Sample records for radical solution polymerization
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Ion-Molecule Association in Acrylonitrile
NASA Technical Reports Server (NTRS)
Wilson, Paul F.; Milligan, Daniel B.; McEwan, Murray J.
1997-01-01
Acrylonitrile (propernenitrile or vinyl cyanide) polymerizes readily via a radical mechanism in solution at room temparature. The propensity to polymerize is sufficiently strong that it is usual to add a radical scavenger to the solution to prevent polymerization when oxygen (an inhibitor) is removed. Polymerization of acrylonitrile is also know to occur via nucleophilic addition of an anion by a michael-type reaction.
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Self-Propagating Frontal Polymerization in Water at Ambient Pressure
NASA Technical Reports Server (NTRS)
Olten, Nesrin; Kraigsley, Alison; Ronney, Paul D.
2003-01-01
Advances in polymer chemistry have led to the development of monomers and initiation agents that enable propagating free-radical polymerization fronts to exist. These fronts are driven by the exothermicity of the polymerization reaction and the transport of heat from the polymerized product to the reactant monomer/solvent/initiator solution. The thermal energy transported to the reactant solution causes the initiator to decompose, yielding free radicals, which start the free radical polymerization process as discussed in recent reviews. The use of polymerization processes based on propagating fronts has numerous applications. Perhaps the most important of these is that it enables rapid curing of polymers without external heating since the polymerization process itself provides the high temperatures necessary to initiate and sustain polymerization. This process also enables more uniform curing of arbitrarily thick samples since it does not rely on heat transfer from an external source, which will necessarily cause the temperature history of the sample to vary with distance from the surface according to a diffusion-like process. Frontal polymerization also enables filling and sealing of structures having cavities of arbitrary shape without having to externally heat the structure. Water at atmospheric pressure is most convenient solvent to employ and the most important for practical applications (because of the cost and environmental issues associated with DMSO and other solvents). Nevertheless, to our knowledge, steady, self-propagating polymerization fronts have not been reported in water at atmospheric pressure. Currently, polymerization fronts require a high boiling point solvent (either water at high pressures or an alternative solvent such as dimethyl sulfoxide (DMSO) (boiling point 189 C at atmospheric pressure.) Early work on frontal polymerization, employed pressures up to 5000 atm in order to avoid boiling of the monomer/solvent/initiator solution. High boiling point solutions are needed because in order to produce a propagating front, a high front temperature is needed to produce sufficiently rapid decomposition of the free radical initiator and subsequent free radical polymerization and heat release at a rate faster than heat losses remove thermal energy from the system. (While the conduction heat loss rate increases linearly with temperature, the free radical initiator decomposition is a high activation energy process whose rate increases much more rapidly than linearly with temperature, thus as the temperature decreases, the ratio of heat loss to heat generation increases, eventually leading to extinction of the front if the temperature is too low.) In order to obtain atmospheric pressure frontal polymerization in water, it is necessary to identify a monomer/initiator combination that is water soluble and will not extinguish even when the peak temperature (T*) is less than 100 C. In this work acrylic acid (AA) was chosen as the monomer because is it one of the most reactive monomers and can polymerize readily at low temperatures even without initiators. Ammonium persulfate (AP) was chosen as the initiator because it decomposes readily at low temperatures, produces relatively few bubbles and is commercially available. The propagation rates and extinction conditions of the fronts are studied for a range of AA and AP concentrations. Small amounts of fumed silica powder (Cab-o-sil, Cabot Corporation) were added to the solutions to inhibit buoyancy induced convection in the solutions; future studies will investigate the effects of buoyant convection within the solutions.
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THE RADIATION-INDUCED POLYMERIZATION OF ISOBUTENE: A LIQUID PHASE IONIC REACTION
DOE Office of Scientific and Technical Information (OSTI.GOV)
Collinson, E.; Dainton, F.S.; Gillis, H.A.
1959-06-01
New evidence is presented in support of the suggestion that the gamma - ray-induced polymerization of liquid isobutene at -78 deg C proceeds solely by a cationic mechanism. Attempts to polymerize isobutene at -78 deg C with free radicals from the photolysis of diacetyl, benzoin and benzil were unsuccessful but the benzil solution irradiated with ultraviolet light at 77 deg K was shown by electron spin resonance measurements to give rise to radicals from the isobutene. Isobutene irradiated in the pure state at a gamma -ray dose rate of 7 x 10/sup 17/ e.v. ml/sup -1/ min/sup -1/ polymerized withmore » G(-C/sub 4/H/sub 8/) = 3.0 plus or minus 1.7 x 10/sup 2/. Solutions of FeCl/sub 3/, DPPH, benzoquinone and iodine in isobutene were also irradiated with gamma -rays. Of these solutes, only benzoquinone reduced the polymerization rate to zero, and DPPH had no significant effect. The effects of FeCl/sub 3/ and I/2 on the polymerization were complicated by other factors. The measured yields of conversion of the solutes after irradiation were G(-DPPH) =3.7 plus or minus 0.2, G(Fe(II)) = 3.0 plus or minus 0.5 and G(-Q) = 1.5 plus or minus 0.2. The electron spin resonance spectrum of isobutene irradiated with gamma -rays at 77 deg K showed the presence of H atoms which disappeared rapidly, and a more stable radical, the spectrum of which consisted of 6 peaks having an over-all spacing of 158 gauss at the operating frequency of 9400 Mc sec./sup -1/. The same six peak pattern was obtained from cyclopropane irradiated with gamma rays at 77 deg K and from a solution of benzil in isoDutene irradiated with ultraviolet light at 77 deg K. It is concluded that the radical responsible for this spectrum is either the cyclopropyl radical or the methyl substituted allyl radical, the latter being the less likely. The most likely initiating ion is considered to be (CH/sub 3/)/sub 3/C/sup +/, and a mechanism consistent with the available data is proposed. (auth)« less
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Korchev, A S; Konovalova, T; Cammarata, V; Kispert, L; Slaten, L; Mills, G
2006-01-03
The present study is centered on the processes involved in the photochemical generation of nanometer-sized Ag particles via illumination at 350 nm of aqueous solutions and cross linked films containing sulfonated poly(ether ether ketone) and poly(vinyl alcohol). Optical and electron paramagnetic resonance experiments, including electron nuclear double resonance data, proved conclusively that the photogenerated chromophore exhibiting a band with lambda(max) = 565 nm is an alpha-hydroxy aromatic (ketyl) radical of the polymeric ketone. This reducing species was produced by illumination of either solutions or films, but the radical lifetime extended from minutes in the fluid phase to hours in the solid. Direct evidence is presented that this long-lived chromophore reduces Ag(I), Cu(II), and Au(III) ions in solution. A rate constant of k = 1.4 x 10(3) M(-)(1) s(-)(1) was obtained for the reduction of Ag(+) by the ketyl radical from the post-irradiation formation of Ag crystallites. FTIR results confirmed that the photoprocess yielding polymeric ketyl radicals involves a reaction between the macromolecules. The photochemical oxidation of the polymeric alcohol, as well as the formation of light-absorbing macromolecular products and polyols, indicates that the sulfonated polyketone experienced transformations similar to those encountered during illumination of the benzophenone/2-propanol system.
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Photogeneration of H2O2 in SPEEK/PVA aqueous polymer solutions.
Little, Brian K; Lockhart, PaviElle; Slaten, B L; Mills, G
2013-05-23
Photolysis of air-saturated aqueous solutions containing sulphonated poly(ether etherketone) and poly(vinyl alcohol) results in the generation of hydrogen peroxide. Consumption of oxygen and H2O2 formation are initially concurrent processes with a quantum yield of peroxide generation of 0.02 in stirred or unstirred solutions within the range of 7 ≤ pH ≤ 9. The results are rationalized in terms of O2 reduction by photogenerated α-hydroxy radicals of the polymeric ketone in competition with radical-radical processes that consume the macromolecular reducing agents. Generation of H2O2 is controlled by the photochemical transformation that produces the polymer radicals, which is most efficient in neutral and slightly alkaline solutions. Quenching of the excited state of the polyketone by both H3O(+) and OH(-) affect the yields of the reducing macromolecular radicals and of H2O2. Deprotonation of the α-hydroxy polymeric radicals at pH > 9 accelerate their decay and contribute to suppressing the peroxide yields in basic solutions. Maxima in [H2O2] are observed when illuminations are performed with static systems, where O2 reduction is faster than diffusion of oxygen into the solutions. Under such conditions H2O2 can compete with O2 for the reducing radicals resulting in a consumption of the peroxide.
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Free-radical solution-polymerization of trifluoronitrosomethane with tetrafluoroethylene
NASA Technical Reports Server (NTRS)
Gdickman, S. A.
1972-01-01
Heavy-walled glass reactor, equipped with aerosol-compatible couplings and needle valve and charged with solvent and initiator, is utilized for polymerization. Polymer conversions and reactor/vessel operation are discussed.
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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.
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Fastest Formation Routes of Nanocarbons in Solution Plasma Processes.
Morishita, Tetsunori; Ueno, Tomonaga; Panomsuwan, Gasidit; Hieda, Junko; Yoshida, Akihito; Bratescu, Maria Antoaneta; Saito, Nagahiro
2016-11-14
Although solution-plasma processing enables room-temperature synthesis of nanocarbons, the underlying mechanisms are not well understood. We investigated the routes of solution-plasma-induced nanocarbon formation from hexane, hexadecane, cyclohexane, and benzene. The synthesis rate from benzene was the highest. However, the nanocarbons from linear molecules were more crystalline than those from ring molecules. Linear molecules decomposed into shorter olefins, whereas ring molecules were reconstructed in the plasma. In the saturated ring molecules, C-H dissociation proceeded, followed by conversion into unsaturated ring molecules. However, unsaturated ring molecules were directly polymerized through cation radicals, such as benzene radical cation, and were converted into two- and three-ring molecules at the plasma-solution interface. The nanocarbons from linear molecules were synthesized in plasma from small molecules such as C 2 under heat; the obtained products were the same as those obtained via pyrolysis synthesis. Conversely, the nanocarbons obtained from ring molecules were directly synthesized through an intermediate, such as benzene radical cation, at the interface between plasma and solution, resulting in the same products as those obtained via polymerization. These two different reaction fields provide a reasonable explanation for the fastest synthesis rate observed in the case of benzene.
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Fastest Formation Routes of Nanocarbons in Solution Plasma Processes
Morishita, Tetsunori; Ueno, Tomonaga; Panomsuwan, Gasidit; Hieda, Junko; Yoshida, Akihito; Bratescu, Maria Antoaneta; Saito, Nagahiro
2016-01-01
Although solution-plasma processing enables room-temperature synthesis of nanocarbons, the underlying mechanisms are not well understood. We investigated the routes of solution-plasma-induced nanocarbon formation from hexane, hexadecane, cyclohexane, and benzene. The synthesis rate from benzene was the highest. However, the nanocarbons from linear molecules were more crystalline than those from ring molecules. Linear molecules decomposed into shorter olefins, whereas ring molecules were reconstructed in the plasma. In the saturated ring molecules, C–H dissociation proceeded, followed by conversion into unsaturated ring molecules. However, unsaturated ring molecules were directly polymerized through cation radicals, such as benzene radical cation, and were converted into two- and three-ring molecules at the plasma–solution interface. The nanocarbons from linear molecules were synthesized in plasma from small molecules such as C2 under heat; the obtained products were the same as those obtained via pyrolysis synthesis. Conversely, the nanocarbons obtained from ring molecules were directly synthesized through an intermediate, such as benzene radical cation, at the interface between plasma and solution, resulting in the same products as those obtained via polymerization. These two different reaction fields provide a reasonable explanation for the fastest synthesis rate observed in the case of benzene. PMID:27841288
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Shiojima, Taro; Inoue, Yuuki; Kyomoto, Masayuki; Ishihara, Kazuhiko
2016-08-01
A highly efficient methodology for preparing a poly(2-methacryloyloxyethyl phosphorylcholine) (PMPC) layer on the surface of poly(ether ether ketone) (PEEK) was examined by photoinduced and self-initiated graft polymerization. To enhance the polymerization rate, we demonstrated the effects of inorganic salt additives in the feed monomer solution on thickness of grafted PMPC layer. Photoinduced polymerization occurred and the PMPC graft layer was successfully formed on the PEEK surface, regardless of inorganic salt additives. Moreover, it was clearly observed that the addition of inorganic salt enhanced the grafting thickness of PMPC layer on the surface even when the photoirradiation time was shortened. The addition of inorganic salt additives in the feed monomer solution enhanced the polymerization rate of MPC and resulted in thicker PMPC layers. In particular, we evaluated the effect of NaCl concentration and how this affected the polymerization rate and layer thickness. We considered that this phenomenon was due to the hydration of ions in the feed monomer solution and subsequent apparent increase in the MPC concentration. A PMPC layer with over 100-nm-thick, which was prepared by 5-min photoirradiation in 2.5mol/L inorganic salt aqueous solution, showed good wettability and protein adsorption resistance compared to that of untreated PEEK. Hence, we concluded that the addition of NaCl into the MPC feed solution would be a convenient and efficient method for preparing a graft layer on PEEK. Photoinduced and self-initiated graft polymerization on the PEEK surface is one of the several methodologies available for functionalization. However, in comparison with free-radical polymerization, the efficiency of polymerization at the solid-liquid interface is limited. Enhancement of the polymerization rate for grafting could solve the problem. In this study, we observed the acceleration of the polymerization rate of MPC in an aqueous solution by the addition of inorganic salt. The salt itself did not show any adverse effects on the radical polymerization; however, the apparent concentration of the monomer in feed may be increased due to the hydration of ions attributed to salt additives. We could obtain PMPC-grafted PEEK with sufficient PMPC thickness to obtain good functionality with only 5-min photoirradiation by using 2.5mol/L NaCl in the feed solution. Copyright © 2016 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
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Preparation of poly(vinyl alcohol)/kaolinite nanocomposites via in situ polymerization
DOE Office of Scientific and Technical Information (OSTI.GOV)
Jia Xin; Department of Chemistry, Hexi University, Zhangye 734000; Li Yanfeng
2008-03-04
Poly(vinyl alcohol)/kaolinite intercalated nanocomposites (Kao-PVA) were prepared via in situ intercalation radical polymerization. Vinyl acetate (VAc) was intercalated into kaolinite by a displacement method using dimethyl sulfoxide/kaolinite (Kao-DMSO) as the intermediate. Then, PVAc/kaolinite (Kao-PVAc) was obtained via radical polymerization with benzoyl peroxide (BPO) as initiator. Last, PVAc/kaolinite was saponified via direct-hydrolysis with NaOH solution in order to obtain PVA/kaolinite nanocomposites, which was characterized by Fourier-Transformation spectroscopy (FTIR), wide X-ray diffraction (WXRD) and transmission electron microscopy (TEM). Their differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) results of the obtained PVA/kaolinite suggested that the thermal properties had an obvious improvement.
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Chain Reaction Polymerization.
ERIC Educational Resources Information Center
McGrath, James E.
1981-01-01
The salient features and importance of chain-reaction polymerization are discussed, including such topics as the thermodynamics of polymerization, free-radical polymerization kinetics, radical polymerization processes, copolymers, and free-radical chain, anionic, cationic, coordination, and ring-opening polymerizations. (JN)
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Korchev, A S; Shulyak, T S; Slaten, B L; Gale, W F; Mills, G
2005-04-28
Illumination of air-free aqueous solutions containing sulfonated poly(ether ether ketone) and poly(vinyl alcohol) with 350 nm light results in benzophenone ketyl radicals of the polyketone. The polymer radicals form with a quantum yield 0.02 and decay with a second-order rate constant 6 orders of magnitude lower than that of typical alpha-hydroxy radicals. Evidence is presented that the polymeric benzophenone ketyl radicals reduce Ag+, Cu2+, and AuCl4- to metal particles of nanometer dimensions. Decreases in the reduction rates with increasing Ag(I), Cu(II), and Au(III) concentrations are explained using a kinetic model in which the metal ions quench the excited state of the polymeric benzophenone groups, which forms the macromolecular radicals. Quenching is fastest for Ag+, whereas Cu2+ and AuCl4- exhibit similar rate constants. Particle formation becomes more complex as the number of equivalents needed to reduce the metal ions increases; the Au(III) system is an extreme case where the radical reactions operate in parallel with secondary light-initiated and thermal reduction channels. For each metal ion, the polymer-initiated photoreactions produce crystallites possessing distinct properties, such as a very strong plasmon in the Ag case or the narrow size distribution exhibited by Au particles.
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Altunkaya, Arzu; Gökmen, Vural; Skibsted, Leif H
2016-01-01
Influence of pH on the antioxidant activities of combinations of lettuce extract (LE) with quercetin (QC), green tea extract (GTE) or grape seed extract (GSE) was investigated for both reduction of Fremy's salt in aqueous solution using direct electron spin resonance (ESR) spectroscopy and in L-α-phosphatidylcholine liposome peroxidation assay measured following formation of conjugated dienes. All examined phenolic antioxidants showed increasing radical scavenging effect with increasing pH values by using both methods. QC, GTE and GSE acted synergistically in combination with LE against oxidation of peroxidating liposomes and with QC showing the largest effect. The pH dependent increase of the antioxidant activity of the phenols is due to an increase of their electron-donating ability upon deprotonation and to their stabilization in alkaline solutions leading to polymerization reaction. Such polymerization reactions of polyphenolic antioxidants can form new oxidizable -OH moieties in their polymeric products resulting in a higher radical scavenging activity. Copyright © 2015 Elsevier Ltd. All rights reserved.
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Berron, Brad J; Johnson, Leah M; Ba, Xiao; McCall, Joshua D; Alvey, Nicholas J; Anseth, Kristi S; Bowman, Christopher N
2011-01-01
We report the first use of a polymerization-based ELISA substrate solution employing enzymatically mediated radical polymerization as a dual-mode amplification strategy. Enzymes are selectively coupled to surfaces to generate radicals that subsequently lead to polymerization-based amplification (PBA) and biodetection. Sensitivity and amplification of the polymerization-based detection system were optimized in a microwell strip format using a biotinylated microwell surface with a glucose oxidase (GOx)–avidin conjugate. The immobilized GOx is used to initiate polymerization, enabling the detection of the biorecognition event visually or through the use of a plate reader. Assay response is compared to that of an enzymatic substrate utilizing nitroblue tetrazolium in a simplified assay using biotinylated wells. The polymerization substrate exhibits equivalent sensitivity (2 µg/mL of GOx-avidin) and over three times greater signal amplification than this traditional enzymatic substrate since each radical that is enzymatically generated leads to a large number of polymerization events. Enzyme-mediated polymerization proceeds in an ambient atmosphere without the need for external energy sources, which is an improvement upon previous PBA platforms. Substrate formulations are highly sensitive to both glucose and iron concentrations at the lowest enzyme concentrations. Increases in amplification time correspond to higher assay sensitivities with no increase in non-specific signal. Finally, the polymerization substrate generated a signal to noise ratio of 14 at the detection limit (156 ng/mL) in an assay of transforming growth factor-beta. Biotechnol. Bioeng. 2011; 108:1521–1528. © 2011 Wiley Periodicals, Inc. PMID:21337335
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Lloyd, Danielle J; Nikolaou, Vasiliki; Collins, Jennifer; Waldron, Christopher; Anastasaki, Athina; Bassett, Simon P; Howdle, Steven M; Blanazs, Adam; Wilson, Paul; Kempe, Kristian; Haddleton, David M
2016-05-05
Aqueous copper-mediated radical polymerization of acrylamides and acrylates in carbonated water resulted in high monomer conversions (t < 10 min) before undergoing depolymerization (60 min > t > 10 min). The regenerated monomer was characterized and repolymerized following deoxygenation of the resulting solutions to reyield polymers in high conversions that exhibit low dispersities.
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Baumgartner, Thomas; Jäkle, Frieder; Rulkens, Ron; Zech, Gernot; Lough, Alan J; Manners, Ian
2002-08-28
To obtain mechanistic insight, detailed studies of the intriguing "spontaneous" ambient temperature ring-opening polymerization (ROP) of tin-bridged [1]ferrocenophanes Fe(eta-C(5)H(4))(2)SnR(2) 3a (R = t-Bu) and 3b (R = Mes) in solution have been performed. The investigations explored the influence of non-nucleophilic additives such as radicals and radical traps, neutral and anionic nucleophiles, Lewis acids, protic species, and other cationic electrophiles. Significantly, two novel methodologies and mechanisms for the ROP of strained [1]ferrocenophanes are proposed based on this study. First, as the addition of amine nucleophiles such as pyridine was found to strongly accelerate the polymerization rate in solution, a new nucleophilicallyassisted ROP methodology was proposed. This operates at ambient temperature in solution even in the presence of chlorosilanes but, unlike the anionic polymerization of ferrocenophanes, does not involve cyclopentadienyl anions. Second, the addition of small quantities of the electrophilic species H(+) and Bu(3)Sn(+) was found to lead to a cationic ROP process. These studies suggest that the "spontaneous" ROP of tin-bridged [1]ferrocenophanes may be a consequence of the presence of spurious, trace quantities of Lewis basic or acidic impurities. The new ROP mechanisms reported are likely to be of general significance for the ROP of other metallocenophanes (e.g., for thermal ROP in the melt) and for other metallacycles containing group 14 elements.
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Spatially controlled, in situ synthesis of polymers
Caneba, Gerard T.; Tirumala, Vijaya Raghavan; Mancini, Derrick C.; Wang, Hsien-Hau
2005-03-22
An in situ polymer microstructure formation method. The monomer mixture is polymerized in a solvent/precipitant through exposure to ionizing radiation in the absence any chemical mediators. If an exposure mask is employed to block out certain regions of the radiation cross section, then a patterned microstructure is formed. The polymerization mechanism is based on the so-called free-radical retrograde-precipitation polymerization process, in which polymerization occurs while the system is phase separating above the lower critical solution temperature. This method was extended to produce a crosslinked line grid-pattern of poly (N-isopropylacrylamide), which has been known to have thermoreversible properties.
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NASA Astrophysics Data System (ADS)
Edeleva, M. V.; Marque, S. R. A.; Bagryanskaya, E. G.
2018-04-01
Controlled, or pseudoliving, radical polymerization provides unique opportunities for the synthesis of structurally diverse polymers with a narrow molecular-weight distribution. These reactions occur under relatively mild conditions with broad tolerance to functional groups in the monomers. The nitroxide-mediated pseudoliving radical polymerization is of particular interest for the synthesis of polymers for biomedical applications. This review briefly describes one of the mechanisms of controlled radical polymerization. The studies dealing with the use of imidazoline and imidazolidine nitroxides as controlling agents for nitroxide-mediated pseudoliving radical polymerization of various monomers are summarized and analyzed. The publications addressing the key steps of the controlled radical polymerization in the presence of imidazoline and imidazolidine nitroxides and new approaches to nitroxide-mediated polymerization based on protonation of both nitroxides and monomers are considered. The bibliography includes 154 references.
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Radical-Mediated Enzymatic Polymerizations
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
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Blasi, Davide; Nikolaidou, Domna M; Terenziani, Francesca; Ratera, Imma; Veciana, Jaume
2017-03-29
In this work, the luminescence properties of new materials based on open-shell molecular systems are studied. In particular, we prepared polymeric films and organic nanoparticles (ONPs) doped with triphenylmethyl radical molecules. ONPs exhibit a uniform size distribution, spherical morphology and high colloidal stability. The emission spectrum of low-doped ONP suspensions and low-doped films is very similar to the emission spectrum of TTM in solution, while the luminescence lifetime and the luminescence quantum yield (LQY) are highly increased. Increasing the radical doping leads to a progressive decrease of the LQY and the appearance of a new broad excimeric band at longer wavelengths, both for ONPs and films. Thus, not only the luminescence properties were improved, but also the formation of excimers from stable and persistent supramolecular radical-pairs was observed for the first time. The good stability and luminescence properties with emission in the red-NIR region (650-800 nm), together with the open-shell nature of the emitter, make these free-radical excimer-forming materials promising candidates for optoelectronic and bioimaging applications.
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Fan, Yifei; Cao, Huatang; van Mastrigt, Frank; Pei, Yutao; Picchioni, Francesco
2018-07-15
Cu 0 -mediated living radical polymerization (Cu 0 -mediated LRP) was employed in this research for the synthesis of starch-g-polyacrylamide (St-g-PAM). The use of a controlled radical grafting technique is necessary, as compared to the traditional free-radical polymerization methods, in order to obtain a well-defined structure of the final product. This is in turn essential for studying the relationship between such structure and the end-properties. Waxy potato starch-based water-soluble macroinitiator was first synthesized by esterification with 2-bromopropionyl bromide in the mixture of dimethylacetamide and lithium chloride. With the obtained macroinitiator, St-g-PAM was homogeneously synthesized by aqueous Cu 0 -mediated LRP using CuBr/hexamethylated tris(2-aminoethyl)amine (Me 6 Tren) as catalyst. The successful synthesis of the macroinitiator and St-g-PAM was proved by NMR, FT-IR, SEM, XRD and TGA analysis. The molecular weight and polydispersity of PAM chains were analyzed by gel permeation chromatography (GPC) after hydrolyzing the starch backbone. Monomer conversion was monitored by gas chromatography (GC), on the basis of which the kinetics were determined. A preliminarily rheological study was performed on aqueous solutions of the prepared materials. Copyright © 2018 Elsevier Ltd. All rights reserved.
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Nakahata, Rina; Yusa, Shin-Ichi
2018-01-05
Amphoteric random copolymers P(AMPS/APTAC50) x , where x = 41, 89, and 117, composed of sodium 2-acrylamido-2-methylpropanesulfonate (AMPS) and 3-acrylamidopropyltrimethylammonium chloride (APTAC) were prepared via reversible addition-fragmentation chain transfer radical polymerization. P(AMPS/APTAC50) x can dissolve in pure water to form small interpolymer aggregates. In aqueous solutions of NaCl, P(AMPS/APTAC50) x can dissolve in the unimer state. Amphoteric random copolymer P(AMPS/APTAC50) c with high molecular weight was prepared via conventional free-radical polymerization. Although P(AMPS/APTAC50) c cannot dissolve in pure water, it can dissolve in aqueous solutions of NaCl. In amphoteric random copolymers with high molecular weight, the possibility of continuous sequences of monomers with the same charge may increase, which may cause strong interactions between polymer chains. When fetal bovine serum (FBS) and polyelectrolytes were mixed in phosphate-buffered saline, the hydrodynamic radius and light-scattering intensity increased. There was no interaction between P(AMPS/APTAC50) x and FBS because corresponding increases could not be observed.
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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...
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Jordan, Alexander T; Hsieh, Jeffery S; Lee, Daniel T
2013-01-01
A method to separate inkjet ink from water was developed using a liquid phase, electric discharge process. The liquid phase, electric discharge process with filtration or sedimentation was shown to remove 97% of inkjet ink from solutions containing between 0.1-0.8 g/L and was consistent over a range of treatment conditions. Additionally, particle size analysis of treated allyl alcohol and treated propanol confirmed the electric discharge treatment has a polymerization mechanism, and small molecule analysis of treated methanol using gas chromatography and mass spectroscopy confirmed the mechanism was free radical initiated polymerization.
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2018-01-01
Black phosphorus (bP) has been recently investigated for next generation nanoelectronic multifunctional devices. However, the intrinsic instability of exfoliated bP (the bP nanoflakes) toward both moisture and air has so far overshadowed its practical implementation. In order to contribute to fill this gap, we report here the preparation of new hybrid polymer-based materials where bP nanoflakes (bPn) exhibit a significantly improved stability. The new materials have been prepared by different synthetic paths including: (i) the mixing of conventionally liquid-phase exfoliated bP (in dimethyl sulfoxide, DMSO) with poly(methyl methacrylate) (PMMA) solution; (ii) the direct exfoliation of bP in a polymeric solution; (iii) the in situ radical polymerization after exfoliating bP in the liquid monomer (methyl methacrylate, MMA). This last methodology concerns the preparation of stable suspensions of bPn–MMA by sonication-assisted liquid-phase exfoliation (LPE) of bP in the presence of MMA followed by radical polymerization. The hybrids characteristics have been compared in order to evaluate the bP dispersion and the effectiveness of the bPn interfacial interactions with polymer chains aimed at their long-term environmental stabilization. The passivation of the bPn is particularly effective when the hybrid material is prepared by in situ polymerization. By using this synthetic methodology, the nanoflakes, even if with a gradient of dispersion (size of aggregates), preserve their chemical structure from oxidation (as proved by both Raman and 31P-solid state NMR studies) and are particularly stable to air and UV light exposure. The feasibility of this approach, capable of efficiently exfoliating bP while protecting the bPn, has been then verified by using different vinyl monomers (styrene and N-vinylpyrrolidone), thus obtaining hybrids where the nanoflakes are embedded in polymer matrices with a variety of intriguing thermal, mechanical, and solubility characteristics.
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Xue, Wentao; Wang, Jie; Wen, Ming; Chen, Gaojian; Zhang, Weidong
2017-03-01
The successful chain-growth copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) polymerization employing Cu(0)/pentamethyldiethylenetriamine (PMDETA) and alkyl halide as catalyst is first investigated by a combination of nuclear magnetic resonance, gel-permeation chromatography, and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. In addition, the electron transfer mediated "click-radical" concurrent polymerization utilizing Cu(0)/PMDETA as catalyst is successfully employed to generate well-defined copolymers, where controlled CuAAC polymerization of clickable ester monomer is progressed in the main chain acting as the polymer backbone, the controlled radical polymerization (CRP) of acrylic monomer is carried out in the side chain. Furthermore, it is found that there is strong collaborative effect and compatibility between CRP and CuAAC polymerization to improve the controllability. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Tunable, Quantitative Fenton-RAFT Polymerization via Metered Reagent Addition.
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.
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Acrylonitrile-Butadiene Rubber (NBR) Prepared via Living/Controlled Radical Polymerization (RAFT).
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.
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Reinelt, Sebastian; Steinke, Daniel
2014-01-01
Summary In this work we report the synthesis of thermo-, oxidation- and cyclodextrin- (CD) responsive end-group-functionalized polymers, based on N,N-diethylacrylamide (DEAAm). In a classical free-radical chain transfer polymerization, using thiol-functionalized 4-alkylphenols, namely 3-(4-(1,1-dimethylethan-1-yl)phenoxy)propane-1-thiol and 3-(4-(2,4,4-trimethylpentan-2-yl)phenoxy)propane-1-thiol, poly(N,N-diethylacrylamide) (PDEAAm) with well-defined hydrophobic end-groups is obtained. These end-group-functionalized polymers show different cloud point values, depending on the degree of polymerization and the presence of randomly methylated β-cyclodextrin (RAMEB-CD). Additionally, the influence of the oxidation of the incorporated thioether linkages on the cloud point is investigated. The resulting hydrophilic sulfoxides show higher cloud point values for the lower critical solution temperature (LCST). A high degree of functionalization is supported by 1H NMR-, SEC-, FTIR- and MALDI–TOF measurements. PMID:24778720
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Xu, Tianchi; Yin, Hongnan; Li, Xiaohong; Zhang, Lifen; Cheng, Zhenping; Zhu, Xiulin
2017-07-01
A new polymerization method, termed as step transfer-addition and radical-termination, is developed for the step-growth radical polymerization of α,ω-unconjugated dienes under irradiation of visible light at room temperature (25 °C) for the first time. α,ω-Diiodoperfluoroalkane monomers (signified as A) are added onto α,ω-unconjugated dienes (signified as B) alternatively and efficiently with the generation of perfluorocarbon-containing alternating copolymers (AB) n . Based on the combined analyses of polymerization kinetics and NMR spectra ( 1 H and 19 F), the mechanism of the novel polymerization method, including the side reaction, is proposed. This novel polymerization method provides a new strategy not only for the step-growth radical polymerization of α,ω-unconjugated dienes but also for the construction of high molecular weight perfluorocarbon-containing alternating copolymers. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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NASA Astrophysics Data System (ADS)
Wisnudel, Marc; Torkelson, John
1997-03-01
Termination between radicals has been simulated by use of phosphorescence quenching interactions, showing that segmental diffusion plays a strong role in the origin of autoacceleration or the gel effect. Quenching rate constants (k_q) were measured between benzil-labeled polymer as a function of anthracene-labeled polymer in polystyrene or polymethylmethacrylate solutions. Values of kq were obtained for interactions involving end- or center-labeled chains as a function of polymer MW and concentration. A large effect of label location was observed as interactions between center-labeled chains resulted in values of kq that were more MW-dependent and smaller in magnitude than those for interactions between end-labeled chains. For interactions between end-labeled chains at concentrations between 0 and 600 g/L, data show only very weak dependencies of kq on MW and concentration dependencies similar to that of segmental mobility. In addition, comparisons of kq data for interactions in PMMA-toluene solutions with termination rate constant (k_t) data for MMA polymerizations, showing weaker concentration dependencies for both kq and kt than translational diffusion coefficients in similar solutions, also indicate that segmental diffusion is important in termination.
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Dai, Xiaojun; He, Yuan; Wei, Yinmao; Gong, Bolin
2011-11-01
A one-step procedure based on surface-initiated atom transfer radical polymerization (SI-ATRP) to hydrophilize monodisperse poly(chloromethylstyrene-co-divinylbenzene) beads has been presented in this work, using 2-hydroxyl-3-[4-(hydroxymethyl)-1H-1,2,3-triazol-1-yl]propyl 2-methylacrylate (HTMA) as a monomer. The chain length of the grafted poly(HTMA) was controlled via varying the ratio of HTMA to initiator on the surface of the beads. When using the grafted beads as a stationary phase in hydrophilic interaction chromatography (HILIC), good resolution for nucleobases/nucleosides was obtained with acetonitrile aqueous solution as an eluent; while for phenolic acids and glycosides, they could be eluted and separated in the presence of TFA. The retention time of the solutes increased with the amount of the grafted HTMA. The retention mechanisms of solutes were investigated by the effects of mobile phase composition and buffer pH on the retention of solutes. The results illustrated that the retention behaviors of the tested solutes were dominated by hydrogen bonding interaction and electrostatic interaction. From the chemical structure of the ligands, the modified beads could not only be used as a stationary phase in HILIC, but also act as a useful building block to develop new stationary phases for other chromatographic modes such as affinity media. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Wang, Kaidong; Huang, Ke; Jiang, Guoqiang
2018-03-01
Acetaminophen is one kind of pharmaceutical contaminant that has been detected in municipal water and is hard to digest. A laccase-catalyzed oxidative coupling reaction is a potential method of removing acetaminophen from water. In the present study, the kinetics of radical polymerization combined with precipitation was studied, and the dual-pH optimization strategy (the enzyme solution at pH7.4 being added to the substrate solution at pH4.2) was proposed to enhance the removal efficiency of acetaminophen. The reaction kinetics that consisted of the laccase-catalyzed oxidation, radical polymerization and precipitation were studied by UV in situ, LC-MS and DLS (dynamic light scattering) in situ. The results showed that the laccase-catalyzed oxidation is the rate-limiting step in the whole process. The higher rate of enzyme-catalyzed oxidation under a dual-pH optimization strategy led to much faster formation of the dimer, trimer and tetramer. Similarly, the formation of polymerized products that could precipitate naturally from water was faster. Under the dual-pH optimization strategy, the initial laccase activity was increased approximately 2.9-fold, and the activity remained higher for >250s, during which approximately 63.7% of the total acetaminophen was transformed into biologically inactive polymerized products, and part of these polymerized products precipitated from the water. Laccase belongs to the family of multi-copper oxidases, and the present study provides a universal method to improve the activity of multi-copper oxidases for the high-performance removal of phenol and its derivatives. Copyright © 2017 Elsevier B.V. All rights reserved.
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Cheng, Fei; Bonder, Edward M; Jäkle, Frieder
2013-11-20
Luminescent triarylborane homo and block copolymers with well-defined chain architectures were synthesized via reversible addition-fragmentation chain transfer polymerization of a vinyl-functionalized borane monomer. The Lewis acid properties of the polymers were exploited in the luminescent detection of fluoride ions. A dual-responsive fluoride sensor was developed by taking advantage of the reversible self-assembly of a PNIPAM-based amphiphilic block copolymer. Anion detection in aqueous solution was realized by introducing positively charged pyridinium moieties along the polymer chain.
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Theriot, Jordan C.; Ryan, Matthew D.; French, Tracy A.; Pearson, Ryan M.; Miyake, Garret M.
2016-01-01
A standardized technique for atom transfer radical polymerization of vinyl monomers using perylene as a visible-light photocatalyst is presented. The procedure is performed under an inert atmosphere using air- and water-exclusion techniques. The outcome of the polymerization is affected by the ratios of monomer, initiator, and catalyst used as well as the reaction concentration, solvent, and nature of the light source. Temporal control over the polymerization can be exercised by turning the visible light source off and on. Low dispersities of the resultant polymers as well as the ability to chain-extend to form block copolymers suggest control over the polymerization, while chain end-group analysis provides evidence supporting an atom-transfer radical polymerization mechanism. PMID:27166728
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Guo, Yi; Zetterlund, Per B
2011-10-18
A novel method for synthesis of ultrafine polymeric nanoparticles of diameters less than 20 nm has been developed. The method is based on miniemulsion polymerization exploiting combination of the in situ surfactant generation approach (whereby the surfactant is formed at the oil-water interface by reaction between an organic acid and a base) and ultrasonication. Conventional radical polymerization and nitroxide-mediated radical polymerization of styrene have been conducted in miniemulsion using oleic acid/potassium hydroxide, demonstrating that particles with diameters less than 20 nm can be obtained by this approach at surfactant contents much lower than traditionally required in microemulsion polymerizations. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Free radical generation by ultrasound in aqueous and nonaqueous solutions.
Riesz, P; Berdahl, D; Christman, C L
1985-01-01
The physical principles underlying the oscillatory behavior of minute gas bubbles in liquids exposed to ultrasound are reviewed. Results from mathematical analyses suggest that these oscillations sometimes become unstable leading to transient cavitation in which a bubble violently collapses during a single acoustic half-cycle producing high temperatures and pressures. The role that micronuclei, resonant bubble size, and rectified diffusion play in the initiation of transient cavitation is explained. Evidence to support these theoretical predictions is presented with particular emphasis on sonoluminescence which provides some non-chemical evidence for the formation of free radicals. Acoustic methods for conducting sonochemical investigations are discussed. In aqueous solutions transient cavitation initially generates hydrogen atoms and hydroxyl radicals which may recombine to form hydrogen and hydrogen peroxide or may react with solutes in the gas phase, at the gas-liquid boundary or in the bulk of the solution. The analogies and differences between sonochemistry and ionizing radiation chemistry are explored. The use of spin trapping and electron spin resonance to identify hydrogen atoms and hydroxyl radicals conclusively and to detect transient cavitation produced by continuous wave and by pulsed ultrasound is described in detail. The study of the chemical effects of cavitation in organic liquids is a relatively unexplored area which has recently become the subject of renewed interest. Examples of the decomposition of solvent and solute, of ultrasonically initiated free-radical polymerization and polymer degradation are presented. Spin trapping has been used to identify radicals in organic liquids, in polymer degradation and in the decomposition of organometallic compounds. PMID:3007091
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Li, Jun; Chen, Xiaoru; Chang, Ying-Chih
2005-10-11
In this work, we report a gas-phase polymerization approach to create end-grafted vinyl based polymer films on silicon oxide based substrates. The "surface-initiated vapor deposition polymerization" (SI-VDP) of vaporized vinyl monomers, via the nitroxide-mediated free radical polymerization mechanism, was developed to fabricate various homo- and block copolymer brushes from surface-bound initiators, 1-(4'-oxa-2'-phenyl-12'-trimethoxysilyldodecyloxy)-2,2,6,6-tetra-methylpiperidine ("TEMPO"). The resulting polymer thin films were characterized by the Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, ellipsometry, and contact angle goniometry, respectively, to identify the surface composition, film thickness, surface coverage, and water contact angles. Through the SI-VDP, end-grafted polymer films of polystyrene (PSt), poly(acrylic acid) (PAAc), poly(N-(2-hydroxypropyl) methacrylamide) (PHPMA), and poly(N-isopropylacrylamide) (PNIPAAm) with 10-200 nm thicknesses were fabricated. Furthermore, the block copolymer films of PAAc (1st block)-b-PSt (2nd block), PSt (1st block)-b-PAAc (2nd block), and a triblock copolymer film of PAAc (1st)-b-PSt (2nd)-b-PHPMA (3rd), were also fabricated, suggesting the "renewability" of the TEMPO-initiated polymerization in the SI-VDP scheme. It is also noticed that the SI-VDP is more efficient than the conventional solution phase polymerization in producing functional polymer brushes such as PNIPAAm, PAAc, or PAAc-b-PSt end-grafted films. In summary, our studies have shown clear advantages of the SI-VDP setup for the nitroxide-mediated polymerization scheme in controlling synthesis of end-grafted homo- and copolymer thin films.
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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...
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Kaastrup, Kaja; Sikes, Hadley D
2012-10-21
Although polymerization-based amplification (PBA) has demonstrated promise as an inexpensive technique for use in molecular diagnostics, oxygen inhibition of radical photopolymerization has hindered its implementation in point-of-care devices. The addition of 0.3-0.7 μM eosin to an aqueous acrylate monomer solution containing a tertiary amine allows an interfacial polymerization reaction to proceed in air only near regions of a test surface where additional eosin initiators coupled to proteins have been localized as a function of molecular recognition events. The dose of light required for the reaction is inversely related to eosin concentration. This system achieves sensitivities comparable to those reported for inert gas-purged systems and requires significantly shorter reaction times. We provide several comparisons of this system with other implementations of polymerization-based amplification.
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Karanikolopoulos, Nikos; Zamurovic, Miljana; Pitsikalis, Marinos; Hadjichristidis, Nikos
2010-02-08
We synthesized a series of well-defined poly(dl-lactide)-b-poly(N,N-dimethylamino-2-ethyl methacrylate) (PDLLA-b-PDMAEMA) amphiphilic diblock copolymers by employing a three-step procedure: (a) ring-opening polymerization (ROP) of dl-lactide using n-decanol and stannous octoate, Sn(Oct)(2), as the initiating system, (b) reaction of the PDLLA hydroxyl end groups with bromoisobutyryl bromide, and (c) atom transfer radical polymerization, ATRP, of DMAEMA with the newly created bromoisobutyryl initiating site. The aggregation behavior of the prepared block copolymers was investigated by dynamic light scattering and zeta potential measurements at 25 degrees C in aqueous solutions of different pH values. The hydrophobic drug dipyridamole was efficiently incorporated into the copolymer aggregates in aqueous solutions of pH 7.40. High partition coefficient values were determined by fluorescence spectroscopy.
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Kocaarslan, Azra; Tabanli, Sevcan; Eryurek, Gonul; Yagci, Yusuf
2017-11-13
A method is presented for the initiation of free-radical and free-radical-promoted cationic photopolymerizations by in-source lighting in the near-infrared (NIR) region using upconverting glass (UCG). This approach utilizes laser irradiation of UCG at 975 nm in the presence of fluorescein (FL) and pentamethyldiethylene triamine (PMDETA). FL excited by light emitted from the UCG undergoes electron-transfer reactions with PMDETA to form free radicals capable of initiating polymerization of methyl methacrylate. To execute the corresponding free-radical-promoted cationic polymerization of cyclohexene oxide, isobutyl vinyl ether, and N-vinyl carbazole, it was necessary to use FL, dimethyl aniline (DMA), and diphenyliodonium hexafluorophosphate as sensitizer, coinitiator, and oxidant, respectively. Iodonium ions promptly oxidize DMA radicals formed to the corresponding cations. Thus, cationic polymerization with efficiency comparable to the conventional irradiation source was achieved. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Stimuli Responsive Morphological Changes of Pnipa Polymer Brushes Synthesized on Silicon Substrate
NASA Astrophysics Data System (ADS)
Huda, Muhammad Nurul; Kabir, A. N. M. Hamidul
2013-08-01
High-density polymer brushes were grown from the silicon surface by atom transfer radical polymerization of Poly(N-isopropylacrylamide) (PNIPA) at different polymerization conditions. PNIPA brushes were prepared using Copper (I) Chloride/tris(2-(dimetylamino)ethyl)amine (Me6TREN) as a catalytic system in DMSO at 20°C. Free polymer formed during the brush formation was characterized by gel permeation chromatography. The grafting densities up to 0.52 chains/nm2 were obtained. The layer thickness of polymer brush increases with the increase of conversion of the monomer conversion as well as polymerization time. Atomic force microscopy and air bubble contact angle under pH solution were employed to study the surface morphology, reversible conformational changes of and stimulus-response behavior. PNIPA brushes exhibited a different nanomorphology after treatment with different pH solution. It also revealed a unique reversible wetting behavior with pH. The reversible properties of the PNIPA brushes can be used to regulate the adsorption of the sulfonated PS nanoparticles.
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NASA Technical Reports Server (NTRS)
Avni, R.; Carmi, U.; Inspektor, A.; Rosenthal, I.
1984-01-01
The ion-molecule and the radical-molecule mechanisms are responsible for the dissociation of hydrocarbons, and chlorosilane monomers and the formation of polymerized species, respectively, in the plasma state of a RF discharge. In the plasma, of a mixture of monomer with Ar, the rate determining step for both dissociation and polymerization is governed by an ion-molecular type interaction. Additions of H2 or NH3 to the monomer Ar(+) mixture transforms the rate determining step from an ion-molecular interaction to a radical-molecule type interaction for both monomer dissociation and polymerization processes.
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NASA Technical Reports Server (NTRS)
Avni, R.; Carmi, U.; Inspektor, A.; Rosenthal, I.
1984-01-01
The ion-molecule and the radical-molecule mechanisms are responsible for the dissociation of hydrocarbons, and chlorosilane monomers and the formation of polymerized species, respectively, in the plasma state of a RF discharge. In the plasma, of a mixture of monomer with Ar, the rate determining step for both dissociation and polymerization is governed by an ion-molecular type interaction. Additions of H2 or NH3 to the monomer Ar(+) mixture transforms the rate determining step from an ion-molecular interaction to a radical-molecule type interaction for both monomer dissociation and polymerization processes.
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Single chain technology: Toward the controlled synthesis of polymer nanostructures
NASA Astrophysics Data System (ADS)
Lyon, Christopher
A technique for fabricating advanced polymer nanostructures enjoying recent popularity is the collapse or folding of single polymer chains in highly dilute solution mediated by intramolecular cross-linking. We term the resultant structures single-chain nanoparticles (SCNP). This technique has proven particularly valuable in the synthesis of nanomaterials on the order of 5 -- 20 nm. Many different types of covalent and non-covalent chemistries have been used to this end. This dissertation investigates the use of so-called single-chain technology to synthesize nanoparticles using modular techniques that allow for easy incorporation of functionality or special structural or characteristic features. Specifically, the synthesis of linear polymers functionalized with pendant monomer units and the subsequent intramolecular polymerization of these monomer units is discussed. In chapter 2, the synthesis of SCNP using alternating radical polymerization is described. Polymers functionalized with pendant styrene and stilbene groups are synthesized via a modular post-polymerization Wittig reaction. These polymers were exposed to radical initiators in the presence (and absence) of maleic anhydride and other electron deficient monomers in order to form intramolecular cross-links. Chapter 3 discusses templated acyclic diene metathesis (ADMET) polymerization using single-chain technology, starting with the controlled ring-opening polymerization of a glycidyl ether functionalized with an ADMET monomer. This polymer was then exposed to Grubbs' catalyst to polymerize the ADMET monomer units. The ADMET polymer was hydrolytically cleaved from the template and separated. Upon characterization, it was found that the daughter ADMET polymer had a similar degree of polymerization, but did not retain the low dispersity of the template. Chapter 4 details the synthesis of aldehyde- and diol-functionalized polymers toward the synthesis of SCNP containing dynamic, acid-degradable acetal cross-links. SCNP fabrication with these materials is beyond the scope of this dissertation.
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Photoinitiated polymerization of 1-vinylimidazole
DOE Office of Scientific and Technical Information (OSTI.GOV)
Joshi, M.G.; Rodriguez, F.
1984-04-01
The photoinitiated polymerization of 1-vinylimidazole (VI) does not follow the classical kinetic scheme for free radical polymerization. Kinetic results for VI suggest a degradative addition reaction between the macroradical and the monomer to produce a relatively stable, unreactive radical, which does not reinitiate polymerization, is low, 1.5 kcal/mol. Among the 3 photoinitiators used, the highest quantum efficiency was demonstrated by 2,2'-diethoxyacetophenone followed by bezoin methyl ether and benzoin isopropyl ether. Under the experimental conditions used, the polymerization of VI does not proceed to complete conversion, and the phenomenon of dead-end polymerization is observed.
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Roles of Segmental and Oligomeric Diffusion on the Gel Effect in Free Radical Polymerization
NASA Astrophysics Data System (ADS)
Wisnudel, M. B.; Torkelson, J. M.
1996-03-01
Termination between radicals has been simulated by phosphorescence quenching, showing strong roles for segmental and oligomeric radical self-diffusion in the origin of the gel effect. Quenching rate constants (k_q) were measured between benzil-terminated polymer as a function of anthracene-terminated polymer in polymer solutions. In dilute solution, interactions between 10k or 73k MW benzil-terminated polystyrene (PS- B) and anthracence-terminated polystyrene (PS-A) of varying MW, the MW effect is weaker than the Smoluchowski eq. prediction (kq MW^- 0.5). At higher concentration, interactions of PS-B and PS-A of like MW show only weak dependence of kq on MW and a concentration dependence similar to that of segmental mobility, indicating that segmental diffusion is important in termination. Finally, with interactions between 73k MW PS-B and PS-A of varying MW at 35 wt% PS, kq decreases by a factor of 10 in going from MW's of 100 to 1000 g/mol; beyond 1000 g/mol, kq is MW independent. Such effects cannot be explained by polymer-radical self-diffusion. However, they support the notion that the gel effect onset is associated with the concentration dependence of oligomeric radical self-diffusion and polymer radical chain-end segmental mobility.
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Hydrophilic crosslinked-polymeric surface capable of effective suppression of protein adsorption
NASA Astrophysics Data System (ADS)
Kamon, Yuri; Inoue, Naoko; Mihara, Erika; Kitayama, Yukiya; Ooya, Tooru; Takeuchi, Toshifumi
2016-08-01
We investigated the nonspecific adsorption of proteins towards three hydrophilic crosslinked-polymeric thin layers prepared by surface-initiated atom transfer radical polymerization using N,N‧-methylenebisacrylamide, 2-(methacryloyloxy)ethyl-[N-(2-methacryloyloxy)ethyl]phosphorylcholine (MMPC), or 6,6‧-diacryloyl-trehalose crosslinkers. Protein binding experiments were performed by surface plasmon resonance with six proteins of different pI values including α-lactalbumin, bovine serum albumin (BSA), myoglobin, ribonuclease A, cytochrome C, and lysozyme in buffer solution at pH 7.4. All of the obtained crosslinked-polymeric thin layers showed low nonspecific adsorption of negatively charged proteins at pH 7.4 such as α-lactalbumin, BSA, and myoglobin. Nonspecific adsorption of positively charged proteins including ribonuclease A, cytochrome C, and lysozyme was the lowest for poly(MMPC). These results suggest poly(MMPC) can effectively reduce nonspecific adsorption of a wide range of proteins that are negatively or positively charged at pH 7.4. MMPC is a promising crosslinker for a wide range of polymeric materials requiring low nonspecific protein binding.
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Electrochemical models for the radical annihilation reactions in organic light-emitting diodes
NASA Astrophysics Data System (ADS)
Armstrong, Neal R.; Anderson, Jeffrey D.; Lee, Paul A.; McDonald, Erin; Wightman, R. M.; Hall, Hank K.; Hopkins, Tracy; Padias, Anne; Thayumanavan, Sankaran; Barlow, Stephen; Marder, Seth R.
1998-12-01
Bilayer organic light emitting diodes (OLEDs), based upon vacuum deposited molecules, or single layer OLEDs, based upon spin-cast polymeric materials, doped with these same molecules, produce light from emissive states of the lumophores which are created through annihilation reactions of radical species, which can be modeled through solution electrochemistry. Difference seen in solution reduction and oxidation potentials of molecular components of OLEDs are a lower limit estimate to the differences in energy of these same radical species in the condensed phase environmental. The light emitted from an aluminum quinolate (Alq3)/triarylamine (TPD)-based OLED, or an Alq3/PVK single layers OLED, can be reproduce from solution cross reactions of Alq3/TPD+. The efficiency of this process increases as the oxidation potential of the TPD increases, due to added substituents. Radical cations and anions of solubilized version of quinacridone dopants (DIQA) which have been used to enhance efficiencies in these OLEDs, are shown to be electrochemically more stable than Alq3 and Alq3, and DIQA radical annihilation reactions produce the same emissive state as in the quinacridone-doped OLEDs. Electrochemical studies demonstrate the ways in which other dopants might enhance the efficiency and shift the color output of OLEDs, across the entire visible and near-IR spectrum. Chemical degradation pathways of these same molecular components, which they may undergo during OLED operation, are also revealed by these electrochemical studies.
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Photoinduced Reversible Morphological Transformation of Azobenzene-Containing Pseudo-2D Polymers.
Li, Zili; Tang, Miao; Jiang, Chen; Bai, Ruke; Bai, Wei
2018-05-02
2D polymer sheets containing azobenzene are successfully prepared by a facile strategy of "2D self-assembly polymerization (2DSP)" via free radical polymerization in solution. A bola amphiphile containing azobenzene as a novel monomer is designed and synthesized. The results indicate that single-layer covalent pseudo-2D polymers on a micrometer scale are obtained after polymerization with vinyl monomers. Moreover, the 2D polymer sheets are highly sensitive to UV light due to incorporation of azobenzene groups into the polymer. Upon alternative irradiation with UV and visible light, the morphological transformation between sheets and rolled-up nanotubes can be achieved based on the reversible trans-to-cis photoisomerization of azobenzene units in the 2D polymer sheets. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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NASA Astrophysics Data System (ADS)
Zhang, Wenyang; Yuan, Zhiwei; Huang, Lulu; Kang, Jie; Jiang, Ruowei; Zhong, Hongying
2016-02-01
Polyacrylamide gel electrophoresis (PAGE) coupled with mass spectrometry has been well established for separating, identifying and quantifying protein mixtures from cell lines, tissues or other biological samples. The copolymerization process of acrylamide and bis-acrylamide is the key to mastering this powerful technique. In general, this is a vinyl addition reaction initiated by free radical-generating reagents such as ammonium persulfate (APS) and tetramethylethylenediamine (TEMED) under basic pH and degassing experimental condition. We report herein a photocatalytic polymerization approach that is based on photo-generated hydroxyl radicals with nanoparticles of titanium dioxide. It was shown that the polymerization process is greatly accelerated in acidic condition when ultraviolet light shots on the gel solution containing TiO2 nanoparticles without degassing. This feature makes it very useful in preparing Triton X-100 acid urea (TAU) gel that has been developed for separating basic proteins such as histones and variants in acidic experimental condition. Additionally, the presence of titanium dioxide in the gel not only improves mechanistic property of gels but also changes the migration pattern of different proteins that have different affinities to titanium dioxide.
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Zhang, Wenyang; Yuan, Zhiwei; Huang, Lulu; Kang, Jie; Jiang, Ruowei; Zhong, Hongying
2016-02-11
Polyacrylamide gel electrophoresis (PAGE) coupled with mass spectrometry has been well established for separating, identifying and quantifying protein mixtures from cell lines, tissues or other biological samples. The copolymerization process of acrylamide and bis-acrylamide is the key to mastering this powerful technique. In general, this is a vinyl addition reaction initiated by free radical-generating reagents such as ammonium persulfate (APS) and tetramethylethylenediamine (TEMED) under basic pH and degassing experimental condition. We report herein a photocatalytic polymerization approach that is based on photo-generated hydroxyl radicals with nanoparticles of titanium dioxide. It was shown that the polymerization process is greatly accelerated in acidic condition when ultraviolet light shots on the gel solution containing TiO2 nanoparticles without degassing. This feature makes it very useful in preparing Triton X-100 acid urea (TAU) gel that has been developed for separating basic proteins such as histones and variants in acidic experimental condition. Additionally, the presence of titanium dioxide in the gel not only improves mechanistic property of gels but also changes the migration pattern of different proteins that have different affinities to titanium dioxide.
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Zhang, Wenyang; Yuan, Zhiwei; Huang, Lulu; Kang, Jie; Jiang, Ruowei; Zhong, Hongying
2016-01-01
Polyacrylamide gel electrophoresis (PAGE) coupled with mass spectrometry has been well established for separating, identifying and quantifying protein mixtures from cell lines, tissues or other biological samples. The copolymerization process of acrylamide and bis-acrylamide is the key to mastering this powerful technique. In general, this is a vinyl addition reaction initiated by free radical-generating reagents such as ammonium persulfate (APS) and tetramethylethylenediamine (TEMED) under basic pH and degassing experimental condition. We report herein a photocatalytic polymerization approach that is based on photo-generated hydroxyl radicals with nanoparticles of titanium dioxide. It was shown that the polymerization process is greatly accelerated in acidic condition when ultraviolet light shots on the gel solution containing TiO2 nanoparticles without degassing. This feature makes it very useful in preparing Triton X-100 acid urea (TAU) gel that has been developed for separating basic proteins such as histones and variants in acidic experimental condition. Additionally, the presence of titanium dioxide in the gel not only improves mechanistic property of gels but also changes the migration pattern of different proteins that have different affinities to titanium dioxide. PMID:26865351
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Yan, Kun; Gao, Xiang; Luo, Yingwu
2015-07-01
A highly living polymer with over 100 kg mol(-1) molecular weight is very difficult to achieve by controlled radical polymerization since the unavoidable side reactions of irreversible radical termination and radical chain transfer to monomer reaction become significant. It is reported that over 500 kg mol(-1) polystyrene with high livingness and low dispersity could be synthesized by a facile two-stage reversible addition-fragmentation transfer emulsion polymerization. The monomer conversion reaches 90% within 10 h. High livingness of the product is ascribed to the extremely low initiator concentration and the chain transfer constant for monomer unexpectedly much lower than the well-accepted values in the conventional radical polymerization. The two-stage monomer feeding policy much decreases the dispersity of the product. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Avens, Heather J.; Bowman, Christopher N.
2009-01-01
A visible light photoinitiator, eosin, in combination with a tertiary amine coinitiator is found to initiate polymerization despite the presence of at least 1000-fold excess dissolved oxygen which functions as an inhibitor of radical polymerizations. Additionally, 0.4 µM eosin is able to overcome 100-fold excess (40 µM) 2,2,6,6-Tetramethyl-1-piperidinyloxy (TEMPO) inhibitor, initiating polymerization after only a 2 minute inhibition period. In contrast, 40 µM Irgacure-2959, a standard cleavage-type initiator, is unable to overcome even an equivalent amount of inhibitor (40 µM TEMPO). Through additional comparisons of these two initiation systems, a reaction mechanism is developed which is consistent with the kinetic data and provides an explanation for eosin’s relative insensitivity to oxygen, TEMPO and other inhibitors. A cyclic mechanism is proposed in which semi-reduced eosin radicals react by disproportionation with radical inhibitors and radical intermediates in the inhibition process to regenerate eosin and effectively consume inhibitor. In behavior similar to that of eosin, rose bengal, fluorescein, and riboflavin are also found to initiate polymerization despite the presence of excess TEMPO, indicating that cyclic regeneration likely enhances the photoinitiation kinetics of many dye photosensitizers. Selection of such dye initiation systems constitutes a valuable strategy for alleviating inhibitory effects in radical polymerizations. PMID:20098667
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Mya, Khine Y; Lin, Esther M J; Gudipati, Chakravarthy S; Gose, Halima B A S; He, Chaobin
2010-07-22
Poly(hexafluorobutyl methacrylate) (PHFBMA) homopolymer was synthesized by reversible addition-fragmentation chain transfer (RAFT)-mediated living radical polymerization in the presence of cyano-2-propyl dithiobenzoate (CPDB) RAFT agent. A block copolymer of PHFBMA-poly(propylene glycol acrylate) (PHFBMA-b-PPGA) with dangling poly(propylene glycol) (PPG) side chains was then synthesized by using CPDB-terminated PHFBMA as a macro-RAFT agent. The amphiphilic properties and self-assembly of PHFBMA-b-PPGA block copolymer in aqueous solution were investigated by dynamic and static light scattering (DLS and SLS) studies, in combination with fluorescence spectroscopy and transmission electron microscopy (TEM). Although PPG shows moderately hydrophilic character, the formation of nanosize polymeric micelles was confirmed by fluorescence and TEM studies. The low value of the critical aggregation concentration exhibited that the tendency for the formation of copolymer aggregates in aqueous solution was very high due to the strong hydrophobicity of the PHFBMA(145)-b-PPGA(33) block copolymer. The combination of DLS and SLS measurements revealed the existence of micellar aggregates in aqueous solution with an association number of approximately 40 +/- 7 for block copolymer micelles. It was also found in TEM observation that there are 40-50 micelles accumulated into one aggregate and these micelles are loosely packed inside the aggregate.
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Feng, Juanjuan; Sun, Min; Xu, Lili; Wang, Shuai; Liu, Xia; Jiang, Shengxiang
2012-12-14
Because of the occurrence of ion exchange between high-ionic-strength solution and anions of polymeric ionic liquids (PILs), PILs based solid-phase microextraction (SPME) fibers were rarely used in direct immersion mode to high-salt-added samples. In this work, a novel double-confined PIL sorbent was prepared by co-polymerization of cation and anion of 1-vinyl-3-octylimidzaolium p-styrenesulfonate (VOIm(+)SS(-)). The poly(VOIm(+)-SS(-)) was chemically bonded onto functionalized stainless steel wire via surface radical chain-transfer reaction. Stability of poly(VOIm(+)-SS(-)) in high-ionic-strength solution was investigated and compared with that of poly(1-vinyl-3-octylimidzaolium benzenesulfonate) (poly(VOIm(+)BS(-))) by elemental analysis of sulfur element, and results turned out that the poly(VOIm(+)-SS(-)) was more stable. Coupled to gas chromatography (GC), the poly(VOIm(+)-SS(-)) fiber was used to extract three sorts of compounds including anilines, phenols and phthalate esters in aqueous solution. The as-established method showed good linearity, low detection limits, and acceptable repeatability. The direct immersion SPME-GC method was applied to determine the model phthalate esters in bottled mineral water. The determination results were satisfactory. Copyright © 2012 Elsevier B.V. All rights reserved.
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NASA Astrophysics Data System (ADS)
Nezhad, Javad Razavi; Jafari, Arezou; Abdollahi, Mahdi
2018-01-01
Enhanced heavy oil recovery methods are widely utilized to increase oil recovery. For this purpose, polymer and surfactant flooding have been used extensively. Recently, polymeric surfactant flooding has become an attractive alternative to sole polymer flooding due to their capability of providing an increase in solution viscosity and a decrease in interfacial tension, which are both beneficial for efficiency of the process. Applying nanoparticles as an additive to polymer solutions is a method to improve viscosity and alter rock wettability. Therefore, in this research, multi-walled carbon nanotube (MWCNT) was mixed with a polymeric surfactant of polyacrylamide-graft-lignin copolymer (PAM-g-L) synthesized via radical grafting reaction. Moreover, several solutions with different concentrations of nanoparticles with PAM-g-L were prepared. The solutions were injected into a micromodel to evaluate the PAM-g-L flooding efficiency in presence of the multi-walled carbon nanotubes. The results of micromodel flooding showed that increasing MWCNT concentration results in lower sweep efficiencies; and consequently, oil production will decrease. Therefore, MWCNT along with PAM-g-L has an unacceptable performance in enhanced heavy oil recovery. But data of wettability tests revealed that MWCNT can change the wettability from oil-wet to water-wet. In addition, the combination of the PAM-g-L and MWCNT in a solution will cause more water-wet condition.
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NASA Astrophysics Data System (ADS)
Baccaro, Stefania; Casieri, Cinzia; Cemmi, Alessia; Chiarini, Marco; D'Aiuto, Virginia; Tortora, Mariagrazia
2017-12-01
The present work is focused on the γ-radiation induced polymerization of ethyl methacrylate (EMA) and methyl acrylate (MA) monomers mixture to obtain a co-polymer with specific features. The effect of the irradiation parameters (radiation absorbed dose, dose rate) and of the environmental atmosphere on the features of the final products was investigated. Attenuated Total Reflectance - Fourier Transform Infrared Spectroscopy (ATR-FTIR) and Nuclear Magnetic Resonance high-resolution analyses of hydrogen and carbon nuclei (1H and 13C NMR) were applied to follow the γ-induced modifications by monitoring the co-polymerization process and allowed the irradiation parameters optimization. Diffusion-Ordered NMR (DOSY-NMR) data were used to evaluate the co-polymers polydispersity and polymerization degree. Since the last parameter is strongly influenced by the γ radiation and environmental conditions, a comparison among samples prepared and irradiated in air and under nitrogen atmosphere was carried out. In presence of oxygen, higher radiation was required to obtain a full solid co-polymer since a partial amount of energy released to the samples was involved in competitive processes, i.e. oxygen-containing free radicals formation and primary radicals recombination. Irrespectively to the environmental atmosphere, more homogeneous samples in term of polymerization degree dispersion was achieved at lower dose rates. At radiation absorbed doses higher than those needed for the formation of the co-polymer, while in case of samples irradiated in air heavy depolymerization was verified, a sensible increase of the samples stability was attained if the irradiation was performed under nitrogen atmosphere.
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Anodic Cyclization Reactions and the Mechanistic Strategies That Enable Optimization.
Feng, Ruozhu; Smith, Jake A; Moeller, Kevin D
2017-09-19
Oxidation reactions are powerful tools for synthesis because they allow us to reverse the polarity of electron-rich functional groups, generate highly reactive intermediates, and increase the functionality of molecules. For this reason, oxidation reactions have been and continue to be the subject of intense study. Central to these efforts is the development of mechanism-based strategies that allow us to think about the reactive intermediates that are frequently central to the success of the reactions and the mechanistic pathways that those intermediates trigger. For example, consider oxidative cyclization reactions that are triggered by the removal of an electron from an electron-rich olefin and lead to cyclic products that are functionalized for further elaboration. For these reactions to be successful, the radical cation intermediate must first be generated using conditions that limit its polymerization and then channeled down a productive desired pathway. Following the cyclization, a second oxidation step is necessary for product formation, after which the resulting cation must be quenched in a controlled fashion to avoid undesired elimination reactions. Problems can arise at any one or all of these steps, a fact that frequently complicates reaction optimization and can discourage the development of new transformations. Fortunately, anodic electrochemistry offers an outstanding opportunity to systematically probe the mechanism of oxidative cyclization reactions. The use of electrochemical methods allows for the generation of radical cations under neutral conditions in an environment that helps prevent polymerization of the intermediate. Once the intermediates have been generated, a series of "telltale indicators" can be used to diagnose which step in an oxidative cyclization is problematic for less successful transformation. A set of potential solutions to address each type of problem encountered has been developed. For example, problems with the initial cyclization reaction leading to either polymerization of the radical cation, elimination of a proton from or solvent trapping of that intermediate, or solvent trapping of the radical cation can be identified in the proton NMR spectrum of the crude reaction material. Such an NMR spectrum shows retention of the trapping group. The problems can be addressed by tuning the radical cation, altering the trapping group, or channeling the reactive intermediate down a radical pathway. Specific examples each are shown in this Account. Problems with the second oxidation step can be identified by poor current efficiency or general decomposition in spite of cyclic voltammetry evidence for a rapid cyclization. Solutions involve improving the oxidation conditions for the radical after cyclization by either the addition of a properly placed electron-donating group in the substrate or an increase in the concentration of electrolyte in the reaction (a change that stabilizes the cation generated from the second oxidation step). Problems with the final cation typically lead to overoxidation. Solutions to this problem require an approach that either slows down elimination side reactions or changes the reaction conditions so that the cation can be quickly trapped in an irreversible fashion. Again, this Account highlights these strategies along with the specific experimental protocols utilized.
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Ma, Yue; Pan, Guoqing; Zhang, Ying; Guo, Xianzhi; Zhang, Huiqi
2013-05-01
Bisphenol A (BPA) and propranolol-imprinted polymers have been prepared via both reversible addition-fragmentation chain transfer "bulk" polymerization (RAFTBP) and traditional radical "bulk" polymerization (TRBP) under similar reaction conditions, and their equilibrium binding properties were compared in detail for the first time. The chemical compositions, specific surface areas, equilibrium bindings, and selectivity of the obtained molecularly imprinted polymers (MIPs) were systematically characterized. The experimental results showed that the MIPs with molecular imprinting effects and quite fast binding kinetics could be readily prepared via RAFTBP, but they did not show improved template binding properties in comparison with those prepared via TRBP, which is in sharp contrast to many previous reports. This could be attributed to the heavily interrupted equilibrium between the dormant species and active radicals in the RAFT mechanism because of the occurrence of fast gelation during RAFTBP. The findings presented here strongly demonstrates that the application of controlled radical polymerizations (CRPs) in molecular imprinting does not always benefit the binding properties of the resultant MIPs, which is of significant importance for the rational use of CRPs in generating MIPs with improved properties. Copyright © 2013 John Wiley & Sons, Ltd.
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NASA Astrophysics Data System (ADS)
Sawada, Shin-ichi; Suzuki, Akihiro; Terai, Takayuki; Maekawa, Yasunari
2010-04-01
We prepared proton exchange membranes (PEMs) by 2,2,6,6-tetramethylpiperidinyl-1-oxy (TEMPO)-mediated living-radical graft polymerization (LRGP) of styrene into fluoropolymer films and subsequent sulfonation. Poly(vinylidene fluoride) (PVDF) and poly(ethylene- co-tetrafluoroethylene) (ETFE) films were first irradiated and then treated with TEMPO solutions in various solvents. TEMPO addition was confirmed by the test of styrene grafting into TEMPO-treated films at 60 °C, at which the LRGP never proceeds. This test enabled us to differentiate the LRGP from the conventional graft polymerization. In order to gain a deep insight about TEMPO-addition reaction, the TEMPO-penetration behavior into the base polymer films was examined by a permeation experiment and computer simulation. Xylene and dioxane were appropriate solvents for the complete introduction of TEMPO into PVDF and ETFE films, respectively. Then, the LRGP of styrene was performed based on the fully TEMPO-capped films at 125 °C with various solvents. By using an alcoholic solvent, the degree of grafting was enhanced and it reached a maximum of 38%. This grafted film was sulfonated to prepare a PEM showing an ion exchange capacity of 2.2 meq/g and proton conductivity of 1.6×10 -1 S/cm.
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Zhou, Tao; Xia, Fafa; Deng, Yue; Zhao, Youcai
2018-05-01
Waste textiles (WTs) are the inevitable outcome of human activity and should be separated and recycled in view of sustainable development. In this work, WT was modified through grafting with acrylic acid (AA) via radical polymerization process using ceric ammonium nitrate (CAN) as an initiator and microwave and/or UV irradiation as energy supply. The acrylic acid-grafted waste textiles (WT-g-AA) thus obtained was then used as an adsorbent to remove Pb(II) from Pb(II)-containing wastewater. The effects of pH, initial concentrations of Pb(II) and adsorbent dose were investigated, and around 95% Pb(II) can be removed from the aqueous solution containing 10mg/L at pH6.0-8.0. The experimental adsorption isotherm data was fitted to the Langmuir model with maximum adsorption capacity of 35.7mg Pb/g WT-g-AA. The Pb-absorbed WT-g-AA was stripped using dilute nitric acid solution and the adsorption capacity of Pb-free material decreased from 95.4% (cycle 1) to 91.1% (cycle 3). It was considered that the WT-g-AA adsorption for Pb(II) may be realized through the ion-exchange mechanism between COOH and Pb(II). The promising results manifested that WT-g-AA powder was an efficient, eco-friendly and reusable adsorbent for the removal of Pb(II) from wastewater. Copyright © 2017. Published by Elsevier B.V.
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Lin, Xiaojie; Ishihara, Kazuhiko
2014-01-01
Water-soluble polymers with equal positive and negative charges in the same monomer unit, such as the phosphorylcholine group and other zwitterionic groups, exhibit promising potential in gene delivery with appreciable transfection efficiency, compared with the traditional poly(ethylene glycol)-based polycation-gene complexes. These zwitterionic polymers with various architectural structures and properties have been synthesized by various polymerization methods, such as conventional radical polymerization, atom-transfer radical-polymerization, reversible addition-fragmentation chain-transfer polymerization, and nitroxide-mediated radical polymerization. These techniques have been used to efficiently facilitate gene therapy by fabrication of non-viral vectors with high cytocompatibility, large gene-carrying capacity, effective cell-membrane permeability, and in vivo gene-loading/releasing functionality. Zwitterionic polymer-based gene delivery vectors systems can be categorized into soluble-polymer/gene mixing, molecular self-assembly, and polymer-gene conjugation systems. This review describes the preparation and characterization of various zwitterionic polymer-based gene delivery vectors, specifically water-soluble phospholipid polymers for carrying gene derivatives.
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Synthesis of nanostructured materials in inverse miniemulsions and their applications.
Cao, Zhihai; Ziener, Ulrich
2013-11-07
Polymeric nanogels, inorganic nanoparticles, and organic-inorganic hybrid nanoparticles can be prepared via the inverse miniemulsion technique. Hydrophilic functional cargos, such as proteins, DNA, and macromolecular fluoresceins, may be conveniently encapsulated in these nanostructured materials. In this review, the progress of inverse miniemulsions since 2000 is summarized on the basis of the types of reactions carried out in inverse miniemulsions, including conventional free radical polymerization, controlled/living radical polymerization, polycondensation, polyaddition, anionic polymerization, catalytic oxidation reaction, sol-gel process, and precipitation reaction of inorganic precursors. In addition, the applications of the nanostructured materials synthesized in inverse miniemulsions are also reviewed.
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Method for molding ceramic powders
Janney, Mark A.
1990-01-01
A method for molding ceramic powders comprises forming a slurry mixture including ceramic powder, a dispersant for the metal-containing powder, and a monomer solution. The monomer solution includes at least one multifunctional monomer, a free-radical initiator, and an organic solvent. The slurry mixture is transferred to a mold, and the mold containing the slurry mixture is heated to polymerize and crosslink the monomer and form a firm polymer-solvent gel matrix. The solid product may be removed from the mold and heated to first remove the solvent and subsequently remove the polymer, whereafter the product may be sintered.
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Method for molding ceramic powders
Janney, M.A.
1990-01-16
A method for molding ceramic powders comprises forming a slurry mixture including ceramic powder, a dispersant for the metal-containing powder, and a monomer solution. The monomer solution includes at least one multifunctional monomer, a free-radical initiator, and an organic solvent. The slurry mixture is transferred to a mold, and the mold containing the slurry mixture is heated to polymerize and crosslink the monomer and form a firm polymer-solvent gel matrix. The solid product may be removed from the mold and heated to first remove the solvent and subsequently remove the polymer, where after the product may be sintered.
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Evolution of material properties during free radical photopolymerization
NASA Astrophysics Data System (ADS)
Wu, Jiangtao; Zhao, Zeang; Hamel, Craig M.; Mu, Xiaoming; Kuang, Xiao; Guo, Zaoyang; Qi, H. Jerry
2018-03-01
Photopolymerization is a widely used polymerization method in many engineering applications such as coating, dental restoration, and 3D printing. It is a complex chemical and physical process, through which a liquid monomer solution is rapidly converted to a solid polymer. In the most common free-radical photopolymerization process, the photoinitiator in the solution is exposed to light and decomposes into active radicals, which attach to monomers to start the polymerization reaction. The activated monomers then attack Cdbnd C double bonds of unsaturated monomers, which leads to the growth of polymer chains. With increases in the polymer chain length and the average molecular weight, polymer chains start to connect and form a network structure, and the liquid polymer solution becomes a dense solid. During this process, the material properties of the cured polymer change dramatically. In this paper, experiments and theoretical modeling are used to investigate the free-radical photopolymerization reaction kinetics, material property evolution and mechanics during the photopolymerization process. The model employs the first order chemical reaction rate equations to calculate the variation of the species concentrations. The degree of monomer conversion is used as an internal variable that dictates the mechanical properties of the cured polymer at different curing states, including volume shrinkage, glass transition temperature, and nonlinear viscoelastic properties. To capture the nonlinear behavior of the cured polymer under low temperature and finite deformation, a multibranch nonlinear viscoelastic model is developed. A phase evolution model is used to describe the mechanics of the coupling between the crosslink network evolution and mechanical loading during the curing process. The comparison of the model and the experimental results indicates that the model can capture property changes during curing. The model is further applied to investigate the internal stress of a thick sample caused by volume shrinkage during photopolymerization. Changes in the conversion degree gradient and the internal stress during photopolymerization are determined using FEM simulation. The model can be extended to many photocuring processes, such as photopolymerization 3D printing, surface coating and automotive part curing processes.
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Polar-Nonpolar Radical Copolymerization under Li+ Catalysis
2008-09-21
bonds or aromatic rings. Thus, we propose that a transfer of a methyl radical from CB11Me12C to IB triggers a radical polymerization chain that yields ...b-PIB and the resulting CB11Me11 byproduct concurrently triggers a cationic polymerization chain that yields l-PIB terminated with a carborate anion...tetrahydrofuran and passed through a column of alumina about five times to remove the bulk of the catalyst. A Soxhlet apparatus was used to recover
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Wang, Michael C P; Gates, Byron D
2012-09-04
Selenium nanostructures, which are otherwise susceptible to oxidative damage, were encapsulated with a thin layer of polystyrene. The thin layer of polystyrene was grafted onto the surfaces of selenium by a surface initiated atom transfer radical polymerization reaction. These encapsulated nanostructures demonstrate an enhanced resistance towards corrosion.
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Magnetic Levitation To Characterize the Kinetics of Free-Radical Polymerization.
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).
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Tang, Mingyi; Xu, Xiaoyang, E-mail: xiaoyangxu2012@163.com; Wu, Tao
Highlights: • Graphene oxide (GO) was modified by chemical reactions to functionalized GO (FGO). • The FGOs and the GO were then subjected to in situ free radical polymerization. • Hydroxyl groups of GO were the most reactive grafting sites. - Abstract: Graphene oxide (GO) was modified using chemical reactions to obtain three types of functionalized GO sheets (FGO). The FGO sheets and the GO were then subjected to in situ free radical polymerization in order to study the grafting polymerization. The FGO and grafted-.FGO were analyzed with Fourier transform infrared spectroscopy, scanning electronic microscopy, thermo-gravimetric analysis (TGA) and X-raymore » photoelectron spectroscopy (XPS). The grafting percentages in the materials were calculated using the TGA and XPS results. The FGO sheets with different functional groups exhibited different grafting abilities, and hydroxyl groups were proven to be the most reactive grafting sites for the in situ free radical grafting polymerization of polyacrylamide.« less
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Synthesis of ethylene-propylene rubber graft copolymers by borane approach
DOE Office of Scientific and Technical Information (OSTI.GOV)
Chung, T.C.; Janvikul, W.; Bernard, R.
1994-01-01
This paper describes a new method to prepare graft copolymers which have an EP rubber backbone and several free radical polymerized polymers grafted thereto. The process involves hydroboration of commercial EPDM rubbers, such as poly(ethylene-co-propylene-co-1,4-hexadiene) and poly(ethylene-co-propylene-co-5-ethylidene-2-norbornene), with 9-borabicyclononane (9-BBN). The resulting secondary alkyl-9-BBN moieties in the EPDM copolymer were then exposed to oxygen in the presence of free radical polymerizable monomers. Under certain conditions, the selective autoxidation reaction of secondary alkyl-9-BBN took place to create desirable polymeric radicals which can in situ initiate free radical polymerization. High graft efficiency was observed with controllable copolymer compositions. The graft copolymer ofmore » EP-g-PMMA is used to show the chemistry as well as some of the physical properties.« less
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Kim, Kwang Ho; Bai, Xianglan; Cady, Sarah; Gable, Preston; Brown, Robert C
2015-03-01
We report on the quantitative analysis of free radicals in bio-oils produced from pyrolysis of cellulose, organosolv lignin, and corn stover by EPR spectroscopy. Also, we investigated their potential role in condensed-phase polymerization. Bio-oils produced from lignin and cellulose show clear evidence of homolytic cleavage reactions during pyrolysis that produce free radicals. The concentration of free radicals in lignin bio-oil was 7.5×10(20) spin g(-1), which was 375 and 138 times higher than free-radical concentrations in bio-oil from cellulose and corn stover. Pyrolytic lignin had the highest concentration in free radicals, which could be a combination of carbon-centered (benzyl radicals) and oxygen-centered (phenoxy radicals) organic species because they are delocalized in a π system. Free-radical concentrations did not change during accelerated aging tests despite increases in molecular weight of bio-oils, suggesting that free radicals in condensed bio-oils are stable. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Kitano, Hiromi; Kondo, Takuya; Suzuki, Hisatomo; Ohno, Kohji
2010-05-15
A polymer brush of 2-(2-methoxyethoxy)ethyl methacrylate (MDM) was prepared by atom transfer radical polymerization (ATRP) using a 11-(2-bromoisobutyroyloxy)undecyl moiety-carrying initiator covalently fixed to a glass substrate. An aqueous solution of the MDM polymer (E-PMDM), which had been prepared for comparison, turned to be opaque above certain temperature (26.2 °C for E-PMDM (M(n,GPC)=1.84×10(4))), which was corresponding to the lower critical solution temperature (LCST) of the polymer. The PMDM polymer brush accumulated on the glass surface also indicated temperature-responsive changes in contact angle of air bubble in the air-in-water system. Furthermore, non-specific adsorption of various proteins (bovine serum albumin (BSA), human immunoglobulin G (IgG) and bovine plasma fibrinogen (BPF)) to the surface of polymer brush on the glass plate was examined by the bicinchoninic acid method. The PMDM brush did not adsorb IgG and BPF significantly below the LCST of the polymer chain, whereas adsorbed a larger amount of the proteins above the LCST. A similar but less significant temperature-responsive adsorption was observed in the case of BSA. These results suggest usability of the temperature-responsive polymer-brushes with pendent ω-methoxy oligo(ethylene glycol) groups to coat various materials for bio-medical applications. Copyright © 2010. Published by Elsevier Inc.
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Synthesis and polymerization of vinyl triazolium ionic liquids
Luebke, David; Nulwala, Hunaid; Matyjaszewski, Krzysztof; Adzima, Brian
2018-05-15
Herein, we describe polymerized ionic liquids, demonstrate the synthesis of polymerized ionic liquids, and demonstrate the polymerization of triazolium monomers. One embodiment shows the polymeriazation of the triazolium monomers with bis(trifluoromethanesulfonyl)imide anions. In another embodiment we show the feasibility of copolymerizing with commodity monomers such as styrene using free radical polymerization techniques.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Chatterjee, S.; Gottschalk, P.; Davis, P.D.
1988-03-30
Photoinitiation of polymerization is a process of immense practical, economic, and theoretical importance. In typical examples the polymerization of an acrylate or styrene-derived monomer is initiated by irradiation of a sensitizer with ultraviolet light. The excited state of the sensitizer may dissociate directly to form active free radicals as in the case of the benzoin ethers, or it may first undergo a bimolecular electron-transfer reaction whose products initiate polymerization as is the case in the benzophenone-dimethylaniline system. Efforts to extend the range of useful photoinitiators of free-radical polymerization to the visible region of the spectrum have heretofore met with onlymore » modest success. These special initiators typically are sensitive only to blue light or suffer from thermal instability and have low quantum efficiencies. The authors report herein the discovery that triphenylalkylborate salts of cyanine dyes (Chart I) are photoinitiators of free-radical polymerization whose sensitivity throughout the entire visible spectral region is the result of a novel intra-ion-pair electron-transfer reaction.« less
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Transdermal gelation of methacrylated macromers with near-infrared light and gold nanorods
NASA Astrophysics Data System (ADS)
Gramlich, William M.; Holloway, Julianne L.; Rai, Reena; Burdick, Jason A.
2014-01-01
Injectable hydrogels provide locally controlled tissue bulking and a means to deliver drugs and cells to the body. The formation of hydrogels in vivo may involve the delivery of two solutions that spontaneously crosslink when mixed, with pH or temperature changes, or with light (e.g., visible or ultraviolet). With these approaches, control over the kinetics of gelation, introduction of the initiation trigger (e.g., limited penetration of ultraviolet light through tissues), or alteration of the material physical properties (e.g., mechanics) may be difficult to achieve. To overcome these limitations, we used the interaction of near-infrared (NIR) light with gold nanorods (AuNRs) to generate heat through the photothermal effect. NIR light penetrates tissues to a greater extent than other wavelengths and provides a means to indirectly initiate radical polymerization. Specifically, this heating coupled with a thermal initiator (VA-044) produced radicals that polymerized methacrylated hyaluronic acid (MeHA) and generated hydrogels. A range of VA-044 concentrations changed the gelation time, yielding a system stable at 37 ° C for 22 min that gels quickly (˜3 min) when heated to 55 ° C. With a constant irradiation time (10 min) and laser power (0.3 W), different VA-044 and AuNR concentrations tuned the compressive modulus of the hydrogel. By changing the NIR irradiation time we attained a wide range of moduli at a set solution composition. In vivo mouse studies confirmed that NIR laser irradiation through tissue could gel an injected precursor solution transdermally.
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NASA Technical Reports Server (NTRS)
Avni, R.; Carmi, U.; Inspektor, A.; Rosenthal, I.
1984-01-01
The ion-molecule and radical-molecule mechanisms are responsible for the dissociation of hydrocarbon, silane, and chlorosilane monomers and the formation of polymerized species, respectively, in an RF plasma discharge. In a plasma containing a mixture of monomer and argon the rate-determining step for both dissociation and polymerization is governed by an ion-molecule type of interaction. Adding hydrogen or ammonia to the monomer-argon mixture transforms the rate-determining step from an ion-molecule interaction to a radical-molecule interaction for both monomer dissociation and polymerization.
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ERIC Educational Resources Information Center
Iler, H. Darrell; Brown, Amber; Landis, Amanda; Schimke, Greg; Peters, George
2014-01-01
A numerical analysis of the free radical addition polymerization system is described that provides those teaching polymer, physical, or advanced organic chemistry courses the opportunity to introduce students to numerical methods in the context of a simple but mathematically stiff chemical kinetic system. Numerical analysis can lead students to an…
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NASA Astrophysics Data System (ADS)
Wei, Lulu; Lu, Beibei; Cui, Lin; Peng, Xueying; Wu, Jianning; Li, Deqiang; Liu, Zhiyong; Guo, Xuhong
2017-12-01
A novel type of amphiphilic pH-responsive folate-poly(ɛ-caprolactone)- block-poly(2-hydroxyethylmethacrylate)- co-poly(2-(dimethylamino)-ethylmethacrylate) (FA-PCL- b-P(HEMA- co-DMAEMA)) (MFP) block copolymers were designed and synthesized via atom transfer radical polymerization (ATRP) and ring opening polymerization (ROP) techniques. The molecular structures of the copolymers were confirmed with 1H NMR, FTIR and GPC measurements. The critical micelle concentration (CMC) of MFP in aqueous solution was extremely low (about 6.54 mg/L). The in vitro release behavior of DOX-loaded micelles was significantly accelerated when the pH value of solution decreased from 7.4 to 5.0. In vitro antitumor efficiency was evaluated by incubating DOX-loaded micelles with Hela cells. The results demonstrated that this copolymer possessed excellent biocompatibility, and FA-decorated micelles MFP showed higher cellular uptake than those micelles without the FA moiety, indicating their unique targetability. These folate-conjugated biodegradable micelles are highly promising for targeted cancer chemothe-rapy.
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Method for molding ceramic powders using a water-based gel casting
Janney, Mark A.; Omatete, Ogbemi O.
1991-07-02
A method for molding ceramic powders comprises forming a slurry mixture including ceramic powder, a dispersant, and a monomer solution. The monomer solution includes at least one monofunctional monomer and at least one difunctional monomer, a free-radical initiator, and a aqueous solvent. The slurry mixture is transferred to a mold, and the mold containing the slurry mixture is heated to polymerize and crosslink the monomer and form a firm polymer-solvent gel matrix. The solid product any be removed from the mold and heated to first remove the solvent and subsequently remove the polymer, whereafter the product may be sintered.
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Method for molding ceramic powders using a water-based gel casting process
Jenny, Mark A.; Omalete, Ogbemi O.
1992-09-08
A method for molding ceramic powders comprises forming a slurry mixture including ceramic powder, a dispersant, and a monomer solution. The monomer solution includes at least one monofunctional monomer and at least one difunctional monomer, a free-radical initiator, and a aqueous solvent. The slurry mixture is transferred to a mold, and the mold containing the slurry mixture is heated to polymerize and crosslink the monomer and form a firm polymer-solvent gel matrix. The solid product may be removed from the mold and heated to first remove the solvent and subsequently remove the polymer, whereafter the product may be sintered.
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NASA Astrophysics Data System (ADS)
Lemarchand, Claire; Bousquet, David; Schnell, Benoît; Pineau, Nicolas
2017-06-01
The behavior of polymer melts under shock loading is a question attracting more and more attention because of applications such as polymer-bonded explosives, light-weight armor and civilian protective equipment, like sports and car equipment. Molecular dynamics (MD) simulations are a very good tool to characterize the microscopic response of the polymer to a shock wave. To do so, the initial configuration of the polymer melt needs to be realistic. The ``radical-like polymerization'' scheme is a method to obtain near equilibrium configurations of a melt of long polymer chains. It consists in adding one neighboring monomer at a time to each growing chain. Between each polymerization step an MD run is performed to relax the new configuration. We test how details of our implementation of the ``radical-like polymerization'' scheme can impact or not Hugoniot curves and changes of chain configuration under shock. We compare our results to other simulation and experimental results on reference polymers.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Redline, Erica Marie; Bolintineanu, Dan S.; Lane, J. Matthew
The aim of this study was to alter polymerization chemistry to improve network homogeneity in free-radical crosslinked systems. It was hypothesized that a reduction in heterogeneity of the network would lead to improved mechanical performance. Experiments and simulations were carried out to investigate the connection between polymerization chemistry, network structure and mechanical properties. Experiments were conducted on two different monomer systems - the first is a single monomer system, urethane dimethacrylate (UDMA), and the second is a two-monomer system consisting of bisphenol A glycidyl dimethacrylate (BisGMA) and triethylene glycol dimethacrylate (TEGDMA) in a ratio of 70/30 BisGMA/TEGDMA by weight. Themore » methacrylate systems were crosslinked using traditional radical polymeriza- tion (TRP) with azobisisobutyronitrile (AIBN) or benzoyl peroxide (BPO) as an initiator; TRP systems were used as the control. The monomers were also cross-linked using activator regenerated by electron transfer atom transfer radical polymerization (ARGET ATRP) as a type of controlled radical polymerization (CRP). FTIR and DSC were used to monitor reac- tion kinetics of the systems. The networks were analyzed using NMR, DSC, X-ray diffraction (XRD), atomic force microscopy (AFM), and small angle X-ray scattering (SAXS). These techniques were employed in an attempt to quantify differences between the traditional and controlled radical polymerizations. While a quantitative methodology for characterizing net- work morphology was not established, SAXS and AFM have shown some promising initial results. Additionally, differences in mechanical behavior were observed between traditional and controlled radical polymerized thermosets in the BisGMA/TEGDMA system but not in the UDMA materials; this finding may be the result of network ductility variations between the two materials. Coarse-grained molecular dynamics simulations employing a novel model of the CRP reaction were carried out for the UDMA system, with parameters calibrated based on fully atomistic simulations of the UDMA monomer in the liquid state. Detailed metrics based on network graph theoretical approaches were implemented to quantify the bond network topology resulting from simulations. For a broad range of polymerization parameters, no discernible differences were seen between TRP and CRP UDMA simulations at equal conversions, although clear differences exist as a function of conversion. Both findings are consistent with experiments. Despite a number of shortcomings, these models have demonstrated the potential of molecular simulations for studying network topology in these systems.« less
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Silica nanoparticles carrying boron-containing polymer brushes
NASA Astrophysics Data System (ADS)
Brozek, Eric M.; Mollard, Alexis H.; Zharov, Ilya
2014-05-01
A new class of surface-modified silica nanoparticles has been developed for potential applications in boron neutron capture therapy. Sub-50 nm silica particles were synthesized using a modified Stöber method and used in surface-initiated atom transfer radical polymerization of two biocompatible polymers, poly(2-(hydroxyethyl)methacrylate) and poly(2-(methacryloyloxy)ethyl succinate). The carboxylic acid and hydroxyl functionalities of the polymeric side chains were functionalized with carboranyl clusters in high yields. The resulting particles were characterized using DLS, TEM, solution 1H NMR, solid state 11B NMR and thermogravimetric analysis. The particles contain between 13 and 18 % of boron atoms by weight, which would provide a high amount of 10B nuclides for BNCT, while the polymer chains are suitable for further modification with cell targeting ligands.
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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
,NNovel polymeric materials from vegetable oils and vinyl monomers: preparation, properties, and applications.
Lu, Yongshang; Larock, Richard C
2009-01-01
Veggie-based products: Vegetable-oil-based polymeric materials, prepared by free radical, cationic, and olefin metathesis polymerizations, range from soft rubbers to ductile or rigid plastics, and to high-performance biocomposites and nanocomposites. They display a wide range of thermophysical and mechanical properties and may find promising applications as alternatives to petroleum-based polymers.Vegetable oils are considered to be among the most promising renewable raw materials for polymers, because of their ready availability, inherent biodegradability, and their many versatile applications. Research on and development of vegetable oil based polymeric materials, including thermosetting resins, biocomposites, and nanocomposites, have attracted increasing attention in recent years. This Minireview focuses on the latest developments in the preparation, properties, and applications of vegetable oil based polymeric materials obtained by free radical, cationic, and olefin metathesis polymerizations. The novel vegetable oil based polymeric materials obtained range from soft rubbery materials to ductile or rigid plastics and to high-performance biocomposites and nanocomposites. These vegetable oil based polymeric materials display a wide range of thermophysical and mechanical properties and should find useful applications as alternatives to their petroleum-based counterparts.
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Polymerization Initiated at the Sidewalls of Carbon Nanotubes
NASA Technical Reports Server (NTRS)
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.
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NASA Astrophysics Data System (ADS)
Flores, Joel Diez
2011-12-01
The need to tailor polymeric architectures with specific physico-chemical properties via the simplest, cleanest, and most efficient synthetic route possible has become the ultimate goal in polymer synthesis. Recent progress in macromolecular science, such as the discoveries of controlled/"living" free radical polymerization (CRP) methods, has brought about synthetic capabilities to prepare (co)polymers with advanced topologies, predetermined molecular weights, narrow molecular weight distributions, and precisely located functional groups. In addition, the establishment of click chemistry has redefined the selected few highly efficient chemical reactions that become highly useful in post-polymerization modification strategies. Hence, the ability to make well-defined topologies afforded by controlled polymerization techniques and the facile incorporation of functionalities along the chain via click-type reactions have yielded complex architectures, allowing the investigation of physical phenomena which otherwise could not be studied with systems prepared via conventional methods. The overarching theme of the research work described in this dissertation is the fusion of the excellent attributes of reversible addition-fragmentation chain transfer (RAFT) polymerization method, which is one of the CRP techniques, and click-type chemical reactions in the precision of synthesis of advanced functional materials. Chapter IV is divided into three sections. In Section I, the direct RAFT homopolymerization of 2-(acryloyloxy)ethyl isocyanate (AOI) and subsequent post-polymerization modifications are described. The polymerization conditions were optimized in terms of the choice of RAFT chain transfer agent (CTA), polymerization temperature and the reaction medium. Direct RAFT polymerization of AOI requires a neutral CTA, and relatively low reaction temperature to yield AOI homopolymers with low polydispersities. Efficient side-chain functionalization of PAOI homopolymers was achieved via reaction with model amine, thiol and alcohol compounds yielding urea, thiourethane and urethane derivatives, respectively. Reactions with amines and thiols (in the presence of base) were rapid, quantitative and efficient. However, the reaction with alcohols catalyzed by dibutyltin dilaurate (DBTDL) was relatively slow but proceeded to completion. Selective reaction pathways for the addition of difunctional ethanolamine and mercaptoethanol were also investigated. A related strategy is described in Section II wherein a hydroxyl-containing diblock copolymer precursor was transformed into a library of functional copolymers via two sequential post-polymerization modification reactions. A diblock copolymer scaffold, poly[(N,N-dimethylacrylamide)-b-( N-(2-hydroxyethyl)acrylamide] (PDMA-b-PHEA) was first prepared. The hydroxyl groups of the HEA block were then reacted with 2-(acryloyloxy)ethylisocyanate (AOI) and allylisocyanate (AI) resulting in acrylate- and allyl-functionalized copolymer precursors, respectively. The efficiencies of Michael-type and free radical thiol addition reactions were investigated using selected thiols having alkyl, aryl, hydroxyl, carboxylic acid, amine and amino acid functionalities. The steps of RAFT polymerization, isocyanate-hydroxyl coupling and thiol-ene addition are accomplished under mild conditions, thus offering facile and modular routes to synthesize functional copolymers. The synthesis and solution studies of pH- and salt-responsive triblock copolymer are described in Section III. This system is capable of forming self-locked micellar structures which may be controlled by changing solution pH as well as ionic strength. A triblock copolymer containing a permanently hydrophilic poly(N,N-dimethylacrylamide) (PDMA) outer block, a salt-sensitive zwitterionic poly(3[2-(N-methylacrylamido)ethyl dimethylammonio]propanesulfonate) (PMAEDAPS) middle block and a pH-responsive 3-acrylamido-3-methylbutanoic acid (PAMBA) core block was synthesized using aqueous RAFT polymerization. A facile formation of "self-locking" shell cross-linked micelles is achieved by changing solution pH and salt concentration. The reversible "self-locking" is attained from the interactions of zwitterionic groups in the middle block that constitutes the shell of the micelles. The structure slowly dissociates into unimers in 2-3 days at pH above the pKa of the PAMBA block.
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2017-01-01
Light-initiated additive manufacturing techniques typically rely on layer-by-layer addition or continuous extraction of polymers formed via nonliving, free radical polymerization methods that render the final materials “dead” toward further monomer insertion; the polymer chains within the materials cannot be reactivated to induce chain extension. An alternative “living additive manufacturing” strategy would involve the use of photocontrolled living radical polymerization to spatiotemporally insert monomers into dormant “parent” materials to generate more complex and diversely functionalized “daughter” materials. Here, we demonstrate a proof-of-concept study of living additive manufacturing using end-linked polymer gels embedded with trithiocarbonate iniferters that can be activated by photoinduced single-electron transfer from an organic photoredox catalyst in solution. This system enables the synthesis of a wide range of chemically and mechanically differentiated daughter gels from a single type of parent gel via light-controlled modification of the parent’s average composition, strand length, and/or cross-linking density. Daughter gels that are softer than their parent, stiffer than their parent, larger but with the same modulus as their parent, thermally responsive, polarity responsive, healable, and weldable are all realized. PMID:28280779
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Chen, Mao; Gu, Yuwei; Singh, Awaneesh; Zhong, Mingjiang; Jordan, Alex M; Biswas, Santidan; Korley, LaShanda T J; Balazs, Anna C; Johnson, Jeremiah A
2017-02-22
Light-initiated additive manufacturing techniques typically rely on layer-by-layer addition or continuous extraction of polymers formed via nonliving, free radical polymerization methods that render the final materials "dead" toward further monomer insertion; the polymer chains within the materials cannot be reactivated to induce chain extension. An alternative "living additive manufacturing" strategy would involve the use of photocontrolled living radical polymerization to spatiotemporally insert monomers into dormant "parent" materials to generate more complex and diversely functionalized "daughter" materials. Here, we demonstrate a proof-of-concept study of living additive manufacturing using end-linked polymer gels embedded with trithiocarbonate iniferters that can be activated by photoinduced single-electron transfer from an organic photoredox catalyst in solution. This system enables the synthesis of a wide range of chemically and mechanically differentiated daughter gels from a single type of parent gel via light-controlled modification of the parent's average composition, strand length, and/or cross-linking density. Daughter gels that are softer than their parent, stiffer than their parent, larger but with the same modulus as their parent, thermally responsive, polarity responsive, healable, and weldable are all realized.
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1990-04-10
the hydroxyl groups. These are liquid oligobutadienes of brand R-15M and R-45M (firm "Sinclair Retgochemical Suc."/OSA) [5, 6, 10] and hydroxyl... ionic mechanism. Most promising, in view of simplicity and cheapness, is considered the I DOC - 90010000 PAGE - method of the radical polymerization of...Initiators of polimerization in this method are the hydroxyl radicals, which are generated during the homolytic decomposition of peroxide of hydrogen PDO
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D'Alpino, Paulo Henrique Perlatti; Silva, Marília Santos; Vismara, Marcus Vinícius Gonçalves; Di Hipólito, Vinicius; Miranda González, Alejandra Hortencia; de Oliveira Graeff, Carlos Frederico
2015-06-01
This study evaluated the degree of conversion, the free radical entrapment, and the chemical interaction of self-adhesive resin cements mixed with pure hydroxyapatite, as a function of the polymerization activation mode among a variety of commercial self-adhesive cements. Four cements (Embrace WetBond, MaxCem Elite, Bifix SE, and RelyX U200) were mixed, combined with hydroxyapatite, dispensed into molds, and distributed into three groups, according to polymerization protocols: IP (photoactivation for 40s); DP (delayed photoactivation, 10 min self-curing plus 40s light-activated); and CA (chemical activation, no light exposure). Infrared (IR) spectra were obtained and monomer conversion (%) was calculated by comparing the aliphatic-to-aromatic IR absorption peak ratio before and after polymerization (n=10). The free radical entrapment values of the resin cements were characterized using Electron Paramagnetic Resonance (EPR) and the concentration of spins (number of spins/mass) calculated (n=3). Values were compared using two-way ANOVA and Tukey's post-hoc test (α=5%). X-ray diffraction (XRD) characterized the crystallinity of hydroxyapatite as a function of the chemical interactions with the resin cements. The tested parameters varied as a function of resin cement and polymerization protocol. Embrace WetBond and RelyX U200 demonstrated dependence on photoactivation (immediate or delayed), whereas MaxCem Elite exhibited dependence on the chemical activation mode. Bifix SE presented the best balance based on the parameters analyzed, irrespective of the activation protocol. Choice of polymerization protocol affects the degree of conversion, free radical entrapment, and the chemical interaction between hydroxyapatite and self-adhesive resin cement mixtures. Copyright © 2015 Elsevier Ltd. All rights reserved.
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Free Radical Polymerization of Styrene: A Radiotracer Experiment
ERIC Educational Resources Information Center
Mazza, R. J.
1975-01-01
Describes an experiment designed to acquaint the chemistry student with polymerization reactions, vacuum techniques, liquid scintillation counting, gas-liquid chromatography, and the handling of radioactive materials. (MLH)
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Heterofunctional Glycopolypeptides by Combination of Thiol-Ene Chemistry and NCA Polymerization.
Krannig, Kai-Steffen; Schlaad, Helmut
2016-01-01
Glycopolypeptides are prepared either by the polymerization of glycosylated amino acid N-carboxyanhydrides (NCAs) or by the post-polymerization functionalization of polypeptides with suitable functional groups. Here we present a method for the in-situ functionalization and (co-) polymerization of allylglycine N-carboxyanhydride in a facile one-pot procedure, combining radical thiol-ene photochemistry and nucleophilic ring-opening polymerization techniques, to yield well-defined heterofunctional glycopolypeptides.
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Ahmadkhani, Lida; Abbasian, Mojtaba; Akbarzadeh, Abolfazl
2017-01-01
Sharply thermo- and pH-responsive pentablock terpolymer with a core-shell-corona structure was prepared by RAFT polymerization of N-isopropylacrylamide and methacrylic acid monomers using PEG-based benzoate-type of RAFT agent. The PEG-based RAFT agent could be easily synthesized by dihydroxyl-capped PEG with 4-cyano-4-(thiobenzoyl) sulfanylpentanoic acids, using esterification reaction. This pentablock terpolymer was characterized by 1 H NMR, FT-IR, and GPC. The PDI was obtained by GPC, indicating that the molecular weight distribution was narrow and the polymerization was well controlled. The thermo- and pH-responsive micellization of the pentablock terpolymer in aqueous solution was investigated using fluorescence spectroscopy technique, UV-vis transmittance, and TEM. The LCST of pentablock terpolymer increased (over 50 °C) compared to the NIPAM homopolymer (~32 °C), due to the incorporation of the hydrophilic PEG and PMA blocks in pentablock terpolymer (PNIPAM block as the core, PEG the block and the hydrophilic PMA block as the shell and the corona). Also, pH-dependent phase transition behavior shows at a pH value of about ~5.8, according to pKa of MAA. Thus, in acidic solution at room temperature, the pentablock terpolymer self-assembled to form core-shell-corona micelles, with the hydrophobic PMA block as the core, the PNIPAM block and the hydrophilic PEG block as the shell and the corona, respectively.
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Ge, Xueping; Ye, Qiang; Song, Linyong; Misra, Anil; Spencer, Paulette
2015-04-01
The effects of polymerization kinetics and chemical miscibility on the crosslinking structure and mechanical properties of polymers cured by visible-light initiated free-radical/cationic ring-opening hybrid photopolymerization are determined. A three-component initiator system is used and the monomer system contains methacrylates and epoxides. The photopolymerization kinetics is monitored in situ by Fourier transform infrared-attenuated total reflectance. The crosslinking structure is studied by modulated differential scanning calorimetry and dynamic mechanical analysis. X-ray microcomputed tomography is used to evaluate microphase separation. The mechanical properties of polymers formed by hybrid formed by free-radical polymerization. These investigations mark the first time that the benefits of the chain transfer reaction between epoxy and hydroxyl groups of methacrylate, on the crosslinking network and microphase separation during hybrid visible-light initiated photopolymerization, have been determined.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Kaetsu, I.; Ito, A.; Hayashi, K.
1973-06-01
The effect of homogeneity of polymerization phase and monomer concentration on the temperature dependence of initial polymerization rate was studied in the radiation-induced radical polymerization of binary systems consisting of glass-forming monomer and solvent. In the polymerization of a completely homogeneous system such as HEMA-propylene glycol, a maximum and a minimum in polymerization rates as a function of temperature, characteristic of the polymerization in glass-forming systems, were observed for all monomer concentrations. However, in the heterogeneous polymerization systems such as HEMA-triacetin and HEMAisoamyl acetate, maximum and minimum rates were observed in monomer-rich compositions but not at low monomer concentrations. Furthermore,more » in the HEMA-dioctyl phthalate polymerization system, which is extremely heterogeneous, no maximum and minimum rates were observed at any monomer concentration. The effect of conversion on the temperature dependence of polymerization rate in homogeneous bulk polymerization of HEMA and GMA was investigated. Maximum and minimum rates were observed clearly in conversions less than 10% in the case of HEMA and less than 50% in the case of GMA, but the maximum and minimum changed to a mere inflection in the curve at higher conversions. A similar effect of polymer concentration on the temperature dependence of polymerization rate in the GMA-poly(methyl methacrylate) system was also observed. It is deduced that the change in temperature dependence of polymerization rate is attributed to the decrease in contribution of mutual termination reaction of growing chain radicals to the polymerization rate. (auth)« less
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Polymerization Simulator for Introductory Polymer and Material Science Courses
ERIC Educational Resources Information Center
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…
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Shirangi, Mehrnoosh; Sastre Toraño, Javier; Sellergren, Börje; Hennink, Wim E; Somsen, Govert W; van Nostrum, Cornelus F
2015-01-21
Free radical polymerization is often used to prepare protein and peptide-loaded hydrogels for the design of controlled release systems and molecular imprinting materials. Peroxodisulfates (ammonium peroxodisulfates (APS) or potassium peroxodisulfates (KPS)) with N,N,N,N-tetramethylethylenediamine (TEMED) are frequently used as initiator and catalyst. However, exposure to these free radical polymerization reagents may lead to modification of the protein and peptide. In this work, we show the modification of lysine residues by ammonium peroxodisulfate (APS)/TEMED of the immunostimulant thymopentin (TP5). Parallel studies on a decapeptide and a library of 15 dipeptides were performed to reveal the mechanism of modification. LC-MS of APS/TEMED-exposed TP5 revealed a major reaction product with an increased mass (+12 Da) with respect to TP5. LC-MS(2) and LC-MS(3) were performed to obtain structural information on the modified peptide and localize the actual modification site. Interpretation of the obtained data demonstrates the formation of a methylene bridge between the lysine and arginine residue in the presence of TEMED, while replacing TEMED with a sodium bisulfite catalyst did not show this modification. Studies with the other peptides showed that the TEMED radical can induce methyleneation on peptides when lysine is next to arginine, proline, cysteine, aspargine, glutamine, histidine, tyrosine, tryptophan, and aspartic acid residues. Stability of peptides and protein needs to be considered when using APS/TEMED in in situ polymerization systems. The use of an alternative catalyst such as sodium bisulfite may preserve the chemical integrity of peptides during in situ polymerization.
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Polymerization as a Model Chain Reaction
ERIC Educational Resources Information Center
Morton, Maurice
1973-01-01
Describes the features of the free radical, anionic, and cationic mechanisms of chain addition polymerization. Indicates that the nature of chain reactions can be best taught through the study of macromolecules. (CC)
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Double-bond-containing polyallene-based triblock copolymers via phenoxyallene and (meth)acrylate
NASA Astrophysics Data System (ADS)
Ding, Aishun; Lu, Guolin; Guo, Hao; Huang, Xiaoyu
2017-03-01
A series of ABA triblock copolymers, consisting of double-bond-containing poly(phenoxyallene) (PPOA), poly(methyl methacrylate) (PMMA), or poly(butyl acrylate) (PBA) segments, were synthesized by sequential free radical polymerization and atom transfer radical polymerization (ATRP). A new bifunctional initiator bearing azo and halogen-containing ATRP initiating groups was first prepared followed by initiating conventional free radical homopolymerization of phenoxyallene with cumulated double bond to give a PPOA-based macroinitiator with ATRP initiating groups at both ends. Next, PMMA-b-PPOA-b-PMMA and PBA-b-PPOA-b-PBA triblock copolymers were synthesized by ATRP of methyl methacrylate and n-butyl acrylate initiated by the PPOA-based macroinitiator through the site transformation strategy. These double-bond-containing triblock copolymers are stable under UV irradiation and free radical circumstances.
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NASA Astrophysics Data System (ADS)
Wu, Shikai; Wen, Shengwu; Xu, Xinmei; Huang, Guozhi; Cui, Yifan; Li, Jinyu; Qu, Ailan
2018-04-01
Porous graphite carbon nitride nanosheets (g-C3N4) are achieved via one-step catalyst-free solution self-polymerization from a single melamine precursor. The resultant porous g-C3N4 nanosheets with the best photodegradation capacity provided the surface area of 669.15 m2/g, which is superior to the surface area of any other porous g-C3N4 reported. Results showed enhanced adsorption and degradation capacity of methyl orange (MO) under UV-visible light irradiation (λ > 350 nm) compared to bulk g-C3N4. The MO oxidation of the porous g-C3N4 nanosheets is driven mostly by the participation of holes, and secondly by rad O2- and rad OH radicals. This approach shed lights on porous g-C3N4 production simply by self-polycondensation of single functional monomer. It also provided a low-cost and eco-friendly method to facilely mass-produce g-C3N4 nanosheets with high surface area for many potential applications.
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Zhang, Xiao-Yun; Liu, Dong-Ming; Lv, Xin-Hu; Sun, Miao; Sun, Xiao-Li; Wan, Wen-Ming
2016-11-01
A one-pot method is introduced for the successful synthesis of narrow-distributed (Đ = 1.22) vinyl polymer with both ultrahigh molecular weight (UHMW) (M w = 1.31 × 10 6 g mol -1 ) and micro-/nanomorphology under mild conditions. The method involves the following four stages: homogeneous polymerization, polymerization-induced self-assembly (PISA), PISA and reorganization, and PISA and multiple reorganizations. The key points to the production of UHMW polystyrene are to minimize radical termination by segregating radicals in different nanoreactors and to ensure sufficient chain propagation by promoting further reorganizations of these reactors in situ. This method therefore endows polymeric materials with the outstanding properties of both UHMW and tunable micro-/nanoparticles under mild conditions in one pot. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Es-Safi, Nour-Eddine; Guyot, Sylvain; Ducrot, Paul-Henri
2006-09-20
The structure of a polymeric proanthocyanidin fraction isolated from pear juice was characterized by NMR, ESI/MS, and MALDI-TOF/MS analyses, and its antioxidant activity was investigated using the DPPH free radical scavenging method. The results obtained from 13C NMR analysis showed the predominance of signals representative of procyanidins. Typical signals in the chemical shift region between 70 and 90 ppm demonstrated the exclusive presence of epicatechin units. The results obtained through negative ESI/MS analysis showed singly and doubly charged ions corresponding to the molecular mass of procyanidins with a degree of polymerization up to 22. The spectra obtained through MALDI-TOF/MS analysis revealed the presence of two series of tannin oligomers. Supporting the observations from NMR spectroscopy, the first series consists of well-resolved tannin identified as procyanidin polymers units with chain lengths of up to 25. A second series of monogalloyl flavan-3-ols polymers with polymerization degree up to 25 were also detected. This is the first mass spectrometric evidence confirming the existence of galloylated procyanidin oligomers in pear fruits. Within each of these oligomers, various signals exist suggesting the presence of several oligomeric tannins. The antioxidant properties of the polymeric fraction were investigated through reduction of the DPPH free radical, and the results obtained showed that the polymeric fraction exhibited a higher antioxidant power compared to those of (+)-catechin and B3 procyanidin dimer.
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Recovery and concentration of antioxidants from winery wastes.
Soto, María Luisa; Conde, Enma; González-López, Noelia; Conde, María Jesús; Moure, Andrés; Sineiro, Jorge; Falqué, Elena; Domínguez, Herminia; Núñez, María José; Parajó, Juan Carlos
2012-03-09
Grape and wine byproducts have been extensively studied for the recovery of phenolic compounds with antioxidant activity and a variety of biological actions. The selective recovery and concentration of the phenolic compounds from the liquid phase separated from further diluted winery wastes has been proposed. Adsorption onto non ionic polymeric resins and further desorption with ethanolic solutions was studied. Several commercial food grade resins were screened with the aim of selecting the most suited for the practical recovery of phenolic compounds with radical scavenging activity. Under the optimized desorption conditions (using Sepabeads SP207 or Diaion HP20 as adsorbents and eluting with 96% ethanol at 50 °C) a powdered yellow-light brown product with 50% phenolic content, expressed as gallic acid equivalents, was obtained. The radical scavenging capacity of one gram of product was equivalent to 2-3 g of Trolox.
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Hydroperoxide Traces in Common Cyclic Ethers as Initiators for Controlled RAFT Polymerizations.
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.
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Arita, Toshihiko
2010-10-01
Commercially available unmodified ceramic nanoparticles (NPs) in dry powder state were surface-modified and dispersed in almost single-crystal size. The surface-initiated living radical polymerization after just UV-ozone soft etching enables one to graft polymers onto the surface of ceramic NPs and disperse them in solvents. Furthermore, a number of NPs were dispersed with single-crystal sizes. The technique developed here could be applied to almost all ceramic NPs including metal nitrides.
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Halide removal from aqueous solution by novel silver-polymeric materials.
A M S, Polo; I, Velo-Gala; M, Sánchez-Polo; U, von Gunten; J J, López-Peñalver; J, Rivera-Utrilla
2016-12-15
The objective of this study was to analyze the behavior of a new material, silver-doped polymeric cloth (Ag-cloth), in the removal of bromide and iodide from waters. Silver is immobilized on the cloth, guaranteeing selective adsorption of the halide ions as retained silver halides that therefore do not pass into the solution. Results indicate that Ag 0 reacts with H 2 O 2 in the first phases of the process, yielding Ag + and superoxide radical; however, as the process advances, this radical favors Ag + reduction. Increases in the concentration of H 2 O 2 augment the capacity of the Ag-cloth to remove halides from the medium up to a maximum concentration (55μM), above which the removal capacity remains constant (Xm≅1.3-1.8mg halide/g Ag-cloth). Thus, when there is excess H 2 O 2 in the medium, secondary competitive reactions that take place in the process guarantee a constant Ag + concentration, which defines the maximum adsorption capacity of Ag-cloth, reducing its ability to remove halides. Ag-cloth has a higher capacity to remove iodide than bromide, and the presence of organic matter or chloride reduces its capacity to remove iodide or bromide from water. The results obtained shown that the capacity of Ag 0 with H 2 O 2 significantly varies as a function of the medium pH from 1mg Br - /g Ag-cloth at very low pH to 1.6mg/g Ag-cloth at pH9. Copyright © 2016 Elsevier B.V. All rights reserved.
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Emulsion Polymerization of Butyl Acrylate: Spin Trapping and EPR Study
NASA Technical Reports Server (NTRS)
Kim, S.; Westmoreland, D.
1994-01-01
The propagating radical in the emulsion polymerization reaction of butyl acrylate was detected by Electron Paramagnetic Resonance spectroscopy using two spin trapping agents, 2-methyl-2nitrosopropane and alpha -N-tert-butylnitrone.
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Shah, Parag K; Stansbury, Jeffrey W; Bowman, Christopher N
2017-08-14
A new addition-fragmentation chain transfer (AFT) capable moiety was incorporated into a dimethacrylate monomer that participated readily in network formation by copolymerizing with multifunctional methacrylates or acrylates. The process of AFT occurred simultaneously with photopolymerization of the AFT monomer (AFM) and other (meth)acrylate monomers leading to polymer stress relaxation via network reconfiguration. At low loading levels of the AFM, a significant reduction in shrinkage stress, especially for acrylate monomers, was observed with nominal effects on conversion. At higher loading levels of the AFM, the photopolymerization reaction kinetics and final double bond conversion were significantly lowered along with a delay in the gel-point conversion. Electron paramagnetic resonance studies during polymerization revealed the presence of a distinct radical species that was present in proportional quantities to the AFM content in the system. The lifetime and the character of the persistent radicals were altered due to the presence of the distinctive radical, in turn affecting the polymerization kinetics. With polymerization conducted at higher irradiance, the differential conversion between the control resin and samples with moderate AFM content was minimal, especially for the methacrylate-based formulations.
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Preparation and Characterization of InP/Poly(methyl methacrylate) Nanocomposite Films.
Kwon, Younghoon; Kim, Jongsung
2017-04-01
Quantum dots (QDs) are nanocrystalline semiconductors with many unusual optical properties. They exhibit very high fluorescence intensities and possess exceptional stability against photo-bleaching. In this study, we report the preparation of InP QDs-poly(methyl methacrylate) (PMMA) hybrids by fabricating QDs via a thermal decomposition reaction, followed by radical polymerization. The InP QDs were synthesized using indium(III) chloride and tris(dimethylamino)phosphine. Flexible composite films were obtained by radical polymerization using methyl methacrylate (MMA) as the monomer and 2,2′-azobis(2-methylpropionitrile) (AIBN) as a radical initiator. The PL intensity of the QDs was lowered upon composite formation with PMMA. However, the composites exhibited higher thermal stability than pure PMMA.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Chen, Mao; Gu, Yuwei; Singh, Awaneesh
Light-initiated additive manufacturing techniques typically rely on layer-by-layer addition or continuous extraction of polymers formed via nonliving, free radical polymerization methods that render the final materials “dead” toward further monomer insertion; the polymer chains within the materials cannot be reactivated to induce chain extension. An alternative “living additive manufacturing” strategy would involve the use of photocontrolled living radical polymerization to spatiotemporally insert monomers into dormant “parent” materials to generate more complex and diversely functionalized “daughter” materials. Here, we demonstrate a proof-of-concept study of living additive manufacturing using end-linked polymer gels embedded with trithiocarbonate iniferters that can be activated by photoinducedmore » single-electron transfer from an organic photoredox catalyst in solution. This system enables the synthesis of a wide range of chemically and mechanically differentiated daughter gels from a single type of parent gel via light-controlled modification of the parent’s average composition, strand length, and/or cross-linking density. Furthermore, daughter gels that are softer than their parent, stiffer than their parent, larger but with the same modulus as their parent, thermally responsive, polarity responsive, healable, and weldable are all realized.« less
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Huang, Zhenhua; Wu, Zhengfang; Yang, Peng; Yang, Wantai
2014-09-01
It is generally accepted that Ce(4+) is unable to directly oxidize unreactive alkyl C-H bonds without the assistance of adjacent polar groups. Herein, we demonstrate in our newly developed confined photochemical reaction system that this recognized issue may be challenged. As we found, when a thin layer of a CeCl(3)/HCl aqueous solution was applied to a polymeric substrate and the substrate subjected to UV irradiation, Ce(3+) was first photooxidized to form Ce(4+) in the presence of H(+), and the in situ formed Ce(4+) then performs an oxidation reaction on the C-H bonds of the polymer surface to form surface-carbon radicals for radical graft polymerization reactions and functional-group transformations, while reducing to Ce(3+) and releasing H(+) in the process. This photoinduced cerium recycling redox (PCRR) reaction behaved as a biomimetic system in an artificial recycling reaction, leading to a sustainable chemical modification strategy for directly transforming alkyl C-H bonds on polymer surfaces into small-molecule groups and polymer brushes. This method is expected to provide a green and economical tool for industrial applications of polymer-surface modification. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Chen, Mao; Gu, Yuwei; Singh, Awaneesh; ...
2017-01-13
Light-initiated additive manufacturing techniques typically rely on layer-by-layer addition or continuous extraction of polymers formed via nonliving, free radical polymerization methods that render the final materials “dead” toward further monomer insertion; the polymer chains within the materials cannot be reactivated to induce chain extension. An alternative “living additive manufacturing” strategy would involve the use of photocontrolled living radical polymerization to spatiotemporally insert monomers into dormant “parent” materials to generate more complex and diversely functionalized “daughter” materials. Here, we demonstrate a proof-of-concept study of living additive manufacturing using end-linked polymer gels embedded with trithiocarbonate iniferters that can be activated by photoinducedmore » single-electron transfer from an organic photoredox catalyst in solution. This system enables the synthesis of a wide range of chemically and mechanically differentiated daughter gels from a single type of parent gel via light-controlled modification of the parent’s average composition, strand length, and/or cross-linking density. Furthermore, daughter gels that are softer than their parent, stiffer than their parent, larger but with the same modulus as their parent, thermally responsive, polarity responsive, healable, and weldable are all realized.« less
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Wang, Huai-Song; Song, Min; Hang, Tai-Jun
2016-02-10
The high-value applications of functional polymers in analytical science generally require well-defined interfaces, including precisely synthesized molecular architectures and compositions. Controlled/living radical polymerization (CRP) has been developed as a versatile and powerful tool for the preparation of polymers with narrow molecular weight distributions and predetermined molecular weights. Among the CRP system, atom transfer radical polymerization (ATRP) and reversible addition-fragmentation chain transfer (RAFT) are well-used to develop new materials for analytical science, such as surface-modified core-shell particles, monoliths, MIP micro- or nanospheres, fluorescent nanoparticles, and multifunctional materials. In this review, we summarize the emerging functional interfaces constructed by RAFT and ATRP for applications in analytical science. Various polymers with precisely controlled architectures including homopolymers, block copolymers, molecular imprinted copolymers, and grafted copolymers were synthesized by CRP methods for molecular separation, retention, or sensing. We expect that the CRP methods will become the most popular technique for preparing functional polymers that can be broadly applied in analytical chemistry.
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Kumar, Santosh; Changez, Mohammad; Murthy, C N; Yamago, Shigeru; Lee, Jae-Suk
2011-10-04
Low-molecular weight amphiphilic diblock copolymers, polystyrene-block-poly (2-vinylpyridine) (PS-b-P2VP), and (P2VP-b-PS) with different block ratios were synthesized for the first time via organotellurium-mediated living radical polymerization (TERP). For both the homo- and block copolymerizations, good agreement between the theoretical, and experimental molecular weights was found with nearly 100% yield in every case. The molecular weight distribution for all the samples ranged between 1.10 and 1.24, which is well below the theoretical lower limit of 1.50 for a conventional free radical polymerization. Furthermore, a very simple approach to producing highly dense arrays of titania nanoparticles (TiO2 ) is presented using a site-selective reaction of titanium tetraisopropoxide within the P2VP domains of micellar film of P2VP-b-PS in toluene through the sol-gel method. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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NASA Astrophysics Data System (ADS)
Barsbay, Murat; Güven, Olgun
2009-12-01
Surface grafting of polymeric materials is attracting increasing attention as it enables the preparation of new materials from known and commercially available polymers having desirable bulk properties such as thermal stability, elasticity, permeability, etc., in conjunction with advantageous newly tailored surface properties such as biocompatibility, biomimicry, adhesion, etc. Ionizing radiation, particularly γ radiation is one of the most powerful tools for preparing graft copolymers as it generates radicals on most substrates. With the advent of living free-radical polymerization techniques, application of γ radiation has been extended to a new era of grafting; grafting in a controlled manner to achieve surfaces with tailored and well-defined properties. This report presents the current use of γ radiation in living free-radical polymerization and highlights the use of both techniques together as a combination to present an advance in the ability to prepare surfaces with desired, tunable and well-defined properties.
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Monodisperse, polymeric microspheres produced by irradiation of slowly thawing frozen drops
NASA Technical Reports Server (NTRS)
Rhim, Won-Kyu (Inventor); Hyson, Michael T. (Inventor); Chung, Sang-Kun (Inventor); Colvin, Michael S. (Inventor); Chang, Manchium (Inventor)
1991-01-01
Monodisperse, polymeric microspheres are formed by injecting uniformly shaped droplets of radiation polymerizable monomers, preferably a biocompatible monomer, having covalent binding sites such as hydroxyethylmethacrylate, into a zone, impressing a like charge on the droplet so that they mutually repel each other, spheroidizing the droplets within the zone and collecting the droplets in a pool of cryogenic liquid. As the droplets enter the liquid, they freeze into solid, glassy microspheres, which vaporizes a portion of the cryogenic liquid to form a layer. The like-charged microspheres, suspended within the layer, move to the edge of the vessel holding the pool, are discharged, fall and are collected. The collected microspheres are irradiated while frozen in the cryogenic liquid to form latent free radicals. The frozen microspheres are then slowly thawed to activate the free radicals which polymerize the monomer to form evenly-sized, evenly-shaped, monodisperse polymeric microspheres.
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Ammonium sensing in aqueous solutions with plastic optical fiber modified by molecular imprinting
NASA Astrophysics Data System (ADS)
Sequeira, F.; Duarte, D.; Rudnitskaya, A.; Gomes, M. T. S. R.; Nogueira, R.; Bilro, L.
2016-05-01
We report the development of a low cost plastic optical fibre (POF) sensor for ammonium detection using molecularly imprinted polymers (MIP's). The cladding of a 1 mm diameter PMMA fiber is removed, in which is grafted a molecular imprinted polymer (MIP), by radical polymerization with thermal initiation, that act as a selective sensing layer. For the polymerization, 2,2'-Azobis(2-methylpropionamidine)dihydrochloride (AAPH) is used as initiator, methacrylic acid (MAA) as a monomer, ethylene glycol dimethacrylate (EDMA) as a cross-linker, ammonium chloride (NH4Cl) as a template and 30% of ethanol in water as a solvent. The sensing method consists of an intensity based scheme. The response to different concentrations of ammonium solutions in water has been evaluated at room temperature. Solutions with (0 - 0.6) M concentration, with the corresponding refractive indexes varying between 1.3325 - 1.3387, at 25°C were used. The response of the fiber with the original cladding, and after cladding removal has been monitored and compared to the response given by the developed sensor. The response is very fast, less than 1 minute and reversible, which allows the continuum use of the sensor. Further developments are focused in optimization of MIP grafting procedure and sensor performance, in order to increase sensitivity.
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Zhang, Pengfei; Li, Mingtao; Jiang, Xueguang; ...
2015-11-02
Polymerized ionic networks (PINs) with six ion pairs per repeating unit are synthesized by nucleophilic-substitution-mediated polymerization or radical polymerization of monomers bearing six 1-vinylimidazolium cations. PIN-based solid-like electrolytes show good ionic conductivities (up to 5.32 × 10 -3 S cm -1 at 22 °C), wide electrochemical stability windows (up to 5.6 V), and good interfacial compatibility with the electrodes.
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Pawar, Amol Ashok; Halivni, Shira; Waiskopf, Nir; Ben-Shahar, Yuval; Soreni-Harari, Michal; Bergbreiter, Sarah; Banin, Uri; Magdassi, Shlomo
2017-07-12
Additive manufacturing processes enable fabrication of complex and functional three-dimensional (3D) objects ranging from engine parts to artificial organs. Photopolymerization, which is the most versatile technology enabling such processes through 3D printing, utilizes photoinitiators that break into radicals upon light absorption. We report on a new family of photoinitiators for 3D printing based on hybrid semiconductor-metal nanoparticles. Unlike conventional photoinitiators that are consumed upon irradiation, these particles form radicals through a photocatalytic process. Light absorption by the semiconductor nanorod is followed by charge separation and electron transfer to the metal tip, enabling redox reactions to form radicals in aerobic conditions. In particular, we demonstrate their use in 3D printing in water, where they simultaneously form hydroxyl radicals for the polymerization and consume dissolved oxygen that is a known inhibitor. We also demonstrate their potential for two-photon polymerization due to their giant two-photon absorption cross section.
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Squarylium-triazine dyad as a highly sensitive photoradical generator for red light.
Kawamura, Koichi; Schmitt, Julien; Barnet, Maxime; Salmi, Hanene; Ley, Christian; Allonas, Xavier
2013-09-16
New dyads, based on squarylium dye and substituted-triazine, were synthesized that exhibit an intramolecular photodissociative electron-transfer reaction. The compounds were used as a red-light photoradical generator. The photochemical activity of the dyad was compared to the corresponding unlinked systems (S+T) by determining the rate constant of electron transfer. The efficiency of the radical generation from the dyad compared to the unlinked system was demonstrated by measuring the maximum rate of free radical polymerization of acrylates in film. An excellent relationship between the rate of electron transfer and the rate of polymerization was found, evidencing the interest of this new approach to efficiently produce radicals under red light. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Lin, Ching Yeh; Coote, Michelle L; Gennaro, Armando; Matyjaszewski, Krzysztof
2008-09-24
High-level ab initio molecular orbital calculations are used to study the thermodynamics and electrochemistry relevant to the mechanism of atom transfer radical polymerization (ATRP). Homolytic bond dissociation energies (BDEs) and standard reduction potentials (SRPs) are reported for a series of alkyl halides (R-X; R = CH 2CN, CH(CH 3)CN, C(CH 3) 2CN, CH 2COOC 2H 5, CH(CH 3)COOCH 3, C(CH 3) 2COOCH 3, C(CH 3) 2COOC 2H 5, CH 2Ph, CH(CH 3)Ph, CH(CH 3)Cl, CH(CH 3)OCOCH 3, CH(Ph)COOCH 3, SO 2Ph, Ph; X = Cl, Br, I) both in the gas phase and in two common organic solvents, acetonitrile and dimethylformamide. The SRPs of the corresponding alkyl radicals, R (*), are also examined. The computational results are in a very good agreement with the experimental data. For all alkyl halides examined, it is found that, in the solution phase, one-electron reduction results in the fragmentation of the R-X bond to the corresponding alkyl radical and halide anion; hence it may be concluded that a hypothetical outer-sphere electron transfer (OSET) in ATRP should occur via concerted dissociative electron transfer rather than a two-step process with radical anion intermediates. Both the homolytic and heterolytic reactions are favored by electron-withdrawing substituents and/or those that stabilize the product alkyl radical, which explains why monomers such as acrylonitrile and styrene require less active ATRP catalysts than vinyl chloride and vinyl acetate. The rate constant of the hypothetical OSET reaction between bromoacetonitrile and Cu (I)/TPMA complex was estimated using Marcus theory for the electron-transfer processes. The estimated rate constant k OSET = approximately 10 (-11) M (-1) s (-1) is significantly smaller than the experimentally measured activation rate constant ( k ISET = approximately 82 M (-1) s (-1) at 25 degrees C in acetonitrile) for the concerted atom transfer mechanism (inner-sphere electron transfer, ISET), implying that the ISET mechanism is preferred. For monomers bearing electron-withdrawing groups, the one-electron reduction of the propagating alkyl radical to the carbanion is thermodynamically and kinetically favored over the one-electron reduction of the corresponding alkyl halide unless the monomer bears strong radical-stabilizing groups. Thus, for monomers such as acrylates, catalysts favoring ISET over OSET are required in order to avoid chain-breaking side reactions.
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Bossi, A; Whitcombe, M J; Uludag, Y; Fowler, S; Chianella, I; Subrahmanyam, S; Sanchez, I; Piletsky, S A
2010-05-15
A "grafting from" approach has been used for controlled deposition of cross-linked polymers by living radical polymerisation. Borosilicate glass was modified with N,N-diethylaminodithiocarbamoylpropyl(trimethoxy)silane, in order to confine the iniferter reactive groups solely at its surface, then placed in solution with monomers and cross-linker. The polymerisation was initiated by UV irradiation. Formation of the cross-linked polymers was studied in terms of time course of the reaction, type of monomers incorporated and influence of oxygen. Grafted surfaces were characterised by AFM, FT-IR, ellipsometry and contact angle measurements. The ability to control the grafted layer improved dramatically when the chain terminator agent, N,N-N',N'-tetraethyl thiuram disulphide (TED) was added. Upon irradiation TED increases the concentration of passive capping radicals and decreases the possibility of recombination of active macro-radicals, thus prolonging their lifetime. In the absence of TED the thickness of produced coatings was below 10 nm. TED added at different concentrations assisted in the formation of grafted layers of 10-130 nm thickness. Iniferter chemistry in the presence of TED can be used for growing nanometre-scale polymer layers on solid supports. It constitutes a robust general platform for controlled grafting and offer a general solution to address the needs of surface derivatisation in sensors technology. 2010 Elsevier B.V. All rights reserved.
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Modeling the chemistry of plasma polymerization using mass spectrometry.
Ihrig, D F; Stockhaus, J; Scheide, F; Winkelhake, Oliver; Streuber, Oliver
2003-04-01
The goal of the project is a solvent free painting shop. The environmental technologies laboratory is developing processes of plasma etching and polymerization. Polymerized thin films are first-order corrosion protection and primer for painting. Using pure acetylene we get very nice thin films which were not bonded very well. By using air as bulk gas it is possible to polymerize, in an acetylene plasma, well bonded thin films which are stable first-order corrosion protections and good primers. UV/Vis spectroscopy shows nitrogen oxide radicals in the emission spectra of pure nitrogen and air. But nitrogen oxide is fully suppressed in the presence of acetylene. IR spectroscopy shows only C=O, CH(2) and CH(3) groups but no nitrogen species. With the aid of UV/Vis spectra and the chemistry of ozone formation it is possible to define reactive traps and steps, molecule depletion and processes of proton scavenging and proton loss. Using a numerical model it is possible to evaluate these processes and to calculate theoretical mass spectra. Adjustment of theoretical mass spectra to real measurements leads to specific channels of polymerization which are driven by radicals especially the acetyl radical. The estimated theoretical mass spectra show the specific channels of these chemical processes. It is possible to quantify these channels. This quantification represents the mass flow through this chemical system. With respect to these chemical processes it is possible to have an idea of pollutant production processes.
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DNA immobilization and detection on cellulose paper using a surface grown cationic polymer via ATRP.
Aied, Ahmed; Zheng, Yu; Pandit, Abhay; Wang, Wenxin
2012-02-01
Cationic polymers with various structures have been widely investigated in the areas of medical diagnostics and molecular biology because of their unique binding properties and capability to interact with biological molecules in complex biological environments. In this work, we report the grafting of a linear cationic polymer from an atom transfer radical polymerization (ATRP) initiator bound to cellulose paper surface. We show successful binding of ATRP initiator onto cellulose paper and grafting of polymer chains from the immobilized initiator with ATRP. The cellulose paper grafted polymer was used in combination with PicoGreen (PG) to demonstrate detection of nucleic acids in the nanogram range in homogeneous solution and in a biological sample (serum). The results showed specific identification of hybridized DNA after addition of PG in both solutions.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Oakdale, James S.; Ye, Jianchao; Smith, William L.
Here, two photon polymerization (TPP) is a precise, reliable, and increasingly popular technique for rapid prototyping of micro-scale parts with sub-micron resolution. The materials of choice underlying this process are predominately acrylic resins cross-linked via free-radical polymerization. Due to the nature of the printing process, the derived parts are only partially cured and the corresponding mechanical properties, i.e. modulus and ultimate strength, are lower than if the material were cross-linked to the maximum extent. Herein, post-print curing via UV-driven radical generation, is demonstrated to increase the overall degree of cross-linking of low density, TPP-derived structures.
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Oakdale, James S.; Ye, Jianchao; Smith, William L.; ...
2016-11-28
Here, two photon polymerization (TPP) is a precise, reliable, and increasingly popular technique for rapid prototyping of micro-scale parts with sub-micron resolution. The materials of choice underlying this process are predominately acrylic resins cross-linked via free-radical polymerization. Due to the nature of the printing process, the derived parts are only partially cured and the corresponding mechanical properties, i.e. modulus and ultimate strength, are lower than if the material were cross-linked to the maximum extent. Herein, post-print curing via UV-driven radical generation, is demonstrated to increase the overall degree of cross-linking of low density, TPP-derived structures.
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Bencherif, Sidi A.; Siegwart, Daniel J.; Srinivasan, Abiraman; Horkay, Ferenc; Hollinger, Jeffrey O.; Washburn, Newell R.; Matyjaszewski, Krzysztof
2012-01-01
A new method to prepare nanostructured hybrid hydrogels by incorporating well-defined poly(oligo (ethylene oxide) monomethyl ether methacrylate) (POEO300MA) nanogels of sizes 110–120 nm into a larger three-dimensional (3D) matrix was developed for drug delivery scaffolds for tissue engineering applications. Rhodamine B isothiocyanate-labeled dextran (RITC-Dx) or fluorescein isothiocyanate-labeled dextran (FITC-Dx)-loaded POEO300MA nanogels with pendant hydroxyl groups were prepared by activators generated electron transfer atom transfer radical polymerization (AGET ATRP) in cyclohexane inverse miniemulsion. Hydroxyl-containing nanogels were functionalized with methacrylated groups to generate photoreactive nanospheres. 1H NMR spectroscopy confirmed that polymerizable nanogels were successfully incorporated covalently into 3D hyaluronic acid-glycidyl methacrylate (HAGM) hydrogels after free radical photo-polymerization (FRP). The introduction of disulfide moieties into the polymerizable groups resulted in a controlled release of nanogels from cross-linked HAGM hydrogels under a reducing environment. The effect of gel hybridization on the macroscopic properties (swelling and mechanics) was studied. It is shown that swelling and nanogel content are independent of scaffold mechanics. In-vitro assays showed the nanostructured hybrid hydrogels were cytocompatible and the GRGDS (Gly–Arg–Gly–Asp–Ser) contained in the nanogel structure promoted cell–substrate interactions within 4 days of incubation. These nanostructured hydrogels have potential as an artificial extracellular matrix (ECM) impermeable to low molecular weight biomolecules and with controlled pharmaceutical release capability. Moreover, the nanogels can control drug or biomolecule delivery, while hyaluronic acid based-hydrogels can act as a macroscopic scaffold for tissue regeneration and regulator for nanogel release. PMID:19592087
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Kim, Su Jin; Joo, Jeong Chan; Song, Bong Keun; Yoo, Young Je; Kim, Yong Hwan
2015-04-01
Peroxidases have great potential as industrial biocatalysts. In particular, the oxidative polymerization of phenolic compounds catalyzed by peroxidases has been extensively examined because of the advantage of this method over other conventional chemical methods. However, the industrial application of peroxidases is often limited because of their rapid inactivation by phenoxyl radicals during oxidative polymerization. In this work, we report a novel protein engineering approach to improve the radical stability of horseradish peroxidase isozyme C (HRPC). Phenylalanine residues that are vulnerable to modification by the phenoxyl radicals were identified using mass spectrometry analysis. UV-Vis and CD spectra showed that radical coupling did not change the secondary structure or the active site of HRPC. Four phenylalanine (Phe) residues (F68, F142, F143, and F179) were each mutated to alanine residues to generate single mutants to examine the role of these sites in radical coupling. Despite marginal improvement of radical stability, each single mutant still exhibited rapid radical inactivation. To further reduce inactivation by radical coupling, the four substitution mutations were combined in F68A/F142A/F143A/F179A. This mutant demonstrated dramatic enhancement of radical stability by retaining 41% of its initial activity compared to the wild-type, which was completely inactivated. Structure and sequence alignment revealed that radical-vulnerable Phe residues of HPRC are conserved in homologous peroxidases, which showed the same rapid inactivation tendency as HRPC. Based on our site-directed mutagenesis and biochemical characterization, we have shown that engineering radical-vulnerable residues to eliminate multiple radical coupling can be a good strategy to improve the stability of peroxidases against radical attack. © 2014 Wiley Periodicals, Inc.
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Lalevée, Jacques; Mokbel, Haifaa; Fouassier, Jean-Pierre
2015-04-20
Photoinitiators (PI) or photoinitiating systems (PIS) usable in light induced cationic polymerization (CP) and free radical promoted cationic polymerization (FRPCP) reactions (more specifically for cationic ring opening polymerization (ROP)) together with the involved mechanisms are briefly reviewed. The recent developments of novel two- and three-component PISs for CP and FRPCP upon exposure to low intensity blue to red lights is emphasized in details. Examples of such reactions under various experimental conditions are provided.
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Reeves, Jennifer A; Allegrezza, Michael L; Konkolewicz, Dominik
2017-07-01
Vinyl ketone polymers, including phenyl vinyl ketone (PVK), are an important class of polymers due to their ability to degrade upon irradiation with ultraviolet light which makes them useful for a variety of applications. However, traditional radical methods for synthesizing PVK polymers give rise to poor control or are unable to produce block copolymers. This work uses reversible addition-fragmentation chain transfer polymerization (RAFT) and photochemistry to polymerize PVK. When visible blue radiation of 440 ± 10 nm is used as the light source for the photopolymerization, rapid polymerization and well-defined polymers are created. This RAFT method uses PVK as both monomer and radical initiator, exciting the PVK mono-mer by 440 ± 10 nm irradiation to avoid the use of an additional radical initiator. Once the poly-mer is synthesized, it is stable against degradation by blue light (440 ± 10 nm), but upon exposure to ultraviolet (UV) radiation (310 ± 20 nm) significant decrease in molecular weight is observed. The degradation is observed for all poly(PVK) materials synthesized. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Poly(meth)acrylates obtained by cascade reaction.
Popescu, Dragos; Keul, Helmut; Moeller, Martin
2011-04-04
Preparation, purification, and stabilization of functional (meth)acrylates with a high dipole moment are complex, laborious, and expensive processes. In order to avoid purification and stabilization of the highly reactive functional monomers, a concept of cascade reactions was developed comprising enzymatic monomer synthesis and radical polymerization. Transacylation of methyl acrylate (MA) and methyl methacrylate (MMA) with different functional alcohols, diols, and triols (1,2,6-hexanetriol and glycerol) in the presence of Novozyme 435 led to functional (meth)acrylates. After the removal of the enzyme by means of filtration, removal of excess (meth)acrylate and/or addition of a new monomer, e.g., 2-hydroxyethyl (meth)acrylate the (co)polymerization via free radical (FRP) or nitroxide mediated radical polymerization (NMP) resulted in poly[(meth)acrylate]s with predefined functionalities. Hydrophilic, hydrophobic as well as ionic repeating units were assembled within the copolymer. The transacylation of MA and MMA with diols and triols carried out under mild conditions is an easy and rapid process and is suitable for the preparation of sensitive monomers. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Wang, Rong; Zhang, Jie; Wan, Xinhua
2015-04-01
Helical vinyl aromatic polymers are emerging as interesting chiral materials due to their dynamic tailorability, synthetic simplicity, and outstanding chemical and physical stabilities. This Personal Account discusses long-range chirality transfer in the radical polymerization of vinylterphenyl monomers and tunable stereomutation of the resultant polymers. It begins with a general introduction to the design, synthesis, and characterization of helical poly{(+)-2,5-bis[4'-((S)-2-methylbutyloxy)phenyl]styrene}, the first one of this series of polymers. Then, long-range chirality transfer during radical polymerization of terphenyl-based vinyl monomers is explained. After that, the chiroptical property control of the resultant polymers by means of the transition from kinetically controlled conformation to thermodynamically controlled conformation and external stimulus is described. This Personal Account concludes by discussing the advantages and disadvantages of the strategy of using vinylterphenyls to obtain optically active helical polymers and providing a short outlook, especially emphasizing the importance of tacticity on the chiroptical properties of polymers. Copyright © 2015 The Chemical Society of Japan and Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
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[Fundamentals of plasma chemistry and its application to drug engineering].
Kuzuya, M
1996-04-01
In this review, our novel research works in both low temperature plasma chemistry and solid state plasma chemistry were described. As for low temperature plasma, the ESR study on plasma-induced radicals of several selected conventional polymers was shown including the detailed analyses of the radical structure and the mechanism by which the radicals were formed on typical degradable methacrylic polymers and cross-linkable polystyrene. One of the pharmaceutical applications of the plasma processing for drug delivery system (DDS) was also described, which includes the preparations of double-compressed tablet consisting of drugs as a core material and various types of polymers as a wall material followed by plasma-irradiation on such a tablet. As for solid state plasma, the detailed reaction mechanism of solid state mechanochemical polymerization was shown including the solid state single electron transfer and the special feature of the resulting polymers. The structural criteria for polymerizable monomer derived from the quantum chemical considerations were also established. Based on the above findings, we synthesized various polymeric prodrugs by mechanochemical polymerization and studied the nature of hydrolyses (drug release).
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Investigation of Solution Polymerizations in Microgravity and 1 G
NASA Technical Reports Server (NTRS)
Kennedy, Alvin P.
1998-01-01
The in-situ dielectric spectra for the solution polymerization of polydiacetylene has been successfully measured. The results show a distinct difference between the response for the bulk solution and surface polymerization. It also shows a low frequency peak in the dissipation factor which is present in both the bulk and surface polymerizations. These features may prove to be significant indicators for important polymerization processes. Future studies will investigate the mechanisms responsible for these dielectric responses. This technique will eventually be used to monitor microgravity polymerizations and provide in-situ data on how microgravity affects solution polymerization.
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Improved hybrid solar cells via in situ UV-polymerization.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Tepavcevic, S.; Darling, S. B.; Dimitrijevic, N. M.
One approach for making inexpensive inorganic-organic hybrid photovoltaic (PV) cells is to fill highly ordered TiO{sub 2} nanotube (NT) arrays with solid organic hole conductors such as conjugated polymers. Here, a new in situ UV polymerization method for growing polythiophene (UV-PT) inside TiO{sub 2} NTs is presented and compared to the conventional approach of infiltrating NTs with pre-synthesized polymer. A nanotubular TiO{sub 2} substrate is immersed in a 2,5-diiodothiophene (DIT) monomer precursor solution and then irradiated with UV light. The selective UV photodissociation of the C-I bond produces monomer radicals with intact {pi}-ring structure that further produce longer oligothiophene/PT molecules.more » Complete photoluminescence quenching upon UV irradiation suggests coupling between radicals created from DIT and at the TiO{sub 2} surface via a charge transfer complex. Coupling with the TiO{sub 2} surface improves UV-PT crystallinity and {pi}-{pi} stacking; flat photocurrent values show that charge recombination during hole transport through the polymer is negligible. A non-ideal, backside-illuminated setup under illumination of 620-nm light yields a photocurrent density of {approx} 5 {micro}A cm{sup -2} - surprisingly much stronger than with comparable devices fabricated with polymer synthesized ex situ. Since in this backside architecture setup we illuminate the cell through the Ag top electrode, there is a possibility for Ag plasmon-enhanced solar energy conversion. By using this simple in situ UV polymerization method that couples the conjugated polymer to the TiO{sub 2} surface, the absorption of sunlight can be improved and the charge carrier mobility of the photoactive layer can be enhanced.« less
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Polymeric Coatings for Combating Biocorrosion
NASA Astrophysics Data System (ADS)
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.
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Huang, Chih-Feng; Aimi, Junko; Lai, Kuan-Yu
2017-02-01
Star copolymers are known to phase separate on the nanoscale, providing useful self-assembled morphologies. In this study, the authors investigate synthesis and assembly behavior of miktoarm star (μ-star) copolymers. The authors employ a new strategy for the synthesis of unprecedented μ-star copolymers presenting poly(N-octyl benzamide) (PBA) and poly(ε-caprolactone) (PCL) arms: a combination of chain-growth condensation polymerization, styrenics-assisted atom transfer radical coupling, and ring-opening polymerization. Gel permeation chromatography, mass-analyzed laser desorption/ionization mass spectrometry, and 1 H NMR spectroscopy reveal the successful synthesis of a well-defined (PBA 11 ) 2 -(PCL 15 ) 4 μ-star copolymer (M n ,NMR ≈ 12 620; Đ = 1.22). Preliminary examination of the PBA 2 PCL 4 μ-star copolymer reveals assembled nanofibers having a uniform diameter of ≈20 nm. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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NASA Astrophysics Data System (ADS)
Niu, Jia; Lunn, David J.; Pusuluri, Anusha; Yoo, Justin I.; O'Malley, Michelle A.; Mitragotri, Samir; Soh, H. Tom; Hawker, Craig J.
2017-06-01
The capability to graft synthetic polymers onto the surfaces of live cells offers the potential to manipulate and control their phenotype and underlying cellular processes. Conventional grafting-to strategies for conjugating preformed polymers to cell surfaces are limited by low polymer grafting efficiency. Here we report an alternative grafting-from strategy for directly engineering the surfaces of live yeast and mammalian cells through cell surface-initiated controlled radical polymerization. By developing cytocompatible PET-RAFT (photoinduced electron transfer-reversible addition-fragmentation chain-transfer polymerization), synthetic polymers with narrow polydispersity (Mw/Mn < 1.3) could be obtained at room temperature in 5 minutes. This polymerization strategy enables chain growth to be initiated directly from chain-transfer agents anchored on the surface of live cells using either covalent attachment or non-covalent insertion, while maintaining high cell viability. Compared with conventional grafting-to approaches, these methods significantly improve the efficiency of grafting polymer chains and enable the active manipulation of cellular phenotypes.
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Initiator system in holographic photopolymer materials
NASA Astrophysics Data System (ADS)
Ortuño, M.; Fernández, E.; Fuentes, R.; Gallego, S.; Márquez, A.
2010-05-01
The photopolymers with a hydrophilic matrix as poly(vinyl alcohol), PVA, are versatile holographic recording materials in hologram recording experiments. They use water as solvent and they can be made in layers with several thickness. One of the photopolymers more used is composed of acrylamide as polymerizable monomer, PVA and water as binder. The pair: triethanolamine, TEA, and the dye yellowish eosin, YE, is widely used as initiator system due to its high sensitivity and efficiency. TEA is the radical initiator more used with dyes derived from fluorescein as YE because they can generate a radical by redox reaction under dye excitation by light. The dye is bleached in this process because is decomposed in the photoinitiation reaction. The ethylenediaminetetraacetic acid EDTA has a molecular structure very similar to TEA and therefore could replace it in this kind of photopolymers. The 4,4' azo-bis-(4-cyanopentanoic acid), ACPA, is a radical initiator that is soluble in water and usually used in polymerizations in solution with thermal initiation. In this work, we use EDTA and ACPA in order to check their properties as radical initiator in the photochemical reaction that takes place inside the photopolymer while a hologram is being recorded. We will compare the results obtained with those derived from TEA and will evaluate the possibilities for these substances.
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FROM ATOM TRANSFER RADICAL ADDITION TO ATOM TRANSFER RADICAL POLYMERIZATION. (R829580)
The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Berstis, Laura; Elder, Thomas; Crowley, Michael
The recently discovered lignin composed of caffeoyl alcohol monolignols or C-lignin is particularly intriguing given its homogeneous, linear polymeric structure and exclusive benzodioxane linkage between monomers. By virtue of this simplified chemistry, the potential emerges for improved valorization strategies with C-lignin relative to other natural heterogeneous lignins. To better understand caffeoyl alcohol polymers, we characterize the thermodynamics of the radical recombination dimerization reactions forming the benzodioxane linkage and the bond dissociation into radical monolignol products. These properties are also predicted for the cross-coupling of caffeoyl alcohol with the natural monolignols, coniferyl alcohol, sinapyl alcohol, and p-coumaryl alcohol, in anticipation of polymers potentially enabled by genetic modification. The average BDEs for the C-lignin benzodioxanemore » $$\\alpha$$- and β-bonds are 56.5 and 63.4 kcal/mol, respectively, with similar enthalpies for heterodimers. The BDE of the $$\\alpha$$-bond within the benzodioxane linkage is consistently greater than that of the β-bond in all dimers of each stereochemical arrangement, explained by the ability the $$\\alpha$$-carbon radical generated to delocalize onto the adjacent phenyl ring. Relative thermodynamics of the heterodimers demonstrates that the substituents on the phenyl ring directly neighboring the bond coupling the monolignols more strongly impact the dimer bond strengths and product stability, compared to the substituents present on the terminal phenyl ring. Enthalpy comparisons furthermore demonstrate that the erythro stereochemical configurations of the benzodioxane bond are slightly less thermodynamically stable than the threo configurations. The overall differences in strength of bonds and reaction enthalpies between stereoisomers are generally found to be insignificant, supporting that postcoupling rearomatization is under kinetic control. Projecting the lowest-energy stereoisomer internal coordinates to longer polymer C-lignin strands highlights how significantly the stereochemical outcomes in polymerization may impact the macromolecular structure and in turn material and chemical properties. Lastly, through these comparisons of geometry, bond strengths, and reaction enthalpies, we shed light on the distinctive properties of C-lignin's radical recombination and decomposition chemistry, and its potential as a natural lignin solution for biorefinery feedstocks and unique materials science applications.« less
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Berstis, Laura; Elder, Thomas; Crowley, Michael; ...
2016-05-17
The recently discovered lignin composed of caffeoyl alcohol monolignols or C-lignin is particularly intriguing given its homogeneous, linear polymeric structure and exclusive benzodioxane linkage between monomers. By virtue of this simplified chemistry, the potential emerges for improved valorization strategies with C-lignin relative to other natural heterogeneous lignins. To better understand caffeoyl alcohol polymers, we characterize the thermodynamics of the radical recombination dimerization reactions forming the benzodioxane linkage and the bond dissociation into radical monolignol products. These properties are also predicted for the cross-coupling of caffeoyl alcohol with the natural monolignols, coniferyl alcohol, sinapyl alcohol, and p-coumaryl alcohol, in anticipation of polymers potentially enabled by genetic modification. The average BDEs for the C-lignin benzodioxanemore » $$\\alpha$$- and β-bonds are 56.5 and 63.4 kcal/mol, respectively, with similar enthalpies for heterodimers. The BDE of the $$\\alpha$$-bond within the benzodioxane linkage is consistently greater than that of the β-bond in all dimers of each stereochemical arrangement, explained by the ability the $$\\alpha$$-carbon radical generated to delocalize onto the adjacent phenyl ring. Relative thermodynamics of the heterodimers demonstrates that the substituents on the phenyl ring directly neighboring the bond coupling the monolignols more strongly impact the dimer bond strengths and product stability, compared to the substituents present on the terminal phenyl ring. Enthalpy comparisons furthermore demonstrate that the erythro stereochemical configurations of the benzodioxane bond are slightly less thermodynamically stable than the threo configurations. The overall differences in strength of bonds and reaction enthalpies between stereoisomers are generally found to be insignificant, supporting that postcoupling rearomatization is under kinetic control. Projecting the lowest-energy stereoisomer internal coordinates to longer polymer C-lignin strands highlights how significantly the stereochemical outcomes in polymerization may impact the macromolecular structure and in turn material and chemical properties. Lastly, through these comparisons of geometry, bond strengths, and reaction enthalpies, we shed light on the distinctive properties of C-lignin's radical recombination and decomposition chemistry, and its potential as a natural lignin solution for biorefinery feedstocks and unique materials science applications.« less
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Sun, Yang; Xu, Fei; Gong, Bolin
2011-09-01
A novel stationary phase was synthesized for chiral ligand-exchange chromatography via atom transfer radical polymerization (ATRP). Glycidyl methacrylate (GMA) was grafted onto the surface of the silica by ATRP using bromoisobutyryl bromide as an initiator, and the organic metal compound formed in the CuCl/2,2'-bipyridine(Bpy) system as a catalyst at room temperature. The chiral stationary phase was then synthesized by grafting L-phenylalanine on the surface of the silica. The stationary phase was characterized by means of elementary analysis and evaluated in detail to determine its separability. The amount of L-phenylalanine on the surface of silica was calculated to be 4.32 mg/m2. The results showed that the good enantioseparations of some DL-amino acids were obtained using ligand-exchange chromatography on the synthesized chiral stationary phase (50 degrees C) with 0.05 mol/L KH2PO4 and 0.1 mmol/L Cu(Ac)2 solution (pH 4.5) as the mobile phase at a flow rate of 1.0 mL/min and a wavelength of 223 nm. The influences of the mobile phase pH, concentration of Cu (II), and temperature of column on the resolution of DL-amino acids by ligand-exchange chromatography were investigated. The results showed that these conditions could affect the resolution of racemates. Compared with the column prepared by radical method using L-phenylalanine directly bonded onto the surface of the silica, the synthesized stationary phase showed a better separation ability, and the DL-aspartic acids and DL-asparagines could be separated at baseline.
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Free-Radical Polymerization Using the Rotating-Sector Method.
ERIC Educational Resources Information Center
Moss, Stephen J.
1982-01-01
Discusses principles of a particular approach in teaching elementary kinetics of polymerization. Although the treatment discussed is more difficult for students to grasp, problems may be reduced using a computer program. The program, written in Applesoft Basic, is available from the author together with sample output. (JN)
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Onoda, Mitsuyoshi
2014-10-01
Conductive polymers are a strong contender for making electronic circuits. The growth pattern in conductive polymer synthesis by the electrolysis polymerization method was examined. The growth pattern is deeply related to the coupling reaction of the radical cation and the deprotonation reaction following it and changes suddenly depending on the kind and concentration of the supporting electrolyte and the solvent used. That is, when the electrophilic substitution coupling reaction becomes predominant, the three-dimensional growth form is observed, and when the radical coupling reaction becomes predominant, the two-dimensional growth morphology is observed. In addition, the growth pattern can be comparatively easily controlled by changing the value of the polymerization constant current, and it is considered that the indicator and development for biocircuit research with neuron-type devices made of conjugated polymers was obtained.
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RAFT polymerization and some of its applications.
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.
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Kuang, Jinghao; Messersmith, Phillip B.
2012-01-01
We report a universal method for the surface-initated polymerization (SIP) of a antifouling polymer brush on various classes of surfaces, including noble metals, metal oxides and inert polymers. Inspired by the versatility of mussel adhesive proteins, we synthesized a novel bifunctional tripeptide bromide (BrYKY) which combines an atom transfer radical polymerization (ATRP) initiating alkyl bromide with l-3,4-dihydroxyphenylalanine (DOPA) and lysine. Simple dip-coating of substrates with variable wetting properties and compositions, including Teflon®, in a BrYKY solution at pH 8.5 led to formation of a thin film of cross-linked BrYKY. Subsequently, we showed that the BrYKY layer initiated the ATRP of a zwitterionic monomer, sulfobetaine methacrylate (SBMA) on all substrates, resulting in high density antifouling pSBMA brushes. Both BrYKY deposition and pSBMA grafting were unambiguously confirmed by ellipsometry, X-ray photoelectron spectroscopy and goniometry. All substrates that were coated with BrYKY/pSBMA dramatically reduced bacterial adhesion for 24 h and also resisted mammalian cell adhesion for at least 4 months, demonstrating the long-term stability of the BrYKY anchoring and antifouling properties of pSBMA. The use of BrYKY as a primer and polymerization initiator has the potential to be widely employed in surface grafted polymer brush modifications for biomedical and other applications. PMID:22506651
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Kermagoret, Anthony; Chau, Ngoc Do Quyen; Grignard, Bruno; Cordella, Daniela; Debuigne, Antoine; Jérôme, Christine; Detrembleur, Christophe
2016-03-01
Cobalt-mediated radical polymerization (CMRP) of vinyl acetate (VAc) is successfully achieved in supercritical carbon dioxide (scCO2). CMRP of VAc is conducted using an alkyl-cobalt(III) adduct that is soluble in scCO2. Kinetics studies coupled to visual observations of the polymerization medium highlight that the melt viscosity and PVAc molar mass (Mn) are key parameters that affect the CMRP in scCO2. It is noticed that CMRP is controlled for Mn up to 10 000 g mol(-1), but loss of control is progressively observed for higher molar masses when PVAc precipitates in the polymerization medium. Low molar mass PVAc macroinitiator, prepared by CMRP in scCO2, is then successfully used to initiate the acrylonitrile polymerization. PVAc-b-PAN block copolymer is collected as a free flowing powder at the end of the process although the dispersity of the copolymer increases with the reaction time. Although optimization is required to decrease the dispersity of the polymer formed, this CMRP process opens new perspectives for macromolecular engineering in scCO2 without the utilization of fluorinated comonomers or organic solvents. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Ji, Weihang; Koepsel, Richard R; Murata, Hironobu; Zadan, Sawyer; Campbell, Alan S; Russell, Alan J
2017-08-14
Antibacterial polymers are potentially powerful biocides that can destroy bacteria on contact. Debate in the literature has surrounded the mechanism of action of polymeric biocides and the propensity for bacteria to develop resistance to them. There has been particular interest in whether surfaces with covalently coupled polymeric biocides have the same mechanism of action and resistance profile as similar soluble polymeric biocides. We designed and synthesized a series of poly(quaternary ammonium) polymers, with tailorable molecular structures and architectures, to engineer their antibacterial specificity and their ability to delay the development of bacterial resistance. These linear poly(quaternary ammonium) homopolymers and block copolymers, generated using atom transfer radical polymerization, had structure-dependent antibacterial specificity toward Gram positive and negative bacterial species. When single block copolymers contained two polymer segments of differing antibacterial specificity, the polymer combined the specificities of its two components. Nanoparticulate human serum albumin-poly(quaternary ammonium) conjugates of these same polymers, synthesized via "grafting from" atom transfer radical polymerization, were strongly biocidal and also exhibited a marked decrease in the rate of bacterial resistance development relative to linear polymers. These protein-biocide conjugates mimicked the behavior of surface-presented polycationic biocides rather than their nonproteinaceous counterparts.
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Huang, Long; Liu, Meiying; Mao, Liucheng; Huang, Qiang; Huang, Hongye; Wan, Qing; Tian, Jianwen; Wen, Yuanqing; Zhang, Xiaoyong; Wei, Yen
2017-12-01
As a new type of mesoporous silica materials with large pore diameter (pore size between 2 and 50nm) and high specific surface areas, SBA-15 has been widely explored for different applications especially in the biomedical fields. The surface modification of SBA-15 with functional polymers has demonstrated to be an effective way for improving its properties and performance. In this work, we reported the preparation of PEGylated SBA-15 polymer composites through surface-initiated chain transfer free radical polymerization for the first time. The thiol group was first introduced on SBA-15 via co-condensation with γ-mercaptopropyltrimethoxysilane (MPTS), that were utilized to initiate the chain transfer free radical polymerization using poly(ethylene glycol) methyl ether methacrylate (PEGMA) and itaconic acid (IA) as the monomers. The successful modification of SBA-15 with poly(PEGMA-co-IA) copolymers was evidenced by a series of characterization techniques, including 1 H NMR, FT-IR, TGA and XPS. The final SBA-15-SH- poly(PEGMA-co-IA) composites display well water dispersity and high loading capability towards cisplatin (CDDP) owing to the introduction of hydrophilic PEGMA and carboxyl groups. Furthermore, the CDDP could be released from SBA-15-SH-poly(PEGMA-co-IA)-CDDP complexes in a pH dependent behavior, suggesting the potential controlled drug delivery of SBA-15-SH-poly(PEGMA-co-IA). More importantly, the strategy should be also useful for fabrication of many other functional materials for biomedical applications owing to the advantages of SBA-15 and well monomer adoptability of chain transfer free radical polymerization. Copyright © 2017 Elsevier B.V. All rights reserved.
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Preparation and assessment of carboxylate polyelectrolyte as draw solute for forward osmosis.
Cui, Hongtao; Zhang, Hanmin; Jiang, Wei; Yang, Fenglin
2018-02-01
Reverse draw solute diffusion not only reduces the water flux in forward osmosis (FO), but also contaminates the feed solution and eventually increases the regeneration cost of draw solution. In the present study, a new polyelectrolyte was synthesized as FO draw solute to address this problem. Acrylic acid and sodium p-styrenesulfonate monomers with hydrophilic group were used to fabricate carboxylate polyelectrolyte through free radical polymerization reaction. Results demonstrated that the osmotic pressure of carboxylate polyelectrolyte solution had a good linear relationship with concentration, and the viscosity of 0.18 g/mL solution was less than 5.4 cP. Active layer facing draw solution produced the initial water flux of 11.77 LMH and active layer facing feed solution yielded the initial water flux of 6.68 LMH when the concentration of draw solution was 0.18 g/mL. The reverse solute flux was around 1 gMH, and specific reverse solute flux of 0.18 g/mL carboxylate polyelectrolyte draw solution was 0.11 g/L which was much lower than that of traditional inorganic salts. Finally, diluted draw solution was regenerated via ultrafiltration, and the recovery efficiency of 94.78% was achieved. So, carboxylate polyelectrolyte can be suitable draw solute for FO.
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NASA Astrophysics Data System (ADS)
Mahajan, Shveta; Koul, Veena; Choudhary, Veena; Shishodia, Gauri; Bharti, Alok C.
2013-01-01
Polymer-SPION hybrids were investigated for receptor-mediated localization in tumour tissue. Superparamagnetic iron oxide nanoparticles (SPIONs) prepared by high-temperature decomposition of iron acetylacetonate were monodisperse (9.27 ± 3.37 nm), with high saturation magnetization of 76.8 emu g-1. Amphiphilic copolymers prepared from methyl methacrylate and PEG methacrylate by atom transfer radical polymerization were conjugated with folic acid (for folate-receptor specificity). The folate-conjugated polymer had a low critical micellar concentration (0.4 mg l-1), indicating stability of the micellar formulation. SPION-polymeric micelle clusters were prepared by desolvation of the SPION dispersion/polymer solution in water. Magnetic resonance imaging of the formulation revealed very good contrast enhancement, with transverse (T2) relaxivity of 260.4 mM-1 s-1. The biological evaluation of the SPION micelles included cellular viability assay (MTT) and uptake in HeLa cells. These studies demonstrated the potential use of these nanoplatforms for imaging and targeting.
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2015-01-01
We report the latent production of free radicals from energy stored in a redox potential through a 2e–/1H+ transfer process, analogous to energy harvesting in photosynthesis, using visible-light organic photoredox catalysis (photocatalysis) of methylene blue chromophore with a sacrificial sterically hindered amine reductant and an onium salt oxidant. This enables light-initiated free-radical polymerization to continue over extended time intervals (hours) in the dark after brief (seconds) low-intensity illumination and beyond the spatial reach of light by diffusion of the metastable leuco-methylene blue photoproduct. The present organic photoredox catalysis system functions via a 2e–/1H+ shuttle mechanism, as opposed to the 1e– transfer process typical of organometallic-based and conventional organic multicomponent photoinitiator formulations. This prevents immediate formation of open-shell (radical) intermediates from the amine upon light absorption and enables the “storage” of light-energy without spontaneous initiation of the polymerization. Latent energy release and radical production are then controlled by the subsequent light-independent reaction (analogous to the Calvin cycle) between leuco-methylene blue and the onium salt oxidant that is responsible for regeneration of the organic methylene blue photocatalyst. This robust approach for photocatalysis-based energy harvesting and extended release in the dark enables temporally controlled redox initiation of polymer syntheses under low-intensity short exposure conditions and permits visible-light-mediated synthesis of polymers at least 1 order of magnitude thicker than achievable with conventional photoinitiated formulations and irradiation regimes. PMID:24786755
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Aguirre-Soto, Alan; Lim, Chern-Hooi; Hwang, Albert T; Musgrave, Charles B; Stansbury, Jeffrey W
2014-05-21
We report the latent production of free radicals from energy stored in a redox potential through a 2e(-)/1H(+) transfer process, analogous to energy harvesting in photosynthesis, using visible-light organic photoredox catalysis (photocatalysis) of methylene blue chromophore with a sacrificial sterically hindered amine reductant and an onium salt oxidant. This enables light-initiated free-radical polymerization to continue over extended time intervals (hours) in the dark after brief (seconds) low-intensity illumination and beyond the spatial reach of light by diffusion of the metastable leuco-methylene blue photoproduct. The present organic photoredox catalysis system functions via a 2e(-)/1H(+) shuttle mechanism, as opposed to the 1e(-) transfer process typical of organometallic-based and conventional organic multicomponent photoinitiator formulations. This prevents immediate formation of open-shell (radical) intermediates from the amine upon light absorption and enables the "storage" of light-energy without spontaneous initiation of the polymerization. Latent energy release and radical production are then controlled by the subsequent light-independent reaction (analogous to the Calvin cycle) between leuco-methylene blue and the onium salt oxidant that is responsible for regeneration of the organic methylene blue photocatalyst. This robust approach for photocatalysis-based energy harvesting and extended release in the dark enables temporally controlled redox initiation of polymer syntheses under low-intensity short exposure conditions and permits visible-light-mediated synthesis of polymers at least 1 order of magnitude thicker than achievable with conventional photoinitiated formulations and irradiation regimes.
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Hrsic, Emin; Keul, Helmut; Möller, Martin
2015-12-01
The preparation of multifunctional polymers and block copolymers by a straightforward one-pot reaction process that combines enzymatic transacylation with light-controlled polymerization is described. Functional methacrylate monomers are synthesized by enzymatic transacylation and used in situ for light-controlled polymerization, leading to multifunctional methacrylate-based polymers with well-defined microstructure. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Advanced Materials by Atom Transfer Radical Polymerization.
Matyjaszewski, Krzysztof
2018-06-01
Atom transfer radical polymerization (ATRP) has been successfully employed for the preparation of various advanced materials with controlled architecture. New catalysts with strongly enhanced activity permit more environmentally benign ATRP procedures using ppm levels of catalyst. Precise control over polymer composition, topology, and incorporation of site specific functionality enables synthesis of well-defined gradient, block, comb copolymers, polymers with (hyper)branched structures including stars, densely grafted molecular brushes or networks, as well as inorganic-organic hybrid materials and bioconjugates. Examples of specific applications of functional materials include thermoplastic elastomers, nanostructured carbons, surfactants, dispersants, functionalized surfaces, and biorelated materials. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Organocatalyzed atom transfer radical polymerization driven by visible light.
Theriot, Jordan C; Lim, Chern-Hooi; Yang, Haishen; Ryan, Matthew D; Musgrave, Charles B; Miyake, Garret M
2016-05-27
Atom transfer radical polymerization (ATRP) has become one of the most implemented methods for polymer synthesis, owing to impressive control over polymer composition and associated properties. However, contamination of the polymer by the metal catalyst remains a major limitation. Organic ATRP photoredox catalysts have been sought to address this difficult challenge but have not achieved the precision performance of metal catalysts. Here, we introduce diaryl dihydrophenazines, identified through computationally directed discovery, as a class of strongly reducing photoredox catalysts. These catalysts achieve high initiator efficiencies through activation by visible light to synthesize polymers with tunable molecular weights and low dispersities. Copyright © 2016, American Association for the Advancement of Science.
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di Lena, Fabio; Matyjaszewski, Krzysztof
2009-11-07
An electrospray ionization mass spectrometer equipped with a quadrupole ion trap as the mass analyzer provided a powerful tool for the investigation of metal ligand affinities of catalysts for atom transfer radical polymerization. It allowed, in particular, (i) the identification, in a library of ligands, of the most stable, and thus active, copper catalysts; (ii) the assessment of the effects of the reaction medium on the relative stabilities of the catalyst complexes; and (iii) the evaluation of the influence of the nature of the ligand on both the complex halogenophilicity and the metal-ligand stabilities in the gas-phase.
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Photo-triggered solvent-free metamorphosis of polymeric materials.
Honda, Satoshi; Toyota, Taro
2017-09-11
Liquefaction and solidification of materials are the most fundamental changes observed during thermal phase transitions, yet the design of organic and polymeric soft materials showing isothermal reversible liquid-nonliquid conversion remains challenging. Here, we demonstrate that solvent-free repeatable molecular architectural transformation between liquid-star and nonliquid-network polymers that relies on cleavage and reformation of a covalent bond in hexaarylbiimidazole. Liquid four-armed star-shaped poly(n-butyl acrylate) and poly(dimethyl siloxane) with 2,4,5-triphenylimidazole end groups were first synthesized. Subsequent oxidation of the 2,4,5-triphenylimidazoles into 2,4,5-triphenylimidazoryl radicals and their coupling with these liquid star polymers to form hexaarylbiimidazoles afforded the corresponding nonliquid network polymers. The resulting nonliquid network polymers liquefied upon UV irradiation and produced liquid star-shaped polymers with 2,4,5-triphenylimidazoryl radical end groups that reverted to nonliquid network polymers again by recoupling of the generated 2,4,5-triphenylimidazoryl radicals immediately after terminating UV irradiation.The design of organic and polymeric soft materials showing isothermal reversible liquid-nonliquid conversion is challenging. Here, the authors show solvent-free repeatable molecular architectural transformation between liquid-star and non-liquid-network polymers by the cleavage and reformation of covalent bonds in the polymer chain.
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Ohno, Kohji; Akashi, Tatsuki; Tsujii, Yoshinobu; Yamamoto, Masaya; Tabata, Yasuhiko
2012-03-12
The physiological properties of polymer brush-afforded silica particles prepared by surface-initiated living radical polymerization were investigated in terms of the circulation lifetime in the blood and distribution in tissues. Hydrophilic polymers consisting mainly of poly(poly(ethylene glycol) methyl ether methacrylate) were grafted onto silica particles by surface-initiated atom transfer radical polymerization that was mediated by a copper complex to produce hairy hybrid particles. A series of hybrid particles was synthesized by varying the diameter of the silica core and the chain length of the polymer brush to examine the relationship between their physicochemical and physiological properties. The hybrid particles were injected intravenously into mice to investigate systematically their blood clearance and body distribution. It was revealed that the structural features of the hybrid particles significantly affected their in vivo pharmacokinetics. Some hybrid particles exhibited an excellently prolonged circulation lifetime in the blood with a half life of ∼20 h. When such hybrid particles were injected intravenously into a tumor-bearing mouse, they preferentially accumulated in tumor tissue. The tumor-targeted delivery was optically visualized using hybrid particles grafted with fluorescence-labeled polymer brushes.
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Software for Demonstration of Features of Chain Polymerization Processes
ERIC Educational Resources Information Center
Sosnowski, Stanislaw
2013-01-01
Free software for the demonstration of the features of homo- and copolymerization processes (free radical, controlled radical, and living) is described. The software is based on the Monte Carlo algorithms and offers insight into the kinetics, molecular weight distribution, and microstructure of the macromolecules formed in those processes. It also…
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Mizutani, Aya; Nagase, Kenichi; Kikuchi, Akihiko; Kanazawa, Hideko; Akiyama, Yoshikatsu; Kobayashi, Jun; Annaka, Masahiko; Okano, Teruo
2010-09-17
Poly(N-isopropylacrylamide-co-N-tert-butylacrylamide) [P(IPAAm-co-tBAAm)] brushes were prepared on poly(hydroxy methacrylate) (PHMA) [hydrolyzed poly(glycidyl methacrylate-co-ethylene glycol dimethacrylate)] beads having large pores by surface-initiated atom transfer radical polymerization (ATRP) and applied to the stationary phases of thermo-responsive chromatography. Optimized amount of copolymer brushes grafted PHMA beads were able to separate peptides and proteins with narrow peaks and a high resolution. The beads were found to have a specific surface area of 43.0 m(2)/g by nitrogen gas adsorption method. Copolymer brush of P(IPAAm-co-tBAAm) grafted PHMA beads improved the stationary phase of thermo-responsive chromatography for the all-aqueous separation of peptides and proteins. 2010 Elsevier B.V. All rights reserved.
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McCarthy, P.; Chattopadhyay, M.; Millhauser, G.L.; Tsarevsky, N.V.; Bombalski, L.; Matyjaszewski, K.; Shimmin, D.; Avdalovic, N.; Pohl, C.
2010-01-01
Atom transfer radical polymerization (ATRP) was employed to create isolated, metal-containing nanoparticles on the surface of non-porous polymeric beads with the goal of developing a new immobilized metal affnity chromatography (IMAC) stationary phase for separating prion peptides and proteins. Transmission electron microscopy was used to visualize nanoparticles on the substrate surface. Individual ferritin molecules were also visualized as ferritin–nanoparticle complexes. The column's resolving power was tested by synthesizing peptide analogs to the copper binding region of prion protein and injecting mixtures of these analogs onto the column. As expected, the column was capable of separating prion-related peptides differing in number of octapeptide repeat units (PHGGGWGQ), (PHGGGWGQ)2, and (PHGGGWGQ)4. Unexpectedly, the column could also resolve peptides containing the same number of repeats but differing only in the presence of a hydrophilic tail, Q → A substitution, or amide nitrogen methylation. PMID:17481564
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Zhu, Chongyu; Schneider, Elena K; Nikolaou, Vasiliki; Klein, Tobias; Li, Jian; Davis, Thomas P; Whittaker, Michael R; Wilson, Paul; Kempe, Kristian; Velkov, Tony; Haddleton, David M
2017-07-19
Through the recently developed copper-mediated photoinduced living radical polymerization (CP-LRP), a novel and well-defined polymeric prodrug of the antimicrobial lipopeptide colistin has been developed. A colistin initiator (Boc 5 -col-Br 2 ) was synthesized through the modification of colistin on both of its threonine residues using a cleavable initiator linker, 2-(2-bromo-2-methylpropanoyloxy) acetic acid (BMPAA), and used for the polymerization of acrylates via CP-LRP. Polymerization proceeds from both sites of the colistin initiator, and through the polymerization of poly(ethylene glycol) methyl ether acrylate (PEGA 480 ), three water-soluble polymer-colistin conjugates (col-PPEGA, having degrees of polymerization of 5, 10, and 20) were achieved with high yield (conversion of ≥93%) and narrow dispersities (Đ < 1.3) in 2-4 h. Little or no effect on the structure and activity of the colistin was observed during the synthesis, and most of the active colistin can be recovered from the conjugates in vitro within 2 days. Furthermore, in vitro biological analyses including disk diffusion, broth microdilution, and time-kill studies suggested that all of the conjugates have the ability to inhibit the growth of multidrug-resistant (MDR) Gram-negative bacteria, of which col-PPEGA DP5 and DP10 showed similar or better antibacterial performance compared to the clinically relevant colistin prodrug CMS, indicating their potential as an alternative antimicrobial therapy. Moreover, considering the control over the polymerization, the CP-LRP technique has the potential to provide an alternative platform for the development of polymer bioconjugates.
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ERIC Educational Resources Information Center
Nguyen, T. L. U.; Bennet, Francesca; Stenzel, Martina H.; Barner-Kowollik, Christopher
2008-01-01
This 8-hour experiment (spread over two 4-hour sessions) is designed to equip students with essential skills in polymer synthesis, particularly in synthesizing polymers of well-defined molecular weight. The experiment involves the synthesis and characterization of poly(vinyl neodecanoate) via living free radical polymerization, specifically the…
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The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...
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Homogeneous catalysts for stereoregular olefin polymerization
Marks, Tobin J.; Eisen, Moris S.; Giardello, Michael A.
1995-01-01
The synthesis, and use as precatalysts of chiral organozirconium complexes for olefin polymerization are disclosed, having the structure (C.sub.5 R'.sub.4-x R*.sub.x) A (C.sub.5 R".sub.4-y R"'.sub.y) M Q.sub.p, where x and y represent the number of unsubstituted locations on the cyclopentadienyl ring; R', R", R"', and R* represent substituted and unsubstituted alkyl groups having 1-30 carbon atoms and R* is a chiral ligand; A is a fragment containing a Group 13, 14, 15, or 16 element of the Periodic Table; M is a Group 3, 4, or 5 metal of the Periodic Table; and Q is a hydrocarbyl radical, or halogen radical, with 3.ltoreq.p.ltoreq.o. Related complexes may be prepared by alkylation of the corresponding dichorides. In the presence of methylalumoxane or triarylborane cocatalysts, these complexes form "cation-like" species which are highly active for olefin polymerization. In combination with a Lewis acid cocatalyst, propylene or other .alpha.-olefin polymerization can be effected with very high efficiency and isospecificity.
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Homogeneous catalysts for stereoregular olefin polymerization
Marks, Tobin J.; Eisen, Moris S.; Giardello, Michael A.
1994-01-01
The synthesis, and use as precatalysts of chiral organozirconium complexes for olefin polymerization are disclosed, having the structure (C.sub.5 R'.sub.4-x R*.sub.x) A (C.sub.5 R".sub.4-y R'".sub.y) M Q.sub.p, where x and y represent the number of unsubstituted locations on the cyclopentadienyl ring; R', R", R'", and R* represent substituted and unsubstituted alkyl groups having 1-30 carbon atoms and R* is a chiral ligand; A is a fragment containing a Group 13, 14, 15, or 16 element of the Periodic Table; M is a Group 3, 4, or 5 metal of the Periodic Table; and Q is a hydrocarbyl radical, or halogen radical, with 3.ltoreq.p.ltoreq.o. Related complexes may be prepared by alkylation of the corresponding dichorides. In the presence of methylalumoxane or triarylborane cocatalysts, these complexes form "cation-like" species which are highly active for olefin polymerization. In combination with a Lewis acid cocatalyst, propylene or other .alpha.-olefin polymerization can be effected with very high efficiency and isospecificity.
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Homogeneous catalysts for stereoregular olefin polymerization
Marks, T.J.; Eisen, M.S.; Giardello, M.A.
1995-10-03
The synthesis, and use as precatalysts of chiral organozirconium complexes for olefin polymerization are disclosed, having the structure (C{sub 5}R{prime}{sub 4{minus}x}R*{sub x})A(C{sub 5}R{double_prime}{sub 4{minus}y}R{double_prime}{prime}{sub y})MQ{sub p}, where x and y represent the number of unsubstituted locations on the cyclopentadienyl ring; R{prime}, R{double_prime}, R{double_prime}{prime}, and R* represent substituted and unsubstituted alkyl groups having 1--30 carbon atoms and R* is a chiral ligand; A is a fragment containing a Group 13, 14, 15, or 16 element of the Periodic Table; M is a Group 3, 4, or 5 metal of the Periodic Table; and Q is a hydrocarbyl radical, or halogen radical, with 3{>=}p{>=}0. Related complexes may be prepared by alkylation of the corresponding dichlorides. In the presence of methylalumoxane or triarylborane cocatalysts, these complexes form ``cation-like`` species which are highly active for olefin polymerization. In combination with a Lewis acid cocatalyst, propylene or other {alpha}-olefin polymerization can be effected with very high efficiency and isospecificity. 1 fig.
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Homogeneous catalysts for stereoregular olefin polymerization
Marks, T.J.; Eisen, M.S.; Giardello, M.A.
1994-07-19
The synthesis, and use as precatalysts of chiral organozirconium complexes for olefin polymerization are disclosed, having the structure (C[sub 5]R[prime][sub 4[minus]x]R*[sub x])-A-(C[sub 5]R[double prime][sub 4[minus]y]R[prime][double prime][sub y])-M-Q[sub p], where x and y represent the number of unsubstituted locations on the cyclopentadienyl ring; R[prime], R[double prime], R[prime][double prime], and R* represent substituted and unsubstituted alkyl groups having 1--30 carbon atoms and R* is a chiral ligand; A is a fragment containing a Group 13, 14, 15, or 16 element of the Periodic Table; M is a Group 3, 4, or 5 metal of the Periodic Table; and Q is a hydrocarbyl radical, or halogen radical, with 3 [<=] p [<=] 0. Related complexes may be prepared by alkylation of the corresponding dichlorides. In the presence of methylalumoxane or triarylborane cocatalysts, these complexes form cation-like'' species which are highly active for olefin polymerization. In combination with a Lewis acid cocatalyst, propylene or other [alpha]-olefin polymerization can be effected with very high efficiency and isospecificity. 1 fig.
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Hedir, Guillaume; Stubbs, Christopher; Aston, Phillip; Dove, Andrew P; Gibson, Matthew I
2017-12-19
Poly(vinyl alcohol) (PVA) is the most active synthetic mimic of antifreeze proteins and has extremely high ice recrystallization inhibition (IRI) activity. Addition of PVA to cellular cryopreservation solutions increases the number of recovered viable cells due to its potent IRI, but it is intrinsically nondegradable in vivo . Here we report the synthesis, characterization, and IRI activity of PVA containing degradable ester linkages. Vinyl chloroacetate (VClAc) was copolymerized with 2-methylene-1,3-dioxepane (MDO) which undergoes radical ring-opening polymerization to install main-chain ester units. The use of the chloroacetate monomer enabled selective deacetylation with retention of esters within the polymer backbone. Quantitative IRI assays revealed that the MDO content had to be finely tuned to retain IRI activity, with higher loadings (24 mol %) resulting in complete loss of IRI activity. These degradable materials will help translate PVA, which is nontoxic and biocompatible, into a range of biomedical applications.
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NASA Astrophysics Data System (ADS)
Wu, Qing; Wang, Xia; Liao, Chuanan; Wei, Qingcong; Wang, Qigang
2015-10-01
This study describes a new strategy for the fabrication of magnetic core-shell microgels by free-radical polymerization triggered by the cascade reaction of glucose oxidase (GOx) and horseradish peroxidase (HRP). The mild polymerization around the interface of the magnetic nanoparticles permits the mild coating of the microgel layer with excellent characteristics for various applications in biocatalysis and medical diagnostics, as well as in clinical fields. The immobilized bienzyme within the microgel has a largely retained activity relative to the non-immobilized one. The confining effect of the microgel and the well designed distance between the two enzymes can benefit the diffusion of intermediates to the HRP active site. The final microgels can be incontestably employed as sensitive biosensors for colorimetric glucose detection.This study describes a new strategy for the fabrication of magnetic core-shell microgels by free-radical polymerization triggered by the cascade reaction of glucose oxidase (GOx) and horseradish peroxidase (HRP). The mild polymerization around the interface of the magnetic nanoparticles permits the mild coating of the microgel layer with excellent characteristics for various applications in biocatalysis and medical diagnostics, as well as in clinical fields. The immobilized bienzyme within the microgel has a largely retained activity relative to the non-immobilized one. The confining effect of the microgel and the well designed distance between the two enzymes can benefit the diffusion of intermediates to the HRP active site. The final microgels can be incontestably employed as sensitive biosensors for colorimetric glucose detection. Electronic supplementary information (ESI) available: Experimental details and ESI figures. See DOI: 10.1039/c5nr05716g
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Unprecedented covalently attached ATRP initiator onto OH-functionalized mica surfaces.
Lego, Béatrice; Skene, W G; Giasson, Suzanne
2008-01-15
Mica substrates were activated by a plasma method leading to OH-functionalized surfaces to which an atom transfer radical polymerization (ATRP) radical initiator was covalently bound using standard siloxane protocols. The unprecedented covalently immobilized initiator underwent radical polymerization with tert-butyl acrylate, yielding for the first time end-grafted polymer brushes that are covalently linked to mica. The initiator grafting on the mica substrate was confirmed by time-of-flight secondary ion mass spectrometry (TOF-SIMS), while the change in the water contact angle of the OH-activated mica surface was used to follow the change in surface coverage of the initiator on the surface. The polymer brush and initiator film thicknesses relative to the virgin mica were confirmed by atomic force microscopy (AFM). This was done by comparing the atomic step-height difference between a protected area of freshly cleaved mica and a zone exposed to plasma activation, initiator immobilization, and then ATRP.
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NASA Technical Reports Server (NTRS)
Braun, D.; Lehmann, P.
1985-01-01
As starting materials for the preparation of polyradicals of triphenylmethyl type linked by p-phenylene units bis(4-iodophenylmethane) and bis(4-iodo-2,5-dimethyl-phenylmethane) were synthesized by a Sandmeyer reaction from the corresponding diamino compounds and subsequently transformed into the corresponding polymeric hydrocarbons 6a and 6b by an Ullmann condensation. In the following step 6a and 6b were brominated at the tert. carbon atom by means of N-bromosuccinimide. The reaction of the resulting poly (4,4'-biphenylylen-alpha-bromobenzylidene)s (7a and 7b) with mercury afforded the corresponding radicals, the ESR spectra of which were recorded. From the methyl substituted polymer 7b poly (2,2'5,5-tetramethyl-4,4'-bi-phenylylen)phenylmethylidyne was formed, whereas the unsubstituted product 7a was transformed into a para-quinoide polymer with radical properties.
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Development of materials from copolyacrylates via atom transfer radical polymerization
NASA Astrophysics Data System (ADS)
Jones, Melody Mersadez
Homopolymerization of 2-(trimethylsilyl)ethyl acrylate, 3,3-dimethylbutyl acrylate, methyl acrylate, and methyl methacrylate using atom transfer radical polymerization (ATRP) is reported. In addition, polymethyl acrylate and polymethyl methacrylate were used as macroinitiators for diblock copolymerizations (via ATRP) with various monomers to yield pMA-b-TMSEA, pMMA-b-TMSEA, and pMMA-b-GMA copolymers; these results are also reported. Controlled polymerizations were performed using the CuBr/hexamethyltriethylenetetramine catalyst system in combination with methyl bromopropionate as the initiator. The protected acid block copolymers pMA-b-TMSEA and pMMA-b-TMSEA were deprotected to afford acrylic and meth acrylic acid block copolymers pMA-b-AA and pMMA-b-AA. Methylene chloride was used to micellize the amphiphilic copolymers in order to obtain the critical micelle concentration of the polymers (CMCpMA-b-AA = 10 mg/mL, CMCpMMA-b-AA = 0.4 mg/mL). The majority of polymerization were done in bulk; however, since poly(trimethylsilyl)ethyl acrylate displayed polydispersity (Mn = 11459, PDI = 1.437) on the high end of the acceptable range, various solvents were utilized to decrease the polymerization rate and afford low polydispersity materials. This differs from the ATRP of polymethyl acrylate or polymethyl methacrylate using this catalytic system, which do not require the addition of a solvent to obtain well-defined polymers. Also, for this polymerization system three different temperatures (60°C, 90°C, and 120°C) were used, in order to reduce the concentration of radicals and the contribution of termination. The homopolymers and protected acid block copolymers were characterized by gel permeation chromatography to determine the relative molecular weights. Differential scanning calorimetry was used to obtain the glass transition temperature of all polymers. Characterization using NMR (1H and 13C) and FTIR confirmed homopolymerization of 3,3-dimethylbutyl acrylate, 2-(trimethylsilyl)ethyl acrylate and complete cleavage of the (trimethylsilyl)ethyl group from the protected acid copolymers.
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Molecular architecture requirements for polymer-grafted lignin superplasticizers.
Gupta, Chetali; Sverdlove, Madeline J; Washburn, Newell R
2015-04-07
Superplasticizers are a class of anionic polymer dispersants used to inhibit aggregation in hydraulic cement, lowering the yield stress of cement pastes to improve workability and reduce water requirements. The plant-derived biopolymer lignin is commonly used as a low-cost/low-performance plasticizer, but attempts to improve its effects on cement rheology through copolymerization with synthetic monomers have not led to significant improvements. Here we demonstrate that kraft lignin can form the basis for high-performance superplasticizers in hydraulic cement, but the molecular architecture must be based on a lignin core with a synthetic-polymer corona that can be produced via controlled radical polymerization. Using slump tests of ordinary Portland cement pastes, we show that polyacrylamide-grafted lignin prepared via reversible addition-fragmentation chain transfer polymerization can reduce the yield stress of cement paste to similar levels as a leading commercial polycarboxylate ether superplasticizer at concentrations ten-fold lower, although the lignin material produced via controlled radical polymerization does not appear to reduce the dynamic viscosity of cement paste as effectively as the polycarboxylate superplasticizer, despite having a similar affinity for the individual mineral components of ordinary Portland cement. In contrast, polyacrylamide copolymerized with a methacrylated kraft lignin via conventional free radical polymerization having a similar overall composition did not reduce the yield stress or the viscosity of cement pastes. While further work is required to elucidate the mechanism of this effect, these results indicate that controlling the architecture of polymer-grafted lignin can significantly enhance its performance as a superplasticizer for cement.
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Maatar, Wafa; Boufi, Sami
2015-08-01
A poly(methacrylic acid-co-maleic acid) grafted nanofibrillated cellulose (NFC-MAA-MA) aerogel was prepared via radical polymerization in an aqueous solution using Fenton's reagent. The ensuing aerogel, in the form of a rigid porous material, was characterized by FTIR and NMR and used as an adsorbent for the removal of heavy metals from aqueous solutions. It showed an efficient adsorption, exceeding 95% toward Pb(2+), Cd(2+), Zn(2+) and Ni(2+) when their concentration was lower than 10 ppm and ranged from 90% to 60% for a metal concentration higher than 10 ppm. Over 98% of the adsorbed metal ion was recovered using EDTA as a desorbing solution, and the subsequent washing allowed the aerogel to be reused repeatedly without noticeable loss of adsorption capacity. It was concluded that the (NFC-MAA-MA) aerogel may be used as a high capacity and reusable sorbent material in heavy-metal removing processes. Copyright © 2015 Elsevier Ltd. All rights reserved.
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Hazer, Baki; Kalaycı, Özlem A
2017-05-01
Autoxidation of poly unsaturated fatty acids makes negative effect on foods. In this work, this negative effect was turned to a great advantage using autoxidized soybean oil as a macroperoxide nanocomposite initiator containing silver nano particles in free radical polymerization of vinyl monomers. The synthesis of soybean oil macro peroxide was carried out by exposing soybean oil to air oxygen with the presence of silver nanoparticles (Ag NPs) at room temperature. Autoxidized soybean oil macroperoxide containing silver nanoparticles (Agsbox) successfully initiated the free radical polymerization of styrene in order to obtain Polystyrene (PS)-g-soybean oil graft copolymer containing Ag NPs. Both autoxidized soybean oil and PS-g-sbox with Ag NPs showed a surface plasmon resonance and high fluorescence emission. Overall rate constant (K) of styrene polymerization initiated by autoxidized soybean oil macroperoxide with Ag NPs was found to be K=1.95.10 -4 Lmol -1 s -1 at 95°C. Antibacterial efficiency was observed in the PS-g-soybean oil graft copolymer film samples containing Ag NPs. 1 H NMR and GPC techniques were used for the structural analysis of the fractionated polymeric oils. Copyright © 2016 Elsevier B.V. All rights reserved.
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USDA-ARS?s Scientific Manuscript database
Hydrophilic poly (vinyl alcohol-co-ethylene) (PVA-co-PE) copolymers with 27 mol %, 32 mol % and 44 mol % ethylene were functionalized by melt radical graft copolymerization with 2,4-diamino-6-diallylamino-1,3,5-triazine (NDAM) using reactive extrusion. This functionalization imparts antibacterial pr...
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Patil, Nagaraj; Soni, Jalpa; Ghosh, Nirmalya; De, Priyadarsi
2012-11-29
Thermodynamically favored polymer-water interactions below the lower critical solution temperature (LCST) caused swelling-induced optical anisotropy (linear retardance) of thermoresponsive hydrogels based on poly(2-(2-methoxyethoxy)ethyl methacrylate). This was exploited to study the macroscopic deswelling kinetics quantitatively by a generalized polarimetry analysis method, based on measurement of the Mueller matrix and its subsequent inverse analysis via the polar decomposition approach. The derived medium polarization parameters, namely, linear retardance (δ), diattenuation (d), and depolarization coefficient (Δ), of the hydrogels showed interesting differences between the gels prepared by conventional free radical polymerization (FRP) and reversible addition-fragmentation chain transfer polymerization (RAFT) and also between dry and swollen state. The effect of temperature, cross-linking density, and polymerization technique employed to synthesize hydrogel on deswelling kinetics was systematically studied via conventional gravimetry and corroborated further with the corresponding Mueller matrix derived quantitative polarimetry characteristics (δ, d, and Δ). The RAFT gels exhibited higher swelling ratio and swelling-induced optical anisotropy compared to FRP gels and also deswelled faster at 30 °C. On the contrary, at 45 °C, deswelling was significantly retarded for the RAFT gels due to formation of a skin layer, which was confirmed and quantified via the enhanced diattenuation and depolarization parameters.
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Photoredox Catalysis for the Generation of Carbon Centered Radicals.
Goddard, Jean-Philippe; Ollivier, Cyril; Fensterbank, Louis
2016-09-20
Radical chemistry has witnessed over the last decades important advances that have positioned it as a methodology of choice in synthetic chemistry. A number of great attributes such as specific reactivities, the knowledge of the kinetics of most elementary processes, the functional group tolerance, and the possibility to operate cascade sequences are clearly responsible for this craze. Nevertheless, at the end of the last century, radical chemistry appeared plagued by several hurdles to overcome such as the use of environmentally problematic mediators or the impossibility of scale up. While the concept of photocatalysis was firmly established in the coordination chemistry community, its diffusion in organic synthetic chemistry remained sporadic for decades until the end of the 2000s with the breakthrough merging of organocatalysis and photocatalysis by the MacMillan group and contemporary reports by the groups of Yoon and Stephenson. Since then, photoredox catalysis has enjoyed particularly active and intense developments. It is now the topic of a still increasing number of publications featuring various applications from asymmetric synthesis, total synthesis of natural products, and polymerization to process (flow) chemistry. In this Account, we survey our own efforts in this domain, focusing on the elaboration of new photocatalytic pathways that could lead to the efficient generation of C-centered functionalized alkyl and aryl radicals. Both reductive and oxidative manifolds are accessible through photoredox catalysis, which has guided us along these lines in our projects. Thus, we studied the photocatalytic reduction of onium salts such as sulfoniums and iodoniums for the production of the elusive aryl radical intermediates. Progressing to more relevant chemistry for synthesis, we examined the cleavage of C-O and the C-Br bonds for the generation of alkyl C-centered radicals. Activated epoxides could serve as valuable substrates of a photocatalyzed variant of the Nugent-RajanBabu-Gansäuer homolytic cleavage of epoxides. Using imidazole based carbamates, we could also devise the first photocatalyzed Barton-McCombie deoxygenation reaction. Finally, bromophenylacetate can be reduced using the [Au2(μ-dppm)2]Cl2 photocatalyst under UVA or visible-light. This was used for the initiation of the controlled atom transfer radical polymerization of methacrylates and acrylates in solution or laminate. Our next endeavors concerned the photocatalyzed oxidation of stabilized carbanions such as enolates of 1,3-dicarbonyl substrates, trifluoroborates, and more extensively bis-catecholato silicates. Because of their low oxidation potentials, the later have proved to be exquisite sources of radical entities, which can be engaged in diverse intermolecular reactions such as vinylation, alkynylation, and conjugate additions. The bis-catecholato silicates were also shown to behave as excellent partners of dual photoredox-nickel catalysis leading in an expeditious manner to libraries of cross coupling products.
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Polymerization of ethylene through reversible addition-fragmentation chain transfer (RAFT).
Dommanget, Cédric; D'Agosto, Franck; Monteil, Vincent
2014-06-23
The present paper reports the first example of a controlled radical polymerization of ethylene using reversible addition-fragmentation chain transfer (RAFT) in the presence of xanthates (Alkyl-OC(=S)S-R) as controlling agents under relative mild conditions (70 °C, <200 bars). The specific reactivity of the produced alkyl-type propagating radicals induces a side fragmentation reaction of the stabilizing O-alkyl Z group of the controlling agents. This fragmentation, rarely observed in RAFT, was proven by NMR analyses. In addition, semicrystalline copolymers of ethylene and vinyl acetate were also prepared with a similar level of control. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Claeys, Bart; De Coen, Ruben; De Geest, Bruno G; de la Rosa, Victor R; Hoogenboom, Richard; Carleer, Robert; Adriaensens, Peter; Remon, Jean Paul; Vervaet, Chris
2013-11-01
Polymethacrylates such as Eudragit® polymers are well established as drug delivery matrix. Here, we synthesize several Eudragit E PO (n-butyl-, dimethylaminoethyl-, methyl-methacrylate-terpolymer) analogues via free radical polymerization. These polymers are processed via hot melt extrusion, followed by injection molding and evaluated as carriers to produce immediate release solid solution tablets. Three chemical modifications increased the glass transition temperature of the polymer: (a) substitution of n-butyl by t-butyl groups, (b) reduction of the dimethylaminoethyl methacrylate (DMAEMA) content, and (c) incorporation of a bulky isobornyl repeating unit. These structural modifications revealed the possibility to increase the mechanical stability of the tablets via altering the polymer Tg without influencing the drug release characteristics and glassy solid solution forming properties. The presence of DMAEMA units proved to be crucial with respect to API/polymer interaction (essential in creating glassy solid solutions) and drug release characteristics. Moreover, these chemical modifications accentuate the need for a more rational design of (methacrylate) polymer matrix excipients for drug formulation via hot melt extrusion and injection molding. Copyright © 2013 Elsevier B.V. All rights reserved.
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Anionic polymerization of p-(2,2'-diphenylethyl)styrene and applications to graft copolymers.
Huang, Minglu; Han, Bingyong; Lu, Jianmin; Yang, Wantai; Fu, Zhifeng
2017-01-01
Well-controlled anionic polymerization of an initiator-functionalized monomer, p -(2,2'-diphenylethyl)styrene (DPES), was achieved for the first time. The polymerization was performed in a mixed solvent of cyclohexane and tetrahydrofuran (THF) at 40 °C with n -BuLi as initiator. When the volume ratio of cyclohexane to THF was 20, the anionic polymerization of DPES showed living polymerization characteristics, and well-defined block copolymer PDPES- b -PS was successfully synthesized. Furthermore, radical polymerization of methyl methacrylate in the presence of PDPES effectively afforded a graft copolymer composed of a polystyrene backbone and poly(methyl methacrylate) branches. The designation of analogous monomers and polymers was of great significance to synthesize a variety of sophisticated copolymer and functionalize polymer materials.
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Nanoscale functionalization and characterization of surfaces with hydrogel patterns and biomolecules
NASA Astrophysics Data System (ADS)
Dinakar, Hariharasudhan Chirra
The advent of numerous tools, ease of techniques, and concepts related to nanotechnology, in combination with functionalization via simple chemistry has made gold important for various biomedical applications. In this dissertation, the development and characterization of planar gold surfaces with responsive hydrogel patterns for rapid point of care sensing and the functionalization of gold nanoparticles for drug delivery are highlighted. Biomedical micro- and nanoscale devices that are spatially functionalized with intelligent hydrogels are typically fabricated using conventional UV-lithography. Herein, precise 3-D hydrogel patterns made up of temperature responsive crosslinked poly(N-isopropylacrylamide) over gold were synthesized. The XY control of the hydrogel was achieved using microcontact printing, while thickness control was achieved using atom transfer radical polymerization (ATRP). Atomic force microscopy analysis showed that to the ATRP reaction time governed the pattern growth. The temperature dependent swelling ratio was tailored by tuning the mesh size of the hydrogel. While nanopatterns exhibited a broad lower critical solution temperature (LCST) transition, surface roughness showed a sharp LCST transition. Quartz crystal microbalance with dissipation showed rapid response behavior of the thin films, which makes them applicable as functional components in biomedical devices. The easy synthesis, relative biocompatibility, inertness, and easy functionalization of gold nanoparticles (GNPs) have made them useful for various biomedical applications. Although ATRP can be successfully carried out over GNPs, the yield of stable solution based GNPs for biomedical applications prove to be low. As an alternative approach, a novel method of ISOlating, FUnctionalizing, and REleasing nanoparticles (ISOFURE) was proposed. Biodegradable poly(beta-amino ester) hydrogels were used to synthesize ISOFURE-GNP composites. ATRP was performed inside the composite, and the final hydrogel coated GNPs were released via matrix degradation. Response analysis confirmed that the ISOFURE method led to the increased stability and yield of the hydrogel coated ISOFURE-GNPs. The ISOFURE protocol was also utilized in functionalizing GNPs with enzyme catalase in the absence of a stabilizing reagent. Biotin-streptavidin affinity was used as the bioconjugation method. Activity analysis of the conjugated enzyme showed that the ISOFURE-GNPs showed enhanced biomolecular loading relative to solution based stabilizing reagent passivated GNPs. KEYWORDS: Hydrogel, Gold nanoparticle, ISOFURE, Atom transfer radical polymerization, Microcontact printing
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NASA Astrophysics Data System (ADS)
McLeod, David Charles
Macromolecules that contain electrophilic moieties, such as benzyl halides, activated esters, and epoxides, will readily undergo efficient nucleophilic substitution reactions with a wide variety of compounds under mild conditions, and are therefore ideally suited to act as "universal" precursors to functional materials. Epoxide-containing polymers derived from the radical polymerization of commercially-available glycidyl methacrylate are often employed in this role; however, methacrylic polymers suffer from certain limitations as a result of the incorporated ester groups, which are not stabile in the presence of strong nucleophiles, acids, bases, or esterase enzymes. Styrenic polymers that do not contain labile carbonyl moieties are usually the precursors of choice when high chemical stability is desired in the end product, but the production of functional materials from epoxide-containing styrenic polymers is relatively unexplored. In this dissertation, improved methods were developed for synthesizing 4-vinylphenyloxirane (4VPO) and 4-vinylphenyl glycidyl ether (4VPGE), two of the better-known epoxide-containing styrenic monomers, in high-yield and purity. Well-defined, epoxide-containing styrenic polymers with targeted molecular weights, narrow molecular weight distributions, and controlled architectures (specifically, linear and star-shaped homopolymers, as well as linear block copolymers with styrene) were produced from 4VPO and 4VPGE for the first time using reversible-deactivation radical polymerization techniques, such as low-catalyst-concentration atom transfer radical polymerization (LCC ATRP) and reversible addition-fragmentation chain-transfer (RAFT) polymerization. The robust nature and utility of poly4VPO and poly4VPGE were then demonstrated by the efficient, ring-opening modification of the pendant epoxide groups with a structurally- and functionally-diverse array of alcohols under acidic conditions at ambient temperature. The macromolecular compositions, architectures, and thermal stabilities of the resulting ?-hydroxy ether-functionalized homopolymers were evaluated using NMR and FTIR spectroscopy, size exclusion chromatography, and thermal gravimetric analysis. Aziridines and thiiranes (saturated, three-membered heterocycles containing either a single nitrogen or sulfur atom, respectively) are also susceptible to nucleophilic ring-opening reactions, and functional materials derived from aziridine- or thiirane-containing polymers could potentially have many interesting properties as a result of their high amine or thiol content, such as the ability to form pH- or redox-responsive structures. The synthesis of polymers containing aziridines that are activated towards nucleophilic ring-opening by C-aryl and/or N-sulfonyl substituents is unprecedented in the literature. Efficient methods for synthesizing styrenic monomers that contain these highly-reactive functionalities, namely 2-(4-vinylphenyl)aziridine (VPA) and its sulfonyl-activated derivative, N-mesyl-2-(4-vinylphenyl)aziridine (NMVPA), were developed utilizing 4VPO as a starting material. VPA was polymerized under LCC ATRP and RAFT conditions, but these methods were ineffective at producing well-defined polymers due to side reactions between the aziridine groups and the polymerization mediating compounds. Nitroxide-mediated radical polymerization (NMRP) produced well-defined polyVPA at low to moderate conversions of monomer, but cross-linking side reactions were evident at higher monomer conversions. Nearly all undesirable side reactions were prevented by attaching a mesyl group to the aziridine nitrogen atom, and well-defined polyNMVPA was realized under RAFT and NMRP conditions. Under ATRP conditions, reactions between the aziridine groups and catalyst still occurred, so the polymerization of NMVPA was not controlled using this technique. The synthesis of thiirane-containing styrenic polymers from either 2-(4-vinylphenyl)thiirane (VPT) or 2-((4-vinylphenoxy)methyl)thiirane (VPOMT), which were produced in a facile manner from 4VPO or 4VPGE, respectively, was attempted under conventional radical polymerization and RAFT polymerization conditions. Rapid desulfurization or ring-opening polymerization of VPT occurred when elevated temperatures or UV radiation was applied to reactions containing this monomer. The more-stable VPOMT monomer was successfully polymerized at elevated temperatures using thermally-labile azo-type initiators, and, under RAFT conditions, polymers of VPOMT increased in molecular weight as higher conversions of monomer were reached; however, the polymers produced under RAFT conditions were ill-defined and eventually underwent macrogelation, due to cross-linking side reactions of the thiirane moieties.
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Sábio, Sérgio; Franciscone, Paulo Afonso; Mondelli, José
2008-01-01
In the present study, two types of tests (tensile strength test and polymerization inhibition test) were performed to evaluate the physical and chemical properties of four impression materials [a polysulfide (Permlastic), a polyether (Impregum), a condensation silicone (Xantopren) and a polyvinylsiloxane (Aquasil)] when polymerized in contact with of one conventional (Hemostop) and two experimental (Vislin and Afrin) gingival retraction solutions. For the tensile strength test, the impression materials were mixed and packed into a steel plate with perforations that had residues of the gingival retraction solutions. After polymerization, the specimens were tested in tensile strength in a universal testing machine. For the polymerization inhibition test, specimens were obtained after taking impressions from a matrix with perforations that contained 1 drop of the gingival retraction solutions. Two independent examiners decided on whether or not impression material remnants remained unpolymerized, indicating interference of the chemical solutions. Based on the analysis of the results of both tests, the following conclusions were reached: 1. The tensile strength of the polysulfide decreased after contact with Hemostop and Afrin. 2. None of the chemical solutions inhibited the polymerization of the polysulfide; 3. The polyether presented lower tensile strength after polymerization in contact with the three gingival retraction agents; 4. The polyether had its polymerization inhibited only by Hemostop; 5. None of the chemical solutions affected the tensile strength of the condensation silicone; 6. Only Hemostop inhibited the polymerization of the condensation silicone; 7. The polyvinylsiloxane specimens polymerized in contact with Hemostop had significantly lower tensile strength; 8. Neither of the chemical solutions (Afrin and Vislin) affected the tensile strength of the polyvinylsiloxane and the condensation silicone; 9. Results of the tensile strength and polymerization inhibition tests suggest that Vislin can be used as substance of gingival retraction without affecting the tested properties of four impression materials. PMID:19089261
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Sábio, Sérgio; Franciscone, Paulo Afonso; Mondelli, José
2008-01-01
In the present study, two types of tests (tensile strength test and polymerization inhibition test) were performed to evaluate the physical and chemical properties of four impression materials [a polysulfide (Permlastic), a polyether (Impregum), a condensation silicone (Xantopren) and a polyvinylsiloxane (Aquasil)] when polymerized in contact with of one conventional (Hemostop) and two experimental (Vislin and Afrin) gingival retraction solutions. For the tensile strength test, the impression materials were mixed and packed into a steel plate with perforations that had residues of the gingival retraction solutions. After polymerization, the specimens were tested in tensile strength in a universal testing machine. For the polymerization inhibition test, specimens were obtained after taking impressions from a matrix with perforations that contained 1 drop of the gingival retraction solutions. Two independent examiners decided on whether or not impression material remnants remained unpolymerized, indicating interference of the chemical solutions. Based on the analysis of the results of both tests, the following conclusions were reached: 1. The tensile strength of the polysulfide decreased after contact with Hemostop and Afrin. 2. None of the chemical solutions inhibited the polymerization of the polysulfide; 3. The polyether presented lower tensile strength after polymerization in contact with the three gingival retraction agents; 4. The polyether had its polymerization inhibited only by Hemostop; 5. None of the chemical solutions affected the tensile strength of the condensation silicone; 6. Only Hemostop inhibited the polymerization of the condensation silicone; 7. The polyvinylsiloxane specimens polymerized in contact with Hemostop had significantly lower tensile strength; 8. Neither of the chemical solutions (Afrin and Vislin) affected the tensile strength of the polyvinylsiloxane and the condensation silicone; 9. Results of the tensile strength and polymerization inhibition tests suggest that Vislin can be used as substance of gingival retraction without affecting the tested properties of four impression materials.
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Majoinen, Johanna; Walther, Andreas; McKee, Jason R; Kontturi, Eero; Aseyev, Vladimir; Malho, Jani Markus; Ruokolainen, Janne; Ikkala, Olli
2011-08-08
Herein we report the synthesis of cellulose nanocrystals (CNCs) grafted with poly(acrylic acid) (PAA) chains of different lengths using Cu-mediated surface initiated-controlled radical polymerization (SI-CRP). First, poly(tert-butylacrylate) (PtBA) brushes were synthesized; then, subsequent acid hydrolysis was used to furnish PAA brushes tethered onto the CNC surfaces. The CNCs were chemically modified to create initiator moieties on the CNC surfaces using chemical vapor deposition (CVD) and continued in solvent phase in DMF. A density of initiator groups of 4.6 bromine ester groups/nm(2) on the CNC surface was reached, suggesting a dense functionalization and a promising starting point for the controlled/living radical polymerization. The SI-CRP of tert-butylacrylate proceeded in a well-controlled manner with the aid of added sacrificial initiator, yielding polymer brushes with polydispersity values typically well below 1.12. We calculated the polymer brush grafting density to almost 0.3 chains/nm(2), corresponding to high grafting densities and dense polymer brush formation on the nanocrystals. Successful rapid acid hydrolysis to remove the tert-butyl groups yielded pH-responsive PAA-polyelectrolyte brushes bound to the CNC surface. Individually dispersed rod-like nanoparticles with brushes of PtBA or PAA were clearly visualized by AFM and TEM imaging.
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NASA Astrophysics Data System (ADS)
Siegwart, Daniel John
In this thesis, atom transfer radical polymerization (ATRP) and reversible addition-fragmentation chain transfer (RAFT) polymerization were utilized in the design of synthetic polymers to create tissue engineering scaffolds and drug delivery systems with improved control over structure and functionality. Thermo-sensitive injectable hydrogels based on poly(NIPAAm) with degradable ester units within the polymer backbone and at the cross-linking sites were prepared using ATRP and RAFT. Solvent induced morphologies of poly(methyl methacrylate-b-ethylene oxide-b-methyl methacrylate) triblock copolymers synthesized by ATRP were described. A micellar structure, composed of a hydrophobic PMMA core and a PEO shell was constructed for delivery of hydrophobic drugs. ATRP was carried out in inverse miniemulsion to prepare well defined functional nanogels that were capable of entrapping and releasing various molecules (Doxorubicin, carbohydrate-based drugs, fluorophores, and gold nanoparticles). The results demonstrated that nanogels prepared by ATRP in inverse miniemulsion could be internalized into cells via clathrin-mediated endocytosis. Nanogels functionalized with integrin-binding peptides increased cellular uptake. A process called Atom Transfer Radical Coupling (ATRC) was also described, which illustrated the power of functionality in ATRP. Finally, linear polymers and cross-linked nanogels were synthesized by ATRP and functionalized with biotin, pyrene, and peptide sequences, tying together the overall themes of structural control and functionality.
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NASA Astrophysics Data System (ADS)
Mstsuura, Hiroto; Fujiyama, Takatomo; Okuno, Yasuki; Furuta, Masakazu; Okuda, Shuichi; Takemura, Yuichiro
2015-09-01
Recently, atmospheric pressure discharge plasma has gathered attention in various fields. Among them, plasma sterilization with many types of plasma source has studied for decades and its mechanism is still an open question. If active radicals produced in plasma has main contribution of killing bacterias, direct contact of the so-called plasma flame might not be necessary. To confirm this, sterilization inside small diameter flexible polymeric tubes is studied in present work. DBD type plasma jet is produce by flowing helium gas in a glass tube. A long polymeric tube is connected and plasma jet is introduced into it. Plasma flame length depends on helium gas flow rate, but limited to about 10 cm in our experimental condition. E.colis set at the exit plasma source is easily killed during 10 min irradiation. At the tube end (about 20 cm away from plasma source exit), sterilization is possible with 30 min operation. This result shows that active radical is produced with helium plasma and mist contained in sample, and it can be transferred more than 20 cm during it life time. More plasma diagnostic data will also be shown at the conference. This work was partially supported by the ''ZE Research Program, IAE(ZE27B-4).
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Solution Kinetics Database on the Web
National Institute of Standards and Technology Data Gateway
SRD 40 NDRL/NIST Solution Kinetics Database on the Web (Web, free access) Data for free radical processes involving primary radicals from water, inorganic radicals and carbon-centered radicals in solution, and singlet oxygen and organic peroxyl radicals in various solvents.
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Michail, Karim; Baghdasarian, Argishti; Narwaley, Malyaj; Aljuhani, Naif; Siraki, Arno G
2013-12-16
We investigated a novel scavenging mechanism of arylamine free radicals by poly- and monoaminocarboxylates. Free radicals of arylamine xenobiotics and drugs did not react with oxygen in peroxidase-catalyzed reactions; however, they showed marked oxygen uptake in the presence of an aminocarboxylate. These free-radical intermediates were identified using the spin trap 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) and electron paramagnetic resonance (EPR) spectrometry. Diethylenetriaminepentaacetic acid (DTPA), a polyaminocarboxylate, caused a concentration-dependent attenuation of N-centered radicals produced by the peroxidative metabolism of arylamines with the subsequent formation of secondary aliphatic carbon-centered radicals stemming from the cosubstrate molecule. Analogously, N,N-dimethylglycine (DMG) and N-methyliminodiacetate (MIDA), but not iminodiacetic acid (IDA), demonstrated a similar scavenging effect of arylamine-derived free radicals in a horseradish peroxidase/H2O2 system. Using human promyelocytic leukemia (HL-60) cell lysate as a model of human neutrophils, DTPA, MIDA, and DMG readily reduced anilinium cation radicals derived from the arylamines and gave rise to the corresponding carbon radicals. The rate of peroxidase-triggered polymerization of aniline was studied as a measure of nitrogen-radical scavenging. Although, IDA had no effect on the rate of aniline polymerization, this was almost nullified in the presence of DTPA and MIDA at half of the molar concentration of the aniline substrate, whereas a 20 molar excess of DMPO caused only a partial inhibition. Furthermore, the yield of formaldehyde, a specific reaction endproduct of the oxidation of aminocarboxylates by aniline free-radical metabolites, was quantitatively determined. Azobenzene, a specific reaction product of peroxidase-catalyzed free-radical dimerization of aniline, was fully abrogated in the presence of DTPA, as confirmed by GC/MS. Under aerobic conditions, a radical-transfer reaction is proposed between aminocarboxylates and arylamine free radicals via the carboxylic group-linked tertiary nitrogen of the deprotonated amino acid derivatives. These findings may have significant implications for the biological fate of arylamine xenobiotic and drug free-radical metabolites.
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Salian, Vishal D; Vaughan, Asa D; Byrne, Mark E
2012-06-01
In this work, living/controlled radical polymerization (LRP) is compared with conventional free radical polymerization in the creation of highly and weakly cross-linked imprinted poly(methacrylic acid-co-ethylene glycol dimethacrylate) networks. It elucidates, for the first time, the effect of LRP on the chain level and begins to explain why the efficiency of the imprinting process is improved using LRP. Imprinted polymers produced via LRP exhibited significantly higher template affinity and capacity compared with polymers prepared using conventional methods. The use of LRP in the creation of highly cross-linked imprinted polymers resulted in a fourfold increase in binding capacity without a decrease in affinity; whereas weakly cross-linked gels demonstrated a nearly threefold increase in binding capacity at equivalent affinity when LRP was used. In addition, by adjusting the double bond conversion, we can choose to increase either the capacity or the affinity in highly cross-linked imprinted polymers, thus allowing the creation of imprinted polymers with tailorable binding parameters. Using free radical polymerization in the creation of polymer chains, as the template-monomer ratio increased, the average molecular weight of the polymer chains decreased despite a slight increase in the double bond conversion. Thus, the polymer chains formed were shorter but greater in number. Using LRP neutralized the effect of the template. The addition of chain transfer agent resulted in slow, uniform, simultaneous chain growth, resulting in the formation of longer more monodisperse chains. Reaction analysis revealed that propagation time was extended threefold in the formation of highly cross-linked polymers when LRP techniques were used. This delayed the transition to the diffusion-controlled stage of the reaction, which in turn led to the observed enhanced binding properties, decreased polydispersity in the chains, and a more homogeneous macromolecular architecture. Copyright © 2012 John Wiley & Sons, Ltd.
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Polymer-modified opal nanopores.
Schepelina, Olga; Zharov, Ilya
2006-12-05
The surface of nanopores in opal films, assembled from 205 nm silica spheres, was modified with poly(acrylamide) brushes using surface-initiated atom transfer radical polymerization. The colloidal crystal lattice remained unperturbed by the polymerization. The polymer brush thickness was controlled by polymerization time and was monitored by measuring the flux of redox species across the opal film using cyclic voltammetry. The nanopore size and polymer brush thickness were calculated on the basis of the limiting current change. Polymer brush thickness increased over the course of 26 h of polymerization in a logarithmic manner from 1.3 to 8.5 nm, leading to nanopores as small as 7.5 nm.
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Moraes, John; Ohno, Kohji; Maschmeyer, Thomas; Perrier, Sébastien
2013-10-14
Hybrid nanoparticles hold great promise for a range of applications such as drug-delivery vectors or colloidal crystal self-assemblies. The challenge of preparing highly monodisperse particles for these applications has recently been overcome by using living radical polymerization techniques. In particular, the use of reversible addition-fragmentation chain transfer (RAFT), initiated from silica surfaces, yields well-defined particles from a range of precursor monomers resulting in nanoparticles of tailored sizes that are accessible via the rational selection of polymerization conditions. Furthermore, using RAFT allows post-polymerization modification to afford multifunctional, monodisperse, nanostructures under mild and non-stringent reaction conditions.
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Well-Defined Macromolecules Using Horseradish Peroxidase as a RAFT Initiase.
Danielson, Alex P; Bailey-Van Kuren, Dylan; Lucius, Melissa E; Makaroff, Katherine; Williams, Cameron; Page, Richard C; Berberich, Jason A; Konkolewicz, Dominik
2016-02-01
Enzymatic catalysis and control over macromolecular architectures from reversible addition-fragmentation chain transfer polymerization (RAFT) are combined to give a new method of making polymers. Horseradish peroxidase (HRP) is used to catalytically generate radicals using hydrogen peroxide and acetylacetone as a mediator. RAFT is used to control the polymer structure. HRP catalyzed RAFT polymerization gives acrylate and acrylamide polymers with relatively narrow molecular weight distributions. The polymerization is rapid, typically exceeding 90% monomer conversion in 30 min. Complex macromolecular architectures including a block copolymer and a protein-polymer conjugate are synthesized using HRP to catalytically initiate RAFT polymerization. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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ERIC Educational Resources Information Center
Colombani, Olivier; Langelier, Ophelie; Martwong, Ekkachai; Castignolles, Patrice
2011-01-01
The use of an internal standard is a conventional and convenient way to monitor the conversion of one or several monomers during a controlled radical polymerization. However, the validity of this technique relies on an accurate determination of the initial monomer-to-internal standard ratio, A[subscript 0], because all subsequent calculations of…
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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.
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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/...
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NASA Astrophysics Data System (ADS)
Zhao, Jing; Chen, Miao; An, Yanqing; Liu, Jianxi; Yan, Fengyuan
2008-12-01
A radical chain-transfer polymerization technique has been applied to graft-polymerize brushes of polystyrene (PSt) on single-crystal silicon substrates. 3-Mercapto-propyltrimethoxysilane (MPTMS), as a chain-transfer agent for grafting, was immobilized on the silicon surface by a self-assembling process. The structure and morphology of the graft-functionalized silicon surfaces were characterized by the means of contact-angle measurement, ellipsometric thickness measurement, Fourier transformation infrared (FTIR) spectroscopy, and atomic force microscopy (AFM). The nanotribological and micromechanical properties of the as-prepared polymer brush films were investigated by frictional force microscopy (FFM), force-volume analysis and scratch test. The results indicate that the friction properties of the grafted polymer films can be improved significantly by the treatment of toluene, and the chemically bonded polystyrene film exhibits superior scratch resistance behavior compared with the spin-coated polystyrene film. The resultant polystyrene brush film is expected to develop as a potential lubrication coating for microelectromechanical systems (MEMS).
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Neti, Venkata S.; Das, Sadananda; Brown, Suree; ...
2017-08-29
Brush-on-brush structures are proposed as one method to overcome support effects in grafted polymers. Utilizing glycidyl methacrylate (GMA) grafted on polyethylene (PE) fibers using radiation-induced graft polymerization (RIGP) provides a hydrophilic surface on the hydrophobic PE. When integrated with atom transfer radical polymerization (ATRP), the grafting of acrylonitrile (AN) and hydroxyethyl acrylate (HEA) can be controlled and manipulated more easily than with RIGP. Poly(acrylonitrile)-co-poly(hydroxyethyl acrylate) chains were grown via ATRP on PE-GMA fibers to generate an adsorbent for the extraction of uranium from seawater. The prepared adsorbents in this study demonstrated promise (159.9 g-U/kg of adsorbent) in laboratory screening testsmore » using a high uranium concentration brine and 1.24 g-U/Kg of adsorbent in the filtered natural seawater in 21-days. Here, 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).« less
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Neti, Venkata S.; Das, Sadananda; Brown, Suree
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 testsmore » using a high uranium concentration brine and 1.24 g-U/Kg of adsorbent in the filtered natural seawater in 21-days. Here, 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).« less
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Neti, Venkata S.; Das, Sadananda; Brown, Suree
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 screeningmore » 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).« less
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Zhou, Shaohong; Yuan, Liang; Hua, Xin; Xu, Lingling; Liu, Songqin
2015-06-02
Demand is increasing for ultrasensitive bioassays for disease diagnosis, environmental monitoring and other research areas. This requires novel signal amplification strategies to maximize the signal output. In this review, we focus on a series of significant signal amplification strategies based on polymeric nanocomposites and polymerization. Some common polymers are used as carriers to increase the local concentration of signal probes and/or biomolecules on their surfaces or in their interiors. Some polymers with special fluorescence and optical properties can efficiently transfer the excitation energy from a single site to the whole polymer backbone. This results in superior fluorescence signal amplification due to the resulting collective effort (integration of signal). Recent polymerization-based signal amplification strategies that employ atom transfer radical polymerization (ATRP) and photo-initiated polymerization are also summarized. Several distinctive applications of polymers in ultrasensitive bioanalysis are highlighted. Copyright © 2015 Elsevier B.V. All rights reserved.
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Free-radical concentrations and other properties of pile-irradiated coals
Friedel, R.A.; Breger, I.A.
1959-01-01
Five coals reacted quite differently when they were exposed to pile-irradiation. Little or no change was found in free-radical content for the three coals of lowest carbon content, whereas the two coals of highest carbon content were found to have a considerable increase in free-radical content. The infrared spectra and the apparent hardness of the irradiated coals of higher carbon content indicate that polymerization occurred. Radiation of these coals in chemical reagents may promote reactivity.
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Development and evaluation of spherical molecularly imprinted polymer beads.
Kempe, Henrik; Kempe, Maria
2006-06-01
The majority of studies on molecularly imprinted polymers has until now been carried out on irregularly shaped particles prepared by grinding of polymer monoliths. The preparation procedures are time- and labor-consuming and produce particles of wide size distributions. To answer the need for fast and straightforward routes to spherical molecularly imprinted polymer beads, we have developed a method comprising the formation of droplets of pre-polymerization solution directly in mineral oil by vigorous mixing followed by transformation of the droplets into solid spherical beads by photoinduced free-radical polymerization. No detergents or stabilizers were required for the droplet formation. Factors influencing the bead synthesis have been investigated and are detailed here. The beads were evaluated in parallel with corresponding irregularly shaped particles prepared from polymer monoliths. Conditions for the synthesis of propranolol-imprinted poly(methacrylic acid-co-trimethylolpropane trimethacrylate) beads in the size range of 1-100 microm in almost quantitative yield are described. The beads were applied as the recognition element in a 96-well plate format radioligand assay of propranolol in human serum.
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Processable high-carbon-yielding polymer for micro- and nanofabrication
NASA Astrophysics Data System (ADS)
Perpall, Mark W.; Zengin, Huseyin; Perera, K. Prasanna U.; Zhou, Wensheng; Shah, Hiren; Wu, Xinyu; Creager, Stephen E.; Smith, Dennis W., Jr.; Foulger, Stephen H.; Ballato, John M.
2003-01-01
Bis-ortho-Diynyl Arene (BODA) monomers polymerize to network polynapthalene by the thermally-driven Bergman cyclization and subsequent radical polymerization via oligomeric intermediates that can be melt or solution processed. Further heating of the network to 1000 °C affords a high-yield glassy carbon structure that retains the approximate size and dimensions of the polymer precursor. The higher carbon-yield for BODA networks (75- 80 % by mass) is significantly greater than that of traditional phenol-formaldehyde resins and other carbon precursor polymers leading to its greater dimensional stability. Phenyl terminated BODA derived polymers were fabricated using microprocessing such as the micromolding in capillaries (MIMIC) technique, direct microtransfer molding, and molding in quartz capillary tubes. Nano-scale fabrication using closed packed silica spheres as templates was demonstrated with an hydroxy-terminated monomer which exhibits greatly enhanced compatibility for silica surfaces. After pyrolysis to glassy carbon, the silica is chemically etched leaving an inverse carbon opal photonic crystal which is electrically conductive. The wavelength of light diffracted is a function of the average refractive index of the carbon/ filler composite, which can be modified for use as sensitive detector elements.
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NASA Astrophysics Data System (ADS)
Topa, Monika; Ortyl, Joanna; Chachaj-Brekiesz, Anna; Kamińska-Borek, Iwona; Pilch, Maciej; Popielarz, Roman
2018-06-01
Applicability of 15 trivalent samarium complexes as novel luminescent probes for monitoring progress of photopolymerization processes or thickness of polymer coatings by the Fluorescence Probe Technique (FPT) was studied. Three groups of samarium(III) complexes were evaluated in cationic photopolymerization of triethylene glycol divinyl ether monomer (TEGDVE) and free-radical photopolymerization of trimethylolpropane triacrylate (TMPTA). The complexes were the derivatives of tris(4,4,4-trifluoro-1-(2-thienyl)-1,3-butanedionate)samarium(III), tris(4,4,4-trifluoro-1-phenyl-1,3-butanedionate)samarium(III) and tris(4,4,4-trifluoro-1-(2-naphthyl)-1,3-butanedionate)samarium(III), which were further coordinated with auxiliary ligands, such as 1,10-phenanthroline, triphenylphosphine oxide, tributylphosphine oxide and trioctylphosphine oxide. It has been found that most of the complexes studied are sensitive enough to be used as luminescent probes for monitoring progress of cationic photopolymerization of vinyl ether monomers over entire range of monomer conversions. In the case of free-radical polymerization processes, the samarium(III) complexes are not sensitive enough to changes of microviscosity and/or micropolarity of the medium, so they cannot be used to monitor progress of the polymerization. However, high stability of luminescence intensity of some of these complexes under free-radical polymerization conditions makes them good candidates for application as thickness sensors for polymer coatings prepared by free-radical photopolymerization. A quantitative relationship between a coating thickness and the luminescence intensity of the samarium(III) probes has been derived and verified experimentally within a broad range of the thicknesses.
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Composition and method of preparation of solid state dye laser rods
Hermes, Robert E.
1992-01-01
The present invention includes solid polymeric-host laser rods prepared using bulk polymerization of acrylic acid ester comonomers which, when admixed with dye(s) capable of supporting laser oscillation and polymerized with a free radical initiator under mild thermal conditions, produce a solid product having the preferred properties for efficient lasing. Unsaturated polymerizable laser dyes can also be employed as one of the comonomers. Additionally, a method is disclosed which alleviates induced optical stress without having to anneal the polymers at elevated temperatures (>85.degree. C.).
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Survey Study of Trunk Materials for Direct ATRP Grafting
DOE Office of Scientific and Technical Information (OSTI.GOV)
Saito, Tomonori; Chatterjee, Sabornie; Johnson, Joseph C.
2015-02-01
In previous study, we demonstrated a new method to prepare polymeric fiber adsorbents via a chemical-grafting method, namely atom-transfer radical polymerization (ATRP), and identified parameters affecting their uranium adsorption capacity. However, ATRP chemical grafting in the previous study still utilized conventional radiation-induced graft polymerization (RIGP) to introduce initiation sites on fibers. Therefore, the objective of the present study is to perform survey study of trunk fiber materials for direct ATRP chemical grafting method without RIGP for the preparation of fiber adsorbents for uranium recovery from seawater.
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Limpoco, F Ted; Bailey, Ryan C
2011-09-28
We directly monitor in parallel and in real time the temporal profiles of polymer brushes simultaneously grown via multiple ATRP reaction conditions on a single substrate using arrays of silicon photonic microring resonators. In addition to probing relative polymerization rates, we show the ability to evaluate the dynamic properties of the in situ grown polymers. This presents a powerful new platform for studying modified interfaces that may allow for the combinatorial optimization of surface-initiated polymerization conditions.
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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.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Y Hu; D Samanta; S Parelkar
Controlled free radical polymerization chemistry is used to graft polymer chains to the corona of horse spleen ferritin (HSF) nanocages. Specifically, poly(methacryloyloxyethyl phosphorylcholine) (polyMPC) and poly(PEG methacrylate) (polyPEGMA) chains are grafted onto the nanocages by atom transfer radical polymerization (ATRP), in which the molecular weight of the polymer grafts is controlled by the monomer-to-initiator feed ratio. PolyMPC and polyPEGMA-grafted ferritin show a generally suppressed inclusion into diblock copolymer films relative to native ferritin, and the polymer coating is seen to mask the ferritin nanocages from antibody recognition. The solubility of polyPEGMA-coated ferritin in organic solvents enables its processing with polystyrene-block-poly(ethylenemore » oxide) copolymers, and selective integration into the PEO domains of microphase-separated copolymer structures.« less
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NASA Astrophysics Data System (ADS)
Wu, Yuanpeng; Guo, Meiling; Liu, Guanfei; Xue, Shishan; Xia, Yuanmeng; Liu, Dan; Lei, Weiwei
2018-04-01
In this study, the surface modification of boron nitride nanosheets (BNNSs) with poly 2-acrylamido-2-methyl- propanesulfonate (PAMPS) brushes is achieved through electron transfer atom transfer radical polymerization (ARGET ATRP). BNNSs surface was first modified with α-bromoisobutyryl bromide (BIBB) via hydroxyl groups, then PAMPS brushes were grown on the surface through ARGET ATRP. Polyelectrolyte brushes modified BNNSs were further characterized by Fourier transform infrared spectroscopy (FTIR), thermogravimetric analyses (TGA), x-ray powder diffraction (XRD) and scanning electron microscopy (SEM). The concentraction of water-dispersion of BNNSs have been enhanced significantly by PAMPS and the high water-dispersible functional BNNSs/PAMPS composites are expected to have potential applications in biomedical and thermal management in electronics.
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Presidential Green Chemistry Challenge: 2009 Academic Award
Presidential Green Chemistry Challenge 2009 award winner, Professor Krzysztof Matyjaszewski, developed Atom Transfer Radical Polymerization to make polymers with copper catalysts and environmentally friendly reducing agents.
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Functionalized Nano and Micro Structured Composite Coatings
2011-06-01
created. Contact angles for water, hexadecane and warfare simulants (tributyl phosphate (TBP), methyl salicylate (MS) and 2-chloroethyl ethyl sulfide... methyl salicylate PAA-POEGMA polyacrylic acid-co-poly(oligoethylene glycol methacrylate) PBMA poly(butyl methacrylate) PD-TDES commercial mixture of...polymerized radically (according to a procedure published elsewhere1) to give PGMA, Mn = 300,000 kDa, PDI = 2. The polymerization was carried out in methyl
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Hydrocarbon polymeric binder for advanced solid propellant
NASA Technical Reports Server (NTRS)
Potts, J. E. (Editor); Ashcraft, A. C., Jr.; Wise, E. W.
1971-01-01
The results of curing vinyl alcohol terpolymers of ethylene, propylene and vinyl acetate are reported for an average functionality of 1.24 when reacted with an equivalent amount of diisocynate, and saturated polyisoprene derivative is described having terminal methyl ester functionality. The development is reported of two hydroxy-telechelic polyisoprenes prepared by DEAB initiated free radical polymerization followed by LiAlH4 reduction of the end groups.
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Krishna, Lekshmi; Jayabalan, Muthu
2009-12-01
Biodegradable poly (caprolactone diol-co-propylene fumarate-co-ethylene glycol) amphiphilic polymer with poly (ethylene glycol) and poly (caprolactone diol) chain ends (PCL-PPF-PEG) was prepared. PCL-PPF-PEG undergoes fast setting with acrylamide (aqueous solution) by free radical polymerization and produces a crosslinked hydrogel. The cross linked and freeze-dried amphiphilic material has porous and interconnected network. It undergoes higher degree of swelling and water absorption to form hydrogel with hydrophilic and hydrophobic domains at the surface and appreciable tensile strength. The present hydrogel is compatible with L929 fibroblast cells. PCL-PPF-PEG/acrylamide hydrogel is a candidate scaffold material for tissue engineering applications.
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Combinatorial and high-throughput approaches in polymer science
NASA Astrophysics Data System (ADS)
Zhang, Huiqi; Hoogenboom, Richard; Meier, Michael A. R.; Schubert, Ulrich S.
2005-01-01
Combinatorial and high-throughput approaches have become topics of great interest in the last decade due to their potential ability to significantly increase research productivity. Recent years have witnessed a rapid extension of these approaches in many areas of the discovery of new materials including pharmaceuticals, inorganic materials, catalysts and polymers. This paper mainly highlights our progress in polymer research by using an automated parallel synthesizer, microwave synthesizer and ink-jet printer. The equipment and methodologies in our experiments, the high-throughput experimentation of different polymerizations (such as atom transfer radical polymerization, cationic ring-opening polymerization and emulsion polymerization) and the automated matrix-assisted laser desorption/ionization time-of-flight mass spectroscopy (MALDI-TOF MS) sample preparation are described.
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Analyses and comparison of a novel, hybrid, multifunctional orthopedic composite and implant
NASA Astrophysics Data System (ADS)
Dicicco, Michael
In the orthopedic/medical device industry, 2, 2' -bis-(4-(2-hydroxy-3-methacryloxypropoxy)phenyl]propane (Bis-GMA)- and diurethanedimethacrylate (DUDMA)-based polymeric biomaterials have become well-known substitutes for polymethylmethacrylate (PMMA)- and ultra-high molecular weight polyethylene (UHMWPE)-based biomaterials, respectively. The development of these polymeric biomaterials cannot continue without direct comparison studies against currently marketed materials. The initiative for this research stems wholly from developing analytical methodologies that assist in qualifying novel biomaterials under development, by evaluating their chemical properties, performance, and safety. The goals of this research were: (i) Characterize the assay/quality of every resin component and quantify elution of extractable monomers from novel, DUDMA-based RHAKOSS(TM) implant, (ii) Determine degree of conversion (alpha) and rate of polymerization (Rp) for novel, Bis-GMA-based CORTOSS(TM) composite, (iii) Assess risk for radical-induced post-surgical cytotoxicity for CORTOSS, (iv) Determine if surface radical chemistries occur for sterilized RHAKOSS and assess its oxidative stability, and (v) Quantify antibiotic elution from antibiotic-impregnated CORTOSS and identify factors that control elution. The phenomena studied necessitated the utilization of several analytical spectroscopic techniques; fluorometry, differential scanning calorimetry (DSC), electron paramagnetic resonance (EPR), ultraviolet-visible (UV-VIS), attenuated total reflectance---Fourier-transform infrared (ATR-FTIR), and high performance liquid chromatography (HPLC). A battery of lateral chemical techniques were employed as well; including molecular derivatization/tagging, phase partitioning, spin-trapping, and thermal annealing. Results demonstrated that RHAKOSS monomer percent compositions were prepared according to formulations and monomer elution was virtually undetectable, serving as an empirical gauge to portend degree of polymerization (DOP). A high alpha was reported for CORTOSS and essentially all bifunctional monomers had at least one functional group polymerized, stressing low monomer elution potential. Regarding cytotoxicity, CORTOSS impeded further production of hydroxyl radicals (•OH), whereas RHAKOSS did not facilitate the Fenton reaction but displayed some chelating abilities. Residual radicals in RHAKOSS were easily terminated, thus not projected to form oxidative degradants. Additionally, significant antibiotic concentrations, over extended durations, eluted from CORTOSS in linear-type fashion, advocating a sustained therapeutic effect, and phase partitioning correlated antibiotic release to hydrophilicity. The incurred data comprehensively argues in favor of the excellent biocompatibility that CORTOSS and RHAKOSS inherently possess, and was definitive in rendering them as advanced biomaterials, possessing favorable chemical properties.
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Roeleveld, Kevin; David, Frank; Lynen, Frédéric
2016-06-17
In this study the merits of polymerized imidazolium based ionic liquid (PIL) stationary phases obtained via condensation and free radical polymerizations are compared as stationary phases in gas chromatography (GC). Poly(1-vinyl-3-butyl-imidazolium - bis(trifluoromethane)sulfonamide) (poly(ViC4Im(+) NTf2(-))) was obtained via a chain-growth mechanism while poly(propylimidazolium-NTf2) (poly(C3Im(+) NTf2(-))) was synthesized via a step-growth polymerization. The thermal stability of both polymers was assessed using thermal gravimetric analysis and compared with bleeding profiles obtained from the statically coated GC columns (30m×0.25mm×0.25μm). The performance was compared to what could be obtained on commercially available 1,5-di(2,3-dimethylimidazolium)pentane(2+) 2NTf2(-) (SLB-IL111) ionic liquid based columns. It was observed that the step-growth polymer was more thermally stable, up to 325°C, while the chain-growth polymer showed initial degradation at 250°C. Both polymers allowed reaching minimal plate heights of 0.400-0.500mm for retained solutes such as benzaldehyde, acetophenone, 1-methylnaphthalene and aniline. Assessment of the McReynolds constants illustrated that the polarity of the step-growth polymer was similar to the SLB-IL111 column, while displaying improved column stability. The PIL phases and particularly the so far little studied condensation based polymer shows particular retention and satisfactory column performance for polar moieties such as esters, amine and carbonyl functionalities. Copyright © 2016 Elsevier B.V. All rights reserved.
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Arginine- and lysine-specific polymers for protein recognition and immobilization.
Renner, Christian; Piehler, Jacob; Schrader, Thomas
2006-01-18
Free radical polymerization of methacrylamide-based bisphosphonates turns weak arginine binders into powerful polymeric protein receptors. Dansyl-labeled homo- and copolymers with excellent water solubility are accessible through a simple copolymerization protocol. Modeling studies point to a striking structural difference between the stiff rodlike densely packed homopolymer 1 and the flexible copolymer 2 with spatially separated bisphosphonate units. Fluorescence titrations in buffered aqueous solution (pH = 7.0) confirm the superior affinity of the homopolymer toward oligoarginine peptides reaching nanomolar K(D) values for the Tat peptide. Basic proteins are bound almost equally well by 1 and 2 with micromolar affinities, with the latter producing much more soluble complexes. The Arg selectivity of the monomer is transferred to the polymer, which binds Arg-rich proteins 1 order of magnitude tighter than lysine-rich pendants of comparable pI, size, and (Arg/Lys vs Glu/Asp) ratio. Noncovalent deposition of both polymers on glass substrates via polyethyleneimine layers results in new materials suitable for peptide and protein immobilization. RIfS measurements allow calculation of association constants K(a) as well as dissociation kinetics k(D). They generally confirm the trends already found in free solution. Close inspection of electrostatic potential surfaces suggest that basic domains favor protein binding on the flat surface. The high specificity of the bisphosphonate polymers toward basic proteins is demonstrated by comparison with polyvinyl sulfate, which has almost no effect in RIfS experiments. Thus, copolymerization of few different comonomer units without cross-linking enables surface recognition of basic proteins in free solution as well as their effective immobilization on surfaces.
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Synthesis of Resveratrol Tetramers via a Stereoconvergent Radical Equilibrium
Keylor, Mitchell H.; Matsuura, Bryan S.; Griesser, Markus; Chauvin, Jean-Philippe R.; Harding, Ryan A.; Kirillova, Mariia S.; Zhu, Xu; Fischer, Oliver J.; Pratt, Derek A.; Stephenson, Corey R. J.
2017-01-01
Persistent free radicals have become indispensable in the synthesis of organic materials by living radical polymerization. However, examples of their use in the synthesis of small molecules are rare. Herein, we report the application of persistent radical and quinone methide intermediates to the synthesis of the resveratrol tetramers nepalensinol B and vateriaphenol C. The spontaneous cleavage and reconstitution of exceptionally weak carbon-carbon bonds has enabled a stereoconvergent oxidative dimerization of racemic materials in a transformation that likely coincides with the biogenesis of these natural products. The efficient synthesis of higher-order oligomers of resveratrol will facilitate the biological studies necessary to elucidate their mechanism(s) of action. PMID:27940867
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NASA Astrophysics Data System (ADS)
Zheng, Yuan; Chen, Dongyun; Li, Najun; Xu, Qingfeng; Li, Hua; He, Jinghui; Lu, Jianmei
2016-02-01
Water contamination becomes one of the most pervasive environmental issues all over the world in recent years. In this paper, the functionalization of graphene oxide (GO) with copolymers containing methacrylic acid (MAA) and butyl methacrylate (BMA) was investigated to prepare a new microcomposite material (PGO) via free radical solution polymerization. PGO was used for the adsorption of N,N-dimethylformamide (DMF) from aqueous solution by utilizing the characteristics of ultralarge surface and the Van der Waals force between DMF molecules and polymers on the surface of PGO. Besides, PGO was used not only a high-capable adsorbent but also a carrier for the immobilization of Paracoccus denitrificans cells in the treatment of high-concentrated DMF. Bacterial cells could immobilized on the PGO (PGO@P. denitrificans) stably by covalent coupling process after acclimatization and high-concentrated DMF (2000 mg/L) could be removed completely and relatively rapidly from aqueous solutions by the simultaneous adsorption-biodegradation (SAB) process of PGO@P. denitrificans. Furthermore, the excellent recycle performance of PGO@P. denitrificans made the whole process more economical and practical.
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Chain Conformation of Phosphorycholine-based Zwitterionic Polymer Brushes in Aqueous Solutions
NASA Astrophysics Data System (ADS)
Mao, Jun; Yu, Jing; Lee, Sungsik; Yuan, Guangcui; Satija, Sushil; Chen, Wei; Tirrell, Matthew
Polyzwitterionic brushes are resistant to nonspecific accumulation of proteins and microorganisms, making them excellent candidates for antifouling applications. It is well-known that polyzwitterions exhibit the so-called antipolyelectrolyte effect: Polyzwitterionic brushes would adopt a collapsed conformation at a low ionic strength due to the electrostatic inter/intra-chain association; whereas at a high ionic strength, they would exhibit an extended conformation because the electrostatic inter/intra-chain dipole-dipole interaction is weakened. However, poly(2-methacryloyloxyethyl phosphorylcholine) (PMPC) is a unique member in polyzwitterionic families. Its ultrahigh affinity to water leads to no detectable shrinks in aqueous solutions even at low ionic strengths. In this study, we synthesized highly dense PMPC brushes via surface initiated radical polymerization and systematically investigate their conformational behaviors at solid-liquid interfaces in the presence of multivalent counterions, combining X-ray and neutron scattering and force measurements. We have demonstrated that despite no obvious changes of the entire lengths of extended PMPC brushes in aqueous solutions, the chain conformations including, but not limited to, polyzwitterion distribution and charge correlation, varied, dependent on salt types, ionic strengths and ion valences.
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Multiple stimulus reversible hydrogels
Gutowska, Anna; Krzyminski, Karol J.
2003-12-09
A polymeric solution capable of gelling upon exposure to a critical minimum value of a plurality of environmental stimuli is disclosed. The polymeric solution may be an aqueous solution utilized in vivo and capable of having the gelation reversed if at least one of the stimuli fall below, or outside the range of, the critical minimum value. The aqueous polymeric solution can be used either in industrial or pharmaceutical environments. In the medical environment, the aqueous polymeric solution is provided with either a chemical or radioisotopic therapeutic agent for delivery to a specific body part. The primary advantage of the process is that exposure to one environmental stimuli alone will not cause gelation, thereby enabling the therapeutic agent to be conducted through the body for relatively long distances without gelation occurring.
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Multiple stimulus reversible hydrogels
Gutowska, Anna; Krzyminski, Karol J.
2006-04-25
A polymeric solution capable of gelling upon exposure to a critical minimum value of a plurality of environmental stimuli is disclosed. The polymeric solution may be an aqueous solution utilized in vivo and capable of having the gelation reversed if at least one of the stimuli fall below, or outside the range of, the critical minimum value. The aqueous polymeric solution can be used either in industrial or pharmaceutical environments. In the medical environment, the aqueous polymeric solution is provided with either a chemical or radioisotopic therapeutic agent for delivery to a specific body part. The primary advantage of the process is that exposure to one environmental stimuli alone will not cause gelation, thereby enabling the therapeutic agent to be conducted through the body for relatively long distances without gelation occurring.
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A Visible Light Initiating System for Free Radical Promoted Cationic Polymerization
1994-02-02
identify the end groups in the polymer of cyclohexene oxide. N,N-Dimethylnaphthyl amine (DNA), a compound with high fluorescence quantum yield, was used...candidates to be polymerized via a cationic mechanism include cyclic ethers, cyclic formals and acetals, vinyl ethers, and epoxy compounds . Of these...reported sensitizer, bears two dimethylamino groups, is direct evidence that an aromatic amine can be present in a cationically photopolymerizable system
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2012-04-01
Methanol Octane Methylene Iodide Water Superhydrophobic /oleophilic dip-coated fabric Tuteja et al, Science, 2007, 318, 1618 Superamphiphobic...building block material for low surface energy materials • Applications – Mechanical robust superhydrophobic /oleophobic/omniphobic surfaces • Via...non-wetting polymeric surfaces 5 mm Methanol Octane Methylene Iodide Water Superhydrophobic /oleophilic dip-coated fabric Tuteja et al, Science, 2007
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Nanoporous thermosetting polymers.
Raman, Vijay I; Palmese, Giuseppe R
2005-02-15
Potential applications of nanoporous thermosetting polymers include polyelectrolytes in fuel cells, separation membranes, adsorption media, and sensors. Design of nanoporous polymers for such applications entails controlling permeability by tailoring pore size, structure, and interface chemistry. Nanoporous thermosetting polymers are often synthesized via free radical mechanisms using solvents that phase separate during polymerization. In this work, a novel technique for the synthesis of nanoporous thermosets is presented that is based on the reactive encapsulation of an inert solvent using step-growth cross-linking polymerization without micro/macroscopic phase separation. The criteria for selecting such a monomer-polymer-solvent system are discussed based on FTIR analysis, observed micro/macroscopic phase separation, and thermodynamics of swelling. Investigation of resulting network pore structures by scanning electron microscopy (SEM) and small-angle X-ray scattering following extraction and supercritical drying using carbon dioxide showed that nanoporous polymeric materials with pore sizes ranging from 1 to 50 nm can be synthesized by varying the solvent content. The differences in the porous morphology of these materials compared to more common free radically polymerized analogues that exhibit phase separation were evident from SEM imaging. Furthermore, it was demonstrated that the chemical activity of the nanoporous materials obtained by our method could be tailored by grafting appropriate functional groups at the pore interface.
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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.
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Lligadas, Gerard; Grama, Silvia; Percec, Virgil
2017-04-10
Single electron transfer-living radical polymerization (SET-LRP) represents a robust and versatile tool for the synthesis of vinyl polymers with well-defined topology and chain end functionality. The crucial step in SET-LRP is the disproportionation of the Cu(I)X generated by activation with Cu(0) wire, powder, or nascent Cu(0) generated in situ into nascent, extremely reactive Cu(0) atoms and nanoparticles and Cu(II)X 2 . Nascent Cu(0) activates the initiator and dormant chains via a homogeneous or heterogeneous outer-sphere single-electron transfer mechanism (SET-LRP). SET-LRP provides an ultrafast polymerization of a plethora of monomers (e.g., (meth)-acrylates, (meth)-acrylamides, styrene, and vinyl chloride) including hydrophobic and water insoluble to hydrophilic and water soluble. Some advantageous features of SET-LRP are (i) the use of Cu(0) wire or powder as readily available catalysts under mild reaction conditions, (ii) their excellent control over molecular weight evolution and distribution as well as polymer chain ends, (iii) their high functional group tolerance allowing the polymerization of commercial-grade monomers, and (iv) the limited purification required for the resulting polymers. In this Perspective, we highlight the recent advancements of SET-LRP in the synthesis of biomacromolecules and of their conjugates.
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Szczepanski, Caroline R.; Pfeifer, Carmem S.; Stansbury, Jeffrey W.
2012-01-01
Non-reactive, thermoplastic prepolymers (poly- methyl, ethyl and butyl methacrylate) were added to a model homopolymer matrix composed of triethylene glycol dimethacrylate (TEGDMA) to form heterogeneous networks via polymerization induced phase separation (PIPS). PIPS creates networks with distinct phase structure that can partially compensate for volumetric shrinkage during polymerization through localized internal volume expansion. This investigation utilizes purely photo-initiated, free-radical systems, broadening the scope of applications for PIPS since these processing conditions have not been studied previously. The introduction of prepolymer into TEGDMA monomer resulted in stable, homogeneous monomer formulations, most of which underwent PIPS upon photo-irradiation, creating heterogeneous networks. During polymerization the presence of prepolymer enhanced autoacceleration, allowing for a more extensive ambient cure of the material. Phase separation, as characterized by dynamic changes in sample turbidity, was monitored simultaneously with monomer conversion and either preceded or was coincident with network gelation. Dynamic mechanical analysis shows a broadening of the tan delta peak and secondary peak formation, characteristic of phase-separated materials, indicating one phase rich in prepolymer and another depleted form upon phase separation. In certain cases, PIPS leads to an enhanced physical reduction of volumetric shrinkage, which is attractive for many applications including dental composite materials. PMID:23109733
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Gong, Honghong; Zhao, Yucheng; Shen, Xianwang; Lin, Jun; Chen, Mao
2018-01-02
Fluorinated polymers are important materials that are widely used in many areas. Herein, we report the development of a metal-free photocontrolled radical polymerization of semifluorinated (meth)acrylates with a new visible-light-absorbing organocatalyst. This method enabled the production of a variety of semifluorinated polymers with narrow molar-weight distributions from semifluorinated trithiocarbonates or perfluoroalkyl iodides. The high performance of "ON/OFF" control and chain-extension experiments further demonstrate the utility and reliability of this method. Furthermore, to streamline the preparation of semifluorinated polymers, a scalable continuous-flow approach has been developed. Given the broad interest in fluorinated materials and photopolymerization, we expect that this method will facilitate the development of advanced materials with unique properties. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Maeda, Satoshi; Fujita, Masato; Idota, Naokazu; Matsukawa, Kimihiro; Sugahara, Yoshiyuki
2016-12-21
Transparent TiO 2 /PMMA hybrids with a thickness of 5 mm and improved refractive indices were prepared by in situ polymerization of methyl methacrylate (MMA) in the presence of TiO 2 nanoparticles bearing poly(methyl methacrylate) (PMMA) chains grown using surface-initiated atom transfer radical polymerization (SI-ATRP), and the effect of the chain length of modified PMMA on the dispersibility of modified TiO 2 nanoparticles in the bulk hybrids was investigated. The surfaces of TiO 2 nanoparticles were modified with both m-(chloromethyl)phenylmethanoyloxymethylphosphonic acid bearing a terminal ATRP initiator and isodecyl phosphate with a high affinity for common organic solvents, leading to sufficient dispersibility of the surface-modified particles in toluene. Subsequently, SI-ATRP of MMA was achieved from the modified surfaces of the TiO 2 nanoparticles without aggregation of the nanoparticles in toluene. The molecular weights of the PMMA chains cleaved from the modified TiO 2 nanoparticles increased with increases in the prolonging of the polymerization period, and these exhibited a narrow distribution, indicating chain growth controlled by SI-ATRP. The nanoparticles bearing PMMA chains were well-dispersed in MMA regardless of the polymerization period. Bulk PMMA hybrids containing modified TiO 2 nanoparticles with a thickness of 5 mm were prepared by in situ polymerization of the MMA dispersion. The transparency of the hybrids depended significantly on the chain length of the modified PMMA on the nanoparticles, because the modified PMMA of low molecular weight induced aggregation of the TiO 2 nanoparticles during the in situ polymerization process. The refractive indices of the bulk hybrids could be controlled by adjusting the TiO 2 content and could be increased up to 1.566 for 6.3 vol % TiO 2 content (1.492 for pristine PMMA).
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NASA Astrophysics Data System (ADS)
Zvaigzne, M. A.; Martynov, I. L.; Krivenkov, V. A.; Samokhvalov, P. S.; Nabiev, I. R.
2017-01-01
Photoluminescent semiconductor nanocrystals, quantum dots (QDs), are nowadays one of the most promising materials for developing a new generation of fluorescent labels, new types of light-emitting devices and displays, flexible electronic components, and solar panels. In many areas the use of QDs is associated with an intense optical excitation, which, in the case of a prolonged exposure, often leads to changes in their optical characteristics. In the present work we examined how the method of preparation of quantum dot/polymethylmethacrylate (QD/PMMA) composite influenced the stability of the optical properties of QD inside the polymer matrix under irradiation by different laser harmonics in the UV (355 nm) and visible (532 nm) spectral regions. The composites were synthesized by spin-coating and radical polymerization methods. Experiments with the samples obtained by spin-coating showed that the properties of the QD/PMMA films remain almost constant at values of the radiation dose below 10 fJ per particle. Irradiating the composites prepared by the radical polymerization method, we observed a monotonic increase in the luminescence quantum yield (QY) accompanied by an increase in the luminescence decay time regardless of the wavelength of the incident radiation. We assume that the observed difference in the optical properties of the samples under exposure to laser radiation is associated with the processes occurring during radical polymerization, in particular, with charge transfer from the radical particles inside QDs. The results of this study are important for understanding photophysical properties of composites on the basis of QDs, as well as for selection of the type of polymer and the composite synthesis method with quantum dots that would allow one to avoid the degradation of their luminescence.
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Antireflective graded index silica coating, method for making
Yoldas, Bulent E.; Partlow, Deborah P.
1985-01-01
Antireflective silica coating for vitreous material is substantially non-reflecting over a wide band of radiations. This is achieved by providing the coating with a graded degree of porosity which grades the index of refraction between that of air and the vitreous material of the substrate. To prepare the coating, there is first prepared a silicon-alkoxide-based coating solution of particular polymer structure produced by a controlled proportion of water to alkoxide and a controlled concentration of alkoxide to solution, along with a small amount of catalyst. The primary solvent is alcohol and the solution is polymerized and hydrolized under controlled conditions prior to use. The prepared solution is applied as a film to the vitreous substrate and rapidly dried. It is thereafter heated under controlled conditions to volatilize the hydroxyl radicals and organics therefrom and then to produce a suitable pore morphology in the residual porous silica layer. The silica layer is then etched in order to enlarge the pores in a graded fashion, with the largest of the pores remaining being sufficiently small that radiations to be passed through the substrate are not significantly scattered. For use with quartz substrates, extremely durable coatings which display only 0.1% reflectivity have been prepared.
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Feng, Juanjuan; Sun, Min; Xu, Lili; Li, Jubai; Liu, Xia; Jiang, Shengxiang
2011-10-28
Polymeric 1-vinyl-3-octylimidazolium hexafluorophosphate was synthesized in situ on stainless steel wire by surface radical chain-transfer polymerization and used as sensitive coatings in solid-phase microextraction. The outer surface of the stainless steel wire was firstly coated with microstructured silver layer via silver mirror reaction and then functionalized with self-assembled monolayers of 1,8-octanedithiol, which acted as chain transfer agent in the polymerization. Coupled to gas chromatography, extraction performance of the fiber was studied with both headspace and direct-immersion modes using benzene, toluene, ethylbenzene and xylenes (BTEX), phenols and polycyclic aromatic hydrocarbon (PAHs) as model analytes. In combination with the microstructured silver layer, the PIL-coated fiber exhibited high extraction efficiency. Linear ranges for BTEX with headspace mode were in the range of 0.2-1000 μg L(-1) for benzene, and 0.1-1000 μg L(-1) for toluene, ethylbenzene and xylenes. Limits of detection (LODs) were from 0.02 to 0.05 μg L(-1). Wide linear ranges of direct-immersion mode for the extraction of several phenols and PAHs were also obtained with correlation coefficients (R) from 0.9943 to 0.9997. The proposed fiber showed good durability with long lifetime. RSDs of 56 times extraction were still in an acceptable range, from 8.85 to 22.8%. Copyright © 2011 Elsevier B.V. All rights reserved.
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Abney, Kent D.; Kinkead, Scott A.; Mason, Caroline F. V.; Rais, Jiri
1997-01-01
Preparation and use of polymeric materials containing hydrophobic anions and plasticizers for extraction of cesium and strontium. The use of polymeric materials containing plasticizers which are solvents for hydrophobic anions such as derivatives of cobalt dicarbollide or tetraphenylborate which are capable of extracting cesium and strontium ions from aqueous solutions in contact with the polymeric materials, is described. The polymeric material may also include a synergistic agent for a given ion like polyethylene glycol or a crown ether, for removal of radioactive isotopes of cesium and strontium from solutions of diverse composition and, in particular, for solutions containing large excess of sodium nitrate.
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Abney, K.D.; Kinkead, S.A.; Mason, C.F.V.; Rais, J.
1997-09-09
Preparation and use is described for polymeric materials containing hydrophobic anions and plasticizers for extraction of cesium and strontium. The use of polymeric materials containing plasticizers which are solvents for hydrophobic anions such as derivatives of cobalt dicarbollide or tetraphenylborate which are capable of extracting cesium and strontium ions from aqueous solutions in contact with the polymeric materials, is described. The polymeric material may also include a synergistic agent for a given ion like polyethylene glycol or a crown ether, for removal of radioactive isotopes of cesium and strontium from solutions of diverse composition and, in particular, for solutions containing large excess of sodium nitrate.
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NASA Astrophysics Data System (ADS)
Jin, Kailong; Li, Lingqiao; Torkelson, John
Rubber tires illustrate well the issues ranging from economic loss to environmental problems and sustainability issues that arise with spent, covalently crosslinked polymers. A nitroxide-mediated polymerization (NMP) strategy has been developed that allows for one-step synthesis of recyclable crosslinked polymers from monomers or polymers that contain carbon-carbon double bonds amenable to radical polymerization. Resulting materials possess dynamic alkoxyamine crosslinks that undergo reversible decrosslinking as a function of temperature. Using polybutadiene as starting material, and styrene, an appropriate nitroxide molecule and bifunctional initiator for initial crosslinking, a model for tire rubber can be produced by reaction at temperatures comparable to those employed in tire molding. Upon cooling, the crosslinks are made permanent due to the extraordinarily strong temperature dependence of the reverisible nitroxide capping and uncapping reaction. Based on thermomechanical property characterization, when the original crosslinked model rubber is chopped into bits and remolded in the melt state, a well-consolidated material is obtained which exhibits full recovery of properties reflecting crosslink density after multiple recycling steps.
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A novel solid state photocatalyst for living radical polymerization under UV irradiation
NASA Astrophysics Data System (ADS)
Fu, Qiang; McKenzie, Thomas G.; Ren, Jing M.; Tan, Shereen; Nam, Eunhyung; Qiao, Greg G.
2016-02-01
This study presents the development of a novel solid state photocatalyst for the photoinduced controlled radical polymerization of methacrylates under mild UV irradiation (λmax ≈ 365 nm) in the absence of conventional photoinitiators, metal-catalysts or dye sensitizers. The photocatalyst design was based on our previous finding that organic amines can act in a synergistic photochemical reaction with thiocarbonylthio compounds to afford well controlled polymethacrylates under UV irradiation. Therefore, in the current contribution an amine-rich polymer was covalently grafted onto a solid substrate, thus creating a heterogeneous catalyst that would allow for facile removal, recovery and recyclability when employed for such photopolymerization reactions. Importantly, the polymethacrylates synthesized using the solid state photocatalyst (ssPC) show similarly excellent chemical and structural integrity as those catalysed by free amines. Moreover, the ssPC could be readily recovered and re-used, with multiple cycles of polymerization showing minimal effect on the integrity of the catalyst. Finally, the ssPC was employed in various photo-“click” reactions, permitting high yielding conjugations under photochemical control.
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Huang, Zhicheng; Gu, Yu; Liu, Xiaodong; Zhang, Lifen; Cheng, Zhenping; Zhu, Xiulin
2017-05-01
It is well known that the recently developed photoinduced metal-free atom transfer radical polymerization (ATRP) has been considered as a promising methodology to completely eliminate transition metal residue in polymers. However, a serious problem needs to be improved, namely, large amount of organic photocatalysts should be used to keep the controllability over molecular weights and molecular weight distributions. In this work, a novel photocatalyst 1,2,3,5-tetrakis(carbazol-9-yl)-4,6-dicyanobenzene (4CzIPN) with strong excited state reduction potential is successfully used to mediate a metal-free ATRP of methyl methacrylate just with parts per million (ppm) level usage under irradiation of blue light emitting diode at room temperature, using ethyl α-bromophenyl-acetate as a typical initiator with high initiator efficiency. The polymerization kinetic study, multiple controlled "on-off" light switching cycle regulation, and chain extension experiment confirm the "living"/controlled features of this promising photoinduced metal-free ATRP system with good molecular weight control in the presence of ppm level photocatalyst 4CzIPN. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Yu, W H; Kang, E T; Neoh, K G
2005-01-04
Surface modification of poly(tetrafluoroethylene) (PTFE) films by well-defined comb copolymer brushes was carried out. Peroxide initiators were generated directly on the PTFE film surface via radio frequency Ar plasma pretreatment, followed by air exposure. Poly(glycidyl methacrylate) (PGMA) brushes were first prepared by surface-initiated reversible addition-fragmentation chain transfer polymerization from the peroxide initiators on the PTFE surface in the presence of a chain transfer agent. Kinetics study revealed a linear increase in the graft concentration of PGMA with the reaction time, indicating that the chain growth from the surface was consistent with a "controlled" or "living" process. alpha-Bromoester moieties were attached to the grafted PGMA by reaction of the epoxide groups with 2-bromo-2-methylpropionic acid. The comb copolymer brushes were subsequently prepared via surface-initiated atom transfer radical polymerization of two hydrophilic vinyl monomers, including poly(ethylene glycol) methyl ether methacrylate and sodium salt of 4-styrenesulfonic acid. The chemical composition of the modified PTFE surfaces was characterized by X-ray photoelectron spectroscopy.
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Zeng, Guangjian; Liu, Meiying; Jiang, Ruming; Heng, Chunning; Huang, Qiang; Mao, Liucheng; Hui, Junfeng; Deng, Fengjie; Zhang, Xiaoyong; Wei, Yen
2017-08-01
We reported a simple and efficient method to prepare the hydrophilic luminescent HAp polymer nanocomposites through the combination of ligand exchange and metal free light initiated surface-initiated atom transfer radical polymerization (SI-ATRP) using 10-phenylphenothiazine (PTH) as organic catalyst and 2-methacryloyloxyethyl phosphorylcholine (MPC) and itaconic acid (IA) as monomers. The biological imaging and drug delivery performance of HAp-poly(MPC-IA) nanorods were examined to evaluate their potential for biomedical applications. Results suggested that hydrophilic HAp-poly(MPC-IA) nanorods can be successfully prepared. More importantly, the HAp-poly(MPC-IA) exhibited excellent water dispersibility, desirable biocompatibility and good performance for biological imaging and controlled drug delivery applications. As compared with other controlled living polymerization reactions, the metal free light initiated SI-ATRP displayed many advantages such as easy for handle, mild reaction conditions, toxicity and fluorescence quenching from metal catalysts. Therefore, we believe that this strategy should be a useful and effective strategy for preparation of HAp nanomaterials for biomedical applications. Copyright © 2017 Elsevier B.V. All rights reserved.
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NASA Astrophysics Data System (ADS)
Kadlubowski, S.; Sawicki, P.; Sowinski, S.; Rokita, B.; Bures, K. D.; Rosiak, J. M.; Ulanski, P.
2018-01-01
Time-resolved pulse radiolysis, utilizing short pulses of high-energy electrons from accelerators, is an effective method for rapidly generating free radicals and other transient species in solution. Combined with fast time-resolved spectroscopic detection (typically in the ultraviolet/visible/near-infrared), it is invaluable for monitoring the reactivity of species subjected to radiolysis on timescales ranging from picoseconds to seconds. When used for polymer solutions, pulse radiolysis can be coupled with light-scattering detection, creating a powerful tool for kinetic and mechanistic analysis of processes like degradation or cross-linking of macromolecules. Changes in the light scattering intensity (LSI) of polymer solutions are indicative of alterations in the molecular weight and/or in the radius of gyration, i.e., the dimensions and shape of the macromolecules. In addition to other detection methods, LSI technique provides a convenient tool to study radiation-induced alterations in macromolecules as a function of time after the pulse. Pulse radiolysis systems employing this detection mode have been so far constructed to follow light scattered at a single angle (typically the right angle) to the incident light beam. Here we present an advanced pulse radiolysis & multi-angle light-scattering-intensity system (PR-MALLS) that has been built at IARC and is currently in the phase of optimization and testing. Idea of its design and operation is described and preliminary results for radiation-induced degradation of pullulan as well as polymerization and crosslinking of poly(ethylene glycol) diacrylate are presented. Implementation of the proposed system provides a novel research tool, which is expected to contribute to the expansion of knowledge on free-radical reactions in monomer- and polymer solutions, by delivering precise kinetic data on changes in molecular weight and size, and thus allowing to formulate or verify reaction mechanisms. The proposed method is universal and can be applied for studying both natural and synthetic polymers. The developed system can be also valuable in studies of the border of biology and medicine, especially on radical reactions of biopolymers and their conformational transitions. Furthermore, capability to follow fast changes in mass and dimensions of nanobjects may be of significant importance for nanoscience and nanotechnology.
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NASA Astrophysics Data System (ADS)
Tian, Zhicheng
The work described in this thesis is divided into three major parts, and all of which involve the exploration of the chemistry of polyphosphazenes. The first part (chapters 2 and 3) of my research is synthesis and study polyphoshazenes for biomedical applications, including polymer drug conjugates and injectable hydrogels for drug or biomolecule delivery. The second part (chapters 4 and 5) focuses on the synthesis of several organic/inorganic hybrid polymeric structures, such as diblock, star, brush and palm tree copolymers using living cationic polymerization and atom transfer radical polymerization techniques. The last part (chapters 6 and 7) is about exploratory synthesis of new polymeric structures with fluorinated side groups or cycloaliphatic side groups, and the study of new structure property relationships. Chapter 1 is an outline of the fundamental concepts for polymeric materials, as such the history, important definitions, and some introductory material for to polymer chemistry and physics. The chemistry and applications of phopshazenes is also briefly described. Chapter 2 is a description of the design, synthesis, and characterization of development of a new class of polymer drug conjugate materials based on biodegradable polyphosphazenes and antibiotics. Poly(dichlorophosphazene), synthesized by a thermal ring opening polymerization, was reacted with up to 25 mol% of ciprofloxacin or norfloxacin and three different amino acid esters (glycine, alanine, or phenylalanine) as cosubstituents via macromolecular substitutions. Nano/microfibers of several selected polymers were prepared by an electrospinning technique. Chapter 3 is concerned with the development of a class of injectable and biodegradable hydrogels based on water-soluble poly(organophosphazenes) containing oligo(ethylene glycol) methyl ethers and glycine ethyl esters. The hydrogels can be obtained by mixing alpha-cyclodextrin aqueous solution and poly(organophosphazenes) aqueous solution in various gelation rates depending on the polymer structures and the concentrations. The rheological measurements of the supramolecular hydrogels indicate a fast gelation process and flowable character under a large stain. Chapter 4 outlines the preparation of a number of amphiphilic diblock copolymers based on poly[bis(trifluoroethoxy)phosphazene] (TFE) as the hydrophobic block and poly(dimethylaminoethylmethacrylate) (PDMAEMA) as the hydrophilic block. The TFE block was synthesized first by the controlled living cationic polymerization of a phosphoranimine, followed by replacement of all the chlorine atoms using sodium trifluoroethoxide. To allow for the growth of the PDMAEMA block, 3-azidopropyl-2-bromo-2-methylpropanoate, an atom transfer radical polymerization (ATRP) initiator, was grafted onto the endcap of the TFE block via the 'click' reaction followed by the ATRP of 2-(dimethylamino)ethyl methacrylate (DMAEMA). Chapter 5 is a report on the design and assembly of polyphosphazene materials based on the non-covalent "host--guest" interactions either at the terminus of the polymeric main-chains or the pendant side-chains. The supramolecular interaction at the main chain terminus was used to produce amphiphilic palm-tree like pseudo-block copolymers via host-guest interactions between an adamantane end-functionalized polyphosphazene and a 4-armed beta-cyclodextrin (beta-CD) initiated poly[poly(ethylene glycol) methyl ether methacylate] branched-star type polymer. The formation of micelles of the obtained amphiphiles was analyzed by fluorescence technique, dynamic light scattering, transmission electron microscopy, and atomic force microscopy. Chapter 6 is an investigation of the influence of bulky fluoroalkoxy side groups on the properties of polyphosphazenes. A new series of mixed-substituent high polymeric poly(fluoroalkoxyphosphazenes) containing trifluoroethoxy and branched fluoroalkoxy side groups was synthesized and characterized by NMR and GPC methods. These polymers contained 19--29 mol% of di-branched hexafluoropropoxy groups or 4mol% of tri-branched tert-perfluorobutoxy groups, which serve as regio-irregularities to reduce the macromolecular microcrystallinity. The structure--property correlations of the polymers were then analyzed and interpreted by several techniques: specifically by the thermal behavior by DSC and TGA methods, the crystallinity by wide-angle X-ray diffraction, and the surface hydrophobicity/oleophobicity by contact angle measurements. (Abstract shortened by UMI.). Chapter 7 is an outline of the exploratory synthesis of a new series of phosphazene model cyclic trimers and single- and mixed- substituent high polymers containing cyclic aliphatic rings, --CnH2n-1 (where n = 4--8). The cylco-aliphatic side group containing phosphazenes expand the structural and property boundaries of phosphazene chemistry, and suggest additional approaches for studying slow macromolecular substitution reactions and substituent exchange reactions.
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Vaysse, C; Guerlou-Demourgues, L; Duguet, E; Delmas, C
2003-07-28
A chimie douce route based on successive redox and exchange reactions has allowed us to prepare new hybrid organic-inorganic materials, composed of polyacrylate macromolecules intercalated into layered double hydroxides (LDHs), deriving from Ni(OH)(2). Monomer intercalation and in situ polymerization mechanisms have appeared to be strongly dependent upon the nature of the substituting cation in the slabs. In the case of iron-based LDHs, a phase containing acrylate monomeric intercalates has been isolated and identified by X-ray diffraction and infrared spectroscopy. Second, interslab free-radical polymerization of acrylate anions has been successfully initiated using potassium persulfate. In cobalt- or manganese-based LDHs, one-step polymerization has been observed, leading directly to a material containing polyacrylate intercalate.
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Biocompatibility of 4-META/MMA-TBB resin used as a dental luting agent.
Nakagawa, Kaori; Saita, Makiko; Ikeda, Takayuki; Hirota, Makoto; Park, Wonhee; Lee, Masaichi Chang-Il; Ogawa, Takahiro
2015-07-01
The bonding and biological properties of currently used luting/cementing materials need to be improved. 4-Acryloyloxyethyl trimellitate anhydride/methyl methacrylate-tri-n-butylborane (4-META/MMA-TBB) resin is primarily used for splinting mobile teeth or treating fractured teeth. It undergoes moisture-resistant polymerization and bonds strongly to dentin and metals. The purpose of this in vitro study was to compare the biological and biochemical properties META/MMA-TBB resin with those of conventional polymethyl methacrylate (PMMA)-MMA resin and other currently used luting materials in order to determine whether it may be a viable dental luting agent. The degree of polymerization of 4-META/MMA-TBB resin, PMMA-MMA autopolymerizing resin, 10-methacryloyloxydecyl dihydrogen phosphate-dimethacrylate (MDP-DMA) adhesive resin, and a glass ionomer cement was measured by Fourier-transformed infrared spectroscopy. Free radical production during setting was evaluated by electron spin resonance (ESR) spectroscopy. Rat dental pulp cells cultured on these materials were examined for cell viability, attachment, proliferation, and functional phenotype. The degree of polymerization of 4-META/MMA-TBB resin was 82% thirty minutes after preparation, compared to 66% for PMMA-MMA autopolymerizing resin. ESR spectroscopy revealed free radical production from 4-META/MMA-TBB resin and glass ionomer cement was equivalent 24 hours after preparation, with no spike in radical generation observed. In contrast, free radical production from PMMA-MMA and MDP-DMA adhesive resins was rapid and sustained and 10 to 20 times greater than that from 4-META/MMA-TBB. The percentage of viable dental pulp cells 24 hours after seeding was considerably higher on MDP-DMA and 4-META/MMA-TBB resin than on glass ionomer cement. Cell number, proliferation, and alkaline phosphatase activity were highest on 4-META/MMA-TBB resin and lowest on the glass ionomer cement. 4-META/MMA-TBB resin is at least as biocompatible, and perhaps even more biocompatible, than other current luting materials, with fast, favorable, and nontoxic polymerization properties. Further in vivo and human studies of 4-META/MMA-TBB resin as a dental luting agent are warranted. Copyright © 2015 Editorial Council for the Journal of Prosthetic Dentistry. Published by Elsevier Inc. All rights reserved.
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INHIBITING THE POLYMERIZATION OF NUCLEAR COOLANTS
Colichman, E.L.
1959-10-20
>The formation of new reactor coolants which contain an additive tbat suppresses polymerization of the primary dissoclation free radical products of the pyrolytic and radiation decomposition of the organic coolants is described. The coolants consist of polyphenyls and condensed ring compounds having from two to about four carbon rings and from 0.1 to 5% of a powdered metal hydride chosen from the group consisting of the group IIA and IVA dispersed in the hydrocarbon.
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Quantification of hydroxyl radical produced during phacoemulsification.
Gardner, Jonathan M; Aust, Steven D
2009-12-01
To quantitate hydroxyl radicals produced during phacoemulsification with various irrigating solutions and conditions used in cataract surgery. Chemistry and Biochemistry Department, Utah State University, Logan, Utah, USA. All experiments were performed using an Infiniti Vision System phacoemulsifier with irrigation and aspiration. Hydroxyl radicals were quantitated using electron spin resonance spectroscopy and a spectrophotometric assay for malondialdehyde, which is formed by the oxidation of deoxyribose by the hydroxyl radical. Hydroxyl radical production increased during longitudinal-stroking phacoemulsification as power levels were increased in a nonlinear, nonexponential fashion. The detection of hydroxyl radical was reduced in irrigating solutions containing organic molecules (eg, citrate, acetate, glutathione, dextrose) and further reduced in Navstel, an irrigating solution containing a viscosity-modifying agent, hydroxypropyl methylcellulose. Hydroxyl radicals produced in settings representative of those used in phacoemulsification cataract surgery were quantitated using the deoxyribose method. Hydroxyl radical production was dependent on the level of ultrasound power applied and the irrigating solution used. Oxidative stress on the eye during phacoemulsification may be minimized by using irrigating solutions that contain organic molecules, including the viscosity-modifying agent hydroxypropyl methylcellulose, that can compete for reaction with hydroxyl radicals.
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Preparation of polymeric diacetylene thin films for nonlinear optical applications
NASA Technical Reports Server (NTRS)
Frazier, Donald O. (Inventor); Mcmanus, Samuel P. (Inventor); Paley, Mark S. (Inventor); Donovan, David N. (Inventor)
1995-01-01
A method for producing polymeric diacetylene thin films having desirable nonlinear optical characteristics has been achieved by producing amorphous diacetylene polymeric films by simultaneous polymerization of diacetylene monomers in solution and deposition of polymerized diacetylenes on to the surface of a transparent substrate through which ultraviolet light has been transmitted. These amorphous polydiacetylene films produced by photo-deposition from solution possess very high optical quality and exhibit large third order nonlinear optical susceptibilities, such properties being suitable for nonlinear optical devices such as waveguides and integrated optics.
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Grover, Gregory N.; Maynard, Heather D.
2011-01-01
Protein-polymer conjugates are of interest to researchers in diverse fields. Attachment of polymers to proteins results in improved pharmacokinetics, which is important in medicine. From an engineering standpoint, conjugates are exciting because they exhibit properties of both the biomolecules and synthetic polymers. This allows the activity of the protein to be altered or tuned, a key aspect in therapeutic design, anchoring conjugates to surfaces, and utilizing these materials for supramolecular self-assembly. Thus, there is broad interest in straightforward synthetic methods to make protein-polymer conjugates. Controlled radical polymerization (CRP) techniques have emerged as excellent strategies to make conjugates because the resulting polymers have narrow molecular weight distributions, targeted molecular weights, and attach to specific sites on proteins. Herein, recent advances in the synthesis and application of protein-polymer conjugates by CRP are highlighted. PMID:21071260
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NASA Astrophysics Data System (ADS)
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.
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Encapsidated Atom-Transfer Radical Polymerization in Qβ Virus-like Nanoparticles
2015-01-01
Virus-like particles (VLPs) are unique macromolecular structures that hold great promise in biomedical and biomaterial applications. The interior of the 30 nm-diameter Qβ VLP was functionalized by a three-step process: (1) hydrolytic removal of endogenously packaged RNA, (2) covalent attachment of initiator molecules to unnatural amino acid residues located on the interior capsid surface, and (3) atom-transfer radical polymerization of tertiary amine-bearing methacrylate monomers. The resulting polymer-containing particles were moderately expanded in size; however, biotin-derivatized polymer strands were only very weakly accessible to avidin, suggesting that most of the polymer was confined within the protein shell. The polymer-containing particles were also found to exhibit physical and chemical properties characteristic of positively charged nanostructures, including the ability to easily enter mammalian cells and deliver functional small interfering RNA. PMID:25073013
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Synthesis of hollow spherical calcium phosphate nanoparticles using polymeric nanotemplates
NASA Astrophysics Data System (ADS)
Tjandra, Wiliana; Ravi, Palaniswamy; Yao, Jia; Tam, Kam C.
2006-12-01
Poly(methylmethacrylate)-block-poly(methacrylic acid) (PMMA-b-PMAA) copolymer was synthesized by an atom transfer radical polymerization (ATRP) technique. The block copolymer was employed as a template for the controlled precipitation of calcium phosphate from aqueous solution at different pH values. A Ca2+ ion selective electrode was used to study the interactions between Ca2+ ions and the polymer, which indicated a possible weak interaction between Ca2+ and un-ionized MAA segments at pH~4.0 in addition to electrostatic interaction between Ca2+ and ionized MAA segments at higher pH. An interesting structure representing that of a superstructure consisting of hybrid nano-filaments was observed by the transmission electron microscope at pH~4.0. The filaments originated from a core of similar size to primary polymer aggregates, suggesting that cooperative interactions at a local level between dissolving calcium phosphate clusters and disassembling polymer segments are responsible for the secondary growth process. A hollow spherical morphology was obtained at pH~7.0 and 9.0. Such calcium phosphate/polymer monohybrids with complex morphologies are interesting and might be useful as novel drug delivery carriers, ceramics precursors, reinforcing fillers or biomedical implants.
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Liu, Caihong; Lee, Jongho; Ma, Jun; Elimelech, Menachem
2017-02-21
In this study, we demonstrate a highly antifouling thin-film composite (TFC) membrane by grafting a zwitterionic polymer brush via atom-transfer radical-polymerization (ATRP), a controlled, environmentally benign chemical process. Initiator molecules for polymerization were immobilized on the membrane surface by bioinspired catechol chemistry, leading to the grafting of a dense zwitterionic polymer brush layer. Surface characterization revealed that the modified membrane exhibits reduced surface roughness, enhanced hydrophilicity, and lower surface charge. Chemical force microscopy demonstrated that the modified membrane displayed foulant-membrane interaction forces that were 1 order of magnitude smaller than those of the pristine TFC membrane. The excellent fouling resistance imparted by the zwitterionic brush layer was further demonstrated by significantly reduced adsorption of proteins and bacteria. In addition, forward osmosis fouling experiments with a feed solution containing a mixture of organic foulants (bovine-serum albumin, alginate, and natural organic matter) indicated that the modified membrane exhibited significantly lower water flux decline compared to the pristine TFC membrane. The controlled architecture of the zwitterionic polymer brush via ATRP has the potential for a facile antifouling modification of a wide range of water treatment membranes without compromising intrinsic transport properties.
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Romano, Edwin F; Holdsworth, Clovia I; Quirino, Joselito P; So, Regina C
2018-01-01
Accurate quantification of histamine levels in food and in biological samples is important for monitoring the quality of food products and for the detection of pathophysiological conditions. In this study, solution processable histamine-imprinted microspheres were synthesized at 30°C via dilute free radical phototochemical polymerization technique using ethylene glycol dimethacrylate (EGDMA) as the crosslinker and methacrylic acid (MAA) as the monomer. The processability of the resulting polymer is dictated by the monomer feed concentration (eg, 4 wt% 80:20 EGDMA:MAA formulation) and solvent (acetonitrile). Whereas, the particle size is influenced by the monomer feed concentration, the presence of template molecule, and independent of the crosslinker content. Evaluation of the binding performance of the photochemically imprinted polymers (PCP) with different crosslinker content (80 and 90 wt%) indicated that the selective binding capacity was notably higher in PCP-80 (N= 16.0 μmol/g) compared to PCP-90 (N= 10.1 μmol/g) when analyzed via frontal analysis capillary electrophoresis (FACE) using Freundlich isotherm. In addition, PCP-80 microspheres are more selective toward histamine than conventional thermal polymers (CTP-80) prepared at 60°C in the presence of structural analogs such as histidine, imidazole, and tryptamine under cross-rebinding and competitive conditions. These results demonstrated that histamine-selective imprinted polymers can be obtained readily using room temperature photochemical polymerization where these materials can be subsequently used as recognition element for optical-based histamine sensing. Copyright © 2017 John Wiley & Sons, Ltd.
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End-Functionalized Palladium SCS Pincer Polymers via Controlled Radical Polymerizations.
Lye, Diane S; Cohen, Aaron E; Wong, Madeleine Z; Weck, Marcus
2017-07-01
A direct and facile route toward semitelechelic polymers, end-functionalized with palladated sulfur-carbon-sulfur pincer (Pd II -pincer) complexes is reported that avoids any post-polymerization step. Key to our methodology is the combination of reversible addition-fragmentation chain-transfer (RAFT) polymerization with functionalized chain-transfer agents. This strategy yields Pd end-group-functionalized materials with monomodal molar mass dispersities (Đ) of 1.18-1.44. The RAFT polymerization is investigated using a Pd II -pincer chain-transfer agent for three classes of monomers: styrene, tert-butyl acrylate, and N-isopropylacrylamide. The ensuing Pd II -pincer end-functionalized polymers are analyzed using 1 H NMR spectroscopy, gel-permeation chromatography, and elemental analysis. The RAFT polymerization methodology provides a direct pathway for the fabrication of Pd II -pincer functionalized polymers with complete end-group functionalization. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Yeow, Jonathan; Joshi, Sanket; Chapman, Robert; Boyer, Cyrille Andre Jean Marie
2018-04-25
Translating controlled/living radical polymerization (CLRP) from batch to the high throughput production of polymer libraries presents several challenges in terms of both polymer synthesis and characterization. Although recently there have been significant advances in the field of low volume, high throughput CLRP, techniques able to simultaneously monitor multiple polymerizations in an "online" manner have not yet been developed. Here, we report our discovery that 5,10,15,20-tetraphenyl-21H,23H-porphine zinc (ZnTPP) is a self-reporting photocatalyst that can mediate PET-RAFT polymerization as well as report on monomer conversion via changes in its fluorescence properties. This enables the use of a microplate reader to conduct high throughput "online" monitoring of PET-RAFT polymerizations performed directly in 384-well, low volume microtiter plates. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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NASA Astrophysics Data System (ADS)
Zeng, Guangjian; Liu, Meiying; Heng, Chunning; Huang, Qiang; Mao, Liucheng; Huang, Hongye; Hui, Junfeng; Deng, Fengjie; Zhang, Xiaoyong; Wei, Yen
2017-03-01
The Eu3+ doped luminescent hydroxyapatite (HAp) nanorods with uniform size and morphology can be synthesized by hydrothermal route. However, these HAp nanorods are coated by hydrophobic oleylamine, which makes them difficult to be dispersed in aqueous solution and impede their biomedical applications. In this work, Eu3+ doped luminescent polymers functionalized HAp nanorods were prepared through the combination of ligand exchange reaction and metal free surface initiated atom transfer radical polymerization (ATRP) method. In this procedure, the amino group functionalized HAp nanorods were first prepared by ligand exchange reaction using adenosine monophosphate (AMP) as ligand. Then the Br-containing initiators (HAp-Br) were introduced onto the surface of HAp-AMP nanorods through the amidation reaction. Finally, polymers functionalized HAp nanorods were prepared by metal free ATRP method using poly(ethylene glycol) methacrylate (PEGMA) as monomer and 10-phenylphenothiazine (PTH) as organic photocatalyst. The properties of these obtained HAp nanocomposites (HAP-polyPEGMA nanorods) were characterized by means of transmission electron microscopy, Fourier transformed infrared spectroscopy, X-ray photoelectron spectroscopy and thermogravimetric analysis in detail. The cell imaging of these HAP-polyPEGMA nanorods was examined using laser scanning confocal microscope to evaluate their biomedical applications. We demonstrated for the first time that hydrophobic luminescent HAp nanorods can be functionalized with polyPEGMA through the combination of ligand exchange reaction and metal free surface initiated ATRP. As compared with the traditional ATRP, the metal free ATRP can overcome the toxic and fluorescence quenching effects of metal catalysts such as copper ions. More importantly, the strategy described in this work should also be utilized for fabrications of many other luminescent polymer nanocomposites due to its good monomer adoptability.
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Shen, Song; Zhu, Chunlei; Huo, Da; Yang, Miaoxin; Xue, Jiajia; Xia, Younan
2017-07-17
Anticancer modalities based on oxygen free radicals, including photodynamic therapy and radiotherapy, have emerged as promising treatments in the clinic. However, the hypoxic environment in tumor tissue prevents the formation of oxygen free radicals. Here we introduce a novel strategy that employs oxygen-independent free radicals generated from a polymerization initiator for eradicating cancer cells. The initiator is mixed with a phase-change material and loaded into the cavities of gold nanocages. Upon irradiation by a near-infrared laser, the phase-change material is melted due to the photothermal effect of gold nanocages, leading to the release and decomposition of the loaded initiator to generate free radicals. The free radicals produced in this way are highly effective in inducing apoptosis in hypoxic cancer cells. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Al-Roomi, Yousef Mohammad; Hussain, Kaneez Fatema
2017-04-01
Calcium sulfate is one of the dominant scales which, unlike carbonate scale, are not easily removable by acid. To inhibit CaSO 4 scale formation in artificial cooling water systems, well-defined low molecular weight maleic anhydride and n-alkylacrylamide copolymers (YMR-S series) were synthesized via nitroxide-mediated radical polymerization initiated by benzoyl peroxide in the presence of 2,2,6,6-tetramethyl-1-piperidinyloxy at varying concentrations. These polymerizations exhibit living polymerization characteristics; that is, they show linear growth in chain length as a function of monomer conversion, and have narrow molecular weight distributions. Resultant polymers were characterized by means of 1 H-NMR and 13 C-NMR. The inhibition behavior of these YMR-S series polymers against CaSO 4 was evaluated using the static scale inhibition method and a dynamic tube block test. The inhibition ability on the CaSO 4 scale is 99.5% with 9 ppm dosage level at pH 10.45 and temperature 70°C. Scanning electronic microscope analysis proved the morphological changes of the CaSO 4 scales due to the strong inhibition action of YMR-S polymers. It is also observed that the antiscaling effect of the copolymers greatly depends on the molecular weight, and the optimum range is below 20,000 and approximately in the range 500-2000.
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NASA Astrophysics Data System (ADS)
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.
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You, Xiaoxiao; Gao, Lei; Qin, Dongli; Chen, Ligang
2017-01-01
A novel and highly efficient approach to obtain magnetic molecularly imprinted polymers is described to detect avermectin in fish samples. The magnetic molecularly imprinted polymers were synthesized by surface imprinting polymerization using magnetic multiwalled carbon nanotubes as the support materials, atom transfer radical polymerization as the polymerization method, avermectin as template, acrylamide as functional monomer, and ethylene glycol dimethacrylate as crosslinker. The characteristics of the magnetic molecularly imprinted polymers were assessed by using transmission electron microscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, vibrating sample magnetometry, X-ray diffraction, and thermogravimetric analysis. The binding characteristics of magnetic molecularly imprinted polymers were researched through isothermal adsorption experiment, kinetics adsorption experiment, and the selectivity experiment. Coupled with ultra high performance liquid chromatography and tandem mass spectrometry, the extraction conditions of the magnetic molecularly imprinted polymers as adsorbents for avermectin were investigated in detail. The recovery of avermectin was 84.2-97.0%, and the limit of detection was 0.075 μg/kg. Relative standard deviations of intra- and inter-day precisions were in the range of 1.7-2.9% and 3.4-5.6%, respectively. The results demonstrated that the extraction method not only has high selectivity and accuracy, but also is convenient for the determination of avermectin in fish samples. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Kaastrup, Kaja; Aguirre-Soto, Alan; Wang, Chen; Bowman, Christopher N; Stansbury, Jeffery; Sikes, Hadley D
In conjunction with a tertiary amine coinitiator, eosin, a photoreducible dye, has been shown to successfully circumvent oxygen inhibition in radical photopolymerization reactions. However, the role of O 2 in the initiation and polymerization processes remains inconclusive. Here, we employ a UV-Vis/FT-NIR analytical tool for real-time, simultaneous monitoring of chromophore and monomer reactive group concentrations to investigate the eosin-activated photopolymerization of PEGDA-based hydrogels under ambient conditions. First, we address the challenges associated with spectroscopic monitoring of the polymerization of hydrogels using UV-Vis and FT-NIR, proposing metrics for quantifying the extent of signal loss from reflection and scattering, and showing their relation to microgelation and network formation. Second, having established a method for extracting kinetic information by eliminating the effects of changing refractive index and scattering, the coupled UV-Vis/FT-NIR system is applied to the study of eosin-activated photopolymerization of PEGDA in the presence of O 2 . Analysis of the inhibition time, rate of polymerization, and rate of eosin consumption under ambient and purged conditions indicates that regeneration of eosin in the presence of oxygen and consumption of oxygen occur via a nonchain process. This suggests that the uniquely high O 2 resilience is due to alternative processes such as energy transfer from photo-activated eosin to oxygen. Uncovering the intricacies of the role of O 2 in eosin-mediated initiation aids the design of O 2 resistant free radical polymerization systems relevant to photonics, optoelectronics, biomaterials, and biosensing.
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Kaastrup, Kaja; Aguirre-Soto, Alan; Wang, Chen; Bowman, Christopher N.; Stansbury, Jeffery; Sikes, Hadley D.
2016-01-01
In conjunction with a tertiary amine coinitiator, eosin, a photoreducible dye, has been shown to successfully circumvent oxygen inhibition in radical photopolymerization reactions. However, the role of O2 in the initiation and polymerization processes remains inconclusive. Here, we employ a UV-Vis/FT-NIR analytical tool for real-time, simultaneous monitoring of chromophore and monomer reactive group concentrations to investigate the eosin-activated photopolymerization of PEGDA-based hydrogels under ambient conditions. First, we address the challenges associated with spectroscopic monitoring of the polymerization of hydrogels using UV-Vis and FT-NIR, proposing metrics for quantifying the extent of signal loss from reflection and scattering, and showing their relation to microgelation and network formation. Second, having established a method for extracting kinetic information by eliminating the effects of changing refractive index and scattering, the coupled UV-Vis/FT-NIR system is applied to the study of eosin-activated photopolymerization of PEGDA in the presence of O2. Analysis of the inhibition time, rate of polymerization, and rate of eosin consumption under ambient and purged conditions indicates that regeneration of eosin in the presence of oxygen and consumption of oxygen occur via a nonchain process. This suggests that the uniquely high O2 resilience is due to alternative processes such as energy transfer from photo-activated eosin to oxygen. Uncovering the intricacies of the role of O2 in eosin-mediated initiation aids the design of O2 resistant free radical polymerization systems relevant to photonics, optoelectronics, biomaterials, and biosensing. PMID:26755925
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Oligonucleotides as probes for studying polymerization reactions in dilute aqueous solution
NASA Technical Reports Server (NTRS)
Kolb, V.; Orgel, L. E.; Miller, S. L. (Principal Investigator)
1994-01-01
We have prepared a [32P]-labled oligonucleotide probe carrying a free primary amine at its 3'-terminus. This probe is used to initiate polymerization of aziridine (ethyleneimine) in aqueous solution. The nature of the oligomeric products and the kinetics of their formation are then monitored by gel electrophoresis. Our results are generally consistent with those obtained using conventional techniques. We have also investigated the effect of polyanionic templates on the rate of oligomerization of aziridine. We find that water-soluble polyanions generally accelerate the polymerization. The sodium salt of polymethacrylic acid is the most effective of the templates that we studied. The methods introduced in this paper should be applicable to a variety of polymerization reactions in aqueous solution. They should greatly simplify the screening of potentially prebiotic polymerization reactions.
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Polymeric peptide pigments with sequence-encoded properties
DOE Office of Scientific and Technical Information (OSTI.GOV)
Lampel, Ayala; McPhee, Scott A.; Park, Hang-Ah
Melanins are a family of heterogeneous polymeric pigments that provide ultraviolet (UV) light protection, structural support, coloration, and free radical scavenging. Formed by oxidative oligomerization of catecholic small molecules, the physical properties of melanins are influenced by covalent and noncovalent disorder. We report the use of tyrosine-containing tripeptides as tunable precursors for polymeric pigments. In these structures, phenols are presented in a (supra-)molecular context dictated by the positions of the amino acids in the peptide sequence. Oxidative polymerization can be tuned in a sequence-dependent manner, resulting in peptide sequence–encoded properties such as UV absorbance, morphology, coloration, and electrochemical properties overmore » a considerable range. Short peptides have low barriers to application and can be easily scaled, suggesting near-term applications in cosmetics and biomedicine.« less
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Synthesis and properties of hemicelluloses-based semi-IPN hydrogels.
Peng, Feng; Guan, Ying; Zhang, Bing; Bian, Jing; Ren, Jun-Li; Yao, Chun-Li; Sun, Run-Cang
2014-04-01
Hemicelluloses were extracted from holocellulose of bamboo by alkaline treatment. The phosphorylated poly(vinyl alcohol) (P-PVA) samples with various substitution degrees were prepared through the esterification of PVA and phosphoric acid. A series of hydrogels of semi-interpenetrating polymeric networks (semi-IPN) composed of hemicelluloses-g-poly(acrylic acid) (HM-g-PAA) and the phosphorylated poly(vinyl alcohol) (P-PVA) were prepared by radical polymerization using potassium persulphate (KPS) as initiator. The HM-g-PAA networks were crosslinked by N,N-methylenebisacrylamide (MBA) as a crosslinking agent in the presence of linear P-PVA. FT-IR results confirmed that the hydrogels comprised a porous crosslink structure of P-PVA and HM with side chains that carried carboxylate and phosphorylate groups. SEM observations indicated that the incorporation of P-PVA induced highly porous structure, and P-PVA was uniformly dispersed in the polymeric network. The interior network structures of the semi-IPN matrix became more porous with increasing P-PVA. The TGA results showed that the thermo-decomposing temperature and thermal stability were increased effectively for intruding the chain of P-PVA. The maximum equilibrium swelling ratio of hydrogels in distilled water and 0.9 wt% sodium chloride solutions was up to 1085 g g(-1) and 87 g g(-1), respectively. The compressive strength increased with increasing the MBA/HM and P-PVA/HM ratios, and decreased with the increment of AA/HM ratio. Copyright © 2014 Elsevier B.V. All rights reserved.
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Zhang, Bingyu; Lei, Xiaoyun; Deng, Lijun; Li, Minsheng; Yao, Sicong; Wu, Xiaoping
2018-06-06
An ionic liquid hybrid monolithic capillary column was prepared within 7 min via photoinitiated free-radical polymerization of an ionic liquid monomer (1-butyl-3-vinylimidazolium-bis[(trifluoromethyl)sulfonyl]imide); VBIMNTF 2 ) and a methacryl substituted polyhedral oligomeric silsesquioxane (POSS-MA) acting as a cross-linker. The effects of composition of prepolymerization solution and initiation time on the porous structure and electroosmotic flow (EOF) of monolithic column were investigated. The hybrid monolith was characterized by scanning electron microscopy and FTIR. Owing to the introduction of a rigid nanosized POSS silica core and ionic liquids with multiple interaction sites, the monolithic column has a well-defined 3D skeleton morphology, good mechanical stability, and a stable anodic electroosmotic flow. The hybrid monolithic stationary phase was applied to the capillary electrochromatographic separation of various alkylbenzenes, phenols, anilines and polycyclic aromatic hydrocarbons (PAHs). The column efficiency is highest (98,000 plates/m) in case of alkylbenzenes. Mixed-mode retention mechanisms including hydrophobic interactions, π-π stacking, electrostatic interaction and electrophoretic mobility can be observed. This indicates the potential of this material in terms of efficient separation of analytes of different structural type. Graphical Abstract Preparation of a mixed-mode ionic liquid hybrid monolithic column via photoinitiated polymerization of methacryl substituted polyhedral oligomeric silsesquioxane (POSS-MA) and 1-butyl-3-vinylimidazolium-bis[(trifluoromethyl)sulfonyl]imide (VBIMNTF 2 ) ionic liquid for use in capillary electrochromatography.
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NASA Astrophysics Data System (ADS)
Fukumori, Minoru; Hara, Shinnosuke; Ogawa, Takuji; Tanaka, Hirofumi
2018-03-01
The mechanism of graphene nanoribbon synthesis by the sonication-assisted unzipping of carbon nanotubes (CNTs) was investigated utilizing 4-methoxyphenol and 1,4-dimethoxybenzene as moieties of poly[(m-phenylenevinylene)-co-(2,5-dioctoxy-p-phenylenevinylene)]. The obtained results revealed that unzipping was promoted by 4-methoxyphenol owing to the facile abstraction of its phenolic hydrogen by sonication-generated radicals on CNTs, whereas 1,4-dimethoxybenzene did not facilitate unzipping, since its methoxy hydrogens were hardly abstracted. Moreover, unzipping was also facilitated by trans-stilbene, the double bond of which reacts with CNT radicals. Furthermore, we succeeded in using a general radical initiator, namely, 2,2‧-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride to promote unzipping, confirming that it is promoted by radical donors/trapping agents.
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Polyimides and Process for Preparing Polyimides Having Thermal-Oxidative Stability
NASA Technical Reports Server (NTRS)
Meador, Mary Ann B. (Inventor)
2001-01-01
Polyimides and the process for preparing polyimides having improved thermal-oxidative stability derived from the polymerization of effective amounts of one or more of the polyamines such as the aromatic diamines, one or more of the tetracarboxylic dianhydrides and a novel dicarboxylic endcap having formula with an R1 group of either hydrogen or an alkyl radical of one to four carbons, an R2 group of either OH, NH2, F, or Cl radical, an R3 group of either H, OH, NH2, F, Cl or an alkylene radical, an R4 group of either an alkyl, aryl, aryloxy, nitro, F, or Cl radical, and/or an R5 group of either H, alkyl, aryl, alkoxy, aryloxy, nitro, F, or Cl radical. The polyimides are useful particularly in the preparation of prepegs and PMR composites.
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NASA Astrophysics Data System (ADS)
Miyazaki, Tetsuo; Yoshimura, Toru; Mita, Kazuya; Suzuki, Keiji; Watanabe, Masami
1995-02-01
When an aqueous solution of albumin (0.1 kg dm -3) is irradiated by γ-rays at 295 K, albumin radicals with a long lifetime are observed by ESR. The reaction of vitamin C with the albumin radicals has been studied at 295 K in the albumin solution, which is considered as a model of cells. The rate constant for the reaction of vitamin C with the albumin radicals was measured as 0.014 dm 3 mol -1 s -1, which is much smaller than the reported rate constants (10 6-10 10 dm 3 mol -1 s -1) for the reaction of vitamin C with radicals in a dilute aqueous solution. The small rate constant for the reaction of vitamin C is ascribed to the reaction in polymer coils in the albumin solution, since vitamin C and albumin radicals diffuse very slowly in the coils.
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Anodic electrodeposition of NiTSPP from aqueous basic media.
Pérez-Morales, Marta; Muñoz, Eulogia; Martín-Romero, María T; Camacho, Luis
2005-06-07
The oxidative electrodeposition of NiTSPP (tetrakis(4-sulfonatophenyl) Ni porphyrin) on ITO electrode from 0.1 M NaOH aqueous solution has been studied, and UV-visible and reflection FTIR spectroscopies have been used to analyze the composition of such film. By use of UV-vis spectroscopy, small absorbance of the film and an almost nulling effect on the Soret band of the porphyrin along the Ni(III)/Ni(II) redox process were observed. The reflection FTIR spectroscopy detected the presence of Ni-OH groups in the reduced film and as well the state of the porphyrin molecules as radical cation. Moreover, the porphyrin has been quantified by means of the area of the vibration bands assigned to the sulfonate groups by using as reference a Langmuir-Blodgett film containing a known surface concentration of NiTSPP. These results lead us propose the formation of a conductor salt by electrocrystallization, with stoichiometries TSPP/Ni(II)(OH)2 and TSPP/Ni(III)OOH, for its reduced and oxidized forms, respectively. In these two forms, the porphyrin rings will be present as radical cation, which may be stabilized through its dimerization or polymerization.
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Lanthanide-IMAC enrichment of carbohydrates and polyols.
Schemeth, Dieter; Rainer, Matthias; Messner, Christoph B; Rode, Bernd M; Bonn, Günther K
2014-03-01
In this study a new type of immobilized metal ion affinity chromatography resin for the enrichment of carbohydrates and polyols was synthesized by radical polymerization reaction of vinyl phosphonic acid and 1,4-butandiole dimethacrylate using azo-bis-isobutyronitrile as radical initiator. Interaction between the chelated trivalent lanthanide ions and negatively charged hydroxyl groups of carbohydrates and polyols was observed by applying high pH values. The new method was evaluated by single standard solutions, mixtures of standards, honey and a more complex extract of Cynara scolymus. The washing step was accomplished by acetonitrile in excess volumes. Elution of enriched carbohydrates was successfully performed with deionized water. The subsequent analysis was carried out with matrix-free laser desorption/ionization-time of flight mass spectrometry involving a TiO2 -coated steel target, especially suitable for the measurement of low-molecular-weight substances. Quantitative analysis of the sugar alcohol xylitol as well as the determination of the maximal loading capacity was performed by gas chromatography in conjunction with mass spectrometric detection after chemical derivatization. In a parallel approach quantum mechanical geometry optimizations were performed in order to compare the coordination behavior of various trivalent lanthanide ions. Copyright © 2013 John Wiley & Sons, Ltd.
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Hedir, Guillaume G; Bell, Craig A; O'Reilly, Rachel K; Dove, Andrew P
2015-07-13
The synthesis of vinyl bromobutanoate (VBr), a new vinyl acetate monomer derivative obtained by the palladium-catalyzed vinyl exchange reaction between vinyl acetate (VAc) and 4-bromobutyric acid is reported. The homopolymerization of this new monomer using the RAFT/MADIX polymerization technique leads to the formation of novel well-defined and controlled polymers containing pendent bromine functional groups able to be modified via postpolymerization modification. Furthermore, the copolymerization of vinyl bromobutanoate with 2-methylene-1,3-dioxepane (MDO) was also performed to deliver a range of novel functional degradable copolymers, poly(MDO-co-VBr). The copolymer composition was shown to be able to be tuned to vary the amount of ester repeat units in the polymer backbone, and hence determine the degradability, while maintaining a control of the final copolymers' molar masses. The addition of functionalities via simple postpolymerization modifications such as azidation and the 1,3-dipolar cycloaddition of a PEG alkyne to an azide is also reported and proven by (1)H NMR spectroscopy, FTIR spectroscopy, and SEC analyses. These studies enable the formation of a novel class of hydrophilic functional degradable copolymers using versatile radical polymerization methods.
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Beil, Andreas; Müller, Georgina; Käser, Debora; Hattendorf, Bodo; Li, Zhongshu; Krumeich, Frank; Rosenthal, Amos; Rana, Vijay Kumar; Schönberg, Hartmut; Benkő, Zoltán; Grützmacher, Hansjörg
2018-05-16
Bismesitoylphosphinic acid, (HO)PO(COMes) 2 (BAPO-OH), is an efficient photoinitiator for free-radical polymerizations of olefins in aqueous phase. Described here are the structures of various copper(II) and copper(I) complexes with BAPO-OH as the ligand. The complex Cu II (BAPO-O) 2 (H 2 O) 2 is photoactive, and under irradiation with UV light in aqueous phase, it serves as a source of metallic copper in high purity and yield (>80 %). Simultaneously, the radical polymerization of acrylates can be initiated and allows the preparation of nanoparticle/polymer nanocomposites in which the metallic Cu nanoparticles are protected against oxidation. The determination of the stoichiometry of the photoreductions suggests an almost quantitative conversion from Cu II into Cu 0 with half an equivalent of BAPO-OH, which serves as a four-electron photoreductant. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Deng, Liandong; He, Xiaohua; Li, Aigui; Yang, Qiuxia; Dong, Anjie
2007-02-01
Poly(methacrylic acid-grafted-poly(ethylene glycol)) (P(MAA-g-EG)) hydrogel nanoparticles (HNPs) were prepared by a thermally-initiated free radical dispersion polymerization method. The effects of various reaction parameters on the preparation of HNPs were investigated, including the quantity of monomer, temperature, initiator dosage, crosslinker dosage, and co-stabilizer concentration. The reaction temperature at 75 degrees C was found to be suitable for preparing stable and small P(MAA-g-EG) HNPs. By adding a little amount of polyvinyl alcohol in the reaction media, P(MAA-g-EG) HNPs with narrow size distribution could be obtained. The effects of pH and the crosslinker dosage on the equilibrium swelling behavior of P(MAA-g-EG) HNPs were also studied. The P(MAA-g-EG) HNPs perform pH-responsive swelling behavior, which is strongly influenced by the crosslinker dosage.
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Synthesis of perm-selective membranes by grafting acrylic acid into air-irradiated Teflon-FEP films
NASA Astrophysics Data System (ADS)
Bozzi, Annick; Chapiro, Adolphe
Grafting acrylic acid into air-irradiated Teflon-FEP films was investigated. Pre-irradiation doses ranged from 0.5 to 10 kGy. Grafting occurred at 45 or 60°C. Homopolymerization inhibitors, ferrous ions or methylene blue, were added to the system. It was found that after completion of the reaction, within 40-100 min, membranes were obtained with very low electric resistivities. The influence of added inhibitors, pre-irradiation dose and grafting temperature was studied. From the results it is concluded that the initiating centers in air-irradiated Teflon-FEP are, on the one hand, peroxides of structure POOP', in which P is a polymeric radical and Pprime; a small fragment, and on the other trapped PO .2 radicals. The latter only react after losing their oxygen. In the presence of polymerization inhibitors, initiation involves a redox process which reduces the overall activation energy.
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New core-pyrene π structure organophotocatalysts usable as highly efficient photoinitiators
Telitel, Sofia; Dumur, Frédéric; Faury, Thomas; Graff, Bernadette; Tehfe, Mohamad-Ali; Fouassier, Jean-Pierre
2013-01-01
Summary Eleven di- and trifunctional compounds based on a core-pyrene π structure (Co_Py) were synthesized and investigated for the formation of free radicals. The application of two- and three-component photoinitiating systems (different Co_Pys with the addition of iodonium or sulfonium salts, alkyl halide or amine) was investigated in detail for cationic and radical photopolymerization reactions under near-UV–vis light. The proposed compounds can behave as new photocatalysts. Successful results in terms of rates of polymerization and final conversions were obtained. The strong MO coupling between the six different cores and the pyrene moiety was studied by DFT calculations. The different chemical intermediates are characterized by ESR and laser flash photolysis experiments. The mechanisms involved in the initiation step are discussed, and relationships between the core structure, the Co_Py absorption property, and the polymerization ability are tentatively proposed. PMID:23766803
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Xiao, Lifen; Zhu, Wen; Chen, Jiqiang; Zhang, Ke
2017-02-01
Cyclic multiblock polymers with high-order blocks are synthesized via the combination of single-electron transfer living radical polymerization (SET-LRP) and copper-catalyzed azide-alkyne cycloaddition (CuAAC). The linear α,ω-telechelic multiblock copolymer is prepared via SET-LRP by sequential addition of different monomers. The SET-LRP approach allows well control of the block length and sequence as A-B-C-D-E, etc. The CuAAC is then performed to intramolecularly couple the azide and alkyne end groups of the linear copolymer and produce the corresponding cyclic copolymer. The block sequence and the cyclic topology of the resultant cyclic copolymer are confirmed by the characterization of 1 H nuclear magnetic resonance spectroscopy, gel permeation chromatography, Fourier transform infrared spectroscopy, and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Gama, Mariana R; Aggarwal, Pankaj; Lee, Milton L; Bottoli, Carla B G
2017-11-01
Organic monolithic columns based on single crosslinking of trimethylolpropane trimethacrylate (TRIM) monomer were prepared in a single step by living/controlled free-radical polymerization. Full optimization of the preparation, such as using different percentages of TRIM and different amounts of radical promoter as well as various porogen solvents were explored. The resulting monolithic columns were characterized by scanning electronic microscopy and nitrogen sorption for structure morphology studies and surface area measurements, respectively. Using capillary liquid chromatography, 150 μm i.d. columns were applied to separate a mixture of small hydrophobic molecules. The results indicated that column performance is highly sensitive to the type and the amount of porogen solvents used in the polymerization mixture composition. Good resolution factors and methylene selectivity were obtained, indicating the promising potential of this material for capillary liquid chromatography separations. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Xu, Yuewen; Wang, Weiyu; Wang, Yangyang; ...
2015-11-25
Bottlebrush polymers are densely grafted polymers with long side-chains attached to a linear polymeric backbone. Their unusual structures endow them with a number of unique and potentially useful properties in solution, in thin films, and in bulk. Despite the many studies of bottlebrushes that have been reported, the structure–property relationships for this class of materials are still poorly understood. In this contribution, we report the synthesis and characterization of fluorinated bottlebrush polymers based on poly(2,2,2-trifluoroethyl methacrylate). The synthesis was achieved by atom transfer radical polymerization (ATRP) using an α-bromoisobutyryl bromide functionalized norbornene initiator, followed by ring-opening metathesis polymerization (ROMP) usingmore » a third generation Grubbs’ catalyst (G3). Rheological characterization revealed that the bottlebrush polymer backbones remained unentangled as indicated by the lack of a rubbery plateau in the modulus. By tuning the size of the backbone of the bottlebrush polymers, near-spherical and elongated particles representing single brush molecular morphologies were observed in a good solvent as evidenced by TEM imaging, suggesting a semi-flexible nature of their backbones in dilute solutions. Thin films of bottlebrush polymers exhibited noticeably higher static water contact angles as compared to that of the macromonomer reaching the hydrophobic regime, where little differences were observed between each bottlebrush polymer. Further investigation by AFM revealed that the surface of the macromonomer film was relatively smooth; in contrast, the surface of bottlebrush polymers displayed certain degrees of nano-scale roughness (R q = 0.8–2.4 nm). The enhanced hydrophobicity of these bottlebrushes likely results from the preferential enrichment of the fluorine containing end groups at the periphery of the molecules and the film surface due to the side chain crowding effect. Furthermore, our results provide key information towards the design of architecturally tailored fluorinated polymers with desirable properties.« less
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Free heme and sickle hemoglobin polymerization
NASA Astrophysics Data System (ADS)
Uzunova, Veselina V.
This work investigates further the mechanism of one of the most interesting of the protein self-assembly systems---the polymerization of sickle hemoglobin and the role of free heme in it. Polymerization of sickle hemoglobin is the primary event in the pathology of a chronic hemolytic condition called sickle cell anemia with complex pathogenesis, unexplained variability and symptomatic treatment. Auto-oxidation develops in hemoglobin solutions exposed to room temperature and causes release of ferriheme. The composition of such solutions is investigated by mass spectrometry. Heme dimers whose amount corresponds to the initial amounts of heme released from the protein are followed. Differences in the dimer peak height are established for hemoglobin variants A, S and C and depending on the exposure duration. The effects of free heme on polymerization kinetics are studied. Growth rates and two characteristic parameters of nucleation are measured for stored Hb S. After dialysis of polymerizing solutions, no spherulites are detected at moderately high supersaturation and prolonged exposure times. The addition of 0.16-0.26 mM amounts of heme to dialyzed solutions leads to restoration of polymerization. The measured kinetic parameters have higher values compared to the ones before dialysis. The amount of heme in non-dialyzed aged solution is characterized using spectrophotometry. Three methods are used: difference in absorbance of dialyzed and non-dialyzed solutions, characteristic absorbance of heme-albumin complex and absorbance of non-dialyzed solutions with added potassium cyanide. The various approaches suggest the presence of 0.12 to 0.18 mM of free ferriheme in such solutions. Open questions are whether the same amounts of free heme are present in vivo and whether the same mechanism operates intracellulary. If the answer to those questions is positive, then removal of free heme from erythrocytes can influence their readiness to sickle.
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Goel, Amit; Ahmad, Farhan Jalees; Singh, Raman Mohan; Singh, Gyanendra Nath
2010-02-01
The aim of this study was to develop 3-acetyl-11-keto-beta-boswellic acid (AKBA)-loaded polymeric nanomicelles for topical anti-inflammatory and anti-arthritic activity. Polymeric nanomicelles of AKBA were developed by a radical polymerization method using N-isopropylacrylamide, vinylpyrrolidone and acrylic acid. The polymeric nanomicelles obtained were characterized by Fourier transform infrared (FTIR), transmission electron microscopy (TEM) and dynamic light scattering (DLS). In-vitro and in-vivo evaluations of AKBA polymeric nanomicelles gel were carried out for enhanced skin permeability and anti-inflammatory and anti-arthritic activity. TEM and DLS results demonstrated that polymeric nanomicelles were spherical with a mean diameter approximately 45 nm. FTIR data indicated a weak interaction between polymer and AKBA in the encapsulated system. The release of drug in aqueous buffer (pH 7.4) from the polymeric nanomicelles was 23 and 55% after 2 and 8 h, respectively, indicating sustained release. In-vitro skin permeation studies through excised abdominal skin indicated a threefold increase in skin permeability compared with AKBA gel containing the same amount of AKBA as the AKBA polymeric nanomicelles gel. The AKBA polymeric nanomicelle gel showed significantly enhanced anti-inflammatory and anti-arthritic activity compared with the AKBA gel. This study suggested that AKBA polymeric nanomicelle gel significantly enhanced skin permeability, and anti-inflammatory and anti-arthritic activity.
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Radical-initiated controlled synthesis of homo- and copolymers based on acrylonitrile
NASA Astrophysics Data System (ADS)
Grishin, D. F.; Grishin, I. D.
2015-07-01
Data on the controlled synthesis of polyacrylonitrile and acrylonitrile copolymers with other (meth)acrylic and vinyl monomers upon radical initiation and metal complex catalysis are analyzed. Primary attention is given to the use of metal complexes for the synthesis of acrylonitrile-based (co)polymers with defined molecular weight and polydispersity in living mode by atom transfer radical polymerization. The prospects for using known methods of controlled synthesis of macromolecules for the preparation of acrylonitrile homo- and copolymers as carbon fibre precursors are estimated. The major array of published data analyzed in the review refers to the last decade. The bibliography includes 175 references.
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Huang, Liqiang; Yuan, Shaojun; Lv, Li; Tan, Guangqun; Liang, Bin; Pehkonen, S O
2013-09-01
Cross-linked chitosan (CCS) microspheres tethered with pH-sensitive poly(methacrylic acid) (PMAA) brushes were developed for the efficient removal of Cd(II) ions from aqueous solutions. Functional PMAA brushes containing dense and active carboxyl groups (COOH) were grafted onto the CCS microsphere surface via surface-initiated atom transfer radical polymerization (ATRP). Batch adsorption results showed that solution pH values had a major impact on cadmium adsorption by the PMAA-grafted CCS microspheres with the optimal removal observed above pH 5. The CCS-g-PMAA microsphere was found to achieve the adsorption equilibrium of Cd(II) within 1 h, much faster than about 7 h on the CCS microsphere. At pH 5 and with an initial concentration 0.089-2.49 mmol dm(-3), the maximum adsorption capacity of Cd(II), derived from the Langmuir fitting on the PMAA-grafted microspheres was around 1.3 mmol g(-1). Desorption and adsorption cycle experimental results revealed that the PMAA-grafted CCS microspheres loaded with Cd(II) can be effectively regenerated in a dilute HNO3 solution, and the adsorption capacity remained almost unchanged upon five cycle reuse. Copyright © 2013 Elsevier Inc. All rights reserved.
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Kobayashi, Kazuo; Seike, Yumiko; Saeki, Akinori; Kozawa, Takahiro; Takeuchi, Fusako; Tsubaki, Motonari
2014-10-06
The dynamics of free-radical species in a model cellular system are examined by measuring the formation and decay of ascorbate radicals within a liposome with pulse radiolysis techniques. Upon pulse radiolysis of an N2O-saturated aqueous solution containing ascorbate-loaded liposome vesicles, ascorbate radicals are formed by the reaction of OH(·) radicals with ascorbate in unilamellar vesicles exclusively, irrespective of the presence of vesicle lipids. The radicals are found to decay rapidly compared with the decay kinetics in an aqueous solution. The distinct radical reaction kinetics in the vesicles and in bulk solution are characterized, and the kinetic data are analyzed. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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NASA Technical Reports Server (NTRS)
Serafini, T. T.
1982-01-01
The basic chemistry, cure processes, properties, and applications of high temperature resins known as polyimides are surveyed. Condensation aromatic polymides are prepared by reacting aromatic diamines with aromatic dianhydrides, aromatic tetracarboxylic acids, or with dialkyl esters of aromatic tetracarboxylic acids, depending on the intended end use. The first is for coatings or films while the latter two are more suitable for polyimide matrix resins. Prepreg solutions are made by dissolving reactants in an aprotic solvent, and advances in the addition of a diamine on the double bond and radical polymerization of the double bond are noted to have yielded a final cure product with void-free characteristics. Attention is given to properties of the Skybond, Pyralin, and NR-150B polyimide prepreg materials and characteristics of aging in the NP-150 polyimides. Finally, features of the NASA-developed PMR polyimides are reviewed.
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Sobolčiak, Patrik; Spírek, Mário; Katrlík, Jaroslav; Gemeiner, Peter; Lacík, Igor; Kasák, Peter
2013-04-25
A novel cationic polymer poly(N,N-dimethyl-N-[3-(methacroylamino) propyl]-N-[2-[(2-nitrophenyl)methoxy]-2-oxo-ethyl]ammonium chloride) is synthesized by free-radical polymerization of N-[3-(dimethylamino)propyl] methacrylamide and subsequent quaternization with o-nitrobenzyl 2-chloroacetate. The photolabile o-nitrobenzyl carboxymethyl pendant moiety is transformed to the zwitterionic carboxybetaine form upon the irradiation at 365 nm. This feature is used to condense and, upon the light irradiation, to release double-strand DNA tested by gel electrophoresis and surface plasmon resonance experiments as well as to switch the antibacterial activity to non-toxic character demonstrated for Escherichia coli bacterial cells in solution and at the surface using the self-assembled monolayers. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Wang, Tianfang; Bowie, John H
2010-10-21
A previous report that the interstellar molecule glycolaldehyde (HOCH(2)CHO) can be made from hydroxymethylene (HOCH:) and formaldehyde has been revisited at the CCSD(T)/6-311++G(3df,2p)//MP2/6-311++G(3df,2p) level of theory. This reaction competes with the formation of acetic acid and methylformate, molecules which have also been detected in interstellar clouds. Other possible modes of formation of glycolaldehyde by radical/radical reactions have been shown to be viable theoretically as follows: HO˙+˙CH2CHO -->HOCH2CHO [ΔG(Γ)(298K)=-303kJ mol⁻¹] HOCH2˙+˙CHO-->HOCH2CHO (-259kJ mol⁻¹). The species in these two processes are known interstellar molecules. Key radicals ˙CH(2)CHO and ˙CH(2)OH in these sequences have been shown to be stable for the microsecond duration of neutralization/reionization experiments in the dual collision cells of a VG ZAB 2HF mass spectrometer. The polymerization reaction HOCH(2)CH˙OH + nCH(2)O → HOCH(2)[CH(OH)](n)˙CHOH (n = 1 to 3) has been studied theoretically and shown to be energetically feasible, as is the cyclization reaction of HOCH(2)[(CH(2)OH)(4)]˙CHOH (in the presence of one molecule of water at the reacting centre) to form glucose. The probability of such a reaction sequence is small even if polymerization were to occur in interstellar ice containing a significant concentration of CH(2)O. The large number of stereoisomers produced by such a reaction sequence makes the formation of a particular sugar, again for example glucose, an inefficient synthesis. The possibility of stereoselectivity occurring during the polymerization was investigated for two diastereoisomers of HOCH(2)[(CHOH)](2)˙CHOH. No significant difference was found in the transition state energies for addition of CH(2)O to these two diastereoisomers, but a barrier difference of 12 kJ mol(-1) was found for the H transfer reactions ˙OCH(2)[(CHOH)](2)CH(2)OH → HOCH(2)[(CHOH)(2)˙CHOH of the two diastereoisomers.
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NASA Astrophysics Data System (ADS)
Roh, H. S.; Kang, Y. C.; Park, H. D.; Park, S. B.
Y2O3:Eu phosphor particles were prepared by large-scale spray pyrolysis. The morphological control of Y2O3:Eu particles in spray pyrolysis was attempted by adding polymeric precursors to the spray solution. The effect of composition and amount of polymeric precursors on the morphology, crystallinity and photoluminescence characteristics of Y2O3:Eu particles was investigated. Particles prepared from a solution containing polyethylene glycol (PEG) with an average molecular weight of 200 had a hollow structure, while those prepared from solutions containing adequate amounts of citric acid (CA) and PEG had a spherical shape, filled morphology and clean surfaces after post-treatment at high temperature. Y2O3:Eu particles prepared from an aqueous solution with no polymeric precursors had a hollow structure and rough surfaces after post-treatment. The phosphor particles prepared from solutions with inadequate amounts of CA and/or PEG also had hollow and/or fragmented structures. The particles prepared from the solution containing 0.3 M CA and 0.3 M PEG had the highest photoluminescence emission intensity, which was 56% higher than that of the particles prepared from aqueous solution without polymeric precursors.
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In situ polymerization of monomers for polyphenylquinoxaline/graphite
NASA Technical Reports Server (NTRS)
Serafini, T. T.; Delvigs, P.; Vannucci, R. D.
1973-01-01
Methods currently used to prepare fiber reinforced, high temperature resistant polyphenylquinoxaline (PPQ) composites employ extremely viscous, low solids content solutions of high molecular weight PPQ polymers. An improved approach, described in this report, consists of impregnating the fiber with a solution of the appropriate monomers instead of a solution of previously synthesized high molecular weight polymer. Polymerization of the monomers occurs in situ on the fiber during the solvent removal and curing stages. The in situ polymerization approach greatly simplifies the fabrication of PPQ graphite fiber composites. The use of low viscosity monomeric type solutions facilitates fiber wetting, permits a high solids content, and eliminates the need for prior polymer synthesis.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Jayaweera, Indira; Krishnan, Gopala N.; Sanjurjo, Angel
2016-04-26
The invention provides methods for preparing an asymmetric hollow fiber, the asymmetric hollow fibers prepared by such methods, and uses of the asymmetric hollow fibers. One method involves passing a polymeric solution through an outer annular orifice of a tube-in-orifice spinneret, passing a bore fluid though an inner tube of the spinneret, dropping the polymeric solution and bore fluid through an atmosphere over a dropping distance, and quenching the polymeric solution and bore fluid in a bath to form an asymmetric hollow fiber.
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Hong, Chang-Young; Park, Se-Yeong; Kim, Seon-Hong; Lee, Su-Yeon; Choi, Won-Sil; Choi, In-Gyu
2016-10-01
This study was carried out to better understand the characteristic modification mechanisms of monolignols by enzyme system of Abortiporus biennis and to induce the degradation of monolignols. Degradation and polymerization of monolignols were simultaneously induced by A. biennis. Whole cells of A. biennis degraded coniferyl alcohol to vanillin and coniferyl aldehyde, and degraded sinapyl alcohol to 2,6-dimethoxybenzene- 1,4-diol, with the production of dimers. The molecular weight of monolignols treated with A. biennis increased drastically. The activities of lignin degrading enzymes were monitored for 24 h to determine whether there was any correlation between monolignol biomodification and ligninolytic enzymes. We concluded that complex enzyme systems were involved in the degradation and polymerization of monolignols. To degrade monolignols, ascorbic acid was added to the culture medium as a reducing agent. In the presence of ascorbic acid, the molecular weight was less increased in the case of coniferyl alcohol, while that of sinapyl alcohol was similar to that of the control. Furthermore, the addition of ascorbic acid led to the production of various degraded compounds: syringaldehyde and acid compounds. Accordingly, these results demonstrated that ascorbic acid prevented the rapid polymerization of monolignols, thus stabilizing radicals generated by enzymes of A. biennis. Thereafter, A. biennis catalyzed the oxidation of stable monolignols. As a result, ascorbic acid facilitated predominantly monolignols degradation by A. biennis through the stabilization of radicals. These findings showed outstanding ability of A. biennis to modify the lignin compounds rapidly and usefully.
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Ding, Mingqiang; Jiang, Xiaowu; Peng, Jinying; Zhang, Lifen; Cheng, Zhenping; Zhu, Xiulin
2015-03-01
A concept based on diffusion-regulated phase-transfer catalysis (DRPTC) in an aqueous-organic biphasic system with copper-mediated initiators for continuous activator regeneration is successfully developed for atom transfer radical polymerization (ICAR ATRP) (termed DRPTC-based ICAR ATRP here), using methyl methacrylate (MMA) as a model monomer, ethyl α-bromophenylacetate (EBrPA) as an initiator, and tris(2-pyridylmethyl)amine (TPMA) as a ligand. In this system, the monomer and initiating species in toluene (organic phase) and the catalyst complexes in water (aqueous phase) are simply mixed under stirring at room temperature. The trace catalyst complexes transfer into the organic phase via diffusion to trigger ICAR ATRP of MMA with ppm level catalyst content once the system is heated to the polymerization temperature (75 °C). It is found that well-defined PMMA with controlled molecular weights and narrow molecular weight distributions can be obtained easily. Furthermore, the polymerization can be conducted in the presence of limited amounts of air without using tedious degassed procedures. After cooling to room temperature, the upper organic phase is decanted and the lower aqueous phase is reused for another 10 recycling turnovers with ultra low loss of catalyst and ligand loading. At the same time, all the recycled catalyst complexes retain nearly perfect catalytic activity and controllability, indicating a facile and economical strategy for catalyst removal and recycling. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Investigation of a new thermosensitive block copolymer micelle: hydrolysis, disruption, and release.
Pelletier, Maxime; Babin, Jérôme; Tremblay, Luc; Zhao, Yue
2008-11-04
Thermosensitive polymer micelles are generally obtained with block copolymers in which one block exhibits a lower critical solution temperature in aqueous solution. We investigate a different design that is based on the use of one block bearing a thermally labile side group, whose hydrolysis upon heating shifts the hydrophilic-hydrophobic balance toward the destabilization of block copolymer micelles. Atom transfer radical polymerization was utilized to synthesize a series of diblock copolymers composed of hydrophilic poly(ethylene oxide) (PEO) and hydrophobic poly(2-tetrahydropyranyl methacrylate) (PTHPMA). We show that micelles of PEO-b-PTHPMA in aqueous solution can be destabilized as a result of the thermosensitive hydrolytic cleavage of tetrahydropyranyl (THP) groups that transforms PTHPMA into hydrophilic poly(methacrylic acid). The three related processes occurring in aqueous solution, namely, hydrolytic cleavage of THP, destabilization of micelles, and release of loaded Nile Red (NR), were investigated simultaneously using 1H NMR, dynamic light scattering, and fluorescence spectroscopy, respectively. At 80 degrees C, the results suggest that the three events proceed with a similar kinetics. Although slower than at elevated temperatures, the disruption of PEO-b-PTHPMA micelles can take place at the body temperature (approximately 37 degrees C), and the release kinetics of NR can be adjusted by changing the relative lengths of the two blocks or the pH of the solution.
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Wang, Lu; Pan, Mingwang; Song, Shaofeng; Zhu, Lei; Yuan, Jinfeng; Liu, Gang
2016-08-09
Herein, we demonstrate a facile approach to prepare anisotropic poly(tert-butyl acrylate)/polystyrene (PtBA/PS) composite particles with controllable morphologies by soap-free seeded emulsion polymerization (SSEP). In the first step, noncrosslinked PtBA seeds with self-stabilizing polar functional groups (e.g., ester groups and radicals) are synthesized by soap-free emulsion polymerization. During the subsequent SSEP of styrene (St), PS bulges are nucleated on the PtBA seeds due to the microphase separation confined in the latex particles. The morphology evolution of PtBA/PS composite particles is tailored by varying the monomer/seed feed ratio, polymerization time, and polymerization temperature. Many intriguing morphologies, including hamburger-like, litchi-like, mushroom-like, strawberry-like, bowl-like, and snowman-like, have been acquired for PtBA/PS composite particles. The polar groups on the PtBA seed surface greatly influence the formation and further merging of PS/St bulges during the polymerization. A possible formation mechanism is proposed on the basis of experimental results. These complex composite particles are promising for applications in superhydrophobic coatings.
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Shanmugam, Sivaprakash; Xu, Jiangtao; Boyer, Cyrille
2016-01-18
Photoregulated polymerizations are typically conducted using high-energy (UV and blue) light, which may lead to undesired side reactions. Furthermore, as the penetration of visible light is rather limited, the range of applications with such wavelengths is likewise limited. We herein report the first living radical polymerization that can be activated and deactivated by irradiation with near-infrared (NIR) and far-red light. Bacteriochlorophyll a (Bachl a) was employed as a photoredox catalyst for photoinduced electron transfer/reversible addition-fragmentation chain transfer (PET-RAFT) polymerization. Well-defined polymers were thus synthesized within a few hours under NIR (λ=850 nm) and far-red (λ=780 nm) irradiation with excellent control over the molecular weight (M(n)/M(w)<1.25). Taking advantage of the good penetration of NIR light, we showed that the polymerization also proceeded smoothly when a translucent barrier was placed between light source and reaction vessel. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Characterization of polymeric solutions as injectable vehicles for hydroxyapatite microspheres.
Oliveira, Serafim M; Almeida, Isabel F; Costa, Paulo C; Barrias, Cristina C; Ferreira, M Rosa Pena; Bahia, M Fernanda; Barbosa, Mário A
2010-06-01
A polymeric solution and a reinforcement phase can work as an injectable material to fill up bone defects. However, the properties of the solution should be suitable to enable the transport of that extra phase. Additionally, the use of biocompatible materials is a requirement for tissue regeneration. Thus, we intended to optimize a biocompatible polymeric solution able to carry hydroxyapatite microspheres into bone defects using an orthopedic injectable device. To achieve that goal, polymers usually regarded as biocompatible were selected, namely sodium carboxymethylcellulose, hydroxypropylmethylcellulose, and Na-alginate (ALG). The rheological properties of the polymeric solutions at different concentrations were assessed by viscosimetry before and after moist heat sterilization. In order to correlate rheological properties with injectability, solutions were tested using an orthopedic device applied for minimal invasive surgeries. Among the three polymers, ALG solutions presented the most suitable properties for our goal and a non-sterile ALG 6% solution was successfully used to perform preliminary injection tests of hydroxyapatite microspheres. Sterile ALG 7.25% solution was found to closely match non-sterile ALG 6% properties and it was selected as the optimal vehicle. Finally, sterile ALG 7.25% physical stability was studied at different temperatures over a 3-month period. It was observed that its rheological properties presented minor changes when stored at 25 degrees C or at 4 degrees C.
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TRANSITION METAL CATALYZED ATOM TRANSFER RADICAL POLYMERIZATION. (R826735)
The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...
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REVERSE ATOM TRANSFER RADICAL POLYMERIZATION IN MINIEMULSION. (R829580)
The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...
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ATOM TRANSFER RADICAL POLYMERIZATION IN SUPERCRITICAL CARBON DIOXIDE. (R826735)
The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...
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COPPER(I)-CATALYZED ATOM TRANSFER RADICAL POLYMERIZATIONS. (R826735)
The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...
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Sieving polymer synthesis by reversible addition fragmentation chain transfer polymerization.
Nai, Yi Heng; Jones, Roderick C; Breadmore, Michael C
2013-12-01
Replaceable sieving polymers are the fundamental component for high resolution nucleic acids separation in CE. The choice of polymer and its physical properties play significant roles in influencing separation performance. Recently, reversible addition fragmentation chain transfer (RAFT) polymerization has been shown to be a versatile polymerization technique capable of yielding well defined polymers previously unattainable by conventional free radical polymerization. In this study, a high molecular weight PDMA at 765 000 gmol-1 with a PDI of 1.55 was successfully synthesized with the use of chain transfer agent - 2-propionic acidyl butyl trithiocarbonate (PABTC) in a multi-step sequential RAFT polymerization approach. This study represents the first demonstration of RAFT polymerization for synthesizing polymers with the molecular weight range suitable for high resolution DNA separation in sieving electrophoresis. Adjustment of pH in the reaction was found to be crucial for the successful RAFT polymerization of high molecular weight polymer as the buffered condition minimizes the effect of hydrolysis and aminolysis commonly associated with trithiocarbonate chain transfer agents. The separation efficiency of PABTC-PDMA was found to have marginally superior separation performance compared to a commercial PDMA formulation, POP™-CAP, of similar molecular weight range.
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Transient alkylaminium radicals in n-hexane. Condensed-phase ion-molecule reactions
DOE Office of Scientific and Technical Information (OSTI.GOV)
Werst, D.W.; Trifunac, A.D.
Time-resolved fluorescence detected magnetic resonance (FDMR) is used to observe alkylaminium radicals formed in n-hexane solutions by electron pulse radiolysis. The ease of observation of aminium radical FDMR signals increases with increasing alkyl substitution of the amine solutes. The results are discussed in terms of the ion-molecule reactions, such as proton transfer, which compete with the electron-transfer processes, i.e, the electron transfer from solute molecules to n-hexane radical cations and geminate recombination.
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Xiao, Min; González, Edurne; Monterroza, Alexis Martell; Frey, Margaret
2017-10-15
A thermo-responsive polymer with hydrophilic to hydrophobic transition behavior, poly(vinyl caprolactam-co-hydroxyethyl acrylamide) P(VCL-co-HEAA), was prepared by copolymerization of vinyl caprolactam and N-hydroxyethyl acrylamide via free radical solution polymerization. The resulting copolymer was characterized by Fourier transform infrared spectroscopy (FTIR), 1 H nuclear magnetic resonance (NMR), gel permeation chromatography (GPC), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). The lower critical solution temperature (LCST) of P(VCL-co-HEAA) was determined at 34.5°C. This thermo-responsive polymer was then grafted onto cotton fabrics using 1,2,3,4-butanetetracarboxylic acid (BTCA) as crosslinker and sodium hypophosphite (SHP) as catalyst. FTIR and energy dispersive X-ray spectroscopy (EDS) studies confirmed the successful grafting reaction. The modified cotton fabric exhibited thermo-responsive behavior as evidenced by water vapor permeability measurement confirming decreased permeability at elevated temperature. This is the first demonstration that a PVCL based copolymer is grafted to cotton fabrics. This study provides a new thermo-responsive polymer for fabrication of smart cotton fabrics with thermally switchable hydrophilicity. Copyright © 2017 Elsevier Ltd. All rights reserved.
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[Mechanoelectric potentials in synthetic hydrogels: possible relation to cytoskeleton].
Shkliar, T F; Safronov, A P; Toropova, O A; Pollack, G N; Bliakhman, F A
2010-01-01
Mechanical and electrical properties of a synthetic polyelectrolyte hydrogel considered as a model of the cytoskeletal gel were studied. Hydrogels were synthesized from polymethacrylic acid by radical polymerization in aqueous solution. The electrical charge was introduced into the gel network by partial neutralization of monomer acids with magnesium (hydro)oxides. Through the use of a motor, triangular longitudinal (axial) deformations were applied to gel samples. Simultaneously, the electrochemical (Donnan) potential of the gel was measured using conventional microelectrodes. We found that: (1) the Young modulus of the gel was 0.53 kPa; (2) at a given deformation velocity, the extent of gel deformation closely correlates with the gel potential; and (3) at the same level of gel deformation, the lower the deformation velocity, the higher the relative change of gel potential. These findings show a striking similarity to the data obtained in living cells, particularly in cardiac myocytes. A hypothesis involving the deformation-induced solvent migration from the gel to the surrounding solution is considered. It is concluded that the physicochemical features of the cytoskeletal gel may play a role in determining the mechanoelectric properties of excited cells.
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Chen, Yiqiong; Chen, Maolin; Chi, Jinxin; Yu, Xia; Chen, Yongxuan; Lin, Xucong; Xie, Zenghong
2018-08-17
A novel aptamer-based polyhedral oligomeric silsesquioxane (POSS)-containing hybrid affinity monolith has been prepared with a facile "one-pot" process simultaneously via "free radical polymerization" and "thiol-ene" click reaction, and used for on-line selective extraction and practical analysis to trace ochratoxin A (OTA). By using the ternary porogenic mixture composed of water/DMF/PEG, a homogeneous polymerization mixture with POSS chemicals, acrylate-based monomers and aptamer aqueous solution was obtained, and the copolymerization of POSS chemicals, polymer monomers and aptamer aqueous solution was systematically studied. Characterizations such as the morphology, FT-IR and fluorescence spectra, mechanical stability, dynamic binding capacity, cross-reactivity and selectivity of the resultant affinity monolith were also evaluated. Attributed to the porous monolithic structure and aptamer-based affinity interaction, acceptable selective recognition and recovery yields towards trace OTA were obtained. With a 5-fold volume enrichment, the limit of detection (LOD) and limit of quantitation (LOQ) of OTA in fortified beer samples were gained at 0.025 ng/mL (S/N = 3) and 0.045 ng/mL (S/N = 10), respectively. It could be competent for the sensitive measure of actual OTA residues in real beer samples. In comparison with the previously reported strategies containing common "sol-gel" chemistry, the proposed protocol to fabricating aptamer-modified POSS-containing hybrid affinity monolith showed a simpler preparation with acceptable selectivity and higher recovery to trace OTA. Copyright © 2018 Elsevier B.V. All rights reserved.
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In situ polymerization of monomers for polyphenylquinoxaline/graphite fiber composites
NASA Technical Reports Server (NTRS)
Serafini, T. T.; Delvigs, P.; Vannucci, R. D.
1974-01-01
Methods currently used to prepare fiber reinforced, high temperature resistant polyphenylquinoxaline (PPQ) composites employ extremely viscous, low solids content solutions of high molecular weight PPQ polymers. An improved approach, described in this report, consists of impregnating the fiber with a solution of the appropriate monomers instead of a solution of previously synthesized high molecular weight polymer. Polymerization of the monomers occurs in situ on the fiber during the solvent removal and curing stages. The in situ polymerization approach greatly simplifies the fabrication of PPQ graphite fiber composites. The use of low viscosity monomeric type solutions facilitates fiber wetting, permits a high solids content, and eliminates the need for prior polymer synthesis.
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Various aspects of ultrasound assisted emulsion polymerization process.
Korkut, Ibrahim; Bayramoglu, Mahmut
2014-07-01
In this paper, the effects of ultrasonic (US) power, pulse ratio, probe area and recipe composition were investigated on two process responses namely, monomer (methyl methacrylate, MMA) conversion and electrical energy consumption per mass of product polymer (PMMA). Pulsed mode US is more suitable than continuous mode US for emulsion polymerization. The probe (tip) area has little effect on the yield of polymerization when comparing 19 and 13 mm probes, 13 mm probe performing slightly better for high conversion levels. Meanwhile, large probe area is beneficial for high conversion efficiency of electric energy to US energy as well as for high radical generation yield per energy consumed. The conversion increased slightly and electrical energy consumption decreased substantially by using a recipe with high SDS and monomer concentrations. Conclusions presented in this paper may be useful for scale-up of US assisted emulsion polymerization. Copyright © 2014 Elsevier B.V. All rights reserved.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Wei, Chan Yi, E-mail: vicchanyiwei@hotmail.com; Ongkudon, Clarence M., E-mail: clarence@ums.edu.my; Kansil, Tamar, E-mail: tamarkansil87@gmail.com
Modern day synthesis protocols of methacrylate monolithic polymer adsorbent are based on existing polymerization blueprint without a thorough understanding of the dynamics of pore structure and formation. This has resulted in unproductiveness of polymer adsorbent consequently affecting purity and recovery of final product, productivity, retention time and cost effectiveness of the whole process. The problems magnified in monolith scaling-up where internal heat buildup resulting from external heating and high exothermic polymerization reaction was reflected in cracking of the adsorbent. We believe that through careful and precise control of the polymerization kinetics and parameters, it is possible to prepare macroporous methacrylatemore » monolithic adsorbents with controlled pore structures despite being carried out in an unstirred mould. This research involved the study of the effect of scaling-up on pore morphology of monolith, in other words, porous polymethacrylate adsorbents that were prepared via bulk free radical polymerization process by imaging the porous morphology of polymethacrylate with scanning electron microscope.« less
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Kaneko, Yoshiro; Kadokawa, Jun-Ichi
2006-01-01
In the first part of this review, we describe the synthesis of nanostructured hybrid materials composed of polysaccharides and synthetic polymers. Amylose-synthetic polymer inclusion complexes were synthesized by amylose-forming polymerization using phosphorylase enzyme in the presence of synthetic polymers such as polyethers and polyesters. Alginate-polymethacrylate hybrid materials were prepared by free-radical polymerization of cationic methacrylate in the presence of sodium alginate. These methods allow the simultaneous control of the nanostructure with polymerization, giving well-defined hybrid materials. In the second part of this review, we describe the synthesis of novel glycopolymers with rigid structures. Polyaniline-based glycopolymers were synthesized by means of oxidative polymerization of N-glycosylaniline. Polysiloxane-based glycopolymers were prepared by means of introduction of sugar-lactone to the rodlike polysiloxane. These glycopolymers had regular higher-ordered structures due to their rigid polymer backbones, resulting in control of the three-dimensional array of sugar-residues.
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Jalil, Aamir; Khan, Samiullah; Naeem, Fahad; Haider, Malik Suleman; Sarwar, Shoaib; Riaz, Amna; Ranjha, Nazar Muhammad
2017-01-01
In present investigation new formulations of Sodium Alginate/Acrylic acid hydrogels with high porous structure were synthesized by free radical polymerization technique for the controlled drug delivery of analgesic agent to colon. Many structural parameters like molecular weight between crosslinks ( M c ), crosslink density ( M r ), volume interaction parameter ( v 2, s ), Flory Huggins water interaction parameter and diffusion coefficient ( Q ) were calculated. Water uptake studies was conducted in different USP phosphate buffer solutions. All samples showed higher swelling ratio with increasing pH values because of ionization of carboxylic groups at higher pH values. Porosity and gel fraction of all the samples were calculated. New selected samples were loaded with the model drug (diclofenac potassium).The amount of drug loaded and released was determined and it was found that all the samples showed higher release of drug at higher pH values. Release of diclofenac potassium was found to be dependent on the ratio of sodium alginate/acrylic acid, EGDMA and pH of the medium. Experimental data was fitted to various model equations and corresponding parameters were calculated to study the release mechanism. The Structural, Morphological and Thermal Properties of interpenetrating hydrogels were studied by FTIR, XRD, DSC, and SEM.
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Chen, Chunyan; Liang, Xiaotong; Wang, Jianping; Zou, Ying; Hu, Huiping; Cai, Qingyun; Yao, Shouzhuo
2014-06-27
A novel solid-phase microextraction (SPME) fiber was developed by chemical binding of a crosslinked polymeric ionic liquid (PIL) on the surface of an anodized Ti wire, and was applied in direct-immersion mode for the extraction of perfluorinated compounds (PFCs) from water samples coupled with high performance liquid chromatography-tandem mass spectrometry analysis. The PIL coatings were synthesized by using 1-vinyl-3-hexylimidazolium hexafluorophosphate as monomer and methylacryloyl-substituted polyhedral oligomeric silsesquioxane (POSS) as cross-linker via free radical reaction. The proposed fiber coating exhibited high mechanical stability due to the chemical bonding between the coating and the Ti wire surface. The integration of POSS reagent enhanced the organic solvent resistance of the coating. The parameters affecting the extraction performance of the fiber coating including extraction time, pH of solution, ionic strength and desorption conditions were optimized. The developed PIL-POSS fiber showed good linearity (R<0.998) between 0.1 and 50ngmL(-1) with method detection limits ranging from 0.005 to 0.08ngmL(-1) depending on the analyte, and with relative standard deviation for single-fiber repeatability and fiber-to-fiber reproducibility less than 8.6% and 9.5%, respectively. Copyright © 2014 Elsevier B.V. All rights reserved.
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Ou, Hongxiang; Chen, Qunhui; Pan, Jianming; Zhang, Yunlei; Huang, Yong; Qi, Xueyong
2015-05-30
Magnetic imprinted polymers (MIPs) were synthesized by Pickering emulsion polymerization and used to adsorb erythromycin (ERY) from aqueous solution. The oil-in-water Pickering emulsion was stabilized by chitosan nanoparticles with hydrophobic Fe3O4 nanoparticles as magnetic carrier. The imprinting system was fabricated by radical polymerization with functional and crosslinked monomer in the oil phase. Batches of static and dynamic adsorption experiments were conducted to analyze the adsorption performance on ERY. Isotherm data of MIPs well fitted the Freundlich model (from 15 °C to 35 °C), which indicated heterogeneous adsorption for ERY. The ERY adsorption capacity of MIPs was about 52.32 μmol/g at 15 °C. The adsorption kinetics was well described by the pseudo-first-order model, which suggested that physical interactions were primarily responsible for ERY adsorption. The Thomas model used in the fixed-bed adsorption design provided a better fit to the experimental data. Meanwhile, ERY exhibited higher affinity during adsorption on the MIPs compared with the adsorption capacity of azithromycin and chloramphenicol. The MIPs also exhibited excellent regeneration capacity with only about 5.04% adsorption efficiency loss in at least three repeated adsorption-desorption cycles. Copyright © 2015 Elsevier B.V. All rights reserved.
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ION EXCHANGE SUBSTANCES BY SAPONIFICATION OF ALLYL PHOSPHATE POLYMERS
Kennedy, J.
1959-04-14
An ion exchange resin having a relatively high adsorption capacity tor uranyl ion as compared with many common cations is reported. The resin comprises an alphyl-allyl hydrogen phosphate polymer, the alphyl group being either allyl or a lower alkyl group having up to 5 carbon atoins. The resin is prepared by polymerizing compounds such as alkyl-diallyl phosphate and triallyl phosphate in the presence of a free radical generating substance and then partially hydrolyzing the resulting polymer to cause partial replacement of organic radicals by cations. A preferred free radical gencrating agent is dibenzoyl peroxide. The partial hydrolysis is brought about by refluxing the polymer with concentrated aqueous NaOH for three or four hours.
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Imidazolium-Based Polymeric Materials as Alkaline Anion-Exchange Fuel Cell Membranes
NASA Technical Reports Server (NTRS)
Narayan, Sri R.; Yen, Shiao-Ping S.; Reddy, Prakash V.; Nair, Nanditha
2012-01-01
Polymer electrolyte membranes that conduct hydroxide ions have potential use in fuel cells. A variety of polystyrene-based quaternary ammonium hydroxides have been reported as anion exchange fuel cell membranes. However, the hydrolytic stability and conductivity of the commercially available membranes are not adequate to meet the requirements of fuel cell applications. When compared with commercially available membranes, polystyrene-imidazolium alkaline membrane electrolytes are more stable and more highly conducting. At the time of this reporting, this has been the first such usage for imidazolium-based polymeric materials for fuel cells. Imidazolium salts are known to be electrochemically stable over wide potential ranges. By controlling the relative ratio of imidazolium groups in polystyrene-imidazolium salts, their physiochemical properties could be modulated. Alkaline anion exchange membranes based on polystyrene-imidazolium hydroxide materials have been developed. The first step was to synthesize the poly(styrene-co-(1-((4-vinyl)methyl)-3- methylimidazolium) chloride through a free-radical polymerization. Casting of this material followed by in situ treatment of the membranes with sodium hydroxide solutions provided the corresponding hydroxide salts. Various ratios of the monomers 4-chloromoethylvinylbenzine (CMVB) and vinylbenzine (VB) provided various compositions of the polymer. The preferred material, due to the relative ease of casting the film, and its relatively low hygroscopic nature, was a 2:1 ratio of CMVB to VB. Testing confirmed that at room temperature, the new membranes outperformed commercially available membranes by a large margin. With fuel cells now in use at NASA and in transportation, and with defense potential, any improvement to fuel cell efficiency is a significant development.
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Metternich, Jan B; Sagebiel, Sven; Lückener, Anne; Lamping, Sebastian; Ravoo, Bart Jan; Gilmour, Ryan
2018-03-20
The covalent immobilization of the biomimetic, photo-organocatalyst (-)-riboflavin on silica micro- and nanoparticles via atom transfer radical polymerization (ATRP) is disclosed. Given the effectiveness of (-)-riboflavin as a versatile, environmentally benign photocatalyst, an immobilization strategy based on acrylate-linker modification of the catalyst core and controlled polymerization on initiator pre-functionalized silica particles has been developed. Validation of this approach is demonstrated in the E→Z isomerization of a benchmark cinnamonitrile (Z/E up to 88:12) with 0.97 mol % catalyst loading. Characterization of the immobilized photocatalyst supports covalent embedding of the catalyst in the polymeric brushes on the silica particle surface. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Polymerization reactivity of sulfomethylated alkali lignin modified with horseradish peroxidase.
Yang, Dongjie; Wu, Xiaolei; Qiu, Xueqing; Chang, Yaqi; Lou, Hongming
2014-03-01
Alkali lignin (AL) was employed as raw materials in the present study. Sulfomethylation was conducted to improve the solubility of AL, while sulfomethylated alkali lignin (SAL) was further polymerized by horseradish peroxidase (HRP). HRP modification caused a significant increase in molecular weight of SAL which was over 20 times. It was also found to increase the amount of sulfonic and carboxyl groups while decrease the amount of phenolic and methoxyl groups in SAL. The adsorption quantity of self-assembled SAL film was improved after HRP modification. Sulfonation and HRP modification were mutually promoted. The polymerization reactivity of SAL in HRP modification was increased with its sulfonation degree. Meanwhile, HRP modification facilitated SAL's radical-sulfonation reaction. Copyright © 2014. Published by Elsevier Ltd.
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Anastasaki, Athina; Nikolaou, Vasiliki; Brandford-Adams, Francesca; Nurumbetov, Gabit; Zhang, Qiang; Clarkson, Guy J; Fox, David J; Wilson, Paul; Kempe, Kristian; Haddleton, David M
2015-04-04
A photo-polymerization protocol, utilizing a pre-formed and well-characterized Cu(II) formate complex, [Cu(Me6-Tren)(O2CH)](ClO4), mediated by UV light is described. In the absence of additional reducing agents and/or photosensitizers, ppm concentrations of the oxidatively stable [Cu(Me6-Tren)(O2CH)](ClO4), furnish near-quantitative conversions within 2 h, yielding poly(acrylates) with low dispersities (∼1.10) and exceptional end-group fidelity, capable of undergoing in situ chain extension and block copolymerization.
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Preparing polymeric matrix composites using an aqueous slurry technique
NASA Technical Reports Server (NTRS)
Johnston, Norman J. (Inventor); Towell, Timothy W. (Inventor)
1993-01-01
An aqueous process was developed to prepare a consolidated composite laminate from an aqueous slurry. An aqueous poly(amic acid) surfactant solution was prepared by dissolving a poly(amic acid) powder in an aqueous ammonia solution. A polymeric powder was added to this solution to form a slurry. The slurry was deposited on carbon fiber to form a prepreg which was dried and stacked to form a composite laminate. The composite laminate was consolidated using pressure and was heated to form the polymeric matrix. The resulting composite laminate exhibited high fracture toughness and excellent consolidation.
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PHOTOLYTIC AND FREE RADICAL POLYMERIZATION OF EPOXIDIZED PLANT OIL TRIGLYCERIDES. (R829576)
The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...
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Fundamentals of Atom Transfer Radical Polymerization
ERIC Educational Resources Information Center
Coessens, Veerle M. C.; Matyjaszewski, Krzysztof
2010-01-01
Today's market increasingly demands sophisticated materials for advanced technologies and high-value applications, such as nanocomposites, optoelectronic, or biomedical materials. Therefore, the demand for well-defined polymers with very specific molecular architecture and properties increases. Until recently, these kinds of polymers could only be…
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IMMOBILIZATION OF THE COPPER CATALYST IN ATOM TRANSFER RADICAL POLYMERIZATION. (R826735)
The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...
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ATOM TRANSFER RADICAL POLYMERIZATION OF STYRENE IN TOLUENE-WATER MIXTURES. (R829580)
The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...
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Saha, Sampa
2011-01-01
Atom transfer radical polymerization (ATRP) is commonly used to grow polymer brushes from Au surfaces, but the resulting film thicknesses are usually significantly less than with ATRP from SiO2 substrates. On Au, growth of poly(methyl methacrylate) (PMMA) blocks from poly(tert-butyl acrylate) brushes occurs more rapidly than growth of PMMA from initiator monolayers, suggesting that the disparity between growth rates from Au and SiO2 stems from the Au surface. Radical quenching by electron transfer from Au is probably not the termination mechanism because polymerization from thin, cross-linked initiators gives film thicknesses that are essentially the same as the thicknesses of films grown from SiO2 under the same polymerization conditions. However, this result is consistent with termination through desorption of thiols from non-cross-linked films, and reaction of these thiols with growing polymer chains. The enhanced stability of cross-linked initiators allows ATRP at temperatures up to ~100 °C and enables the growth of thick films of PMMA (350 nm), polystyrene (120 nm) and poly(vinyl pyridine) (200 nm) from Au surfaces in 1 hour. At temperatures >100 °C, the polymer brush layers delaminate as large area films. PMID:21728374
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The Nanoconfined Free Radical Polymerization: Reaction Kinetics and Thermodynamics
NASA Astrophysics Data System (ADS)
Zhao, Haoyu; Simon, Sindee
The reaction kinetics and thermodynamics of nanoconfined free radical polymerizations are investigated for methyl methacrylate (MMA) and ethyl methacrylate (EMA) monomers using differential scanning calorimetry. Controlled pore glass is used as the confinement medium with pore diameters as small as 7.5 nm; the influence of both hydrophobic (silanized such that trimethylsilyl groups cover the surface) and hydrophilic (native silanol) surfaces is investigated. Propagation rates increase when monomers are reacted in the hydrophilic pores presumably due to the specific interactions between the carbonyl and silanol groups; however, the more flexible EMA monomer shows weaker effects. On the other hand, initial rates of polymerization in hydrophobic pores are unchanged from the bulk. In both pores, the onset of autoacceleration occurs earlier due to the reduced diffusivity of confined chains, which may be compensated at high temperatures. In addition to changes in kinetics, the reaction thermodynamics can be affected under nanoconfinement. Specifically, the ceiling temperature (Tc) is shifted to lower temperatures in nanopores, with pore surface chemistry showing no significant effects; the equilibrium conversion is also reduced at high temperatures below Tc. These observations are attributed to a larger negative change in entropy on propagation for the confined system, with the MMA system again showing greater effects. Funding from ACS PRF is gratefully acknowledged.
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NASA Astrophysics Data System (ADS)
Abdullah, N. H.; Selamat, M. K. A.; Nasuha, N.; Hassan, H.; Zubir, N. A.
2018-06-01
Iron–immobilized montmorillonite KSF (Fe-MKSF) has been recognized as promising catalyst in degrading persistence organic contaminants. However, detailed mechanistic insight during the catalysis which involving the formation and identification of radical species were remained indeterminate due to complex reaction. Inspiring by this gap, iron-immobilized clay (Fe-MKSF) was synthesized and used as heterogeneous catalyst in the oxidative degradation of methyl orange (MO) solution. Identification of radical species were determined through the inclusion of different types of radical scavenging agent during the Fenton-like reaction at optimum condition. Interestingly, dominant radical species were found to be hydroperoxyl radicals (•OOH) which subsequently followed by hydroxyl radicals (•OH) during the catalysis. Based on the percentage of MO removal, it was suggested that approximately 88% of the •OOH radicals existed at the interface of catalyst while 39% presence in bulk solution. Meanwhile, the interface •OH radicals promoted 38% of MO removal, whilst 4% by the bulk •OH radicals. Hence, these findings have conveyed novel insight on detailed radicals’ identification as well as its’ interaction during the catalysis.
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Polymerization in the gas phase, in clusters, and on nanoparticle surfaces.
El-Shall, M Samy
2008-07-01
Gas phase and cluster experiments provide unique opportunities to quantitatively study the effects of initiators, solvents, chain transfer agents, and inhibitors on the mechanisms of polymerization. Furthermore, a number of important phenomena, unique structures, and novel properties may exist during gas-phase and cluster polymerization. In this regime, the structure of the growing polymer may change dramatically and the rate coefficient may vary significantly upon the addition of a single molecule of the monomer. These changes would be reflected in the properties of the oligomers deposited from the gas phase. At low pressures, cationic and radical cationic polymerizations may proceed in the gas phase through elimination reactions. In the same systems at high pressure, however, the ionic intermediates may be stabilized, and addition without elimination may occur. In isolated van der Waals clusters of monomer molecules, sequential polymerization with several condensation steps can occur on a time scale of a few microseconds following the ionization of the gas-phase cluster. The cluster reactions, which bridge gas-phase and condensed-phase chemistry, allow examination of the effects of controlled states of aggregation. This Account describes several examples of gas-phase and cluster polymerization studies where the most significant results can be summarized as follows: (1) The carbocation polymerization of isobutene shows slower rates with increasing polymerization steps resulting from entropy barriers, which could explain the need for low temperatures for the efficient propagation of high molecular weight polymers. (2) Radical cation polymerization of propene can be initiated by partial charge transfer from an ionized aromatic molecule such as benzene coupled with covalent condensation of the associated propene molecules. This novel mechanism leads exclusively to the formation of propene oligomer ions and avoids other competitive products. (3) Structural information on the oligomers formed by gas-phase polymerization can be obtained using the mass-selected ion mobility technique where the measured collision cross-sections of the selected oligomer ions and collision-induced dissociation can provide fairly accurate structural identifications. The identification of the structures of the dimers and trimers formed in the gas-phase thermal polymerization of styrene confirms that the polymerization proceeds according to the Mayo mechanism. Similarly, the ion mobility technique has been utilized to confirm the formation of benzene cations by intracluster polymerization following the ionization of acetylene clusters. Finally, it has been shown that polymerization of styrene vapor on the surface of activated nanoparticles can lead to the incorporation of a variety of metal and metal oxide nanoparticles within polystyrene films. The ability to probe the reactivity and structure of the small growing oligomers in the gas phase can provide fundamental insight into mechanisms of polymerization that are difficult to obtain from condensed-phase studies. These experiments are also important for understanding the growth mechanisms of complex organics in flames, combustion processes, interstellar clouds, and solar nebula where gas-phase reactions, cluster polymerization, and surface catalysis on dust nanoparticles represent the major synthetic pathways. This research can lead to the discovery of novel initiation mechanisms and reaction pathways with applications in the synthesis of oligomers and nanocomposites with unique and improved properties.
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Preparation and evaluation of a novel star-shaped polyacid-constructed dental glass-ionomer system.
Howard, Leah; Weng, Yiming; Xie, Dong
2014-06-01
The objective of this study was to synthesize and characterize novel star-shaped poly(acrylic acid-co-itaconic acid)s via chain-transfer radical polymerization technique, use these polyacids to formulate the resin-modified glass-ionomer cements, and evaluate the mechanical strengths of the formed cements The star-shaped poly(acrylic acid-co-itaconic acid)s were synthesized via a chain-transfer radical polymerization reaction using a newly synthesized star-shaped chain-transfer agent. The effects of MW, GM-tethering ratio, P/L ratio and aging on the compressive properties of the formed experimental cements were studied. Compressive, diametral tensile as well as flexural strengths were evaluated and compared to those of Fuji II and Fuji II LC cements. The star-shaped polyacids showed significantly lower viscosities in water as compared to their linear counterparts. The cements formulated with these novel polyacids showed significantly improved mechanical strengths i.e., 49% in yield strength, 41% in modulus, 25% in CS, 20% in DTS and 36% in FS, higher than commercial Fuji II LC. After aging in water for 30 days, the compressive strengths of the experimental cements were significantly changed with an increase of 29% in YS, 19% in modulus as well as 23% in CS and a decrease of 5% in toughness, indicating that aging in water enhances the salt-bridge formation and increases brittleness. A novel light-cured glass-ionomer cement system composed of the star-shaped poly(carboxylic acid)s has been developed via a cost-effective and time-efficient chain-transfer radical polymerization. Copyright © 2014 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.
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Gamage, Pubudu; Basel, Matthew T; Lovell, Kimberly; Pokhrel, Megh Raj; Battle, Deletria; Ito, Takashi; Pavlenok, Mikhail; Niederweis, Michael; Bossmann, Stefan H
2009-09-17
The work presented here aims at utilizing poly-N-isopropyl-acrylamide/acrylic acid copolymers to create nanostructured layers on mica surfaces by a simple spin-casting procedure. The average composition of the copolymers determined by elemental analysis correlates excellently with the feed composition indicating that the radical polymerization process is statistical. The resulting surfaces were characterized by Atomic Force Microscopy (magnetic AC-mode) at the copolymer/air interface. Postpolymerization modification of the acrylic acid functions with perfluoro-octyl-iodide decreased the tendency towards spontaneous formation of nanopores. Crosslinking of individual polymer chains permitted the generation of ultraflat layers, which hosted the mycobacterial channel protein MspA, without compromising its channel function. The comparison of copolymers of very similar chemical composition that have been prepared by living radical polymerization and classic radical polymerization indicated that differences in polydispersity played only a minor role when poly-N-isopropyl-acrylamide/acrylic acid copolymers were spincast, but a major role when copolymers featuring the strongly hydrophobic perfluoro-octyl-labels were used. The mean pore diameters were 23.8+/-4.4 nm for P[(NIPAM)(95.5)-co-(AA)(4.5)] (PDI (polydispersity index)=1.55) and 21.8+/-4.2 nm for P[(NIPAM)(95.3)-co-(AA)(4.7)] (PDI=1.25). The depth of the nanopores was approx. 4 nm. When depositing P[(NIPAM)(95)-co-(AA)(2.8)-AAC(8)F(17 2.2)] (PDI=1.29) on Mica, the resulting mean pore diameter was 35.8+/-7.1 nm, with a depth of only 2 nm.
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Gamage, Pubudu; Basel, Matthew T.; Lovell, Kimberly; Pokhrel, Megh Raj; Battle, Deletria; Ito, Takashi; Pavlenok, Mikhail; Niederweis, Michael
2009-01-01
The work presented here aims at utilizing poly-N-isopropyl-acrylamide/acrylic acid copolymers to create nanostructured layers on mica surfaces by a simple spin-casting procedure. The average composition of the copolymers determined by elemental analysis correlates excellently with the feed composition indicating that the radical polymerization process is statistical. The resulting surfaces were characterized by Atomic Force Microscopy (magnetic AC-mode) at the copolymer/air interface. Postpolymerization modification of the acrylic acid functions with perfluoro-octyl-iodide decreased the tendency towards spontaneous formation of nanopores. Crosslinking of individual polymer chains permitted the generation of ultraflat layers, which hosted the mycobacterial channel protein MspA, without compromising its channel function. The comparison of copolymers of very similar chemical composition that have been prepared by living radical polymerization and classic radical polymerization indicated that differences in polydispersity played only a minor role when poly-N-isopropyl-acrylamide/acrylic acid copolymers were spincast, but a major role when copolymers featuring the strongly hydrophobic perfluoro-octyl-labels were used. The mean pore diameters were 23.8±4.4 nm for P[(NIPAM)95.5-co-(AA)4.5] (PDI (polydispersity index)=1.55) and 21.8±4.2 nm for P[(NIPAM)95.3-co-(AA)4.7] (PDI=1.25). The depth of the nanopores was approx. 4 nm. When depositing P[(NIPAM)95-co-(AA)2.8-AAC8F17 2.2] (PDI=1.29) on Mica, the resulting mean pore diameter was 35.8±7.1 nm, with a depth of only 2 nm. PMID:20161351
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Synthesis and phase behavior of end-functionalized associating polymers
NASA Astrophysics Data System (ADS)
Wrue, Michelle H.
We have explored polymer blend phase behavior in the presence of multiple hydrogen bonding end-groups. This work details the synthesis of functionalized polymers and their subsequent use in miscibility studies. The synthesis of end-functionalized hydrogen bonding polymers and the investigation of their physical properties and miscibility is presented. Mono-functional and telechelic ureidopyrimidinone (UPy) functionalized polymers were prepared by two main routes: post-polymerization functionalization (of commercially available or synthesized polymers); and polymerization of monomers using a functionalized initiator. UPy-functionalized polymers were prepared with a variety of polymer backbones including poly(ethylene oxide)s; poly(butadiene)s, poly(dimethyl siloxanxe)s; poly(styrene)s and poly(methyl methacrylate)s. The most successful route to polymers with UPy end-groups was atom transfer radical polymerization (ATRP) using a UPy-functionalized initiator, followed by atom transfer radical coupling (ATRC). The incorporation of ureidopyrimidinone end-groups was shown to affect the physical properties of the polymer backbone. Parent polymers that were liquids became viscous liquids or waxy solids upon UPy-functionalization of chain end. UPy-functionalization of a hydroxyl-terminated polybutadiene (HO-PB-OH) resulted in a waxy solid while the HO-PB-OH precursor was a viscous liquid. The thermal properties of functionalized polymers also differed from those of the unfunctionalized parent polymers. Hot-stage optical microscopy revealed that UPy-functionalized PEO displayed a depressed melting point relative to the analogous unfunctionalized precursor. Differential scanning calorimetry was also used to investigate the synthesized UPy-polymers. UPy-functionalized polystyrenes and poly(methyl methacrylate)s showed an increased T g compared to the equivalent homopolymer standards. This increased Tg was determined to be dependent upon the fraction of UPy groups present and chemical cleavage of the end-groups resulted in Tgs near those observed for polymer standards of comparable molecular weight. Aggregation of UPy end-groups in solution was observed using gel permeation chromatography. Aggregation was only observed for telechelic samples of low molecular weight, indicating that the aggregation of end-groups is dependent upon the concentration of the end-groups. The effect of UPy end-groups on blend miscibility was studied in solution using laser light scattering and in the melt state was using laser light scattering, optical microscopy and differential scanning calorimetry. The incorporation of associating groups onto one end of either blend component decreases miscibility relative to unfunctionalized parent blends. Lower miscibility was also observed for blends in which both components were mono-functionalized with associating end-groups. The largest decrease in miscibility was observed for blends containing telechelic UPy-functionalized polymers, which were immiscible across the entire composition range.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Ross, F; Ross, A B
1977-01-01
Rates of reactions of OH and HO/sub 2/ with organic and inorganic molecules, ions and transients in aqueous solution have been tabulated, as well as the rates for the corresponding radical ions in aqueous solution (O/sup -/ and O/sub 2//sup -/). Most of the rates have been obtained by radiation chemistry methods, both pulsed and steady-state; data from photochemistry and thermal methods are also included. Rates for over one thousand reactions are listed.
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Orihara, Kouhei; Hikichi, Atsushi; Arita, Tomohiko; Muguruma, Hitoshi; Yoshimi, Yasuo
2018-03-20
Heparin, a highly sulfated glycosaminoglycan, is an important biomaterial having biological and therapeutic functionalities such as anticoagulation, regeneration, and protein stabilization. This study addresses a label-free quartz crystal microbalance (QCM) biosensor for heparin detection based on a macromolecularly imprinted polymer (MIP) as an artificial recognition element. We demonstrate the novel strategy for MIP in the form of thin film on a gold (Au) electrode with the plasma-induced graft polymerization (PIP) technique. The procedure of PIP is as follows: (i) Hexamethyldisiloxane plasma-polymerized thin film (PPF) as a pre-coating scaffold of active species for PIP (post-polymerization) is deposited on an Au electrode. (ii) The PPF/Au electrode is soaked in an water solution containing heparin (template), (2-(methacryloxy)-ethyl)trimethylammonium chloride acrylamide (functional monomer), acrylamide, and N,N-methylenebisacrylamide (crosslinker). Double bonds of monomer and crosslinker attacked by residually active species in pre-coating PPF cause radical chain reaction. Consequently, a growing polymer network of 20 nm thickness of PIP-MIP thin film is formed and grafted on the PPF/Au surface. (iii) The PIP-MIP/PPF/Au is washed by sodium chloride solution so as to remove the template. Non-imprinted polymer (NIP) is carried out like the same procedure without a template. The AFM, XPS, and QCM measurements show that the PIP process facilitates macromolecularly surface imprinting of template heparin where the template is easily removed and is rapidly rebound to PIP-MIP without a diffusional barrier. The heparin-PIP-MIP specifically binds to heparin compared with heparin analog chondroitin sulfate C (selective factor: 4.0) and a detectable range of heparin in the presence of CS (0.1 wt%) was 0.001-0.1 wt%. The PIP-NIP does not show selectivity between them. The evaluated binding kinetics are association (k a = 350 ± 100 M -1 s -1 ), dissociation (k d = (5.0 ± 2.0) × 10 -4 s -1 ), and binding (K D = 1.3 ± 0.6 μM) constants, demonstrating that the PIP-MIP as a synthetic antibody can be applied to analytical chemistry. Copyright © 2018 Elsevier B.V. All rights reserved.
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How actin binds and assembles onto plasma membranes from Dictyostelium discoideum
1988-01-01
We have shown previously (Schwartz, M. A., and E. J. Luna. 1986. J. Cell Biol. 102: 2067-2075) that actin binds with positive cooperativity to plasma membranes from Dictyostelium discoideum. Actin is polymerized at the membrane surface even at concentrations well below the critical concentration for polymerization in solution. Low salt buffer that blocks actin polymerization in solution also prevents actin binding to membranes. To further explore the relationship between actin polymerization and binding to membranes, we prepared four chemically modified actins that appear to be incapable of polymerizing in solution. Three of these derivatives also lost their ability to bind to membranes. The fourth derivative (EF actin), in which histidine-40 is labeled with ethoxyformic anhydride, binds to membranes with reduced affinity. Binding curves exhibit positive cooperativity, and cross- linking experiments show that membrane-bound actin is multimeric. Thus, binding and polymerization are tightly coupled, and the ability of these membranes to polymerize actin is dramatically demonstrated. EF actin coassembles weakly with untreated actin in solution, but coassembles well on membranes. Binding by untreated actin and EF actin are mutually competitive, indicating that they bind to the same membrane sites. Hill plots indicate that an actin trimer is the minimum assembly state required for tight binding to membranes. The best explanation for our data is a model in which actin oligomers assemble by binding to clustered membrane sites with successive monomers on one side of the actin filament bound to the membrane. Individual binding affinities are expected to be low, but the overall actin-membrane avidity is high, due to multivalency. Our results imply that extracellular factors that cluster membrane proteins may create sites for the formation of actin nuclei and thus trigger actin polymerization in the cell. PMID:3392099
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Lee, Yeonju; Hanif, Sadaf; Theato, Patrick; Zentel, Rudolf; Lim, Jeewoo; Char, Kookheon
2015-06-01
Emission wavelength control in fluorescent nanoparticles (NPs) is crucial for their applications. In the case of inorganic quantum dots or dye-impregnated silica NPs, such a control is readily achieved by changing the size of the particles or choosing appropriate fluorescent dyes, respectively. A similar modular approach for controlling the emission wavelength of fluo-rescent polymer NPs, however, is difficult. This article reports on fluorescent polymer NPs, the synthesis of which provides a platform for a modular approach towards the preparation of fluorescent NPs of desired emission wavelength. Atom-transfer radical polymerization (ATRP) is employed to synthesize reactive ester polymers, which are then easily modified with a commercially available dye and subsequently subjected to nanoprecipitation. The resulting NPs, with low size polydispersity, show an enhanced emission quantum yield when compared with the same dye molecules in solution. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Solution Exchange Lithography: A Versatile Tool for Sequential Surface Engineering
NASA Astrophysics Data System (ADS)
Pester, Christian; Mattson, Kaila; Bothman, David; Klinger, Daniel; Lee, Kenneth; Discekici, Emre; Narupai, Benjaporn; Hawker, Craig
The covalent attachment of polymers has emerged as a viable strategy for the preparation of multi-functional surfaces. Patterned, surface-grafted polymer brushes provide spatial control over wetting, mechanical, biological or electronic properties, and allow fabrication of `intelligent' substrates which selectively adapt to their environment. However, the route towards patterned polymer brush surfaces often remains challenging, creating a demand for more efficient and less complicated fabrication strategies. We describe the design and application of a novel experimental setup to combine light-mediated and flow chemistry for the fabrication of hierarchical surface-grafted polymer brushes. Using light-mediated, surface initiated controlled radical polymerization and post-functionalization via well-established, and highly efficient chemistries, polymer brush films of previously unimaginable complexity are now shown to be accessible. This methodology allows full flexibility to exchange both lithographic photomasks and chemical environments in-situ, readily affording multidimensional thin film architectures, all from uniformly functionalized substrates.
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Horák, D; Svec, F; Kálal, J; Gumargalieva, K; Adamyan, A; Skuba, N; Titova, M; Trostenyuk, N
1986-05-01
Spherical macroporous particles based on poly(2-hydroxyethyl methacrylate) with defined porosity, swelling and morphology have been developed, and are suitable for endovascular occlusion of various organs. Unlike cylindrical particles, spherical particles are specifically suited for transcatheteral introduction. The method chosen for the preparation of such particles was suspension radical polymerization, where the monomers were dissolved in a mixture of higher-boiling alcohols, and the solution dispersed in water. Physicochemical and medico-biological properties of spherical particles were examined. The residual amounts of monomers and other low-molecular compounds were checked; haematological analyses showed that the value 10(-5) g/g of the polymer was not toxic and contributed to an irreversible aggregation of thrombocytes. The occlusion effect in the vascular lumen was stable. The histomorphological results fully demonstrated the perfect biocompatibility of artificial spherical emboli. The latter met the requirements of application to clinical practice.
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NASA Astrophysics Data System (ADS)
Srikanth, A. P.; Lavanya, A.; Nanjundan, S.; Rajendran, N.
2006-12-01
The copolymers from different feed ratios of N-(methacryloyloxymethyl) benzotriazole (MMBT) and methyl methacrylate (MMA) has been synthesised using free radical solution polymerization technique and characterized using FT-IR and 13C NMR spectroscopy. The thermal stability of the polymers was studied using theremogravimetrtic analysis (TGA). The corrosion behaviors of mild steel specimens dip coated with different composition of copolymers have been evaluated by potentiodynamic polarization and electrochemical impedance spectroscopic (EIS) method. These electrochemical properties were observed in 0.1 M HCl medium. The polarization and impedance measurements showed different corrosion protection efficiency with change in composition of the copolymers. It was found that the corrosion protection properties are owing to the barrier effect of the polymer layer covered on the mild steel surfaces. However, it was observed that the copolymer obtained from 1:1 mole ratio of MMBT and MMA exhibited better protection efficiency than other combinations.
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Radiolysis of ethanol and ethanol-water solutions: A tool for studying bioradical reactions
NASA Astrophysics Data System (ADS)
Jore, D.; Champion, B.; Kaouadji, N.; Jay-Gerin, J.-P.; Ferradini, C.
Radiolysis of pure ethanol and ethanol-water solutions is examined in view of its relevance to the study of biological radical mechanisms. On the basis of earlier studies, a consistent reaction scheme is adopted. New data on radical yields are obtained from the radiolysis of dilute solutions of vitamins E and C in these solvents. It is shown that the radiolysis of ethanolic solutions provide an efficient tool to study radical reactions of water-insoluble biomolecules.
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Impact of reaction conditions on grafting acrylamide onto starch
USDA-ARS?s Scientific Manuscript database
We have explored the radical initiated graft polymerization reaction of acrylamide onto starch where the solvent, concentration, temperature and reaction times were varied. We have found that the morphology of the resulting grafted polymer is dramatically different and is dependent on the reaction c...
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Competency Based Modular Experiments in Polymer Science and Technology.
ERIC Educational Resources Information Center
Pearce, Eli M; And Others
1980-01-01
Describes a competency-based, modular laboratory course emphasizing the synthesis and characterization of polymers and directed toward senior undergraduate and/or first-year graduate students in science and engineering. One module, free-radical polymerization kinetics by dilatometry, is included as a sample. (CS)
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Code of Federal Regulations, 2010 CFR
2010-07-01
... polymerization process which initiates from free radical catalyst sites and is sold undried. (i) Bulk resin means... as follows: (a) Ethylene dichloride plant includes any plant which produces ethylene dichloride by reaction of oxygen and hydrogen chloride with ethylene. (b) Vinyl chloride plant includes any plant which...
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Code of Federal Regulations, 2011 CFR
2011-07-01
... polymerization process which initiates from free radical catalyst sites and is sold undried. (i) Bulk resin means... as follows: (a) Ethylene dichloride plant includes any plant which produces ethylene dichloride by reaction of oxygen and hydrogen chloride with ethylene. (b) Vinyl chloride plant includes any plant which...
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REMOVAL OF CATALYST IN ATOM TRANSFER RADICAL POLYMERIZATION USING ION EXCHANGE RESINS. (R826735)
The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...
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The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...
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Obstals, Fabian; Vorobii, Mariia; Riedel, Tomáš; de Los Santos Pereira, Andres; Bruns, Michael; Singh, Smriti; Rodriguez-Emmenegger, Cesar
2018-03-01
Nonthrombogenic modifications of membranes for extracorporeal membrane oxygenators (ECMOs) are of key interest. The absence of hemocompatibility of these membranes and the need of anticoagulation of patients result in severe and potentially life-threatening complications during ECMO treatment. To address the lack of hemocompatibility of the membrane, surface modifications are developed, which act as barriers to protein adsorption on the membrane and, in this way, prevent activation of the coagulation cascade. The modifications are based on nonionic and zwitterionic polymer brushes grafted directly from poly(4-methyl-1-pentene) (TPX) membranes via single electron transfer-living radical polymerization. Notably, this work introduces the first example of well-controlled surface-initiated radical polymerization of zwitterionic brushes. The antifouling layers markedly increase the recalcification time (a proxy of initiation of coagulation) compared to bare TPX membranes. Furthermore, platelet and leukocyte adhesion is drastically decreased, rendering the ECMO membranes hemocompatible. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Kinetic and Mechanistic Study of Vapor-Phase Free Radical Polymerization onto Liquid Surfaces
DOE Office of Scientific and Technical Information (OSTI.GOV)
Gupta, Malancha
The primary objective of this proposal was to study vapor deposition of polymers onto liquid surfaces. Deposition onto liquid surfaces is a relatively new area of research because the past few decades have focused on deposition onto solid materials. We used initiated chemical vapor deposition to deposit polymers onto the liquid surfaces. The process is a one-step, solventless, free-radical polymerization process in which monomer and initiator molecules are flowed into a vacuum chamber. We found that the surface tension interaction between the polymer and the liquid determines whether a film or nanoparticles are formed. We also found that we couldmore » form gels by using soluble monomers. We found that we could tune the size of the nanoparticles by varying the viscosity of the liquid and the process parameters including pressure and time. These insights allow scalable synthesis of polymer materials for a variety of separation and catalysis applications.« less
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Li, Shuzhao; Xiao, Miaomiao; Zheng, Anna; Xiao, Huining
2011-09-12
Immobilizing poly(butyl acrylate) (PBA) on cellulose microfibrils (CMFs) by atom transfer radical polymerization (ATRP) of butyl acrylate (BA) on the surface of 2-bromoisobutyryl-functionalized CMF generated highly hydrophobic microfibrils (CMF-PBA) with a hard core and a soft-shell structure. TGA and static water contact angle results suggested that the surfaces of the modified CMF samples were not completely covered by PBA chains until the molecular weight of grafts became sufficiently long. The GPC results indicated that the grafts with low molecular weight showed controlled/"living" characteristics of the surface-initiated ATRP; however, there existed more side reactions with the increase in molecular weights. Biocomposites consisting of polypropylene (PP) and CMF-PBA samples exhibited significantly improved compatibility, interface adhesion, and mechanical properties with the increase in PBA graft length. The findings confirmed that the longer grafts facilitated the better entanglement of PBA grafts with PP macromolecules and thus further improved the mechanical properties.
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NASA Astrophysics Data System (ADS)
Deineka, V. I.; Lapshova, M. S.; Zakharenko, E. V.; Deineka, L. A.
2013-11-01
The principles of sorption on polymeric reversed phase (PRP) YMS C30 for members of the two classes of esters formed by higher saturated fatty acids, i.e., lutein diesters ( I) and triacylglycerols ( II), are investigated. It is shown that the logarithm of the retention factor increases nonlinearly with an increase of the length of the acid radical, although the retention on PRP is higher in the case of I and lower in the case of II, compared to their retention on traditional monomeric reversed phase (MRP) Kromasil-100 5C18; however, the equivalence of the contributions to the retention of I that correspond to an identical change in acids, does not depend on the length of the hydrocarbon radical of the second acid. It is noted that the Van't Hoff plot for PRP contains a curve break, indicating a change in the retention mechanism upon a rise in temperature.
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Electron-beam-induced post-grafting polymerization of acrylic acid onto the surface of Kevlar fibers
NASA Astrophysics Data System (ADS)
Xu, Lu; Hu, Jiangtao; Ma, Hongjuan; Wu, Guozhong
2018-04-01
The surface of Kevlar fibers was successfully modified by electron beam (EB)-induced post-grafting of acrylic acid (AA). The generation of radicals in the fibers was confirmed by electron spin resonance (ESR) measurements, and the concentration of radicals was shown to increase as the absorbed dose increased, but decrease with increasing temperature. The influence of the synthesis conditions on the degree of grafting was also investigated. The surface microstructure and chemical composition of the modified Kevlar fibers were characterized by scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). The SEM images revealed that the surface of the grafted fibers was rougher than those of the pristine and irradiated fibers. XPS analysis confirmed an increase in C(O)OH groups on the surface of the Kevlar fibers, suggesting successful grafting of AA. These results indicate that EB-induced post-grafting polymerization is effective for modifying the surface properties of Kevlar fibers.
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Synthesis of Biocompatible Surfaces by Different Techniques
2002-04-01
production . In the other hand, polymers are widely used in bone/cartilage implants, both, as polymeric materials themselves and as a polymeric surface on a...focus on the production of HA scaffolds by a sol-gel method using different drying processes, and on the study of the plasma polymerization technique to...precursor at 3. SA-stoichiometric amount (to maintain Ca/P= 1,67) of the calcium precursor solution (3 M solution in anhidrous etanol ) was added dropwise
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Thiol-Ene functionalized siloxanes for use as elastomeric dental impression materials
Cole, Megan A.; Jankousky, Katherine C.; Bowman, Christopher N.
2014-01-01
Objectives Thiol- and allyl-functionalized siloxane oligomers are synthesized and evaluated for use as a radical-mediated, rapid set elastomeric dental impression material. Thiol-ene siloxane formulations are crosslinked using a redox-initiated polymerization scheme, and the mechanical properties of the thiol-ene network are manipulated through the incorporation of varying degrees of plasticizer and kaolin filler. Formulations with medium and light body consistencies are further evaluated for their ability to accurately replicate features on both the gross and microscopic levels. We hypothesize that thiol-ene functionalized siloxane systems will exhibit faster setting times and greater detail reproduction than commercially available polyvinylsiloxane (PVS) materials of comparable consistencies. Methods Thiol-ene functionalized siloxane mixtures formulated with varying levels of redox initiators, plasticizer, and kaolin filler are made and evaluated for their polymerization speed (FTIR), consistency (ISO4823.9.2), and surface energy (goniometer). Feature replication is evaluated quantitatively by SEM. The Tg, storage modulus, and creep behavior are determined by DMA. Results Increasing redox initiation rate increases the polymerization rate but at high levels also limits working time. Combining 0.86 wt% oxidizing agent with up to 5 wt% plasticizer gave a working time of 3 min and a setting time of 2 min. The selected medium and light body thiol-ene formulations also achieved greater qualitative detail reproduction than the commercial material and reproduced micrometer patterns with 98% accuracy. Significance Improving detail reproduction and setting speed is a primary focus of dental impression material design and synthesis. Radical-mediated polymerizations, particularly thiol-ene reactions, are recognized for their speed, reduced shrinkage, and ‘click’ nature. PMID:24553250
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Method for forming polymerized microfluidic devices
Sommer, Gregory J [Livermore, CA; Hatch, Anson V [Tracy, CA; Wang, Ying-Chih [Pleasanton, CA; Singh, Anup K [Danville, CA; Renzi, Ronald F [Tracy, CA; Claudnic, Mark R [Livermore, CA
2011-11-01
Methods for making a micofluidic device according to embodiments of the present invention include defining a cavity. Polymer precursor solution is positioned in the cavity, and exposed to light to begin the polymerization process and define a microchannel. In some embodiments, after the polymerization process is partially complete, a solvent rinse is performed, or fresh polymer precursor introduced into the microchannel. This may promote removal of unpolymerized material from the microchannel and enable smaller feature sizes. The polymer precursor solution may contain an iniferter. Polymerized features therefore may be capped with the iniferter, which is photoactive. The iniferter may aid later binding of a polyacrylamide gel to the microchannel surface.
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Method for forming polymerized microfluidic devices
Sommer, Gregory J.; Hatch, Anson V.; Wang, Ying-Chih; Singh, Anup K.; Renzi, Ronald F.; Claudnic, Mark R.
2013-03-12
Methods for making a microfluidic device according to embodiments of the present invention include defining.about.cavity. Polymer precursor solution is positioned in the cavity, and exposed to light to begin the polymerization process and define a microchannel. In some embodiments, after the polymerization process is partially complete, a solvent rinse is performed, or fresh polymer precursor introduced into the microchannel. This may promote removal of unpolymerized material from the microchannel and enable smaller feature sizes. The polymer precursor solution may contain an iniferter. Polymerized features therefore may be capped with the iniferter, which is photoactive. The iniferter may aid later binding of a polyacrylamide gel to the microchannel surface.
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Qiu, Guihua; Wang, Qi; Wang, Chao; Lau, Willie; Guo, Yili
2007-01-01
Ultrasonically initiated miniemulsion polymerization of styrene in the presence of Fe3O4 nanoparticles was successfully employed to prepare polystyrene (PS)/Fe3O4 magnetic emulsion and nanocomposite. The effects of Fe3O4 nanoparticles on miniemulsion polymerization process, the structure, morphology and properties of PS/Fe3O4 nanocomposite were investigated. The increase in the amount of Fe3O4 nanoparticles drastically increases the polymerization rate due to that Fe3O4 nanoparticles increase the number of radicals and the cavitation bubbles. Polymerization kinetics of ultrasonically initiated miniemulsion polymerization is similar to that of conventional miniemulsion polymerization. PS/Fe3O4 magnetic emulsion consists of two types of particles: latex particles with Fe3O4 nanoparticles and latex particles with no encapsulated Fe3O4 nanoparticles. Fe3O4 nanoparticles lower the molecular weight of PS and broaden the molecular weight and particle size distribution. Thermal stability of PS/Fe3O4 nanocomposite increases with the increase in Fe3O4 content. PS/Fe3O4 emulsion and nanocomposite exhibit magnetic properties. PS/Fe3O4 magnetic particles can be separated from the magnetic emulsion by an external magnetic field and redispersed into the emulsion with agitation.
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Photochemical method for generating superoxide radicals (O.sub.2.sup.-) in aqueous solutions
Holroyd, Richard A.; Bielski, Benon H. J.
1980-01-01
A photochemical method and apparatus for generating superoxide radicals (ub.2.sup.-) in an aqueous solution by means of a vacuum-ultraviolet lamp of simple design. The lamp is a microwave powered rare gas device that emits far-ultraviolet light. The lamp includes an inner loop of high purity quartz tubing through which flows an oxygen-saturated sodium formate solution. The inner loop is designed so that the solution is subjected to an intense flux of far-ultraviolet light. This causes the solution to photodecompose and form the product radical (O.sub.2.sup.-).
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Wang, Hongwei; Ou, Junjie; Lin, Hui; Liu, Zhongshan; Huang, Guang; Dong, Jing; Zou, Hanfa
2014-11-07
Two kinds of hybrid monolithic columns were prepared by using methacrylate epoxy cyclosiloxane (epoxy-MA) as functional monomer, containing three epoxy moieties and one methacrylate group. One column was in situ fabricated by ring-opening polymerization of epoxy-MA and 1,10-diaminodecane (DAD) using a porogenic system consisting of isopropanol (IPA), H2O and ethanol at 65°C for 12h. The other was prepared by free radical polymerization of epoxy-MA and ethylene dimethacrylate (EDMA) using 1-propanol and 1,4-butanediol as the porogenic solvents at 60°C for 12h. Two hybrid monoliths were investigated on the morphology and chromatographic assessment. Although two kinds of monolithic columns were prepared with epoxy-MA, their morphologies looked rather different. It could be found that the epoxy-MA-DAD monolith possessed higher column efficiencies (25,000-34,000plates/m) for the separation of alkylbenzenes than the epoxy-MA-EDMA monolith (12,000-13,000plates/m) in reversed-phase nano-liquid chromatography (nano-LC). Depending on the remaining epoxy or methacrylate groups on the surface of two pristine monoliths, the epoxy-MA-EDMA monolith could be easily modified with 1-octadecylamine (ODA) via ring-opening reaction, while the epoxy-MA-DAD monolith could be modified with stearyl methacrylate (SMA) via free radical reaction. The chromatographic performance for the separation of alkylbenzenes on SMA-modified epoxy-MA-DAD monolith was remarkably improved (42,000-54,000 plates/m) when compared with that on pristine epoxy-MA-DAD monolith, while it was not obviously enhanced on ODA-modified epoxy-MA-EDMA monolith when compared with that on pristine epoxy-MA-EDMA monolith. The enhancement of the column efficiency of epoxy-MA-DAD monolith after modification might be ascribed to the decreased mass-transfer resistence. The two kinds of hybrid monoliths were also applied for separations of six phenols and seven basic compounds in nano-LC. Copyright © 2014 Elsevier B.V. All rights reserved.
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The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...
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THE EFFECT OF LIGANDS ON ATOM TRANSFER RADICAL POLYMERIZATION IN WATER-BORNE SYSTEMS. (R826735)
The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...
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The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...
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RATIONAL DESIGN OF THE CATALYST FOR ATOM TRANSFER RADICAL POLYMERIZATION IN AQUEOUS MEDIA. (R829580)
The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...
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The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...
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De Smet, Lieselot; Vancoillie, Gertjan; Minshall, Peter; Lava, Kathleen; Steyaert, Iline; Schoolaert, Ella; Van De Walle, Elke; Dubruel, Peter; De Clerck, Karen; Hoogenboom, Richard
2018-03-16
Here, we introduce a novel concept for the fabrication of colored materials with significantly reduced dye leaching through covalent immobilization of the desired dye using plasma-generated surface radicals. This plasma dye coating (PDC) procedure immobilizes a pre-adsorbed layer of a dye functionalized with a radical sensitive group on the surface through radical addition caused by a short plasma treatment. The non-specific nature of the plasma-generated surface radicals allows for a wide variety of dyes including azobenzenes and sulfonphthaleins, functionalized with radical sensitive groups to avoid significant dye degradation, to be combined with various materials including PP, PE, PA6, cellulose, and PTFE. The wide applicability, low consumption of dye, relatively short procedure time, and the possibility of continuous PDC using an atmospheric plasma reactor make this procedure economically interesting for various applications ranging from simple coloring of a material to the fabrication of chromic sensor fabrics as demonstrated by preparing a range of halochromic materials.
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Process for radiation grafting hydrogels onto organic polymeric substrates
Ratner, Buddy D.; Hoffman, Allan S.
1976-01-01
An improved process for radiation grafting of hydrogels onto organic polymeric substrates is provided comprising the steps of incorporating an effective amount of cupric or ferric ions in an aqueous graft solution consisting of N-vinyl-2 - pyrrolidone or mixture of N-vinyl-2 - pyrrolidone and other monomers, e.g., 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, propylene glycol acrylate, acrylamide, methacrylic acid and methacrylamide, immersing an organic polymeric substrate in the aqueous graft solution and thereafter subjecting the contacted substrate with ionizing radiation.
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Pervaporation separation of ethanol-water mixtures using polyethylenimine composite membranes
Neidlinger, H.H.; Schissel, P.O.; Orth, R.A.
1987-04-21
Synthetic, organic, polymeric membranes were prepared from polyethylenimine for use with pervaporation apparatus in the separation of ethanol-water mixtures. The polymeric material was prepared in dilute aqueous solution and coated onto a polysulfone support film, from which excess polymeric material was subsequently removed. Cross-links were then generated by limited exposure to toluene-2,4-diisocyanate solution, after which the prepared membrane was heat-cured. The resulting membrane structures showed high selectivity in permeating ethanol or water over a wide range of feed concentrations.
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Pervaporation separation of ethanol-water mixtures using polyethylenimine composite membranes
Neidlinger, Hermann H.; Schissel, Paul O.; Orth, Richard A.
1987-01-01
Synthetic, organic, polymeric membranes were prepared from polyethylenimine for use with pervaporation apparatus in the separation of ethanol-water mixtures. The polymeric material was prepared in dilute aqueous solution and coated onto a polysulfone support film, from which excess polymeric material was subsequently removed. Cross-links were then generated by limited exposure to toluene-2,4-diisocyanate solution, after which the prepared membrane was heat-cured. The resulting membrane structures showed high selectivity in permeating ethanol or water over a wide range of feed concentrations.
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Light-harvesting organic photoinitiators of polymerization.
Lalevée, Jacques; Tehfe, Mohamad-Ali; Dumur, Frédéric; Gigmes, Didier; Graff, Bernadette; Morlet-Savary, Fabrice; Fouassier, Jean-Pierre
2013-02-12
Two new photoinitiators with unprecedented light absorption properties are proposed on the basis of a suitable truxene skeleton where several UV photoinitiators PI units such as benzophenone and thioxanthone are introduced at the periphery and whose molecular orbitals MO can be coupled with those of the PI units: a red-shifted absorption and a strong increase of the molecular extinction coefficients (by a ≈ 20-1000 fold factor) are found. These compounds are highly efficient light-harvesting photoinitiators. The scope and practicality of these photoinitiators of polymerization can be dramatically expanded, that is, both radical and cationic polymerization processes are accessible upon very soft irradiation conditions (halogen lamp, LED…︁) thanks to the unique light absorption properties of the new proposed structures. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Light-Directed Tuning of Plasmon Resonances via Plasmon-Induced Polymerization Using Hot Electrons
2017-01-01
The precise morphology of nanoscale gaps between noble-metal nanostructures controls their resonant wavelengths. Here we show photocatalytic plasmon-induced polymerization can locally enlarge the gap size and tune the plasmon resonances. We demonstrate light-directed programmable tuning of plasmons can be self-limiting. Selective control of polymer growth around individual plasmonic nanoparticles is achieved, with simultaneous real-time monitoring of the polymerization process in situ using dark-field spectroscopy. Even without initiators present, we show light-triggered chain growth of various monomers, implying plasmon initiation of free radicals via hot-electron transfer to monomers at the Au surface. This concept not only provides a programmable way to fine-tune plasmons for many applications but also provides a window on polymer chemistry at the sub-nanoscale. PMID:28670601
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Pauly, Anja C; Schöller, Katrin; Baumann, Lukas; Rossi, René M; Dustmann, Kathrin; Ziener, Ulrich; de Courten, Damien; Wolf, Martin; Boesel, Luciano F; Scherer, Lukas J
2015-01-01
The grafting of poly(hydroxyethylmethacrylate) on polymeric porous membranes via atom transfer radical polymerization (ATRP) and subsequent modification with a photo-responsive spiropyran derivative is described. This method leads to photo-responsive membranes with desirable properties such as light-controlled permeability changes, exceptional photo-stability and repeatability of the photo-responsive switching. Conventional track etched polyester membranes were first treated with plasma polymer coating introducing anchoring groups, which allowed the attachment of ATRP-initiator molecules on the membrane surface. Surface initiated ARGET–ATRP of hydroxyethylmethacrylate (where ARGET stands for activator regenerated by electron transfer) leads to a membrane covered with a polymer layer, whereas the controlled polymerization procedure allows good control over the thickness of the polymer layer in respect to the polymerization conditions. Therefore, the final permeability of the membranes could be tailored by choice of pore diameter of the initial membranes, applied monomer concentration or polymerization time. Moreover a remarkable switch in permeability (more than 1000%) upon irradiation with UV-light could be achieved. These properties enable possible applications in the field of transdermal drug delivery, filtration, or sensing. PMID:27877791
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NASA Astrophysics Data System (ADS)
Pauly, Anja C.; Schöller, Katrin; Baumann, Lukas; Rossi, René M.; Dustmann, Kathrin; Ziener, Ulrich; de Courten, Damien; Wolf, Martin; Boesel, Luciano F.; Scherer, Lukas J.
2015-06-01
The grafting of poly(hydroxyethylmethacrylate) on polymeric porous membranes via atom transfer radical polymerization (ATRP) and subsequent modification with a photo-responsive spiropyran derivative is described. This method leads to photo-responsive membranes with desirable properties such as light-controlled permeability changes, exceptional photo-stability and repeatability of the photo-responsive switching. Conventional track etched polyester membranes were first treated with plasma polymer coating introducing anchoring groups, which allowed the attachment of ATRP-initiator molecules on the membrane surface. Surface initiated ARGET-ATRP of hydroxyethylmethacrylate (where ARGET stands for activator regenerated by electron transfer) leads to a membrane covered with a polymer layer, whereas the controlled polymerization procedure allows good control over the thickness of the polymer layer in respect to the polymerization conditions. Therefore, the final permeability of the membranes could be tailored by choice of pore diameter of the initial membranes, applied monomer concentration or polymerization time. Moreover a remarkable switch in permeability (more than 1000%) upon irradiation with UV-light could be achieved. These properties enable possible applications in the field of transdermal drug delivery, filtration, or sensing.
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Solution-Phase Photochemical Nanopatterning Enabled by High-Refractive-Index Beam Pen Arrays.
Xie, Zhuang; Gordiichuk, Pavlo; Lin, Qing-Yuan; Meckes, Brian; Chen, Peng-Cheng; Sun, Lin; Du, Jingshan S; Zhu, Jinghan; Liu, Yuan; Dravid, Vinayak P; Mirkin, Chad A
2017-08-22
A high-throughput, solution-based, scanning-probe photochemical nanopatterning approach, which does not require the use of probes with subwavelength apertures, is reported. Specifically, pyramid arrays made from high-refractive-index polymeric materials were constructed and studied as patterning tools in a conventional liquid-phase beam pen lithography experiment. Two versions of the arrays were explored with either metal-coated or metal-free tips. Importantly, light can be channeled through both types of tips and the appropriate solution phase (e.g., H 2 O or CH 3 OH) and focused on subwavelength regions of a substrate to effect a photoreaction in solution that results in localized patterning of a self-assembled monolayer (SAM)-coated Au thin film substrate. Arrays with as many as 4500 pyramid-shaped probes were used to simultaneously initiate thousands of localized free-radical photoreactions (decomposition of a lithium acylphosphinate photoinitiator in an aqueous solution) that result in oxidative removal of the SAM. The technique is attractive since it allows one to rapidly generate features less than 200 nm in diameter, and the metal-free tips afford more than 10-fold higher intensity than the tips with nanoapertures over a micrometer propagation length. In principle, this mask-free method can be utilized as a versatile tool for performing a wide variety of photochemistries across multiple scales that may be important in high-throughput combinatorial screening applications related to chemistry, biology, and materials science.
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Heurich, Tobias; Qu, Zheng-Wang; Kunzmann, Robert; Schnakenburg, Gregor; Engeser, Marianne; Nožinović, Senada; Streubel, Rainer
2018-04-25
A combined theoretical and experimental study on the formation and reactivity of a P-OTEMP (P-bound TEMPO (TEMPO=2,2,6,6-tetramethyl-piperidin-1-oxyl)) substituted 1,3,2-diazaphospholane W(CO) 5 complex is presented, including DFT-based mechanistic details. The complex possesses a thermally labile O-N bond that cleaves homolytically yielding the transient 1,3,2-diazaphospholane-2-oxyl complex [(CO) 5 W(R 2 PO . )], which acts as a radical initiator for styrene polymerization under ambient conditions. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Monomer and metallopolymer compounds of Tb(III) as precursors for OLEDs
NASA Astrophysics Data System (ADS)
Irina, Savchenko; Oleksandra, Berezhnytska; Olena, Trunova; Yaroslav, Fedorov; Sergiy, Smola; Nataliya, Rusakova
2018-03-01
The Terbium (III) complexes [Tb(III)-water, mixed-ligand complex Tb(III)-phenanthroline] with 2-methyl-5-phenyl-1-pentene-3,5-dione were synthesized. The polycomplex was obtained by free-radical polymerization. The results of above studies have shown that the configuration of the chelate unit is unchanged during the polymerization. As a result, the type of coordination was determined and the structure of coordination polyhedra was assumed. The luminescence spectra of obtained metallocomplexes and polymer were investigated and analyzed. The solubilization of terbium complex with phenanthroline, was shown to change luminescence intensity in this complex.
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Fast Disinfecting Antimicrobial Surfaces
Madkour, Ahmad E.; Dabkowski, Jeffery M.; Nüsslein, Klaus; Tew, Gregory N.
2013-01-01
Silicon wafers and glass surfaces were functionalized with facially amphiphilic antimicrobial copolymers using the “grafting from” technique. Surface initiated atom transfer radical polymerization (ATRP) was used to grow poly(butylmethacrylate)-co-poly(Boc-aminoethyl methacrylate) from the surfaces. Upon Boc-deprotection, these surfaces became highly antimicrobial and killed S. aureus and E. coli 100% in less than 5 min. The molecular weight and grafting density of the polymer were controlled by varying the polymerization time and initiator surface density. Antimicrobial studies showed that the killing efficiency of these surfaces was independent of polymer layer thickness or grafting density within the range of surfaces studied. PMID:19177651
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Toluene nitration in irradiated nitric acid and nitrite solutions
NASA Astrophysics Data System (ADS)
Elias, Gracy; Mincher, Bruce J.; Mezyk, Stephen P.; Muller, Jim; Martin, Leigh R.
2011-04-01
The kinetics, mechanisms, and stable products produced for the nitration of aryl alkyl mild ortho-para director toluene in irradiated nitric acid and neutral nitrite solutions were investigated using γ and pulse radiolysis. Electron pulse radiolysis was used to determine the bimolecular rate constants for the reaction of toluene with different transient species produced by irradiation. HPLC with UV detection, GC-MS and LC-MS, were used to assess the stable reaction products. Free-radical based nitration reaction products were found in irradiated acidic and neutral media. In 6.0 M HNO3, ring substitution, side chain substitution, and oxidation, produced different nitrated toluene products. For ring substitution, nitrogen oxide radicals were added mainly to cyclohexadienyl radicals, whereas for side chain substitution, these radicals were added to the carbon-centered benzyl radical produced by H-atom abstraction. In neutral nitrite solutions, radiolytically-induced ring nitration products approached a statistically random distribution, suggesting a direct free-radical reaction involving addition of the rad NO2 radical.
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Differential natural organic matter fouling of ceramic versus polymeric ultrafiltration membranes.
Lee, Seung-Jin; Kim, Jae-Hong
2014-01-01
Ceramic ultrafiltration membranes has drawn increasing attention in drinking water treatment sectors as an alternative to traditional polymeric counterparts, yet only limited information has been made available about the characteristics of ceramic membrane fouling by natural organic matter. The effects of solution chemistry including ionic strength, divalent ion concentration and pH on the flux behavior were comparatively evaluated for ceramic and polymeric ultrafiltration of synthetic water containing model natural organic matter. Filtration characteristics were further probed via resistance-in-series model analysis, fouling visualization using quantum dots, batch adsorption test, contact angle measurement, solute-membrane surface adhesion force measurement, and quantitative comparison of fouling characteristics between ceramic and polymeric membranes. The results collectively suggested that the effects of solution chemistry on fouling behavior of ceramic membranes were generally similar to polymeric counterparts in terms of trends, while the extent varied significantly depending on water quality parameters. Lower fouling tendency and enhanced cleaning efficiency were observed with the ceramic membrane, further promoting the potential for ceramic membrane application to surface water treatment. Copyright © 2013 Elsevier Ltd. All rights reserved.
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Ahmad, Mansor Bin; Gharayebi, Yadollah; Salit, Mohd. Sapuan; Hussein, Mohd. Zobir; Shameli, Kamyar
2011-01-01
In this paper, Polyimide/Montmorillonite Nanocomposites (PI/MMT NCs), based on aromatic diamine (4-Aminophenyl sulfone) (APS) and aromatic dianhydride (3,3′,4,4′-benzophenonetetracarboxylic dianhydride) (BTDA) were prepared using in situ polymerization and solution-dispersion techniques. The prepared PI/MMT NCs films were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM) and thermogravimetric analysis (TGA). The XRD results showed that at the content of 1.0 wt % Organo Montmorillonite (OMMT) for two techniques and 3.0 wt % OMMT for the in situ polymerization technique, the OMMT was well-intercalated, exfoliated and dispersed into polyimide matrix. The OMMT agglomerated when its amount exceeded 10 wt % and 3.0 wt % for solution-dispersion and in situ polymerization techniques respectively. These results were confirmed by the TEM images of the prepared PI/MMT NCs. The TGA thermograms indicated that thermal stability of prepared PI/MMT NCs were increased with the increase of loading that, the effect is higher for the samples prepared by in situ polymerization technique. PMID:22016643
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Ahmad, Mansor Bin; Gharayebi, Yadollah; Salit, Mohd Sapuan; Hussein, Mohd Zobir; Shameli, Kamyar
2011-01-01
In this paper, Polyimide/Montmorillonite Nanocomposites (PI/MMT NCs), based on aromatic diamine (4-Aminophenyl sulfone) (APS) and aromatic dianhydride (3,3',4,4'-benzophenonetetracarboxylic dianhydride) (BTDA) were prepared using in situ polymerization and solution-dispersion techniques. The prepared PI/MMT NCs films were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM) and thermogravimetric analysis (TGA). The XRD results showed that at the content of 1.0 wt % Organo Montmorillonite (OMMT) for two techniques and 3.0 wt % OMMT for the in situ polymerization technique, the OMMT was well-intercalated, exfoliated and dispersed into polyimide matrix. The OMMT agglomerated when its amount exceeded 10 wt % and 3.0 wt % for solution-dispersion and in situ polymerization techniques respectively. These results were confirmed by the TEM images of the prepared PI/MMT NCs. The TGA thermograms indicated that thermal stability of prepared PI/MMT NCs were increased with the increase of loading that, the effect is higher for the samples prepared by in situ polymerization technique.
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Nanoreinforced biocompatible hydrogels from wood hemicelluloses and cellulose whiskers
Muzaffer Ahmet Karaaslan; Mandla A. Tshabalala; Daniel J. Yelle; Gisela Buschle-Diller
2011-01-01
Nanoreinforced hydrogels with a unique network structure were prepared from wood cellulose whiskers coated with chemically modified wood hemicelluloses. The hemicelluloses were modified with 2-hydroxyethylmethacrylate prior to adsorption onto the cellulose whiskers in aqueous medium. Synthesis of the hydrogels was accomplished by in situ radical polymerization of the...
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2012-10-01
Methylene Iodide Water Superhydrophobic /oleophilic dip-coated fabric Tuteja et al, Science, 2007, 318, 1618 Superamphiphobic electrospun surfaces...door for use a building block material for low surface energy materials • Applications – Mechanical robust superhydrophobic /oleophobic/omniphobic
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The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...
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The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...
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The Preparation and Simple Analysis of a Clay Nanoparticle Composite Hydrogel
ERIC Educational Resources Information Center
Warren, David S.; Sutherland, Sam P. H.; Kao, Jacqueline Y.; Weal, Geoffrey R.; Mackay, Sean M.
2017-01-01
Samples of a composite hydrogel incorporating clay (Laponite XLG and S-482) nanoparticles were prepared using N-isopropylacrylamide. The hydrogels were formed via a radical-initiated addition polymerization using potassium persulfate and N,N,N',N'-tetramethylethylenediamine. Students then measured the force required to stretch the gels and…
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Naumov, Sergej; von Sonntag, Clemens
2011-11-01
Free radicals are common intermediates in the chemistry of ozone in aqueous solution. Their reactions with ozone have been probed by calculating the standard Gibbs free energies of such reactions using density functional theory (Jaguar 7.6 program). O(2) reacts fast and irreversibly only with simple carbon-centered radicals. In contrast, ozone also reacts irreversibly with conjugated carbon-centered radicals such as bisallylic (hydroxycylohexadienyl) radicals, with conjugated carbon/oxygen-centered radicals such as phenoxyl radicals, and even with nitrogen- oxygen-, sulfur-, and halogen-centered radicals. In these reactions, further ozone-reactive radicals are generated. Chain reactions may destroy ozone without giving rise to products other than O(2). This may be of importance when ozonation is used in pollution control, and reactions of free radicals with ozone have to be taken into account in modeling such processes.
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Click polymerization for the synthesis of reduction-responsive polymeric prodrug
NASA Astrophysics Data System (ADS)
Zhang, Xiaojin; Wang, Hongquan; Dai, Yu
2018-05-01
Click polymerization is a powerful polymerization technique for the construction of new macromolecules with well-defined structures and multifaceted functionalities. Here, we synthesize reduction-responsive polymeric prodrug PEG- b-(PSS- g-MTX)- b-PEG containing disulfide bonds and pendant methotrexate (MTX) via two-step click polymerization followed by conjugating MTX to pendant hydroxyl. MTX content in polymeric prodrug is 13.5%. Polymeric prodrug is able to form polymeric micelles by self-assembly in aqueous solution. Polymeric micelles are spherical nanoparticles with tens of nanometers in size. Of note, polymeric micelles are reduction-responsive due to disulfide bonds in the backbone of PEG- b-(PSS- g-MTX)- b-PEG and could release pendant drugs in the presence of the reducing agents such as dl-dithiothreitol (DTT).
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Yang, Yang; Liu, Xuegang; Ye, Gang; Zhu, Shan; Wang, Zhe; Huo, Xiaomei; Matyjaszewski, Krzysztof; Lu, Yuexiang; Chen, Jing
2017-04-19
Developing green and efficient technologies for surface modification of magnetic nanoparticles (MNPs) is of crucial importance for their biomedical and environmental applications. This study reports, for the first time, a novel strategy by integrating metal-free photoinduced electron transfer-atom transfer radical polymerization (PET-ATRP) with the bioinspired polydopamine (PDA) chemistry for controlled architecture of functional polymer brushes from MNPs. Conformal PDA encapsulation layers were initially generated on the surfaces of MNPs, which served as the protective shells while providing an ideal platform for tethering 2-bromo-2-phenylacetic acid (BPA), a highly efficient initiator. Metal-free PET-ATRP technique was then employed for controlled architecture of poly(glycidyl methacrylate) (PGMA) brushes from the core-shell MNPs by using diverse organic dyes as photoredox catalysts. Impacts of light sources (including UV and visible lights), photoredox catalysts, and polymerization time on the composition and morphology of the PGMA brushes were investigated. Moreover, the versatility of the PGMA-functionalized core-shell MNPs was demonstrated by covalent attachment of ethylenediamine (EDA), a model functional molecule, which afforded the MNPs with improved hydrophilicity, dispersibility, and superior binding ability to uranyl ions. The green methodology by integrating metal-free PET-ATRP with facile PDA chemistry would provide better opportunities for surface modification of MNPs and miscellaneous nanomaterials for biomedical and electronic applications.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Brown, Suree; Chatterjee, Sabornie; Li, Meijun
Seawater contains a large amount of uranium (~4.5 billion tons) which can serve as a limitless supply of an energy source. However, in order to make the recovery of uranium from seawater economically feasible, lower manufacturing and deployment costs are required, and thus, solid adsorbents must have high uranium uptake, reusability, and high selectivity toward uranium. In this study, atom-transfer radical polymerization (ATRP), without the radiation-induced graft polymerization (RIGP), was used for grafting acrylonitrile (AN) and tert-butyl acrylate (tBA) from a new class of trunk fibers, forming adsorbents in a readily deployable form. The new class of trunk fibers wasmore » prepared by the chlorination of PP round fiber, hollow-gear-shaped PP fiber, and hollow-gear-shaped PE fiber. During ATRP, degrees of grafting (d.g.) varied according to the structure of active chlorine sites on trunk fibers and ATRP conditions, and the d.g. as high as 2570% was obtained. Resulting adsorbent fibers were evaluated in U-spiked simulated seawater and the maximum adsorption capacity of 146.6 g U/kg, much higher than that of a standard adsorbent JAEA fiber (75.1 g/kg), was obtained. This new type of trunk fibers can be used for grafting a variety of uranium-interacting ligands, including designed ligands that are highly selective toward uranium.« less
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Brown, Suree; Chatterjee, Sabornie; Li, Meijun; ...
2015-12-10
Seawater contains a large amount of uranium (~4.5 billion tons) which can serve as a limitless supply of an energy source. However, in order to make the recovery of uranium from seawater economically feasible, lower manufacturing and deployment costs are required, and thus, solid adsorbents must have high uranium uptake, reusability, and high selectivity toward uranium. In this study, atom-transfer radical polymerization (ATRP), without the radiation-induced graft polymerization (RIGP), was used for grafting acrylonitrile (AN) and tert-butyl acrylate (tBA) from a new class of trunk fibers, forming adsorbents in a readily deployable form. The new class of trunk fibers wasmore » prepared by the chlorination of PP round fiber, hollow-gear-shaped PP fiber, and hollow-gear-shaped PE fiber. During ATRP, degrees of grafting (d.g.) varied according to the structure of active chlorine sites on trunk fibers and ATRP conditions, and the d.g. as high as 2570% was obtained. Resulting adsorbent fibers were evaluated in U-spiked simulated seawater and the maximum adsorption capacity of 146.6 g U/kg, much higher than that of a standard adsorbent JAEA fiber (75.1 g/kg), was obtained. This new type of trunk fibers can be used for grafting a variety of uranium-interacting ligands, including designed ligands that are highly selective toward uranium.« less
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Characterization of photochemical-cured acrylates with calorimetric methods
NASA Astrophysics Data System (ADS)
Strehmel, Bernd; Anwand, Dirk; Wetzel, Henrik
1994-05-01
Radical polymerization kinetics of different kinds of diacrylates was investigated in linear polymers (binders) by using an isoperibolic calorimeter. For all experiments benzoin compounds were added as photoinitiator. The ester between acrylic acid and bisphenol-A-diglycidylether (DDGDA) and hexamethylenediacrylate were used as monomers. Both compounds have a high limiting conversion and a large polymerization rate in the binders investigated. Additionally, three kinds of termination reaction were observed: first order, second order, and primary radical termination. The last reaction was mainly found in the case of using the hexamethylenediacrylate monomer. The materials were investigated by DSC to determine the phase behavior. Both monomers form one phase with the binder (polymethylmethacrylate, PMMA). In contrast, a phase separation was observed between the crosslinked hexamethylenediacrylate and PMMA. Formations of semi- interpenetrating networks were found in the case of crosslinked DDGDA and PMMA. The glass transition temperatures were determined at different polymerization degrees also. The obtained results indicate that most of the network formation occurred in the glassy state. Fluorescence probe technique was applied to study changes in the mobility during network formation. The fluorescence probe crystal violet (CV) was used because this compound shows a strong free volume-dependent fluorescence. It was found that in the glassy state, where most of networks were formed, a large variation of the molecular mobility was observed during irradiation of the photopolymers. This result was in agreement with the observations during DSC experiments.
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Uyar, Zafer; Degirmenci, Mustafa; Genli, Nasrettin; Yilmaz, Ayse
2017-01-01
Abstract A new well-defined bisbenzoin group end-functionalized poly(ε-caprolactone) macrophotoinitiator (PCL-(PI)2) was synthesized by combination of ring opening polymerization (ROP) and click chemistry. The ROP of ε-CL monomer in bulk at 110 °C, by means of a hydroxyl functional initiator namely, 3-cyclohexene-1-methanol in conjunction with stannous-2-ethylhexanoate, (Sn(Oct)2), yielded a well-defined PCL with a cyclohexene end-chain group (PCL-CH). The bromination and subsequent azidation of the cyclohexene end-chain group gave bisazido functionalized poly(ε-caprolactone) (PCL-(N3)2). Separately, an acetylene functionalized benzoin photoinitiator (PI-alkyne) was synthesized by using benzoin and propargyl bromide. Then the click reaction between PCL-(N3)2 and PI-alkyne was performed by Cu(I) catalysis. The spectroscopic studies revealed that poly(ε-caprolactone) with bisbenzoin photoactive functional group at the chain end (PCL-(PI)2) with controlled chain length and low-polydispersity was obtained. This PCL-(PI)2 macrophotoinitiator was used as a precursor in photoinduced free radical promoted cationic polymerization to synthesize an AB2-type miktoarm star copolymer consisting of poly(ε-caprolactone) (PCL, as A block) and poly(cyclohexene oxide) (PCHO, as B block), namely PCL(PCHO)2. PMID:29491778
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OH radical induced depolymerization of poly(methacrylic acid)
NASA Astrophysics Data System (ADS)
Ulanski, Piotr; Bothe, Eberhard; von Sonntag, Clemens
1999-05-01
Hydroxyl radicals (generated pulse radiolytically in dilute N 2O-saturated aqueous solutions) react with poly(methacrylic acid) producing two kinds of radicals. The primary radical is converted into a secondary one by H-abstraction ( k=3.5 × 10 2 s -1) as monitored by changes in the UV spectrum. Subsequently, the secondary radicals undergo chain scission ( k=1.8 s -1 at pH 7-9). This process has been followed both by spectrophotometry as well as by conductometry. In competition with the bimolecular decay of the radicals the ensuing end-chain radicals undergo efficient depolymerization resulting in the release of monomer. Since the lifetime of the radicals is much longer at high pH, where the polymer attains a rod-like conformation, depolymerization is most efficient in basic solution.
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Wu, Ying; Wang, Jixiao; Ou, Bin; Zhao, Song; Wang, Zhi; Wang, Shichang
2018-02-12
Electrochemical polymerization of aniline is one of the most promising methods to prepare polyaniline (PANI) materials. However, during this process, the electrolyte solution must be replaced after electropolymerization of a certain time because of the generation and the accumulation of the by-products, which have significant effects on the morphology, purity and properties of PANI products. Treatment and recycling of the used electrolyte solution are worthwhile to study to reduce the high treatment cost of the used electrolyte solution containing aniline and its polymerization by-products. Here, the composition of the used electrolyte solution was separated and determined by high performance liquid chromatography coupled with diode array detection (HPLC-DAD) in the range of ultraviolet and visible (UV-Vis) light. The analysis results revealed that the used electrolyte solution consisted of aniline, p-hydroquinone (HQ), p-benzoquinone (BQ), co-oligomers of aniline and p-benzoquinone (CAB) and acid. Then, n-octanol and 2-octanone were selected as extracts to remove HQ, BQ and CAB from the used electrolyte solution. Following that, the recycled electrolyte solution was prepared by adjusting the concentration of aniline and acid of the aqueous phase, and the electrochemical polymerization process was conducted. Finally, the obtained PANI was characterized by scanning electron microscope (SEM) and electrochemical methods. The experimental results clearly demonstrate that the morphology and specific capacitance of PANI produced from the recycled electrolyte solution can be recovered completely. This research paves the way for reusing the used electrolyte solution for aniline electrochemical polymerization.
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Wu, Ying; Wang, Jixiao; Ou, Bin; Zhao, Song; Wang, Zhi; Wang, Shichang
2018-01-01
Electrochemical polymerization of aniline is one of the most promising methods to prepare polyaniline (PANI) materials. However, during this process, the electrolyte solution must be replaced after electropolymerization of a certain time because of the generation and the accumulation of the by-products, which have significant effects on the morphology, purity and properties of PANI products. Treatment and recycling of the used electrolyte solution are worthwhile to study to reduce the high treatment cost of the used electrolyte solution containing aniline and its polymerization by-products. Here, the composition of the used electrolyte solution was separated and determined by high performance liquid chromatography coupled with diode array detection (HPLC-DAD) in the range of ultraviolet and visible (UV-Vis) light. The analysis results revealed that the used electrolyte solution consisted of aniline, p-hydroquinone (HQ), p-benzoquinone (BQ), co-oligomers of aniline and p-benzoquinone (CAB) and acid. Then, n-octanol and 2-octanone were selected as extracts to remove HQ, BQ and CAB from the used electrolyte solution. Following that, the recycled electrolyte solution was prepared by adjusting the concentration of aniline and acid of the aqueous phase, and the electrochemical polymerization process was conducted. Finally, the obtained PANI was characterized by scanning electron microscope (SEM) and electrochemical methods. The experimental results clearly demonstrate that the morphology and specific capacitance of PANI produced from the recycled electrolyte solution can be recovered completely. This research paves the way for reusing the used electrolyte solution for aniline electrochemical polymerization. PMID:29439514
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Iodine versus Bromine Functionalization for Bottom-Up Graphene Nanoribbon Growth: Role of Diffusion
Bronner, Christopher; Marangoni, Tomas; Rizzo, Daniel J.; ...
2017-08-08
Deterministic bottom-up approaches for synthesizing atomically well-defined graphene nanoribbons (GNRs) largely rely on the surface-catalyzed activation of selected labile bonds in a molecular precursor followed by step-growth polymerization and cyclodehydrogenation. While the majority of successful GNR precursors rely on the homolytic cleavage of thermally labile C–Br bonds, the introduction of weaker C–I bonds provides access to monomers that can be polymerized at significantly lower temperatures, thus helping to increase the flexibility of the GNR synthesis process. Scanning tunneling microscopy imaging of molecular precursors, activated intermediates, and polymers resulting from stepwise thermal annealing of both Br and I substituted precursors formore » chevron GNRs reveals that the polymerization of both precursors proceeds at similar temperatures on Au(111). Finally, this surprising observation is consistent with diffusion-controlled polymerization of the surface-stabilized radical intermediates that emerge from homolytic cleavage of either the C–Br or the C–I bonds.« less
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Ogunwuyi, O; Adesina, S; Akala, E O
2015-03-01
We report here our efforts on the development of stealth biodegradable crosslinked poly-ε-caprolactone nanoparticles by free radical dispersion polymerization suitable for the delivery of bioactive agents. The uniqueness of the dispersion polymerization technique is that it is surfactant free, thereby obviating the problems known to be associated with the use of surfactants in the fabrication of nanoparticles for biomedical applications. Aided by a statistical software for experimental design and analysis, we used D-optimal mixture statistical experimental design to generate thirty batches of nanoparticles prepared by varying the proportion of the components (poly-ε-caprolactone macromonomer, crosslinker, initiators and stabilizer) in acetone/water system. Morphology of the nanoparticles was examined using scanning electron microscopy (SEM). Particle size and zeta potential were measured by dynamic light scattering (DLS). Scheffe polynomial models were generated to predict particle size (nm) and particle surface zeta potential (mV) as functions of the proportion of the components. Solutions were returned from simultaneous optimization of the response variables for component combinations to (a) minimize nanoparticle size (small nanoparticles are internalized into disease organs easily, avoid reticuloendothelial clearance and lung filtration) and (b) maximization of the negative zeta potential values, as it is known that, following injection into the blood stream, nanoparticles with a positive zeta potential pose a threat of causing transient embolism and rapid clearance compared to negatively charged particles. In vitro availability isotherms show that the nanoparticles sustained the release of docetaxel for 72 to 120 hours depending on the formulation. The data show that nanotechnology platforms for controlled delivery of bioactive agents can be developed based on the nanoparticles.
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Wan, Xuejuan; Liu, Tao; Liu, Shiyong
2011-04-11
We report on the facile synthesis of well-defined amphiphilic and thermoresponsive tadpole-shaped linear-cyclic diblock copolymers via ring-opening polymerization (ROP) directly initiating from cyclic precursors, their self-assembling behavior in aqueous solution, and the application of micellar assemblies as controlled release drug nanocarriers. Starting from a trifunctional core molecule containing alkynyl, hydroxyl, and bromine moieties, alkynyl-(OH)-Br, macrocyclic poly(N-isopropylacrylamide) (c-PNIPAM) bearing a single hydroxyl functionality was prepared by atom transfer radical polymerization (ATRP), the subsequent end group transformation into azide functionality, and finally the intramacromolecular ring closure reaction via click chemistry. The target amphiphilic tadpole-shaped linear-cyclic diblock copolymer, (c-PNIPAM)-b-PCL, was then synthesized via the ROP of ε-caprolactone (CL) by directly initiating from the cyclic precursor. In aqueous solution at 20 °C, (c-PNIPAM)-b-PCL self-assembles into spherical micelles consisting of hydrophobic PCL cores and well-solvated coronas of cyclic PNIPAM segments. For comparison, linear diblock copolymer with comparable molecular weight and composition, (l-PNIPAM)-b-PCL, was also synthesized. It was found that the thermoresponsive coronas of micelles self-assembled from (c-PNIPAM)-b-PCL exhibit thermoinduced collapse and aggregation at a lower critical thermal phase transition temperature (T(c)) compared with those of (l-PNIPAM)-b-PCL. Temperature-dependent drug release profiles from the two types of micelles of (c-PNIPAM)-b-PCL and (l-PNIPAM)-b-PCL loaded with doxorubicin (Dox) were measured, and the underlying mechanism for the observed difference in releasing properties was proposed. Moreover, MTT assays revealed that micelles of (c-PNIPAM)-b-PCL are almost noncytotoxic up to a concentration of 1.0 g/L, whereas at the same polymer concentration, micelles loaded with Dox lead to ∼60% cell death. Overall, chain topologies of thermoresponsive block copolymers, that is, (c-PNIPAM)-b-PCL versus (l-PNIPAM)-b-PCL, play considerable effects on the self-assembling and thermal phase transition properties and their functions as controlled release drug nanocarriers.
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Flash photolysis and pulse radiolysis studies on collagen Type I in acetic acid solution.
Sionkowska, Alina
2006-07-03
An investigation of the photochemical properties of collagen Type I in acetic acid solution was carried out using nanosecond laser irradiation. The transient spectra of collagen solution excited at 266 nm show two bands. One of them with maximum at 295 nm and the second one with maximum at 400 nm. The peak at 400 nm is assigned to tyrosyl radicals. The first peak of the transient absorption spectra at 295 nm is probably due to photoionisation producing collagen radical cation. The transient for collagen solution in acetic acid at 640 nm was not observed. It is evidence that there is no hydrated electron in the irradiated collagen solution. The reactions of hydrated electrons and (*)OH radicals with collagen have been studied by pulse radiolysis. In the absorption spectra of products resulting from the reaction of collagen with e(aq)(-) no characteristic maximum absorption in UV and visible light region has been observed. In the absorption spectra of products resulting from the reaction of the hydroxyl radicals with collagen two bands have been observed. The first one at 320 nm and the second one at 405 nm. Reaction of (*)OH radicals with tyrosine residues in collagen chains gives rise to Tyr phenoxyl radicals (absorption at 400 nm).
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Pervaporation separation of ethanol-water mixtures using polyacrylic acid composite membranes
Neidlinger, H.H.
1985-05-07
Synthetic, organic, polymeric membranes were prepared from polyacrylic acid salts for use with pervaporation apparatus in the separation of ehthanol-water mixtures. The polymeric material was prepared in dilute aqueous solution and coated onto a polysulfone support film, from which excess polymeric material was subsequently removed. Cross-links were then generated by limited exposure to toluene-2,4-diisocyanata solution, after which the prepared membrane was heat-cured. The resulting membrane structure showed selectivity in permeating water over a wide range of feed concentrations. 4 tabs.
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Pervaporation separation of ethanol-water mixtures using polyethylenimine composite membranes
Neidlinger, H.H.; Schissel, P.O.; Orth, R.A.
1985-06-19
Synthetic, organic, polymeric membranes were prepared from polyethylenimine for use with pervaporation apparatus in the separation of ethanol-water mixtures. The polymeric material was prepared in dilute aqueous solution and coated onto a polysulfone support film, from which excess polymeric material was subsequently removed. Cross-links were then generated by limited exposure to toluene-2,4-diisocyanate solution, after which the prepared membrane was heat-cured. The resulting membrane structures showed high selectivity in permeating ethanol or water over a wide range of feed concentrations. 2 tabs.
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Technique for the polymerization of monomers for PPQ/graphite fiber composites
NASA Technical Reports Server (NTRS)
Serafini, T. T.; Delvigs, P.; Vannucci, R. D.
1973-01-01
Impregnation of fiber prior to appreciable polymerization completely eliminates impregnation problems encountered with use of high viscosity high molecular weight polyphenylquinoxalines (PPQ) solutions. Major part of polymerization of reactant mixture is conducted on fiber during solvent removal and final curing stages.
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NASA Astrophysics Data System (ADS)
Li, Mengmeng; Wang, Shiwen; Jiang, Jia; Sun, Jiashu; Li, Yuzhuo; Huang, Deyong; Long, Yun-Ze; Zheng, Wenfu; Chen, Shiyi; Jiang, Xingyu
2015-04-01
The Ligament Advanced Reinforcement System (LARS) has been considered as a promising graft for ligament reconstruction. To improve its biocompatibility and effectiveness on new bone formation, we modified the surface of a polyethylene terephthalate (PET) ligament with nanoscale silica using atom transfer radical polymerization (ATRP) and silica polymerization. The modified ligament is tested by both in vitro and in vivo experiments. Human osteoblast testing in vitro exhibits an ~21% higher value in cell viability for silica-modified grafts compared with original grafts. Animal testing in vivo shows that there is new formed bone in the case of a nanoscale silica-coated ligament. These results demonstrate that our approach for nanoscale silica surface modification on LARS could be potentially applied for ligament reconstruction.The Ligament Advanced Reinforcement System (LARS) has been considered as a promising graft for ligament reconstruction. To improve its biocompatibility and effectiveness on new bone formation, we modified the surface of a polyethylene terephthalate (PET) ligament with nanoscale silica using atom transfer radical polymerization (ATRP) and silica polymerization. The modified ligament is tested by both in vitro and in vivo experiments. Human osteoblast testing in vitro exhibits an ~21% higher value in cell viability for silica-modified grafts compared with original grafts. Animal testing in vivo shows that there is new formed bone in the case of a nanoscale silica-coated ligament. These results demonstrate that our approach for nanoscale silica surface modification on LARS could be potentially applied for ligament reconstruction. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr01439e
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Ma, Shujuan; Zhang, Haiyang; Li, Ya; Li, Yanan; Zhang, Na; Ou, Junjie; Ye, Mingliang; Wei, Yinmao
2018-02-23
Although several approaches have been developed to fabricate hybrid monoliths, it would still take a few hours to finish the formation of monoliths. Herein, photo-initiated thiol-yne polymerization was first adopted to in situ fabricate hybrid monoliths within the confines of UV-transparent fused-silica capillary. A silicon-containing diyne (1,3-diethynyltetramethyl-disiloxane, DYDS) was copolymerized with three multithiols, 1,6-hexanedithiol, trimethylolpropane tris(3-mercaptopropionate) and pentaerythriol tetrakis(3-mercaptopropionate), by using a binary porogenic system of diethylene glycol diethyl ether (DEGDE)/poly(ethylene glycol) (PEG200) within 10 min. Several characterizations of three hybrid monoliths (assigned as I, II and III, respectively) were performed. The results showed that these hybrid monoliths possessed bicontinuous porous structure, which was remarkably different from that via typical free-radical polymerization. The highest column efficiency of 76,000 plates per meter for butylbenzene was obtained on the column I in reversed-phase liquid chromatography (RPLC). It was observed that the efficiencies for strong-retained butylbenzene were almost close to those of weak-retained benzene, indicating a retention-independent efficient performance of small molecules on hybrid column I. The surface area of this hybrid monolith was very small in the dry state (less than 10.0 m 2 /g), and the chromatographic behavior of hybrid monolithic columns would be possibly explained by radical-mediated step-growth process of thiol-yne polymerization. Finally, the column I was applied for separation of BSA tryptic digest by cLC-MS/MS, indicating satisfactory separation ability for complicated samples. Copyright © 2018 Elsevier B.V. All rights reserved.
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Temperature-responsive chromatography for the separation of biomolecules.
Kanazawa, Hideko; Okano, Teruo
2011-12-09
Temperature-responsive chromatography for the separation of biomolecules utilizing poly(N-isopropylacrylamide) (PNIPAAm) and its copolymer-modified stationary phase is performed with an aqueous mobile phase without using organic solvent. The surface properties and function of the stationary phase are controlled by external temperature changes without changing the mobile-phase composition. This analytical system is based on nonspecific adsorption by the reversible transition of a hydrophilic-hydrophobic PNIPAAm-grafted surface. The driving force for retention is hydrophobic interaction between the solute molecules and the hydrophobized polymer chains on the stationary phase surface. The separation of the biomolecules, such as nucleotides and proteins was achieved by a dual temperature- and pH-responsive chromatography system. The electrostatic and hydrophobic interactions could be modulated simultaneously with the temperature in an aqueous mobile phase, thus the separation system would have potential applications in the separation of biomolecules. Additionally, chromatographic matrices prepared by a surface-initiated atom transfer radical polymerization (ATRP) exhibit a strong interaction with analytes, because the polymerization procedure forms a densely packed polymer, called a polymer brush, on the surfaces. The copolymer brush grafted surfaces prepared by ATRP was an effective tool for separating basic biomolecules by modulating the electrostatic and hydrophobic interactions. Applications of thermally responsive columns for the separations of biomolecules are reviewed here. Copyright © 2011 Elsevier B.V. All rights reserved.
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Jalil, Aamir; Khan, Samiullah; Naeem, Fahad; Haider, Malik Suleman; Sarwar, Shoaib; Riaz, Amna; Ranjha, Nazar Muhammad
2017-01-01
Abstract In present investigation new formulations of Sodium Alginate/Acrylic acid hydrogels with high porous structure were synthesized by free radical polymerization technique for the controlled drug delivery of analgesic agent to colon. Many structural parameters like molecular weight between crosslinks (M c), crosslink density (M r), volume interaction parameter (v 2,s), Flory Huggins water interaction parameter and diffusion coefficient (Q) were calculated. Water uptake studies was conducted in different USP phosphate buffer solutions. All samples showed higher swelling ratio with increasing pH values because of ionization of carboxylic groups at higher pH values. Porosity and gel fraction of all the samples were calculated. New selected samples were loaded with the model drug (diclofenac potassium).The amount of drug loaded and released was determined and it was found that all the samples showed higher release of drug at higher pH values. Release of diclofenac potassium was found to be dependent on the ratio of sodium alginate/acrylic acid, EGDMA and pH of the medium. Experimental data was fitted to various model equations and corresponding parameters were calculated to study the release mechanism. The Structural, Morphological and Thermal Properties of interpenetrating hydrogels were studied by FTIR, XRD, DSC, and SEM. PMID:29491802
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Biochemical separations by continuous-bed chromatography.
Tisch, T L; Frost, R; Liao, J L; Lam, W K; Remy, A; Scheinpflug, E; Siebert, C; Song, H; Stapleton, A
1998-08-07
Innovations in column-packing media for biomolecule purification have progressed from large spherical, porous polysaccharide beads to advanced polymeric supports. Continuous-bed technology is a radical new technology for chromatography based on the polymerization of advanced monomers and ionomers directly in the chromatographic column. The polymer chains form aggregates which coalesce into a dense, homogeneous network of interconnected nodules consisting of microparticles with an average diameter of 3000 A. The voids or channels between the nodules are large enough to permit a high hydrodynamic flow. Due to the high cross-linking of the polymer matrix, the surface of each nodule is nonporous yet the polymeric microparticles provide a very large surface area for high binding capacity. This paper will demonstrate the properties and advantages of using a continuous bed support for high resolution biomolecule separations at high flow-rates without sacrificing capacity.
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Controlled Assembly of Fibronectin Nanofibrils Triggered by Random Copolymer Chemistry.
Mnatsakanyan, Hayk; Rico, Patricia; Grigoriou, Eleni; Candelas, Aarón Maturana; Rodrigo-Navarro, Aleixandre; Salmeron-Sanchez, Manuel; Sabater i Serra, Roser
2015-08-19
Fibronectin fibrillogenesis is the physiological process by which cells elaborate a fibrous FN matrix. Poly(ethyl acrylate), PEA, has been described to induce a similar process upon simple adsorption of fibronectin (FN) from a protein solution-in the absence of cells-leading to the so-called material-driven fibronectin fibrillogenesis. Poly(methyl acrylate), PMA, is a polymer with very similar chemistry to PEA, on which FN is adsorbed, keeping the globular conformation of the protein in solution. We have used radical polymerization to synthesize copolymers with controlled EA/MA ratio, seeking to modulate the degree of FN fibrillogenesis. The physicochemical properties of the system were studied using dynamic-mechanical analysis, differential scanning calorimetry, and water contact angle. Both the degree of FN fibrillogenesis and the availability of the integrin binding region of FN directly depend on the percentage of EA in the copolymer, whereas the same total amount of FN was adsorbed regardless the EA/MA ratio. Cell morphology adhesion and differentiation of murine C2C12 were shown to depend on the degree of FN fibrillogenesis previously attained on the material surface. Myogenic differentiation was enhanced on the copolymers with higher EA content, i.e. more interconnected FN fibrils.
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Direct fabrication of hybrid nanofibres composed of SiO2-PMMA nanospheres via electrospinning.
Zhang, Ran; Shang, Tinghua; Yang, Guang; Jia, Xiaolong; Cai, Qing; Yang, Xiaoping
2016-08-01
The direct fabrication of hybrid nanofibres composed of poly(methyl methacrylate)-grafted SiO2 (SiO2-PMMA) nanospheres via electrospinning was investigated in detail. SiO2-PMMA nanospheres were successfully prepared, with the SiO2 nanospheres synthesized via the Stober method, followed by in situ surface-initiated atom transfer radical polymerization of methyl methacrylate (MMA). Electrospinning was carried out with N,N-dimethylformamide (DMF) as the solvent to disperse SiO2-PMMA nanospheres. The size of the SiO2 core, the molecular weight of the PMMA shell and the concentration of the SiO2-PMMA/DMF solution all had substantial effects on the morphology and structure of electrospun nanofibres composed of SiO2-PMMA nanospheres. When these determining factors were well-tailored, it was found that one-dimensional necklace-like nanofibres were obtained, with SiO2-PMMA nanospheres aligned one by one along the fibre. The successful fabrication of nanofibres by directly electrospinning the SiO2-PMMA/DMF solution verified that polymer-grafted particles possess polymer-like characteristics, which endowed them with the ability to be processed into desirable shapes and structures. Copyright © 2016 Elsevier B.V. All rights reserved.
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Irradiation of aqueous solutions with high-energy electrons results in the formation of the aqueous electron, hydrogen radical, H-, and the hydroxyl radical, OH-. These reactive transient species initiate chemical reactions capable of destroying organic compounds in aqueous solut...
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Powering up the future: radical polymers for battery applications.
Janoschka, Tobias; Hager, Martin D; Schubert, Ulrich S
2012-12-18
Our society's dependency on portable electric energy, i.e., rechargeable batteries, which permit power consumption at any place and in any time, will eventually culminate in resource wars on limited commodities like lithium, cobalt, and rare earth metals. The substitution of conventional metals as means of electric charge storage by organic and polymeric materials, which may ultimately be derived from renewable resources, appears to be the only feasible way out. In this context, the novel class of organic radical batteries (ORBs) excelling in rate capability (i.e., charging speed) and cycling stability (>1000 cycles) sets new standards in battery research. This review examines stable nitroxide radical bearing polymers, their processing to battery systems, and their promising performance. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Wang, Wenya; Zhang, Chao; Sun, Xinxiao; Su, Sisi; Li, Qiang; Linhardt, Robert J
2017-06-01
Lignin is the second most abundant bio-resource in nature. It is increasingly important to convert lignin into high value-added chemicals to accelerate the development of the lignocellulose biorefinery. Over the past several decades, physical and chemical methods have been widely explored to degrade lignin and convert it into valuable chemicals. Unfortunately, these developments have lagged because of several difficulties, of which high energy consumption and non-specific cleavage of chemical bonds in lignin remain the greatest challenges. A large number of enzymes have been discovered for lignin degradation and these are classified as radical lignolytic enzymes and non-radical lignolytic enzymes. Radical lignolytic enzymes, including laccases, lignin peroxidases, manganese peroxidases and versatile peroxidases, are radical-based bio-catalysts, which degrade lignins through non-specific cleavage of chemical bonds but can also catalyze the radical-based re-polymerization of lignin fragments. In contrast, non-radical lignolytic enzymes selectively cleave chemical bonds in lignin and lignin model compounds and, thus, show promise for use in the preparation of high value-added chemicals. In this mini-review, recent developments on non-radical lignolytic enzymes are discussed. These include recently discovered non-radical lignolytic enzymes, their metabolic pathways for lignin conversion, their recent application in the lignin biorefinery, and the combination of bio-catalysts with physical/chemical methods for industrial development of the lignin refinery.
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Keddie, Daniel J
2014-01-21
The discovery of reversible-deactivation radical polymerization (RDRP) has provided an avenue for the synthesis of a vast array of polymers with a rich variety of functionality and architecture. The preparation of block copolymers has received significant focus in this burgeoning research field, due to their diverse properties and potential in a wide range of research environments. This tutorial review will address the important concepts behind the design and synthesis of block copolymers using reversible addition-fragmentation chain transfer (RAFT) polymerization. RAFT polymerization is arguably the most versatile of the RDRP methods due to its compatibility with a wide range of functional monomers and reaction media along with its relative ease of use. With an ever increasing array of researchers that possess a variety of backgrounds now turning to RDRP, and RAFT in particular, to prepare their required polymeric materials, it is pertinent to discuss the important points which enable the preparation of high purity functional block copolymers with targeted molar mass and narrow molar mass distribution using RAFT polymerization. The key principles of appropriate RAFT agent selection, the order of monomer addition in block synthesis and potential issues with maintaining high end-group fidelity are addressed. Additionally, techniques which allow block copolymers to be accessed using a combination of RAFT polymerization and complementary techniques are touched upon.
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Kuipers, Gitta K; Slotman, Ben J; Reitsma-Wijker, Carola A; van Andel, Rob J; Poldervaart, Hester A; Lafleur, M Vincent M
2004-12-21
When DNA is irradiated in aqueous solution, most of the damage is inflicted by water-derived radicals. This is called the indirect effect of ionizing radiation. However in whole cells not only the primary formed water radicals play a role, because some cellular compounds form secondary radicals which can also damage DNA. It is known that the amino acid phenylalanine is able to react with water radicals, resulting in the production of secondary phenylalanine radicals which can damage and inactivate DNA. In a previous study the influence of the presence of phenylalanine during gamma-irradiation of DNA in aqueous solution under oxic conditions was studied. Under anoxic irradiation conditions different amounts and types of reactive water-derived radicals are formed compared to oxic conditions and also different phenylalanine radicals are formed. Therefore, this study examines the influence of the presence of phenylalanine under anoxic conditions on the gamma-radiation-induced mutation spectrum. The results indicate that phenylalanine radicals are damaging to DNA, but less effective compared to primary water radicals. On the mutational level, in the presence of phenylalanine radicals under anoxic conditions, the amount of mutations on G:C base pairs was significantly decreased as compared to oxic conditions. Furthermore, the results of this study indicate that nucleotide excision repair is involved in repair of both inactivating and mutagenic damage induced by phenylalanine radicals under anoxic conditions.
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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.
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NASA Astrophysics Data System (ADS)
Schuchardt, Patrick; Unger, Miriam; Siesler, Heinz W.
2018-01-01
In the present communication the potential of 2DCOS analysis and the spin-off technique perturbation-correlation moving window 2D (PCMW2D) analysis is illustrated with reference to spectroscopic changes observed in a data set recorded by in-line fiber-coupled FT-IR spectroscopy in the attenuated total reflection (ATR) mode during a polyurethane solution polymerization at different temperatures. In view of the chemical functionalities involved, hydrogen bonding plays an important role in this polymerization reaction. Based on the 2DCOS and PCMW2D analysis, the sequence of hydrogen bonding changes accompanying the progress of polymerization and precipitation of solid polymer can be determined. Complementary to the kinetic data derived from the original variable-temperature spectra in a previous publication the results provide a more detailed picture of the investigated solution polymerization.
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Allen, Ranulfo; Pan, Lijia; Fuller, Gerald G; Bao, Zhenan
2014-07-09
Single-walled carbon nanotubes/polymer composites typically have limited conductivity due to a low concentration of nanotubes and the insulating nature of the polymers used. Here we combined a method to align carbon nanotubes with in-situ polymerization of conductive polymer to form composite films and fibers. Use of the conducting polymer raised the conductivity of the films by 2 orders of magnitude. On the other hand, CNT fiber formation was made possible with in-situ polymerization to provide more mechanical support to the CNTs from the formed conducting polymer. The carbon nanotube/conductive polymer composite films and fibers had conductivities of 3300 and 170 S/cm, respectively. The relatively high conductivities were attributed to the polymerization process, which doped both the SWNTs and the polymer. In-situ polymerization can be a promising solution-processable method to enhance the conductivity of carbon nanotube films and fibers.
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Star-shaped PHB-PLA block copolymers: immortal polymerization with dinuclear indium catalysts.
Yu, I; Ebrahimi, T; Hatzikiriakos, S G; Mehrkhodavandi, P
2015-08-28
The first example of a one-component precursor to star-shaped polyesters, and its utilization in the synthesis of previously unknown star-shaped poly(hydroxybutyrate)-poly(lactic acid) block copolymers, is reported. A series of such mono- and bis-benzyl alkoxy-bridged complexes were synthesized, fully characterized, and their solvent dependent solution structures and reactivity were examined. These complexes were highly active catalysts for the controlled polymerization of β-butyrolactone to form poly(hydroxybutyrate) at room temperature. Solution studies indicate that a mononuclear propagating species formed in THF and that the dimer-monomer equilibrium affects the rates of BBL polymerization. In the presence of linear and branched alcohols, these complexes catalyze well-controlled immortal polymerization and copolymerization of β-butyrolactone and lactide.
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Selective extraction of metal ions with polymeric extractants by ion exchange/redox
Alexandratos, Spiro D.
1987-01-01
The specification discloses a method for the extraction of metal ions having a reduction potential of above about +0.3 from an aqueous solution. The method includes contacting the aqueous solution with a polymeric extractant having primary phosphinic acid groups, secondary phosphine oxide groups, or both phosphinic acid and phosphine oxide groups.
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Stress-tuned conductor-polymer composite for use in sensors
Martin, James E; Read, Douglas H
2013-10-22
A method for making a composite polymeric material with electrical conductivity determined by stress-tuning of the conductor-polymer composite, and sensors made with the stress-tuned conductor-polymer composite made by this method. Stress tuning is achieved by mixing a miscible liquid into the polymer precursor solution or by absorbing into the precursor solution a soluble compound from vapor in contact with the polymer precursor solution. The conductor may or may not be ordered by application of a magnetic field. The composite is formed by polymerization with the stress-tuning agent in the polymer matrix. The stress-tuning agent is removed following polymerization to produce a conductor-polymer composite with a stress field that depends on the amount of stress-tuning agent employed.
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ERIC Educational Resources Information Center
Tsarevsky, Nicolay V.; Woodruf, Shannon R.; Wisian-Neilson, Patty J.
2016-01-01
A two-session experiment is designed to introduce undergraduate students to concepts in catalysis, transition metal complexes, polymer synthesis, and postpolymerization modifications. In the first session, students synthesize poly(glycidyl methacrylate) via low-catalyst-concentration atom transfer radical polymerization (ATRP). The…
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NASA Astrophysics Data System (ADS)
Lucon, Janice; Qazi, Shefah; Uchida, Masaki; Bedwell, Gregory J.; Lafrance, Ben; Prevelige, Peter E.; Douglas, Trevor
2012-10-01
Virus-like particles (VLPs) have emerged as important and versatile architectures for chemical manipulation in the development of functional hybrid nanostructures. Here we demonstrate a successful site-selective initiation of atom-transfer radical polymerization reactions to form an addressable polymer constrained within the interior cavity of a VLP. Potentially, this protein-polymer hybrid of P22 and cross-linked poly(2-aminoethyl methacrylate) could be useful as a new high-density delivery vehicle for the encapsulation and delivery of small-molecule cargos. In particular, the encapsulated polymer can act as a scaffold for the attachment of small functional molecules, such as fluorescein dye or the magnetic resonance imaging (MRI) contrast agent Gd-diethylenetriaminepentacetate, through reactions with its pendant primary amine groups. Using this approach, a significant increase in the labelling density of the VLP, compared to that of previous modifications of VLPs, can be achieved. These results highlight the use of multimeric protein-polymer conjugates for their potential utility in the development of VLP-based MRI contrast agents with the possibility of loading other cargos.
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Yuan, S J; Pehkonen, S O; Ting, Y P; Neoh, K G; Kang, E T
2010-05-04
To enhance the corrosion resistance of stainless steel (SS) and to impart its surface with antibacterial functionality for inhibiting biofilm formation and biocorrosion, well-defined inorganic-organic hybrid coatings, consisting of a polysilsesquioxane inner layer and quaternized poly(2-(dimethyamino)ethyl methacrylate) (P(DMAEMA)) outer blocks, were prepared via successive surface-initiated atom transfer radical polymerization (ATRP) of 3-(trimethoxysilyl)propyl methacrylate (TMSPMA) and 2-(dimethylamino)ethyl methacrylate (DMAEMA). The cross-linked P(TMASPMA), or polysilsesquioxane, inner layer provided a durable and resistant coating to electrolytes. The pendant tertiary amino groups of the P(DMAEMA) outer block were quaternized with alkyl halide to produce a high concentration of quaternary ammonium groups with biocidal functionality. The so-synthesized inorganic-organic hybrid coatings on the SS substrates exhibited good anticorrosion and antibacterial effects and inhibited biocorrosion induced by sulfate-reducing bacteria (SRB) in seawater media, as revealed by antibacterial assay and electrochemical analyses, and they are potentially useful to steel-based equipment under harsh industrial and marine environments.
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NASA Astrophysics Data System (ADS)
Pikulin, Alexander; Bityurin, Nikita; Sokolov, Viktor I.
2015-12-01
Diffusion-assisted direct laser writing (DA-DLW) by multiphoton polymerization has been recently shown to be one of the most promising methods for the high-resolution 3D nanofabrication [I. Sakellari, et al., ACS Nano 6, 2302 (2012)]. The improvement of the writing spatial resolution has been observed under certain conditions when the mobile radical quencher (polymerization inhibitor) is added to the photosensitive composition. In this work, we present a theoretical study of this method, focusing on the resolution capabilities and optimal writing parameters. The laser beam absorption in the polymerizable composition causes the localized depletion of the quencher molecules. If the quencher depletion is balanced by its diffusion from the outside of the focal volume, the quasi-stationary non-equillibrium concentration spatial profile with zero minimum can be obtained. The polymer is then effectively formed only in the domain where the quencher is depleted. The spatially-distributed quencher, in this case, has the effect similar to that of the vortex beam in STimulated Emission Microscopy (STED).
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Yue, Yanfeng; Zhang, Chenxi; Tang, Qing; ...
2015-10-30
In order to ensure a sustainable reserve of fuel for nuclear power generation, tremendous research efforts have been devoted to developing advanced sorbent materials for extracting uranium from seawater. In this work, a porous aromatic framework (PAF) was surface-functionalized with poly(acrylonitrile) through atom-transfer radical polymerization (ATRP). Batches of this adsorbent were conditioned with potassium hydroxide (KOH) at room temperature or 80 °C prior to contact with a uranium-spiked seawater simulant, with minimal differences in uptake observed as a function of conditioning temperature. A maximum capacity of 4.81 g-U/kg-ads was obtained following 42 days contact with uranium-spiked filtered environmental seawater, whichmore » demonstrates a comparable adsorption rate. A kinetic investigation revealed extremely rapid uranyl uptake, with more than 80% saturation reached within 14 days. Furthermore, relying on the semiordered structure of the PAF adsorbent, density functional theory (DFT) calculations reveal cooperative interactions between multiple adsorbent groups yield a strong driving force for uranium binding.« less
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Pikulin, Alexander, E-mail: pikulin@ufp.appl.sci-nnov.ru; Bityurin, Nikita; Institute of Applied Physics of Russian Academy of Sciences, 46, Ul’yanov Str., Nizhniy Novgorod, 603950
Diffusion-assisted direct laser writing (DA-DLW) by multiphoton polymerization has been recently shown to be one of the most promising methods for the high-resolution 3D nanofabrication [I. Sakellari, et al., ACS Nano 6, 2302 (2012)]. The improvement of the writing spatial resolution has been observed under certain conditions when the mobile radical quencher (polymerization inhibitor) is added to the photosensitive composition. In this work, we present a theoretical study of this method, focusing on the resolution capabilities and optimal writing parameters. The laser beam absorption in the polymerizable composition causes the localized depletion of the quencher molecules. If the quencher depletionmore » is balanced by its diffusion from the outside of the focal volume, the quasi-stationary non-equillibrium concentration spatial profile with zero minimum can be obtained. The polymer is then effectively formed only in the domain where the quencher is depleted. The spatially-distributed quencher, in this case, has the effect similar to that of the vortex beam in STimulated Emission Microscopy (STED)« less
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Bo, Chun Miao; Wang, Chaozhan; Wei, Yin Mao
2017-12-01
A novel approach that involved the grafting of diblock copolymer with two types of monomer onto substrate by sequential surface initiated-atom transfer radical polymerization was proposed to prepare a mixed-mode chromatographic stationary phase. The distinguishing feature of this method is that it can be applied in the preparation of various mixed-mode stationary phases. In this study, a new reverse-phase/ion-exchange stationary phase was prepared by grafting hydrophobic styrene and cationic sodium 4-styrenesulfonate by the proposed approach onto silica surface. The chromatographic properties of the prepared stationary phase were evaluated by the separation of benzene derivatives, anilines, and β-agonists, and by the effect of pH values and acetonitrile content on the retention. Compared with typical RP columns, the prepared stationary phase achieved the better resolution and higher selectivity at a shorter separation time and lower organic content. Moreover, the application of the prepared column was proved by separating widely distributed polar and charged compounds simultaneously. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Yu, Juan; Wang, Chunpeng; Wang, Jifu; Chu, Fuxiang
2016-05-05
Recently, the utilization of cellulose nanocrystals (CNCs) as a reinforcing material has received a great attention due to its high elastic modulus. In this article, a novel strategy for the synthesis of self-reinforced CNCs based thermoplastic elastomers (CTPEs) is presented. CNCs were first surface functionalized with an initiator for surface-initiated atom transfer radical polymerization (SI-ATRP). Subsequently, SI-ATRP of methyl methacrylate (MMA) and butyl acrylate (BA) was carried out in the presence of sacrificial initiator to form CTPEs in situ. The CTPEs together with the simple blends of CNCs and linear poly(MMA-co-BA) copolymer (P(MMA-co-BA)) were characterized for comparative study. The results indicated that P(MMA-co-BA) was successfully grafted onto the surface of CNCs and the compatibility between CNCs and the polymer matrix in CTPEs was greatly enhanced. Specially, the CTPEs containing 2.15wt% CNCs increased Tg by 19.2°C and tensile strength by 100% as compared to the linear P(MMA-co-BA). Copyright © 2016 Elsevier Ltd. All rights reserved.
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Khachatryan, Lavrent; Dellinger, Barry
2011-11-01
A chemical spin trap, 5,5-dimethyl-1-pyrroline-N-oxide (DMPO), in conjunction with electron paramagnetic resonance (EPR) spectroscopy was employed to measure the production of hydroxyl radical (·OH) in aqueous suspensions of 5% Cu(II)O/silica (3.9% Cu) particles containing environmentally persistent free radicals (EPFRs) of 2-monochlorophenol (2-MCP). The results indicate: (1) a significant differences in accumulated DMPO-OH adducts between EPFR containing particles and non-EPFR control samples, (2) a strong correlation between the concentration of DMPO-OH adducts and EPFRs per gram of particles, and (3) a slow, constant growth of DMPO-OH concentration over a period of days in solution containing 50 μg/mL EPFRs particles + DMPO (150 mM) + reagent balanced by 200 μL phosphate buffered (pH = 7.4) saline. However, failure to form secondary radicals using standard scavengers, such as ethanol, dimethylsulfoxide, sodium formate, and sodium azide, suggests free hydroxyl radicals may not have been generated in solution. This suggests surface-bound, rather than free, hydroxyl radicals were generated by a surface catalyzed-redox cycle involving both the EPFRs and Cu(II)O. Toxicological studies clearly indicate these bound free radicals promote various types of cardiovascular and pulmonary disease normally attributed to unbound free radicals; however, the exact chemical mechanism deserves further study in light of the implication of formation of bound, rather than free, hydroxyl radicals.
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Localized in situ polymerization on graphene surfaces for stabilized graphene dispersions.
Das, Sriya; Wajid, Ahmed S; Shelburne, John L; Liao, Yen-Chih; Green, Micah J
2011-06-01
We demonstrate a novel in situ polymerization technique to develop localized polymer coatings on the surface of dispersed pristine graphene sheets. Graphene sheets show great promise as strong, conductive fillers in polymer nanocomposites; however, difficulties in dispersion quality and interfacial strength between filler and matrix have been a persistent problem for graphene-based nanocomposites, particularly for pristine graphene. With this in mind, a physisorbed polymer layer is used to stabilize graphene sheets in solution. To create this protective layer, we formed an organic microenvironment around dispersed graphene sheets in surfactant solutions, and created a nylon 6, 10 or nylon 6, 6 coating via interfacial polymerization. Technique lies at the intersection of emulsion and admicellar polymerization; a similar technique was originally developed to protect luminescent properties of carbon nanotubes in solution. These coated graphene dispersions are aggregation-resistant and may be reversibly redispersed in water even after freeze-drying. The coated graphene holds promise for a number of applications, including multifunctional graphene-polymer nanocomposites. © 2011 American Chemical Society
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Membrane surface engineering for protein separations: experiments and simulations.
Liu, Zizhao; Du, Hongbo; Wickramasinghe, S Ranil; Qian, Xianghong
2014-09-09
A bisphosphonate derived ligand was successfully synthesized and grafted from the surface of regenerated cellulose membrane using atom transfer radical polymerization (ATRP) for protein separations. This ligand has a remarkable affinity for arginine (Arg) residues on protein surface. Hydrophilic residues N-(2-hydroxypropyl) methacrylamide (HPMA) was copolymerized to enhance the flexibility of the copolymer ligand and further improve specific protein adsorption. The polymerization of bisphosphonate derivatives was successful for the first time using ATRP. Static and dynamic binding capacities were determined for binding and elution of Arg rich lysozyme. The interaction mechanism between the copolymer ligand and lysozyme was elucidated using classical molecular dynamics (MD) simulations.
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Block copolymers from ionic liquids for the preparation of thin carbonaceous shells
Hanif, Sadaf; Oschmann, Bernd; Spetter, Dmitri; Tahir, Muhammad Nawaz; Tremel, Wolfgang
2017-01-01
This paper describes the controlled radical polymerization of an ionic-liquid monomer by RAFT polymerization. This allows the control over the molecular weight of ionic liquid blocks in the range of 8000 and 22000 and of the block-copolymer synthesis. In this work we focus on block copolymers with an anchor block. They can be used to control the formation of TiO2 nanoparticles, which are functionalized thereafter with a block of ionic-liquid polymer. Pyrolysis of these polymer functionalized inorganic nanoparticles leads to TiO2 nanoparticles coated with a thin carbonaceous shell. Such materials may, e.g., be interesting as battery materials. PMID:28904612
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Block copolymers from ionic liquids for the preparation of thin carbonaceous shells.
Hanif, Sadaf; Oschmann, Bernd; Spetter, Dmitri; Tahir, Muhammad Nawaz; Tremel, Wolfgang; Zentel, Rudolf
2017-01-01
This paper describes the controlled radical polymerization of an ionic-liquid monomer by RAFT polymerization. This allows the control over the molecular weight of ionic liquid blocks in the range of 8000 and 22000 and of the block-copolymer synthesis. In this work we focus on block copolymers with an anchor block. They can be used to control the formation of TiO 2 nanoparticles, which are functionalized thereafter with a block of ionic-liquid polymer. Pyrolysis of these polymer functionalized inorganic nanoparticles leads to TiO 2 nanoparticles coated with a thin carbonaceous shell. Such materials may, e.g., be interesting as battery materials.
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Al-Majid, Abdullah M; Shamsan, Waseem Sharaf; Al-Odayn, Abdel-Basit Mohammed; Nahra, Fady; Aouak, Taieb; Nolan, Steven P
2017-01-01
The homopolymerization and copolymerization of styrene and methyl methacrylate, initiated for the first time by the combination of azo-bis-isobutyronitrile (AIBN) with [(SiMes)Ru(PPh 3 )(Ind)Cl 2 ] complex. The reactions were successfully carried out, on a large scale, in presence this complex at 80 °C. It was concluded from the data obtained that the association of AIBN with the ruthenium complex reduces considerably the transfer reactions and leads to the controlled radical polymerization and the well-defined polymers.
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Chemical control of rate and onset temperature of nadimide polymerization
NASA Technical Reports Server (NTRS)
Lauver, R. W.
1985-01-01
The chemistry of norbornenyl capped imide compounds (nadimides) is briefly reviewed with emphasis on the contribution of Diels-Alder reversion in controlling the rate and onset of the thermal polymerization reaction. Control of onset temperature of the cure exotherm by adjusting the concentration of maleimide is demonstrated using selected model compounds. The effects of nitrophenyl compounds as free radical retarders on nadimide reactivity are discussed. A simple copolymerization model is proposed for the overall nadimide cure reaction. An approximate numerical analysis is carried out to demonstrate the ability of the model to simulate the trends observed for both maleimide and nitrophenyl additions.
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pH-sensitive Itaconic acid based polymeric hydrogels for dye removal applications.
Sakthivel, M; Franklin, D S; Guhanathan, S
2016-12-01
A series of Itaconic Acid (IA) based pH-sensitive polymeric hydrogels were synthesized by condensation polymerization of Itaconic Acid (IA) with Ethylene Glycol (EG) in the presence of an acid medium resulted into pre-polymer. Further, pre-polymer were co-polymerized with Acrylic Acid (AA) through free radical polymerization using Potassium persulphate (KPS). The structural and surface morphological characterizations of the synthesized hydrogels were studied using FT-IR spectroscopy and Scanning Electron Microscope (SEM) respectively. The swelling and swelling equilibrium were performed at varies pH (4.0-10.0). Further, the effects of IA, EG and AA on swelling properties have also been investigated. Thermal stability of synthesized hydrogels have been investigated by TGA, DTA and DSC. The synthesized hydrogels have shown good ability to uptake a Cationic dye. The Methylene blue has been chosen as a model cationic dye. The results of dye removal using IA hydrogels found to have excellent dye removal capacity. Such kind of IA based hydrogels may be recommended for eco-friendly environmental application. viz., removal of dyes and metal ions and sewage water treatment, purification of water etc. Copyright © 2015 Elsevier Inc. All rights reserved.
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NASA Astrophysics Data System (ADS)
Wink, David A.; Desrosiers, Marc F.
The reaction of the potent carcinogen N-nitrosodimethylamine (NDMA) with hydroxyl radical generated via radiolysis was studied using EPR techniques. Attempts to spin trap NDMA radical intermediates with 3,5-dibromo-4-nitrosobenzene sulfonate (DBNBS) produced only unusual DBNBS radicals. One of these radicals was shown to be generated by both reaction of DBNBS with nitric oxide, and direct oxidation of DBNBS with an inorganic oxidant ( .Br -2). Another DBNBS radical was identified as a sulfite spin adduct resulting from the degradation of DBNBS by a NDMA reactive intermediate. In the absence of DBNBS, hydroxyl radical reaction with NDMA gave the dimethylnitroxide radical. Unexpectedly, addition of DBNBS to a solution containing dimethylnitroxide produced an EPR spectrum nearly identical to that of NDMA solutions with DBNBS added before radiolysis. A proposed mechanism accounting for these observations is presented.
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Tang, Heqing; Li, Jing; Bie, Yeqiang; Zhu, Lihua; Zou, Jing
2010-03-15
Organic pollutants may be treated by either a degradation process or a recovery process in the view point of sustainable chemistry. Photocatalytic removal of aniline was investigated in aqueous solutions. It was found that the photocatalytic oxidation of aniline resulted in its degradation or polymerization, depending on its concentration. Hence a new treatment strategy was proposed in combination of photocatalytic degradation and polymerization, where the polymerization was in fact a recovery process. When aniline concentration was as low as 0.1 mmol L(-1), it was possible to photocatalytically degrade aniline, which could be further enhanced by increasing solution pH, modifying TiO(2) surface with the addition of anions, or coupling with the photoreduction of added oxidants. When aniline concentration was increased to about 1 mmol L(-1), the photocatalytic oxidation was observed to yield the polymerization of aniline, leading to nanocomposites of polyaniline (PAN) and TiO(2). Alternatively, the photo-enhanced chemical polymerization of aniline at higher concentrations (>or=50 mmol L(-1)) in the presence of chemical oxidants produced PAN nanostructures. The conversion of pollutant aniline to valuable PAN nanostructures or nano-PAN/TiO(2) composites is suggestive for possible applications in the treatment of aniline wastewaters as a sustainable environmental protection measure. (c) 2009 Elsevier B.V. All rights reserved.
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Effect of hemoglobin polymerization on oxygen transport in hemoglobin solutions.
Budhiraja, Vikas; Hellums, J David
2002-09-01
The effect of hemoglobin (Hb) polymerization on facilitated transport of oxygen in a bovine hemoglobin-based oxygen carrier was studied using a diffusion cell. In high oxygen tension gradient experiments (HOTG) at 37 degrees C the diffusion of dissolved oxygen in polymerized Hb samples was similar to that in unpolymerized Hb solutions during oxygen uptake. However, in the oxygen release experiments, the transport by diffusion of dissolved oxygen was augmented by diffusion of oxyhemoglobin over a range of oxygen saturations. The augmentation was up to 30% in the case of polymerized Hb and up to 100% in the case of unpolymerized Hb solution. In experiments performed at constant, low oxygen tension gradients in the range of physiological significance, the augmentation effect was less than that in the HOTG experiments. Oxygen transport in polymerized Hb samples was approximately the same as that in unpolymerized samples over a wide range of oxygen tensions. However, at oxygen tensions lower than 30 mm Hg, there were more significant augmentation effects in unpolymerized bovine Hb samples than in polymerized Hb. The results presented here are the first accurate, quantitative measurements of effective diffusion coefficients for oxygen transport in hemoglobin-based oxygen carriers of the type being evaluated to replace red cells in transfusions. In all cases the oxygen carrier was found to have higher effective oxygen diffusion coefficients than blood.
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Liang, Xing; Su, Yibing; Yang, Ying; Qin, Wenwu
2012-02-15
The PbZn separation/preconcentration technique, based on the complex formation reaction of Pb(II) and Zn(II), using a copolymer poly(styrene-co-maleic anhydride) (PSMA), without adding any carrier element was developed. The effects of several experimental parameters such as solution pH, temperature and adsorption time were studied. The experimental results show that the PSMA resin-Pb equilibrium was achieved in 2 min and the Pb(II) loading capacity is up to 641.62 mg g(-1) in aqueous solution under optimum conditions, which is much higher than the Zn(II) loading capacity within 80 min. The adsorption test for Pb(II) indicates that PSMA can recover Pb(II) from a mixed solution of Pb(II), Zn(II) and light metals such as Ca(II) and Mg(II) with higher adsorption rate and larger selective coefficient. A further study indicates that PSMA as chelating resins recovering Pb(II) can be regenerated via mineral acid (6M H(2)SO(4)). PSMA was synthesized by radical polymerization and tested as an adsorbent for the selective recovery of Pb(II). In addition, the formation procedure and structure of Pb-PSMA complex were also studied. Both the PSMA and the Pb-PSMA complex were characterized by means of FTIR spectroscopy, elemental analysis, gel permeation chromatography (GPC) and atomic absorption spectrometry (AAS). Copyright © 2011 Elsevier B.V. All rights reserved.
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Guan, Chaoting; Jiang, Jin; Pang, Suyan; Luo, Congwei; Ma, Jun; Zhou, Yang; Yang, Yi
2017-09-19
This work demonstrated that bromophenols (BrPs) could be readily oxidized by peroxydisulfate (PDS) activated by a commercial carbon nanotube (CNT), while furfuryl alcohol (a chemical probe for singlet oxygen ( 1 O 2 )) was quite refractory. Results obtained by radical quenching experiments, electron paramagnetic resonance spectroscopy, and Fourier transform infrared spectroscopy further confirmed the involvement of nonradical PDS-CNT complexes rather than 1 O 2 . Bicarbonate and chloride ion exhibited negligible impacts on BrPs degradation by the PDS/CNT system, while a significant inhibitory effect was observed for natural organic matter. The oxidation of BrPs was influenced by solution pH with maximum rates occurring at neutral pH. Linear free energy relationships (LFERs) were established between the observed pseudo-first-order oxidation rates of various substituted phenols and the classical descriptor variables (i.e., Hammett constant σ + , and half-wave oxidation potential E 1/2 ). Products analyses by liquid chromatography tandem mass spectrometry clearly showed the formation of hydroxylated polybrominated diphenyl ethers and hydroxylated polybrominated biphenyls on CNT surface. Their formation pathway possibly involved the generation of bromophenoxyl radicals from BrPs one-electron oxidation and their subsequent coupling reactions. These results suggest that the novel nonradical PDS/CNT oxidation technology is a good alternative for selectively eliminating BrPs with alleviating toxic byproducts in treated water effluent.
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Ceylan, Şeyda; Odabaşı, Mehmet
2013-12-01
The aim of this study is to prepare supermacroporous cryogels embedded with Fe(3+)-attached sporopollenin particles (Fe(3++)-ASPs) having large surface area for high DNA adsorption capacity. Supermacroporous poly(2-hydroxyethyl methacrylate) (PHEMA)-based monolithic cryogel column embedded with Fe3+(+)-ASPs was prepared by radical cryo-copolymerization of 2-hydroxyethyl methacrylate (HEMA) with N,N´-methylene- bis-acrylamide (MBAAm) as cross-linker directly in a plastic syringe for DNA adsorption studies. Firstly, Fe3+(+) ions were attached to the sporopollenin particles (SPs), then the supermacroporous PHEMA cryogel with embedded Fe(3++)-ASPs was produced by free radical polymerization using N,N,N´, N´-Tetramethylethylenediamine (TEMED) and ammonium persulfate (APS) as initiator/activator pair in an ice bath. Optimum conditions of adsorption experiments were performed at pH 6.0 (0.02 M Tris buffer containing 0.2 M NaCl), with flow rate of 0.5 mL/min, and at 5°C. The maximum amount of DNA adsorption from aqueous solution was very high (109 mg/g SPs) with initial concentration of 3 mg/mL. It was observed that DNA could be repeatedly adsorbed and desorbed with this composite cryogel without significant loss of adsorption capacity. As a result, higher amounts of DNA adsorbed these composite cryogels are expected to be good candidate for achieving higher removal of anti-DNA antibodies from systemic lupus erythematosus (SLE) patients plasma.
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Hydroxyl radical production in plasma electrolysis with KOH electrolyte solution
DOE Office of Scientific and Technical Information (OSTI.GOV)
Saksono, Nelson; Febiyanti, Irine Ayu, E-mail: irine.ayu41@ui.ac.id; Utami, Nissa
2015-12-29
Plasma electrolysis is an effective technology for producing hydroxyl radical (•OH). This method can be used for waste degradation process. This study was conducted to obtain the influence of applied voltage, electrolyte concentration, and anode depth in the plasma electrolysis system for producing hydroxyl radical. The materials of anode and cathode, respectively, were made from tungsten and stainless steel. KOH solution was used as the solution. Determination of hydroxyl radical production was done by measuring H{sub 2}O{sub 2} amount formed in plasma system using an iodometric titration method, while the electrical energy consumed was obtained by measuring the electrical currentmore » throughout the process. The highest hydroxyl radical production was 3.51 mmol reached with 237 kJ energy consumption in the power supply voltage 600 V, 0.02 M KOH, and 0.5 cm depth of anode.« less
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Dark Photocatalysis: Storage of Solar Energy in Carbon Nitride for Time-Delayed Hydrogen Generation.
Lau, Vincent Wing-Hei; Klose, Daniel; Kasap, Hatice; Podjaski, Filip; Pignié, Marie-Claire; Reisner, Erwin; Jeschke, Gunnar; Lotsch, Bettina V
2017-01-09
While natural photosynthesis serves as the model system for efficient charge separation and decoupling of redox reactions, bio-inspired artificial systems typically lack applicability owing to synthetic challenges and structural complexity. We present herein a simple and inexpensive system that, under solar irradiation, forms highly reductive radicals in the presence of an electron donor, with lifetimes exceeding the diurnal cycle. This radical species is formed within a cyanamide-functionalized polymeric network of heptazine units and can give off its trapped electrons in the dark to yield H 2 , triggered by a co-catalyst, thus enabling the temporal decoupling of the light and dark reactions of photocatalytic hydrogen production through the radical's longevity. The system introduced here thus demonstrates a new approach for storing sunlight as long-lived radicals, and provides the structural basis for designing photocatalysts with long-lived photo-induced states. © 2016 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.
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Šponer, Judit E; Šponer, Jiří; Giorgi, Alessandra; Di Mauro, Ernesto; Pino, Samanta; Costanzo, Giovanna
2015-02-19
The high-energy 3',5' phosphodiester linkages conserved in 3',5' cyclic GMPs offer a genuine solution for monomer activation required by the transphosphorylation reactions that could lead to the emergence of the first simple oligonucleotide sequences on the early Earth. In this work we provide an in-depth characterization of the effect of the reaction conditions on the yield of the polymerization reaction of 3',5' cyclic GMPs both in aqueous environment as well as under dehydrating conditions. We show that the threshold temperature of the polymerization is about 30 °C lower under dehydrating conditions than in solution. In addition, we present a plausible exergonic reaction pathway for the polymerization reaction, which involves transient formation of anionic centers at the O3' positions of the participating riboses. We suggest that excess Na(+) cations inhibit the polymerization reaction because they block the anionic mechanism via neutralizing the negatively charged O3'. Our experimental findings are compatible with a prebiotic scenario, where gradual desiccation of the environment could induce polymerization of 3',5' cyclic GMPs synthesized in liquid.
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NASA Astrophysics Data System (ADS)
Albertsen, Anders N.; Szymański, Jan K.; Pérez-Mercader, Juan
2017-01-01
Giant micrometer sized vesicles are of obvious interest to the natural sciences as well as engineering, having potential application in fields ranging from drug delivery to synthetic biology. Their formation often requires elaborate experimental techniques and attempts to obtain giant vesicles from chemical media in a one-pot fashion have so far led to much smaller nanoscale structures. Here we show that a tailored medium undergoing controlled radical polymerization is capable of forming giant polymer vesicles. Using a protocol which allows for an aqueous reaction under mild conditions, we observe the macroscale consequences of amphiphilic polymer synthesis and the resulting molecular self-assembly using fluorescence microscopy. The polymerization process is photoinitiated by blue light granting complete control of the reaction, including on the microscope stage. The self-assembly process leads to giant vesicles with radii larger than 10 microns, exhibiting several emergent properties, including periodic growth and collapse as well as phototaxis.
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Preparing high-density polymer brushes by mechanically assisted polymer assembly (MAPA)
NASA Astrophysics Data System (ADS)
Wu, Tao; Efimenko, Kirill; Genzer, Jan
2001-03-01
We introduce a novel method of modifying the surface properties of materials. This technique, called MAPA (="mechanically assisted polymer assembly"), is based on: 1) chemically attaching polymerization initiators to the surface of an elastomeric network that has been previously stretched by a certain length, Δx, and 2) growing end-anchored macromolecules using surface initiated ("grafting from") atom transfer living radical polymerization. After the polymerization, the strain is removed from the substrate, which returns to its original size causing the grafted macromolecules to stretch away from the substrate and form a dense polymer brush. We demonstrate the feasibility of the MAPA method by preparing high-density polymer brushes of poly(acryl amide), PAAm. We show that, as expected, the grafting density of the PAAm brushes can be increased by increasing Δx. We demonstrate that polymer brushes with extremely high grafting densities can be successfully prepared by MAPA.
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Copper mediated polymerization without external deoxygenation or oxygen scavengers.
Liarou, Evelina; Whitfield, Richard; Anastasaki, Athina; Engelis, Nikolaos G; Jones, Glen R; Velonia, Kelly; Haddleton, David
2018-05-14
Overcoming the challenge of rigorous deoxygenation in copper mediated controlled radical polymerization processes (e.g. ATRP), we report a simple Cu(0)-RDRP system in the absence of external additives (e.g. reducing agents, enzymes etc.). By simply adjusting the headspace of the reaction vessel, a wide range of monomers, namely acrylates, methacrylates, acrylamides and styrene, can be polymerized in a controlled manner yielding polymers with low dispersities, near-quantitative conversions and high end group fidelity. Significantly, this approach is scalable (~ 125 g), tolerant to elevated temperatures, compatible with both organic and aqueous media and does not rely on external stimuli which may limit the monomer pool. The robustness and versatility of this methodology is further demonstrated by the applicability to a number of other copper mediated techniques including conventional ATRP and light-mediated approaches. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Bolton, Justin; Rzayev, Javid
Polystyrene–poly(methyl methacrylate)–polylactide (PS–PMMA–PLA) triblock bottlebrush copolymer with nearly symmetric volume fractions was synthesized by grafting from a symmetrical triblock backbone and the resulting melt was characterized by scanning electron microscopy and small-angle X-ray scattering. The copolymer backbone was prepared by sequential reversible addition–fragmentation chain transfer (RAFT) polymerization of solketal methacrylate (SM), 2-(bromoisobutyryl)ethyl methacrylate (BIEM), and 5-(trimethylsilyl)-4-pentyn-1-ol methacrylate (TPYM). PMMA branches were grafted by atom transfer radical polymerization from the poly(BIEM) segment, PS branches were grafted by RAFT polymerization from the poly(TPYM) block after installment of the RAFT agents, while PLA side chains were grafted from the deprotected poly(SM) block. Themore » resulting copolymer was found to exhibit a lamellae morphology with a domain spacing of 79 nm. Differential scanning calorimetry analysis indicated that PMMA was preferentially mixing with PS while phase separating from PLA domains.« less
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Rapid removal of aniline from contaminated water by a novel polymeric adsorbent.
Huang, Yunhong; Xu, Yang; He, Qinghua; Cao, Yusheng; Du, Bibai
2014-01-01
Dummy molecularly imprinted polymers (DMIPs) for aniline were synthesized by a thermal polymerization method using acrylamide as a functional monomer, ethylene dimethacrylate as a crosslinker, 2,2-azobisisobutyronitrile as a free radical initiator, acetonitrile as a porogenic solvent, and analogues of aniline, namely sulfadiazine, as the template. The DMIPs that were obtained showed a high affinity to aniline compared to non-imprinted polymers. It was proven that the DMIPs obtained using sulfadiazine as the template were much better than the molecularly imprinted polymers using aniline as the template. The results indicated that the Freundlich model was fit for the adsorption model of DMIP for aniline and the adsorption model of the DMIP for aniline was multilayer adsorption. Furthermore, the results showed that the DMIP synthesized by bulk polymerization could be used as a novel adsorbent for removal of aniline from contaminated water.
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Mussel inspired polymerized P(TA-TETA) for facile functionalization of carbon nanotube
NASA Astrophysics Data System (ADS)
Si, Shuxian; Gao, Tingting; Wang, Junhao; Liu, Qinze; Zhou, Guowei
2018-03-01
This article describes a novel and effective approach for non-covalent modification of carbon nanotube (CNT) via the mussel inspired polymerization of tannic acid (TA) and triethylenetetramine (TETA) and subsequent surface initiated atom transfer radical polymerization (SI-ATRP). Fourier transform infrared spectroscopy (FT-IR), thermo-gravimetric analysis (TGA), transmission electron microscope (TEM), X-ray photoelectron spectroscopy (XPS) and photograph were used to study the successful preparation of polymer brush grafted CNT (CNT-P(TA-TETA)-PDMAEMA) composite as well as the pH-responsive behavior of the composite. Furthermore, by amine protonation and in situ reduction, gold nanoparticles were successfully uploaded and the catalytic property of CNT-P(TA-TETA)-PDMAEMA/Au was investigated. We believe that the surface functionalization strategy can be extended to graphene and other substrates, and the surface properties can be regulated by grafting polymer brushes with different functionalities.
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Poly(ionic liquid) based chemosensors for detection of basic amino acids in aqueous medium
NASA Astrophysics Data System (ADS)
Li, Xinjuan; Wang, Kai; Ma, Nana; Jia, Xianbin
2017-09-01
Naked-eye detection of amino acids in water is of great significance in the field of bio-analytical applications. Herein, polymerized ionic liquids (PILs) with controlled chain length structures were synthesized via reversible addition-fragmentation chain-transfer (RAFT) polymerization and post-quaternization approach. The amino acids recognition performance of PILs with different alkyl chain lengths and molecular weights was evaluated by naked-eye color change and ultraviolet-visible (UV-vis) spectral studies. These PILs were successfully used for highly sensitive and selective detection of Arg, Lys and His in water. The recognition performance was improved effectively with increased molecular weight of PILs. The biosensitivity of the PILs in water was strongly dependent on their aggregation effect and polarization effect. Highly sensitive and selective detection of amino acids was successfully accomplished by introducing positively charged pyridinium moieties and controlled RAFT radical polymerization.
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NASA Astrophysics Data System (ADS)
Cho, Sunghun; Lee, Jun Seop; Jun, Jaemoon; Kim, Sung Gun; Jang, Jyongsik
2014-11-01
This work describes the fabrication of poly(4-styrenesulfonic acid)-doped polyaniline/graphene (PSS-doped PANI/graphene) nanocomposites and their use as sensing elements for hydrogen sulfide (H2S) detection. PSS with a weight-average molecular weight (Mw) of 1.96 × 106 was synthesized using low-temperature free-radical polymerization. The PSS was used as both a doping agent and a binding agent for the polymerization of aniline monomers in a biphasic system (water-chloroform) at -50 °C. The high Mw of PSS resulted in relatively large particle sizes and smooth surfaces of the PSS-doped PANI. These physical characteristics, in turn, resulted in low interparticle resistance and high conductivity. In addition, the PSS allowed homogeneous dispersion of reduced graphene sheets through electrostatic repulsion. The prepared PSS-doped PANI/graphene solutions showed good compatibility with flexible poly(ethylene terephthalate) (PET) substrates, making them suitable for flexible sensor electrodes. Changes in the charge-transport properties, such as protonation level, conjugation length, crystalline structure, and charge-transfer resistance, of the electrode materials were the main factors influencing the electrical and sensor performance of the PSS-doped PANI-based electrodes. PSS-doped PANI/graphene composites containing 30 wt% graphene showed the highest conductivity (168.4 S cm-1) and the lowest minimum detection level (MDL) for H2S gas (1 ppm). This result is consistent with the observed improvements in charge transport in the electrode materials via strong π-π stacking interactions between the PANI and the graphene sheets.This work describes the fabrication of poly(4-styrenesulfonic acid)-doped polyaniline/graphene (PSS-doped PANI/graphene) nanocomposites and their use as sensing elements for hydrogen sulfide (H2S) detection. PSS with a weight-average molecular weight (Mw) of 1.96 × 106 was synthesized using low-temperature free-radical polymerization. The PSS was used as both a doping agent and a binding agent for the polymerization of aniline monomers in a biphasic system (water-chloroform) at -50 °C. The high Mw of PSS resulted in relatively large particle sizes and smooth surfaces of the PSS-doped PANI. These physical characteristics, in turn, resulted in low interparticle resistance and high conductivity. In addition, the PSS allowed homogeneous dispersion of reduced graphene sheets through electrostatic repulsion. The prepared PSS-doped PANI/graphene solutions showed good compatibility with flexible poly(ethylene terephthalate) (PET) substrates, making them suitable for flexible sensor electrodes. Changes in the charge-transport properties, such as protonation level, conjugation length, crystalline structure, and charge-transfer resistance, of the electrode materials were the main factors influencing the electrical and sensor performance of the PSS-doped PANI-based electrodes. PSS-doped PANI/graphene composites containing 30 wt% graphene showed the highest conductivity (168.4 S cm-1) and the lowest minimum detection level (MDL) for H2S gas (1 ppm). This result is consistent with the observed improvements in charge transport in the electrode materials via strong π-π stacking interactions between the PANI and the graphene sheets. Electronic supplementary information (ESI) available: FE-SEM images of PSS-doped PANI/graphene nanocomposites and graphene sheets, FT-IR spectra of PSS with different Mw, XRD patterns of PSS-doped PANI polymerized with different Mw of PSS, FT-IR spectra of GO, RGO, PSS-coated GO, and PSS-coated RGO, fully XPS scanned spectra of PSS-doped PANI/graphene nanocomposites, cyclic voltammogram of PSS-doped PANI/graphene nanocomposites at different scan rates (10 to 50 mV-1), and I-V characteristics of PSS-doped PANI/graphene nanocomposites with a thickness of 5 μm. See DOI: 10.1039/c4nr04413d
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Kitayama, Yukiya; Takeuchi, Toshifumi
2014-10-28
CO2/N2-triggered stability-controllable gold nanoparticles (AuNPs) grafted with poly(2-(diethylamino)ethyl methacrylate) (PDEAEMA) layers (PDEAEMA-g-AuNPs) were synthesized by the surface-initiated atom transfer radical polymerization of DEAEMA with AuNPs bearing the bis[2-(2-bromoisobutyryloxy)undecyl] layer (grafting from method). Extension of the PDEAEMA chain length increased the stability of the PDEAEMA-g-AuNPs in CO2-bubbled water because of the electrosteric repulsion of the protonated PDEAEMA layer. The chain-length-dependent stability of PDEAEMA-g-AuNPs was confirmed by DLS and UV-vis spectra by using the localized surface plasmon resonance property of the AuNPs, where the extinction wavelength was shifted toward shorter wavelength with increasing PDEAEMA chain length. The reversible stability change with the gas stimuli of CO2/N2 was also successfully demonstrated. Finally, the transfer across the immiscible interface between water and organic solvent was successfully demonstrated by N2-triggered insolubilization of PDEAEMA layer on AuNPs in the aqueous phase, leading to the successful collection of AuNPs using organic solvent from the aqueous phase. Our "grafting from" method of reversible stability-controllable AuNPs can be applied to develop advanced materials such as reusable optical AuNP-based nanosensors because the molecular recognition layer can be constructed by two-step polymerization.
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Pathogenic Roles for Fungal Melanins
Jacobson, Eric S.
2000-01-01
Melanins represent virulence factors for several pathogenic fungi; the number of examples is growing. Thus, albino mutants of several genera (in one case, mutated precisely in the melanizing enzyme) exhibit decreased virulence in mice. We consider the phenomenon in relation to known chemical properties of melanin, beginning with biosynthesis from ortho-hydroquinone precursors which, when oxidized enzymatically to quinones, polymerize spontaneously to melanin. It follows that melanizing intermediates are cross-linking reagents; melanization stabilizes the external cell wall against hydrolysis and is thought to determine semipermeability in the osmotic ram (the appressorium) of certain plant pathogens. Polymeric melanins undergo reversible oxidation-reduction reactions between cell wall-penetrating quinone and hydroquinone oxidation states and thus represent polymeric redox buffers; using strong oxidants, it is possible to titrate the melanin on living cells and thereby demonstrate protection conferred by melanin in several species. The amount of buffering per cell approximately neutralizes the amount of oxidant generated by a single macrophage. Moreover, the intermediate oxidation state, the semiquinone, is a very stable free radical and is thought to trap unpaired electrons. We have suggested that the oxidation state of external melanin may be regulated by external Fe(II). An independent hypothesis holds that in Cryptococcus neoformans, an important function of the melanizing enzyme (apart from melanization) is the oxidation of Fe(II) to Fe(III), thereby forestalling generation of the harmful hydroxyl radical from H2O2. Thus, problems in fungal pathogenesis have led to evolving hypotheses regarding melanin functioning. PMID:11023965
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Preparation of heterocyclic block copolymer from perfluoroalkylene oxide alpha, omega-diamidoximes
NASA Technical Reports Server (NTRS)
Ross, L. O.; Rosser, R. W.; Iannone, M. (Inventor)
1979-01-01
Diamidoxime monomers are intermolecularly and thermally condensed to form a heat and chemical resistant polymer containing 1,2,4-oxadiazole linkages with identical bivalent organic radicals or any combination of bivalent organic radicals selected from the group consisting of -(CX(sub 2))p-, wherein P ranges from 2 to 8 when X is fluorine and 2 to 18 when X is hydrogen, chlorine, nitro or aryl; arylene; and an oligometric or polymeric radical prepared by reacting a dicarboxylic acid halide with a fluorinated epoxide and having the formula: (CFY(OCF(sub 2)CFY)sub m)O(CX(sub 2))(sub p)O(CFYCF(sub 2)O)(sub n)CFY wherein Y is flourine or tryifluoromethyl, X is nitro, aryl, hydrogen, chlorine or fluorine, preferably the latter, p ranges from 1 to 18 and m+n ranges from 2 to 7.
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Thongrakard, Ticha; Wiwatwarrapan, Chairat
2016-08-01
This study evaluated the effect of chemical surface treatment using methyl formate-methyl acetate (MF-MA) solution on the tensile bond strength between acrylic denture teeth and auto-polymerized acrylic resin. Seventy maxillary central incisor acrylic denture teeth for each of three different brands (Yamahachi New Ace; Major Dent; Cosmo HXL) were embedded with incisal edge downwards in auto-polymerized resin in polyethylene pipes and ground with silicone carbide paper on their ridge lap surfaces. The teeth of each brand were divided into seven groups (n=10): no surface treatment (control group), MF-MA solution at a ratio of 25:75 (v/v) for 15 seconds, 30 seconds, 60 seconds, 120 seconds, 180 seconds, and MMA for 180 seconds. Auto-polymerized acrylic resin (Unifast Trad) was applied to the ground surface and polymerized in a pressure cooker. A tensile strength test was performed with a universal testing machine. Statistical analysis of the results was performed using two-way analysis of variance (ANOVA) and post-hoc Dunnett T3 test (α=.05). The surface treatment groups had significantly higher mean tensile bond strengths compared with the control group (P<.05) when compared within the same brand. Among the surface treatment groups of each brand, there were no significantly different tensile bond strengths between the MF-MA groups and the MMA 180 second group (P>.05), except for the Yamahachi New Ace MF-MA 180-second group (P<.05). 15-second MF-MA solution can be an alternative chemical surface treatment for repairing a denture base and rebonding acrylic denture teeth with auto-polymerized acrylic resin, for both conventional and cross-linked teeth.
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Barocelli, Elisabetta; Cavazzoni, Andrea; Petronini, Piergiorgio; Mucchino, Claudio; Cantoni, Anna Maria; Leonardi, Fabio; Ventura, Luigi; Barbieri, Stefano; Colombo, Paolo; Fusari, Antonella; Carbognani, Paolo; Rusca, Michele; Sonvico, Fabio
2018-01-01
Background Malignant pleural mesothelioma (MPM) continues to be a distressing tumor due to its aggressive biologic behavior and scanty prognosis. Several therapeutic approaches have been tested both in clinical and preclinical settings, being intrapleural chemotherapy one of the most promising. Some years ago, our interest focused on polymeric films loaded with cisplatin for the adjuvant intrapleural treatment of surgical patients. After in vitro and in vivo studies in a rat recurrence model of MPM, the aim of this study was to evaluate the pharmacokinetics of the polymeric films in a sheep model in view of further studies in a clinical setting. Methods An ovine model was used. Animals were divided into four groups according to pharmacologic treatment: control group (three animals undergoing left pneumonectomy and saline-NaCl solution); intrapleural hyaluronate cisplatin films (HYALCIS) group (six animals undergoing left pneumonectomy and intrapleural application of polymeric films loaded with cisplatin); intrapleural cisplatin solution (six animals undergoing left pneumonectomy and intrapleural application of cisplatin solution); intravenous cisplatin (five animals undergoing left pneumonectomy and intravenous administration of cisplatin solution). The primary objective was the plasmatic and pleural concentration of cisplatin in the treatment groups. The secondary objective was the treatment-related toxicity evaluated by plasmatic analysis performed at prearranged time intervals and histological examinations of tissue samples collected during animal autopsy. Analysis of variance (ANOVA) was used for statistical analysis. Bonferroni correction was applied for comparison between all groups. Results Twenty female Sardinian sheep with a mean weight of 45.1 kg were studied. All animals survived the surgical procedures. The whole surgical procedure had a mean duration of 113 minutes. Cisplatin blood levels obtained from polymeric films application were low during the first 24 hours after the application; then, the cisplatin blood level increased gradually and progressively until it reached significantly higher plasmatic concentrations after 120 hours compared to intrapleural cisplatin solution (P=0.004) and intravenous administration (P=0.001), respectively. Considering cisplatin concentration at 168 hours after the application, animals treated with polymeric films had higher plasmatic values than animals treated with intrapleural cisplatin solution and intravenous cisplatin (P=0.001). Despite the high cisplatin plasmatic concentrations, treatment related-toxicity towards kidneys and liver was comparatively lower compared to the intravenous and intrapleural cisplatin administration and closer to the control levels. Conclusions Polymeric films loaded with cisplatin allowed to reach significantly higher intrapleural and plasmatic cisplatin concentrations compared to intrapleural and intravenous cisplatin solution, providing at the same time, a significant reduction of treatment related toxicity. PMID:29507788
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Ampollini, Luca; Barocelli, Elisabetta; Cavazzoni, Andrea; Petronini, Piergiorgio; Mucchino, Claudio; Cantoni, Anna Maria; Leonardi, Fabio; Ventura, Luigi; Barbieri, Stefano; Colombo, Paolo; Fusari, Antonella; Carbognani, Paolo; Rusca, Michele; Sonvico, Fabio
2018-01-01
Malignant pleural mesothelioma (MPM) continues to be a distressing tumor due to its aggressive biologic behavior and scanty prognosis. Several therapeutic approaches have been tested both in clinical and preclinical settings, being intrapleural chemotherapy one of the most promising. Some years ago, our interest focused on polymeric films loaded with cisplatin for the adjuvant intrapleural treatment of surgical patients. After in vitro and in vivo studies in a rat recurrence model of MPM, the aim of this study was to evaluate the pharmacokinetics of the polymeric films in a sheep model in view of further studies in a clinical setting. An ovine model was used. Animals were divided into four groups according to pharmacologic treatment: control group (three animals undergoing left pneumonectomy and saline-NaCl solution); intrapleural hyaluronate cisplatin films (HYALCIS) group (six animals undergoing left pneumonectomy and intrapleural application of polymeric films loaded with cisplatin); intrapleural cisplatin solution (six animals undergoing left pneumonectomy and intrapleural application of cisplatin solution); intravenous cisplatin (five animals undergoing left pneumonectomy and intravenous administration of cisplatin solution). The primary objective was the plasmatic and pleural concentration of cisplatin in the treatment groups. The secondary objective was the treatment-related toxicity evaluated by plasmatic analysis performed at prearranged time intervals and histological examinations of tissue samples collected during animal autopsy. Analysis of variance (ANOVA) was used for statistical analysis. Bonferroni correction was applied for comparison between all groups. Twenty female Sardinian sheep with a mean weight of 45.1 kg were studied. All animals survived the surgical procedures. The whole surgical procedure had a mean duration of 113 minutes. Cisplatin blood levels obtained from polymeric films application were low during the first 24 hours after the application; then, the cisplatin blood level increased gradually and progressively until it reached significantly higher plasmatic concentrations after 120 hours compared to intrapleural cisplatin solution (P=0.004) and intravenous administration (P=0.001), respectively. Considering cisplatin concentration at 168 hours after the application, animals treated with polymeric films had higher plasmatic values than animals treated with intrapleural cisplatin solution and intravenous cisplatin (P=0.001). Despite the high cisplatin plasmatic concentrations, treatment related-toxicity towards kidneys and liver was comparatively lower compared to the intravenous and intrapleural cisplatin administration and closer to the control levels. Polymeric films loaded with cisplatin allowed to reach significantly higher intrapleural and plasmatic cisplatin concentrations compared to intrapleural and intravenous cisplatin solution, providing at the same time, a significant reduction of treatment related toxicity.
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Laura Berstis; Thomas Elder; Michael Crowley; Gregg T. Beckham
2016-01-01
The recently discovered lignin composed of caffeoyl alcohol monolignols or C-lignin is particularly intriguing given its homogeneous, linear polymeric structure and exclusive benzodioxane linkage between monomers. By virtue of this simplified chemistry, the potential emerges for improved valorization strategies with C-lignin relative to other natural heterogeneous...
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Synthesis and Characterization of Polymer-Metal Nanostructured Membranes
ions creating unique polymer -metal nanostructured membranes. A comprehensive materials characterization study was performed to understand their...fluoropolymers were also investigated. First the polymer -metal nanostructure of Nafion with several counter-ions was studied upon supercritical fluid CO2...processing. Then, novel fluorinated block copolymers were synthesized using atom transfer radical polymerization (ATRP) and their resulting nanostructure was
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Oil-soluble hairy nanoparticles as lubricant additives
DOE Office of Scientific and Technical Information (OSTI.GOV)
Zhao, Bin
Oil-soluble polymer brush-grafted nanoparticles (hairy NPs) were synthesized by surface-initiated atom transfer radical polymerization of lauryl methacrylate from initiator-functionalized silica nanoparticles and used as an additive for polyalphaolefin (PAO) for friction and wear reduction. Addition of 1 wt% hairy nanoparticles into PAO led to significant friction and wear reduction compared with PAO base oil.
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The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...
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Roman, Maxine J; Decker, Eric A; Goddard, Julie M
2016-07-13
Oxidation causes lipid rancidity, discoloration, and nutrient degradation that decrease shelf life of packaged foods. Synthetic additives are effective oxidation inhibitors, but are undesirable to consumers who prefer "clean" label products. The aim of this study was to improve oxidative stability of emulsified foods by a novel nonmigratory polyphenol coated active packaging. Polyphenol coatings were applied to chitosan functionalized polypropylene (PP) by laccase assisted polymerization of catechol and catechin. Polyphenol coated PP exhibited both metal chelating (39.3 ± 2.5 nmol Fe(3+) cm(-2), pH 4.0) and radical scavenging (up to 52.9 ± 1.8 nmol Trolox eq cm(-2)) capacity, resulting in dual antioxidant functionality to inhibit lipid oxidation and lycopene degradation in emulsions. Nonmigratory polyphenol coated PP inhibited ferric iron promoted degradation better than soluble chelators, potentially by partitioning iron from the emulsion droplet interface. This work demonstrates that polyphenol coatings can be designed for advanced material chemistry solutions in active food packaging.
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Frictional properties of the end-grafted polymer layer in presence of salt solution
NASA Astrophysics Data System (ADS)
Raftari, Maryam; Zhang, Zhenyu; Leggett, Graham J.; Geoghegan, Mark
2012-02-01
We have studied the frictional behaviour of grafted poly[2-(dimethylamino)ethyl methacrylate] (PDMAEMA) films using friction force microscopy (FFM). The films were prepared on native oxide-terminated silicon substrates using the technique of atom transfer radical polymerization (ATRP). These brushes had constant grafting density (1.18 nm2), and of a thickness of ˜66 nm, as measured by ellipsometry. We show that single asperity contact mechanics (Johnson-Kendall-Roberts (JKR) and Derjaguin-M"uller-Toporov (DMT) models) as well as a linear (Amontons) relation between applied load and frictional load all apply to these systems depending on the concentration of salt and the nature of the FFM probe. Measurements were made using gold-coating and polymer functionalized silicon nitride triangular probes. Polymer functionalized probe included growth the PDMAEMA with same method on tips. The frictional behaviour are investigated between PDMAEMA and gold coated and PDMAEMA tips immersed in different concentrations of KCl, KBr and KI.
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Effect of synthesis parameters on polymethacrylic acid xerogel structures and equilibrium swelling
NASA Astrophysics Data System (ADS)
Panić, V.; Jovanović, J.; Adnadjević, B.; Velicković, S.
2009-09-01
Hydrogels based on crosslinked polymethacrylic acid were synthesized via free-radical polymerization in aqueous solution, using N,N'-methylene bisacrylamide as a crosslinking agent and 2,2'-azobis-[2-(2-imidazolin-2-yl)propane] dihydrochloride as an initiator. The influence of the reaction parameters (the neutralization degree of methacrylic acid and the initial monomer concentration) on the equilibrium swelling degree, the swelling kinetic parameters and the basic structural properties of xerogels was investigated. The change of synthesis parameters leads to the change of the basic structural parameters of xerogel, as well as the equilibrium swelling degree and the initial swelling rate of the hydrogels. It is found that there are power form relationships between the equilibrium swelling degree, the initial swelling rate and the structural xerogel’s properties and the change of the neutralization degree of monomer, i.e. the monomer concentration. The examined correlations proved that the crosslinking density is the crucial parameter which determines all the other investigated structural and swelling parameters.
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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.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Kaetsu, I.; Ito, A.; Hayashi, K.
1973-08-01
The effect of temperature and composition on the inflection point in the time-conversion curve and the saturated conversion was investigated in the gamma -radio-induced radical polymerization of binary systems consisting of a glass- forming monomer and a solvent. In the polymerization of completely homogeneous systems such as glycidyl methacrylate (GMA) -triacetin and hydroxyethyl methacrylate (HEMA) --propylene glycol systems, the time-conversion curve has an inflection point at polymerization temperatures between T/sub vm/(T/sub v/ of monomer system) and T/sub vp/ (T/sub v/ of polymer system). Such conversions at the inflection point changed monotonically between 0 and 100% in this temperature range. T/submore » v/ was found to be 30 to 50 deg C higher than T/sub g/ (glass transition temperature) and a monotonic function of composition (monomer -- polymer -- solvent). The acceleration effect continued to 100% conversion above T/sub vp/, and no acceleration effect was observed below T/sub vm/. The saturated conversion in homogeneous systems changed monotonically between 0 and 100% for polymerization temperatures between T/sub gm/ (T/sub g/ of monomer system) and T/sub gp/(T of polymer system). T/sub g/ was also a monotonic function of composition. No saturation in conversion was observed above T/sub gp/ , and no polymerization occurred below T/sub gm/. In the polymerization of completely heterogeneous systems such as HEMA-dioctyl phthalate, no acceleration effect was observed at any temperature and composition. The saturated conversion was 100% sbove T/sub g/ of pure HEMA, and no polymerization occurred below this temperature in this system. (auth)« less
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Nita, Loredana Elena; Chiriac, Aurica P; Neamtu, Iordana; Bercea, Maria
2010-03-01
The interpenetrated macromolecular chains complexation between poly(aspartic acid) and poly(vinyl alcohol) in aqueous solution it was investigated. The interpolymer complexation process was evaluated through dynamic rheology. The aspects concerning the stability of the tested homopolymers and the prepared interpolymeric complex there were achieved from the evaluation of the aqueous solutions'zeta potential and also by determining the pH influence upon the zeta potential and the conductivity. The data obtained through the rheological dynamic measurements were correlated with the composition of the polymeric mixture, the dependence of zeta potential and conductivity. The study reveals the conditions for the formation of interpenetrated polymeric complex as being a ratio of 70wt.% PAS to 30wt.% PVA at 22 degrees C and 50/50 PAS/PVA ratio at 37 degrees C temperature. From the pH influence upon the zeta potential values it was evidenced the PAS aqueous solution does not reach the isoelectric point. At the same time, PVA solution and the complex PAS/PVA reaches the isoelectric point at strongly acid pH. The better stability of PAS, PVA and their mixture in solution is recorded in the alkaline domain (7.5
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Plasma-induced graft-polymerization of polyethylene glycol acrylate on polypropylene substrates
NASA Astrophysics Data System (ADS)
Zanini, S.; Orlandi, M.; Colombo, C.; Grimoldi, E.; Riccardi, C.
2009-08-01
A detailed study of argon plasma-induced graft-polymerization of polyethylene glycol acrylate (PEGA) on polypropylene (PP) substrates (membranes and films) is presented. The process consists of four steps: (a) plasma pre-activation of the PP substrates; (b) immersion in a PEGA solution; (c) argon plasma-induced graft-polymerization; (d) washing and drying of the samples. Influence of the solution and plasma parameters on the process efficiency evaluated in terms of amount of grafted polymer, coverage uniformity and substrates wettability, are investigated. The plasma-induced graft-polymerization of PEGA is then followed by sample weighting, water droplet adsorption time and contact angle measurements, attenuated total reflection infrared spectroscopy (ATR-IR), X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM) analyses. The stability of the obtained thin films was evaluated in water and in phosphate buffer saline (PBS) at 37 °C. Results clearly indicates that plasma-induced graft-polymerization of PEGA is a practical methodology for anti-fouling surface modification of materials.
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NASA Astrophysics Data System (ADS)
Matsumoto, Takuro; Miyazaki, Tetsuo; Kosugi, Yoshio; Kumada, Takayuki; Koyama, Sinji; Kodama, Seiji; Watanabe, Masami
1997-05-01
When golden hamster embryo (GHE) cells or concentrated albumin solution (0.1 kg dm -3) that is a model system of cells is irradiated with γ-rays at 295 K, organic radicals produced can be observed by ESR. The organic radicals survive at both 295 and 310 K for such a long time as 20 h. The long-lived radicals in GHE cells and the albumin solution react with vitamin C by the rate constants of 0.007 dm 3 mol -1 s -1 and 0.014 dm 3 mol -1 s -1, respectively. The long-lived radicals in human cells cause gene mutation, which is suppressed by addition of vitamin C. The isotope effect on the rate constant ( k) for the reaction of the long-lived radicals and vitamin C has been studied in the albumin solution by use of protonated vitamin C and deuterated vitamin C. The isotope effect ( kH/ kD) was more than 20 ≈ 50 and was interpreted in terms of tunneling reaction.
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NASA Astrophysics Data System (ADS)
Takai, Eisuke; Ikawa, Satoshi; Kitano, Katsuhisa; Kuwabara, Junpei; Shiraki, Kentaro
2013-07-01
Sterilization of certain infected areas of the human body surface is necessary for dental and surgical therapies. Because the blood is filled with body fluid, sterilization in solution is essential. In vitro solution sterilization has been successively carried out using a combination of low-temperature atmospheric-pressure plasma and the reduced pH method, where the solution is sufficiently acidic. Here, we show the molecular mechanism of such plasma sterilization in solution based on microbiology. Three kinds of bacteria were inactivated by plasma treatment under various pH conditions. The theoretical and experimental models revealed that the sterilization was characterized by the concentration of hydroperoxy radicals (HOO·), which were dependent on the pH value. Bacterial inactivation rates were proportional to the HOO· concentrations calculated by the theoretical model. To evaluate the penetration of radicals into the cell membrane, a bacterial model using dye-included micelles was used. Decolouration rates of the model were also in proportion with the calculated HOO· concentrations. These results indicate that the key species for plasma sterilization were hydroperoxy radicals. More importantly, the high permeation of hydroperoxy radicals into the cell membrane plays a key role for efficient bactericidal inactivation using the reduced pH method.
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2018-01-01
High molecular weight water-soluble polymers are widely used as flocculants or thickeners. However, synthesis of such polymers via solution polymerization invariably results in highly viscous fluids, which makes subsequent processing somewhat problematic. Alternatively, such polymers can be prepared as colloidal dispersions; in principle, this is advantageous because the particulate nature of the polymer chains ensures a much lower fluid viscosity. Herein we exemplify the latter approach by reporting the convenient one-pot synthesis of high molecular weight poly(glycerol monomethacrylate) (PGMA) via the reversible addition–fragmentation chain transfer (RAFT) aqueous emulsion polymerization of a water-immiscible protected monomer precursor, isopropylideneglycerol methacrylate (IPGMA) at 70 °C, using a water-soluble poly(glycerol monomethacrylate) (PGMA) chain transfer agent as a steric stabilizer. This formulation produces a low-viscosity aqueous dispersion of PGMA–PIPGMA diblock copolymer nanoparticles at 20% solids. Subsequent acid deprotection of the hydrophobic core-forming PIPGMA block leads to particle dissolution and affords a viscous aqueous solution comprising high molecular weight PGMA homopolymer chains with a relatively narrow molecular weight distribution. Moreover, it is shown that this latex precursor route offers an important advantage compared to the RAFT aqueous solution polymerization of glycerol monomethacrylate since it provides a significantly faster rate of polymerization (and hence higher monomer conversion) under comparable conditions. PMID:29805184
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Method of cross-linking polyvinyl alcohol and other water soluble resins
NASA Technical Reports Server (NTRS)
Phillipp, W. H.; May, C. E.; Hsu, L. C.; Sheibley, D. W. (Inventor)
1980-01-01
A self supporting sheet structure comprising a water soluble, noncrosslinked polymer such as polyvinyl alcohol which is capable of being crosslinked by reaction with hydrogen atom radicals and hydroxyl molecule radicals is contacted with an aqueous solution having a pH of less than 8 and containing a dissolved salt in an amount sufficient to prevent substantial dissolution of the noncrosslinked polymer in the aqueous solution. The aqueous solution is then irradiated with ionizing radiation to form hydrogen atom radicals and hydroxyl molecule radicals and the irradiation is continued for a time sufficient to effect crosslinking of the water soluble polymer to produce a water insoluble polymer sheet structure. The method has particular application in the production of battery separators and electrode envelopes for alkaline batteries.
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An insight into polymerization-induced self-assembly by dissipative particle dynamics simulation.
Huang, Feng; Lv, Yisheng; Wang, Liquan; Xu, Pengxiang; Lin, Jiaping; Lin, Shaoliang
2016-08-14
Polymerization-induced self-assembly is a one-pot route to produce concentrated dispersions of block copolymer nano-objects. Herein, dissipative particle dynamics simulations with a reaction model were employed to investigate the behaviors of polymerization-induced self-assembly. The polymerization kinetics in the polymerization-induced self-assembly were analyzed by comparing with solution polymerization. It was found that the polymerization rate enhances in the initial stage and decreases in the later stage. In addition, the effects of polymerization rate, length of macromolecular initiators, and concentration on the aggregate morphologies and formation pathway were studied. The polymerization rate and the length of the macromolecular initiators are found to have a marked influence on the pathway of the aggregate formations and the final structures. Morphology diagrams were mapped correspondingly. A comparison between simulation results and experimental findings is also made and an agreement is shown. This work can enrich our knowledge about polymerization-induced self-assembly.
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1993-09-12
the liquid -air interface could be monitored by changes in the surface area. Deposition of monolayers by Langmuir - Blodgett technique is possible and...polymerization product from the LB trough in chloroform solution. Figure 10 Langmuir - Blodgett transfer of poly (3-hexadecyl pyrrole) onto hydrophobized glass... Langmuir - Blodgett Techniques, 2: The Polymerization of Monolayers of 3-Substituted Pyrroles by W.M. Sigmund, C. Marestin, S. Keil, H. Zhou and R.S
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Supramolecular intermediates in the synthesis of polymeric carbon nitride from melamine cyanurate
DOE Office of Scientific and Technical Information (OSTI.GOV)
Dante, Roberto C., E-mail: rcdante@yahoo.com; Sánchez-Arévalo, Francisco M.; Chamorro-Posada, Pedro
The adduct of melamine and cyanuric acid (MCA) was used in past research to produce polymeric carbon nitride and precursors. The reaction yield was considerably incremented by the addition of sulfuric acid. The polymeric carbon nitride formation occurs around 450 °C at temperatures above the sublimation of the adduct components, which occurs around 400 °C. In this report the effect of sulfuric acid on MCA was investigated. It was found that the MCA rosette supramolecular channel structures behave as a solid solvent able to host small molecules, such as sulfuric acid, inside these channels and interact with them. Therefore, themore » sulfuric acid effect was found to be close to that of a solute that causes a temperature increment of the “solvent sublimation” enough to allowing the formation of polymeric carbon nitride to occur. Sulfate ions are presumably hosted in the rosette channels of MCA as shown by simulations. - Graphical abstract: The blend of melamine cyanurate and sulfuric acid behaves like a solution so that melamine cyanurate decomposition is shifted to temperatures high enough to react and form polymeric carbon nitride. - Highlights: • The adduct of melamine and cyanuric acid behaves as a solid solvent. • The blend of sulfuric acid and melamine cyanurate behaves like a solution. • Melamine cyanurate decomposition is shifted to higher temperatures by sulfuric acid. • The formation of polymeric carbon nitride occurs for these higher temperatures.« less
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Standard Electrode Potentials Involving Radicals in Aqueous Solution: Inorganic Radicals
DOE Office of Scientific and Technical Information (OSTI.GOV)
Armstrong, David A.; Huie, Robert E.; Koppenol, Willem H.
2015-12-01
Recommendations are made for standard potentials involving select inorganic radicals in aqueous solution at 25 °C. These recommendations are based on a critical and thorough literature review and also by performing derivations from various literature reports. The recommended data are summarized in tables of standard potentials, Gibbs energies of formation, radical pK a’s, and hemicolligation equilibrium constants. In all cases, current best estimates of the uncertainties are provided. An extensive set of Data Sheets is appended that provide original literature references, summarize the experimental results, and describe the decisions and procedures leading to each of the recommendations
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NASA Astrophysics Data System (ADS)
Samovich, S. N.; Brinkevich, S. D.; Shadyro, O. I.
2013-01-01
Benzaldehyde and its derivatives efficaciously oxidize in aqueous solutions α-hydroxyl-containing carbon-centered radicals (α-HCR) of various structures, suppressing thereby the radical recombination and fragmentation reactions. The compounds containing cinnamic moieties are capable of adding α-hydroxyethyl radicals (α-HER) to the carbon-carbon double bonds conjugated with the aromatic system to form molecular products identifiable by mass spectrometry. On radiolysis of aqueous ethanol solutions, reduction of α-HER by aromatic alcohols and acids has been shown to proceed via formation of their adducts with hydrated electron species.
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Enhanced protein retention on poly(caprolactone) via surface initiated polymerization of acrylamide
NASA Astrophysics Data System (ADS)
Ma, Yuhao; Cai, Mengtan; He, Liu; Luo, Xianglin
2016-01-01
To enhance the biocompatibility or extend the biomedical application of poly(caprolactone) (PCL), protein retention on PCL surface is often required. In this study, poly(acrylamide) (PAAm) brushes were grown from PCL surface via surface-initiated atom transfer radical polymerization (SI-ATRP) and served as a protein-capturing platform. Grafted PAAm was densely packed on surface and exhibited superior protein retention ability. Captured protein was found to be resistant to washing under detergent environment. Furthermore, protein structure after being captured was investigated by circular dichroism (CD) spectroscopy, and the CD spectra verified that secondary structure of captured proteins was maintained, indicating no denaturation of protein happened for retention process.
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Figueiredo, Ana R P; Figueiredo, Andrea G P R; Silva, Nuno H C S; Barros-Timmons, Ana; Almeida, Adelaide; Silvestre, Armando J D; Freire, Carmen S R
2015-06-05
Antimicrobial bacterial cellulose/poly(2-aminoethyl methacrylate) (BC/PAEM) nanocomposites were prepared by in situ radical polymerization of 2-aminoethyl methacrylate, using variable amounts of N,N-methylenebis(acrylamide) (MBA) as cross-linker. The obtained nanocomposites were characterized in terms of their structure, morphology, thermal stability, mechanical properties and antibacterial activity. The ensuing composite membranes were significantly more transparent than those of pure BC and showed improved thermal and mechanical properties. The antibacterial activity of the obtained nanocomposites was assessed towards a recombinant bioluminescent Escherichia coli and only the non-crosslinked nanocomposite (BC/PAEM) proved to have antibacterial activity. Copyright © 2015 Elsevier Ltd. All rights reserved.
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Reddy, G. Suresh Kumar; Greenhalgh, Kerriann; Ramaraju, Praveen; Abeylath, Sampath C.; Jang, Seyoung; Dickey, Sonja; Lim, Daniel V.
2007-01-01
This report describes the preparation of antibacterially-active emulsified polyacrylate nanoparticles in which a penicillin antibiotic is covalently conjugated onto the polymeric framework. These nanoparticles were prepared in water by emulsion polymerization of an acrylated penicillin analogue pre-dissolved in a 7:3 (w:w) mixture of butyl acrylate and styrene in the presence of sodium dodecyl sulfate (surfactant) and potassium persulfate (radical initiator). Dynamic light scattering analysis and atomic force microscopy images show that the emulsions contain nanoparticles of approximately 40 nm in diameter. The nanoparticles have equipotent in vitro antibacterial properties against methicillin-susceptible and methicillin-resistant forms of Staphylococcus aureus and indefinite stability towards β-lactamase. PMID:17420125
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Siddiqi, M.A.; Bothe, E.
The yields of single- and double-strand breaks (SSB and DSB) in calf thymus DNA, after /sup 60/Co gamma irradiation in dilute aqueous solution, have been determined via molecular weight measurements using a low-angle laser light scattering technique. The irradiations were administered to N/sub 2/O-containing solutions of DNA in the absence and presence of oxygen and with different concentrations of the OH radical scavengers phenol, tertiary butanol, and methanol. OH radicals were found to produce SSB linearly with dose with a G value of 55 nmol J-1 and 54 nmol J-1 in deoxygenated and oxygenated solutions, respectively. DSB were formed accordingmore » to a linear-quadratic dose relationship and the G value of linearly formed DSB were GDSB alpha(r.t.) = 3.5 nmol J-1 in deoxygenated and 3.2 nmol J-1 in oxygenated solution. The ratio of GSSB/GDSB alpha(r.t.) = gamma of 19 +/- 6 was independent of the scavenger concentration in the case of tertiary butanol and methanol-containing solutions. GDSB alpha(r.t.) is interpreted to result from a radical site transferred from a sugar moiety of the cleaved strand to the complementary intact strand. This process of radical transfer and subsequent cleavage of the second strand occurs with a probability of about 6 +/- 2% in the presence of oxygen at all scavenger concentrations studied. These data on scavenging capacity on GDSB alpha(r.t.) suggest that the double-strand breakage produced via radical transfer remains higher than that resulting from direct effect, up to scavenging capacities of about 10(9) s-1.« less
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Uchiyama, Hidefumi; Zhao, Qing-Li; Hassan, Mariame Ali; Andocs, Gabor; Nojima, Nobuyuki; Takeda, Keigo; Ishikawa, Kenji; Hori, Masaru; Kondo, Takashi
2015-01-01
Electron paramagnetic resonance (EPR)-spin trapping and flow cytometry were used to identify free radicals generated using argon-cold atmospheric plasma (Ar-CAP) in aqueous solutions and intracellularly in comparison with those generated by X-irradiation. Ar-CAP was generated using a high-voltage power supply unit with low-frequency excitation. The characteristics of Ar-CAP were estimated by vacuum UV absorption and emission spectra measurements. Hydroxyl (·OH) radicals and hydrogen (H) atoms in aqueous solutions were identified with the spin traps 5,5-dimethyl-1-pyrroline N-oxide (DMPO), 3,3,5,5-tetramethyl-1-pyrroline-N-oxide (M4PO), and phenyl N-t-butylnitrone (PBN). The occurrence of Ar-CAP-induced pyrolysis was evaluated using the spin trap 3,5-dibromo-4-nitrosobenzene sulfonate (DBNBS) in aqueous solutions of DNA constituents, sodium acetate, and L-alanine. Human lymphoma U937 cells were used to study intracellular oxidative stress using five fluorescent probes with different affinities to a number of reactive species. The analysis and quantification of EPR spectra revealed the formation of enormous amounts of ·OH radicals using Ar-CAP compared with that by X-irradiation. Very small amounts of H atoms were detected whereas nitric oxide was not found. The formation of ·OH radicals depended on the type of rare gas used and the yield correlated inversely with ionization energy in the order of krypton > argon = neon > helium. No pyrolysis radicals were detected in aqueous solutions exposed to Ar-CAP. Intracellularly, ·OH, H2O2, which is the recombination product of ·OH, and OCl- were the most likely formed reactive oxygen species after exposure to Ar-CAP. Intracellularly, there was no practical evidence for the formation of NO whereas very small amounts of superoxides were formed. Despite the superiority of Ar-CAP in forming ·OH radicals, the exposure to X-rays proved more lethal. The mechanism of free radical formation in aqueous solutions and an intracellular milieu is discussed.
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Uchiyama, Hidefumi; Zhao, Qing-Li; Hassan, Mariame Ali; Andocs, Gabor; Nojima, Nobuyuki; Takeda, Keigo; Ishikawa, Kenji; Hori, Masaru; Kondo, Takashi
2015-01-01
Electron paramagnetic resonance (EPR)-spin trapping and flow cytometry were used to identify free radicals generated using argon-cold atmospheric plasma (Ar-CAP) in aqueous solutions and intracellularly in comparison with those generated by X-irradiation. Ar-CAP was generated using a high-voltage power supply unit with low-frequency excitation. The characteristics of Ar-CAP were estimated by vacuum UV absorption and emission spectra measurements. Hydroxyl (·OH) radicals and hydrogen (H) atoms in aqueous solutions were identified with the spin traps 5,5-dimethyl-1-pyrroline N-oxide (DMPO), 3,3,5,5-tetramethyl-1-pyrroline-N-oxide (M4PO), and phenyl N-t-butylnitrone (PBN). The occurrence of Ar-CAP-induced pyrolysis was evaluated using the spin trap 3,5-dibromo-4-nitrosobenzene sulfonate (DBNBS) in aqueous solutions of DNA constituents, sodium acetate, and L-alanine. Human lymphoma U937 cells were used to study intracellular oxidative stress using five fluorescent probes with different affinities to a number of reactive species. The analysis and quantification of EPR spectra revealed the formation of enormous amounts of ·OH radicals using Ar-CAP compared with that by X-irradiation. Very small amounts of H atoms were detected whereas nitric oxide was not found. The formation of ·OH radicals depended on the type of rare gas used and the yield correlated inversely with ionization energy in the order of krypton > argon = neon > helium. No pyrolysis radicals were detected in aqueous solutions exposed to Ar-CAP. Intracellularly, ·OH, H2O2, which is the recombination product of ·OH, and OCl- were the most likely formed reactive oxygen species after exposure to Ar-CAP. Intracellularly, there was no practical evidence for the formation of NO whereas very small amounts of superoxides were formed. Despite the superiority of Ar-CAP in forming ·OH radicals, the exposure to X-rays proved more lethal. The mechanism of free radical formation in aqueous solutions and an intracellular milieu is discussed. PMID:26318000
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Primary radical yields in pulse irradiated alkaline aqueous solution
NASA Technical Reports Server (NTRS)
Fielden, E. M.; Hart, E. J.
1969-01-01
Primary radical yields of hydrated electrons, H atoms, and OH radicals are determined by measuring hydrated electron formation following a 4 microsecond pulse of X rays. The pH dependence of free radical yields beyond pH 12 is determined by observation of the hydrated electrons.
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Liu, Xianli; Xu, Dong; Wu, Feng; Liao, Zhenhuan; Liu, Jiantong; Deng, Nansheng
2004-03-01
Under a high-pressure mercury lamp (HPML) and using an exposure time of 4 h, the photoproduction of hydroxyl radicals (*OH) could be induced in an aqueous solution containing humic acid (HA). Hydroxyl radicals were determined by high-performance liquid chromatography using benzene as a probe. The results showed that *OH photoproduction increased from 1.80 to 2.74 microM by increasing the HA concentration from 10 to 40 mg L(-1) at an exposure time of 4 h (pH 6.5). Hydroxyl radical photoproduction in aqueous solutions of HA containing algae was greater than that in the aqueous solutions of HA without algae. The photoproduction of *OH in the HA solution with Fe(III) was greater than that of the solution without Fe(III) at pH ranging from 4.0 to 8.0. The photoproduction of *OH in HA solution with algae with or without Fe(III) under a 250 W HPML was greater than that under a 125 W HPML. The photoproduction of *OH in irradiated samples was influenced by the pH. The results showed that HPML exposure for 4 h in the 4-8 pH range led to the highest *OH photoproduction at pH 4.0.
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Wang, Wenwen; Wang, Weiyu; Li, Hui; ...
2015-01-14
In this study, high molecular weight “comb-shaped” graft copolymers, poly(isoprene-g-styrene), with polyisoprene as the backbone and polystyrene as side chains, were synthesized via free radical emulsion polymerization by copolymerization of isoprene with a polystyrene macromonomer synthesized using anionic polymerization. A small amount of toluene was used in order to successfully disperse the macromonomer. Both a redox and thermal initiation system were used in the emulsion polymerization, and the latex particle size and distribution were investigated by dynamic light scattering. The structural characteristics of the macromonomer and comb graft copolymers were investigated through use of size exclusion chromatography, spectroscopy, microscopy, thermalmore » analysis, and rheology. While the macromonomer was successfully copolymerized to obtain the desired multigraft copolymers, small amounts of unreacted macromonomer remained in the products, reflecting its reduced reactivity due to steric effects. Nevertheless, the multigraft copolymers obtained were very high in molecular weight (5–12 × 10 5 g/mol) and up to 10 branches per chain, on average, could be incorporated. A material incorporating 29 wt% polystyrene exhibits a disordered microphase separated morphology and elastomeric properties. As a result, these materials show promise as new, highly tunable, and potentially low cost thermoplastic elastomers.« less
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Facile preparation of a cationic poly(amino acid) vesicle for potential drug and gene co-delivery
NASA Astrophysics Data System (ADS)
Ding, Jianxun; Xiao, Chunsheng; He, Chaoliang; Li, Mingqiang; Li, Di; Zhuang, Xiuli; Chen, Xuesi
2011-12-01
A novel pH-responsive poly(amino acid) grafted with oligocation was prepared through the combination of ring-opening polymerization (ROP) and subsequent atom transfer radical polymerization (ATRP). Firstly, poly(γ-2-chloroethyl-L-glutamate) (PCELG) with a pendent 2-chloroethyl group was synthesized through ROP of γ-2-chloroethyl-L-glutamate N-carboxyanhydride (CELG NCA) using n-hexylamine as the initiator. Then, PCELG was used to initiate the ARTP of 2-aminoethyl methacrylate hydrochloride (AMA), yielding poly(L-glutamate)-graft-oligo(2-aminoethyl methacrylate hydrochloride) (PLG-g-OAMA). The pKa of PLG-g-OAMA was 7.3 established by the acid-base titration method. The amphiphilic poly(amino acid) could directly self-assemble into a vesicle in PBS. The vesicle was characterized by TEM and DLS. Hydrophilic DOX·HCl was loaded into the hollow core of the vesicle. The in vitro release behavior of DOX·HCl from the vesicle in PBS could be adjusted by the solution pH. In vitro cell experiments revealed that the vesicle could reduce the toxicity of the DOX·HCl. In addition, the preliminary gel retardation assay displayed that PLG-g-OAMA could efficiently bind DNA at a PLG-g-OAMA/DNA weight ratio of 0.3 or above, indicating its potential use as a gene carrier. More in-depth studies of the PLG-g-OAMA vesicle for drug and gene co-delivery in vitro and in vivo are in progress.
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NASA Astrophysics Data System (ADS)
Suk, Jungdon; Lee, Yu Hwa; Kim, Do Youb; Kim, Dong Wook; Cho, Song Yun; Kim, Ji Man; Kang, Yongku
2016-12-01
We developed highly promising solid polymer electrolytes (SPEs) based on a novel cross-linker containing star-shaped phosphazene with poly(ethylene oxide) (PEO) branches with very high ionic conductivity (7.6 × 10-4 S cm-1), improved mechanical stability, and good electrochemical stability for all-solid-state lithium batteries. In particular, allyl groups were introduced at the ends of the cross-linker in order to overcome the easy self-polymerization of existing cross-linking acrylate end groups. A novel semi-interpenetrating network (semi-IPN) SPE was prepared by in-situ radical polymerization of a precursor solution containing lithium salt, poly(ethylene glycol) dimethyl ether as a plasticizer, and a mixture of pentaerythritol tetrakis(3-mercaptopropionate) and a synthesized hexakis(allyloxy)cyclotriphosphazene (thiol-ene PAL) as the cross-linker. Batteries employing LiFePO4 as the cathode, lithium foil as the anode, and the SPE thin film as the electrolyte were assembled and tested. At ambient temperature, the initial discharge capacity was 147 mAh/g at 0.1 °C and 132 mAh/g at 0.5 °C, and 97% of the capacity was retained at the 100th cycle. All-solid-state pouch-package lithium cells assembled with the SPEs exhibited stable electrochemical performance, even under a severely wrinkled state. These outstanding properties of SPEs based on thiol-ene PAL demonstrate feasibility for practical battery applications with improved reliability and safety.
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Side reactions of nitroxide-mediated polymerization: N-O versus O-C cleavage of alkoxyamines.
Hodgson, Jennifer L; Roskop, Luke B; Gordon, Mark S; Lin, Ching Yeh; Coote, Michelle L
2010-09-30
Free energies for the homolysis of the NO-C and N-OC bonds were compared for a large number of alkoxyamines at 298 and 393 K, both in the gas phase and in toluene solution. On this basis, the scope of the N-OC homolysis side reaction in nitroxide-mediated polymerization was determined. It was found that the free energies of NO-C and N-OC homolysis are not correlated, with NO-C homolysis being more dependent upon the properties of the alkyl fragment and N-OC homolysis being more dependent upon the structure of the aminyl fragment. Acyclic alkoxyamines and those bearing the indoline functionality have lower free energies of N-OC homolysis than other cyclic alkoxyamines, with the five-membered pyrrolidine and isoindoline derivatives showing lower free energies than the six-membered piperidine derivatives. For most nitroxides, N-OC homolysis is normally favored above NO-C homolysis only when a heteroatom that is α to the NOC carbon center stabilizes the NO-C bond and/or the released alkyl radical is not sufficiently stabilized. As part of this work, accurate methods for the calculation of free energies for the homolysis of alkoxyamines were determined. Accurate thermodynamic parameters to within 4.5 kJ mol(-1) of experimental values were found using an ONIOM approximation to G3(MP2)-RAD combined with PCM solvation energies at the B3-LYP/6-31G(d) level.