IRIS Toxicological Review of Vinyl Chloride (Final Report ...

EPA Pesticide Factsheets

EPA is announcing the release of the final report, Toxicological Review of Vinyl Chloride: in support of the Integrated Risk Information System (IRIS). The updated Summary for Vinyl Chloride and accompanying Quickview have also been added to the IRIS Database. Common synonyms of vinyl chloride (VC) include chloroethene, chloroethylene, ethylene monochloride, and monochloroethene. VC is a synthetic chemical used as a chemical intermediate in the polymerization of polyvinyl chloride.

Synthesis and polymerization of vinyl triazolium ionic liquids

DOEpatents

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.

Biomedical applications of stereoregular poly(vinyl alcohol) micro- and nanoparticles

NASA Astrophysics Data System (ADS)

Lyoo, Won Seok; Kim, Joon Ho; Kim, Sam Soo; Ghim, Han Do

2002-11-01

Syndiotactic poly(vinyl alcohol) (PVA)/poly(vinyl pivalate/vinyl acetate) (P(VPi/VAc)) and atactic PVA/PVAc micro- and nanoparticles with skin/core structure have been prepared by heterogeneous saponification of P(VPi/VAc) and PVAc micro- and nanoparticles. Especially, to prepare P(VPi/VAc) and PVAc microparticles having various particle sizes and uniform particle size distribution, vinyl pivalate (VPi)/vinyl acetate (VAc) and VAc were suspension-polymerized using a low-temperature initiator, 2,2"-azobis(2,4-dimethylvaleronitrile). P(VPi/VAc) particles are promising precursor of stereoregular PVA embolic materials which can be introduced through catheters in the management of gastrointestinal bleeders, arteriovenous malformations, hemangiomas, and traumatic rupture of blood vessels. Monodisperse and/or nearly monodisperse P(VPi/VAc) and PVAc microparticles with various particle diameters were obtained by controlling suspension polymerization conditions. Monodisperse P(VPi/VAc) and PVAc microparticles having various particle sizes were partially saponified in the heterogeneous system. PVA/P(VPi/VAc) and PVA/PVAc microparticles having various tacticity and degree of saponification were produced by controlling various polymerization and saponification conditions. The coating of stereoregular PVA micro- and nanoparticles for drug release experiments was conducted with the strepo-avidin-alkaline phosphatase conjugate in variable conditions of pH value, coating buffer, and reaction temperature. Protein-coated syndiotactic PVA micro- and nanoparticles, which does not crosslinking, were more superior to controllability of drug release, durability, and dimensional stability to water and blood than atactic one.

Antithrombogenic and antibiotic composition and methods of preparation thereof

DOEpatents

Hermes, R.E.

1990-04-17

Antithrombogenic and antibiotic composition of matter and method of preparation are disclosed. A random copolymer of a component of garlic and a biocompatible polymer has been prepared and found to exhibit antithrombogenic and antibiotic properties. Polymerization occurs selectively at the vinyl moiety in 2-vinyl-4H-1,3-dithiin when copolymerized with N-vinyl pyrrolidone. 4 figs.

Antithrombogenic and antibiotic composition and methods of preparation thereof

DOEpatents

Hermes, Robert E.

1990-01-01

Antithrombogenic and antibiotic composition of matter and method of preparation thereof. A random copolymer of a component of garlic and a biocompatible polymer has been prepared and found to exhibit antithrombogenic and antibiotic properties. Polymerization occurs selectively at the vinyl moiety in 2-vinyl-4H-1,3-dithiin when copolymerized with N-vinyl pyrrolidone.

Vinyl Monomers Double as UV Stabilizers: 179th ACS Meeting Houston.

ERIC Educational Resources Information Center

Chemical and Engineering News, 1980

1980-01-01

Synthesis and polymerization of vinyl monomers that double as stabilizers against degradation of plastics by ultraviolet light has been accomplished. Potential applications include protection of photovoltaic cells in solar power plants. (Author/RE)

Polyethylenimine-immobilized core-shell nanoparticles: synthesis, characterization, and biocompatibility test.

PubMed

Ratanajanchai, Montri; Soodvilai, Sunhapas; Pimpha, Nuttaporn; Sunintaboon, Panya

2014-01-01

Herein, we prepared PEI-immobilized core-shell particles possessing various types of polymer cores via a visible light-induced surfactant-free emulsion polymerization (SFEP) of three vinyl monomers: styrene (St), methyl methacrylate (MMA), and 2-hydroxyethyl methacrylate (HEMA). An effect of monomers on the polymerization and characteristics of resulting products was investigated. Monomers with high polarity can provide high monomer conversion, high percentage of grafted PEI, stable particles with uniform size distribution but less amino groups per particles. All prepared nanoparticles exhibited a core-shell nanostructure, containing PEI on the shell with hydrodynamic size around 140-230nm. For in-vitro study in Caco-2 cells, we found that the incorporation of PEI into these core-shell nanoparticles can significantly reduce its cytotoxic effect and also be able to internalized within the cells. Accordingly, these biocompatible particles would be useful for various biomedical applications, including gene transfection and intracellular drug delivery. © 2013.

Antithrombogenic and antibiotic compositions and methods of preparation thereof

DOEpatents

Hermes, R.E.

1988-04-19

Antithrombogenic and antibiotic composition of matter and method of preparation thereof. A random copolymer of a component of garlic and a biocompatible polymer has been prepared and found to exhibit antithrombogenic and antibiotic properties. Polymerization occurs selectively at the vinyl moiety in 2-vinyl-4H-1,3-dithiin when copolymerized with N-vinyl pyrrolidone. 4 figs., 2 tabs.

Optimization of esterification of dicarboxylic acids and 2-ethyl-1-hexanol

NASA Astrophysics Data System (ADS)

Jafri, Nur Hafifah Nahdirah; Othman, Nor Hamidah Abu; Salimon, Jumat

2018-04-01

Dicarboxylate ester has the potential alternative as plasticizer which environmentally friendly in polymeric formulation especially for poly (vinyl chloride) (PVC). Dicarboxylate ester compounds were synthesized via esterification between dicarboxylic acid and 2-ethyl-1-hexanol by using sulfuric acid as catalyst. The effects of reaction parameters were studied by optimizing temperature, mole ratio of reactants, amount of catalyst and reaction to obtain highest ester conversion. The optimum results showed dicarboxylic acid successfully converted to the dicarboxylate ester at parameters; 4 hours; 120 °C; catalyst amount: 2% w/w of diacid; and mole ratio: 1:2.5. Functional group analysis was conducted by using ATR-FTIR spectroscopy.

Stereodynamic insight into the thermal history effects on poly(vinyl chloride) calorimetric sub-glass and glass transitions as a fragile glass model.

PubMed

Pin, Jean-Mathieu; Behazin, Ehsan; Misra, Manjusri; Mohanty, Amar

2018-05-02

The dynamic thermal history impact of poly(vinyl chloride) (PVC) has been explored for a wide range of pre-cooling rates, from 1 to 30 °C min-1. A first macroscopic insight into the dynamic thermal history influence has been highlighted through a decrease in the apparent activation energy (Eapp) in the first stage of the glass transition. The overall glass transition Eapp surface was successfully modeled in a polynomial fashion regarding the pre-cooling range. Raman scattering was used to associate the Eapp variations along the glass transition conversion with the stereochemistry evolution during the polymeric relaxation. Herein, the selection of atactic PVC as the polymer model permits us to monitor the glassy polymer segment stereodynamics during the heating ramp through the C-Cl stretching. The intermolecular H-Cl dipole interactions, as well as intramolecular conformational reorganizations among syndiotactic, isotactic and heterotactic polymer sequences, have been associated with non-cooperative and cooperative motions, i.e. the β- and α-process, respectively. The fruitful comparison of the two extreme values of the pre-cooling rates permits us to propose a thermokinetic scenario that explains the occurrence, intensity, and inter-dependence of β- and α-processes in the glassy state and during the glass transition. This scenario could potentially be generalized to all the other polymeric glass-formers.

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

PubMed

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.

Levels of CEA among vinyl chloride and polyvinyl chloride exposed workers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Anderson, H.A.; Snyder, J.; Lewinson, T.

1978-09-01

In 1974, vinyl chloride exposed workers were found to have an increased risk of malignant disease (hemangiosarcoma of the liver). We have examined 1,147 workers exposed to vinyl chloride monomer in three VC/PVC polymerization plants, and 269 workers from a PVC extrusion plant manufacturing PVC textile leather, exposed to much lower concentrations of vinyl chloride. Included among the comprehensive clinical and laboratory studies conducted was the CEA titer. We obtained, respectively, 1,115 and 248 CEA titers. Multiple factors were demonstrated which affected the distribution of CEA titers. Cigarette use had the greatest effect, followed by history of specific past illnessesmore » and alcohol intake history. After removing these possible confounding effects, the distribution of CEA titers among the polymerization workers was significantly different from the extrusion plant group and from an unexposed comparison group. Of the six job categories analyzed, only production and maintenance workers had CEA titer distributions significantly different from the comparison group and the extrusion workers. The investigation demonstrates that occupational exposures in VC/PVC polymerization plants can cause elevations in the CEA titers of otherwise healthy individuals. Prospective follow-up is necessary before conclusions can be drawn concerning the usefulness of the CEA titer as a predictive indicator of possible increased risk.« less

Reactivity of vinyl ethers and vinyl ribosides in UV-initiated free radical copolymerization with acceptor monomers.

PubMed

Pichavant, Loic; Guillermain, Céline; Coqueret, Xavier

2010-09-13

The reactivity of various vinyl ethers and vinyloxy derivatives of ribose in the presence of diethyl fumarate or diethyl maleate was investigated for evaluating the potential of donor-acceptor-type copolymerization applied to unsaturated monomers derived from renewable feedstock. The photochemically induced polymerization of model monomer blends in the bulk state was monitored by infrared spectroscopy. The method allowed us to examine the influence of monomer pair structure on the kinetic profiles. The simultaneous consumption of both monomers was observed, supporting an alternating copolymerization mechanism. A lower reactivity of the blends containing maleates compared with fumarates was confirmed. The obtained kinetic data revealed a general correlation between the initial polymerization rate and the Hansen parameter δ(H) associated with the H-bonding aptitude of the donor monomer.

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.

Rise and Fall: Poly(phenyl vinyl ketone) Photopolymerization and Photodegradation under Visible and UV Radiation.

PubMed

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.

21 CFR 178.3950 - Tetrahydrofuran.

Code of Federal Regulations, 2010 CFR

2010-04-01

... section. (a) It is used as a solvent in the casting of film from a solution of polymeric resins of vinyl... another in any combination, or it may be used as a solvent in the casting of film prepared from vinyl... in the film does not exceed 1.5 percent by weight of film. ...

POLY(VINYL ACETATE) AND POLY(VINYL ACETATE-CO-ETHYLENE) LATEXES VIA DISPERSION POLYMERIZATIONS IN CARBON DIOXIDE. (R826115)

EPA Science Inventory

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...

Process parameters in the manufacture of ceramic ZnO nanofibers made by electrospinning

NASA Astrophysics Data System (ADS)

Nonato, Renato C.; Morales, Ana R.; Rocha, Mateus C.; Nista, Silvia V. G.; Mei, Lucia H. I.; Bonse, Baltus C.

2017-01-01

Zinc oxide (ZnO) nanofibers were prepared by electrospinning under different conditions using a solution of poly(vinyl alcohol) and zinc acetate as precursor. A 23 factorial design was made to study the influence of the process parameters in the electrospinning (collector distance, flow rate and voltage), and a 22 factorial design was made to study the influence of the calcination process (time and temperature). SEM images were made to analyze the fiber morphology before and after calcination process, and the images were made to measure the nanofiber diameter. X-ray diffraction was made to analyze the total precursor conversion to ZnO and the elimination of the polymeric carrier.

21 CFR 700.14 - Use of vinyl chloride as an ingredient, including propellant of cosmetic aerosol products.

Code of Federal Regulations, 2010 CFR

2010-04-01

..., DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) COSMETICS GENERAL Requirements for Specific Cosmetic... inhaled at high concentrations. Studies also demonstrate carcinogenic effects in animals as a result of..., including liver cancer, in workers engaged in the polymerization of vinyl chloride. It is the view of the...

Heat resistant polymers of oxidized styrylphosphine

NASA Technical Reports Server (NTRS)

Paciorek, K. J. L. (Inventor)

1978-01-01

Homopolymers, copolymers and terpolymers of a styrene based monomer are prepared by polymerizing at least one oxidized styrylphosphine monomer or by polymerizing p-diphenylphosphinestyrene and then oxidizing the polymerized monomer with an organoazide. Copolymers can also be prepared by copolymerizing styrene with at least one oxidized styrylphosphine monomer. Flame resistant vinyl based polymers whose degradation products are non toxic and non corrosive are obtained.

Molecular Engineering of Liquid Crystalline Polymers by Living Polymerization. 8. Influence of Molecular Weight on the Phase Behavior pf Poly(Omega-((4-cyano-4’Biphenyl)oxy)alkyl Vinyl Ether)s with Ethyl, Propyl and Butyl Alkyl Groups

DTIC Science & Technology

1990-10-16

methanol (15 ml). The mixture was refluxed for 12 hr. After cooling and filtration (to remove the catalyst ) the solvent was distilled in a rotavapor and...was controlled by the monomer/initiator ([M]/[I]0 ) ratio. After quenching the polymerization with ammoniacal methanol , the reaction mixture was...The Phase Behavior of Poly(co-[(4-cyano-4’- biphenyl)oxy] alkyl Vinyl Ether]s with Ethyl, Propyl and Butyl Alkyl Groups Acc,--.o ,; ., x .... V

Coating gigaporous polystyrene microspheres with cross-linked poly(vinyl alcohol) hydrogel as a rapid protein chromatography matrix.

PubMed

Qu, Jian-Bo; Huan, Guan-Sheng; Chen, Yan-Li; Zhou, Wei-Qing; Liu, Jian-Guo; Huang, Fang

2014-08-13

Gigaporous polystyrene (PS) microspheres were hydrophilized by in situ polymerization to give a stable cross-linked poly(vinyl alcohol) (PVA) hydrogel coating, which can shield proteins from the hydrophobic PS surface underneath. The amination of microspheres (PS-NH2) was first carried out through acetylization, oximation and reduction, and then 4,4'-azobis (4-cyanovaleric acid) (ACV), a polymerization initiator, was covalently immobilized on PS-NH2 through amide bond formation, and the cross-linked poly(vinyl acetate) (PVAc) was prepared by radical polymerization at the surfaces of ACV-immobilized PS microspheres (PS-ACV). Finally, the cross-linked PVA hydrogel coated gigaporous PS microspheres (PS-PVA) was easily achieved through alcoholysis of PVAc. Results suggested that the PS microspheres were effectively coated with cross-linked PVA hydrogel, where the gigaporrous structure remained under optimal conditions. After hydrophilic modification (PS-PVA), the protein-resistant ability of microspheres was greatly improved. The hydroxyl-rich PS-PVA surface can be easily derivatized by classical chemical methods. Performance advantages of the PS-PVA column in flow experiment include good permeability, low backpressure, and mechanical stability. These results indicated that PS-PVA should be promising in rapid protein chromatography.

40 CFR 63.12005 - What definitions apply to this subpart?

Code of Federal Regulations, 2012 CFR

2012-07-01

... venting episode that is associated with a single unit operation. A unit operation may have more than one... characterized by a two-step anhydrous polymerization process: the formation of small resin particles in a pre... of the resin particles in a post-polymerization reactor using additional vinyl chloride monomer...

Synthesis and biological evaluation of cis-locked vinylogous combretastatin-A4 analogues: derivatives with a cyclopropyl-vinyl or a cyclopropyl-amide bridge.

PubMed

Ty, Nancy; Kaffy, Julia; Arrault, Alban; Thoret, Sylviane; Pontikis, Renée; Dubois, Joelle; Morin-Allory, Luc; Florent, Jean-Claude

2009-03-01

A series of novel combretastatin A4 analogues, in which the cis-olefinic bridge is replaced by a cyclopropyl-vinyl or a cyclopropyl-amide moiety, were synthesized and evaluated for inhibition of tubulin polymerization and antiproliferative activity. The derivative 9a with a (cis,E)-cyclopropyl-vinyl unit is the most promising compound. As expected, molecular docking of 9a has shown that only one of the cis-cyclopropyl enantiomers is a good ligand for tubulin.

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

PubMed

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.

Novel alkyd-type coating resins produced using cationic polymerization

DOE PAGES

Chisholm, Bret J.; Kalita, Harjyoti; Alam, Samim; ...

2015-05-06

Novel, partially bio-based poly(vinyl ether) copolymers derived from soybean oil and cyclohexyl vinyl ether (CHVE) were produced by cationic polymerization and investigated for application as alkyd-type surface coatings. Compared to conventional alkyd resins, which are produced by high temperature melt condensation polymerization, the poly(v9nyl ether)s provide several advantages. These advantages include milder, more energy efficient polymer synthesis, elimination of issues associated with gelation during polymer synthesis, production of polymers with well-defined composition and relatively narrow molecular weight distribution, and elimination of film formation and physical property issues associated with entrained monomers, dimers, trimers, etc. The results of the studied showedmore » that the thermal, mechanical, and physical properties of the coatings produced from these novel polymers varied considerably as a function of polymer composition and cure temperature. Overall, the results suggest a good potential for these novel copolymers to be used for coatings cured by autoxidation.« less

UV recording with vinyl acetate and muicle dye film

NASA Astrophysics Data System (ADS)

Toxqui-Lopez, S.; Olivares-Pérez, A.; Santacruz-Vazquez, V.; Fuentes-Tapia, I.; Ordoñez-Padilla, J.

2015-03-01

Nowadays, there are many types of holographic recording medium some of them are photopolymer systems that generally consist of a polymeric host matrix, photopolymerizable momomer, photosensitizing dye and charge transfer agent but some of them have an undesirable feature, the toxicity of their components. Therefore, the present research study material recording, vinyl acetate is selected as polymeric matrix and natural dye from "muicle plant" is used as the photoinitiation these components are not toxic. The films are fabricated using gravity settling method at room temperature by this method, uniform films is obtained with good optical quality. To characterize the medium, been obtained when the coherent reed light (632.8 nm) was sent normally to the grating.

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

PubMed

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.

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

DOE PAGES

Brown, Suree; Yue, Yanfeng; Kuo, Li-Jung; ...

2016-03-11

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

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brown, Suree; Yue, Yanfeng; Kuo, Li-Jung

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

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brown, Suree; Yue, Yanfeng; Kuo, Li-Jung

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

Reversible Addition Fragmentation Chain Transfer (RAFT) Polymerization in Undergraduate Polymer Science Lab

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…

Electron-beam-initiated polymerization of poly(ethylene glycol)-based wood impregnants.

PubMed

Trey, Stacy M; Netrval, Julia; Berglund, Lars; Johansson, Mats

2010-11-01

The current study demonstrates that methacrylate and acrylate poly(ethylene glycol) (PEG) functional oligomers can be effectively impregnated into wood blocks, and cured efficiently to high conversions without catalyst by e-beam radiation, allowing for less susceptibility to leaching, and favorable properties including higher Brinell hardness values. PEG based monomers were chosen because there is a long history of this water-soluble monomer being able to penetrate the cell wall, thus bulking it and decreasing the uptake of water which further protects the wood from fungal attack. Diacrylate, dimethacrylate, and dihydroxyl functional PEG of M(w) 550-575, of concentrations 0, 30, 60, and 100 wt % in water, were vacuum pressure impregnated into Scots Pine blocks of 15 × 25 × 50 mm in an effort to bulk the cell wall. The samples were then irradiated and compared with nonirradiated samples. It was shown by IR, DSC that the acrylate polymers were fully cured to much higher conversions than can be reached with conventional methods. Leaching studies indicated a much lower amount of oligomer loss from the cured vinyl functional PEG chains in comparison to hydroxyl functional PEG indicating a high degree of fastening of the polymer in the wood. The Brinell hardness indicated a significant increase in hardness to hardwood levels in the modified samples compared to the samples of hydroxyl functional PEG and uncured vinyl PEG samples, which actually became softer than the untreated Scots Pine. By monitoring the dimensions of the sample it was found by weight percent gain calculations (WPG %) that water helps to swell the wood structure and allow better access of the oligomers into the cell wall. Further, the cure shrinkage of the wood samples demonstrated infiltration of the oligomers into the cell wall as this was not observed for methyl methacrylate which is well-documented to remain in the lumen. However, dimensional stability of the vinyl polymer modified blocks when placed in water was not observed to the same extent as PEG.

Friction-induced surface activity of some hydrocarbons with clean and oxide-covered iron

NASA Technical Reports Server (NTRS)

Buckley, D. H.

1973-01-01

Sliding friction studies were conducted on a clean and oxide-covered iron surface with exposure of that surface to various hydrocarbons. The hydrocarbons included ethane, ethylene ethyl chloride, methyl chloride, and vinyl chloride. Auger cylindrical mirror analysis was used to follow interactions of the hydrocarbon with the iron surface. Results with vinyl chloride indicate friction induced surface reactivity, adsorption to surface oxides, friction sensitivity to concentration and polymerization. Variation in the loads employed influence adsorption and accordingly friction. In contrast with ethyl and vinyl chloride, friction induced surface reactivity was not observed with ethane and ethylene.

Radical-Mediated Enzymatic Polymerizations

PubMed Central

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

Synthesis of light-selective poly(ethylene-co-vinyl acetate) nanofilms in supercritical carbon dioxide

NASA Astrophysics Data System (ADS)

Xu, William (Zhiming)

Due to the increased requirements of environmental protection, significant effort has been made to develop new "green" chemistry and engineering methods. Two effective approaches for "green" processes are: (1) to employ routes with fewer synthetic and separation steps, and (2) to replace volatile organic solvents with environmentally friendly solvents. Supercritical carbon dioxide (scCO2) has emerged as such a viable "green" alternative to organic solvents for several applications including extraction, polymerization, and nanotechnology, etc. In addition, it is an enabling solvent, allowing new types of chemistry and materials to be formed. In order to effectively utilize scCO2, it is required to study its effect on the relevant chemical process. This thesis focuses on the copolymerization of ethylene and vinyl acetate in scCO2, and the application of scCO2 in the synthesis of novel poly(vinyl acetate) (PVAc) and poly(ethylene-co-vinyl acetate) (PEVA) nanocomposites. Firstly, the kinetics of the process was investigated. The thermal decomposition of the free-radical initiator diethyl peroxydicarbonate (DEPDC) was monitored by in situ attenuate total reflection Fourier transform infrared spectroscopy (ATR-FTIR) in heptane, and in scCO2. The rate constant and activation energy of the thermal decomposition of DEPDC in scCO2 were determined, and a decomposition mechanism was proposed. Further, with a knowledge of the initiator kinetics, in situ ATR-FTIR was employed to monitor the initial formation of copolymers of ethylene and vinyl acetate during polymerization in scCO2. The reactivity ratios for the copolymerization of ethylene and vinyl acetate in scCO2 were determined using both the Kelen-Tudos and the non-linear least-squares methods. The potential of scCO2 was further examined to synthesize advanced and novel nanomaterials based on an understanding of the polymerization mechanism. A novel one-step synthesis route was developed for making silica-PVAc nanocomposites in scCO2, where the parallel reactions of free radical polymerization, hydrolysis/condensation, and linkage of the nanoparticles to the polymer chains, were found to take place simultaneously. This provides a new process featuring significant energy-saving, waste-reduction, and excellent distribution of nanoparticles in the polymer matrix. In addition, the incorporation of quantum dots (QDs) into a transparent polymer matrix was investigated to form light-selective nanofilms. Both CdS and CdS-ZnS core-shell QDs were synthesized, then functionalized with a methoxysilane group, and finally used to synthesize novel QD-PVAc and QD-PEVA nanocomposites in scCO2. The synthesized QD-PEVA nanofilms displayed significant absorption in the ultraviolet and violet regions of the electromagnetic spectrum, while providing a characteristic emission in the region from orange to red light. These materials have significant potential in green houses, and solar absorber films. Key words. supercritical CO2, initiator, thermal decomposition, kinetics, mechanism, ATR-FTIR, reactivity ratios, ethylene, vinyl acetate, silica, nanocomposite, one-pot synthesis, light-selective, nanofilm, quantum dots.

Effect of crosslinking concentration on properties of 3-(trimethoxysilyl) propyl methacrylate/N-vinyl pyrrolidone gels.

PubMed

Mohammed, Ameen Hadi; Ahmad, Mansor B; Ibrahim, Nor Azowa; Zainuddin, Norhazlin

2018-02-13

The incorporation of two different monomers, having different properties, in the same polymer molecule leads to the formation of new materials with great scientific and commercial importance. The basic requirements for polymeric materials in some areas of biomedical applications are that they are hydrophilic, having good mechanical and thermal properties, soft, and oxygen-permeable. A series of 3-(trimethoxysilyl) propyl methacrylate/N-vinyl pyrrolidone (TMSPM/NVP) xerogels containing different concentration of ethylene glycol dimethacrylate (EGDMA) as crosslinking agent were prepared by bulk polymerization to high conversion using BPO as initiator. The copolymers were characterized by FTIR. The corresponding hydrogels were obtained by swelling the xerogels in deionized water to equilibrium. Addition of EGDMA increases the transparency of xerogels and hydrogels. The minimum amount of EGDMA required to produce a transparent xerogel is 1%. All the Swelling parameters, including water content (EWC), volume fraction of polymer (ϕ 2 ) and weight loss during swelling decrease with increasing EGDMA. Young's and shear modulus (E and G) increase as EGDMA increases. The hydrogels were characterized in terms of modulus cross-linking density (v e and v t ) and polymer-solvent interaction parameters (χ). Thermal properties include TGA and glass transition temperature (T g ) enhance by adding EGDMA whereas the oxygen permeability (P) of hydrogels decreases as water content decrease. This study prepared and studied the properties for new copolymer (TMSPM-co-NVP) contains different amounts of (EGDMA). These copolymers possess new properties with potential use in different biomedical applications. The properties of the prepared hydrogels are fit with the standard properties of materials which should be used for contact lenses.

Measurement of Viscosity of Reacting Vinyl-Ester Resins Using Direct-Current Sensing

DTIC Science & Technology

2000-01-01

ARMY RESEARCH LABORATORY ___ ^:5T",g?"r/:"/:^SS^ fö’^^;^>.^.^^^^M^^^^^; Measurement of Viscosity of Reacting Vinyl-Ester Resins Using Direct...under development at the U.S. Army Research Laboratory (ARL) is sensors mounted as roving threads (SMARTweave), a patented sensor system that...in viscosity characterizes the initial stages of chain polymerization reaction. The point at which viscosity tends toward infinity is gelation and is

Poly(vinyl Chloride) Photostabilization in the Presence of Schiff Bases Containing a Thiadiazole Moiety.

PubMed

Shaalan, Naser; Laftah, Nawres; El-Hiti, Gamal A; Alotaibi, Mohammad Hayal; Muslih, Raad; Ahmed, Dina S; Yousif, Emad

2018-04-15

Five Schiff bases containing a thiadiazole moiety have been used as poly(vinyl chloride) photostabilizers at low concentrations. The efficiency of Schiff bases as photostabilizers was investigated using various techniques, for example, the changes in poly(vinyl chloride) infrared spectra, molecular weight, chain scission quantum yield, and surface morphology were monitored upon irradiation with an ultraviolet light. Evidently, all the additives used inhibited poly(vinyl chloride) photodegradation at a significant level. The most efficient Schiff base exhibited a high level of aromaticity and contained a hydroxyl group. It seems possible that such photostabilization could be due to the direct absorption of ultraviolet radiation by the additives. In addition, Schiff bases could act as radical scavengers and proton transfer facilitators to stabilize the polymeric materials.

Antimicrobial fabric adsorbed iodine produced by radiation-induced graft polymerization

NASA Astrophysics Data System (ADS)

Aoki, Shoji; Fujiwara, Kunio; Sugo, Takanobu; Suzuki, Koichi

2013-03-01

Antimicrobial fabric was synthesized by radiation-induced graft polymerization of N-vinyl pyrrolidone onto polyolefine nonwoven fabric and subsequent adsorption of iodine. In response of the huge request for the antimicrobial material applied to face masks for swine flu in 2009, operation procedure of continuous radiation-induced graft polymerization apparatus was improved. The improved grafting production per week increased 3.8 times compared to the production by former operation procedure. Shipped antimicrobial fabric had reached 130,000 m2 from June until December, 2009.

Preparation and characterization of a magneto-polymeric nanocomposite: Fe 3O 4 nanoparticles in a grafted, cross-linked and plasticized poly(vinyl chloride) matrix

NASA Astrophysics Data System (ADS)

Rodríguez-Fernández, Oliverio S.; Rodríguez-Calzadíaz, C. A.; Yáñez-Flores, Isaura G.; Montemayor, Sagrario M.

In this work two kind of materials: (1) grafted, cross-linked and plasticized poly(vinyl chloride) (PVC) "plastic films" and (2) magnetic plastic films "magneto-polymeric nanocomposites" were prepared. Precursor solutions or "plastisols" used to obtain the plastic films were obtained by mixing PVC (emulsion grade) as polymeric matrix, di(2-ethylhexyl)phthalate (DOP) as plasticizer, a thermal stabilizer based in Ca/Zn salts, and a cross-linking agent, 3-mercaptopropyltrimethoxysilane (MTMS) or 3-aminopropyltriethoxysilane (ATES), at several concentrations. Flexible films were obtained from the plastisols using static casting. The stress-strain behavior and the gel content (determined by Soxhlet extraction with boiling THF) of the flexible films were measured in order to evaluate the effect of the cross-linking agent and their content on the degree of cross-linking. The magneto-polymeric nanocomposites were obtained by mixing the optimum composition of the plastisols (analyzed previously) with magnetite (Fe 3O 4)-based ferrofluid and DOP. Later, flexible films were obtained by static casting of the plastisol/ferrofluid systems. The magnetic films were characterized by the above-mentioned techniques and X-ray diffraction, vibrating sample magnetometry and thermogravimetrical analysis.

Compound oxidized styrylphosphine. [flame resistant vinyl polymers

NASA Technical Reports Server (NTRS)

Paciorek, K. J. L. (Inventor)

1979-01-01

A process is described for preparing flame resistant, nontoxic vinyl polymers which contain phosphazene groups and which do not emit any toxic or corrosive products when they are oxidatively degraded. Homopolymers, copolymers, and terpolymers of a styrene based monomer are prepared by polymerizing at least one oxidized styrylphosphine monomer from a group of organic azides, or by polymerizing p-diphenylphosphinestyrene and then oxidizing that monomer with an organoazide from the group of (C6H5)2P(O)N3, (C6H5O)2P(O)N3, (C6H5)2C3N3(N3), and C6H5C3N3(N3)2. Copolymers can also be prepared by copolymerizing styrene with at least one oxidized styrylphosphine monomer.

High temperature chemically resistant polymer concrete

DOEpatents

Sugama, T.; Kukacka, L.E.

High temperature chemically resistant, non-aqueous polymer concrete composites consist of about 12 to 20% by weight of a water-insoluble polymer binder. The binder is polymerized in situ from a liquid vinyl-type monomer or mixture of vinyl containing monomers such as triallylcyanurate, styrene, acrylonitrile, acrylamide, methacrylamide, methyl-methacrylate, trimethylolpropane trimethacrylate and divinyl benzene. About 5 to 40% by weight of a reactive inorganic filler selected from the group consisting of tricalcium silicate and dicalcium silicate and mixtures containing less than 2% free lime, and about 48 to 83% by weight of silica sand/ and a free radical initiator such as di-tert-butyl peroxide, azobisisobutyronitrile, benzoyl peroxide, lauryl peroxide, other orgaic peroxides and combinations to initiate polymerization of the monomer in the presence of the inorganic filers are used.

Biodegradable starch-based polymeric materials

NASA Astrophysics Data System (ADS)

Suvorova, Anna I.; Tyukova, Irina S.; Trufanova, Elena I.

2000-05-01

The effects of low-molecular-weight additives, temperature and mechanical action on the structure and properties of starch are discussed. Special attention is given to mixtures of starch with synthetic polymers, e.g., co-polymers of ethylene with vinyl acetate, vinyl alcohol, acrylic acid, cellulose derivatives and other natural polymers. These mixtures can be used in the development of novel environmentally safe materials (films, coatings, packaging materials) and various articles for short-term use. The bibliography includes 105 references.

[Quantitative evaluation of health risk associated with occupational inhalation exposure to vinyl chloride at production plants in Poland].

PubMed

Szymczak, W

1997-01-01

Vinyl chloride is classified by the IARC in group 1-human carcinogens. In Poland occupational exposure to vinyl chloride is found among workers employed in many branches of industry, among others in the industry of vinyl chloride synthesis and polymerization as well as in the plastics, footwear, rubber, pharmaceutical and metallurgical industries. Concentrations observed range from the noon-determinable level to 90 mg/m3, at the MAC value equal to 5 mg/m3. Neoplasm of liver is a major carcinogenic effect of vinyl chloride. Hence, the health assessment focused on this critical risk. Four different linear dose-response models, developed by several authors and based on results of different epidemiological studies, were used to characterise the extent of cancer risk depending on the level of vinyl chloride concentrations. The estimated risk related to a forty-year employment under exposure equal to MAC values (5 mg/m3) fell within the range from 2.9.10(-4) to 2.6.10(-3). As the figures depict it did not exceed the acceptable level (10(-3)).

Nanostructural surface engineering of grafted polymers on inorganic oxide substrates for membrane separations

NASA Astrophysics Data System (ADS)

Yoshida, Wayne Hiroshi

Nanostructural engineering of inorganic substrates by free radical graft polymerization was studied with the goal of developing new membrane materials for pervaporation. Graft polymerization consisted of modification of surface hydroxyls with vinyl trimethoxysilane, followed by solution graft polymerization reaction using either vinyl acetate (VAc) or vinyl pyrrolidone (VP). The topology of the modified surfaces was studied by atomic force microscopy (AFM) on both atomically smooth silicon wafer substrates and microporous inorganic membrane supports in order to deduce the effects of modification on the nanostructural properties of the membrane. While unmodified wafers showed a root-mean-square (RMS) surface roughness of 0.21 +/- 0.03 nm, roughness increased to 3.15 +/- 0.23 nm upon silylation. Under poor solvent conditions (i.e., air), surfaces modified with higher poly(vinyl acetate) (PVAc) or poly(vinyl pyrrolidone) (PVP) polymer graft yields displayed lateral inhomogeneities in the polymer layer. Although RMS surface roughness was nearly identical (0.81--0.85 nm) for PVAc-modified surfaces grafted at different monomer concentrations, the skewness of the height distribution decreased from 2.22 to 0.78 as polymer graft yield increased from 0.8 to 3.5 mg/m2. The polymer-modified surfaces were used to create inorganic pervaporation membranes consisting of a single macromolecular separation layer formed by graft polymerization. PVAc grafted silica membranes (500A native pore size) were found selective for MTBE in the separation of 0.1--1% (v/v) MTBE from water, achieving MTBE enrichment factors as high as 371 at a permeate flux of 0.38 l/m2 hr and a Reynolds number of 6390; however, these membranes could not separate anhydrous organic mixtures. Pervaporative separation of methanol/MTBE mixtures was possible with PVAc and PVP-modified alumina supports of 50A native pore size, where the separation layer consisted of grafted polymer chains with estimated radius of gyration 4.5--6.8 times larger than the membrane pore radius. Methanol separation factors for the PVP and PVAc-grafted alumina pervaporation membranes reached values of 26 and 100 (respectively) at total permeate fluxes of 0.055--1.26 kg/m 2 hr and 0.55--6.19 kg/m2 hr. The present study demonstrated that selective pervaporation membranes for separation of both organic/organic and organic/aqueous mixtures can be effectively designed by careful selection of the surface-grafted polymer chain density and the ratio of the polymer chain size to the native support pore size.

ESEM analysis of polymeric film in EVA-modified cement paste

DOE Office of Scientific and Technical Information (OSTI.GOV)

Silva, D.A.; Monteiro, P.J.M.

2005-10-01

Portland cement pastes modified by 20% weight (polymer/cement ratio) of poly(ethylene-co-vinyl acetate) (EVA) were prepared, cured, and immersed in water for 11 days. The effects of water saturation and drying on the EVA polymeric film formed in cement pastes were observed using environmental scanning electron microscopy (ESEM). This technique allowed the imaging of the EVA film even in saturated samples. The decrease of the relative humidity inside the ESEM chamber did not cause any visual modification of the polymeric film during its drying.

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

PubMed

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.

A Visible Light Initiating System for Free Radical Promoted Cationic Polymerization

DTIC Science & Technology

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

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

PubMed

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.

Poly(1-Vinyl-1,2,4-triazolium) Poly(Ionic Liquid)s: Synthesis and the Unique Behavior in Loading Metal Ions.

PubMed

Zhang, Weiyi; Yuan, Jiayin

2016-07-01

Herein, the synthesis of a series of poly(4-alkyl-1-vinyl-1,2,4-triazolium) poly(ionic liquid)s is reported either via straightforward free radical polymerization of their corresponding ionic liquid monomers or via anion metathesis of the polymer precursors bearing halide as counter anion. The ionic liquid monomers are first prepared via N-alkylation reaction of commercially available 1-vinyl-1,2,4-triazole with alkyl iodides, followed by anion metathesis with targeted fluorinated anions. The thermal properties and solubilities of these poly(ionic liquid)s have been systematically investigated. Interestingly, it is found that the poly(4-ethyl-1-vinyl-1,2,4-triazolium) poly(ionic liquid) exhibited an improved loading capacity of transition metal ions in comparison with its imidazolium counterpart. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis of amphipathic block copolymers based on polyisobutylene and polyoxyethylene and their application in emulsion polymerization

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sar, B.

1992-12-31

Polymer colloids stabilized by polymeric surfactants are of great interest both commercially and academically. It has been found that these materials enhance latex stabilization in a number of applications. The polymeric surfactants are amphipathic block and graft copolymers containing both hydrophilic and hydrophobic moieties. The current study involved the synthesis of a series of amphipathic triblock copolymers, polyisobutylene-block-polyoxyethylene-block-polyisobutylene (PIB-b-POE-b-PIB), for use in the emulsion polymerization of styrene (STY), methyl methacrylate (MMA), and vinyl acetate (VAc). The stabilizing effectiveness of these triblock copolymers was studied as a function of their blocklength. When the molecular weight of the POE center block wasmore » changed from M{sub n} = 2,000 to 20,000 g/mole, stable lattices were obtained in emulsion polymerization with MMA, STY, and VAc as the monomers. In all cases, the polymerization rates remained constant, while the number of particles/volume decreased with increasing POE chain length. When the molecular weight of the PIB end blocks was changed from M{sub n} = 400 to 2,600 g/mole keeping the molecular weight of the POE center block constant at M{sub n} = 20,000 g/mole, the poly(methyl methacrylate) and poly(vinyl acetate) lattices exhibited similar behavior, i.e., the number of particles and particle sizes remained the same, but the rate of polymerization reached a maximum at 87 wt% POE content. In the case of poly(styrene) both the rate of polymerization and the number of particles remained constant. The emulsion polymerization of other monomers such as butadiene, acrylonitrile, methyl acrylate, ethyl acrylate, and butyl acrylate was carried out by using one triblock copolymer, i.e., PIB(400)-b-POE (8,000)-b-PIB-(400). Stable lattices were also formed in all cases.« less

Magnetic properties of the Fe{sup II} spin crossover complex in emulsion polymerization of trifluoroethylmethacrylate using poly(vinyl alcohol)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Suzuki, Atsushi, E-mail: suzuki@mat.usp.ac.j; Iguchi, Motoi; Oku, Takeo

2010-04-15

Influence of chemical substitution in the Fe{sup II} spin crossover complex on magnetic properties in emulsion polymerization of trifluoroethylmethacrylate using poly(vinyl alcohol) as a protective colloid was investigated near its high spin/low spin (HS/LS) phase transition. The obvious bi-stability of the HS/LS phase transition was considered by the identification of multiple spin states between the quintet (S=2) states to single state (S=0) across the excited triplet state (S=1). Magnetic parameters of gradual shifts of anisotropy g-tensor supported by the molecular distortion of the spin crossover complex would arise from a Jahn-Teller effect regarding ligand field theory on the basis ofmore » a B3LYP density functional theory using electron spin resonance (ESR) spectrum and X-ray powder diffraction. - Graphical abstract: AFM surface image of the emulsion particles with the spin crossover complex.« less

Field and laboratory determination of a poly(vinyl/vinylidene chloride) additive in brick mortar.

PubMed

Law, S L; Newman, J H; Ptak, F L

1990-02-01

A polymerized vinyl/vinylidene chloride additive, used in brick mortar during the 60s and 70s, is detected at the building site by the field method, which employs a commercially available chloride test strip. The field test results can then be verified by the laboratory methods. In one method, total chlorine in the mortar is determined by an oxygen-bomb method and the additive chloride is determined by difference after water-soluble chlorides have been determined on a separate sample. In the second method, the polymerized additive is extracted directly from the mortar with tetrahydrofuran (THF). The difference in weight before and after extraction of the additive gives the weight of additive in the mortar. Evaporation of the THF from the extract leaves a thin film of the polymer, which gives an infrared "fingerprint" spectrum characteristic of the additive polymer.

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

PubMed

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

2018-03-26

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

Radiation-hardened polymeric films

DOEpatents

Arnold, C. Jr.; Hughes, R.C.; Kepler, R.G.; Kurtz, S.R.

1984-07-16

The radiation-induced conductivity of polymeric dielectrics with low electronic mobility is reduced by doping with electron donor or electron acceptor compounds at a level of 10/sup 15/ to 10/sup 21/ molecules of dopant/cm/sup 3/. Polyesters, polyolefins, perfluoropolyolefins, vinyl polymers, vinylidene polymers, polycarbonates, polysulfones and polyimides can benefit from such a treatment. Usable dopants include 2,4,7-trinitro-9-fluorenone, tetracyanethylene, 7,7,8,8-tetracyanoquinodimethane, m-dinitrobenzene, 2-isopropylcarbazole, and triphenylamine.

Radiation-hardened polymeric films

DOEpatents

Arnold, Jr., Charles; Hughes, Robert C.; Kepler, R. Glen; Kurtz, Steven R.

1986-01-01

The radiation-induced conductivity of polymeric dielectrics with low electronic mobility is reduced by doping with electron donor or electron acceptor compounds at a level of 10.sup.15 to 10.sup.21 molecules of dopant/cm.sup.3. Polyesters, polyolefins, perfluoropolyolefins, vinyl polymers, vinylidene polymers, polycarbonates, polysulfones and polyimides can benefit from such a treatment. Usable dopants include 2,4,7-trinitro-9-fluorenone, tetracyanethylene, 7,7,8,8-tetracyanoquinodimethane, m-dinitrobenzene, 2-isopropylcarbazole, and triphenylamine.

Molecular engineering of side-chain liquid crystalline polymers by living cationic polymerization using Webster`s initiating system

DOE Office of Scientific and Technical Information (OSTI.GOV)

Percec, V.

1993-12-31

Webster`s cationic initiating system (HO{sub 3}SCF{sub 3}/SMe{sub 2}) (Macromolecules, 23, 1918 (1990)) was shown by us (for a review see Adv. Mater., 4, 548 (1992)) to polymerize, via a living mechanism, mesogenic vinyl ethers which contain a large variety of functional groups. This is mostly because SMe{sub 2} is a softer nucleophile than any of the functional groups available in these monomers. The molecular engineering of side-chain liquid crystalline polymers with conventional and complex architectures via this polymerization technique will be discussed.

A Ballistic Material Model for Cross-Plied Unidirectional Ultra-High Molecular-Weight Polyethylene Fiber-Reinforced Armor-Grade Composites

DTIC Science & Technology

2008-01-01

strength polymeric fibers such as aramid (e.g. Kevlar ®, Twaron®, etc.) or oriented polyethy- lene fibers (e.g. Spectra®, Dyneema®, etc.) with an... phenolic -poly-vinyl-butyral resin and on 0◦/90◦ cross- plied oriented polyethylene fiber-reinforced vinyl-ester resin are widely used in hard personnel...are: (a) poly-aramids (e.g. Kevlar ®, Twaron®, Technora®); (b) highly oriented ultra-highmolecular-weight polyethylene, UHMWPE (e.g. Spectra®, Dyneema

Indirect fabrication of multiple post-and-core patterns with a vinyl polysiloxane matrix.

PubMed

Sabbak, Sahar Asaad

2002-11-01

In the described technique, a vinyl polysiloxane material is used as a matrix for the indirect fabrication of multiple custom-cast posts and cores. The matrix technique enables the clinician to fabricate multiple posts and cores in a short period of time. The form, harmony, and common axis of preparation for all cores are well controlled before the definitive crown/fixed partial denture restorations are fabricated. Oral tissues are not exposed to the heat of polymerization or the excess monomer of the resin material when this technique is used.

[Acroosteolysis in PVC autoclave cleaners: history of an occupational disease].

PubMed

Zocchetti, C; Osculati, A; Colosio, C

2010-01-01

This paper examines the history of an occupational disease which has now disappeared: acroosteolysis of manual tank cleaners in the production of polyvinyl chloride (PVC), which is a rare disease characterized by destructive alterations of the distal phalanges of the hands. All the available literature on this disease was examined. The history of acroosteolysis was studied within the general framework of the history of the discovery of adverse health effects of exposure to vinyl chloride, and this history was studied up to the end of the 1960's. The disease was observed for the first time in mid-1963 in Belgium (Jemeppe) in a chemical plant operated by Solvay, and affected two workers whose job was the manual cleaning of vessels used for the polymerization of vinyl chloride; similar cases occurred in almost all PVC production plants all over the world, but not in the plants where the main activity was the production of vinyl chloride monomer (VCM). Little more than one hundred cases are described in the scientific literature, and this number increases by a few dozen if we consider known but unpublished cases. These figures confirm the rarity of the disease, which peaked at the end of the 1960's and disappeared during the 1970's, probably due to the complete elimination of manual reactor cleaning. Observation of the disease lasted no more than fifteen years and the disease was not replicated in experimental conditions on animals. The disease was clinically characterized, had a short latency (from several months to several years), was rare and unequivocally linked to the manual cleaning of PVC polymerization tanks. However many questions still remain open: the period when the disease first appeared (many years after the start of PVC production in the world), the etiology of the disease (the most accredited hypothesis considers three concomitant factors: a chemical factor--one of the many substances used during polymerization, and particularly vinyl chloride monomer, a physical factor--microtraumas of the fingers during manual cleaning, individual susceptibility), the pathogenetic mechanism (in particular: the role of skin, respiratory, or digestive system, as entrance door), a method (or test) to screen subjects potentially predisposed to the disease. In our view acroosteolysis of manual tank cleaners in PVC production is an occupational disease which is distinct from "vinyl chloride disease" as identified by Viola (1974).

Radiation-induced polymerization of glass forming systems. VI. Polymerization rate at higher conversion in binary systems

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

Cell adhesion and guidance by micropost-array chemical sensors

NASA Astrophysics Data System (ADS)

Pantano, Paul; Quah, Soo-Kim; Danowski, Kristine L.

2002-06-01

An array of ~50,000 individual polymeric micropost sensors was patterned across a glass coverslip by a photoimprint lithographic technique. Individual micropost sensors were ~3-micrometers tall and ~8-micrometers wide. The O2-sensitive micropost array sensors (MPASs) comprised a ruthenium complex encapsulated in a gas permeable photopolymerizable siloxane. The pH-sensitive MPASs comprised a fluorescein conjugate encapsulated in a photocrosslinkable poly(vinyl alcohol)-based polymer. PO2 and pH were quantitated by acquiring MPAS luminescence images with an epifluorescence microscope/charge coupled device imaging system. O2-sensitive MPASs displayed linear Stern-Volmer quenching behavior with a maximum Io/I of ~8.6. pH-sensitive MPASs displayed sigmoidal calibration curves with a pKa of ~5.8. The adhesion of undifferentiated rat pheochromocytoma (PC12) cells across these two polymeric surface types was investigated. The greatest PC12 cell proliferation and adhesion occurred across the poly(vinyl alcohol)-based micropost arrays relative to planar poly(vinyl alcohol)-based surfaces and both patterned and planar siloxane surfaces. An additional advantage of the patterned MPAS layers relative to planar sensing layers was the ability to direct the growth of biological cells. Preliminary data is presented whereby nerve growth factor-differentiated PC12 cells grew neurite-like processes that extended along paths defined by the micropost architecture.

High-Tg Polynorbornene-Based Block and Random Copolymers for Butanol Pervaporation Membranes

NASA Astrophysics Data System (ADS)

Register, Richard A.; Kim, Dong-Gyun; Takigawa, Tamami; Kashino, Tomomasa; Burtovyy, Oleksandr; Bell, Andrew

Vinyl addition polymers of substituted norbornene (NB) monomers possess desirably high glass transition temperatures (Tg); however, until very recently, the lack of an applicable living polymerization chemistry has precluded the synthesis of such polymers with controlled architecture, or copolymers with controlled sequence distribution. We have recently synthesized block and random copolymers of NB monomers bearing hydroxyhexafluoroisopropyl and n-butyl substituents (HFANB and BuNB) via living vinyl addition polymerization with Pd-based catalysts. Both series of polymers were cast into the selective skin layers of thin film composite (TFC) membranes, and these organophilic membranes investigated for the isolation of n-butanol from dilute aqueous solution (model fermentation broth) via pervaporation. The block copolymers show well-defined microphase-separated morphologies, both in bulk and as the selective skin layers on TFC membranes, while the random copolymers are homogeneous. Both block and random vinyl addition copolymers are effective as n-butanol pervaporation membranes, with the block copolymers showing a better flux-selectivity balance. While polyHFANB has much higher permeability and n-butanol selectivity than polyBuNB, incorporating BuNB units into the polymer (in either a block or random sequence) limits the swelling of the polyHFANB and thereby improves the n-butanol pervaporation selectivity.

Polysulfone hemodiafiltration membranes with enhanced anti-fouling and hemocompatibility modified by poly(vinyl pyrrolidone) via in situ cross-linked polymerization.

PubMed

Zhu, Lijing; Song, Haiming; Wang, Jiarong; Xue, Lixin

2017-05-01

Poly(vinyl pyrrolidone) (PVP) and its copolymers have been widely employed for the modification of hemodiafiltration membranes due to their excellent hydrophilicity, antifouling and hemocompatibility. However, challenges still remain to simplify the modification procedure and to improve the utilization efficiency. In this paper, antifouling and hemocompatibility polysulfone (PSf) hemodiafiltration membranes were fabricated via in situ cross-linked polymerization of vinyl pyrrolidone (VP) and vinyltriethoxysilane (VTEOS) in PSf solutions and non-solvent induced phase separation (NIPS) technique. The prepared membranes were characterized by attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM), which suggested that VP and VTEOS have been cross-linked copolymerized in PSf membranes. The modified PSf membranes with high polymer content showed improved hydrophilicity, ultrafiltration and protein antifouling ability. In addition, the modified PSf membranes showed lower protein adsorption, inhibited platelet adhesion and deformation, prolonged the activated partial thromboplastin time (APTT), prothrombin time (PT), and decreased the content of fibrinogen (FIB) transferring to fibrin, indicating enhanced hemocompatibility. In a word, the present work provides a simple and effective one-step modification method to construct PSf membranes with improved hydrophilicity, antifouling and hemocompatibility. Copyright © 2017 Elsevier B.V. All rights reserved.

Heterogeneous chemical reactions: Preparation of monodisperse latexes

NASA Technical Reports Server (NTRS)

Vanderhoff, J. W.; Micale, F. J.; El-Aasser, M. S.; Sterk, A. A.; Bethke, G. W.

1977-01-01

It is demonstrated that a photoinitiated emulsion polymerization can be carried out to a significant conversion in a SPAR rocket prototype polymerization vessel within the six minutes allowed for the experiment. The percentage of conversion was determined by both dilatometry and gravimetric methods with good agreement. The experimental results lead to the following conclusions: (1) emulsion polymerizations can be carried out to conversions as high as 75%, using a stable micellized styrene-SLS system plus photoinitiator; (2) dilatometry can be used to accurately determine both the rate and conversion of polymerization; (3) thermal expansion due to the light source and heat of reaction is small and can be corrected for if necessary; (4) although seeded emulsion polymerizations are unfavorable in photoinitiation, as opposed to chemical initiation, polymerizations can be carried out to at least 15% conversion using 7940A seed particles, with 0.05% solids; and (5) photoinitiation should be used to initiate polymerization in the SPAR rocket experiments because of the mechanical simplicity of the experiment.

Multi-stage Mass Spectrometry of Poly(vinyl pyrrolidone) and Its Vinyl Succinimide Copolymer Formed upon Exposure to Sodium Hypochlorite

PubMed Central

Fouquet, Thierry; Torimura, Masaki; Sato, Hiroaki

2016-01-01

The degradation routes of poly(vinyl pyrrolidone) (PVP) exposed to sodium hypochlorite (bleach) have been previously investigated using chemical analyses such as infrared spectroscopy. So far, no reports have proposed mass spectrometry (MS) as an alternative tool despite its capability to provide molecular and structural information using its single stage electrospray (ESI) or matrix assisted laser desorption ionization (MALDI) and multi stage (MSn) configurations, respectively. The present study thus reports on the characterization of PVP after its exposure to bleach by high resolution MALDI spiralTOF-MS and Kendrick mass defect analysis providing clues as to the formation of a vinyl pyrrolidone/vinyl succinimide copolymeric degradation product. A thorough investigation of the fragmentation pathways of PVP adducted with sodium and proton allows one main route to be described—namely the release of the pyrrolidone pendant group in a charge remote and charge driven mechanism, respectively. Extrapolating this fragmentation pathway, the oxidation of vinyl pyrrolidone into vinyl succinimide hypothesized from the single stage MS is validated by the detection of an alternative succinimide neutral loss in lieu of the pyrrolidone release in the ESI-MSn spectra of the aged PVP sample. It constitutes an example of application of multi-stage mass spectrometry for the characterization of the degradation of polymeric samples at a molecular level. PMID:27800293

Poly(ethylene oxide) surfactant polymers.

PubMed

Vacheethasanee, Katanchalee; Wang, Shuwu; Qiu, Yongxing; Marchant, Roger E

2004-01-01

We report on a series of structurally well-defined surfactant polymers that undergo surface-induced self-assembly on hydrophobic biomaterial surfaces. The surfactant polymers consist of a poly(vinyl amine) backbone with poly(ethylene oxide) and hexanal pendant groups. The poly(vinyl amine) (PVAm) was synthesized by hydrolysis of poly(N-vinyl formamide) following free radical polymerization of N-vinyl formamide. Hexanal and aldehyde-terminated poly(ethylene oxide) (PEO) were simultaneously attached to PVAm via reductive amination. Surfactant polymers with different PEO:hexanal ratios and hydrophilic/hydrophobic balances were prepared, and characterized by FT-IR, 1H-NMR and XPS spectroscopies. Surface active properties at the air/water interface were determined by surface tension measurements. Surface activity at a solid surface/water interface was demonstrated by atomic force microscopy, showing epitaxially molecular alignment for surfactant polymers adsorbed on highly oriented pyrolytic graphite. The surfactant polymers described in this report can be adapted for simple non-covalent surface modification of biomaterials and hydrophobic surfaces to provide highly hydrated interfaces.

Methacrylate derivatives incorporating pyroglutamic acid.

PubMed

Smith, Tara J; Mathias, Lon J

2002-01-01

Methacrylates containing pyroglutamic acid were synthesized in good yields. Methyl alpha-pyroglutamyl methylacrylate (PyMM) and methyl alpha-pyroglutamidoundecanoyl methylacrylate (PyUM) give very fast photopolymerization rates both in homopolymerizations and with widely used commercial monomers N-vinyl pyrrolidinone (NVP) and hydroxyethyl methacrylate (HEMA). Soluble or cross-linked homopolymers can be obtained depending upon polymerization temperature. Pyroglutamic methacrylates polymerize without added initiator in the melt. Solution cast, photocured, and thermally cured coatings gave good to excellent adhesion to poly(ethylene terephthalate) and glass surfaces.

Relationship between Leakage Current and Pollution Deposits on the Surface of Polymeric Insulator

NASA Astrophysics Data System (ADS)

Miyake, Takuma; Seo, Yuya; Sakoda, Tatsuya; Otsubo, Masahisa

Application of polymeric materials used for housing insulators is considered. However, because polymeric insulator is organic matter, the aged deterioration is anxious. The lifetime of polymeric insulator is influenced by environmental conditions such as ultraviolet, acid rain, and polluted deposits. A change of the surface condition of polymeric material causes the dry band arc discharge and the discharge may lower the insulation strength. To investigate the relationship between insoluble pollution and occurrence of dry band arc discharge, we performed a salt-fog test with ethylene vinyl acetate (EVA) samples. The results showed that the heavy erosion caused by frequent dry band arc discharges occurred even in the case of a light polluted condition. Additionally, a very characteristic increase tendency in leakage current with a period of about 5 h was observed during the mist period.

Facile high-yield synthesis of polyaniline nanosticks with intrinsic stability and electrical conductivity.

PubMed

Li, Xin-Gui; Li, Ang; Huang, Mei-Rong

2008-01-01

Chemical oxidative polymerization at 15 degrees C was used for the simple and productive synthesis of polyaniline (PAN) nanosticks. The effect of polymerization media on the yield, size, stability, and electrical conductivity of the PAN nanosticks was studied by changing the concentration and nature of the acid medium and oxidant and by introducing organic solvent. Molecular and supramolecular structure, size, and size distribution of the PAN nanosticks were characterized by UV/Vis and IR spectroscopy, X-ray diffraction, laser particle-size analysis, and transmission electron microscopy. Introduction of organic solvent is advantageous for enhancing the yield of PAN nanosticks but disadvantageous for formation of PAN nanosticks with small size and high conductivity. The concentration and nature of the acid medium have a major influence on the polymerization yield and conductivity of the nanosized PAN. The average diameter and length of PAN nanosticks produced with 2 M HNO(3) and 0.5 M H(2)SO(4) as acid media are about 40 and 300 nm, respectively. The PAN nanosticks obtained in an optimal medium (i.e., 2 M HNO(3)) exhibit the highest conductivity of 2.23 S cm(-1) and the highest yield of 80.7 %. A mechanism of formation of nanosticks instead of nanoparticles is proposed. Nanocomposite films of the PAN nanosticks with poly(vinyl alcohol) show a low percolation threshold of 0.2 wt %, at which the film retains almost the same transparency and strength as pure poly(vinyl alcohol) but 262 000 times the conductivity of pure poly(vinyl alcohol) film. The present synthesis of PAN nanosticks requires no external stabilizer and provides a facile and direct route for fabrication of PAN nanosticks with high yield, controllable size, intrinsic self-stability, strong redispersibility, high purity, and optimizable conductivity.

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

PubMed

Gilbert, Jeremy L

2006-12-15

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

Applications of ethylene vinyl acetate as an encapsulation material for terrestrial photovoltaic modules

NASA Technical Reports Server (NTRS)

Cuddihy, E. F.; Coulbert, C. D.; Liang, R. H.; Gupta, A.; Willis, P.; Baum, B.

1983-01-01

Terrestrial photovoltaic modules must undergo substantial reductions in cost in order to become economically attractive as practical devices for large scale production of electricity. Part of the cost reductions must be realized by the encapsulation materials that are used to package, protect, and support the solar cells, electrical interconnects, and other ancillary components. As many of the encapsulation materials are polymeric, cost reductions necessitate the use of low cost polymers. The performance and status of ethylene vinyl acetate, a low cost polymer that is being investigated as an encapsulation material for terrestrial photovoltaic modules, are described.

Surface-functionalized mesoporous carbon materials

DOEpatents

Dai, Sheng; Gorka, Joanna; Mayes, Richard T.

2016-02-02

A functionalized mesoporous carbon composition comprising a mesoporous carbon scaffold having mesopores in which polyvinyl polymer grafts are covalently attached, wherein said mesopores have a size of at least 2 nm and up to 50 nm. Also described is a method for producing the functionalized mesoporous composition, wherein a reaction medium comprising a precursor mesoporous carbon, vinyl monomer, initiator, and solvent is subjected to sonication of sufficient power to result in grafting and polymerization of the vinyl monomer into mesopores of the precursor mesoporous carbon. Also described are methods for using the functionalized mesoporous carbon, particularly in extracting metal ions from metal-containing solutions.

40 CFR 61.61 - Definitions.

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...

40 CFR 61.61 - Definitions.

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...

DISPERSION POLYMERIZATION OF 1-VINYL-2-PYRROLIDONE IN SUPERCRITICAL CARBON DIOXIDE. (R826115)

EPA Science Inventory

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...

Poly(vinyl alcohol) stabilization of acrylic emulsion polymers using the miniemulsion approach

NASA Astrophysics Data System (ADS)

Kim, Noma

Miniemulsion approach was employed to obtain stable acrylic latexes of n-butyl acrylate and methyl methacrylate (50/50 wt%) stabilized with poly(vinyl alcohol) (PVA) and to enhance the grafting reaction between PVA and acrylic monomers at the water/droplet interface. The stability of miniemulsions were studied in terms of the type and concentration of' the stabilizer, and the PVA partitioning were determined as a function of the PVA concentration. Using the comparison of PVA partitioning at droplet surface and grafted PVA as a function of concentration, it was suggested that the water/monomer interface is the main grafting site in the miniemulsion polymerization. Seeded emulsion and miniemulsion copolymerizations initiated with water-soluble (hydrogen peroxide, HPO), partially water-soluble (t-butyl peroxide, TBHP), and oil-soluble (t-butyl peroxyoctoate, TBPO) initiators were carried out to further investigate the oil/water interface as the grafting site for PVA. The interaction between the capillary wall in the CHDF (capillary hydrodynamic fractionation) chromatographic particle sizer and the water-soluble polymers adsorbed on the particle surface was studied using different types of water-soluble polymers and eluants. Different grafting architectures depending on the initiation site were suggested based on the CHDF results. The amounts of grafted PVA produced in miniemulsion polymers initiated with TBHP and TBPO were substantially less than those in the corresponding seeded emulsion polymerizations. The effect on the internal viscosity at the interface was proposed to explain the difference in grafting in terms of polymerization methods. Aqueous phase and interface grafting were studied using the measurement of the degree of hydrolysis (DH) of the serum PVA and adsorbed PVA after miniemulsion polymerizations. Based on the results, it was found that aqueous phase and interface grafting occurred in the HPO system; however, interface grafting dominated the TBHP system. Colloidal instability in conventional emulsion polymerizations was investigated and compared with the corresponding miniemulsion polymerization. It was found that the grafted PVA in conventional emulsion polymerizations was more hydrophobic presumably due to a greater amount of grafted chains than that in similar miniemulsion polymerizations and this could be correlated with the colloidal instability during conventional emulsion polymerizations.

Novel synthesis of cobalt/poly vinyl alcohol/gamma alumina nanocomposite for catalytic application

NASA Astrophysics Data System (ADS)

Hatamie, Shadie; Ahadian, Mohammad Mahdi; Rashidi, Alimoradeh; Karimi, Ali; Akhavan, Omid

2017-05-01

In this manuscript, synthesis of cobalt/poly vinyl alcohol (PVA)/gamma alumina nanocomposite via a simple room temperature, as well as its catalyst performance were explored. Brunauer-Emmett-Teller analysis, X-ray diffraction, X-ray photoelectron spectroscopy, and Fourier transform infrared spectroscopy were conducted. The surface area of the polymeric composite was obtained to be 280 m2/g. The cobalt loading on the nanocomposite was measured using inductivity couple plasma. Transmission electron microscopy analysis showed that the size of cobalt crystalline encapsulate inside the polymer was confined to 5 nm. Magnetic property analysis, using vibrating sample magnetometer, confirmed ferromagnetic nature of the composite. Thermo-gravimetric analyses were employed to explain the degradation process for the polymeric base nanocomposite. Temperature-programmed reduction was used to evaluate the structural form of cobalt oxide in nanocomposite. The catalysis activity was determined by Fischer-Tropsch synthesize, which showed a high catalyst selectivity to C2-C4 hydrocarbons.

Non-fouling surfaces produced by gas phase pulsed plasma polymerization of an ultra low molecular weight ethylene oxide containing monomer.

PubMed

Wu; Timmons; Jen; Molock

2000-10-01

The pulsed plasma polymerization of low molecular weight molecules containing only one (ethylene oxide vinyl ether) and two (diethylene oxide vinyl ether) ethylene oxide units were investigated. The surface density of EO units retained in the polymer films increases sharply with decreasing average power input during deposition, particularly at very low plasma duty cycles. The protein adsorption properties of these plasma synthesized polymer were investigated using 125I-labeled albumin and fibrinogen. Surprisingly effective, non-fouling surfaces were observed with films synthesized from the monomer containing two ethylene oxide units; however, the monomer containing only one EO unit gave surfaces that were not particularly effective in preventing protein adsorptions. The results obtained show that ultra short chain length PEO modified surfaces can be biologically non-fouling. This, in turn, has interesting consequences in terms of trying to identify the basic reason for the effectiveness of EO units in preventing biomolecule adsorptions on surfaces.

Nonaqueous polypyrrole colloids

DOEpatents

Armes, Steven P.; Aldissi, Mahmoud

1991-01-01

Processable conductive polymers including an oxidized, polymerized aromatic heterocyclic monomer, e.g., pyrrole, an stabilizing effective amount of a poly(vinyl acetate) and dopant anions, and a process of preparing said processable conductive polymers directly in a nonaqueous medium such as methyl acetate, methyl formate, ethyl formate, and propyl formate are disclosed.

Polymeric blend nanocomposite membranes for ethanol dehydration-effect of morphology and membrane-solvent interactions

EPA Science Inventory

Nanocomposite membranes (NCMs) of sodium alginate/poly(vinyl pyrrolidone) blend polymers incorporated with varying concentrations of phosphotungstic acid (H3PW12O40) (PWA) nanoparticles have been prepared and used in ethanol dehydration by the pervaporation (PV) technique. Effe...

Amidine-Functionalized Poly(2-vinyl-4,4-dimethylazlactone) for Selective and Efficient CO 2 Fixing

DOE Office of Scientific and Technical Information (OSTI.GOV)

Barkakaty, Balaka; Browning, Katie L.; Sumpter, Bobby

Development of novel polymeric materials capable of efficient CO 2 capture and separation under ambient conditions is crucial for cost-effective and practical industrial applications. Here we report the facile synthesis of a new CO 2-responsive polymer through post-polymerization modification of poly(2 vinyl-4,4-dimethylazlactone) (PVDMA). The reactive pendant azlactone groups of PVDMA are easily modified with 4-(N-methyltetrahydropyrimidine) benzyl alcohol (PBA) without any by-product formation. FTIR and TGA experiments show the new PBA functionalized polymer powder can reversibly capture CO 2 at room temperature and under atmospheric pressure. CO2 capture was selective, showing a high fixing efficiency even with a mixed gas systemmore » (20% CO 2, 80% N 2) similar to flue gas. CO 2 release occurred at room temperature and release profiles were investigated as a function of temperature. Density Functional Theory (DFT) calculations coupled with modeling and simulation reveal the presence of two CO 2 binding sites in the PBA functionalized polymer resulting in a two-step CO 2 release at room temperature. Finally, we find that the ease of material preparation, high fixing efficiency, and robust release characteristics suggest that post-polymerization modification may be a useful route to designing new materials for CO 2 capture.« less

Facile Synthesis of Thick Films of Poly(methyl methacrylate), Poly(styrene), and Poly(vinyl pyridine) from Au Surfaces

PubMed Central

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

Flavonoids preservation and release by methacrylic acid-grafted (N-vinyl-pyrrolidone).

PubMed

Parisi, Ortensia Ilaria; Puoci, Francesco; Iemma, Francesca; Curcio, Manuela; Cirillo, Giuseppe; Spizzirri, Umile Gianfranco; Picci, Nevio

2013-01-01

Flavonoids preservation and release. Synthesis of a polymeric material able to prevent thermal and photo degradation of a flavonoid model compound, such as (+)-catechin, and suitable for a controlled/sustained delivery of this molecule in gastro-intestinal simulating fluids. Methacrylic acid (MAA) was grafted onto poly(N-vinyl-pyrrolidone) (PVP) by a free radical grafting procedure involving a single-step reaction at room temperature. For this purpose, hydrogen peroxide/ascorbic acid redox pair was employed as water-soluble and biocompatible initiator system. FT-IR spectra confirmed the insertion of MAA onto the polymeric chain. Stability studies, performed under various conditions, such as freeze-thaw cycles, exposure to strong light, thermal stability studies under constant humidity and with light protection at different temperatures, showed the preservative properties of the polymeric material towards flavonoids. Furthermore, the biocompatibility was highlighted by Hen's Egg Test-Chorioallantoic Membrane assay and in vitro release studies demonstrated the possibility to employ PVP-MAA copolymer as a device for gastro-intestinal release of flavonoids. The coupling of good preservative properties together with biocompatibility and the usefulness as carrier in controlled release make this kind of material very interesting from an industrial point of view for different applications in food, pharmaceutical, and cosmetic fields.

Amidine-Functionalized Poly(2-vinyl-4,4-dimethylazlactone) for Selective and Efficient CO 2 Fixing

DOE PAGES

Barkakaty, Balaka; Browning, Katie L.; Sumpter, Bobby; ...

2016-02-12

Development of novel polymeric materials capable of efficient CO 2 capture and separation under ambient conditions is crucial for cost-effective and practical industrial applications. Here we report the facile synthesis of a new CO 2-responsive polymer through post-polymerization modification of poly(2 vinyl-4,4-dimethylazlactone) (PVDMA). The reactive pendant azlactone groups of PVDMA are easily modified with 4-(N-methyltetrahydropyrimidine) benzyl alcohol (PBA) without any by-product formation. FTIR and TGA experiments show the new PBA functionalized polymer powder can reversibly capture CO 2 at room temperature and under atmospheric pressure. CO2 capture was selective, showing a high fixing efficiency even with a mixed gas systemmore » (20% CO 2, 80% N 2) similar to flue gas. CO 2 release occurred at room temperature and release profiles were investigated as a function of temperature. Density Functional Theory (DFT) calculations coupled with modeling and simulation reveal the presence of two CO 2 binding sites in the PBA functionalized polymer resulting in a two-step CO 2 release at room temperature. Finally, we find that the ease of material preparation, high fixing efficiency, and robust release characteristics suggest that post-polymerization modification may be a useful route to designing new materials for CO 2 capture.« less

Novel double-confined polymeric ionic liquids as sorbents for solid-phase microextraction with enhanced stability and durability in high-ionic-strength solution.

PubMed

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.

Applicability of samarium(III) complexes for the role of luminescent molecular sensors for monitoring progress of photopolymerization processes and control of the thickness of polymer coatings

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.

Novel polymeric materials from vegetable oils and vinyl monomers: preparation, properties, and applications.

PubMed

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.

Thermo- and electro-dual responsive poly(ionic liquid) electrolyte based smart windows.

PubMed

Chen, Fei; Ren, Yongyuan; Guo, Jiangna; Yan, Feng

2017-01-31

Thermo- and electro-dual responsive poly(ionic liquid) (PIL) based electrolytes were synthesized by co-polymerization of N-isopropylacrylamide (NIPAM) with (or without) 3-butyl-1-vinyl-imidazolium bromide ([BVIm][Br]) using diallyl-viologen (DAV) as both the cross-linking agent and electrochromic material.

21 CFR 178.3790 - Polymer modifiers in semirigid and rigid vinyl chloride plastics.

Code of Federal Regulations, 2014 CFR

2014-04-01

...), (ii), and (iii) of this section; provided that no chemical reactions, other than addition reactions... their polymerization with butadiene-styrene copolymers; provided that no chemical reactions, other than addition reactions, occur when they are combined. Such combined polymers may contain 50 weight-percent or...

Electron-deficient triarylborane block copolymers: synthesis by controlled free radical polymerization and application in the detection of fluoride ions.

PubMed

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.

Hydrogel Nanoparticles from Supercritical Technology for Pharmaceutical and Seismological Applications

NASA Astrophysics Data System (ADS)

Hemingway, Melinda Graham

This research focuses on hydrogel nanoparticle formation using miniemulsion polymerization and supercritical carbon dioxide. Hydrogel nanopowder is produced by a novel combination of inverse miniemulsion polymerization and supercritical drying (MPSD) methods. Three drying methods of miniemulsions are examined: (1) a conventional freeze drying technique, and (2) two supercritical drying techniques: (2a) supercritical fluid injection into miniemulsions, and (2b) the polymerized miniemulsion injection into supercritical fluid. Method 2b can produce non-agglomerated hydrogel nanoparticles that are free of solvent or surfactant (Chapter 2). The optimized MPSD method was applied for producing an extended release drug formulation with mucoadhesive properties. Drug nanoparticles of mesalamine, were produced using supercritical antisolvent technology and encapsulation within two hydrogels, polyacrylamide and poly(acrylic acid-co-acrylamide). The encapsulation efficiency and release profile of drug nanoparticles is compared with commercial ground mesalamine particles. The loading efficiency is influenced by morphological compatibility (Chapter 3). The MPSD method was extended for encapsulation of zinc oxide nanoparticles for UV protection in sunscreens (Chapter 4). ZnO was incorporated into the inverse miniemulsion during polymerization. The effect of process parameters are examined on absorbency of ultraviolet light and transparency of visible light. For use of hydrogel nanoparticles in a seismological application, delayed hydration is needed. Supercritical methods extend MPSD so that a hydrophobic coating can be applied on the particle surface (Chapter 5). Multiple analysis methods and coating materials were investigated to elucidate compatibility of coating material to polyacrylamide hydrogel. Coating materials of poly(lactide), poly(sulphone), poly(vinyl acetate), poly(hydroxybutyrate), Geluice 50-13, Span 80, octadecyltrichlorosilane, and perfluorobutane sulfate (PFBS) were tested, out of which Gelucire, perfluorobutane sulfate, and poly(vinyl acetate) materials were able to provide some coating and perfluorobutane sulfate, poly(lactide), poly(vinyl acetate) delayed hydration of hydrogel particles, but not to a sufficient extent. The interactions of the different materials with the hydrogel are examined based on phenomena observed during the production processes and characterization of the particles generated. This work provides understanding into the interactions of polyacrylamide hydrogel particles both internally by encapsulation and externally by coating.

Biodegradability of poly(3-hydroxybutyrate) film grafted with vinyl acetate: Effect of grafting and saponification

NASA Astrophysics Data System (ADS)

Wada, Yuki; Seko, Noriaki; Nagasawa, Naotsugu; Tamada, Masao; Kasuya, Ken-ichi; Mitomo, Hiroshi

2007-06-01

Radiation-induced graft polymerization of vinyl acetate (VAc) onto poly(3-hydroxybutyrate) (PHB) film was carried out. At a degree of grafting higher than 5%, the grafted films (PHB-g-VAc) completely lost the enzymatic degradability that is characteristic of PHB due to the grafted VAc covering the surface of the PHB film. However, the biodegradability of the PHB-g-VAc films was recovered when the films were saponified in alkali solution under optimum conditions. Graft chains of the PHB-g-VAc film reacted selectively to become biodegradable polyvinyl alcohol (PVA). The biodegradability of the saponified PHB-g-VAc film increased rapidly with time.

RAFT-Polymerization-Induced Self-Assembly and Reorganizations: Ultrahigh-Molecular-Weight Polymer and Morphology-Tunable Micro-/Nanoparticles in One Pot.

PubMed

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.

Chapter 16 Lumen Modification

Treesearch

Rebecca E. Ibach; Roger M. Rowell

2012-01-01

When wood is vacuum impregnated with liquid vinyl monomers that do not swell wood, and then in situ polymerized either by chemical catalyst-heat, or gamma radiation, the polymer is located almost solely in the lumens of the wood. Figure 16.1 is a scanning electron microscopy (SEM) micrograph of unmodified wood showing open cells that are...

Radical graft polymerization of an Allyl Monomer onto Hydrophilic Polymers and their antibacterial nanofibrous membranes

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...

Polyvinyl pyridine microspheres

NASA Technical Reports Server (NTRS)

Rembaum, Alan (Inventor); Gupta, Amitava (Inventor); Volksen, Willi (Inventor)

1980-01-01

Microspheres are produced by cobalt gamma radiation initiated polymerization of a dilute aqueous vinyl pyridine solution. Addition of cross-linking agent provides higher surface area beads. Addition of monomers such as hydroxyethylmethacrylate acrylamide or methacrylamide increases hydrophilic properties and surface area of the beads. High surface area catalytic supports are formed in the presence of controlled pore glass substrate.

Polyvinyl pyridine microspheres

NASA Technical Reports Server (NTRS)

Rembaum, Alan (Inventor); Gupta, Amitava (Inventor); Volksen, Willi (Inventor)

1979-01-01

Microspheres are produced by cobalt gamma radiation initiated polymerization of a dilute aqueous vinyl pyridine solution. Addition of cross-linking agent provides higher surface area beads. Addition of monomers such as hydroxyethylmethacrylate acrylamide or methacrylamide increases hydrophilic properties and surface area of the beads. High surface area catalytic supports are formed in the presence of controlled pore glass substrate.

21 CFR 175.320 - Resinous and polymeric coatings for polyolefin films.

Code of Federal Regulations, 2010 CFR

2010-04-01

...-formaldehyde as the basic polymer or chemically modified with methyl alcohol Methacrylic acid and its ethyl or... 68083-18-1), with methyl hydrogen polysiloxane (CAS Reg. No. 63148-57-2). Dimethyl maleate (CAS Reg. No... product of vinyl-containing dimethylpolysiloxane (CAS Reg. Nos. 68083-19-2 and 68083-18-1), with methyl...

21 CFR 175.320 - Resinous and polymeric coatings for polyolefin films.

Code of Federal Regulations, 2011 CFR

2011-04-01

...-formaldehyde as the basic polymer or chemically modified with methyl alcohol Methacrylic acid and its ethyl or... 68083-18-1), with methyl hydrogen polysiloxane (CAS Reg. No. 63148-57-2). Dimethyl maleate (CAS Reg. No... product of vinyl-containing dimethylpolysiloxane (CAS Reg. Nos. 68083-19-2 and 68083-18-1), with methyl...

Catalytic Effect of Pd Clusters in the Poly( N-vinyl-2-pyrrolidone) Combustion

NASA Astrophysics Data System (ADS)

Schiavo, L.; De Nicola, S.; Carotenuto, G.

2018-01-01

Pd(0) is able to catalyze oxygen-involving reactions because of its capability to convert molecular oxygen to the very reactive atomic form. Consequently, the embedding of a little amount of Pd(0) clusters in polymeric phases can be technologically exploited to enhance the incineration kinetic of these polymers. The effect of nanostructuration on the Pd(0) catalytic activity in the polymer incineration reaction has been studied using poly( N-vinyl-2-pyrrolidone) ( \\overline{Mw} = 10,000 gmol-1) as polymeric model system. A change in the PVP incineration kinetic mechanism with significant increase in the reaction rate was experimentally found. The kinetic of the Pd(0)-catalyzed combustion has been studied by isothermal thermogravimetric analysis. After a short induction time, the combustion in presence of Pd(0) clusters shifted to a zero-order kinetic from a second-order kinetic control, which is operative in pure PVP combustion reaction. In addition, the activation energy resulted much lowered compared to the pure PVP incineration case (from 300 to 260 kJ/mol).

Recyclable magnetic nanocluster crosslinked with poly(ethylene oxide)-block-poly(2-vinyl-4,4-dimethylazlactone) copolymer for adsorption with antibody.

PubMed

Prai-In, Yingrak; Boonthip, Chatchai; Rutnakornpituk, Boonjira; Wichai, Uthai; Montembault, Véronique; Pascual, Sagrario; Fontaine, Laurent; Rutnakornpituk, Metha

2016-10-01

Surface modification of magnetic nanoparticle (MNP) with poly(ethylene oxide)-block-poly(2-vinyl-4,4-dimethylazlactone) (PEO-b-PVDM) diblock copolymers and its application as recyclable magnetic nano-support for adsorption with antibody were reported herein. PEO-b-PVDM copolymers were first synthesized via a reversible addition-fragmentation chain-transfer (RAFT) polymerization using poly(ethylene oxide) chain-transfer agent as a macromolecular chain transfer agent to mediate the RAFT polymerization of VDM. They were then grafted on amino-functionalized MNP by coupling with some azlactone rings of the PVDM block to form magnetic nanoclusters with tunable cluster size. The nanocluster size could be tuned by adjusting the chain length of the PVDM block. The nanoclusters were successfully used as efficient and recyclable nano-supports for adsorption with anti-rabbit IgG antibody. They retained higher than 95% adsorption of the antibody during eight adsorption-separation-desorption cycles, indicating the potential feasibility in using this novel hybrid nanocluster as recyclable support in cell separation applications. Copyright © 2016 Elsevier B.V. All rights reserved.

The Quest for Converting Biorenewable Bifunctional α-Methylene-γ-butyrolactone into Degradable and Recyclable Polyester: Controlling Vinyl-Addition/Ring-Opening/Cross-Linking Pathways.

PubMed

Tang, Xiaoyan; Hong, Miao; Falivene, Laura; Caporaso, Lucia; Cavallo, Luigi; Chen, Eugene Y-X

2016-11-02

α-Methylene-γ-butyrolactone (MBL), a naturally occurring and biomass-sourced bifunctional monomer, contains both a highly reactive exocyclic C═C bond and a highly stable five-membered γ-butyrolactone ring. Thus, all previous work led to exclusive vinyl-addition polymerization (VAP) product P(MBL) VAP . Now, this work reverses this conventional chemoselectivity to enable the first ring-opening polymerization (ROP) of MBL, thereby producing exclusively unsaturated polyester P(MBL) ROP with M n up to 21.0 kg/mol. This elusive goal was achieved through uncovering the thermodynamic, catalytic, and processing conditions. A third reaction pathway has also been discovered, which is a crossover propagation between VAP and ROP processes, thus affording cross-linked polymer P(MBL) CLP . The formation of the three types of polymers, P(MBL) VAP , P(MBL) CLP , and P(MBL) ROP , can be readily controlled by adjusting the catalyst (La)/initiator (ROH) ratio, which is determined by the unique chemoselectivity of the La-X (X = OR, NR 2 , R) group. The resulting P(MBL) ROP is degradable and can be readily postfunctionalized into cross-linked or thiolated materials but, more remarkably, can also be fully recycled back to its monomer thermochemically. Computational studies provided the theoretical basis for, and a mechanistic understanding of, the three different polymerization processes and the origin of the chemoselectivity.

The development and characterization of degradable poly(vinyl ester) and poly(vinyl ester)/PEO block copolymers

NASA Astrophysics Data System (ADS)

Lipscomb, Corinne Elizabeth

The development of biodegradable materials is a challenging and important problem in polymer science. A review of the state of the art in degradable materials is presented, which reveals that current biodegradable materials do not exhibit the thermal or mechanical properties necessary for widespread applications. One strategy for toughening polymeric materials, which has previously been applied to non-degradable thermoplastics and thermoplastic elastomers, is the formation of block copolymers. Poly(vinyl esters) (PVE) homopolymers are known to have a wide range of properties, but PVE block copolymers comprise a class of inexpensive and (bio)degradable materials that were previously unknown. Therefore, the synthesis and properties of these block copolymers were explored in an effort to develop robust degradable materials. This thesis research probes the reaction conditions necessary for the reversible-addition fragmentation chain transfer (RAFT) polymerization and chain extension reactions of vinyl ester monomers. PVE di- and triblock copolymers are synthesized and studied, and the triblock copolymers display extremely poor toughness due to their relatively low molecular weights in light of the high entanglement molecular weight of the poly(vinyl acetate) center block. Attempts to improve the mechanical properties of these materials focus on the incorporation of poly(ethylene oxide) (PEO) as a low entanglement molecular weight and biocompatible center block in PVE-containing triblock copolymers. Depending on the choice of PVE endblocks and the overall polymer composition, crystallization of the PEO block can be controlled, confined, or inhibited. Polymers in which PEO crystallization is completely inhibited exhibit enhanced mechanical properties and behave as weak thermoplastics. In order to understand the relationship between the inhibition of PEO crystallization and the mechanical properties of PVE/PEO materials, these polymers were studied using dynamic mechanical spectroscopy, wide angle X-ray scattering, small angle X-ray scattering, differential scanning calorimetry, and uniaxial tensile tests. By combining insights gained from these techniques, a complex picture emerges that explains the enhanced mechanical properties of these materials based on the type and location of thermal transitions, amorphous PEO entanglements, and the strain-induced crystallization of PEO. This work represents an important step toward developing robust materials with tunable properties containing (bio)degradable components.

Structure-Composition-Property Relationships in Polymeric Amorphous Calcium Phosphate-Based Dental Composites †

PubMed Central

O’Donnell, Justin N.R.; Schumacher, Gary E.; Antonucci, Joseph M.; Skrtic, Drago

2009-01-01

Our studies of amorphous calcium phosphate (ACP)-based materials over the last decade have yielded bioactive polymeric composites capable of protecting teeth from demineralization or even regenerating lost tooth mineral. The anti-cariogenic/re-mineralizing potential of these ACP composites originates from their propensity, when exposed to the oral environment, to release in a sustained manner sufficient levels of mineral-forming calcium and phosphate ions to promote formation of stable apatitic tooth mineral. However, the less than optimal ACP filler/resin matrix cohesion, excessive polymerization shrinkage and water sorption of these experimental materials can adversely affect their physicochemical and mechanical properties, and, ultimately, limit their lifespan. This study demonstrates the effects of chemical structure and composition of the methacrylate monomers used to form the matrix phase of composites on degree of vinyl conversion (DVC) and water sorption of both copolymers and composites and the release of mineral ions from the composites. Modification of ACP surface via introducing cations and/or polymers ab initio during filler synthesis failed to yield mechanically improved composites. However, moderate improvement in composite’s mechanical stability without compromising its remineralization potential was achieved by silanization and/or milling of ACP filler. Using ethoxylated bisphenol A dimethacrylate or urethane dimethacrylate as base monomers and adding moderate amounts of hydrophilic 2-hydroxyethyl methacrylate or its isomer ethyl-α-hydroxymethacrylate appears to be a promising route to maximize the remineralizing ability of the filler while maintaining high DVC. Exploration of the structure/composition/property relationships of ACP fillers and polymer matrices is complex but essential for achieving a better understanding of the fundamental mechanisms that govern dissolution/re-precipitation of bioactive ACP fillers, and, ultimately, the suitability of the composites for clinical evaluation. PMID:21966588

Hydroacylation of 2-vinyl benzaldehyde systems: an efficient method for the synthesis of chiral 3-substituted indanones.

PubMed

Kundu, Kousik; McCullagh, James V; Morehead, Andrew T

2005-11-23

Asymmetric rhodium-catalyzed hydroacylation has been utilized in the synthesis of 3-substituted indanones with high conversions and enantioselectivity. The hydroacylation reaction of 2-vinyl benzaldehyde had been previously reported to give a low yield of indanone and an unidentified product. We have identified this compound as a dimer of the starting material. Substitution at the alpha-position of the 2-vinyl benzaldehyde substrates blocks the competitive dimerization reaction and allows the reaction to proceed with yields generally greater than 90%. Utilization of BINAP as a chiral ligand results in good chemical yields and enantioselectivity greater than 95% in most cases.

A novel headspace gas chromatographic method for in situ monitoring of monomer conversion during polymerization in an emulsion environment.

PubMed

Chai, Xin-Sheng; Zhong, Jin-Feng; Hu, Hui-Chao

2012-05-18

This paper describes a novel multiple-headspace extraction/gas chromatographic (MHE-GC) technique for monitoring monomer conversion during a polymerization reaction in a water-based emulsion environment. The polymerization reaction of methyl methacrylate (MMA) in an aqueous emulsion is used as an example. The reaction was performed in a closed headspace sample vial (as a mini-reactor), with pentane as a tracer. In situ monitoring of the vapor concentration of the tracer, employing a multiple headspace extraction (sampling) scheme, coupled to a GC, makes it possible to quantitatively follow the conversion of MMA during the early stages of polymerization. Data on the integrated amount of the tracer vapor released from the monomer droplet phase during the polymerization is described by a mathematic equation from which the monomer conversion can be calculated. The present method is simple, automated and economical, and provides an efficient tool in the investigation of the reaction kinetics and effects of the reaction conditions on the early stage of polymerization. Copyright © 2012 Elsevier B.V. All rights reserved.

Influence of Block Copolymerization on the Antifreeze Protein Mimetic Ice Recrystallization Inhibition Activity of Poly(vinyl alcohol).

PubMed

Congdon, Thomas R; Notman, Rebecca; Gibson, Matthew I

2016-09-12

Antifreeze (glyco) proteins are produced by many cold-acclimatized species to enable them to survive subzero temperatures. These proteins have multiple macroscopic effects on ice crystal growth which makes them appealing for low-temperature applications-from cellular cryopreservation to food storage. Poly(vinyl alcohol) has remarkable ice recrystallization inhibition activity, but its mode of action is uncertain as is the extent at which it can be incorporated into other high-order structures. Here the synthesis and characterization of well-defined block copolymers containing poly(vinyl alcohol) and poly(vinylpyrrolidone) by RAFT/MADIX polymerization is reported, as new antifreeze protein mimetics. The effect of adding a large second hydrophilic block is studied across a range of compositions, and it is found to be a passive component in ice recrystallization inhibition assays, enabling retention of all activity. In the extreme case, a block copolymer with only 10% poly(vinyl alcohol) was found to retain all activity, where statistical copolymers of PVA lose all activity with very minor changes to composition. These findings present a new method to increase the complexity of antifreeze protein mimetic materials, while retaining activity, and also to help understand the underlying mechanisms of action.

Influence of Block Copolymerization on the Antifreeze Protein Mimetic Ice Recrystallization Inhibition Activity of Poly(vinyl alcohol)

PubMed Central

2016-01-01

Antifreeze (glyco) proteins are produced by many cold-acclimatized species to enable them to survive subzero temperatures. These proteins have multiple macroscopic effects on ice crystal growth which makes them appealing for low-temperature applications—from cellular cryopreservation to food storage. Poly(vinyl alcohol) has remarkable ice recrystallization inhibition activity, but its mode of action is uncertain as is the extent at which it can be incorporated into other high-order structures. Here the synthesis and characterization of well-defined block copolymers containing poly(vinyl alcohol) and poly(vinylpyrrolidone) by RAFT/MADIX polymerization is reported, as new antifreeze protein mimetics. The effect of adding a large second hydrophilic block is studied across a range of compositions, and it is found to be a passive component in ice recrystallization inhibition assays, enabling retention of all activity. In the extreme case, a block copolymer with only 10% poly(vinyl alcohol) was found to retain all activity, where statistical copolymers of PVA lose all activity with very minor changes to composition. These findings present a new method to increase the complexity of antifreeze protein mimetic materials, while retaining activity, and also to help understand the underlying mechanisms of action. PMID:27476873

Composite poly(vinyl alcohol)/poly(vinyl acetate) electrospun nanofibrous mats as a novel wound dressing matrix for controlled release of drugs

PubMed Central

Jannesari, Marziyeh; Varshosaz, Jaleh; Morshed, Mohammad; Zamani, Maedeh

2011-01-01

The aim of this study was to develop novel biomedicated nanofiber electrospun mats for controlled drug release, especially drug release directly to an injury site to accelerate wound healing. Nanofibers of poly(vinyl alcohol) (PVA), poly(vinyl acetate) (PVAc), and a 50:50 composite blend, loaded with ciprofloxacin HCl (CipHCl), were successfully prepared by an electrospinning technique for the first time. The morphology and average diameter of the electrospun nanofibers were investigated by scanning electron microscopy. X-ray diffraction studies indicated an amorphous distribution of the drug inside the nanofiber blend. Introducing the drug into polymeric solutions significantly decreased solution viscosities as well as nanofiber diameter. In vitro drug release evaluations showed that both the kind of polymer and the amount of drug loaded greatly affected the degree of swelling, weight loss, and initial burst and rate of drug release. Blending PVA and PVAc exhibited a useful and convenient method for electrospinning in order to control the rate and period of drug release in wound healing applications. Also, the thickness of the blend nanofiber mats strongly influenced the initial release and rate of drug release. PMID:21720511

Photoinduced Reversible Morphological Transformation of Azobenzene-Containing Pseudo-2D Polymers.

PubMed

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.

Influence of gamma irradiation on polymerization of pyrrole and glucose oxidase immobilization onto poly (pyrrole)/poly (vinyl alcohol) matrix

NASA Astrophysics Data System (ADS)

Idris, Sarada; A. Bakar, Ahmad Ashrif; Thevy Ratnam, Chantara; Kamaruddin, Nur Hasiba; Shaari, Sahbudin

2017-04-01

This paper describes the immobilization of glucose oxidase, GOx onto polymer matrix comprising of poly(pyrrole), PPy and poly(vinyl alcohol), PVA using gamma irradiation technique. Py/PVA-GOx film was prepared by spreading PVA:GOx, 1:1 solution onto dried pyrrole film and exposed to gamma irradiation from cobalt 60 source at doses ranging from 0 to 60 kGy. The films were subjected to structural and morphological analyses by using Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), Scanning electron microscope (SEM), Field emission scanning electron microscope (FESEM) and Atomic-force microscopy (AFM) techniques. Similar studies were also made on pristine pyrrole film which served as control. The SEM and FTIR spectra of Py/PVA-GOx film revealed that pyrrole has been successfully polymerized through irradiation-induced reactions. The results on the morphological properties of the samples characterize using FESEM, SEM and AFM further confirmed the occurrence of radiation-induced modification of Py/PVA-GOx film. The FTIR spectra showed the existence of intermolecular interaction between polymer matrix and GOx indicating that GOx had been successfully immobilized onto Ppy/PVA matrix by radiation-induced reactions. Results revealed that radiation induced reactions such as polymerization of pyrrole, crosslinking of PVA, grafting between the adjacent PVA and pyrrole molecules as well as immobilization of GOx onto Ppy/PVA matrix occurred simultaneously upon gamma irradiation. The optimum dose for GOx immobilization in the polymer matrix found to be 40 kGy. Therefore it is clear that this irradiation technique offered a simple single process to produce Py/PVA-GOx film without additional crosslinking and polymerization agents.

Effect of fluorinated groups on photooxidative stability of polymeric protectives applied on marble.

PubMed

Chiantore, O; Poli, T; Colombo, C; Peruzzi, R; Toniolo, L

2001-01-01

Some new protective copolymers and a commercial one have been tested on Candoglia marble, a very low porosity stone. Two of the polymers contained a partially fluorinated methacrylic monomer, 2,2,2 trifluoro ethyl methacrylate (TFEMA), in combination with either an acrylic, methyl acrylate (MA) or a vinyl ether, n-butyl vinyl ether (n-BVE) unit. Two copolymers, ethyl methacrylate/n-butyl vinyl ether and ethyl methacrylate (EMA)/methyl acrylate (Paraloid B72), were non-fluorinated and similar in compositions and molar ratio. The aim of the work is to test the copolymers and compare the performances of fluorinated new polymers with the non fluorinated one and with the largely used commercial product. The results obtained demonstrate that the introduction, even in limited amounts, of fluorine atoms in the side ester groups of methacrylic type polymers really improves their protective effect and the durability of the stone treatments. The best results were obtained with the copolymer TFEM/MA which is the fluorinated homologous of Paraloid B72.

In situ electron microscopy of Braille microsystems: photo-actuation of ethylene vinyl acetate/carbon nanotube composites

NASA Astrophysics Data System (ADS)

Czaniková, Klaudia; Krupa, Igor; Račko, Dušan; Šmatko, Vasilij; Campo, Eva M.; Pavlova, Ewa; Omastová, Mária

2015-02-01

The development of new types of tactile displays based on the actuation of composite materials can aid the visually impaired. Micro/nano systems based on ethylene vinyl acetate (EVA) polymeric matrices enriched with multiwalled carbon nanotubes (MWCNT) can produce ensembles capable of light-induced actuation. In this report, we investigate two types of commercial EVA copolymers matrices containing 28 and 50 wt% vinyl-acetate (VA). Non-covalent modification of carbon nanotubes was achieved through a compatibilization technique that appends the pyrenenyl and cholesteryl groups on the carbon nanotubes (CNTs) surface. EVA/MWCNT nanocomposites were prepared by casting from a solution. These composites were shaped into Braille elements using molds. The deformation of the Braille element (BE) under light-emitting diode (LED) illumination was observed for the first time by in situ scanning electron microscopy (SEM). The superior actuation performance promoted by the EVA/MWCNT nanocomposites indicates that these materials will be useful in the future as light-driven micro/nano system actuators.

Synthesis of Degradable Poly(vinyl alcohol) by Radical Ring-Opening Copolymerization and Ice Recrystallization Inhibition Activity.

PubMed

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.

Radiation-induced polymerization of glass-forming systems. IV. Effect of the homogeneity of polymerization phase and polymer concentration on temperature dependence of initial polymerization rate

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

Synthesis and properties of hemicelluloses-based semi-IPN hydrogels.

PubMed

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.

Synthesis and characterization of poly (benzyl trimethyl ammonium chloride) ionic polymer

NASA Astrophysics Data System (ADS)

Mathew, Manjusha Elizabeth; Ahmad, Ishak; Thomas, Sabu; Daik, Rusli; Kassim, Muhammad

2018-04-01

Poly vinyl benzyl chloride (PVBC) was synthesized by free radical polymerization of 4-vinyl benzyl chloride (VBC) using benzoyl peroxide initiator at 80°C. Amine functionalised polymer prepared by treatment of PVBC with trimethyl amine in different solvents such as water, ethanol, tetra hydro furan(THF) and dimethyl formamide(DMF). The polymers characterized structurally by nuclear magnetic resonance and infrared spectroscopic techniques. The thermal decomposition of the polymer is studied by Thermo Gravimetric Analysis(TGA) and found that the polymer has stability up to 230°C. The nitrogen content of the aminated polymer determined by elemental analysis. The nitrogen content obtained from tetra hydro furan and dimethyl formamide solvents are 20.1% and 19.9% respectively.

[Comparative study of polymerization shrinkage and related properties of flowable composites and an unfilled resin].

PubMed

Bukovinszky, Katalin; Molnár, Lilla; Bakó, József; Szalóki, Melinda; Hegedus, Csaba

2014-03-01

The polymerization shrinkage and shrinkage stress of dental composites are in the center of the interest of researchers and manufacturers. It is a great challenge to minimize this important property as low as possible. Many factors are related and are in complicated correlation with each other affecting the polymerization shrinkage. Polymerization shrinkage stress degree of conversion and elasticity has high importance from this aspect. Our aim was to study the polymerization shrinkage and related properties (modulus of elasticity, degree of conversion, shrinkage stress) of three flowable composite (Charisma Opal Flow, SDR, Filtek Ultimate) and an unfilled composite resin. Modulus of elasticity was measured using three point flexure tests on universal testing machine. The polymerization shrinkage stress was determined using bonded-disc technique. The degree of conversion measurements were performed by FT-IR spectroscopy. And the volumetric shrinkage was investigated using Archimedes principle and was measured on analytical balance with special additional equipment. The unfilled resin generally showed higher shrinkage (8,26%), shrinkage stress (0,8 MPa) and degree of conversion (38%), and presented the lowest modulus of elasticity (3047,02MPa). Highest values of unfilled resin correspond to the literature. The lack of fillers enlarges the shrinkage, and the shrinkage stress, but gives the higher flexibility and higher degree of conversion. Further investigations needs to be done to understand and reveal the differences between the composites.

Chiral Polymers.

DTIC Science & Technology

1984-10-01

regardless of the method of polymerization. The styrene-bead copolymers were packed in HPLC columns, but none were especiall, effective in separating...enantiomers in a racemic mixture. The chiral butyrolactone polymer was coated on silica, but this material did not effect resolution of racemic mixtures in an...been effected utilizing chiral oxazolines3 prompted the initial efforts to synthesize various chiral 2-vinyl- oxazoline monomers for incorporation

Evaluation of Rigid-Rod Polymeric Fibers by Post-Treatment in scC02

DTIC Science & Technology

2008-12-30

small molecular weight vinyl substituted polysiloxane prepolymer and hydride containing crosslinker to the fiber, swelling the fiber with the siloxane... prepolymer and subsequently initiating crosslinking by introduction of a Karstedt’s catalyst known to be highly soluble and robust in a scCO2...polydimethylsiloxane Prepolymer (PVMS) Polymethylvinylsiloxane-polydimethylsiloxane resin was prepared in a condensation reaction from

Electrically controlled polymeric gel actuators

DOEpatents

Adolf, Douglas B.; Shahinpoor, Mohsen; Segalman, Daniel J.; Witkowski, Walter R.

1993-01-01

Electrically controlled polymeric gel actuators or synthetic muscles capable of undergoing substantial expansion and contraction when subjected to changing pH environments, temperature, or solvent. The actuators employ compliant containers for the gels and their solvents. The gels employed may be cylindrical electromechanical gel fibers such as polyacrylamide fibers or a mixture of poly vinyl alcohol-polyacrylic acid arranged in a parallel aggregate and contained in an electrolytic solvent bath such as salt water. The invention includes smart, electrically activated devices exploiting this phenomenon. These devices are capable of being manipulated via active computer control as large displacement actuators for use in adaptive structure such as robots.

Electrically controlled polymeric gel actuators

DOEpatents

Adolf, D.B.; Shahinpoor, M.; Segalman, D.J.; Witkowski, W.R.

1993-10-05

Electrically controlled polymeric gel actuators or synthetic muscles are described capable of undergoing substantial expansion and contraction when subjected to changing pH environments, temperature, or solvent. The actuators employ compliant containers for the gels and their solvents. The gels employed may be cylindrical electromechanical gel fibers such as polyacrylamide fibers or a mixture of poly vinyl alcohol-polyacrylic acid arranged in a parallel aggregate and contained in an electrolytic solvent bath such as salt water. The invention includes smart, electrically activated devices exploiting this phenomenon. These devices are capable of being manipulated via active computer control as large displacement actuators for use in adaptive structure such as robots. 11 figures.

Cationic Bulk Polymerization of Vinyl Ethers in the Liquid Crystalline Phase

DTIC Science & Technology

1991-10-30

mesophase, if any, cannot alone be responsible for the unusual results obtained in this study. Table 3 . Polymerization of’ 2 -[(4-cyano-4’-biphenvl)oxy...NCC 11-H-( /C20 \\ / z 0 h ab cd e f S(7.43-7.47) Li (1.27-1.73) d (6.88-6.93) ab(7.53-7.64) ( 3 8 - , 4 9 h ( 3 .4 4 ) 10 9 8 7 6 5 4 3 2 1 0 Figure...Macromol. Sci.-Rev. Makromol. Chem. 171, 137 (1979) 2 . C. M. Paleos, Chem. Soc. Rev. 14, 45 (1985) 3 . R. G. Weiss, Tetrahedron 44, 3413 (1988) 4. D. J

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

PubMed

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

2009-03-01

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

Development of a fiber coating based on molecular sol-gel imprinting technology for selective solid-phase micro extraction of caffeine from human serum and determination by gas chromatography/mass spectrometry.

PubMed

Rajabi Khorrami, Afshin; Rashidpur, Amene

2012-05-21

In this work, a molecular sol-gel imprinting approach has been introduced to produce a fiber coating for selective direct immersion solid-phase microextraction (SPME) of caffeine. The polymerization mixture was composed of vinyl trimethoxysilane and methacrylic acid as vinyl sol-gel precursor and functional monomer, respectively. Caffeine was used as template molecule during polymerization process. The prepared fibers could be coupled directly to gas chromatography/mass spectrometry (GC/MS) and used for trace analysis of caffeine in a complex sample such as human serum. The parameters influencing SPME such as time, temperature and stirring speed were optimized. The prepared coating showed good selectivity towards caffeine in the presence of some structurally related compounds. Also, it offered high imprinting capability in comparison to bare fiber and non-imprinted coating. Linear range for caffeine detection was 1-80 μg mL(-1) and the limit of detection was 0.1 μg mL(-1). The intra-day and inter-day precisions of the peak areas for five replicates were 10 and 16%, respectively. Copyright © 2012 Elsevier B.V. All rights reserved.

The Mediterranean Plastic Soup: synthetic polymers in Mediterranean surface waters.

PubMed

Suaria, Giuseppe; Avio, Carlo G; Mineo, Annabella; Lattin, Gwendolyn L; Magaldi, Marcello G; Belmonte, Genuario; Moore, Charles J; Regoli, Francesco; Aliani, Stefano

2016-11-23

The Mediterranean Sea has been recently proposed as one of the most impacted regions of the world with regards to microplastics, however the polymeric composition of these floating particles is still largely unknown. Here we present the results of a large-scale survey of neustonic micro- and meso-plastics floating in Mediterranean waters, providing the first extensive characterization of their chemical identity as well as detailed information on their abundance and geographical distribution. All particles >700 μm collected in our samples were identified through FT-IR analysis (n = 4050 particles), shedding for the first time light on the polymeric diversity of this emerging pollutant. Sixteen different classes of synthetic materials were identified. Low-density polymers such as polyethylene and polypropylene were the most abundant compounds, followed by polyamides, plastic-based paints, polyvinyl chloride, polystyrene and polyvinyl alcohol. Less frequent polymers included polyethylene terephthalate, polyisoprene, poly(vinyl stearate), ethylene-vinyl acetate, polyepoxide, paraffin wax and polycaprolactone, a biodegradable polyester reported for the first time floating in off-shore waters. Geographical differences in sample composition were also observed, demonstrating sub-basin scale heterogeneity in plastics distribution and likely reflecting a complex interplay between pollution sources, sinks and residence times of different polymers at sea.

Probing the Biomimetic Ice Nucleation Inhibition Activity of Poly(vinyl alcohol) and Comparison to Synthetic and Biological Polymers.

PubMed

Congdon, Thomas; Dean, Bethany T; Kasperczak-Wright, James; Biggs, Caroline I; Notman, Rebecca; Gibson, Matthew I

2015-09-14

Nature has evolved many elegant solutions to enable life to flourish at low temperatures by either allowing (tolerance) or preventing (avoidance) ice formation. These processes are typically controlled by ice nucleating proteins or antifreeze proteins, which act to either promote nucleation, prevent nucleation or inhibit ice growth depending on the specific need, respectively. These proteins can be expensive and their mechanisms of action are not understood, limiting their translation, especially into biomedical cryopreservation applications. Here well-defined poly(vinyl alcohol), synthesized by RAFT/MADIX polymerization, is investigated for its ice nucleation inhibition (INI) activity, in contrast to its established ice growth inhibitory properties and compared to other synthetic polymers. It is shown that ice nucleation inhibition activity of PVA has a strong molecular weight dependence; polymers with a degree of polymerization below 200 being an effective inhibitor at just 1 mg.mL(-1). Other synthetic and natural polymers, both with and without hydroxyl-functional side chains, showed negligible activity, highlighting the unique ice/water interacting properties of PVA. These findings both aid our understanding of ice nucleation but demonstrate the potential of engineering synthetic polymers as new biomimetics to control ice formation/growth processes.

Probing the Biomimetic Ice Nucleation Inhibition Activity of Poly(vinyl alcohol) and Comparison to Synthetic and Biological Polymers

PubMed Central

2015-01-01

Nature has evolved many elegant solutions to enable life to flourish at low temperatures by either allowing (tolerance) or preventing (avoidance) ice formation. These processes are typically controlled by ice nucleating proteins or antifreeze proteins, which act to either promote nucleation, prevent nucleation or inhibit ice growth depending on the specific need, respectively. These proteins can be expensive and their mechanisms of action are not understood, limiting their translation, especially into biomedical cryopreservation applications. Here well-defined poly(vinyl alcohol), synthesized by RAFT/MADIX polymerization, is investigated for its ice nucleation inhibition (INI) activity, in contrast to its established ice growth inhibitory properties and compared to other synthetic polymers. It is shown that ice nucleation inhibition activity of PVA has a strong molecular weight dependence; polymers with a degree of polymerization below 200 being an effective inhibitor at just 1 mg.mL–1. Other synthetic and natural polymers, both with and without hydroxyl-functional side chains, showed negligible activity, highlighting the unique ice/water interacting properties of PVA. These findings both aid our understanding of ice nucleation but demonstrate the potential of engineering synthetic polymers as new biomimetics to control ice formation/growth processes PMID:26258729

The Mediterranean Plastic Soup: synthetic polymers in Mediterranean surface waters

NASA Astrophysics Data System (ADS)

Suaria, Giuseppe; Avio, Carlo G.; Mineo, Annabella; Lattin, Gwendolyn L.; Magaldi, Marcello G.; Belmonte, Genuario; Moore, Charles J.; Regoli, Francesco; Aliani, Stefano

2016-11-01

The Mediterranean Sea has been recently proposed as one of the most impacted regions of the world with regards to microplastics, however the polymeric composition of these floating particles is still largely unknown. Here we present the results of a large-scale survey of neustonic micro- and meso-plastics floating in Mediterranean waters, providing the first extensive characterization of their chemical identity as well as detailed information on their abundance and geographical distribution. All particles >700 μm collected in our samples were identified through FT-IR analysis (n = 4050 particles), shedding for the first time light on the polymeric diversity of this emerging pollutant. Sixteen different classes of synthetic materials were identified. Low-density polymers such as polyethylene and polypropylene were the most abundant compounds, followed by polyamides, plastic-based paints, polyvinyl chloride, polystyrene and polyvinyl alcohol. Less frequent polymers included polyethylene terephthalate, polyisoprene, poly(vinyl stearate), ethylene-vinyl acetate, polyepoxide, paraffin wax and polycaprolactone, a biodegradable polyester reported for the first time floating in off-shore waters. Geographical differences in sample composition were also observed, demonstrating sub-basin scale heterogeneity in plastics distribution and likely reflecting a complex interplay between pollution sources, sinks and residence times of different polymers at sea.

Preparation of hydrophilic monolithic capillary column by in situ photo-polymerization of N-vinyl-2-pyrrolidinone and acrylamide for highly selective and sensitive enrichment of N-linked glycopeptides.

PubMed

Jiang, Hao; Yuan, Huiming; Qu, Yanyan; Liang, Yu; Jiang, Bo; Wu, Qi; Deng, Nan; Liang, Zhen; Zhang, Lihua; Zhang, Yukui

2016-01-01

In this study, a novel kind of amide functionalized hydrophilic monolith was synthesized by the in situ photo-polymerization of N-vinyl-2-pyrrolidinone (NVP), acrylamide (AM), and N, N'-methylenebisacrylamide (MBA) in a UV transparent capillary, and successfully applied for hydrophilic interaction chromatography (HILIC) based enrichment of N-linked glycopeptides. With 2 μg of the tryptic digests of IgG as the sample, after enrichment, 18 glycopeptides could be identified by MALDI-TOF/TOF MS analysis. Furthermore, with the mixture of BSA and IgG digests (10,000:1, m/m) as the sample, 6 N-linked glycopeptides were unambiguously identified after enrichment, indicating the high selectivity and good specificity of such material. Moreover, such a monolithic capillary column was also applied for the N-glycosylation sites profiling of 6 μg protein digests from HeLa cells and 1 μL human serum. In total, 530 and 262 unique N-glycosylated peptides were identified, respectively, corresponding to 282 and 124N-glycoproteins, demonstrating its great potential for the large scale glycoproteomics analysis. Copyright © 2015 Elsevier B.V. All rights reserved.

Various aspects of ultrasound assisted emulsion polymerization process.

PubMed

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.

Biocatalytic Asymmetric Synthesis of (1R, 2S)-N-Boc-vinyl-ACCA Ethyl Ester with a Newly Isolated Sphingomonas aquatilis.

PubMed

Zhu, Shaozhou; Shi, Ying; Zhang, Xinyu; Zheng, Guojun

2018-02-01

1-amino cyclopropane-1-carboxylic acid (ACCA) and its derivatives are essential pharmacophoric unit that widely used in drug research and development. Specifically, (1R, 2S)-N-Boc-vinyl-ACCA ethyl ester (vinyl-ACCA) is a key chiral intermediate in the synthesis of highly potent hepatitis C virus (HCV) NS3/4A protease inhibitors such as asunaprevir and simeprevir. Developing strategies for the asymmetric synthesis of vinyl-ACCA is thus extremely high demand. In this study, 378 bacterial strains were isolated from soil samples using N-Boc-vinyl-ACCA ethyl ester as the sole carbon source and were screened for esterase activity. Fourteen of which worked effectively for the asymmetric synthesis of (1R, 2S)-N-Boc-1-vinyl ACCA ethyl ester. The strain CY-2, identified as Sphingomonas aquatilis, which showed the highest stability and enantioselectivity was selected as whole cell biocatalyst for further study. A systematic study of all factors influencing the enzymatic hydrolysis was performed. Under optimized conditions, resolution of rac-vinyl-ACCA to (1R, 2S)-N-Boc-1-vinyl ACCA ethyl ester with 88.2% ee and 62.4% conversion (E = 9) was achieved. Besides, S. aquatilis was also used to transform other 10 different substrates. Notably, it was found that 7 of them could be stereoselectively hydrolyzed, especially for (1R,2S)-1-amino-vinyl-ACCA ethyl ester hydrochloride (99.6% ee, E>200). Our investigations provide a new efficient whole cell biocatalyst for resolution of ACCA and might be developed for industry application.

Construction of Nontoxic Polymeric UV-Absorber with Great Resistance to UV-Photoaging

PubMed Central

Huang, Zhong; Ding, Aishun; Guo, Hao; Lu, Guolin; Huang, Xiaoyu

2016-01-01

In this article, we developed a series of new nontoxic polymeric UV-absorbers through covalently attaching a benzophenone derivative onto the main chain of poly(vinyl chloride) (PVC) via mild and quantitative click chemistry. Azide groups were firstly introduced into the backbone of PVC via a nucleophilic reaction without affecting polymeric skeleton. Copper-catalyzed Husigen-Click cycloaddition reaction was performed between the pendant azide groups of PVC and alkynyl of (2-hydroxy-4-(prop-2-ynyloxy)phenyl)(phenyl)methanone at ambient temperature for affording the desired PVC-based UV-absorbers (PVC-UV) with different amounts of benzophenone moieties, which displayed great resistance to photoaging without degradation while exposed to UV irradiation. These polymeric UV-absorbers also showed good solubilities in common organic solvents and no cytotoxicity vs. HaCat cell. Small amounts of PVC-UV were homogeneously mixed with PVC as additive for stabilizing PVC against UV-photoaging without degradation and releasing small molecule even after 200 h while keeping thermal stability. This route of polymeric additive clearly paved an efficient way for solving the puzzle of separation of small molecule additive. PMID:27138547

Chemoselective Polymerization of Polar Divinyl Monomers with Rare-Earth/Phosphine Lewis Pairs.

PubMed

Xu, Pengfei; Wu, Lei; Dong, Liqiu; Xu, Xin

2018-02-08

This work reports the chemoselective polymerization of polar divinyl monomers, including allyl methacrylate (AMA), vinyl methacrylate (VMA), and 4-vinylbenzyl methacrylate (VBMA), by using simple Lewis pairs comprised of homoleptic rare-earth (RE) aryloxide complexes RE(OAr)₃ (RE = Sc ( 1 ), Y ( 2 ), Sm ( 3 ), La ( 4 ), Ar = 2,6- t Bu₂C₆H₃) and phosphines PR₃ (R = Ph, Cy, Et, Me). Catalytic activities of polymerizations relied heavily upon the cooperation of Lewis acid and Lewis base components. The produced polymers were soluble in common organic solvents and often had a narrow molecular weight distribution. A highly syndiotactic poly(allyl methacrylate) (PAMA) with rr ~88% could be obtained by the scandium complex 1 /PEt₃ pair at -30 °C. In the case of poly(4-vinylbenzyl methacrylate) (PVBMA), it could be post-functionalized with PhCH₂SH. Mechanistic study, including the isolation of the zwitterionic active species and the end-group analysis, revealed that the frustrated Lewis pair (FLP)-type addition was the initiating step in the polymerization.

[Evaluation of chromatographic performance of polymerized ionic liquid stationary phase for capillary gas chromatography].

PubMed

Chen, Xiaoyan; Lu, Kai; Qi, Meiling; Fu, Ruonong

2009-11-01

The selectivity and thermal stability of ionic liquids as the stationary phases for capillary gas chromatography (CGC) have attracted much attention of researchers in recent years. In this study, 1-vinyl-3-benzyl imidazolium-bis(trifluoromethane-sulphonyl)imidate (VBIm-NTf2) was synthesized and polymerized (PVBIm-NTf2) in a CGC column. In comparison with VBIm-NTf2, PVBIm-NTf2 exhibits much better thermal stability and chromatographic selectivity, and achieves satisfactory resolution for Grob test mixture, alcohols mixture, esters mixture and aromatics mixture with narrow and symmetric peak shapes. The satisfactory resolution and selectivity of the polymerized column still remain after conditioned at 250 degrees C for 6 h. Additionally, the Abraham solvation parameters of PVBIm-NTf2 were determined and the interactions between the stationary phase and solutes were elucidated. The present work demonstrates that the polymerization is an effective way to improve the selectivity and thermal stability of common ionic liquids as CGC stationary phases.

Acrylates and Methacrylates,

DTIC Science & Technology

1987-09-15

and methacrylic acids and especially their esters. Acrylic and methacrylic monomers can be polymerized and copolymerized with other vinyl monomers by...contributed to reduction in the cost/value of these monomers and to expansion of the market for sale. For the first time acrylic acid was obtained in...a-dibromopropionic acid . In the Soviet Union for the development of the method of * production of acrylates the synthesis of methylacrylate began in

Thermally Stable Siloxane Hybrid Matrix with Low Dielectric Loss for Copper-Clad Laminates for High-Frequency Applications.

PubMed

Kim, Yong Ho; Lim, Young-Woo; Kim, Yun Hyeok; Bae, Byeong-Soo

2016-04-06

We report vinyl-phenyl siloxane hybrid material (VPH) that can be used as a matrix for copper-clad laminates (CCLs) for high-frequency applications. The CCLs, with a VPH matrix fabricated via radical polymerization of resin blend consisting of sol-gel-derived linear vinyl oligosiloxane and bulky siloxane monomer, phenyltris(trimethylsiloxy)silane, achieve low dielectric constant (Dk) and dissipation factor (Df). The CCLs with the VPH matrix exhibit excellent dielectric performance (Dk = 2.75, Df = 0.0015 at 1 GHz) with stability in wide frequency range (1 MHz to 10 GHz) and at high temperature (up to 275 °C). Also, the VPH shows good flame resistance without any additives. These results suggest the potential of the VPH for use in high-speed IC boards.

Facile fabrication of mesoporous poly(ethylene-co-vinyl alcohol)/chitosan blend monoliths.

PubMed

Wang, Guowei; Xin, Yuanrong; Uyama, Hiroshi

2015-11-05

Poly(ethylene-co-vinyl alcohol) (EVOH)/chitosan blend monoliths were fabricated by thermally-induced phase separation method. Chitosan was successfully incorporated into the polymeric monolith by selecting EVOH as the main component of the monolith. SEM images exhibit that the chitosan was located on the inner surface of the monolith. Fourier-transform infrared analysis and elemental analysis indicate the successful blend of EVOH and chitosan. BET results show that the blend monoliths had high specific surface area and uniform mesopore structure. Good adsorption ability toward various heavy metal ions was found in the blend monoliths due to the large chelation capacity of chitosan. The blend monoliths have potential application for waste water purification or bio-related applications. Copyright © 2015 Elsevier Ltd. All rights reserved.

Fabrication of thermo-responsive cotton fabrics using poly(vinyl caprolactam-co-hydroxyethyl acrylamide) copolymer.

PubMed

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.

Optimization of lipase-catalyzed synthesis of ginsenoside Rb1 esters using response surface methodology.

PubMed

Hu, Jiang-Ning; Lee, Jeung-Hee; Zhu, Xue-Mei; Shin, Jung-Ah; Adhikari, Prakash; Kim, Jae-Kyung; Lee, Ki-Teak

2008-11-26

In the lipase (Novozyme 435)-catalyzed synthesis of ginsenoside Rb1 esters, different acyl donors were found to affect not only the degree of conversion but also the regioselectivity. The reaction of acyl donors with short carbon chain was more effective, showing higher conversion than those with long carbon chain. Among the three solvent systems, the reaction in tert-amyl alcohol showed the highest conversion rate, while the reaction in the mixed solvent of t-BuOH and pyridine (1:1) had the lowest conversion rate. To allow the increase of GRb1 lipophilicity, we decided to further study the optimal condition of synthesis of GRb1 with vinyl decanoate with 10 carbon chain fatty acids in tert-amyl alcohol. Response surface methodology (RSM) was employed to optimize the synthesis condition. From the ridge analysis with maximum responses, the maximum GRb1 conversion was predicted to be 61.51% in a combination of factors (40.2 h, 52.95 degrees C, substrate mole ratio 275.57, and enzyme amount 39.81 mg/mL). Further, the adequacy of the predicted model was examined by additional independent experiments at the predicted maximum synthesis conditions. Results showed that the RSM was effective to optimize a combination of factors for lipase-catalyzed synthesis of ginsenoside Rb1 with vinyl decanoate.

Polymerization of ethylene through reversible addition-fragmentation chain transfer (RAFT).

PubMed

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.

A Study of Energy Conversion Devices Using Photoactive Organometallic Electrocatalysts.

DTIC Science & Technology

1986-05-23

arylisocyanide complexes confined to polymeric thin films in solar energy conversion systems . The chemical systems of interest were chromium...The goals of the project then became threefold: 1) examine the thermo- dynamics an- ’ kinetics of charge transfer in the systems in which we had shown...complexes confined to polymeric thin films in solar energy conversion systems . The chemical systems of interest were chromium, molybdenum and

High performance dental resin composites with hydrolytically stable monomers.

PubMed

Wang, Xiaohong; Huyang, George; Palagummi, Sri Vikram; Liu, Xiaohui; Skrtic, Drago; Beauchamp, Carlos; Bowen, Rafael; Sun, Jirun

2018-02-01

The objectives of this project were to: 1) develop strong and durable dental resin composites by employing new monomers that are hydrolytically stable, and 2) demonstrate that resin composites based on these monomers perform superiorly to the traditional bisphenol A glycidyl dimethacrylate/triethylene glycol dimethacrylate (Bis-GMA/TEGDMA) composites under testing conditions relevant to clinical applications. New resins comprising hydrolytically stable, ether-based monomer, i.e., triethylene glycol divinylbenzyl ether (TEG-DVBE), and urethane dimethacrylate (UDMA) were produced via composition-controlled photo-polymerization. Their composites contained 67.5wt% of micro and 7.5wt% of nano-sized filler. The performances of both copolymers and composites were evaluated by a battery of clinically-relevant assessments: degree of vinyl conversion (DC: FTIR and NIR spectroscopy); refractive index (n: optical microscopy); elastic modulus (E), flexural strength (F) and fracture toughness (K IC ) (universal mechanical testing); Knoop hardness (HK; indentation); water sorption (W sp ) and solubility (W su ) (gravimetry); polymerization shrinkage (S v ; mercury dilatometry) and polymerization stress (tensometer). The experimental UDMA/TEG-DVBE composites were compared with the Bis-GMA/TEGDMA composites containing the identical filler contents, and with the commercial micro hybrid flowable composite. UDMA/TEG-DBVE composites exhibited n, E, W sp , W su and S v equivalent to the controls. They outperformed the controls with respect to F (up to 26.8% increase), K IC (up to 27.7% increase), modulus recovery upon water sorption (full recovery vs. 91.9% recovery), and stress formation (up to 52.7% reduction). In addition, new composites showed up to 27.7% increase in attainable DC compared to the traditional composites. Bis-GMA/TEGDMA controls exceeded the experimental composites with respect to only one property, the composite hardness. Significantly, up to 18.1% lower HK values in the experimental series (0.458GPa) were still above the clinically required threshold of approx. 0.4GPa. Hydrolytic stability, composition-controlled polymerization and the overall enhancement in clinically-relevant properties of the new resin composites make them viable candidates to replace traditional resin composites as a new generation of strong and durable dental restoratives. Copyright © 2017 The Academy of Dental Materials. All rights reserved.

Method of making carbon nanotube composite materials

DOEpatents

O'Bryan, Gregory; Skinner, Jack L; Vance, Andrew; Yang, Elaine Lai; Zifer, Thomas

2014-05-20

The present invention is a method of making a composite polymeric material by dissolving a vinyl thermoplastic polymer, un-functionalized carbon nanotubes and hydroxylated carbon nanotubes and optionally additives in a solvent to make a solution and removing at least a portion of the solvent after casting onto a substrate to make thin films. The material has enhanced conductivity properties due to the blending of the un-functionalized and hydroxylated carbon nanotubes.

Preparation of Sic/AIN Solid Solutions Using Organometallic Precursors

DTIC Science & Technology

1989-02-15

pyrolysis of organoaluminum and organosilicon compounds was investigated as a potential source of SiC /AUI solid solutions. Using two different co... pyrolysis methods, homogeneous mixtures of organoaluminum amides and both a vinylic polysilane and a poly- carbosilane were convertec to a preceramic ...solid that transformed to crystalline SiC /AiN solid solutions at 򒸀 C. Moreover, the liquid, polymeric , form of these precursor mixtures provides a

Cross-linked polyvinyl pyridine coated glass particle catalyst support and aqueous composition or polyvinyl pyridine adducted microspheres

NASA Technical Reports Server (NTRS)

Rembaum, Alan (Inventor); Gupta, Amitava (Inventor); Volksen, Willi (Inventor)

1981-01-01

Microspheres are produced by cobalt gamma radiation initiated polymerization of a dilute aqueous vinyl pyridine solution. Addition of cross-linking agent provides higher surface area beads. Addition of monomers such as hydroxyethylmethacrylate acrylamide or methacrylamide increases hydrophilic properties and surface area of the beads. High surface area catalytic supports are formed in the presence of controlled pore glass substrate.

Sulfonated poly(ether ether ketone)/poly(vinyl alcohol) sensitizing system for solution photogeneration of small Ag, Au, and Cu crystallites.

PubMed

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.

The Mediterranean Plastic Soup: synthetic polymers in Mediterranean surface waters

PubMed Central

Suaria, Giuseppe; Avio, Carlo G.; Mineo, Annabella; Lattin, Gwendolyn L.; Magaldi, Marcello G.; Belmonte, Genuario; Moore, Charles J.; Regoli, Francesco; Aliani, Stefano

2016-01-01

The Mediterranean Sea has been recently proposed as one of the most impacted regions of the world with regards to microplastics, however the polymeric composition of these floating particles is still largely unknown. Here we present the results of a large-scale survey of neustonic micro- and meso-plastics floating in Mediterranean waters, providing the first extensive characterization of their chemical identity as well as detailed information on their abundance and geographical distribution. All particles >700 μm collected in our samples were identified through FT-IR analysis (n = 4050 particles), shedding for the first time light on the polymeric diversity of this emerging pollutant. Sixteen different classes of synthetic materials were identified. Low-density polymers such as polyethylene and polypropylene were the most abundant compounds, followed by polyamides, plastic-based paints, polyvinyl chloride, polystyrene and polyvinyl alcohol. Less frequent polymers included polyethylene terephthalate, polyisoprene, poly(vinyl stearate), ethylene-vinyl acetate, polyepoxide, paraffin wax and polycaprolactone, a biodegradable polyester reported for the first time floating in off-shore waters. Geographical differences in sample composition were also observed, demonstrating sub-basin scale heterogeneity in plastics distribution and likely reflecting a complex interplay between pollution sources, sinks and residence times of different polymers at sea. PMID:27876837

Assessment of vinyl polysiloxane as an innovative injection material for the anatomical study of vasculature.

PubMed

Dargaud, Jacques; Chalvet, Laurane; Del Corso, Marco; Cerboni, Elsa; Feugier, Patrick; Mertens, Patrick; Simon, Emile

2016-04-01

There are numerous injection materials for the study of vasculature in anatomical specimens, each having its own advantages and disadvantages. Latex and resins are the most widely used injection materials but need several days to set. The development of new materials taking shorter time to polymerize might be very useful to improve anatomic specimen study conditions. The aim of the present study was to evaluate vinyl polysiloxane (VPS), a silicon material widely used for dental impressions with the advantage to set very rapidly, as an injection material. We assessed the preparation, use, diffusion and setting time of the product in different anatomical regions (central nervous system, external carotid/jugular, lower limb) to observe its behavior in variably sized vessels. Our results suggest that VPS might be of interest for the study of vessels in anatomical specimens. The main strengths of the product are represented by (1) simplicity of use, as it is a ready-to-use material, (2) very rapid polymerization, (3) availability in a range of viscosities making easier the exploration of small vessels, (4) its better elasticity compared to resins, (5) and finally its availability in a range of colors making it a material of choice for vascular system dissections including those with very small caliber vessels.

Processable dodecylbenzene sulfonic acid (DBSA) doped poly(N-vinyl carbazole)-poly(pyrrole) for optoelectronic applications

PubMed Central

Hammed, W. A.; Rahman, M. S.; Mahmud, H. N. M. E.; Yahya, R.; Sulaiman, K.

2017-01-01

Abstract A soluble poly (n-vinyl carbazole)–polypyrrole (PNVC–Ppy) copolymer was prepared through oxidative chemical polymerization wherein dodecyl benzene sulfonic acid (DBSA) was used as a dopant to facilitate polymer-organic solvent interaction and ammonium persulfate (APS) was used as an oxidant. Compared with undoped PNVC–Ppy, the DBSA-doped PNVC–Ppy copolymer showed higher solubility in some selected organic solvents. The composition and structural characteristics of the DBSA-doped PNVC–Ppy were determined by Fourier transform infrared, ultraviolet–visible, and X-ray diffraction spectroscopic methods. Field emission scanning electron microscopic method was employed to observe the morphology of the DBSA-doped PNVC–Ppy copolymer. The electrical conductivity of the DBSA-doped PNVC–Ppy copolymer was measured at room temperature. The conductivity increased with increasing concentration of APS oxidant, and the highest conductivity was recorded at 0.004 mol/dm3 APS at a polymerization temperature of −5 °C. The increased conductivity can be explained by the extended half-life of pyrrole free radical at a lower temperature and a gradual increase in chain length over a prolonged time due to the slow addition of APS. Furthermore, the obtained soluble copolymer exhibits unique optical and thermal properties different from those of PNVC and Ppy. PMID:29491808

Novel Biocompatible Thermoresponsive Poly(N-vinyl Caprolactam)/Clay Nanocomposite Hydrogels with Macroporous Structure and Improved Mechanical Characteristics.

PubMed

Shi, Kun; Liu, Zhuang; Yang, Chao; Li, Xiao-Ying; Sun, Yi-Min; Deng, Yi; Wang, Wei; Ju, Xiao-Jie; Xie, Rui; Chu, Liang-Yin

2017-07-05

Poly(N-vinyl caprolactam) (PVCL) hydrogels usually suffer from the imporous structure and poor mechanical characteristics as well as the toxicity of cross-linkers, although PVCL itself is biocompatible. In this paper, novel biocompatible thermoresponsive poly(N-vinyl caprolactam)/clay nanocomposite (PVCL-Clay) hydrogels with macroporous structure and improved mechanical characteristics are developed for the first time. The macroporosity in the hydrogel is introduced by using Pickering emulsions as templates, which contain N-vinyl caprolactam (VCL) monomer as dispersed phase and clay sheets as stabilizers at the interface. After polymerization, macropores are formed inside the hydrogels with the residual unreacted VCL droplets as templates. The three-dimensional PVCL polymer networks are cross-linked by the clay nanosheets. Due to the nanocomposite structure, the hydrogel exhibits better mechanical characteristics in comparison to the conventional PVCL hydrogels cross-linked by N,N'-methylene diacrylamide (BIS). The prepared PVCL-Clay hydrogel possesses remarkable temperature-responsive characteristics with a volume phase transition temperature (VPTT) around 35 °C, and provides a feasible platform for cell culture. With macroporous structure and good mechanical characteristics as well as flexible assembly performance, the proposed biocompatible thermoresponsive PVCL-Clay nanocomposite hydrogels are ideal material candidates for biomedical, analytical, and other applications such as entrapment of enzymes, cell culture, tissue engineering, and affinity and displacement chromatography.

Synthesis and characterization of Pd-poly(N-vinyl-2-pyrrolidone)/KIT-5 nanocomposite as a polymer-inorganic hybrid catalyst for the Suzuki-Miyaura cross-coupling reaction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kalbasi, Roozbeh Javad, E-mail: rkalbasi@iaush.ac.ir; Mosaddegh, Neda

2011-11-15

Composite poly(N-vinyl-2-pyrrolidone)/KIT-5 (PVP/KIT-5) was prepared by in situ polymerization method and used as a support for palladium nanoparticles obtained through the reduction of Pd(OAc){sub 2} by hydrazine hydrate. The physical and chemical properties of the catalyst were investigated by XRD, FT-IR, UV-vis, TG, BET, SEM, and TEM techniques. The catalytic performance of this novel heterogeneous catalyst was determined for the Suzuki-Miyaura cross-coupling reaction between aryl halides and phenylboronic acid in the presence of water at room temperature. The stability of the nanocomposite catalyst was excellent and could be reused 8 times without much loss of activity in the Suzuki-Miyaura cross-couplingmore » reaction. - Graphical Abstract: Pd-poly(N-vinyl-2-pyrrolidone)/KIT-5 was prepared as an organic-inorganic hybrid catalyst for the Suzuki-Miyaura reaction. The stability of the catalyst was excellent and could be reused 8 times in the Suzuki-Miyaura reaction. Highlights: > Pd-poly(N-vinyl-2-pyrrolidone)/KIT-5 was prepared as a novel nanocomposite. > Nanocomposite was prepared based on a cage-type mesoporous system. > Catalyst showed excellent activity for Suzuki-Miyaura reaction in water. > Stability of the catalyst was excellent and could be reused 8 times.« less

Poly(n-hexyl methacrylate) polymerization in three-component microemulsion stabilized by a cationic surfactant.

PubMed

Katime, Issa; Arellano, Jesús; Schulz, Pablo

2006-04-15

The polymerization of n-hexyl methacrylate (n-HMA) in three-component microemulsion stabilized with dodecyltrimethylammonium bromide (DTAB) is reported as a function of monomer and initiator concentrations and temperature. The obtained latices were bluish, transparent, and translucent. Particle sizes and molar masses were on the order of 20 nm and 3 x 10(6) g/mol, respectively. In all cases, high reaction rates and final conversions of 98% were obtained. Polymerization temperature has a strong effect on reaction rate and conversion.

Multifunctional organized mesoporous tin oxide films templated by graft copolymers for dye-sensitized solar cells.

PubMed

Park, Jung Tae; Ahn, Sung Hoon; Roh, Dong Kyu; Lee, Chang Soo; Kim, Jong Hak

2014-07-01

The synthesis of organized mesoporous SnO2 films with high porosity, larger pores, and good interconnectivity, obtained by sol-gel templating with an amphiphilic graft copolymer, poly(vinyl chloride)-graft-poly(oxyethylene methacrylate), is reported. An improved performance of dye-sensitized solar cells (DSSCs) is demonstrated by the introduction of a 400 nm thick organized mesoporous SnO2 interfacial (om-SnO2 IF) layer between nanocrystalline TiO2 (nc-TiO2 ) and a fluorine-doped tin oxide substrate. To elucidate the improved efficiency, the structural, optical, and electrochemical properties of the devices were characterized by SEM, UV/Vis spectroscopy, noncontact 3D surface profilometry, intensity-modulated photocurrent/voltage spectroscopy, incident photon-to-electron conversion efficiency, and electrochemical impedance spectroscopy measurements. The energy-conversion efficiency of the solid polymerized ionic liquid based DSSC fabricated with the om-SnO2 IF/nc-TiO2 photoanode reached 5.9% at 100 mW cm(-2) ; this is higher than those of neat nc-TiO2 (3.5%) and organized mesoporous TiO2 interfacial/nc-TiO2 layer (5.4%) photoanodes. The improved efficiency is attributed to the antireflective property, cascadal energy band gap, good interconnectivity, and high electrical conductivity of the om-SnO2 IF layer, which results in enhanced light harvesting, increased electron transport, reduced charge recombination, and decreased interfacial/internal resistance. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Activation of Ice Recrystallization Inhibition Activity of Poly(vinyl alcohol) using a Supramolecular Trigger.

PubMed

Phillips, Daniel J; Congdon, Thomas R; Gibson, Matthew I

2016-03-07

Antifreeze (glyco)proteins (AF(G)Ps) have potent ice recrystallisation inhibition (IRI) activity - a desirable phenomenon in applications such as cryopreservation, frozen food and more. In Nature AF(G)P activity is regulated by protein expression levels in response to an environmental stimulus; temperature. However, this level of regulation is not possible in synthetic systems. Here, a synthetic macromolecular mimic is introduced, using supramolecular assembly to regulate activity. Catechol-terminated poly(vinyl alcohol) was synthesised by RAFT polymerization. Upon addition of Fe 3+ , larger supramolecular star polymers form by assembly with two or three catechols. This increase in molecular weight effectively 'switches on' the IRI activity and is the first example of external control over the function of AFP mimetics. This provides a simple but elegant solution to the challenge of external control of AFP-mimetic function.

Effect of γ irradiation on poly(vinyl alcohol) and bacterial cellulose composites used as packaging materials

NASA Astrophysics Data System (ADS)

Stoica-Guzun, Anicuta; Stroescu, Marta; Jipa, Iuliana; Dobre, Loredana; Zaharescu, Traian

2013-03-01

The aim of this paper is to present the influence of bacterial cellulose microfibrils and γ-radiation dose on poly(vinyl alcohol) (PVA)-bacterial cellulose (BC) composites. Two composite materials were obtained: the first one from PVA aqueous solution 4% and 5% wet bacterial cellulose and the second from the same PVA solution and 10% wet bacterial cellulose. In terms of PVA/dry BC ratios (w/w) for these films the ratios are 1/0.025 and 1/0.050. The obtained composite materials were characterized by infrared spectroscopy with Fourier transform (FT-IR) and UV-vis spectroscopy in order to evaluate the irradiation effect on their stability. The swelling behavior of the polymeric composites was also studied. The composite materials were compared with a film of pure PVA and a dry BC membrane.

Radiation preparation of drug carriers based polyacrylic acid (PAAc) using poly(vinyl pyrrolidone) (PVP) as a template polymer

NASA Astrophysics Data System (ADS)

Abd El-Rehim, H. A.; Hegazy, E. A.; Khalil, F. H.; Hamed, N. A.

2007-01-01

The present study deals with the radiation synthesis of stimuli response hydrophilic polymers from polyacrylic acid (PAAc). To maintain the property of PAAc and control the water swellibility for its application as a drug delivery system, radiation polymerization of AAc in the presence of poly(vinyl pyrrolidone) (PVP) as a template polymer was carried out. Characterization of the prepared PAA/PVP inter-polymer complex was investigated by determining gel content, swelling property, hydrogel microstructure and the release rate of caffeine as a model drug. The release rate of caffeine from the PAA/PVP inter-polymer complexes showed pH-dependency, and seemed to be mainly controlled by the dissolution rate of the complex above a p Ka of PAAc. The prepared inter-polymer complex could be used for application as drug carriers.

Influence of UV and Gamma radiations on the induced birefringence of stretched poly(vinyl) alcohol foils

NASA Astrophysics Data System (ADS)

Nechifor, Cristina-Delia; Zelinschi, Carmen Beatrice; Dorohoi, Dana-Ortansa

2014-03-01

The aim of our paper is to evidence the influence of Gamma and UV radiations on the induced birefringence of poly(vinyl alcohol) stretched foils. Thin foils of PVA were prepared and dried without modifying their surfaces. The polymeric foils were irradiated from 15 min to 6 h using UV and Gamma radiations. The induced by stretching under heating birefringence of PVA films was measured at λ = 589.3 nm with a Babinet Compensator. Physico-chemical processes (photo stabilization, photo degradation, oxidation) induced by irradiation of polymer matrix influence both the stretching degree and the anisotropy of etired foils. An increase of birefringence versus the stretching ratio of the PVA foils was evidenced for all studied samples. The dependence of the birefringence on the exposure time, stretching ratio and nature of radiation was also confirmed.

Influence of light-curing sources on polymerization reaction kinetics of a restorative system.

PubMed

D'Alpino, Paulo H P; Svizero, Nádia R; Pereira, José C; Rueggeberg, Frederick A; Carvalho, Ricardo M; Pashley, David H

2007-02-01

To determine the effect of using a variety of commercial light-curing units on polymerization of a dentin-bonding agent (Adper Single Bond) and of a resin composite (Filtek Z250). Infrared (IR) spectra were obtained kinetically at one scan/second at 2 cm(-1) resolution for a period of 5 minutes and were analyzed for: maximum conversion rate (%/s), time into exposure when maximum rate occurred (seconds), conversion at maximum rate (%), and total conversion (%) at 300 seconds by comparison of aliphatic-to-aromatic absorption IR peak ratios, before and after polymerization. Light units used were: QTH 540 mW/cm2 (XL3000); LED 750 mW/cm2 (Elipar FreeLight 2); PAC 2,130 mW/cm2 (ARC II). Exposure followed manufacturers' recommendations: dentin bonding agent for 10 seconds, RC for 20 seconds (QTH), and 10 seconds (LED and PAC). Polymerization kinetics was evaluated at the bottom surface (2.5 mm thick) for the resin composite and as a thin film for the dentin bonding agent on the diamond surface of an attenuated total reflectance accessory in the IR spectrometer. Values (n = 5) were compared using ANOVA and Tukey's pairwise post-hoc test: pre-set alpha 0.05. PAC produced the highest total conversion and conversion rate for the resin composite (P < 0.05). Total conversion was lower for dentin bonding adhesive using PAC than with LED or QTH (P < 0.05). LED provided the highest proportion of conversion at the maximum rate with respect to conversion at 300 seconds for both materials. QTH demonstrated the lowest maximum rate value that occurred at a longer time into exposure (P < 0.05). Polymerization kinetic parameters varied greatly between the restorative materials as well as among light-curing unit types when compared to values observed when using a QTH light as control.

Polymerization Behavior and Polymer Properties of Eosin-Mediated Surface Modification Reactions.

PubMed

Avens, Heather J; Randle, Thomas James; Bowman, Christopher N

2008-10-17

Surface modification by surface-mediated polymerization necessitates control of the grafted polymer film thicknesses to achieve the desired property changes. Here, a microarray format is used to assess a range of reaction conditions and formulations rapidly in regards to the film thicknesses achieved and the polymerization behavior. Monomer formulations initiated by eosin conjugates with varying concentrations of poly(ethylene glycol) diacrylate (PEGDA), N-methyldiethanolamine (MDEA), and 1-vinyl-2-pyrrolidone (VP) were evaluated. Acrylamide with MDEA or ascorbic acid as a coinitiator was also investigated. The best formulation was found to be 40 wt% acrylamide with MDEA which yielded four to eight fold thicker films (maximum polymer thickness increased from 180 nm to 1420 nm) and generated visible films from 5-fold lower eosin surface densities (2.8 vs. 14 eosins/µm(2)) compared to a corresponding PEGDA formulation. Using a microarray format to assess multiple initiator surface densities enabled facile identification of a monomer formulation that yields the desired polymer properties and polymerization behavior across the requisite range of initiator surface densities.

Polymerization Behavior and Polymer Properties of Eosin-Mediated Surface Modification Reactions

PubMed Central

Avens, Heather J.; Randle, Thomas James; Bowman, Christopher N.

2008-01-01

Surface modification by surface-mediated polymerization necessitates control of the grafted polymer film thicknesses to achieve the desired property changes. Here, a microarray format is used to assess a range of reaction conditions and formulations rapidly in regards to the film thicknesses achieved and the polymerization behavior. Monomer formulations initiated by eosin conjugates with varying concentrations of poly(ethylene glycol) diacrylate (PEGDA), N-methyldiethanolamine (MDEA), and 1-vinyl-2-pyrrolidone (VP) were evaluated. Acrylamide with MDEA or ascorbic acid as a coinitiator was also investigated. The best formulation was found to be 40 wt% acrylamide with MDEA which yielded four to eight fold thicker films (maximum polymer thickness increased from 180 nm to 1420 nm) and generated visible films from 5-fold lower eosin surface densities (2.8 vs. 14 eosins/µm2) compared to a corresponding PEGDA formulation. Using a microarray format to assess multiple initiator surface densities enabled facile identification of a monomer formulation that yields the desired polymer properties and polymerization behavior across the requisite range of initiator surface densities. PMID:19838291

Investigation of Proposed Process Sequence for the Array Automated Assembly Task, Phase 2. [low cost silicon solar array fabrication

NASA Technical Reports Server (NTRS)

Mardesich, N.; Garcia, A.; Bunyan, S.; Pepe, A.

1979-01-01

The technological readiness of the proposed process sequence was reviewed. Process steps evaluated include: (1) plasma etching to establish a standard surface; (2) forming junctions by diffusion from an N-type polymeric spray-on source; (3) forming a p+ back contact by firing a screen printed aluminum paste; (4) forming screen printed front contacts after cleaning the back aluminum and removing the diffusion oxide; (5) cleaning the junction by a laser scribe operation; (6) forming an antireflection coating by baking a polymeric spray-on film; (7) ultrasonically tin padding the cells; and (8) assembling cell strings into solar circuits using ethylene vinyl acetate as an encapsulant and laminating medium.

Investigation of compression behavior of PE/EVA foam injection molded parts

NASA Astrophysics Data System (ADS)

Spina, Roberto

2017-10-01

The main objective of the presented work is to evaluate the compression behavior of a polymeric foam blend by using a robust framework for the testing sequence of foaming injection molded parts, with the aim of establishing a standard testing cycle for the evaluation of new matrix material. The research purpose is to assess parameters influencing compression behavior and give useful suggestions for the implementation of a finite element analysis. The polymeric blend consisted of a mixture of low density polyethylenes (LDPEs), a high-density polyethylene (HDPE), an ethylene-vinyl acetate (EVA) and an azodicarbonamide (ADC). The thermal, rheological and compression properties of the blend are fully described, as well as the injection molding process for two specimen types.

Preparation Characterization and Electrical Study of New Polymeric Mixture (Consist of Three Polymers) Nanocomposites

NASA Astrophysics Data System (ADS)

AL-Abodi, Entisar E.; Farouk, Azhar

2018-05-01

By using hummers’ method, graphene oxide (GO) was synthesized and by reducing it gave reduced graphene oxide (RGO). The polymeric blend contain three polymers; Poly Aniline (PANI), Poly Vinyl Acetate( PVAc),and Pecten(Pc) wich have been prepared at studied amount. The composites for above polymers with various concentrations of, graphene oxide (GO) and with reduced graphene oxide (RGO)were prepared, and than pour into films(chips). The dielectric constant properties of chips were measured, which its point the electrical conductivity values for the prepared chips increase with increasing of frequency. As well, the electrical conductivity is research in terms of the Arrhenius plot, it is plotted against the reverse temperature for the prepared films at different applied frequencies.

Porous Carriers for Controlled/Modulated Drug Delivery

PubMed Central

Ahuja, G.; Pathak, K.

2009-01-01

Considerable research efforts have been directed in recent years towards the development of porous carriers as controlled drug delivery matrices because of possessing several features such as stable uniform porous structure, high surface area, tunable pore size and well-defined surface properties. Owing to wide range of useful properties porous carriers have been used in pharmaceuticals for many purposes including development of floating drug delivery systems, sustained drug delivery systems. Various types of pores like open, closed, transport and blind pores in the porous solid allow them to adsorb drugs and release them in a more reproducible and predictable manner. Pharmaceutically exploited porous adsorbents includes, silica (mesoporous), ethylene vinyl acetate (macroporous), polypropylene foam powder (microporous), titanium dioxide (nanoporous). When porous polymeric drug delivery system is placed in contact with appropriate dissolution medium, release of drug to medium must be preceded by the drug dissolution in the water filled pores or from surface and by diffusion through the water filled channels. The porous carriers are used to improve the oral bioavailability of poorly water soluble drugs, to increase the dissolution of relatively insoluble powders and conversion of crystalline state to amorphous state. PMID:20376211

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

PubMed

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.

The reciprocity law concerning light dose relationships applied to BisGMA/TEGDMA photopolymers: theoretical analysis and experimental characterization.

PubMed

Wydra, James W; Cramer, Neil B; Stansbury, Jeffrey W; Bowman, Christopher N

2014-06-01

A model BisGMA/TEGDMA unfilled resin was utilized to investigate the effect of varied irradiation intensity on the photopolymerization kinetics and shrinkage stress evolution, as a means for evaluation of the reciprocity relationship. Functional group conversion was determined by FTIR spectroscopy and polymerization shrinkage stress was obtained by a tensometer. Samples were polymerized with UV light from an EXFO Acticure with 0.1wt% photoinitiator. A one-dimensional kinetic model was utilized to predict the conversion-dose relationship. As irradiation intensity increased, conversion decreased at a constant irradiation dose and the overall dose required to achieve full conversion increased. Methacrylate conversion ranged from 64±2% at 3mW/cm(2) to 78±1% at 24mW/cm(2) while the final shrinkage stress varied from 2.4±0.1MPa to 3.0±0.1MPa. The ultimate conversion and shrinkage stress levels achieved were dependent not only upon dose but also the irradiation intensity, in contrast to an idealized reciprocity relationship. A kinetic model was utilized to analyze this behavior and provide theoretical conversion profiles versus irradiation time and dose. Analysis of the experimental and modeling results demonstrated that the polymerization kinetics do not and should not be expected to follow the reciprocity law behavior. As irradiation intensity is increased, the overall dose required to achieve full conversion also increased. Further, the ultimate conversion and shrinkage stress that are achieved are not dependent only upon dose but rather upon the irradiation intensity and corresponding polymerization rate. Copyright © 2014 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

The effect of photopolymerization on the degree of conversion, polymerization kinetic, biaxial flexure strength, and modulus of self-adhesive resin cements.

PubMed

Aguiar, Thaiane R; de Oliveira, Michele; Arrais, César A G; Ambrosano, Glaucia M B; Rueggeberg, Frederick; Giannini, Marcelo

2015-02-01

Understanding the effect of the degree of conversion on the mechanical properties of auto- and dual-polymerizing self-adhesive resin cements leads to a better estimation of their performance in different clinical scenarios. The purpose of this study was to evaluate the effect of photopolymerization on the degree of conversion (DC) and polymerization kinetic of 4 dual-polymerized resin cements, 20 minutes after mixing, and its effects on the mechanical properties (biaxial flexural strength [FS] and modulus [FM]) after short-term aging. Conventional (RelyX ARC and Clearfil Esthetic Cement) and self-adhesive resin cements (RelyX Unicem and Clearfil SA Cement) were applied to a Fourier infrared spectrometer to assess the DC (n=5) under the following 3 polymerization conditions: direct light exposure (dual-polymerizing mode), exposure through the prepolymerized disk, or autopolymerizing. The polymerization kinetic was recorded for 20 minutes. Then, disk-shaped specimens (n=11) were prepared to evaluate the effect of polymerization on the FS and FM in both extreme polymerization conditions (dual-polymerizing or autopolymerizing). Data were statistically analyzed by 2-way repeated measure ANOVA (DC) and by 2-way ANOVA (FS and FM), followed by the Tukey-Kramer post hoc test (α=.05). Autopolymerizing groups exhibited reduced DC means, whereas intermediate values were observed when resin cements were polymerized through the disk. All groups exhibited higher DC at the end of 20 minutes. The polymerization kinetic revealed a rising curve, and materials, when directly photopolymerized, reached a plateau immediately after light exposure. Regarding the flexural biaxial testing, most of the resin cements were affected by polymerization mode and differences among groups were product dependent. The resin cements achieved immediate higher DC and mechanical properties when photopolymerized. The total absence of photoactivation may still impair their mechanical properties even after short-term aging. Copyright © 2015 Editorial Council for the Journal of Prosthetic Dentistry. Published by Elsevier Inc. All rights reserved.

Redox-responsive solid lipid microparticles composed of octadecyl acrylate and allyl disulfide.

PubMed

Kim, Tae Hoon; Kim, Jin-Chul

2018-04-01

Redox-responsive solid lipid microparticles were prepared by an emulsification photo-polymerization method. Octadecyl acrylate (ODA) and a cross-linker (i.e. allyl disulfide (ADS) and octadiene (ODE)) were dissolved in dichloromethane, it was emulsified in poly(vinyl alcohol) solution, and the resulting O/W emulsion was irradiated with UV light. On the scanning electron microscope micrographs, the microparticles were sphere-like and they were not markedly different from the oil droplets in size. Using the atomic compositions analyzed by energy dispersive X-ray spectroscopy, the ODA to cross-linker molar ratio of ODA/ADS microparticles and ODA/ODE ones were calculated to be 1:0.13 and 1:0.15, respectively. In the FT-IR spectra of the microparticles, the signal of the vinyl group was hardly detected, implying that the monomer and the cross-linkers participated in the photo-polymerization. In differential scanning calorimetry study, ODA/ADS microparticles and ODA/ODE ones exhibited their endothermic peaks around 42.9 and 41.3 °C, respectively, possibly due to the melting of polymeric ODA. Dithiothreitol (DTT, a reducing agent) concentration had little effect on the release degree of dye loaded in ODA/ODE microparticles. Whereas, DTT concentration had a significant effect on the release degree of dye loaded in ODA/ADS microparticles. The release degree at 26 °C was weakly affected by DTT concentration. When the temperature was 37 °C, DTT concentration had a strong effect on the release degree. The disulfide cross-linker (i.e. ADS) can be broken to thiol compounds by the reducing agent, resulting in an increase in the release degree.

Effect of delayed polymerization time and bracket manipulation on orthodontic bracket bonding

NASA Astrophysics Data System (ADS)

Ponikvar, Michael J.

This study examined the effect of bracket manipulation in combination with delayed polymerization times on orthodontic bracket shear bond strength and degree of resin composite conversion. Orthodontics brackets were bonded to extracted third molars in a simulated oral environment after a set period of delayed polymerization time and bracket manipulation. After curing the bracket adhesive, each bracket underwent shear bond strength testing followed by micro-Raman spectroscopy analysis to measure the degree of conversion of the resin composite. Results demonstrated the shear bond strength and the degree of conversion of ceramic brackets did not vary over time. However, with stainless steel brackets there was a significant effect (p ≤ 0.05) of delay time on shear bond strength between the 0.5 min and 10 min bracket groups. In addition, stainless steel brackets showed significant differences related to degree of conversion over time between the 0.5 min and 5 min groups, in addition to the 0.5 min and 10 min groups. This investigation suggests that delaying bracket adhesive polymerization up to a period of 10 min then adjusting the orthodontic bracket may increase both shear bond strength and degree of conversion of stainless steel brackets while having no effect on ceramic brackets.

Development of a practical photochemical energy storage system. Quarterly report. [Interconversion between norbornadiene and quadricyclene for thermochemical heat storage

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hautala, R.R.; Kutal, C.R.

1977-06-15

Research on polymeric organic sensitizers and polymeric inorganic sensitizers for the conversion of norbornadine to quadricyclene and catalysts for the conversion of quadricyclene to norbornadine is described. The interconversion of norbornadine and quadricyclene is studied for its possible use for thermochemical solar energy storage. (WHK)

Polymerization development of "low-shrink" resin composites: Reaction kinetics, polymerization stress and quality of network.

PubMed

Yamasaki, Lilyan C; De Vito Moraes, André G; Barros, Mathew; Lewis, Steven; Francci, Carlos; Stansbury, Jeffrey W; Pfeifer, Carmem S

2013-09-01

To evaluate "low-shrink" composites in terms of polymerization kinetics, stress development and mechanical properties. "Low-shrink" materials (Kalore/KAL, N'Durance/NDUR, and Filtek P90/P90) and one control (Esthet X HD/EHD) were tested. Polymerization stress (PS) was measured using the Instron 5565 tensometer. Volumetric shrinkage (VS) was determined by the ACTA linometer. Elastic modulus (E) and flexural strength (FS) were obtained by a three-point bending test. Degree of conversion (DC) and polymerization rate (Rp) were determined by NIR spectroscopy (6165cm(-1) for dimethacrylates; 4156 and 4071cm(-1) for P90). Photopolymerization was performed at 740mW/cm(2)×27s. Glass transition temperature (Tg), degree of heterogeneity and crosslink density were obtained in a DMA for the fully cured specimens. Analysis of extracts was done by (1)H NMR. Data were analyzed with one-way ANOVA/Tukey's test (α=0.05). The control presented the highest shrinkage and Tg. P90 showed the highest modulus, and NDUR demonstrated the highest conversion. The polymerization rates were comparable for all materials. NDUR and KAL had the highest and the lowest network homogeneity, respectively. The multifunctional P90 had the highest crosslink density, with no difference between other composites. The control had the greatest stress development, similar to NDUR. Crosslinking density and polymer network homogeneity were influenced by degree of conversion and monomer structure. Not all "low-shrink" composites reduced polymerization stress. P90 and NDUR had no leachable monomers, which was also a function of high crosslinking (P90) and high conversion (NDUR). Copyright © 2013 Academy of Dental Materials. All rights reserved.

Protection of moisture-sensitive drugs with aqueous polymer coatings: importance of coating and curing conditions.

PubMed

Bley, O; Siepmann, J; Bodmeier, R

2009-08-13

The aim of this study was to better understand the importance of coating and curing conditions of moisture-protective polymer coatings. Tablets containing freeze-dried garlic powder were coated with aqueous solutions/dispersions of hydroxypropyl methylcellulose (HPMC), poly(vinyl alcohol), ethyl cellulose and poly(methacrylate-methylmethacrylates). The water content of the tablets during coating and during storage at different temperatures and relative humidities (RH) was determined gravimetrically. In addition, changes in the allicin (active ingredient in garlic powder) content were monitored. During the coating process, the water uptake was below 2.7% and no drug degradation was detectable. Thermally induced drug degradation occurred only at temperatures above the coating temperatures. Different polymer coatings effectively decreased the rate, but not the extent of water uptake during open storage at room temperature and 75% RH. Tablets coated with poly(vinyl alcohol) and poly(methacrylate-methylmethacrylates) showed the lowest moisture uptake rates (0.49 and 0.57%/d, respectively). Curing at elevated temperature after coating did not improve the moisture-protective ability of the polymeric films, but reduced the water content of the tablets. Drug stability was significantly improved with tablets coated with poly(vinyl alcohol) and poly(methacrylate-methylmethacrylates).

Nanocomposites of phosphonic-acid-functionalized polyethylenes with inorganic quantum dots.

PubMed

Rünzi, Thomas; Baier, Moritz C; Negele, Carla; Krumova, Marina; Mecking, Stefan

2015-01-01

Insertion of diethyl vinyl phosphonates and free vinyl phosphonic acid, respectively, into [(P^O)Pd(Me)(dmso)] ((P^O) = κ(2)-P,O-Ar2PC6H4SO2O with Ar = 2-MeOC6H4) (1-dmso) occurs in a 2,1- as well as 1,2-fashion, to form a four-and a five-membered chelate [(P^O)Pd{κ(2)-C,O-CH(P(O)(OR)2)CH2CH3}] and [(P^O)Pd{κ(2)-C,O-CH2CH(P(O)(OR)2)CH3}] (R = H, Et). No decomposition or other reactions of 1 by free phosphonic acid moieties occur. Copolymerization in a pressure reactor by 1-dmso yields linear random poly(ethylene-co-diethyl vinyl phosphonate) and poly(ethylene-co-vinyl phosphonic acid). In these copolymerizations, reversible coordination of the phosphonate moieties of free monomer as well as chelate formation by incorporated monomer retards chain growth as also evidenced by relative binding studies of diethyl phosphonate towards 1. Post-polymerization emulsification of poly(ethylene-co-vinyl phosphonic acid) together with CdSe/CdS quantum dots (QDs) yields submicron (ca. 50 nm from dynamic light scattering (DLS) and transmission electron microscopy (TEM)) polymer particles with the QDs embedded in the functionalized polyethylene in a nonaggregated fashion. This embedding benefits the fluorescence behavior in terms of continuous emission and life-time as revealed by wide-field fluorescence measurements. These composite particle dispersions are employed as a ″masterbatch" together with an aqueous high density polyethylene (HDPE) dispersion to generate thin films (by spin-coating) and bulk materials (from the melt), respectively, in which the inorganic nanoparticles remain highly disperse. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Activation of Ice Recrystallization Inhibition Activity of Poly(vinyl alcohol) using a Supramolecular Trigger†

PubMed Central

Phillips, Daniel J.; Congdon, Thomas R.; Gibson, Matthew I.

2016-01-01

Antifreeze (glyco)proteins (AF(G)Ps) have potent ice recrystallisation inhibition (IRI) activity – a desirable phenomenon in applications such as cryopreservation, frozen food and more. In Nature AF(G)P activity is regulated by protein expression levels in response to an environmental stimulus; temperature. However, this level of regulation is not possible in synthetic systems. Here, a synthetic macromolecular mimic is introduced, using supramolecular assembly to regulate activity. Catechol-terminated poly(vinyl alcohol) was synthesised by RAFT polymerization. Upon addition of Fe3+, larger supramolecular star polymers form by assembly with two or three catechols. This increase in molecular weight effectively ‘switches on’ the IRI activity and is the first example of external control over the function of AFP mimetics. This provides a simple but elegant solution to the challenge of external control of AFP-mimetic function. PMID:28003855

Study on the performance of eosin-doped poly(vinyl alcohol)/acrylamide photopolymer films for holographic recording using 488-nm wavelength

NASA Astrophysics Data System (ADS)

Rajesh, Chelakkal Sukumaran; Sreeroop, Sasidharan Savithrydevi; Pramitha, Vayalamkuzhi; Joseph, Rani; Sreekumar, Krishnapillai; Kartha, Cheranellore Sudha

2011-12-01

This article reports a study done on eosin-doped poly(vinyl alcohol)/acrylamide films for holographic recording using 488 nm Ar+ laser. Films were fabricated using gravity settling method at room temperature and were stored under normal laboratory conditions. Ar+ laser (488 nm) was used for fringe recording. Characterization was done by real time transmittance measurement, optical absorption studies, and diffraction efficiency measurements. Various holographic parameters such as exposure energy, recording power, spatial frequency, etc., were optimized so as to ensure maximum performance. More than 85% diffraction efficiency was obtained at an exposure energy of 50 mJ/cm2 in the optimized film. Efforts were taken to study the environmental stability of this self-developing polymeric material by looking at its shelf life and storage life. Compatibility for recording transmission hologram was also checked.

Polymerization Kinetics: Monitoring Monomer Conversion Using an Internal Standard and the Key Role of Sample "t[subscript 0]"

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…

Controlled aqueous polymerization of acrylamides and acrylates and "in situ" depolymerization in the presence of dissolved CO2.

PubMed

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.

Application of an Addition-Fragmentation-Chain Transfer Monomer in Di(meth)acrylate Network Formation to Reduce Polymerization Shrinkage Stress.

PubMed

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.

Photonic crystal borax competitive binding carbohydrate sensing motif†

PubMed Central

Cui, Qingzhou; Muscatello, Michelle M. Ward; Asher, Sanford A.

2009-01-01

We developed a photonic crystal sensing method for diol containing species such as carbohydrates based on a poly(vinyl alcohol) (PVA) hydrogel containing an embedded crystalline colloidal array (CCA). The polymerized CCA (PCCA) diffracts visible light. We show that in the presence of borax the diffraction wavelength shifts as the concentration of glucose changes. The diffraction shifts result from the competitive binding of glucose to borate, which reduces the concentration of borate bound to the PVA diols. PMID:19381378

An analytical approach for the non-invasive selection of consolidants in rubber artworks.

PubMed

Manfredi, Marcello; Barberis, Elettra; Rava, Antonio; Poli, Tommaso; Chiantore, Oscar; Marengo, Emilio

2016-08-01

The effectiveness of five polymeric materials for the long-term conservation and restoration of rubber artworks was evaluated by accelerated photo-oxidative degradation studies. Two different ethylene vinyl-acetate resins, generally used in industry and uncommon in conservation field, a new water-based polyurethane, and two ethylene butyl-acrylate resins were assessed for the consolidation of rubber. By monitoring their degradation along time with LED imaging coupled to statistics and Fourier transform infrared spectroscopy (FTIR), the polymeric materials with the best properties that ensure the protection and security of the artwork were identified. The degradation was performed in solar box simulating the light exposure in a museum, under controlled temperature at no more than 35 °C in order to exclude the thermal effects that could influence the ageing of polymers. The mechanical stress of the treated samples was also investigated. The spectroscopic analyses, the chromatic changes study, and the mechanical degradation were used as indicators of the consolidant stability, allowing the evaluation of the materials selected for the consolidation and conservation of rubber. The ethylene-vinyl acetate copolymers resulted the most stable and suitable for the conservation of rubber artworks. Lastly, the conservation treatment identified in this research was employed for the restoration of the contemporary artwork "Presagi di Birnam" made with bicycle inner tubes by the artist Carol Rama.

Preparation, characterization, and application of poly(vinyl alcohol)-graft-poly(ethylene glycol) resins: novel polymer matrices for solid-phase synthesis.

PubMed

Luo, Juntao; Pardin, Christophe; Zhu, X X; Lubell, William D

2007-01-01

Spherical crosslinked poly(vinyl alcohol) (PVA) beads with good mechanical stability were prepared by reverse-suspension polymerization, using dimethyl sulfoxide (DMSO) as a cosolvent in an aqueous phase. Poly(ethylene glycol)s with varying chain lengths were grafted onto the PVA beads by anionic polymerization of ethylene oxide. The thermal behavior, morphology, and swelling were evaluated for each of the new polymer matrices. High loading and good swelling in water and organic solvents were characteristic of the PEG-grafted PVA beads. The polymer beads also exhibited good mechanical and chemical stability and were unaffected by treatment with 6 N HCl and with 6 N NaOH. The hydroxyl groups of the PVA-PEG beads were converted into aldehyde, carboxylic acid, and isocyanate functions to provide scavenger resins and were extended by way of a benzyl alcohol in a Wang linker. The transglutaminase substrates dipeptides (Z-Gln-Gly) and heptapeptides (Pro-Asn-Pro-Gln-Leu-Pro-Phe) were synthesized on PVA-PEG_5, PVA-PEG_20, and the Wang linker-derivatized PVA-PEG resins. The cleavage of the peptides from the resins using MeOH/NH3 mixture at different temperatures (0 degrees C and room temp) and 50% TFA/DCM provided, respectively, peptide methyl esters, amides, and acids in good yields and purity as assessed by LC-MS analysis.

The effects of energetic proton bombardment on polymeric materials: Experimental studies and degradation models

NASA Technical Reports Server (NTRS)

Coulter, D. R.; Gupta, A.; Smith, M. V.; Fornes, R. E.

1986-01-01

This report describes 3 MeV proton bombardment experiments on several polymeric materials of interest to NASA carried out on the Tandem Van De Graff Accelerator at the California Institute of Technology's Kellogg Radiation Laboratory. Model aromatic and aliphatic polymers such as poly(1-vinyl naphthalene) and poly(methyl methacrylate), as well as polymers for near term space applications such as Kapton, Epoxy and Polysulfone, have been included in this study. Chemical and physical characterization of the damage products have been carried out in order to develop a model of the interaction of these polymers with the incident proton beam. The proton bombardment methodology developed at the Jet Propulsion Laboratory and reported here is part of an ongoing study on the effects of space radiation on polymeric materials. The report is intended to provide an overview of the mechanistic, as well as the technical and experimental, issues involved in such work rather than to serve as an exhaustive description of all the results.

Lignin model compounds as bio-based reactive diluents for liquid molding resins.

PubMed

Stanzione, Joseph F; Sadler, Joshua M; La Scala, John J; Wool, Richard P

2012-07-01

Lignin is a copious paper and pulping waste product that has the potential to yield valuable, low molecular weight, single aromatic chemicals when strategically depolymerized. The single aromatic lignin model compounds, vanillin, guaiacol, and eugenol, were methacrylated by esterification with methacrylic anhydride and a catalytic amount of 4-dimethylaminopyridine. Methacrylated guaiacol (MG) and methacrylated eugenol (ME) exhibited low viscosities at room temperature (MG: 17 cP and ME: 28 cP). When used as reactive diluents in vinyl ester resins, they produced resin viscosities higher than that of vinyl ester-styrene blends. The relative volatilities of MG (1.05 wt% loss in 18 h) and ME (0.96 wt% loss in 18 h) measured by means of thermogravimetric analysis (TGA) were considerably lower than that of styrene (93.7 wt% loss in 3 h) indicating the potential of these chemicals to be environmentally friendly reactive diluents. Bulk polymerization of MG and ME generated homopolymers with glass transition temperatures (T(g)s) of 92 and 103 °C, respectively. Blends of a standard vinyl ester resin with MG and ME (50 wt % reactive diluent) produced thermosets with T(g)s of 127 and 153 °C, respectively, which are comparable to vinyl ester-styrene resins, thus demonstrating the ability of MG and ME to completely replace styrene as reactive diluents in liquid molding resins without sacrificing cured-resin thermal performance. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

High fluorescence emission silver nano particles coated with poly (styrene-g-soybean oil) graft copolymers: Antibacterial activity and polymerization kinetics.

PubMed

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.

Soluble, High Molecular Weight Polysilsesquioxanes with Carboxylate Functionalities

DOE Office of Scientific and Technical Information (OSTI.GOV)

RAHIMIAN,KAMYAR; LOY,DOUGLAS A.; WHEELER,DAVID R.

2000-07-14

Trialkoxysilyl-containing monomers of the type (RO){sub 3}Si(CH{sub 2}){sub 3}C(O)OtBu (R = Me, Et) were prepared by hydrosilation of the corresponding vinylic tert-butyl esters CH{sub 3}CHCH{sub 2}C(O)OtBu. Acid- or base-catalyzed polymerization of the monomers leads to very high molecular weight polymers with relatively narrow polydispersities. The polymerization results in complete condensation of the alkoxy groups while the tert-butyl ester functionality remains fully intact. Partial or full deprotection of the tert-butyl group can easily be achieved to yield the corresponding carboxylic acid polymers. The ester and carboxylic acid functionalities of these new materials allow for their potential use in a variety ofmore » applications such as scavenging of heavy metals.« less

Functionalizing the Surface of Lithium-Metal Anodes

DOE PAGES

Buonaiuto, Megan; Neuhold, Susanna; Schroeder, David J.; ...

2014-09-03

Metal-air batteries are an important aspect of many beyond lithium ion research efforts. However, as our understanding of how molecular oxygen can act as a rechargeable cathode has progressed; the problems associated with how these materials at various states of charge interact with the lithium metal anode are only beginning to come to the surface. In this study we have devised a method to coat the surface a lithium with a functional group to act as either an anchor for further derivation studies or be polymerized to create a nanometer thick polymer coating attached to the surface by silane groups.more » These stable films, formed by polymerization of vinyl substituents, lower cell impedance at the electrode and over the first 50 cycles, increase cycling efficiency and demonstrate lower capacity fade.« less

Synthesis and characterization of hydrolysed starch-g-poly(methacrylic acid) composite.

PubMed

Zahran, Magdy K; Ahmed, Enas M; El-Rafie, Mohamed H

2016-06-01

A novel method for the synthesis of starch-g-poly(methacrylic acid) composite was adopted by graft polymerization of hydrolysed starch (HS) and methacrylic acid (MAA) in aqueous medium using an efficient sodium perborate (SPB)-thiourea (TU) redox initiation system. The parameters influencing the redox system efficiency and thence the polymerization method were considered. These parameters comprehended the concentrations of MAA, SPB, TU and SPB/TU molar ratio as well as the polymerization temperature. The polymerization reaction was scrutinized through calculation of the MAA total conversion percent (TC%). The resultant poly(MAA-HS) composite was assessed by evaluating the polymer criteria (the graft yield, GY%; the grafting efficiency, GE%; the homopolymer, HP%; and the total conversion). The comportment of the apparent viscosity of the cooked poly(MAA)-starch composite paste, obtained under diverse polymerization conditions, was examined. Tentative mechanisms, which depict all occasions that happen amid the entire course of the polymerization reaction, have been proffered. Copyright © 2016 Elsevier B.V. All rights reserved.

A novel composite of SiO2-coated graphene oxide and molecularly imprinted polymers for electrochemical sensing dopamine.

PubMed

Zeng, Yanbo; Zhou, Ying; Kong, Lei; Zhou, Tianshu; Shi, Guoyue

2013-07-15

A novel imprinting route based on graphene oxide (GO) was proposed for preparing a composite of SiO2-coated GO and molecularly imprinted polymers (GO/SiO2-MIPs). In this route, SiO2-coated GO sheets were synthesized in a water-alcohol mixture with sol-gel technique. Prior to polymerization, the vinyl groups were introduced onto the surface of GO/SiO2 through chemical modification with γ-methacryloxypropyl trimethoxysilane (γ-MAPS), which can direct the selective polymerization on the GO/SiO2 surface. Then a novel composite of GO/SiO2-MIPs was successfully obtained by the copolymerization in presence of vinyl groups functionalized GO/SiO2, dopamine (DA), methacrylic acid and ethylene glycol dimethacrylate. The GO/SiO2-MIPs composite was characterized by FTIR, TGA, Raman spectroscopy, SEM and AFM. The properties such as special binding, adsorption dynamics and selective recognition ability using differential pulse voltammetry (DPV) were evaluated. The DPV current response of GO/SiO2-MIPs sensor was nearly 3.2 times that of the non-imprinted polymers (NIPs). In addition, the GO/SiO2-MIPs sensor could recognize DA from its relatively similar molecules of norepinephrine and epinephrine, while the sensors based on GO/SiO2-NIPs and vinyl groups functionalized GO/SiO2 did not have the ability. The GO/SiO2-MIPs sensor had a wide linear range over DA concentration from 5.0 × 10(-8) to 1.6 × 10(-4)M with a detection limit of 3.0 × 10(-8)M (S/N=3). The sensor based on this novel imprinted composite was applied to the determination of DA in injections and human urine samples with satisfactory results. Copyright © 2013 Elsevier B.V. All rights reserved.

A novel approach to fabricate dye-encapsulated polymeric micro- and nanoparticles by thin film dewetting technique.

PubMed

Chatterjee, Manosree; Hens, Abhiram; Mahato, Kuldeep; Jaiswal, Namita; Mahato, Nivedita; Nagahanumaiah; Chanda, Nripen

2017-11-15

A new method is reported for fabrication of polymeric micro- and nanoparticles from an intermediate patterned surface originated by dewetting of a polymeric thin film. Poly (d, l-lactide-co-glycolide) or PLGA, a biocompatible polymer is used to develop a thin film over a clean glass substrate which dewets spontaneously in the micro-/nano-patterned surface of size range 50nm to 3.5µm. Since another water-soluble polymer, poly vinyl alcohol (PVA) is coated on the same glass substrate before PLGA thin film formation, developed micro-/nano-patterns are easily extracted in water in the form of micro- and nanoparticle mixture of size range 50nm to 3.0µm. This simplified method is also used to effectively encapsulate a dye molecule, rhodamine B inside the PLGA micro-/nanoparticles. The developed dye-encapsulated nanoparticles, PLGA-rhodamine are separated from the mixture and tested for in-vitro delivery application of external molecules inside human lung cancer cells. For the first time, the use of thin film dewetting technique is reported as a potential route for the synthesis of polymeric micro-/nanoparticles and effective encapsulation of external species therein. Copyright © 2017 Elsevier Inc. All rights reserved.

Detection Of Uric Acid Based On Multi-Walled Carbon Nanotubes Polymerized With A Layer Of Molecularly Imprinted PMAA

NASA Astrophysics Data System (ADS)

Chen, Po-Yen; Lin, Chia-Yu; Ho, Kuo-Chuan

2009-05-01

A molecularly imprinted poly-metharylic acid (PMAA), polymerizing on the surface of multi-walled carbon nanotube (MWCNT), was synthesized. The MWCNT was modified by a layer of carboxylic acid and reacted with EDC and NHS to activate the carboxylic acid, which was prepared for the purpose of bonding allyl amine and getting an unsaturated side chain (-C=C). The resultant structure is abbreviated as MWCNTs-CH=CH2. It is well known that the vinyl group side chain provides good attachment between the MWCNTs and the molecularly imprinted polymer (MIP). The MIP based on PMAA was polymerized on the surface of MWCNTs-CH=CH2 with the addition of uric acid (UA). The non-imprinted polymer (NIP) was polymerized without adding UA. The adsorbed amount of UA approached the equilibrium value upon 60 min adsorption. The adsorption isotherm was obtained by immersing 10 mg of MIP or NIP in 5 mL aqueous solution containing different concentrations of UA. The adsorbed amounts were measured via a UV-Vis spectrometer at a wavelength of 292 nm. From the adsorption isotherm, it is seen that the MIP particles possess a good imprinting efficiency of about 4.41.

Preparation of Poly(Dinitropropyl Vinyl Ether) with Crosslinking Sites, for Use as a Castable Binder

DTIC Science & Technology

1978-12-01

acetic acid . 4 Baum, K., Fluorochem, Inc., and Adolph, H., this Center, unpublished results. 11 NSWC/WOL TR 78-120 AFATL TR-78-86 In Table 1 are...for successful hydroxymethyla- tion (Figure 6): The peak for the acidic proton in Figure 5 at 6 4.85 is absent in Figure 6, and the doublet E in Figure...Poly-DNPVE, the work was terminated in favor of screening other cationic initiators. Initiation of DNPVE polymerization with epoxide/Lewis acid

The effect of polymerization mode on monomer conversion, free radical entrapment, and interaction with hydroxyapatite of commercial self-adhesive cements.

PubMed

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.

In vitro mechanical fatigue behavior of poly-ɛ-caprolactone macroporous scaffolds for cartilage tissue engineering: Influence of pore filling by a poly(vinyl alcohol) gel.

PubMed

Panadero, J A; Vikingsson, L; Gomez Ribelles, J L; Lanceros-Mendez, S; Sencadas, V

2015-07-01

Polymeric scaffolds used in regenerative therapies are implanted in the damaged tissue and submitted to repeated loading cycles. In the case of articular cartilage engineering, an implanted scaffold is typically subjected to long-term dynamic compression. The evolution of the mechanical properties of the scaffold during bioresorption has been deeply studied in the past, but the possibility of failure due to mechanical fatigue has not been properly addressed. Nevertheless, the macroporous scaffold is susceptible to failure after repeated loading-unloading cycles. In this work fatigue studies of polycaprolactone scaffolds were carried by subjecting the scaffold to repeated compression cycles in conditions simulating the scaffold implanted in the articular cartilage. The behavior of the polycaprolactone sponge with the pores filled with a poly(vinyl alcohol) gel simulating the new formed tissue within the pores was compared with that of the material immersed in water. Results were analyzed with Morrow's criteria for failure and accurate fittings are obtained just up to 200 loading cycles. It is also shown that the presence of poly(vinyl alcohol) increases the elastic modulus of the scaffolds, the effect being more pronounced with increasing the number of freeze/thawing cycles. © 2014 Wiley Periodicals, Inc.

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.

Glucose biosensor based on the immobilization of glucose oxidase on electrochemically synthesized polypyrrole-poly(vinyl sulphonate) composite film by cross-linking with glutaraldehyde.

PubMed

Colak, Ozlem; Yaşar, Ahmet; Cete, Servet; Arslan, Fatma

2012-10-01

In this study, a novel amperometric glucose biosensor was developed by immobilizing glucose oxidase (GOX) by cross-linking via glutaraldehyde on electrochemically polymerized polypyrrole-poly(vinyl sulphonate) (PPy-PVS) films on the surface of a platinum (Pt) electrode. Electropolymerization of pyrrole and poly(vinyl sulphonate) on the Pt surface was carried out with an electrochemical cell containing pyrrole and poly(vinyl sulphonate) by cyclic voltammetry between -1.0 and + 2.0 V (vs.Ag/AgCl) at a scan rate of 50 mV/s upon the Pt electrode. The amperometric determination was based on the electrochemical detection of H(2)O(2) generated in enzymatic reaction of glucose. Determination of glucose was carried out by the oxidation of enzymatically produced H(2)O(2) at 0.4 V vs. Ag/AgCl. The effects of pH and temperature were investigated and optimum parameters were found to be 7.5 and 65°C, respectively. The effect of working potential was investigated and optimum potential was determined to be 0.4 V. The operational stability of the enzyme electrode was also studied. The response of the PPy/PVS-GOX glucose biosensor exhibited good reproducibility with a relative standard deviation (RSD) of 2.48%. The glucose biosensor retained 63% of initial activity after 93 days when stored in 0.1 M phosphate buffer solution of pH 7.5 at 4°C. With the low operating potential, the biosensor demonstrated little interference from the possible interferants.

Moisture-induced phase separation and recrystallization in amorphous solid dispersions.

PubMed

Luebbert, Christian; Sadowski, Gabriele

2017-10-30

Active Pharmaceutical Ingredients (APIs) are often dissolved in polymeric matrices to control the gastrointestinal dissolution and to stabilize the amorphous state of the API. During the pharmaceutical development of new formulations, stability studies via storage at certain temperature and relative humidity (RH) have to be carried out to verify the long-term thermodynamic stability of these formulations against unwanted recrystallization and moisture-induced amorphous-amorphous phase separation (MIAPS). This study focuses on predicting the MIAPS of API/polymer formulations at elevated RH. In a first step, the phase behavior of water-free formulations of ibuprofen (IBU) and felodipine (FEL) combined with the polymers poly(vinyl pyrrolidone) (PVP), poly(vinyl acetate) (PVAC) and poly (vinyl pyrrolidone-co-vinyl acetate) (PVPVA64) was determined experimentally by differential scanning calorimetry (DSC). The phase behavior of these water-free formulations was modeled using the Perturbed-Chain Statistical Associating Fluid Theory (PC-SAFT). Based on this, the API solubility and MIAPS in the above-mentioned formulations at humid conditions was predicted in perfect agreement with the results of two-year lasting stability studies at 25°C/0% RH and 40°C/75% RH. MIAPS was predicted and also experimentally found for the FEL/PVP, FEL/PVPVA64 and IBU/PVP formulations, whereas MIAPS was neither predicted nor measured for the IBU/PVPVA64 system and PVAC-containing formulations. It was thus shown that the results of time-consuming long-term stability tests can be correctly predicted via thermodynamic modeling with PC-SAFT. Copyright © 2017 Elsevier B.V. All rights reserved.

Highly efficient reversible addition-fragmentation chain-transfer polymerization in ethanol/water via flow chemistry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ye, Piaoran; Cao, Peng -Fei; Su, Zhe

Here, utilization of a flow reactor under high pressure allows highly efficient polymer synthesis via reversible addition–fragmentation chain-transfer (RAFT) polymerization in an aqueous system. Compared with the batch reaction, the flow reactor allows the RAFT polymerization to be performed in a high-efficiency manner at the same temperature. The adjustable pressure of the system allows further elevation of the reaction temperature and hence faster polymerization. Other reaction parameters, such as flow rate and initiator concentration, were also well studied to tune the monomer conversion and the molar mass dispersity (Ð) of the obtained polymers. Gel permeation chromatography, nuclear magnetic resonance (NMR),more » and Fourier transform infrared spectroscopies (FTIR) were utilized to monitor the polymerization process. With the initiator concentration of 0.15 mmol L –1, polymerization of poly(ethylene glycol) methyl ethermethacrylate with monomer conversion of 52% at 100 °C under 73 bar can be achieved within 40 min with narrow molar mass dispersity (D) Ð (<1.25). The strategy developed here provides a method to produce well-defined polymers via RAFT polymerization with high efficiency in a continuous manner.« less

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

PubMed

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

2014-04-01

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Johnson, Kyle J.; Glynos, Emmanouil; Maroulas, Serafeim-Dionysios

Incorporating nanoparticles (NPs) within a polymer host to create polymer nanocomposites (PNCs) while having the effect of increasing the functionality (e.g.: sensing, energy conversion) of these materials, introduces additional complications with regard to the processing-morphology-function behavior. A primary challenge is to understand and control the viscosity of a PNC with decreasing film thickness confinement for nanoscale applications. Using a combination of X-ray photon correlation spectroscopy (XPCS) and X-ray standing wave based resonance enhanced XPCS to study the dynamics of neat poly-2-vinyl pyridine (P2VP) chains and the nanoparticle dynamics, respectively, we identified a new mechanism that dictates the viscosity of PNCmore » films in the nanoscale regime. We show that while the viscosities of neat P2VP films as thin as 50 nm remained the same as the bulk, PNC films containing P2VP brush-coated gold NPs, spaced 50 nm apart, exhibited unprecedented increases in viscosities of over an order of magnitude. For thicker films or more widely separated NPs, the chain dynamics and viscosities were equal to the bulk values. These results -NP proximities and suppression of their dynamics -suggest a new mechanism by which the viscosities of polymeric liquids could be controlled for 2D and 3D nanoscale applications.« less

Controlled Release of Antimicrobial ClO2 Gas from a Two-Layer Polymeric Film System.

PubMed

Bai, Zhifeng; Cristancho, Diego E; Rachford, Aaron A; Reder, Amy L; Williamson, Alexander; Grzesiak, Adam L

2016-11-16

We report a two-component label system comprising a chlorite-containing polymer film and an acid-containing polymer film that can release antimicrobial ClO 2 gas upon adhering the two films together to enable a reaction of the chlorite and acid under moisture exposure. The chlorite-containing film comprises a commercial acrylate-based pressure-sensitive adhesive polymer impregnated with sodium chlorite. The acid-containing film comprises a commercial poly(vinyl alcohol) polymer loaded with tartaric acid. Both of the films were prepared on low ClO 2 -absorbing substrate films from stable aqueous systems of the polymers with high reagent loading. Rapid and sustained releases of significant amounts of ClO 2 gas from the label system were observed in an in situ quantification system using UV-vis spectroscopy. It was found that the ClO 2 release is slower at a lower temperature and can be accelerated by moisture in the atmosphere and the films. Controlled release of ClO 2 gas from the label system was demonstrated by tailoring film composition and thickness. A model was developed to extract release kinetics and revealed good conversions of the label system. This two-component system can potentially be applied as a two-part label without premature release for applications in food packaging.

Properties of iopamidol-incorporated poly(vinyl alcohol) microparticle as an X-ray imaging flow tracer.

PubMed

Ahn, Sungsook; Jung, Sung Yong; Lee, Jin Pyung; Lee, Sang Joon

2011-02-10

We have recently reported on poly(vinyl alcohol) microparticles containing X-ray contrast agent, iopamidol, designed as a flow tracer working in synchrotron X-ray imaging ( Biosens. Bioelectron. 2010 , 25 , 1571 ). Although iopamidol is physically encapsulated in the microparticles, it displays a great contrast enhancement and stable feasibility in in vitro human blood pool. Nonetheless, a direct relation between the absolute amount of incorporated iopamidol and the enhancement in imaging efficiency was not observed. In this study, physical properties of the designed microparticle are systematically investigated experimentally with theoretical interpretation to correlate an enhancement in X-ray imaging efficiency. The compositional ratio of X-ray contrast agent in polymeric microparticle is controlled as 1/1 and 10/1 [contrast agent/polymer microparticle (w/w)] with changed degree of cross-linkings. Flory-Huggins interaction parameter (χ), retractive force (τ) and degree of swelling of the designed polymeric microparticles are investigated. In addition, the hydrodynamic size (D(H)) and ζ-potential are evaluated in terms of environment responsiveness. The physical properties of the designed flow tracer microparticles under a given condition are observed to be strongly related with the X-ray absorption efficiency, which are also supported by the Beer-Lambert-Bouguer law. The designed microparticles are almost nontoxic with a reasonable concentration and time period, enough to be utilized as a flow tracer in various biomedical applications. This study would contribute to the basic understanding on the physical property connected with the imaging efficiency of contrast agents.

Fluorescent porous film modified polymer optical fiber via "click" chemistry: stable dye dispersion and trace explosive detection.

PubMed

Ma, Jiajun; Lv, Ling; Zou, Gang; Zhang, Qijin

2015-01-14

In this paper, we report a facile strategy to fabricate fluorescent porous thin film on the surface of U-bent poly(methyl methacrylate) optical fiber (U-bent POF) in situ via "click" polymerization for vapor phase sensing of explosives. Upon irradiation of evanescent UV light transmitting within the fiber under ambient condition, a porous film (POSS-thiol cross-linking film, PTCF) is synthesized on the side surface of the fiber by a thiol-ene "click" reaction of vinyl-functionalized polyhedral oligomeric silsesquioxanes (POSS-V8) and alkane dithiols. When vinyl-functionalized porphyrin, containing four allyl substituents at the periphery, is added into precursors for the polymerization, fluorescence porphyrin can be covalently bonded into the cross-linked network of PTCF. This "fastened" way reduces the aggregation-induced fluorescence self-quenching of porphyrin and enhances the physicochemical stability of the porous film on the surface of U-bent POF. Fluorescent signals of the PTCF/U-bent POF probe made by this method exhibit high fluorescence quenching toward trace TNT and DNT vapor and the highest fluorescence quenching efficiency is observed for 1, 6-hexanedimercaptan-based film. In addition, because of the presence of POSS-V8 with multi cross-linkable groups, PTCF exhibits well-organized pore network and stable dye dispersion, which not only causes fast and sensitive fluorescence quenching against vapors of nitroaromatic compounds, but also provides a repeatability of the probing performance.

Photo-responsive polymeric micelles.

PubMed

Huang, Yu; Dong, Ruijiao; Zhu, Xinyuan; Yan, Deyue

2014-09-07

Photo-responsive polymeric micelles have received increasing attention in both academic and industrial fields due to their efficient photo-sensitive nature and unique nanostructure. In view of the photo-reaction mechanism, photo-responsive polymeric micelles can be divided into five major types: (1) photoisomerization polymeric micelles, (2) photo-induced rearrangement polymeric micelles, (3) photocleavage polymeric micelles, (4) photo-induced crosslinkable polymeric micelles, and (5) photo-induced energy conversion polymeric micelles. This review highlights the recent advances of photo-responsive polymeric micelles, including the design, synthesis and applications in various biomedical fields. Especially, the influence of different photo-reaction mechanisms on the morphology, structure and properties of the polymeric micelles is emphasized. Finally, the possible future directions and perspectives in this emerging area are briefly discussed.

Well-defined single polymer nanoparticles for the antibody-targeted delivery of chemotherapeutic agents.

PubMed

Lane, D D; Chiu, D Y; Su, F Y; Srinivasan, S; Kern, H B; Press, O W; Stayton, P S; Convertine, A J

2015-02-28

Aqueous reversible addition-fragmentation chain transfer (RAFT) polymerization was employed to prepare a series of linear copolymers of N,N-dimethylacrylamide (DMA) and 2-hydroxyethylacrylamide (HEAm) with narrow Đ values over a molecular weight range spanning three orders of magnitude (10 3 to 10 6 Da). Trithiocarbonate-based RAFT chain transfer agents (CTAs) were grafted onto these scaffolds using carbodiimide chemistry catalyzed with DMAP. The resultant graft chain transfer agent (gCTA) was subsequently employed to synthesize polymeric brushes with a number of important vinyl monomer classes including acrylamido, methacrylamido, and methacrylate. Brush polymerization kinetics were evaluated for the aqueous RAFT polymerization of DMA from a 10 arm gCTA. Polymeric brushes containing hydroxyl functionality were further functionalized in order to prepare 2nd generation gCTAs which were subsequently employed to prepare polymers with a brushed-brush architecture with molecular weights in excess of 10 6 Da. These resultant single particle nanoparticles (SNPs) were employed as drug delivery vehicles for the anthracycline-based drug doxorubicin via copolymerization of DMA with a protected carbazate monomer (bocSMA). Cell-specific targeting functionality was also introduced via copolymerization with a biotin-functional monomer (bioHEMA). Drug release of the hydrazone linked doxorubicin was evaluated as function of pH and serum and chemotherapeutic activity was evaluated in SKOV3 ovarian cancer cells.

Polymerization Stress Development in Dental Composites: Effect of Cavity Design Factor

PubMed Central

Antonucci, Joseph M.; Giuseppetti, Anthony A.; O’Donnell, Justin N.R.; Schumacher, Gary E.; Skrtic, Drago

2009-01-01

The objective of the study was to assess the effect of the cavity design factor (C-factor) on polymerization stress development (PSD) in resin composites. An experimental resin (BT resin) was prepared, which contained 2,2-bis[p-(2’-hydroxy-3’-methacryloxypropoxy)phenylene]propane (B) and triethylene glycol dimethacrylate (T) in 1:1 mass ratio, and an activator for visible light polymerization. An experimental composite with demonstrated remineralizing potential was also formulated by inclusion into the BT resin of zirconia-hybridized amorphous calcium phosphate (ACP) filler at a mass fraction of 40 % (BT/ACP composite). A commercial glass-filled composite (TPH) was used as a control. To assess the effect of the test geometry on PSD, C-factor was systematically varied between 0.8 and 6.0 by varying the height of the cylindrical composite specimens. The measured PSD values obtained by cantilever beam tensometry for specimens with variable C-factors were normalized for mass to specimens with a C-factor of 1.33 (h=2.25 mm) as controls to give calculated PSD values. Degrees of vinyl conversions (DC) attained in the TPH control and in the experimental BT/ACP composites were measured by near-infrared spectroscopy. In both the TPH and BT/ACP composite series, PSDcalc increased with the increasing C-factor, confirming the hypothesis that the C-factor value influences PSD values. The higher PSDmeas and PSDcalc values for the experimental BT/ACP composite compared to the commercial TPH composite probably reflect differences in the type and mass of the resin and filler phases in the two types of composite. These differences also account for the observed variation (21 %) in DC attained in a BT/ACP composite 2 h after cure (69.5 %) and in the DC of the TPH composite (57.5 %) having the same C-factor. The cavity design factor seems to play a key role in influencing the PSD of bonded composites, but other factors such as composite mass and composition also must be considered for their effects on PSD. PMID:26413236

Synthesis of Eugenol–Lauryl Methacrylate Copolymers via Cationic Polymerization

NASA Astrophysics Data System (ADS)

Fajrin, A.; Marliana, SD; Handayani, D. S.

2018-04-01

Eugenol is one of the most abundant natural resources in Indonesia. The recently bio-based polymer resin is created based on eugenol because eugenol is functionalized with the polymerizable group. In order to improve the functional properties of eugenol, in this research Eugenol–Lauryl Methacrylate copolymers (co-poly(Eg-LMA)) were synthesized by cationic polymerization using H2SO4 as an initiator under the nitrogen atmosphere. Structure identification of the copolymer showed the absorption of the vinyl group from the monomers disappear at the analysis through FTIR at the wave number 1637-1639 and 985-995 cm-1 and also 1H-NMR on the chemical shift 5,97 and 5,08 ppm. The resulting copolymers obtained brown powder in 32.03 % yieldsand melting point at 96 – 97 °C. Solubility test of the co-poly(Eg-LMA) showed that the polymer couldnot soluble in water but soluble in chloroform, diethyl ether, and benzene. Average molecular weight of co-poly(Eg-LMA) Led Ostwald viscometry was obtained 42020 with the degree of polymerization by 200.

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

PubMed

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.

Poly(ionic liquids) functionalized polypyrrole/graphene oxide nanosheets for electrochemical sensor to detect dopamine in the presence of ascorbic acid.

PubMed

Mao, Hui; Liang, Jiachen; Zhang, Haifeng; Pei, Qi; Liu, Daliang; Wu, Shuyao; Zhang, Yu; Song, Xi-Ming

2015-08-15

Novel poly(ionic liquids) functionalized polypyrrole/graphene oxide nanosheets (PILs/PPy/GO) were prepared by the polymerization of 1-vinyl-3-ethylimidazole bromide (VEIB) on the surface of N-vinyl imidazolium modified PPy/GO nanosheets. Due to the synergistic effects of GO with well-defined lamellar structures, conductive PPy and biocompatible PILs, PILs/PPy/GO modified glassy carbon electrode (GCE) presented the excellent electrochemical catalytic activity towards dopamine (DA) with good stability, high sensitivity and wide linear range in the present of ascorbic acid (AA) with high concentration. PILs played an essential role for the simultaneous determination of DA and AA in a mixture, whose existence effectively improved the transmission mode of electrons and resulted in the different electrocatalytic performance towards the oxidation of DA and AA. It is indicated that PILs/PPy/GO nanosheets can act as a good steady and sensitive electrode material for the development of improved DA sensors. Copyright © 2015 Elsevier B.V. All rights reserved.

Fluorescent Polymer Incorporating Triazolyl Coumarin Units for Cu2+ Detection via Planarization of Ict-Based Fluorophore

PubMed Central

Ngororabanga, Jean Marie Vianney; Du Plessis, Jacolien; Mama, Neliswa

2017-01-01

A novel fluorescent polymer with pendant triazolyl coumarin units was synthesized through radical polymerization. The polymer showed reasonable sensitivity and selectivity towards Cu2+ in acetonitrile in comparison to other tested metal ions with a significant quenching effect on fluorescence and blue shifting in the range of 20 nm. The blue shift was assigned to the conformation changes of the diethylamino group from the coumarin moiety which led to planarization of the triazolyl coumarin units. The possible binding modes for Cu2+ towards the polymer were determined through the comparison of the emission responses of the polymer, starting vinyl monomer and reference compound, and the triazole ring was identified as one of the possible binding sites for Cu2+. The detection limits of the polymer and vinyl monomer towards Cu2+ were determined from fluorescence titration experiments and a higher sensitivity (35 times) was observed for the polymer compared with its starting monomer. PMID:28867764

Ethylene vinyl acetate based radiation grafted hydrophilic matrices: Process parameter standardization, grafting kinetics and characterization

NASA Astrophysics Data System (ADS)

Chaudhari, C. V.; Mondal, R. K.; Dubey, K. A.; Grover, V.; Panicker, L.; Bhardwaj, Y. K.; Varshney, L.

2016-08-01

A transparent, elastomeric, grafted matrix for several potential applications was synthesized by single-step simultaneous radiation grafting of methacrylic acid onto ethylene vinyl acetate (EVA). CuSO4 was found to be the most suitable homo-polymerization inhibitor among different inhibitors tried. The grafting kinetics was found to be a strong function of dose rate (D) and monomer content (M) and an equation relating grafting rate Rg=Kg [M]1.13D0.23 was deduced. Crystallinity of the grafted matrices as assessed from XRD and DSC measurements indicated decrease in crystalline content with increase in grafting yield, suggesting crystalline domain of EVA get disrupted on grafting. Elastic modulus increased linearly with the increase in grafting yield, though elongation at break decreased precipitously from 900% to 30% at even 9% grafting. Thermo-gravimetric analysis showed three step weight loss of the grafted EVA matrix. The grafting of MAA resulted in increase in surface energy mainly due to enhanced polar component.

Fluorescent Polymer Incorporating Triazolyl Coumarin Units for Cu2+ Detection via Planarization of Ict-Based Fluorophore.

PubMed

Ngororabanga, Jean Marie Vianney; Du Plessis, Jacolien; Mama, Neliswa

2017-08-30

A novel fluorescent polymer with pendant triazolyl coumarin units was synthesized through radical polymerization. The polymer showed reasonable sensitivity and selectivity towards Cu 2+ in acetonitrile in comparison to other tested metal ions with a significant quenching effect on fluorescence and blue shifting in the range of 20 nm. The blue shift was assigned to the conformation changes of the diethylamino group from the coumarin moiety which led to planarization of the triazolyl coumarin units. The possible binding modes for Cu 2+ towards the polymer were determined through the comparison of the emission responses of the polymer, starting vinyl monomer and reference compound, and the triazole ring was identified as one of the possible binding sites for Cu 2+ . The detection limits of the polymer and vinyl monomer towards Cu 2+ were determined from fluorescence titration experiments and a higher sensitivity (35 times) was observed for the polymer compared with its starting monomer.

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.

Surface grafting of poly(ethylene glycol) onto poly(acrylamide-co-vinyl amine) cross-linked films under mild conditions.

PubMed

Yamamoto, Y; Sefton, M V

1998-01-01

Poly(ethylene glycol) (PEG) was grafted onto poly(acrylamide-co-vinyl amine) (poly(AM-co-VA)) film using tresylated PEG (TPEG) at 37 degrees C in aqueous buffers (pH 7.4) with a view to surface-modifying microencapsulated mammalian cells. Poly(AM-co-VA) film was synthesized by Hofmann degradation of a cross-linked poly(acrylamide) film. Conversion to vinyl amine on the surface of the film was approximately 50%, but bulk conversion was not observed; surface specificity was thought to be the result of cleavage of aminated polymer chains at the surface due to chain scission. Reaction between primary amine and TPEG gave a graft yield of 2 mol% (based on XPS) with respect to available surface amine groups, equivalent to 54 mol% ethylene oxide based on monomer units. Physical adsorption of non-activated polymer was done under identical conditions as a control and the difference in oxygen content was significant compared to TPEG. The type of buffer agent and buffer concentration did not influence graft yields. This graft reaction, which was completed in as little as 2 h was considered to be mild enough to be used for a surface modification of microcapsules containing cells without affecting their viability. Such a surface modification technique may prove to be a useful means of enhancing the biocompatibility of microcapsules (or any tissue engineering construct) even after cell encapsulation or seeding.

Effect of amine structure on CO2 capture by polymeric membranes.

PubMed

Taniguchi, Ikuo; Kinugasa, Kae; Toyoda, Mariko; Minezaki, Koki

2017-01-01

Poly(amidoamine)s (PAMAMs) incorporated into a cross-linked poly(ethylene glycol) exhibited excellent CO 2 separation properties over H 2 . However, the CO 2 permeability should be increased for practical applications. Monoethanolamine (MEA) used as a CO 2 determining agent in the current CO 2 capture technology at demonstration scale was readily immobilized in poly(vinyl alcohol) (PVA) matrix by solvent casting of aqueous mixture of PVA and the amine. The resulting polymeric membranes can be self-standing with the thickness above 3 μm and the amine fraction less than 80 wt%. The gas permeation properties were examined at 40 °C and under 80% relative humidity. The CO 2 separation performance increased with increase of the amine content in the polymeric membranes. When the amine fraction was 80 wt%, the CO 2 permeability coefficient of MEA containing membrane was 604 barrer with CO 2 selectivity of 58.5 over H 2 , which was much higher than the PAMAM membrane (83.7 barrer and 51.8, respectively) under the same operation conditions. On the other hand, ethylamine (EA) was also incorporated into PVA matrix to form a thin membrane. However, the resulting polymeric membranes exhibited slight CO 2 -selective gas permeation properties. The hydroxyl group of MEA was crucial for high CO 2 separation performance.

Effect of amine structure on CO2 capture by polymeric membranes

PubMed Central

Taniguchi, Ikuo; Kinugasa, Kae; Toyoda, Mariko; Minezaki, Koki

2017-01-01

Abstract Poly(amidoamine)s (PAMAMs) incorporated into a cross-linked poly(ethylene glycol) exhibited excellent CO2 separation properties over H2. However, the CO2 permeability should be increased for practical applications. Monoethanolamine (MEA) used as a CO2 determining agent in the current CO2 capture technology at demonstration scale was readily immobilized in poly(vinyl alcohol) (PVA) matrix by solvent casting of aqueous mixture of PVA and the amine. The resulting polymeric membranes can be self-standing with the thickness above 3 μm and the amine fraction less than 80 wt%. The gas permeation properties were examined at 40 °C and under 80% relative humidity. The CO2 separation performance increased with increase of the amine content in the polymeric membranes. When the amine fraction was 80 wt%, the CO2 permeability coefficient of MEA containing membrane was 604 barrer with CO2 selectivity of 58.5 over H2, which was much higher than the PAMAM membrane (83.7 barrer and 51.8, respectively) under the same operation conditions. On the other hand, ethylamine (EA) was also incorporated into PVA matrix to form a thin membrane. However, the resulting polymeric membranes exhibited slight CO2-selective gas permeation properties. The hydroxyl group of MEA was crucial for high CO2 separation performance. PMID:29383045

Thermal plasma process for recovering monomers and high value carbons from polymeric materials

DOEpatents

Knight, Richard; Grossmann, Elihu D.; Guddeti, Ravikishan R.

2002-01-01

The present invention relates to a method of recycling polymeric waste products into monomers and high value forms of carbon by pyrolytic conversion using an induction coupled RF plasma heated reactor.

Synthesis and characterization of PEG-P(MAA-SS-VCL) nanoparticles

NASA Astrophysics Data System (ADS)

Yu, L. L.; Yang, K.; Mu, R. H.; Zhang, N.; Su, L.

2016-07-01

The PEG-P(MAA-SS-VCL) nanoparticles were obtained using disulfide containing dimethacrylate (SS) as cross-linking agent, using polyethylene glycol methyl acrylate (PEGMA), N-Vinyl-ε-caprolactam (VCL), and methacrylic acid (MAA) as monomers via homogeneous polymerization in aqueous. The PEG-P(MAA-SS-VCL) nanoparticles were characterized by FT-IR and TGA. The particle size and morphology variation in different environments were detected by dynamic light scattering (DLS) and scanning electron microscopy (SEM). It is the very method that PEG-P(MAA-SS-VCL) nanoparticles can be obtained in this study.

Electrophoretic cell separation by means of immunomicrospheres

NASA Technical Reports Server (NTRS)

Rembaum, A.; Smolka, A. J. K.

1980-01-01

The electrophoretic mobility of fixed human red blood cells immunologically labeled with polymeric (4-vinyl)pyridine or polyglutaraldehyde microspheres was altered to a considerable extent. This observation was utilized in the preparative scale electrophoretic separation of human and turkey fixed red blood cells, whose mobilities under normal physiological conditions do not differ sufficiently to allow their separation by continuous flow electrophoresis. It is suggested that resolution in the electrophoretic separation of cell subpopulations, currently limited by finite and often overlapping mobility distributions, may be significantly enhanced by immuno-specific labeling of target populations using microspheres.

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

NASA Astrophysics Data System (ADS)

Sütekin, S. Duygu; Güven, Olgun

2018-01-01

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

Properties of wine polymeric pigments formed from anthocyanin and tannins differing in size distribution and subunit composition.

PubMed

Bindon, Keren; Kassara, Stella; Hayasaka, Yoji; Schulkin, Alex; Smith, Paul

2014-11-26

To explore the effect of tannin composition on pigment formation, model ferments of purified 3-O-monoglucoside anthocyanins (ACN) were conducted either alone or in the presence of two different tannins. Tannins were isolated from grape seeds (Sd) or skins (Sk) following exhaustive extraction in 70% v/v acetone. The Sd and Sk tannin fractions had a mean degree of polymerization of 5.2 and 25.6, respectively. The Sd fraction was highly galloylated, at 22%, but galloylation was <2% in the Sk fraction. The Sk fraction was distinguished by a high proportion of prodelphinidin, at 58%. After a 6 month aging period, polymeric pigments were quantified and their color properties determined following isolation by solid-phase extraction. Wine color and polymeric pigment were highest in the treatment containing ACN+Sd and similar in the ACN+Sk and ACN treatments. The same trend between treatments was observed for total and polymeric nonbleachable pigments. Only minor changes in tannin subunit composition were found following ACN incorporation, but the size distribution of polymeric pigments determined by gel permeation chromatography decreased, in particular for the ACN+Sk treatment. Color incorporation in the higher molecular mass range was lower for ACN+Sk wines than for ACN+Sd wines. Compositional differences between the two tannin fractions may therefore limit the incorporation of ACNs in the colored form. The results suggest that in the ACN+Sk and ACN treatments, the formation of lower molecular mass oligomeric pigments was favored. In polymeric pigments derived from ACNs, the presence of ethyl- and vinyl-linked ACNs to the level of trimers was identified using mass spectrometry.

Silyl Ketene Acetals/B(C₆F₅)₃ Lewis Pair-Catalyzed Living Group Transfer Polymerization of Renewable Cyclic Acrylic Monomers.

PubMed

Hu, Lu; Zhao, Wuchao; He, Jianghua; Zhang, Yuetao

2018-03-15

This work reveals the silyl ketene acetal (SKA)/B(C₆F₅)₃ Lewis pair-catalyzed room-temperature group transfer polymerization (GTP) of polar acrylic monomers, including methyl linear methacrylate (MMA), and the biorenewable cyclic monomers γ-methyl-α-methylene-γ-butyrolactone (MMBL) and α-methylene-γ-butyrolactone (MBL) as well. The in situ NMR monitored reaction of SKA with B(C₆F₅)₃ indicated the formation of Frustrated Lewis Pairs (FLPs), although it is sluggish for MMA polymerization, such a FLP system exhibits highly activity and living GTP of MMBL and MBL. Detailed investigations, including the characterization of key reaction intermediates, polymerization kinetics and polymer structures have led to a polymerization mechanism, in which the polymerization is initiated with an intermolecular Michael addition of the ester enolate group of SKA to the vinyl group of B(C₆F₅)₃-activated monomer, while the silyl group is transferred to the carbonyl group of the B(C₆F₅)₃-activated monomer to generate the single-monomer-addition species or the active propagating species; the coordinated B(C₆F₅)₃ is released to the incoming monomer, followed by repeated intermolecular Michael additions in the subsequent propagation cycle. Such neutral SKA analogues are the real active species for the polymerization and are retained in the whole process as confirmed by experimental data and the chain-end analysis by matrix-assisted laser desorption/ionization time of flight mass spectroscopy (MALDI-TOF MS). Moreover, using this method, we have successfully synthesized well-defined PMMBL- b -PMBL, PMMBL- b -PMBL- b -PMMBL and random copolymers with the predicated molecular weights ( M n ) and narrow molecular weight distribution (MWD).

Antibiofilm Effect of Poly(Vinyl Alcohol-co-Ethylene) Halamine Film against Listeria innocua and Escherichia coli O157:H7

PubMed Central

Cossu, Andrea; Si, Yang; Sun, Gang

2017-01-01

ABSTRACT Bacterial biofilm formation is linked to several infections and foodborne disease outbreaks. To address this challenge, there is an unmet need to develop rechargeable antimicrobial materials that can provide continuous sanitation of contact surfaces, especially in the food industry. This study was aimed at evaluating a novel rechargeable antimicrobial polymer formed using poly(vinyl alcohol-co-ethylene) (PVA-co-PE) with halamine functionality to prevent biofilm formation with repeated exposure to high loads of bacteria and organic content and also to aid in inactivation of preformed biofilms upon contact with this novel material. The antibiofilm activity of this rechargeable antimicrobial material was evaluated using a combination of fluorescence and scanning electron microscopy techniques and biofilm metabolic activity analyses. The results determined on the basis of imaging and metabolic activity measurements demonstrated that halamine-functionalized polymer films significantly reduced Listeria innocua and Escherichia coli O157:H7 biofilm formation. This novel polymeric material maintained its antibiofilm activity with repeated cycles of extended exposure to high levels of bacterial load. These polymeric films were recharged using bleach and cleaned using mechanical sonication after each cycle of extended incubation with bacteria. Halamine-functionalized polymeric material also exhibited significant antibacterial activity against preformed biofilms on a model surface. In summary, our results demonstrate the potential of this antimicrobial material to provide continuous sanitation of surfaces and applications for inactivating preformed biofilms without extensive use of resources, including water and heat. This polymeric material may be used as a replacement for existing polymeric materials or as a coating on diverse materials. IMPORTANCE Conventional sanitizers can have limited efficacy in inactivating biofilms in areas with limited accessibility and buildup of organic biomass. Furthermore, none of the current approaches provide continuous sanitation of surfaces. There is a significant unmet need to develop and validate materials that can prevent biofilm formation as well as inactivate preformed biofilms. In this study, the efficacy of a copolymer film containing N-halamine against biofilms of L. innocua and E. coli O157:H7 was evaluated. The polymer film showed strong inhibitory activity against pregrown biofilm or prevented the growth of a new biofilm. The polymer film also maintained its antibiofilm activity after multiple cycles of exposure to high titers of bacterial load with recharging of the polymer film using bleach at intermediate steps between the cycles. Overall, the results demonstrate the potential of a novel antimicrobial material to inhibit and treat biofilms in food industry applications. PMID:28802271

Evaluation of Polymerization Efficacy in Composite Resins via FT-IR Spectroscopy and Vickers Microhardness Test.

PubMed

Jafarzadeh, Tahereh-Sadat; Erfan, Mohammad; Behroozibakhsh, Marjan; Fatemi, Mostafa; Masaeli, Reza; Rezaei, Yashar; Bagheri, Hossein; Erfan, Yasaman

2015-01-01

Background and aims. Polymerization efficacy affects the properties and performance of composite resin restorations.The purpose of this study was to evaluate the effectiveness of polymerization of two micro-hybrid, two nano-hybrid and one nano-filled ormocer-based composite resins, cured by two different light-curing systems, using Fourier transformation infrared (FT-IR) spectroscopy and Vickers microhardness testing at two different depths (top surface, 2 mm). Materials and methods. For FT-IR spectrometry, five cylindrical specimens (5mm in diameter × 2 mm in length) were prepared from each composite resin using Teflon molds and polymerized for 20 seconds. Then, 70-μm wafers were sectioned at the top surface and at2mm from the top surface. The degree of conversion for each sample was calculated using FT-IR spectroscopy. For Vickers micro-hardness testing, three cylindrical specimens were prepared from each composite resin and polymerized for 20 seconds. The Vickers microhardness test (Shimadzu, Type M, Japan) was performed at the top and bottom (depth=2 mm) surfaces of each specimen. Three-way ANOVA with independent variables and Tukey tests were performed at 95% significance level. Results. No significant differences were detected in degree of conversion and microhardness between LED and QTH light-curing units except for the ormocer-based specimen, CeramX, which exhibited significantly higher DC by LED. All the composite resins showed a significantly higher degree of conversion at the surface. Microhardness was not significantly affected by depth, except for Herculite XRV Ultra and CeramX, which showed higher values at the surface. Conclusion. Composite resins containing nano-particles generally exhibited more variations in degree of conversion and microhardness.

Evaluation of Polymerization Efficacy in Composite Resins via FT-IR Spectroscopy and Vickers Microhardness Test

PubMed Central

Jafarzadeh, Tahereh-Sadat; Erfan, Mohammad; Behroozibakhsh, Marjan; Fatemi, Mostafa; Masaeli, Reza; Rezaei, Yashar; Bagheri, Hossein; Erfan, Yasaman

2015-01-01

Background and aims. Polymerization efficacy affects the properties and performance of composite resin restorations.The purpose of this study was to evaluate the effectiveness of polymerization of two micro-hybrid, two nano-hybrid and one nano-filled ormocer-based composite resins, cured by two different light-curing systems, using Fourier transformation infrared (FT-IR) spectroscopy and Vickers microhardness testing at two different depths (top surface, 2 mm). Materials and methods. For FT-IR spectrometry, five cylindrical specimens (5mm in diameter × 2 mm in length) were prepared from each composite resin using Teflon molds and polymerized for 20 seconds. Then, 70-μm wafers were sectioned at the top surface and at2mm from the top surface. The degree of conversion for each sample was calculated using FT-IR spectroscopy. For Vickers micro-hardness testing, three cylindrical specimens were prepared from each composite resin and polymerized for 20 seconds. The Vickers microhardness test (Shimadzu, Type M, Japan) was performed at the top and bottom (depth=2 mm) surfaces of each specimen. Three-way ANOVA with independent variables and Tukey tests were performed at 95% significance level. Results. No significant differences were detected in degree of conversion and microhardness between LED and QTH light-curing units except for the ormocer-based specimen, CeramX, which exhibited significantly higher DC by LED. All the composite resins showed a significantly higher degree of conversion at the surface. Microhardness was not significantly affected by depth, except for Herculite XRV Ultra and CeramX, which showed higher values at the surface. Conclusion. Composite resins containing nano-particles generally exhibited more variations in degree of conversion and microhardness. PMID:26889359

NDE of polymeric composite material bridge components

NASA Astrophysics Data System (ADS)

Duke, John C., Jr.; Horne, Michael R.

1998-03-01

Rapid advancements with respect to utilization of polymeric composite materials for bridge components is occurring. This situation is driven primarily by the potential improvements offered by these materials with respect to long term durability. However, because of the developmental nature of these materials much of the materials characterization has involved short term testing without the synergistic effects of environmental exposure. Efforts to develop nondestructive evaluation procedures, essential for any wide spread use in critical structural applications, have been consequently limited. This paper discuses the effort to develop NDE methods for field inspection of hybrid glass and carbon fiber reinforced vinyl ester pultruded 'double box' I beams that are installed in a small bridge over Tom's Creek, in Blacksburg, Virginia. Integrated structural element sensors, dormant infrared devices, as well as acousto-ultrasonic methods are under development for detecting and monitoring the occurrence and progression of life limiting deterioration mechanisms.

Polybenzimidazole compounds, polymeric media, and methods of post-polymerization modifications

DOEpatents

Klaehn, John R [Idaho Falls, ID; Peterson, Eric S [Idaho Falls, ID; Wertsching, Alan K [Idaho Falls, ID; Orme, Christopher J [Shelley, ID; Luther, Thomas A [Idaho Falls, ID; Jones, Michael G [Pocatello, ID

2007-08-21

A PBI compound includes imidazole nitrogens at least a portion of which are substituted with an organic-inorganic hybrid moiety. At least 85% of the imidazole nitrogens may be substituted. The organic-inorganic hybrid moiety may be an organosilane moiety, for example, (R)Me.sub.2SiCH.sub.2-- where R is selected from among methyl, phenyl, vinyl, and allyl. The PBI compound may exhibit similar thermal properties in comparison to the unsubstituted PBI. The PBI compound may exhibit a solubility in an organic solvent greater than the solubility of the unsubstituted PBI. The PBI compound may be included in separatory media. A substituted PBI synthesis method may include providing a parent PBI in a less than 5 wt % solvent solution. Substituting may occur at about room temperature and/or at about atmospheric pressure. Substituting may use at least 5 equivalents in relation to the imidazole nitrogens to be substituted or, preferably, about 15.

Amphiphilic conjunct of methyl cellulose and well-defined polyvinyl acetate.

PubMed

Xiao, Congming; Xia, Cunping

2013-01-01

Tailor-made conjunct of methyl cellulose (MC) and polyvinyl acetate (PVAc) was synthesized through the combination of reversible addition-fragmentation chain transfer (RAFT) polymerization and thiol-ene click reaction. MC was firstly transferred into unsaturated MC (UMC), and then covalently connected with well-defined PVAc obtained by RAFT polymerization of vinyl acetate. The structure of the conjunct polymer (MCV) was confirmed with Fourier transform infrared spectra (FTIR) and proton nuclear magnetic resonance ((1)H NMR). Well-defined MCV was amphiphilic and able to self-assemble into size controllable micelles, which was verified with transmission electron microscopy (TEM) and size distribution analysis. It was found that the mean diameters of the micelles in aqueous solution were 105.6, 96.0 and 75.9 nm when the number average molecular weights of PVAc segments of MCV were 49,300, 32,500 and 18,200, respectively. Copyright © 2012 Elsevier B.V. All rights reserved.

Design of water-repellant coating using dual scale size of hybrid silica nanoparticles on polymer surface

NASA Astrophysics Data System (ADS)

Conti, J.; De Coninck, J.; Ghazzal, M. N.

2018-04-01

The dual-scale size of the silica nanoparticles is commonly aimed at producing dual-scale roughness, also called hierarchical roughness (Lotus effect). In this study, we describe a method to build a stable water-repellant coating with controlled roughness. Hybrid silica nanoparticles are self-assembled over a polymeric surface by alternating consecutive layers. Each one uses homogenously distributed silica nanoparticles of a particular size. The effect of the nanoparticle size of the first layer on the final roughness of the coating is studied. The first layer enables to adjust the distance between the silica nanoparticles of the upper layer, leading to a tuneable and controlled final roughness. An optimal size nanoparticle has been found for higher water-repellency. Furthermore, the stability of the coating on polymeric surface (Polycarbonate substrate) is ensured by photopolymerization of hybridized silica nanoparticles using Vinyl functional groups.

The use of elemental sulfur as an alternative feedstock for polymeric materials

NASA Astrophysics Data System (ADS)

Chung, Woo Jin; Griebel, Jared J.; Kim, Eui Tae; Yoon, Hyunsik; Simmonds, Adam G.; Ji, Hyun Jun; Dirlam, Philip T.; Glass, Richard S.; Wie, Jeong Jae; Nguyen, Ngoc A.; Guralnick, Brett W.; Park, Jungjin; Somogyi, Árpád; Theato, Patrick; Mackay, Michael E.; Sung, Yung-Eun; Char, Kookheon; Pyun, Jeffrey

2013-06-01

An excess of elemental sulfur is generated annually from hydrodesulfurization in petroleum refining processes; however, it has a limited number of uses, of which one example is the production of sulfuric acid. Despite this excess, the development of synthetic and processing methods to convert elemental sulfur into useful chemical substances has not been investigated widely. Here we report a facile method (termed ‘inverse vulcanization’) to prepare chemically stable and processable polymeric materials through the direct copolymerization of elemental sulfur with vinylic monomers. This methodology enabled the modification of sulfur into processable copolymer forms with tunable thermomechanical properties, which leads to well-defined sulfur-rich micropatterned films created by imprint lithography. We also demonstrate that these copolymers exhibit comparable electrochemical properties to elemental sulfur and could serve as the active material in Li-S batteries, exhibiting high specific capacity (823 mA h g-1 at 100 cycles) and enhanced capacity retention.

Accelerated Thermal Depolymerization of Cyclic Polyphthalaldehyde with a Polymeric Thermoacid Generator.

PubMed

Lopez Hernandez, Hector; Lee, Olivia P; Possanza, Catherine; Kaitz, Joshua A; Park, Chan Woo; Plantz, Christopher L; Moore, Jeffrey S; White, Scott R

2018-04-30

Thermally triggerable polymer films that degrade at modest temperatures (≈85 °C) are created from a blend of cyclic polyphthalaldehyde (cPPA) and a polymeric thermoacid generator, poly(vinyl tert-butyl carbonate sulfone) (PVtBCS). PVtBCS depolymerizes when heated, generating acid which initiates the depolymerization of cPPA into volatile byproducts. The mass loss onset for 2 wt% PVtBCS/cPPA is 22 °C lower than the onset for neat cPPA alone in dynamic thermogravimetric analysis experiments. Increased concentrations of PVtBCS increase the rate of depolymerization of cPPA. Raman spectroscopy reveals that the monomer, o-phthalaldehyde, is the main depolymerization product of the acid-catalyzed depolymerization of cPPA. The PVtBCS/cPPA blend is a promising material for the design and manufacture of transient electronic packaging and polymers. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Sequence-controlled methacrylic multiblock copolymers via sulfur-free RAFT emulsion polymerization

NASA Astrophysics Data System (ADS)

Engelis, Nikolaos G.; Anastasaki, Athina; Nurumbetov, Gabit; Truong, Nghia P.; Nikolaou, Vasiliki; Shegiwal, Ataulla; Whittaker, Michael R.; Davis, Thomas P.; Haddleton, David M.

2017-02-01

Translating the precise monomer sequence control achieved in nature over macromolecular structure (for example, DNA) to whole synthetic systems has been limited due to the lack of efficient synthetic methodologies. So far, chemists have only been able to synthesize monomer sequence-controlled macromolecules by means of complex, time-consuming and iterative chemical strategies such as solid-state Merrifield-type approaches or molecularly dissolved solution-phase systems. Here, we report a rapid and quantitative synthesis of sequence-controlled multiblock polymers in discrete stable nanoscale compartments via an emulsion polymerization approach in which a vinyl-terminated macromolecule is used as an efficient chain-transfer agent. This approach is environmentally friendly, fully translatable to industry and thus represents a significant advance in the development of complex macromolecule synthesis, where a high level of molecular precision or monomer sequence control confers potential for molecular targeting, recognition and biocatalysis, as well as molecular information storage.

Template Synthesis of Nanostructured Polymeric Membranes by Inkjet Printing.

PubMed

Gao, Peng; Hunter, Aaron; Benavides, Sherwood; Summe, Mark J; Gao, Feng; Phillip, William A

2016-02-10

The fabrication of functional nanomaterials with complex structures has been serving great scientific and practical interests, but current fabrication and patterning methods are generally costly and laborious. Here, we introduce a versatile, reliable, and rapid method for fabricating nanostructured polymeric materials. The novel method is based on a combination of inkjet printing and template synthesis, and its utility and advantages in the fabrication of polymeric nanomaterials is demonstrated through three examples: the generation of polymeric nanotubes, nanowires, and thin films. Layer-by-layer-assembled nanotubes can be synthesized in a polycarbonate track-etched (PCTE) membrane by printing poly(allylamine hydrochloride) and poly(styrenesulfonate) sequentially. This sequential deposition of polyelectrolyte ink enables control over the surface charge within the nanotubes. By a simple change of the printing conditions, polymeric nanotubes or nanowires were prepared by printing poly(vinyl alcohol) in a PCTE template. In this case, the high-throughput nature of the method enables functional nanomaterials to be generated in under 3 min. Furthermore, we demonstrate that inkjet printing paired with template synthesis can be used to generate patterns comprised of chemically distinct nanomaterials. Thin polymeric films of layer-by-layer-assembled poly(allylamine hydrochloride) and poly(styrenesulfonate) are printed on a PCTE membrane. Track-etched membranes covered with the deposited thin films reject ions and can potentially be utilized as nanofiltration membranes. When the fabrication of these different classes of nanostructured materials is demonstrated, the advantages of pairing template synthesis with inkjet printing, which include fast and reliable deposition, judicious use of the deposited materials, and the ability to design chemically patterned surfaces, are highlighted.

Antifreeze (glyco)protein mimetic behavior of poly(vinyl alcohol): detailed structure ice recrystallization inhibition activity study.

PubMed

Congdon, Thomas; Notman, Rebecca; Gibson, Matthew I

2013-05-13

This manuscript reports a detailed study on the ability of poly(vinyl alcohol) to act as a biomimetic surrogate for antifreeze(glyco)proteins, with a focus on the specific property of ice-recrystallization inhibition (IRI). Despite over 40 years of study, the underlying mechanisms that govern the action of biological antifreezes are still poorly understood, which is in part due to their limited availability and challenging synthesis. Poly(vinyl alcohol) (PVA) has been shown to display remarkable ice recrystallization inhibition activity despite its major structural differences to native antifreeze proteins. Here, controlled radical polymerization is used to synthesize well-defined PVA, which has enabled us to obtain the first quantitative structure-activity relationships, to probe the role of molecular weight and comonomers on IRI activity. Crucially, it was found that IRI activity is "switched on" when the polymer chain length increases from 10 and 20 repeat units. Substitution of the polymer side chains with hydrophilic or hydrophobic units was found to diminish activity. Hydrophobic modifications to the backbone were slightly more tolerated than side chain modifications, which implies an unbroken sequence of hydroxyl units is necessary for activity. These results highlight that, although hydrophobic domains are key components of IRI activity, the random inclusion of addition hydrophobic units does not guarantee an increase in activity and that the actual polymer conformation is important.

Synthesis and evaluation of acryloylated starch-g-poly (Acrylamide/Vinylmethacrylate/1-Vinyl-2-pyrrolidone) crosslinked terpolymer functionalized by dimethylphenylvinylsilane derivative as a novel polymer-flooding agent.

PubMed

El-Hoshoudy, A N; Desouky, S M

2018-05-16

Starch is a natural biopolymer that subjected to various chemical modifications through different industrial applications. Molecular structure of starch allow its grafting with different vinyl monomers in the presence of crosslinking agents to synthesize cross-linked hydrogels, which used in enhanced oil recovery (EOR) applications, water shutoff and drag reduction. Application of native starch in the field of petroleum reservoirs as a flooding agent suffer from some limitations concerned with microbial degradation, thermal and salinity resistance under harsh petroleum reservoir conditions. In the current research, we stated the synthesis of acryloylated starch then it's grafting with poly (Acrylamide/Vinylmethacrylate/1-Vinyl-2-pyrrolidone) terpolymer in presence of dimethylphenylvinylsilane through emulsification polymerization. Characterization and structure determination occur by different spectroscopic techniques as stated throughout the manuscript. Rheological and solution properties carried out as a function of shear rate, salinity and temperature at simulated reservoir conditions. Flooding tests carried out through linear-dimensional sandstone model at simulated reservoir conditions, and recovered oil amount calculated on volumetric basis. The obtained results indicate that the prepared starch-g-terpolymer can tolerate to severe flooding conditions of high temperature and salinity, moreover it can increase recovery factor up to 49% of residual oil saturation so considered as a promised EOR candidate. Copyright © 2017 Elsevier B.V. All rights reserved.

Reversible Addition Fragmentation Chain Transfer (RAFT) Polymerization of 4-Vinylbenzaldehyde

PubMed Central

Sun, Guorong; Cheng, Chong; Wooley, Karen L.

2008-01-01

The direct reversible addition fragmentation chain transfer (RAFT) polymerization of 4-vinylbenzaldehyde (VBA) was established as a new synthetic method for the preparation of well-defined poly(vinylbenzaldehyde) (PVBA), a polymer having reactive aldehyde side chain substiuents. RAFT polymerization of VBA was investigated using S-1-dodecyl-S’-(α,α’-dimethyl-α”-acetic acid)trithiocarbonate (DDMAT) as chain transfer agent (CTA) and 2,2′-azobis(isobutyronitrile) (AIBN) as initiator in 1,4-dioxane or 2-butanone at 70-75 °C for 7.5-22.5 h. With 45-76% of monomer conversion, the resulting PVBA had well controlled number-average molecular weight (Mn) and low polydispersity (PDI < 1.17). The living characteristic of the RAFT polymerization process was confirmed by the linearity between the Mn values of PVBA and monomer conversions. Well-defined PVBA was further used as a macromolecular chain transfer agent (macro-CTA) in RAFT polymerization of styrene (St), and a block copolymer PVBA-b-PSt with relatively low polydispersity (PDI = 1.20) was successfully synthesized. PMID:19066633

Effect of various visible light photoinitiators on the polymerization and color of light-activated resins.

PubMed

Arikawa, Hiroyuki; Takahashi, Hideo; Kanie, Takahito; Ban, Seiji

2009-07-01

The purpose of this study was to investigate effects of various visible light photoinitiators on the polymerization efficiency and color of the light-activated resins. Four photoinitiators, including camphorquinone, phenylpropanedione, monoacrylphosphine oxide (TPO), and bisacrylphosphine oxide (Ir819), were used. Each photoinitiator was dissolved in a Bis-GMA and TEGDMA monomer mixture. Materials were polymerized using dental quartz-tungsten halogen lamp (QTH), plasma-ark lamp and blue LED light-curing units, and a custom-made violet LED light unit. The degree of monomer conversion and CIE L*a*b* color values of the resins were measured using a FTIR and spectral transmittance meter. The degree of monomer conversions of TPO- and Ir819-containing resins polymerized with the violet-LED unit were higher than camphorquinone-containing resin polymerized with the QTH light-curing unit. The lowest color values were observed for the TPO-containing resin. Our results indicate that the TPO photoinitiator and the violet-LED light unit may provide a useful and improved photopolymerization system for dental light-activated resins.

Supported organometallic catalysts for hydrogenation and Olefin Polymerization

DOEpatents

Marks, Tobin J.; Ahn, Hongsang

2001-01-01

Novel heterogeneous catalysts for the which hydrogenation of olefins and arenes with high conversion rates under ambient conditions and the polymerization of olefins have been developed. The catalysts are synthesized from Ziegler-type precatalysts by supporting them on sulfate-modified zirconia.

Photocatalytic CO2 conversion by polymeric carbon nitrides.

PubMed

Fang, Yuanxing; Wang, Xinchen

2018-05-10

CO2 is a vital compond for life, and its concentration significantly affects the living environment of the Earth. Extensive effort has been devoted to balance its concentration. Among the developed approaches, photocatalytic CO2 conversion is considered as an ideal option. Previous reports suggest polymeric carbon nitride (PCN) can be effectively used as a metal-free photocatalyst to convert CO2. Herein, the recent developments of PCN and the related photocatalysts for CO2 conversion are summarized from the fundamental of using PCN, and their extended applications through molecular modification and physical/chemical coupling with other substances. The concluding remarks finally indicate the future challenges of using PCN materials for relevant solar-driven applications.

Preparation of a polymeric ionic liquid-coated solid-phase microextraction fiber by surface radical chain-transfer polymerization with stainless steel wire as support.

PubMed

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.

Development of polymeric nanopaclitaxel and comparison with free paclitaxel for effects on cell proliferation of MCF-7 and B16F0 carcinoma cells.

PubMed

Yadav, Deepak; Anwar, Mohammad Faiyaz; Garg, Veena; Kardam, Hemant; Beg, Mohd Nadeem; Suri, Suruchi; Gaur, Sikha; Asif, Mohd

2014-01-01

Paclitaxel is hydrophobic in nature and is recognized as a highly toxic anticancer drug, showing adverse effects in normal body sites. In this study, we developed a polymeric nano drug carrier for safe delivery of the paclitaxel to the cancer that releases the drug in a sustained manner and reduces side effects. N-isopropylacrylamide/ vinyl pyrrolidone (NIPAAm/VP) nanoparticles were synthesized by radical polymerization. Physico- chemical characterization of the polymeric nanoparticles was conducted using dynamic light scattering, transmission electron microscopy, scanning electron microscopy and nuclear magnetic resonance, which confirmed polymerization of formulated nanoparticles. Drug release was assessed using a spectrophotometer and cell viability assays were carried out on the MCF-7 breast cancer and B16F0 skin cancer cell lines. NIPAAm/ VP nanoparticles demonstrated a size distribution in the 65-108 nm range and surface charge measured -15.4 mV. SEM showed the nanoparticles to be spherical in shape with a slow drug release of ~70% in PBS at 38° over 96 h. Drug loaded nanoparticles were associated with increased viability of MCF-7 and B16F0 cells in comparison to free paclitaxel. Nano loaded paclitaxel shows high therapeutic efficiency by sustained release action for the longer period of time, i increasing its efficacy and biocompatibility for human cancer therapy. Therefore, paclitaxel loaded (NIPAAm/VP) nanoparticles may provide opportunities to expand delivery of the drug for clinical selection.

Effects of poly(2-hydroxyethyl methacrylate) and poly(vinyl-pyrrolidone) hydrogel implants on myopic and normal chick sclera

PubMed Central

Su, James; Iomdina, Elena; Tarutta, Elena; Ward, Brian; Song, Jie; Wildsoet, Christine F.

2008-01-01

There has been generally little attention paid to the utilization of biomaterials as an anti-myopia treatment. The purpose of this study was to investigate whether polymeric hydrogels, either implanted or injected adjacent to the outer scleral surface, slow ocular elongation. White Leghorn (gallus gallus domesticus) chicks were used at 2 weeks of age. Chicks had either (1) strip of poly(2-hydroxyethyl methacrylate) (pHEMA) implanted monocularly against the outer sclera at the posterior pole, or (2) an in situ polymerizing gel [main ingredient: poly(vinyl-pyrrolidone) (PVP)] injected monocularly at the same location. Some of the eyes injected with the polymer were fitted with a diffuser or a −10D lens. In each experiment, ocular lengths were measured at regular intervals by high frequency A-scan ultrasonography, and chicks were sacrificed for histology at staged intervals. No in vivo signs of either orbital or ocular inflammation were observed. The pHEMA implant significantly increased scleral thickness by the third week, and the implant became encapsulated with fibrous tissue. The PVP-injected eyes left otherwise untreated, showed a significant increase in scleral thickness, due to increased chondrocyte proliferation and extracellular matrix deposition. However, there was no effect of the PVP injection on ocular elongation. In eyes wearing optical devices, there was no effect on either scleral thickness or ocular elongation. These results represent “proof of principle” that scleral growth can be manipulated without adverse inflammatory responses. However, since neither approach slowed ocular elongation, additional factors must influence scleral surface area expansion in the avian eye. PMID:19109950

Silver/poly(vinyl alcohol) nanocomposite film prepared using water in oil microemulsion for antibacterial applications.

PubMed

Fatema, Ummul K; Rahman, M Muhibur; Islam, M Rakibul; Mollah, M Yousuf A; Susan, Md Abu Bin Hasan

2018-03-15

Water in oil microemulsion (w/o) is a simple preparative route for nanoparticles where water droplets (dispersed in continuous oil medium and stabilized by surfactants and cosurfactants) act as nanoreactors to carry out chemical reactions. If polymeric matrix is incorporated inside the core of the microemulsions, it should prevent the agglomeration of nanoparticles after separation from microemulsions. Thus polymer nanocomposite films prepared from w/o microemulsions are expected to give narrow and homogeneous size distribution of nanoparticles throughout the polymer host. Silver/poly(vinyl alcohol) (Ag/PVA) nanocomposite film was successfully prepared, for the first time, using Triton X-100 (TX-100)/1-butanol/cyclohexane/water microemulsion. Reduction of the metal salt was carried out in the core of w/o microemulsion droplets containing PVA polymeric matrix. After separation from the microemulsion, Ag/PVA nanocomposite film was then prepared by solution casting method. The antibacterial activity of the nanocomposites was tested against Gram-negative, Escherichia coli and Gram-positive, Staphylococcus aureus by agar diffusion method. Ag nanoparticles with an average diameter of 105 nm could be synthesized using PVA, whereas in the absence of PVA the nanoparticles agglomerated. The distribution of Ag nanoparticles on PVA surface of the nanocomposite film prepared using microemulsion was uniform, whereas the film prepared through in situ generation of Ag nanoparticles by chemical reduction process on PVA host showed non-uniform, coagulated, bunches of Ag nanoparticles. The film synthesized using microemulsion exhibited enhanced antibacterial efficacy compared to that prepared through in situ synthesis under the same test condition. Copyright © 2017 Elsevier Inc. All rights reserved.

Rapid and Stereoselective Conversion of a "trans"-Cinnamic Acid to a beta-Bromostyrene

ERIC Educational Resources Information Center

Evans, Thomas A.

2006-01-01

The stereoselective synthesis of an aryl vinyl bromide is accomplished in a rapid microscale reaction of "trans"-4-methoxycinnamic acid with N-bromosuccinimide in dichloromethane. The product is purified by dry column vacuum chromatography and its stereochemistry is determined by [superscript 1]H NMR. TLC, GC and GC-MSD can also be used. This…

Effect of a non-thermal, atmospheric-pressure, plasma brush on conversion of model self-etch adhesive formulations compared to conventional photo-polymerization

PubMed Central

Chen, Mingsheng; Zhang, Ying; Yao, Xiaomei; Li, Hao; Yu, Qingsong; Wang, Yong

2012-01-01

Objective To determine the effectiveness and efficiency of non-thermal, atmospheric plasmas for inducing polymerization of model dental self-etch adhesives. Methods The monomer mixtures used were bis-[2-(methacryloyloxy)ethyl] phosphate (2MP) and 2-hydroxyethyl methacrylate (HEMA), with mass ratios of 70/30, 50/50 and 30/70. Water was added to the above formulations: 10–30 wt%. These monomer/water mixtures were treated steadily for 40 s under a non-thermal atmospheric plasma brush working at temperatures from 32° to 35°C. For comparison, photo-initiators were added to the above formulations for photo-polymerization studies, which were light-cured for 40 s. The degree of conversion (DC) of both the plasma- and light-cured samples was measured using FTIR spectroscopy with an attenuated total reflectance attachment. Results The non-thermal plasma brush was effective in inducing polymerization of the model self-etch adhesives. The presence of water did not negatively affect the DC of plasma-cured samples. Indeed, DC values slightly increased, with increasing water content in adhesives: from 58.3% to 68.7% when the water content increased from 10% to 30% in the adhesives with a 50/50 (2MP/HEMA) mass ratio. Conversion values of the plasma-cured groups were higher than those of light-cured samples with the same mass ratio and water content. Spectral differences between the plasma- and light-cured groups indicate subtle structural distinctions in the resultant polymer networks. Significance This research if the first to demonstrate that the non-thermal plasma brush induces polymerization of model adhesives under clinical settings by direct/indirect energy transfer. This device shows promise for polymerization of dental composite restorations having enhanced properties and performance. PMID:23018084

Gel Point Suppression in RAFT Polymerization of Pure Acrylic Cross-Linker Derived from Soybean Oil.

PubMed

Yan, Mengguo; Huang, Yuerui; Lu, Mingjia; Lin, Fang-Yi; Hernández, Nacú B; Cochran, Eric W

2016-08-08

Here we report the reversible addition-fragmentation chain transfer (RAFT) polymerization of acrylated epoxidized soybean oil (AESO), a cross-linker molecule, to high conversion (>50%) and molecular weight (>100 kDa) without macrogelation. Surprisingly, gelation is suppressed in this system far beyond the expectations predicated both on Flory-Stockmeyer theory and multiple other studies of RAFT polymerization featuring cross-linking moieties. By varying AESO and initiator concentrations, we show how intra- versus intermolecular cross-linking compete, yielding a trade-off between the degree of intramolecular linkages and conversion at gel point. We measured polymer chain characteristics, including molecular weight, chain dimensions, polydispersity, and intrinsic viscosity, using multidetector gel permeation chromatography and NMR to track polymerization kinetics. We show that not only the time and conversion at macrogelation, but also the chain architecture, is largely affected by these reaction conditions. At maximal AESO concentration, the gel point approaches that predicted by the Flory-Stockmeyer theory, and increases in an exponential fashion as the AESO concentration decreases. In the most dilute solutions, macrogelation cannot be detected throughout the entire reaction. Instead, cyclization/intramolecular cross-linking reactions dominate, leading to microgelation. This work is important, especially in that it demonstrates that thermoplastic rubbers could be produced based on multifunctional renewable feedstocks.

Conversion of 2,3-butanediol to butadiene

DOEpatents

Lilga, Michael A.; Frye, Jr, John G.; Lee, Suh-Jane; Albrecht, Karl O.

2016-09-06

A composition comprising 2,3-butanediol is dehydrated to methyl vinyl carbinol and/or 1,3-butadiene by exposure to a catalyst comprising (a) M.sub.xO.sub.y wherein M is a rare earth metal, a group IIIA metal, Zr, or a combination thereof, and x and y are based upon an oxidation state of M, or (b) M.sup.3.sub.a(PO.sub.4).sub.b where M.sup.3 is a group IA, a group IIA metal, a group IIIA metal, or a combination thereof, and a and b are based upon the oxidation state of M.sup.3. Embodiments of the catalyst comprising M.sub.xO.sub.y may further include M.sup.2, wherein M.sup.2 is a rare earth metal, a group IIA metal, Zr, Al, or a combination thereof. In some embodiments, 2,3-butanediol is dehydrated to methyl vinyl carbinol and/or 1,3-butadiene by a catalyst comprising M.sub.xO.sub.y, and the methyl vinyl carbinol is subsequently dehydrated to 1,3-butadiene by exposure to a solid acid catalyst.

Influence of light polymerization modes on degree of conversion and crosslink density of dental composites.

PubMed

da Silva, Eduardo Moreira; Poskus, Laiza Tatiana; Guimarães, José Guilherme Antunes; de Araújo Lima Barcellos, Alexandre; Fellows, Carlos Eduardo

2008-03-01

This study analyzed the influence of light polymerization modes on crosslink density (CD) and the degree of conversion (DC) of dental composites. A minifilled hybrid and a nanofilled dental composite were photoactivated with two light polymerization modes: Conventional-850 mW/cm2 for 20 s and Gradual-50 up to 1,000 mW/cm2 for 10 s+1,000 mW/cm2 for 10 s. DC was determined by the use of FT-Raman-spectrometer. A softening test, using Knoop diamond indentation, was carried out at the top and bottom of 2 mm thick dental composite disks, before and after storage in 100% ethanol for 24 h, in order to represent the amount of crosslink density. Data were analyzed by ANOVA and Student-Newman-Keuls' multiple range test (alpha=0.05). The DC was influenced by light polymerization modes, with Gradual mode presenting lower DC. On bottom surfaces, the nanofilled dental composite was more susceptible to softening by ethanol than minifilled hybrid, and gradual light polymerization of nanofilled dental composite resulted in more softening than when conventional light polymerization was used. The results suggest that nanofilled composites are capable undergoing more plasticization if applied in thick increments.

Impact of solvent selection on graft polymerization of acrylamide onto starch

USDA-ARS?s Scientific Manuscript database

The impact on polymer properties [molecular weight, monomer conversion, graft content, graft efficiency and anhydroglucose units between grafts (AGU/graft)] that result from changing the solvent for the graft co-polymerization of acrylamide onto starch from water to dimethylsulfoxide (DMSO) was eval...

Methods of forming single source precursors, methods of forming polymeric single source precursors, and single source precursors formed by such methods

DOEpatents

Fox, Robert V.; Rodriguez, Rene G.; Pak, Joshua J.; Sun, Chivin; Margulieux, Kelsey R.; Holland, Andrew W.

2016-04-19

Methods of forming single source precursors (SSPs) include forming intermediate products having the empirical formula 1/2{L.sub.2N(.mu.-X).sub.2M'X.sub.2}.sub.2, and reacting MER with the intermediate products to form SSPs of the formula L.sub.2N(.mu.-ER).sub.2M'(ER).sub.2, wherein L is a Lewis base, M is a Group IA atom, N is a Group IB atom, M' is a Group IIIB atom, each E is a Group VIB atom, each X is a Group VIIA atom or a nitrate group, and each R group is an alkyl, aryl, vinyl, (per)fluoro alkyl, (per)fluoro aryl, silane, or carbamato group. Methods of forming polymeric or copolymeric SSPs include reacting at least one of HE.sup.1R.sup.1E.sup.1H and MER with one or more substances having the empirical formula L.sub.2N(.mu.-ER).sub.2M'(ER).sub.2 or L.sub.2N(.mu.-X).sub.2M'(X).sub.2 to form a polymeric or copolymeric SSP. New SSPs and intermediate products are formed by such methods.

Methods of forming single source precursors, methods of forming polymeric single source precursors, and single source precursors formed by such methods

DOEpatents

Fox, Robert V.; Rodriguez, Rene G.; Pak, Joshua J.; Sun, Chivin; Margulieux, Kelsey R.; Holland, Andrew W.

2014-09-09

Methods of forming single source precursors (SSPs) include forming intermediate products having the empirical formula 1/2{L.sub.2N(.mu.-X).sub.2M'X.sub.2}.sub.2, and reacting MER with the intermediate products to form SSPs of the formula L.sub.2N(.mu.-ER).sub.2M'(ER).sub.2, wherein L is a Lewis base, M is a Group IA atom, N is a Group IB atom, M' is a Group IIIB atom, each E is a Group VIB atom, each X is a Group VIIA atom or a nitrate group, and each R group is an alkyl, aryl, vinyl, (per)fluoro alkyl, (per)fluoro aryl, silane, or carbamato group. Methods of forming polymeric or copolymeric SSPs include reacting at least one of HE.sup.1R.sup.1E.sup.1H and MER with one or more substances having the empirical formula L.sub.2N(.mu.-ER).sub.2M'(ER).sub.2 or L.sub.2N(.mu.-X).sub.2M'(X).sub.2 to form a polymeric or copolymeric SSP. New SSPs and intermediate products are formed by such methods.

Titanium Dioxide Photocatalytic Polymerization of Acrylamide for Gel Electrophoresis (TIPPAGE) of Proteins and Structural Identification by Mass Spectrometry

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.

Fabrication and biological imaging of polyhedral oligomeric silsesquioxane cross-linked fluorescent polymeric nanoparticles with aggregation-induced emission feature

NASA Astrophysics Data System (ADS)

Mao, Liucheng; Liu, Meiying; Xu, Dazhuang; Wan, Qing; Huang, Qiang; Jiang, Ruming; Shi, Yingge; Deng, Fengjie; Zhang, Xiaoyong; Wei, Yen

2017-11-01

Aggregation-induced emission (AIE) dyes based fluorescent polymeric nanoparticles (FNPs) have been intensively explored for biomedical applications. However, many of these AIE-active FNPs are relied on the self-assembly of amphiphilic copolymers, which are not stable in diluted solution. Therefore, the introduction of cross-linkages into these micelles has demonstrated to be an efficient route to overcome this stability problem and endow ultra-low critical micelle concentrations (CMC) of these AIE-active FNPs. In this work, we reported the fabrication of cross-linked AIE-active FNPs through controllable reversible addition fragmentation chain transfer polymerization by using commercially available octavinyl-T8-silsesquioxane (8-vinyl POSS) as the cross-linkage for the first time. The resultant cross-linked amphiphilic copolymers (named as PEG-POSS-PhE) are prone to self-assemble into stable core-shell nanoparticles with well water dispersity, strong red fluorescence and low CMC (0.0069 mg mL-1) in aqueous solution. More importantly, PEG-POSS-PhE FNPs possess some other properties such as high water dispersity, uniform morphology and small size, excellent biocompatibility and cellular internalization, providing great potential of PEG-POSS-PhE FNPs for biological imaging application.

Titanium Dioxide Photocatalytic Polymerization of Acrylamide for Gel Electrophoresis (TIPPAGE) of Proteins and Structural Identification by Mass Spectrometry.

PubMed

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.

Titanium Dioxide Photocatalytic Polymerization of Acrylamide for Gel Electrophoresis (TIPPAGE) of Proteins and Structural Identification by Mass Spectrometry

PubMed Central

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

A novel approach for UV-patterning with binary polymer brushes.

PubMed

Li, Lifu; Nakaji-Hirabayashi, Tadashi; Kitano, Hiromi; Ohno, Kohji; Saruwatari, Yoshiyuki; Matsuoka, Kazuyoshi

2018-01-01

A mixed self-assembled monolayer (SAM) of an initiator (3-(2-bromo-2-isobutyryloxy)propyl triethoxysilane) for atom transfer radical polymerization (ATRP) and an agent (6-(triethoxysilyl)hexyl 2-(((methylthio)carbonothioyl)thio)-2-phenylacetate) for reversible addition-fragmentation chain transfer (RAFT) polymerization was constructed on the surface of a silicon wafer or glass plate by a silane coupling reaction. When a UV light at 254nm was irradiated at the mixed SAM through a photomask, the surface density of the bromine atom at the end of BPE in the irradiated region was drastically reduced by UV-driven scission of the BrC bond, as observed by X-ray photoelectron spectroscopy. Consequently, the surface-initiated (SI)-ATRP of 2-ethylhexyl methacrylate (EHMA) was used to easily construct the poly(EHMA) (PEHMA) brush domain. Subsequently, SI-RAFT polymerization of a zwitterionic vinyl monomer, carboxymethyl betaine (CMB), was performed. Using the sequential polymerization, the PCMB and PEHMA brush domains on the solid substrate could be very easily patterned. Patterning proteins and cells with the binary polymer brush is expected because the PCMB brush indicated strong suppression of protein adsorption and cell adhesion, and the PEHMA brush had non-polar properties. This technique is very simple and useful for regulating the shape and size of bio-fouling and anti-biofouling domains on solid surfaces. Copyright © 2017 Elsevier B.V. All rights reserved.

Study of a binary interpenetrated polymeric complex by correlation of rheological parameters with zeta potential and conductivity.

PubMed

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 (7.5or=12). The conductivity increases with the rising of the PAS content, pH and temperature. Other characteristics of the prepared interpenetrated polymeric structure, as for example thermal stability, there are also presented.

Recycling WEEE: Polymer characterization and pyrolysis study for waste of crystalline silicon photovoltaic modules.

PubMed

Dias, Pablo; Javimczik, Selene; Benevit, Mariana; Veit, Hugo

2017-02-01

Photovoltaic (PV) modules contain both valuable and hazardous materials, which makes its recycling meaningful economically and environmentally. In general, the recycling of PV modules starts with the removal of the polymeric ethylene-vinyl acetate (EVA) resin using pyrolysis, which assists in the recovery of materials such as silicon, copper and silver. The pyrolysis implementation, however, needs improvement given its importance. In this study, the polymers in the PV modules were characterized by Fourier transform infrared spectroscopy (FTIR) and the removal of the EVA resin using pyrolysis has been studied and optimized. The results revealed that 30min pyrolysis at 500°C removes >99% of the polymers present in photovoltaic modules. Moreover, the behavior of different particle size milled modules during the pyrolysis process was evaluated. It is shown that polymeric materials tend to remain at a larger particle size and thus, this fraction has the greatest mass loss during pyrolysis. A thermo gravimetric analysis (TGA) performed in all polymeric matter revealed the optimum pyrolysis temperature is around 500°C. Temperatures above 500°C continue to degrade matter, but mass loss rate is 6.25 times smaller. This study demonstrates the use of pyrolysis can remove >99% of the polymeric matter from PV modules, which assists the recycling of this hazardous waste and avoids its disposal. Copyright © 2016 Elsevier Ltd. All rights reserved.

Biomimetic polymeric superhydrophobic surfaces and nanostructures: from fabrication to applications.

PubMed

Wen, Gang; Guo, ZhiGuang; Liu, Weimin

2017-03-09

Numerous research studies have contributed to the development of mature superhydrophobic systems. The fabrication and applications of polymeric superhydrophobic surfaces have been discussed and these have attracted tremendous attention over the past few years due to their excellent properties. In general, roughness and chemical composition, the two most crucial factors with respect to surface wetting, provide the basic criteria for yielding polymeric superhydrophobic materials. Furthermore, with their unique properties and flexible configurations, polymers have been one of the most efficient materials for fabricating superhydrophobic materials. This review aims to summarize the most recent progress in polymeric superhydrophobic surfaces. Significantly, the fundamental theories for designing these materials will be presented, and the original methods will be introduced, followed by a summary of multifunctional superhydrophobic polymers and their applications. The principles of these methods can be divided into two categories: the first involves adding nanoparticles to a low surface energy polymer, and the other involves combining a low surface energy material with a textured surface, followed by chemical modification. Notably, surface-initiated radical polymerization is a versatile method for a variety of vinyl monomers, resulting in controlled molecular weights and low polydispersities. The surfaces produced by these methods not only possess superhydrophobicity but also have many applications, such as self-cleaning, self-healing, anti-icing, anti-bioadhesion, oil-water separation, and even superamphiphobic surfaces. Interestingly, the combination of responsive materials and roughness enhances the responsiveness, which allows the achievement of intelligent transformation between superhydrophobicity and superhydrophilicity. Nevertheless, surfaces with poor physical and chemical properties are generally unable to withstand the severe conditions of the outside world; thus, it is necessary to optimize the performances of such materials to yield durable superhydrophobic surfaces. To sum up, some challenges and perspectives regarding the future research and development of polymeric superhydrophobic surfaces are presented.

Diffuse polymer interfaces in lobed nanoemulsions preserved in aqueous media.

PubMed

Kim, Ginam; Sousa, Alioscka; Meyers, Deborah; Shope, Marilyn; Libera, Matthew

2006-05-24

Using valence electron energy loss spectroscopy (EELS) in the cryo-scanning transmission electron microscopy (STEM), we found that the polymer-polymer interface in two-phase nanocolloids of polydimethyl siloxane (PDMS) and copolymer (methyl acrylate (MA)-methyl methacrylate (MMA)-vinyl acetate (VA)) preserved in water was diffuse despite the fact that equilibrium thermodynamics indicates it should only be on the order of a few nanometers. The diffuse interface is a result of the kinetic trapping of the copolymer within the PDMS phase, and this finding suggests new nonequilibrium pathways to control interfaces during the synthesis of multicomponent polymeric nanostructures.

Molecular Engineering of Liquid Crystalline Polymers by Living Polymerization. 10. Influence of Molecular Weight on the Phase Transitions of Poly(Omega-((4-Cyano-4’-Biphenyl)oxy)alkyl Vinyl Ethers)s with Nonyl and Decanyl Alkyl Groups

DTIC Science & Technology

1990-10-16

washed with concentrated sulfuric acid , then with water, dried over anhydrous magnesium sulfate, refluxed over calcium hydride and freshly distilled...oxide, filtered, and fractionally distilled under reduced pressure. Trifluoromethane sulfonic acid (triflic acid , 98%, Aldrich) w s distilled under...flask. Then the flask was filled with argon, cooled to 0°C and the methylene chloride, dimethyl sulfide and triflic acid were added via a syringe. The

Metallocene Catalytic Insertion Polymerization of 1-Silene to Polycarbosilanes

NASA Astrophysics Data System (ADS)

Tian, Yuelong; Ge, Min; Zhang, Weigang; Lv, Xiaoxu; Yu, Shouquan

2015-11-01

Metallocene of zirconium were used as a catalyst for an insertion polymerization of 1-methylsilene directly into pre-ceramic precursor polyzirconocenecarbosilane (PZCS) during dechlorination of dichlorodimethylesilane by sodium, which exhibits high catalytic effectiveness with the maximum conversion ratio of polycarbosilane up to 91%. The average molecular weights of polymers synthesized are less than 1400, all with very narrow polymolecularities. The mechanism of catalytic polymerization was assumed to be similar to a coordination insertion polymerization of 1-olefins by metallocenes. The obtained PZCS show high ceramic yields with formation of composite ceramics of ZrC-SiC, which are novel polymeric precursors of ultra-high temperature ceramic (UHTC) fiber and composite.

Metallocene Catalytic Insertion Polymerization of 1-Silene to Polycarbosilanes.

PubMed

Tian, Yuelong; Ge, Min; Zhang, Weigang; Lv, Xiaoxu; Yu, Shouquan

2015-11-06

Metallocene of zirconium were used as a catalyst for an insertion polymerization of 1-methylsilene directly into pre-ceramic precursor polyzirconocenecarbosilane (PZCS) during dechlorination of dichlorodimethylesilane by sodium, which exhibits high catalytic effectiveness with the maximum conversion ratio of polycarbosilane up to 91%. The average molecular weights of polymers synthesized are less than 1400, all with very narrow polymolecularities. The mechanism of catalytic polymerization was assumed to be similar to a coordination insertion polymerization of 1-olefins by metallocenes. The obtained PZCS show high ceramic yields with formation of composite ceramics of ZrC-SiC, which are novel polymeric precursors of ultra-high temperature ceramic (UHTC) fiber and composite.

Composite Materials for Hazard Mitigation of Reactive Metal Hydrides.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pratt, Joseph William; Cordaro, Joseph Gabriel; Sartor, George B.

2012-02-01

In an attempt to mitigate the hazards associated with storing large quantities of reactive metal hydrides, polymer composite materials were synthesized and tested under simulated usage and accident conditions. The composites were made by polymerizing vinyl monomers using free-radical polymerization chemistry, in the presence of the metal hydride. Composites with vinyl-containing siloxane oligomers were also polymerized with and without added styrene and divinyl benzene. Hydrogen capacity measurements revealed that addition of the polymer to the metal hydride reduced the inherent hydrogen storage capacity of the material. The composites were found to be initially effective at reducing the amount of heatmore » released during oxidation. However, upon cycling the composites, the mitigating behavior was lost. While the polymer composites we investigated have mitigating potential and are physically robust, they undergo a chemical change upon cycling that makes them subsequently ineffective at mitigating heat release upon oxidation of the metal hydride. Acknowledgements The authors would like to thank the following people who participated in this project: Ned Stetson (U.S. Department of Energy) for sponsorship and support of the project. Ken Stewart (Sandia) for building the flow-through calorimeter and cycling test stations. Isidro Ruvalcaba, Jr. (Sandia) for qualitative experiments on the interaction of sodium alanate with water. Terry Johnson (Sandia) for sharing his expertise and knowledge of metal hydrides, and sodium alanate in particular. Marcina Moreno (Sandia) for programmatic assistance. John Khalil (United Technologies Research Corp) for insight into the hazards of reactive metal hydrides and real-world accident scenario experiments. Summary In an attempt to mitigate and/or manage hazards associated with storing bulk quantities of reactive metal hydrides, polymer composite materials (a mixture of a mitigating polymer and a metal hydride) were synthesized and tested under simulated usage and accident conditions. Mitigating the hazards associated with reactive metal hydrides during an accident while finding a way to keep the original capability of the active material intact during normal use has been the focus of this work. These composites were made by polymerizing vinyl monomers using free-radical polymerization chemistry, in the presence of the metal hydride, in this case a prepared sodium alanate (chosen as a representative reactive metal hydride). It was found that the polymerization of styrene and divinyl benzene could be initiated using AIBN in toluene at 70°C. The resulting composite materials can be either hard or brittle solids depending on the cross-linking density. Thermal decomposition of these styrene-based composite materials is lower than neat polystyrene indicating that the chemical nature of the polymer is affected by the formation of the composite. The char-forming nature of cross-linked polystyrene is low and therefore, not an ideal polymer for hazard mitigation. To obtain composite materials containing a polymer with higher char-forming potential, siloxane-based monomers were investigated. Four vinyl-containing siloxane oligomers were polymerized with and without added styrene and divinyl benzene. Like the styrene materials, these composite materials exhibited thermal decomposition behavior significantly different than the neat polymers. Specifically, the thermal decomposition temperature was shifted approximately 100 °C lower than the neat polymer signifying a major chemical change to the polymer network. Thermal analysis of the cycled samples was performed on the siloxane-based composite materials. It was found that after 30 cycles the siloxane-containing polymer composite material has similar TGA/DSC-MS traces as the virgin composite material indicating that the polymer is physically intact upon cycling. Hydrogen capacity measurements revealed that addition of the polymer to the metal hydride in the form of a composite material reduced the inherent hydrogen storage capacity of the material. This reduction in capacity was observed to be independent of the amount of charge/discharge cycles except for the composites containing siloxane, which showed less of an impact on hydrogen storage capacity as it was cycled further. While the reason for this is not clear, it may be due to a chemically stabilizing effect of the siloxane on the metal hydride. Flow-through calorimetry was used to characterize the mitigating effectiveness of the different composites relative to the neat (no polymer) material. The composites were found to be initially effective at reducing the amount of heat released during oxidation, and the best performing material was the siloxane-containing composite which reduced the heat release to less than 50% of the value of the neat material. However, upon cycling the composites, all mitigating behavior was lost. The combined results of the flow-through calorimetry, hydrogen capacity, and thermogravimetric analysis tests lead to the proposed conclusion that while the polymer composites have mitigating potential and are physically robust under cycling, they undergo a chemical change upon cycling that makes them ineffective at mitigating heat release upon oxidation of the metal hydride.« less

Fabrication and characterization of a novel hydrophobic CaCO3 grafted by hydroxylated poly(vinyl chloride) chains

NASA Astrophysics Data System (ADS)

Bao, Lixia; Yang, Simei; Luo, Xin; Lei, Jingxin; Cao, Qiue; Wang, Jiliang

2015-12-01

The hydroxylated PVC (PVC-OH) was successfully synthesized by a suspension polymerization of vinyl chloride (VC), butyl acrylate (BA) and hydroxyethyl acrylate (HEA). Novel hydrophobic CaCO3 was then prepared by a urethane formation reaction between methylene diphenyl diisocyanate (MDI) and the sbnd OH groups both in the PVC-OH chains and on the surface of pristine CaCO3 particles. The effect of the PVC-OH content on the grafting ratio of treated CaCO3 particles was extensively investigated. Combining the result of Fourier transform infrared (FTIR) with that of water contact angle, it can be concluded that the hydrophobicity of CaCO3 had been efficiently improved by the PVC-OH segments grafted on the surface of CaCO3 particles. X-ray diffraction (XRD), thermal gravity analysis (TGA), scanning electron microscope (SEM) and transmission electron microscope (TEM) were also used to study crystalline behaviors, thermal stability and surface morphology of the modified CaCO3 particles, respectively. The change of specific surface area implying surface modification was investigated as well.

Synthesis and photopolymerization of low shrinkage methacrylate monomers containing bulky substituent groups.

PubMed

Ge, Junhao; Trujillo, Marianela; Stansbury, Jeffrey

2005-12-01

This study was conducted to determine whether novel photopolymerizable formulations based on dimethacrylate monomers with bulky substituent groups could provide low polymerization shrinkage without sacrifice to degree of conversion, and mechanical properties of the polymers. Relatively high molecular weight dimethacrylate monomers were prepared from rigid bisphenol A core groups. Photopolymerization kinetics and shrinkage as well as flexural strength and glass transition temperatures were evaluated for various comonomer compositions. Copolymerization of the bulky monomers with TEGDMA show higher conversion but similar shrinkage compared with Bis-GMA/TEGDMA controls. The resulting polymers have suitable mechanical strength properties for potential dental restorative materials applications. When copolymerized with PEGDMA, the bulky monomers show lower shrinkage, comparable conversion, and more homogeneous polymeric network structures compared with Bis-EMA/PEGDMA systems. The novel dimethacrylate monomers with reduced reactive group densities can decrease the polymerization shrinkage as anticipated, but there is no significant evidence that the bulky substituent groups have any additional effect on reducing shrinkage based on the physical interactions as polymer side chains. The bulky groups improve the double bond conversion and help maintain the mechanical properties of the resulting polymer, which would otherwise decrease rapidly due to the reduced crosslinking density. Further, it was found that bulky monomers help produce more homogeneous copolymer networks.

Experimental conditions affecting the kinetics of aqueous HCN polymerization as revealed by UV-vis spectroscopy.

PubMed

Marín-Yaseli, Margarita R; Moreno, Miguel; de la Fuente, José L; Briones, Carlos; Ruiz-Bermejo, Marta

2018-02-15

HCN polymerization is one of the most important and fascinating reactions in prebiotic chemistry, and interest in HCN polymers in the field of materials science is growing. However, little is known about the kinetics of the HCN polymerization process. In the present study, a first approach to the kinetics of two sets of aqueous HCN polymerizations, from NH 4 CN and NaCN, at middle temperatures between 4 and 38°C, has been carried out. For each series, the presence of air and salts in the reaction medium has been systematically explored. A previous kinetic analysis was conducted during the conversion of the insoluble black HCN polymers obtained as gel fractions in these precipitation polymerizations for a reaction of one month, where a limit conversion was achieved at the highest polymerization temperature. The kinetic description of the gravimetric data for this complex system shows a clear change in the linear dependence with the polymerization temperature for the reaction from NH 4 CN, besides a relevant catalytic effect of ammonium, in comparison with those data obtained from the NaCN series. These results also demonstrated the notable influence of air, oxygen, and the saline medium in HCN polymer formation. Similar conclusions were reached when the sol fractions were monitored by UV-vis spectroscopy, and a Hill type correlation was used to describe the polymerization profiles obtained. This technique was chosen because it provides an easy, prompt and fast method to follow the evolution of the liquid or continuous phase of the process under study. Copyright © 2017 Elsevier B.V. All rights reserved.

Experimental conditions affecting the kinetics of aqueous HCN polymerization as revealed by UV-vis spectroscopy

NASA Astrophysics Data System (ADS)

Marín-Yaseli, Margarita R.; Moreno, Miguel; de la Fuente, José L.; Briones, Carlos; Ruiz-Bermejo, Marta

2018-02-01

HCN polymerization is one of the most important and fascinating reactions in prebiotic chemistry, and interest in HCN polymers in the field of materials science is growing. However, little is known about the kinetics of the HCN polymerization process. In the present study, a first approach to the kinetics of two sets of aqueous HCN polymerizations, from NH4CN and NaCN, at middle temperatures between 4 and 38 °C, has been carried out. For each series, the presence of air and salts in the reaction medium has been systematically explored. A previous kinetic analysis was conducted during the conversion of the insoluble black HCN polymers obtained as gel fractions in these precipitation polymerizations for a reaction of one month, where a limit conversion was achieved at the highest polymerization temperature. The kinetic description of the gravimetric data for this complex system shows a clear change in the linear dependence with the polymerization temperature for the reaction from NH4CN, besides a relevant catalytic effect of ammonium, in comparison with those data obtained from the NaCN series. These results also demonstrated the notable influence of air, oxygen, and the saline medium in HCN polymer formation. Similar conclusions were reached when the sol fractions were monitored by UV-vis spectroscopy, and a Hill type correlation was used to describe the polymerization profiles obtained. This technique was chosen because it provides an easy, prompt and fast method to follow the evolution of the liquid or continuous phase of the process under study.

Biological and physicochemical properties of carbon-graphite fibre-reinforced polymers intended for implant suprastructures.

PubMed

Segerström, Susanna; Sandborgh-Englund, Gunilla; Ruyter, Eystein I

2011-06-01

The aim of this study was to determine water sorption, water solubility, dimensional change caused by water storage, residual monomers, and possible cytotoxic effects of heat-polymerized carbon-graphite fibre-reinforced composites with different fibre loadings based on methyl methacrylate/poly(methyl methacrylate) (MMA/PMMA) and the copolymer poly (vinyl chloride-co-vinyl acetate). Two different resin systems were used. Resin A contained ethylene glycol dimethacrylate (EGDMA) and 1,4-butanediol dimethacrylate (1,4-BDMA); the cross-linker in Resin B was diethylene glycol dimethacrylate (DEGDMA). The resin mixtures were reinforced with 24, 36 and 47 wt% surface-treated carbon-graphite fibres. In addition, polymer B was reinforced with 58 wt% fibres. Water sorption was equal to or below 3.34±1.18 wt%, except for the 58 wt% fibre loading of polymer B (5.27±1.22 wt%). Water solubility was below 0.36±0.015 wt%, except for polymer B with 47 and 58 wt% fibres. For all composites, the volumetric increase was below 0.01±0.005 vol%. Residual MMA monomer was equal to or below 0.68±0.05 wt% for the fibre composites. The filter diffusion test and the (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide) (MTT) assay demonstrated no cytotoxicity for the carbon-graphite fibre-reinforced composites, and residual cross-linking agents and vinyl chloride were not detectable by high-performance liquid chromatography (HPLC) analysis. © 2011 Eur J Oral Sci.

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

PubMed

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.

Optical Analysis of Transparent Polymeric Material Exposed to Simulated Space Environment

NASA Technical Reports Server (NTRS)

Edwards, David L.; Finckenor, Miria M.

1999-01-01

Transparent polymeric materials are being designed and utilized as solar concentrating lenses for spacecraft power and propulsion systems. These polymeric lenses concentrate solar energy onto energy conversion devices such as solar cells and thermal energy systems. The conversion efficiency is directly related to the transmissivity of the polymeric lens. The Environmental Effects Group of the Marshall Space Flight Center's Materials, Processes, and Manufacturing Department exposed a variety of materials to a simulated space environment and evaluated them for an, change in optical transmission. These materials include Lexan(TM), polyethylene terephthalate (PET). several formulations of Tefzel(TM). and Teflon(TM), and silicone DC 93-500. Samples were exposed to a minimum of 1000 Equivalent Sun Hours (ESH) of near-UV radiation (250 - 400 nm wavelength). Data will be presented on materials exposed to charged particle radiation equivalent to a five-year dose in geosynchronous orbit. These exposures were performed in MSFC's Combined Environmental Effects Test Chamber, a unique facility with the capability to expose materials simultaneously or sequentially to protons, low-energy electrons, high-energy electrons, near UV radiation and vacuum UV radiation.Prolonged exposure to the space environment will decrease the polymer film's transmission and thus reduce the conversion efficiency. A method was developed to normalize the transmission loss and thus rank the materials according to their tolerance to space environmental exposure. Spectral results and the material ranking according to transmission loss are presented.

Solid polymeric electrolyte based dye-sensitized solar cell with improved stability

NASA Astrophysics Data System (ADS)

Prasad, Narottam; Kumar, Manish; Patel, K. R.; Roy, M. S.

2018-05-01

The impact of polymeric electrolyte was investigated over the performance of dye-sensitized solar cell made with Rose Bengal as sensitizer. Further, the selective influence of TiCl4 treatment and pre-sensitizer deoxycholic acid on nc-TiO2 photoanode was determined in terms of improvement in conversion efficiency of the cell. It is found that the effect of TiCl4 treatment was comparatively more than pre-sensitization with de-oxy cholic acid towards improving the efficiency of the cell. The conversion efficiency on TiCl4 treatment was 0.2% whereas on pre-sensitization with deoxy chollic acid it was 0.1%. The combined effect of both TiCl4 treatment & pre-sensitization with deoxycholic acid leads conversion efficiency to 0.33%.

Synthesis, Characterization and Conductivity Study of Poly(vinyl 4-HYDROXY-3-METHOXY Benzal) and its Sodio Salt in Solid State

NASA Astrophysics Data System (ADS)

Borah, P.; Hussain, S.; Dutta, A.

Among the various ion-conducting materials, polymer salt complexes are of current interest due to their possible application as solid electrolyte as well as their physical nature in advanced high-energy electrochemical devices such as batteries, fuel cells, electrochromic display devices, photo electro-chemical solar cells52-55 etc. The main advantages of polymeric electrolytes are their mechanical properties, ease of fabrication of thin films of desired sizes and their ability to form proper electrode-electrolyte contact. Polymer electrolyte usually consists of a polymer and a salt and is considered to be solid solutions in which the polymer functions as solvent. In the present paper the synthesis, characterization and the conductivity study of the polymer poly (vinyl 4-hydroxy-3-methoxy benzal) (PV-HMB) and its sodio salt (PV-HMB-Na) have been reported. The polymer was prepared by carrying out homogenous acetalization between the prepolymer poly vinylalcohol (PVA) and 4-hydroxy-3-methoxy benzaldehyde (vanilline). PVA was dissolved in dimethyl formamide (DMF) and lithium chloride (LiCl) system i.e., in non-aqueous medium. The sodio salt was prepared by alkalization. The polymer and its salt were characterized by IR, 1H NMR and DSC. Frequency and temperature dependence of ac conductivity has been studied to learn about the electrical conduction behaviour in this material. The electrical conductivity of the new polymeric salt was found to be in the range 10-4 to 10-6 Scm-1. There is about 103 to 104 fold increase in the conductivity of the new polymer salt. Apparent activation energy of the polymer and its salt were found to be 0.139 and 0.08998 ev respectively.

Nanoporous array anodic titanium-supported co-polymeric ionic liquids as high performance solid-phase microextraction sorbents for hydrogen bonding compounds.

PubMed

Jia, Jing; Liang, Xiaojing; Wang, Licheng; Guo, Yong; Liu, Xia; Jiang, Shengxiang

2013-12-13

A nanoporous array anodic titanium-supported co-polymeric ionic liquids (NAAT/PILs) solid-phase microextraction (SPME) fiber was prepared in situ on the titanium wire. NAAT was selected as the substrate, in view of its high surface-to-volume ratio, easy preparation, mechanical stability, and rich titanol groups on its surface which can anchor silica coupling agent containing vinyl and then introduce ionic liquid copolymers as sorbents. In this work, 1-vinyl-3-nonanol imidazolium bromide ([C9OHVIm]Br) and 1,4-di(3-vinylimidazolium) butane dibromide ([(VIM)2C4]2[Br]) were synthesized and used as monomer and crosslinker, respectively. Extraction properties of the NAAT/PILs fiber for polar alcohols and volatile fatty acids (VFAs) in aqueous matrix were examined using gaseous sampling-SPME (GS-SPME) and headspace SPME (HS-SPME) mode, respectively. Combining the superior properties of NAAT substrate and the strong hydrogen bond interaction of PILs to polar compounds, the NAAT/PILs SPME fiber showed much higher adsorption affinity to aliphatic alcohols than bare NAAT and pure PILs fibers. The detection limits (LOD) of established GS-SPME-GC-FID method are in the range of 0.35-17.30ngL(-1) with a linear range from 0.01 to 500ngmL(-1). Also, it showed high extraction performance toward volatile fatty acids (VFAs) compounds from aqueous matrix. Under the optimized SPME conditions, wide linear ranges were obtained with correlation coefficients (R(2)) greater than 0.99 and limits of detection were in the range of 0.85-8.74ngL(-1). Moreover, real-world samples were analyzed and good results were obtained. Copyright © 2013. Published by Elsevier B.V.

Preparation, characterization, and in vitro activity evaluation of triblock copolymer-based polymersomes for drugs delivery

NASA Astrophysics Data System (ADS)

Besada, Lucas N.; Peruzzo, Pablo; Cortizo, Ana M.; Cortizo, M. Susana

2018-03-01

Polymersomes are polymer-based vesicles that form upon hydration of amphiphilic block copolymers and display high stability and durability, due to their mechanical and physical properties. They have hydrophilic reservoirs as well as thick hydrophobic membranes; allowing to encapsulate both water-soluble bioactive agent and hydrophobic drugs. In this study, poly ethylene glycol (PEG3350 and PEG6000) were used as hydrophilic part and poly(vinyl benzoate) (PVBz) as hydrophobic block to synthesize amphiphilic triblock copolymers (PVBz- b-PEG- b-PVBz). Different proportions of hydrophilic/hydrophobic part were assayed in order to obtain polymersomes by solvent injection method. For the synthesis of the copolymers, the initial block of PEG was derived to obtain a macroinitiator through a xanthate functional group (PEGX3 or PEGX6) and the polymerization of vinyl benzoate was carried out through reversible addition-fragmentation chain transfer polymerization (RAFT). The structure of PEGX and copolymers was confirmed by Infrared, 1H-NMR and UV-Vis spectrometry, while the average molecular weight (Mw) and polydispersity index (PI) were determined by size exclusion chromatography (SEC). The structures adopted by the copolymers in aqueous solution by self-assembly were investigated using transmission electron microscopy (TEM), dynamic light scattering (DLS) and small-angle X-ray scattering (SAXS). Both techniques confirm that polymersomes were obtained for a fraction of hydrophilic block ( f) ≈ 35 ± 10%, with a diameter of 38.3 ± 0.3 nm or 22.5 ± 0.7 nm, as determined by TEM and according to the M w of the precursor block copolymer. In addition, we analyzed the possible cytotoxicity in view of its potential application as biomedical nanocarrier. The results suggest that polymersomes seem not induce cytotoxicity during the periods of time tested.

Covalent attachment of polymeric monolith to polyether ether ketone (PEEK) tubing.

PubMed

Lv, Chunguang; Heiter, Jaana; Haljasorg, Tõiv; Leito, Ivo

2016-08-17

A new method of reproducible preparation of vinylic polymeric monolithic columns with a key step of covalently anchoring the monolith to PEEK surface is described. In order to chemically attach the polymer monolith to the tube wall, methacrylate functional groups were introduced onto PEEK surface by a three-step procedure, including surface etching, surface reduction and surface methacryloylation. The chemical state of the modified tubing surface was characterized by attenuated total reflectance infrared (ATR-IR) spectroscopy. It was found that the etching step is the key to successfully modifying the PEEK tubing surface. Poly(styrene-co-divinylbenzene) monoliths were in situ synthesized by thermally initiated free radical copolymerization within the confines of surface-vinylized PEEK tubings of dimensions close to ones conventionally used in HPLC and UHPLC (1.6 mm internal diameter, 10.0-12.5 cm length). Adhesion test was done by measuring the operating pressure drop, which the prepared stationary phases can withstand. Good pressure resistance, up to 140 bar/10 cm (flow rate 0.5 mL min(-1), acetonitrile as a mobile phase), indicates strong bonding of monolith to the tubing wall. The monolithic material was proven to have a permeability of 1.7 × 10 (-14) m(2), applying acetonitrile-water 70:30 (v/v) as a mobile phase. The column performance was reproducible from column to column and was evaluated via the isocratic separation of a series of alkylbenzenes in the reversed-phase mode (acetonitrile-water 70:30, v/v). The numbers of plates per meter at optimal flow rate were found to be between 26 000 and 32 000 for the different analytes. Copyright © 2016 Elsevier B.V. All rights reserved.

Ketoprofen-loaded polymer carriers in bigel formulation: an approach to enhancing drug photostability in topical application forms

PubMed Central

Andonova, Velichka; Peneva, Petya; Georgiev, George S; Toncheva, Vencislava T; Apostolova, Elisaveta; Peychev, Zhivko; Dimitrova, Stela; Katsarova, Mariana; Petrova, Nadia; Kassarova, Margarita

2017-01-01

The purpose of the study was to investigate the stability and biopharmaceutical characteristics of ketoprofen, loaded in polymeric carriers, which were included into a bigel in a semisolid dosage form. The polymer carriers with in situ-included ketoprofen were obtained by emulsifier-free emulsion polymerization of the monomers in aqueous medium or a solution of the polymers used. The morphological characteristics of the carriers, the in vitro release and the photochemical stability of ketoprofen were evaluated. The model with optimal characteristics was included in a bigel formulation. The bigel was characterized in terms of pH, rheological behavior, spreadability, and in vitro drug release. Acute skin toxicity, antinociceptive activity, anti-inflammatory activity, and antihyperalgesic effects of the prepared bigel with ketoprofen-loaded polymer carrier were evaluated. The carriers of ketoprofen were characterized by a high yield and drug loading. The particle size distribution varied widely according to the polymer used, and a sustained release was provided for up to 6 hours. The polymer mixture poly(vinyl acetate) and hydroxypropyl cellulose as a drug carrier, alone or included in the bigel composition, improved the photostability of the drug compared with unprotected ketoprofen. The bigel with ketoprofen-loaded particles provided sustained release of the drug and had optimal rheological parameters. In vivo experiments on the bigel showed no skin inflammation or irritation. Four hours after its application, a well-defined analgesic, anti-inflammatory, and antihyperalgesic effect was registered. The polymer mixture of poly(vinyl acetate) and hydroxypropyl cellulose as a carrier of ketoprofen and the bigel in which it was included provided an enhanced photostability and sustained drug release. PMID:28894363

Ketoprofen-loaded polymer carriers in bigel formulation: an approach to enhancing drug photostability in topical application forms.

PubMed

Andonova, Velichka; Peneva, Petya; Georgiev, George S; Toncheva, Vencislava T; Apostolova, Elisaveta; Peychev, Zhivko; Dimitrova, Stela; Katsarova, Mariana; Petrova, Nadia; Kassarova, Margarita

2017-01-01

The purpose of the study was to investigate the stability and biopharmaceutical characteristics of ketoprofen, loaded in polymeric carriers, which were included into a bigel in a semisolid dosage form. The polymer carriers with in situ-included ketoprofen were obtained by emulsifier-free emulsion polymerization of the monomers in aqueous medium or a solution of the polymers used. The morphological characteristics of the carriers, the in vitro release and the photochemical stability of ketoprofen were evaluated. The model with optimal characteristics was included in a bigel formulation. The bigel was characterized in terms of pH, rheological behavior, spreadability, and in vitro drug release. Acute skin toxicity, antinociceptive activity, anti-inflammatory activity, and antihyperalgesic effects of the prepared bigel with ketoprofen-loaded polymer carrier were evaluated. The carriers of ketoprofen were characterized by a high yield and drug loading. The particle size distribution varied widely according to the polymer used, and a sustained release was provided for up to 6 hours. The polymer mixture poly(vinyl acetate) and hydroxypropyl cellulose as a drug carrier, alone or included in the bigel composition, improved the photostability of the drug compared with unprotected ketoprofen. The bigel with ketoprofen-loaded particles provided sustained release of the drug and had optimal rheological parameters. In vivo experiments on the bigel showed no skin inflammation or irritation. Four hours after its application, a well-defined analgesic, anti-inflammatory, and antihyperalgesic effect was registered. The polymer mixture of poly(vinyl acetate) and hydroxypropyl cellulose as a carrier of ketoprofen and the bigel in which it was included provided an enhanced photostability and sustained drug release.

Preparation, Physical-Chemical Characterization, and Cytocompatibility of Polymeric Calcium Phosphate Cements

PubMed Central

Khashaba, Rania M.; Moussa, Mervet; Koch, Christopher; Jurgensen, Arthur R.; Missimer, David M.; Rutherford, Ronny L.; Chutkan, Norman B.; Borke, James L.

2011-01-01

Aim. Physicochemical mechanical and in vitro biological properties of novel formulations of polymeric calcium phosphate cements (CPCs) were investigated. Methods. Monocalcium phosphate, calcium oxide, and synthetic hydroxyapatite were combined with either modified polyacrylic acid, light activated polyalkenoic acid, or polymethyl vinyl ether maleic acid to obtain Types I, II, and III CPCs. Setting time, compressive and diametral strength of CPCs was compared with zinc polycarboxylate cement (control). Specimens were characterized using X-ray diffraction, scanning electron microscopy, and infrared spectroscopy. In vitro cytotoxicity of CPCs and control was assessed. Results. X-ray diffraction analysis showed hydroxyapatite, monetite, and brushite. Acid-base reaction was confirmed by the appearance of stretching peaks in IR spectra of set cements. SEM revealed rod-like crystals and platy crystals. Setting time of cements was 5–12 min. Type III showed significantly higher strength values compared to control. Type III yielded high biocompatibility. Conclusions. Type III CPCs show promise for dental applications. PMID:21941551

Effects of PVA(Polyvinyl Alcohol) on Supercooling Phenomena of Water

NASA Astrophysics Data System (ADS)

Kumano, Hiroyuki; Saito, Akio; Okawa, Seiji; Takizawa, Hiroshi

In this paper, effects of polymer additive on supercooling of water were investigated experimentally. Poly-vinyl alcohol (PVA) were used as the polymer, and the samples were prepared by dissolving PVA in ultra pure water. Concentration, degree of polymerization and saponification of PVA were varied as the experimental parameters. The sample was cooled, and the temperature at the instant when ice appears was measured. Since freezing of supercooled water is statistical phenomenon, many experiments were carried out and average degrees of supercooling were obtained for each experimental condition. As the result, it was found that PVA affects nucleation of supercooling and the degree of supercooling increases by adding the PVA. Especially, it is found that the average degree of supercooling increases and the standard deviation of average degree of supercooling decreases with increase of degree of saponification of PVA. However, the average degree of supercooling are independent of the degree of polymerization of PVA in the range of this study.

Toward a versatile toolbox for cucurbit[n]uril-based supramolecular hydrogel networks through in situ polymerization.

PubMed

Liu, Ji; Soo Yun Tan, Cindy; Lan, Yang; Scherman, Oren A

2017-09-15

The success of exploiting cucurbit[ n ]uril (CB[ n ])-based molecular recognition in self-assembled systems has sparked a tremendous interest in polymer and materials chemistry. In this study, polymerization in the presence of host-guest complexes is applied as a modular synthetic approach toward a diverse set of CB[8]-based supramolecular hydrogels with desirable properties, such as mechanical strength, toughness, energy dissipation, self-healing, and shear-thinning. A range of vinyl monomers, including acrylamide-, acrylate-, and imidazolium-based hydrophilic monomers, could be easily incorporated as the polymer backbones, leading to a library of CB[8] hydrogel networks. This versatile strategy explores new horizons for the construction of supramolecular hydrogel networks and materials with emergent properties in wearable and self-healable electronic devices, sensors, and structural biomaterials. © 2017 The Authors. Journal of Polymer Science Part A: Polymer Chemistry Published by Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55 , 3105-3109.

Novel "anchor modification" of polymeric biomaterial surfaces by the utilization of cyclodextrin inclusion complex supramolecules.

PubMed

Zhao, Xiaobin; Courtney, James M

2009-07-01

In this article, a novel approach for the surface modification of polymeric biomaterials by the utilization of supramolecules was studied. The supramolecules selected were cyclodextrin inclusion complexes (CICs). The biomaterial selected for surface modification was plasticized poly (vinyl chloride) (PVC-P). Results indicate that when the CICs were blended into PVC-P, they tend to migrate and "anchor" on the surface to achieve a remarkable protein-resistant surface, with improved blood compatibility. In comparison with a physical mixture of cyclodextrins and a "guest" molecule, such as poly(ethylene oxide) (PEO)-poly(propylene oxide) (PPO)-PEO and PPO-PEO-PPO for PVC-P modification, CICs modified PVC-P are more consistent in processing and achieve reproducible surface characteristics. Based on this study, a novel "anchor modification" was proposed regarding CICs modified surface. This "anchor modification" is likely to reduce plasticizer extraction from PVC-P and also can be utilized for the modification of polymers other than PVC-P.

Organotin Polyethers as Biomaterials

PubMed Central

Carraher, Charles E.; Roner, Michael R.

2009-01-01

Organotin polyethers are easily synthesized employing interfacial polymerization systems involving the reaction of hydroxyl-containing Lewis bases and organotin halides. A wide variety of organotin-containing polymeric products have been synthesized including those derived from natural and synthetic polymers such as lignin, xylan, cellulose, dextran, and poly(vinyl alcohol). Others have been synthesized employing known drug diols such as dicumarol, DES, and dienestrol and a wide variety of synthetic diols. Included in these materials are the first water soluble organotin polymers. The organotin polyethers exhibit a wide range of biological activities. Some selectively inhibit a number of unwanted bacteria, including Staph. MRSA, and unwanted yeasts such as Candida albicans. Some also inhibit a variety of viruses including those responsible for herpes infections and smallpox. Others show good inhibition of a wide variety of cancer cell lines including cell lines associated with ovarian, colon, lung, prostrate, pancreatic and breast cancer. The synthesis, structural characterization, and biological characterization of these materials is described in this review.

Dual soft-template system based on colloidal chemistry for the synthesis of hollow mesoporous silica nanoparticles.

PubMed

Li, Yunqi; Bastakoti, Bishnu Prasad; Imura, Masataka; Tang, Jing; Aldalbahi, Ali; Torad, Nagy L; Yamauchi, Yusuke

2015-04-20

A new dual soft-template system comprising the asymmetric triblock copolymer poly(styrene-b-2-vinyl pyridine-b-ethylene oxide) (PS-b-P2VP-b-PEO) and the cationic surfactant cetyltrimethylammonium bromide (CTAB) is used to synthesize hollow mesoporous silica (HMS) nanoparticles with a center void of around 17 nm. The stable PS-b-P2VP-b-PEO polymeric micelle serves as a template to form the hollow interior, while the CTAB surfactant serves as a template to form mesopores in the shells. The P2VP blocks on the polymeric micelles can interact with positively charged CTA(+) ions via negatively charged hydrolyzed silica species. Thus, dual soft-templates clearly have different roles for the preparation of the HMS nanoparticles. Interestingly, the thicknesses of the mesoporous shell are tunable by varying the amounts of TEOS and CTAB. This study provides new insight on the preparation of mesoporous materials based on colloidal chemistry. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Bimodal porous TiO2 structures templated by graft copolymer/homopolymer blend for dye-sensitized solar cells with polymer electrolyte

NASA Astrophysics Data System (ADS)

Kim, Jin Kyu; Lee, Chang Soo; Lee, Sang-Yup; Cho, Hyung Hee; Kim, Jong Hak

2016-12-01

Bimodal porous TiO2 (BP-TiO2) with large surface area, high porosity, good interconnectivity, and excellent light-scattering ability are synthesized via a facile one-step method using a self-assembled blend template consisting of an amphiphilic poly(vinyl chloride)-g-poly(oxyethylene methacrylate) (PVC-g-POEM) graft copolymer and a hydrophobic poly(vinyl chloride) (PVC) homopolymer. The hydrophilically surface-modified TiO2 nanoparticles selectively interact with the hydrophilic POEM chains, while the addition of the PVC homopolymer increases the hydrophobic domain size, resulting in the formation of dual pores (i.e., macropores and mesopores). The sizes and numbers of macropores can easily be controlled by changing the molecular weight and amount of the PVC homopolymer. The polymer electrolyte dye-sensitized solar cells (DSSCs) fabricated with BP-TiO2 photoanodes exhibited energy conversion efficiencies of up to 7.6% at 100 mW cm-2, which is much higher than those of mesoporous TiO2 (5.8%) with PVC-g-POEM only and conventional nanocrystalline TiO2 (4.9%) with commercial Dyesol paste. The enhanced energy conversion efficiencies mostly resulted from the light-scattering effects of the macropores, which increased the light-harvesting efficiencies. The improved light-harvesting and photovoltaic performances of the DSSCs were characterized by UV-vis spectroscopy, incident photon-to-current conversion efficiency analysis, electrochemical impedance spectroscopy, intensity-modulated photocurrent spectroscopy, and intensity-modulated photovoltage spectroscopy.

Preparation and characterization of poly(acrylic acid)-hydroxyethyl cellulose graft copolymer.

PubMed

Abdel-Halim, E S

2012-10-01

Poly(acrylic acid) hydroxyethyl cellulose [poly(AA)-HEC] graft copolymer was prepared by polymerizing acrylic acid (AA) with hydroxyethyl cellulose (HEC) using potassium bromate/thiourea dioxide (KBrO(3)/TUD) as redox initiation system. The polymerization reaction was carried out under a variety of conditions including concentrations of AA, KBrO(3) and TUD, material to liquor ratio and polymerization temperature. The polymerization reaction was monitored by withdrawing samples from the reaction medium and measuring the total conversion. The rheological properties of the poly(AA)-HEC graft copolymer were investigated. The total conversion and rheological properties of the graft copolymer depended on the ratio of KBrO(3) to TUD and on acrylic acid concentration as well as temperature and material to liquor ratio. Optimum conditions of the graft copolymer preparation were 30 mmol KBrO(3) and 30 mmol TUD/100g HEC, 100% AA (based on weight of HEC), duration 2h at temperature 50 °C using a material to liquor ratio of 1:10. Copyright © 2012. Published by Elsevier Ltd.

Highly Active N,O Zinc Guanidine Catalysts for the Ring-Opening Polymerization of Lactide.

PubMed

Schäfer, Pascal M; Fuchs, Martin; Ohligschläger, Andreas; Rittinghaus, Ruth; McKeown, Paul; Akin, Enver; Schmidt, Maximilian; Hoffmann, Alexander; Liauw, Marcel A; Jones, Matthew D; Herres-Pawlis, Sonja

2017-09-22

New zinc guanidine complexes with N,O donor functionalities were prepared, characterized by X-Ray crystallography, and examined for their catalytic activity in the solvent-free ring-opening polymerization (ROP) of technical-grade rac-lactide at 150 °C. All complexes showed a high activity. The fastest complex [ZnCl 2 (DMEGasme)] (C1) produced colorless poly(lactide) (PLA) after 90 min with a conversion of 52 % and high molar masses (M w =69 100, polydispersity=1.4). The complexes were tested with different monomer-to-initiator ratios to determine the rate constant k p . Furthermore, a polymerization with the most active complex C1 was monitored by in situ Raman spectroscopy. Overall, conversion of up to 90 % can be obtained. End-group analysis was performed to clarify the mechanism. All four complexes combine robustness against impurities in the lactide with high polymerization rates, and they represent the fastest robust lactide ROP catalysts to date, opening new avenues to a sustainable ROP catalyst family for industrial use. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Property evolution during vitrification of dimethacrylate photopolymer networks

PubMed Central

Abu-Elenain, Dalia; Lewis, Steven H.; Stansbury, Jeffrey W.

2013-01-01

Objectives This study seeks to correlate the interrelated properties of conversion, shrinkage, modulus and stress as dimethacrylate networks transition from rubbery to glassy states during photopolymerization. Methods An unfilled BisGMA/TEGDMA resin was photocured for various irradiation intervals (7–600 s) to provide controlled levels of immediate conversion, which was monitored continuously for 10 min. Fiber optic near-infrared spectroscopy permitted coupling of real-time conversion measurement with dynamic polymerization shrinkage (linometer), modulus (dynamic mechanical analyzer) and stress (tensometer) development profiles. Results The varied irradiation conditions produced final conversion ranging from 6 % to more than 60 %. Post-irradiation conversion (dark cure) was quite limited when photopolymerization was interrupted either at very low or very high levels of conversion while significant dark cure contributions were possible for photocuring reactions suspended within the post-gel, rubbery regime. Analysis of conversion-based property evolution during and subsequent to photocuring demonstrated that the shrinkage rate increased significantly at about 40 % conversion followed by late-stage suppression in the conversion-dependent shrinkage rate that begins at about 45–50 % conversion. The gradual vitrification process over this conversion range is evident based on the broad but well-defined inflection in the modulus versus conversion data. As limiting conversion is approached, modulus and, to a somewhat lesser extent, stress rise precipitously as a result of vitrification with the stress profile showing little if any late-stage suppression as seen with shrinkage. Significance Near the limiting conversion for this model resin, the volumetric polymerization shrinkage rate slows while an exponential rise in modulus promotes the vitrification process that appears to largely dictate stress development. PMID:24080378

Photoinduced crystallization of calcium carbonate from a homogeneous precursor solution in the presence of partially hydrolyzed poly(vinyl alcohol)

NASA Astrophysics Data System (ADS)

Nishio, Takashi; Naka, Kensuke

2015-04-01

Photoinduced crystallization of calcium carbonate (CaCO3) was demonstrated by the photodecarboxylation of ketoprofen (KP, 2-(3-benzoylphenyl)propionic acid) under alkaline conditions (pH 10). In this method, a homogeneous solution comprising KP, calcium chloride, ammonia, and partially hydrolyzed poly(vinyl alcohol) (PVAPS, degree of saponification: 86.5-89.0 mol %) was used as the precursor solution and was exposed to ultraviolet (UV) irradiation for different time periods. Thermogravimetric analysis of the obtained xerogels showed that increasing the UV irradiation time increased the amount of CaCO3 formed and the complete conversion of calcium ions to calcite was achieved after 50 min of UV irradiation. Furthermore, solid phase analyses suggested that nanometer-to-micron-sized calcite crystals were formed and dispersed in the obtained PVAPS matrix.

Influence of irradiance on Knoop hardness, degree of conversion, and polymerization shrinkage of nanofilled and microhybrid composite resins.

PubMed

Fugolin, Ana Paula Piovezan; Correr-Sobrinho, Lourenço; Correr, Américo Bortolazzo; Sinhoreti, Mário Alexandre Coelho; Guiraldo, Ricardo Danil; Consani, Simonides

2016-01-01

The purpose of this study was to investigate the influence of the irradiance emitted by a light-curing unit on microhardness, degree of conversion (DC), and gaps resulting from shrinkage of 2 dental composite resins. Cylinders of nanofilled and microhybrid composites were fabricated and light cured. After 24 hours, the tops and bottoms of the specimens were evaluated via indentation testing and Fourier transform infrared spectroscopy to determine Knoop hardness number (KHN) and DC, respectively. Gap width (representing polymerization shrinkage) was measured under a scanning electron microscope. The nanofilled composite specimens presented significantly greater KHNs than did the microhybrid specimens (P < 0.05). The microhybrid composite resin exhibited significantly greater DC and gap width than the nanofilled material (P < 0.05). Irradiance had a mostly material-dependent influence on the hardness and DC, but not the polymerization shrinkage, of composite resins.

Vertical phase separation in bulk heterojunction solar cells formed by in situ polymerization of fulleride

PubMed Central

Zhang, Lipei; Xing, Xing; Zheng, Lingling; Chen, Zhijian; Xiao, Lixin; Qu, Bo; Gong, Qihuang

2014-01-01

Vertical phase separation of the donor and the acceptor in organic bulk heterojunction solar cells is crucial to improve the exciton dissociation and charge transport efficiencies. This is because whilst the exciton diffusion length is limited, the organic film must be thick enough to absorb sufficient light. However, it is still a challenge to control the phase separation of a binary blend in a bulk heterojunction device architecture. Here we report the realization of vertical phase separation induced by in situ photo-polymerization of the acrylate-based fulleride. The power conversion efficiency of the devices with vertical phase separation increased by 20%. By optimising the device architecture, the power conversion efficiency of the single junction device reached 8.47%. We believe that in situ photo-polymerization of acrylate-based fulleride is a universal and controllable way to realise vertical phase separation in organic blends. PMID:24861168

Effect of polyvinyl siloxane impression material on the polymerization of composite resin.

PubMed

Chen, Liang; Kleverlaan, Cornelis Johannes; Liang, Kunneng; Yang, Deqin

2017-04-01

Polyvinyl siloxane impression material has been widely used as a lingual matrix for rebuilding missing tooth structure with composite resin. The composite resin is light polymerized in contact with the polyvinyl siloxane impression material. However, polyvinyl siloxane impression material has been shown to interact with other dental materials. The purpose of this study was to assess the effect of polyvinyl siloxane impression materials on the polymerization of composite resins by assessing the Vickers microhardness and degree of conversion of polyvinyl siloxane. The composite resins were light polymerized in contact with 3 polyvinyl siloxane impression materials (Flexitime Easy Putty; President Light Body; Xantopren L Blue) (n=8) and in contact with a matrix strip as the control group (n=8). Vickers microhardness and degree of conversion on contact surfaces were measured to evaluate the polymerization of composite resins. The depth of the effect was assessed by Vickers microhardness on section surfaces and observed with scanning electron microscopy. The results were analyzed by 1-way analysis of variance and the post hoc Tukey honest significant differences test (α=.05). The Vickers microhardness and degree of conversion values on the contact surfaces of the experiment groups were significantly lower than those of the control group (P<.05); the Vickers microhardness values on the section surfaces indicated that there was no significant difference at the same depth of different groups (P>.05). The scanning electron microscope observation showed that an approximately 10-μm deep unpolymerized layer was found in the experimental group. Polyvinyl siloxane impression materials have an inhibitory effect on the polymerization of the composite resins, but just limited to within approximately 10 μm from the surface in contact with the impression material. Copyright © 2016 Editorial Council for the Journal of Prosthetic Dentistry. Published by Elsevier Inc. All rights reserved.

Evidence for existence in human tissues of monomers for plastics and rubber manufacture.

PubMed Central

Wolff, M S

1976-01-01

Although exposure to many industrially important monomers is controlled by law, few of these reactive chemicals have been determined in human tissues. Analogy with other fat-soluble organic substances strongly implies that these monomers may be retained in tissue, subject to the usual physiological constraints of metabolism, solubility and volatility. The storage of DDT and PCBs is discussed, as well as tetrachloro-ethylene (PCE) and trichloroethylene (TCE), which are chemically similar to many industrially used monomers. Styrene in blood and breath and its metabolites in urine have been studied in humans. Styrene and vinyl chloride have been measured in fat tissue of polymerization workers. PMID:829070

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.

Methods of forming single source precursors, methods of forming polymeric single source precursors, and single source precursors and intermediate products formed by such methods

DOEpatents

Fox, Robert V.; Rodriguez, Rene G.; Pak, Joshua J.; Sun, Chivin; Margulieux, Kelsey R.; Holland, Andrew W.

2012-12-04

Methods of forming single source precursors (SSPs) include forming intermediate products having the empirical formula 1/2{L.sub.2N(.mu.-X).sub.2M'X.sub.2}.sub.2, and reacting MER with the intermediate products to form SSPs of the formula L.sub.2N(.mu.-ER).sub.2M'(ER).sub.2, wherein L is a Lewis base, M is a Group IA atom, N is a Group IB atom, M' is a Group IIIB atom, each E is a Group VIB atom, each X is a Group VIIA atom or a nitrate group, and each R group is an alkyl, aryl, vinyl, (per)fluoro alkyl, (per)fluoro aryl, silane, or carbamato group. Methods of forming polymeric or copolymeric SSPs include reacting at least one of HE.sup.1R.sup.1E.sup.1H and MER with one or more substances having the empirical formula L.sub.2N(.mu.-ER).sub.2M'(ER).sub.2 or L.sub.2N(.mu.-X).sub.2M'(X).sub.2 to form a polymeric or copolymeric SSP. New SSPs and intermediate products are formed by such methods.

New ROMP Synthesis of Ferrocenyl Dendronized Polymers.

PubMed

Liu, Xiong; Ling, Qiangjun; Zhao, Li; Qiu, Guirong; Wang, Yinghong; Song, Lianxiang; Zhang, Ying; Ruiz, Jaime; Astruc, Didier; Gu, Haibin

2017-10-01

First- and second-generation Percec-type dendronized ferrocenyl norbornene macromonomers containing, respectively, three and nine ferrocenyl termini are synthesized and polymerized by ring-opening metathesis polymerization using Grubbs' third-generation olefin metathesis catalyst with several monomer/catalyst feed ratios between 10 and 50. The rate of polymerization is highly dependent on the generation of the dendronized macromonomers, but all these ring-opening metathesis polymerization reactions are controlled, and near-quantitative monomer conversions are achieved. The numbers of ferrocenyl groups obtained are in agreement with the theoretical ones according to the cyclic voltammetry studies as determined using the Bard-Anson method. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Well-Defined Macromolecules Using Horseradish Peroxidase as a RAFT Initiase.

PubMed

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.

Measurements of Dynamic Viscoelasticity of Poly (vinyl alcohol) Hydrogel for the Development of Blood Vessel Biomodeling

NASA Astrophysics Data System (ADS)

Kosukegawa, Hiroyuki; Mamada, Keisuke; Kuroki, Kanju; Liu, Lei; Inoue, Kosuke; Hayase, Toshiyuki; Ohta, Makoto

In vitro blood vessel biomodeling with realistic mechanical properties and geometrical structures is helpful for training in surgical procedures, especial those used in endovascular treatment. Poly (vinyl alcohol) hydrogel (PVA-H), which is made of Poly (vinyl alcohol) (PVA) and water, may be useful as a material for blood vessel biomodeling due to its low surface friction resistance and good transparency. In order to simulate the mechanical properties of blood vessels, measurements of mechanical properties of PVA-H were carried out with a dynamic mechanical analyzer, and the storage modulus (G’) and loss modulus (G”) of PVA-H were obtained. PVA-Hs were prepared by the low-temperature crystallization method. They were made of PVA with various concentrations (C) and degrees of polymerization (DP), and made by blending two kinds of PVA having different DP or saponification values (SV). The G’ and G” of PVA-H increased, as the C or DP of PVA increased, or as the proportion of PVA with higher DP or SV increased. These results indicate that it is possible to obtain PVA-H with desirable dynamic viscoelasticity. Furthermore, it is suggested that PVA-H is stable in the temperature range of 0°C to 40°C, indicating that biomodeling made of PVA-H should be available at 37°C, the physiological temperature. The dynamic viscoelasticity of PVA-H obtained was similar to that of the dog blood vessel measured in previous reports. In conclusion, PVA-H is suggested to be useful as a material of blood vessel biomodeling.

Development of Real Time Ultrasonic Imaging

DTIC Science & Technology

1999-01-01

piezoelectric material known as poly vinyl difluoride ( PVDF ) which enables the conversion of mechanical energy to charge the CCD chip. The system...geometries such as curved (wing) surfaces. Other future applications might include heavy gauge welds in plate, corrosion in piping, welds in piping...Harrison, G. "A Novel High Speed, High Resolution Ultrasound Imaging System", QNDE Review of Progress In Quantitative NDE, Plenum Press, Volume 17B, pp

Property evolution during vitrification of dimethacrylate photopolymer networks.

PubMed

Abu-elenain, Dalia A; Lewis, Steven H; Stansbury, Jeffrey W

2013-11-01

This study seeks to correlate the interrelated properties of conversion, shrinkage, modulus and stress as dimethacrylate networks transition from rubbery to glassy states during photopolymerization. An unfilled BisGMA/TEGDMA resin was photocured for various irradiation intervals (7-600 s) to provide controlled levels of immediate conversion, which was monitored continuously for 10 min. Fiber optic near-infrared spectroscopy permitted coupling of real-time conversion measurement with dynamic polymerization shrinkage (linometer), modulus (dynamic mechanical analyzer) and stress (tensometer) development profiles. The varied irradiation conditions produced final conversion ranging from 6% to more than 60%. Post-irradiation conversion (dark cure) was quite limited when photopolymerization was interrupted either at very low or very high levels of conversion while significant dark cure contributions were possible for photocuring reactions suspended within the post-gel, rubbery regime. Analysis of conversion-based property evolution during and subsequent to photocuring demonstrated that the shrinkage rate increased significantly at about 40% conversion followed by late-stage suppression in the conversion-dependent shrinkage rate that begins at about 45-50% conversion. The gradual vitrification process over this conversion range is evident based on the broad but well-defined inflection in the modulus versus conversion data. As limiting conversion is approached, modulus and, to a somewhat lesser extent, stress rise precipitously as a result of vitrification with the stress profile showing little if any late-stage suppression as seen with shrinkage. Near the limiting conversion for this model resin, the volumetric polymerization shrinkage rate slows while an exponential rise in modulus promotes the vitrification process that appears to largely dictate stress development. Copyright © 2013 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Tunable Mechanics in Electrospun Composites via Hierarchical Organization.

PubMed

Wanasekara, Nandula D; Matolyak, Lindsay E; Korley, LaShanda T J

2015-10-21

Design strategies from nature provide vital clues for the development of synthetic materials with tunable mechanical properties. Employing the concept of hierarchy and controlled percolation, a new class of polymer nanocomposites containing a montmorillonite (MMT)-reinforced electrospun poly(vinyl alcohol) (PVA) filler embedded within a polymeric matrix of either poly(vinyl acetate) (PVAc) or ethylene oxide-epichlorohydrin copolymer (EO-EPI) were developed to achieve a tunable mechanical response upon exposure to specific stimuli. Mechanical response and switching times upon hydration were shown to be dependent on the weight-fraction of MMT in the PVA electrospun fibers and type of composite matrix. PVA/MMT.PVAc composite films retained excellent two-way switchability for all MMT fractions; however, the switching time upon hydration was decreased dramatically as the MMT content was increased due to the highly hydrophilic nature of MMT. Additionally, for the first time, significant two-way switchability of PVA/MMT.EO-EPI composites was achieved for higher weight fractions (12 wt %) of MMT. An extensive investigation into the effects of fiber diameter, crystallinity, and MMT content revealed that inherent rigidity of MMT platelets plays an important role in controlling the mechanical response of these hierarchical electrospun composites.

Solution spinning of a high-? oxide superconductor: the effect of poly(vinyl alcohol) spinning medium on the critical current density of melt-processed ? superconducting filaments

NASA Astrophysics Data System (ADS)

Tomita, Hisayo; Sunohara, Makoto; Goto, Tomoko; Takahashi, Kiyohisa

1996-12-01

The precursor 0953-2048/9/12/014/img9 filament was prepared by solution spinning through a homogeneous aqueous poly(vinyl alcohol) (PVA) solution of Y, Ba and Cu acetates. The solution spinning was successfully performed using PVA with degrees of polymerization (DP) of 1700 and 2450 and a degree of saponification of 85 mol%. The as-drawn filament was heated to remove volatile components and partially melted to generate a superconducting phase. The effects of the DP of PVA and a content of mixed acetates in the precursor filament on the critical current density 0953-2048/9/12/014/img10 of the melt-processed filament were examined. The higher 0953-2048/9/12/014/img11 was obtained for the filament spun from PVA solution of higher DP and lower acetate content. The highest 0953-2048/9/12/014/img11 value of 0953-2048/9/12/014/img13 at 77 K and 0 T was achieved for the filament spun from the DP 2450 PVA with an acetate to PVA ratio of two.

Nanostructured starch combined with hydroxytyrosol in poly(vinyl alcohol) based ternary films as active packaging system.

PubMed

Luzi, Francesca; Fortunati, Elena; Di Michele, Alessandro; Pannucci, Elisa; Botticella, Ermelinda; Santi, Luca; Kenny, José Maria; Torre, Luigi; Bernini, Roberta

2018-08-01

Novel ternary films have been realized by using poly(vinyl alcohol) (PVA) as polymeric matrix, nanostructured starch as reinforcement phase and hydroxytyrosol (HTyr), a low-molecular phenolic compound present in olive oil, as antioxidant agent. Nanostructured starch, in the form of starch nanocrystals (NC) and nanoparticles (NP) obtained by acid hydrolysis and ultrasound irradiation of starch derived from the bread wheat variety Cadenza (WT, amylose content 33%) and a derived-high amylose line (HA, amylose content 75%), was considered. The developed multifunctional films were characterized in terms of morphological, thermal and optical properties, water absorption capacity, overall and specific migration into a food simulant and antioxidant properties. Experimental data showed a prolonged release of HTyr from all ternary films and the released HTyr retained a strong antioxidant activity. The data, compared to those of PVA/HTyr binary films, demonstrated the key role of nanostructured starch in the ternary formulations in promoting a gradual release of HTyr. Overall, PVA fillm combined with nanoparticles from low amylose starch and hydroxytyrosol resulted as the most promising ternary formulation for food packaging applications. Copyright © 2018 Elsevier Ltd. All rights reserved.

Combined use of crystalline sodium salt and polymeric precipitation inhibitors to improve pharmacokinetic profile of ibuprofen through supersaturation.

PubMed

Terebetski, Jenna L; Cummings, John J; Fauty, Scott E; Michniak-Kohn, Bozena

2014-10-01

To maximize the pharmacological effect of a pain reliever such as ibuprofen, early onset of action is critical. Unfortunately, the acidic nature of ibuprofen minimizes the amount of drug that can be solubilized under gastric conditions and would be available for immediate absorption upon entry into the intestine. Although the sodium salt of ibuprofen has higher solubility, rapid conversion from the salt to the poorly soluble free acid phase occurs under gastric conditions. Therefore, the combination of the highly soluble sodium salt form of ibuprofen with polymers was evaluated as an approach to prolong supersaturation of ibuprofen during the disproportionation of the salt. Binary combinations of ibuprofen sodium with polymers resulted in the identification of several formulations that demonstrated high degrees and extended durations of supersaturation during in vitro dissolution experiments. These formulations included HPMC, polyvinyl pyrrolidone-vinyl acetate copolymer (PVP-VA64), methylcellulose (MC), and hydroxypropyl cellulose (HPC). The in vitro supersaturation observed with these ibuprofen-polymer formulations translated to an increase in Cmax and an earlier Tmax for the PVP-VA64, MC, and HPC formulations relative to ibuprofen only controls when administered orally to rats under fasted conditions. Based on these observations, combining ibuprofen sodium with polymers such as PVP-VA64, MC, or HPC is a viable formulation approach to prolong supersaturation in the stomach and enable an optimized pharmacokinetic profile in vivo where rapid onset of action is desired.

Combinatorial enzyme technology: Conversion of pectin to oligo species and its effect on microbial growth

USDA-ARS?s Scientific Manuscript database

Plant cell wall polysaccharides, which consist of polymeric backbones with various types of substitution, were studied using the concept of combinatorial enzyme technology for conversion of agricultural fibers to functional products. Using citrus pectin as the starting substrate, an active oligo spe...

Vinyl Sulfonate Esters: Efficient Chain Transfer Agents for the 3D-Printing of Tough Photopolymers without Retardation.

PubMed

Seidler, Konstanze; Griesser, Markus; Kury, Markus; Reghunathan, Harikrishna; Dorfinger, Peter; Koch, Thomas; Svirkova, Anastasiya; Marchetti-Deschmann, Martina; Stampfl, Jürgen; Moszner, Norbert; Gorsche, Christian; Liska, Robert

2018-05-04

Photoinitiated radical polymer network formation is lacking freedom for tailored network design. Resulting inhomogeneous network architectures and brittle material behavior of such glassy-type networks limit the commercial application of photopolymers in 3D printing, biomedicine or microelectronics. An ester-activated vinyl sulfonate ester (EVS) is presented for the rapid formation of tailored methacrylate-based networks with nearly no retardation, reduced shrinkage stress, high monomer conversion and improved material toughness. Laser flash photolysis followed by theoretical calculations and photoreactor studies elucidate the fast chain transfer reaction and exceptional regulating ability of EVS. Final photopolymer networks exhibit high tensile strength, improved elongation at break and high impact resistance, while maintaining high modulus and hardness at ambient conditions. These findings make EVS an exceptional candidate for the 3D printing of tough photopolymers. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Kinetic Monte Carlo study of vinyl acetate synthesis from ethylene acetoxylation on Pd(100) and Pd/Au(100)

NASA Astrophysics Data System (ADS)

Huang, Yanping; Dong, Xiuqin; Yu, Yingzhe; Zhang, Minhua

2017-11-01

On the basis of the activation barriers and reaction energies from DFT calculations, kinetic Monte Carlo (kMC) simulations of vinyl acetate (VA) synthesis from ethylene acetoxylation on Pd(100) and Pd/Au(100) were carried out. Through kMC simulation, it was found that VA synthesis from ethylene acetoxylation proceeds via Moiseev mechanism on both Pd(100) and Pd/Au(100). The addition of Au into Pd can suppress ethylene dehydrogenation while it can promote acetic acid dehydrogenation, which can eventually facilitate VA synthesis as a whole. The addition of Au into Pd can further improve the conversion and selectivity of VA synthesis from ethylene acetoxylation. When the reaction network is analyzed, besides the energetics of each elementary reaction, the surface coverage of each species and the occupancy of the surface sites on the catalyst should also be taken into consideration.

Conversion of the. mu. ketene ligand in (PPN)(Os/sub 3/(CO)/sub 10/(. mu. -I)(. mu. -CH/sub 2/CO)) into enolate, acyl, and vinyl ligands

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bassner, S.L.; Morrison, E.D.; Geoffroy, G.L.

1986-08-20

Free ketene is a valuable organic synthetic reagent, but its utility is somewhat limited by its high reactivity and tendency to dimerize to yield diketene. The ketene ligand is obviously stabilized by metal coordination in a variety of bonding modes, but it is not yet known how coordination influences the chemistry of this important molecule. The authors have studied the reactivity of the coordinated ketene ligand of type II found in the anionic cluster compound (PPN)(Os/sub 3/(CO)/sub 10/(..mu..-I)(..mu..-CH/sub 2/CO)) (1) (PPN/sup +/ = (Ph/sub 3/P)/sub 2/N/sup +/) and herein show that this ligand is readily converted into eta-enolate ligands uponmore » reaction with simple nucleophiles and into vinyl and acetyl ligands upon reaction with electrophiles.« less

Biocatalytic Synthesis of Poly(δ-Valerolactone) Using a Thermophilic Esterase from Archaeoglobus fulgidus as Catalyst

PubMed Central

Cao, Hong; Han, Haobo; Li, Guangquan; Yang, Jiebing; Zhang, Lingfei; Yang, Yan; Fang, Xuedong; Li, Quanshun

2012-01-01

The ring-opening polymerization of δ-valerolactone catalyzed by a thermophilic esterase from the archaeon Archaeoglobus fulgidus was successfully conducted in organic solvents. The effects of enzyme concentration, temperature, reaction time and reaction medium on monomer conversion and product molecular weight were systematically evaluated. Through the optimization of reaction conditions, poly(δ-valerolactone) was produced in 97% monomer conversion, with a number-average molecular weight of 2225 g/mol, in toluene at 70 °C for 72 h. This paper has produced a new biocatalyst for the synthesis of poly(δ-valerolactone), and also deeper insight has been gained into the mechanism of thermophilic esterase-catalyzed ring-opening polymerization. PMID:23202895

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.

Synthesis and characterization of poly-3-((2,5-hydroquinone)vinyl)-1H-pyrrole: investigation on backbone/pendant interactions in a conducting redox polymer.

PubMed

Huang, Hao; Karlsson, Christoffer; Strømme, Maria; Gogoll, Adolf; Sjödin, Martin

2017-04-19

We herein report the synthesis and electrochemical characterization of poly-3-((2,5-hydroquinone)vinyl)-1H-pyrrole, consisting of a polypyrrole backbone derivatized at the beta position by a vinyl-hydroquinone pendant group. The structure of the polymer was characterized by solid state NMR spectroscopy. The interactions between the polypyrrole backbone and the oxidized quinone or reduced hydroquinone pendant groups are probed by several in situ methods. In situ attenuated total reflectance-Fourier transform infrared spectroscopy shows a spectroscopic response from both the doping of the polymer backbone and the redox activity of the pendant groups. Using an in situ Electrochemical Quartz Crystal Microbalance we reveal that the polymer doping is unaffected by the pendant group redox chemistry, as opposed to previous reports. Despite the continuous doping the electrochemical conversion from the hydroquinone state to the quinone state results in a significant conductance drop, as observed by in situ conductivity measurements using an Interdigitated Array electrode set-up. Twisting of the conducting polymer backbone as a result of a decreased separation between pendant groups due to π-π stacking in the oxidized state is suggested as the cause of this conductance drop.

POLYMERIZATION OF /cap alpha/-METHYLSTYRENE BY ELECTRON IRRADIATION (in German)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Braun, D.; Heufer, G.; Seufert, W.

1964-01-01

Ampoules of alpha -methylstyrene sealed under vacuum were irradiated with 1-Mev electrons in a type JS Van de Graaff generator; comparative experiments with gamma rays were carried out with a /sup 60/Co source of 3000 deg C. High doses of electrons (ca. 10/sup 8/ rad) are necessary for polymerization. The conversion is graphed as a function of dose at 0 deg C; it reaches a maximum plateau of 65% at 4 x 10/sup 8/ rad; this may point to radiolysis of the polymer at doses above this. Polymerization conversion increases with decreasing dose rate, when dose and temperature are heldmore » constant; and conversion increases with decreasing temperature (22% at --22 deg C; 10% at 15 deg C; <1% at 60 deg C), as has been found with gamma rays. In the solid state between --40 deg C and --80 deg C the maximum yield is only about 5%. The molecular weights of all poly- alpha -methylstyrenes thus formed lie between 3000 and 12,000, independently of dose rate and temperature. All polymethylstyrenes formed in the liquid state have approximately the same tacticity independent of temperature (isotactic about 20%; syndiotactic about 80%). This corresponds to the tacticity of polymers formed cationically with Lewis acids. In the solid state the tacticity is: isotactic 38%, syndiotactic, 62%, comparable with the tacticity of anionic polymerization. In the liquid state the tacticity and the sensitivity towards water indicate a cationic mechanism for the reaction. NMR studies also indicate a cationic mechanism. (BBB)« less

Co-sensitization of ZnO by CdS quantum dots in natural dye-sensitized solar cells with polymeric electrolytes to improve the cell stability

DOE Office of Scientific and Technical Information (OSTI.GOV)

Junhom, W.; Magaraphan, R.

2015-05-22

The CdS quantum dots (QDs) were deposited on ZnO layer by chemical bath deposition method to absorb light in the shorter wavelength region and used as photoanode in the dye sensitized solar cell (DSSCs) with natural dye extracted from Noni leaves. Microstructures of CdS-ZnO from various dipping time were characterized by XRD, FE-SEM and EDX. The results showed that the CdS is hexagonal structure and the amount of CdS increases when the dipping time increases. The maximal conversion efficiency of 0.292% was achieved by the DSSCs based on CdS QDs-sensitized ZnO film obtained from 9 min-dipping time. Furthermore, the stability ofmore » DSSCs was improved by using polymeric electrolyte. Poly (acrylic acid) (PAA) and Polyacrylamide (PAM) were introduced to CdS QDs-sensitized ZnO film from 9 min-dipping time. Each polymeric electrolyte was prepared by swelling from 0.1-2.0 %w in H2O. The maximal conversion efficiency of 0.207% was achieved for DSSCs based on CdS QDs-sensitized ZnO film with PAM 1.0% and the conversion efficiency was decreased 25% when it was left for1 hr.« less

Co-sensitization of ZnO by CdS quantum dots in natural dye-sensitized solar cells with polymeric electrolytes to improve the cell stability

NASA Astrophysics Data System (ADS)

Junhom, W.; Magaraphan, R.

2015-05-01

The CdS quantum dots (QDs) were deposited on ZnO layer by chemical bath deposition method to absorb light in the shorter wavelength region and used as photoanode in the dye sensitized solar cell (DSSCs) with natural dye extracted from Noni leaves. Microstructures of CdS-ZnO from various dipping time were characterized by XRD, FE-SEM and EDX. The results showed that the CdS is hexagonal structure and the amount of CdS increases when the dipping time increases. The maximal conversion efficiency of 0.292% was achieved by the DSSCs based on CdS QDs-sensitized ZnO film obtained from 9 min-dipping time. Furthermore, the stability of DSSCs was improved by using polymeric electrolyte. Poly (acrylic acid) (PAA) and Polyacrylamide (PAM) were introduced to CdS QDs-sensitized ZnO film from 9 min-dipping time. Each polymeric electrolyte was prepared by swelling from 0.1-2.0 %w in H2O. The maximal conversion efficiency of 0.207% was achieved for DSSCs based on CdS QDs-sensitized ZnO film with PAM 1.0% and the conversion efficiency was decreased 25% when it was left for1 hr.

Industrially relevant epoxy-acrylate hybrid resin photopolymerizations

NASA Astrophysics Data System (ADS)

Ajiboye, Gbenga I.

Photopolymerization of epoxy-acrylate hybrid resins takes advantages of inherent properties present in the free-radical and cationic reactions to reduce oxygen inhibition problems that plague free-radical reactions. Similarly, the combined reaction mechanisms reduce moisture sensitivity of the cationic reactions. Despite the advantages of epoxy-acrylate hybrid resins, problems persist that need to be addressed. For example, low conversion and polymerization rate of the epoxides are a problem, because the fast acrylate conversion prevents the epoxide from reaching high conversion. Controlling phase separation is challenging, since two moieties with different properties are reacting. The physical properties of the polymer will be impacted by the availability of different moieties. High shrinkage stress results from the acrylate moiety, causing buckling and cracking in film and coating applications. The overall goal of this study is to use the fundamental knowledge of epoxy-acrylate hybrid resins to formulate industrially viable polymers. In order to achieve this goal, the study focuses on the following objectives: (I) determine the apparent activation energy of the hybrid monomer METHB, (II) increase epoxide conversion and polymerization rate of hybrid formulations, and (III) control physical properties in epoxy-acrylate hybrid resins. In order to increase the epoxide conversion and rate of polymerization, the sensitivity of epoxides to alcohol is used to facilitate the activated monomer (AM) mechanism and induce a covalent bond between the epoxide and acrylate polymers through the hydroxyl group. It is hypothesized that if the AM mechanism is facilitated, epoxide conversion will increase. As a result, the resins can be tailored to control phase separation and physical properties, and shrinkage stress can be reduced. In pursuit of these objectives, the hybrid monomer METHB was polymerized at temperatures ranging from 30°C to 70°C to obtain apparent activation energy of 23.49 kJ/mol for acrylate and 57 kJ/mol for epoxide moeities. Then, hybrid systems pairing hydroxyl-containing acrylates with epoxides were formulated to promote the faster AM mechanism. Monomer composition was changed in the presence of hydroxyl-containing acrylate, and initiators were carefully selected in order to control phase separation. The conversion of acrylate and epoxide was monitored in real time by Raman spectroscopy. The physical and mechanical properties were monitored using dynamic mechanical analysis. Epoxide conversion and rate of polymerization in epoxide-acrylate hybrid monomer systems were shown to increase through the introduction of a hydroxyl group on the meth/acrylate monomer, taking advantage of the faster AM mechanism. In addition, this covalent bond linking the epoxide network to the meth/acrylate polymer chains resulted in little or no phase separation and a reduction of the Tg for the hybrid polymer compared to the neat epoxide. Fundamental knowledge gained from this research will enable the use of epoxy-acrylate hybrid resins in variety of applications. For instance, shrinkage may be reduced in dental fillings, noise and vibration problems in aircraft and other machinery may be controlled, and photopolymerization cost could be reduced in thin film applications.

Interfacial Stacks of Polymeric Nanofilms on Soft Biological Surfaces that Release Multiple Agents.

PubMed

Herron, Maggie; Schurr, Michael J; Murphy, Christopher J; McAnulty, Jonathan F; Czuprynski, Charles J; Abbott, Nicholas L

2016-10-03

We report a general and facile method that permits the transfer (stacking) of multiple independently fabricated and nanoscopically thin polymeric films, each containing a distinct bioactive agent, onto soft biomedically relevant surfaces (e.g., collagen-based wound dressings). By using polyelectrolyte multilayer films (PEMs) formed from poly(allyl amine hydrochloride) and poly(acrylic acid) as representative polymeric nanofilms and micrometer-thick water-soluble poly(vinyl alcohol) sacrificial films to stack the PEMs, we demonstrate that it is possible to create stacked polymeric constructs containing multiple bioactive agents (e.g., antimicrobial and antibiofilm agents) on soft and chemically complex surfaces onto which PEMs cannot be routinely transferred by stamping. We illustrate the characteristics and merits of the approach by fabricating stacks of Ga 3+ (antibiofilm agent)- and Ag + (antimicrobial agent)-loaded PEMs as prototypical examples of agent-containing PEMs and demonstrate that the stacked PEMs incorporate precise loadings of the agents and provide flexibility in terms of tuning release rates. Specifically, we show that simultaneous release of Ga 3+ and Ag + from the stacked PEMs on collagen-based wound dressings can lead to synergistic effects on bacteria, killing and dispersing biofilms formed by Pseudomonas aeruginosa (two strains: ATCC 27853 and MPAO1) at sufficiently low loadings of agents such that cytotoxic effects on mammalian cells are avoided. The approach is general (a wide range of bioactive agents other than Ga 3+ and Ag + can be incorporated into PEMs), and the modular nature of the approach potentially allows end-user functionalization of soft biological surfaces for programmed release of multiple bioactive agents.

Comparison between polymerized ionic liquids synthesized using chain-growth and step-growth mechanisms used as stationary phase in gas chromatography.

PubMed

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.

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

PubMed

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

2015-01-01

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Khezri, Khezrollah, E-mail: kh.khezri@ut.ac.ir; Roghani-Mamaqani, Hossein

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

Nanocomposites Based on Luminescent Colloidal Nanocrystals and Polymeric Ionic Liquids towards Optoelectronic Applications

PubMed Central

Panniello, Annamaria; Ingrosso, Chiara; Coupillaud, Paul; Tamborra, Michela; Binetti, Enrico; Curri, Maria Lucia; Agostiano, Angela; Taton, Daniel; Striccoli, Marinella

2014-01-01

Polymeric ionic liquids (PILs) are an interesting class of polyelectrolytes, merging peculiar physical-chemical features of ionic liquids with the flexibility, mechanical stability and processability typical of polymers. The combination of PILs with colloidal semiconducting nanocrystals leads to novel nanocomposite materials with high potential for batteries and solar cells. We report the synthesis and properties of a hybrid nanocomposite made of colloidal luminescent CdSe nanocrystals incorporated in a novel ex situ synthesized imidazolium-based PIL, namely, either a poly(N-vinyl-3-butylimidazolium hexafluorophosphate) or a homologous PIL functionalized with a thiol end-group exhibiting a chemical affinity with the nanocrystal surface. A capping exchange procedure has been implemented for replacing the pristine organic capping molecules of the colloidal CdSe nanocrystals with inorganic chalcogenide ions, aiming to disperse the nano-objects in the PILs, by using a common polar solvent. The as-prepared nanocomposites have been studied by TEM investigation, UV-Vis, steady-state and time resolved photoluminescence spectroscopy for elucidating the effects of the PIL functionalization on the morphological and optical properties of the nanocomposites. PMID:28788477

Novel Polymer Aerogel toward High Dimensional Stability, Mechanical Property, and Fire Safety.

PubMed

Shang, Ke; Yang, Jun-Chi; Cao, Zhi-Jie; Liao, Wang; Wang, Yu-Zhong; Schiraldi, David A

2017-07-12

Inorganc silica-based aerogels, the earliest and widely used aerogels, have poorer mechanical properties than their organic substitutes, which are flammable. In this study, a novel polymeric aerogel with high strength, inherent flame retardancy, and cost-effectiveness, which is based on poly(vinyl alcohol) (PVA) cross-linked with melamine-formaldehyde (MF), was prepared under aqueous condition with an ecofriendly freeze-drying and postcuring process. Combined with the additional rigid MF network and benifited from the resulting unique infrastructure of inter-cross-linked flexible PVA segments and rigid MF segments, PVA-based aerogels exibited a significantly decreased degradation rate and sharply decreased peak heat release rate (PHRR) in cone calorimeter tests (by as much as 83%) compared with neat PVA. The polymer aerogels have a limiting oxygen index (LOI) as high as 36.5% and V-0 rating in UL-94 test. Furthermore, the aerogel samples exposured to harsh temperatures maintain their dimensions (<10% change), original mechanical strength and fire safety. Therefore, this work provides a novel stragegy for preparing pure organic polymeric aerogel materials with high mechanical strength, dimensional stability, and fire safety.

Radical-induced generation of small silver particles in SPEEK/PVA polymer films and solutions: UV-Vis, EPR, and FT-IR studies.

PubMed

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.

'One-component' ultrathin multilayer films based on poly(vinyl alcohol) as stabilizing coating for phenytoin-loaded liposomes.

PubMed

Zasada, Katarzyna; Łukasiewicz-Atanasov, Magdalena; Kłysik, Katarzyna; Lewandowska-Łańcucka, Joanna; Gzyl-Malcher, Barbara; Puciul-Malinowska, Agnieszka; Karewicz, Anna; Nowakowska, Maria

2015-11-01

Ultrathin "one-component" multilayer polymeric films for potential biomedical applications were designed based on polyvinyl alcohol,-a non-toxic, fully degradable synthetic polymer. Good uniformity of the obtained film and adequate adsorption properties of the polymeric layers were achieved by functional modification of the polymer, which involved synthesis of cationic and anionic derivatives. Synthesized polymers were characterized by FTIR, NMR spectroscopy, dynamic light scattering measurements and elemental analysis. The layer by layer assembly technique was used to build up a multilayer film and this process was followed using UV-Vis spectroscopy and ellipsometry. The morphology and thickness of the obtained multilayered film material was evaluated by atomic force microscopy (AFM). Preliminary studies on the application of the obtained multilayer film for coating of liposomal nanocarriers containing phenytoin, an antiarrhythmic drug, were performed. The coating effectively stabilizes liposomes and the effect increases with an increasing number of deposited layers until the polymeric film reaches the optimal thickness. The obtained release profiles suggest that bilayer-coated liposomes release phenytoin less rapidly than uncoated ones. The cytotoxicity studies performed for all obtained nanocarriers confirmed that none of them has negative effect on cell viability. All of the performed experiments suggest that liposomes coated with ultrathin film obtained from PVA derivatives can be attractive drug nanocarriers. Copyright © 2015 Elsevier B.V. All rights reserved.

Molecularly imprinted polymers coated on multi-walled carbon nanotubes through a simple indirect method for the determination of 2,4-dichlorophenoxyacetic acid in environmental water

NASA Astrophysics Data System (ADS)

Yang, Weijie; Jiao, Feipeng; Zhou, Lei; Chen, Xiaoqing; Jiang, Xinyu

2013-11-01

A new and facile method was presented to graft molecularly imprinted polymers (MIPs) on carbon nanotubes (CNTs) for 2,4-dichlorophenoxyacetic acid (2,4-D) analysis. In brief, CNTs were firstly coated with a layer of vinyl group modified silica, followed by a common precipitation polymerization with 2,4-D as the template, ethylene glycol dimethacrylate (EGDMA) as the crosslinker and 2,2-azobisisobutyronitrile (AIBN) as the initiator. The imprinted effects obtained by using different monomers were investigated, and the results showed that acrylamide (AM) and styrene as mixed monomers was the best choice. This functionalized material was characterized by Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM) and thermogravimetry (TG), which demonstrated a successful polymerization reaction on CNTs with MIPs grafting ratio of about 80%. The results of static adsorption experiments indicated the imprinted material possessed fast kinetics and good selectivity for 2,4-D molecules. A corresponding analytical method was developed and demonstrated to be applicable for the determination of 2,4-D in environmental water. The recoveries were in the range from 74.6% to 81.2% with relative standard deviation below 7.0%. To be emphasized, the method for MIPs coating proposed herein also provides a significant reference for other radical polymerization reactions based on CNTs.

Advanced drug and gene delivery systems based on functional biodegradable polycarbonates and copolymers.

PubMed

Chen, Wei; Meng, Fenghua; Cheng, Ru; Deng, Chao; Feijen, Jan; Zhong, Zhiyuan

2014-09-28

Biodegradable polymeric nanocarriers are one of the most promising systems for targeted and controlled drug and gene delivery. They have shown several unique advantages such as excellent biocompatibility, prolonged circulation time, passive tumor targeting via the enhanced permeability and retention (EPR) effect, and degradation in vivo into nontoxic products after completing their tasks. The current biodegradable drug and gene delivery systems exhibit, however, typically low in vivo therapeutic efficacy, due to issues of low loading capacity, inadequate in vivo stability, premature cargo release, poor uptake by target cells, and slow release of therapeutics inside tumor cells. To overcome these problems, a variety of advanced drug and gene delivery systems has recently been designed and developed based on functional biodegradable polycarbonates and copolymers. Notably, polycarbonates and copolymers with diverse functionalities such as hydroxyl, carboxyl, amine, alkene, alkyne, halogen, azido, acryloyl, vinyl sulfone, pyridyldisulfide, and saccharide, could be readily obtained by controlled ring-opening polymerization. In this paper, we give an overview on design concepts and recent developments of functional polycarbonate-based nanocarriers including stimuli-sensitive, photo-crosslinkable, or active targeting polymeric micelles, polymersomes and polyplexes for enhanced drug and gene delivery in vitro and in vivo. These multifunctional biodegradable nanosystems might be eventually developed for safe and efficient cancer chemotherapy and gene therapy. Copyright © 2014 Elsevier B.V. All rights reserved.

Design considerations for multi component molecular-polymeric nonlinear optical materials

NASA Astrophysics Data System (ADS)

Singer, K. D.; Kuzyk, M. G.; Fang, T.; Holland, W. R.; Cahill, P. A.

1990-08-01

We review our work on multi component polymeric nonlinear optical materials. These materials consist of nonlinear optical molecules incorporated in a polymeric host. A cross-linked triazine polymer incorporating a dicyanovinyl terminated azo dye was found to be relatively stable at 85 deg and possess an electro-optic coefficient of 11pm/V. We have also observed the zero dispersion condition in a new anomalous dispersion dye for phase matched second harmonic generation, and expect efficient conversion to the blue. A squarylium dye, ISQ, has been found to possess a large third order nonlinearity, and may display two-level behavior.

Coating of Carbon Fiber with Polyhedral Oligomeric Silsesquioxane (POSS) to Enhance Mechanical Properties and Durability of Carbon/Vinyl Ester Composites

PubMed Central

Mahfuz, Hassan; Powell, Felicia; Granata, Richard; Hosur, Mahesh; Khan, Mujib

2011-01-01

Our continuing quest to improve the performance of polymer composites under moist and saltwater environments has gained momentum in recent years with the reinforcement of inorganic nanoparticles into the polymer. The key to mitigate degradation of composites under such environments is to maintain the integrity of the fiber/matrix (F/M) interface. In this study, the F/M interface of carbon/vinyl ester composites has been modified by coating the carbon fiber with polyhedral oligomeric silsesquioxane (POSS). POSS is a nanostructured inorganic-organic hybrid particle with a cubic structure having silicon atoms at the core and linked to oxygen atoms. The advantage of using POSS is that the silicon atoms can be linked to a substituent that can be almost any chemical group known in organic chemistry. Cubic silica cores are ‘hard particles’ and are about 0.53 nm in diameter. The peripheral organic unit is a sphere of about 1–3 nm in diameter. Further, cubic structure of POSS remains intact during the polymerization process and therefore with appropriate functional groups, if installed on the fiber surface, would provide a stable and strong F/M interface. Two POSS systems with two different functional groups; namely, octaisobutyl and trisilanolphenyl have been investigated. A set of chemical and mechanical procedures has been developed to coat carbon fibers with POSS, and to fabricate layered composites with vinyl ester resin. Interlaminar shear and low velocity impact tests have indicated around 17–38% improvement in mechanical properties with respect to control samples made without the POSS coating. Saltwater and hygrothermal tests at various environmental conditions have revealed that coating with POSS reduces water absorption by 20–30% and retains the composite properties. PMID:28824160

Polymeric carbon nitride nanomesh as an efficient and durable metal-free catalyst for oxidative desulfurization.

PubMed

Shen, Lijuan; Lei, Ganchang; Fang, Yuanxing; Cao, Yanning; Wang, Xinchen; Jiang, Lilong

2018-03-06

We report the first use of polymeric carbon nitride (CN) for the catalytic selective oxidation of H 2 S. The as-prepared CN with unique ultrathin "nanomeshes" structure exhibits excellent H 2 S conversion and high S selectivity. In particular, the CN nanomesh also displays better durability in the desulfurization reaction than traditional catalysts, such as carbon- and iron-based materials.

Synthesis, properties and applications of bio-based materials

NASA Astrophysics Data System (ADS)

Srinivasan, Madhusudhan

Bio-based feedstock have become very significant as they offer a value proposition in terms of carbon balance and also in terms of endowing biodegradability where needed. Thus a lot of attention is being given to the modification such feedstock for different applications. Soybean oil is one such feedstock. The oil is a triglyceride ester composed of different fatty acids, which are common to other plant oils. Thus soybean oil serves as a platform for plant oils, as modifications of this oil, can in theory be extended to cover other plant oils. Methyl oleate was used as a model fatty acid ester, to synthesize hydroxyesters with ethylene glycol via a two stage oxidative cleavage of the double bonds. Ozone was chosen as the oxidant due to its many advantages. The first stage involved oxidation of the double bond to aldehydes, ozonides and acetals, which were subsequently converted to hydroxyesters (hydroxy values of 220 - 270) in near quantitative yield by treatment with Oxone. This method could be extended to soybean oil to make "polyols" which could find applications in resin syntheses. Silylation was employed as another platform to functionalize soybean oil and fatty acid methyl esters with a reactive silane (vinyltrimethoxy silane). This simple modification produced materials that are cured by atmospheric moisture and are useful as coatings. The silylation was controlled by varying the grafting time, cure temperature and the concentration of the silane. Products with gel content as high as 90% could be achieved. The coating exhibited good adhesion to metal, glass, concrete and paper. Steel panels coated with these coatings exhibited good stability against corrosion in high humidity conditions and moderate stability against a salt spray. The silylation was also successfully utilized to improve the tensile strength of the blend of biodegradable polyester, poly (butylene adipate-co-terephthalate) with talc. A reactive extrusion process was employed to graft vinyl silanes on the polyester in short reaction times of 5 minutes. This improved the compatibility with the talc filler. This biodegradable polyester product was characterized by high tensile strength and moderate elongation. The modification method is simple is applicable to a variety of aliphatic biodegradable polyesters. Finally a rapid polymerization of 1, 4-dioxan-2-one in very short times was accomplished with titanium alkoxides as initiators. At low [monomer]/ [initiator] ratios (100:1), nearly all the alkoxide groups initiated polymerization. High conversions up to 90% were achieved even at high ratios (2400:1). The activation energy for polymerization for titanium tetraisopropoxide is the lowest reported (33.5 kJ/mol) for this monomer system.

Use of near-IR to monitor the influence of external heating on dental composite photopolymerization.

PubMed

Trujillo, Marianela; Newman, Sheldon M; Stansbury, Jeffrey W

2004-10-01

This study was conducted to determine the effect of modest external heating on the photopolymerization kinetics and conversion of commercial dental composite restorative materials. A transmission-mode, real-time near-infrared spectroscopic technique was used to monitor the photopolymerization process in the composite materials at various temperatures between 23 and 70 degrees C. Several light curing units, differing in spectral output and power densities were compared at the different cure temperatures. Several significantly different commercial composites were compared for their response. Regardless of the curing light or composite material used, photopolymerization at a moderate curing temperature of 54.5 degrees C resulted in significantly higher immediate and final conversion values compared with room temperature photocuring. Contrary to the room temperature cured materials, at the elevated cure temperature the extent of post-cure was minor and different curing lights produced very uniform conversion values within a given material. The time required to reach a given level of conversion, established as full conversion with the room temperature cure, was reduced typically by 80-90% using the elevated curing conditions. Complementary kinetic studies confirmed the effect of cure temperature on increasing the polymerization rate in dental composites as significant. Increasing the temperature of composite resin within potentially biologically compatible limits can significantly influences resin polymerization. These increased rates and conversion could lead to improved properties of composite restorative materials.

Characterization of dimethacrylate polymeric networks: a study of the crosslinked structure formed by monomers used in dental composites

PubMed Central

Shelton, Zachary R.; Braga, Roberto R.; Windmoller, Dario; Machado, José C.

2011-01-01

The resin phase of dental composites is mainly composed of combinations of dimethacrylate comonomers, with final polymeric network structure defined by monomer type/reactivity and degree of conversion. This fundamental study evaluates how increasing concentrations of the flexible triethylene glycol dimethacrylate (TEGDMA) influences void formation in bisphenol A diglycidyl dimethacrylate (BisGMA) co-polymerizations and correlates this aspect of network structure with reaction kinetic parameters and macroscopic volumetric shrinkage. Photopolymerization kinetics was followed in real-time by a near-infrared (NIR) spectroscopic technique, viscosity was assessed with a viscometer, volumetric shrinkage was followed with a linometer, free volume formation was determined by positron annihilation lifetime spectroscopy (PALS) and the sol-gel composition was determined by extraction with dichloromethane followed by 1H-NMR analysis. Results show that, as expected, volumetric shrinkage increases with TEGDMA concentration and monomer conversion. Extraction/1H-NMR studies show increasing participation of the more flexible TEGDMA towards the limiting stages of conversion/crosslinking development. As the conversion progresses, either based on longer irradiation times or greater TEGDMA concentrations, the network becomes more dense, which is evidenced by the decrease in free volume and weight loss after extraction in these situations. For the same composition (BisGMA/TEGDMA 60–40 mol%) light-cured for increasing periods of time (from 10 to 600 s), free volume decreased and volumetric shrinkage increased, in a linear relationship with conversion. However, the correlation between free volume and macroscopic volumetric shrinkage was shown to be rather complex for variable compositions exposed for the same time (600 s). The addition of TEGDMA decreases free-volume up to 40 mol% (due to increased conversion), but above that concentration, in spite of the increase in conversion/crosslinking, free volume pore size increases due to the high concentration of the more flexible monomer. In those cases, the increase in volumetric shrinkage was due to higher functional group concentration, in spite of the greater free volume. Therefore, through the application of the PALS model, this study elucidates the network formation in dimethacrylates commonly used in dental materials. PMID:21499538

Characterization of dimethacrylate polymeric networks: a study of the crosslinked structure formed by monomers used in dental composites.

PubMed

Pfeifer, Carmem S; Shelton, Zachary R; Braga, Roberto R; Windmoller, Dario; Machado, José C; Stansbury, Jeffrey W

2011-02-01

The resin phase of dental composites is mainly composed of combinations of dimethacrylate comonomers, with final polymeric network structure defined by monomer type/reactivity and degree of conversion. This fundamental study evaluates how increasing concentrations of the flexible triethylene glycol dimethacrylate (TEGDMA) influences void formation in bisphenol A diglycidyl dimethacrylate (BisGMA) co-polymerizations and correlates this aspect of network structure with reaction kinetic parameters and macroscopic volumetric shrinkage. Photopolymerization kinetics was followed in real-time by a near-infrared (NIR) spectroscopic technique, viscosity was assessed with a viscometer, volumetric shrinkage was followed with a linometer, free volume formation was determined by positron annihilation lifetime spectroscopy (PALS) and the sol-gel composition was determined by extraction with dichloromethane followed by (1)H-NMR analysis. Results show that, as expected, volumetric shrinkage increases with TEGDMA concentration and monomer conversion. Extraction/(1)H-NMR studies show increasing participation of the more flexible TEGDMA towards the limiting stages of conversion/crosslinking development. As the conversion progresses, either based on longer irradiation times or greater TEGDMA concentrations, the network becomes more dense, which is evidenced by the decrease in free volume and weight loss after extraction in these situations. For the same composition (BisGMA/TEGDMA 60-40 mol%) light-cured for increasing periods of time (from 10 to 600 s), free volume decreased and volumetric shrinkage increased, in a linear relationship with conversion. However, the correlation between free volume and macroscopic volumetric shrinkage was shown to be rather complex for variable compositions exposed for the same time (600 s). The addition of TEGDMA decreases free-volume up to 40 mol% (due to increased conversion), but above that concentration, in spite of the increase in conversion/crosslinking, free volume pore size increases due to the high concentration of the more flexible monomer. In those cases, the increase in volumetric shrinkage was due to higher functional group concentration, in spite of the greater free volume. Therefore, through the application of the PALS model, this study elucidates the network formation in dimethacrylates commonly used in dental materials.

Kinetics of bulk photo-initiated copper(i)-catalyzed azide-alkyne cycloaddition (CuAAC) polymerizations.

PubMed

Song, Han Byul; Baranek, Austin; Bowman, Christopher N

2016-01-21

Photoinitiation of polymerizations based on the copper(i)-catalyzed azide-alkyne cycloaddition (CuAAC) reaction enables spatio-temporal control and the formation of mechanically robust, highly glassy photopolymers. Here, we investigated several critical factors influencing photo-CuAAC polymerization kinetics via systematic variation of reaction conditions such as the physicochemical nature of the monomers; the copper salt and photoinitiator types and concentrations; light intensity; exposure time and solvent content. Real time Fourier transform infrared spectroscopy (FTIR) was used to monitor the polymerization kinetics in situ . Six different di-functional azide monomers and four different tri-functional alkyne monomers containing either aliphatic, aromatic, ether and/or carbamate substituents were synthesized and polymerized. Replacing carbamate structures with ether moieties in the monomers enabled an increase in conversion from 65% to 90% under similar irradiation conditions. The carbamate results in stiffer monomers and higher viscosity mixtures indicating that chain mobility and diffusion are key factors that determine the CuAAC network formation kinetics. Photoinitiation rates were manipulated by altering various aspects of the photo-reduction step; ultimately, a loading above 3 mol% per functional group for both the copper catalyst and the photoinitiator showed little or no rate dependence on concentration while a loading below 3 mol% exhibited 1 st order rate dependence. Furthermore, a photoinitiating system consisting of camphorquinone resulted in 60% conversion in the dark after only 1 minute of 75 mW cm -2 light exposure at 400-500 nm, highlighting a unique characteristic of the CuAAC photopolymerization enabled by the combination of the copper(i)'s catalytic lifetime and the nature of the step-growth polymerization.

A Study of Functional Polymer Colloids Prepared Using Thiol-Ene/Yne Click Chemistry

NASA Astrophysics Data System (ADS)

Durham, Olivia Z.

This project demonstrates the first instance of thiol-ene chemistry as the polymerization method for the production of polymer colloids in two-phase heterogeneous suspensions, miniemulsions, and emulsions. This work was also expanded to thiol-yne chemistry for the production of polymer particles containing increased crosslinking density. The utility of thiol-ene and thiol-yne chemistries for polymerization and polymer modification is well established in bulk systems. These reactions are considered 'click' reactions, which can be defined as processes that are both facile and simple, offering high yields with nearly 100% conversion, no side products, easy product separation, compatibility with a diverse variety of commercially available starting materials, and orthogonality with other chemistries. In addition, thiol-ene and thiol-yne chemistry follow a step-growth mechanism for the development of highly uniform polymer networks, where polymer growth is dependent on the coupling of functional groups. These step-growth polymerization systems are in stark contrast to the chain-growth mechanisms of acrylic and styrenic monomers that have dominated the field of conventional heterogeneous polymerizations. Preliminary studies evaluated the mechanism of particle production in suspension and miniemulsion systems. Monomer droplets were compared to the final polymer particles to confirm that particle growth occurred through the polymerization of monomer droplets. Additional parameters examined include homogenization energy (mechanical mixing), diluent species and concentration, and monomer content. These reactions were conducted using photoinitiation to yield particles in a matter of minutes with diameters in the size range of several microns to hundreds of microns in suspensions or submicron particles in miniemulsions. Improved control over the particle size and size distribution was examined through variation of reaction parameters. In addition, a method of seeded suspension polymerization was attempted. This project was further expanded through an extensive evaluation of stabilizers in thiol-ene suspension polymerizations. The scope of stabilizers used included synthetic surfactants (ionic and nonionic), natural gums, and colloidal silica (Pickering stabilization). Suspension polymerizations were further expanded to include thiol-yne chemistry for the evaluation of polymer composition and thermal properties. In addition, polymer particles with excess ene, yne, or thiol functionality were successfully developed to demonstrate the potential for further functionalization. The self-limiting behavior of thiol-ene/yne reactions allows for successful synthesis of functional polymer colloids using off-stoichiometric amounts of monomers. This capacity to control functionality is illustrated through the creation of fluorescent polymer particles using both an in situ thiol-ene polymerization reaction with a vinyl chromophore as well as through post-polymerization modification of thiol-ene and thiol-yne polymers with excess thiol functionality via thiol-isocyanate chemistry. To produce smaller polymer particles without the need for intense homogenization energy or high stabilizer concentrations, an emulsion polymerization system was implemented using a water soluble-thermal initiator. It was found that unlike thiol-ene suspensions, which are limited to crosslinked systems, thiol-ene emulsion polymerizations allowed for the production of polymer particles comprised of either crosslinked or linear polymer networks. For the crosslinked systems, various anionic SDS surfactant concentrations were examined to observe the influence on particle size. In linear polymer systems, variations in polymer composition were examined. Preliminary studies performed with a monomer with an ethylene glycol-like structure indicated that the synthesis of polymer particles with narrower size distributions compared to any of the other emulsion compositions was possible. Finally, thiol-ene chemistry was also employed toward the synthesis of degradable polyanhydride polymer particles. Unlike the aforementioned studies, the approach to particle synthesis was conducted by using a premade thiol-ene polymer. Various linear thiol-ene polyanhydrides were emulsified in water or buffered solutions via sonication. Polymer latex was obtained upon solvent evaporation of the dichloromethane (DCM) solvent used to solubilize the polymer. In this work, variation of polymer composition as well as degradation was examined. Additional experiments included a study of the release of Rhodamine B dye, functionalization of the linear polymers, and studies involving the delay of degradation through the incorporation of crosslinking in the polymer particles. The projects presented herein provide an innovative approach to the synthesis of polymer colloids using thiol-ene and thiol-yne 'click' chemistry in both heterogeneous polymerizations as well as through solvent evaporation of premade polymer solutions. Polymer colloids prove to be an area of great interest for numerous applications that encompass various areas involving biomedical and industrial technologies including paints and coatings, cosmetics, diagnostics, and drug delivery. Improvements in methods of chemical synthesis as well as advances in the tailoring of material properties are of utmost importance for the ever increasing demands of new technologies and educational enlightenment.

A Self-Reporting Photocatalyst for Online Fluorescence Monitoring of High Throughput RAFT Polymerization.

PubMed

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.

Time-Dependent Effect of Refrigeration on Viscosity and Conversion Kinetics of Dental Adhesive Resins

PubMed Central

Faria-e-Silva, André L; Piva, Evandro; Moraes, Rafael R

2010-01-01

Objectives: This study evaluated the effect of refrigeration at 4°C and post-refrigeration times (immediate, 5, 10, 15, or 20 min) on the viscosity and conversion kinetics of adhesive bonding resins. Methods: Scotchbond Dual-Cure (3M ESPE) and Clearfil SE Bond (Kuraray) were tested. Control samples were kept at 25°C for 24 h. At each post-refrigeration time, the temperature was checked with a K-type thermocouple. Viscosity measurements as a function of temperature were performed using a cone-plate viscometer. Real-time polymerization was monitored by infrared spectroscopy. Degree of conversion (DC) was calculated for each second during polymerization, and the rate of polymerization analyzed. Data were separately submitted to two-way ANOVA and Tukey’s test (P<.05). Results: Clearfil presented faster increase in temperature after exposure to room temperature than Scotchbond. A continuous decrease in viscosity (Pa.s) was observed for both Scotchbond (0.49, 0.34, 0.30, 0.26, 0.23, 0.23) and Clearfil (0.38, 0.37, 0.34, 0.25, 0.24, 0.22). For Scotchbond, higher final DC was detected for the control (62.7%) compared with the immediate (53.3%) and 5 min (54.7%) groups. For Clearfil, the control sample (81.4%) showed higher DC than all refrigerated groups (68.8–69.5%). Clearfil always showed significantly higher DC than Scotchbond. Conclusions: Refrigeration presented a significant time- and material-dependent effect on the viscosity and polymerization kinetics of the bonding resins. Under clinical conditions, adhesive agents should be removed from the refrigerator at least 20 min before being used. PMID:20396445

Understanding How the Presence of Uniform Electric Fields Can Shift the Miscibility of Polystyrene/Poly(vinyl methyl ether) Blends

NASA Astrophysics Data System (ADS)

Kriisa, Annika; Roth, Connie B.

2015-03-01

Techniques which can externally control and manipulate the phase behavior of polymeric systems, without altering chemistry on a molecular level, have great practical benefits. One such possible mechanism is the use of electric fields, shown to cause interfacial instabilities, orientation of morphologies, and phase transitions in polymer blends and block copolymers. We have recently demonstrated that the presence of uniform electric fields can also strongly enhance the miscibility of polystyrene (PS) / poly(vinyl methyl ether) (PVME) blends [J. Chem. Phys. 2014, 141, 134908]. Using fluorescence to measure the phase separation temperature Ts of PS/PVME blends with and without electric fields, we show that Ts can be reproducibly and reversibly increased by 13.5 +/- 1.4 K for electric fields of 17 kV/mm for this lower critical solution temperature (LCST) blend. This increase in blend miscibility with electric fields represents some of the largest absolute shifts in Ts ever recorded, well outside of experimental error. The best theoretical prediction for the expected shift in Ts with electric field for this system is still two orders of magnitude smaller than that observed experimentally. We discuss the limitations of this theoretical prediction and consider possible factors affecting miscibility that may need to be also included.

Thermal Conductivity of Polymer Copoly(Ethylene Vinyl Acetate)/Nano-Filler Blends

NASA Technical Reports Server (NTRS)

Ghose, S.; Watson, K. A.; Working, D. C.; Connell, J. W.; Smith, J. G., Jr.; Lin, Y.; Sun, Y. P.

2007-01-01

The development of flexible, thermally conductive fabrics and plastic tubes for the Liquid Cooling and Ventilation Garment (LCVG) are needed to reduce weight and improve the mobility, comfort, and performance of future spacesuits. Such improvements would allow astronauts to operate more efficiently and safely for extended extravehicular activities. As a continuation of our work on the improvement of thermal conductivity (TC) of polymeric materials, nanocomposites were prepared from copoly(ethylene vinyl acetate), trade name Elvax 260 , metallized carbon nanofibers (CNFs), nickel (Ni) nanostrands, boron nitride both alone and as mixtures with aluminum powder. The nanocomposites were prepared by melt mixing at various loading levels and subsequently fabricated into several material forms (i.e., ribbons, tubes, and compression molded plaques) for analysis. Ribbons and tubes were extruded to form samples in which the nanoparticles were aligned in the direction of flow. The degree of dispersion and alignment of the nanoparticles were investigated using high-resolution scanning electron microscopy. Tensile properties of the aligned samples were determined at room temperature. TC measurements were performed using a laser flash (Nanoflash ) technique. The TC of the samples was measured in both the direction of alignment as well as transverse. Tubing of comparable dimensions to that used in the LCVG was extruded from select compositions and the thermal conductivities of the tubes measured.

Next generation ultrasound platforms for theranostics.

PubMed

Oddo, Letizia; Cerroni, Barbara; Domenici, Fabio; Bedini, Angelico; Bordi, Federico; Chiessi, Ester; Gerbes, Stefan; Paradossi, Gaio

2017-04-01

Microbubbles are a well-established contrast agent which improves diagnostic ultrasound imaging. During the last decade research has focused on expanding their use to include molecular imaging, targeted therapy and imaging modalities other than ultrasound. However, bioadhesion of targeted microbubbles under physiological flow conditions is still difficult to achieve, the main challenge being connected to the poor stability of lipid microbubbles in the body's circulation system. In this article, we investigate the use of polymeric microbubbles based on a poly (vinyl alcohol) shell as an alternative to lipid microbubbles. In particular, we report on the development of microbubble shell modification, using mild reaction conditions, with the aim of designing a multifunctional platform to enable diagnosis and therapy. Superparamagnetic iron oxide nanoparticles and a near infrared fluorescent probe, indocyanine green, are coupled to the bubbles surface in order to support magnetic resonance and fluorescence imaging. Furthermore, anchoring cyclic arginyl-glycyl-aspartic acid (RGD) peptide, and cyclodextrin molecules, allows targeting and drug loading, respectively. Last but not least, shell topography is provided by atomic force microscopy. These applications and features, together with the high echogenicity of poly (vinyl alcohol) microbubbles, may offer a more stable alternative to lipid microbubbles for the development of a multimodal theranostic platform. Copyright © 2016 Elsevier Inc. All rights reserved.

Characterization of hydrophilic-rich phase mimic in dentin adhesive and computer-aided molecular design of water compatible visible light initiators

NASA Astrophysics Data System (ADS)

Abedin, Farhana

The clinical lifetime of moderate-to-large dental composite restorations is lower than dental amalgam restorations. With the imminent and significant reduction in the use and availability of dental amalgam, the application of composite for the restoration of teeth will increase. Since composite has a higher failure rate, the increased use of composite will translate to an increase in the frequency of dental restoration replacement, overall cost for dental health and discomfort for patients. The composite is too viscous to bond directly to the tooth and thus, a low viscosity adhesive is used to form the bond between the composite and tooth. The bond at the adhesive/tooth is intended to form an impervious seal that protects the restored tooth from acids, oral fluids and bacteria that will undermine the composite restoration. The integrity of the adhesive/tooth bond (the exposed tooth structure is largely composed of enamel and dentin) plays an important role in preventing secondary caries which undermine the composite restoration. This study focuses on the durability of etch-and-rinse dental adhesives. As the adhesive infiltrates the demineralized dentin matrix, it undergoes phase separation into hydrophobic- and hydrophilic-rich phases. The hydrophilic-rich phase contains the conventional hydrophobic photo-initiator system (camphorquinone/ethyl 4-(dimethylamino)benzoate) and cross-linker both in inadequate concentrations. This may compromise the polymerization reaction and the cross-linking density of this phase, making it vulnerable to failure. The goal of this study is to characterize the hydrophilic-rich phase of the dental adhesive by monitoring its polymerization kinetics and glass transition temperature under the presence of an iodonium salt (reaction accelerator), and varying water concentration, photo-initiator concentration and light intensity. The final goal is to develop a computational framework for designing water compatible visible light photosensitizers specifically for the hydrophilic-rich phase of dental adhesives. It was observed that the degree of conversion of the hydrophilic-rich mimics is dominated by the photo-initiator concentration and not the cross-linker. A secondary rate maxima was observed in the case of hydrophilic-rich phase mimics which was associated with the formation of microgels during polymerization. A polymerization mechanism involving polymerization- and solvent-induced phase separation was proposed for the hydrophilic-rich mimics. The hydrophilic dental resins were sensitive to light intensity, i.e. at low light intensities the degree of conversion of the hydrophilic resin was reduced substantially in the presence of camphorquinone/ethyl 4-(dimethylamino)benzoate as photo-initiators, whereas a substantial degree of conversion was observed for the hydrophobic resin even at these lower light intensities. The addition of iodonium salt in the hydrophilic resin significantly improved the degree of conversion of the hydrophilic resin at low light intensities. These studies also showed that the iodonium salt could lead to enhanced cyclization and shorter polymer chain lengths within the hydrophilic-rich phase. For the physically separated hydrophilic-rich phase specimens, it was observed that in the presence of the conventional photo-initiator system (camphorquinone/ethyl 4-(dimethylamino)benzoate), there was no polymerization, mostly due to the insufficient partition concentrations of the photo-initiator components within this phase. The addition of iodoinum salt in this case significantly improved the degree of conversion but it was still significantly lower. These studies indicated that the overall polymerization efficiency of the hydrophilic-rich phase was lower than the hydrophobic-rich phase. The lower polymerization efficiency of the hydrophilic-rich phase led to a phase that lacks integrity; the hydrophilic-rich phase could be infiltrated by oral fluids and cariogenic bacteria. The infiltration of these noxious agents at the interface between the material and tooth could pave the way for enhanced degradation of the tooth structure (collagen and mineral) as well as the adhesive polymer. Novel photosensitizer molecules were proposed to improve the polymerization efficiency of this phase. Computer-aided molecular design (CAMD) was employed to obtain the new photosensitizers. These photosensitizers were capable of improving the degree of conversion of the hydrophilic-rich phase. An enhanced degree of conversion of the hydrophilic-rich phase would lead to a better seal at the adhesive/dentin interface and higher bond strength. Computer-aided molecular design (CAMD) is a fast and inexpensive technique compared to the conventional trial-and-error method to rationally design products. (Abstract shortened by ProQuest.).

Nanofibrous nonmulberry silk/PVA scaffold for osteoinduction and osseointegration.

PubMed

Bhattacharjee, Promita; Kundu, Banani; Naskar, Deboki; Maiti, Tapas K; Bhattacharya, Debasis; Kundu, Subhas C

2015-05-01

Poly-vinyl alcohol and nonmulberry tasar silk fibroin of Antheraea mylitta are blended to fabricate nanofibrous scaffolds for bone regeneration. Nanofibrous matrices are prepared by electrospinning the equal volume ratio blends of silk fibroin (2 and 4 wt%) with poly-vinyl alcohol solution (10 wt%) and designated as 2SF/PVA and 4SF/PVA, respectively with average nanofiber diameters of 177 ± 13 nm (2SF/PVA) and 193 ± 17 nm (4SF/PVA). Fourier transform infrared spectroscopy confirms retention of the secondary structure of fibroin in blends indicating the structural stability of neo-matrix. Both thermal stability and contact angle of the blends decrease with increasing fibroin percentage. Conversely, fibroin imparts mechanical stability to the blends; greater tensile strength is observed with increasing fibroin concentration. Blended scaffolds are biodegradable and support well the neo-bone matrix synthesis by human osteoblast like cells. The findings indicate the potentiality of nanofibrous scaffolds of nonmulberry fibroin as bone scaffolding material. © 2014 Wiley Periodicals, Inc.

Is the Chemical Strategy for Imbuing "Polyene" Character in Diketopyrrolopyrrole-Based Chromophores Sufficient for Singlet Fission?

PubMed

Mukhopadhyay, Tushita; Musser, Andrew J; Puttaraju, Boregowda; Dhar, Joydeep; Friend, Richard H; Patil, Satish

2017-03-02

In this work, we have rationally designed and synthesized a novel thiophene-diketopyrrolopyrrole (TDPP)-vinyl-based dimer. We have investigated the optical and electronic properties and have probed the photophysical dynamics using transient absorption to investigate the possibility of singlet exciton fission. These revealed extremely rapid decay to the ground state (<50 ps), which we confirm is due to intramolecular excitonic processes rather than large-scale conformational change enabled by the vinyl linker. In all cases, the main excited state appears to be "dark", suggesting rapid internal conversion into a dark 2A g -type singlet state. We found no evidence of triplet formation in TDPP-V-TDPP under direct photoexcitation. This may be a consequence of significant singlet stabilization in the dimer, bringing it below the energy needed to form two triplets. Our studies on this model compound set valuable lessons for design of novel triplet-forming materials and highlight the need for more broadly applicable design principles.

Facile Preparation of Doxorubicin-Loaded and Folic Acid-Conjugated Carbon Nanotubes@Poly(N-vinyl pyrrole) for Targeted Synergistic Chemo-Photothermal Cancer Treatment.

PubMed

Wang, Daquan; Ren, Yibo; Shao, Yongping; Yu, Demei; Meng, Lingjie

2017-11-15

We developed a bifunctional nanoplatform for targeted synergistic chemo-photothermal cancer treatment. The nanoplatform was constructed through a facile method in which poly(N-vinyl pyrrole) (PVPy) was coated on cut multiwalled carbon nanotubes (c-MWNTs); FA-PEG-SH was then linked by thiol-ene click reaction to improve the active targeting ability, water dispersibility, and biocompatibility and to extend the circulation time in blood. The PVPy shell not only enhanced the photothermal effect of c-MWNTs significantly but also provided a surface that could tailor targeting molecules and drugs. The resulting MWNT@PVPy-S-PEG-FA possessed high drug-loading ratio as well as pH-sensitive unloading capacity for a broad-spectrum anticancer agent, doxorubicin. Owing to its outstanding efficiency in photothermal conversion and ability in targeted drug delivery, the material could potentially be used as an efficient chemo-photothermal therapeutic nanoagent to treat cancer.

Ring-opening polymerization of DD-lactide catalyzed by Novozyme 435.

PubMed

Hans, Marc; Keul, Helmut; Moeller, Martin

2009-03-10

In contrast to LLA, DLA is converted in toluene solution under mild reaction conditions (50-70 degrees C) using Novozyme 435 (immobilized CALB) to form the corresponding polymer. The influence of several parameters, such as enzyme concentration, temperature and monomer concentration, on the polymerization rate and the monomer conversion was studied. In contrast to the Novozyme 435 catalyzed polymerization of epsilon-caprolactone, enzyme deactivation occurs. It is attributed to the deprivation of water from the enzyme. This work points out that by careful selection of the reaction conditions, it is possible to obtain poly(D-lactide) in reasonable molecular weights and in high yields using Novozyme 435 catalysis.

4-Vinyl-1,3-Dioxolane-2-One as an Additive for Li-Ion Cells

NASA Technical Reports Server (NTRS)

Smart, Marshall; Bugga, Ratnakumar

2006-01-01

Electrolyte additive 4-vinyl-1,3-dioxolane-2-one has been found to be promising for rechargeable lithium-ion electrochemical cells. This and other additives, along with advanced electrolytes comprising solutions of LiPF6 in various mixtures of carbonate solvents, have been investigated in a continuing effort to improve the performances of rechargeable lithium-ion electrochemical cells, especially at low temperatures. In contrast to work by other researchers who have investigated the use of this additive to improve the high-temperature resilience of Li-ion cells, the current work involves the incorporation of 4-vinyl-1,3-dioxolane-2-one into quaternary carbonate electrolyte mixtures, previously optimized for low-temperature applications, resulting in improved low-temperature performance. The benefit afforded by 4-vinyl-1,3- dioxolane-2-one can be better understood in the light of relevant information from a number of prior NASA Tech Briefs articles about electrolytes and additives for such cells. To recapitulate: The loss of performance with decreasing temperature is attributable largely to a decrease of ionic conductivity and the increase in viscosity of the electrolyte. What is needed to extend the lower limit of operating temperature is a stable electrolyte solution with relatively small lowtemperature viscosity, a large electric permittivity, adequate coordination behavior, and appropriate ranges of solubilities of liquid and salt constituents. Whether the anode is made of graphitic or non-graphitic carbon, a film on the surface of the anode acts as a solid/electrolyte interface (SEI), the nature of which is critical to low-temperature performance. Desirably, the surface film should exert a chemically protective (passivating) effect on both the anode and the electrolyte, yet should remain conductive to lithium ions to facilitate intercalation and de-intercalation of the ions into and out of the carbon during discharging and charging, respectively. The additives investigated previously include alkyl pyrocarbonates. Those additives help to improve low-temperature performances by giving rise to the formation of SEIs having desired properties. The formation of the SEIs is believed to be facilitated by products (e.g., CO2) of the decomposition of these additives. These decomposition products are believed to react to form Li2CO3-based films on the carbon electrodes. The present additive, 4-vinyl-1,3-dioxolane-2-one, also helps to improve lowtemperature performance by contributing to the formation of SEIs having desired properties, but probably in a different manner: It is believed that, as part of the decomposition process, the compound polymerizes on the surfaces of carbon electrodes.

Mechanistic Kinetic Modeling of Thiol-Michael Addition Photopolymerizations via Photocaged "Superbase" Generators: An Analytical Approach.

PubMed

Claudino, Mauro; Zhang, Xinpeng; Alim, Marvin D; Podgórski, Maciej; Bowman, Christopher N

2016-11-08

A kinetic mechanism and the accompanying mathematical framework are presented for base-mediated thiol-Michael photopolymerization kinetics involving a photobase generator. Here, model kinetic predictions demonstrate excellent agreement with a representative experimental system composed of 2-(2-nitrophenyl)propyloxycarbonyl-1,1,3,3-tetramethylguanidine (NPPOC-TMG) as a photobase generator that is used to initiate thiol-vinyl sulfone Michael addition reactions and polymerizations. Modeling equations derived from a basic mechanistic scheme indicate overall polymerization rates that follow a pseudo-first-order kinetic process in the base and coreactant concentrations, controlled by the ratio of the propagation to chain-transfer kinetic parameters ( k p / k CT ) which is dictated by the rate-limiting step and controls the time necessary to reach gelation. Gelation occurs earlier as the k p / k CT ratio reaches a critical value, wherefrom gel times become nearly independent of k p / k CT . The theoretical approach allowed determining the effect of induction time on the reaction kinetics due to initial acid-base neutralization for the photogenerated base caused by the presence of protic contaminants. Such inhibition kinetics may be challenging for reaction systems that require high curing rates but are relevant for chemical systems that need to remain kinetically dormant until activated although at the ultimate cost of lower polymerization rates. The pure step-growth character of this living polymerization and the exhibited kinetics provide unique potential for extended dark-cure reactions and uniform material properties. The general kinetic model is applicable to photobase initiators where photolysis follows a unimolecular cleavage process releasing a strong base catalyst without cogeneration of intermediate radical species.

Transportation and Accumulation of Redox Active Species at the Buried Interfaces of Plasticized Membrane Electrodes.

PubMed

Sohail, Manzar; De Marco, Roland; Jarolímová, Zdeňka; Pawlak, Marcin; Bakker, Eric; He, Ning; Latonen, Rose-Marie; Lindfors, Tom; Bobacka, Johan

2015-09-29

The transportation and accumulation of redox active species at the buried interface between glassy carbon electrodes and plasticized polymeric membranes have been studied using synchrotron radiation X-ray photoelectron spectroscopy (SR-XPS), near edge X-ray absorption fine structure (NEXAFS), in situ electrochemical Fourier transform infrared-attenuated total reflectance (FTIR-ATR) spectroscopy, cyclic voltammetry (CV), chronoamperometry (CA), and electrochemical impedance spectroscopy (EIS). Ferrocene tagged poly(vinyl chloride) [FcPVC], ferrocene (Fc), and its derivatives together with tetracyanoquinodimethane (TCNQ) doped plasticized polymeric membrane electrodes have been investigated, so as to extend the study of the mechanism of this reaction chemistry to different time scales (both small and large molecules with variable diffusion coefficients) using a range of complementary electrochemical and surface analysis techniques. This study also provides direct spectroscopic evidence for the transportation and electrochemical reactivity of redox active species, regardless of the size of the electrochemically reactive molecule, at the buried interface of the substrate electrode. With all redox dopants, when CA electrolysis was performed, redox active species were undetectable (<1 wt % of signature elements or below the detection limit of SR-XPS and NEXAFS) in the outermost surface layers of the membrane, while a high concentration of redox species was located at the electrode substrate as a consequence of the deposition of the reaction product (Fc(+)-anion complex) at the buried interface between the electrode and the membrane. This reaction chemistry for redox active species within plasticized polymeric membranes may be useful in the fashioning of multilayered polymeric devices (e.g., chemical sensors, organic electronic devices, protective laminates, etc.) based on an electrochemical tunable deposition of redox molecules at the buried substrate electrode beneath the membrane.

Characterization of ultrahigh-molecular weight cationic polyacrylamide using frit-inlet asymmetrical flow field-flow fractionation and multi-angle light scattering.

PubMed

Woo, Sohee; Lee, Ju Yong; Choi, Woonjin; Moon, Myeong Hee

2016-01-15

In this study, frit inlet asymmetrical flow field-flow fractionation (FlFFF) with multi-angle light scattering (MALS) and differential refractive index (DRI) detection is utilized for size separation, determination of molecular weight (MW), and conformation of ultrahigh-MW (10(7)-10(9) g/mol) cationic polyacrylamides (C-PAMs), a class of water-soluble copolymers based on acrylamide and vinyl-type comonomers with quaternary ammonium cations that are widely used in wastewater treatment and in paper industries. Linear and branched C-PAM copolymers prepared in two different polymerization methods (solution and emulsion) from varying amounts of crosslinking agent and initiator were size fractionated by FlFFF with field-programming. It was found experimentally that the linear copolymers from both polymerization methods were less than 10(8) g/mol in MW with compact, nearly spherical structures, while the branched C-PAM copolymers from the emulsion polymerization showed a significant increase in average MW up to ∼ 10(9)g/mol, which was about 20-fold greater than those from the solution method, and the branched copolymers had more compact or shrunken conformations. While both linear and branched copolymers less than 10(8) g/mol MW were well resolved in an increasing order of MW (normal mode), it was noted that branched copolymers prepared through emulsion polymerization exhibited significantly larger MWs of 10(8-)10(9) g/mol and eluted in the steric/hyperlayer mode, in which the elution order is reversed in an extreme run condition (strong initial field strength followed by a fast field decay during programming). Copyright © 2015 Elsevier B.V. All rights reserved.

Polymer-Based Black Phosphorus (bP) Hybrid Materials by in Situ Radical Polymerization: An Effective Tool To Exfoliate bP and Stabilize bP Nanoflakes

PubMed Central

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.

Polymeric ionic liquid coatings versus commercial solid-phase microextraction coatings for the determination of volatile compounds in cheeses.

PubMed

Trujillo-Rodríguez, María J; Yu, Honglian; Cole, William T S; Ho, Tien D; Pino, Verónica; Anderson, Jared L; Afonso, Ana M

2014-04-01

The extraction performance of four polymeric ionic liquid (PIL)-based solid-phase microextraction (SPME) coatings has been studied and compared to that of commercial SPME coatings for the extraction of 16 volatile compounds in cheeses. The analytes include 2 free fatty acids, 2 aldehydes, 2 ketones and 10 phenols and were determined by headspace (HS)-SPME coupled to gas chromatography (GC) with flame-ionization detection (FID). The PIL-based coatings produced by UV co-polymerization were more efficient than PIL-based coatings produced by thermal AIBN polymerization. Partition coefficients of analytes between the sample and the coating (Kfs) were estimated for all PIL-based coatings and the commercial SPME fiber showing the best performance among the commercial fibers tested: carboxen-polydimethylsyloxane (CAR-PDMS). For the PIL-based fibers, the highest K(fs) value (1.96 ± 0.03) was obtained for eugenol. The normalized calibration slope, which takes into account the SPME coating thickness, was also used as a simpler approximate tool to compare the nature of the coating within the determinations, with results entirely comparable to those obtained with estimated K(fs) values. The PIL-based materials obtained by UV co-polymerization containing the 1-vinyl-3-hexylimidazolium chloride IL monomer and 1,12-di(3-vinylimiazolium)dodecane dibromide IL crosslinker exhibited the best performance in the extraction of the select analytes from cheeses. Despite a coating thickness of only 7 µm, this copolymeric sorbent coating was capable of quantitating analytes in HS-SPME in a 30 to 2000 µg L(-1) concentration range, with correlation coefficient (R) values higher than 0.9938, inter-day precision values (as relative standard deviation in %) varying from 6.1 to 20%, and detection limits down to 1.6 µg L(-1). Copyright © 2013 Elsevier B.V. All rights reserved.

[Polymer Gel Dosimeter].

PubMed

Hayashi, Shin-Ichiro

2017-01-01

With rapid advances being made in radiotherapy treatment, three-dimensional (3D) dose measurement techniques of great precision are required more than ever before. It is expected that 3D polymer gel dosimeters will satisfy clinical needs for an effective detector that can measure the complex 3D dose distributions. Polymer gel dosimeters are devices that utilize the radiation-induced polymerization reactions of vinyl monomers in a gel to store information about radiation dose. The 3D absorbed dose distribution can be deduced from the resulting polymer distribution using several imaging modalities, such as MRI, X-ray and optical CTs. In this article, the fundamental characteristics of polymer gel dosimeter are reviewed and some challenging keys are also suggested for the widely spread in clinical use.

Can nature's design be improved upon? High strength, transparent nacre-like nanocomposites with double network of sacrificial cross links.

PubMed

Podsiadlo, Paul; Kaushik, Amit K; Shim, Bong Sup; Agarwal, Ashish; Tang, Zhiyong; Waas, Anthony M; Arruda, Ellen M; Kotov, Nicholas A

2008-11-20

The preparation of a high-strength and highly transparent nacre-like nanocomposite via layer-by-layer assembly technique from poly(vinyl alcohol) (PVA) and Na+-montmorillonite clay nanosheets is reported in this article. We show that a high density of weak bonding interactions between the polymer and the clay particles: hydrogen, dipole-induced dipole, and van der Waals undergoing break-reform deformations, can lead to high strength nanocomposites: sigmaUTS approximately 150 MPa and E' approximately 13 GPa. Further introduction of ionic bonds into the polymeric matrix creates a double network of sacrificial bonds which dramatically increases the mechanical properties: sigmaUTS approximately 320 MPa and E' approximately 60 GPa.

[Prolonged-release drug formulations for parenteral administration. Part II. Microspheres and implants for injection].

PubMed

Płaczek, Margin; Jacyna, Julia; Sznitowska, Małgorzata

2014-01-01

Microspheres and implants are injectable drug forms, which by special design and selection of appropriate excipients, provide for a long time constant release rate of an active substance in the body. Development of both would not be possible without advances in polymer technology and invention of safe and biocompatible polymers such as: polyesters, vinyl acetate derivatives or silicones. Polymeric matrices provide retardation of drug release--for some implants up to a few years. In addition, this paper presents examples of all commercially available medicinal products containing microspheres and implants, currently registered in Poland, together with their characteristics: composition, time course and frequency of administration. Comments are also enclosed on frequently occurring inconsistent terminology in pharmaceutical forms.

Numerical-experimental investigation of PE/EVA foam injection molded parts

NASA Astrophysics Data System (ADS)

Spina, Roberto

The main objective of the presented work is to propose a robust framework to test foaming injection molded parts, with the aim of establishing a standard testing cycle for the evaluation of a new foam material based on numerical and experimental results. The research purpose is to assess parameters influencing several aspects, such as foam morphology and compression behavior, using useful suggestions from finite element analysis. The investigated polymeric blend consisted of a mixture of low density polyethylenes (LDPEs), a high-density polyethylene (HDPE), an ethylene-vinyl acetate (EVA) and an azodicarbonamide (ADC). The thermal, rheological and compression properties of the blend are fully described, as well as the numerical models and the parameters of the injection molding process.

Reversible addition-fragmentation chain transfer polymerization of N-isopropylacrylamide: a comparison between a conventional and a fast initiator.

PubMed

Bouchékif, Hassen; Narain, Ravin

2007-09-27

The reversible addition-fragmentation chain transfer (RAFT) polymerization of N-isopropylacrylamide (NIPAM) was studied to determine the reasons for deviation of experimental molecular weights to lower molecular weight at high monomer conversion when S-1-dodecyl-S-(alpha,alpha'-dimethyl-alpha' '-acetic acid)trithiocarbonate (CTAm) and S,S-bis(alpha,alpha'-dimethyl-alpha' '-acetic acid)trithiocarbonate (CTAd) were used as RAFT agents at 65 degrees C. For this purpose, experiments were performed in N,N'-dimethylformamide (DMF) at the NIPAM/CTA ratio of 200 with initiators capable of yielding fast and slow initiation, respectively by photochemical and thermal process, either at ambient temperature or at 65 degrees C. When the polymerization of NIPAM was conducted under these conditions with Irgacure-2959 (IRGC) as photoinitiator, a continuing supply of primary radicals by incremental initiator addition was required to achieve reasonably high conversion. This effect was also apparent by the loss of linearity of the first-order kinetic plot with a conventional initiator (4,4-azobis(4-cyanovaleric acid) (ACVA) as azo-initiator, 10h (t1/2) decomposition at 65 degrees C) indicating that steady-state concentration of the macroradical decreases significantly with the initiator consumption. Nevertheless, polymers with predictable number-average molecular weight Mn (i.e., based on [monomer]/([CTA] + [initiator]) ratio) and narrow polydispersities were obtained (PDIs < 1.2) with CTAm indicating that the process of chain growth was controlled. When CTAd was used, instead of CTAm, the polymers obtained were characterized by a larger polydispersity (1.2 < PDIs < 1.3). The so-called "living steady-state concentration" in chain equilibration together with the linear dependence of Mn vs conversion was observed only when the 200/1 NIPAM/CTA mixture in DMF was subjected to a permanent photoirradiation at 65 degrees C. With ACVA, the deviation of the experimentally measured molecular weights at high conversion was accounted for by the simultaneous self-initiated polymerization of NIPAM with the controlled process in the presence of CTA at 65 degrees C. Similar drift from the linear dependence Mn vs conversion was also observed at 65 degrees C when a significant number of low molecular weight polymer chains were generated intentionally by photodecomposition of IRGC.

21 CFR 177.1360 - Ethylene-vinyl acetate-vinyl alcohol copolymers.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Ethylene-vinyl acetate-vinyl alcohol copolymers... for Use as Basic Components of Single and Repeated Use Food Contact Surfaces § 177.1360 Ethylene-vinyl acetate-vinyl alcohol copolymers. Ethylene-vinyl acetate-vinyl alcohol copolymers (CAS Reg. No. 26221-27-2...

Design of smart optical sensor using polyvinyl alcohol/Fluorescein sodium salt: Laser filters and optical limiting effect

NASA Astrophysics Data System (ADS)

Yahia, I. S.; Bouzidi, A.; Zahran, H. Y.; Jilani, W.; AlFaify, S.; Algarni, H.; Guermazi, H.

2018-03-01

Pure poly (vinyl alcohol) (PVA) and PVA doped Fluorescein-Sodium salt (FSS/PVA composite films) have synthesized on wide scale laser optical filters. The investigated polymeric composite films have been characterized using several methods. The XRD patterns exhibit a decrease of the average crystalline size and an increase of the internal strain, which explained the imperfection and distortion in the prepared films. The optical characterizations showed a decrease in the transmission of the incident light for different samples, which may be explained to the layer formed by intermolecular hydrogen bonding between the PVA matrix and the FSS particles. The FSS/PVA polymeric composite films are being a completely blocking in the UV-Vis light at the range between 190 and 560 nm, agreement with the optical limiting effect, which makes the composite films suitable for CUT-OFF laser filters applications. The decrease in its, directly and indirectly, allowed transition band gaps were controlled by the added FSS dyes molecules. The variation of the exponent frequency (s) of the power law for FSS/PVA polymeric composite films has been characterized to improve the hopping conduction mechanism in the materials. The dielectric permittivity (e‧) and dielectric loss (e'') have been decreased with increasing the applied frequency, and the incorporated FSS molecules due to the DC electric conductivity can cause the decreases of the polarization of the as-prepared films over the studied ranges.

Boron Nitride Nanotubes and Nanoplatelets as Reinforcing Agents of Polymeric Matrices for Bone Tissue Engineering

PubMed Central

Farshid, Behzad; Lalwani, Gaurav; Mohammadi, Meisam Shir; Simonsen, John; Sitharaman, Balaji

2016-01-01

This study investigates the mechanical properties and in vitro cytotoxicity of one- and two-dimensional boron nitride nanomaterials-reinforced biodegradable polymeric nanocomposites. Poly(propylene fumarate) (PPF) nanocomposites were fabricated using crosslinking agent N-vinyl pyrrolidone (NVP) and inorganic nanomaterials: boron nitride nanotubes (BNNTs) and boron nitride nanoplatelets (BNNPs) dispersed at 0.2 wt.% in the polymeric matrix. The incorporation of BNNPs and BNNTs resulted in a ~38% and ~15% increase in compressive (young's) modulus, and ~31% and ~6% increase in compressive yield strength compared to PPF control, respectively. The nanocomposites showed a time-dependent increased protein adsorption for only collagen-I protein. The cytotoxicity evaluation of aqueous BNNT and BNNP dispersions (at 1-100 μg/mL concentrations) using a representative murine MC3T3 preosteoblast cell line showed cytocompatibility of BNNTs and BNNPs (~73-99% viability). The cytotoxicity evaluation of media extracts of nanocomposites prior to crosslinking, after crosslinking and upon degradation (using 1X-100X dilutions) showed dose-dependent cytotoxicity responses. Crosslinked nanocomposites showed excellent (~79-100%) cell viability, cellular attachment (~57-67%), and spreading similar to cells grown on the surface of tissue culture polystyrene (TCPS) control. The media extracts of degradation products showed a dose-dependent cytotoxicity. The favorable cytocompatibility results in combination with improved mechanical properties of BNNT and BNNP nanocomposites opens new avenues for further in vitro and in vivo safety and efficacy studies for their bone tissue engineering applications. PMID:26526153

Crosslinked polymeric ionic liquids as solid-phase microextraction sorbent coatings for high performance liquid chromatography.

PubMed

Yu, Honglian; Merib, Josias; Anderson, Jared L

2016-03-18

Neat crosslinked polymeric ionic liquid (PIL) sorbent coatings for solid-phase microextraction (SPME) compatible with high-performance liquid chromatography (HPLC) are reported for the first time. Six structurally different PILs were crosslinked to nitinol supports and applied for the determination of select pharmaceutical drugs, phenolics, and insecticides. Sampling conditions including sample solution pH, extraction time, desorption solvent, desorption time, and desorption solvent volume were optimized using design of experiment (DOE). The developed PIL sorbent coatings were stable when performing extractions under acidic pH and remained intact in various organic desorption solvents (i.e., methanol, acetonitrile, acetone). The PIL-based sorbent coating polymerized from the IL monomer 1-vinyl-3-(10-hydroxydecyl) imidazolium chloride [VC10OHIM][Cl] and IL crosslinker 1,12-di(3-vinylbenzylimidazolium) dodecane dichloride [(VBIM)2C12] 2[Cl] exhibited superior extraction performance compared to the other studied PILs. The extraction efficiency of pharmaceutical drugs and phenolics increased when the film thickness of the PIL-based sorbent coating was increased while many insecticides were largely unaffected. Satisfactory analytical performance was obtained with limits of detection (LODs) ranging from 0.2 to 2 μg L(-1) for the target analytes. The accuracy of the analytical method was examined by studying the relative recovery of analytes in real water samples, including tap water and lake water, with recoveries varying from 50.2% to 115.9% and from 48.8% to 116.6%, respectively. Copyright © 2016 Elsevier B.V. All rights reserved.

Effect of Chain Rigidity on the Decoupling of Ion Motion from Segmental Relaxation in Polymerized Ionic Liquids: Ambient and Elevated Pressure Studies

DOE PAGES

Wojnarowska, Zaneta; Feng, Hongbo; Fu, Yao; ...

2017-08-21

Conductivity in polymer electrolytes has been generally discussed with the assumption that the segmental motions control charge transport. However, much less attention has been paid to the mechanism of ion conductivity where the motions of ions are less dependent (decoupled) on segmental dynamics. We present that this phenomenon is observed in ionic materials as they approach their glass transition temperature and becomes essential for design and development of highly conducting solid polymer electrolytes. In this paper, we study the effect of chain rigidity on the decoupling of ion transport from segmental motion in three polymerized ionic liquids (polyILs) containing themore » same cation–anion pair but differing in flexibility of the polymer backbones and side groups. Analysis of dielectric and rheology data reveals that decoupling is strong in vinyl-based rigid polymers while almost negligible in novel siloxane-based flexible polyILs. To explain this behavior, we investigated ion and chain dynamics at ambient and elevated pressure. Our results suggest that decoupling has a direct relationship to the frustration in chain packing and free volume. Finally, these conclusions are also supported by coarse-grained molecular dynamics simulations.« less

Comparison of Positively and Negatively Charged Achiral Co-Monomers Added to Cyclodextrin Monolith: Improved Chiral Separations in Capillary Electrochromatography

PubMed Central

Lu, Yang; Shamsi, Shahab A.

2014-01-01

Cyclodextrins (CDs) and their derivatives have been one of the most popular and successful chiral additives used in electrokinetic chromatography because of the presence of multiple chiral centers, which leads to multiple chiral interactions. However, there has been relatively less published work on the use of CDs as monolithic media for capillary electrochromatography (CEC). The goal of this study was to show how the addition of achiral co-monomer to a polymerizable CD such as glycidyl methacrylate β-cyclodextrin (GMA/β-CD) can affect the enantioselective separations in monolithic CEC. To achieve this goal, polymeric monoliths columns were prepared by co-polymerizing GMA/β-CD with cationic or anionic achiral co-monomers [(2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS) and vinyl benzyltrimethyl-ammonium (VBTA)] in the presence of conventional crosslinker (ethylene dimethacrylate) and ternary porogen system including butanediol, propanol and water. A total of 34 negatively charged compounds, 30 positively charged compounds and 33 neutral compounds were screened to compare the enantioresolution capability on the GMA/β-CD, GMA/β-CD-VBTA and GMA/β-CD-AMPS monolithic columns. PMID:24108813

Effect of Chain Rigidity on the Decoupling of Ion Motion from Segmental Relaxation in Polymerized Ionic Liquids: Ambient and Elevated Pressure Studies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wojnarowska, Zaneta; Feng, Hongbo; Fu, Yao

Conductivity in polymer electrolytes has been generally discussed with the assumption that the segmental motions control charge transport. However, much less attention has been paid to the mechanism of ion conductivity where the motions of ions are less dependent (decoupled) on segmental dynamics. We present that this phenomenon is observed in ionic materials as they approach their glass transition temperature and becomes essential for design and development of highly conducting solid polymer electrolytes. In this paper, we study the effect of chain rigidity on the decoupling of ion transport from segmental motion in three polymerized ionic liquids (polyILs) containing themore » same cation–anion pair but differing in flexibility of the polymer backbones and side groups. Analysis of dielectric and rheology data reveals that decoupling is strong in vinyl-based rigid polymers while almost negligible in novel siloxane-based flexible polyILs. To explain this behavior, we investigated ion and chain dynamics at ambient and elevated pressure. Our results suggest that decoupling has a direct relationship to the frustration in chain packing and free volume. Finally, these conclusions are also supported by coarse-grained molecular dynamics simulations.« less

Facile synthesis of main-chain degradable block copolymers for performance enhanced dismantlable adhesion.

PubMed

Sato, Eriko; Hagihara, Takashi; Matsumoto, Akikazu

2012-04-01

Block copolymers consisting of readily degradable polyperoxides and non-degradable vinyl polymers as the block segments were successfully synthesized by reversible chain transfer catalyzed polymerization, which is one of living radical polymerization techniques. The block copolymers showed characteristic morphology and wettability being different from the polymer blends. When block copolymers containing polyperoxide and polymethacrylate blocks were heated below 150 °C, the polyperoxide blocks were completely degraded and the polymethacrylate blocks were recovered without degradation. Block copolymers containing a poly(2-ethylhexyl methacrylate) block were then investigated as a dismantlable adhesion material, which requires adequate bonding strength during use and easy debonding on demand. Among the several block copolymers, the one consisting of poly(2-ethylhexyl methacrylate) and polyperoxide from methyl sorbate (PPMS) (M(n) = 4900) exhibited good performance as a pressure-sensitive adhesive (PSA). After heating the test specimens in a temperature range from 60 to 100 °C, PSA performance, which was evaluated by 180° peel strength and shear holding power measurements, was significantly diminished. Especially, after heating at 100 °C for 1 h, spontaneous debonding of some test specimens was observed because of the evolution of volatile acetaldehyde from PPMS.

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

PubMed

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

2016-03-01

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

Synthesis and Characterization of a Novel Borazine-Type UV Photo-Induced Polymerization of Ceramic Precursors.

PubMed

Wei, Dan; Chen, Lixin; Xu, Tingting; He, Weiqi; Wang, Yi

2016-06-21

A preceramic polymer of B,B',B''-(dimethyl)ethyl-acrylate-silyloxyethyl-borazine was synthesized by three steps from a molecular single-source precursor and characterized by Fourier transform infrared (FTIR) and nuclear magnetic resonance (NMR) spectrometry. Six-member borazine rings and acrylate groups were effectively introduced into the preceramic polymer to activate UV photo-induced polymerization. Photo-Differential Scanning Calorimetry (Photo-DSC) and real-time FTIR techniques were adapted to investigate the photo-polymerization process. The results revealed that the borazine derivative exhibited dramatic activity by UV polymerization, the double-bond conversion of which reached a maximum in 40 s. Furthermore, the properties of the pyrogenetic products were studied by scanning electron microscopy (SEM) and X-ray diffraction (XRD), which proved the ceramic annealed at 1100 °C retained the amorphous phase.

Oil-in-oil emulsions: a unique tool for the formation of polymer nanoparticles.

PubMed

Klapper, Markus; Nenov, Svetlin; Haschick, Robert; Müller, Kevin; Müllen, Klaus

2008-09-01

Polymer latex particles are nanofunctional materials with widespread applications including electronics, pharmaceuticals, photonics, cosmetics, and coatings. These materials are typically prepared using waterborne heterogeneous systems such as emulsion, miniemulsion, and suspension polymerization. However, all of these processes are limited to water-stable catalysts and monomers mainly polymerizable via radical polymerization. In this Account, we describe a method to overcome this limitation: nonaqueous emulsions can serve as a versatile tool for the synthesis of new types of polymer nanoparticles. To form these emulsions, we first needed to find two nonmiscible nonpolar/polar aprotic organic solvents. We used solvent mixtures of either DMF or acetonitrile in alkanes and carefully designed amphiphilic block and statistical copolymers, such as polyisoprene- b-poly(methyl methacrylate) (PI- b-PMMA), as additives to stabilize these emulsions. Unlike aqueous emulsions, these new emulsion systems allowed the use of water-sensitive monomers and catalysts. Although polyaddition and polycondensation reactions usually lead to a large number of side products and only to oligomers in the aqueous phase, these new conditions resulted in high-molecular-weight, defect-free polymers. Furthermore, conducting nanoparticles were produced by the iron(III)-induced synthesis of poly(ethylenedioxythiophene) (PEDOT) in an emulsion of acetonitrile in cyclohexane. Because metallocenes are sensitive to nitrile and carbonyl groups, the acetonitrile and DMF emulsions were not suitable for carrying out metallocene-catalyzed olefin polymerization. Instead, we developed a second system, which consists of alkanes dispersed in perfluoroalkanes. In this case, we designed a new amphipolar polymeric emulsifier with fluorous and aliphatic side chains to stabilize the emulsions. Such heterogeneous mixtures facilitated the catalytic polymerization of ethylene or propylene to give spherical nanoparticles of high molecular weight polyolefins. These nonaqueous systems also allow for the combination of different polymerization techniques to obtain complex architectures such as core-shell structures. Previously, such structures primarily used vinylic monomers, which greatly limited the number of polymer combinations. We have demonstrated how nonaqueous emulsions allow the use of a broad variety of hydrolyzable monomers and sensitive catalysts to yield polyester, polyurethane, polyamide, conducting polymers, and polyolefin latex particles in one step under ambient reaction conditions. This nonpolar emulsion strategy dramatically increases the chemical palette of polymers that can form nanoparticles via emulsion polymerization.

Design and synthesis of multifunctional poly(ethylene glycol)s using enzymatic catalysis for multivalent cancer drug delivery

NASA Astrophysics Data System (ADS)

Seo, Kwang Su

The objective of this research was to design and synthesize multifunctional poly(ethylene glycol)s (PEG)s using enzyme-catalyzed reactions for multivalent targeted drug delivery. Based on computer simulation for optimum folate binding, a four-arm PEG star topology with Mn = 1000 g/mol was proposed. First, a four-functional core based on tetraethylene glycol (TEG) was designed and synthesized using transesterification and Michael addition reactions in the presence of Candida antarctica lipase B (CALB) as a biocatalyst. The four-functional core (HO)2-TEG-(OH)2 core was successfully prepared by the CALB-catalyzed transesterification of vinyl acrylate (VA) with TEG and then Michael addition of diethanolamine to the resulting TEG diacrylate with/without the use of solvent. The functional PEG arms with fluorescein isothiocyanate (FITC) and folic acid (FA) were prepared using both traditional organic chemistry and enzyme-catalyzed reactions. FITC was reacted with the amine group of H2N-PEG-OH in the presence of triethylamine via nucleophilic addition onto the isothiocyanate group. Then, divinyl adipate (DVA) was transesterified with the FITC-PEG-OH product in the presence of CALB to produce the FITC-PEG vinyl ester that will be attached to the four-functional core via CALC-catalyzed transesterification. For the synthesis of FA-PEG vinyl ester arm, DVA was first reacted with PEG-monobenzyl ether (BzPEG-OH) in bulk in the presence of CALB. The BzPEG vinyl ester was then transesterified with 12-bromo-1-dodecanol in the presence of CALB. Finally, BzPEG-Br was attached to FA exclusively in the gamma position using a new method. The thesis also discusses fundamental studies that were carried out in order to get better understanding of enzyme catalyzed transesterification and Michael addition reactions. First, in an effort to investigate the effects of reagent and enzyme concentrations in transesterification, vinyl methacrylate (VMA) was reacted with 2-(hydroxyethyl) acrylate (2HEA) in the presence of CALB. When the reaction was performed in tetrahydrofuran (THF) with a 2HEA concentration of 0.10 mol/L, only 19% conversion was observed within 4 hours, whereas complete conversion was achieved under solventless conditions. The effect of enzyme concentration in reactions with and without solvent was also studied. The effect of DVA concentration on the CALB-catalyzed transesterification with TEG was studied under solventless conditions. When 1.5 molar equivalent of DVA per OH in TEG was used, 42% divinyl-functionalized product was observed together with 56.5% oligomerized (di-, tri-, tetra- and pentamer) products. At 10 eq. of DVA, only 18.4% oligomerized products were obtained. The effect of diol molecular weight was also investigated. At 10.0 eq. DVA per OH only 2% dimer was observed with PEG Mn=1000 g/mol, and a single divinyl functionalized product was obtained with M n=2000 g/mol. The effects of polymer molecular weight and DVA concentration were also studied in the reaction of DVA with PEG monomethyl ether (MPEG-OH, Mn=1100 g/mol and 2000 g/mol). The extent of coupling decreased from 35% to 0.4% when the DVA concentration was increased from 1.5 to 10 per -OH in the MPEG-OH. No coupling was observed with MPEG-OH Mn=2000 g/mol at 5 eq. DVA per -OH. Following these fundamental studies, TEGs and PEGs were enzymatically functionalized. TEGs were transesterified with VMA and vinyl crotonate in the presence of CALB under solventless conditions within 4 hours of reaction time. Benzyl protected TEG-OHs were also successfully functionalized with VMA and vinyl crotonate in the presence of CALB under solventless conditions within 2 hours. An eight-functional molecule was also synthesized from (HO)2-TEG-(OH) 2. First an alpha-vinyl-o-acrylate linker was prepared by the transesterification of DVA with 2HEA. This linker was then transesterified with (HO)-TEG-(OH)2, followed by Michael addition of DEA to the tetra-acrylated TEG. (Abstract shortened by UMI.)

Novel (meth)acrylate monomers for ultrarapid polymerization and enhanced polymer properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Beckel, E. R.; Berchtold, K. A.; Nie, J.

2002-01-01

Ultraviolet light is known to be one of the most efficient methods to initiatc polymeric reactions in the presence of a photonitiator. Photopolymerizations are advantageous because the chemistry of the materials can be tailored to design liquid monomers for ultrarapid polymerization into a solid polymer material. One way to achieve rapid photopolymerizations is to utilize multifunctional (meth)acrylate monomers. which form highly crosslinked polymers; however, these monomers typically do not achieve complete functional group conversion. Recently, Decker et al. developed novel monovinyl acrylate monomers that display polyriicrization kinetics that rival those of multifunctional acrylate monomers. These novel acrylate monomers incorporate secondarymore » functionalities and end groups such as carbonates, carbamates, cyclic carbonates and oxazolidone which promote the increased polymerization kinetics of these monomers. In addition to thc polynierization kinetics, these novel monovinyl monomers form crosslinked polymers, which are characterized by having high strength and high flexibility. Unfortunately, the exact mechanism or mechanisms responsible for the polymerization kinetics and crosslinking are not well understood.« less

Superwettability-Induced Confined Reaction toward High-Performance Flexible Electrodes.

PubMed

Xiong, Weiwei; Liu, Hongliang; Zhou, Yahong; Ding, Yi; Zhang, Xiqi; Jiang, Lei

2016-05-18

To find a general strategy to realize confinement of the conductive layer for high-performance flexible electrodes, with improved interfacial adhesion and high conductivity, is of important scientific significance. In this work, superwettability-induced confined reaction is used to fabricate high-performance flexible Ag/polymer electrodes, showing significantly improved silver conversion efficiency and interfacial adhesion. The as-prepared flexible electrodes by superhydrophilic polymeric surface under oil are highly conductive with an order of magnitude higher than the Ag/polymer electrodes obtained from original polymeric surface. The high conductivity achieved via superhydrophilic confinement is ascribed to the fact that the superhydrophilic polymeric surface can enhance the reaction rate of silver deposition and reduce the size of silver nanoparticles to achieve the densest packing. This new approach will provide a simple method to fabricate flexible and highly conductive Ag/polymer electrodes with excellent adhesion between the conductive layer and the substrate, and can be extended to other metal/polymeric electrodes or alloy/polymeric electrodes.

A New Route for High-Purity Organic Materials: High-Pressure-Ramp-Induced Ultrafast Polymerization of 2-(Hydroxyethyl)Methacrylate

NASA Astrophysics Data System (ADS)

Evlyukhin, E.; Museur, L.; Traore, M.; Perruchot, C.; Zerr, A.; Kanaev, A.

2015-12-01

The synthesis of highly biocompatible polymers is important for modern biotechnologies and medicine. Here, we report a unique process based on a two-step high-pressure ramp (HPR) for the ultrafast and efficient bulk polymerization of 2-(hydroxyethyl)methacrylate (HEMA) at room temperature without photo- and thermal activation or addition of initiator. The HEMA monomers are first activated during the compression step but their reactivity is hindered by the dense glass-like environment. The rapid polymerization occurs in only the second step upon decompression to the liquid state. The conversion yield was found to exceed 90% in the recovered samples. The gel permeation chromatography evidences the overriding role of HEMA2•• biradicals in the polymerization mechanism. The HPR process extends the application field of HP-induced polymerization, beyond the family of crystallized monomers considered up today. It is also an appealing alternative to typical photo- or thermal activation, allowing the efficient synthesis of highly pure organic materials.

Chemoselective catalytic conversion of glycerol as a biorenewable source to valuable commodity chemicals.

PubMed

Zhou, Chun-Hui Clayton; Beltramini, Jorge N; Fan, Yong-Xian; Lu, G Q Max

2008-03-01

New opportunities for the conversion of glycerol into value-added chemicals have emerged in recent years as a result of glycerol's unique structure, properties, bioavailability, and renewability. Glycerol is currently produced in large amounts during the transesterification of fatty acids into biodiesel and as such represents a useful by-product. This paper provides a comprehensive review and critical analysis on the different reaction pathways for catalytic conversion of glycerol into commodity chemicals, including selective oxidation, selective hydrogenolysis, selective dehydration, pyrolysis and gasification, steam reforming, thermal reduction into syngas, selective transesterification, selective etherification, oligomerization and polymerization, and conversion of glycerol into glycerol carbonate.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kennemur, Justin G.; Bates, Frank S.; Hillmyer, Marc A.

Synthesis of poly(methyl ethacrylate), (PMEA), in tetrahydrofuran at -78 °C using anionic polymerization techniques results in high molar mass (>30 kg mol-1), low dispersity (1.3), and high conversion (>81%). The molar masses of a series of samples are consistent with values anticipated by the monomer-to-initiator ratio and conversion. These results represent a significant improvement to earlier reported attempts to prepare PMEA using anionic methods. Successful diblock polymerization of polystyrene-block-PMEA, (PS-PMEA), and poly(4-tert-butylstyrene)-block-PMEA, (PtBS-PMEA), is achieved through sequential anionic polymerization techniques with dispersities as low as 1.06 and segment molar fractions close to those targeted. Broad principal scattering peaks observed bymore » small-angle X-ray scattering (SAXS) for symmetric PS-PMEA at relatively high molar mass (39 kg mol-1) suggests an effective interaction parameter (χeff) that is smaller than for PS-block-poly(methyl methacrylate). On the other hand, PtBS-PMEA block polymers form a well-ordered morphology based on SAXS measurements and is attributable to the more hydrophobic PtBS segment. These results confirm the viability of PMEA as a new constituent in the expanding suite of polymers suitable for preparing nanostructured block polymers.« less

Photo-triggered solvent-free metamorphosis of polymeric materials.

PubMed

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.

Methacrylic Zwitterionic, Thermoresponsive, and Hydrophilic (Co)Polymers via Cu(0)-Polymerization: The Importance of Halide Salt Additives.

PubMed

Simula, Alexandre; Anastasaki, Athina; Haddleton, David M

2016-02-01

The synthesis of hydrophilic, thermoresponsive, and zwitterionic polymethacrylates is reported by Cu(0)-mediated reversible deactivation radical polymerization in water and/or water/alcohol mixtures. The predisproportionation of [Cu(I) (PMDETA)Cl] in water prior to initiator and monomer addition is exploited to yield well-defined polymethacrylates with full monomer conversions in 30 min. The addition of supplementary halide salts (NaCl) enables the synthesis of various molecular weight poly[poly(ethylene glycol) methyl ether methacrylate] (PEGMA475) (DPn = 10-80, Mn ≈ 10,000-40 000 g mol(-1)) with full monomer conversion and narrow molecular weight distributions attained in all cases (Đ ≈ 1.20-1.30). A bifunctional PEG initiator (average Mn ≈ 1000 g mol(-1)) is utilized for the polymerization of a wide range of methacrylates including 2-dimethylaminoethyl methacrylate, 2-morpholinoethyl methacrylate, [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide, and 2-methacryloyloxyethyl phosphorylcholine. Despite the high water content, high end group fidelity is demonstrated by in situ chain extensions and block copolymerizations with PEGMA475 yielding well-defined functional telechelic pentablock copolymers within 2.5 h. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Kinetics of bulk photo-initiated copper(i)-catalyzed azide–alkyne cycloaddition (CuAAC) polymerizations†

PubMed Central

Song, Han Byul; Baranek, Austin; Bowman, Christopher N.

2016-01-01

Photoinitiation of polymerizations based on the copper(i)-catalyzed azide–alkyne cycloaddition (CuAAC) reaction enables spatio-temporal control and the formation of mechanically robust, highly glassy photopolymers. Here, we investigated several critical factors influencing photo-CuAAC polymerization kinetics via systematic variation of reaction conditions such as the physicochemical nature of the monomers; the copper salt and photoinitiator types and concentrations; light intensity; exposure time and solvent content. Real time Fourier transform infrared spectroscopy (FTIR) was used to monitor the polymerization kinetics in situ. Six different di-functional azide monomers and four different tri-functional alkyne monomers containing either aliphatic, aromatic, ether and/or carbamate substituents were synthesized and polymerized. Replacing carbamate structures with ether moieties in the monomers enabled an increase in conversion from 65% to 90% under similar irradiation conditions. The carbamate results in stiffer monomers and higher viscosity mixtures indicating that chain mobility and diffusion are key factors that determine the CuAAC network formation kinetics. Photoinitiation rates were manipulated by altering various aspects of the photo-reduction step; ultimately, a loading above 3 mol% per functional group for both the copper catalyst and the photoinitiator showed little or no rate dependence on concentration while a loading below 3 mol% exhibited 1st order rate dependence. Furthermore, a photoinitiating system consisting of camphorquinone resulted in 60% conversion in the dark after only 1 minute of 75 mW cm−2 light exposure at 400–500 nm, highlighting a unique characteristic of the CuAAC photopolymerization enabled by the combination of the copper(i)’s catalytic lifetime and the nature of the step-growth polymerization. PMID:27429650

Effect of post-polymerization heat-treatments on degree of conversion, leaching residual MMA and in vitro cytotoxicity of autopolymerizing acrylic repair resin.

PubMed

Bural, Canan; Aktaş, Esin; Deniz, Günnur; Ünlüçerçi, Yeşim; Kızılcan, Nilgün; Bayraktar, Gülsen

2011-11-01

This study evaluated the effect of post-polymerization heat-treatments on degree of conversion (DC), residual methyl methacrylate concentration (MMA(r)) and in vitro cytotoxicity of autopolymerizing acrylic repair resin. A total of 336 specimens were prepared by bench- and hydroflask-curing and subjected to post-polymerization heat-treatments: a) water immersion at 60°C for 30 min, b) microwaving at 500 W for 3 min, c) combined use of water immersion and microwaving d) no treatment (as control). Specimens were eluted in cell culture medium for 1, 2, 5 and 7 days. DC and MMA(r) in eluates were measured by FTIR spectrometry and HPLC, respectively. In vitro cytotoxicity of eluates on L-929 fibroblasts was determined by XTT assay. Data were statistically analyzed with Dunn's multiple comparison and Pearson correlation tests (p≤0.05). DC was highest (99.9%) in bench- and hydroflask-cured groups which were subjected to water immersion. At all elution periods, MMA(r) was detected in eluates of all treatment groups and were higher in bench-cured groups than hydro-flask cured groups. Cell proliferation values indicated slightly cytotoxic effect throughout 7 days; regardless of the curing method or post-polymerization treatment. The correlation between MMA(r) and cell proliferation was negative after elution of 1, 2, 5 days and was only statistically significant (p<0.05) at 5 days. At elution of 7 days, the correlation was positive with no significance. Post-polymerization heat-treatment of autopolymerizing acrylic repair resin by immersion in water at 60°C for 30 min is clinically recommended to improve the DC while reducing the leaching residual MMA. Copyright © 2011 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Modification of linear prepolymers to tailor heterogeneous network formation through photo-initiated Polymerization-Induced Phase Separation

PubMed Central

Szczepanski, Caroline R.; Stansbury, Jeffrey W.

2015-01-01

Polymerization-induced phase separation (PIPS) was studied in ambient photopolymerizations of triethylene glycol dimethacrylate (TEGDMA) modified by poly(methyl methacrylate) (PMMA). The molecular weight of PMMA and the rate of network formation (through incident UV-irradiation) were varied to influence both the promotion of phase separation through increases in overall free energy, as well as the extent to which phase development occurs during polymerization through diffusion prior to network gelation. The overall free energy of the polymerizing system increases with PMMA molecular weight, such that PIPS is promoted thermodynamically at low loading levels (5 wt%) of a higher molecular weight PMMA (120 kDa), while a higher loading level (20 wt%) is needed to induce PIPS with lower PMMA molecular weight (11 kDa), and phase separation was not promoted at any loading level tested of the lowest molecular weight PMMA (1 kDa). Due to these differences in overall free energy, systems modified by PMMA (11 kDa) underwent phase separation via Nucleation and Growth, and systems modified by PMMA (120 kDa), followed the Spinodal Decomposition mechanism. Despite differences in phase structure, all materials form a continuous phase rich in TEGDMA homopolymer. At high irradiation intensity (Io=20mW/cm2), the rate of network formation prohibited significant phase separation, even when thermodynamically preferred. A staged curing approach, which utilizes low intensity irradiation (Io=300µW/cm2) for the first ~50% of reaction to allow phase separation via diffusion, followed by a high intensity flood-cure to achieve a high degree of conversion, was employed to form phase-separated networks with reduced polymerization stress yet equivalent final conversion and modulus. PMID:26190865

Nanoscaffold matrices for size-controlled, pulsatile transdermal testosterone delivery: nanosize effects on the time dimension

NASA Astrophysics Data System (ADS)

Malik, Ritu; Tondwal, Shailesh; Venkatesh, K. S.; Misra, Amit

2008-10-01

Pulsatile transdermal testosterone (T) has applications in hormone supplementation and male contraception. Pulsatile T delivery was achieved by assembling crystalline and nanoparticulate T in nucleation-inhibiting polymer matrices of controlled porosity. Different interference patterns observed from various polymeric films containing T were due to the various particle sizes of T present in the polymer matrices. Scanning electron microscopy was used to determine the size and shape of T crystals. Skin-adherent films containing T nanoparticles of any size between 10-500 nm could be prepared using pharmaceutically acceptable vinylic polymers. Drug release and skin permeation profiles were studied. The dissolution-diffusion behavior of nanoparticles differed from crystalline and molecular states. Nanosize may thus be used to engineer chronopharmacologically relevant drug delivery.

Synthesis of poly(3-hydroxybutyrate) nanospheres and deposition thereof into porous thin film

NASA Astrophysics Data System (ADS)

Abid, S.; Raza, Z. A.; Rehman, A.

2016-10-01

Polymeric nanostructures have gained importance in medical science as drug delivery carriers due to their biocompatibility and biodegradability. Polyhydroxybutyrate (PHB) is one of the natural biodegradable polymers used to deliver drugs in the form of nano/microcapsules. In this study, solvent evaporation method has been used for the synthesis of PHB nanospheres using poly(vinyl) alcohol (PVA) both as emulsifier and stabilizer. The produced PHB nanospheres were analyzed using dynamic light scattering and scanning electron microscopy. The size of nanospheres decreased whereas the zeta potential increased on increasing the concentration of emulsifier. The PHB nanospheres were then deposited into porous thin film on a glass surface and characterized against bulk PHB film by using atomic force microscopy, contact angle measurement and x-ray diffraction.

ZnO thin-film transistors with a polymeric gate insulator built on a polyethersulfone substrate

NASA Astrophysics Data System (ADS)

Hyung, Gun Woo; Park, Jaehoon; Koo, Ja Ryong; Choi, Kyung Min; Kwon, Sang Jik; Cho, Eou Sik; Kim, Yong Seog; Kim, Young Kwan

2012-03-01

Zinc oxide (ZnO) thin-film transistors (TFTs) with a cross-linked poly(vinyl alcohol) (c-PVA) insulator are fabricated on a polyethersulfone substrate. The ZnO film, formed by atomic layer deposition, shows a polycrystalline hexagonal structure with a band gap energy of about 3.37 eV. The fabricated ZnO TFT exhibits a field-effect mobility of 0.38 cm2/Vs and a threshold voltage of 0.2 V. The hysteresis of the device is mainly caused by trapped electrons at the c-PVA/ZnO interface, whereas the positive threshold voltage shift occurs as a consequence of constant positive gate bias stress after 5000 s due to an electron injection from the ZnO film into the c-PVA insulator.

46 CFR 151.50-34 - Vinyl chloride (vinyl chloride monomer).

Code of Federal Regulations, 2010 CFR

2010-10-01

... 46 Shipping 5 2010-10-01 2010-10-01 false Vinyl chloride (vinyl chloride monomer). 151.50-34... chloride (vinyl chloride monomer). (a) Copper, aluminum, magnesium, mercury, silver, and their alloys shall... equipment that may come in contact with vinyl chloride liquid or vapor. (b) Valves, flanges, and pipe...

Spray-Dried Nanoparticle-in-Microparticle Delivery Systems (NiMDS) for Gene Delivery, Comprising Polyethylenimine (PEI)-Based Nanoparticles in a Poly(Vinyl Alcohol) Matrix.

PubMed

Schulze, Jan; Kuhn, Stephanie; Hendrikx, Stephan; Schulz-Siegmund, Michaela; Polte, Tobias; Aigner, Achim

2018-03-01

Nucleic acid-based therapies rely on efficient formulations for nucleic acid protection and delivery. As nonviral strategies, polymeric and lipid-based nanoparticles have been introduced; however, biological efficacy and biocompatibility as well as poor storage properties due to colloidal instability and their unavailability as ready-to-use systems are still major issues. Polyethylenimine is the most widely explored and promising candidate for gene delivery. Polyethylenimine-based polyplexes and their combination with liposomes, lipopolyplexes, are efficient for DNA or siRNA delivery in vitro and in vivo. In this study, a highly potent spray-dried nanoparticle-in-microparticle delivery system is presented for the encapsulation of polyethylenimine-based polyplexes and lipopolyplexes into poly(vinyl alcohol) microparticles, without requiring additional stabilizing agents. This easy-to-handle gene delivery device allows prolonged nanoparticle storage and protection at ambient temperature. Biological analyses reveal further advantages regarding profoundly reduced cytotoxicity and enhanced transfection efficacies of polyethylenimine-based nanoparticles from the nanoparticle-in-microparticle delivery system over their freshly prepared counterparts, as determined in various cell lines. Importantly, this nanoparticle-in-microparticle delivery system is demonstrated as ready-to-use dry powder to be an efficient device for the inhalative delivery of polyethylenimine-based lipopolyplexes in vivo, as shown by transgene expression in mice after only one administration. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Composite films based on biorelated agro-industrial waste and poly(vinyl alcohol). Preparation and mechanical properties characterization.

PubMed

Chiellini, E; Cinelli, P; Imam, S H; Mao, L

2001-01-01

As a part of an ongoing project on the production of composite materials based on poly(vinyl alcohol) (PVA) and polymeric materials from renewable resources, the present paper reports on the incorporation of agricultural waste materials as organic fillers in a film matrix based on PVA as continuous phase. In this study lignocellulosic fibers byproducts, derived from sugar cane (SC) and apple (AP) and orange (OR) fruit juice extraction, were cast from PVA aqueous solutions. The effect of fiber type and composition on the relative properties of cast films was evaluated and compared. OR resulted to be suitable for blending in higher amounts by weight than SC and AP. Glycerol and urea were added as plasticizing agents and were observed to be effective in giving flexible films. Additionally, cornstarch was added to further increase the composition of polymers from renewable resources in cost-effective and ecoefficient composite film formulations. The prepared films resulted sensitive to moisture and water. To reduce water sensitivity, hexamethoxymethylmelamine (HMMM) was tested as a cross-linking agent for the present composite formulations. Cross-linked films exhibited significant improvement in water-resistance that can be taken as a tuneable structural feature for customized applications. The mechanical properties of the prepared composite films (elongation at break, tensile strength, Young modulus) were found to be dependent upon the nature and content of the filler and on environmental conditions.

Thermal Conductivity of Copoly(ethylene vinyl acetate)/Nano-Filler Blends

NASA Technical Reports Server (NTRS)

Ghose, S.; Watson, K. A.; Working, D. C.; Connell, J. W.; Smith, J. G.; Lin, Y.; Sun, Y. P.

2007-01-01

The development of flexible, thermally conductive fabrics and plastic tubes for the Liquid Cooling and Ventilation Garment (LCVG) are needed to reduce weight and improve the mobility, comfort, and performance of future spacesuits. Such improvements would allow astronauts to operate more efficiently and safely for extended extravehicular activities. As a continuation of our work on the improvement of thermal conductivity (TC) of polymeric materials, nanocomposites were prepared from copoly(ethylene vinyl acetate), trade name Elvax 260TradeMark), metallized carbon nanofibers (CNFs), nickel (Ni) nanostrands, boron nitride both alone and as mixtures with aluminum powder. The nanocomposites were prepared by melt mixing at various loading levels and subsequently fabricated into several material forms (i.e., ribbons, tubes, and compression molded plaques) for analysis. Ribbons and tubes were extruded to form samples in which the nanoparticles were aligned in the direction of flow. The degree of dispersion and alignment of the nanoparticles were investigated using high-resolution scanning electron microscopy. Tensile properties of the aligned samples were determined at room temperature. TC measurements were performed using a laser flash (Nanoflash(TradeMark) technique. The TC of the samples was measured in both the direction of alignment as well as transverse. Tubing of comparable dimensions to that used in the LCVG was extruded from select compositions and the thermal conductivities of the tubes measured.

Synthesis biolubricant from rubber seed oil

NASA Astrophysics Data System (ADS)

Hung, Nguyen Tran Dong; Tuyen, Dang Thi Hong; Viet, Tran Tan

2017-09-01

The objective was biolubricant preparation from rubber seed oil (RSO) using polymerization reactor with/without catalyst in batch reactor. Before become reactant in polymerization reaction, a non-edible rubber seed oil was converted into methyl ester by esterification/tranesterification reaction with methanol and acid/base catalyst. The polymerization reaction parameters investigated were reaction time, temperature and weight ratio (catalyst with feed), and their effect on the bio lubricant formation. The result show significant conversion of methyl ester to bio lubricant in the temperature reaction of 160°C, reaction time of 2h min and ratio of super acid catalyst (tetrafluoroboric acid-sHBF4) of 3 %w/w. The resulting products were confirmed by GC-MS, FTIR spectroscopy and also analyzed for the viscosity. The best viscosity value of RSOFAME polymer was 110.6 cSt when the condition polymerization reaction were 160 °C, reaction time 3h, 6 wt% mass ratio of oil:catalyst.

Well-Defined High Molecular Weight Polystyrene with High Rates and High Livingness Synthesized via Two-Stage RAFT Emulsion Polymerization.

PubMed

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.

pH responsiveness of dendrimer-like poly(ethylene oxide)s.

PubMed

Feng, Xiaoshuang; Taton, Daniel; Borsali, Redouane; Chaikof, Elliot L; Gnanou, Yves

2006-09-06

Poly(ethylene oxide) (PEO) and poly(acrylic acid) (PAA), two polymers known to form pH-sensitive aggregates through noncovalent interactions, were assembled in purposely designed architecture -a dendrimer-like PEO scaffold carrying short inner PAA chains-to produce unimolecular systems that exhibit pH responsiveness. Because of the particular placement of the PAA chains within the dendrimer-like structure, intermolecular complexation between acrylic acid (AA) and ethylene oxide (EO) units-and thus macroscopic aggregation or even mesoscopic micellization-could be avoided in favor of the sole intramolecular complexation. The sensitivity of such interactions to pH was exploited to generate dendrimer-like PEOs that reversibly shrink and expand with the pH. Such PAA-carrying dendrimer-like PEOs were synthesized in two main steps. First, a fifth-generation dendrimer-like PEO was obtained by combining anionic ring-opening polymerization (AROP) of ethylene oxide from a tris-hydroxylated core and selective branching reactions of PEO chain ends. To this end, an AB(2)C-type branching agent was designed: the latter includes a chloromethyl (A) group for its covalent attachment to the arm ends, two geminal hydroxyls (B(2)) protected in the form of a ketal ring for the growth of subsequent PEO generations by AROP, and a vinylic (C) double bonds for further functionalization of the interior of dendrimer-like PEOs. Reiteration of AROP and derivatization of PEO branches allowed us to prepare a dendrimer-like PEO of fourth generation with a total molar mass of 52,000 g x mol(-1), containing 24 external hydroxyl functions and 21 inner vinylic groups in the interior. A fifth generation of PEO chains was generated from this parent dendrimer-like PEO of fourth generation using a "conventional" AB(2)-type branching agent, and 48 PEO branches could be grown by AROP. The 48 outer hydroxy-end groups of the fifth-generation dendrimer-like PEO obtained were subsequently quantitatively converted into inert benzylic groups using benzyl bromide. The 21 internal vinylic groups carried by the PEO scaffold were then chemically modified in a two-step sequence into bromoester groups. The latter which are atom transfer radical polymerization (ATRP) initiating sites thus served to grow poly(tert-butylacrylate) chains. After a final step of hydrolysis of the tert-butyl ester groups, double, hydrophilic, dendrimer-like PEOs comprising 21 internal junction-attached poly(acrylic acid) (PAA) blocks could be obtained. Dynamic light scattering was used to determine the size of these dendrimer-like species in water and to investigate their response to pH variation: in particular, how the pH-sensitive complexation of EO and AA units affects their overall behavior.

Toxicity, Mutagenicity, and Mutational Spectra of Vinyl Chloride, 2- Chloroethylene Oxide, and Chloracetaldehyde in a Human Lymphoblastoid Line Expressing Cytochrome P450IIE1.

DTIC Science & Technology

1992-01-01

concluded that CEO was the alkylating agent involved in conversion of adenosine to l,N 6 -ethenoadenosine. 1,N6 - Ethenoadenosine was not produced by CEO...guanines as nearest neighbors upon the alkylation of a guanine residue in DNA. N-methyl-N- nitrosourea (MNU) was reacted with a synthetic polynucleotide...the alkylating agent MNNG or the intercalating agent ICR-191. In the study they determined that mutants comprising at least one percent of the total

Candida antartica lipase B catalyzed polycaprolactone synthesis: effects of organic media and temperature.

PubMed

Kumar, A; Gross, R A

2000-01-01

Engineering of the reaction medium and study of an expanded range of reaction temperatures were carried out in an effort to positively influence the outcome of Novozyme-435 (immobilized Lipase B from Candida antarctica) catalyzed epsilon-CL polymerizations. A series of solvents including acetonitrile, dioxane, tetrahydrofuran, chloroform, butyl ether, isopropyl ether, isooctane, and toluene (log P from -1.1 to 4.5) were evaluated at 70 degrees C. Statistically (ANOVA), two significant regions were observed. Solvents having log P values from -1.1 to 0.49 showed low propagation rates (< or = 30% epsilon-CL conversion in 4 h) and gave products of short chain length (Mn < or = 5200 g/mol). In contrast, solvents with log P values from 1.9 to 4.5 showed enhanced propagation rates and afforded polymers of higher molecular weight (Mn = 11,500-17,000 g/mol). Toluene, a preferred solvent for this work, was studied at epsilon-CL to toluene (wt/vol) ratios from 1:1 to 10:1. The ratio 1:2 was selected since, for polymerizations at 70 degrees C, 0.3 mL of epsilon-CL and 4 h, gave high monomer conversions and Mn values (approximately 85% and approximately 17,000 g/mol, respectively). Increasing the scale of the reaction from 0.3 to 10 mL of CL resulted in a similar isolated product yield, but the Mn increased from 17,200 to 44,800 g/mol. Toluene appeared to help stabilize Novozyme-435 so that lipase-catalyzed polymerizations could be conducted effectively at 90 degrees C. For example, within only 2 h at 90 degrees C (toluene-d8 to epsilon-CL, 5:1, approximately 1% protein), the % monomer conversion reached approximately 90%. Also, the controlled character of these polymerizations as a function of reaction temperature was evaluated.

Hydroxyapatite induces spontaneous polymerization of model self-etch dental adhesives.

PubMed

Zhang, Ying; Wu, Ningjing; Bai, Xinyan; Xu, Changqi; Liu, Yi; Wang, Yong

2013-10-01

The objective of this study is to report for the first time the spontaneous polymerization phenomenon of self-etch dental adhesives induced by hydroxylapatite (HAp). Model self-etch adhesives were prepared by using a monomer mixture of bis[2-(methacryloyloxy)ethyl] phosphate (2MP) with 2-hydroxyethyl methacrylate (HEMA). The initiator system consisted of camphorquinone (CQ, 0.022 mmol/g) and ethyl 4-dimethylaminobenzoate (4E, 0.022-0.088 mmol/g). HAp (2-8 wt.%) was added to the neat model adhesive. In a dark environment, the polymerization was monitored in-situ using ATR/FT-IR, and the mechanical properties of the polymerized adhesives were evaluated using nanoindentation technique. Results indicated that spontaneous polymerization was not observed in the absence of HAp. However, as different amounts of HAp were incorporated into the adhesives, spontaneous polymerization was induced. Higher HAp content led to higher degree of conversion (DC), higher rate of polymerization (RP) and shorter induction period (IP). In addition, higher 4E content also elevated DC and RP and reduced IP of the adhesives. Nanoindentation result suggested that the Young's modulus of the polymerized adhesives showed similar dependence on HAp and 4E contents. In summary, interaction with HAp could induce spontaneous polymerization of the model self-etch adhesives. This result provides important information for understanding the initiation mechanism of the self-etch adhesives, and may be of clinical significance to strengthen the adhesive/dentin interface based on the finding. Copyright © 2013 Elsevier B.V. All rights reserved.

Hydroxyapatite induces spontaneous polymerization of model self-etch dental adhesives

PubMed Central

Zhang, Ying; Wu, Ningjing; Bai, Xinyan; Xu, Changqi; Liu, Yi; Wang, Yong

2013-01-01

The objective of this study is to report for the first time the spontaneous polymerization phenomenon of self-etch dental adhesives induced by hydroxylapatite (HAp). Model self-etch adhesives were prepared by using a monomer mixture of bis[2-(methacryloyloxy)ethyl] phosphate (2MP) with 2-hydroxyethyl methacrylate (HEMA). The initiator system consisted of camphorquinone (CQ, 0.022 mmol/g) and ethyl 4-dimethylaminobenzoate (4E, 0.022–0.088 mmol/g). HAp (2–8 wt.%) was added to the neat model adhesive. In a dark environment, the polymerization was monitored in-situ using ATR/FT-IR, and the mechanical properties of the polymerized adhesives were evaluated using nanoindentation technique. Results indicated that spontaneous polymerization was not observed in the absence of HAp. However, as different amounts of HAp were incorporated into the adhesives, spontaneous polymerization was induced. Higher HAp content led to higher degree of conversion (DC), higher rate of polymerization (RP) and shorter induction period (IP). In addition, higher 4E content also elevated DC and RP and reduced IP of the adhesives. Nanoindentation result suggested that the Young's modulus of the polymerized adhesives showed similar dependence on HAp and 4E contents. In summary, interaction with HAp could induce spontaneous polymerization of the model self-etch adhesives. This result provides important information for understanding the initiation mechanism of the self-etch adhesives, and may be of clinical significance to strengthen the adhesive/dentin interface based on the finding. PMID:23910263

Preparation and characterization of a photocrosslinkable bioadhesive inspired by marine mussel.

PubMed

Xue, Jie; Wang, Tao; Nie, Jun; Yang, Dongzhi

2013-02-05

Synthetic adhesives inspired by marine mussel have attracted great attention due to its excellent water-resistance and good biocompatibility. In this study, a photocrosslinkable bioadhesive containing 3,4-Dihydroxy-l-phenylalanine (DOPA) functional group, which is central to curing mussel adhesive proteins, was prepared by ultraviolet (UV) irradiation of a new photocurable monomer ethylene glycol acrylate methacrylate-dopamine (EGAMA-DOPA) and a UV photocrosslinkable crosslinking agent poly(vinyl alcohol) (UV-PVA) derivative. The chemical structures of EGAMA-DOPA and UV-PVA were confirmed by Fourier Transform Infrared Reflection (FTIR) and (1)H NMR spectroscopy, respectively. The effects of UV light intensity, content of photoinitiator, EGAMA-DOPA and UV-PVA on the photopolymerization kinetics were studied, and the effects of the content of UV-PVA and temperature on the adhesive strength were also investigated. It was found that the higher UV light intensity, the faster polymerization rate and the higher final conversion that was the same as the trend of photoinitiator, EGAMA-DOPA and UV-PVA. And the adhesion strength measurement showed that, for gels with 30wt.% EGAMA-DOPA, the adhesion strength was obviously improved by about 150% with 3.0wt.% UV-PVA instead of pure PVA, and for gels containing 40wt.% EGAMA-DOPA, the adhesion strength sharply enhanced by 123% with increasing the content of UV-PVA from 1.0wt.% to 3.0wt.%. Cell attachment results showed good cell viability of L929 cell on the EGAMA-DOPA/UV-PVA adhesive gels. Thanks to its strong adhesion strength and good biocompatibility, such photocrosslinkable gels could be applied to the areas of biomedical field. Copyright © 2012 Elsevier B.V. All rights reserved.

Control of polymerization shrinkage and stress in nanogel-modified monomer and composite materials

PubMed Central

Moraes, Rafael R.; Garcia, Jeffrey W.; Barros, Matthew D.; Lewis, Steven H.; Pfeifer, Carmem S.; Liu, JianCheng; Stansbury, Jeffrey W.

2011-01-01

Objectives This study demonstrates the effects of nano-scale prepolymer particles as additives to model dental monomer and composite formulations. Methods Discrete nanogel particles were prepared by solution photopolymerization of isobornyl methacrylate and urethane dimethacrylate in the presence of a chain transfer agent, which also provided a means to attach reactive groups to the prepolymer. Nanogel was added to triethylene glycol dimethacrylate (TEGDMA) in increments between 5 and 40 wt% with resin viscosity, reaction kinetics, shrinkage, mechanical properties, stress and optical properties evaluated. Maximum loading of barium glass filler was determined as a function of nanogel content and composites with varied nanogel content but uniform filler loading were compared in terms of consistency, conversion, shrinkage and mechanical properties. Results High conversion, high molecular weight internally crosslinked and cyclized nanogel prepolymer was efficiently prepared and redispersed into TEGDMA with an exponential rise in viscosity accompanying nanogel content. Nanogel addition at any level produced no deleterious effects on reaction kinetics, conversion or mechanical properties, as long as reactive nanogels were used. A reduction in polymerization shrinkage and stress was achieved in proportion to nanogel content. Even at high nanogel concentrations, the maximum loading of glass filler was only marginally reduced relative to the control and high strength composite materials with low shrinkage were obtained. Significance The use of reactive nanogels offers a versatile platform from which resin and composite handling properties can be adjusted while the polymerization shrinkage and stress development that challenge the adhesive bonding of dental restoratives are controllably reduced. PMID:21388669

Impedance changes during setting of amorphous calcium phosphate composites.

PubMed

Par, Matej; Šantić, Ana; Gamulin, Ozren; Marovic, Danijela; Moguš-Milanković, Andrea; Tarle, Zrinka

2016-11-01

To investigate the electrical properties of experimental light-curable composite materials based on amorphous calcium phosphate (ACP) with the admixture of silanized barium glass and silica fillers. Short-term setting was investigated by impedance measurements at a frequency of 1kHz, while for the long-term setting the impedance spectra were measured consecutively over a frequency range of 0.05Hz to 1MHz for 24h. The analysis of electrical resistivity changes during curing allowed the extraction of relevant kinetic parameters. The impedance results were correlated to the degree of conversion assessed by Raman spectroscopy, water content determined by gravimetry, light transmittance measured by CCD spectrometer and microstructural features observed by scanning electron microscopy. ACP-based composites have shown higher immediate degree of conversion and less post-cure polymerization than the control composites, but lower polymerization rate. The polymerization rate assessed by impedance measurements correlated well with the light transmittance. The differences in the electrical conductivity values observed among the materials were correlated to the amount of water introduced into composites by the ACP filler. High correlation was found between the degree of conversion and electrical resistivity. Equivalent circuit modeling revealed two electrical contributions for the ACP-based composites and a single contribution for the control composites. The impedance spectroscopy has proven a valuable method for gaining insight into various features of ACP-based composites. Better understanding of the properties of ACP-based composites should further the development of these promising bioactive materials. Copyright © 2016 The Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Control of polymerization shrinkage and stress in nanogel-modified monomer and composite materials.

PubMed

Moraes, Rafael R; Garcia, Jeffrey W; Barros, Matthew D; Lewis, Steven H; Pfeifer, Carmem S; Liu, JianCheng; Stansbury, Jeffrey W

2011-06-01

This study demonstrates the effects of nano-scale prepolymer particles as additives to model dental monomer and composite formulations. Discrete nanogel particles were prepared by solution photopolymerization of isobornyl methacrylate and urethane dimethacrylate in the presence of a chain transfer agent, which also provided a means to attach reactive groups to the prepolymer. Nanogel was added to triethylene glycol dimethacrylate (TEGDMA) in increments between 5 and 40 wt% with resin viscosity, reaction kinetics, shrinkage, mechanical properties, stress and optical properties evaluated. Maximum loading of barium glass filler was determined as a function of nanogel content and composites with varied nanogel content but uniform filler loading were compared in terms of consistency, conversion, shrinkage and mechanical properties. High conversion, high molecular weight internally crosslinked and cyclized nanogel prepolymer was efficiently prepared and redispersed into TEGDMA with an exponential rise in viscosity accompanying nanogel content. Nanogel addition at any level produced no deleterious effects on reaction kinetics, conversion or mechanical properties, as long as reactive nanogels were used. A reduction in polymerization shrinkage and stress was achieved in proportion to nanogel content. Even at high nanogel concentrations, the maximum loading of glass filler was only marginally reduced relative to the control and high strength composite materials with low shrinkage were obtained. The use of reactive nanogels offers a versatile platform from which resin and composite handling properties can be adjusted while the polymerization shrinkage and stress development that challenge the adhesive bonding of dental restoratives are controllably reduced. Copyright © 2011 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Delayed photo-activation and addition of thio-urethane: Impact on polymerization kinetics and stress of dual-cured resin cements.

PubMed

Faria-E-Silva, André L; Pfeifer, Carmem S

2017-10-01

1) to determine the moment during the redox polymerization reaction of dual cure cements at which to photo-activate the material in order to reduce the polymerization stress, and 2) to evaluate possible synergistic effects between adding chain transfer agents and delayed photo-activation. The two pastes of an experimental dual-cure material were mixed, and the polymerization kinetics of the redox phase was followed. The moment when the material reached its maximum rate of redox polymerization (MRRP) of cement was determined. The degree of conversion (DC) and maximum rates of polymerization (Rp max ) were assessed for materials where: the photoactivation immediately followed material mixing, at MRRP, 1min before and 1min after MRRP. Thio-urethane (TU) additives were synthesized and added to the cement (20% wt), which was then cured under the same conditions. The polymerization kinetics was evaluated for both cements photo-activated immediately or at MRRP, followed by measurements of polymerization stress, flexural strength (FS) and elastic modulus (EM). Knoop hardness was measured before and after ethanol storage. Photo-activating the cement at or after MRRP reduced the Rp max and the polymerization stress. Addition of TU promoted additional and more significant reduction, while not affecting the Rp max . Greater hardness loss was observed for cements with TU, but the final hardness was similar for all experimental conditions. Addition of TU slightly reduced the EM and did not affect the FS. Delayed photo-activation and addition of TU significantly reduce the polymerization stress of dual-cured cements. Copyright © 2017 Elsevier Ltd. All rights reserved.

Green polymer chemistry: The role of Candida antarctica lipase B in polymer functionalization

NASA Astrophysics Data System (ADS)

Castano Gil, Yenni Marcela

The synthesis of functional polymers with well-defined structure, end-group fidelity and physico-chemical properties useful for biomedical applications has proven challenging. Chemo-enzymatic methods are an alternative strategy to increase the diversity of functional groups in polymeric materials. Specifically, enzyme-catalyzed polymer functionalization carried out under solventless conditions is a great advancement in the design of green processes for biomedical applications, where the toxicity of solvents and catalyst residues need to be considered. Enzymes offer several distinct advantages, including high efficiency, catalyst recyclability, and mild reaction conditions. This reseach aimed to precisely functionalized polymers using two methods: enzyme-catalyzed functionalization via polymerization and chemo-enzymatic functionalization of pre-made polymers for drug delivery. In the first method, well-defined poly(caprolactone)s were generated using alkyne-based initiating systems catalyzed by CALB. Propargyl alcohol and 4-dibenzocyclooctynol (DIBO) were shown to efficiently initiate the ring opening polymerization of epsilon-caprolactone under metal free conditions and yielded polymers with Mn ~4 to 24 KDa and relatively narrow molecular mass distribution. In the second methodology, we present quantitative enzyme-catalyzed transesterification of vinyl esters and ethyl esters with poly(ethylene glycol)s (PEG)s that will serve as building blocks for dendrimer synthesis, followed by introducing a new process for the exclusive gamma-conjugation of folic acid. Specifically, fluorescein-acrylate was enzymatically conjugated with PEG. Additionally, halo-ester functionalized PEGs were successfully prepared by the transesterification of alkyl halo-esters with PEGs. 1H and 13C NMR spectroscopy, SEC and MALDI-ToF mass spectrometry confirmed the structure and purity of the products.

Boron nitride nanotubes and nanoplatelets as reinforcing agents of polymeric matrices for bone tissue engineering.

PubMed

Farshid, Behzad; Lalwani, Gaurav; Shir Mohammadi, Meisam; Simonsen, John; Sitharaman, Balaji

2017-02-01

This study investigates the mechanical properties and in vitro cytotoxicity of one- and two-dimensional boron nitride nanomaterials-reinforced biodegradable polymeric nanocomposites. Poly(propylene fumarate) (PPF) nanocomposites were fabricated using crosslinking agent N-vinyl pyrrolidone and inorganic nanomaterials: boron nitride nanotubes (BNNTs) and boron nitride nanoplatelets (BNNPs) dispersed at 0.2 wt % in the polymeric matrix. The incorporation of BNNPs and BNNTs resulted in a ∼38 and ∼15% increase in compressive (Young's) modulus, and ∼31 and ∼6% increase in compressive yield strength compared to PPF control, respectively. The nanocomposites showed a time-dependent increased protein adsorption for collagen I protein. The cytotoxicity evaluation of aqueous BNNT and BNNP dispersions (at 1-100 μg/mL concentrations) using murine MC3T3 preosteoblast cells showed ∼73-99% viability. The cytotoxicity evaluation of media extracts of nanocomposites before crosslinking, after crosslinking, and upon degradation (using 1×-100× dilutions) showed dose-dependent cytotoxicity responses. Crosslinked nanocomposites showed excellent (∼79-100%) cell viability, cellular attachment (∼57-67%), and spreading similar to cells grown on the surface of tissue culture polystyrene control. The media extracts of degradation products showed a dose-dependent cytotoxicity. The favorable cytocompatibility results in combination with improved mechanical properties of BNNT and BNNP nanocomposites opens new avenues for further in vitro and in vivo safety and efficacy studies towards bone tissue engineering applications. © 2015 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 105B: 406-419, 2017. © 2015 Wiley Periodicals, Inc.

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.

Thermally resistant polymers for fuel tank sealants

NASA Technical Reports Server (NTRS)

Webster, J. A.

1972-01-01

Conversion of fluorocarbon dicarboxylic acid to intermediates whose terminal functional groups permit polymerization is discussed. Resulting polymers are used as fuel tank sealers for jet fuels at elevated temperatures. Stability and fuel resistance of the prototype polymers is explained.

Biosynthesis of Plant and Animal Foods.

ERIC Educational Resources Information Center

Dunne, C. Patrick

1984-01-01

Presents a biochemical overview of the synthesis of food biopolymers that constitute macronutrients in the plant or animal cell. Emphasizes involvement of enzymes in steps characterized by accumulation of materials, activation, polymerization, postpolymerization conversion, and formation of structural components. (JN)

In vitro assessment of polymerization procedures in Class II restorations: sealing, FTIR, and microhardness evaluations.

PubMed

Tassery, H; de Donato, P; Barrès, O; Déjou, J

2001-01-01

This study was undertaken to evaluate several polymerization and filling procedures (incremental, bulk, light-tip, soft-cured, plasma devices) in Class II restorations through (1) a sealing evaluation of restorations filled with Tetric Ceram (TC) and Bisfil 2B (B2B, self-cured composite used as a control), (2) a FTIR analysis measuring the variations of the degree of conversion in terms of area unit ratio of the relevant resin composites and (3) a microhardness test to corroborate the FTIR analysis. The length of the tracer penetration was measured from the gingival margin up to the cavity wall with an episcope on sectioned teeth. A ceramic mould, simulating a Class II, was filled according to the different groups and the samples were analyzed with a Bruker IFS 55 spectrometer on ultrathin sections (3 mu). The results were analyzed in terms of area unit ratio and total exposed energy. Under the same conditions, a microhardness test was run with a Frank Weihem machine. The results of the sealing evaluation for light-tip, incremental and self-cured techniques did not differ. The plasma procedure failed in this evaluation as the bottom increment was not polymerized. The smallest area unit ratio (the best degree of conversion) was observed in 2 groups: one, the combination of the light-tip and soft process, and two, the self-cured resin composite (B2B). The distance at which the plasma procedure failed to cure the resin composite was between 3.5 and 4.5 mm. The microhardness test confirmed the FTIR analysis except for the group G2 (TC + light-tip). As also shown by FTIR analysis, no difference between the two relevant levels was observed with the hardness test. The dentin marginal sealing efficiency of Tetric Ceram restorations was increased with the light-tip technique, but was not better than the self-cured resin composite (B2B). For Tetric Ceram, the combination of the light-tip and soft process leads to a higher degree of conversion than the other groups. There is no linear relationship between the degree of conversion, the microhardness and the total exposed energy. The combination of the soft polymerization and the light-tip device might be an alternative restorative technique to the current incremental technique.

42 CFR 84.250 - Vinyl chloride respirators; description.

Code of Federal Regulations, 2010 CFR

2010-10-01

... 42 Public Health 1 2010-10-01 2010-10-01 false Vinyl chloride respirators; description. 84.250... Respirators § 84.250 Vinyl chloride respirators; description. Vinyl chloride respirators, including all... escape from vinyl chloride atmospheres containing adequate oxygen to support life, are described...

Photo-induced living radical polymerization of acrylates utilizing a discrete copper(II)-formate complex.

PubMed

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.

Cu-catalyzed multicomponent polymerization to synthesize a library of poly(N-sulfonylamidines).

PubMed

Lee, In-Hwan; Kim, Hyunseok; Choi, Tae-Lim

2013-03-13

We report a versatile Cu-catalyzed multicomponent polymerization (MCP) technique that enables the synthesis of high-molecular-weight, defect-free poly(N-sulfonylamidines) from monomers of diynes, sulfonyl azides, and diamines. Through a series of optimizations, we discovered that the addition of excess triethylamine and the use of N,N'-dimethylformamide as a solvent are key factors to ensure efficient MCP. Formation of cyclic polyamidines was a side reaction during polymerization, but it was readily controlled by using diynes or diamines with long or rigid moieties. In addition, this polymerization is highly selective for three-component reactions over click reactions. The combination of the above factors enables the synthesis of high-molecular-weight polymers, which was challenging in previous MCPs. All three kinds of monomers (diynes, sulfonyl azides, and diamines) are readily accessible and stable under the reaction conditions, with various monomers undergoing successful polymerization regardless of their steric and electronic properties. Thus, we synthesized various high-molecular-weight, defect-free polyamidines from a broad range of monomers while overcoming the limitations of previous MCPs, such as low conversion and defects in the polymer structures.

The Effect of Surfactant and Compatibilizer on Inorganic Loading and Properties of PPO-based EPMM Membranes

NASA Astrophysics Data System (ADS)

Bissadi, Golnaz

Hybrid membranes represent a promising alternative to the limitations of organic and inorganic materials for high productivity and selectivity gas separation membranes. In this study, the previously developed concept of emulsion-polymerized mixed matrix (EPMM) membranes was further advanced by investigating the effects of surfactant and compatibilizer on inorganic loading in poly(2,6-dimethyl-1,4-phenylene oxide) (PPO)-based EPMM membranes, in which inorganic part of the membranes originated from tetraethylorthosilicate (TEOS). The polymerization of TEOS, which consists of hydrolysis of TEOS and condensation of the hydrolyzed TEOS, was carried out as (i) one- and (ii) two-step processes. In the one-step process, the hydrolysis and condensation take place in the same environment of a weak acid provided by the aqueous solution of aluminum hydroxonitrate and sodium carbonate. In the two-step process, the hydrolysis takes place in the environment of a strong acid (solution of hydrochloric acid), whereas the condensation takes place in weak base environment obtained by adding excess of the ammonium hydroxide solution to the acidic solution of the hydrolyzed TEOS. For both one- and two-step processes, the emulsion polymerization of TEOS was carried out in two types of emulsions made of (i) pure trichloroethylene (TCE) solvent, and (ii) 10 w/v% solution of PPO in TCE, using different combinations of the compatibilizer (ethanol) and the surfactant (n-octanol). The experiments with pure TCE, which are referred to as a gravimetric powder method (GPM) allowed assessing the effect of different experimental parameters on the conversion of TEOS. The GPM tests also provided a guide for the synthesis of casting emulsions containing PPO, from which the EPMM membranes were prepared using a spin coating technique. The synthesized EPMM membranes were characterized using 29Si nuclear magnetic resonance (29Si NMR), differential scanning calorimetry (DSC), inductively coupled plasma mass spectrometry (ICP-MS), and gas permeation measurements carried out in a constant pressure (CP) system. The 29Si NMR analysis verified polymerization of TEOS in the emulsions made of pure TCE, and the PPO solution in TCE. The conversions of TEOS in the two-step process in the two types of emulsions were very close to each other. In the case of the one-step process, the conversions in the TCE emulsion were significantly greater than those in the emulsion of the PPO solution in TCE. Consequently, the conversions of TEOS in the EPMM membranes made in the two-step process were greater than those in the EPMM membranes made in the one-step process. The latter ranged between 10 - 20%, while the highest conversion in the two-step process was 74% in the presence of pure compatibilizer with no surfactant. Despite greater conversions and hence the greater inorganic loadings, the EPMM membranes prepared in the two-step process had glass transition temperatures (Tg) only slightly greater than the reference PPO membranes. In contrast, despite relatively low inorganic loadings, the EPMM membranes prepared in the one-step process had Tgs markedly greater than PPO, and showed the expected trend of an increase in Tg with the inorganic loading. These results indicate that in the case of the one-step process the polymerized TEOS was well integrated with the PPO chains and the interactions between the two phases lead to high Tgs. On the other hand, this was not the case for the EPMM membranes prepared in the two-step process, suggesting possible phase separation between the polymerized TEOS and the organic phase. The latter was confirmed by detecting no selectivity in the EPMM membranes prepared by the two-step process. In contrast, the EPMM membranes prepared in the one-step process in the presence of the compatibilizer and no surfactant showed 50% greater O2 permeability coefficient and a slightly greater O2/N2 permeability ratio compared to the reference PPO membranes.

Effect of antioxidants on the dentin interface bond stability of adhesives exposed to hydrolytic degradation.

PubMed

Gotti, Valéria B; Feitosa, Victor P; Sauro, Salvatore; Correr-Sobrinho, Lourenço; Leal, Fernanda B; Stansbury, Jeffrey W; Correr, Américo B

2015-02-01

This study assessed the effect of antioxidants vitamin C (Vit. C), vitamin E (Vit. E) and quercetin (Querc) on the dentin bonding performance, degree of conversion, and rate of polymerization of three commercial adhesive systems (Adper Single Bond 2 [SB], Clearfil SE Bond [CSE], Adper Easy Bond [EB]). Human premolars were restored using antioxidant-doped adhesives. The samples were stored for 24 h in distilled water or 6 months under simulated pulpal pressure. Teeth were cut into sticks and the microtensile bond strength (μTBS) to dentin was tested in a universal testing machine. Qualitative nanoleakage analysis was performed from a central stick of each restored tooth. Degree of conversion and rate of polymerization of adhesive systems were evaluated in triplicate using real-time FT-IR. Although the inclusion of the antioxidants negatively affected the μTBS over 24 h, the antioxidant-doped adhesives maintained (SB-Vit. C, SB-Vit. E, CSE-Vit. C, EB-Querc) or increased (SB-Querc, CSE-Vit. E, CSE-Querc, EB-Vit. E, and EB-Vit. C) their μTBS during 6 months of storage. Only the μTBS of Adper Single Bond 2 dropped significantly after 6 months among the control groups. Slight changes in the nanoleakage pattern after aging were observed in all groups, except for the EB-control group, which showed a noteworthy increase in nanoleakage after 6 months, and for EB-Vit. C, which presented a remarkable decrease. A lower degree of conversion was obtained with all antioxidants in SB and EB, except for the EB-Vit. E group. Similar degrees of conversion were attained in control and experimental groups for CSE. The rate of polymerization was reduced in antioxidant-doped adhesives. The performance of antioxidants changed according to the adhesive system to which they were added, and antioxidant-doped adhesives appear to have a positive effect on the adhesive interface durability, since their bond strength obtained after 24 h was maintained or increased over time.

An in situ evaluation of the polymerization shrinkage, degree of conversion, and bond strength of resin cements used for luting fiber posts.

PubMed

Pulido, Camilo Andrés; de Oliveira Franco, Ana Paula Gebert; Gomes, Giovana Mongruel; Bittencourt, Bruna Fortes; Kalinowski, Hypolito José; Gomes, João Carlos; Gomes, Osnara Maria Mongruel

2016-10-01

The behavior and magnitude of the deformations that occur during polymerization and the behavior of the luting agents of glass fiber posts inside the root canal require quantification. The purpose of this in vitro study was to investigate the in situ polymerization shrinkage, degree of conversion, and bond strength inside the root canal of resin cements used to lute fiber posts. Thirty maxillary canines were prepared to lute fiber posts. The teeth were randomly divided into 2 groups (n=15) according to the cementation system used, which included ARC, the conventional dual-polymerized resin cement RelyX ARC, and the U200 system, a self-adhesive resin cement, RelyX U200. Two fiber optic sensors with recorded Bragg gratings (FBG) were attached to each post before inserting the resin cement inside the root canal to measure the polymerization shrinkage (PS) of the cements in the cervical and apical root regions (με). Specimens were sectioned (into cervical and apical regions) to evaluate bond strength (BS) with a push-out test and degree of conversion (DC) with micro-Raman spectroscopy. Data were statistically analyzed with 2-way ANOVA and the Tukey honestly significant difference post hoc test (α=.05). The ARC and U200 system showed similar PS values (-276.4 ±129.2 με and -252.1 ±119.2 με, respectively). DC values from ARC were higher (87.5 ±2.7%) than those of U200 (55.9 ±9.7%). The cervical region showed higher DC values (74.8 ±15.2%) and PS values (-381.6 ±53.0 με) than those of the apical region (68.5 ±20.1% and -146.9 ±43.5 με, respectively) for both of the resin cements. BS was only statistically different between the cervical and apical regions for ARC (P<.05). The ARC system showed the highest PS and DC values compared with U200; and for both of the resin cements, the PS and DC values were higher at the cervical region than at the apical region of the canal root. BS was higher in the cervical region only for ARC. Copyright © 2016 Editorial Council for the Journal of Prosthetic Dentistry. Published by Elsevier Inc. All rights reserved.

Thiol-vinyl systems as shape memory polymers and novel two-stage reactive polymer systems

NASA Astrophysics Data System (ADS)

Nair, Devatha P.

2011-12-01

The focus of this research was to formulate, characterize and tailor the reaction methodologies and material properties of thiol-vinyl systems to develop novel polymer platforms for a range of engineering applications. Thiol-ene photopolymers were demonstrated to exhibit several advantageous characteristics for shape memory polymer systems for a range of biomedical applications. The thiol-ene shape memory polymer systems were tough and flexible as compared to the acrylic control systems with glass transition temperatures between 30 and 40 °C; ideal for actuation at body temperature. The thiol-ene polymers also exhibited excellent shape fixity and a rapid and distinct shape memory actuation response along with free strain recoveries of greater than 96% and constrained stress recoveries of 100%. Additionally, two-stage reactive thiol-acrylate systems were engineered as a polymer platform technology enabling two independent sets of polymer processing and material properties. There are distinct advantages to designing polymer systems that afford two distinct sets of material properties -- an intermediate polymer that would enable optimum handling and processing of the material (stage 1), while maintaining the ability to tune in different, final properties that enable the optimal functioning of the polymeric material (stage 2). To demonstrate the range of applicability of the two-stage reactive systems, three specific applications were demonstrated; shape memory polymers, lithographic impression materials, and optical materials. The thiol-acrylate reactions exhibit a wide range of application versatility due to the range of available thiol and acrylate monomers as well as reaction mechanisms such as Michael Addition reactions and free radical polymerizations. By designing a series of non-stoichiometeric thiol-acrylate systems, a polymer network is initially formed via a base catalyzed 'click' Michael addition reaction. This self-limiting reaction results in a Stage 1 polymer with excess acrylic functional groups within the network. At a later point in time, the photoinitiated, free radical polymerization of the excess acrylic functional groups results in a highly crosslinked, robust material system. By varying the monomers within the system as well as the stoichiometery of thiol to acrylate functional groups, the ability of the two-stage reactive systems to encompass a wide range of properties at the end of both the stage 1 and stage 2 polymerizations was demonstrated. The thiol-acrylate networks exhibited intermediate Stage 1 rubbery moduli and glass transition temperatures that range from 0.5 MPa and -10 ºC to 22 MPa and 22 ºC respectively. The same polymer networks can then attain glass transition temperatures that range from 5 ºC to 195 ºC and rubbery moduli of up to 200 MPa after the subsequent photocure stage. Two-stage reactive polymer composite systems were also formulated and characterized for thermomechanical and mechanical properties. Thermomechanical analysis showed that the fillers resulted in a significant increase in the modulus at both stage 1 and stage 2 polymerizations without a significant change in the glass transition temperatures (Tg). The two-stage reactive matrix composite formed with a hexafunctional acrylate matrix and 20 volume % silica particles showed a 125% increase in stage 1 modulus and 101% increase in stage 2 modulus, when compared with the modulus of the neat matrix. Finally, the two-stage reactive polymeric devices were formulated and designed as orthopedic suture anchors for arthroscopic surgeries and mechanically characterized. The Stage 1 device was designed to exhibit properties ideal for arthroscopic delivery and device placement with glass transition temperatures 25 -- 30 °C and rubbery moduli ˜ 95 MPa. The subsequent photopolymerization generated Stage 2 polymers designed to match the local bone environment with moduli ranging up to 2 GPa. Additionally, pull-out strengths of 140 N were demonstrated and are equivalent to the pull-strengths achieved by other commercially available suture anchors.

46 CFR 151.50-34 - Vinyl chloride (vinyl chloride monomer).

Code of Federal Regulations, 2011 CFR

2011-10-01

... 46 Shipping 5 2011-10-01 2011-10-01 false Vinyl chloride (vinyl chloride monomer). 151.50-34 Section 151.50-34 Shipping COAST GUARD, DEPARTMENT OF HOMELAND SECURITY (CONTINUED) CERTAIN BULK DANGEROUS... chloride (vinyl chloride monomer). (a) Copper, aluminum, magnesium, mercury, silver, and their alloys shall...

Effect of chain structure on hydrogen bonding in vinyl acetate - vinyl alcohol copolymers

NASA Astrophysics Data System (ADS)

Merekalova, Nadezhda D.; Bondarenko, Galina N.; Denisova, Yuliya I.; Krentsel, Liya B.; Litmanovich, Arkadiy D.; Kudryavtsev, Yaroslav V.

2017-04-01

FTIR spectroscopy and semi-empirical AM1 method are used to study hydrogen bonding in multiblock and random equimolar copolymers of vinyl acetate and vinyl alcohol. An energetically beneficial zip-holder complex, built on multiple inter- and intrachain hydroxyl-hydroxyl bonds and an intrachain hydroxyl-acetyloxy bond, can be formed between two vinyl alcohol sequences. As a result, multiblock copolymers reveal stronger degree of association that affects crystallinity, as well as various rheological and relaxation properties discussed in the literature. Macromolecular complexes in random copolymers are weak and tend to be destroyed in the presence of residual DMF solvent and adsorbed water. Nevertheless, a rather stable interchain quaternary complex can be formed that includes vinyl alcohol and vinyl acetate units and DMF and water molecules. For a single chain it is shown that an H-bond between neighboring vinyl alcohol and vinyl acetate monomer units mostly engages a carbonyl oxygen atom of the vinyl acetate, if the vinyl alcohol belongs to a short (<5 units) sequence, and an ether oxygen atom in the other case. On the whole, the quantum chemistry calculations shed much light on the origin of distinctions in the copolymer FTIR spectra, which may seem subtle when considered standalone.

Nano-network with dual temperature and pH responsiveness based on copolymers of 2-hydroxyethyl methacrylate with 3,9-divinyl-2,4,8,10-tetraoxaspiro[5.5]-undecane

NASA Astrophysics Data System (ADS)

Chiriac, Aurica P.; Nita, Loredana E.; Nistor, Manuela T.

2011-12-01

This study refers to the synthesis of a nano-network with dual temperature and pH responsiveness based on the 2-hydroxyethyl methacrylate (HEMA) copolymers with a comonomer with spiroacetal moiety and crosslinking capacity, namely 3,9-divinyl-2,4,8,10-tetraoxaspiro[5.5]-undecane (U). The copolymers were synthesized by radical emulsion polymerization, using 4,4'-azobis(cyanopentanoic acid) as initiator, in the presence of sodium lauryl sulfate as tensioactive agent and poly(vinyl alcohol) as protective colloid. Three copolymer variants were taken into study resulted from the different ratio between the comonomers (HEMA/U), which was about 98/2, 95/5, and 90/10, respectively. The copolymers were characterized by FTIR and thermal analysis. The copolymers sensitivity was evidenced by studying the evolution of the hydrodynamic radius and zeta potential of the polymeric particles as a function of pH. Thus, the particles size increases with the comonomer amount, from 193 nm in case of the homopolymer up to 253 nm for the copolymer with maximum content of the comonomer (10%). The increase of the particle hydrodynamic radius with the growth of temperature was also put into evidence.

Radiation graft modification of EPDM rubber

NASA Astrophysics Data System (ADS)

Katbab, A. A.; Burford, R. P.; Garnett, J. L.

N-Vinyl pyrrolidone (NVP), 2-hydroxyethylmethacrylate (HEMA) and acrylamide (AAm) have been grafted to the surface of rubber vulcanizates based on ethylene-propylene-terpolymer (EPDM) using the simultaneous radiation method to alter surface properties such as wettability and therefore biocompatibility. The effect of monomer concentration, solvent and EPDM structural factors on the grafting behavior have been investigated. The inhibitory effect upon homopolymerization of various salts has also been evaluated for the three monomers. NVP and HEMA could be grafted onto EPDM rubber in the presence of aqueous solutions of cupric nitrate at 0.005 M and 1.0 M concentrations respectively. Aqueous solutions of Mohr's salt (ammonium ferrous sulphate) at 0.05 M not only suppressed the homopolymerization of AAm but also increased grafting yield. The percentage grafting also increased with increasing AAm concentration. A mechanism has been proposed to explain the behaviour of these monomers. The inclusion of multifunctional acrylates in additive amounts (1.0 vol%) enhanced the graft degree. Modified samples were able to be efficiently stained, allowing the depth of the graft copolymerization to be determined by light microscopy. Water was found to have an accelerating effect on the polymerization of these monomers, but methanol prevented their polymerization completely. The effect of EPDM structural factors upon degree of grafting was found to vary, depending upon the monomer type.

Polyaniline - Carrageenan - Polyvinyl Alcohol Composite Material Synthesized Via Interfacial Polymerization, its Morphological Characteristics and Enhanced Solubility in Water

NASA Astrophysics Data System (ADS)

Montalbo, R. C. K.; Marquez, M. C.

2017-09-01

In recent years, conducting polyaniline (PAni) has been a popular interest of research in the field of conducting polymers due to its relatively low cost, ease of production, good conductivity, and environmental stability. Many studies however, have focused on improving its short-comings such as its limited processability and solubility in common solvents. In this study, PAni, soluble in water was produced via interfacial polymerization with chloroform as the organic solvent. Poly(vinyl alcohol) (PVA) and kappa(κ), iota(ι) and lambda(λ) - carrageenan (κCGN, ιCGN, λCGN) were added to the aqueous layer to stabilize PAni in the medium. FTIR and UV-Vis absorption spectra of the solutions as well as the fabricated film confirmed the existence of PAni emeraldine salt (PAni-ES). FTIR spectrum also confirmed the peaks corresponding to the interaction of PAni with the CGNs. Moreover, PVA-CGN played a very large role on the stability of the PAni nanofibers integrated on the PVA-CGN matrix. The morphologies of the products were further investigated using SEM and TEM. Polymer electrolyte for supercapacitor or an interfacial layer for organic solar cell is being targeted as potential application of the synthesized water soluble PAni.

Development of a polymeric ionic liquid coating for direct-immersion solid-phase microextraction using polyhedral oligomeric silsesquioxane as cross-linker.

PubMed

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.

A novel route to prepare a multilayer system via the combination of interface-mediated catalytic chain transfer polymerization and thiol-ene click chemistry.

PubMed

Zengin, Adem; Caykara, Tuncer

2017-05-01

Herein, we have designed a novel multilayer system composed of poly(methyl methacrylate) [poly(MMA)] brush, biotin, streptavidin and protein-A on a silicon substrate to attach onanti-immunoglobulin G (anti-IgG). poly(MMA) brush with vinyl end-group was first synthesized by the interface-mediated catalytic chain transfer polymerization. The brush was then modified with cysteamine molecules to generate the polymer chains with amine end-group via a thiol-ene click chemistry. The amine end-groups of poly(MMA) chains were also modified with biotin units to ensure selective connection points for streptavidin molecules. Finally, a multilayer system on the silicon substrate was formed by using streptavidin and protein-A molecules, respectively. This multilayer system was employed to attach anti-IgG molecules in a highly oriented manner and provide anti-IgG molecular functional configuration on the multilayer. High reproducibility of the amount of anti-IgG adsorption and homogeneous anti-IgG adsorption layer on the silicon surface could be provided by this multilayer system. The multilayer system with protein A may be opened the door for designing an efficient immunoassay protein chip. Copyright © 2017. Published by Elsevier B.V.

Mechanism of the formation and growth of fine particles clustered polymer microspheres by simple one-step polymerization in aqueous alcohol system

NASA Astrophysics Data System (ADS)

Mao, Hui; Wen, Chao; Wu, Shuyao; Liu, Daliang; Zhang, Yu; Song, Xi-Ming

2016-02-01

By using the one-step copolymerization of styrene (St) and 1-vinyl-3-ethylimidazolium bromide (VEIB), fine particles clustered (FPC) poly(St-co-VEIB) microspheres have been successfully prepared in the present of sodium dodecylsulfonate (SDS) in aqueous alcohol system. The FPC poly(St-co-VEIB) microspheres are composed of small poly(St-co-VEIB) nanospheres with the average diameter of 40 nm. The formation mechanism of FPC poly(St-co-VEIB) microspheres is proposed by investigating the influence of reaction conditions on their morphologies and observing their growth process. It can be well convinced that VEIB not only acted as a kind of monomers, which participated in the polymerization and provided electropositivity for FPC poly(St-co-VEIB) microspheres, but also acted as emulsifier and reactive stabilizer. The FPC poly(St-co-VEI[SO3CF3]) microspheres, which were obtained by anion-exchange between -SO3CF3 of HSO3CF3 and Br- in FPC poly(St-co-VEIB) microspheres due to the existence of imidazolium groups with electropositivity, showed higher catalytic efficiency for hydration of 1,2-epoxypropane with H2O and esterification between acetic acid and ethanol than that of H2SO4.

Graft polymerization of styryl bisphosphonate monomer onto polypropylene films for inhibition of biofilm formation.

PubMed

Steinmetz, Hanna P; Rudnick-Glick, Safra; Natan, Michal; Banin, Ehud; Margel, Shlomo

2016-11-01

There has been increased concern during the past few decades over the role bacterial biofilms play in causing a variety of health problems, especially since they exhibit a high degree of resistance to antibiotics and are able to survive in hostile environments. Biofilms consist of bacterial aggregates enveloped by a self-produced matrix attached to the surface. Ca(2+) ions promote the formation of biofilms, and enhance their stability, viscosity, and strength. Bisphosphonates exhibit a high affinity for Ca(2+) ions, and may inhibit the formation of biofilms by acting as sequestering agents for Ca(2+) ions. Although the antibacterial activity of bisphosphonates is well known, research into their anti-biofilm behavior is still in its early stages. In this study, we describe the synthesis of a new thin coating composed of poly(styryl bisphosphonate) grafted onto oxidized polypropylene films for anti-biofilm applications. This grafting process was performed by graft polymerization of styryl bisphosphonate vinylic monomer onto O2 plasma-treated polypropylene films. The surface modification of the polypropylene films was confirmed using surface measurements, including X-ray photoelectron spectroscopy, atomic force microscopy, and water contact angle goniometry. Significant inhibition of biofilm formation was achieved for both Gram-negative and Gram-positive bacteria. Copyright © 2016 Elsevier B.V. All rights reserved.

Forensic engineering of advanced polymeric materials Part IV: Case study of oxo-biodegradable polyethylene commercial bag - Aging in biotic and abiotic environment.

PubMed

Musioł, Marta; Rydz, Joanna; Janeczek, Henryk; Radecka, Iza; Jiang, Guozhan; Kowalczuk, Marek

2017-06-01

The public awareness of the quality of environment stimulates the endeavor to safe polymeric materials and their degradation products. The aim of the forensic engineering case study presented in this paper is to evaluate the aging process of commercial oxo-degradable polyethylene bag under real industrial composting conditions and in distilled water at 70°C, for comparison. Partial degradation of the investigated material was monitored by changes in molecular weight, thermal properties and Keto Carbonyl Bond Index and Vinyl Bond Index, which were calculated from the FTIR spectra. The results indicate that such an oxo-degradable product offered in markets degrades slowly under industrial composting conditions. Even fragmentation is slow, and it is dubious that biological mineralization of this material would occur within a year under industrial composting conditions. The slow degradation and fragmentation is most likely due to partially crosslinking after long time of degradation, which results in the limitation of low molecular weight residues for assimilation. The work suggests that these materials should not be labeled as biodegradable, and should be further analyzed in order to avoid the spread of persistent artificial materials in nature. Copyright © 2017 Elsevier Ltd. All rights reserved.

Well-dispersed cellulose nanocrystals in hydrophobic polymers by in situ polymerization for synthesizing highly reinforced bio-nanocomposites.

PubMed

Geng, Shiyu; Wei, Jiayuan; Aitomäki, Yvonne; Noël, Maxime; Oksman, Kristiina

2018-04-20

In nanocomposites, dispersing hydrophilic nanomaterials in a hydrophobic matrix using simple and environmentally friendly methods remains challenging. Herein, we report a method based on in situ polymerization to synthesize nanocomposites of well-dispersed cellulose nanocrystals (CNCs) and poly(vinyl acetate) (PVAc). We have also shown that by blending this PVAc/CNC nanocomposite with poly(lactic acid) (PLA), a good dispersion of the CNCs can be reached in PLA. The outstanding dispersion of CNCs in both PVAc and PLA/PVAc matrices was shown by different microscopy techniques and was further supported by the mechanical and rheological properties of the composites. The in situ PVAc/CNC nanocomposites exhibit enhanced mechanical properties compared to the materials produced by mechanical mixing, and a theoretical model based on the interphase effect and dispersion that reflects this behavior was developed. Comparison of the rheological and thermal behaviors of the mixed and in situ PVAc/CNC also confirmed the great improvement in the dispersion of nanocellulose in the latter. Furthermore, a synergistic effect was observed with only 0.1 wt% CNCs when the in situ PVAc/CNC was blended with PLA, as demonstrated by significant increases in elastic modulus, yield strength, elongation to break and glass transition temperature compared to the PLA/PVAc only material.

Acid-Labile Amphiphilic PEO-b-PPO-b-PEO Copolymers: Degradable Poloxamer Analogs.

PubMed

Worm, Matthias; Kang, Biao; Dingels, Carsten; Wurm, Frederik R; Frey, Holger

2016-05-01

Poly ((ethylene oxide)-b-(propylene oxide)-b-(ethylene oxide)) triblock copolymers commonly known as poloxamers or Pluronics constitute an important class of nonionic, biocompatible surfactants. Here, a method is reported to incorporate two acid-labile acetal moieties in the backbone of poloxamers to generate acid-cleavable nonionic surfactants. Poly(propylene oxide) is functionalized by means of an acetate-protected vinyl ether to introduce acetal units. Three cleavable PEO-PPO-PEO triblock copolymers (Mn,total = 6600, 8000, 9150 g·mol(-1) ; Mn,PEO = 2200, 3600, 4750 g·mol(-1) ) have been synthesized using anionic ring-opening polymerization. The amphiphilic copolymers exhibit narrow molecular weight distributions (Ð = 1.06-1.08). Surface tension measurements reveal surface-active behavior in aqueous solution comparable to established noncleavable poloxamers. Complete hydrolysis of the labile junctions after acidic treatment is verified by size exclusion chromatography. The block copolymers have been employed as surfactants in a miniemulsion polymerization to generate polystyrene (PS) nanoparticles with mean diameters of ≈200 nm and narrow size distribution, as determined by dynamic light scattering and scanning electron microscopy. Acid-triggered precipitation facilitates removal of surfactant fragments from the nanoparticles, which simplifies purification and enables nanoparticle precipitation "on demand." © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Evaluation of the Effect of Porcelain Laminate Thickness on Degree of Conversion of Light Cure and Dual Cure Resin Cements Using FTIR

PubMed Central

Hoorizad Ganjkar, Maryam; Heshmat, Haleh; Hassan Ahangari, Reza

2017-01-01

Statement of the Problem: Increasing the thickness of the veneering porcelain may affect the polymerization of resin cements. Incomplete polymerization of resin cements can lead to compromised quality of restoration and decrease the longevity of indirect restorations. Purpose: This study sought to assess the effect of IPS Empress porcelain thickness on the degree of conversion of light-cure and dual-cure resin cements using Fourier transform infrared spectroscopy. Materials and Method: In this experimental study, IPS Empress porcelain discs (A2 shade) with 10mm diameter and 0.5, 1 and 1.5 mm thicknesses were fabricated. Choice2 (Bisco, USA) and Nexus3 (Kerr, USA) resin cements were light cured through the three porcelain thicknesses in two groups of 3 samples using a LED light-curing unit (LEDemetron II; Kerr, USA). The control group samples were cured individually with no porcelain disc. The degree of conversion of resin cements was determined using FTIR (Bruker; Equinox55, Germany). The data were analyzed using Dunn’s test. Results: The degree of conversion (in percent) beneath the 0.5, 1.5 and 2 mm thicknesses of IPS Empress was 68.67±0.88, 71.06±0.94 and 72.51±0.41 for Choice2 resin cement and 69.60±2.12, 69.64±1.63 and 69.24±2.12 for Nexus3, respectively. Porcelain thickness and type of resin cement had no significant effect on degree of conversion (p≥ 0.05). Conclusion: It seems that increasing the porcelain thickness by up to 1.5 mm has no adverse effect on degree of conversion of both dual cure and light cure resin cements evaluated in this study. PMID:28280757

Conjugated Polymers Via Direct Arylation Polymerization in Continuous Flow: Minimizing the Cost and Batch-to-Batch Variations for High-Throughput Energy Conversion.

PubMed

Gobalasingham, Nemal S; Carlé, Jon E; Krebs, Frederik C; Thompson, Barry C; Bundgaard, Eva; Helgesen, Martin

2017-11-01

Continuous flow methods are utilized in conjunction with direct arylation polymerization (DArP) for the scaled synthesis of the roll-to-roll compatible polymer, poly[(2,5-bis(2-hexyldecyloxy)phenylene)-alt-(4,7-di(thiophen-2-yl)-benzo[c][1,2,5]thiadiazole)] (PPDTBT). PPDTBT is based on simple, inexpensive, and scalable monomers using thienyl-flanked benzothiadiazole as the acceptor, which is the first β-unprotected substrate to be used in continuous flow via DArP, enabling critical evaluation of the suitability of this emerging synthetic method for minimizing defects and for the scaled synthesis of high-performance materials. To demonstrate the usefulness of the method, DArP-prepared PPDTBT via continuous flow synthesis is employed for the preparation of indium tin oxide (ITO)-free and flexible roll-coated solar cells to achieve a power conversion efficiency of 3.5% for 1 cm 2 devices, which is comparable to the performance of PPDTBT polymerized through Stille cross coupling. These efforts demonstrate the distinct advantages of the continuous flow protocol with DArP avoiding use of toxic tin chemicals, reducing the associated costs of polymer upscaling, and minimizing batch-to-batch variations for high-quality material. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Shape-Persistent, Thermoresponsive Polypeptide Brushes Prepared by Vapor Deposition Surface-Initiated Ring-Opening Polymerization of α-Amino Acid N -Carboxyanhydrides

DOE PAGES

Shen, Yong; Desseaux, Solenne; Aden, Bethany; ...

2015-04-20

We report that surface-grafting thermoresponsive polymers allows the preparation of thin polymer brush coatings with surface properties that can be manipulated by variation of temperature. In most instances, thermoresponsive polymer brushes are produced using polymers that dehydrate and collapse above a certain temperature. This report presents the preparation and properties of polymer brushes that show thermoresponsive surface properties, yet are shape-persistent in that they do not undergo main chain collapse. The polymer brushes presented here are obtained via vapor deposition surface-initiated ring-opening polymerization (SI-ROP) of γ-di- or tri(ethylene glycol)-modified glutamic acid N-carboxyanhydrides. Vapor deposition SI-ROP of γ-di- or tri(ethylene glycol)-modifiedmore » L- or D-glutamic acid N-carboxyanhydrides affords helical surface-tethered polymer chains that do not show any changes in secondary structure between 10 and 70 °C. QCM-D experiments, however, revealed significant dehydration of poly(γ-(2-(2-methoxyethoxy)ethyl)-l-glutamate) (poly(L-EG 2-Glu)) brushes upon heating from 10 to 40 °C. At the same time, AFM and ellipsometry studies did not reveal significant variations in film thickness over this temperature range, which is consistent with the shape-persistent nature of these polypeptide brushes and indicates that the thermoresponsiveness of the films is primarily due to hydration and dehydration of the oligo(ethylene glycol) side chains. The results we present here illustrate the potential of surface-initiated NCA ring-opening polymerization to generate densely grafted assemblies of polymer chains that possess well-defined secondary structures and tunable surface properties. These polypeptide brushes complement their conformationally unordered counterparts that can be generated via surface-initiated polymerization of vinyl-type monomers and represent another step forward to biomimetic surfaces and interfaces.« less

Polymeric Optical Sensors for Selective and Sensitive Nitrite Detection Using Cobalt(III) Corrole and Rh(III) Porphyrin as Ionophores

PubMed Central

Yang, Si; Wo, Yaqi; Meyerhoff, Mark E.

2014-01-01

Cobalt(III) 5, 10, 15-tris(4-tert-butylphenyl) corrole with a triphenylphosphine axial ligand and rhodium(III) 5,10,15,20-tetra(p-tert-butylphenyl)porphyrin are incorporated into plasticized poly(vinyl chloride) films to fabricate nitrite-selective bulk optodes via absorbance measurements. The resulting films yield sensitive, fast and fully reversible response toward nitrite with significantly enhanced nitrite selectivity over other anions including lipophilic anions such as thiocyanate and perchlorate. The selectivity patterns differ greatly from the Hofmeister series based on anion lipophilicity and are consistent with selectivity obtained with potentiometric sensors based on the same ionophores. The optical nitrite sensors are shown to be useful for detecting rates of emission of nitric oxide (NO) from NO releasing polymers containing S-nitroso-N-acetyl-penicillamine. PMID:25150700

Synthesis and characterization of functional acrylic copolymers via RAFT mini-emulsion polymerization

NASA Astrophysics Data System (ADS)

Yılmaz, Onur; Özkan, ćiǧdem Kılıçarislan; Yılmaz, Catalina N.; Yorgancıoǧlu, Ali; Özgünay, Hasan; Karavana, Hüseyin Ata

2017-12-01

Copolymers bearing reactive functional groups with controlled molecular weights are of importance since they can be used in many fields such as composites, coatings, membranes, catalysis, biology, optoelectronics, pharmaceuticals, etc. In the present study low molecular weight copolymers based on butyl acrylate (BA) and methyl methacrylate (MMA) in combination with reactive functional monomers of vinyl trietoxysilane (VTES), 3-trimetoxysilylpropyl methacrylate (TMSPMA) and glycidyl methacrylate (GMA) were synthesized via RAFT mini-emulsion technique using 2-cyano 2-propyldodecyldithiocarbonate as CTA agent. The results showed that the average molecular weights of copolymers were close to the theoretical values. On the other hand, PDI values were found to be higher than conventional RAFT polymers. The particle sizes of the latexes were small with very homogenous distributions and good stability. FTIR, H-NMR and TGA results verified the success of copolymer syntheses.

21 CFR 175.270 - Poly(vinyl fluoride) resins.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Poly(vinyl fluoride) resins. 175.270 Section 175... Substances for Use as Components of Coatings § 175.270 Poly(vinyl fluoride) resins. Poly(vinyl fluoride... the purpose of this section, poly(vinyl fluoride) resins consist of basic resins produced by the...

21 CFR 175.270 - Poly(vinyl fluoride) resins.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Poly(vinyl fluoride) resins. 175.270 Section 175... Substances for Use as Components of Coatings § 175.270 Poly(vinyl fluoride) resins. Poly(vinyl fluoride... the purpose of this section, poly(vinyl fluoride) resins consist of basic resins produced by the...

Mild copper-catalyzed vinylation reactions of azoles and phenols with vinyl bromides.

PubMed

Taillefer, Marc; Ouali, Armelle; Renard, Brice; Spindler, Jean-Francis

2006-07-05

An efficient and straightforward copper-catalyzed method allowing vinylation of N- or O-nucleophiles with di- or trisubstituted vinyl bromides is reported. The procedure is applicable to a broad range of substrates since N-vinylation of mono-, di-, and triazoles as well as O-vinylation of phenol derivatives can be performed with catalytic amounts of copper iodide and inexpensive nitrogen ligands 3 or 8. In the case of more hindered vinyl bromides, the use of the original bidentate chelator 8 was shown to be more efficient to promote the coupling reactions than our key tetradentate ligand 3. The corresponding N-(1-alkenyl)azoles and alkenyl aryl ethers are obtained in high yields and selectivities under very mild temperature conditions (35-110 degrees C for N-vinylation reactions and 50-80 degrees C for O-vinylation reactions). Moreover, to our knowledge, this method is the first example of a copper-catalyzed vinylation of various azoles. Finally, this protocol, practical on a laboratory scale and easily adaptable to an industrial scale, is very competitive compared to the existing methods that allow the synthesis of such compounds.

Effect of immediate or delayed light activation on curing kinetics and shrinkage stress of dual-cure resin cements.

PubMed

Faria-e-Silva, Andre; Boaro, Leticia; Braga, Roberto; Piva, Evandro; Arias, Vanessa; Martins, Luis

2011-01-01

This study evaluated the effect of light activation (absence, immediate, or delayed) on conversion kinetics and polymerization stress of three commercial dual-cured resin cements (Enforce, RelyX ARC, and Panavia F). Degree of conversion (DC) was monitored for 30 minutes using real-time near–Fourier transform infrared spectroscopy. The cement was mixed, placed on the spectrometer sample holder, and light activated either immediately or after five minutes (delayed light activation). When no light activation was performed, the materials were protected from light exposure (control). DC was evaluated at five and 30 minutes postmixture. Maximum rates of polymerization (Rp(max)) were obtained from the first derivative of the DC vs time curve. Polymerization stress was monitored for 30 minutes in 1-mm-thick specimens inserted between two cylinders attached to a universal testing machine. Data were submitted to analysis of variance/Tukey tests (α=0.05). Immediate light activation promoted the highest DC at five minutes. At 30 minutes, only RelyX ARC did not present a significant difference in DC between activation modes. Enforce and Panavia F presented higher Rp(max) for immediate and delayed light-activation, respectively. RelyX ARC showed similar Rp(max) for all activation modes. The absence of light activation resulted in the lowest stress followed by delayed light activation, while immediate light activation led to the highest values. RelyX ARC showed higher stress than Enforce, while the stress of Panavia F was similar to that of the others. Delayed light activation reduced the polymerization stress of the resin cements tested without jeopardizing DC.

One-Pot Enzymatic Production of Lignin-Composites.

PubMed

Ion, Sabina; Opris, Cristina; Cojocaru, Bogdan; Tudorache, Madalina; Zgura, Irina; Galca, Aurelian C; Bodescu, Adina M; Enache, Madalin; Maria, Gabriel-Mihai; Parvulescu, Vasile I

2018-01-01

A novel and efficient one-pot system for green production of artificial lignin bio-composites has been developed. Monolignols such as sinapyl (SA) and coniferyl (CA) alcohols were linked together with caffeic acid (CafAc) affording a polymeric network similar with natural lignin. The interaction of the dissolved SA/CA with CafAc already bound on a solid support (S C2 /S C6 -CafAc) allowed the attachment of the polymeric product direct on the support surface (S C2 /S C6 -CafAc-L 1 and S C2 /S C6 -CafAc-L 2 , from CA and SA, respectively). Accordingly, this procedure offers the advantage of a simultaneous polymer production and deposition. Chemically, oxi-copolymerization of phenolic derivatives (SA/CA and CAfAc) was performed with H 2 O 2 as oxidation reagent using peroxidase enzyme (2-1B mutant of versatile peroxidase from Pleurotus eryngii ) as catalyst. The system performance reached a maximum of conversion for SA and CA of 71.1 and 49.8%, respectively. The conversion is affected by the system polarity as resulted from the addition of a co-solvent (e.g., MeOH, EtOH, or THF). The chemical structure, morphology, and properties of the bio-composites surface were investigated using different techniques, e.g., FTIR, TPD-NH 3 , TGA, contact angle, and SEM. Thus, it was demonstrated that the SA monolignol favored bio-composites with a dense polymeric surface, high acidity, and low hydrophobicity, while CA allowed the production of thinner polymeric layers with high hydrophobicity.

Synthesis and structures of bis-ligated zinc complexes supported by tridentate ketoimines that initiate L-lactide polymerization.

PubMed

Gerling, Kimberly A; Rezayee, Nomaan M; Rheingold, Arnold L; Green, David B; Fritsch, Joseph M

2014-11-21

Eight bis-ligated, homoleptic, zinc complexes were synthesized through the reaction of NNO Schiff base ketoimines bearing varying substituents with diethyl zinc in an inert atmosphere glovebox at room temperature and isolated in 62-95% yield. The complexes were characterized with (1)H, (13)C, and (19)F nuclear magnetic resonance spectroscopy, absorbance spectroscopy, high resolution mass spectrometry, elemental analysis, and single crystal X-ray crystallography. The complexes were shown to adopt distorted octahedral coordination geometry around zinc. The (1)H and (19)F NMR spectra of complexes 1-7 showed stable zinc coordination at 300 K while the effect of steric encumbrance and two trifluoromethyl groups in complex 8 was investigated with variable temperature NMR. The bis-ligated zinc complexes were effective initiators for the ring opening polymerization of L-lactide into poly-L-lactic acid (PLLA). With [L-lac]/[Zn complex] = 50, the bis-ligated zinc complexes yielded percentage conversion of 14-98% with polymerization times varying from 15-1440 min, where the longest reaction times were required when two trifluoromethyl groups were present. The addition of 4-fluorophenol co-catalyst resulted in up to a 5-fold increase in the percentage conversion in toluene solution and up to a 14-fold increase in bulk melt polymerization with reductions in the poly-dispersity index values for the isolated PLLA. Addition of 4-fluorophenol to complex 1 was studied with (1)H and (19)F NMR and appeared to yield an in situ generated zinc alkoxide complex.

A convenient catalyst for aqueous and protein Suzuki-Miyaura cross-coupling.

PubMed

Chalker, Justin M; Wood, Charlotte S C; Davis, Benjamin G

2009-11-18

A phosphine-free palladium catalyst for aqueous Suzuki-Miyaura cross-coupling is presented. The catalyst is active enough to mediate hindered, ortho-substituted biaryl couplings but mild enough for use on peptides and proteins. The Suzuki-Miyaura couplings on protein substrates are the first to proceed in useful conversions. Notably, hydrophobic aryl and vinyl groups can be transferred to the protein surface without the aid of organic solvent since the aryl- and vinylboronic acids used in the coupling are water-soluble as borate salts. The convenience and activity of this catalyst prompts use in both general synthesis and bioconjugation.

Formation, Structure and Properties of Boron Nitride Fibers from Polymer Precursors

DTIC Science & Technology

1992-02-25

conversion, have been demonstrated in this study. Poly(ethylene oxide) (PEO), poly(N-vinyl-2-pyrrolidinone) ( PVP ), and poly(methyl methacrylate) (PMMA) were...vinylpyrrolidinone ( PVP , Mw = 360,000). A 100 ml reaction flask with teflon boiling chips and a 100 ml receiving flask were used on a high boiling distilling...CH 3 OBO) 3 : B(OH)3 Predicted 2 Experiment Experiment, 1 wt% PVP 2:1 47.8 mole% CH 3 OH 39.6 mole% CH 3OH 35.2 mole% CH3 OH 3:1 47.8 - 35.5 4:1 47.8

Nucleation of polystyrene latex particles in the presence of gamma-methacryloxypropyltrimethoxysilane: functionalized silica particles.

PubMed

Bourgeat-Lami, Elodie; Insulaire, Mickaelle; Reculusa, Stéphane; Perro, Adeline; Ravaine, Serge; Duguet, Etienne

2006-02-01

Silica/polystyrene nanocomposite particles with different morphologies were synthesized through emulsion polymerization of styrene in the presence of silica particles previously modified by gamma-methacryloxypropyltrimethoxysilane (MPS). Grafting of the silane molecule was performed by direct addition of MPS to the aqueous silica suspension in the presence of an anionic surfactant under basic conditions. The MPS grafting density on the silica surface was determined using the depletion method and plotted against the initial MPS concentration. The influence of the MPS grafting density, the silica particles size and concentration and the nature of the surfactant on the polymerization kinetics and the particles morphology was investigated. When the polymerization was performed in the presence of an anionic surfactant, transmission electron microscopy images showed the formation of polymer spheres around silica for MPS grafting densities lower than typically 1 micromole x m(-2) while the conversion versus time curves indicated a strong acceleration effect under such conditions. In contrast, polymerizations performed in the presence of a larger amount of MPS moieties or in the presence of a non ionic emulsifier resulted in the formation of "excentered" core-shell morphologies and lower polymerization rates. The paper identifies the parameters that allow to control particles morphology and polymerization kinetics and describes the mechanism of formation of the nanocomposite colloids.

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

PubMed Central

Kim, Moon Suk; Lee, Sang Bong

2014-01-01

In order to study the capability of pyrazinium salt derivatives to act as photo-initiators of epoxide monomers, benzyl pyrazinium hexafluoroantimonate (BPH), benzyl 3,5-dimethyl pyrazine hexafluoroantimonate (BDH) and benzyl quinoxalinium hexafluoroantimonate (BQH) were synthesized by the Menschutkin reaction of benzyl bromide with pyrazine, 2,6-dimethyl pyrazine, and quinoxaline, followed by exchanging with hexafluoroantimonate (SbF6). BPH, BDH, and BQH exhibited characteristic ultraviolet (UV) absorbance as well as exothermic peaks as a function of irradiation time in a differential photo-calorimeter (DPC). In the absence of photo-irradiation, cyclohexene oxide (CHO) underwent slow polymerization at 25 °C using BPH derivatives, but quantitative conversion was achieved even after a 5-min photo-irradiation. In addition, photo-irradiation was required for the photo-polymerization of CHO and styrene oxide (STO), which was characterized by a short induction period followed by a very rapid and exothermic polymerization. While glycidyl methyl ether (GME) required long induction periods, glycidyl phenyl ether (GPE) underwent rather slow and/or no photo-polymerization. The reactivity order of the monomers was CHO > STO >> GME >>> GPE, and the reactivity order for the photo-polymerization of CHO was BPH > BQH > BDH. It was found that BPH, BDH, and BQH could serve as photo-latent initiators for CHO, STO and GME, respectively. PMID:28788147

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

PubMed

Kim, Moon Suk; Lee, Sang Bong

2014-07-31

In order to study the capability of pyrazinium salt derivatives to act as photo-initiators of epoxide monomers, benzyl pyrazinium hexafluoroantimonate (BPH), benzyl 3,5-dimethyl pyrazine hexafluoroantimonate (BDH) and benzyl quinoxalinium hexafluoroantimonate (BQH) were synthesized by the Menschutkin reaction of benzyl bromide with pyrazine, 2,6-dimethyl pyrazine, and quinoxaline, followed by exchanging with hexafluoroantimonate (SbF₆). BPH, BDH, and BQH exhibited characteristic ultraviolet (UV) absorbance as well as exothermic peaks as a function of irradiation time in a differential photo-calorimeter (DPC). In the absence of photo-irradiation, cyclohexene oxide (CHO) underwent slow polymerization at 25 °C using BPH derivatives, but quantitative conversion was achieved even after a 5-min photo-irradiation. In addition, photo-irradiation was required for the photo-polymerization of CHO and styrene oxide (STO), which was characterized by a short induction period followed by a very rapid and exothermic polymerization. While glycidyl methyl ether (GME) required long induction periods, glycidyl phenyl ether (GPE) underwent rather slow and/or no photo-polymerization. The reactivity order of the monomers was CHO > STO > GME > GPE, and the reactivity order for the photo-polymerization of CHO was BPH > BQH > BDH. It was found that BPH, BDH, and BQH could serve as photo-latent initiators for CHO, STO and GME, respectively.

Sequential development of hepatocellular carcinoma and liver angiosarcoma in a vinyl chloride-exposed worker.

PubMed

Guido, Maria; Sarcognato, Samantha; Pelletti, Guido; Fassan, Matteo; Murer, Bruno; Snenghi, Rossella

2016-11-01

Strong experimental and clinical evidences have definitely linked occupational vinyl chloride exposure to development of angiosarcoma of the liver. In contrast, despite the International Agency for Research on Cancer having included vinyl chloride among the causes of hepatocellular carcinoma, the association between vinyl chloride exposure and hepatocellular carcinoma remains debated. This issue is relevant, because occupational exposure to high levels of vinyl chloride may still occur. We report a unique case of sequential occurrences of hepatocellular carcinoma and angiosarcoma of the liver, in a vinyl chloride-exposed worker without cirrhosis and any known risk factor for chronic liver disease. Both the hepatocellular carcinoma and the surrounding normal liver showed micronucleus formation, which reflects genotoxic effect of vinyl chloride. Angiosarcoma showed a KRAS G12D point mutation, which is considered to be characteristic of vinyl chloride-induced angiosarcoma. This case supports the pathogenic role of vinyl chloride in both hepatocellular carcinoma and angiosarcoma development. Copyright © 2016 Elsevier Inc. All rights reserved.

Syntheses and Post-Polymerization Modifications of Well-Defined Styrenic Polymers Containing Three-Membered Heterocyclic Functionalities

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.

Theoretical prediction and experimental determination of the effect of mold characteristics on temperature and monomer conversion fraction profiles during polymerization of a PMMA-based bone cement.

PubMed

Vallo, Claudia I

2002-01-01

The present work is concerned with applications of a kinetic model for free-radical polymerization of a polymethylmethacrylate-based bone cement. Autocatalytic behavior at the first part of the reaction as well as a diffusion control phenomenon near vitrification are described by the model. Comparison of theoretical computations with experimental measurements for the temperature evolution during batch casting demonstrated the capacity of the proposed model to represent the kinetic behavior of the polymerization reaction. Temperature evolution and monomer conversion were simulated for the cure of the cement in molds made of different materials. The maximum monomer conversion fraction was markedly influenced by the physical properties of the mold material. The unreacted monomer acts as a plasticizer that influences the mechanical behavior of the cement. Hence, the same cement formulation cured in molds of different materials may result in different mechanical response because of the differences in the amounts of residual monomer. Standardization of the mold type to prepare specimens for the mechanical characterization of bone cements is recommended. Theoretical prediction of temperature evolution during hip replacement indicated that for cement thickness lower than 6 mm the peak temperature at the bone-cement interface was below the limit stated for thermal injury (50 degrees C for more than 1 min). The use of thin cement layers is recommended to diminish the risk of thermal injury; however, it is accompanied by an increase in the amount of unreacted monomer present in the cured material. Copyright 2002 Wiley Periodicals, Inc. J Biomed Mater Res (Appl Biomater) 63: 627-642, 2002

Synthesis of mesoporous hollow silica nanospheres using polymeric micelles as template and their application as a drug-delivery carrier.

PubMed

Sasidharan, Manickam; Zenibana, Haruna; Nandi, Mahasweta; Bhaumik, Asim; Nakashima, Kenichi

2013-10-07

Mesoporous hollow silica nanospheres with uniform particle sizes of 31-33 nm have been successfully synthesized by cocondensation of tetramethoxysilane (TMOS) and alkyltrimethoxysilanes [RSi(OR)3], where the latter also acts as a porogen. ABC triblock copolymer micelles of poly(styrene-b-2-vinyl pyridine-b-ethylene oxide) (PS-PVP-PEO) with a core-shell-corona architecture have been employed as a soft template at pH 4. The cationic shell block with 2-vinyl pyridine groups facilitates the condensation of silica precursors under the sol-gel reaction conditions. Phenyltrimethoxysilane, octyltriethoxysilane, and octadecyltriethoxysilanes were used as porogens for generating mesopores in the shell matrix of hollow silica and the octadecyl precursor produced the largest mesopore among the different porogens, of dimension ca. 4.1 nm. The mesoporous hollow particles were thoroughly characterized by small-angle X-ray diffraction (SXRD), thermal (TG/DTA) and nitrogen sorption analyses, infra-red (FTIR) and nuclear magnetic resonance ((13)C-CP MAS NMR and (29)Si MAS NMR) spectroscopies, and transmission electron microscopy (TEM). The mesoporous hollow silica nanospheres have been investigated for drug-delivery application by an in vitro method using ibuprofen as a model drug. The hollow silica nanospheres exhibited higher storage capacity than the well-known mesoporous silica MCM-41. Propylamine functionalized hollow particles show a more sustained release pattern than their unfunctionalized counterparts, suggesting a huge potential of hollow silica nanospheres in the controlled delivery of small drug molecules.

Novel monolithic enzymatic microreactor based on single-enzyme nanoparticles for highly efficient proteolysis and its application in multidimensional liquid chromatography.

PubMed

Gao, Mingxia; Zhang, Peng; Hong, Guangfeng; Guan, Xia; Yan, Guoquan; Deng, Chunhui; Zhang, Xiangmin

2009-10-30

In this work, a novel and facile monolithic enzymatic microreactor was prepared in the fused-silica capillary via a two-step procedure including surface acryloylation and in situ aqueous polymerization/immobilization to encapsulate a single enzyme, and its application to fast protein digestion through a direct matrix-assisted laser desorption/ionization time-of-flight mass spectrometer (MALDI-TOF-MS) analysis was demonstrated. At first, vinyl groups on the protein surface were generated by a mild acryloylation with N-acryloxysuccinimide in alkali buffer. Then, acryloylated enzyme was encapsulated into polyacrylates by free-radical copolymerization with acrylamide as the monomer, N,N'-methylenebisacrylamide as the cross-linker, and N,N,N',N'-tetramethylethylenediamine/ammonium persulfate as the initiator. Finally, polymers were immobilized onto the activated inner wall of capillaries via the reaction of vinyl groups. Capability of the enzyme-immobilized monolithic microreactor was demonstrated by myoglobin and bovine serum albumin as model proteins. The digestion products were characterized using MALDI-TOF-MS with sequence coverage of 94% and 29% observed. This microreactor was also applied to the analysis of fractions through two-dimensional separation of weak anion exchange/reversed-phase liquid chromatography of human liver extract. After a database search, 16 unique peptides corresponding to 3 proteins were identified when two RPLC fractions of human liver extract were digested by the microreactor. This opens a route for its future application in top-down proteomic analysis.

Letrozole dispersed on poly (vinyl alcohol) anchored maleic anhydride grafted low density polyethylene: a controlled drug delivery system for treatment of breast cancer.

PubMed

Siddiqa, Akhtar Jahan; Chaudhury, Koel; Adhikari, Basudam

2014-04-01

The present work focuses on the design of a drug delivery system for systemic, controlled release of the poorly soluble breast cancer drug, letrozole. The drug delivery system was prepared in two steps: a low density polyethylene (LDPE) substrate surface was grafted with maleic anhydride (MA) via solution grafting technique. Next, the grafted substrate was used to anchor a hydrophilic polymeric drug release system consisting of poly (vinyl alcohol) (PVA). The PVA anchored MA grafted LDPE (PVA/MA-g-LDPE) drug release system was used for the controlled release of letrozole. This system was characterized using ATR-FTIR spectrophotometry, surface profilometry, and scanning electron microscopy. Biocompatibility studies were also carried out. In vitro release studies of letrozole from the system were performed in distilled water and phosphate buffer saline (PBS) at 37°C. Release of ∼90% letrozole from hydrophilic PVA matrix was observed within a period of 35 days. A high correlation coefficient (R(2)=0.99) was seen between the release of letrozole in distilled water and PBS. Cytotoxicity studies using MTT colorimetric assay suggested that all samples were biocompatible. It is concluded that the letrozole delivery system appears to overcome the limitations associated with letrozole by providing enhanced drug dissolution rate, controlled release and improved bioavailability of the incorporated drug and, therefore, seems to have extended therapeutic effects. Copyright © 2014 Elsevier B.V. All rights reserved.

The use of poly(vinyl phosphonic acid) microgels for the preparation of inherently magnetic Co metal catalyst particles in hydrogen production

NASA Astrophysics Data System (ADS)

Sahiner, Nurettin; Sagbas, Selin

2014-01-01

Novel poly(vinyl phosphonic acid) (p(VPA)) micro particle and composite p(VPA)-silica micro particle hydrogels are synthesized using a micro-emulsion polymerization technique. Porous p(VPA) particles are generated after removal of silica particles upon treatment of composite p(VPA) with 0.5 M NaOH solution. Bare, composite with silica, and porous p(VPA) micro particle hydrogels are used as templates and as reactors. Metal nanoparticles, Co, Ni, and Cu are generated in situ inside these hydrogels by chemical reduction of the absorbed metal ions with a reducing agent such as sodium boron hydride (NaBH4), and are used as catalyst in hydrogen production by hydrolysis of NaBH4 in a basic medium and ammonia borane (AB). The effects of reloaded metal ions, the reaction temperature, the porosity, the reusability, and the type of metal (Co, Ni, Cu) are investigated. The activation energy for hydrolysis of NaBH4, and AB by p(VPA)-Co is 28.02 and 25.51 kJ mol-1, respectively. The mass susceptibility measurements of composite p(VPA)-Co microgel is found as ferromagnetic. It is found that p(VPA) microgels provided better catalytic performance in comparison to macro p(VPA) hydrogels due to improved properties such as higher surface area, pore structure, and inherently magnetic behavior after multiple loadings-reduction of Co(II) from aqueous medium.

Investigation of yeast invertase immobilization onto cupric ion-chelated, porous, and biocompatible poly(hydroxyethyl methacrylate-n-vinyl imidazole) microspheres.

PubMed

Sari, Müfrettin Murat

2011-04-01

Cupric ion-chelated poly(hydroxyethyl methacrylate-n-vinyl imidazole) (poly(HEMA-VIM)) microspheres prepared by suspension polymerization were investigated as a specific adsorbent for immobilization of yeast invertase in a batch system. They were characterized by scanning electron microscopy, surface area, and pore size measurements. They have spherical shape and porous structure. The specific surface area of the p(HEMA-VIM) spheres was found to be 81.2 m²/g with a size range of 70-120 μm in diameter, and the swelling ratio was 86.9%. Then, Cu(II) ion chelated on the microspheres (546 μmol Cu(II)/g), and they were used in the invertase adsorption. Maximum invertase adsorption was 51.2 mg/g at pH 4.5. Cu(II) chelation increases the tendency from Freundlich-type to Langmuir-type adsorption model. The optimum activity for both free and adsorbed invertase was observed at pH 4.5. The optimum temperature for the poly(HEMA-VIM)/Cu(II)-invertase system was found to be at 55 °C, 10 °C higher than that of the free enzyme at 45 °C. V(max) values were determined as 342 and 304 U/mg enzyme, for free and adsorbed invertase, respectively. K(m) values were found to be same for free and adsorbed invertase (20 mM). Thermal and pH stability and reusability of invertase increased with immobilization.

Polymer-based materials to be used as the active element in microsensors: a scanning force microscopy study

PubMed

Porter; Eastman; Pace; Bradley

2000-09-01

Polymer-based materials can be incorporated as the active sensing elements in chemiresistor devices. Most of these devices take advantage of the fact that certain polymers will swell when exposed to gaseous analytes. To measure this response, a conducting material such as carbon black is incorporated within the nonconducting polymer matrix. In response to analytes, polymer swelling results in a measurable change in the conductivity of the polymer/carbon composite material. Arrays of these sensors may be used in conjunction with pattern recognition techniques for purposes of analyte recognition and quantification. We have used the technique of scanning force microscopy (SFM) to investigate microstructural changes in carbon-polymer composites formed from the polymers poly (isobutylene) (PIB), poly (vinyl alcohol) (PVA), and poly (ethylene-vinyl acetate) (PEVA) when exposed to the analytes hexane, toluene, water, ethanol, and acetone. Using phase-contrast imaging (PI), changes in the carbon nanoparticle distribution on the surface of the polymer matrix are measured as the polymers are exposed to the analytes in vapor phase. In some but not all cases, the changes were reversible (at the scale of the SFM measurements) upon removal of the analyte vapor. In this paper, we also describe a new type of microsensor based on piezoresistive microcantilever technology. With these new devices, polymeric volume changes accompanying exposure to analyte vapor are measured directly by a piezoresistive microcantilever in direct contact with the polymer. These devices may offer a number of advantages over standard chemiresistor-based sensors.

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

RAFT Aqueous Dispersion Polymerization of N-(2-(Methacryloyloxy)ethyl)pyrrolidone: A Convenient Low Viscosity Route to High Molecular Weight Water-Soluble Copolymers

PubMed Central

2016-01-01

RAFT solution polymerization of N-(2-(methacryoyloxy)ethyl)pyrrolidone (NMEP) in ethanol at 70 °C was conducted to produce a series of PNMEP homopolymers with mean degrees of polymerization (DP) varying from 31 to 467. Turbidimetry was used to assess their inverse temperature solubility behavior in dilute aqueous solution, with an LCST of approximately 55 °C being observed in the high molecular weight limit. Then a poly(glycerol monomethacylate) (PGMA) macro-CTA with a mean DP of 63 was chain-extended with NMEP using a RAFT aqueous dispersion polymerization formulation at 70 °C. The target PNMEP DP was systematically varied from 100 up to 6000 to generate a series of PGMA63–PNMEPx diblock copolymers. High conversions (≥92%) could be achieved when targeting up to x = 5000. GPC analysis confirmed high blocking efficiencies and a linear evolution in Mn with increasing PNMEP DP. A gradual increase in Mw/Mn was also observed when targeting higher DPs. However, this problem could be minimized (Mw/Mn < 1.50) by utilizing a higher purity grade of NMEP (98% vs 96%). This suggests that the broader molecular weight distributions observed at higher DPs are simply the result of a dimethacrylate impurity causing light branching, rather than an intrinsic side reaction such as chain transfer to polymer. Kinetic studies confirmed that the RAFT aqueous dispersion polymerization of NMEP was approximately four times faster than the RAFT solution polymerization of NMEP in ethanol when targeting the same DP in each case. This is perhaps surprising because both 1H NMR and SAXS studies indicate that the core-forming PNMEP chains remain relatively solvated at 70 °C in the latter formulation. Moreover, dissolution of the initial PGMA63–PNMEPx particles occurs on cooling from 70 to 20 °C as the PNMEP block passes through its LCST. Hence this RAFT aqueous dispersion polymerization formulation offers an efficient route to a high molecular weight water-soluble polymer in a rather convenient low-viscosity form. Finally, the relatively expensive PGMA macro-CTA was replaced with a poly(methacrylic acid) (PMAA) macro-CTA. High conversions were also achieved for PMAA85–PNMEPx diblock copolymers prepared via RAFT aqueous dispersion polymerization for x ≤ 4000. Again, better control was achieved when using the 98% purity NMEP monomer in such syntheses. PMID:27375300

RAFT Aqueous Dispersion Polymerization of N-(2-(Methacryloyloxy)ethyl)pyrrolidone: A Convenient Low Viscosity Route to High Molecular Weight Water-Soluble Copolymers.

PubMed

Cunningham, Victoria J; Derry, Matthew J; Fielding, Lee A; Musa, Osama M; Armes, Steven P

2016-06-28

RAFT solution polymerization of N -(2-(methacryoyloxy)ethyl)pyrrolidone (NMEP) in ethanol at 70 °C was conducted to produce a series of PNMEP homopolymers with mean degrees of polymerization (DP) varying from 31 to 467. Turbidimetry was used to assess their inverse temperature solubility behavior in dilute aqueous solution, with an LCST of approximately 55 °C being observed in the high molecular weight limit. Then a poly(glycerol monomethacylate) (PGMA) macro-CTA with a mean DP of 63 was chain-extended with NMEP using a RAFT aqueous dispersion polymerization formulation at 70 °C. The target PNMEP DP was systematically varied from 100 up to 6000 to generate a series of PGMA 63 -PNMEP x diblock copolymers. High conversions (≥92%) could be achieved when targeting up to x = 5000. GPC analysis confirmed high blocking efficiencies and a linear evolution in M n with increasing PNMEP DP. A gradual increase in M w / M n was also observed when targeting higher DPs. However, this problem could be minimized ( M w / M n < 1.50) by utilizing a higher purity grade of NMEP (98% vs 96%). This suggests that the broader molecular weight distributions observed at higher DPs are simply the result of a dimethacrylate impurity causing light branching, rather than an intrinsic side reaction such as chain transfer to polymer. Kinetic studies confirmed that the RAFT aqueous dispersion polymerization of NMEP was approximately four times faster than the RAFT solution polymerization of NMEP in ethanol when targeting the same DP in each case. This is perhaps surprising because both 1 H NMR and SAXS studies indicate that the core-forming PNMEP chains remain relatively solvated at 70 °C in the latter formulation. Moreover, dissolution of the initial PGMA 63 -PNMEP x particles occurs on cooling from 70 to 20 °C as the PNMEP block passes through its LCST. Hence this RAFT aqueous dispersion polymerization formulation offers an efficient route to a high molecular weight water-soluble polymer in a rather convenient low-viscosity form. Finally, the relatively expensive PGMA macro-CTA was replaced with a poly(methacrylic acid) (PMAA) macro-CTA. High conversions were also achieved for PMAA 85 -PNMEP x diblock copolymers prepared via RAFT aqueous dispersion polymerization for x ≤ 4000. Again, better control was achieved when using the 98% purity NMEP monomer in such syntheses.

Polymeric capsule-cushioned leukocyte cell membrane vesicles as a biomimetic delivery platform

NASA Astrophysics Data System (ADS)

Gao, Changyong; Wu, Zhiguang; Lin, Zhihua; Lin, Xiankun; He, Qiang

2016-02-01

We report a biomimetic delivery of microsized capsule-cushioned leukocyte membrane vesicles (CLMVs) through the conversion of freshly reassembled leukocyte membrane vesicles (LMVs), including membrane lipids and membrane-bound proteins onto the surface of layer-by-layer assembled polymeric multilayer microcapsules. The leukocyte membrane coating was verified by using electron microscopy, a quartz crystal microbalance, dynamic light scattering, and confocal laser scanning microscopy. The resulting CLMVs have the ability to effectively evade clearance by the immune system and thus prolong the circulation time in mice. Moreover, we also show that the right-side-out leukocyte membrane coating can distinctly improve the accumulation of capsules in tumor sites through the molecular recognition of membrane-bound proteins of CLMVs with those of tumor cells in vitro and in vivo. The natural cell membrane camouflaged polymeric multilayer capsules with the immunosuppressive and tumor-recognition functionalities of natural leukocytes provide a new biomimetic delivery platform for disease therapy.We report a biomimetic delivery of microsized capsule-cushioned leukocyte membrane vesicles (CLMVs) through the conversion of freshly reassembled leukocyte membrane vesicles (LMVs), including membrane lipids and membrane-bound proteins onto the surface of layer-by-layer assembled polymeric multilayer microcapsules. The leukocyte membrane coating was verified by using electron microscopy, a quartz crystal microbalance, dynamic light scattering, and confocal laser scanning microscopy. The resulting CLMVs have the ability to effectively evade clearance by the immune system and thus prolong the circulation time in mice. Moreover, we also show that the right-side-out leukocyte membrane coating can distinctly improve the accumulation of capsules in tumor sites through the molecular recognition of membrane-bound proteins of CLMVs with those of tumor cells in vitro and in vivo. The natural cell membrane camouflaged polymeric multilayer capsules with the immunosuppressive and tumor-recognition functionalities of natural leukocytes provide a new biomimetic delivery platform for disease therapy. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr08407e

Photopolymerization of N,N-dimethylaminobenzyl alcohol as amine co-initiator for light-cured dental resins.

PubMed

Schroeder, Walter F; Cook, Wayne D; Vallo, Claudia I

2008-05-01

The present study was carried out in order to assess the suitability of N,N-dimethylaminobenzyl alcohol (DMOH) as co-initiator of camphorquinone (CQ) and 1-phenyl-1,2-propanedione (PPD) in light-cured dental resins. DMOH was synthesized and used as co-initiator for the photopolymerization of a model resin based on {2,2-bis[4-(2-hydroxy-3-methacryloxyprop-1-oxy)phenyl]propane} (Bis-GMA)/triethylene glycol dimethacrylate (TEGDMA). Experimental formulations containing CQ or PPD in combination with DMOH at different concentrations were studied. The photopolymerization was carried out by means of a commercial light-emitting diode (LED) curing unit. The evolution of double bonds consumption versus irradiation time was followed by near-infrared spectroscopy (NIR). The photon absorption efficiency (PAE) of the photopolymerization process was calculated from the spectral distribution of the LED unit and the molar absorption coefficient distributions of PPD and CQ. DMOH is an efficient photoreducer of CQ and PPD resulting in higher polymerization rate and higher double bond conversion compared with dimethylaminoethylmethacrylate. The PAE for PPD was higher than that for CQ. However, the polymerization initiated by PPD progressed at a lower rate and exhibited lower values of final conversion compared with the resins containing CQ. This observation indicates that the lower polymerization rate of the PPD/amine system should be explained in terms of the mechanism of generating primary radicals by PPD, which is less efficient compared with CQ. The DMOH/benzoyl peroxide redox system, has recently been proposed as a more biocompatible accelerator for the polymerization of bone cements based on poly(methyl methacrylate), because cytotoxity tests have demonstrated that DMOH possesses better biocompatibility properties compared with traditional tertiary amines. The results obtained in the present study reveal the suitability of the CQ/DMOH initiator system for the polymerization of light-cured dental composites.

Polymerization of plant oils in carbon dioxide media

USDA-ARS?s Scientific Manuscript database

The conversion of plant oils to polymers has attracted renewed attention in recent years to replace or augment the traditional petrochemical-based polymers and resins. This is because of concern for the environment, waste disposal, and depletion of fossil and non-renewable feedstocks. Usually, polym...

Competitive light absorbers in photoactive dental resin-based materials.

PubMed

Hadis, Mohammed A; Shortall, Adrian C; Palin, William M

2012-08-01

The absorbance profile of photoinitiators prior to, during and following polymerization of light curable resin-based materials will have a significant effect on the cure and color properties of the final material. So-called "colorless" photoinitiators are used in some light-activated resin-based composite restorative materials to lessen the yellowing effect of camphoroquinone (CQ) in order to improve the esthetic quality of dental restorations. This work characterizes absorption properties of commonly used photoinitiators, an acylphosphine oxide (TPO) and CQ, and assesses their influence on material discoloration. Dimethacrylate resin formulations contained low (0.0134 mol/dm(3)), intermediate (0.0405 mol/dm(3)) or high (0.0678 mol/dm(3)) concentrations of the photoinitiators and the inhibitor, butylated hydroxytoluene (BHT) at 0, 0.1 or 0.2% by mass. Disc shaped specimens (n = 3) of each resin were polymerized for 60s using a halogen light curing unit. Dynamic measurements of photoinitiator absorption, polymer conversion and reaction temperature were performed. A spectrophotometer was used to measure the color change before and after cure. GLM three-way analysis of variance revealed significant differences (p<0.001), where photoinitiator concentration (df = 2; F = 618.83)>photoinitiator type (df = 1; F = 176.12)>% BHT (df = 2, F = 13.17). BHT concentration affected the rate of polymerization and produced lower conversion in some of the CQ-based resins. Significant differences between photoinitiator type and concentrations were seen in color (where TPO resins became yellower and camphoroquinone resins became less yellow upon irradiation). Reaction temperature, kinetics and conversion also differed significantly for both initiators (p<0.001). Despite TPO-based resins producing a visually perceptible color change upon polymerization, the color change was significantly less than that produced with CQ-based resins. Although some photoinitiators such as TPO may be a more esthetic alternative to CQ, they may actually cause significant color contamination when used in high concentrations and therefore manufacturers should limit its concentration in order to improve its esthetic quality. Copyright © 2012 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hinderliter, Paul M.; Thrall, Karla D.; Corley, Rick A.

Vinyl acetate has been shown to induce nasal lesions in rodents in inhalation bioassays. A physiologically based pharmacokinetic (PBPK) model for vinyl acetate has been used in human risk assessment, but previous in vivo validation was conducted only in rats. Controlled human exposures to vinyl acetate were conducted to provide validation data for the application of the model in humans. Five volunteers were exposed to 1, 5, and 10 ppm 13 C1 , 13 C2 vinyl acetate via inhalation. A probe inserted into thenasopharyngeal region sampled both 13 C1 , 13 C2 vinyl acetate and the major metabolite 13 C1more » , 13 C2 acetaldehyde during rest and light exercise. Nasopharyngeal air concentrations were analyzed in real time by ion trap mass spectrometry (MS/MS). Experimental concentrations of both vinyl acetate and acetaldehyde were then compared to predicted concentrations calculated from the previously published human model. Model predictions of vinyl acetate nasal extraction compared favorably with measured values of vinyl acetate, as did predictions of nasopharyngeal acetaldehyde when compared to measured acetaldehyde. The results showed that the current PBPK model structure and parameterization are appropriate for vinyl acetate. These analyses were conducted from 1 to 10 ppm vinyl acetate, a range relevant to workplace exposure standards but which would not be expected to saturate vinyl acetate metabolism. Risk assessment based on this model further concluded that 24 h per day exposures up to 1 ppm do not present concern regarding cancer or non-cancer toxicity. Validation of the vinyl acetate human PBPK model provides support for these conclusions.« less

Phosphines bearing alkyne substituents: synthesis and hydrophosphination polymerization.

PubMed

Greenberg, Sharonna; Stephan, Douglas W

2009-09-07

A synthetic route is described for a series of phosphines bearing pendant alkyne substituents, from the conversion of BrC(6)H(2)R(2)C[triple bond]CR' (R = Me, i-Pr; R' = Ph, SiMe(3)) to [(mu-Br)Cu(Et(2)N)(2)PC(6)H(2)R(2)C[triple bond]CR'](2) and subsequently to Cl(2)PC(6)H(2)R(2)C[triple bond]CR' and H(2)PC(6)H(2)R(2)C[triple bond]CR'. Lithiation and subsequent alkylation yield the secondary phosphines R(H)PC(6)H(2)(i-Pr)(2)C[triple bond]CPh (R = CH(2)i-Pr, CH(2)Ph). Intermolecular hydrophosphination-polymerization is used to prepare the polymeric species [RPC(6)H(2)(i-Pr)(2)CH=CPh](n), which can then be sulfurized to give [RP(S)C(6)H(2)(i-Pr)(2)CH=CPh](n). The polymeric products were characterized by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry and gel permeation chromatography. These data indicate a degree of polymerization (DP(n)) of up to 60. Discussion of the mechanism is augmented with gas-phase density functional theory calculations.

Real-time synchronous measurement of curing characteristics and polymerization stress in bone cements with a cantilever-beam based instrument

NASA Astrophysics Data System (ADS)

Palagummi, Sri Vikram; Landis, Forrest A.; Chiang, Martin Y. M.

2018-03-01

An instrumentation capable of simultaneously determining degree of conversion (DC), polymerization stress (PS), and polymerization exotherm (PE) in real time was introduced to self-curing bone cements. This comprises the combination of an in situ high-speed near-infrared spectrometer, a cantilever-beam instrument with compliance-variable feature, and a microprobe thermocouple. Two polymethylmethacrylate-based commercial bone cements, containing essentially the same raw materials but differ in their viscosity for orthopedic applications, were used to demonstrate the applicability of the instrumentation. The results show that for both the cements studied the final DC was marginally different, the final PS was different at the low compliance, the peak of the PE was similar, and their polymerization rates were significantly different. Systematic variation of instrumental compliance for testing reveals differences in the characteristics of PS profiles of both the cements. This emphasizes the importance of instrumental compliance in obtaining an accurate understanding of PS evaluation. Finally, the key advantage for the simultaneous measurements is that these polymerization properties can be correlated directly, thus providing higher measurement confidence and enables a more in-depth understanding of the network formation process.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shen, Yong; Desseaux, Solenne; Aden, Bethany

We report that surface-grafting thermoresponsive polymers allows the preparation of thin polymer brush coatings with surface properties that can be manipulated by variation of temperature. In most instances, thermoresponsive polymer brushes are produced using polymers that dehydrate and collapse above a certain temperature. This report presents the preparation and properties of polymer brushes that show thermoresponsive surface properties, yet are shape-persistent in that they do not undergo main chain collapse. The polymer brushes presented here are obtained via vapor deposition surface-initiated ring-opening polymerization (SI-ROP) of γ-di- or tri(ethylene glycol)-modified glutamic acid N-carboxyanhydrides. Vapor deposition SI-ROP of γ-di- or tri(ethylene glycol)-modifiedmore » L- or D-glutamic acid N-carboxyanhydrides affords helical surface-tethered polymer chains that do not show any changes in secondary structure between 10 and 70 °C. QCM-D experiments, however, revealed significant dehydration of poly(γ-(2-(2-methoxyethoxy)ethyl)-l-glutamate) (poly(L-EG 2-Glu)) brushes upon heating from 10 to 40 °C. At the same time, AFM and ellipsometry studies did not reveal significant variations in film thickness over this temperature range, which is consistent with the shape-persistent nature of these polypeptide brushes and indicates that the thermoresponsiveness of the films is primarily due to hydration and dehydration of the oligo(ethylene glycol) side chains. The results we present here illustrate the potential of surface-initiated NCA ring-opening polymerization to generate densely grafted assemblies of polymer chains that possess well-defined secondary structures and tunable surface properties. These polypeptide brushes complement their conformationally unordered counterparts that can be generated via surface-initiated polymerization of vinyl-type monomers and represent another step forward to biomimetic surfaces and interfaces.« less

Facile fabrication of redox-responsive thiol-containing drug delivery system via RAFT polymerization.

PubMed

Zhuang, Yuanyuan; Su, Yue; Peng, Yu; Wang, Dali; Deng, Hongping; Xi, Xiaodong; Zhu, Xinyuan; Lu, Yunfeng

2014-04-14

A novel kind of redox-responsive polymeric drug delivery system has been designed and prepared successfully through the coupling of the multithiol branched polymers and thiol-containing drugs. The branched poly((S-(4-vinyl) benzyl S'-propyltrithiocarbonate)-co-(poly(ethylene glycol) methacrylate)) (poly(VBPT-co-PEGMA)) was synthesized by one-pot reaction via reversible addition-fragmentation chain transfer (RAFT) copolymerization. Subsequently, the hydrophobic thiol-containing anticancer drug 6-mercaptopurine (MP) was conjugated to poly(VBPT-co-PEGMA) by thiol-disulfide exchange reaction, resulting in the formation of poly(VBPT-co-PEGMA)-S-S-MP conjugate. Due to its amphiphilicity, poly(VBPT-co-PEGMA)-S-S-MP conjugate self-assembled into amphiphilic micelles in aqueous solution. Under a reductive environment, the disassembly of polymeric micelles resulted in the MP release. Flow cytometry and confocal laser scanning microscopy (CLSM) measurements demonstrated that the poly(VBPT-co-PEGMA)-S-S-MP micelles could be taken up by Raji cells (a Burkitt lymphoma cell line). The viability of the Raji cells incubated with the glutathione (GSH) mediated poly(VBPT-co-PEGMA)-S-S-MP micelles was investigated by Cell Counting Kit-8 (CCK-8) assay. The experimental results showed that the viability of the glutathione monoester (GSH-OEt) pretreated cells was lower than that without pretreatment, while the viability of the buthionine sulfoximine (BSO) pretreated cells was higher than that without pretreatment. The poly(VBPT-co-PEGMA)-S-S-MP micelles could induce the apoptosis of Raji cells, and the apoptosis behavior was dose-dependent. This redox-responsive polymer-drug conjugate provides a promising platform for the delivery of thiol-containing biological molecules.

Floorward thinking.

PubMed Central

Fisher, B E

1999-01-01

From its creation to its disposal, there are environmental and health problems associated with polyvinyl chloride (vinyl), the major component of vinyl flooring. The production of vinyl creates toxic waste that must be dumped or incinerated. Because very little vinyl is recycled, the waste material must also be landfilled or burned. Furthermore, the heavy chlorine content of these materials result in the release of dioxins into the environment. A new flooring alternative to vinyl recently entered the market. Stratica, manufactured by Amtico Company Limited based in Coventry, United Kingdom, is made from polymer resins and offers the durability of vinyl without the environmental impact. PMID:10379015

Floorward thinking.

PubMed

Fisher, B E

1999-07-01

From its creation to its disposal, there are environmental and health problems associated with polyvinyl chloride (vinyl), the major component of vinyl flooring. The production of vinyl creates toxic waste that must be dumped or incinerated. Because very little vinyl is recycled, the waste material must also be landfilled or burned. Furthermore, the heavy chlorine content of these materials result in the release of dioxins into the environment. A new flooring alternative to vinyl recently entered the market. Stratica, manufactured by Amtico Company Limited based in Coventry, United Kingdom, is made from polymer resins and offers the durability of vinyl without the environmental impact.

Elucidation of a side reaction occurring during nitroxide-mediated polymerization of cyclic ketene acetals by tandem mass spectrometric end-group analysis of aliphatic polyesters.

PubMed

Albergaria Pereira, Bruna de Fátima; Tardy, Antoine; Monnier, Valérie; Guillaneuf, Yohann; Gigmes, Didier; Charles, Laurence

2015-12-15

In order to prevent side reactions while developing new polymerization processes, their mechanism has to be understood and one first key insight is the structure of the end-groups in polymeric by-products. The synthetic method scrutinized here is the nitroxide-mediated polymerization (NMP) of a cyclic ketene acetal, a promising alternative process to the production of polyesters. Polymer end-group characterization was performed by mass spectrometry (MS), combining elemental composition information derived from accurate mass data in the MS mode with fragmentation features recorded in the MS/MS mode. Electrospray was used as the ionization method to ensure the integrity of original chain terminations and a quadrupole time-of-flight (QTOF) instrument was employed for high-resolution mass measurements in both MS and tandem mass spectrometry (MS/MS) modes. Occurrence of side reactions in the studied polymerization method, first evidenced by an unusual increase in dispersity with conversion, was confirmed in MS with the detection of two polymeric impurities in addition to the expected species. Fragmentation rules were first established for this new polyester family in order to derive useful structural information from MS/MS data. In addition to a usual NMP by-product, the initiating group of the second polymeric impurities revealed the degradation of the nitroxide moiety. Unambiguous MS/MS identification of end-groups in by-products sampled from the polymerization medium allowed an unusual side reaction to be identified during the NMP preparation of polyesters. On-going optimization of the polymerization method aims at preventing this undesired process. Copyright © 2015 John Wiley & Sons, Ltd.

Effect of low-shrinkage monomers on the physicochemical properties of experimental composite resin

PubMed Central

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

2018-01-01

Abstract This study was conducted to determine whether novel experimental low-shrinkage dimethacrylate co-monomers could provide low polymerization shrinkage composites without sacrifice to degree of conversion, and mechanical properties of the composites. Experimental composites were prepared by mixing 28.6 wt% of bisphenol-A-glycidyl dimethacrylate based resin matrix (bis-GMA) with various weight-fractions of co-monomers; tricyclo decanedimethanol dacrylate (SR833s) and isobornyl acrylate (IBOA) to 71.4 wt% of particulate-fillers. A composite based on bis-GMA/TEGDMA (triethylene glycol dimethacrylate) was used as a control. Fracture toughness and flexural strength were determined for each experimental material following international standards. Degree of monomer-conversion (DC%) was determined by FTIR spectrometry. The volumetric shrinkage in percent was calculated as a buoyancy change in distilled water by means of the Archimedes’ principle. Polymerization shrinkage-strain and -stress of the specimens were measured using the strain-gage technique and tensilometer, respectively with respect to time. Statistical analysis revealed that control group had the highest double-bond conversion (p < .05) among the experimental resins tested. All of the experimental composite resins had comparable flexural strength, modulus, and fracture toughness (p > .05). Volumetric shrinkage and shrinkage stress decreased with increasing IBOA concentration. Replacing TEGDMA with SR833s and IBOA can decrease the volumetric shrinkage, shrinkage strain, and shrinkage stress of composite resins without affecting the mechanical properties. However, the degree of conversion was also decreased. PMID:29536025

Effect of low-shrinkage monomers on the physicochemical properties of experimental composite resin.

PubMed

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

2018-01-01

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

Hydrolyzable Poly[Poly(Ethylene Glycol) Methyl Ether Acrylate]-Colistin Prodrugs through Copper-Mediated Photoinduced Living Radical Polymerization.

PubMed

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.

Li2S/Carbon Nanocomposite Strips from a Low-Temperature Conversion of Li2SO4 as High-Performance Lithium-Sulfur Cathodes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ye, Fangmin; Noh, Hyungjun; Lee, Jin Hong

2018-03-12

Carbothermal conversion of Li2SO4 provides a cost-effective strategy to fabricate high-capacity Li2S cathodes, however, Li2S cathodes derived from Li2SO4 at high temperatures (> 800 oC), having high crystallinity and large crystal size, result in a low utilization of Li2S. Here, we report a Li2SO4/poly(vinyl alcohol)-derived Li2S/Carbon nanocomposite (Li2S@C) strips at a record low temperature of 635 oC. These Li2S@C nanocomposite strips as a cathode shows a low initial activation potential (2.63 V), a high initial discharge capacity (805 mAh g-1 Li2S) and a high cycling stability (0.2 C and 1 C). These improvedresults could be ascribed to the nano-sized Li2Smore » particles as well as their low crystallinity due to the PVA-induced carbon network and the low conversion temperature, respectively. An XPS analysis reveals that the C=C and C=O bonds derived from the carbonization of PVA can promote the conversion of Li2SO4 at the low temperature.« less

Kinetics and mechanics of photo-polymerized triazole-containing thermosetting composites via the copper(I)-catalyzed azide-alkyne cycloaddition

PubMed Central

Song, Han Byul; Wang, Xiance; Patton, James R.; Stansbury, Jeffrey W.; Bowman, Christopher N.

2017-01-01

Objectives Several features necessary for polymer composite materials in practical applications such as dental restorative materials were investigated in photo-curable CuAAC (copper(I)-catalyzed azide-alkyne cycloaddition) thermosetting resin-based composites with varying filler loadings and compared to a conventional BisGMA/TEGDMA based composite. Methods Tri-functional alkyne and di-functional azide monomers were synthesized for CuAAC resins and incorporated with alkyne-functionalized silica microfillers for CuAAC composites. Polymerization kinetics, in situ temperature change, and shrinkage stress were monitored simultaneously with a tensometer coupled with FTIR spectroscopy and a data-logging thermocouple. The glass transition temperature was analyzed by dynamic mechanical analysis. Flexural modulus/strength and flexural toughness were characterized in three-point bending on a universal testing machine. Results The photo-CuAAC polymerization of composites containing between 0 and 60 wt% microfiller achieved ~99% conversion with a dramatic reduction in the maximum heat of reaction (~20 °C decrease) for the 60 wt% filled CuAAC composites as compared with the unfilled CuAAC resin. CuAAC composites with 60 wt% microfiller generated more than twice lower shrinkage stress of 0.43±0.01 MPa, equivalent flexural modulus of 6.1±0.7 GPa, equivalent flexural strength of 107±9 MPa, and more than 10 times higher energy absorption of 10±1 MJ m−3 when strained to 11% relative to BisGMA-based composites at equivalent filler loadings. Significance Mechanically robust and highly tough, photo-polymerized CuAAC composites with reduced shrinkage stress and a modest reaction exotherm were generated and resulted in essentially complete conversion. PMID:28363645

Kinetics and mechanics of photo-polymerized triazole-containing thermosetting composites via the copper(I)-catalyzed azide-alkyne cycloaddition.

PubMed

Song, Han Byul; Wang, Xiance; Patton, James R; Stansbury, Jeffrey W; Bowman, Christopher N

2017-06-01

Several features necessary for polymer composite materials in practical applications such as dental restorative materials were investigated in photo-curable CuAAC (copper(I)-catalyzed azide-alkyne cycloaddition) thermosetting resin-based composites with varying filler loadings and compared to a conventional BisGMA/TEGDMA based composite. Tri-functional alkyne and di-functional azide monomers were synthesized for CuAAC resins and incorporated with alkyne-functionalized glass microfillers for CuAAC composites. Polymerization kinetics, in situ temperature change, and shrinkage stress were monitored simultaneously with a tensometer coupled with FTIR spectroscopy and a data-logging thermocouple. The glass transition temperature was analyzed by dynamic mechanical analysis. Flexural modulus/strength and flexural toughness were characterized in three-point bending on a universal testing machine. The photo-CuAAC polymerization of composites containing between 0 and 60wt% microfiller achieved ∼99% conversion with a dramatic reduction in the maximum heat of reaction (∼20°C decrease) for the 60wt% filled CuAAC composites as compared with the unfilled CuAAC resin. CuAAC composites with 60wt% microfiller generated more than twice lower shrinkage stress of 0.43±0.01MPa, equivalent flexural modulus of 6.1±0.7GPa, equivalent flexural strength of 107±9MPa, and more than 10 times higher energy absorption of 10±1MJm -3 when strained to 11% relative to BisGMA-based composites at equivalent filler loadings. Mechanically robust and highly tough, photo-polymerized CuAAC composites with reduced shrinkage stress and a modest reaction exotherm were generated and resulted in essentially complete conversion. Copyright © 2017 The Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Microbial reductive dehalogenation of vinyl chloride

DOEpatents

Spormann, Alfred M [Stanford, CA; Muller, Jochen A [Baltimore, MD; Rosner, Bettina M [Berlin, DE; Von Abendroth, Gregory [Nannhein, DE; Meshulam-Simon, Galit [Los Altos, CA; McCarty, Perry L [Stanford, CA

2011-11-22

Compositions and methods are provided that relate to the bioremediation of chlorinated ethenes, particularly the bioremediation of vinyl chloride by Dehalococcoides-like organisms. An isolated strain of bacteria, Dehalococcoides sp. strain VS, that metabolizes vinyl chloride is provided; the genetic sequence of the enzyme responsible for vinyl chloride dehalogenation; methods of assessing the capability of endogenous organisms at an environmental site to metabolize vinyl chloride; and a method of using the strains of the invention for bioremediation.

Microbial reductive dehalogenation of vinyl chloride

DOEpatents

Spormann, Alfred M [Stanford, CA; Muller, Jochen A [Baltimore, MD; Rosner, Bettina M [Berlin, DE; Von Abendroth, Gregory [Mannheim, DE; Meshulam-Simon, Galit [Los Angeles, CA; McCarty, Perry L [Stanford, CA

2014-02-11

Compositions and methods are provided that relate to the bioremediation of chlorinated ethenes, particularly the bioremediation of vinyl chloride by Dehalococcoides-like organisms. An isolated strain of bacteria, Dehalococcoides sp. strain VS, that metabolizes vinyl chloride is provided; the genetic sequence of the enzyme responsible for vinyl chloride dehalogenation; methods of assessing the capability of endogenous organisms at an environmental site to metabolize vinyl chloride; and a method of using the strains of the invention for bioremediation.

Tailor-made polyfluoroacrylate and its block copolymer by RAFT polymerization in miniemulsion; improved hydrophobicity in the core-shell block copolymer.

PubMed

Chakrabarty, Arindam; Singha, Nikhil K

2013-10-15

Controlled/living radical polymerization (CRP) of a fluoroacrylate was successfully carried out in miniemulsion by Reversible Addition Fragmentation chain Transfer (RAFT) process. In this case, 2,2,3,3,4,4,4-heptafluorobutyl acrylate (HFBA) was polymerized using 2-cyanopropyl dodecyl trithiocarbonate (CPDTC) as RAFT agent, Triton X-405 and sodium dodecyl sulfonate (SDS) as surfactant, and potassium persulphate (KPS) or 2,2'-azobis isobutyronitrile (AIBN) as initiator. Being compatible with hydrophobic fluoroacrylate, this RAFT agent offered very high conversion and good control over the molecular weight of the polymer. The miniemulsion was stable without any costabilizer. The long chain dodecyl group (-C12H25) (Z-group in the RAFT agent) had beneficial effect in stabilizing the miniemulsion. When 2-cyano 2-propyl benzodithioate (CPBD) (Z=-C6H5) was used as RAFT agent, the conversion was less and particle size distribution was very broad. Block copolymerization with butyl acrylate (BA) using PHFBA as macro-RAFT agent showed core-shell morphology with the aggregation of PHFBA segment in the shell. GPC as well as DSC analysis confirmed the formation of block copolymer. The core-shell morphology was confirmed by TEM analysis. The block copolymers (PHFBA-b-PBA) showed significantly higher water contact angle (WCA) showing much better hydrophobicity compared to PHFBA alone. Copyright © 2013 Elsevier Inc. All rights reserved.

Net-Immobilization of β-glucosidase on Nonwoven Fabrics to Lower the Cost of “Cellulosic Ethanol” and Increase Cellulose Conversions

PubMed Central

Zhu, Xing; He, Bin; Zhao, Changwen; Fan, Rong; Zhang, Lihua; Wang, Guan; Ma, Yuhong; Yang, Wantai

2016-01-01

The main limitation preventing the use of enzymatic cellulosic ethanol in industrial production is its higher cost which is mainly due to the elevated price of β-glucosidase (BG). Herein, we report on a simple strategy for the in-situ encapsulation of BG for repeated cellulosic ethanol production. In this strategy, BG was net-immobilized into a poly(ethylene glycol) (PEG) net-cloth layer on a PP nonwoven fabric by way of the visible light-induced surface controlled/living graft cross-linking polymerization. The visible light and mild reaction conditions could ensure the activity retention of BG during immobilization, while the non-swelling uniform net-mesh formed by living cross-linking polymerization could prevent the leakage of BG effectively (at the immobilization rate of more than 98.6% and the leakage rate of only 0.4%). When the BG-loaded fabric was used in combination with free cellulase (CEL), the results of the catalytic reaction demonstrated that these BG-loaded fabrics could not only give a 40% increase in cellulose conversions but also be reused for more than fifteen batches without losing the activity. These BG-loaded fabrics with characteristics including easy separation, excellent operation stability, a low cost of the polymeric matrix and a simple fabrication process are particularly interesting for a future bio-fuel production strategy. PMID:27009788

Net-Immobilization of β-glucosidase on Nonwoven Fabrics to Lower the Cost of “Cellulosic Ethanol” and Increase Cellulose Conversions

NASA Astrophysics Data System (ADS)

Zhu, Xing; He, Bin; Zhao, Changwen; Fan, Rong; Zhang, Lihua; Wang, Guan; Ma, Yuhong; Yang, Wantai

2016-03-01

The main limitation preventing the use of enzymatic cellulosic ethanol in industrial production is its higher cost which is mainly due to the elevated price of β-glucosidase (BG). Herein, we report on a simple strategy for the in-situ encapsulation of BG for repeated cellulosic ethanol production. In this strategy, BG was net-immobilized into a poly(ethylene glycol) (PEG) net-cloth layer on a PP nonwoven fabric by way of the visible light-induced surface controlled/living graft cross-linking polymerization. The visible light and mild reaction conditions could ensure the activity retention of BG during immobilization, while the non-swelling uniform net-mesh formed by living cross-linking polymerization could prevent the leakage of BG effectively (at the immobilization rate of more than 98.6% and the leakage rate of only 0.4%). When the BG-loaded fabric was used in combination with free cellulase (CEL), the results of the catalytic reaction demonstrated that these BG-loaded fabrics could not only give a 40% increase in cellulose conversions but also be reused for more than fifteen batches without losing the activity. These BG-loaded fabrics with characteristics including easy separation, excellent operation stability, a low cost of the polymeric matrix and a simple fabrication process are particularly interesting for a future bio-fuel production strategy.

Antibacterial effect of composite resins containing quaternary ammonium polyethyleneimine nanoparticles

NASA Astrophysics Data System (ADS)

Yudovin-Farber, Ira; Beyth, Nurit; Weiss, Ervin I.; Domb, Abraham J.

2010-02-01

Quaternary ammonium polyethyleneimine (QA-PEI)-based nanoparticles were synthesized by crosslinking with dibromopentane followed by N-alkylation with various alkyl halides and further N-methylation with methyl iodide. Insoluble pyridinium-type particles were prepared by suspension polymerization of 4-vinyl pyridine followed by N-alkylation with alkyl halides. Polyamine-based nanoparticles embedded in restorative composite resin at 1% w/w were tested for antibacterial activity against Streptococcus mutans using direct contact test. Activity analysis revealed that the alkyl chain length of the QA-PEI nanoparticles plays a significant role in antibacterial activity of the reagent. The most potent compound was octyl-alkylated QA-PEI embedded in restorative composite resin at 1% w/w that totally inhibited S. mutans growth in 3-month-aged samples. This data indicates that restorative composite resin with antibacterial properties can be produced by the incorporation of QA-PEI nanoparticles.

Synthesis of a large-sized mesoporous phosphosilicate thin film through evaporation-induced polymeric micelle assembly.

PubMed

Li, Yunqi; Bastakoti, Bishnu Prasad; Imura, Masataka; Suzuki, Norihiro; Jiang, Xiangfen; Ohki, Shinobu; Deguchi, Kenzo; Suzuki, Madoka; Arai, Satoshi; Yamauchi, Yusuke

2015-01-01

A triblock copolymer, poly(styrene-b-2-vinyl pyridine-b-ethylene oxide) (PS-b-P2VP-b-PEO) was used as a soft template to synthesize large-sized mesoporous phosphosilicate thin films. The kinetically frozen PS core stabilizes the micelles. The strong interaction of the inorganic precursors with the P2VP shell enables the fabrication of highly robust walls of phosphosilicate and the PEO helps orderly packing of the micelles during solvent evaporation. The molar ratio of phosphoric acid and tetraethyl orthosilicate is crucial to achieve the final mesostructure. The insertion of phosphorus species into the siloxane network is studied by (29) Si and (31) P MAS NMR spectra. The mesoporous phosphosilicate films exhibit steady cell adhesion properties and show great promise as excellent materials in bone-growth engineering applications. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A temperature, pH and sugar triple-stimuli-responsive nanofluidic diode.

PubMed

Zheng, Yu-Bin; Zhao, Shuang; Cao, Shuo-Hui; Cai, Sheng-Lin; Cai, Xiu-Hong; Li, Yao-Qun

2017-01-07

In this article, we have demonstrated for the first time a triple stimuli-responsive nanofluidic diode that can rectify ionic current under multiple external stimuli including temperature, pH, and sugar. This diode was fabricated by immobilizing poly[2-(dimethylamino)ethyl methacrylate]-co-[4-vinyl phenylboronic acid] (P(DMAEMA-co-VPBA)) onto the wall of a single glass conical nanopore channel via surface-initiator atom transfer radical polymerization (SI-ATRP). The copolymer brushes contain functional groups sensitive to pH, temperature and sugar that can induce charge and configuration change to affect the status of the pore wall. The experimental results confirmed that the P(DMAEMA-co-VPBA) brush modified nanochannel regulated the ionic current rectification successfully under three different external stimuli. This biomimetically inspired research simulates the complex biological multi-functions of ion channels and promotes the development of "smart" biomimetic nanochannel systems for actuating and sensing applications.

Grafting of 2 (2-hydroxy-5-vinylphenyl) 2H-benzotriazole onto polymers with aliphatic groups. Synthesis and polymerization of 2 (2-hydroxy-5-isopropenylphenyl) 2H-benzotriazole and a new synthesis of 2 (2-hydroxy-5-vinylphenyl) 2H-benzotriazole

NASA Technical Reports Server (NTRS)

Pradellok, W.; Nir, Z.; Vogl, O.

1981-01-01

Successful grafting of 2(2-hydroxy-5-vinylphenyl)2H-benzotriazole onto saturated aliphatic C-H groups of polymers has been accomplished. When the grafting reaction was carried out in chlorobenzene at 150 C = 160 C with di-tertiarybutylperoxide as the grafting initiator, grafts as high as 20 percent - 30 percent at a grafting efficiency of 50 percent and 80 percent have readily been obtained. The grafting reaction was carried out in tubes sealed under high vacuum since trace amounts of oxygen cause complete inhibition of the grafting reaction by the phenolic monomer. On a variety of different polymers including atactic polypropylene, ethylene/vinyl acetate copolymer, poly(methyl methacrylate), poly(butyl acrylate), and polycarbonate were used.

Bergman cyclization in polymer chemistry and material science.

PubMed

Xiao, Yuli; Hu, Aiguo

2011-11-01

Bergman cyclization of enediynes, regarded as a promising strategy for anticancer drugs, now finds its own niche in the area of polymer chemistry and material science. The highly reactive aromatic diradicals generated from Bergman cyclization can undergo polymerization acting as either monomers or initiators of other vinyl monomers. The former, namely homopolymerization, leads to polyphenylenes and polynaphthalenes with excellent thermal stability, good solubility, and processability. The many remarkable properties of these aromatic polymers have further endowed them to be manufactured into carbon-rich materials, e.g., glassy carbons and carbon nanotubes. Whereas used as initiators, enediynes provide a novel resource for high molecular weight polymers with narrow polydispersities. The aromatic diradicals are also useful for introducing oligomers or polymers onto pristine carbonous nanomaterials, such as carbon nano-onions and carbon nanotubes, to improve their dispersibility in organic solvents and polymer solutions. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The preparations of novel cellulose/phenylboronic acid composite intelligent bio-hydrogel and its glucose, pH-responsive behaviors.

PubMed

Peng, Huafeng; Ning, Xiaoyu; Wei, Gang; Wang, Shaopeng; Dai, Guoliang; Ju, Anqi

2018-09-01

Novel intelligent cellulose/4-vinyl-phenylboronic acid (VPBA) composite bio-hydrogels with glucose and pH-responsiveness were successfully prepared via electron beam irradiation technology at room temperature. The composites were characterized by Fourier transform infrared spectrum (FT-IR) and X-ray photoelectron spectroscopy (XPS). The electron beam irradiation results in the appearance of carbonyl in the polymerization of 4-ethenyl-phenylboronic acid, grafting and cross linking reaction in composites, and a novel composite hydrogel was formed between the poly-4-ethenyl-phenylboronic acid and cellulose matrix. By means of the incorporation of phenylboronic acid groups, the composite hydrogels with pH and glucose responsive properties was produced, and glucose responsive properties were investigated by the self-regulation of insulin release of composite hydrogel through a serial glucose solution with different concentrations, which is having great potential applications in many fields. Copyright © 2018 Elsevier Ltd. All rights reserved.