gr surface during Gr polymer support transfer to an arbitrary substrate, and these residues degrade CVD Gr electrical properties. In this paper, we propose that a thin layer of gold be used as a CVD Gr transfer layer, instead of a polymer support layer, to enable a polymer residue-free transfer. Comparative investigation of the surface morphological and qualitative analysis of residues on Gr surfaces and Gr field-effect transistors (GFETs) using two transfer methods demonstrates that gold-transferred Gr, with uniform, smooth, and clean surfaces, enable GFETs to perform better than Gr transferred by the polymer, polymethylmethacrylate (PMMA). In GFETs fabricated by the gold transfer method, field-effect carrier mobility was greatly enhanced and the position of the Dirac point was significantly reduced compared to GFETs fabricated by the PMMA transfer method. In addition, compared to the PMMA-transferred GFETs, the gold-transferred GFETs showed greatly increased stability with smaller hysteresis and higher resistance to gate bias stress effects. These results suggest that the gold transfer method for Gr provides significant improvements in GFET performance and reliability by minimizing the polymeric residues and defects on Gr.

ATOM TRANSFER RADICAL POLYMERIZATION OF N-BUTYL METHACRYLATE IN AQUEOUS DISPERSED SYSTEMS: A MINIEMULSION APPROACH. (R826735)

Science.gov (United States)

Ultrasonication was applied in combination with a hydrophobe for the copper-mediated atom transfer radical polymerization of n-butyl methacrylate in an aqueous dispersed system. A controlled polymerization was successfully achieved, as demonstrated by a linear correlation between...

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...

Development of double chain phosphatidylcholine functionalized polymeric monoliths for immobilized artificial membrane chromatography.

Science.gov (United States)

Wang, Qiqin; Peng, Kun; Chen, Weijia; Cao, Zhen; Zhu, Peijie; Zhao, Yumei; Wang, Yuqiang; Zhou, Haibo; Jiang, Zhengjin

2017-01-06

This study described a simple synthetic methodology for preparing biomembrane mimicking monolithic column. The suggested approach not only simplifies the preparation procedure but also improves the stability of double chain phosphatidylcholine (PC) functionalized monolithic column. The physicochemical properties of the optimized monolithic column were characterized by scanning electron microscopy, energy-dispersive X-ray spectrometry, and nano-LC. Satisfactory column permeability, efficiency, stability and reproducibility were obtained on this double chain PC functionalized monolithic column. It is worth noting that the resulting polymeric monolith exhibits great potential as a useful alternative of commercial immobilized artificial membrane (IAM) columns for in vitro predication of drug-membrane interactions. Furthermore, the comparative study of both double chain and single chain PC functionalized monoliths indicates that the presence or absence of glycerol backbone and the number of acyl chains are not decisive for the predictive ability of IAM monoliths on drug-membrane interactions. This novel PC functionalized monolithic column also exhibited good selectivity for a protein mixture and a set of pharmaceutical compounds. Copyright © 2016 Elsevier B.V. All rights reserved.

Efficient quantum state transfer in an engineered chain of quantum bits

Science.gov (United States)

Sandberg, Martin; Knill, Emanuel; Kapit, Eliot; Vissers, Michael R.; Pappas, David P.

2016-03-01

We present a method of performing quantum state transfer in a chain of superconducting quantum bits. Our protocol is based on engineering the energy levels of the qubits in the chain and tuning them all simultaneously with an external flux bias. The system is designed to allow sequential adiabatic state transfers, resulting in on-demand quantum state transfer from one end of the chain to the other. Numerical simulations of the master equation using realistic parameters for capacitive nearest-neighbor coupling, energy relaxation, and dephasing show that fast, high-fidelity state transfer should be feasible using this method.

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.

High-speed organocatalytic polymerization of a renewable methylene butyrolactone by a phosphazene superbase

KAUST Repository

Schmitt, Meghan L.; Falivene, Laura; Caporaso, Lucia; Cavallo, Luigi; Chen, Eugene You Xian

2014-01-01

The organic phosphazene superbase, 1-tert-butyl-4,4,4-tris(dimethylamino)- 2,2-bis[tris(dimethylamino)phosphoranylid-enamino]-2λ5, 4λ5-catenadi(phosphazene) (t-Bu-P4), is found to directly initiate high-speed polymerization of the biomass-derived renewable γ-methyl-α-methylene-γ-butyrolactone (MMBL), in contrast to other polymerization systems using t-Bu-P4 which typically require addition of an organic acid or a nucleophile as a co-initiating component. This MMBL polymerization by t-Bu-P4 alone is extremely rapid; even with a low t-Bu-P4 loading of 0.1 mol% or 0.02 mol%, quantitative monomer conversion is achieved in 20 s or 1 min, respectively, affording medium to high molecular weight PMMBL bioplastics in a catalytic fashion. The combined experimental and theoretical/computational studies have yielded mechanisms of chain initiation through abstraction of a proton from a monomer by t-Bu-P 4, essentially barrier-less chain propagation through rapid conjugate addition of the enolate anion stabilized by the nano-size cation [t-Bu-P 4H]+ to the monomer, and chain termination through chain transfer to the monomer which generates a saturated termination chain end and the [t-Bu-P4H]+-stabilized anionic active species that starts a new chain. This journal is © the Partner Organisations 2014.

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.

Biomimetic PEGylation of carbon nanotubes through surface-initiated RAFT polymerization.

Science.gov (United States)

Shi, Yingge; Zeng, Guanjian; Xu, Dazhuang; Liu, Meiying; Wang, Ke; Li, Zhen; Fu, Lihua; Zhang, Qingsong; Zhang, Xiaoyong; Wei, Yen

2017-11-01

Carbon nanotubes (CNTs) are a type of one-dimensional carbon nanomaterials that possess excellent physicochemical properties and have been potentially utilized for a variety of applications. Surface modification of CNTs with polymers is a general route to expand and improve the performance of CNTs and has attracted great research interest over the past few decades. Although many methods have been developed previously, most of these methods still showed some disadvantages, such as low efficiency, complex experimental procedure and harsh reaction conditions etc. In this work, we reported a practical and novel way to fabricate CNTs based polymer composites via the combination of mussel inspired chemistry and reversible addition fragmentation chain transfer (RAFT) polymerization. First, the amino group was introduced onto the surface of CNTs via self-polymerization of dopamine. Then, chain transfer agent can be immobilized on the amino groups functionalized CNTs to obtain CNT-PDA-CTA, which can be utilized for surface-initiated RAFT polymerization. A water soluble and biocompatible monomer poly(ethylene glycol) monomethyl ether methacrylate (PEGMA) was adopted to fabricate pPEGMA functionalized CNTs through RAFT polymerization. The successful preparation of CNTs based polymer composites (CNT-pPEGMA) was confirmed by transmission electron microscopy, Fourier transform infrared spectroscopy, thermogravimetric analysis and X-ray photoelectron spectroscopy in details. The CNT-pPEGMA showed good dispersibility and desirable biocompatibility, making them highly potential for biomedical applications. More importantly, a large number of CNTs based polymer composites could also be fabricated through the same strategy when different monomers were used due to the good monomer adaptability of RAFT polymerization. Therefore, this strategy should be a general method for preparation of various multifunctional CNTs based polymer composites. Copyright © 2017 Elsevier B.V. All rights

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

DEFF Research Database (Denmark)

Gao, Bo; Chen, Xianyi; Ivan, Bela

1997-01-01

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

Synthesis of amphiphilic poly(ε-caprolactone)-b-poly( N-vinylcaprolactam) block copolymers via the combination of RAFT polymerization and click chemistry

International Nuclear Information System (INIS)

Assis, Paulo Henrique; Aguiar, Graziele Aparecida de Jesus; Moraes, Rodolfo Minto de; Medeiros, Simone de Fatima; Santos, Amilton Martins

2016-01-01

Full text: In recent years, well-defined block copolymers composed of a hydrophilic and hydrophobic segments have gained much interest as drug carriers, because of their enhanced solubility and sustained release of the drug in controlled delivery systems [1]. The development of strategies to obtain block copolymers has attracted considerable attention, due to the possibility to combine characteristic properties of the homopolymers. A wide variety of well-defined block copolymers have been successfully synthesized by combining the efficiency and selectivity of click chemistry with the powerful RAFT polymerization mechanism. In the present work, well-defined amphiphilic, biocompatible, partially biodegradable, and thermosensitive poly(ε-caprolactone)-b-poly(N-vinylcaprolactam) (PCL-b-PNVCL) block copolymers were synthesized by combining ring opening polymerization (ROP), reversible addition-fragmentation chain transfer (RAFT) polymerization and subsequent click chemistry reaction. Alkyne-terminated poly(ε-caprolactone) (alkyne-PCL) was obtained by the ring opening polymerization of ε-caprolactone (ε-CL) using propargyl alcohol as initiator and stannous-2-ethylhexanoate [Sn(Oct) 2 ] as catalyst. The azide end-capped-poly(N-vinylcaprolactam) (PNVCL-N 3 ) was synthesized by reversible addition-fragmentation chain transfer/macromolecular design via interchange of xanthates (RAFT/MADIX) polymerization of the N-vinylcaprolactam (NVCL) mediated by a novel chain transfer agent comprising an azide function , 2-azidoethyl[(ethoxycarbonothioyl)thio](phenyl)acetate. These functionalized homopolymers, alkyne-PCL and PNVCL-N 3 , were coupled by the 1,3 dipolar cycloaddition reaction in order to obtain the corresponding block copolymers. These (co)polymers were characterized by FTIR, 1 H NMR and GPC measurements. Reference: 1. RAMESH, K., SINGH, S., MITRA, K., CHATTOPADHYAY, D., MISRA, N., & RAY, B. (2015). Colloid and Polymer Science, 1-9. (author)

Process Chain for the Manufacture of Polymeric Tubular Micro-Components and “POLYTUBES Micro-Factory” Concept

DEFF Research Database (Denmark)

Qin, Yi; Perzon, Erik; Chronakis, Ioannis S.

The paper presents a process chain for the shaping of poly-meric tubular micro-components for the volume production as well as presents a concept for the integration of the developed processes and modular machines onto a platform to form a "POLYTUBES Micro-Factory", being resulting from the Europ...

Revealing the Supramolecular Nature of Side-Chain Terpyridine-Functionalized Polymer Networks

Directory of Open Access Journals (Sweden)

Jérémy Brassinne

2015-01-01

Full Text Available Nowadays, finely controlling the mechanical properties of polymeric materials is possible by incorporating supramolecular motifs into their architecture. In this context, the synthesis of a side-chain terpyridine-functionalized poly(2-(dimethylaminoethyl methacrylate is reported via reversible addition-fragmentation chain transfer polymerization. By addition of transition metal ions, concentrated aqueous solutions of this polymer turn into metallo-supramolecular hydrogels whose dynamic mechanical properties are investigated by rotational rheometry. Hence, the possibility for the material to relax mechanical constrains via dissociation of transient cross-links is brought into light. In addition, the complex phenomena occurring under large oscillatory shear are interpreted in the context of transient networks.

Shapley value based transfer pricing in supply chains with stochastic demand

Directory of Open Access Journals (Sweden)

Lihua Chen

2015-01-01

Full Text Available We study the question of how to ideally divide total profits among supply chain members, especially in a stochastic demand market. The Shapley value is used as the methodology solution to divide profits in a supply chain. To illustrate the Shapley value solution and procedures, a two-echelon supply chain consisting of one supplier and two heterogeneous retailers is examined. The goal is to figure out ideal transfer prices for products delivered among supply chain members. These transfer prices will achieve the suggested profit allocations among three companies.

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

International Nuclear Information System (INIS)

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

2013-01-01

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

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

Science.gov (United States)

Li, Bin; Yu, Bo; Zhou, Feng

2013-02-12

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

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

Science.gov (United States)

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

2015-04-22

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

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

DEFF Research Database (Denmark)

Nielsen, Mads Møller

The cornerstone in this dissertation is made up by three individual assessments of the diversity in the macromolecular landscape that can be obtained by applying relatively few efficient chemical tools. The intention is to gain deeper knowledge on the chemical tuning of proton exchange membranes...... 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...... of control by ATRP and click chemistry enables a wide selection of polymer structures with the handles: degree of substitution (DS), polymerization and sulfonation, and blending....

Some regularities of separate and simultaneous radiation polymerization of vinyl acetate and acrylonitrile in adsorption layer on aerosil surface

International Nuclear Information System (INIS)

Mund, S.L.; Bruk, M.A.; Abkin, A.D.

1976-01-01

The kinetics has been studied of initial stage radiation copolymerization and separate radiation polymerization of aerosil adsorbed vinylacetate (VA) and acrylonitrile (AN). The monomers were irradiated using a Co 60 gamma source or a RUP-400 X-ray unit. Infrared spectroscopy, nuclear magnetic resonance and gravimetry were used in the study. It has been found that in the dose rate interval studied (over 60-450 rad./sec) the break of kinetic chains during the polymerization of VA and its mixtures with AN is due to the reaction of degenerate transfer of the chains to the surface hydroxyl groups. When AN is polymerized, biomolecular break of chains prevails. The effective activation energy of polymerization is 1.5 kcal/mol for VA and 2.5 kcal/mol for AN. The order of polymerization rates by the concentration of adsorbed monomers at 50 deg, as well as by the irradiation dose rate is equal to 1 and 1 for VA and 3/2 and 0.7 for AN, respectively. The calculated values of copolymerization constants coincide with those characteristic of their radical polymerization in liquid phase. Isotherms for adsorption of VA and AN on aerosil at 30, 50 and 70 deg have been studied [ru

Study of energy transfer to solvent in radiation graft polymerization of styrene onto polyethylene

International Nuclear Information System (INIS)

Rabie, A.; Odian, G.

1977-01-01

The radiation-initiated graft polymerization of styrene onto polyethylene was studied to determine whether energy transfer to diluent was responsible for the previously observed high orders of dependence of the grafting rate on monomer concentration. n-Octane was used as the diluent instead of benzene. If energy transfer from excited polyethylene to benzene were present, it should not be with n-octane. The percent swelling of polyethylene by various n-octane--styrene mixtures was determined. The compositions of various n-octane--styrene mixtures absorbed inside polyethylene were determined by ultraviolet and refractive index measurements and found to be richer in styrene than the corresponding mixtures in which the polyethylene had been placed. The graft polymerization rates were determined at 0.000761, 0.0371, and 0.213 Mrad/hr and plotted against the inside styrene concentrations on a log-log scale to yield the kinetic orders of dependence of rate on monomer as 2, 3, and 3, respectively. It was concluded that energy transfer to diluent was not responsible for the high-order dependence observed

Synthesis of click-reactive HPMA copolymers using RAFT polymerization for drug delivery applications

DEFF Research Database (Denmark)

Ebbesen, Morten F; Schaffert, D.H.; Crowley, Michael L

2013-01-01

This study describes a versatile strategy combining reversible addition fragmentation transfer (RAFT) polymerization and click chemistry to synthesize well-defined, reactive copolymers of N-(2-hydroxypropyl)methacrylamide (HPMA) for drug delivery applications. A novel azide containing monomer N-(3......-azidopropyl)methacrylamide (AzMA) was synthesized and copolymerized with HPMA using RAFT polymerization to provide p(HPMA-co-AzMA) copolymers with high control of molecular weight (∼10–54 kDa) and polydispersity (≤1.06). The utility of the side-chain azide functionality by Cu(I)-catalyzed azide...

Transfer of long-lived radionuclides through marine food chains: a review of transfer data

International Nuclear Information System (INIS)

Belot, Y.

1986-01-01

Experimental data on the transfer of long-lived radionuclides through food chains have been summarized from the available literature. The transfer to a given organism is characterized by a transfer factor (TF), defined as the activity in the organism relative to that in the ingested food or sediment. The TFs of Pu, Am and Tc from sediment to benthic species have been directly measured and generally do not exceed a value of 0.1. The TFs from prey to predator are related to uptake and retention parameters whose values can be derived from experimental data. It was estimated that these TFs do not generally exceed unity and that an increase of concentration through a food chain is very unlikely. (author)

Luminescent sensing of organophosphates using europium(III) containing imprinted polymers prepared by RAFT polymerization

International Nuclear Information System (INIS)

Southard, Glen E.; Van Houten, Kelly A.; Ott, Edward W.; Murray, George M.

2007-01-01

Molecularly imprinted polymers capable of sensing organophosphorous compounds by luminescence have been prepared by reversible addition fragmentation chain transfer (RAFT) polymerization. The polymer contained a dithiobenzoate substituted tris(β-diketonate) europium(III) complex which served as a polymerization substrate and as a luminescent binding site for pinacolyl methylphosphonate (PMP), the hydrolysis product of the nerve agent Soman. The resultant polymer allowed quantitation of PMP in the low ppb range with minimal interference from similar compounds. Polymers were characterized by luminescence spectroscopy and scanning electron microscopy

In Situ Monitoring of RAFT Polymerization by Tetraphenylethylene-Containing Agents with Aggregation-Induced Emission Characteristics.

Science.gov (United States)

Liu, Shunjie; Cheng, Yanhua; Zhang, Haoke; Qiu, Zijie; Kwok, Ryan T K; Lam, Jacky W Y; Tang, Ben Zhong

2018-05-22

A facile and efficient approach is demonstrated to visualize the polymerization in situ. A group of tetraphenylethylene (TPE)-containing dithiocarbamates were synthesized and screened as agents for reversible addition fragmentation chain transfer (RAFT) polymerizations. The spatial-temporal control characteristics of photochemistry enabled the RAFT polymerizations to be ON and OFF on demand under alternating visible light irradiation. The emission of TPE is sensitive to the local viscosity change owing to its aggregation-induced emission characteristic. Quantitative information could be easily acquired by the naked eye without destroying the reaction system. Furthermore, the versatility of such a technique was well demonstrated by 12 different polymerization systems. The present approach thus demonstrated a powerful platform for understanding the controlled living radical polymerization process. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Radiation induced emulsion polymerization

International Nuclear Information System (INIS)

Stannett, V.T.; Stahel, E.P.

1990-01-01

High energy radiation is particularly favored for the initiation of emulsion polymerization. The yield of free radicals, for example, from the radiolysis of the aqueous phase, is high; G(radical) values of 5-7. In addition, the rather special kinetics associated with emulsion polymerization lead, in general, to very large kinetic chain lengths, even with 'non-ideal' monomers such as vinyl acetate. Together, high polymerization rates at low doses become possible. There are some important advantages of radiation polymerization compared with chemical initiators, such as potassium persulfate. Perhaps the most important among them is the temperature independence of the initiation step. This makes low temperature polymerization very accessible. With monomers such as vinyl acetate, where chain termination to monomer is predominant, low temperatures lead to often highly desirable higher molecular weights. With styrene, the classical ideally behaved monomer, there are the advantages such as, for example, the feasibility of using cationic monomers. These and some attendant disadvantages are discussed in detail, including pilot plant studies

Inhibition of synthesis of heparan sulfate by selenate: Possible dependence on sulfation for chain polymerization

International Nuclear Information System (INIS)

Dietrich, C.P.; Nader, H.B.; Buonassisi, V.; Colburn, P.

1988-01-01

Selenate, a sulfation inhibitor, blocks the synthesis of heparan sulfate and chondroitin sulfate by cultured endothelial cells. In contrast, selenate does not affect the production of hyaluronic acid, a nonsulfated glycosaminoglycan. No differences in molecular weight, [ 3 H]glucosamine/[ 35 S]sulfuric acid ratios, or disaccharide composition were observed when the heparan sulfate synthesized by selenate-treated cells was compared with that of control cells. The absence of undersulfated chains in preparations from cultures exposed to selenate supports the concept that, in the intact cell, the polymerization of heparan sulfate might be dependent on the sulfation of the saccharide units added to the growing glycosaminoglycan chain

Study of the chain termination in the polymerization of seven-membered carbonate cyclic

International Nuclear Information System (INIS)

Carpentier, Jean-Francois; Casagrande Junior, Osvaldo de; Gil, Marcelo Priebe

2011-01-01

Methyl substituted seven-membered ring carbonate (7CC), namely 4-methyl-1,3-dioxepan-2-one (α-Me7CC) have been synthesized in good yield (up to 50%) upon cyclization of the corresponding α-diols issued from green renewable acid. ( I mmortal ) Ring-opening polymerization (iROP) of this monomer has been carried out using various catalysts combined with an alcohol acting as a co-initiator and a chain transfer agent. The Lewis acid Al(OTf) 3 or the organometallic complexes [(BDI iPr )Zn(N(SiMe 3 ) 2 )] ((BDI iPr ) = 2-((2,6-diisopropylphenyl)amido)-4-((2,6- diisopropylphenyl)-imino)-2-pentene] and [(ONOO tBu )Y(N(SiHMe 2 ) 2 )(THF)] (ONOO tBu = amino-alkoxy-bis( phenolate)) successfully afforded the corresponding poly(α-Me7CC) with quite good control and activities. Detailed microstructural analysis of the poly(a-Me7CC) using 1 H and 13 C NMR and MALDI-TOF-MS techniques revealed the higher regioselectivity -with preferential ring-opening at the most hindered oxygen-acyl O-C(O)O bond, i.e. close to the α-Me substituent- of the zinc-based system followed by the yttrium as compared to the lack of selectivity of the aluminum one, in the ROP of α-Me7CC. (author)

Tailoring Copolymer Properties by Gradual Changes in the Distribution of the Chains Composition Using Semicontinuous Emulsion Polymerization

Directory of Open Access Journals (Sweden)

Carlos Federico Jasso-Gastinel

2017-02-01

Full Text Available To design the properties of a copolymer using free radical polymerization, a semicontinuous process can be applied to vary the instantaneous copolymer composition along the conversion searching for a specific composition spectrum of copolymer chains, which can be termed as weight composition distribution (WCD of copolymer chains. Here, the styrene-n-butyl acrylate (S/BA system was polymerized by means of a semicontinuous emulsion process, varying the composition of the comonomer feed to obtain forced composition copolymers (FCCs. Five different feeding profiles were used, searching for a scheme to obtain chains rich in S (looking for considerable modulus, and chains rich in BA (looking for large deformation as a technique to achieve synergy in copolymer properties; the mechanostatic and dynamic characterization discloses the correspondence between WCD and the bulk properties. 1H-nuclear magnetic resonance (1H-NMR analysis enabled the determination of the cumulative copolymer composition characterization, required to estimate the WCD. The static test (stress-strain and dynamic mechanical analysis (DMA were performed following normed procedures. This is the first report that shows very diverse mechanostatic performances of copolymers obtained using the same chemical system and global comonomer composition, forming a comprehensive failure envelope, even though the tests were carried out at the same temperature and cross head speed. The principles for synergic performance can be applied to controlled radical copolymerization, designing the composition variation in individual molecules along the conversion.

Subwavelength dielectric nanorod chains for energy transfer in the visible range.

Science.gov (United States)

Li, Dongdong; Zhang, Jingjing; Yan, Changchun; Xu, Zhengji; Zhang, Dao Hua

2017-10-15

We report a new type of energy transfer device, formed by a dielectric nanorod array embedded in a silver slab. Such dielectric chain structures allow surface plasmon wave guiding with large propagation length and highly suppressed crosstalk between adjacent transmission channels. The simulation results show that our proposed design can be used to enhance the energy transfer along the waveguide-like dielectric nanorod chains via coupled plasmons, where the energy spreading is effectively suppressed, and superior imaging properties in terms of resolution and energy transfer distance can be achieved.

Direct dry transfer of CVD graphene to an optical substrate by in situ photo-polymerization

Science.gov (United States)

Kessler, Felipe; Muñoz, Pablo A. R.; Phelan, Ciaran; Romani, Eric C.; Larrudé, Dunieskys R. G.; Freire, Fernando L.; Thoroh de Souza, Eunézio A.; de Matos, Christiano J. S.; Fechine, Guilhermino J. M.

2018-05-01

Here, we report on a method that allows graphene produced by chemical vapor deposition (CVD) to be directly transferred to an optically transparent photo resin, by in situ photo-polymerization of the latter, with high efficiency and low contamination. Two photocurable resins, A and B, with different viscosities but essentially the same chemical structure, were used. Raman spectroscopy and surface energy results show that large continuous areas of graphene were transferred with minimal defects to the lower viscosity resin (B), due to the better contact between the resin and graphene. As a proof-of-principle optical experiment, graphene on the polymeric substrate was subjected to high-intensity femtosecond infrared pulses and third-harmonic generation was observed with no noticeable degradation of the sample. A sheet third-order susceptibility χ (3) = 0.71 ×10-28m3V-2 was obtained, matching that of graphene on a glass substrate. These results indicate the suitability of the proposed transfer method, and of the photo resin, for the production of nonlinear photonic components and devices.

Synthesis of Photocrosslinkable and Amine Containing Multifunctional Nanoparticles via Polymerization-Induced Self-Assembly.

Science.gov (United States)

Huang, Jianbing; Li, Decai; Liang, Hui; Lu, Jiang

2017-08-01

Photo-crosslinkable and amine-containing block copolymer nanoparticles are synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization-induced self-assembly of a multifunctional core-forming monomer, 2-((3-(4-(diethylamino)phenyl)acryloyl)oxy)ethyl methacrylate (DEMA), using poly(2-hydroxypropyl methacrylate) macromolecular chain transfer agent as a steric stabilizer in methanol at 65 °C. By tuning the chain length of PDEMA, a range of nanoparticle morphologies (sphere, worm, and vesicle) can be obtained. Since cinnamate groups can easily undergo a [2 + 2] cycloaddition of the carbon-carbon double bonds upon UV irradiation, the as-prepared block copolymer nanoparticles are readily stabilized by photo-crosslinking to produce anisotropic nanoparticles. The crosslinked block copolymer nanoparticles can be used as templates for in situ formation polymer/gold hybrid nanoparticles. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

RAFT polymerization and some of its applications.

Science.gov (United States)

Moad, Graeme; Rizzardo, Ezio; Thang, San H

2013-08-01

Reversible addition-fragmentation chain transfer (RAFT) is one of the most robust and versatile methods for controlling radical polymerization. With appropriate selection of the RAFT agent for the monomers and reaction conditions, it is applicable to the majority of monomers subject to radical polymerization. The process can be used in the synthesis of well-defined homo-, gradient, diblock, triblock, and star polymers and more complex architectures, which include microgels and polymer brushes. In this Focus Review we describe how the development of RAFT and RAFT application has been facilitated by the adoption of continuous flow techniques using tubular reactors and through the use of high-throughput methodology. Applications described include the use of RAFT in the preparation of polymers for optoelectronics, block copolymer therapeutics, and star polymer rheology control agents. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

International Nuclear Information System (INIS)

Aikins, J.A.; Williams, F.

1985-01-01

After suitable drying, the subject monomers in the form of neat liquids undergo radiation-induced polymerization with no apparent side reactions and high conversions to precipitatable polymers of low molecular weights. A high frequency of chain (proton) transfer to monomer is indicated by the fact that the kinetic chain lengths are estimated to be several hundred times larger than the range of DP/sub n/ values (12-4). Structural characterization of the limonene oxide polymer by 1 H and 13 C NMR spectroscopy provides conclusive evidence that the polymerization proceeds by the opening of the epoxide ring to yield a 1,2-trans polyether. Similar NMR studies on the polymers formed from the α-pinene and β-pinene oxides show that the opening of the epoxide ring for these monomers is generally accompanied by the concomitant ring opening of the cyclobutane ring structure to yield a gem-di-methyl group in the main chain

Transfer of d-level quantum states through spin chains by random swapping

International Nuclear Information System (INIS)

Bayat, A.; Karimipour, V.

2007-01-01

We generalize an already proposed protocol for quantum state transfer to spin chains of arbitrary spin. An arbitrary unknown d-level state is transferred through a chain with rather good fidelity by the natural dynamics of the chain. We compare the performance of this protocol for various values of d. A by-product of our study is a much simpler method for picking up the state at the destination as compared with the one proposed previously. We also discuss entanglement distribution through such chains and show that the quality of entanglement transition increases with the number of levels d

Fluorinated polyimides grafted with poly(ethylene glycol) side chains by the RAFT-mediated process and their membranes

International Nuclear Information System (INIS)

Chen Yiwang; Chen Lie; Nie Huarong; Kang, E.T.; Vora, R.H.

2005-01-01

Graft polymerization of poly(ethylene glycol) methyl ether methacrylate (PEGMA) from fluorinated polyimide (FPI) was carried out by the reversible addition-fragmentation chain transfer (RAFT)-mediated process. The peroxides generated by the ozone treatment on FPI facilitated the thermally-initiated graft copolymerization from FPI backbone. The 'living' character of the graft chain growing was ascertained in the subsequent chain extension of PEGMA. Nuclear magnetic resonance (NMR) and molecular weight measurements were used to characterize the chemical composition and structure of the copolymers. Microfiltration (MF) membranes were fabricated from the FPI-g-PEGMA comb copolymers by phase inversion in aqueous media. Surface composition analysis of the membranes scanned by X-ray photoelectron spectroscopy (XPS) revealed a substantial surface enrichment of the hydrophilic components. The pore size distribution of the resulting membranes was found to be much more uniform than that of the corresponding membranes cast from FPI-g-PEGMA prepared by the conventional radical polymerization process in the absence of the chain transfer agent. The morphology of the membranes was characterized by scanning electron microscopy (SEM)

Olefin copolymerization via reversible addition-fragmentation chain transfer

NARCIS (Netherlands)

Venkatesh, R.; Staal, B.B.P.; Klumperman, B.

2004-01-01

Successful statistical copolymn. of an a-olefin (1-octene) with an acrylate (Bu acrylate, BA) and with a methacrylate (Me methacrylate, MMA), employing reversible addn.-fragmentation chain transfer (RAFT) mediated polymn. has been accomplished

Surface modification of silk fibroin fibers with poly(methyl methacrylate) and poly(tributylsilyl methacrylate) via RAFT polymerization for marine antifouling applications

Energy Technology Data Exchange (ETDEWEB)

Buga, Mihaela-Ramona [National Research and Development Institute for Cryogenics and Isotopic Technologies, ICIT Rm. Valcea, 240050 Rm. Valcea, Uzinei 4, CP7, Raureni, Valcea (Romania); Zaharia, Cătălin, E-mail: zaharia.catalin@gmail.com [Advanced Polymer Materials Group, University Politehnica of Bucharest, 1-7, Gh. Polizu Street, Sector 1, 011061 Bucharest (Romania); Bălan, Mihai [National Research and Development Institute for Cryogenics and Isotopic Technologies, ICIT Rm. Valcea, 240050 Rm. Valcea, Uzinei 4, CP7, Raureni, Valcea (Romania); Bressy, Christine [Université de Toulon, MAPIEM, EA 4323, 83957 La Garde (France); Ziarelli, Fabio [Fédération des Sciences Chimiques de Marseille, CNRS-FR1739, Spectropole, 13397 Marseille (France); Margaillan, André [Université de Toulon, MAPIEM, EA 4323, 83957 La Garde (France)

2015-06-01

In this study, silk fibroin surface containing hydroxyl and aminogroups was firstly modified using a polymerizable coupling agent 3-(trimethoxysilyl) propyl methacrylate (MPS), in order to induce vinyl groups onto the fiber surface. The reversible addition–fragmentation chain transfer (RAFT)-mediated polymerization of methyl methacrylate (MMA) and tributylsilyl methacrylate (TBSiMA) through the immobilized vinyl bond on the silk fibroin surface in the presence of 2-cyanoprop-2-yl dithiobenzoate (CPDB) as chain-transfer agent and 2,2′-azobis(isobutyronitrile) (AIBN) as initiator was conducted in toluene solution at 70 °C for 24 h. The structure and properties of the modified fiber were characterized by Fourier Transform Infrared Spectroscopy, {sup 13}C, {sup 29}Si Nuclear Magnetic Resonance (NMR) spectroscopy, thermogravimetric analysis (TGA), scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS), confirming the presence of the coupling molecule and the methacrylate groups onto the silk fibroin fiber surface. Molecular weight distributions were assessed by triple detection size exclusion chromatography (TD-SEC) in order to verify the livingness of the polymerization. - Highlights: • SF surface containing hydroxyl and amino groups was firstly modified with MPS. • RAFT polymerizations of MMA and TBSiMA were studied. • TD-SEC was used to verify the livingness of the RAFT polymerization. • The grafted polymer chains enhance the thermal stability of the SF fibers. • The grafted fibers could be potentially promising candidates as antifouling agents.

Surface modification of silk fibroin fibers with poly(methyl methacrylate) and poly(tributylsilyl methacrylate) via RAFT polymerization for marine antifouling applications

International Nuclear Information System (INIS)

Buga, Mihaela-Ramona; Zaharia, Cătălin; Bălan, Mihai; Bressy, Christine; Ziarelli, Fabio; Margaillan, André

2015-01-01

In this study, silk fibroin surface containing hydroxyl and aminogroups was firstly modified using a polymerizable coupling agent 3-(trimethoxysilyl) propyl methacrylate (MPS), in order to induce vinyl groups onto the fiber surface. The reversible addition–fragmentation chain transfer (RAFT)-mediated polymerization of methyl methacrylate (MMA) and tributylsilyl methacrylate (TBSiMA) through the immobilized vinyl bond on the silk fibroin surface in the presence of 2-cyanoprop-2-yl dithiobenzoate (CPDB) as chain-transfer agent and 2,2′-azobis(isobutyronitrile) (AIBN) as initiator was conducted in toluene solution at 70 °C for 24 h. The structure and properties of the modified fiber were characterized by Fourier Transform Infrared Spectroscopy, 13 C, 29 Si Nuclear Magnetic Resonance (NMR) spectroscopy, thermogravimetric analysis (TGA), scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS), confirming the presence of the coupling molecule and the methacrylate groups onto the silk fibroin fiber surface. Molecular weight distributions were assessed by triple detection size exclusion chromatography (TD-SEC) in order to verify the livingness of the polymerization. - Highlights: • SF surface containing hydroxyl and amino groups was firstly modified with MPS. • RAFT polymerizations of MMA and TBSiMA were studied. • TD-SEC was used to verify the livingness of the RAFT polymerization. • The grafted polymer chains enhance the thermal stability of the SF fibers. • The grafted fibers could be potentially promising candidates as antifouling agents

Surface-Confined Aqueous Reversible Addition-Fragmentation Chain Transfer (SCARAFT) Polymerization Method for Preparation of Coated Capillary Leads to over 10 000 Peptides Identified from 25 ng HeLa Digest by Using Capillary Zone Electrophoresis-Tandem Mass Spectrometry.

Science.gov (United States)

Zhang, Zhenbin; Peuchen, Elizabeth H; Dovichi, Norman J

2017-06-20

A surface-confined aqueous reversible addition-fragmentation chain transfer (SCARAFT) polymerization method was developed to coat capillaries for use in capillary zone electrophoresis (CZE). SCARAFT polymerization primarily takes place on the inner surface of the capillary instead of in solution, which greatly improves the homogeneity of the coating. Capillaries treated with this coating produced an electroosmotic mobility of 2.8 ± 0.2 × 10 -6 cm 2 ·V -1 ·s -1 (N = 3), which is roughly an order of magnitude lower than that of commercial linear polyacrylamide (LPA)-coated capillaries. Coated capillaries were evaluated for bottom-up proteomic analysis using CZE. The very low electroosmotic mobility results in a 200 min separation and improved single-shot analysis. An average of 977 protein groups and 5605 unique peptides were identified from 50 ng of an E. coli digest, and 2158 protein groups and 10 005 peptides were identified from 25 ng of a HeLa digest using single-shot analysis with a SCARAFT-acrylamide capillary coupled to a Q Exactive HF mass spectrometer. The coating is stable. A single capillary was used for over 200 h (8.4 days) of continuous operation. RSD in migration time was between 2 and 3% for selected ion electropherograms (SIEs) generated for six ions; median theoretical plate counts ranged from 240 000 to 600 000 for these SIEs. Various types of coatings could be prepared by simply changing the functional vinyl monomers in the polymerization mixture. Positively charged coatings using direct attachment and formation of a block copolymer were prepared and demonstrated for the separation of mixtures of intact proteins.

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...

Improved Livingness and Control over Branching in RAFT Polymerization of Acrylates: Could Microflow Synthesis Make the Difference?

Science.gov (United States)

Derboven, Pieter; Van Steenberge, Paul H M; Vandenbergh, Joke; Reyniers, Marie-Francoise; Junkers, Thomas; D'hooge, Dagmar R; Marin, Guy B

2015-12-01

The superior capabilities of structured microreactors over batch reactors are demonstrated for reversible addition-fragmentation chain transfer (RAFT) solution polymerization of n-butyl acrylate with the aid of simulations, explicitly accounting for the chain length distribution of all macrospecies types. Since perfect isothermicity can be established in a microreactor, less side products due to backbiting and β-scission are formed compared to the batch operation in which ineffective heat removal leads to an undesirable temperature spike. For a given RAFT chain transfer agent (CTA), additional microstructural control results under microflow conditions by optimizing the reaction temperature, lowering the dilution degree, or decreasing the initial molar ratio of monomer to RAFT CTA. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Polymerization of Acetonitrile via a Hydrogen Transfer Reaction from CH3 to CN under Extreme Conditions.

Science.gov (United States)

Zheng, Haiyan; Li, Kuo; Cody, George D; Tulk, Christopher A; Dong, Xiao; Gao, Guoying; Molaison, Jamie J; Liu, Zhenxian; Feygenson, Mikhail; Yang, Wenge; Ivanov, Ilia N; Basile, Leonardo; Idrobo, Juan-Carlos; Guthrie, Malcolm; Mao, Ho-Kwang

2016-09-19

Acetonitrile (CH3 CN) is the simplest and one of the most stable nitriles. Reactions usually occur on the C≡N triple bond, while the C-H bond is very inert and can only be activated by a very strong base or a metal catalyst. It is demonstrated that C-H bonds can be activated by the cyano group under high pressure, but at room temperature. The hydrogen atom transfers from the CH3 to CN along the CH⋅⋅⋅N hydrogen bond, which produces an amino group and initiates polymerization to form a dimer, 1D chain, and 2D nanoribbon with mixed sp(2) and sp(3) bonded carbon. Finally, it transforms into a graphitic polymer by eliminating ammonia. This study shows that applying pressure can induce a distinctive reaction which is guided by the structure of the molecular crystal. It highlights the fact that very inert C-H can be activated by high pressure, even at room temperature and without a catalyst. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Evaluation of shrinkage polymerization and temperature of different acrylic resins used to splinting transfer copings in indirect impression technique

Science.gov (United States)

Franco, Ana Paula G. O.; Karam, Leandro Z.; Galvão, José R.; Kalinowski, Hypolito J.

2015-09-01

The aim of the present study was evaluate the shrinkage polymerization and temperature of different acrylic resins used to splinting transfer copings in indirect impression technique. Two implants were placed in an artificial bone, with the two transfer copings joined with dental floss and acrylic resins; two dental resins are used. Measurements of deformation and temperature were performed with Fiber Braggs grating sensor for 17 minutes. The results revealed that one type of resin shows greater values of polymerization shrinkage than the other. Pattern resins did not present lower values of shrinkage, as usually reported by the manufacturer.

Hydroperoxide Traces in Common Cyclic Ethers as Initiators for Controlled RAFT Polymerizations.

Science.gov (United States)

Eggers, Steffen; Abetz, Volker

2018-04-01

Herein, a reversible addition-fragmentation chain transfer (RAFT) polymerization is introduced for reactive monomers like N-acryloylpyrrolidine or N,N-dimethylacrylamide working without a conventional radical initiator. As a very straightforward proof of principle, the method takes advantage of the usually inconvenient radical-generating hydroperoxide contaminations in cyclic ethers like tetrahydrofuran or 1,4-dioxane, which are very common solvents in polymer sciences. The polymerizations are surprisingly well controlled and the polymers can be extended with a second block, indicating their high livingness. "Solvent-initiated" RAFT polymerizations hence prove to be a feasible access to tailored materials with minimal experimental effort and standard laboratory equipment, only requiring the following ingredients: hydroperoxide-contaminated solvent, monomer, and RAFT agent. In other respects, however, the potential coinitiating ability of the used solvent is to be considered when investigating the kinetics of RAFT polymerizations or aiming for the synthesis of high-livingness polymers, e.g., multiblock copolymers. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Multiblock Copolymers of Styrene and Butyl Acrylate via Polytrithiocarbonate-Mediated RAFT Polymerization

Directory of Open Access Journals (Sweden)

Bastian Ebeling

2011-03-01

Full Text Available When linear polytrithiocarbonates as Reversible Addition-Fragmentation chain Transfer (RAFT agents are employed in a radical polymerization, the resulting macromolecules consist of several homogeneous polymer blocks, interconnected by the functional groups of the respective RAFT agent. Via a second polymerization with another monomer, multiblock copolymers—polymers with alternating segments of both monomers—can be prepared. This strategy was examined mechanistically in detail based on subsequent RAFT polymerizations of styrene and butyl acrylate. Size-exclusion chromatography (SEC of these polymers showed that the examined method yields low-disperse products. In some cases, resolved peaks for molecules with different numbers of blocks (polymer chains separated by the trithiocarbonate groups could be observed. Cleavage of the polymers at the trithiocarbonate groups and SEC analysis of the products showed that the blocks in the middle of the polymers are longer than those at the ends and that the number of blocks corresponds to the number of functional groups in the initial RAFT agent. Furthermore, the produced multiblock copolymers were analyzed via differential scanning calorimetry (DSC. This work underlines that the examined methodology is very well suited for the synthesis of well-defined multiblock copolymers.

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...

Sulfonated amphiphilic block copolymers : synthesis, self-assembly in water, and application as stabilizer in emulsion polymerization

Science.gov (United States)

Jiguang Zhang; Matthew R. Dubay; Carl J. Houtman; Steven J. Severtson

2009-01-01

Described is the synthesis of diblock copolymers generated via sequential atom transfer radical polymerization (ATRP) of poly(n-butyl acrylate) (PnBA) followed by chain augmentation with either sulfonated poly(2-hydroxyethyl methacrylate) (PHEMA) or poly(2-hydroxyethyl acrylate) (PHEA) blocks. ATRP of PHEMA or PHEA from PnBA macroinitiator was conducted in acetone/...

Facile synthesis of polymeric fluorescent organic nanoparticles based on the self-polymerization of dopamine for biological imaging.

Science.gov (United States)

Shi, Yingge; Jiang, Ruming; Liu, Meiying; Fu, Lihua; Zeng, Guangjian; Wan, Qing; Mao, Liucheng; Deng, Fengjie; Zhang, Xiaoyong; Wei, Yen

2017-08-01

Polymeric fluorescent organic nanoparticles (polymer-FONs) have raised considerable research attention for biomedical applications owing to their advantages as compared with fluorescent inorganic nanoparticles and small organic molecules. In this study, we presented an efficient, facile and environment-friendly strategy to produce polymer-FONs, which relied on the self-polymerization of dopamine and polyethyleneimine (PEI) in rather mild conditions. To obtain the final polymer-FONs, aldehyde group-containing copolymers (named as poly(UA-co-PEGMA)) were synthesized by reversible addition-fragmentation chain-transfer polymerization using polyethylene glycol methyl ether methacrylate (PEGMA) and 1-undecen-10-al (UA) as monomers. The dopamine was conjugated onto poly(UA-co-PEGMA) through a multicomponent reaction between UA and dopamine to obtain poly(UA-co-PEGMA)-DA, which was further utilized for preparation of polymer-FONs through self-polymerization of dopamine and PEI. 1 H nuclear magnetic resonance, Fourier transform infrared spectroscopy, transmission electron microscopy and fluorescence spectroscopy were employed to characterize the structure, morphology, compositions and optical properties of these polymer-FONs. Cell viability and cell uptake behavior results suggested that these polymer-FONs possess good biocompatibility and can be potentially utilized for biomedical applications. More importantly, the method can be also applied to fabricate many other multifunctional polymer-FONs with great potential for biomedical applications. Copyright © 2017 Elsevier B.V. All rights reserved.

Equilibrium polymerization of cyclic carbonate oligomers. III. Chain branching and the gel transition

Science.gov (United States)

Ballone, P.; Jones, R. O.

2002-10-01

Ring-opening polymerization of cyclic polycarbonate oligomers, where monofunctional active sites act on difunctional monomers to produce an equilibrium distribution of rings and chains, leads to a "living polymer." Monte Carlo simulations [two-dimensional (2D) and three-dimensional (3D)] of the effects of single [J. Chem. Phys. 115, 3895 (2001)] and multiple active sites [J. Chem. Phys. 116, 7724 (2002)] are extended here to trifunctional active sites that lead to branching. Low concentrations of trifunctional particles c3 reduce the degree of polymerization significantly in 2D, and higher concentrations (up to 32%) lead to further large changes in the phase diagram. Gel formation is observed at high total density and sizable c3 as a continuous transition similar to percolation. Polymer and gel are much more stable in 3D than in 2D, and both the total density and the value of c3 required to produce high molecular weight aggregates are reduced significantly. The degree of polymerization in high-density 3D systems is increased by the addition of trifunctional monomers and reduced slightly at low densities and low c3. The presence of branching makes equilibrium states more sensitive (in 2D and 3D) to changes in temperature T. The stabilities of polymer and gel are enhanced by increasing T, and—for sufficiently high values of c3—there is a reversible polymer-gel transformation at a density-dependent floor temperature.

Controlled radical copolymerization of styrene and maleic anhydride and the synthesis of novel polyolefin-based block copolymers by reversible addition-fragmentation chain-transfer (RAFT) polymerization

NARCIS (Netherlands)

Brouwer, de J.A.M.; Schellekens, M.A.J.; Klumperman, B.; Monteiro, M.J.; German, A.L.

2000-01-01

Reversible addn.-fragmentation chain transfer (RAFT) was applied to the copolymn. of styrene and maleic anhydride. The product had a low polydispersity and a predetd. molar mass. Novel, well-defined polyolefin-based block copolymers were prepd. with a macromol. RAFT agent prepd. from a com.

Thermoresponsive Poly(2-Oxazoline) Molecular Brushes by Living Ionic Polymerization: Modulation of the Cloud Point by Random and Block Copolymer Pendant Chains

KAUST Repository

Zhang, Ning

2012-08-10

Molecular brushes (MBs) of poly(2-oxazoline)s were prepared by living anionic polymerization of 2-isopropenyl-2-oxazoline to form the backbone and living cationic ring-opening polymerization of 2-n-propyl-2-oxazoline and 2-methyl-2-oxazoline to form random and block copolymers. Their aqueous solutions displayed a distinct thermoresponsive behavior as a function of the side-chain composition and sequence. The cloud point (CP) of MBs with random copolymer side chains is a linear function of the hydrophilic monomer content and can be modulated in a wide range. For MBs with block copolymer side chains, it was found that the block sequence had a strong and surprising effect on the CP. While MBs with a distal hydrophobic block had a CP at 70 °C, MBs with hydrophilic outer blocks already precipitated at 32 °C. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ring Opening Metathesis Polymerization of Cyclopentene Using a Ruthenium Catalyst Confined by a Branched Polymer Architecture

KAUST Repository

Mugemana, Clement; Bukhriakov, Konstantin; Bertrand, Olivier; Vu, Khanh B.; Gohy, Jean-Francois; Hadjichristidis, Nikolaos; Rodionov, Valentin

2016-01-01

Multi-arm polystyrene stars functionalized with Grubbs-type catalysts in their cores were synthesized and used for the ring-opening metathesis polymerization (ROMP) of cyclopentene. The spatial confinement of the catalytic sites and the nanoscale phase separation between polystyrene and the growing polypentenamer chains lead to a dramatic inhibition of the ROMP termination and chain transfer steps. Consequently, cyclopentene polymerizations proceeded fast and with a high degree of conversion even in air. The Grubbs second generation catalyst was oxidatively inactivated under the same conditions. In contrast to conventional small-molecule catalysts, the ultimate degree of conversion of cyclopentene monomer and the polydispersity of the product polypentenamer are not affected by the temperature. This indicates that spatial confinement of the catalyst resulted in a significant change in the activation parameters for the alkene metathesis ring-opening.

Ring Opening Metathesis Polymerization of Cyclopentene Using a Ruthenium Catalyst Confined by a Branched Polymer Architecture

KAUST Repository

Mugemana, Clement

2016-03-22

Multi-arm polystyrene stars functionalized with Grubbs-type catalysts in their cores were synthesized and used for the ring-opening metathesis polymerization (ROMP) of cyclopentene. The spatial confinement of the catalytic sites and the nanoscale phase separation between polystyrene and the growing polypentenamer chains lead to a dramatic inhibition of the ROMP termination and chain transfer steps. Consequently, cyclopentene polymerizations proceeded fast and with a high degree of conversion even in air. The Grubbs second generation catalyst was oxidatively inactivated under the same conditions. In contrast to conventional small-molecule catalysts, the ultimate degree of conversion of cyclopentene monomer and the polydispersity of the product polypentenamer are not affected by the temperature. This indicates that spatial confinement of the catalyst resulted in a significant change in the activation parameters for the alkene metathesis ring-opening.

Photoinitiated Polymerization-Induced Self-Assembly of Glycidyl Methacrylate for the Synthesis of Epoxy-Functionalized Block Copolymer Nano-Objects.

Science.gov (United States)

Tan, Jianbo; Liu, Dongdong; Huang, Chundong; Li, Xueliang; He, Jun; Xu, Qin; Zhang, Li

2017-08-01

Herein, a novel photoinitiated polymerization-induced self-assembly formulation via photoinitiated reversible addition-fragmentation chain transfer dispersion polymerization of glycidyl methacrylate (PGMA) in ethanol-water at room temperature is reported. It is demonstrated that conducting polymerization-induced self-assembly (PISA) at low temperatures is crucial for obtaining colloidal stable PGMA-based diblock copolymer nano-objects. Good control is maintained during the photo-PISA process with a high rate of polymerization. The polymerization can be switched between "ON" and "OFF" in response to visible light. A phase diagram is constructed by varying monomer concentration and degree of polymerization. The PGMA-based diblock copolymer nano-objects can be further cross-linked by using a bifunctional primary amine reagent. Finally, silver nanoparticles are loaded within cross-linked vesicles via in situ reduction, exhibiting good catalytic properties. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Controlled radical polymerization of an acrylamide containing L-alanine moiety via ATRP.

Science.gov (United States)

Rafiee, Zahra

2016-02-01

Homopolymerization of an optically active acrylamide having an amino acid moiety in the side chain, N-acryloyl-L-alanine (AAla) was carried out via atom transfer radical polymerization (ATRP) at room temperature using 2-hydroxyethyl-2'-methyl-2'-bromopropionate (HMB) or sodium-4-(bromomethyl)benzoate (SBB) as initiator in pure water, methanol/water mixture and pure methanol solvents. The polymerization reaction resulted in the optically active biocompatible amino acid-based homopolymer in good yield with narrow molecular weight distribution. The number average molecular weight increased with conversion and polydispersity was low. The structure and molecular weight of synthesized polymer were characterized by (1)H NMR, FT-IR spectroscopic techniques and size-exclusion chromatography.

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.

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.

Controlled and selective placement of boron subphthalocyanines on either chain end of polymers synthesized by nitroxide mediated polymerization

Directory of Open Access Journals (Sweden)

Benoît H. Lessard

2015-10-01

Full Text Available In previous studies, we synthesized the first organic light emitting diode (OLED using boron subphthalocyanines (BsubPcs based polymers. When designing new polymer materials for organic electronic applications such as OLEDs or organic photovoltaic (OPV devices it is important to consider not only the contribution of each monomer but also the polymer chain ends. In this paper we establish a post-polymerization strategy to couple BsubPcs onto either the α- or the ω-chain end using chemically selective BsubPc derivatives. We outline how the chain ends of two representative polymers, poly(styrene (PS and poly(n-butylacrylate (BA, synthesized by nitroxide mediated polymerization (NMP, using BlocBuilder-MA as the initiating species, can be chemically modified by the incorporation of BsubPc chromophores. The addition of the BsubPc chromophore was confirmed through the use of a photodiode array detector (PDA connected in-line with a gel permeation chromatography (GPC setup. These findings represent the first reported method for the controlled and selective placement of a BsubPc chromophores on either end of a polymer produced by NMP. This strategy will therefore be utilized to make next generation BsubPc polymers for OLEDs and OPV devices. The extremely high molar extinction coefficient of BsubPc also make these polymers ideally suited for dye-labelling of polymers.

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.

A model for the chain-to-plane charge transfer in YBa2Cu3O6+x

International Nuclear Information System (INIS)

Matic, V. M.; Lazarov, N. Dj.; Milic, M.

2012-01-01

A model for the chain-to-plane charge transfer is proposed to account for the two plateaus, at 60 K and at 90 K, of the T c (x) characteristics of the YBa 2 Cu 3 O 6+x high-T c superconductor. It is assumed that the number of holes transferred from a CuO chain of length l to two nearby CuO 2 sheets is proportional to l (that is, to the number of oxygen atoms in the chain), if the chain length is greater than, or equal to, a certain critical chain length, l cr , that is required to trigger the charge transfer process. No holes are assumed to have been transferred from chains of length l cr . The calculated T c (x) dependence is found to be in excellent agreement with the experimentally reported T c (x). The critical chain length parameter is estimated to be equal to l cr = 11 (eleven oxygen atoms in a chain), which is a greater value than that obtained in the previously proposed model for the chain-to-plane charge transfer (l cr = 4). The results obtained out of the proposed model are briefly discussed

Kinetics and Mechanism of the Polymerization of Methyl Methacrylate in a Y(acac)3/n-BuMgCl System

Institute of Scientific and Technical Information of China (English)

无

2000-01-01

Based on the kinetics equation proposed by T. Kagiya, the kinetic study on the polymerization of methyl methacrylate(MMA) by Y(acac)3/n-BuMgCl was carried out with a dilatometer. It was found that the rate of propagation is the first order with respect to the concentration of both active center and monomer. Thus, the equation of propagation rate can be described as Rp=Kp[c*][M]. In addition, the instantaneous chain initiation and single molecular termination were concluded for the present system. The activation energy is close to 32 kJ/mol. In the polymerization, n-BuMgCl acts not only as the cocatalyst, but also as chain transfer agent with cI=3.6×10-4.

Preparations of spherical polymeric particles from Tanzanian ...

African Journals Online (AJOL)

Spherical Polymeric Particles (SPP) have been prepared from Tanzanian Cashew Nut Shell Liquid (CNSL) by suspension polymerization technique involving either step-growth or chain- growth polymerization mechanisms. The sizes of the SPP, which ranged from 0.1 to 2.0 mm were strongly influenced by the amounts of ...

Chain chemical reactions during matrix devitrification

International Nuclear Information System (INIS)

Barkalov, I.M.

1980-01-01

Investigation results of chain reaction mechanisms, proceeding at devitrification of glass-like matrices under the effect of γ-irradiation are summarized. Peculiarities of kinetics and mechanism of chain reactions proceeding at devitrification are considered: hydrocarbon chlorination, polymerization of vinyl monomers, copolymerization and graft polymerization. Possible application aspects of the chain reaction conducting during matrix devitrification are also considered

Quantum state transfer in spin chains with q-deformed interaction terms

International Nuclear Information System (INIS)

Jafarov, E I; Van der Jeugt, J

2010-01-01

We study the time evolution of a single spin excitation state in certain linear spin chains, as a model for quantum communication. Some years ago it was discovered that when the spin chain data (the nearest-neighbour interaction strengths and the magnetic field strengths) are related to the Jacobi matrix entries of Krawtchouk polynomials or dual Hahn polynomials the so-called perfect state transfer takes place. The extension of these ideas to other types of discrete orthogonal polynomials did not lead to new models with perfect state transfer, but did allow more insight in the general computation of the correlation function. In this paper, we extend the study to discrete orthogonal polynomials of q-hypergeometric type. A remarkable result is a new analytic model where perfect state transfer is achieved: this is when the spin chain data are related to the Jacobi matrix of q-Krawtchouk polynomials. The other cases studied here (affine q-Krawtchouk polynomials, quantum q-Krawtchouk polynomials, dual q-Krawtchouk polynomials, q-Hahn polynomials, dual q-Hahn polynomials and q-Racah polynomials) do not give rise to models with perfect state transfer. However, the computation of the correlation function itself is quite interesting, leading to advanced q-series manipulations.

Multinational firms, global value chains and the organization of technology transfer

OpenAIRE

Federica Saliola; Antonello Zanfei

2007-01-01

This paper combines insights from different streams of literature to develop a more comprehensive framework for the analysis of technology transfer via value chain relationships. We integrate the existing literature in three ways. First, we consider value chain relationships as a multi-facet process of interaction between buyers and suppliers, involving different degrees of knowledge transmission and development. Second, we assess whether and to what extent value chain relationships are assoc...

Multinational Firms, Global Value Chains and the Organization of Knowledge Transfer

OpenAIRE

Saliola, Federica; Zanfei, Antonello

2009-01-01

This paper combines insights from different streams of literature to develop a more comprehensive framework for the analysis of knowledge transfer via value chain relationships. We integrate the existing literature in three ways. First, we consider value chain relationships as a multi-facet process of interaction between buyers and suppliers, involving different modes of knowledge transmission and development. Second, we assess whether and to what extent value chain relationships are associat...

Polymer@gold Nanoparticles Prepared via RAFT Polymerization for Opto-Biodetection

Directory of Open Access Journals (Sweden)

Sónia O. Pereira

2018-02-01

Full Text Available Colloidal gold nanoparticles (Au NPs have been used in several biological applications, which include the exploitation of size- and shape-dependent Localized Surface Plasmon Resonance (LSPR in biosensing devices. In order to obtain functional and stable Au NPs in a physiological medium, surface modification and functionalization are crucial steps in these endeavors. Reversible addition-fragmentation chain transfer (RAFT polymerization meets this need offering the possibility of control over the composition and architecture of polymeric shells coating Au NPs. Furthermore, playing with a careful choice of monomers, RAFT polymerization allows the possibility to design a polymer shell with the desired functional groups aiming at Au based nanocomposites suitable for biorecognition and biotargeting. This review provides important aspects concerning the synthesis and optical properties of Au NPs as well as concepts of RAFT polymerization. Understanding these concepts is crucial to appreciate the chemical strategies available towards RAFT-polymer coated Au core-shell nanostructures, which are here reviewed. Finally, examples of applications in opto-biodetection devices are provided and the potential of responsive “smart” nanomaterials based on such structures can be applied to other biological applications.

Electrophoresis- and FRET-Based Measures of Serpin Polymerization.

Science.gov (United States)

Faull, Sarah V; Brown, Anwen E; Haq, Imran; Irving, James A

2017-01-01

Many serpinopathies, including alpha-1 antitrypsin (A1AT) deficiency, are associated with the formation of unbranched polymer chains of mutant serpins. In vivo, this deficiency is the result of mutations that cause kinetic or thermodynamic destabilization of the molecule. However, polymerization can also be induced in vitro from mutant or wild-type serpins under destabilizing conditions. The characteristics of the resulting polymers are dependent upon induction conditions. Due to their relationship to disease, serpin polymers, mainly those formed from A1AT, have been widely studied. Here, we describe Förster resonance energy transfer (FRET) and gel-based approaches for their characterization.

Innovation and technology transfer through global value chains: Evidence from China's PV industry

International Nuclear Information System (INIS)

Zhang, Fang; Gallagher, Kelly Sims

2016-01-01

China's success as a rapid innovation follower in the infant Photovoltaic (PV) industry surprised many observers. This paper explores how China inserted itself into global clean energy innovation systems by examining the case of the solar PV industry. The paper decomposes the global PV industrial value chain, and determines the main factors shaping PV technology transfer and diffusion. Chinese firms first entered PV module manufacturing through technology acquisition, and then gradually built their global competitiveness by utilizing a vertical integration strategy within segments of the industry as well as the broader PV value chain. The main drivers for PV technology transfer from the global innovation system to China are global market formation policy, international mobilization of talent, the flexibility of manufacturing in China, and belated policy incentives from China's government. The development trajectory of the PV industry in China indicates that innovation in cleaner energy technologies can occur through both global and national innovation processes, and knowledge exchange along the global PV value chain. - Highlights: •The value chain analytical approach is synergized with the theories of technology transfer and innovation systems. •A detailed review of how China integrated itself into the global solar PV innovation system is provided. •Four main factors shape PV technology transfer to China across various value chain segments. •Innovation in cleaner energy technologies is a combination of global and national innovation processes.

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

Energy Technology Data Exchange (ETDEWEB)

Tanaka, Hidenori; Iwasaki, Isao; Kunai, Yuichiro [Research Reactor Institute, Kyoto University, Asashironishi 2-1010, Kumatori-cho, Sennan-gun, Osaka 590-0494 (Japan); Sato, Nobuhiro, E-mail: sato-n@rri.kyoto-u.ac.j [Research Reactor Institute, Kyoto University, Asashironishi 2-1010, Kumatori-cho, Sennan-gun, Osaka 590-0494 (Japan); Matsuyama, Tomochika [Research Reactor Institute, Kyoto University, Asashironishi 2-1010, Kumatori-cho, Sennan-gun, Osaka 590-0494 (Japan)

2011-08-15

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

Bioaccumulation and food chain transfer of corrosion products from radioactive stainless steel

International Nuclear Information System (INIS)

Young, J.S.

1986-07-01

Two sets of experiments were conducted to determine if corrosion products from radioactive Type 347 stainless steel could be biologically transferred from sediment through a marine food chain, and whether corrosion products dissolved in seawater could be bioaccumulated and then eliminated. Corrosion products containing 60 Co and 63 Ni from the radioactive stainless steel were introduced into marine sediments. Infaunal polychaete worms exposed to these sediments bioaccumulated the radionuclides. The feeding of these worms to shrimp and fish resulted in a trophic transfer of the radioactive products across a one-step food chain. The magnitude of the transfers are described in terms of transfer factors. Dissolved corrosion products as measured by the radionuclides were also bioaccumulated by shrimp and fish concentrating more than fish. Concentration factors were calculated

Simulation of radionuclide transfer in agricultural food chains

International Nuclear Information System (INIS)

Matthies, M.; Eisfeld, K.; Mueller, H.; Paretzke, H.G.; Proehl, G.; Wirth, E.

1982-12-01

Radioactive releases from nuclear facilities could pose longterm potential hazards to man if radionuclides enter food chains leading to man. The aim of the study was to develop radioecological and dosimetric models for the assessments of the activity intake by man via ingestion and the resulting radiation exposure for members of the population, in particular after accidental releases from fuel reprocessing plants and related installations. A dynamic compartment model for the transfer of radionuclides through agricultural food chains has been developed. Special emphasis is given to the time dependence and the biological and site specific variability of the various transfer and accumulation processes. Agricultural practices representative for Western Europe have been taken into consideration for food production (grain, potatoes, vegetables, beef and pork, milk). For the most relevant long-lived radionuclides a short-term initial deposition of 1 Ci/km 2 on agricultural areas at different months has been assumed and the time dependent transport through various food chains has been assessed. As a main result great differences have been calculated for the various months of releases because of plant foliar uptake and translocation into edible parts of the plants during the vegetation cycle. The potential activity intake over 50 years for the various nuclides and the resulting radiation exposure is dominated by the first two years after the release if no food restrictions are assumed. (orig./MG) [de

Proton-transfer lasers based on solid copolymers of modified 2-(2'-hydroxyphenyl)benzimidazoles with methacrylate monomers

Science.gov (United States)

Costela, A.; García-Moreno, I.; Mallavia, Ricardo; Amat-Guerri, F.; Barroso, J.; Sastre, R.

1998-06-01

We report on the lasing action of two newly synthesized 2-(2'-hydroxyphenyl) benzimidazole derivatives copolymerized with methyl methacrylate. The laser samples were transversely pumped with a N 2 laser at 337 nm. The influence on the proton-transfer laser performance of the distance between the chromophore group and the polymeric main chain and of the rigidity of the polymeric host matrix, were studied. Significant increases in lasing efficiency and photostability are demonstrated for some of the new materials, as compared to those previously obtained with related proton-transfer dyes also covalently bound to methacrylic monomers.

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

Directory of Open Access Journals (Sweden)

Vikas Mittal

2010-05-01

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

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.

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.

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.

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

International Nuclear Information System (INIS)

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

1982-01-01

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

Complexity in modeling of residual stresses and strains during polymerization of bone cement: effects of conversion, constraint, heat transfer, and viscoelastic property changes.

Science.gov (United States)

Gilbert, Jeremy L

2006-12-15

Aseptic loosening of cemented joint prostheses remains a significant concern in orthopedic biomaterials. One possible contributor to cement loosening is the development of porosity, residual stresses, and local fracture of the cement that may arise from the in-situ polymerization of the cement. In-situ polymerization of acrylic bone cement is a complex set of interacting processes that involve polymerization reactions, heat generation and transfer, full or partial mechanical constraint, evolution of conversion- and temperature-dependent viscoelastic material properties, and thermal and conversion-driven changes in the density of the cement. Interactions between heat transfer and polymerization can lead to polymerization fronts moving through the material. Density changes during polymerization can, in the presence of mechanical constraint, lead to the development of locally high residual strain energy and residual stresses. This study models the interactions during bone cement polymerization and determines how residual stresses develop in cement and incorporates temperature and conversion-dependent viscoelastic behavior. The results show that the presence of polymerization fronts in bone cement result in locally high residual strain energies. A novel heredity integral approach is presented to track residual stresses incorporating conversion and temperature dependent material property changes. Finally, the relative contribution of thermal- and conversion-dependent strains to residual stresses is evaluated and it is found that the conversion-based strains are the major contributor to the overall behavior. This framework provides the basis for understanding the complex development of residual stresses and can be used as the basis for developing more complex models of cement behavior.

Fabrication of luminescent hydroxyapatite nanorods through surface-initiated RAFT polymerization: Characterization, biological imaging and drug delivery applications

Energy Technology Data Exchange (ETDEWEB)

Heng, Chunning [Shaanxi Key Laboratory of Degradable Biomedical Materials, Shaanxi R& D Center of Biomaterials and Fermentation Engineering, School of Chemical and Engineering, Northwest University, Xi’an, 710069 (China); Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Zheng, Xiaoyan [Shaanxi Key Laboratory of Degradable Biomedical Materials, Shaanxi R& D Center of Biomaterials and Fermentation Engineering, School of Chemical and Engineering, Northwest University, Xi’an, 710069 (China); Liu, Meiying; Xu, Dazhuang; Huang, Hongye; Deng, Fengjie [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Hui, Junfeng, E-mail: huijunfeng@126.com [Shaanxi Key Laboratory of Degradable Biomedical Materials, Shaanxi R& D Center of Biomaterials and Fermentation Engineering, School of Chemical and Engineering, Northwest University, Xi’an, 710069 (China); 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)

2016-11-15

Highlights: • Hydrophobic hydroxyapatite nanorods were obtained from hydrothermal synthesis. • Surface initiated RAFT polymerization was adopted to surface modification of hydroxyapatite nanorods. • These modified hydroxyapatite nanorods showed high water dispersibility and biocompatibility. • These modified hydroxyapatite nanorods can be used for controlled drug delivery. - Abstract: Hydroxyapatite nanomaterials as an important class of nanomaterials, have been widely applied for different biomedical applications for their excellent biocompatibility, biodegradation potential and low cost. In this work, hydroxyapatite nanorods with uniform size and morphology were prepared through hydrothermal synthesis. The surfaces of these hydroxyapatite nanorods are covered with hydrophobic oleic acid, making them poor dispersibility in aqueous solution and difficult for biomedical applications. To overcome this issue, a simple surface initiated polymerization strategy has been developed via combination of the surface ligand exchange and reversible addition fragmentation chain transfer (RAFT) polymerization. Hydroxyapatite nanorods were first modified with Riboflavin-5-phosphate sodium (RPSSD) via ligand exchange reaction between the phosphate group of RPSSD and oleic acid. Then hydroxyl group of nHAp-RPSSD was used to immobilize chain transfer agent, which was used as the initiator for surface-initiated RAFT polymerization. The nHAp-RPSSD-poly(IA-PEGMA) nanocomposites were characterized by means of {sup 1}H nuclear magnetic resonance, Fourier transform infrared spectroscopy, fluorescence spectroscopy and thermal gravimetric analysis in detailed. The biocompatibility, biological imaging and drug delivery of nHAp-RPSSD-poly(IA-PEGMA) were also investigated. Results showed that nHAp-RPSSD-poly(IA-PEGMA) exhibited excellent water dispersibility, desirable optical properties, good biocompatibility and high drug loading capability, making them promising candidates for

Fabrication of luminescent hydroxyapatite nanorods through surface-initiated RAFT polymerization: Characterization, biological imaging and drug delivery applications

International Nuclear Information System (INIS)

Heng, Chunning; Zheng, Xiaoyan; Liu, Meiying; Xu, Dazhuang; Huang, Hongye; Deng, Fengjie; Hui, Junfeng; Zhang, Xiaoyong; Wei, Yen

2016-01-01

Highlights: • Hydrophobic hydroxyapatite nanorods were obtained from hydrothermal synthesis. • Surface initiated RAFT polymerization was adopted to surface modification of hydroxyapatite nanorods. • These modified hydroxyapatite nanorods showed high water dispersibility and biocompatibility. • These modified hydroxyapatite nanorods can be used for controlled drug delivery. - Abstract: Hydroxyapatite nanomaterials as an important class of nanomaterials, have been widely applied for different biomedical applications for their excellent biocompatibility, biodegradation potential and low cost. In this work, hydroxyapatite nanorods with uniform size and morphology were prepared through hydrothermal synthesis. The surfaces of these hydroxyapatite nanorods are covered with hydrophobic oleic acid, making them poor dispersibility in aqueous solution and difficult for biomedical applications. To overcome this issue, a simple surface initiated polymerization strategy has been developed via combination of the surface ligand exchange and reversible addition fragmentation chain transfer (RAFT) polymerization. Hydroxyapatite nanorods were first modified with Riboflavin-5-phosphate sodium (RPSSD) via ligand exchange reaction between the phosphate group of RPSSD and oleic acid. Then hydroxyl group of nHAp-RPSSD was used to immobilize chain transfer agent, which was used as the initiator for surface-initiated RAFT polymerization. The nHAp-RPSSD-poly(IA-PEGMA) nanocomposites were characterized by means of "1H nuclear magnetic resonance, Fourier transform infrared spectroscopy, fluorescence spectroscopy and thermal gravimetric analysis in detailed. The biocompatibility, biological imaging and drug delivery of nHAp-RPSSD-poly(IA-PEGMA) were also investigated. Results showed that nHAp-RPSSD-poly(IA-PEGMA) exhibited excellent water dispersibility, desirable optical properties, good biocompatibility and high drug loading capability, making them promising candidates for biological

A phenomenological approach of solidification of polymeric phase change materials

Science.gov (United States)

Bahrani, Seyed Amir; Royon, Laurent; Abou, Bérengère; Osipian, Rémy; Azzouz, Kamel; Bontemps, André

2017-01-01

Phase Change Materials (PCMs) are widely used in thermal energy storage and thermal management systems due to their small volume for a given stored energy and their capability for maintaining nearly constant temperatures. However, their performance is limited by their low thermal conductivity and possible leaks while in the liquid phase. One solution is to imprison the PCM inside a polymer mesh to create a Polymeric Phase Change Material (PPCM). In this work, we have studied the cooling and solidification of five PPCMs with different PCMs and polymer fractions. To understand the heat transfer mechanisms involved, we have carried out micro- and macrorheological measurements in which Brownian motion of tracers embedded in PPCMs has been depicted and viscoelastic moduli have been measured, respectively. Beyond a given polymer concentration, it was shown that the Brownian motion of the tracers is limited by the polymeric chains and that the material exhibits an elastic behavior. This would suggest that heat transfer essentially occurs by conduction, instead of convection. Experiments were conducted to measure temperature variation during cooling of the five samples, and a semi-empirical model based on a phenomenological approach was proposed as a practical tool to choose and size PPCMs.

Extended linear chain compounds

CERN Document Server

Linear chain substances span a large cross section of contemporary chemistry ranging from covalent polymers, to organic charge transfer com­ plexes to nonstoichiometric transition metal coordination complexes. Their commonality, which coalesced intense interest in the theoretical and exper­ imental solid state physics/chemistry communities, was based on the obser­ vation that these inorganic and organic polymeric substrates exhibit striking metal-like electrical and optical properties. Exploitation and extension of these systems has led to the systematic study of both the chemistry and physics of highly and poorly conducting linear chain substances. To gain a salient understanding of these complex materials rich in anomalous aniso­ tropic electrical, optical, magnetic, and mechanical properties, the conver­ gence of diverse skills and talents was required. The constructive blending of traditionally segregated disciplines such as synthetic and physical organic, inorganic, and polymer chemistry, crystallog...

Novel Tertiary Amino Containing Blinding Composite Membranes via Raft Polymerization and Their Preliminary CO2 Permeation Performance.

Science.gov (United States)

Zhu, Lifang; Zhou, Mali; Yang, Shanshan; Shen, Jiangnan

2015-04-23

Facile synthesis of poly (N,N-dimethylaminoethyl methacrylate) (PDMAEMA) star polymers on the basis of the prepolymer chains, PDMAEMA as the macro chain transfer agent and divinyl benzene (DVB) as the cross-linking reagent by reversible addition-fragmentation chain transfer (RAFT) polymerization was described. The RAFT polymerizations of DMAEMA at 70 °C using four RAFT agents with different R and Z group were investigated. The RAFT agents used in these polymerizations were dibenzyl trithiocarbonate (DBTTC), s-1-dodecyl-s'-(α,α'-dimethyl-α-acetic acid) trithiocarbonate (MTTCD), s,s'-bis (2-hydroxyethyl-2'-dimethylacrylate) trithiocarbonate (BDATC) and s-(2-cyanoprop-2-yl)-s-dodecyltrithiocarbonate (CPTCD). The results indicated that the structure of the end-group of RAFT agents had significant effects on the ability to control polymerization. Compared with the above-mentioned RAFT agents, CPTCD provides better control over the molecular weight and molecular weight distribution. The polydispersity index (PDI) was determined to be within the scope of 1.26 to 1.36. The yields, molecular weight, and distribution of the star polymers can be tuned by changing the molar ratio of DVB/PDMAEMA-CPTCD. The chemical composition and structure of the linear and star polymers were characterized by GPC, FTIR, 1H NMR, XRD analysis. For the pure Chitosan membrane, a great improvement was observed for both CO₂ permeation rate and ideal selectivity of the blending composite membrane upon increasing the content of SPDMAEMA-8. At a feed gas pressure of 37.5 cmHg and 30 °C, the blinding composite membrane (Cs: SPDMAEMA-8 = 4:4) has a CO₂ permeation rate of 8.54 × 10⁻⁴ cm³ (STP) cm⁻²∙s⁻¹∙cm∙Hg⁻¹ and a N₂ permeation rate of 6.76 × 10⁻⁵ cm³ (STP) cm⁻²∙s⁻¹∙cm∙Hg⁻¹, and an ideal CO₂/N₂ selectivity of 35.2.

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...

Dynamic modeling system for the transfer of radioactivity in terrestrial food chains

International Nuclear Information System (INIS)

Simmonds, J.R.; Linsley, G.S.

1981-01-01

A dynamic modeling system is described for the transfer of radionuclides in terrestrial food chains. The main features of the system are its ability to predict the time dependence of the major transfer processes and its flexibility and applicability to a range of contamination scenarios. The modeling system is regarded as a basic framework on which more realistic models can be based, given the availability of reliable environmental transfer data. An example of such a development is included for 90 Sr in the pasture-cow-milk pathway. The model predicts annual average concentrations of 90 Sr in milk caused by fallout in the United Kingdom to within 15% of measured values for over most of the 20-y period for which data exist. It makes possible the evaluation of the time dependence of the contributions of various transfer processes. Following acute releases to the atmosphere or releases in any other contamination scenario where direct deposition is absent, certain pathways often not considered in food-chain models, such as the external contamination of plants caused by resuspension processes or the ingestion of contaminants together with soil by grazing animals, are shown to be potentially important in the transfer of activity to man. The main application of dynamic food-chain models is the prediction of the consequences of accidental releases to the terrestrial environment. The predictions can be used in planning countermeasures and in assessing the health, economic, and social impacts of accidental release

A general model for the transfer of radioactive materials in terrestrial food chains

International Nuclear Information System (INIS)

Simmonds, J.R.; Linsley, G.S.; Jones, J.A.

1979-09-01

A general methodology for modelling the transfer of radionuclides in the food chains to man is described. The models are dynamic in nature so that the long-term time dependence of processes in environmental materials can be represented, for example, the build-up of activity concentrations in soils during continuous deposition from atmosphere. Modules for radionuclide migration are described in well-mixed (cultivated) soil and undisturbed soil (pasture). The methods by which the transfer coefficients used in plant and animal modules are derived are also given. The foodstuffs considered are those derived from green vegetables, grain, and root vegetables together with meat and liver products from the cow and sheep and cow dairy products. The dynamic model permits the time dependence of food chain transfer processes to be represented for different land contamination scenarios; in particular, the model can be adapted to represent behaviour following a single deposit. Using the sensitivity of results to the variation of transfer parameters the model can be used to determine the parts of the food chain where improved data would be most effective in increasing the reliability of radiological assessments; a worked example is given. (author)

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

Energy Technology Data Exchange (ETDEWEB)

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

2010-08-31

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

Theoretical study of chain transfer to solvent reactions of alkyl acrylates.

Science.gov (United States)

Moghadam, Nazanin; Srinivasan, Sriraj; Grady, Michael C; Rappe, Andrew M; Soroush, Masoud

2014-07-24

This computational and theoretical study deals with chain transfer to solvent (CTS) reactions of methyl acrylate (MA), ethyl acrylate (EA), and n-butyl acrylate (n-BA) self-initiated homopolymerization in solvents such as butanol (polar, protic), methyl ethyl ketone (MEK) (polar, aprotic), and p-xylene (nonpolar). The results indicate that abstraction of a hydrogen atom from the methylene group next to the oxygen atom in n-butanol, from the methylene group in MEK, and from a methyl group in p-xylene by a live polymer chain are the most likely mechanisms of CTS reactions in MA, EA, and n-BA. Energy barriers and molecular geometries of reactants, products, and transition states are predicted. The sensitivity of the predictions to three hybrid functionals (B3LYP, X3LYP, and M06-2X) and three different basis sets (6-31G(d,p), 6-311G(d), and 6-311G(d,p)) is investigated. Among n-butanol, sec-butanol, and tert-butanol, tert-butanol has the highest CTS energy barrier and the lowest rate constant. Although the application of the conductor-like screening model (COSMO) does not affect the predicted CTS kinetic parameter values, the application of the polarizable continuum model (PCM) results in higher CTS energy barriers. This increase in the predicted CTS energy barriers is larger for butanol and MEK than for p-xylene. The higher rate constants of chain transfer to n-butanol reactions compared to those of chain transfer to MEK and p-xylene reactions suggest the higher CTS reactivity of n-butanol.

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

DEFF Research Database (Denmark)

Hvilsted, Søren

2014-01-01

The versatility of the atom transfer radical polymerization (ATRP) of pentafluorostyrene (FS) is comprehensively evaluated. The ATRP of a wide range of monomers derived from FS is likewise discussed with emphasis on the potential polymer applications. A large number of block and star copolymers...... centred around polypentafluorostyrene (PFS) and prepared primarily using the bromomacroinitiator concept is surveyed. Here the main emphasis is on the feasibility of the polymer design, but also the very many different applications are highlighted. The potential grafting onto PFS and PFS block copolymers...... 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...

Efficient sampling of reversible cross-linking polymers: Self-assembly of single-chain polymeric nanoparticles

Science.gov (United States)

Oyarzún, Bernardo; Mognetti, Bortolo Matteo

2018-03-01

We present a new simulation technique to study systems of polymers functionalized by reactive sites that bind/unbind forming reversible linkages. Functionalized polymers feature self-assembly and responsive properties that are unmatched by the systems lacking selective interactions. The scales at which the functional properties of these materials emerge are difficult to model, especially in the reversible regime where such properties result from many binding/unbinding events. This difficulty is related to large entropic barriers associated with the formation of intra-molecular loops. In this work, we present a simulation scheme that sidesteps configurational costs by dedicated Monte Carlo moves capable of binding/unbinding reactive sites in a single step. Cross-linking reactions are implemented by trial moves that reconstruct chain sections attempting, at the same time, a dimerization reaction between pairs of reactive sites. The model is parametrized by the reaction equilibrium constant of the reactive species free in solution. This quantity can be obtained by means of experiments or atomistic/quantum simulations. We use the proposed methodology to study the self-assembly of single-chain polymeric nanoparticles, starting from flexible precursors carrying regularly or randomly distributed reactive sites. We focus on understanding differences in the morphology of chain nanoparticles when linkages are reversible as compared to the well-studied case of irreversible reactions. Intriguingly, we find that the size of regularly functionalized chains, in good solvent conditions, is non-monotonous as a function of the degree of functionalization. We clarify how this result follows from excluded volume interactions and is peculiar of reversible linkages and regular functionalizations.

Analysis of the polymerization initiation and activity of Pasteurella multocida heparosan synthase PmHS2, an enzyme with glycosyltransferase and UDP-sugar hydrolase activity

NARCIS (Netherlands)

Chavaroche, A.A.E.; Broek, van den L.A.M.; Springer, J.; Boeriu, C.; Eggink, G.

2011-01-01

Heparosan synthase catalyzes the polymerization of heparosan [-4GlcUAß1-4GlcNAca1-]n by transferring alternatively the monosaccharide units from UDP-GlcUA and UDP-GlcNAc to an acceptor molecule. Details on the heparosan chain initiation by Pasteurella multocida heparosan synthase PmHS2 and its

SAN-b-P4VP block copolymer synthesis by chain extension from RAFT-functional poly(4-vinylpyridine) in solution and in emulsion

NARCIS (Netherlands)

Bozovic, J.S.; Tello Manon, H.M; Meuldijk, J.; Koning, C.E.; Klumperman, B.

2007-01-01

Reversible addition fragmentation chain transfer (RAFT)-mediated polymerization was successfully applied for the synthesis of poly(4-vinylpyridine) (P4VP) polymers of predetermined molar mass and of low polydispersity index. These RAFT end-functionalized polymers were then used as macro-RAFT agents

Poly(n-isopropylacrylamide)-based hydrogel coatings on magnetite nanoparticles via atom transfer radical polymerization

Energy Technology Data Exchange (ETDEWEB)

Frimpong, Reynolds A; Hilt, J Zach [Department of Chemical and Materials Engineering, University of Kentucky, Lexington, KY 40506 (United States)], E-mail: hilt@engr.uky.edu

2008-04-30

Core magnetite (Fe{sub 3}O{sub 4}) nanoparticles have been functionalized with a model intelligent hydrogel system based on the temperature responsive polymer poly(n-isopropyl acrylamide) (PNIPAAm) to obtain magnetically responsive core-shell nanocomposites. Fe{sub 3}O{sub 4} nanoparticles were obtained from a one-pot co-precipitation method which provided either oleic acid (hydrophobic) or citric acid (hydrophilic) coated nanoparticles. Subsequent ligand exchange of these coatings with various bromine alkyl halides and a bromo silane provided initiating sites for functionalization with NIPAAm using atom transfer radical polymerization (ATRP). The bromine alkyl halides that were used were 2-bromo-2-methyl propionic acid (BMPA) and 2-bromopropionyl bromide (BPB). The bromo silane that was used was 3-bromopropyl trimethoxysilane (BPTS). The intelligent polymeric shell consists of NIPAAm crosslinked with poly(ethylene glycol) 400 dimethacrylate (PEG400DMA). Fourier transform infrared (FTIR) spectroscopy, thermogravimetric analysis (TGA), and transmission electron microscopy (TEM) were used to confirm the presence of the polymeric shell. Dynamic light scattering (DLS) was used to characterize the nanocomposites for particle size changes with temperature. Their magnetic and temperature responsiveness show great promise for further biomedical applications. This platform for functionalizing magnetic nanoparticles with intelligent hydrogels promises to impact a wide range of medical and biological applications of magnetic nanoparticles.

Poly(n-isopropylacrylamide)-based hydrogel coatings on magnetite nanoparticles via atom transfer radical polymerization

International Nuclear Information System (INIS)

Frimpong, Reynolds A; Hilt, J Zach

2008-01-01

Core magnetite (Fe 3 O 4 ) nanoparticles have been functionalized with a model intelligent hydrogel system based on the temperature responsive polymer poly(n-isopropyl acrylamide) (PNIPAAm) to obtain magnetically responsive core-shell nanocomposites. Fe 3 O 4 nanoparticles were obtained from a one-pot co-precipitation method which provided either oleic acid (hydrophobic) or citric acid (hydrophilic) coated nanoparticles. Subsequent ligand exchange of these coatings with various bromine alkyl halides and a bromo silane provided initiating sites for functionalization with NIPAAm using atom transfer radical polymerization (ATRP). The bromine alkyl halides that were used were 2-bromo-2-methyl propionic acid (BMPA) and 2-bromopropionyl bromide (BPB). The bromo silane that was used was 3-bromopropyl trimethoxysilane (BPTS). The intelligent polymeric shell consists of NIPAAm crosslinked with poly(ethylene glycol) 400 dimethacrylate (PEG400DMA). Fourier transform infrared (FTIR) spectroscopy, thermogravimetric analysis (TGA), and transmission electron microscopy (TEM) were used to confirm the presence of the polymeric shell. Dynamic light scattering (DLS) was used to characterize the nanocomposites for particle size changes with temperature. Their magnetic and temperature responsiveness show great promise for further biomedical applications. This platform for functionalizing magnetic nanoparticles with intelligent hydrogels promises to impact a wide range of medical and biological applications of magnetic nanoparticles

Optimization of excitation transfer in a spin chain

International Nuclear Information System (INIS)

Gurman, Vladimir I.; Guseva, Irina S.; Fesko, Oles V.

2016-01-01

A revised formulation of the problem of fastest transfer of the excitation in a spin chain is considered on the base of Shrödinger equation which Hamiltonian depends linearly on control. It is taken into account that the excitation of the first or last spin means that it has greatest amplitude equal to the chain invariant whereas its phase is undefined and can be considered as an additional control variable. The role of this additional control is analyzed via transformation of the original problem with unbounded linear control to the regular derived problem known from the theory of degenerate problems [1, 2], in the same way as in [2]. The overall procedure is demonstrated in computational experiments with the use of visual examples.

Polonium (210Po) and lead (210Pb) in marine organisms and their transfer in marine food chains

International Nuclear Information System (INIS)

Carvalho, Fernando P.

2011-01-01

The determination of 210 Po and 210 Pb was performed in marine organisms from the seashore to abyssal depths, encompassing a plethora of species from the microscopic plankton to the sperm whale. Concentrations of those radionuclides ranged from low values of about 5 x 10 -1 Bq kg -1 (wet wt.) in jellyfish, to very high values of about of 3 x 10 4 Bq kg -1 (wet wt.) in the gut walls of sardines, with a common pattern of 210 Po > 210 Pb.These radionuclides are primarily absorbed from water and concentrated by phyto- and microzooplankton, and then are transferred to the next trophic level along marine food chains. Investigation in epipelagic, mesopelagic, bathypelagic and abyssobenthic organisms revealed that 210 Po is transferred in the marine food webs with transfer factors ranging from 0.1 to 0.7, and numerically similar to those of the energy transfer in the marine food chains. As 210 Po preferentially binds to amino acids and proteins, its transfer in food chains likely traces protein transfer and, thus, 210 Po transfer factors are similar to ecotrophic coefficients. 210 Pb is transferred less efficiently in marine food chains and this contributes to increased 210 Po: 210 Pb activity ratios in some trophic levels.

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.

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.

Antifouling coatings via plasma polymerization and atom transfer radical polymerization on thin film composite membranes for reverse osmosis

Science.gov (United States)

Hirsch, Ulrike; Ruehl, Marco; Teuscher, Nico; Heilmann, Andreas

2018-04-01

A major drawback to otherwise highly efficient membrane-based desalination techniques like reverse osmosis (RO) is the susceptibility of the membranes to biofouling. In this work, a combination of plasma activation, plasma bromination and surface-initiated atom transfer radical polymerization (si-ATRP) of hydrophilic and zwitterionic monomers, namely hydroxyethyl methacrylate (HEMA), 2-methacryloyloxyethyl phosphorylcholine (MPC) and [2-(methacryloyloxy)ethyl]-dimethyl-(3-sulfopropyl)ammonium hydroxide (SBMA), was applied to generate non-specific, anti-adhesive coatings on thin film composite (TFC) membranes. The antifouling effect of the coatings was shown by short-time batch as well as long-time steady state cultivation experiments with the microorganism Pseudomonas fluorescens. It could be shown that plasma functionalization and polymerization is possible on delicate thin film composite membranes without restricting their filtration performance. All modified membranes showed an increased resistance towards the adhesion of Pseudomonas fluorescens. On average, the biofilm coverage was reduced by 51.4-12.6% (for HEMA, SBMA, and MPC), the highest reduction was monitored for MPC with a biofilm reduction by 85.4%. The hydrophilic coatings applied did not only suppress the adhesion of Pseudomonas fluorescens, but also significantly increase the permeate flux of the membranes relative to uncoated membranes. The stability of the coatings was however not ideal and will have to be improved for future commercial use.

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

Directory of Open Access Journals (Sweden)

Bérangère Bailly

2006-01-01

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

RAFT Polymerization of Styrene and Maleimide in the Presence of Fluoroalcohol: Hydrogen Bonding Effects with Classical Alternating Copolymerization as Reference

Directory of Open Access Journals (Sweden)

Fangjun Yao

2017-03-01

Full Text Available The impacts of hydrogen bonding on polymerization behavior has been of interest for a long time; however, universality and in-depth understanding are still lacking. For the first time, the effect of hydrogen bonding on the classical alternating-type copolymerization of styrene and maleimide was explored. N-phenylmaleimide (N-PMI/styrene was chosen as a model monomer pair in the presence of hydrogen bonding donor solvent 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP, which interacted with N-PMI via hydrogen bonding. Reversible addition-fragmentation chain transfer polymerization (RAFT technique was used to guarantee the “living” polymerization and thus the homogeneity of chain compositions. In comparison with the polymerization in nonhydrogen bonding donor solvent (toluene, the copolymerization in HFIP exhibited a high rate and a slight deviation from alternating copolymerization tendency. The reactivity ratios of N-PMI and St were revealed to be 0.078 and 0.068, respectively, while the reactivity ratios in toluene were 0.026 and 0.050. These interesting results were reasonably explained by using computer simulations, wherein the steric repulsion and electron induction by the hydrogen bonding between HFIP and NPMI were revealed. This work first elucidated the hydrogen bonding interaction in the classical alternating-type copolymerization, which will enrich the research on hydrogen bonding-induced polymerizations.

Synthesis of Amphiphilic Copolymwers by Atom Transfer Radical Polymerization

DEFF Research Database (Denmark)

Hansen, Natanya Majbritt Louie

2007-01-01

Fluorerede polymerer besidder en række enestående egenskaber såsom god biokom-patibilitet og lav overfladeenergi såvel som god kemisk og termisk stabilitet. Målsæt-ningen for denne afhandling var at fremstille fluorerede polymerer og copolymerer, der potentielt kunne finde anvendelse som...... egenskaber der genfindes i homopolymerer af den dominerende monomer i copolymeren. Som indikation af de nye materialers mulige vekselvirkning med omgivelserne udførtes omfattende studier af kontaktvinkler. Film fremstillet af de fluorerede copolymerer og polymerer udviste øget hydrofobicitet (vandafvisning...

A theory for fracture of polymeric gels

Science.gov (United States)

Mao, Yunwei; Anand, Lallit

2018-06-01

A polymeric gel is a cross-linked polymer network swollen with a solvent. If the concentration of the solvent or the deformation is increased to substantial levels, especially in the presence of flaws, then the gel may rupture. Although various theoretical aspects of coupling of fluid permeation with large deformation of polymeric gels are reasonably well-understood and modeled in the literature, the understanding and modeling of the effects of fluid diffusion on the damage and fracture of polymeric gels is still in its infancy. In this paper we formulate a thermodynamically-consistent theory for fracture of polymeric gels - a theory which accounts for the coupled effects of fluid diffusion, large deformations, damage, and also the gradient effects of damage. The particular constitutive equations for fracture of a gel proposed in our paper, contain two essential new ingredients: (i) Our constitutive equation for the change in free energy of a polymer network accounts for not only changes in the entropy, but also changes in the internal energy due the stretching of the Kuhn segments of the polymer chains in the network. (ii) The damage and failure of the polymer network is taken to occur by chain-scission, a process which is driven by the changes in the internal energy of the stretched polymer chains in the network, and not directly by changes in the configurational entropy of the polymer chains. The theory developed in this paper is numerically implemented in an open-source finite element code MOOSE, by writing our own application. Using this simulation capability we report on our study of the fracture of a polymeric gel, and some interesting phenomena which show the importance of the diffusion of the fluid on fracture response of the gel are highlighted.

Iron halide mediated atom transfer radical polymerization of methyl methacrylate with N-Alkyl-2-pyridylmethanimine as the ligand

NARCIS (Netherlands)

Zhang, H.; Schubert, U.S.

2004-01-01

The controlled atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) catalyzed by iron halide/N-(n-hexyl)-2-pyridylmethanimine (NHPMI) is described. The ethyl 2-bromoisobutyrate (EBIB)-initiated ATRP with [MMA]0/[EBIB]0/[iron halide]0/[NHPMI]0 = 150/1/1/2 was better controlled in

Synthesis and characterization of associating polymers which contain siloxanes chains; Synthese et caracterisation de polymeres associatifs porteurs de groupes siloxanes

Energy Technology Data Exchange (ETDEWEB)

Meyer, V

1999-01-11

Polymers that associate via physical interactions in solutions have received much attention as viscosifiers. Such associating polymers are now used in variety of applications due to their unique theological properties coating, food thickeners, paints, enhanced oil recovery, water treatment). They contain a hydrophilic main chain with hydrophobic side chain that is generally constituted of hydrocarbon or fluorocarbon groups. Novel copolymers with sites of association in aqueous solution were prepared by co-polymerizing acrylamide with an hydrophobic monomer containing siloxane parts. Rheological properties were studied as a function of polymer concentration, microstructure, shear rate and frequency in order to show intra intermolecular associations between the hydrophobic parts. The polymer solution viscosity increases as a function of the hydrophobic group content. Tests of adsorption show a high affinity of these copolymers with clay and the amount absorbed increase with the quantity of hydrophobic entities containing in the chain. These properties are enhanced compared to copolymers containing hydrocarbon chains. (authors) 456 refs.

Metallocene-catalyzed ethylene−α-olefin isomeric copolymerization: A perspective from hydrodynamic boundary layer mass transfer and design of MAO anion

KAUST Repository

Adamu, Sagir

2015-11-28

This study reports a novel conceptual framework that can be easily experimented to evaluate the effects of hydrodynamic boundary layer mass transfer, methylaluminoxane (MAO) anion design, and comonomer steric hindrance on metallocene-catalyzed ethylene polymerization. This approach was illustrated by conducting homo- and isomeric copolymerization of ethylene with 1-hexene and 4-methyl-1-pentene in the presence of bis(n-butylcyclopentadienyl) zirconium dichloride (nBuCp)2ZrCl2, using (i) MAO anion 1 (unsupported [MAOCl2]−) and pseudo-homogeneous reference polymerization, and (ii) MAO anion 2 (supported Si−O−[MAOCl2]−) and in-situ heterogeneous polymerization. The measured polymer morphology, catalyst productivity, molecular weight distribution, and inter-chain composition distribution were related to the locus of polymerization, comonomer effect, in-situ chain transfer process, and micromixing effect, respectively. The peak melting and crystallization temperatures and %crystallinity were mathematically correlated to the parameters of microstructural composition distributions, melt fractionation temperatures, and average lamellar thickness. These relations showed to be insightful. The comonomer-induced enchainment defects and the eventual partial disruption of the crystal lattice were successfully modeled using Flory and Gibbs–Thompson equations. The present methodology can also be applied to study ethylene−α-olefin copolymerization, performed using MAO-activated non-metallocene precatalysts.

Polonium (210Po) and lead (210Pb) in marine organisms and their transfer in marine food chains.

Science.gov (United States)

Carvalho, Fernando P

2011-05-01

The determination of (210)Po and (210)Pb was performed in marine organisms from the seashore to abyssal depths, encompassing a plethora of species from the microscopic plankton to the sperm whale. Concentrations of those radionuclides ranged from low values of about 5 × 10(-1) Bq kg(-1) (wet wt.) in jellyfish, to very high values of about of 3 × 10(4) Bq kg(-1) (wet wt.) in the gut walls of sardines, with a common pattern of (210)Po > (210)Pb.These radionuclides are primarily absorbed from water and concentrated by phyto- and microzooplankton, and then are transferred to the next trophic level along marine food chains. Investigation in epipelagic, mesopelagic, bathypelagic and abyssobenthic organisms revealed that (210)Po is transferred in the marine food webs with transfer factors ranging from 0.1 to 0.7, and numerically similar to those of the energy transfer in the marine food chains. As (210)Po preferentially binds to amino acids and proteins, its transfer in food chains likely traces protein transfer and, thus, (210)Po transfer factors are similar to ecotrophic coefficients. (210)Pb is transferred less efficiently in marine food chains and this contributes to increased (210)Po:(210)Pb activity ratios in some trophic levels. Copyright © 2010 Elsevier Ltd. All rights reserved.

Stability of guest molecules in urea canal complexes by canal polymerization

International Nuclear Information System (INIS)

Yoshii, Fumio; Makuuchi, Keizo

1995-01-01

It was found that various organic materials are attracted into urea canal by hexanediol diacrylate (HDDA) and long chain compounds. This means that materials which does not form complex by itself are induced in canal by HDDA and long chain compounds. To include with stability perfumes, insecticides, attractants and repellents in urea canal, leaf alcohol was used as a model compound for guest molecules in the canal. The leaf alcohol from the canal released gradually over many days and the release was inhibited for 15 days by long chain compounds and for 30 days by polymerized HDDA after irradiation. After releasing, the leaf alcohol in the canal remained 25 % stable for long chain compounds and 40 % for polymerized HDDA. The dose required for stabilization of leaf alcohol in the urea canal by canal polymerization of HDDA was 30 kGy. (author)

Tunable self-assembled spin chains of strongly interacting cold atoms for demonstration of reliable quantum state transfer

DEFF Research Database (Denmark)

Loft, N. J. S.; Marchukov, O. V.; Petrosyan, D.

2016-01-01

We have developed an efficient computational method to treat long, one-dimensional systems of strongly-interacting atoms forming self-assembled spin chains. Such systems can be used to realize many spin chain model Hamiltonians tunable by the external confining potential. As a concrete...... demonstration, we consider quantum state transfer in a Heisenberg spin chain and we show how to determine the confining potential in order to obtain nearly-perfect state transfer....

Influence of dispersants on trophic transfer of petroleum hydrocarbons in a marine food chain

International Nuclear Information System (INIS)

Wolfe, M. F.; Schwartz, G. J. B.; Singaram, S.; Tjeerdema, R. S.

1997-01-01

Experiments were conducted to determine the impact of dispersing agents on petroleum hydrocarbons (PH) bioavailability and trophic transfer in primary levels of a marine food chain. Uptake, bioaccumulation and metabolic transformation of a model PH, ( 1 4C)naphthalene, were measured and compared with Prudhoe Bay Crude Oil (PBCO) dispersed with Corexit 9527, and undispersed preparations of PBCO. The model food chain consisted of a primary algae producer and a primary rotifer consumer. Results showed that uptake of naphthalene increased significantly in the presence of a dispersant in algae. A significant increase in uptake was also recorded in rotifers via trophic transfer. Trophic transfer played a significant, sometimes even dominant, role in uptake and bioaccumulation. 27 refs., 6 figs

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

Screening models to predict food-chain transfer of environmental toxicants

International Nuclear Information System (INIS)

Johnson, J.E.; Ward, G.M.; Colorado State Univ., Fort Collins, CO

1989-01-01

The objectives of the research effort were to determine transfer coefficients to milk, beef, eggs, and poultry meat of six radionuclides for which transfer coefficients were either undetermined or based upon secondary data. The radionuclides were isotopes of Tc, Mo, Te, Ba, Zr, and Nb. In addition, 131 I was used in experiments with hens to determine egg and poultry meat transfer coefficients. The new information on transfer coefficients obtained during this project indicates that, in some cases, lower values are appropriate and that those currently in use may provide an overestimate of the risks to man from the animal food chain. The objective of the second phase of this research was to provide information to clarify the physiological parameters that control transfer of radionuclides to animal food products. The data from the first phase has been published but this data has not appeared in the literature and thus is presented here in some detail. 10 refs., 4 figs., 6 tabs

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.

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

DEFF Research Database (Denmark)

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

2010-01-01

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

AFM Imaging of Hybridization Chain Reaction-Mediated Signal Transmission Between two DNA Origami Structures

DEFF Research Database (Denmark)

Helmig, Sarah Wendelbo; Gothelf, Kurt Vesterager

2017-01-01

transfer between two connected DNA nanostructures, using the hybridization chain reaction (HCR). Two sets of metastable DNA hairpins - of which one is immobilized in specific points along tracks on DNA origami structures - are polymerized to form a continuous DNA duplex, which is visible using atomic force...... microscopy (AFM). Upon addition of a designed initiator, the initiation signal is efficiently transferred >200 nm from a specific location on one origami structure to an end point on another origami structure. The system shows no significant loss of signal when crossing from one nanostructure to another...

Self-Assembled Colloidal Particle Clusters from In Situ Pickering-Like Emulsion Polymerization via Single Electron Transfer Mechanism.

Science.gov (United States)

Yuan, Jinfeng; Zhao, Weiting; Pan, Mingwang; Zhu, Lei

2016-08-01

A simple route is reported to synthesize colloidal particle clusters (CPCs) from self-assembly of in situ poly(vinylidene fluoride)/poly(styrene-co-tert-butyl acrylate) [PVDF/P(St-co-tBA)] Janus particles through one-pot seeded emulsion single electron transfer radical polymerization. In the in situ Pickering-like emulsion polymerization, the tBA/St/PVDF feed ratio and polymerization temperature are important for the formation of well-defined CPCs. When the tBA/St/PVDF feed ratio is 0.75 g/2.5 g/0.5 g and the reaction temperature is 35 °C, relatively uniform raspberry-like CPCs are obtained. The hydrophobicity of the P(St-co-tBA) domains and the affinity of PVDF to the aqueous environment are considered to be the driving force for the self-assembly of the in situ formed PVDF/P(St-co-tBA) Janus particles. The resultant raspberry-like CPCs with PVDF particles protruding outward may be promising for superhydrophobic smart coatings. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Neutral Polymeric Micelles for RNA Delivery

Science.gov (United States)

Lundy, Brittany B.; Convertine, Anthony; Miteva, Martina; Stayton, Patrick S.

2013-01-01

RNA interference (RNAi) drugs have significant therapeutic potential but delivery systems with appropriate efficacy and toxicity profiles are still needed. Here, we describe a neutral, ampholytic polymeric delivery system based on conjugatable diblock polymer micelles. The diblock copolymer contains a hydrophilic poly[N-(2-hydroxypropyl) methacrylamide-co-N-(2-(pyridin-2- yldisulfanyl)ethyl)methacrylamide) (poly[HPMA-co-PDSMA]) segment to promote aqueous stability and facilitate thiol-disulfide exchange reactions, and a second ampholytic block composed of propyl acrylic acid (PAA), dimethylaminoethyl methacrylate (DMAEMA), and butyl methacrylate (BMA). The poly[(HPMA-co-PDSMA)-b-(PAA-co-DMAEMA-co-BMA)] was synthesized using Reversible Addition-Fragmentation chain Transfer (RAFT) polymerization with an overall molecular weight of 22,000 g/mol and a PDI of 1.88. Dynamic light scattering and fluorescence measurements indicated that the diblock copolymers self-assemble under aqueous conditions to form polymeric micelles with a hydrodynamic radius and critical micelle concentration of 25 nm and 25 μg/mL respectively. Red blood cell hemolysis experiments show that the neutral hydrophilic micelles have potent membrane destabilizing activity at endosomal pH values. Thiolated siRNA targeting glyceraldehyde 3-phosphate dehydrogenase (GAPDH) was directly conjugated to the polymeric micelles via thiol exchange reactions with the pyridal disulfide groups present in the micelle corona. Maximum silencing activity in HeLa cells was observed at a 1:10 molar ratio of siRNA to polymer following a 48 h incubation period. Under these conditions 90 % mRNA knockdown and 65 % and protein knockdown of at 48 h was achieved with negligible toxicity. In contrast the polymeric micelles lacking a pH-responsive endosomalytic segment demonstrated negligible mRNA and protein knockdown under these conditions. The potent mRNA knockdown and excellent biocompatibility of the neutral siRNA conjugates

Supramolecular Nanoparticles via Single-Chain Folding Driven by Ferrous Ions.

Science.gov (United States)

Wang, Fei; Pu, Hongting; Jin, Ming; Wan, Decheng

2016-02-01

Single-chain nanoparticles can be obtained via single-chain folding assisted by intramolecular crosslinking reversibly or irreversibly. Single-chain folding is also an efficient route to simulate biomacromolecules. In present study, poly(N-hydroxyethylacrylamide-co-4'-(propoxy urethane ethyl acrylate)-2,2':6',2''-terpyridine) (P(HEAm-co-EMA-Tpy)) is synthesized via reversible addition fragmentation chain transfer polymerization. Single-chain folding and intramolecular crosslinking of P(HEAm-co-EMA-Tpy) are achieved via metal coordination chemistry. The intramolecular interaction is characterized on ultraviolet/visible spectrophotometer (UV-vis spectroscopy), proton nuclear magnetic resonance ((1)H NMR), and differential scanning calorimetry (DSC). The supramolecular crosslinking mediated by Fe(2+) plays an important role in the intramolecular collapsing of the single-chain and the formation of the nanoparticles. The size and morphology of the nanoparticles can be controlled reversibly via metal coordination chemistry, which can be characterized by dynamic light scattering (DLS), transmission electron microscope (TEM), and atomic force microscope (AFM). © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Elucidation of the Key Role of [Ru(bpy)3 ](2+) in Photocatalyzed RAFT Polymerization.

Science.gov (United States)

Christmann, Julien; Ibrahim, Ahmad; Charlot, Vincent; Croutxé-Barghorn, Céline; Ley, Christian; Allonas, Xavier

2016-08-04

Photocatalysis reactions using [Ru(II) (bpy)3 ](2+) were studied on the example of visible-light-sensitized reversible addition-fragmentation chain transfer (RAFT) polymerization. Although both photoinduced electron- and energy-transfer mechanisms are able to describe this interaction, no definitive experimental proof has been presented so far. This paper investigates the actual mechanism governing this reaction. A set of RAFT agents was selected, their redox potentials measured by cyclic voltammetry, and relaxed triplet energies calculated by quantum mechanics. Gibbs free-energy values were calculated for both electron- and energy-transfer mechanisms. Quenching rate constants were determined by laser flash photolysis. The results undoubtedly evidence the involvement of a photoinduced energy-transfer reaction. Controlled photopolymerization experiments are discussed in the light of the primary photochemical process and photodissociation ability of RAFT agent triplet states. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Azo polymers with electronical push and pull structures prepared via RAFT polymerization and its photoinduced birefringence behavior

Directory of Open Access Journals (Sweden)

2008-08-01

Full Text Available Two methacrylate monomers containing azo and electronical push and pull structure, e.g. 2-Methyl-acrylic-acid-2-{[4-(4-cyano-phenylazo-3-methyl-phenyl]-ethyl-amino-ethyl ester (MACP with cyano substituted and 2-Methylacrylic-acid-2-{ethyl-[4-(4-methoxy-phenylazo-3-methyl-phenyl]-amino}-ethyl ester (MAMP with methoxy substituted, were synthesized and polymerized using 2-cyanoprop-2-yl dithiobenzoate (CPDB as chain transfer agent and 2,2'-azobisisobutyronitrile (AIBN as initiator. The results showed that the polymerization displayed characteristics of ‘living’/controlled free radical polymerization. Thus, the obtained polymers, polyMACP (pMACP and polyMAMP (pMAMP, had controlled molecular weights and narrow molecular weights distribution. The chain extension experiments of pMACP and pMAMP using styrene as the second monomer were successfully carried out. The photo-induced trans-cis-trans isomerization kinetic of pMACP and pMAMP in chloroform solution were described. Marked differences in rate for the trans-cis and cis-trans isomerization of pMACP and pMAMP were observed in chloroform solution due to the different electronic effects in these two polymers. Photoinduced birefringence and surface relief grating (SRG of the pMACP and pMAMP were investigated in thin film state.

Bioaccumulation of 14C-Labeled Graphene in an Aquatic Food Chain through Direct Uptake or Trophic Transfer.

Science.gov (United States)

Dong, Shipeng; Xia, Tian; Yang, Yu; Lin, Sijie; Mao, Liang

2018-01-16

The growing applications of graphene materials warrant a careful evaluation of their environmental fate in aquatic food webs. Escherichia coli (Bacteria), Tetrahymena thermophila (protozoa), Daphnia magna (zooplankton), and Danio rerio (vertebrate) were used to build aquatic food chains to investigate the waterborne uptake and trophic transfer of 14 C-labeled graphene. Body burden factor (BBF) and trophic transfer factor (TTF) were analyzed for each organism and food chain to assess the bioaccumulation and biomagnification of graphene. The test organisms have high potential of accumulating graphene via direct uptake from culture medium with log-transformed BBF (log BBF) values of 3.66, 5.1, 3.9, and 1.62 for each organism, respectively. In the food chain from E. coli to T. thermophila, the calculated TTFs of 0.2 to 8.6 indicate the high trophic transfer potential in this aquatic food chain. However, the TTFs calculated for the food chain from T. thermophila to D. magna and from D. magna to D. rerio are much lower than 1, indicating that biomagnification was unlikely to occur in these food chains. Body burden measured for dietary uptake by T. thermophila, D. magna, and D. rerio are higher than that via waterborne exposure in a similar nominal concentration, respectively, indicating that trophic transfer is a nonnegligible route for the bioaccumulation of graphene in organisms.

Acyclic Diene Metathesis (ADMET Polymerization for Precise Synthesis of Defect-Free Conjugated Polymers with Well-Defined Chain Ends

Directory of Open Access Journals (Sweden)

Tahmina Haque

2015-03-01

Full Text Available This accounts introduces unique characteristics by adopting the acyclic diene metathesis (ADMET polymerization for synthesis of conjugated polymers, poly(arylene vinylenes, known as promising molecular electronics. The method is more suitable than the other methods in terms of atom efficiency affording defect-free, stereo-regular (exclusive trans polymers with well-defined chain ends; the resultant polymers possess better property than those prepared by the conventional methods. The chain ends (vinyl group in the resultant polymer prepared by ruthenium-carbene catalyst(s can be modified by treating with molybdenum-alkylidene complex (olefin metathesis followed by addition of various aldehyde (Wittig type cleavage, affording the end-functionalized polymers exclusively. An introduction of initiating fragment, the other conjugated segment, and one-pot synthesis of end-functionalized block copolymers, star shape polymers can be achieved by adopting this methodology.

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

Science.gov (United States)

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

2010-09-15

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

Stereospecific polymerization of acrylonitrile using acrylonitrile-urea canal complex initiated by γ-ray irradiation

International Nuclear Information System (INIS)

Yamazaki, Hitoshi; Miyazaki, Yukio; Kamide, Kenji

1991-01-01

An attempt was made to clarify the effect of polymerization conditions (e.g., the content of chain transfer reagent, irradiation dose, acrylonitrile (AN)-urea ratio, aging time) on the stereoregularity, the viscosity-average molecular weight M ν , and the conversion in the radiation-induced polymerization of AN-urea canal complex in the presence of radical chain transfer reagent including alkyl mercaptans, alkylamines, alkyl alcohols and chloroform. The addition of n-butyl mercaptan (n-BM) to AN-urea system slowed down the rate of the canal complex formation and decreased the amount of the canal complexes formed. The role of n-BM on the formation of AN-urea canal complex was also examined by DSC. The enthalpy of fusion (ΔH) of AN solid in AN-n-BM-urea system decreased with elapse of aging time, although ΔH of n-BM was almost constant in the whole range of aging time. From these findings, it was concluded that n-BM is not included in the AN-urea canal complex. The conversion decreased remarkably with an increase in n-BM content. When 2 mol%/AN of n-BM was added to AN, M ν was almost constant (ca. M ν = 2.0 x 10 5 ), irrespective of the amount of n-BM added. Addition of n-BM to AN-urea system brings about a small, but significant increase in the content of isotactic triad (mm) by 5 to 14%. (author)

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.

Cotton fibers encapsulated with homo- and block copolymers: synthesis by the atom transfer radical polymerization grafting-from technique and solid-state NMR dynamic investigations.

Science.gov (United States)

Castelvetro, Valter; Geppi, Marco; Giaiacopi, Simone; Mollica, Giulia

2007-02-01

Cotton fibers were modified by surface-initiated atom transfer radical polymerization of ethyl acrylate (EA) followed by copolymerization with styrene. Either ethyl 2-bromopropionate as a sacrificial free initiator or Cu(II) as a deactivator was used to optimize the EA grafting yield and to preserve the livingness of the chain ends for the subsequent growth of a poly(styrene) (PSty) block from the poly(ethyl acrylate) (PEA) grafts. The polymer-encapsulated cotton fibers were analyzed by Fourier transform infrared spectroscopy, scanning electron microscopy, differential scanning calorimetry (DSC), thermogravimetric analysis, and solid-state NMR (high-resolution 13C cross-polarization magic angle spinning, 1H spin-lattice relaxation times, and 1H free induction decay analysis NMR). The latter allowed the detection of the dynamic modifications associated with the presence of homo- and block copolymer grafts. In particular, the results of the DSC and NMR investigations suggest a heterogeneous morphology of the g-PEA-b-PSty grafted skin, which could be described as an inner layer of g-PEA sandwiched between the semicrystalline cellulose of the core fiber and the high glass transition temperature PSty of the covalently linked outer layer. Such morphology results in a reduced molecular mobility of the PEA chains.

Control of Chain Walking by Weak Neighbouring Group Interac-tions in Unsymmetric Catalysts

KAUST Repository

Falivene, Laura

2017-12-20

A combined theoretical and experimental study shows how weak attractive interactions of a neighbouring group can strongly promote chain walking and chain transfer. This accounts for the previously observed very different micro-structures obtained in ethylene polymerization by [κ^{2-N,O-{(2,6-(3\\',5\\'-R2C6H3)2C6H3-N=C(H)-(3,5-X,Y2-2-O-C6H2)}]NiCH3(pyridine)], namely hyperbranched oligomers for remote substituents R = CH3 versus. high molecular weight polyethylene for R = CF3. From a full mechanistic consideration the alkyl olefin complex with the growing chain cis to the salicylaldiminato oxygen donor is identified as the key species. Alternative to ethylene chain growth by insertion in this species, decoordination of the monomer to form a cis ß-agostic complex provides an entry into branching and chain transfer pathways. This release of monomer is promoted and made competitive by a weak η2-coordination of the distal aryl rings to the metal center, operative only for the case of sufficiently electron rich aryls. This concept for controlling chain walking is underlined by catalysts with other weakly coordinating furane and thio-phene motifs, which afford highly branched oligomers with > 120 branches per 1000 carbon atoms.}

Carrier transfer in vertically stacked quantum ring-quantum dot chains

Energy Technology Data Exchange (ETDEWEB)

Mazur, Yu. I., E-mail: ymazur@uark.edu; Dorogan, V. G.; Benamara, M.; Salamo, G. J. [Arkansas Institute for Nanoscale Materials Science and Engineering, University of Arkansas, Fayetteville, Arkansas 72701 (United States); Lopes-Oliveira, V.; Lopez-Richard, V.; Teodoro, M. D.; Marques, G. E. [Departamento de Fisica, Universidade Federal de São Carlos, 13565-905 São Carlos, São Paulo (Brazil); Souza, L. D. de [Departamento de Fisica, Universidade Federal de São Carlos, 13565-905 São Carlos, São Paulo (Brazil); Arkansas Institute for Nanoscale Materials Science and Engineering, University of Arkansas, Fayetteville, Arkansas 72701 (United States); Wu, J.; Wang, Z. M. [State Key Laboratory of Electronic Thin Film and Integrated Devices, University of Electronic Science and Technology of China, Chengdu (China); Tarasov, G. G. [Institute of Semiconductor Physics, National Academy of Sciences, pr. Nauki 45, Kiev 03028 (Ukraine); Marega, E. [Instituto de Fisica de São Carlos, Universidade de São Paulo, 13.566-590 São Carlos, São Paulo (Brazil)

2015-04-21

The interplay between structural properties and charge transfer in self-assembled quantum ring (QR) chains grown by molecular beam epitaxy on top of an InGaAs/GaAs quantum dot (QD) superlattice template is analyzed and characterized. The QDs and QRs are vertically stacked and laterally coupled as well as aligned within each layer due to the strain field distributions that governs the ordering. The strong interdot coupling influences the carrier transfer both along as well as between chains in the ring layer and dot template structures. A qualitative contrast between different dynamic models has been developed. By combining temperature and excitation intensity effects, the tuning of the photoluminescence gain for either the QR or the QD mode is attained. The information obtained here about relaxation parameters, energy scheme, interlayer and interdot coupling resulting in creation of 1D structures is very important for the usage of such specific QR–QD systems for applied purposes such as lasing, detection, and energy-harvesting technology of future solar panels.

Surface modification of nanodiamond through metal free atom transfer radical polymerization

Energy Technology Data Exchange (ETDEWEB)

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

2016-12-30

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

Surface modification of nanodiamond through metal free atom transfer radical polymerization

International Nuclear Information System (INIS)

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

2016-01-01

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

Modular in situ-Functionalization Strategy: Multicomponent Polymerization via Palladium/Norbornene Cooperative Catalysis.

Science.gov (United States)

Yoon, Ki-Young; Dong, Guangbin

2018-05-23

Herein, we report the palladium/norbornene cooperatively catalyzed polymerization, which simplifies synthesis of functional aromatic polymers, including conjugated polymers. Specifically, an A2B2C-type multicomponent polymerization is developed using ortho-amination/ipso-alkynylation reaction for preparing various amine-functionalized arylacetylene-containing polymers. Within a single catalytic cycle, the amine side-chains are site-selectively installed in situ via C-H activation during the polymerization process, which represents a major difference from conventional cross-coupling polymerizations. This in situ-functionalization strategy enables modular incorporation of functional side-chains from simple monomers, thereby conveniently affording a diverse range of functional polymers. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Controlled quantum-state transfer in a spin chain

International Nuclear Information System (INIS)

Gong, Jiangbin; Brumer, Paul

2007-01-01

Control of the transfer of quantum information encoded in quantum wave packets moving along a spin chain is demonstrated. Specifically, based on a relationship with control in a paradigm of quantum chaos, it is shown that wave packets with slow dispersion can automatically emerge from a class of initial superposition states involving only a few spins, and that arbitrary unspecified traveling wave packets can be nondestructively stopped and later relaunched with perfection. The results establish an interesting application of quantum chaos studies in quantum information science

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

International Nuclear Information System (INIS)

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

2016-01-01

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

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.

Biomimetic surface modification of polypropylene by surface chain transfer reaction based on mussel-inspired adhesion technology and thiol chemistry

Energy Technology Data Exchange (ETDEWEB)

Niu, Zhijun; Zhao, Yang; Sun, Wei; Shi, Suqing, E-mail: shisq@nwu.edu.cn; Gong, Yongkuan

2016-11-15

Highlights: • Biomimetic surface modification of PP was successfully conducted by integrating mussel-inspired technology, thiol chemistry and cell outer membranes-like structures. • The resultant biomimetic surface exhibits good interface and surface stability. • The obvious suppression of protein adsorption and platelet adhesion is also achieved. • The residue thoil groups on the surface could be further functionalized. - Abstract: Biomimetic surface modification of polypropylene (PP) is conducted by surface chain transfer reaction based on the mussel-inspired versatile adhesion technology and thiol chemistry, using 2-methacryloyloxyethylphosphorylcholine (MPC) as a hydrophilic monomer mimicking the cell outer membrane structure and 2,2-azobisisobutyronitrile (AIBN) as initiator in ethanol. A layer of polydopamine (PDA) is firstly deposited onto PP surface, which not only offers good interfacial adhesion with PP, but also supplies secondary reaction sites (-NH{sub 2}) to covalently anchor thiol groups onto PP surface. Then the radical chain transfer to surface-bonded thiol groups and surface re-initiated polymerization of MPC lead to the formation of a thin layer of polymer brush (PMPC) with cell outer membrane mimetic structure on PP surface. X-ray photoelectron spectrophotometer (XPS), atomic force microscopy (AFM) and water contact angle measurements are used to characterize the PP surfaces before and after modification. The protein adsorption and platelet adhesion experiments are also employed to evaluate the interactions of PP surface with biomolecules. The results show that PMPC is successfully grafted onto PP surface. In comparison with bare PP, the resultant PP-PMPC surface exhibits greatly improved protein and platelet resistance performance, which is the contribution of both increased surface hydrophilicity and zwitterionic structure. More importantly, the residue thiol groups on PP-PMPC surface create a new pathway to further functionalize such

Biomimetic surface modification of polypropylene by surface chain transfer reaction based on mussel-inspired adhesion technology and thiol chemistry

International Nuclear Information System (INIS)

Niu, Zhijun; Zhao, Yang; Sun, Wei; Shi, Suqing; Gong, Yongkuan

2016-01-01

Highlights: • Biomimetic surface modification of PP was successfully conducted by integrating mussel-inspired technology, thiol chemistry and cell outer membranes-like structures. • The resultant biomimetic surface exhibits good interface and surface stability. • The obvious suppression of protein adsorption and platelet adhesion is also achieved. • The residue thoil groups on the surface could be further functionalized. - Abstract: Biomimetic surface modification of polypropylene (PP) is conducted by surface chain transfer reaction based on the mussel-inspired versatile adhesion technology and thiol chemistry, using 2-methacryloyloxyethylphosphorylcholine (MPC) as a hydrophilic monomer mimicking the cell outer membrane structure and 2,2-azobisisobutyronitrile (AIBN) as initiator in ethanol. A layer of polydopamine (PDA) is firstly deposited onto PP surface, which not only offers good interfacial adhesion with PP, but also supplies secondary reaction sites (-NH 2 ) to covalently anchor thiol groups onto PP surface. Then the radical chain transfer to surface-bonded thiol groups and surface re-initiated polymerization of MPC lead to the formation of a thin layer of polymer brush (PMPC) with cell outer membrane mimetic structure on PP surface. X-ray photoelectron spectrophotometer (XPS), atomic force microscopy (AFM) and water contact angle measurements are used to characterize the PP surfaces before and after modification. The protein adsorption and platelet adhesion experiments are also employed to evaluate the interactions of PP surface with biomolecules. The results show that PMPC is successfully grafted onto PP surface. In comparison with bare PP, the resultant PP-PMPC surface exhibits greatly improved protein and platelet resistance performance, which is the contribution of both increased surface hydrophilicity and zwitterionic structure. More importantly, the residue thiol groups on PP-PMPC surface create a new pathway to further functionalize such

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

DEFF Research Database (Denmark)

Chernyy, Sergey

2012-01-01

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

Construction of dual-functional polymer nanomaterials with near-infrared fluorescence imaging and polymer prodrug by RAFT-mediated aqueous dispersion polymerization.

Science.gov (United States)

Tian, Chun; Niu, Jinyun; Wei, Xuerui; Xu, Yujie; Zhang, Lifen; Cheng, Zhenping; Zhu, Xiulin

2018-05-31

The performance of functional polymer nanomaterials is a vigorously discussed topic in polymer science. We devoted ourselves to investigating polymer nanomaterials based on near-infrared (NIR) fluorescence imaging and polymer prodrug in this study. Aza-boron dipyrromethene (BODIPY) is an important organic dye, having characteristics such as environmental resistance, light resistance, high molar extinction coefficient, and fluorescence quantum yield. We incorporated it into our target monomer, which can be polymerized without changing its parent structure in a polar solvent and copolymerized with water-soluble monomer to improve the solubility of the dye in an aqueous solution. At the same time, the hydrophobic drug camptothecin (CPT) was designed as a prodrug monomer, and the polymeric nanoparticles (NPs) with NIR fluorescence imaging and prodrug were synthesized in situ in reversible addition-fragmentation chain transfer (RAFT)-mediated aqueous dispersion polymerization. The dynamic light scattering (DLS) and transmission electron microscopy (TEM) revealed the final uniform size of the dual-functional polymeric NPs morphology. The dual-functional polymeric NPs had a strong absorption and emission signal in the NIR region (>650 nm) based on the fluorescence tests. In consideration of the long-term biological toxicity, confocal laser scanning microscopy (CLSM) results indicated that the dual-functional NPs with controlled drug content exhibited effective capability of killing HeLa cells. In addition, in vivo imaging of the dual-functional NPs was observed in real time, and the fluorescent signals clearly demonstrated the dynamic process of prodrug transfer.

Cascade synthesis of chiral block copolymers combining lipase catalyzed ring opening polymerization and atom transfer radical polymerization

NARCIS (Netherlands)

Peeters, J.W.; Palmans, A.R.A.; Veld, M.A.J.; Scheijen, F.J.E.; Heise, A.; Meijer, E.W.

2004-01-01

The enantioselective polymerization of methyl-substituted -caprolactones using Novozym 435 as the catalyst was investigated. All substituted monomers could be polymerized except 6-methyl--caprolactone (6-MeCL), which failed to propagate after ring opening. Interestingly, an odd-even effect in the

Influence of semisynthetic modification of the scaffold of a contact domain of HbS on polymerization: role of flexible surface topology in polymerization inhibition.

Science.gov (United States)

Sonati, Srinivasulu; Bhutoria, Savita; Prabhakaran, Muthuchidambaran; Acharya, Seetharama A

2018-02-01

A new variant of HbS, HbS-Einstein with a deletion of segment α 23-26 in the B-helix, has been assembled by semisynthetic approach. B-helix of the α chain of cis αβ-dimer of HbS plays dominant role in the quinary interactions of deoxy HbS dimer. This B-helix is the primary scaffold that provides the orientation for the side chains of contact residues of this intermolecular contact domain. The design of HbS-Einstein has been undertaken to map the influence of perturbation of molecular surface topology and the flexibility of surface residues in the polymerization. The internal deletion exerts a strong inhibitory influence on Val-6 (β)-dependent polymerization, comparable to single contact site mutations and not for complete neutralization of Val-6(β)-dependent polymerization. The scaffold modification in cis-dimer is inhibitory, and is without any effect when present on the trans dimer. The flexibility changes in the surface topology in the region of scaffold modification apparently counteracts the intrinsic polymerization potential of the molecule. The inhibition is close to that of Le Lamentin mutation [His-20 (α) → Gln] wherein a mutation engineered without much change in flexibility of the contact domain. Interestingly, the chimeric HbS with swine-human chimeric α chain with multiple non-conservative mutations completely inhibits the Val-6(β)-dependent polymerization. The deformabilities of surface topology of chimeric HbS are comparable to HbS in spite of the multiple contact site mutations in the α-chain. We conclude that the design of antisickling Hbs for gene therapy of sickle cell disease should involve multiple mutations of intermolecular contact sites.

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

Directory of Open Access Journals (Sweden)

Khezrollah Khezri

2014-04-01

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

Polonium ({sup 210}Po) and lead ({sup 210}Pb) in marine organisms and their transfer in marine food chains

Energy Technology Data Exchange (ETDEWEB)

Carvalho, Fernando P., E-mail: carvalho@itn.p [Instituto Tecnologico e Nuclear, Departamento de Proteccao Radiologica e Seguranca Nuclear, E.N. 10, 2686-953 Sacavem (Portugal)

2011-05-15

The determination of {sup 210}Po and {sup 210}Pb was performed in marine organisms from the seashore to abyssal depths, encompassing a plethora of species from the microscopic plankton to the sperm whale. Concentrations of those radionuclides ranged from low values of about 5 x 10{sup -1} Bq kg{sup -1} (wet wt.) in jellyfish, to very high values of about of 3 x 10{sup 4} Bq kg{sup -1} (wet wt.) in the gut walls of sardines, with a common pattern of {sup 210}Po > {sup 210}Pb.These radionuclides are primarily absorbed from water and concentrated by phyto- and microzooplankton, and then are transferred to the next trophic level along marine food chains. Investigation in epipelagic, mesopelagic, bathypelagic and abyssobenthic organisms revealed that {sup 210}Po is transferred in the marine food webs with transfer factors ranging from 0.1 to 0.7, and numerically similar to those of the energy transfer in the marine food chains. As {sup 210}Po preferentially binds to amino acids and proteins, its transfer in food chains likely traces protein transfer and, thus, {sup 210}Po transfer factors are similar to ecotrophic coefficients. {sup 210}Pb is transferred less efficiently in marine food chains and this contributes to increased {sup 210}Po:{sup 210}Pb activity ratios in some trophic levels.

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

International Nuclear Information System (INIS)

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

1981-01-01

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

Transfer and accumulation of metals in a soil-diet-wood mouse food chain along a metal pollution gradient

International Nuclear Information System (INIS)

Rogival, Damien; Scheirs, Jan; Blust, Ronny

2007-01-01

We studied the accumulation and transfer of As, Cd, Cu, Pb and Zn in the compartments of a soil-diet-wood mouse (Apodemus sylvaticus) food chain at five sites located along a metal pollution gradient. We observed a clear gradient in metal exposure at increasing distance from the smelter in all compartments of the food chain for the non-essential metals. The gradient was less clear or absent for the essential metals in acorn and mice target tissues. Regression analysis showed overall strong relationships within the soil-diet and diet-wood mouse compartments for the non-essential metals, while relationships for the essential metals were weak or absent. Total metal in soil appeared as a better predictor for the diet metal content than the available metal fraction. Our results suggest a more important transfer of non-essential elements through the food chain than essential elements, which is probably a consequence of homeostatic control of the latter group. - Non-essential metal transfer through a soil-diet-wood mouse food chain is more important than essential metal transfer

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…

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

International Nuclear Information System (INIS)

Galhardo, Eduardo; Lona, Liliane M.F.

2009-01-01

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

Nitroxide radicals formed in situ as polymer chain growth regulators

International Nuclear Information System (INIS)

Kolyakina, Elena V; Grishin, Dmitry F

2009-01-01

Published data on controlled synthesis of macromolecules using nitroxide radicals, formed in situ during polymerization, as polymer chain growth regulators are systematized and generalized. The attention is focused on the mechanism of polymer chain growth control during reversibly inhibited radical homopolymerization and the effect of structure of precursors and regulating additives on the polymerization kinetics of monomers of different nature and the molecular-mass characteristics of the polymers thus formed. The key methods for generation of nitroxide radicals directly during polymerization are considered. The prospects for development and practical use of these approaches for the synthesis of new polymeric materials are evaluated.

Inferring properties of disordered chains from FRET transfer efficiencies

Science.gov (United States)

Zheng, Wenwei; Zerze, Gül H.; Borgia, Alessandro; Mittal, Jeetain; Schuler, Benjamin; Best, Robert B.

2018-03-01

Förster resonance energy transfer (FRET) is a powerful tool for elucidating both structural and dynamic properties of unfolded or disordered biomolecules, especially in single-molecule experiments. However, the key observables, namely, the mean transfer efficiency and fluorescence lifetimes of the donor and acceptor chromophores, are averaged over a broad distribution of donor-acceptor distances. The inferred average properties of the ensemble therefore depend on the form of the model distribution chosen to describe the distance, as has been widely recognized. In addition, while the distribution for one type of polymer model may be appropriate for a chain under a given set of physico-chemical conditions, it may not be suitable for the same chain in a different environment so that even an apparently consistent application of the same model over all conditions may distort the apparent changes in chain dimensions with variation of temperature or solution composition. Here, we present an alternative and straightforward approach to determining ensemble properties from FRET data, in which the polymer scaling exponent is allowed to vary with solution conditions. In its simplest form, it requires either the mean FRET efficiency or fluorescence lifetime information. In order to test the accuracy of the method, we have utilized both synthetic FRET data from implicit and explicit solvent simulations for 30 different protein sequences, and experimental single-molecule FRET data for an intrinsically disordered and a denatured protein. In all cases, we find that the inferred radii of gyration are within 10% of the true values, thus providing higher accuracy than simpler polymer models. In addition, the scaling exponents obtained by our procedure are in good agreement with those determined directly from the molecular ensemble. Our approach can in principle be generalized to treating other ensemble-averaged functions of intramolecular distances from experimental data.

Molecularly imprinted polymer beads for nicotine recognition prepared by RAFT precipitation polymerization: a step forward towards multifunctionalities

DEFF Research Database (Denmark)

Zhou, Tongchang; Jørgensen, Lars; Mattebjerg, Maria Ahlm

2014-01-01

A nicotine imprinted polymer was synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization using methacrylic acid (MAA) as a functional monomer. The resulting molecularly imprinted polymers were monodispersed beads with an average diameter of 1.55 mm. The molecular...... selectivity of the imprinted polymer beads was evaluated by studying the uptake of nicotine and its structural analogs by the polymer beads. Equilibrium binding results indicate that the amount of nicotine bound to the imprinted polymer beads is significantly higher than that bound to the nonimprinted polymer...

PREPARATION AND PROPERTIES OF MMA/1-PROPYLMETHACRYLATE-POSS COPOLYMER WITH ATOM TRANSFER RADICAL POLYMERIZATION

Institute of Scientific and Technical Information of China (English)

He-xin Zhang; Ho-young Lee; Young-jun Shin; Dong-ho Lee; Seok Kyun Noh

2008-01-01

The methyl methacrylate(MMA)/1-propylmethacrylate-polyhedral oligomeric silsesquioxane(PM-POSS) copolymers were synthesized via atom transfer radical polymerization with CuBr as catalyst.The unreacted PM-POSS monomer could be removed completely by washing the copolymerization product with n-hexane.The copolymers were characterized with 1H-NMR,X-ray diffraction,difierential scanning calorimetry,thermogravimetric analysis and gel permeatlon chromatography.With increasing PM-POSS feed ratio.the total conversion increased while the glass transition temperatures of copolymer decreased.The thermogravimetric analysis demonstrated that the thermal stability of copolymer improved slightly with PM-POSS addition.The molecular weight of copolymers increased with incorporation of PM-POSS.

High performance nature of biodegradable polymeric nanocomposites for oil-well drilling fluids

Directory of Open Access Journals (Sweden)

Tarek M. Madkour

2016-06-01

Full Text Available Multi-walled carbon nanotube (MWCNT and graphene nanoplatelet reinforced thermoplastic poly(lactic acid (PLA biodegradable nanocomposites were designed and prepared using solution casting techniques. The prepared biodegradable polymers are expected to provide an environmentally friendly alternative to petroleum-based polymers. Both nanocomposite systems exhibited better thermal stability and improved mechanical performance over the unreinforced polymer exhibiting excellent strength and degradability. The addition of graphene nanofiller in varied amounts was aimed to enhance the thermal and mechanical properties of the nanocomposites even further and incorporate the outstanding characteristics of graphene nanoplatelets into the nanocomposites. The polymeric nanocomposites showed also superior advantages for oil drilling relevances, automotive lubricating purposes, membrane technology and food packaging. Scanning electron microscopy images indicated a homogeneous dispersion of the nanofiller within the polymeric matrix at low filler loadings and a cluster formation at higher loadings that could be responsible for the polymeric matrix movement restrictions. The enthalpy of mixing (the polymer and the nanofiller measured could explain the cause of the repulsive interactions between the nanoparticles and the polymeric chains, which created an additional excluded volume that the polymeric segments were restricted to occupy, thus forcing the conformational characteristics of the polymeric chains to deviate away from those of the bulk chains. The prepared polymeric nano composites (poly lactic acid carbon nano tube and poly lactic acid graphene nanoplatelets were utilized in the formulation of oil-base mud as a viscosifier. The rheological, filtration properties and electrical stability of the oil based mud formulation with the new polymeric nanocomposite were studied and the result compared to the oil-based mud formulation with commercial viscosifier.

Transfer of lead (Pb) in the soil-plant-mealybug-ladybird beetle food chain, a comparison between two host plants.

Science.gov (United States)

Zhang, Can; Wang, Xingmin; Ashraf, Umair; Qiu, Baoli; Ali, Shaukat

2017-09-01

Contamination of soil with heavy metals has become an issue of concern on global scale. This study investigates the translocation of lead (Pb) along the soil - plant (eggplant and tomato) - mealybug (Dysmicoccus neobrevipes) - ladybird beetle (Cryptolaemus montrouzieri) food chain. Soil amendments used for this study were adjusted to 0, 25, 50 and 100mg/kg of Pb (w/w). The results revealed significantly higher transfer of Pb in tomato when compared to eggplant. Bio-magnification of Pb (2-4 times) was observed for soil - root transfer whereas Pb was bio-minimized in later part of food chain (shoot - mealybug - ladybird transfer). A dose dependent increase in transfer of Pb across the multi-trophic food chain was observed for both host plants. A decrease in coefficients of Pb transfer (from root - shoot and shoot - mealybug) was observed with increase in Pb concentrations. Our results also showed removal of Pb from the bodies of ladybird beetle during metamorphosis. Further studies are required to explain the mechanisms or physiological pathways involved in the bio-minimization of Pb across the food chain. Copyright © 2017 Elsevier Inc. All rights reserved.

Effect of organoelemental compounds of group 3 elements on radical polymerization of vinyl monomers

International Nuclear Information System (INIS)

Grishin, D.F.; Mojkin, A.A.

1996-01-01

When alkyl, alkyl alkoxy, and alkyl halide derivatives of boron and aluminium are introduced into the system in amounts that are comparable to the concentration of initiator, they coordinate to the growing macroradicals, thus changing their reactivity, and exert regulating effect on the rate of polymerization of vinyl monomers and the molecular mass of the resulting polymers. The said organoelemental compounds accelerate the polymerization of butyl acrylate, methyl methacrylate, acrylonitrile, vinyl acetate, and vinylidene chloride, reduce the molecular mass of acrylic polymers, and virtually do not affect the polymerization of styrene. The specific features of vinyl polymerization are associated with participation of organoelemental additives at the stages of chain growth and chain termination and can be explained within the framework of the mechanism of radical-coordination polymerization. 32 refs., 3 tabs

Hyperbranched polymers from polymerization in solid state

International Nuclear Information System (INIS)

Tomaz, Vivian A.; Silva, Rafael; Muniz, Edvani C.; Rubira, Adley F.

2009-01-01

The macroscopic properties of polymers are directly related to the chemical characteristics of the monomeric units and also with the geometric arrangement of polymer chains. Thus, polymers were synthesized from two well-known chelators EDTA and EDA. We evaluated the conditions for the polymerization of the precursors in the solid state. The polymerization was carried out varying the proportions of reagents, aiming the polymers with different degrees of chain branching and the materials were characterized by FTIR. The materials obtained from the best condition for synthesis were purified by size-exclusion chromatography of and were subjected to characterization by FTIR and NMR of 1 H and 13 C. The content of end groups in these samples was determined by back titration. (author)

Investigations in the field of solid state polymerization Pt. 38

International Nuclear Information System (INIS)

Hardy, Gy.; Cser, F.; Nyitrai, K.; Fedorova, N.

1980-01-01

The stuctural and radiation chemical data of vinyl monomers with long chain paraffinic or cholesteric side groups are critically reviewed. Based on their structural and polymerization kinetical characteristics the monomers may be classified into three groups. Oblique layers are favourable for homogeneous topotactic polymerization. This is characterized by a low activation energy and a radiochemical efficiency very similar to that measured in liquid state polymerization. The tilted layers are not favourable for homogeneous topotactic polymerization. Allyl monomers yield polymers with higher molecular weights in the layer structure than in liquid states. (author)

Amphiphilic Fluorinated Block Copolymer Synthesized by RAFT Polymerization for Graphene Dispersions

Directory of Open Access Journals (Sweden)

Hyang Moo Lee

2016-03-01

Full Text Available Despite the superior properties of graphene, the strong π–π interactions among pristine graphenes yielding massive aggregation impede industrial applications. For non-covalent functionalization of highly-ordered pyrolytic graphite (HOPG, poly(2,2,2-trifluoroethyl methacrylate-block-poly(4-vinyl pyridine (PTFEMA-b-PVP block copolymers were prepared by reversible addition-fragmentation chain transfer (RAFT polymerization and used as polymeric dispersants in liquid phase exfoliation assisted by ultrasonication. The HOPG graphene concentrations were found to be 0.260–0.385 mg/mL in methanolic graphene dispersions stabilized with 10 wt % (relative to HOPG PTFEMA-b-PVP block copolymers after one week. Raman and atomic force microscopy (AFM analyses revealed that HOPG could not be completely exfoliated during the sonication. However, on-line turbidity results confirmed that the dispersion stability of HOPG in the presence of the block copolymer lasted for one week and that longer PTFEMA and PVP blocks led to better graphene dispersibility. Force–distance (F–d analyses of AFM showed that PVP block is a good graphene-philic block while PTFEMA is methanol-philic.

Radiation-induced polymerization of hydrogen cyanide

International Nuclear Information System (INIS)

Mozhaev, P.S.; Kichigina, G.A.; Kiryukhin, D.P.

1995-01-01

The chain reaction of HCN polymerization in a γ-radiation field does not occur at 77 K. When irradiated HCN is warmed up to ambient temperature, a polymer is formed. The heat of polymerization of HCN is 44.0±6.0 kJ/mol and the polymer yield reaches 2.5% for a dose of 725 kGy. Amorphous polymer products (with yields increasing up to 33.5%) and needle crystals (presumably HCN tetramer) are formed upon storage of irradiated HCN at room temperature. The polymer is stable below 700 K, has a conductivity of 3x10 -5 Ω -1 cm -f1 , and displays an EPR spectrum typical of polyconjugated systems. A radical mechanism of the formation of conjugated chain -C=N-C=N- is suggested. The tetramer is produced by a combination of aminocyanocarbene biradicals

Fed-Batch Control and Visualization of Monomer Sequences of Individual ICAR ATRP Gradient Copolymer Chains

Directory of Open Access Journals (Sweden)

Dagmar R. D'hooge

2014-04-01

Full Text Available Based on kinetic Monte Carlo simulations of the monomer sequences of a representative number of copolymer chains (≈ 150,000, optimal synthesis procedures for linear gradient copolymers are proposed, using bulk Initiators for Continuous Activator Regeneration Atom Transfer Radical Polymerization (ICAR ATRP. Methyl methacrylate and n-butyl acrylate are considered as comonomers with CuBr2/PMDETA (N,N,N′,N′′,N′′-pentamethyldiethylenetriamine as deactivator at 80 °C. The linear gradient quality is determined in silico using the recently introduced gradient deviation ( polymer property. Careful selection or fed-batch addition of the conventional radical initiator I2 allows a reduction of the polymerization time with ca. a factor 2 compared to the corresponding batch case, while preserving control over polymer properties ( ≈ 0.30; dispersity ≈ 1.1. Fed-batch addition of not only I2, but also comonomer and deactivator (50 ppm under starved conditions yields a below 0.25 and, hence, an excellent linear gradient quality for the dormant polymer molecules, albeit at the expense of an increase of the overall polymerization time. The excellent control is confirmed by the visualization of the monomer sequences of ca. 1000 copolymer chains.

Characterization of inclusion complexes of organic ions with hydrophilic hosts by ion transfer voltammetry with solvent polymeric membranes.

Science.gov (United States)

Olmos, José Manuel; Laborda, Eduardo; Ortuño, Joaquín Ángel; Molina, Ángela

2017-03-01

The quantitative characterization of inclusion complexes formed in aqueous phase between organic ions and hydrophilic hosts by ion-transfer voltammetry with solvent polymeric membrane ion sensors is studied, both in a theoretical and experimental way. Simple analytical solutions are presented for the determination of the binding constant of the complex from the variation with the host concentration of the electrochemical signal. These solutions are valid for any voltammetric technique and for solvent polymeric membrane ion sensors comprising one polarisable interface (1PI) and also, for the first time, two polarisable interfaces (2PIs). Suitable experimental conditions and data analysis procedures are discussed and applied to the study of the interactions of a common ionic liquid cation (1-octyl-3-metyl-imidazolium) and an ionisable drug (clomipramine) with two hydrophilic cyclodextrins: α-cyclodextrin and 2-hydroxypropyl-β-cyclodextrin. The experimental study is performed via square wave voltammetry with 2PIs and 1PI solvent polymeric membranes and in both cases the electrochemical experiments enable the detection of inclusion complexes and the determination of the corresponding binding constant. Copyright © 2016 Elsevier B.V. All rights reserved.

The potential of Cu(I)Cl/2,2'-bipyridine catalysis in a triblock copolymer preparation by atom transfer radical polymerization

Czech Academy of Sciences Publication Activity Database

Masař, Bohumil; Vlček, Petr; Kříž, Jaroslav

2001-01-01

Roč. 81, č. 14 (2001), s. 3514-3522 ISSN 0021-8995 R&D Projects: GA MŠk OC P1.10; GA AV ČR KSK2050602 Institutional research plan: CEZ:AV0Z4050913 Keywords : atom transfer radical polymerization * triblock copolymers * sequential synthesis Subject RIV: CD - Macromolecular Chemistry Impact factor: 0.992, year: 2001

PREPARATION OF BLOCK COPOLYMERS OF POLY(STYRENE) AND POLY(T-BUTYL ACRYLATE) OF VARIOUS MOLECULAR WEIGHTS AND ARCHITECTURES BY ATOM TRANSFER RADICAL POLYMERIZATION. (R826735)

Science.gov (United States)

Block copolymers of polystyrene and poly(t-butyl acrylate) were prepared using atom transfer radical polymerization techniques. These polymers were synthesized with a CuBr/N,N,N,NRadical-Scavenging Activity of Thiols, Thiobarbituric Acid Derivatives and Phenolic Antioxidants Determined Using the Induction Period Method for Radical Polymerization of Methyl Methacrylate

Directory of Open Access Journals (Sweden)

Seiichiro Fujisawa

2012-04-01

Full Text Available The radical-scavenging activities of two thiols, eight (thiobarbituric acid derivatives and six chain-breaking phenolic antioxidants were investigated using the induction period method for polymerization of methyl methacrylate (MMA initiated by thermal decomposition of 2,2’-azobisisobutyronitrile (AIBN and monitored by differential scanning calorimetry (DSC. The induction period (IP for the thiols 2-mercaptoethanol (ME and 2-mercapto-1-methylimidazole (MMI was about half that for phenolic antioxidants. Except for the potent inhibitor 5,5-dimethyl-2-thiobarbituric acid (3, the IP for thiobarbituric acid derivatives was about one tenth of that for phenolic antioxidants. The IP for 1,3,5-trimethyl-2-thiobarbituric acid (1 and 5-allyl-1, 3-dimethyl-2-thiobarbituric acid (7 was less than that of the control, possibly due to inhibition by a small amount of atmospheric oxygen in the DSC container. The ratio of the chain inhibition to that of chain propagation (CI/CP for the thiols and thiobarbituric acid compounds except for 1, 3 and 7 was about 10 times greater or greater than that for phenolic compounds. A kinetic chain length (KCL about 10% greater than that of the control was observed for 1, suggesting that 1 had chain transfer reactivity in the polymerization of MMA. The average molecular weight of polymers formed from thiobarbituric acid derivatives is discussed.

A One-Step Route to CO2 -Based Block Copolymers by Simultaneous ROCOP of CO2 /Epoxides and RAFT Polymerization of Vinyl Monomers.

Science.gov (United States)

Wang, Yong; Zhao, Yajun; Ye, Yunsheng; Peng, Haiyan; Zhou, Xingping; Xie, Xiaolin; Wang, Xianhong; Wang, Fosong

2018-03-26

The one-step synthesis of well-defined CO 2 -based diblock copolymers was achieved by simultaneous ring-opening copolymerization (ROCOP) of CO 2 /epoxides and RAFT polymerization of vinyl monomers using a trithiocarbonate compound bearing a carboxylic group (TTC-COOH) as the bifunctional chain transfer agent (CTA). The double chain-transfer effect allows for independent and precise control over the molecular weight of the two blocks and ensures narrow polydispersities of the resultant block copolymers (1.09-1.14). Notably, an unusual axial group exchange reaction between the aluminum porphyrin catalyst and TTC-COOH impedes the formation of homopolycarbonates. By taking advantage of the RAFT technique, it is able to meet the stringent demand for functionality control to well expand the application scopes of CO 2 -based polycarbonates. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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...

Syringyl Methacrylate, a Hardwood Lignin-Based Monomer for High-Tg Polymeric Materials.

Science.gov (United States)

Holmberg, Angela L; Reno, Kaleigh H; Nguyen, Ngoc A; Wool, Richard P; Epps, Thomas H

2016-05-17

As viable precursors to a diverse array of macromolecules, biomass-derived compounds must impart wide-ranging and precisely controllable properties to polymers. Herein, we report the synthesis and subsequent reversible addition-fragmentation chain-transfer polymerization of a new monomer, syringyl methacrylate (SM, 2,6-dimethoxyphenyl methacrylate), that can facilitate widespread property manipulations in macromolecules. Homopolymers and heteropolymers synthesized from SM and related monomers have broadly tunable and highly controllable glass transition temperatures ranging from 114 to 205 °C and zero-shear viscosities ranging from ∼0.2 kPa·s to ∼17,000 kPa·s at 220 °C, with consistent thermal stabilities. The tailorability of these properties is facilitated by the controlled polymerization kinetics of SM and the fact that one vs two o -methoxy groups negligibly affect monomer reactivity. Moreover, syringol, the precursor to SM, is an abundant component of depolymerized hardwood (e.g., oak) and graminaceous (e.g., switchgrass) lignins, making SM a potentially sustainable and low-cost candidate for tailoring macromolecular properties.

Spin-state transfer in laterally coupled quantum-dot chains with disorders

International Nuclear Information System (INIS)

Yang Song; Bayat, Abolfazl; Bose, Sougato

2010-01-01

Quantum dot arrays are a promising medium for transferring quantum information between two distant points without resorting to mobile qubits. Here we study the two most common disorders, namely hyperfine interaction and exchange coupling fluctuations, in quantum dot arrays and their effects on quantum communication through these chains. Our results show that the hyperfine interaction is more destructive than the exchange coupling fluctuations. The average optimal time for communication is not affected by any disorder in the system and our simulations show that antiferromagnetic chains are much more resistive than the ferromagnetic ones against both kind of disorders. Even when time modulation of a coupling and optimal control is employed to improve the transmission, the antiferromagnetic chain performs much better. We have assumed the quasistatic approximation for hyperfine interaction and time-dependent fluctuations in the exchange couplings. Particularly for studying exchange coupling fluctuations we have considered the static disorder, white noise, and 1/f noise.

Gamma Radiation-Induced Template Polymerization Technique

International Nuclear Information System (INIS)

Siyam, T.

2005-01-01

Gamma radiation induced copolymerization of acrylamide sodiumacrylate (AM-AANa) in the presence and absence of the polymer additive was studied at low monomer concentration(1.4M/l). The results showed that the exponents of the dose rate for the polymerization rate was found to be 1.3 and 1.4 in the absence and in the presence of the polymer additive respectively. The molecular weight of the formed polymer increased by addition of the polymer to the system. In the presence of the polymer the comonomers polymerize on the added polymer. In the absence of the added polymer the comonomers polymerize according to the copolymerization process at the initial stage of the copolymerization. While at high conversion the residual comonomers polymerize on the formed macromolecular chains of the produced polymer. These studies showed that the copolymerization in the presence of added polymer is completely template copolymerization while in the absence of the polymer the copolymerization process is only template process with a high conversion

Radiation sterilization of polymeric implant materials

International Nuclear Information System (INIS)

Bruck, S.D.; Mueller, E.P.

1988-01-01

High-energy irradiation sterilization of medical devices and implants composed of polymeric biomaterials that are in contact with tissue and/or blood, may adversely affect their long-term mechanical and/or biological performance (tissue and/or blood compatibility). Since many polymeric implants may contain trace quantities of catalysts and/or other additives, the effect of high-energy radiation on these additives, and possible synergistic effects with the polymer chains under the influence of high-energy radiation, must be considered. It is essential to indicate whether polymeric implants are used in short-term (acute) or long-term (chronic) applications. Relatively small changes in their physicochemical, mechanical, and biological properties may be tolerable in the short term, whereas similar changes may lead to catastrophic failures in long-term applications. Therefore, polymeric implants which are to be sterilized by high-energy irradiation should be carefully evaluated for long-term property changes which may be induced by the radiation

Activation and deactivation of neutral palladium(II) phosphinesulfonato polymerization catalysts

KAUST Repository

Rünzi, Thomas

2012-12-10

13C-Labeled ethylene polymerization (pre)catalysts [κ2-(anisyl)2P,O]Pd(13CH3)(L) (1-13CH3-L) (L = pyridine, dmso) based on di(2-anisyl)phosphine benzenesulfonate were used to assess the degree of incorporation of 13CH3 groups into the formed polyethylenes. Polymerizations of variable reaction time reveal that ca. 60-85% of the 13C-label is found in the polymer after already 1 min polymerization time, which provides evidence that the pre-equilibration between the catalyst precursor 1-13CH3-L and the active species 1-13CH3-(ethylene) is fast with respect to chain growth. The fraction of 1-13CH3-L that initiates chain growth is likely higher than the 60-85% determined from the 13C-labeled polymer chain ends since (a) chain walking results in in-chain incorporation of the 13C-label, (b) irreversible catalyst deactivation by formation of saturated (and partially volatile) alkanes diminishes the amount of 13CH3 groups incorporated into the polymer, and (c) palladium-bound 13CH3 groups, and more general palladium-bound alkyl(polymeryl) chains, partially transfer to phosphorus by reductive elimination. NMR and ESI-MS analyses of thermolysis reactions of 1-13CH3-L provide evidence that a mixture of phosphonium salts (13CH3)xP+(aryl)4-x (2-7) is formed in the absence of ethylene. In addition, isolation and characterization of the mixed bis(chelate) palladium complex [κ2-(anisyl)2P,O]Pd[κ2-(anisyl) (13CH3)P,O] (11) by NMR and X-ray diffraction analyses from these mixtures indicate that oxidative addition of phosphonium salts to palladium(0) species is also operative. The scrambling of palladium-bound carbyls and phosphorus-bound aryls is also relevant under NMR, as well as preparative reactor polymerization conditions exemplified by the X-ray diffraction analysis of [κ2-(anisyl)2P,O] Pd[κ2-(anisyl)(CH2CH3)P,O] (12) and [κ2-(anisyl)2P,O]Pd[κ2-(anisyl) ((CH2)3CH3)P,O] (13) isolated from pressure reactor polymerization experiments. In addition, ESI-MS analyses of reactor

Magnetic Levitation To Characterize the Kinetics of Free-Radical Polymerization.

Science.gov (United States)

Ge, Shencheng; Semenov, Sergey N; Nagarkar, Amit A; Milette, Jonathan; Christodouleas, Dionysios C; Yuan, Li; Whitesides, George M

2017-12-27

This work describes the development of magnetic levitation (MagLev) to characterize the kinetics of free-radical polymerization of water-insoluble, low-molecular-weight monomers that show a large change in density upon polymerization. Maglev measures density, and certain classes of monomers show a large change in density when monomers covalently join in polymer chains. MagLev characterized both the thermal polymerization of methacrylate-based monomers and the photopolymerization of methyl methacrylate and made it possible to determine the orders of reaction and the Arrhenius activation energy of polymerization. MagLev also made it possible to monitor polymerization in the presence of solids (aramid fibers, and carbon fibers, and glass fibers). MagLev offers a new analytical technique to materials and polymer scientists that complements other methods (even those based on density, such as dilatometry), and will be useful in investigating polymerizations, evaluating inhibition of polymerizations, and studying polymerization in the presence of included solid materials (e.g., for composite materials).

DMFC Performance of Polymer Electrolyte Membranes Prepared from a Graft-Copolymer Consisting of a Polysulfone Main Chain and Styrene Sulfonic Acid Side Chains

Directory of Open Access Journals (Sweden)

Nobutaka Endo

2016-08-01

Full Text Available Polymer electrolyte membranes (PEMs for direct methanol fuel cell (DMFC applications were prepared from a graft-copolymer (PSF-g-PSSA consisting of a polysulfone (PSF main chain and poly(styrene sulfonic acid (PSSA side chains with various average distances between side chains (Lav and side chain lengths (Lsc. The polymers were synthesized by grafting ethyl p-styrenesulfonate (EtSS on macro-initiators of chloromethylated polysulfone with different contents of chloromethyl (CM groups, and by changing EtSS content in the copolymers by using atom transfer radical polymerization (ATRP. The DMFC performance tests using membrane electrode assemblis (MEAs with the three types of the PEMs revealed that: a PSF-g-PSSA PEM (SF-6 prepared from a graft copolymer with short average distances between side chains (Lav and medium Lsc had higher DMFC performance than PEMs with long Lav and long Lsc or with short Lav and short Lsc. SF-6 had about two times higher PDmax (68.4 mW/cm2 than Nafion® 112 at 30 wt % of methanol concentration. Furthermore, it had 58.2 mW/cm2 of PDmax at 50 wt % of methanol concentration because of it has the highest proton selectivity during DMFC operation of all the PSF-g-PSSA PEMs and Nafion® 112.

Polymerization-Driven Immobilization of dc-APGD Synthesized Gold Nanoparticles into a Quaternary Ammonium-Based Hydrogel Resulting in a Polymeric Nanocomposite with Heat-Transfer Applications

Directory of Open Access Journals (Sweden)

Piotr Cyganowski

2018-03-01

Full Text Available A new method for the production of nanocomposites, composed of gold nanoparticles (AuNPs and (vinylbenzyltrimethylammonium chloride-co-N,N-methylene bisacrylamide (VBTAC-co-MBA hydrogel, is described. Raw-AuNPs of defined optical and granulometric properties were synthesized using direct current atmospheric pressure glow discharge (dc-APGD generated in contact with a solution of HAuCl4. Different approaches to the polymerization-driven synthesis of Au/VBTAC-co-MBA nanocomposites were tested. It was established that homogenous dispersion of AuNPs in this new nanomaterial with was achieved in the presence of NaOH in the reaction mixture. The new nanocomposite was found to have excellent heat-transfer properties.

Transfer coefficient study of Sr-90 in the soil-grass-milk chain for Cuba

International Nuclear Information System (INIS)

Zerquera, J. T.; Sarria P, R.

1996-01-01

One of the most important problems in modern radioecology is the lack of able information about the features of radionuclide migration in tropical and subtropical environment. The development of nuclear energy and the enhancing in the applications of nuclear techniques in those latitudes indicate that studies in this area are necessary. Cuba is carrying out studies on radioecological characterization of the principal food chains in the country. One of the objectives of these studies is to define the values of the transfer coefficients to be used in the evaluation programs for the assessment of the radiological impact of practices which involve ionizing radiation. This paper shows the results obtained in the determination of Sr-90 transfer coefficients in soil-grass-milk food chain in 'La Quebrada', a place near the Havana City where an important part of the milk that the citizens consume is produced. Transfer coefficients for Sr-90 were calculated on the basis of data collected during 5 years in the region. Soil-grass transfer coefficients are in the range 0.18-5 while grass-milk coefficients are in the range of 1.2x10 -4 - 6x10 -3 day/L. These values are in accordance with values reported by other authors in the literature. (authors). 4 refs., 2 tabs

Chain length distribution and kinetic characteristics of an enzymatically produced polymer

NARCIS (Netherlands)

Mulders, K.J.M.; Beeftink, H.H.

2013-01-01

Non-processive enzymatic polymerization leads to a distribution of polymer chain lengths. A polymerization model was developed to investigate the relation between the extent of this distribution on one hand, and the polymerization start conditions and reaction kinetics on the other hand. The model

On the mechanism of activation of copper-catalyzed atom transfer radical polymerization

International Nuclear Information System (INIS)

Isse, Abdirisak Ahmed; Bortolamei, Nicola; De Paoli, Patrizia; Gennaro, Armando

2013-01-01

The mechanism of activation of atom transfer radical polymerization (ATRP) has been analyzed by investigating the kinetics of dissociative electron transfer (ET) to alkyl halides (RX) in acetonitrile. Using a series of alkyl halides, including both bromides and chlorides, the rate constants of ET (k ET ) to RX by electrogenerated aromatic radical anions (A· − ) acting as outer-sphere donors have been measured and analyzed according to the current theories of dissociative ET. This has shown that the kinetic data fit very well the “sticky” dissociative ET model with the formation of a weak adduct held together by electrostatic interactions. The rate constants of activation, k act , of some alkyl halides, namely chloroacetonitrile, methyl 2-bromopropionate and ethyl chloroacetate, by [Cu I L] + (L = tris(2-dimethylaminoethyl)amine, tris(2-pyridylmethyl)amine, 1,1,4,7,7-pentamethyldiethylenetriamine) have also been measured in the same experimental conditions. Comparisons of the measured k act values with those predicted assuming an outer-sphere ET for the complexes have shown that activation by Cu(I) is 7–10 orders of magnitude faster than required by outer-sphere ET. Therefore, the mechanism of RX activation by Cu(I) complexes used as catalysts in ATRP occurs by an inner-sphere ET or more appropriately by a halogen atom abstraction

Mechanism of isotactic styrene polymerization with a C 6F 5-substituted bis(phenoxyimine) titanium system

KAUST Repository

Caporaso, Lucia; Loria, Marianna; Mazzeo, Mina; Michiue, Kenji; Nakano, Takashi; Fujita, Terunori; Cavallo, Luigi

2012-01-01

We report a combined, experimental and theoretical, study of styrene polymerization to clarify the regio- and stereocontrol mechanism operating with a C 6F 5-substituted bis(phenoxyimine) titanium dichloride complex. Styrene homopolymerization, styrene-propene and styrene-ethene-propene copolymerizations have been carried out to this aim. A combination of 13C NMR analysis of the chain-end groups and of the microstructure of the homopolymers and copolymers reveals that styrene polymerization is highly regioselective and occurs prevalently through 2,1-monomer insertion. DFT calculations evidenced that steric interaction between the growing chain and the monomer in the transition state insertion stage is at the origin of this selectivity. The formation of isotactic polystyrene with a chain-end like microstructure is rationalized on the base of a mechanism similar to that proposed for the syndiospecific propene polymerization catalyzed by bis(phenoxyimine) titanium dichloride complexes. Finally, a general stereocontrol mechanism operative in olefin polymerization with this class of complexes is proposed. © 2012 American Chemical Society.

Mechanism of isotactic styrene polymerization with a C 6F 5-substituted bis(phenoxyimine) titanium system

KAUST Repository

Caporaso, Lucia

2012-11-13

We report a combined, experimental and theoretical, study of styrene polymerization to clarify the regio- and stereocontrol mechanism operating with a C 6F 5-substituted bis(phenoxyimine) titanium dichloride complex. Styrene homopolymerization, styrene-propene and styrene-ethene-propene copolymerizations have been carried out to this aim. A combination of 13C NMR analysis of the chain-end groups and of the microstructure of the homopolymers and copolymers reveals that styrene polymerization is highly regioselective and occurs prevalently through 2,1-monomer insertion. DFT calculations evidenced that steric interaction between the growing chain and the monomer in the transition state insertion stage is at the origin of this selectivity. The formation of isotactic polystyrene with a chain-end like microstructure is rationalized on the base of a mechanism similar to that proposed for the syndiospecific propene polymerization catalyzed by bis(phenoxyimine) titanium dichloride complexes. Finally, a general stereocontrol mechanism operative in olefin polymerization with this class of complexes is proposed. © 2012 American Chemical Society.

Aromatic Side Chain Water-to-Lipid Transfer Free Energies Show a Depth Dependence across the Membrane Normal.

Science.gov (United States)

McDonald, Sarah K; Fleming, Karen G

2016-06-29

Quantitating and understanding the physical forces responsible for the interactions of biomolecules are fundamental to the biological sciences. This is especially challenging for membrane proteins because they are embedded within cellular bilayers that provide a unique medium in which hydrophobic sequences must fold. Knowledge of the energetics of protein-lipid interactions is thus vital to understand cellular processes involving membrane proteins. Here we used a host-guest mutational strategy to calculate the Gibbs free energy changes of water-to-lipid transfer for the aromatic side chains Trp, Tyr, and Phe as a function of depth in the membrane. This work reveals an energetic gradient in the transfer free energies for Trp and Tyr, where transfer was most favorable to the membrane interfacial region and comparatively less favorable into the bilayer center. The transfer energetics follows the concentration gradient of polar atoms across the bilayer normal that naturally occurs in biological membranes. Additional measurements revealed nearest-neighbor coupling in the data set are influenced by a network of aromatic side chains in the host protein. Taken together, these results show that aromatic side chains contribute significantly to membrane protein stability through either aromatic-aromatic interactions or placement at the membrane interface.

Monte Carlo simulation of non-linear free radical polymerization using a percolation kinetic gelation model (I): free radical homo polymerization

International Nuclear Information System (INIS)

Ghiass, M.; Dabir, B.; Nikazar, M.; Rey, A.D.; Mirzadeh, H.

2001-01-01

A kinetic gelation model that incorporates the kinetics of free radical homo polymerization is implemented to determine the effects of kinetics on polymerization statistics and microstructures. The simulation is performed on a simple cubic lattice that has 100 sites in each direction. A new algorithm for random selecting of the next step in a self-avoiding random walk and very efficient mechanisms of mobility of components are introduced to improve the generality of the predictions by removing commonly accruing deficiencies due to early trapping of radicals. A first order kinetics is considered for decomposition of initiator that enables us to consider the effect of temperature on polymerization reaction. Better understanding of microstructural evolution during polymerization and providing a framework to produce a realistic system of highly packed random chains within polymer network are among the benefits of model

Three Arm Star Homo- And Co-Polymers Via Atom Transfer Radical Polymerization

International Nuclear Information System (INIS)

Amin, A.; Sobh, R.A.; Ayoub, M.M.H.

2005-01-01

Star homo and co-polymers of some vinyl monomers such as methylmethacrylate, butylmethacrylate and styrene (MMA, BMA, St.) were prepared using N, N, N', N' tetramethylethylenediamine ligand/ CuBr catalytic system via atom transfer radical polymerization (ATRP). Three armed benzene based core was successfully used as initiator. Low polydispersities and regular molecular weight values were obtained in most cases especially at low conversions. MMA and BuMA showed comparable behavior where controlled and true ATRP was observed even at the high conversions. However, styrene monomer recorded irregular high polydispersities at high conversions in spite of the relatively low molecular weight values. 1HNMR confirmed the structures of the resulting polymers. Transmission Electron microscope (TEM) proved the nano-structure of the star polymers. The thermal behavior of the MMA star homo and copolymers was studied. The effect of the star shape on the thermal behavior was very clear with respect to the linear ones

Study on irradiated polymerization of acrylonitrile by NMR

International Nuclear Information System (INIS)

Zhao Xin; Lin Hao

1999-01-01

Sup 13 C CP/MAS spectra and nuclear Overhauser effects (NOE) at room temperature have been measured for acrylonitrile (AN) in homophase irradiated polymerization. With the increase of radiation dose the chemical shift of cracking peaks and NOE are variation. This implies that the polymerized mechanism of AN were changed with the variation of irradiated doses and dose rate. There is the stronger affinity electron group (-CN) in acrylonitrile monomer. It may be polymerized by various ways and mechanism and be gained the polymer of difference structures and molecular weight of polyacrylonitrile (PAN). Starmicarbon and Starker obtained higher molecular weight of polyacrylonitrile by peroxysulfate-pyrosulfite in oxidation-reduction system. The superhigh molecular weight of PAN was synthesized chemically according to the method of Wu et. al. by suspension polymerization. In this paper we discussed that the relative concentrations of steric dyads and triads in the chain structure in PAN and the irradiation polymerized mechanism of acrylonitrile monomer in room temperature by different dose and dose rate

The Synthesis of Cellulose Graft Copolymers Using Cu(0)-Mediated Polymerization

Science.gov (United States)

Donaldson, Jason L.

Cellulose is the most abundant renewable polymer on the planet and there is great interest in expanding its use beyond its traditional applications. However, its hydrophilicity and insolubility in most common solvent systems are obstacles to its widespread use in advanced materials. One way to counteract this is to attach hydrophobic polymer chains to cellulose: this allows the properties of the copolymer to be tailored by the molecular weight, density, and physical properties of the grafts. Two methods were used here to synthesize the graft copolymers: a 'grafting-from' approach, where synthetic chains were grown outward from bromoester moieties on cellulose (Cell-BiB) via Cu(0)-mediated polymerization; and a 'grafting-to' approach, where fully formed synthetic chains with terminal sulfide functionality were added to cellulose acetate with methacrylate functionality (CA-MAA) via thiol-ene Michael addition. The Cell-BiB was synthesized in the ionic liquid 1-butyl-3-methylimidazolium chloride and had a degree of substitution of 1.13. Polymerization from Cell-BiB proceeded at similar but slightly slower rate than an analogous non-polymeric initiator (EBiB). The average graft density of poly(methyl acrylate) chains was 0.71 chains/ring, with a maximum of 1.0 obtained. The graft density when grafting poly(methyl methacrylate) was only 0.15, and this appeared to be due to the slow initiation of BiB groups. Using EBiB to model the reaction and improve the design should allow this to be overcome. Chain extension experiments demonstrated the living behaviour of the polymer. The CA-MAA was synthesized by esterification with methacrylic acid. Reactions of CA-MAA with thiophenol and dodecanethiol resulted in quantitative addition of the thiol to the alkene. The grafts were synthesized by Cu(0)-mediated polymerization from a bifunctional initiator containing a disulfide bond, followed by reduction to sulfides. The synthetic polymers were successfully grafted to CA-MAA but the

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�

RADAL: a dynamic model for the transfer of radionuclides through agricultural food chains

International Nuclear Information System (INIS)

Jerez Vegueria, S.F.; Frometa Suarez, I.; Jerez Vegueria, P.F.

1996-01-01

The contamination of agricultural products by radionuclides is a mechanism which results in radiation dose commitment to the population, following fallout deposits from the atmosphere to the landscape. This paper describes the structure of the dynamic food chain model RADAL. This model simulates an acute environmental transport of fallout radionuclides through agricultural food chains to man and estimates the levels of radiation doses resulting from consumption of contaminated food. The development of RADAL was based on different existing models. For mathematical representation the transport of radionuclides was modeled through compartments representing environmental elements and/or food products. The model solves a set of linear, first-order, differential equations to estimate the concentrations of radionuclides in soil, vegetation, animal tissues and animal products as a function of time following their deposition. Dynamic physico-chemical processes of the model include the following: deposition and foliar interception, weathering, foliar absorption, soil resuspension, transfer from soil surface to the root zone, absorption by plant roots, transfer to deep soil, transfer to animal products, and human consumption of agricultural products. A parameter sensitivity analyses, performed for the main parameters of the model, showed that the foliar interception constant and resuspension factor are the most influential parameters over the radiation doses / model output. (author)

Synthesis and Self-Assembly of Block Copolymers Containing Temperature Sensitive and Degradable Chain Segments.

Science.gov (United States)

Gong, Hong-Liang; Lei, Lei; Shi, Shu-Xian; Xia, Yu-Zheng; Chen, Xiao-Nong

2018-05-01

In this work, polylactide-b-poly(N-isopropylacrylamide) were synthesized by the combination of controlled ring-opening polymerization and reversible addition fragmentation chain transfer polymerization. These block copolymers with molecular weight range from 7,900 to 12,000 g/mol and narrow polydispersity (≤1.19) can self-assemble into micelles (polylactide core, poly(N-isopropylacrylamide) shell) in water at certain temperature range, which have been evidenced by laser particle size analyzer proton nuclear magnetic resonance and transmission electron microscopy. Such micelles exhibit obvious thermo-responsive properties: (1) Poly(N-isopropylacrylamide) blocks collapse on the polylactide core as system temperature increase, leading to reduce of micelle size. (2) Micelles with short poly(N-isopropylacrylamide) blocks tend to aggregate together when temperature increased, which is resulted from the reduction of the system hydrophilicity and the decreased repulsive force between micelles.

Poly(vinyl acetate-Based Block Copolymer/Clay Nanocomposites Prepared by In Situ Atom Transfer Radical Polymerization

Directory of Open Access Journals (Sweden)

M.A. Semsarzadeh

2009-12-01

Full Text Available Atom transfer radical polymerization of styrene (St and methyl methacrylate (MMA was performed at 90oC in the absence and presence of nanoclay (Cloisite 30B. Trichloromethyl-terminated poly(vinyl acetate telomerand CuCl/ PMDETA were used as a macroinitiator and catalyst system, respectively. The experimental results showed that the atom transfer radical polymerization of St and MMA in the absence or presence of nanoclay proceeds via a controlled/living mode. It was observed that nanoclay significantly enhances the homopolymerization rate of MMA, which was attributed to the activated conjugated C=C bond of MMA monomer via interaction between the carbonyl group of MMA monomer and the hydroxyl moiety (Al-O-H of nanoclay as well as the effect of nanoclay on the dynamic equilibrium between the active (macro radicals and dormant species.Homopolymerization rate of St (a non-coordinative monomer with nanoclay decreased slightly in the presence of nanoclay. This could be explained by insertion of a portion of macroinitiator into the clay galleries, where no sufficient St monomer exists due to the low compatibility or interaction of St monomer with nanoclay to react with the macroinitiator. The results obtained from XRD, TEM and TGA analyses were fully in agreement with the kinetic data. Structure of the poly(vinyl acetate-bpolystyrene nanocomposite was found to be a combination of stacking layers and exfoliated structures while poly(vinyl acetate-b-poly(methyl methacryale nanocomposite had an exfoliated structure. This difference in the structure of nanocomposites was attributed to the different capability of the monomers (styrene and methyl methacrylate to react with the hydroxyl moiety (Al-O-H of nanoclay.

Radiation-Induced Graft Polymerization: Gamma Radiation and Electron Beam Technology for Materials Development

International Nuclear Information System (INIS)

Madrid, Jordan F.; Cabalar, Patrick Jay; Lopez, Girlie Eunice; Abad, Lucille V.

2015-01-01

The formation of functional hybrid materials by attaching polymer chains with advantageous tailored properties to the surface of a base polymer with desirable bulk character is an attractive application of graft copolymerization. Radiation-induced graft polymerization (RIGP) has been a popular approach for surface modification of polymers because of its merits over conventional chemical processes. RIGP, which proceeds primarily via free radical polymerization process, has the advantages such as simplicity, low cost, control over process and adjustment of the materials composition and structure. RIGP can be performed using either electron beam or gamma radiation and it can be applied to both synthetic and natural polymers. These merits make RIGP a popular research topic worldwide. Moreover, the materials synthesized and produced via RIGP has found applications, and were proposed to produce continuous impact, in the fields of medicine, agriculture, pollution remediation, rare earth and valuable metals recovery, fuel cell membrane synthesis and catalysis to name a few. From 2012 our group has performed electron beam and gamma radiation-induced graft polymerization of various monomers onto polymers of natural and synthetic origins (e.g. monomers - glycidyl methacrylate, styrene, acrylonitrile, N,N-dimethylaminoethyl methacrylate; base polymers – polyethylene/polypropylene nonwoven fabric, polypropylene nonwoven fabric pineapple fibers, cellulose nonwoven fabric microcrystalline cellulose). We tested these grafted materials for heavy metals (Pb, Ni, Cu) and organic molecule removal from aqueous solutions and E. coli activity (using reversible addition fragmentation chain transfer RAFT mediated grafting). The results clearly showed the success of materials modified via FIGP in these applications. Currently, we are studying the applications of grafted materials on treatment of waste waters from tanning industry, value addition to abaca nonwoven fabrics cell sheet

Analysis of knowledge tacitness in the transfer of food and beverage practices: Evidence from new chain hotels

Directory of Open Access Journals (Sweden)

Desiderio García-Almeida

2018-01-01

Full Text Available Knowledge is a valuable resource that can provide a firm competitive advantages. Food and beverage practices require the existence of knowledge to effectively perform the activities in this key department for many hotels. When hotel firms grow by integrating new hotels in the organizational structure, managers usually want to transfer the knowledge underlying the key practices. However, the transfer is affected by the level of knowledge tacitness, since this characteristic is considered to render the transfer more difficult. With data from 93 new chain hotels where F&B knowledge has been transferred, the results shed some light about the tacitness of F&B knowledge and its transfer. Thus, customer service knowledge is the knowledge with the lowest degree of tacitness, and food planning, production and preparation is the most tacit. The most frequent mechanism to transfer the knowledge on food planning, production and preparation and the knowledge on management and control of purchases and consumption is the use of staff from the headquarters or other chain hotels in long-term assignments; the preferred method for F&B customer service is training courses, lectures and seminars. Moreover, the tacitness of knowledge about F&B customer service negatively affects the knowledge transfer process in several success dimensions.

Effects of medium-chain fatty acids and oleic acid on blood lipids, lipoproteins, glucose, insulin, and lipid transfer protein activities

DEFF Research Database (Denmark)

Tholstrup, T.; Ehnholm, C.; Jauhiainen, M.

2004-01-01

Background: Dietary medium-chain fatty acids (MCFAs) are of nutritional interest because they are more easily absorbed from dietary medium-chain triacylglycerols (MCTs) than are long-chain fatty acids from, for example, vegetable oils. It has generally been claimed that MCFAs do not increase plasma...... cholesterol, although this claim is poorly documented. Objective: We compared the effects of a diet rich in either MCFAs or oleic acid on fasting blood lipids, lipoproteins, glucose, insulin, and lipid transfer protein activities in healthy men. Design: In a study with a double-blind, randomized, crossover...... plasma total triacylglycerol (P = 0.0361), and higher plasma glucose (P = 0.033). Plasma HDL-cholesterol and insulin concentrations and activities of cholesterol ester transfer protein and phospholipid transfer protein did not differ significantly between the diets. Conclusions: Compared with fat high...

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

International Nuclear Information System (INIS)

Zhen Weijun; Lu Canhui

2012-01-01

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

The tempered polymerization of human neuroserpin.

Directory of Open Access Journals (Sweden)

Rosina Noto

Full Text Available Neuroserpin, a member of the serpin protein superfamily, is an inhibitor of proteolytic activity that is involved in pathologies such as ischemia, Alzheimer's disease, and Familial Encephalopathy with Neuroserpin Inclusion Bodies (FENIB. The latter belongs to a class of conformational diseases, known as serpinopathies, which are related to the aberrant polymerization of serpin mutants. Neuroserpin is known to polymerize, even in its wild type form, under thermal stress. Here, we study the mechanism of neuroserpin polymerization over a wide range of temperatures by different techniques. Our experiments show how the onset of polymerization is dependent on the formation of an intermediate monomeric conformer, which then associates with a native monomer to yield a dimeric species. After the formation of small polymers, the aggregation proceeds via monomer addition as well as polymer-polymer association. No further secondary mechanism takes place up to very high temperatures, thus resulting in the formation of neuroserpin linear polymeric chains. Most interesting, the overall aggregation is tuned by the co-occurrence of monomer inactivation (i.e. the formation of latent neuroserpin and by a mechanism of fragmentation. The polymerization kinetics exhibit a unique modulation of the average mass and size of polymers, which might suggest synchronization among the different processes involved. Thus, fragmentation would control and temper the aggregation process, instead of enhancing it, as typically observed (e.g. for amyloid fibrillation.

Parameters on the radionuclide transfer in crop plants for Korean food chain dose assessment

International Nuclear Information System (INIS)

Choi, Yong Ho; Lim, K. M.; Cho, Y. H.

2001-12-01

For more realistic assessment of Korean food chain radiation doses due to the operation of nuclear facilities, it is required to use domestically produced data for radionuclide transfer parameters in crop plants. In this report, results of last about 15 years' studies on radionuclide transfer parameters in major crop plants by the Korea Atomic Energy Research Institute, were summarized and put together. Soil-to-plant transfer factors, parameters quantifying the root uptake of radionuclides, were measured through greenhouse experiments and field studies. In addition to traditional transfer factors, which are based on the activity in unit weight of soil, those based on the activity applied to unit area of soil surface were also investigated. Interception factors, translocation factors and weathering half lives, parameters in relation to direct plant contamination, were investigated through greenhouse experiments. The levels of initial plant contamination with HTO and I2 vapor were described with absorption factors. Especially for HTO vapor, 3H levels in crop plants at harvest were expressed with TFWT (tissue free water tritium) reduction factors and OBT (organically bound tritium) production factors. The above-mentioned parameters generally showed great variations with soils, crops and radionuclide species and application times. On the basis of summarized results, the points to be amended or improved in food chain dose assessment models were discussed both for normal operation and for accidental release

Green-function description of dense polymeric systems

NARCIS (Netherlands)

Schoot, van der P.P.A.M.

2000-01-01

A self-consistent Green-function description of concentrated polymer solutions and dense polymeric melts is presented. The method, which applies to both uniform and nonuniform systems, is used in this work to calculate the static structure factor of a homogeneous fluid of Gaussian model chains.

''adding'' algorithm for the Markov chain formalism for radiation transfer

International Nuclear Information System (INIS)

Esposito, L.W.

1979-01-01

The Markov chain radiative transfer method of Esposito and House has been shown to be both efficient and accurate for calculation of the diffuse reflection from a homogeneous scattering planetary atmosphere. The use of a new algorithm similar to the ''adding'' formula of Hansen and Travis extends the application of this formalism to an arbitrarily deep atmosphere. The basic idea for this algorithm is to consider a preceding calculation as a single state of a new Markov chain. Successive application of this procedure makes calculation possible for any optical depth without increasing the size of the linear system used. The time required for the algorithm is comparable to that for a doubling calculation for a homogeneous atmosphere, but for a non-homogeneous atmosphere the new method is considerably faster than the standard ''adding'' routine. As with he standard ''adding'' method, the information on the internal radiation field is lost during the calculation. This method retains the advantage of the earlier Markov chain method that the time required is relatively insensitive to the number of illumination angles or observation angles for which the diffuse reflection is calculated. A technical write-up giving fuller details of the algorithm and a sample code are available from the author

Modelling of radiocesium transfer in the lichen-reindeer/caribou-wolf food chain

Directory of Open Access Journals (Sweden)

D. F. Holleman

1990-09-01

Full Text Available The environmental contaminate radiocesium (cesium-137 has been shown to be of value as a marker in food selection and intake studies. Its greatest potential value as a food marker is in the subarctic/arctic regions, particularly in the lichen to reindeer/caribou to wolf food chain. A kinetic model describing the movement of radiocesium through the food chain has been developed using the SAAM computer program and is presented here. The program has been written so that the various paramenters affecting the transfer of radiocesium in the food chain can be altered more realistically to describe the system being modeled. The values of the parameters as given in this example are realistic for interior Alaska, however caution should be exercised in the application of the present results to regions that may be vastly different from the Alaskan interior without first evaluating the parameters and assumptions of the model.

Electrochemical studies of a reconstituted photosynthetic electron-transfer chain or towards a biomimetic photoproduction of hydrogen

International Nuclear Information System (INIS)

Fourmond, V.

2007-04-01

The aim of this work is to find an efficient process to convert solar energy into hydrogen. The electrons transfers in reconstituted photosynthetic chains have been particularly studied with the aims 1)in one hand, to better understand the interactions of the different molecules of the photosynthetic chain in order to optimize the changes of the entire organisms for hydrogen production 2)in another hand, to insert the hydrogenases in a photosynthetic chain and then to photo reduce them in order to obtain kinetic data to better understand how it works. (O.M.)

Forming of Polymeric Tubular Micro-components

DEFF Research Database (Denmark)

Qin, Yi; Zhao, Jie; Anyasodor, Gerald

2015-01-01

platform for the production of functional polymeric tubular micro-components. The chapter gives background on the current market and process development trends, followed by description of materials, process configuration, tool design and machine development for each processing technology as well......This chapter is intended to provide an overview of three nontraditional shaping technologies for the forming of polymeric micro-tubes, which are hot embossing, blow molding, and cross rolling, as well as realization of a process chain and the integration of a modular machine-based manufacturing...... as strategy for integration of the technologies and equipment into a common platform. Finally, potential applications of the technologies and facilities developed are highlighted....

AFM Imaging of Hybridization Chain Reaction Mediated Signal Transmission between Two DNA Origami Structures.

Science.gov (United States)

Helmig, Sarah; Gothelf, Kurt Vesterager

2017-10-23

Signal transfer is central to the controlled exchange of information in biology and advanced technologies. Therefore, the development of reliable, long-range signal transfer systems for artificial nanoscale assemblies is of great scientific interest. We have designed such a system for the signal transfer between two connected DNA nanostructures, using the hybridization chain reaction (HCR). Two sets of metastable DNA hairpins, one of which is immobilized at specific points along tracks on DNA origami structures, are polymerized to form a continuous DNA duplex, which is visible using atomic force microscopy (AFM). Upon addition of a designed initiator, the initiation signal is efficiently transferred more than 200 nm from a specific location on one origami structure to an end point on another origami structure. The system shows no significant loss of signal when crossing from one nanostructure to another and, therefore, has the potential to be applied to larger multi-component DNA assemblies. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fabrication of high-capacity polyelectrolyte brush-grafted porous AAO-silica composite membrane via RAFT polymerization.

Science.gov (United States)

Song, Cunfeng; Wang, Meijie; Liu, Xin; Wang, He; Chen, Xiaoling; Dai, Lizong

2017-09-01

Surface-initiated reversible addition-fragmentation chain transfer (RAFT) polymerization has been utilized to fabricate high-capacity strong anion-exchange (AEX) membrane for the separation of protein. By means of RAFT polymerization, quaternized poly(3-(methacrylamidomethyl)-pyridine) brushes formed 3-dimensional nanolayers on the surface of porous anodic aluminum oxide (AAO)-silica composite membrane. The surface properties of the membranes were analyzed by SEM, water contact angle, ATR-FTIR, XPS and TGA. To investigate the adsorption performance, the new AEX membranes were applied to recover a model protein, ovalbumin (OVA). High adsorption capacities of 95.8mg/g membranes (static) and 65.3mg/g membranes (dynamic) were obtained at ambient temperature. In the further studies, up to 90% of the adsorbed OVA was efficiently eluted by using phosphate buffer-1M NaCl as elution medium. The successful separation of OVA with high purity from a mixture protein solution was also achieved by using the AEX membranes. The present study demonstrated that under mild reaction condition, RAFT polymerization can be used to fabricate ion-exchange membrane which has many remarkable features, such as high capacity and selectivity, easy elution and so on. Copyright © 2017. Published by Elsevier B.V.

Investigations in the field of solid-state polymerization Pt. 37

International Nuclear Information System (INIS)

Mahr, L.; Cser, F.; Kovacs, G.; Hardy, Gy.

1978-01-01

Chloranil (CA) and bromanil (BA) which have otherwise similar radiation-chemical properties affect the solid state polymerization of acenaphthylene (ACN) in different manner. CA decreases the rate of polymerization proportionally to its concentration and besides, it also decreases the conversion limit and the molecular weight of the product. BA does not influence the reaction up to a conversion of 20%, but soon afterwards the conversion limit of the polymerization is reached. This limit, above 8M% BA content, is independent of the BA concentration. The reason for the different behaviour is that while BA forms an ideal eutectics with ACN, CA forms a solid solution of limited miscibility at the temperature of the experiments. Both pairs of compounds give charge transfer complex in solid state. The charge transfer complex of BA exists merely at the boundary layer of the crystals, but that of CA is within the crystal lattice of ACN as in a solid solvent. In none of the studied cases could be detected the charge transfer complex with its own specific crystal structure. The effect of CA on the solid state polymerization of ACN is discussed on the basis of the results obtained by PPP and CNDO/2 calculations on ACN and CA. (author)

Controlling the Plasma-Polymerization Process of N-Vinyl-2-pyrrolidone

DEFF Research Database (Denmark)

Norrman, Kion; Winther-Jensen, Bjørn

2005-01-01

N-vinyl-2-pyrrolidone was plasma-polymerized on glass substrates using a pulsed AC plasma. Pulsed AC plasma produces a chemical surface structure different from that produced by conventional RF plasma; this is ascribed to the different power regimes used. A high degree of control over the structure...... of the chemical surface was obtained using pulsed AC plasma, as shown by ToF-SIMS. It is demonstrated how the experimental conditions to some extent control the chemical structure of the plasma-polymerized film, e.g., film thickness, density of post-plasma-polymerized oligomeric chains, and the density of intact...

[Verification of a decrease in the rigidity of the phage lambda DNA polymeric chain in low ionic strength aqueous solutions by testing the polymer-polymer interlink interactions].

Science.gov (United States)

Arutiunian, A V; Ivanova, M A; Kurliand, D I; Kapshin, Iu S; Landa, S B; Poshekhonov, S T; Drobchenko, E A; Shevelev, I V

2011-01-01

Changes in the rigidity of the polymetric chain of phage lambda double-strand DNA have been studied by laser correlation spectroscopy. It was shown that, as the ionic strength increases, the effect of the screening of the hydrodynamic interaction of the links of the polymeric chain specific for polymeric coils arises in a DNA solution. It is assumed that the screening occurs when the threshold of the overlapping of DNA coils is achieved. The overlapping of coils is the result of a previously observed significant rise of DNA coil size from abnormally small DNA coils in low ionic strength buffers (about 10(-2) M Na+ or less) to maximum possible large coils in the 5SSC and 5SSC-like buffers. Further analysis of the far interlink interactions in linear lambda phage DNA coils in similar buffers at pH 7 and 4 confirms the earlier proposal about the role of H+ ions in the appearance of abnormally small DNA coils. The abnormal decrease in the DNA coil size in low ionic strength buffers is not a specific feature of lambda phage DNA only.

Possible mechanisms for the interaction of polymeric composite resins with Cu(II) ions in aqueous solution

International Nuclear Information System (INIS)

El-Zahhhar, A.A.; Abdel-Aziz, H.M.; Siyam, T.

2005-01-01

The interaction between the active groups of polymeric composite resins such as Poly(acrylamide-acrylic acid)-ethylenediaminetetra acetic acid disodium salt P(AM-AA)EDTANa 2 , Poly(acrylamide-acrylic acid)- montmorillonite P(AM-AA)-montmorillonite, and Poly(acrylamide-acrylic acid)-potassium nickel hexacyanoferrate P(AM-AA)-KNiHCF, with copper sulfate as a test ion has been studied. The spectroscopic studies show that the mechanism of interaction between polymeric composite resins and copper sulfate is a bond formation between the active groups of polymeric chains and copper ion. The bond formation depends on nature of polymeric chains. It was also found that the amide groups form complexes with hydrated cations, while carboxylate group interact by ion exchange mechanism through complex formation. Montmorillonite and hexacyanoferrate of the resins interact with metal ions by ion exchange mechanism

Proton Transfer in Perfluorosulfonic Acid Fuel Cell Membranes with Differing Pendant Chains and Equivalent Weights.

Science.gov (United States)

Thomaz, Joseph E; Lawler, Christian M; Fayer, Michael D

2017-05-04

Proton transfer in the nanoscopic water channels of polyelectrolyte fuel cell membranes was studied using a photoacid, 8-hydroxypyrene-1,3,6-trisulfonic acid sodium salt (HPTS), in the channels. The local environment of the probe was determined using 8-methoxypyrene-1,3,6-trisulfonic acid sodium salt (MPTS), which is not a photoacid. Three fully hydrated membranes, Nafion (DuPont) and two 3M membranes, were studied to determine the impact of different pendant chains and equivalent weights on proton transfer. Fluorescence anisotropy and excited state population decay data that characterize the local environment of the fluorescent probes and proton transfer dynamics were measured. The MPTS lifetime and anisotropy results show that most of the fluorescent probes have a bulk-like water environment with a relatively small fraction interacting with the channel wall. Measurements of the HPTS protonated and deprotonated fluorescent bands' population decays provided information on the proton transport dynamics. The decay of the protonated band from ∼0.5 ns to tens of nanoseconds is in part determined by dissociation and recombination with the HPTS, providing information on the ability of protons to move in the channels. The dissociation and recombination is manifested as a power law component in the protonated band fluorescence decay. The results show that equivalent weight differences between two 3M membranes resulted in a small difference in proton transfer. However, differences in pendant chain structure did significantly influence the proton transfer ability, with the 3M membranes displaying more facile transfer than Nafion.

Early career: Templating of liquid crystal microstructures by reversible addition-fragmentation chain transfer polymerization

Energy Technology Data Exchange (ETDEWEB)

Heinen, Jennifer M. (O' Donnell) [Iowa State Univ., Ames, IA (United States)

2014-12-31

This research has shown that the microstructure of self-assembled copolymers can be decoupled from the polymer chemistry. The simplest polymer architecture, linear block copolymers, is valuable for a broad range of applications, including adhesives and coatings, medical devices, electronics and energy storage, because these block copolymers reproducibly self-assemble into microphase separated nanoscale domains. Unfortunately, the self-assembled microstructure is tuned by polymer composition, thus limiting the potential to simultaneously optimize chemical, mechanical, and transport properties for desired applications. To this end, much work was been put into manipulating block copolymer self-assembly independently of polymer composition. These efforts have included the use of additives or solvents to alter polymer chain conformation, the addition of a third monomer to produce ABC triblock terpolymers, architectures with mixed blocks, such as tapered/gradient polymers, and the synthesis of other nonlinear molecular architectures. This work has shown that the microstructures formed by linear ABC terpolymers can be altered by controlling the architecture of the polymer molecules at a constant monomer composition, so that the microstructure is tuned independently from the chemical properties.

Copolymerization of Styrene and Methacrylates in the presence of Catalytic Chain Transfer Agents (Cacti's)

International Nuclear Information System (INIS)

Hussain, M.Sakhawat; Khan, M.A.; Ahmad, Shafique

2005-01-01

The present paper focuses on the use of a Co (II) complex, [Co(afdo-H)] as a catalytic chain transfer agent (CCTA) for controlling molecular weight in copolymerization of styrene (STY) with butyl methacrylate (BMA) and methylmethacrylate (MMA). The catalyst is structurally similar to [co(dmg-H) (BF)] patented by Du Pont as a CCTA. Average catalytic chain transfer constant, C8 of [co(afdo-H) (BF)] for coplymerization of STY with BMA and MMA determined from Maya plot, was found to be in the range of 10-10.This value is lower than the value reported for the [Co(dmg-H)(BF)). In the case of STY-BMA or STY-MMA copolymerization, a considerable reduction in the viscosity average molecular weights (Mv) was observed in the copolymers. The average molecular weight of poly (MMA-BMA) was reduced by a factor of ten compared to the reduction in poly (STY-MMA) and poly (STY-BMA) for the same concentration of the CCTA. (author)

Surfactant-Free RAFT Emulsion Polymerization of Styrene Using Thermoresponsive macroRAFT Agents: Towards Smart Well-Defined Block Copolymers with High Molecular Weights

Directory of Open Access Journals (Sweden)

Steffen Eggers

2017-12-01

Full Text Available The combination of reversible addition–fragmentation chain transfer (RAFT and emulsion polymerization has recently attracted much attention as a synthetic tool for high-molecular-weight block copolymers and their micellar nano-objects. Up to recently, though, the use of thermoresponsive polymers as both macroRAFT agents and latex stabilizers was impossible in aqueous media due to their hydrophobicity at the usually high polymerization temperatures. In this work, we present a straightforward surfactant-free RAFT emulsion polymerization to obtain thermoresponsive styrenic block copolymers with molecular weights of around 100 kDa and their well-defined latexes. The stability of the aqueous latexes is achieved by adding 20 vol % of the cosolvent 1,4-dioxane (DOX, increasing the phase transition temperature (PTT of the used thermoresponsive poly(N-acryloylpyrrolidine (PAPy macroRAFT agents above the polymerization temperature. Furthermore, this cosolvent approach is combined with the use of poly(N,N-dimethylacrylamide-block-poly(N-acryloylpiperidine-co-N-acryloylpyrrolidine (PDMA-b-P(APi-co-APy as the macroRAFT agent owning a short stabilizing PDMA end block and a widely adjustable PTT of the P(APi-co-APy block in between 4 and 47 °C. The temperature-induced collapse of the latter under emulsion polymerization conditions leads to the formation of RAFT nanoreactors, which allows for a very fast chain growth of the polystyrene (PS block. In dynamic light scattering (DLS, as well as cryo-transmission electron microscopy (cryoTEM, moreover, all created latexes indeed reveal a high (temperature stability and a reversible collapse of the thermoresponsive coronal block upon heating. Hence, this paper pioneers a versatile way towards amphiphilic thermoresponsive high-molecular-weight block copolymers and their nano-objects with tailored corona switchability.

Transfer of radionuclides at the uranium and thorium decay chains in aquatic and terrestrial environments

International Nuclear Information System (INIS)

Letourneau, C.

1987-04-01

This report examines the transfer of radionuclides from the uranium and thorium decay chains (U-238, Ra-226, Th-232, Th-230, Po-210 and Pb-210) through the aquatic and terrestrial environment. This transfer is characterized by a transfer coefficient; environmental and experimental factors which cause this coefficient to vary are presented and discussed in this report. Furthermore, based on a literature survey, the report indicates the range of coefficients found for the aquatic sector (that is, sediment and freshwater and marine organisms) and for the terrestrial sector (that is, plants and domestic and wild animals). Afterwards, generalisations are formulated on the transfer of the different radionuclides through the multiple environmental compartments. 75 refs

Time-resolved small-angle neutron scattering study on soap-free emulsion polymerization

Energy Technology Data Exchange (ETDEWEB)

Motokawa, Ryuhei [Research Group of Soft Matter and Neutron Scattering, Advanced Science Research Center, Japan Atomic Energy Research Institute, Tokai, Ibaraki 319-1195 (Japan); Koizumi, Satoshi [Research Group of Soft Matter and Neutron Scattering, Advanced Science Research Center, Japan Atomic Energy Research Institute, Tokai, Ibaraki 319-1195 (Japan)]. E-mail: koizumi@neutrons.tokai.jaeri.go.jp; Hashimoto, Takeji [Research Group of Soft Matter and Neutron Scattering, Advanced Science Research Center, Japan Atomic Energy Research Institute, Tokai, Ibaraki 319-1195 (Japan); Nakahira, Takayuki [Department of Applied Chemistry and Biotechnology, Chiba University, Chiba-shi, Chiba 263-8522 (Japan); Annaka, Masahiko [Department of Chemistry, Kyushu University, Fukuoka 812-8581 (Japan)

2006-11-15

We investigated an aqueous soap-free emulsion polymerization process of Poly(N-isopropylacrylamide)-block-poly(ethylene glycol) by ultra-small-angle and time-resolved small-angle neutron scattering methods. The results indicate that the compartmentalization of chain end radicals into solid-like micelle cores crucially leads to the quasi-living behavior of the radical polymerization by prohibiting recombination process.

Silicon and aluminum doping effects on the microstructure and properties of polymeric amorphous carbon films

Energy Technology Data Exchange (ETDEWEB)

Liu, Xiaoqiang, E-mail: lxq_suse@sina.com [Material Corrosion and Protection Key Laboratory of Sichuan province, Sichuan University of Science and Engineering, Zigong 643000 (China); Hao, Junying, E-mail: jyhao@licp.cas.cn [State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000 (China); Xie, Yuntao [Material Corrosion and Protection Key Laboratory of Sichuan province, Sichuan University of Science and Engineering, Zigong 643000 (China)

2016-08-30

Highlights: • Evolution of nanostructure and properties of the polymeric amorphous carbon films were firstly studied. • Si doping enhanced polymerization of the hydrocarbon chains and Al doping resulted in increase in the ordered carbon clusters of polymeric amorphous carbon films. • Soft polymeric amorphous carbon films exhibited an unconventional frictional behaviors with a superior wear resistance. • The mechanical and vacuum tribological properties of the polymeric amorphous carbon films were significantly improved by Si and Al co-doping. - Abstract: Polymeric amorphous carbon films were prepared by radio frequency (R.F. 13.56 MHz) magnetron sputtering deposition. The microstructure evolution of the deposited polymeric films induced by silicon (Si) and aluminum(Al) doping were scrutinized through infrared spectroscopy, multi-wavelength Raman spectroscopy, scanning electron microscopy (SEM) and high resolution transmission electron microscopy (HRTEM). The comparative results show that Si doping can enhance polymerization and Al doping results in an increase in the ordered carbon clusters. Si and Al co-doping into polymeric films leads to the formation of an unusual dual nanostructure consisting of cross-linked polymer-like hydrocarbon chains and fullerene-like carbon clusters. The super-high elasticity and super-low friction coefficients (<0.002) under a high vacuum were obtained through Si and Al co-doping into the films. Unconventionally, the co-doped polymeric films exhibited a superior wear resistance even though they were very soft. The relationship between the microstructure and properties of the polymeric amorphous carbon films with different elements doping are also discussed in detail.

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

Copolymer Synthesis and Characterization by Post-Polymerization Modification

Science.gov (United States)

Galvin, Casey James

This PhD thesis examines the physical behavior of surface-grafted polymer assemblies (SGPAs) derived from post-polymerization modification (PPM) reactions in aqueous and vapor enriched environments, and offers an alternative method of creating SGPAs using a PPM approach. SGPAs comprise typically polymer chains grafted covalently to solid substrates. These assemblies show promise in a number of applications and technologies due to the stability imparted by the covalent graft and ability to modify interfacial properties and stability. SGPAs also offer a set of rich physics to explore in fundamental investigations as a result of confining macromolecules to a solid substrate. PPM reactions (also called polymer analogous reactions) apply small molecule organic chemistry reactions to the repeat units of polymer chains in order to generate new chemistries. By applying a PPM strategy to SGPAs, a wide variety of functional groups can be introduced into a small number of well-studied and well-behaved model polymer systems. This approach offers the advantage of holding constant other properties of the SGPA (e.g., molecular weight, MW, and grafting density, sigma) to isolate the effect of chemistry on physical behavior. Using a combination of PPM and fabrication methods that facilitate the formation of SPGAs with position-dependent gradual variation of sigma on flat impenetrable substrate, the influence of polymer chemistry and sigma is examined on the stability of weak polyelectrolyte brushes in aqueous environments at different pH levels. Degrafting of polymer chains in SGPAs exhibits a complex dependence on side chain chemistry, sigma, pH and the charge fraction (alpha) within the brush. Results of these experiments support a proposed mechanism of degrafting, wherein extension of the grafted chains away from the substrate generates tension along the polymer backbone, which activates the grafting chemistry for hydrolysis. The implications of these findings are important in

Biodegradable Polyelectrolyte Obtained by Radiation Polymerization

International Nuclear Information System (INIS)

Craciun, G.; Martin, D.; Manaila, E.; Nemtanu, M.; Brasoveanu, M.; Ighigeanu, D.

2009-01-01

Poly electrolytes are water-soluble polymers carrying ionic charge along the polymer chain. Depending upon the charge, these polymers are anionic or cationic. The inherent solid - liquid separating efficiency makes these poly electrolytes a unique class of polymers which find extensive application in potable water, industrial raw and process water, municipal sewage treatment, mineral processing and metallurgy, oil drilling and recovery, etc. Also, due to their ability to produce advanced induced coagulation, a considerable amount of bacteria and viruses are precipitated together with the suspended solids. Especially the acrylamide polymers are very efficacious for water treatment but acrylamide is a toxic monomer and therefore their use are governed by international standards that provide the residual acrylamide monomer content (RAMC) in them be less than 0.05%. Under these circumstances our attention was focused on the following research steps that are presented in this paper: 1) Preparation of a special class of poly electrolytes, named Pn, with very low RAMC values, based on electron beam (EB), microwave (MW) and EB + MW induced co-polymerization of aqueous solutions containing appropriate mixtures of acrylamide (AMD) and acrylic acid (AA) monomers (AMD - AA co-polymers). The Pn were obtained by radiation technology with very small RAMC (under 0.01%) as well as in a wide range of molecular weights and charge densities. Very low AMD monomer content of Pn is due to the major advantages of radiation induced polymerization in aqueous solution containing monomers. Due to water presence in the EB irradiated system, irradiated water radicals facilitate the polymerization process and increase rate and level of monomers conversion in co-polymers. Also, once again, by the presence of water, which absorbs MW energy very strongly, the MW polymerization reaction rate is much enhanced resulting in a reaction time about 50-100 times lowers than by conventional heating. Also

Radiation-induced polymerization of unsaturated phospholipid mixtures for the synthesis of artificial red cells

Science.gov (United States)

Hosoi, F.; Omichi, H.; Akama, K.; Awai, K.; Endo, S.; Nakano, Y.

1997-08-01

Radiation induced polymerization of phospholipid containing unsaturated acyl chains was applied to the synthesis of artificial red cells. Vesicles of 1,2-bis-(2,4-octadecadienoyl)-phosphatidylcholine (DODPC) and 1-stearoyl-2-(2,4-octadecadienoyl)-phosphatidylcholine (AODPC) were irradiated by 60Co γ-rays to obtain polymerized bilayer structure of these monomers. It was found that the polymerization of unsaturated groups located at 2-acyl chain of DODPC polymerized faster than those of AODPC. The difference was explained by the packed state of these monomers in the bilayer vesicles. The artificial red cell was obtained by irradiating the mixture of DODPC or AODPC with hemoglobin, cholesterol and palmitic acid sodium salt. The integrity of the irradiated hemoglobin in the vesicle was maintained by keeping the suspended solution at low temperature. On the other hand, oxidation of heme part became remarkable when the vesicle was kept at 37°C. The presence of extra hemoglobin outside the vesicle was found useful to prevent this oxidation.

Identification and evaluation of modularization practices in an automotive supplier: progressivity analysis of transferring activities in the supply chain

Directory of Open Access Journals (Sweden)

Evandro Prieto

2013-08-01

Full Text Available The automotive value chain has more and more been making room to a strategy of which activities of product design and production have been transferred to the module suppliers. The transfer of value-added activities occurs from assembler to the module suppliers. The former assume the role of integrators within the supply chain. The supply chain participants have started to strengths their competencies in order to obtain advantages in the economy of scale and scope. In this context, the present work aims at investigating the valued-added transfer between first and second tiers of automotive supply chain in new product development and production. The work was carried out from an evaluation of a supplier with regard to modularization. The theoretical background considers the concepts of integrated and modular architecture as well as the progressiveness of competencies among suppliers. It adopts single cased as the research methodological approach. The literature points out that the process of modularization either in product development or in production offer benefits for both sides: assemblers and suppliers. The results from the investigated supplier shows inherent benefits due to the acquisition of new technologies that enable an increase of technical and management learning in projects of new products. Therefore, it demonstrates that in this modularity environment, the potential of value-added transfer is associated to the level of progressiveness of competencies that are incorporated to deliver module solutions to assemblers; the investigated supplier can be categorized in an “embrionary” stage.

A grafting from approach to graft polystyrene chains at the surface of graphene nanolayers by RAFT polymerization: Various graft densities from hydroxyl groups

Energy Technology Data Exchange (ETDEWEB)

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

2016-01-01

Graphical abstract: (3-Aminopropyl) triethoxysilane was grafted at the surface of GO in low and high different graft densities to yield GOHAL and GOHAH, respectively. Subsequently, 2-(dodecylthiocarbonothioylthio)-2-methylpropionic acid (RA) was attached at the surface of GOHAL and GOHAH by an amidation reaction to yield GOHRL and GOHRH, respectively. Then, GOHRL and GOHRH were used in grafting from RAFT polymerization of styrene. - Highlights: • A RAFT agent grafted GO was used in grafting from RAFT polymerization of styrene. • The efficiency of RAFT agent attachment at the surface of GO is 41.12% for high density sample. • Polystyrene molecular weight is decreased by the addition of graphene content and also graft density of RAFT agent. - Abstract: (3-Aminopropyl) triethoxysilane was grafted at the surface of GO in low and high different graft densities to yield GOHAL and GOHAH, respectively. Subsequently, 2-(dodecylthiocarbonothioylthio)-2-methylpropionic acid (RA) was attached at the surface of GOHAL and GOHAH by an amidation reaction to yield GOHRL and GOHRH, respectively. Then, GOHRL and GOHRH were used in grafting from RAFT polymerization of styrene. Grafting of APTES and RA was approved by Fourier transform infrared spectroscopy, X-ray photo electron spectroscopy, and Raman spectroscopy. Expansion of graphene interlayer by oxidation and functionalization processes was evaluated by X-ray diffraction. Conversion values of styrene were calculated using gas chromatography. Molecular weight and PDI values of attached polystyrene (PS) chains were studied by size exclusion chromatography. Thermogravimetric analysis was also used to investigate the degradation temperatures, char contents, and graft contents of modifiers and PS chains. GOHRH and GOHRL reach to char content of 55.3 and 45.2% at 600 °C, which shows that weight ratio of modifier (APTES and RA moieties) is 15.3 and 5.2%, respectively. Scanning and transmission electron microscopies show that

Isolation and characterization of inulin with a high degree of polymerization from roots of Stevia rebaudiana (Bert.) Bertoni.

Science.gov (United States)

Lopes, Sheila M S; Krausová, Gabriela; Rada, Vojtěch; Gonçalves, José E; Gonçalves, Regina A C; de Oliveira, Arildo J B

2015-06-26

The polysaccharide inulin has great importance in the food and pharmaceutical industries. The degree of polymerization (DP) of inulin influences important properties, such as, solubility, thermal stability, sweetness power and prebiotic activity. Molecules with a high degree of polymerization are obtained through physical techniques for enrichment of the inulin chains because they are not commonly obtained from plants extract. Gas chromatography/Mass Spectrometry and (1)H Nuclear Magnetic Resonance analysis showed that inulin from Stevia rebaudiana roots has a degree of polymerization (DPn 28) higher than the value of DPn 12-15 for inulins from other plant species. Furthermore, the methodology of freeze/thaw to enrich the chains allowed us to increase the DP, similarly to other methodologies used for the enrichment of inulin chains. The prebiotic assays confirm that inulin from S. rebaudiana has a high DP. The combined use of these molecules with low degree of polymerization fructans seems to be advantageous to prolong the prebiotic effect in the colon. Our results suggest that S. rebaudiana roots are a promising source of high degree polymerization inulins. Copyright © 2015 Elsevier Ltd. All rights reserved.

Novel Polymeric Prodrugs of Valproic Acid as Anti- Epilepsy Drugs ...

African Journals Online (AJOL)

Epilepsy Drugs: Synthesis, Characterization and In-vitro ... The release of VPA from polymeric prodrugs was studied using cellophane ... pharmacokinetics and accessibility in market [8]. ..... between the drug and polymer chain can affect.

The influence of polymeric membrane gas spargers on hydrodynamics and mass transfer in bubble column bioreactors.

Science.gov (United States)

Tirunehe, Gossaye; Norddahl, B

2016-04-01

Gas sparging performances of a flat sheet and tubular polymeric membranes were investigated in 3.1 m bubble column bioreactor operated in a semi batch mode. Air-water and air-CMC (Carboxymethyl cellulose) solutions of 0.5, 0.75 and 1.0 % w/w were used as interacting gas-liquid mediums. CMC solutions were employed in the study to simulate rheological properties of bioreactor broth. Gas holdup, bubble size distribution, interfacial area and gas-liquid mass transfer were studied in the homogeneous bubbly flow hydrodynamic regime with superficial gas velocity (U(G)) range of 0.0004-0.0025 m/s. The study indicated that the tubular membrane sparger produced the highest gas holdup and densely populated fine bubbles with narrow size distribution. An increase in liquid viscosity promoted a shift in bubble size distribution to large stable bubbles and smaller specific interfacial area. The tubular membrane sparger achieved greater interfacial area and an enhanced overall mass transfer coefficient (K(L)a) by a factor of 1.2-1.9 compared to the flat sheet membrane.

Living Polycondensation: Synthesis of Well-Defined Aromatic Polyamide-Based Polymeric Materials

KAUST Repository

Alyami, Mram Z.

2016-11-01

Chain growth condensation polymerization is a powerful tool towards the synthesis of well-defined polyamides. This thesis focuses on one hand, on the synthesis of well-defined aromatic polyamides with different aminoalkyl pendant groups with low polydispersity and controlled molecular weights, and on the other hand, on studying their thermal properties. In the first project, well-defined poly (N-octyl-p-aminobenzoate) and poly (N-butyl-p-aminobenzoate) were synthesized, and for the first time, their thermal properties were studied. In the second project, ethyl4-aminobenzoate, ethyl 4-octyl aminobenzoate and 4-(hydroxymethyl) benzoic acid were used as novel efficient initiators of ε-caprolactone with t-BuP2 as a catalyst. Macroinitiator and Macromonomer of poly (ε-caprolactone) were synthesized with ethyl 4-octyl aminobenzoate and ethyl 4-aminobenzoate as initiators to afford polyamide-block-poly (ε-caprolactone) and polyamide-graft-poly (ε-caprolactone) by chain growth condensation polymerization (CGCP). In the third project, a new study has been done on chain growth condensation polymerization to discover the probability to synthesize new polymers and studied their thermal properties. For this purpose, poly (N-cyclohexyl-p-aminobenzoate) and poly (N-hexyl-p-aminobenzoate) were synthesized with low polydispersity and controlled molecular weights.

Enantioselective polymerization of epoxides using biaryl-linked bimetallic cobalt catalysts: A mechanistic study

KAUST Repository

Ahmed, Syud M.

2013-12-18

The enantioselective polymerization of propylene oxide (PO) using biaryl-linked bimetallic salen Co catalysts was investigated experimentally and theoretically. Five key aspects of this catalytic system were examined: (1) the structural features of the catalyst, (2) the regio- and stereoselectivity of the chain-growth step, (3) the probable oxidation and electronic state of Co during the polymerization, (4) the role of the cocatalyst, and (5) the mechanism of monomer enchainment. Several important insights were revealed. First, density functional theory (DFT) calculations provided detailed structural information regarding the regio- and stereoselective chain-growth step. Specifically, the absolute stereochemistry of the binaphthol linker determines the enantiomer preference in the polymerization, and the interaction between the salen ligand and the growing polymer chain is a fundamental aspect of enantioselectivity. Second, a new bimetallic catalyst with a conformationally flexible biphenol linker was synthesized and found to enantioselectively polymerize PO, though with lower enantioselectivity than the binaphthol linked catalysts. Third, DFT calculations revealed that the active form of the catalyst has two active exo anionic ligands (chloride or carboxylate) and an endo polymer alkoxide which can ring-open an adjacent cobalt-coordinated epoxide. Fourth, calculations showed that initiation is favored by an endo chloride ligand, while propagation is favored by the presence of two exo carboxylate ligands. © 2013 American Chemical Society.

Enantioselective polymerization of epoxides using biaryl-linked bimetallic cobalt catalysts: A mechanistic study

KAUST Repository

Ahmed, Syud M.; Poater, Albert; Childers, M. Ian; Widger, Peter C B; Lapointe, Anne M.; Lobkovsky, Emil B.; Coates, Geoffrey W.; Cavallo, Luigi

2013-01-01

The enantioselective polymerization of propylene oxide (PO) using biaryl-linked bimetallic salen Co catalysts was investigated experimentally and theoretically. Five key aspects of this catalytic system were examined: (1) the structural features of the catalyst, (2) the regio- and stereoselectivity of the chain-growth step, (3) the probable oxidation and electronic state of Co during the polymerization, (4) the role of the cocatalyst, and (5) the mechanism of monomer enchainment. Several important insights were revealed. First, density functional theory (DFT) calculations provided detailed structural information regarding the regio- and stereoselective chain-growth step. Specifically, the absolute stereochemistry of the binaphthol linker determines the enantiomer preference in the polymerization, and the interaction between the salen ligand and the growing polymer chain is a fundamental aspect of enantioselectivity. Second, a new bimetallic catalyst with a conformationally flexible biphenol linker was synthesized and found to enantioselectively polymerize PO, though with lower enantioselectivity than the binaphthol linked catalysts. Third, DFT calculations revealed that the active form of the catalyst has two active exo anionic ligands (chloride or carboxylate) and an endo polymer alkoxide which can ring-open an adjacent cobalt-coordinated epoxide. Fourth, calculations showed that initiation is favored by an endo chloride ligand, while propagation is favored by the presence of two exo carboxylate ligands. © 2013 American Chemical Society.

Heat conduction in chain polymer liquids: molecular dynamics study on the contributions of inter- and intramolecular energy transfer.

Science.gov (United States)

Ohara, Taku; Yuan, Tan Chia; Torii, Daichi; Kikugawa, Gota; Kosugi, Naohiro

2011-07-21

In this paper, the molecular mechanisms which determine the thermal conductivity of long chain polymer liquids are discussed, based on the results observed in molecular dynamics simulations. Linear n-alkanes, which are typical polymer molecules, were chosen as the target of our studies. Non-equilibrium molecular dynamics simulations of bulk liquid n-alkanes under a constant temperature gradient were performed. Saturated liquids of n-alkanes with six different chain lengths were examined at the same reduced temperature (0.7T(c)), and the contributions of inter- and intramolecular energy transfer to heat conduction flux, which were identified as components of heat flux by the authors' previous study [J. Chem. Phys. 128, 044504 (2008)], were observed. The present study compared n-alkane liquids with various molecular lengths at the same reduced temperature and corresponding saturated densities, and found that the contribution of intramolecular energy transfer to the total heat flux, relative to that of intermolecular energy transfer, increased with the molecular length. The study revealed that in long chain polymer liquids, thermal energy is mainly transferred in the space along the stiff intramolecular bonds. This finding implies a connection between anisotropic thermal conductivity and the orientation of molecules in various organized structures with long polymer molecules aligned in a certain direction, which includes confined polymer liquids and self-organized structures such as membranes of amphiphilic molecules in water.

Study on transfer coefficients of 90Sr, 137Cs, natural U, 226Ra and 239Pu in terrestrial food chains

International Nuclear Information System (INIS)

Qin Suyun; Qi Yong; Li Shuqin; Zhou Caiyun; Zhang Jingjuan; Li Jikai; Li Xuequn

1995-01-01

The aim of study was to provide values of transfer parameter of 90 Sr, 137 Cs, Natural U, 226 Ra and 239 Pu in terrestrial food chains, more applicable for Chinese socio-natural conditions. Data of radionuclides contents in agricultural crops and in associated soils, in sheep tissues and in associated grasses were collected in couples. The transfer coefficients in terrestrial food chains (soil-crops, grasses-sheep tissues) were calculated. On basis of statistical analysis, the representative values and 95% ranges of transfer coefficient for 5 radionuclides in 7 kind of agricultural products for southern moist areas and north dry areas were given. Regression analysis showed that relation between the transfer coefficients and the radionuclide contents in their associated soils present a negative correlation, it could be described with a equation: Y = aX -b

RADIOCHEMICAL YIELDS OF GRAFT POLYMERIZATION REACTIONS OF CELLULOSE

Energy Technology Data Exchange (ETDEWEB)

Arthur, Jr, J C; Blouin, F A

1963-12-15

The preparation of radioinduced graft polymers of cotton cellulose, while retaining the fibrous nature and high molecular weight of the cellulose, depended primarily on the radiochemical yields of cellulose reactions and of graft polymerization reactions. Yields of the initial major molecular changes in cellulosic polymer indicated that, in the case of scission of the molecule and carboxyl group formation, chain reactions were not initiated by radiation; however, in the case of carbonyl group formation chain reactions were initiated but quickly terminated. Generally, experimental procedures, used in graft polymerization reactions, were: simultaneous irradiation reactions, that is, application of monomers or solutions of monomers to cellulose or chemically modified celluloses, then irradiation; and post-irradiation reactions, that is, irradiation of cellulose or chemically modified celluloses, then after removal from the field of radiation, contacting the irradiated cellulose with monomer. Some of the most important factors influencing the radiochemical yields of graft polymerization reactions, of styrene and acrylonitrile onto cellulose were: concentration of monomer in treating solution; solvent; ratio of monomer solution to cellulose; prior chemical modification of cellulose; and absence of oxygen, particularly in post-irradiation reactions. Experimental data are presented, and the direct and indirect effects of Co/sup 60/ gamma radiation on these reactions are discussed. (auth)

Well-defined block copolymers for gene delivery to dendritic cells: probing the effect of polycation chain-length.

Science.gov (United States)

Tang, Rupei; Palumbo, R Noelle; Nagarajan, Lakshmi; Krogstad, Emily; Wang, Chun

2010-03-03

The development of safe and efficient polymer carriers for DNA vaccine delivery requires mechanistic understanding of structure-function relationship of the polymer carriers and their interaction with antigen-presenting cells. Here we have synthesized a series of diblock copolymers with well-defined chain-length using atom transfer radical polymerization and characterized the influence of polycation chain-length on the physico-chemical properties of the polymer/DNA complexes as well as the interaction with dendritic cells. The copolymers consist of a hydrophilic poly(ethylene glycol) block and a cationic poly(aminoethyl methacrylate) (PAEM) block. The average degree of polymerization (DP) of the PAEM block was varied among 19, 39, and 75, with nearly uniform distribution. With increasing PAEM chain-length, polyplexes formed by the diblock copolymers and plasmid DNA had smaller average particle size and showed higher stability against electrostatic destabilization by salt and heparin. The polymers were not toxic to mouse dendritic cells (DCs) and only displayed chain-length-dependent toxicity at a high concentration (1mg/mL). In vitro gene transfection efficiency and polyplex uptake in DCs were also found to correlate with chain-length of the PAEM block with the longer polymer chain favoring transfection and cellular uptake. The polyplexes induced a modest up-regulation of surface markers for DC maturation that was not significantly dependent on PAEM chain-length. Finally, the polyplex prepared from the longest PAEM block (DP of 75) achieved an average of 20% enhancement over non-condensed anionic dextran in terms of uptake by DCs in the draining lymph nodes 24h after subcutaneous injection into mice. Insights gained from studying such structurally well-defined polymer carriers and their interaction with dendritic cells may contribute to improved design of practically useful DNA vaccine delivery systems. Copyright 2009 Elsevier B.V. All rights reserved.

The influence of temperature on the polymerization of ethyl cyanoacrylate from the vapor phase

Energy Technology Data Exchange (ETDEWEB)

Dadmun, Mark D [ORNL; Algaier, Dana [University of Tennessee, Knoxville (UTK); Baskaran, Durairaj [University of Tennessee, Knoxville (UTK)

2011-01-01

The polymerization of ethyl cyanoacrylate fumes from surface bound initiators is an important step in many novel and mature technologies. Understanding the effect of temperature on the rate of poly(ethyl cyanoacrylate) (PECA) growth and its molecular weight during its polymerization from the vapor phase from surface bound initiators provides insight into the important mechanistic aspects that impact the polymerizations success. In these studies, it is shown that the amount of PECA formed during the polymerization of ECA from a latent fingerprint increases with decreasing temperature, while the polymer molecular weight varies little. This is interpreted to be the result of the loosening of the ion pair that initiates the polymer chain growth and resides on the end of the growing polymer chain with decreasing temperature. Comparison of temperature effects and counter-ion studies show that in both cases loosening the ion pair results in the formation of more polymer with similar molecular weight, verifying this interpretation. These results further suggest that lowering the temperature may be an effective method to optimize anionic vapor phase polymerizations, including the improvement of the quality of aged latent prints and preliminary results are presented that substantiate this prediction.

High efficiency transfer of quantum information and multiparticle entanglement generation in translation-invariant quantum chains

International Nuclear Information System (INIS)

Plenio, Martin B; Semiao, Fernando L

2005-01-01

We demonstrate that a translation-invariant chain of interacting quantum systems can be used for high efficiency transfer of quantum entanglement and the generation of multiparticle entanglement over large distances and between arbitrary sites without the requirement of precise spatial or temporal control. The scheme is largely insensitive to disorder and random coupling strengths in the chain. We discuss harmonic oscillator systems both in the case of arbitrary Gaussian states and in situations when at most one excitation is in the system. The latter case, which we prove to be equivalent to an xy-spin chain, may be used to generate genuine multiparticle entanglement. Such a 'quantum data bus' may prove useful in future solid state architectures for quantum information processing

Optimal control of fast and high-fidelity quantum state transfer in spin-1/2 chains

Energy Technology Data Exchange (ETDEWEB)

Zhang, Xiong-Peng [School of Physics, Beijing Institute of Technology, Beijing 100081 (China); Shao, Bin, E-mail: sbin610@bit.edu.cn [School of Physics, Beijing Institute of Technology, Beijing 100081 (China); Hu, Shuai; Zou, Jian [School of Physics, Beijing Institute of Technology, Beijing 100081 (China); Wu, Lian-Ao [Department of Theoretical Physics and History of Science, The Basque Country University (EHU/UPV), PO Box 644, 48080 Bilbao (Spain); Ikerbasque, Basque Foundation for Science, 48011 Bilbao (Spain)

2016-12-15

Spin chains are promising candidates for quantum communication and computation. Using quantum optimal control (OC) theory based on the Krotov method, we present a protocol to perform quantum state transfer with fast and high fidelity by only manipulating the boundary spins in a quantum spin-1/2 chain. The achieved speed is about one order of magnitude faster than that is possible in the Lyapunov control case for comparable fidelities. Additionally, it has a fundamental limit for OC beyond which optimization is not possible. The controls are exerted only on the couplings between the boundary spins and their neighbors, so that the scheme has good scalability. We also demonstrate that the resulting OC scheme is robust against disorder in the chain.

Polymeric Coatings for Combating Biocorrosion

Science.gov (United States)

Guo, Jing; Yuan, Shaojun; Jiang, Wei; Lv, Li; Liang, Bin; Pehkonen, Simo O.

2018-03-01

Biocorrosion has been considered as big trouble in many industries and marine environments due to causing great economic loss. The main disadvantages of present approaches to prevent corrosion include being limited by environmental factors, being expensive, inapplicable to field, and sometimes inefficient. Studies show that polymer coatings with anti-corrosion and anti-microbial properties have been widely accepted as a novel and effective approach to preventbiocorrosion. The main purpose of this review is to summarize up the progressive status of polymer coatings used for combating microbially-induced corrosion. Polymers used to synthesize protective coatings are generally divided into three categories: i) traditional polymers incorporated with biocides, ii) antibacterial polymers containing quaternary ammonium compounds, and iii) conductive polymers. The strategies to synthesize polymer coatings resort mainly to grafting anti-bacterial polymers from the metal substrate surface using novel surface-functionalization approaches, such as free radical polymerization, chemically oxidative polymerization and surface-initiated atom transfer radical polymerization, as opposed to the traditional approaches of dip coating or spin coating.

Estimating side-chain order in methyl-protonated, perdeuterated proteins via multiple-quantum relaxation violated coherence transfer NMR spectroscopy

International Nuclear Information System (INIS)

Sun Hechao; Godoy-Ruiz, Raquel; Tugarinov, Vitali

2012-01-01

Relaxation violated coherence transfer NMR spectroscopy (Tugarinov et al. in J Am Chem Soc 129:1743–1750, 2007) is an established experimental tool for quantitative estimation of the amplitudes of side-chain motions in methyl-protonated, highly deuterated proteins. Relaxation violated coherence transfer experiments monitor the build-up of methyl proton multiple-quantum coherences that can be created in magnetically equivalent spin-systems as long as their transverse magnetization components relax with substantially different rates. The rate of this build-up is a reporter of the methyl-bearing side-chain mobility. Although the build-up of multiple-quantum 1 H coherences is monitored in these experiments, the decay of the methyl signal during relaxation delays occurs when methyl proton magnetization is in a single-quantum state. We describe a relaxation violated coherence transfer approach where the relaxation of multiple-quantum 1 H– 13 C methyl coherences during the relaxation delay period is quantified. The NMR experiment and the associated fitting procedure that models the time-dependence of the signal build-up, are applicable to the characterization of side-chain order in [ 13 CH 3 ]-methyl-labeled, highly deuterated protein systems up to ∼100 kDa in molecular weight. The feasibility of extracting reliable measures of side-chain order is experimentally verified on methyl-protonated, perdeuterated samples of an 8.5-kDa ubiquitin at 10°C and an 82-kDa Malate Synthase G at 37°C.

Modeling and sensitivity analysis of mass transfer in active multilayer polymeric film for food applications

Science.gov (United States)

Bedane, T.; Di Maio, L.; Scarfato, P.; Incarnato, L.; Marra, F.

2015-12-01

The barrier performance of multilayer polymeric films for food applications has been significantly improved by incorporating oxygen scavenging materials. The scavenging activity depends on parameters such as diffusion coefficient, solubility, concentration of scavenger loaded and the number of available reactive sites. These parameters influence the barrier performance of the film in different ways. Virtualization of the process is useful to characterize, design and optimize the barrier performance based on physical configuration of the films. Also, the knowledge of values of parameters is important to predict the performances. Inverse modeling and sensitivity analysis are sole way to find reasonable values of poorly defined, unmeasured parameters and to analyze the most influencing parameters. Thus, the objective of this work was to develop a model to predict barrier properties of multilayer film incorporated with reactive layers and to analyze and characterize their performances. Polymeric film based on three layers of Polyethylene terephthalate (PET), with a core reactive layer, at different thickness configurations was considered in the model. A one dimensional diffusion equation with reaction was solved numerically to predict the concentration of oxygen diffused into the polymer taking into account the reactive ability of the core layer. The model was solved using commercial software for different film layer configurations and sensitivity analysis based on inverse modeling was carried out to understand the effect of physical parameters. The results have shown that the use of sensitivity analysis can provide physical understanding of the parameters which highly affect the gas permeation into the film. Solubility and the number of available reactive sites were the factors mainly influencing the barrier performance of three layered polymeric film. Multilayer films slightly modified the steady transport properties in comparison to net PET, giving a small reduction

The influence of polymeric membrane gas spargers on hydrodynamics and mass transfer in bubble column bioreactors

DEFF Research Database (Denmark)

Tirunehe, Gossay; Norddahl, B.

2016-01-01

Gas sparging performances of a flat sheet and tubular polymeric membranes were investigated in 3.1 m bubble column bioreactor operated in a semi batch mode. Air–water and air–CMC (Carboxymethyl cellulose) solutions of 0.5, 0.75 and 1.0 % w/w were used as interacting gas–liquid mediums. CMC....../s. The study indicated that the tubular membrane sparger produced the highest gas holdup and densely populated fine bubbles with narrow size distribution. An increase in liquid viscosity promoted a shift in bubble size distribution to large stable bubbles and smaller specific interfacial area. The tubular...... membrane sparger achieved greater interfacial area and an enhanced overall mass transfer coefficient (KLa) by a factor of 1.2–1.9 compared to the flat sheet membrane....

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.

Highly Defined Multiblock Copolypeptoids: Pushing the Limits of Living Nucleophilic Ring-Opening Polymerization

KAUST Repository

Fetsch, Corinna; Luxenhofer, Robert

2012-01-01

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.

Surface plasmon resonance methodology for monitoring polymerization kinetics and morphology changes of brushes—evaluated with poly(N-isopropylacrylamide)

Energy Technology Data Exchange (ETDEWEB)

Emilsson, Gustav [Dept. of Chemistry and Chemical Engineering, Chalmers University of Technology, 41296 Göteborg (Sweden); Schoch, Rafael L.; Oertle, Philipp [Biozentrum and the Swiss Nanoscience Institute, University of Basel, 4056 Basel (Switzerland); Xiong, Kunli [Dept. of Chemistry and Chemical Engineering, Chalmers University of Technology, 41296 Göteborg (Sweden); Lim, Roderick Y.H. [Biozentrum and the Swiss Nanoscience Institute, University of Basel, 4056 Basel (Switzerland); Dahlin, Andreas B., E-mail: adahlin@chalmers.se [Dept. of Chemistry and Chemical Engineering, Chalmers University of Technology, 41296 Göteborg (Sweden)

2017-02-28

Highlights: • Real-time monitoring of thickness and the kinetics of polymerization. • Probing brush height both above and below the lower critical solution temperature. • Quantitative analysis of thermal actuation of poly(N-isopropylacrylamide) brushes. - Abstract: Polymerization from surfaces and the resulting “brushes” have many uses in the development of novel materials and functional interfaces. However, it is difficult to accurately monitor the polymerization rate, which limits the use of polymer brushes in applications where control of thickness is desirable. We present a new methodology based on angular surface plasmon resonance (SPR) which provides real-time measurements of the thickness evolution during atom transfer radical polymerization, using poly(N-isopropylacrylamide) as an example. Our data analysis shows that the growth is linear with a rate of ∼20 nm/min in a water/methanol mixture up to ∼100 nm after which chain termination gradually reduces the growth rate. Further, we introduce an improved method in SPR which makes it possible to determine changes in brush height and refractive index during switching of responsive polymers. The ratio between heights in the coil to globule transition at 32 °C in water was found to be almost 5, independent of the initial absolute height up to ∼200 nm, in agreement with theory. Complementary quartz crystal microbalance and atomic force microscopy data confirm the accuracy of our results. With the methodology presented here the established SPR technique can be used for quantitative characterization of surface-initiated polymerization and responsive polymer brushes.

A novel pH-sensitive polymeric fluorescent probe: Synthesis, characterization and optical properties

Energy Technology Data Exchange (ETDEWEB)

Chen Dongyun; Xu Qingfeng; Xia Xuewei; Ge Jianfeng [Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Material Science, Soochow University, Suzhou, Jiangsu, 215123 (China); Lu Jianmei, E-mail: lujm@suda.edu.cn [Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Material Science, Soochow University, Suzhou, Jiangsu, 215123 (China); Li Najun, E-mail: linajun@sina.com [Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Material Science, Soochow University, Suzhou, Jiangsu, 215123 (China)

2010-04-15

A novel initiator containing proflavine derivative moiety, 3,6-dibromo-isobutyramide acridine (DIA), was synthesized and initiated the atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA). A water-soluble monomer, N,N-dimethylacrylamide (DMAA) was also initiated by DIA for comparison. The obtained fluorescent polymers, PMMA-DIA and PDMAA-DIA, were characterized by {sup 1}H NMR, GPC and TGA. The emission spectra of the fluorescent polymers exhibit obvious changes in color and fluorescence intensity along with pH varied in range of 3.0-9.0. In addition, the obtained polymers present good film-forming capacity and the films also have a high quantum yield and pH response. Both oil-soluble PMMA-DIA and water-soluble PDMAA-DIA have steady optical and chemical properties by containing proflavine moiety in the main chain.

Donor-acceptor random copolyesters containing perylenebisimide (PBI) and oligo(p-phenylene vinylene) (OPV) by melt condensation polymerization: energy transfer studies.

Science.gov (United States)

Nisha, S Kumari; Asha, S K

2013-10-31

Novel copolyesters consisting of oligo(p-phenylene vinylene) (OPV) as donor (D) and perylenebisimide (PBI) as acceptor (A) were synthesized by melt polycondensation. Photoinduced energy transfer and photoinduced charge separation in these polyesters were studied in solution as well as in the solid state. Selective excitation of OPV moiety resulted in the energy transfer with >90% efficiency from OPV to PBI chromophore in the solution state. The direct excitation of PBI in the D-A copolyester resulted in reduced fluorescence emission of acceptor, indicating electron transfer between the D and A moieties. The effect of distance between donor and acceptor on the energy transfer efficiency from donor to acceptor was studied. Compared to a physical mixture of D and A polyesters alone, the energy transfer was 4 times more efficient in the D-A copolyester, highlighting the influence of covalently linking D and A in a single polymer chain. A strong fluorescence quenching (∼ 100%) of both chromophores in solid state indicated an efficient photoinduced charge transfer after photoexcitation of either D or A. Thus, OPV-PBI main chain copolyester is an excellent system for the study of energy- and electron-transfer processes in organic semiconductor. Reactive blend of D/A copolyester was also prepared by the transesterification reaction between D and A alone copolyesters. The energy transfer efficiency from D to A moiety upon selective excitation of D chromophore in the D/A copolyester blend was ∼4 times higher compared to a physical mixture of D and A alone copolyesters, which gave direct proof for the transesterification reaction in polyester/polyester reactive blending.

The effect of glutathione as chain transfer agent in PNIPAAm-based thermo-responsive hydrogels for controlled release of proteins.

Science.gov (United States)

Drapala, Pawel W; Jiang, Bin; Chiu, Yu-Chieh; Mieler, William F; Brey, Eric M; Kang-Mieler, Jennifer J; Pérez-Luna, Victor H

2014-03-01

To control degradation and protein release using thermo-responsive hydrogels for localized delivery of anti-angiogenic proteins. Thermo-responsive hydrogels derived from N-isopropylacrylamide (NIPAAm) and crosslinked with poly(ethylene glycol)-co-(L-lactic acid) diacrylate (Acry-PLLA-b-PEG-b-PLLA-Acry) were synthesized via free radical polymerization in the presence of glutathione, a chain transfer agent (CTA) added to modulate their degradation and release properties. Immunoglobulin G (IgG) and the recombinant proteins Avastin® and Lucentis® were encapsulated in these hydrogels and their release was studied. The encapsulation efficiency of IgG was high (75-87%) and decreased with CTA concentration. The transition temperature of these hydrogels was below physiological temperature, which is important for minimally invasive therapies involving these materials. The toxicity from unreacted monomers and free radical initiators was eliminated with a minimum of three buffer extractions. Addition of CTA accelerated degradation and resulted in complete protein release. Glutathione caused the degradation products to become solubilized even at 37°C. Hydrogels prepared without glutathione did not disintegrate nor released protein completely after 3 weeks at 37°C. PEGylation of IgG postponed the burst release effect. Avastin® and Lucentis® released from degraded hydrogels retained their biological activity. These systems offer a promising platform for the localized delivery of proteins.

Oxygen sensitive polymeric nanocapsules for optical dissolved oxygen sensors

Science.gov (United States)

Sun, Zhijuan; Cai, Chenxin; Guo, Fei; Ye, Changhuai; Luo, Yingwu; Ye, Shuming; Luo, Jianchao; Zhu, Fan; Jiang, Chunyue

2018-04-01

Immobilization of the oxygen-sensitive probes (OSPs) in the host matrix greatly impacts the performance and long-term usage of the optical dissolved oxygen (DO) sensors. In this work, fluorescent dyes, as the OSPs, were encapsulated with a crosslinked fluorinated polymer shell by interfacial confined reversible addition fragmentation chain transfer miniemulsion polymerization to fabricate oxygen sensitive polymeric nanocapsules (NCs). The location of fluorescent dyes and the fluorescent properties of the NCs were fully characterized by fourier transform infrared spectrometer, x-ray photoelectron spectrometer and fluorescent spectrum. Dye-encapsulated capacity can be precisely tuned from 0 to 1.3 wt% without self-quenching of the fluorescent dye. The crosslinked fluorinated polymer shell is not only extremely high gas permeability, but also prevents the fluorescent dyes from leakage in aqueous as well as in various organic solvents, such as ethanol, acetone and tetrahydrofuran (THF). An optical DO sensor based on the oxygen sensitive NCs was fabricated, showing high sensitivity, short response time, full reversibility, and long-term operational stability of online monitoring DO. The sensitivity of the optical DO sensor is 7.02 (the ratio of the response value in fully deoxygenated and saturated oxygenated water) in the range 0.96-14.16 mg l-1 and the response time is about 14.3 s. The sensor’s work curve was fit well using the modified Stern-Volmer equation by two-site model, and its response values are hardly affected by pH ranging from 2 to 12 and keep constant during continuous measurement for 3 months. It is believed that the oxygen sensitive polymeric NCs-based optical DO sensor could be particularly useful in long-term online DO monitoring in both aqueous and organic solvent systems.

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

Directory of Open Access Journals (Sweden)

Ryo Endo

2015-08-01

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

Scaling of the dynamics of flexible Lennard-Jones chains

DEFF Research Database (Denmark)

Veldhorst, Arno; Dyre, J. C.; Schrøder, Thomas

2014-01-01

functions of excess entropy) which has been observed in simulations of both molecular and polymeric systems. Doing molecular dynamics simulations of flexible Lennard-Jones chains (LJC) with rigid bonds, we here provide the first detailed test of the isomorph theory applied to flexible chain molecules. We...

Preparation of self-supporting molecularly imprinted films via transition layer construction and RAFT polymerization, and their use in HPLC

International Nuclear Information System (INIS)

Ding, Peng; Tang, Shengfu; Shi, Liyi; Li, Zongzhou; Song, Na

2013-01-01

Molecularly imprinted films with self-supporting property (SS-MIFs) have been prepared by using the strategy of transition layer construction followed by reversible addition-fragmentation chain transfer (RAFT) polymerization. The structure, composition and selectivity of the SS-MIFs as well as the mechanism of mass transfer were characterized by scanning electron microscopy, X-ray diffraction, Fourier transform IR spectrometry, specific surface area analysis, thermogravimetric analysis, and HPLC. Surface area analysis showed the samples possessed specific surface areas as high as 80.5 m 2 .g −1 . This is almost 9 times more than that of the original porous anodic aluminum oxide substrate. Thermogravimetric analysis also showed the samples to be thermally stable up to 350 °C. The separating power was investigated by HPLC and revealed a selective separation effect for the target molecules theobromine. The separation factor is 5.37. (author)

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.

Designing materials for advanced microelectronic patterning applications using controlled polymerization RAFT technology

Science.gov (United States)

Sheehan, Michael T.; Farnham, William B.; Chambers, Charles R.; Tran, Hoang V.; Okazaki, Hiroshi; Brun, Yefim; Romberger, Matthew L.; Sounik, James R.

2011-04-01

Reversible Addition Fragmentation Chain Transfer (RAFT) polymerization technology enables the production of polymers possessing low polydispersity (PD) in high yield for many applications. RAFT technology also enables control over polymer architecture. With synthetic control over these polymer characteristics, a variety of polymers can be designed and manufactured for use in advanced electronic applications. By matching the specific RAFT reagent and monomer combinations, we can accommodate monomer reactivity and optimize acrylate or methacrylate polymerizations (193 and 193i photoresist polymers) or optimize styrenic monomer systems (248 nm photoresist polymers) to yield polymers with PD as low as 1.05. For 193i lithography, we have used RAFT technology to produce block copolymers comprising of a random "resist" block with composition and size based on conventional dry photoresist materials and a "low surface energy" block The relative block lengths and compositions may be varied to tune solution migration behavior, surface energy, contact angles, and solubility in developer. Directed self assembly is proving to be an interesting and innovative method to make 2- and even 3-dimensional periodic, uniform patterns. Two keys to acceptable performance of directed self assembly from block copolymers are the uniformity and the purity of the materials will be discussed.

Leading coordinate analysis of reaction pathways in proton chain transfer: Application to a two-proton transfer model for the green fluorescent protein

International Nuclear Information System (INIS)

Wang Sufan; Smith, Sean C.

2006-01-01

The 'leading coordinate' approach to computing an approximate reaction pathway, with subsequent determination of the true minimum energy profile, is applied to a two-proton chain transfer model based on the chromophore and its surrounding moieties within the green fluorescent protein (GFP). Using an ab initio quantum chemical method, a number of different relaxed energy profiles are found for several plausible guesses at leading coordinates. The results obtained for different trial leading coordinates are rationalized through the calculation of a two-dimensional relaxed potential energy surface (PES) for the system. Analysis of the 2-D relaxed PES reveals that two of the trial pathways are entirely spurious, while two others contain useful information and can be used to furnish starting points for successful saddle-point searches. Implications for selection of trial leading coordinates in this class of proton chain transfer reactions are discussed, and a simple diagnostic function is proposed for revealing whether or not a relaxed pathway based on a trial leading coordinate is likely to furnish useful information

Polymeric hollow fiber heat exchanger as an automotive radiator

International Nuclear Information System (INIS)

Krásný, Ivo; Astrouski, Ilya; Raudenský, Miroslav

2016-01-01

Highlights: • Polymeric hollow fiber heat exchanger as an automotive radiator is proposed. • The mechanism of heat transfer (HT) relies on diameter of polymeric hollow fiber. • Grimson equation is sufficient for approximate prediction of the heat transfers. - Abstract: Nowadays, different automotive parts (tubing, covers, manifolds, etc.) are made of plastics because of their superior characteristics, low weight, chemical resistance, reasonable price and several other aspects. Manufacturing technologies are already well-established and the application of plastics is proven. Following this trend, the production of compact and light all-plastic radiators seems reasonable. Two plastic heat exchangers were manufactured based on polypropylene tubes of diameter 0.6 and 0.8 mm (so-called fibers) and tested. The heat transfer performance and pressure drops were studied with hot (60 °C) ethyleneglycol-water brine flowing inside the fibers and air (20 °C) outside because these conditions are conventional for car radiator operation. It was observed that heat transfer rates (up to 10.2 kW), overall heat transfer coefficients (up to 335 W/m"2 K), and pressure drops are competitive to conventional aluminium finned-tube radiators. Moreover, influence of fiber diameter was studied. It was observed that air-side convective coefficients rise with a decrease of fiber diameter. Air-side pressure drops of plastic prototypes were slightly higher than of aluminium radiator but it is expected that additional optimization will eliminate this drawback. Experimentally obtained air-side heat transfer coefficients were compared with the theoretical prediction using the Grimson equation and the Churchill and Bernstein approach. It was found that the Grimson equation is sufficient for approximate prediction of the outer HTCs and can be used for engineering calculations. Further work will concentrate on optimizing and developing a polymeric hollow fiber heat exchanger with reduced size

SCATTERING FROM RAMIFIED POLYMERIC SYSTEMS

Directory of Open Access Journals (Sweden)

M.Benhamou

2004-01-01

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

Allylthioketone Mediated Free Radical Polymerization of Methacrylates

Directory of Open Access Journals (Sweden)

Feng Zhong

2017-11-01

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

C1 Polymerization: a unique tool towards polyethylene-based complex macromolecular architectures

KAUST Repository

Wang, De

2017-05-09

The recent developments in organoborane initiated C1 polymerization (chain grows by one atom at a time) of ylides opens unique horizons towards well-defined/perfectly linear polymethylenes (equivalent to polyethylenes, PE) and PE-based complex macromolecular architectures. The general mechanism of C1 polymerization (polyhomologation) involves the formation of a Lewis complex between a methylide (monomer) and a borane (initiator), followed by migration/insertion of a methylene into the initiator and after oxidation/hydrolysis to afford OH-terminated polyethylenes. This review summarizes efforts towards conventional and newly discovered borane-initiators and ylides (monomers), as well as a combination of polyhomologation with other polymerization methods. Initial efforts dealing with C3 polymerization and the synthesis of the first C1/C3 copolymers are also given. Finally, some thoughts for the future of these polymerizations are presented.

Pre-irradiation induced emulsion graft polymerization of acrylonitrile onto polyethylene nonwoven fabric

International Nuclear Information System (INIS)

Liu Hanzhou; Yu Ming; Deng Bo; Li Linfan; Jiang Haiqing; Li Jingye

2012-01-01

Acrylonitrile has been widely used in the modification of polymers by graft polymerization. In the present work, pre-irradiation induced emulsion graft polymerization method is used to introduce acrylonitrile onto PE nonwoven fabric instead of the traditional reaction in organic solvents system. The degree of grafting (DG) is measured by gravimetric method and the kinetics of the graft polymerization is studied. The existence of the graft chains is proven by Fourier transform infrared spectroscopy (FT-IR) analysis. Thermal stability of the grafted polymer is measured by Thermogravimetric analysis (TGA). - Highlights: → Acrylonitrile is grafted onto pre-irradiated polyethylene (PE) nonwoven fabrics. → Emulsion system is applied, for the graft polymerization avoids organic solvent. → Kinetic of the pre-irradiation induced graft polymerization is studied. → Optimal condition is determined at the temperature below the b.p. of acrylonitrile.

C1 Polymerization: a unique tool towards polyethylene-based complex macromolecular architectures

KAUST Repository

Wang, De; Zhang, Zhen; Hadjichristidis, Nikolaos

2017-01-01

The recent developments in organoborane initiated C1 polymerization (chain grows by one atom at a time) of ylides opens unique horizons towards well-defined/perfectly linear polymethylenes (equivalent to polyethylenes, PE) and PE-based complex macromolecular architectures. The general mechanism of C1 polymerization (polyhomologation) involves the formation of a Lewis complex between a methylide (monomer) and a borane (initiator), followed by migration/insertion of a methylene into the initiator and after oxidation/hydrolysis to afford OH-terminated polyethylenes. This review summarizes efforts towards conventional and newly discovered borane-initiators and ylides (monomers), as well as a combination of polyhomologation with other polymerization methods. Initial efforts dealing with C3 polymerization and the synthesis of the first C1/C3 copolymers are also given. Finally, some thoughts for the future of these polymerizations are presented.

The Emulsion Polymerization of Each of Vinyl Acetate and Butyl Acrylate Monomers Using bis (2-ethylhexyl) Maleate for Improving the Physicomechanical Properties of Paints and Adhesive Films

International Nuclear Information System (INIS)

Shaffei, K.A.; Moustafa, A.B.; Hamed, A.I.

2009-01-01

Improving the water sensitivity of polyvinyl acetate PVAc films as well as pressure sensitivity, adhesion and washability of poly butyl acrylate were achieved by using bis (2-ethylhexyl) maleate (BEHM). The emulsion polymerization kinetics of vinyl acetate and butyl acrylate in presence of BEHM was studied. The order of the polymerization reaction with respect to the BEHM in presence of each of vinyl acetate and butyl acrylate was studied. The physicomechanical properties of the polyvinyl acetate films and vinyl acetate-butyl acrylate copolymer films were studied in presence of BEHM and the obtained results were matched with those prepared in the presence of pluronic F 108 and showed superior values. The obtained mean average molecular weights were found to be smaller in presence of BEHM assuring the presence of chain transfer reaction.

The Emulsion Polymerization of Each of Vinyl Acetate and Butyl Acrylate Monomers Using bis (2-ethylhexyl Maleate for Improving the Physicomechanical Properties of Paints and Adhesive Films

Directory of Open Access Journals (Sweden)

K. A. Shaffei

2009-01-01

Full Text Available Improving the water sensitivity of polyvinyl acetate PVAc films as well as pressure sensitivity, adhesion and washability of polybutyl acrylate were achieved by using bis (2-ethylhexyl maleate (BEHM. The emulsion polymerization kinetics of vinyl acetate and butyl acrylate in presence of BEHM was studied. The order of the polymerization reaction with respect to the BEHM in presence of each of vinyl acetate and butyl acrylate was studied. The physicomechanical properties of the polyvinyl acetate films and vinyl acetate-butyl acrylate copolymer films were studied in presence of BEHM and the obtained results were matched with those prepared in the presence of pluronic F 108 and showed superior values. The obtained mean average molecular weights were found to be smaller in presence of BEHM assuring the presence of chain transfer reaction.

Synthesis of HNTs@PEDOT composites via in situ chemical oxidative polymerization and their application in electrode materials

Science.gov (United States)

Wang, Fang; Zhang, Xianhong; Ma, Yuhong; Yang, Wantai

2018-01-01

The hybrid composite of poly(3,4-ethylenedioxythiophene) (PEDOT) and halloysite nanotubes (HNTs) was synthesized by a two-step process. First, poly(sodium styrene sulfonate) (PSSNa) was grafted onto HNTs via surface initiated atom transfer radical polymerization. Then with the HNTs-g-PSS as a template and the grafted PSS chains as the counterion dopant, PEDOT was precipitated onto the template via in situ oxidization polymerization of EDOT to form HNTs@PEDOT hybrid composites. The conductivity of HNTs@PEDOT can reach up to 9.35 S/cm with the content of 40% HNTs-g-PSS, which increased almost 78 times than that of pure PEDOT (about 0.12 S/cm) prepared at the similar condition. Further treated with p-toluenesulfonic acid (TsOH) as external dopant, the conductivity of HNTs@PEDOT increased to 24.3 S/cm. The electrochemical properties of the composites were investigated with cyclic voltammetry, galvanostatic charge-discharge and electrochemical impedance spectroscopy with three-electrode cell configuration. The results showed that the capacitance of HNTs@PEDOT composite increased 55% than that of pure PEDOT.

Polyisoprene Nanoparticles Prepared by Polymerization in Microemulsion

Directory of Open Access Journals (Sweden)

Y. Apolinar

2010-01-01

Full Text Available Batch polymerization of isoprene was carried out at 25∘C in a normal microemulsion stabilized with sodium dodecyl sulfate and initiated with the redox couple tert-butyl hydroperoxide/tetraethylene-pentamine. Characterization by transmission electronic microscopy showed that polyisoprene nanoparticles with number-average diameter close to 20 nm were obtained. The low molecular weights obtained, as determined by gel permeation chromatography, were probably due to chain scission as inferred from the oxidative ambient at which polymerization was carried out. Microstructure calculated from infrared spectroscopy data indicates that the obtained polyisoprene contains around 80% total 1,4 units, which is in accordance with its glass transition temperature (-60.8∘C determined by differential scanning calorimetry.

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

Institute of Scientific and Technical Information of China (English)

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

2009-01-01

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

Poly(BODIPY)s : A New Class of Tunable Polymeric Dyes

NARCIS (Netherlands)

Alemdaroglu, Fikri E.; Alexander, Seth C.; Ji, Dongmei; Prusty, Deepak K.; Boersch, Michael; Herrmann, Andreas

2009-01-01

We present a new class of polymeric dyes bearing the difluoroboraindacene (BODIPY) chromophore within the main chain. Starting from a diiodinated BODIPY monomer, homo- and copolymers with a fully conjugated backbone were efliciently synthesized by transition-metal-catalyzed polycondensation

Microencapsulated Comb-Like Polymeric Solid-Solid Phase Change Materials via In-Situ Polymerization

Directory of Open Access Journals (Sweden)

Wei Li

2018-02-01

Full Text Available To enhance the thermal stability and permeability resistance, a comb-like polymer with crystallizable side chains was fabricated as solid-solid phase change materials (PCMs inside the cores of microcapsules and nanocapsules prepared via in-situ polymerization. In this study, the effects on the surface morphology and microstructure of micro/nanocapsules caused by microencapsulating different types of core materials (i.e., n-hexadecane, ethyl hexadecanoate, hexadecyl acrylate and poly(hexadecyl acrylate were systematically studied via field emission scanning electron microscope (FE-SEM and transmission electron microscope (TEM. The confined crystallization behavior of comb-like polymer PCMs cores was investigated via differential scanning calorimeter (DSC. Comparing with low molecular organic PCMs cores, the thermal stability of PCMs microencapsulated comb-like polymer enhanced significantly, and the permeability resistance improved obviously as well. Based on these resultant analysis, the microencapsulated comb-like polymeric PCMs with excellent thermal stability and permeability resistance showed promising foreground in the field of organic solution spun, melt processing and organic coating.

Synthesis and self-assembly of well-defined block copolypeptides via controlled NCA polymerization

OpenAIRE

Deming, TJ

2013-01-01

This article summarizes advances in the synthesis of well-defined polypeptides and block copolypeptides. Traditional methods used to polymerize α-amino acid-N-carboxyanhydrides (NCAs) are described, and limitations in the utility of these systems for the preparation of polypeptides are discussed. Improved initiators and methods that allow polypeptide synthesis with good control over chain length, chain length distribution, and chain-end functionality are also discussed. Using these methods, b...

Evaluation of food chain transfer data for use in accident consequence assessment

International Nuclear Information System (INIS)

Coughtrey, P.J.; Kirton, J.A.; Mitchell, N.G.

1991-01-01

Input data for the food chain transport component of radiological assessment models are summarised in the context of the sources of information available prior to the Chernobyl accident and those derived after the accident. Particular attention is devoted to interception and retention soil-to-plant, and plant-to-animal transfer, and to the applicability of environmental data to both equilibrium and time-dependent models. It is argued that much of the current uncertainty in parameter values for use in radiological assessment models reflects lack of understanding of processes involved in the various stages of transfer of radionuclides to man. The Chernobyl accident highlighted this lack of fundamental knowledge and illustrated a number of areas where further research and model development is justified. These areas are identified and suggestions given for appropriate research to support model development

Plasmon assisted control of photo-induced excitation energy transfer in a molecular chain

Science.gov (United States)

Wang, Luxia; May, Volkhard

2017-08-01

The strong and ultrafast laser pulse excitation of a molecular chain in close vicinity to a spherical metal nano-particle (MNP) is studied theoretically. Due to local-field enhancement around the MNP, pronounced excited-state formation has to be expected for the part of the chain which is in proximity to the MNP. Here, the description of this phenomenon will be based on a uniform quantum theory of the MNP-molecule system. It accounts for local-field effects due to direct consideration of the strong excitation energy transfer coupling between the MNP and the various molecules. The molecule-MNP distances are chosen in such a way as to achieve a correct description of the MNP via dipole-plasmon excitations. Short plasmon life-times are incorporated in the framework of a density matrix approach. By extending earlier work the present description allows for multi-exciton formation and multiple dipole-plasmon excitation. The region of less intense and not-too-short optical excitation is identified as being best suited for excitation energy localization in the chain.

Resistance of a 1D random chain: Hamiltonian version of the transfer matrix approach

Science.gov (United States)

Dossetti-Romero, V.; Izrailev, F. M.; Krokhin, A. A.

2004-01-01

We study some mesoscopic properties of electron transport by employing one-dimensional chains and Anderson tight-binding model. Principal attention is paid to the resistance of finite-length chains with disordered white-noise potential. We develop a new version of the transfer matrix approach based on the equivalency of a discrete Schrödinger equation and a two-dimensional Hamiltonian map describing a parametric kicked oscillator. In the two limiting cases of ballistic and localized regime we demonstrate how analytical results for the mean resistance and its second moment can be derived directly from the averaging over classical trajectories of the Hamiltonian map. We also discuss the implication of the single parameter scaling hypothesis to the resistance.

Resistance of a 1D random chain: Hamiltonian version of the transfer matrix approach

International Nuclear Information System (INIS)

Dossetti-Romero, V.; Izrailev, F.M.; Krokhin, A.A.

2004-01-01

We study some mesoscopic properties of electron transport by employing one-dimensional chains and Anderson tight-binding model. Principal attention is paid to the resistance of finite-length chains with disordered white-noise potential. We develop a new version of the transfer matrix approach based on the equivalency of a discrete Schroedinger equation and a two-dimensional Hamiltonian map describing a parametric kicked oscillator. In the two limiting cases of ballistic and localized regime we demonstrate how analytical results for the mean resistance and its second moment can be derived directly from the averaging over classical trajectories of the Hamiltonian map. We also discuss the implication of the single parameter scaling hypothesis to the resistance

Ziegler–Natta Polymerization and the Remaining Challenges

Indian Academy of Sciences (India)

known to humankind since a very long period and have con- tributed significantly ..... chain growth and chain transfer are fast, and either chain walking ... field of insertion copolymerization of functional vinyl monomers .... open up the industrial.

Mirage, a food chain transfer and dosimetric impact code in relation with atmospheric and liquid dispersion codes

International Nuclear Information System (INIS)

Van Dorpe, F.; Jourdain, F.

2006-01-01

Full text: The numerical code M.I.R.A.G.E. (Module of Radiological impact calculations on the Environment due to accidental or chronic nuclear releases through Aqueous and Gas media) has been developed to simulate the radionuclides transfer in the biosphere and food chains, as well as the dosimetric impact on man, after accidental or chronic releases in the environment by nuclear installations. The originality of M.I.R.A.G.E. is to propose a single tool chained downstream with various atmospheric and liquid dispersion codes. The code M.I.R.A.G.E. is a series of modules which makes it possible to carry out evaluations on the transfers in food chains and human dose impact. Currently, M.I.R.A.G.E. is chained with a Gaussian atmospheric dispersion code H.A.R.M.A.T.T.A.N. (Cea), a 3 D atmospheric dispersion code with Lagrangian model named M.I.N.E.R.V.E.-S.P.R.A.Y. (Aria Technology) and a 3 D groundwater transfer code named M.A.R.T.H.E. (B.R.G.M.). M.I.R.A.G.E. uses concentration or activity result files as initial data input for its calculations. The application initially calculates the concentrations in the various compartments of the environment (soils, plants, animals). The results are given in the shape of concentration and dose maps and also on a particular place called a reference group for dosimetric impact (like a village or a specific population group located around a nuclear installation). The input and output data of M.I.R.A.G.E. can have geographic coordinates and thus readable by a G.I.S. M.I.R.A.G. E.is an opened system with which it is easy to chain other codes of dispersion that those currently used. The calculations uncoupled with dispersion calculations are also possible by manual seizure of the dispersion data (contamination of a tablecloth, particular value in a point, etc.). M.I.R.A.G.E. takes into account soil deposits and resuspension phenomenon, transfers in plants and animals (choice of agricultural parameters, types of plants and animals, etc

Well-defined copolymers synthesized by RAFT polymerization as effective modifiers to enhance the photocatalytic performance of TiO_2

International Nuclear Information System (INIS)

Vasilaki, E.; Kaliva, M.; Katsarakis, N.; Vamvakaki, M.

2017-01-01

Highlights: • Well-defined, random functional copolymers were synthesized by RAFT polymerization. • Novel TiO_2 particles in-situ modified with copolymers were synthesized. • The hybrid catalysts exhibited reduced aggregation and particle size. • The photocatalytic removal of methylene blue was higher for the hybrid catalysts. - Αbstract: The enhancement of the photocatalytic performance of anatase TiO_2 nanoparticles is demonstrated by a facile route, involving their in-situ surface modification with preformed polymer chains. Random copolymers of poly(ethylene glycol) methyl ether acrylate-co-methacrylic acid (PEGA-co-MAA) or poly(ethylene glycol) methyl ether acrylate-co-dopamine methacrylamide (PEGA-co-DMA) were synthesized by reversible addition−fragmentation chain-transfer (RAFT) polymerization and were bound onto the surface of anatase titania nanoparticles via the “grafting to” method. The hybrid nanocatalysts were characterized by fourier transform infrared spectroscopy, zeta-potential measurements, X-ray powder diffraction, thermogravimetric analysis and transmission electron microscopy. Their photocatalytic performance was evaluated by the decoloration of methylene blue (MB) dye in aqueous media under UV–vis light irradiation. The enhanced photoactivity and reusability of the polymer modified photocatalysts compared to that of bare TiO_2 nanoparticles was attributed to their improved dispersability and colloidal stability, the smaller particle size that leads to a larger surface area and the increased adsorption capacity of the dye onto the polymer modified nanoparticles.

Living Polycondensation: Synthesis of Well-Defined Aromatic Polyamide-Based Polymeric Materials

KAUST Repository

Alyami, Mram Z.

2016-01-01

Chain growth condensation polymerization is a powerful tool towards the synthesis of well-defined polyamides. This thesis focuses on one hand, on the synthesis of well-defined aromatic polyamides with different aminoalkyl pendant groups with low

Some observations on plutonium transfers in human and animal food-chains and Gi tract: plutonium complexation parameters

International Nuclear Information System (INIS)

Bittel, R.

1986-06-01

Although many data have been accumulated concerning the distribution of Pu in waters, soils, and foodchains, recent studies have raised the question of the Pu physico-chemical species and their differential availability. Accordingly, we reviewed published data on the transfer of Pu in foodchains and in the gastrointestinal tracts. Dietetic, physico-chemical, biochemical and microbiological parameters have been studied and their incidence on the intestinal transfer factor f 1 of Pu in man briefly discussed: the transfer in the trophic chains often increases Pu mobility and perhaps f 1 . Experimental research is needed to obtain quantitative data [fr

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

International Nuclear Information System (INIS)

Gao Yuan; Zhou Yongfeng; Yan Deyue; Gao Xueping

2008-01-01

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

Advances in single chain technology.

Science.gov (United States)

Gonzalez-Burgos, Marina; Latorre-Sanchez, Alejandro; Pomposo, José A

2015-10-07

The recent ability to manipulate and visualize single atoms at atomic level has given rise to modern bottom-up nanotechnology. Similar exquisite degree of control at the individual polymeric chain level for producing functional soft nanoentities is expected to become a reality in the next few years through the full development of so-called "single chain technology". Ultra-small unimolecular soft nano-objects endowed with useful, autonomous and smart functions are the expected, long-term valuable output of single chain technology. This review covers the recent advances in single chain technology for the construction of soft nano-objects via chain compaction, with an emphasis in dynamic, letter-shaped and compositionally unsymmetrical single rings, complex multi-ring systems, single chain nanoparticles, tadpoles, dumbbells and hairpins, as well as the potential end-use applications of individual soft nano-objects endowed with useful functions in catalysis, sensing, drug delivery and other uses.

On the formation of polymer non-grafted onto the surface during radiation-induced polymerization of monomers adsorbed on mineral substrates

International Nuclear Information System (INIS)

Bruk, M.A.; Mund, S.L.; Aksman, I.B.; Abkin, A.D.

1977-01-01

It has been established that during radiation polymerization of vinylacetate and acrylonitrile, adsorbed on aerosil from the vapour phase, considerable amounts of the polymer are formed even at the initial stage of the process which is extracted by the organic solvents. It has been shown for polyvinylacetate as an example that probability of the polymer chain located on the surface to transfer into the solution depends not only on the ''quality'' of the solvent with respect to the given polymer but on the energy of solvent interaction with the surface adsorption centers as well. It has been observed that the molecular mass of PVA extracted from the aerosil surface by acetone is several times lower than that of PVA which remains on the surface after treating with acetone. Probable participation of low-molecular radicals in the formation of polymer chains not forming a chemical bond with the surface has been considered

A pulse radiolysis study of emulsion polymerization

International Nuclear Information System (INIS)

McAskill, N.A.

1976-01-01

The emulsion polymerisation of slightly water soluble monomers such as styrene occurs initially in micelles of surfactant swollen with monomer and later in larger particles consisting of polymer swollen with monomer and stabilized with an outer layer of surfactant. There is considerable controversy on whether the reaction sites of polymerization are inside or on the surface of the particle or micelle. The relative amounts of micelle and particles present at various stages of the polymerization are also nuclear. In the present study the OH radical formed by pulse radiolysis has been used as a probe to investigate the site of solubilization of styrene in various surfactant micelles. Two products can be distinguished by UV spectrometry, a benzyl type radical formed by OH addition to the side chain of styrene and a cyclohexadienyl type radical formed by addition to the ring. Wide differences in the relative amounts of each product were observed suggesting that in some surfactants the styrene ring is buried inside the micelle whilst in other systems the styrene appears to be so solubilized at the interface leaving both the ring and the side chain open to attack by the OH radical. (author)

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.

Study of the chain termination in the polymerization of seven-membered carbonate cyclic; Estudo da terminacao de cadeia na polymerizacao de carbonatos ciclicos de 7 membros

Energy Technology Data Exchange (ETDEWEB)

Carpentier, Jean-Francois [Laboratoire Catalyse et Organometalliques, CNRS - Universite de Rennes 1 - Sciences Chimiques de Rennes (France); Casagrande Junior, Osvaldo de; Gil, Marcelo Priebe [Laboratorio de Catalise Molecular, Instituto de Quimica, Universidade Federal do Rio Grande do Sul (Brazil)

2011-07-01

Methyl substituted seven-membered ring carbonate (7CC), namely 4-methyl-1,3-dioxepan-2-one ({alpha}-Me7CC) have been synthesized in good yield (up to 50%) upon cyclization of the corresponding {alpha}-diols issued from green renewable acid. ('Immortal') Ring-opening polymerization (iROP) of this monomer has been carried out using various catalysts combined with an alcohol acting as a co-initiator and a chain transfer agent. The Lewis acid Al(OTf){sub 3} or the organometallic complexes [(BDI{sup iPr})Zn(N(SiMe{sub 3}){sub 2})] ((BDI{sup iPr}) = 2-((2,6-diisopropylphenyl)amido)-4-((2,6- diisopropylphenyl)-imino)-2-pentene] and [(ONOO{sup tBu})Y(N(SiHMe{sub 2}){sub 2})(THF)] (ONOO{sup tBu} = amino-alkoxy-bis(phenolate)) successfully afforded the corresponding poly({alpha}-Me7CC) with quite good control and activities. Detailed microstructural analysis of the poly(a-Me7CC) using {sup 1}H and {sup 13}C NMR and MALDI-TOF-MS techniques revealed the higher regioselectivity -with preferential ring-opening at the most hindered oxygen-acyl O-C(O)O bond, i.e. close to the {alpha}-Me substituent- of the zinc-based system followed by the yttrium as compared to the lack of selectivity of the aluminum one, in the ROP of {alpha}-Me7CC. (author)

Activation of vanadium-based Ziegler-Natta catalysts by halocarbons for ethylene polymerization: results and mechanism

International Nuclear Information System (INIS)

Deffieux, A.; Amorin, C.; Fontanille, M.; Adisson, E.; Bujadoux, K.

1994-01-01

The reactions for the low productivity of the heterogeneous and homogenous V-based catalysts in the synthesis of LLDPE were discussed and some routes of improving their activity and stability were proposed. Ethylene polymerizations were performed in the isododecane solutions at 160 C and under constant ethylene pressure of 5 bars. One Ti-based catalytic system (TiCl 3 - 0.3 AlCl 3 ) and two V-based systems (TiCl 3 - 0.3 AlCl 3 and VCl 4 ) were investigated. The main reason of activity loss is a rapid reduction of V 4+ and V 3+ to inactive V 2+ form. AlR 3 cocatalysts are also involved in the deactivation process. The effect of addition to the system of various alkyl halides (a.o. of CCl 4 , CH 3 Cl 3 , CF 3 CCCl 3 , CHCl 3 , CHBr 3 , CH 2 Cl 2 , CH 2 BrCl and CH 2 Br 2 ) on the yield of polyethylene was investigated. The alkyl halides act as efficient activators for the heterogeneous and homogeneous vanadium catalysts in the high temperature ethylene polymerization and its copolymerization with 1-hexane. The effect of the presence of CHCl 3 on the short chain branching and the molecular weight distribution (GPC) of these copolymers was also investigated. Halocarbons do not act as chain transfer agents. The peak molecular weight remains almost unchanged but a narrowing of molecular weight distribution is observed due to the suppression of the amount of high-molecular-weight fraction in polymer. (author). 4 refs, 3 figs, 2 tabs

Inter-Basin Water Transfer Green Supply Chain Equilibrium and Coordination under Social Welfare Maximization

Directory of Open Access Journals (Sweden)

Zhisong Chen

2018-04-01

Full Text Available The inter-basin water transfer (IBWT projects have quasi-public-welfare characteristics, whose operations should take into account the water green level (WGL and social welfare maximization (SWM. This paper explores the interactions between multiple stakeholders of an IBWT green supply chain through the game-theoretic and coordination research approaches considering the government’s subsidy to the WGL improvement under the SWM. The study and its findings complement the IBWT literature in the area of the green supply chain and social welfare maximization modeling. The analytical modeling results with and without considering the SWM are compared. A numerical analysis for a hypothetical IBWT green supply chain is conducted to draw strategic insights from this study. The research results indicate that (1 If the SWM is not considered, coordination strategy could effectively improve the operations performances of the IBWT supply chain and its members, the consumers’ surplus, and the social welfare when compared with the equilibrium strategy; (2 If the SWM is considered, the IBWT green supply chain and its members have a strong intention to adopt the equilibrium strategy to gain more profits, while the government has a strong intention to encourage the IBWT green supply chain and its members to adopt the coordination strategy to maximize social welfare with a smaller public subsidy; (3 The government’s subsidy policy should be designed and provided to encourage the IBWT green supply chain and its members to improve WGL and pursue the SWM, and a subsidy threshold policy can be designed to maximize social welfare with a lower subsidy budget: only when the IBWT green supply chain and its members adopt the coordination strategy can they get a subsidy from the government.

Well-defined copolymers synthesized by RAFT polymerization as effective modifiers to enhance the photocatalytic performance of TiO{sub 2}

Energy Technology Data Exchange (ETDEWEB)

Vasilaki, E., E-mail: euavasilakh@gmail.com [Department of Chemistry, University of Crete, 710 03, Heraklion, Crete (Greece); Center of Materials Technology and Photonics, School of Applied Technology, Technological Educational Institute of Crete, 710 04 Heraklion, Crete (Greece); Kaliva, M. [Institute of Electronic Structure and Laser, Foundation for Research & Technology-Hellas, P.O. Box 1385, Vassilika Vouton, 711 10 Heraklion, Crete (Greece); Department of Materials Science and Technology, University of Crete, 710 03, Heraklion, Crete (Greece); Katsarakis, N. [Center of Materials Technology and Photonics, School of Applied Technology, Technological Educational Institute of Crete, 710 04 Heraklion, Crete (Greece); Institute of Electronic Structure and Laser, Foundation for Research & Technology-Hellas, P.O. Box 1385, Vassilika Vouton, 711 10 Heraklion, Crete (Greece); Vamvakaki, M. [Institute of Electronic Structure and Laser, Foundation for Research & Technology-Hellas, P.O. Box 1385, Vassilika Vouton, 711 10 Heraklion, Crete (Greece); Department of Materials Science and Technology, University of Crete, 710 03, Heraklion, Crete (Greece)

2017-03-31

Highlights: • Well-defined, random functional copolymers were synthesized by RAFT polymerization. • Novel TiO{sub 2} particles in-situ modified with copolymers were synthesized. • The hybrid catalysts exhibited reduced aggregation and particle size. • The photocatalytic removal of methylene blue was higher for the hybrid catalysts. - Αbstract: The enhancement of the photocatalytic performance of anatase TiO{sub 2} nanoparticles is demonstrated by a facile route, involving their in-situ surface modification with preformed polymer chains. Random copolymers of poly(ethylene glycol) methyl ether acrylate-co-methacrylic acid (PEGA-co-MAA) or poly(ethylene glycol) methyl ether acrylate-co-dopamine methacrylamide (PEGA-co-DMA) were synthesized by reversible addition−fragmentation chain-transfer (RAFT) polymerization and were bound onto the surface of anatase titania nanoparticles via the “grafting to” method. The hybrid nanocatalysts were characterized by fourier transform infrared spectroscopy, zeta-potential measurements, X-ray powder diffraction, thermogravimetric analysis and transmission electron microscopy. Their photocatalytic performance was evaluated by the decoloration of methylene blue (MB) dye in aqueous media under UV–vis light irradiation. The enhanced photoactivity and reusability of the polymer modified photocatalysts compared to that of bare TiO{sub 2} nanoparticles was attributed to their improved dispersability and colloidal stability, the smaller particle size that leads to a larger surface area and the increased adsorption capacity of the dye onto the polymer modified nanoparticles.

Tailor-made polyfluoroacrylate and its block copolymer by RAFT polymerization in miniemulsion; improved hydrophobicity in the core-shell block copolymer.

Science.gov (United States)

Chakrabarty, Arindam; Singha, Nikhil K

2013-10-15

Controlled/living radical polymerization (CRP) of a fluoroacrylate was successfully carried out in miniemulsion by Reversible Addition Fragmentation chain Transfer (RAFT) process. In this case, 2,2,3,3,4,4,4-heptafluorobutyl acrylate (HFBA) was polymerized using 2-cyanopropyl dodecyl trithiocarbonate (CPDTC) as RAFT agent, Triton X-405 and sodium dodecyl sulfonate (SDS) as surfactant, and potassium persulphate (KPS) or 2,2'-azobis isobutyronitrile (AIBN) as initiator. Being compatible with hydrophobic fluoroacrylate, this RAFT agent offered very high conversion and good control over the molecular weight of the polymer. The miniemulsion was stable without any costabilizer. The long chain dodecyl group (-C12H25) (Z-group in the RAFT agent) had beneficial effect in stabilizing the miniemulsion. When 2-cyano 2-propyl benzodithioate (CPBD) (Z=-C6H5) was used as RAFT agent, the conversion was less and particle size distribution was very broad. Block copolymerization with butyl acrylate (BA) using PHFBA as macro-RAFT agent showed core-shell morphology with the aggregation of PHFBA segment in the shell. GPC as well as DSC analysis confirmed the formation of block copolymer. The core-shell morphology was confirmed by TEM analysis. The block copolymers (PHFBA-b-PBA) showed significantly higher water contact angle (WCA) showing much better hydrophobicity compared to PHFBA alone. Copyright © 2013 Elsevier Inc. All rights reserved.

The Morphology of Emulsion Polymerized Latex Particles

Science.gov (United States)

Wignall, G. D.; Ramakrishnan, V. R.; Linne, M. A.; Klein, A.; Sperling, L. H.; Wai, M. P.; Gelman, R. A.; Fatica, M. G.; Hoerl, R. H.; Fisher, L. W.

1987-11-01

Under monomer starved feed conditions, emulsion polymerization of perdeuterated methyl methacrylate and styrene in the presence of preformed polymethylmethacrylate latexes resulted in particles with a core-shell morphology, as determined by small-angle neutron scattering (SANS) analysis for a hollow sphere. The locus of polymerization of the added deuterated monomer is therefore at the particle surface. In similar measurements a statistical copolymer of styrene and methyl methacrylate was used as seed particles for further polymerization of trideuteromethyl methacrylate. The resulting polymer latex was again shown to have a core-shell morphological structure as determined by SANS. SANS experiments were also undertaken on polystyrene latexes polymerized by equilibrium swelling methods, with deuterated polymer forming the first or second step. The experiments covered a molecular weight range of 6 x 10{sup 4} 10{sup 6} the molecular weights are consistent with the experimental errors, indicating that the deuterium labeled molecules are randomly distributed in the latex. These results led to the finding that the polymer chains were constrained in the latex particles by factors of 2 to 4 from the relaxed coil dimensions. For M molecules. Several models were examined, including the possible development of core-shell structures at lower molecular weights.

Studies on radiation-induced graft polymerization

International Nuclear Information System (INIS)

Omichi, Hideki

1978-09-01

Radiation-induced graft polymerization is used extensively to improve physical properties of polymers, but few processes are now commercialized. The reason for this is partly inadequate basic research on the reaction and partly the difficulty in developing the grafting process with large radiation source. Firstly, new techniques are proposed of studying kinetics of the graft polymerization in heterogeneous system. Based on the grafting yield, the molecular weight of graft chains, and the amount of radicals given by ESR and activation analysis, kinetic parameters are obtained and the reaction mechanism of grafting process is discussed. Secondly, the development of grafting process of poly (vinyl chloride)-butadiene is described. By study of the reaction, process design, construction and operation of the pilot plant, and economic analysis of the process, this process with 60 Co gamma ray sources is shown to be industrially promising. (author)

The effect of ethanol on the γ radiation induced polymerization of styrene

International Nuclear Information System (INIS)

Zhang Xujia; Ha Hongfei; Wu Jilan

1990-01-01

The γ radiation induced polymerization of styrene in the presence of ethanol was studied at dose rate of 5 x 10 17 eV/ml min. The result showed that the radiation induced polymerization of styrene was sensitized by ethanol. The experimental results were in agreement with the theoretical calculation of WAS equation. The mechanism of sensitization was proposed as proton transfer reaction

Spectroscopic Investigation of Composite Polymeric and Monocrystalline Systems with Ionic Conductivity

Directory of Open Access Journals (Sweden)

Darya V. Radziuk

2011-03-01

Full Text Available The conductivity mechanism is studied in the LiCF3SO3-doped polyethylene oxide by monitoring the vibrations of sulfate groups and mobility of Li+ ion along the polymeric chain at different EO/Li molar ratios in the temperature range from 16 to 90 °С. At the high EO/Li ratio (i.e., 30, the intensity of bands increases and a triplet appears at 1,045 cm−1, indicating the presence of free anions, ionic pairs and aggregates. The existence of free ions in the polymeric electrolyte is also proven by the red shift of bands in Raman spectra and a band shift to the low frequency Infra-red region at 65 < T < 355 °С. Based on quantum mechanical modeling, (method MNDO/d, the energies (minimum and maximum correspond to the most probable and stable positions of Li+ along the polymeric chain. At room temperature, Li+ ion overcomes the intermediate state (minimum energy through non-operating transitions (maximum energy due to permanent intrapolymeric rotations (rotation of C, H and O atoms around each other. In solid electrolyte (Li2SO4 the mobility of Li+ ions increases in the temperature range from 20 to 227 °С, yielding higher conductivity. The results of the present work can be practically applied to a wide range of compact electronic devices, which are based on polymeric or solid electrolytes.

A single-chain variable fragment intrabody prevents intracellular polymerization of Z α1-antitrypsin while allowing its antiproteinase activity.

Science.gov (United States)

Ordóñez, Adriana; Pérez, Juan; Tan, Lu; Dickens, Jennifer A; Motamedi-Shad, Neda; Irving, James A; Haq, Imran; Ekeowa, Ugo; Marciniak, Stefan J; Miranda, Elena; Lomas, David A

2015-06-01

Mutant Z α1-antitrypsin (E342K) accumulates as polymers within the endoplasmic reticulum (ER) of hepatocytes predisposing to liver disease, whereas low levels of circulating Z α1-antitrypsin lead to emphysema by loss of inhibition of neutrophil elastase. The ideal therapy should prevent polymer formation while preserving inhibitory activity. Here we used mAb technology to identify interactors with Z α1-antitrypsin that comply with both requirements. We report the generation of an mAb (4B12) that blocked α1-antitrypsin polymerization in vitro at a 1:1 molar ratio, causing a small increase of the stoichiometry of inhibition for neutrophil elastase. A single-chain variable fragment (scFv) intrabody was generated based on the sequence of mAb4B12. The expression of scFv4B12 within the ER (scFv4B12KDEL) and along the secretory pathway (scFv4B12) reduced the intracellular polymerization of Z α1-antitrypsin by 60%. The scFv4B12 intrabody also increased the secretion of Z α1-antitrypsin that retained inhibitory activity against neutrophil elastase. MAb4B12 recognized a discontinuous epitope probably located in the region of helices A/C/G/H/I and seems to act by altering protein dynamics rather than binding preferentially to the native state. This novel approach could reveal new target sites for small-molecule intervention that may block the transition to aberrant polymers without compromising the inhibitory activity of Z α1-antitrypsin. © FASEB.

TiO2@C Core-Shell Nanoparticles Formed by Polymeric Nano-Encapsulation

Directory of Open Access Journals (Sweden)

Mitra eVasei

2014-07-01

Full Text Available TiO2 semiconducting nanoparticles are known to be photocatalysts of moderate activity due to their high band-gap and high rate of electron-hole recombination. The formation of a shell of carbon around the core of TiO2, i.e. the formation of TiO2@C nanoparticles, is believed to partly alleviate these problems. It is usually achieved by a hydrothermal treatment in a presence of a sugar derivative. We present here a novel method for the formation of highly uniform C shell around TiO2 nanoparticles. For this purpose, TiO2 nanoparticles were dispersed in water using an oligomeric dispersant prepared by Reversible Addition-Fragmentation chain Transfer (RAFT polymerization. Then the nanoparticles were engaged into an emulsion polymerization of acrylonitrile, resulting in the formation of a shell of polyacrylonitrile (PAN around each TiO2 nanoparticles. Upon pyrolisis, the PAN was transformed into carbon, resulting in the formation of TiO2@C nanoparticles. The structure of the resulting particles was elucidated by X-Ray diffraction, FTIR, UV-VIS and Raman spectroscopy as well as TEM microscopy. Preliminary results about the use of the TiO2@C particles as photocatalysts for the splitting of water are presented. They indicate that the presence of the C shell is responsible for a significant enhancement of the photocurrent.

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

International Nuclear Information System (INIS)

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

2010-01-01

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

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

Science.gov (United States)

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

2010-12-01

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

Strain hardening in startup shear of long-chain branched polymer solutions.

Science.gov (United States)

Liu, Gengxin; Cheng, Shiwang; Lee, Hyojoon; Ma, Hongwei; Xu, Hongde; Chang, Taihyun; Quirk, Roderic P; Wang, Shi-Qing

2013-08-09

We show for the first time that entangled polymeric liquids containing long-chain branching can exhibit strain hardening upon startup shear. As the significant long-chain branching impedes chain disentanglement, Gaussian coils between entanglements can deform to reach the finite extensibility limit where the intrachain retraction force exceeds the value expected from the usual conformational entropy loss evaluated based on Gaussian chain statistics. The phenomenon is expected to lead to further theoretical understanding.

(1-Adamantyl)methyl glycidyl ether: a versatile building block for living polymerization.

Science.gov (United States)

Moers, Christian; Wrazidlo, Robert; Natalello, Adrian; Netz, Isabelle; Mondeshki, Mihail; Frey, Holger

2014-06-01

(1-Adamantyl)methyl glycidyl ether (AdaGE) is introduced as a versatile monomer for oxyanionic polymerization, enabling controlled incorporation of adamantyl moieties in aliphatic polyethers. Via copolymerization with ethoxyethyl glycidyl ether (EEGE) and subsequent cleavage of the acetal protection groups of EEGE, hydrophilic linear polyglycerols with an adjustable amount of pendant adamantyl moieties are obtained. The adamantyl unit permits control over thermal properties and solubility profile of these polymers (LCST). Additionally, AdaGE is utilized as a termination agent in carbanionic polymerization, affording adamantyl-terminated polymers. Using these structures as macroinitiators for the polymerization of ethylene oxide affords amphiphilic, in-chain adamantyl-functionalized block copolymers. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A chiroptical switch based on supramolecular chirality transfer through alkyl chain entanglement and dynamic covalent bonding.

Science.gov (United States)

Lv, Kai; Qin, Long; Wang, Xiufeng; Zhang, Li; Liu, Minghua

2013-12-14

Chirality transfer is an interesting phenomenon in Nature, which represents an important step to understand the evolution of chiral bias and the amplification of the chirality. In this paper, we report the chirality transfer via the entanglement of the alkyl chains between chiral gelator molecules and achiral amphiphilic Schiff base. We have found that although an achiral Schiff base amphiphile could not form organogels in any kind of organic solvents, it formed co-organogels when mixed with a chiral gelator molecule. Interestingly, the chirality of the gelator molecules was transferred to the Schiff base chromophore in the mixed co-gels and there was a maximum mixing ratio for the chirality transfer. Furthermore, the supramolecular chirality was also produced based on a dynamic covalent chemistry of an imine formed by the reaction between an aldehyde and an amine. Such a covalent bond of imine was formed reversibly depending on the pH variation. When the covalent bond was formed the chirality transfer occurred, when it was destroyed, the transfer stopped. Thus, a supramolecular chiroptical switch is obtained based on supramolecular chirality transfer and dynamic covalent chemistry.

Falling chains

OpenAIRE

Wong, Chun Wa; Yasui, Kosuke

2005-01-01

The one-dimensional fall of a folded chain with one end suspended from a rigid support and a chain falling from a resting heap on a table is studied. Because their Lagrangians contain no explicit time dependence, the falling chains are conservative systems. Their equations of motion are shown to contain a term that enforces energy conservation when masses are transferred between subchains. We show that Cayley's 1857 energy nonconserving solution for a chain falling from a resting heap is inco...

An RFID-Based Smart Structure for the Supply Chain: Resilient Scanning Proofs and Ownership Transfer with Positive Secrecy Capacity Channels

Directory of Open Access Journals (Sweden)

Mike Burmester

2017-07-01

Full Text Available The National Strategy for Global Supply Chain Security published in 2012 by the White House identifies two primary goals for strengthening global supply chains: first, to promote the efficient and secure movement of goods, and second to foster a resilient supply chain. The Internet of Things (IoT, and in particular Radio Frequency Identification (RFID technology, can be used to realize these goals. For product identification, tracking and real-time awareness, RFID tags are attached to goods. As tagged goods move along the supply chain from the suppliers to the manufacturers, and then on to the retailers until eventually they reach the customers, two major security challenges can be identified: (I to protect the shipment of goods that are controlled by potentially untrusted carriers; and (II to secure the transfer of ownership at each stage of the chain. For the former, grouping proofs in which the tags of the scanned goods generate a proof of “simulatenous” presence can be employed, while for the latter, ownership transfer protocols (OTP are used. This paper describes enhanced security solutions for both challenges. We first extend earlier work on grouping proofs and group codes to capture resilient group scanning with untrusted readers; then, we describe a modified version of a recently published OTP based on channels with positive secrecy capacity adapted to be implemented on common RFID systems in the supply chain. The proposed solutions take into account the limitations of low cost tags employed in the supply chain, which are only required to generate pseudorandom numbers and compute one-way hash functions.

An RFID-Based Smart Structure for the Supply Chain: Resilient Scanning Proofs and Ownership Transfer with Positive Secrecy Capacity Channels.

Science.gov (United States)

Burmester, Mike; Munilla, Jorge; Ortiz, Andrés; Caballero-Gil, Pino

2017-07-04

The National Strategy for Global Supply Chain Security published in 2012 by the White House identifies two primary goals for strengthening global supply chains: first, to promote the efficient and secure movement of goods, and second to foster a resilient supply chain. The Internet of Things (IoT), and in particular Radio Frequency Identification (RFID) technology, can be used to realize these goals. For product identification, tracking and real-time awareness, RFID tags are attached to goods. As tagged goods move along the supply chain from the suppliers to the manufacturers, and then on to the retailers until eventually they reach the customers, two major security challenges can be identified: (I) to protect the shipment of goods that are controlled by potentially untrusted carriers; and (II) to secure the transfer of ownership at each stage of the chain. For the former, grouping proofs in which the tags of the scanned goods generate a proof of "simulatenous" presence can be employed, while for the latter, ownership transfer protocols (OTP) are used. This paper describes enhanced security solutions for both challenges. We first extend earlier work on grouping proofs and group codes to capture resilient group scanning with untrusted readers; then, we describe a modified version of a recently published OTP based on channels with positive secrecy capacity adapted to be implemented on common RFID systems in the supply chain. The proposed solutions take into account the limitations of low cost tags employed in the supply chain, which are only required to generate pseudorandom numbers and compute one-way hash functions.

Fundamental radiation effect on polymers energy transfer from radiation to polymer

International Nuclear Information System (INIS)

Seguchi, T.

2007-01-01

Polymer modification as cross-link, chain scission, and graft-polymerization by radiation is initiated by the quantum energy transferred from radiation to polymers. The active species for chemical reactions are produced through ionization or activation of polymer molecules for any radiation source. The energy transfer occurs mainly by ionic interaction between radiation and polymer molecule, and the contribution from the collision interaction is miner. The radiation of electromagnetic wave as X-ray or γ-ray generates the energetic electron which induces ionic interaction with polymer molecule. The energy loss profile along the penetration to polymer material is much different among the radiation sources of EB, γ-ray, and ion beams in the macroscopic mechanism. In this article, the behavior of single event, that is, the event induced by one electron, γ-ray, ion, and neutron is described by the macroscopic mechanism and by the microscopic mechanism. (authors)

Preparation of molecularly imprinted nanoparticles with superparamagnetic susceptibility through atom transfer radical emulsion polymerization for the selective recognition of tetracycline from aqueous medium

International Nuclear Information System (INIS)

Dai, Jiangdong; Pan, Jianming; Xu, Longcheng; Li, Xiuxiu; Zhou, Zhiping; Zhang, Rongxian; Yan, Yongsheng

2012-01-01

Highlights: ► Atom transfer radical emulsion polymerization is a “living” and green technique. ► Nanoparticles can overcome mass transfer limitations and improve accessibility. ► Molecular imprinted nanoparticles with magnetic property for fast separation. ► The performance of imprinted nanoparticles was investigated in detail. ► Nanoparticles were used to selective recognize Tetracycline from water medium. - Abstract: In the work, we reported an effective method for the preparation of molecularly imprinted nanoparticles with superparamagnetic susceptibility through atom transfer radical emulsion polymerization (ATREP), and then as-prepared magnetic molecularly imprinted nanoparticles (MMINs) were evaluated as adsorbents for selective recognition of tetracycline (TC) molecules from aqueous medium. The resulting nanoparticles were characterized by FT-IR, TGA, VSM, SEM and TEM. The results demonstrated MMINs with a narrow diameter distribution were cross-linked with modified Fe 3 O 4 particles, composed of imprinted layer and exhibited good magnetic sensitivity, magnetic and thermal stability. Batch rebinding studies were carried out to determine the specific adsorption equilibrium, kinetics, and selective recognition. The estimated adsorption capacity of MMINs towards TC by the Langmuir isotherm model was 12.10 mg g −1 at 298 K, which was 6.33 times higher than that of magnetic non-molecularly imprinted nanoparticles (MNINs). The kinetic property of MMINs was well-described by the pseudo-second-order rate equation. The results of selective recognition experiments demonstrated outstanding affinity and selectivity towards TC over competitive antibiotics. The reusability of MMINs showed no obviously deterioration at least five repeated cycles in performance. In addition, the MMINs prepared were successfully applied to the extraction of TC from the spiked pork sample.

Unique effects of microwave heating on polymerization kinetics of poly(methyl methacrylate) composites

Energy Technology Data Exchange (ETDEWEB)

Spasojević, Pavle [Faculty of Technology and Metallurgy, University of Belgrade, Karnegijeva 4, 11120 Belgrade (Serbia); Jovanović, Jelena, E-mail: jelenaj@ffh.bg.ac.rs [Faculty of Physical Chemistry, University of Belgrade, Studentski trg 12-16, 11001 Belgrade (Serbia); Adnadjevic, Borivoj [Faculty of Physical Chemistry, University of Belgrade, Studentski trg 12-16, 11001 Belgrade (Serbia)

2013-09-16

The effects of heating mode (conventional and microwave) on the kinetics of isothermal polymerization of MMA composite materials were investigated. Isothermal kinetics curves at temperature range from 343 K to 363 K for both conventional (CH) and microwave heating (MWH) were determined. It was found that the polymerization of MMA composite materials was kinetically elementary reaction for both CH and MWH. The kinetics of CH polymerization can be described by the model of phase-boundary controlled process (contracting volume), whereas the kinetics of MWH polymerization can be described by the model of first-order chemical reaction. The kinetics parameters (E{sub a} and ln A) of the polymerization under microwave heating are lower than for conventional heating. The established decreases in the activation energy and pre-exponential factor under the MWH compared to the CH is explained with the increase in the energy of ground vibrational level of the C–O valence vibrations (ν = 987 cm{sup −1}) in methyl methacrylate molecule and with the decrease in its anharmonicity factor which is caused with the selective resonant transfer of energy from the energetic reservoir to the oscillators in methyl methacrylate molecules. - Graphical abstract: Display Omitted - Highlights: • The MWH speeds the MMA material polymerization and changes the kinetics model. • A novel concept of MWH action based on activation complexes formation is presented. • The Selective Energy Transfer model is used to explain the effects of MWH. • The kinetics parameters under MWH are lower than for CH. • The activation energy for both MWH and CH polymerization is quantized.

Dynamic model for tritium transfer in an aquatic food chain.

Science.gov (United States)

Melintescu, A; Galeriu, D

2011-08-01

Tritium ((3)H) is released from some nuclear facilities in relatively large quantities. It is a ubiquitous isotope because it enters straight into organisms, behaving essentially identically to its stable analogue (hydrogen). Tritium is a key radionuclide in the aquatic environment, in some cases, contributing significantly to the doses received by aquatic, non-human biota and by humans. The updated model presented here is based on more standardized, comprehensive assessments than previously used for the aquatic food chain, including the benthic flora and fauna, with an explicit application to the Danube ecosystem, as well as an extension to the special case of dissolved organic tritium (DOT). The model predicts the organically bound tritium (OBT) in the primary producers (the autotrophs, such as phytoplankton and algae) and in the consumers (the heterotrophs) using their bioenergetics, which involves the investigation of energy expenditure, losses, gains and efficiencies of transformations in the body. The model described in the present study intends to be more specific than a screening-level model, by including a metabolic approach and a description of the direct uptake of DOT in marine phytoplankton and invertebrates. For a better control of tritium transfer into the environment, not only tritiated water must be monitored, but also the other chemical forms and most importantly OBT, in the food chain.

Functionalization of multi-walled carbon nanotubes by epoxide ring-opening polymerization

International Nuclear Information System (INIS)

Jin Fanlong; Rhee, Kyong Yop; Park, Soo-Jin

2011-01-01

In this study, covalent functionalization of carbon nanotubes (CNTs) was accomplished by surface-initiated epoxide ring-opening polymerization. FT-IR spectra showed that polyether and epoxide group covalently attached to the sidewalls of CNTs. TGA results indicated that the polyether was successfully grown from the CNT surface, with the final products having a polymer weight percentage of ca. 14–74 wt%. The O/C ratio of CNTs increased significantly from 5.1% to 29.8% after surface functionalization of CNTs. SEM and TEM images of functionalized CNTs exhibited that the tubes were enwrapped by polymer chains with thickness of several nanometers, forming core–shell structures with CNTs at the center. - Graphical abstract: Functionalized CNTs were enwrapped by polymer chains with thickness of several nanometers, forming core–shell structures with CNTs at the center. Highlights: ► CNTs were functionalized by epoxide ring-opening polymerization. ► Polyether and epoxide group covalently attached to the sidewalls of CNTs. ► Functionalized CNTs have a polymer weight percentage of ca. 14–74 wt%. ► Functionalized CNTs were enwrapped by polymer chains with thickness of several nanometers.

Preparation of nanocomposites based on poly(Butylene Succinate) and montmorillonite organoclay via in situ polymerization

International Nuclear Information System (INIS)

Ferreira, Leticia P.; Moreira, Andrei N.; Souza Junior, Fernando G. de; Pinto, Jose Carlos Costa da Silva

2014-01-01

Nanocomposites based on poly(butylene succinate) (PBS) and organophilic montmorillonite were synthesized via in situ polymerization using three different clay compositions (4, 6 and 8 wt%). The products were characterized by several different techniques. X-ray diffraction was useful to confirm the increase of the interlayer spacing of the clay due to the presence of the polymer chains among layers. Thermal analysis indicated that the polymerization method chosen led to materials with lower thermal stability compared to the pure PBS, due to the difficulty of chain growth in the presence of the clay. Low-field NMR technique was used to assess clay dispersion in the polymer, with exfoliated structures predominating in the nanocomposites. (author)

Precision design of ethylene- and polar-monomer-based copolymers by organometallic-mediated radical polymerization

Science.gov (United States)

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

2014-03-01

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

THE KINETICS OF METHYL METHACRYLATE POLYMERIZATION INITIATED BY THE VOLATILE PRODUCTS OF A METHYL METHACRYLATE PLASMA

Institute of Scientific and Technical Information of China (English)

杨梅林; 马於光; 郑莹光; 沈家骢

1990-01-01

It is found that the volatile products of methyl methacrylate plasma can very actively initiate the polymerization of the monomer to produce ultrahigh molecular weight polymers. This polymerization of MMA occurs by a livlng free radical mechanism with instantaneous initiation and monomer transfer.

The use of radiation-induced graft polymerization for obtaining polymeric biomaterial on the basis of preparation 'Piyavit'

International Nuclear Information System (INIS)

Kudryavtsev, V.N.; Degtyareva, T.V.; Kabanov, V.Ya.

1998-01-01

The purpose of the present study is to obtain hemocompatible polymeric materials. The method of modification of polymer surface have been elaborated using the radiation-induced graft polymerization after which the surface is capable of coupling with the biologically active substances (BAS) produced from the medicinal leeches. At the Biological Department of Lomonosov Moscow State University was created a medicinal preparation 'Piyavit' isolated from the salivary glands secretion of the medicinal leeches (Hirudo medicinalis). It possess a wide spectrum of biological action on the human organism thanks to the presence of an unique complex natural of BAS (enzymes, inhibitors of proteolityc ensymes, prostanoids and et. al) guaranteed the anticoagulating, thrombolytic, antithrombotic, antiphlogistic, antiatherosclerotic, hypotentic effects and et al.. It has several advantages over anticoagulant heparin which is widely used for above mentioned purpose. 'Piyavit' is the multifunctional preparation, has not negative side-effects and is more cheap. The method of obtaining biocompatible polymers (basically polyethylene) with immobilized 'Piyavit' consist of three stages: 1. The modification of polymer surface by the radiation-induced graft polymerization of acrylic acid to obtain grafted chains polyacrylic acid (PAA) with controlled number and length. 2. The treatment of radiation grafted PAA by thionyl chloride that lead to conversion carboxyl groups of PAA in highly reactive acide chloride groups. 3. The covalent immobilization BAS of 'Piyavit' by acylation amino- and hydroxy-groups (functional groups in BAS) by acide chloride of PAA grafted on the polymere. (author)

Metallophilic interactions in polymeric group 11 thiols

Science.gov (United States)

Kolari, Kalle; Sahamies, Joona; Kalenius, Elina; Novikov, Alexander S.; Kukushkin, Vadim Yu.; Haukka, Matti

2016-10-01

Three polymeric group 11 transition metal polymers featuring metallophilic interactions were obtained directly via self-assembly of metal ions and 4-pyridinethiol ligands. In the cationic [Cu2(S-pyH)4]n2+ with [ZnCl4]n2- counterion (1) and in the neutral [Ag(S-py) (S-pyH)]n (2) 4-pyridinethiol (S-pyH) and its deprotonated form (S-py) are coordinated through the sulfur atom. Both ligands are acting as bridging ligands linking the metal centers together. In the solid state, the gold(I) polymer [Au(S-pyH)2]Cl (3) consists of the repeating cationic [Au(S-pyH)2]+ units held together by aurophilic interactions. Compound 1 is a zig-zag chain, whereas the metal chains in the structures of 2 and 3 are linear. The protonation level of the thiol ligand had an impact on the crystallization of polymers. Both nature of the metal center and reaction conditions affected the polymerization. QTAIM analysis confirmed direct metal-metal contacts only in polymers 1 and 3. In polymer 2, no theoretical evidence of argentophilic contacts was obtained even though the AgṡṡṡAg distance was found to be less than sum of the Bondi's van der Waals radius of silver.

The Research on Modeling and Simulation of TFE Polymerization Process

Directory of Open Access Journals (Sweden)

Jing Gao Sun

2014-01-01

Full Text Available PTFE (polytetrafluoroethylene is the fluorinated straight-chain polymer, made by the polymerization of tetrafluoroethylene monomer; it is used widely because of its excellent performance and can be obtained by the polymerization of body, solutions, suspensions, and emulsions. But only the last two are the main ways. This research paper makes simulation based on Polymer Plus. It uses the emulsion polymerization method at background to carry out a semibatch reactor system. Upon the actual production conditions, simulation process under the steady state conditions is used to analyze the effects of the changes on operating conditions; the corresponding dynamic model is created to analyze the impact of the changes of conditions on the entire system. Moreover, the amount of APS which plays an important part in this reaction is discussed for getting the most suitable amount of initiator. Because of less research work on this job, it is so difficult to find the related data from the literature. Therefore, this research will have a great significance for the process of the tetrafluoroethylene emulsion polymerization in the future.

The inhibition mechanisms of quinones and phenols present in wood for the vinyl polymerization

International Nuclear Information System (INIS)

Nobashi, Kenzo; Yokota, Tokuo

1977-01-01

The inhibitory effects and mechanisms of the quinones and phenols present in wood for the vinyl polymerization initiated with γ-rays and other initiation systems were investigated. The results obtained are summarized as follows; (1) Although phenolic compounds like isotaxiresinol inhibit the γ-ray initiated polymerization of methyl methacrylate (MMA) under the presence of air, they have no inhibitory effects in vacuo. On the other hand, o-benzoquinone and mansonones show strong inhibitory or retarding effects in vacuo. These facts indicate that oxygen may be important for the phenols to inhibit the vinyl polymerization. (2) It is shown qualitatively that there is a relationship between the strength of inhibitory action of quinones and their normal redox potentials. (3) PMMA produced under the presence of o-benzoquinone is found to include the fraction having extremely large chain length based on gel permeation chromatogram. (4) Based on the reaction products of orthoquinones and azobisisobutyronitrile, which was assumed as a model of polymer radicals, the inhibition reaction with polymer chain radical is concluded to take place upon the oxygen atoms of the quinones. (auth.)

A KIND OF FLUORESCENCE PROBE TO STUDY THE KINETICS OF POLYMERIZATION PROCESS

Institute of Scientific and Technical Information of China (English)

YANG Guoqiang; WU Shikang

1994-01-01

Fluorescence properties of 1-phenyl-3-(4'-nitrophenyl) pyrazoline (PNP) were studied in bulk polymerization process of methylmethacrylate (MMA). The fluorescence intensity of PNP was enhanced and the emission maximum was blue shifted with the polymerization progress. In the period of auto-acceleration of the polymerization the enhancement of fluorescence intensity and blue shift of peak wavelength in spectra could be observed evidently. This means that the solvatochromic properties of PNP are influenced not only by the solvent polarity but also by the viscosity of the medium(especially by the phase transition). In solid state PNP emits from the charge transfer excited state without solvent relaxation. The transient emission spectra and the results from Bakhshiev model of solvent relaxation coincide with that from the polymerization experiment.

Quasi-one-dimensional Heisenberg antiferromagnetic model for an organic polymeric chain

International Nuclear Information System (INIS)

Wu, F; Wang, W Z

2006-01-01

Using the exact diagonalization technique, we study the properties of the ground state of a spin-1/2 antiferromagnetic Heisenberg model for a zigzag polymer chain with side radicals connected to the even sites. We consider the nearest-neighbour exchange J and the next-nearest-neighbour exchange αJ along the main chain, and J 1 between the even site on the main chain and the radical site. For small α the ground state is ferrimagnetic. For α>α c1 , the ground state is a spiral phase, which is characterized by a peak of the static structure factor S(q) locating at an incommensurate value q max . For α>α c2 , the ground state is antiferromagnetic. With increasing J 1 , α c1 decreases while α c2 has a maximum at about J 1 = 0.5. For very small J 1 and α = 0.5, the spin configuration on the main chain is a product of nearest-neighbour singlets. In the antiferromagnetic phase, if J 1 is large enough the even site and the radical site form a singlet with exchange-decoupling from the odd site while the odd sites approximately form an antiferromagnetic chain

Simulation of radioactive cesium transfer in the southern Fukushima coastal biota using a dynamic food chain transfer model

International Nuclear Information System (INIS)

Tateda, Yutaka; Tsumune, Daisuke; Tsubono, Takaki

2013-01-01

The Fukushima Dai-ichi Nuclear Power Plant (1F NPP) accident occurred on 11 March 2011. The accident introduced 137 Cs into the coastal waters which was subsequently transferred to the local coastal biota thereby elevating the concentration of this radionuclide in coastal organisms. In this study, the radioactive cesium levels in coastal biota from the southern Fukushima area were simulated using a dynamic biological compartment model. The simulation derived the possible maximum radioactive cesium levels in organisms, indicating that the maximum 137 Cs concentrations in invertebrates, benthic fish and predator fish occurred during late April, late May and late July, respectively in the studied area where the source was mainly the direct leakage of 137 Cs effluent from the 1F NPP. The delay of a 137 Cs increase in fish was explained by the gradual food chain transfer of 137 Cs introduced to the ecosystem from the initial contamination of the seawater. The model also provided the degree of radionuclide depuration in organisms, and it demonstrated the latest start of the decontamination phase in benthic fish. The ecological half-lives, derived both from model simulation and observation, were 1–4 months in invertebrates, and 2–9 months in plankton feeding fish and coastal predator fish from the studied area. In contrast, it was not possible to similarly calculate these parameters in benthic fish because of an unidentified additional radionuclide source which was deduced from the biological compartment model. To adequately reconstruct the in-situ depuration of radiocesium in benthic fish in the natural ecosystem, a contamination source associated with the bottom sediments is necessary. -- Highlights: • Cs-137 in the southern Fukushima coastal biota were simulated using a dynamic biological compartment model. • Simulation derived contamination phase of marine biota was completed until late April to July 2011. • The delay of Cs-137 concentration increase in fish

Involvement of a cytosine side chain in proton transfer in the rate-determining step of ribozyme self-cleavage

Science.gov (United States)

Shih, I-hung; Been, Michael D.

2001-01-01

Ribozymes of hepatitis delta virus have been proposed to use an active-site cytosine as an acid-base catalyst in the self-cleavage reaction. In this study, we have examined the role of cytosine in more detail with the antigenomic ribozyme. Evidence that proton transfer in the rate-determining step involved cytosine 76 (C76) was obtained from examining cleavage activity of the wild-type and imidazole buffer-rescued C76-deleted (C76Δ) ribozymes in D2O and H2O. In both reactions, a similar kinetic isotope effect and shift in the apparent pKa indicate that the buffer is functionally substituting for the side chain in proton transfer. Proton inventory of the wild-type reaction supported a mechanism of a single proton transfer at the transition state. This proton transfer step was further characterized by exogenous base rescue of a C76Δ mutant with cytosine and imidazole analogues. For the imidazole analogues that rescued activity, the apparent pKa of the rescue reaction, measured under kcat/KM conditions, correlated with the pKa of the base. From these data a Brønsted coefficient (β) of 0.51 was determined for the base-rescued reaction of C76Δ. This value is consistent with that expected for proton transfer in the transition state. Together, these data provide strong support for a mechanism where an RNA side chain participates directly in general acid or general base catalysis of the wild-type ribozyme to facilitate RNA cleavage. PMID:11171978

An RFID-Based Smart Structure for the Supply Chain: Resilient Scanning Proofs and Ownership Transfer with Positive Secrecy Capacity Channels †

Science.gov (United States)

Ortiz, Andrés

2017-01-01

The National Strategy for Global Supply Chain Security published in 2012 by the White House identifies two primary goals for strengthening global supply chains: first, to promote the efficient and secure movement of goods, and second to foster a resilient supply chain. The Internet of Things (IoT), and in particular Radio Frequency Identification (RFID) technology, can be used to realize these goals. For product identification, tracking and real-time awareness, RFID tags are attached to goods. As tagged goods move along the supply chain from the suppliers to the manufacturers, and then on to the retailers until eventually they reach the customers, two major security challenges can be identified: (I) to protect the shipment of goods that are controlled by potentially untrusted carriers; and (II) to secure the transfer of ownership at each stage of the chain. For the former, grouping proofs in which the tags of the scanned goods generate a proof of “simulatenous” presence can be employed, while for the latter, ownership transfer protocols (OTP) are used. This paper describes enhanced security solutions for both challenges. We first extend earlier work on grouping proofs and group codes to capture resilient group scanning with untrusted readers; then, we describe a modified version of a recently published OTP based on channels with positive secrecy capacity adapted to be implemented on common RFID systems in the supply chain. The proposed solutions take into account the limitations of low cost tags employed in the supply chain, which are only required to generate pseudorandom numbers and compute one-way hash functions. PMID:28677637

J chain in the nurse shark: implications for function in a lower vertebrate.

Science.gov (United States)

Hohman, Valerie S; Stewart, Sue E; Rumfelt, Lynn L; Greenberg, Andrew S; Avila, David W; Flajnik, Martin F; Steiner, Lisa A

2003-06-15

J chain is a small polypeptide covalently attached to polymeric IgA and IgM. In humans and mice, it plays a role in binding Ig to the polymeric Ig receptor for transport into secretions. The putative orthologue of mammalian J chain has been identified in the nurse shark by sequence analysis of cDNA and the polypeptide isolated from IgM. Conservation with J chains from other species is relatively poor, especially in the carboxyl-terminal portion, and, unlike other J chains, the shark protein is not acidic. The only highly conserved segment in all known J chains is a block of residues surrounding an N-linked glycosylation site. Of the eight half-cystine residues that are conserved in mammalian J chains, three are lacking in the nurse shark, including two in the carboxyl-terminal segment that have been reported to be required for binding of human J chain-containing IgA to secretory component. Taken together with these data, the relative abundance of J chain transcripts in the spleen and their absence in the spiral valve (intestine) suggest that J chain in nurse sharks may not have a role in Ig secretion. Analysis of J chain sequences in diverse species is in agreement with accepted phylogenetic relationships, with the exception of the earthworm, suggesting that the reported presence of J chain in invertebrates should be reassessed.

Preparation of molecularly imprinted nanoparticles with superparamagnetic susceptibility through atom transfer radical emulsion polymerization for the selective recognition of tetracycline from aqueous medium

Energy Technology Data Exchange (ETDEWEB)

Dai, Jiangdong; Pan, Jianming; Xu, Longcheng; Li, Xiuxiu [School of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang 212013 (China); Zhou, Zhiping [School of Material Science and Engineering, Jiangsu University, Zhenjiang 212013 (China); Zhang, Rongxian [School of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang 212013 (China); Yan, Yongsheng, E-mail: djdxxx123@163.com [School of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang 212013 (China); State Key Laboratory of Natural and Biomimetic Drugs, Peking University, Beijing, 100191 (China)

2012-02-29

Highlights: Black-Right-Pointing-Pointer Atom transfer radical emulsion polymerization is a 'living' and green technique. Black-Right-Pointing-Pointer Nanoparticles can overcome mass transfer limitations and improve accessibility. Black-Right-Pointing-Pointer Molecular imprinted nanoparticles with magnetic property for fast separation. Black-Right-Pointing-Pointer The performance of imprinted nanoparticles was investigated in detail. Black-Right-Pointing-Pointer Nanoparticles were used to selective recognize Tetracycline from water medium. - Abstract: In the work, we reported an effective method for the preparation of molecularly imprinted nanoparticles with superparamagnetic susceptibility through atom transfer radical emulsion polymerization (ATREP), and then as-prepared magnetic molecularly imprinted nanoparticles (MMINs) were evaluated as adsorbents for selective recognition of tetracycline (TC) molecules from aqueous medium. The resulting nanoparticles were characterized by FT-IR, TGA, VSM, SEM and TEM. The results demonstrated MMINs with a narrow diameter distribution were cross-linked with modified Fe{sub 3}O{sub 4} particles, composed of imprinted layer and exhibited good magnetic sensitivity, magnetic and thermal stability. Batch rebinding studies were carried out to determine the specific adsorption equilibrium, kinetics, and selective recognition. The estimated adsorption capacity of MMINs towards TC by the Langmuir isotherm model was 12.10 mg g{sup -1} at 298 K, which was 6.33 times higher than that of magnetic non-molecularly imprinted nanoparticles (MNINs). The kinetic property of MMINs was well-described by the pseudo-second-order rate equation. The results of selective recognition experiments demonstrated outstanding affinity and selectivity towards TC over competitive antibiotics. The reusability of MMINs showed no obviously deterioration at least five repeated cycles in performance. In addition, the MMINs prepared were successfully

Spectroscopic studies on novel donor-acceptor and low band-gap polymeric semiconductors

International Nuclear Information System (INIS)

Cravino, A.

2002-11-01

Novel low band-gap conjugated polymeric semiconductors as well as conjugated electron donor chains carrying electron acceptor substituents were electrochemically prepared and investigated by means of different spectroscopic techniques. Using in situ FTIR and ESR spectroelectrochemistry, the spectroscopic features of injected positive charges are found to be different as opposed to the negative charge carriers on the same conjugated polymer. These results, for which the theoretical models so far developed do not account, demonstrate the different structure and delocalization of charge carriers with opposite signs. In addition, vibrational spectroscopy results proof the enhanced 'quinoid' character of low band-gap conjugated chains. Excited state spectroscopy was applied to study photoexcitations in conjugated polymers carrying tetracyanoanthraquinone type or fullerene moieties. This novel class of materials, hereafter called double-cable polymers, was found promising as alternative to the conjugated polymer:fullerene mixtures currently used for the preparation of 'bulk-heterojunction' polymeric solar cells. (author)

Concentrations and congener profiles of chlorinated paraffins in domestic polymeric products in China.

Science.gov (United States)

Wang, Chu; Gao, Wei; Liang, Yong; Wang, Yawei; Jiang, Guibin

2018-03-21

Chlorinated paraffins (CPs) are widely used in domestic polymeric products as plasticizers and fire retardants. In this study, concentrations and congener profiles of short-chain and medium-chain chlorinated paraffins (SCCPs and MCCPs) were investigated in domestic polymeric products, including plastics, rubber and food packaging in China. The average concentrations of SCCPs in polyethylene terephthalate (PET), polypropylene (PP), polyethylene (PE) and food packaging were 234, 3968, 150 and 188 ng/g, respectively and the corresponding average concentrations of MCCPs in these samples were 37.4, 2537, 208 and 644 ng/g, respectively. The concentrations of CPs in rubber and polyvinylchloride (PVC) were significantly higher than in other matrices. The highest concentrations of SCCPs and MCCPs were found in a PVC cable sheath with 191 mg/g and 145 mg/g, respectively. Congener group profiles analysis indicated C 11 - and C 13 -congener groups were predominant in carbon homologues of SCCPs, and C 14 -congener groups were predominant in MCCPs. High levels of SCCPs and MCCPs in domestic polymeric products implied that they might be a significant source to the environment and human exposure. Copyright © 2018. Published by Elsevier Ltd.