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

Sulfonated poly(ether ether ketone)/polypyrrole core-shell nanofibers: a novel polymeric adsorbent/conducting polymer nanostructures for ultrasensitive gas sensors.

PubMed

Wang, Wei; Li, Zhenyu; Jiang, Tingting; Zhao, Zhiwei; Li, Ye; Wang, Zhaojie; Wang, Ce

2012-11-01

Conducting polymers-based gas sensors have attracted increasing research attention these years. The introduction of inorganic sensitizers (noble metals or inorganic semiconductors) within the conducting polymers-based gas sensors has been regarded as the generally effective route for further enhanced sensors. Here we demonstrate a novel route for highly-efficient conducting polymers-based gas sensors by introduction of polymeric sensitizers (polymeric adsorbent) within the conducting polymeric nanostructures to form one-dimensional polymeric adsorbent/conducting polymer core-shell nanocomposites, via electrospinning and solution-phase polymerization. The adsorption effect of the SPEEK toward NH₃ can facilitate the mass diffusion of NH₃ through the PPy layers, resulting in the enhanced sensing signals. On the basis of the SPEEK/PPy nanofibers, the sensors exhibit large gas responses, even when exposed to very low concentration of NH₃ (20 ppb) at room temperature.

Preparation of porous carbons from polymeric precursors modified with acrylated kraft lignin

NASA Astrophysics Data System (ADS)

Sobiesiak, M.

2016-04-01

The presented studies concern the preparation of porous carbons from a BPA.DA-St polymer containing acrylated kraft lignin as a monomer. The porous polymeric precursor in the form of microspheres was synthesized in suspension polymerization process. Next samples of the polymer were impregnated with acetic acid or aqueous solution of acetates (potassium or ammonia), dried and carbonised in nitrogen atmosphere at 450°C. After carbonization microspherical shape of the materials was remained, that is desired feature for potential application in chromatography or SPE technique. Chemical and textural properties of the porous carbon adsorbents were characterized using infrared spectroscopy (ATR-FTIR), thermogravimetry analyses with mass spectrometry of released gases (TG-MS) and nitrogen sorption experiments. The presented studies revealed the impregnation is useful method for development of porous structure of carbonaceous materials. The highest values of porous structure parameters were obtained when acetic acid and ammonium acetate were used as impregnating substances. On the surface of the materials oxygen functional groups are present that is important for specific interactions during sorption processes. The highest contents of functionalities were observed for carbon BPA.DA-St-LA-C-AcNH4.

Study of improved resins for advanced supersonic technology composites. Part 1: Heteroaromatic polymers containing ether groups. Part 2: Curing chemistry of aromatic polymers and composite studies

NASA Technical Reports Server (NTRS)

Takekoshi, T.; Hillig, W. B.; Mellinger, G. A.

1975-01-01

Fourteen ether-containing, aromatic dianhydrides have been synthesized from N-phenyl-3 or 4-nitrophthalimide and various bisphenols. The process involves nucleophilic displacement of activated nitro groups with bisphenolate ions. Ether-containing dianhydrides were indefinitely stable in the presence of atmospheric moisture. One-step, high temperature solution polymerization of the ether-containing dianhydrides with m-phenylene diamine, 4,4'-oxydianiline and 1, 3-bis(4-aminophenoxy)benzene afforded 42 polyetherimides. The polyetherimides were all soluble in m-cresol except two which were found to be crystalline. The glass transition temperatures of the polyetherimides ranged from 178 to 277 C. Soluble polybenzimidazopyrrolones containing ether groups were also prepared from the same ether-containing dianhydrides and aromatic tetraamines by one-step solution polymerization. Using low molecular weight polyetherimides, various thermoset resin systems were developed and tested as matrices for fiber-reinforced composites. The curing chemistry involving reaction of the phthalonitrile group and the o-diaminophenyl group was found to be generally applicable to crosslinking various aromatic polymers other than polyimides.

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

Madhukar, M. S.; Martovetsky, N. N.

Large superconducting electromagnets used in fusion reactors utilize a large amount of glass/epoxy composite for electrical insulation and mechanical and thermal strengths. Moreover, the manufacture of these magnets involves wrapping each superconducting cable bundle with dry glass cloth followed by the vacuum-assisted resin transfer molding of the entire magnet. Due to their enormous size (more than 100 tons), it requires more than 40 h for resin impregnation and the subsequent pressure cycles to ensure complete impregnation and removal of any trapped air pockets. Diglycidyl ether of bisphenol F epoxy resin cross-linked with methyltetrahydrophthalic anhydride with an accelerator has been shownmore » to be a good candidate for use in composite parts requiring long impregnation cycles. Viscosity, gel time, and glass transition temperature of four resin-blends of diglycidyl ether of bisphenol F resin system were monitored as a function of time and temperature with an objective to find the blend that provides a working window longer than 40h at low viscosity without lowering its glass transition temperature. A resin-blend in the weight ratios of resin:hardener:accelerator=100:82:0.125 is shown to provide more than 60h at low resin viscosity while maintaining the same glass transition temperature as obtained with previously used resin-blends, based on the results.« less

High-efficiency preparation of poly(2-methacryloyloxyethyl phosphorylcholine) grafting layer on poly(ether ether ketone) by photoinduced and self-initiated graft polymerization in an aqueous solution in the presence of inorganic salt additives.

PubMed

Shiojima, Taro; Inoue, Yuuki; Kyomoto, Masayuki; Ishihara, Kazuhiko

2016-08-01

A highly efficient methodology for preparing a poly(2-methacryloyloxyethyl phosphorylcholine) (PMPC) layer on the surface of poly(ether ether ketone) (PEEK) was examined by photoinduced and self-initiated graft polymerization. To enhance the polymerization rate, we demonstrated the effects of inorganic salt additives in the feed monomer solution on thickness of grafted PMPC layer. Photoinduced polymerization occurred and the PMPC graft layer was successfully formed on the PEEK surface, regardless of inorganic salt additives. Moreover, it was clearly observed that the addition of inorganic salt enhanced the grafting thickness of PMPC layer on the surface even when the photoirradiation time was shortened. The addition of inorganic salt additives in the feed monomer solution enhanced the polymerization rate of MPC and resulted in thicker PMPC layers. In particular, we evaluated the effect of NaCl concentration and how this affected the polymerization rate and layer thickness. We considered that this phenomenon was due to the hydration of ions in the feed monomer solution and subsequent apparent increase in the MPC concentration. A PMPC layer with over 100-nm-thick, which was prepared by 5-min photoirradiation in 2.5mol/L inorganic salt aqueous solution, showed good wettability and protein adsorption resistance compared to that of untreated PEEK. Hence, we concluded that the addition of NaCl into the MPC feed solution would be a convenient and efficient method for preparing a graft layer on PEEK. Photoinduced and self-initiated graft polymerization on the PEEK surface is one of the several methodologies available for functionalization. However, in comparison with free-radical polymerization, the efficiency of polymerization at the solid-liquid interface is limited. Enhancement of the polymerization rate for grafting could solve the problem. In this study, we observed the acceleration of the polymerization rate of MPC in an aqueous solution by the addition of inorganic salt. The salt itself did not show any adverse effects on the radical polymerization; however, the apparent concentration of the monomer in feed may be increased due to the hydration of ions attributed to salt additives. We could obtain PMPC-grafted PEEK with sufficient PMPC thickness to obtain good functionality with only 5-min photoirradiation by using 2.5mol/L NaCl in the feed solution. Copyright © 2016 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Influence of graphene-oxide nanosheets impregnation on properties of sterculia gum-polyacrylamide hydrogel formed by radiation induced polymerization.

PubMed

Singh, Baljit; Singh, Baldev

2017-06-01

Present work is an attempt, to explore the potential of graphene oxide nanoplates impregnation, on the mechanical and drug delivery properties of sterculia gum-polyacrylamide composite hydrogel formed by radiation induced polymerization. These polymers were characterized by SEM, cryo-SEM, AFM, FTIR's, 13 C NMR and swelling studies. Release profile of an anticancer drug 'gemcitabine' was studied to determine the drug release mechanism and best fit kinetic model. Furthermore, some important biomedical properties of the polymers such as blood compatibility, mucoadhesion, antioxidant properties and gel strength were also studied. Impregnation of GO into sterculia gum-poly(AAm) hydrogels decreased the swelling of hydrogels but improved the mechanical, drug loading and drug release properties of the hydrogels. Release of gemcitabine from drug loaded hydrogels occurred through non-Fickian diffusion mechanism and release profile was best fitted in first order kinetic model. These hydrogels have been found as haemocompatible, mucoadhesive, and antioxidant in nature. Copyright © 2017 Elsevier B.V. All rights reserved.

Impregnated metal-polymeric functional beads

NASA Technical Reports Server (NTRS)

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

1980-01-01

Amine containing polymeric microspheres such as polyvinyl pyridine are complexed with metal salts or acids containing metals such as gold, platinum or iron. After reduction with sodium borohydride, the salt is reduced to finely divided free metal or metal oxides, useful as catalysts. Microspheres containing covalent bonding sites can be used for labeling or separating proteins.

Impregnated metal-polymeric functional beads

NASA Technical Reports Server (NTRS)

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

1978-01-01

Amine containing polymeric microspheres such as polyvinyl pyridine are complexed with metal salts or acids containing metals such as gold, platinum or iron. After reduction with sodium borohydride, the salt is reduced to finely divided free metal or metal oxides, useful as catalysts. Microspheres containing covalent bonding sites can be used for labeling or separating proteins.

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

PubMed

Eggers, Steffen; Abetz, Volker

2018-04-01

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

Method for production of ceramic oxide and carbide bodies by polymer inclusion and decomposition

DOEpatents

Quinby, Thomas C.

1985-01-01

A method for the preparation of thin, free-standing metal oxide films which are useful as nuclear accelerator target materials. Cations of any metal except those of Group IA and precious metals, such as, U, Zr, Nd, Ce, Th, pr or Cr, are absorbed on a thin film of polymeric material, such as, carboxymethylcellulose, viscose rayon or cellophane. The cation impregnated polymeric material is dried. Then the impregnated film is heated in an inert atmosphere to form a carbonized membrane. The carbonized membrane is oxidized to yield a thin, self-supporting, metal oxide membrane. Or, the membrane can be heated in an inert atmosphere to yield a thin, self-supporting, metal carbide-containing membrane.

Method for production of ceramic oxide and carbide bodies by polymer inclusion and decomposition

DOEpatents

Quinby, T.C.

1984-08-30

A method for the preparation of thin, free-standing metal oxide films which are useful as nuclear accelerator target materials is described. Cations of any metal except those of Group IA and precious metals, such as, U, Zr, Nd, Ce, Th, Pr or Cr, are absorbed on a thin film of polymeric material, such as carboxymethylcellulose, viscose rayon or cellophane. The cation impregnated polymeric material is dried. Then the impregnated film is heated in an inert atmosphere to form a carbonized membrane. The carbonized membrane is oxidized to yield a thin, self-supporting, metal oxide membrane. Or, the membrane can be heated in an inert atmosphere to yield a thin, self-supporting, metal carbide-containing membrane.

Functional Aromatic Poly(1,3,4-Oxadiazole-Ether)s with Benzimidazole Pendants: Synthesis, Thermal and Dielectric Studies

PubMed Central

Ganesh, Shimoga D.; Pai, Vasantakumar K.; Kariduraganavar, Mahadevappa Y.; Jayanna, Madhu B.

2014-01-01

Poly(1,3,4-oxadiazole-ether) with reactive carboxylic acid pendants was synthesized from solution polymerization via nucleophilic displacement polycondensation among 2,5-bis(4-fluorophenyl)-1,3,4-oxadiazole (BFPOx) and 4,4′-bis(4-hydroxyphenyl) valeric acid (BHPA). Without altering the polymeric segments, benzimidazole modified poly(1,3,4-oxadiazole-ether)s were prepared by varying stoichiometric ratios of 1,2-phenylenediamine. The molecular structural characterization of these polymers was achieved by, FT-IR, NMR, TGA, elemental analysis, and analytical techniques. The weight-average molecular weight of virgin polymer with carboxylic acid functionality was determined by gel permeation chromatography (GPC) and was found to be 22400 (Mw/Mn = 2.07). All the synthesized polyethers were compressed into pellets and electrical contacts were established to perform dielectric properties. PMID:27437448

Preparation, Fabrication, and Evaluation of Advanced Polymeric and Composite Materials

NASA Technical Reports Server (NTRS)

Orwoll, Robert A.

1997-01-01

The thesis titles are given below: physical and mechanical behavior of amorphous poly(arylene ether-co-imidasole)s and poly(arylene ether-co-imidasole) modification epoxies; the requirements of patentability as applied to the chemical arts; fabrication of thermoplastic polymer composite ribbon; blend of reactive diluents with phenylethynyl-terminated arylene ether oligomers; the synthesis, characterization, and application of ether-containing polyimides; the synthesis of reflective and electrically conductive polyimide films via an in-situ self-metalization procedure using silver (I) complexes; the thermal cure of phenylethynyl terminated polyimides and selected model compounds; and the synthesis, characterization, and molecular modeling of cyclic arylene ether oligomers.

Preparation of Soypolymers by Ring-opening Polymerization of Epoxdized Soybean Oil

USDA-ARS?s Scientific Manuscript database

Ring opening polymerization of epoxidized soybean oil (ESO) initiated by boron trifluoride diethyl etherate in methylene chloride was conducted in an effort to develop useful biodegradable polymers. The resulting polymers (PESO) were characterized using Infrared (IR), differential scanning calorime...

Ring-opening Polymerization of Epoxidized Soybean Oil

USDA-ARS?s Scientific Manuscript database

Ring opening polymerization of epoxidized soybean oil (ESO) initiated by boron trifluoride diethyl etherate, (BF3•OEt2), in methylene chloride was conducted in an effort to develop useful biodegradable polymers. The resulting polymers (PESO) were characterized using Infrared (IR), differential scan...

Polymeric micellar pH-sensitive drug delivery system for doxorubicin.

PubMed

Hrubý, Martin; Konák, Cestmír; Ulbrich, Karel

2005-03-02

A novel polymeric micellar pH-sensitive system for delivery of doxorubicin (DOX) is described. Polymeric micelles were prepared by self-assembly of amphiphilic diblock copolymers in aqueous solutions. The copolymers consist of a biocompatible hydrophilic poly(ethylene oxide) (PEO) block and a hydrophobic block containing covalently bound anthracycline antibiotic DOX. The starting block copolymers poly(ethylene oxide)-block-poly(allyl glycidyl ether) (PEO-PAGE) with a very narrow molecular weight distribution (Mw/Mn ca. 1.05) were prepared by anionic ring opening polymerization using sodium salt of poly(ethylene oxide) monomethyl ether as macroinitiator and allyl glycidyl ether as functional monomer. The copolymers were covalently modified via reactive double bonds by the addition of methyl sulfanylacetate. The resulting ester subsequently reacted with hydrazine hydrate yielding polymer hydrazide. The hydrazide was coupled with DOX yielding pH-sensitive hydrazone bonds between the drug and carrier. The resulting conjugate containing ca. 3 wt.% DOX forms micelles with Rh(a)=104 nm in phosphate-buffered saline. After incubation in buffers at 37 degrees C DOX was released faster at pH 5.0 (close to pH in endosomes; 43% DOX released within 24 h) than at pH 7.4 (pH of blood plasma; 16% DOX released within 24 h). Cleavage of hydrazone bonds between DOX and carrier continues even after plateau in the DOX release from micelles incubated in aqueous solutions is reached.

Polymerization of euphorbia oil with Lewis acid in carbon dioxide media

USDA-ARS?s Scientific Manuscript database

Boron trifluoride diethyl etherate (BF3-OEt2) Lewis acid catalyzed ring-opening polymerization of euphorbia oil (EO), a natural epoxy oil, in liquid carbon dioxide was conducted in an effort to develop useful vegetable oil based polymers. The resulting polymers (RPEO) were characterized by FTIR, 1H-...

Polymerization of euphorbia oil in carbon dioxide media

USDA-ARS?s Scientific Manuscript database

Boron trifluoride diethyl etherate (BF3•OEt2), Lewis acid, catalyzed ring-opening polymerization of euphorbia oil (EO), a natural epoxy oil, was conducted in carbon dioxide. The resulting polymers (RPEO) were characterized by FTIR, 1H-NMR, 13C-NMR, solid state 13C-NMR spectroscopies, differential sc...

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.

Anhydrous polymer-based coating with sustainable controlled release functionality for facile, efficacious impregnation, and delivery of antimicrobial peptides.

PubMed

Lim, Kaiyang; Saravanan, Rathi; Chong, Kelvin K L; Goh, Sharon H M; Chua, Ray R Y; Tambyah, Paul A; Chang, Matthew W; Kline, Kimberly A; Leong, Susanna S J

2018-04-17

Anhydrous polymers are actively explored as alternative materials to overcome limitations of conventional hydrogel-based antibacterial coating. However, the requirement for strong organic solvent in polymerization reactions often necessitates extra protection steps for encapsulation of target biomolecules, lowering encapsulation efficiency, and increasing process complexity. This study reports a novel coating strategy that allows direct solvation and encapsulation of antimicrobial peptides (HHC36) into anhydrous polycaprolactone (PCL) polymer-based dual layer coating. A thin 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) film is layered onto the peptide-impregnated PCL as a diffusion barrier, to modulate and enhance release kinetics. The impregnated peptides are eventually released in a controlled fashion. The use of 2,2,2-trifluoroethanol (TFE), as polymerization and solvation medium, induces the impregnated peptides to adopt highly stable turned conformation, conserving peptide integrity, and functionality during both encapsulation and subsequent release processes. The dual layer coating showed sustained antibacterial functionality, lasting for 14 days. In vivo assessment using an experimental mouse wounding model demonstrated good biocompatibility and significant antimicrobial efficacy of the coating under physiological conditions. The coating was translated onto silicone urinary catheters and showed promising antibacterial efficacy, even outperforming commercial silver-based Dover cather. This anhydrous polymer-based platform holds immense potential as an effective antibacterial coating to prevent clinical device-associated infections. The simplicity of the coating process enhances its industrial viability. © 2018 Wiley Periodicals, Inc.

Cost efficient carbon fibre reinforced thermoplastics with in-situ polymerization of polyamide

NASA Astrophysics Data System (ADS)

Köhler, T.; Akdere, M.; Röding, T.; Gries, T.; Seide, G.

2017-10-01

Lightweight design has gained more and more relevance over the last decades. Especially in automotive industry it is of paramount importance to reduce weight and save fuel. At the same time the demand for safety and performance increases the components’ weight. To reach a trade-off between driving comfort and efficiency new lightweight materials have to be developed. One possible solution is the usage of carbon fibre reinforced thermoplastics (CFRTP) as a lightweight substitute material. In contrast to conventional carbon fibre reinforced plastics (CFRP), CFRTPs are cheaper and have a higher impact resistance. Furthermore they are characterized by hot forming ability, weldability and recyclability. However, the impregnation of the textile requires high pressure, because of the melted polymer’s high viscosity. A new innovative approach for CFRTP is the usage of in-situ polymerization with ɛ-caprolactam as matrix, which has a much lower viscosity and thus requires much lower pressure for impregnation and consolidation.

PIC-container for containment and disposal of low and intermediate level radioactive wastes

NASA Astrophysics Data System (ADS)

Araki, K.; Shinji, Y.; Maki, Y.; Ishizaki, K.; Minegishi, K.; Sudoh, G.

1981-03-01

Steel fiber reinforced polymer impregnated concrete (SFPIC) was investigated for low and intermediate level radioactive waste containers. The 60 L and 200 L containers were designed as pressure container (without equalizer) for 500 kg/square cm and 700 kg/square cm. Polymerization of impregnated methylmethacrylate monomer was performed by 60 Co-gamma ray radiation and thermal catalytic polymerization respectively. Under the loading of 500 kg/square cm and 700 kg/square cm-outside hydraulic pressure, these containers were kept in their good condition. The observed maximum strains were about .001380 and .003950 at the outside central position of container body for circumferential direction of the 60 L and 200 L container, respectively. The containers were immersed in deionized water for 400 days, nuclides were not leached from the container. The SFPIC container was suitable for containment and disposal of low and intermediate level radioactive wastes.

Azidated Ether-Butadiene-Ether Block Copolymers as Binders for Solid Propellants

NASA Astrophysics Data System (ADS)

Cappello, Miriam; Lamia, Pietro; Mura, Claudio; Polacco, Giovanni; Filippi, Sara

2016-07-01

Polymeric binders for solid propellants are usually based on hydroxyl-terminated polybutadiene (HTPB), which does not contribute to the overall energy output. Azidic polyethers represent an interesting alternative but may have poorer mechanical properties. Polybutadiene-polyether copolymers may combine the advantages of both. Four different ether-butadiene-ether triblock copolymers were prepared and azidated starting from halogenated and/or tosylated monomers using HTPB as initiator. The presence of the butadiene block complicates the azidation step and reduces the storage stability of the azidic polymer. Nevertheless, the procedure allows modifying the binder properties by varying the type and lengths of the energetic blocks.

Polymer blends based on epoxy resin and polyphenylene ether as a matrix material for high-performance composites

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

Venderbosch, R.W.; Nelissen, J.G.L.; Peijs, A.A.J.M.

1993-12-31

The application of poly(2,6-dimethyl-1,4-phenylene ether), PPE, as a matrix material for continuous carbon fiber reinforced composites was studied. PPE is an amorphous thermoplastic exhibiting a high glass transition temperature (220 C) and outstanding mechanical properties with respect to e.g. toughness. However, due to the limited thermal stability at temperatures above T{sub g}, PPE can be regarded as an intractable polymer. Consequently, the introduction of PPE in a composite structure via a melt impregnation route is not feasible. In this investigation a solution impregnation route, using epoxy resin as a reactive solvent, was developed. During impregnation epoxy resin acts as amore » solvent which results in enhanced flow and a reduced processing temperature enabling the preparation of high quality composites, avoiding any degradation. Upon curing of the neat system, phase separation and phase inversion occurs resulting in a continuous PPE matrix filled with glassy epoxy spheres. As a result of this morphology the mechanical and thermal properties of the final material are mainly dominated by the PPE component. In composite applications, a strong influence of the polarity of the carbon fiber surface on the resulting matrix morphology was found. Upon curing, phase separation is initiated at the fiber surface resulting in an epoxy `interlayer` at the fiber surface. This phenomenon can provide a high level of interfacial adhesion. A preliminary investigation of the resulting composite materials revealed outstanding mechanical properties with respect to e.g. interlaminar toughness and strength.« less

Synthesis and Characterization of a Poly(ethylene glycol)-Poly(simvastatin) Diblock Copolymer

PubMed Central

Asafo-Adjei, Theodora A.; Dziubla, Thomas D.; Puleo, David A.

2014-01-01

Biodegradable polyesters are commonly used as drug delivery vehicles, but their role is typically passive, and encapsulation approaches have limited drug payload. An alternative drug delivery method is to polymerize the active agent or its precursor into a degradable polymer. The prodrug simvastatin contains a lactone ring that lends itself to ring-opening polymerization (ROP). Consequently, simvastatin polymerization was initiated with 5 kDa monomethyl ether poly(ethylene glycol) (mPEG) and catalyzed via stannous octoate. Melt condensation reactions produced a 9.5 kDa copolymer with a polydispersity index of 1.1 at 150 °C up to a 75 kDa copolymer with an index of 6.9 at 250 °C. Kinetic analysis revealed first-order propagation rates. Infrared spectroscopy of the copolymer showed carboxylic and methyl ether stretches unique to simvastatin and mPEG, respectively. Slow degradation was demonstrated in neutral and alkaline conditions. Lastly, simvastatin, simvastatin-incorporated molecules, and mPEG were identified as the degradation products released. The present results show the potential of using ROP to polymerize lactone-containing drugs such as simvastatin. PMID:25431653

Dehalogenation of Polybrominated Diphenyl Ethers and Polychlorinated Biphenyl by Bimetallic, Impregnated, and Nanoscale Zerovalent Iron

PubMed Central

Zhuang, Yuan; Ahn, Sungwoo; Seyfferth, Angelia L.; Masue-Slowey, Yoko; Fendorf, Scott; Luthy, Richard G.

2011-01-01

Nanoscale zerovalent iron particles (nZVI), bimetallic nanoparticles (nZVI/Pd), and nZVI/Pd impregnated activated carbon (nZVI/Pd-AC) composite particles were synthesized and investigated for their effectiveness to remove polybrominated diphenyl ethers (PBDEs) and/or polychlorinated biphenyls (PCBs). Palladization of nZVI promoted the dehalogenation kinetics for mono- to tri-BDEs and 2,3,4-trichlorobiphenyl (PCB 21). Compared to nZVI, the iron-normalized rate constants for nZVI/Pd were about 2-, 3-, and 4-orders of magnitude greater for tri-, di-, and mono-BDEs, respectively, with diphenyl ether as a main reaction product. The reaction kinetics and pathways suggest an H-atom transfer mechanism. The reaction pathways with nZVI/Pd favor preferential removal of para-halogens on PBDEs and PCBs. X-ray fluorescence mapping of nZVI/Pd-AC showed that Pd mainly deposits on the outer part of particles, while Fe was present throughout the activated carbon particles. While BDE 21 was sorbed onto activated carbon composites quickly, debromination was slower compared to reaction with freely dispersed nZVI/Pd. Our XPS and chemical data suggest about 7% of the total iron within the activated carbon was zero-valent, which shows the difficulty with in-situ synthesis of a significant fraction of zero-valent iron in the micro-porous material. Related factors that likely hinder the reaction with nZVI/Pd-AC are the heterogenous distribution of nZVI and Pd on activated carbon and/or immobilization of hydrophobic organic contaminants at the adsorption sites thereby inhibiting contact with nZVI. PMID:21557574

Lewis acid catalyzed ring-opening polymerization of natural epoxy oil (Euphorbia oil) in carbon dioxide media

USDA-ARS?s Scientific Manuscript database

In an attempt to build up useful application of plant oil based polymers, natural epoxy oil (euphorbia oil-EuO) was polymerized in liquid carbon dioxide in the presence of Lewis acid catalyst [Boron trifluoride diethyl etherate (BF3•OEt2)]. The resulting polymers (RPEuO) were characterized by FTIR ...

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.

Materials for use as proton conducting membranes for fuel cells

DOEpatents

Einsla, Brian R [Blacksburg, VA; McGrath, James E [Blacksburg, VA

2009-01-06

A family of polymers having pendent sulfonate moieties connected to polymeric main chain phenyl groups are described. These polymers are prepared by the steps of polymerization (using a monomer with a phenyl with an alkoxy substitution), deportation by converting the alkoxy to a hydroxyl, and functionalization of the polymer with a pendant sulfonate group. As an example, sulfonated poly(arylene ether sulfone) copolymers with pendent sulfonic acid groups are synthesized by the direct copolymerization of methoxy-containing poly(arylene ether sulfone)s, then converting the methoxy groups to the reactive hydroxyl form, and finally functionalizing the hydroxyl form with proton-conducting sites through nucleophilic substitution. The family of polymers may have application in proton exchange membranes and in other applications.

Process for preparing tapes from thermoplastic polymers and carbon fibers

NASA Technical Reports Server (NTRS)

Chung, Tai-Shung (Inventor); Furst, Howard (Inventor); Gurion, Zev (Inventor); McMahon, Paul E. (Inventor); Orwoll, Richard D. (Inventor); Palangio, Daniel (Inventor)

1986-01-01

The instant invention involves a process for use in preparing tapes or rovings, which are formed from a thermoplastic material used to impregnate longitudinally extended bundles of carbon fibers. The process involves the steps of (a) gas spreading a tow of carbon fibers; (b) feeding the spread tow into a crosshead die; (c) impregnating the tow in the die with a thermoplastic polymer; (d) withdrawing the impregnated tow from the die; and (e) gas cooling the impregnated tow with a jet of air. The crosshead die useful in the instant invention includes a horizontally extended, carbon fiber bundle inlet channel, means for providing melted polymer under pressure to the die, means for dividing the polymeric material flowing into the die into an upper flow channel and a lower flow channel disposed above and below the moving carbon fiber bundle, means for applying the thermoplastic material from both the upper and lower channels to the fiber bundle, and means for withdrawing the resulting tape from the die.

Impregnation of glass fibres with polymethylmethacrylate using a powder-coating method

NASA Astrophysics Data System (ADS)

Vallittu, Pekka K.

1995-01-01

The aim of this study was to evaluate the usefulness of a powder-coating method to impregnate glass fibres with polymethylmethacrylate (PMMA) for dental purposes. The continuous unidirectional E-glass fibres, the surface of which had been treated with precured silane, were powder-coated with spherical PMMA particles. Before the powder-coated prepregs were used, the incorporated PMMA powder was dissolved with methylmethacrylate monomer. The degree of impregnation of the polymerized composite was determined with a scanning electron microscope. The results revealed that the mean degree of impregnation varied from 0.87 to 0.92, being lower in the heat-cured PMMA group (which simulated fabrication of a new denture), and higher in the autopolymerizing group (which simulated the repair of a fractured denture). The means between the two groups did not, however, differ significantly ( p=0.249). The results suggest that, even though the method has some shortcomings in terms of dental laboratory technology, the powder-coating method can be used to fabricate or repair acrylic resin-based dentures.

The bactericidal activity of glutaraldehyde-impregnated polyurethane.

PubMed

Sehmi, Sandeep K; Allan, Elaine; MacRobert, Alexander J; Parkin, Ivan

2016-10-01

Although glutaraldehyde is known to be bactericidal in solution, its potential use to create novel antibacterial polymers suitable for use in healthcare environments has not been evaluated. Here, novel materials were prepared in which glutaraldehyde was either incorporated into polyurethane using a simple "swell-encapsulation-shrink" method (hereafter referred to as "glutaraldehyde-impregnated polyurethane"), or simply applied to the polymer surface (hereafter referred to as "glutaraldehyde-coated polyurethane"). The antibacterial activity of glutaraldehyde-impregnated and glutaraldehyde-coated polyurethane samples was tested against Escherichia coli and Staphylococcus aureus. Glutaraldehyde-impregnated polyurethane resulted in a 99.9% reduction in the numbers of E. coli within 2 h and a similar reduction of S. aureus within 1 h, whereas only a minimal reduction in bacterial numbers was observed when the biocide was bound to the polymer surface. After 15 days, however, the bactericidal activity of the impregnated material was substantially reduced presumably due to polymerization of glutaraldehyde. Thus, although glutaraldehyde retains antibacterial activity when impregnated into polyurethane, activity is not maintained for extended periods of time. Future work should examine the potential of chemical modification of glutaraldehyde and/or polyurethane to improve the useful lifespan of this novel antibacterial polymer. © 2016 The Authors. MicrobiologyOpen published by John Wiley & Sons Ltd.

In situ polymerization of monomers for polyphenylquinoxaline/graphite

NASA Technical Reports Server (NTRS)

Serafini, T. T.; Delvigs, P.; Vannucci, R. D.

1973-01-01

Methods currently used to prepare fiber reinforced, high temperature resistant polyphenylquinoxaline (PPQ) composites employ extremely viscous, low solids content solutions of high molecular weight PPQ polymers. An improved approach, described in this report, consists of impregnating the fiber with a solution of the appropriate monomers instead of a solution of previously synthesized high molecular weight polymer. Polymerization of the monomers occurs in situ on the fiber during the solvent removal and curing stages. The in situ polymerization approach greatly simplifies the fabrication of PPQ graphite fiber composites. The use of low viscosity monomeric type solutions facilitates fiber wetting, permits a high solids content, and eliminates the need for prior polymer synthesis.

Non-Leaching, Benign Antifouling Multilayer Polymer Coatings for Marine Applications

DTIC Science & Technology

2010-03-01

polymerization b block BF3•Et2O boron trifluoride diethyl etherate BNL Brookhaven National Labs BF3•Et2O boron trifluoride diethyl etherate BSA...surface characterization of the polymers. We also acknowledge Brookhaven National Laboratory ( BNL ) where the NEXAFS surface characterization was...National Synchrotron Light Source at Brookhaven National Laboratory ( BNL ). The X-ray beam was elliptically polarized (polarization factor = 0.85

Secondary Li battery incorporating 12-Crown-4 ether

NASA Technical Reports Server (NTRS)

Nagasubramanian, Ganesan (Inventor); Distefano, Salvador (Inventor)

1992-01-01

A rechargeable lithium battery which utilizes a polyethylene oxide (PEO) solid polymeric electrolyte complexed with a lithium salt is disclosed. The conductivity is increased an order of magnitude and interfacial charge transfer resistance is substantially decreased by incorporating a minor amount of 12-Crown-4 ether in the PEO-lithium salt solid electrolyte film. Batteries containing the improved electrolyte permit operation at a lower temperature with improved efficiency.

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.

Preparation and use of polymeric materials containing hydrophobic anions and plasticizers for separation of cesium and strontium

DOEpatents

Abney, Kent D.; Kinkead, Scott A.; Mason, Caroline F. V.; Rais, Jiri

1997-01-01

Preparation and use of polymeric materials containing hydrophobic anions and plasticizers for extraction of cesium and strontium. The use of polymeric materials containing plasticizers which are solvents for hydrophobic anions such as derivatives of cobalt dicarbollide or tetraphenylborate which are capable of extracting cesium and strontium ions from aqueous solutions in contact with the polymeric materials, is described. The polymeric material may also include a synergistic agent for a given ion like polyethylene glycol or a crown ether, for removal of radioactive isotopes of cesium and strontium from solutions of diverse composition and, in particular, for solutions containing large excess of sodium nitrate.

Preparation and use of polymeric materials containing hydrophobic anions and plasticizers for separation of cesium and strontium

DOEpatents

Abney, K.D.; Kinkead, S.A.; Mason, C.F.V.; Rais, J.

1997-09-09

Preparation and use is described for polymeric materials containing hydrophobic anions and plasticizers for extraction of cesium and strontium. The use of polymeric materials containing plasticizers which are solvents for hydrophobic anions such as derivatives of cobalt dicarbollide or tetraphenylborate which are capable of extracting cesium and strontium ions from aqueous solutions in contact with the polymeric materials, is described. The polymeric material may also include a synergistic agent for a given ion like polyethylene glycol or a crown ether, for removal of radioactive isotopes of cesium and strontium from solutions of diverse composition and, in particular, for solutions containing large excess of sodium nitrate.

Composite material impregnation unit

NASA Technical Reports Server (NTRS)

Wilkinson, S. P.; Marchello, J. M.; Johnston, N. J.

1993-01-01

This memorandum presents an introduction to the NASA multi-purpose prepregging unit which is now installed and fully operational at the Langley Research Center in the Polymeric Materials Branch. A description of the various impregnation methods that are available to the prepregger are presented. Machine operating details and protocol are provided for its various modes of operation. These include, where appropriate, the related equations for predicting the desired prepreg specifications. Also, as the prepregger is modular in its construction, each individual section is described and discussed. Safety concerns are an important factor and a chapter has been included that highlights the major safety features. Initial experiences and observations for fiber impregnation are described. These first observations have given great insight into the areas of future work that need to be addressed. Future memorandums will focus on these individual processes and their related problems.

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.

Apparatus for consolidating a pre-impregnated, filament-reinforced polymeric prepreg material

NASA Technical Reports Server (NTRS)

Sandusky, Donald A. (Inventor)

1995-01-01

An apparatus and method were developed for providing a uniform, consolidated, unidirectional, continuous, fiber-reinforced polymeric material. The apparatus comprises a supply means, a forming means, a shaping means, and a take-up means. The forming means further comprises a pre-melting chamber and a stationary bar assembly. The shaping means is a loaded cooled nip-roller apparatus. Forming takes place by heating a polymeric prepreg material to a temperature where the polymer becomes viscous and applying pressure gradients at separate locations along the prepreg material. Upon exiting the forming means, the polymeric prepreg material is malleable, consolidated, and flattened. Shaping takes place by passing the malleable, consolidated, flattened prepreg material through a shaped, matched groove in a loaded, cooled nip-roller apparatus to provide the final solid product.

Reciprocating sliding wear evaluation of a polymeric/coating tribological system

NASA Astrophysics Data System (ADS)

Braza, J. F.; Furst, R. E.

1993-04-01

Reciprocating screening tests aimed at simulating a control bearing in a contaminated environment to discern the optimum polymeric/coating combination are described. The polymeric/coating systems were compared with the wear of a baseline phenolic impregnated polytetrafluoroethylene (PTFE) polyester woven fabric composite against an uncoated stainless steel substrate. The polymeric composites under consideration include a polyamide-imide (PAI), a polybenzimidazole, and an injection-moldable PEEK. Results indicate that the system of either PEEK or PAI with an E-Ni-PTFE- or TiN-coated substrate produced the best tribological system. These two composites also exhibited a significant improvement over the baseline fabric when tested against the high-velocity oxygen-fuel thermal spray coating. To discern better the optimum polymeric composite/coating system, full-scale testing must be conducted to study system dynamics, vibrations, counterface hardness and roughness, temperature, external environment and application specific conditions.

Chemistry and adhesive properties of poly(arylene ether)s containing heterocyclic units

NASA Technical Reports Server (NTRS)

Connell, John W.

1991-01-01

Novel poly(arylene ether)s containing heterocyclic units were prepared, characterized, and evaluated as adhesives and composite matrices. The polymers were prepared by reacting a heterocyclic bisphenol with an activated aromatic dihalide in a polar aprotic solvent, using potassium carbonate. The polymerizations were generally carried out in N,N-dimethylacetamide at 155 C. In some cases, where the polymers were semicrystalline, higher temperatures and thus higher boiling solvents were necessary to keep the polymers in solution. Heterocyclic rings incorporated into the poly(arylene ether) backbone include phenylquinoxaline, phenylimidazole, benzimidazole, benzoxazole, 1,3,4-oxadiazole, and 1,2,4-triazole. The polymers were characterized by differential scanning calorimetry, solution viscosity, X-ray diffraction, thin film, and adhesive and (in some cases) composite properties. The glass transition temperatures, crystalline melt temperature, solubility, and mechanical properties varied depending upon the heterocyclic ring. The chemistry and properties of these materials are discussed.

Instruments for preparation of heterogeneous catalysts by an impregnation method

NASA Astrophysics Data System (ADS)

Yamada, Yusuke; Akita, Tomoki; Ueda, Atsushi; Shioyama, Hiroshi; Kobayashi, Tetsuhiko

2005-06-01

Instruments for the preparation of heterogeneous catalysts in powder form have been developed. The instruments consist of powder dispensing robot and an automated liquid handling machine equipped with an ultrasonic and a vortex mixer. The combination of these two instruments achieves the catalyst preparation by incipient wetness and ion exchange methods. The catalyst library prepared with these instruments were tested for dimethyl ether steam reforming and characterized by transmission electron microscopy observations.

In situ polymerization of monomers for polyphenylquinoxaline/graphite fiber composites

NASA Technical Reports Server (NTRS)

Serafini, T. T.; Delvigs, P.; Vannucci, R. D.

1974-01-01

Methods currently used to prepare fiber reinforced, high temperature resistant polyphenylquinoxaline (PPQ) composites employ extremely viscous, low solids content solutions of high molecular weight PPQ polymers. An improved approach, described in this report, consists of impregnating the fiber with a solution of the appropriate monomers instead of a solution of previously synthesized high molecular weight polymer. Polymerization of the monomers occurs in situ on the fiber during the solvent removal and curing stages. The in situ polymerization approach greatly simplifies the fabrication of PPQ graphite fiber composites. The use of low viscosity monomeric type solutions facilitates fiber wetting, permits a high solids content, and eliminates the need for prior polymer synthesis.

Status review of PMR polyimides. [Polymerization of Monomer Reactants

NASA Technical Reports Server (NTRS)

Serafini, T. T.

1979-01-01

In the NASA developed PMR (polymerization of monomer reactants) the reinforcing fibers are impregnated with a solution containing a mixture of monomers dissolved in a low boiling point alkyl alcohol solvent, with the monomers reacting in situ at elevated temperatures to form a thermo-oxidatively stable polyimide matrix. The current status of first and second generation PMR polyimides is reviewed, considering synthesis and properties, processing, and applications. It is concluded that the PMR approach offers various significant advantages, especially superior high temperature properties and processing versatility, to fabricators and users of polyimide/fiber composites.

Development of a protective decorative fire resistant low smoke emitting, thermally stable coating material

NASA Technical Reports Server (NTRS)

1976-01-01

The development of suitable electrocoatings and subsequent application to nonconductive substrates are discussed. Substrates investigated were plastics or resin-treated materials such as FX-resin (phenolic-type resin) impregnated fiberglass mat, polyphenylene sulfide, polyether sulfone and polyimide-impregnated unidirectional fiberglass. Efforts were aimed at formulating a fire-resistant, low smoke emitting, thermally stable, easily cleaned coating material. The coating is to be used for covering substrate panels, such as aluminum, silicate foam, polymeric structural entities, etc., all of which are applied in the aircraft cabin interior and thus subject to the spillages, scuffing, spotting and the general contaminants which prevail in aircraft passenger compartments.

Toughening reinforced epoxy composites with brominated polymeric additives

NASA Technical Reports Server (NTRS)

Nir, Z. (Inventor); Gilwee, W. J., Jr. (Inventor)

1985-01-01

Cured polyfunctional epoxy resins including tris(hydroxyphenyl)methane triglycidyl ether are toughened by addition of polybrominated polymeric additives having an EE below 1500 to the pre-cure composition. Carboxy-terminated butadiene-acrylonitrile rubber is optionally present in the pre-cure mixture as such or as a pre-formed copolymer with other reactants. Reinforced composites, particularly carbon-reinforced composites, of these resins are disclosed and shown to have improved toughness.

Toughening reinforced epoxy composites with brominated polymeric additives

NASA Technical Reports Server (NTRS)

Nir, Z.; Gilwee, W. J., Jr. (Inventor)

1985-01-01

Cured polyfunctional epoxy resins including tris (hydroxyphenyl) methane triglycidyl ether are toughened by addition of polybrominated polymeric additives having an EE below 1500 to the pre-cure composition. Carboxy terminated butadiene acrylonitrile rubber is optionally present in the precure mixture as such or as a pre-formed copolymer with other reactants. Reinforced composites, particularly carbon reinforced composites, of these resins are disclosed and shown to have improved toughness.

Polyimides containing oxyethylene units. Part 4: Polymerization of dianhydrides containing ether linkages

NASA Technical Reports Server (NTRS)

Harris, F. W.; Karnavas, A. J.; Das, S.; Cucuras, C. N.; Hergenrother, P. M.

1986-01-01

The development of new composite resins for various aerospace applications is attempted. Although it is highly desirable that these polymers be soluble in order to facilitate processing, they must display considerable solvent-resistance in use. A recent approach has involved the synthesis of a new series of polyimides containing flexible linkages. The polymers were prepared by the polymerization of aromatic dianhydrides with diamines containing oxyethylene linkages. For example, the polymerization of 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA) with 1,2-bis(4-aminophenoxy)ethane (1a) and bis2-(4-aminophenoxy)ethylether (lb), afforded highly crystalline polyimides that were completely insoluble. However, a polyimide that was amorphous and soluble was obtained from the polymerization of BTDA and an isomer of lb, i.e., bis2-(3-aminophenoxy)ethyl ether (4b). In an attempt to obtain a soluble, amorphous polyimide that could be annealed into a crysalline state, block copolymers of 1b and 4b and BTDA were prepared. Copolymers containing less than 20 weight % 1b were soluble in organic solvents. However, these polymers did not crystallize when heated above their Tg's. Copolymers containing higher levels of 1b were semicrystalline and insoluble. The polymerization of the diamines containing oxyethylene linkages with 4,4'-oxydiphthalic anhydride (ODPA) and a new dianhydride, i.e., 4,4'-oxyethyleneoxyethyleneoxydiphthalic anhydride (OEDA) was investigated. It was postulated that the use of these more flexible dianhydrides would result in more processable polyimides.

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...

Several vapor phase chemical treatments for dimensional stabilization of wood

Treesearch

H.M. Barnes; E.T. Choong; R.C. Mcllhenny

1969-01-01

A bench-scale system for the impregnation of wood with volatile compounds was constructed for the purpose of testing the system concept and evaluating various polymeric bulking materials as dimensional stabilizing agents. Provisions were incorporated for recycling the treating material, introduction of two separate materials alternately or simultaneously, timed-cycle...

Selective separation of furfural and hydroxymethylfurfural from an aqueous solution using a supported hydrophobic deep eutectic solvent liquid membrane.

PubMed

Dietz, Carin H J T; Kroon, Maaike C; Di Stefano, Michela; van Sint Annaland, Martin; Gallucci, Fausto

2017-12-14

For the first time, 12 different supported deep eutectic solvent (DES) liquid membranes were prepared and characterized. These membranes consist of a polymeric support impregnated with a hydrophobic DES. First, the different membranes were characterized and their stability in water and air was determined. Subsequently, the supported DES liquid membranes were applied for the recovery of furfural (FF) and hydroxymethylfurfural (HMF) from aqueous solutions. The effects of substrate properties (e.g. pore size), DES properties (e.g. viscosity) and concentrations of FF and HMF in the feed phase on the observed diffusivities and permeabilities were assessed. It was found that the addition of DES enhances the transport of FF and HMF through the polymeric membrane support. In particular, the use of the DES consisting of thymol + lidocaine (in the molar ratio 2 : 1) impregnated in a polyethylene support resulted in enhanced transport for both FF and HMF, and is most interesting for (in situ) isolation of FF and HMF from aqueous solutions, e.g. in biorefinery processes.

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.

Synthesis and electronic factors in thermal cyclodimerization of functionalized aromatic trifluorovinyl ethers.

PubMed

Spraul, Bryan K; Suresh, S; Jin, Jianyong; Smith, Dennis W

2006-05-31

A series of 19 p-substituted aromatic trifluorovinyl ether compounds were prepared from versatile intermediate p-Br-C(6)H(4)-O-CF=CF(2) and underwent thermal radical mediated cyclodimerization to new difunctional compounds containing the 1,2-disubstituted perfluorocyclobutyl (PFCB) linkage. The synthetic scope demonstrates the functional group transformation tolerance of the fluorovinyl ether, and the dimers are useful as monomers for traditional step-growth polymerization methods. (19)F NMR spectra confirmed that p-substitution affects the trifluorovinyl ether group chemical shifts. The first kinetic studies and substituent effects on thermal cyclodimerization were performed, and the results indicated that electron-withdrawing groups slow the rate of cyclodimerization. The data were further analyzed using the Hammett equation, and reaction constants (rho) of -0.46 at 120 degrees C and -0.59 at 130 degrees C were calculated. This study presents the first liner free energy relationship reported for the cyclodimerization of aromatic trifluorovinyl ethers to PFCB compounds.

Process for disposal of aqueous solutions containing radioactive isotopes

DOEpatents

Colombo, Peter; Neilson, Jr., Robert M.; Becker, Walter W.

1979-01-01

A process for disposing of radioactive aqueous waste solutions whereby the waste solution is utilized as the water of hydration to hydrate densified powdered portland cement in a leakproof container; said waste solution being dispersed without mechanical inter-mixing in situ in said bulk cement, thereafter the hydrated cement body is impregnated with a mixture of a monomer and polymerization catalyst to form polymer throughout the cement body. The entire process being carried out while maintaining the temperature of the components during the process at a temperature below 99.degree. C. The container containing the solid polymer-impregnated body is thereafter stored at a radioactive waste storage dump such as an underground storage dump.

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.

In situ investigation of supercritical CO2 assisted impregnation of drugs into a polymer by high pressure FTIR micro-spectroscopy.

PubMed

Champeau, M; Thomassin, J-M; Jérôme, C; Tassaing, T

2015-02-07

An original experimental set-up combining a FTIR micro-spectrometer with a high pressure cell has been built in order to analyze in situ the impregnation of a solute into microscopic polymer samples, such as fibers or films, subjected to supercritical CO2. Thanks to this experimental set-up, key factors governing the impregnation process can be simultaneously followed such as the swelling of the polymeric matrix, the CO2 sorption, the kinetics of impregnation and the drug loading into the matrix. Moreover, the solute/polymer interactions and the speciation of the solute can be analyzed. We have monitored in situ the impregnation of aspirin and ketoprofen into PEO (Polyethylene Oxide) platelets at T = 40 °C and P = 5; 10 and 15 MPa. The kinetics of impregnation of aspirin was quicker than the one of ketoprofen and the final drug loading was also higher in the case of aspirin. Whereas the CO2 sorption and the PEO swelling remain constant when PEO is just subjected to CO2 under isobaric conditions, we noticed that both parameters can increase while the drug impregnates PEO. Coupling these results with DSC measurements, we underlined the plasticizing effect of the drug that also leads to a decrease in the crystallinity of PEO in situ thus favoring the sorption of CO2 molecules into the matrix and the swelling of the matrix. The plasticizing effect increases with the drug loading. Finally, the speciation of drugs was investigated considering the shift of the carboxyl bands of the drugs. Both drugs were found to be mainly homogeneously dispersed into PEO.

Gels as battery separators for soluble electrode cells

NASA Technical Reports Server (NTRS)

Sheibley, D. W.; Gahn, R. F. (Inventor)

1977-01-01

Gels are formed from silica powders and hydrochloric acid. The gels are then impregnated into a polymeric foam and the resultant sheet material is then used in applications where the transport of chloride ions is desired. Specifically disclosed is the utilization of the sheet in electrically rechargeable redox flow cells which find application in bulk power storage systems.

Polymerization contraction stress in dentin adhesives bonded to dentin and enamel.

PubMed

Hashimoto, Masanori; de Gee, Anton J; Feilzer, Albert J

2008-10-01

In a previous study on of polymerization contraction stress determinations of adhesives bonded to dentin a continuous decline of stress was observed after the adhesives had been light-cured. The decline was ascribed to stress relief caused by diffusion into the adhesive layer of water and/or solvents, left in the impregnated dentin surface after drying and/or evaporation in the application procedure. The purpose of the present study was to test the hypothesis that the contraction stress of adhesives bonded to enamel will not decline after light-curing, based on the assumption that water and/or solvents are more efficiently removed from impregnated enamel surfaces in the drying and/or evaporation step. Contraction stress was determined in a tensilometer for three total-etching adhesives Scotchbond multi-purpose, Single bond and One-step plus and four self-etching adhesives Clearfil SE Bond, Clearfil Protect Bond, AdheSE, and Xeno III. The adhesives were placed in a thin layer between a glass plate and a flat dentin or enamel surface pre-treated with phosphoric acid or self-etching primer and light-cured under constrained conditions. All adhesives bonded to enamel showed a stress decline, but significantly less than for dentin with the exception of two self-etching adhesives. The greatest decline was found for the total-etching adhesive systems bonded to dentin. The presence of hydrophobic monomers in the adhesives had a significant influence on the decline. The experiments indicate that fluids are withdrawn from the resin impregnated tooth structures, which may result in small defects in the tooth-resin interfaces.

New Development of Polymer-Based Cotton for Breathable Material

USDA-ARS?s Scientific Manuscript database

Recently, we converted the poly (ethylene oxide) dibromide to poly (ethylene oxide) diazides and reacted to study cycloaddition polymerization with bisphenol-A dipropargyl ether to produce elastomers compatible with cotton (Polymer Preprints, 2005, 46(1), 737-738). The reactants were characterized w...

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.

Advanced Materials for PEM-Based Fuel Cell Systems

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

James E. McGrath; Donald G. Baird; Michael von Spakovsky

2005-10-26

Proton exchange membrane fuel cells (PEMFCs) are quickly becoming attractive alternative energy sources for transportation, stationary power, and small electronics due to the increasing cost and environmental hazards of traditional fossil fuels. Two main classes of PEMFCs include hydrogen/air or hydrogen/oxygen fuel cells and direct methanol fuel cells (DMFCs). The current benchmark membrane for both types of PEMFCs is Nafion, a perfluorinated sulfonated copolymer made by DuPont. Nafion copolymers exhibit good thermal and chemical stability, as well as very high proton conductivity under hydrated conditions at temperatures below 80 degrees C. However, application of these membranes is limited due tomore » their high methanol permeability and loss of conductivity at high temperatures and low relative humidities. These deficiencies have led to the search for improved materials for proton exchange membranes. Potential PEMs should have good thermal, hydrolytic, and oxidative stability, high proton conductivity, selective permeability, and mechanical durability over long periods of time. Poly(arylene ether)s, polyimides, polybenzimidazoles, and polyphenylenes are among the most widely investigated candidates for PEMs. Poly(arylene ether)s are a promising class of proton exchange membranes due to their excellent thermal and chemical stability and high glass transition temperatures. High proton conductivity can be achieved through post-sulfonation of poly(arylene ether) materials, but this most often results in very high water sorption or even water solubility. Our research has shown that directly polymerized poly(arylene ether) copolymers show important advantages over traditional post-sulfonated systems and also address the concerns with Nafion membranes. These properties were evaluated and correlated with morphology, structure-property relationships, and states of water in the membranes. Further improvements in properties were achieved through incorporation of inorganic fillers, such as phosphotungstic acid and zirconium hydrogen phosphate. Block copolymers were also studied due to the possibility to achieve a desired combination of homopolymer properties as well as the unique morphologies that are possible with block copolymers. Bezoyl substituted poly(p-phenylene) blocks were combined with poly(arylene ether) blocks to merge the structural rigidity of the poly(p-phenylene) with the ductility and high protonic conductivity of the poly(arylene ether)s. As evidenced by our many refereed publications and preprints, the research that we have conducted over the past several years has made a valuable and significant contribution to the literature and to the state of understanding of proton exchange membranes. Our early efforts at scale-up have suggested that the directly polymerized disulfonated poly(arylene ether sulfone) copolymers are commercially viable alternatives for proton exchange membranes. A new process for bipolar plates was developed and is described. An important single domain PEMFC model was developed and is documented in herein.« less

From oligomers to molecular giants of soybean oil in supercritical carbon dioxide medium: 1. Preparation of polymers with lower molecular weight from soybean oil.

PubMed

Liu, Zengshe; Sharma, Brajendra K; Erhan, Sevim Z

2007-01-01

Polymers with a low molecular weight derived from soybean oil have been prepared in a supercritical carbon dioxide medium by cationic polymerization. Boron trifluoride diethyl etherate was used as an initiator. Influences of polymerization temperature, amount of initiator, and carbon dioxide pressure on the molecular weight were investigated. It is shown that the higher polymerization temperature favors polymers with relatively higher molecular weights. Larger amounts of initiator also provide polymers with higher molecular weights. Higher pressure favors polymers with relatively higher molecular weights. The applications of these soy-based materials will be in the lubrication and hydraulic fluid areas.

Unique reversibility in extraction mechanism of U compared to solvent extraction for sorption of U(VI) and Pu(IV) by a novel solvent impregnated resin containing trialkyl phosphine oxide functionalized ionic liquid.

PubMed

Paramanik, M; Panja, S; Dhami, P S; Yadav, J S; Kaushik, C P; Ghosh, S K

2018-07-15

Novel Solvent Impregnated Resin (SIR) material was prepared by impregnating a trialkyl phosphine oxide functionalized ionic liquid (IL) into an inert polymeric material XAD-7. A series of SIR materials were prepared by varying the IL quantity. Sorption of both U(VI) and Pu(IV) were found to increase with increasing IL concentration in SIR up to an optimum IL concentration of 435 mg g -1 of SIR beyond which no effect of IL concentration was observed. A change of mechanism of sorption for U(VI) by SIR was observed in comparison to solvent extraction. The dependency of U(VI) sorption with nitric acid concentration showed a reverse trend compared to solvent extraction studies while for Pu(IV) the trend remained same as observed with solvent extraction. Sorption of both the radionuclides was found to follow pseudo second order mechanism and Langmuir adsorption isotherm. Distribution co-efficient measurements on IL impregnated SIR showed highly selective sorption of U(VI) and Pu(IV) over other trivalent f-elements and fission products from nitric acid medium. Copyright © 2018 Elsevier B.V. All rights reserved.

Determination of acrolein and other carbonyls in cigarette smoke using coupled silica cartridges impregnated with hydroquinone and 2,4-dinitrophenylhydrazine.

PubMed

Uchiyama, Shigehisa; Inaba, Yohei; Kunugita, Naoki

2010-06-25

A new method for the determination of acrolein and other carbonyls in cigarette smoke using a dual cartridge system has been developed. Each cartridge consists of reagent-impregnated silica particles. The first contains hydroquinone (HQ) for the inhibition of acrolein polymerization, while the second contains 2,4-dinitrophenylhydrazine (DNPH) for the derivatization of carbonyls. Smoke samples were firstly drawn through the cartridge containing HQ-impregnated silica (HQ-silica) and then through the DNPH-impregnated silica (DNPH-silica). Acrolein in the sample was completely trapped in the first HQ-silica cartridge. Some other airborne carbonyls were also trapped by the HQ-silica, and those that pass through were trapped in the second DNPH-silica cartridge. Extraction was performed in the reverse direction to air sampling. When solvent was eluted through the dual-cartridges, excess DNPH was washed into the HQ bed where it reacted with acrolein and other trapped carbonyls to form the corresponding hydrazone derivatives. All of the hydrazones derived from airborne carbonyls were completely separated and measured using high-performance liquid chromatography. This HQ-DNPH-method can be applied for the determination of acrolein and other alpha,beta-unsaturated aldehydes, such as crotonaldehyde, in cigarette smoke. Copyright 2010 Elsevier B.V. All rights reserved.

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

Cross-linked sulfonated poly(ether ether ketone) by using diamino-organosilicon for proton exchange fuel cells.

PubMed

Kayser, Marie J; Reinholdt, Marc X; Kaliaguine, Serge

2011-03-31

Fuel cells are at the battlefront to find alternate sources of energy to the highly polluting, economically and environmentally constraining fossil fuels. This work uses an organosilicon molecule presenting two amine functions, bis(3-aminopropyl)-tetramethyldisiloxane (APTMDS) with the aim of preparing cross-linked sulfonated poly(ether ether ketone) (SPEEK) based membranes. The hybrid membranes obtained at varying APTMDS loadings are characterized for their acid, proton conductivity, water uptake, and swelling properties. APTMDS may be considered as an extreme case of silica nanoparticle and is therefore most advantageously distributed within the polymeric matrix. The two amine groups can interact, via electrostatic interactions, with the sulfonic acid groups of SPEEK, resulting in a double anchoring of the molecule. The addition of a small amount of APTMDS is enhancing the mechanical and hydrolytic properties of the membranes and allows some unfolding of the polymer chains, rendering some acid sites accessible to water molecules and thus available for proton transport.

Novel Precursor Approached for CMC Derived by Polymer Pyrolysis

DTIC Science & Technology

1994-02-15

to remove signals from probe polymer materials. C. Pyrolysis Methods The conversion of polymeric PMVS to SiC -containing ceramic was studied by... Composite Fabrication Methods Ceramic matrix composites with different matrix compositions were fabricated using the Polymer Impregnation- Pyrolysis (PIP...Pyrolyzed composites were re- infiltrated with the appropriate polymer matrix source under vacuum, and cured in an autoclave under 100 psi overpressure of N2

Marine Exposure of Preservative-Treated Small Wood Panels.

DTIC Science & Technology

1984-10-01

oxide (table 5) are unattacked after 5-1/2 years. Impregnation with tributyltin ( TBT ) oxide (table 6-1), TBT -modified methacrylate polymers (table 6...1), or TBT - modified monomers (with subsequent polymerization) (tables 6-2, 6-3) has prevented borer damage for 6 to 6-112 years. Methacrylates...copper zinc 5 arsenate 3-10 Polymers Prepolymerized tributyltin Dual treatments methacrylate and Chromated copper methyl methacrylate arsenate (B

Architecture of Amylose Supramolecules in Form of Inclusion Complexes by Phosphorylase-Catalyzed Enzymatic Polymerization

PubMed Central

Kadokawa, Jun-ichi

2013-01-01

This paper reviews the architecture of amylose supramolecules in form of inclusion complexes with synthetic polymers by phosphorylase-catalyzed enzymatic polymerization. Amylose is known to be synthesized by enzymatic polymerization using α-d-glucose 1-phosphate as a monomer, by phosphorylase catalysis. When the phosphorylase-catalyzed enzymatic polymerization was conducted in the presence of various hydrophobic polymers, such as polyethers, polyesters, poly(ester-ether), and polycarbonates as a guest polymer, such inclusion supramolecules were formed by the hydrophobic interaction in the progress of polymerization. Because the representation of propagation in the polymerization is similar to the way that a vine of a plant grows, twining around a rod, this polymerization method for the formation of amylose-polymer inclusion complexes was proposed to be named “vine-twining polymerization”. To yield an inclusion complex from a strongly hydrophobic polyester, the parallel enzymatic polymerization system was extensively developed. The author found that amylose selectively included one side of the guest polymer from a mixture of two resemblant guest polymers, as well as a specific range in molecular weights of the guest polymers poly(tetrahydrofuran) (PTHF) in the vine-twining polymerization. Selective inclusion behavior of amylose toward stereoisomers of chiral polyesters, poly(lactide)s, also appeared in the vine-twining polymerization. PMID:24970172

A New Approach to Prepare Vegetable Oil-Based Polymers

USDA-ARS?s Scientific Manuscript database

Polymers from vegetable oils, such as soybean oil, were prepared by cationic polymerization in supercritical carbon dioxide (scCO2) medium. Boron trifluoride diethyl etherate (BF3.OEt2) was selected as catalyst. The resulting polymers have molecular weight ranging from 21,842 to 118,300 g/mol. Nu...

REMOVAL OF MTBE FROM WATER BY MEMBRANE-BASED PERVAPORATION TECHNOLOGY

EPA Science Inventory

The ability of pervaporation to remove methyl t-butyl ether (MTBE) from water has been evaluated at both bench- and pilot-scales. In pervaporation, a liquid stream containing two or more components is placed in contact with one side of a non-porous polymeric membrane while a vac...

Hydrogel nanoparticle based immunoassay

DOEpatents

Liotta, Lance A; Luchini, Alessandra; Petricoin, Emanuel F; Espina, Virginia

2015-04-21

An immunoassay device incorporating porous polymeric capture nanoparticles within either the sample collection vessel or pre-impregnated into a porous substratum within fluid flow path of the analytical device is presented. This incorporation of capture particles within the immunoassay device improves sensitivity while removing the requirement for pre-processing of samples prior to loading the immunoassay device. A preferred embodiment is coreshell bait containing capture nanoparticles which perform three functions in one step, in solution: a) molecular size sieving, b) target analyte sequestration and concentration, and c) protection from degradation. The polymeric matrix of the capture particles may be made of co-polymeric materials having a structural monomer and an affinity monomer, the affinity monomer having properties that attract the analyte to the capture particle. This device is useful for point of care diagnostic assays for biomedical applications and as field deployable assays for environmental, pathogen and chemical or biological threat identification.

In-Situ Immobilization of Ni Complex on Amine-Grafted SiO₂ for Ethylene Polymerization.

PubMed

Lee, Sang Yun; Ko, Young Soo

2018-02-01

The results on the In-Situ synthesis of Ni complex on amine-grafted SiO2 and its ethylene polymerization were explained. SiO2/2NS/(DME)NiBr2 and SiO2/3NS/(DME)NiBr2(Ni(II) bromide ethylene glycol dimethyl ether) catalysts were active for ethylene polymerization. The highest activity was shown at the polymerization temperature of 25 °C, and SiO2/2NS/(DME)NiBr2 exhibited higher activity than SiO2/3NS/(DME)NiBr2. The PDI values of SiO2/2NS/(DME)NiBr2 were in the range of 8~18. The aminosilane compounds and Ni were evenly grafted and distributed in the silica. It was proposed that DME ligand was mostly removed during the supporting process, and only NiBr2 was complexed with the amine group of 2NS based on the results of FT-IR and ethylene polymerization.

Antimicrobial activities of the rhizome extract of Zingiber zerumbet Linn.

PubMed

Kader, Golam; Nikkon, Farjana; Rashid, Mohammad Abdur; Yeasmin, Tanzima

2011-10-01

To investigate antimicrobial effects of ethanolic extract of Zingiber zerumbet (Z. zerumbet) (L.) Smith and its chloroform and petroleum ether soluble fractions against pathogenic bacteria and fungi. The fresh rhizomes of Zingiber zerumbet were extracted in cold with ethanol (4.0 L) after concentration. The crude ethanol extract was fractionated by petroleum ether and chloroform to form a suspension of ethanol extract (15.0 g), petroleum ether fraction (6.6 g) and chloroform soluble fraction (5.0 g). The crude ethanol extract and its petroleum ether and chloroform fractions were evaluated for antibacterial and antifungal activity against thirteen pathogenic bacteria and three fungi by the disc diffusion method. Commercially available kanamycin (30 µg/disc) was used as standard disc and blank discs impregnated with the respective solvents were used as negative control. At a concentration of 400 µg/disc, all the samples showed mild to moderate antibacterial and antifungal activity and produced the zone of inhibition ranging from 6 mm to 10 mm. Among the tested samples, the crude ethanol extract showed the highest activity against Vibrio parahemolyticus (V. parahemolyticus). The minimum inhibitory concentration (MIC) of the crude ethanol extract and its fractions were within the value of 128-256 µg/mL against two Gram positive and four Gram negative bacteria and all the samples showed the lowest MIC value against V. parahemolyticus (128 µg/mL). It can be concluded that, potent antibacterial and antifungal phytochemicals are present in ethanol extract of Z. zerumbet (L).

Characterization of double oxide system Cu-Cr-O supported on γ-Al2O3

NASA Astrophysics Data System (ADS)

Cherkezova-Zheleva, Z.; Kolev, H.; Krstić, J.; Dimitrov, D.; Ivanov, K.; Loncarević, D.; Jovanović, D.; Mitov, I.

2009-09-01

Series of alumina supported chromium-copper catalysts were prepared by co-impregnation method. The samples were characterized by X-ray diffraction, X-ray photoelectron spectroscopy and UV-visible diffuse reflectance spectroscopy. Dispersion and porosity was also obtained. The experimental and catalytic test results have drawn a conclusion that an interaction between copper and chromium ions takes place. This interaction is responsible for the enhanced catalytic activity of studied catalysts in reaction of total oxidation of industrial formaldehyde production exhaust gas, which contains CO, dimethyl ether and methanol as main components.

Polymer-Based Nanofibers Impregnated with Drug Infused Plant Virus Particles as a Responsive Fabric for Therapeutic Delivery

NASA Astrophysics Data System (ADS)

Honarbakhsh, Sara

A biodegradable and controlled drug delivery system has been developed herein composed of electrospun polymeric nanofibers impregnated with cargo loaded Red clover necrotic mosaic virus (RCNMV)---a robust plant virus---as the drug carrier nanoparticle. In this system, controlled drug release is achieved by altering the porosity of the biodegradable matrix as well as controlling the position and distribution of the cargo loaded nanocarriers in the matrix. Solution electrospinning as well as dipping method are used to create and to impregnate the matrix (the fibers of which possess uniformly distributed nano-size surface pores) with cargo loaded nanocarriers. Prior to the impregnation stage of cargo loaded nanocarriers into the matrix, compatibility of a group of candidate cargos (Ampicillin, Novanthrone, Doxorubicin and Ethidium Bromide) and RCNMV functionality with potential electrospinning solvents were investigated and a solvent with the least degradative effect was selected. In order to achieve both sustained and immediate drug release profiles, cargo loaded nanocarriers were embedded into the matrix---through co-spinning process---as well as on the surface of matrix fibers---through dipping method. SEM, TEM and Fluorescent Light Microscopy images of the medicated structures suggested that the nanocarriers were incorporated into/on the matrix. In vitro release assays were also carried out the results of which confirmed having obtained sustained release in the co-spun medicated structures where as dipped samples showed an immediate release profile.

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.

21 CFR 173.20 - Ion-exchange membranes.

Code of Federal Regulations, 2014 CFR

2014-04-01

... subjecting a polyethylene base conforming to § 177.1520 of this chapter to polymerization with styrene until the polystyrene phase of the base is not less than 16 percent nor more than 30 percent by weight. The base is then modified by reaction with chloromethyl methyl ether, and by subsequent amination with tri...

All-SPEEK flexible supercapacitor exploiting laser-induced graphenization

NASA Astrophysics Data System (ADS)

Lamberti, A.; Serrapede, M.; Ferraro, G.; Fontana, M.; Perrucci, F.; Bianco, S.; Chiolerio, A.; Bocchini, S.

2017-09-01

Flexible supercapacitors have emerged as one of the more promising and efficient space-saving energy storage system for portable and wearable electronics. Laser-induced graphenization has been recently proposed as a powerful and scalable method to directly convert a polymeric substrate into a 3D network of few layer graphene as high-performance supercapacitor electrode. Unfortunately this outstanding process has been reported to be feasible only for few thermoplastic polymers, strongly limiting its future developments. Here we show that laser induced graphenization of sulfonated poly(ether ether ketone) (SPEEK) can be obtained and the mechanism of this novel process is proposed. The resulting material can act at the same time as binder-free electrode and current collector. Moreover SPEEK is also used both as separator and polymeric electrolyte allowing the assembling of an all-SPEEK flexible supercapacitor. Chemico-physical characterization provides deep understanding of the laser-induced graphenization process, reported on this polymer for the first time, while the device performance studied by cyclic voltammetry, charging-discharging, and impedance spectroscopy prove the enormous potential of the proposed approach.

Thermal analysis of hydroxypropylmethylcellulose and methylcellulose: powders, gels and matrix tablets.

PubMed

Ford, J L

1999-03-15

This review focuses on the thermal analysis of hydroxypropylmethylcellulose (HPMC) and methylcellulose. Differential scanning calorimetry (DSC) of their powders is used to determine temperatures of moisture loss (in conjunction with thermogravimetric analysis) and glass transition temperatures. However, sample preparation and encapsulation affect the values obtained. The interaction of these cellulose ethers with water is evaluated by DSC. Water is added to the powder directly in DSC pans or preformed gels can be evaluated. Data quality depends on previous thermal history but estimates of the quantity of water bound to the polymers may be made. Water uptake by cellulose ethers may be evaluated by the use of polymeric wafers and by following loss of free water, over a series of timed curves, into wafers in contact with water. Cloud points, which assess the reduction of polymer solubility with increase of temperature, may be assessed spectrophotometrically. DSC and rheometric studies are used to follow thermogelation, a process involving hydrophobic interaction between partly hydrated polymeric chains. The advantages and disadvantages of the various methodologies are highlighted. Copyright.

Surface-initiated polymerization within mesoporous silica spheres for the modular design of charge-neutral polymer particles.

PubMed

Müllner, Markus; Cui, Jiwei; Noi, Ka Fung; Gunawan, Sylvia T; Caruso, Frank

2014-06-03

We report a templating approach for the preparation of functional polymer replica particles via surface-initiated polymerization in mesoporous silica templates. Subsequent removal of the template resulted in discrete polymer particles. Furthermore, redox-responsive replica particles could be engineered to disassemble in a reducing environment. Particles, made of poly(methacryloyloxyethyl phosphorylcholine) (PMPC) or poly[oligo(ethylene glycol) methyl ether methacrylate] (POEGMA), exhibited very low association to human cancer cells (below 5%), which renders the reported charge-neutral polymer particles a modular and versatile class of highly functional carriers with potential applications in drug delivery.

Solid sorbents for removal of carbon dioxide from gas streams at low temperatures

DOEpatents

Sirwardane, Ranjani V.

2005-06-21

New low-cost CO.sub.2 sorbents are provided that can be used in large-scale gas-solid processes. A new method is provided for making these sorbents that involves treating substrates with an amine and/or an ether so that the amine and/or ether comprise at least 50 wt. percent of the sorbent. The sorbent acts by capturing compounds contained in gaseous fluids via chemisorption and/or physisorption between the unit layers of the substrate's lattice where the polar amine liquids and solids and/or polar ether liquids and solids are located. The method eliminates the need for high surface area supports and polymeric materials for the preparation of CO.sub.2 capture systems, and provides sorbents with absorption capabilities that are independent of the sorbents' surface areas. The sorbents can be regenerated by heating at temperatures in excess of 35.degree. C.

Selective sorption of lead, cadmium and zinc ions by a polymeric cation exchanger containing nano-Zr(HPO3S)2.

PubMed

Zhang, Qingrui; Pan, Bingcai; Pan, Bingjun; Zhang, Weiming; Jia, Kun; Zhang, Quanxing

2008-06-01

A novel polymeric hybrid sorbent, namely ZrPS-001, was fabricated for enhanced sorption of heavy metal ions by impregnating Zr(HPO3S)2 (i.e., ZrPS) nanoparticles within a porous polymeric cation exchanger D-001. The immobilized negatively charged groups bound to the polymeric matrix D-001 would result in preconcentration and permeation enhancement of target metal ions prior to sequestration, and ZrPS nanoparticles are expected to sequester heavy metals selectively through an ion-exchange process. Highly effective sequestration of lead, cadmium, and zinc ions from aqueous solution can be achieved by ZrPS-001 even in the presence of competing calcium ion at concentration several orders of magnitude greater than the target species. The exhausted ZrPS-001 beads are amenable to regeneration with 6 M HCI solution for repeated use without any significant capacity loss. Fixed-bed column treatment of simulated waters containing heavy metals at high or trace levels was also performed. The content of heavy metals in treated effluent approached or met the WHO drinking water standard.

Evaluation of Thermal Control Coatings and Polymeric Materials Exposed to Ground Simulated Atomic Oxygen and Vacuum Ultraviolet Radiation

NASA Technical Reports Server (NTRS)

Kamenetzky, R. R.; Vaughn, J. A.; Finckenor, M. M.; Linton, R. C.

1995-01-01

Numerous thermal control and polymeric samples with potential International Space Station applications were evaluated for atomic oxygen and vacuum ultraviolet radiation effects in the Princeton Plasma Physics Laboratory 5 eV Neutral Atomic Oxygen Facility and in the MSFC Atomic Oxygen Drift Tube System. Included in this study were samples of various anodized aluminum samples, ceramic paints, polymeric materials, and beta cloth, a Teflon-impregnated fiberglass cloth. Aluminum anodizations tested were black duranodic, chromic acid anodize, and sulfuric acid anodize. Paint samples consisted of an inorganic glassy black paint and Z-93 white paint made with the original PS7 binder and the new K2130 binder. Polymeric samples evaluated included bulk Halar, bulk PEEK, and silverized FEP Teflon. Aluminized and nonaluminized Chemfab 250 beta cloth were also exposed. Samples were evaluated for changes in mass, thickness, solar absorptance, and infrared emittance. In addition to material effects, an investigation was made comparing diffuse reflectance/solar absorptance measurements made using a Beckman DK2 spectroreflectometer and like measurements made using an AZ Technology-developed laboratory portable spectroreflectometer.

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

Adur, A.M.

Three species of bamboo were converted to bamboo-polymer composites by vacuum impregnation with monomer and in situ polymerization using gamma irradiation. Resistance of the composites to various chemicals present in concrete was tested. Resistance to termites, fungus and other forms of biological attack was examined. Strength-to-weight ratios were calculated based on mechanical tests performed earlier (paper II of this three-part series). Possible application for tensile reinforcement of concrete is discussed in considerable detail. 2 figures, 4 tables.

Densely quaternized poly(arylene ether)s with distinct phase separation for highly anion-conductive membranes

NASA Astrophysics Data System (ADS)

Hu, Yuanfang; Wang, Bingxi; Li, Xiao; Chen, Dongyang; Zhang, Weiying

2018-05-01

To develop high performance anion exchange membranes (AEMs), a novel bisphenol monomer bearing eight benzylmethyl groups at the outer edge of the molecule was synthesized, which after condensation polymerization with various amounts of 4,4‧-dihydroxydiphenylsulfone and 4,4‧-difluorobenzophenone yielded novel poly(arylene ether)s with densely located benzylmethyl groups. These benzylmethyl groups were then converted to quaternary ammonium groups by radical-initiated bromination and quaternization in tandem, leading to the emergence of densely quaternized poly(arylene ether sulfone)s (QA-PAEs) with controlled ion exchange capacities (IECs) ranging from 1.61 to 2.32 mmol g-1. Both small-angle X-ray scattering (SAXS) and transmission electron microscopy (TEM) studies revealed distinct phase separation in the QA-PAEs. The QA-PAE-40 with an IEC of 2.32 mmol g-1 exhibited a Br- conductivity of 9.2 mS cm-1 and a SO42- conductivity of 14.0 mS cm-1 at room temperature, much higher than those of a control membrane with a similar IEC but without obvious phase separation. Therefore, phase separation of AEMs was validated to be advantageous for the efficient conducting of anions. The experimental results also showed that the QA-PAEs were promising AEM materials, especially for non-alkaline applications.

Composite perfluorohydrocarbon membranes, their preparation and use

DOEpatents

Ding, Yong; Bikson, Benjamin

2017-04-04

Composite porous hydrophobic membranes are prepared by forming a perfluorohydrocarbon layer on the surface of a preformed porous polymeric substrate. The substrate can be formed from poly (aryl ether ketone) and a perfluorohydrocarbon layer can be chemically grafted to the surface of the substrate. The membranes can be utilized for a broad range of fluid separations, such as microfiltration, nanofiltration, ultrafiltration as membrane contactors for membrane distillation and for degassing and dewatering of fluids. The membranes can further contain a dense ultra-thin perfluorohydrocarbon layer superimposed on the porous poly (aryl ether ketone) substrate and can be utilized as membrane contactors or as gas separation. membranes for natural gas treatment and gas dehydration.

Advanced Materials for PEM-Based Fuel Cell Systems

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

James E. McGrath

2005-10-26

Proton exchange membrane fuel cells (PEMFCs) are quickly becoming attractive alternative energy sources for transportation, stationary power, and small electronics due to the increasing cost and environmental hazards of traditional fossil fuels. Two main classes of PEMFCs include hydrogen/air or hydrogen/oxygen fuel cells and direct methanol fuel cells (DMFCs). The current benchmark membrane for both types of PEMFCs is Nafion, a perfluorinated sulfonated copolymer made by DuPont. Nafion copolymers exhibit good thermal and chemical stability, as well as very high proton conductivity under hydrated conditions at temperatures below 80 °C. However, application of these membranes is limited due to theirmore » high methanol permeability and loss of conductivity at high temperatures and low relative humidities. These deficiencies have led to the search for improved materials for proton exchange membranes. Potential PEMs should have good thermal, hydrolytic, and oxidative stability, high proton conductivity, selective permeability, and mechanical durability over long periods of time. Poly(arylene ether)s, polyimides, polybenzimidazoles, and polyphenylenes are among the most widely investigated candidates for PEMs. Poly(arylene ether)s are a promising class of proton exchange membranes due to their excellent thermal and chemical stability and high glass transition temperatures. High proton conductivity can be achieved through post-sulfonation of poly(arylene ether) materials, but this most often results in very high water sorption or even water solubility. Our research has shown that directly polymerized poly(arylene ether) copolymers show important advantages over traditional post-sulfonated systems and also address the concerns with Nafion membranes. These properties were evaluated and correlated with morphology, structure-property relationships, and states of water in the membranes. Further improvements in properties were achieved through incorporation of inorganic fillers, such as phosphotungstic acid and zirconium hydrogen phosphate. Block copolymers were also studied due to the possibility to achieve a desired combination of homopolymer properties as well as the unique morphologies that are possible with block copolymers. Bezoyl substituted poly(p-phenylene) blocks were combined with poly(arylene ether) blocks to merge the structural rigidity of the poly(p-phenylene) with the ductility and high protonic conductivity of the poly(arylene ether)s. As evidenced by our many refereed publications and preprints, the research that we have conducted over the past several years has made a valuable and significant contribution to the literature and to the state of understanding of proton exchange membranes. Our early efforts at scale-up have suggested that the directly polymerized disulfonated poly(arylene ether sulfone) copolymers are commercially viable alternatives for proton exchange membranes. A new process for bipolar plates was developed and is described. An important single domain PEMFC model was developed and is documented in this final report.« less

Electron-transfer reactions in cyanine borate ion pairs: photopolymerization initiators sensitive to visible light

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

Chatterjee, S.; Gottschalk, P.; Davis, P.D.

1988-03-30

Photoinitiation of polymerization is a process of immense practical, economic, and theoretical importance. In typical examples the polymerization of an acrylate or styrene-derived monomer is initiated by irradiation of a sensitizer with ultraviolet light. The excited state of the sensitizer may dissociate directly to form active free radicals as in the case of the benzoin ethers, or it may first undergo a bimolecular electron-transfer reaction whose products initiate polymerization as is the case in the benzophenone-dimethylaniline system. Efforts to extend the range of useful photoinitiators of free-radical polymerization to the visible region of the spectrum have heretofore met with onlymore » modest success. These special initiators typically are sensitive only to blue light or suffer from thermal instability and have low quantum efficiencies. The authors report herein the discovery that triphenylalkylborate salts of cyanine dyes (Chart I) are photoinitiators of free-radical polymerization whose sensitivity throughout the entire visible spectral region is the result of a novel intra-ion-pair electron-transfer reaction.« less

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

The improvement of rechargeable lithium battery electrolyte performance with additives

NASA Technical Reports Server (NTRS)

Dominey, L. A.; Goldman, J. L.

1990-01-01

The deliberate introduction of additives like 2-methylfuran (2-MeF) is known to improve Li cycleability in cyclic ether electrolytes. The authors found that the proclivity of 2-MeF to polymerize in the bulk electrolyte or on a TiS2 cathode was inhibited by the addition of reduced oxygen species, such as O2- and OH-. Additionally, the polymerization of tetrahydrofuran and dioxolane and the destructive processes initiated by AsF6- decomposition to AsF5 and AsF3 were inhibited by the introduction of reduced oxygen species, particularly OH- at the 10-ppm to 100-ppm level.

Automated Tow Placement Processing and Characterization of Composites

NASA Technical Reports Server (NTRS)

Prabhakaran, R.

2004-01-01

The project had one of the initial objectives as automated tow placement (ATP), in which a robot was used to place a collimated band of pre-impregnated ribbons or a wide preconsolidated tape onto a tool surface. It was proposed to utilize the Automated Tow Placement machine that was already available and to fabricate carbon fiber reinforced PEEK (polyether-ether-ketone) matrix composites. After initial experiments with the fabrication of flat plates, composite cylinders were to be fabricated. Specimens from the fabricated parts were to be tested for mechanical characterization. A second objective was to conduct various types of tests for characterizing composite specimens cured by different fabrication processes.

Polymerization and photochromism of ammonium molybdate in porous glass

NASA Astrophysics Data System (ADS)

Pak, V. N.; Borisov, A. N.

2016-08-01

Modification of porous glass (PG) plates is carried out by impregnation with aqueous solutions of ammonium molybdate (NH4)2MoO4 with subsequent removal of water at 120°C. A long-wavelength shift of absorption spectra upon accumulation of the salt in PG indicates polymerization of MoO 4 2- anions at low concentrations of the encapsulated salt. Photochromism manifests itself as the anionic forms in PG become larger. UV irradiation of the modified plates causes enhancement of continuous absorption in the visible range. The proposed mechanism of photoreduction of the polianions in PG involves the removal of oxygen atoms from the bridging-Mo-O-Mo-bonds and stabilization of the colored forms by means of conjugation of the electrons released from the 4 d-levels of pentavalent molybdenum.

Graft-crosslinked copolymers based on poly(arylene ether ketone)-gc-sulfonated poly(arylene ether sulfone) for PEMFC applications.

PubMed

Zhang, Xuan; Hu, Zhaoxia; Luo, Linqiang; Chen, Shanshan; Liu, Jianmei; Chen, Shouwen; Wang, Lianjun

2011-07-15

Novel poly(arylene ether ketone) polymers with fluorophenyl pendants and phenoxide-terminated wholly sulfonated poly(arylene ether sulfone) oligomers are prepared via Ni(0)-catalyzed and nucleophilic polymerization, respectively, and subsequently used as starting materials to obtain graft-crosslinked membranes as polymer electrolyte membranes. The phenoxide-terminated sulfonated moieties are introduced as hydrophilic parts as well as crosslinking units. The chemical structure and morphology of the obtained membranes are confirmed by (1) H NMR and tapping-mode AFM. The properties required for fuel cell applications, including water uptake and dimensional change, as well as proton conductivity, are investigated. AFM results show a clear nanoscale phase-separation microstructure of the obtained membranes. The membranes show good dimensional stability and reasonably high proton conductivities under 30-90% relative humidity. The anisotropic proton conductivity ratios (σ(formula see text) ) of the membranes in water are in the range 0.65-0.92, and increase with an increase in hydrophilic block length. The results indicate that the graft-crosslinked membranes are promising candidates for applications as polymer electrolyte membranes. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Maleimido substituted aromatic cyclotriphosphazenes

NASA Technical Reports Server (NTRS)

Kumar, D.; Fohlen, G. M.; Parker, J. A. (Inventor)

1985-01-01

4-Aminophenoxy cyclotriphosphazenes are reacted with maleic anhydride to produce maleamic acids which are converted to the maleimides. The maleimides are polymerized. By selection of starting materials (e.g., hexakis amino or trisaminophenoxy-trisphenoxy-cyclo-triphosphazenes), selection of molar proportions of reactants, use of mixtures of anhydrides and use of dianhydrides as bridging groups a variety of maleimides and polymers are produced. The polymers have high limiting oxygen indices, high char yields and other useful heat and fire resistant properties making them useful as, for example, impregnants of fabrics.

Wood-Polymer composites obtained by gamma irradiation

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

Gago, J.; Lopez, A.; Rodriguez, J.

2007-10-26

In this work we impregnate three Peruvian woods (Calycophy spruceanum Be, Aniba amazonica Meiz and Hura crepitans L) with styrene-polyester resin and methyl methacrylate. The polymerization of the system was promoted by gamma radiation and the experimental optimal condition was obtained with styrene-polyester 1:1 and 15 kGy. The obtained composites show reduced water absorption and better mechanical properties compared to the original wood. The structure of the wood-polymer composites was studied by light microscopy. Water absorption and hardness were also obtained.

Aromatic cyclotriphosphazenes

NASA Technical Reports Server (NTRS)

Kamar, Devendra (Inventor); Fohlen, George M. (Inventor); Parker, John A. (Inventor)

1988-01-01

Four-Aminophenoxy cyclotriphosphazenes are reacted with maleic anhydride to produce maleamic acids which are converted to the maleimides. The maleimides are polymerized. By selection of starting materials (e.g., hexakis amino or trisaminophenoxy trisphenoxy cyclotrisphosphazenes), selection of molar porportions of reactants, use of mixtures of anhydrides and use of dianhydrides as bridging groups a variety of maleimides and polymers are produced. The polymers have high limiting oxygen indices, high char yields and other useful heat and fire resistant properties making them useful as, for example, impregnants of fabrics.

Tailor making high performance graphite fiber reinforced PMR polyimides

NASA Technical Reports Server (NTRS)

Serafini, T. T.; Vannucci, R. D.

1974-01-01

Studies performed to demonstrate the feasibility of using the polymerization of monomer reactants (PMR) approach to tailor make processable polyimide matrix resins are described. Monomeric reactant solutions containing the dimethyl ester of 3,3',4,4' -benzophenonetetracarboxylic acid, 4, 4' -methylenedianiline and the monomethyl ester of 5-norbornene-2, 3-dicarboxylic acid were used to impregnate Hercules HTS graphite fiber. Six different monomeric reactant stoichiometries were studied. The processing characteristics and elevated temperature mechanical properties of the PMR polyimide/HTS graphite fiber composites are described.

Preparation and characterization of poly (arylene ether isoxazole)s by fluoride ion-mediated aromatic nucleophilic displacement reactions

NASA Technical Reports Server (NTRS)

Herbert, C. G.; Bass, R. G.

1994-01-01

As part of a continuing effort to prepare novel thermally stable high-performance polymers, poly(arylene ether isoxazole)s have been prepared by fluoride ion-catalyzed aromatic nucleophilic substitution reactions with bis(trimethylsiloxyphenyl) isoxazoles and activated bisarylhalides in diphenyl sulfone. Initial investigation involving the preparation of these materials with isoxazole bisphenols and activated bisarylhalides in the presence of potassium carbonate indicated that, under reaction conditions necessary to prepare high-molecular-weight materials, the isoxazole monomer was converted to an enamino ketone. This side reaction was avoided by using fluoride as a base. However, trimethylsilyl ether derivatives of the isoxazole bisphenols were required in these polymerizations for the preparation of high-molecular-weight materials. Moderate to high inherent viscosity eta(sub inh): 0.43-0.87 dl/g) materials with good thermal stability (air: 409-477 C, helium: 435-512 C) can be prepared by the silyl ether method. Glass transition temperatures ranged from 182 to 225 C for polymers with phenyl pendants and from 170 to 214 C for those without. Molecular weight control by 2% endcapping and the incorporation of a phenyl pendant at the 4 position of the isoxazole is necessary to yield polymers soluble in polar aprotic solvents at room temperature. There is evidence, however, indicating the existence of crosslinks between the polymer chains when the silyl ether approach is utilized.

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.

Development of octreotide-conjugated polymeric prodrug of bufalin for targeted delivery to somatostatin receptor 2 overexpressing breast cancer in vitro and in vivo

PubMed Central

Liu, Tao; Jia, Tingting; Yuan, Xia; Liu, Cheng; Sun, Jian; Ni, Zhenhua; Xu, Jian; Wang, Xuhui; Yuan, Yi

2016-01-01

Background Development of polymeric prodrugs of small molecular anticancer drugs has become one of the most promising strategies to overcome the intrinsic shortcomings of small molecular anticancer drugs and improve their anticancer performance. Materials and methods In the current work, we fabricated a novel octreotide (Oct)-modified esterase-sensitive tumor-targeting polymeric prodrug of bufalin (BUF) and explored its anticancer performance against somatostatin receptor 2 overexpressing breast cancer. Results The obtained tumor-targeting polymeric prodrug of BUF, P(oligo[ethylene glycol] monomethyl ether methacrylate [OEGMA]-co-BUF-co-Oct), showed a nanosize dimension and controlled drug release features in the presence of esterase. It was demonstrated by in vitro experiment that P(OEGMA-co-BUF-co-Oct) showed enhanced cytotoxicity, cellular uptake, and apoptosis in comparison with those of free BUF. In vivo experiment further revealed the improved accumulation of drugs in tumor tissues and enhanced anticancer performance of P(OEGMA-co-BUF-co-Oct). Conclusion Taken together, this study indicated that polymeric prodrug of BUF holds promising potential toward the treatment of somatostatin receptor 2 overexpressing breast cancer. PMID:27284243

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.

Removal of toxic metal ions from landfill leachate by complementary sorption and transport across polymer inclusion membranes.

PubMed

Zawierucha, Iwona; Kozlowski, Cezary; Malina, Grzegorz

2013-10-01

In this study, performance of a lab-scale two-step treatment system was evaluated for removal of toxic metal ions from landfill leachate. The technology of polymer inclusion membranes (PIMs) was the first step, while the second step of the treatment system was based on sorption on impregnated resin. The PIMs were synthesized from cellulose triacetate as a support, macrocyclic compound i.e. alkyl derivative of resorcinarene as a ionic carrier and o-nitrophenyl pentyl ether as a plasticizer. The transport experiments through PIM were carried out in a permeation cell, in which the membrane film was tightly clamped between two cell compartments. The sorption tests were carried out using a column filled with a resin impregnated with resorcinarene derivative. The obtained results show the good performance with respect to the removal of heavy metals from landfill leachate with the overall removal efficiency of 99%, 88% and 55% for Pb(II), Cd(II) and Zn(II) ions, respectively. Moreover the contents of metal ions in the leachate sample after treatment system were below permissible limit for wastewater according to the Polish Standards. Copyright © 2012 Elsevier Ltd. All rights reserved.

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.

Lithium-coated polymeric matrix as a minimum volume-change and dendrite-free lithium metal anode

PubMed Central

Liu, Yayuan; Lin, Dingchang; Liang, Zheng; Zhao, Jie; Yan, Kai; Cui, Yi

2016-01-01

Lithium metal is the ideal anode for the next generation of high-energy-density batteries. Nevertheless, dendrite growth, side reactions and infinite relative volume change have prevented it from practical applications. Here, we demonstrate a promising metallic lithium anode design by infusing molten lithium into a polymeric matrix. The electrospun polyimide employed is stable against highly reactive molten lithium and, via a conformal layer of zinc oxide coating to render the surface lithiophilic, molten lithium can be drawn into the matrix, affording a nano-porous lithium electrode. Importantly, the polymeric backbone enables uniform lithium stripping/plating, which successfully confines lithium within the matrix, realizing minimum volume change and effective dendrite suppression. The porous electrode reduces the effective current density; thus, flat voltage profiles and stable cycling of more than 100 cycles is achieved even at a high current density of 5 mA cm−2 in both carbonate and ether electrolyte. The advantages of the porous, polymeric matrix provide important insights into the design principles of lithium metal anodes. PMID:26987481

Lithium-coated polymeric matrix as a minimum volume-change and dendrite-free lithium metal anode

DOE PAGES

Liu, Yayuan; Lin, Dingchang; Liang, Zheng; ...

2016-03-18

Lithium metal is the ideal anode for the next generation of high-energy-density batteries. Nevertheless, dendrite growth, side reactions and infinite relative volume change have prevented it from practical applications. Here, we demonstrate a promising metallic lithium anode design by infusing molten lithium into a polymeric matrix. The electrospun polyimide employed is stable against highly reactive molten lithium and, via a conformal layer of zinc oxide coating to render the surface lithiophilic, molten lithium can be drawn into the matrix, affording a nano-porous lithium electrode. Importantly, the polymeric backbone enables uniform lithium stripping/plating, which successfully confines lithium within the matrix, realizingmore » minimum volume change and effective dendrite suppression. The porous electrode reduces the effective current density; thus, flat voltage profiles and stable cycling of more than 100 cycles is achieved even at a high current density of 5 mA cm -2 in both carbonate and ether electrolyte. Furthermore, the advantages of the porous, polymeric matrix provide important insights into the design principles of lithium metal anodes.« less

Lithium-coated polymeric matrix as a minimum volume-change and dendrite-free lithium metal anode

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

Liu, Yayuan; Lin, Dingchang; Liang, Zheng

Lithium metal is the ideal anode for the next generation of high-energy-density batteries. Nevertheless, dendrite growth, side reactions and infinite relative volume change have prevented it from practical applications. Here, we demonstrate a promising metallic lithium anode design by infusing molten lithium into a polymeric matrix. The electrospun polyimide employed is stable against highly reactive molten lithium and, via a conformal layer of zinc oxide coating to render the surface lithiophilic, molten lithium can be drawn into the matrix, affording a nano-porous lithium electrode. Importantly, the polymeric backbone enables uniform lithium stripping/plating, which successfully confines lithium within the matrix, realizingmore » minimum volume change and effective dendrite suppression. The porous electrode reduces the effective current density; thus, flat voltage profiles and stable cycling of more than 100 cycles is achieved even at a high current density of 5 mA cm -2 in both carbonate and ether electrolyte. Furthermore, the advantages of the porous, polymeric matrix provide important insights into the design principles of lithium metal anodes.« less

Potentiometric Response Characteristics of Membrane-Based Cs + -Selective Electrodes Containing Ionophore-Functionalized Polymeric Microspheres

DOE PAGES

Peper, Shane; Gonczy, Chad

2011-01-01

Csmore » + -selective solvent polymeric membrane-based ion-selective electrodes (ISEs) were developed by doping ethylene glycol-functionalized cross-linked polystyrene microspheres (P-EG) into a plasticized poly(vinyl chloride) (PVC) matrix containing sodium tetrakis-(3,5-bis(trifluoromethyl)phenyl) borate (TFPB) as the ion exchanger. A systematic study examining the effects of the membrane plasticizers bis(2-ethylhexyl) sebacate (DOS), 2-nitrophenyl octyl ether (NPOE), and 2-fluorophenyl nitrophenyl ether (FPNPE) on the potentiometric response and selectivity of the corresponding electrodes was performed. Under certain conditions, P-EG-based ion-selective electrodes (ISEs) containing TFPB and plasticized with NPOE exhibited a super-Nernstian response between 1 × 10 − 3 and 1 × 10 − 4  M + , a response characteristic not observed in analogous membranes plasticized with either DOS or FPNPE. Additionally, the performance of P-EG-based ISEs was compared to electrodes based on two mobile ionophores, a neutral lipophilic ethylene glycol derivative (ethylene glycol monooctadecyl ether (U-EG)) and a charged metallacarborane ionophore, sodium bis(dicarbollyl)cobaltate(III) (CC). In general, P-EG-based electrodes plasticized with FPNPE yielded the best performance, with a linear range from 10 -1 –10 -5  M + , a conventional lower detection limit of 8.1 × 10 − 6  M + , and a response slope of 57.7 mV/decade. The pH response of P-EG ISEs containing TFPB was evaluated for membranes plasticized with either NPOE or FPNPE. In both cases, the electrodes remained stable throughout the pH range 3–12, with only slight proton interference observed below pH 3.« less

"Leaching or not leaching": an alternative approach to antimicrobial materials via copolymers containing crown ethers as active groups.

PubMed

De Rosa, M; Vigliotta, G; Soriente, A; Capaccio, V; Gorrasi, G; Adami, R; Reverchon, E; Mella, M; Izzo, L

2017-03-28

In this work, new copolymers containing either MMA and 18C6 crown-ether pendants, or PEG, MMA and 18C6 crown-ether pendants were synthesized to test the idea that sequestering structural alkali-earth ions from the bacterial outer membrane (OM) may lead to bacterial death. The copolymers were obtained either via uncontrolled radical polymerization or ATRP; the latter approached allowed us to produce not only linear copolymers but also branched Y-like structures. After checking for the capability of complexing magnesium and calcium ions, the antimicrobial activity of all copolymers was tested placing their casted plaques in contact with pure water E. coli suspensions. All plaques adsorbed alkali-earth ions and killed bacteria, albeit with different antimicrobial efficiencies. Differences in the latter characteristic were attributed to different plaque roughness. The role of the 18C6 crown-ether pendants was elucidated by pre-saturating plaques with Mg/Ca ions, the marked reduction in antimicrobial efficiency indicating that losing the latter from OM due to surface complexation does play an important role in killing bacteria at short (<5 h) contact times. At longer times, the mode of action is instead related to the poly-cationic nature acquired by the plaques due to ion sequestering.

Monodisperse microbeads of hypercrosslinked polystyrene for liquid and supercritical fluid chromatography

NASA Astrophysics Data System (ADS)

Tsyurupa, M. P.; Blinnikova, Z. K.; Il'in, M. M.; Davankov, V. A.; Parenago, O. O.; Pokrovskii, O. I.; Usovich, O. I.

2015-11-01

Monodisperse styrene-divinylbenzene (1 wt %) copolymer microbeads are obtained via the elaborate method of high-productivity precipitation polymerization. The crosslinking of this copolymer with chloromethyl methyl ether in the presence of Friedel-Crafts catalyst yields porous hypercrosslinked polymers with degrees of crosslinking that range from 200 to 500%. Microbead sorbents are shown to be suited for selective stationary phases for high-performance liquid chromatography and supercritical fluid chromatography.

Nitric Oxide Generating Polymeric Coatings for Subcutaneous Glucose Sensors

DTIC Science & Technology

2008-10-14

polymers for RSe immobilization. They both are thermoplastic poly(ether) polyurethanes but differ in composition of soft segments, hydrophobicity...thin layers of silicone rubber and Teflon AF, and the resulting device has yielded excellent NO sensitivity, high selectivity over NO2- and NH4Cl...layers over the sensor represent PDADM, 1% silicone rubber, and Teflon AF, respectively. This sensor can be coated with polymers containing RSe

Research in Energetic Compounds

DTIC Science & Technology

1983-01-01

with hypochlorous acid gave a chlorohydrocarbon, but reaction of the dioxime with chlorine gave 2,6-dichloro-2.6-dinitrosobicyclo[3.3.1)- non&ne. This...Catalyst Concentration on Yield . .3 III. Effect of Monomer Concentration on Yield... 4 IV. Boron Trifluoride and I.q-Butanedzol Catalysis. o V...from 3-azidooxetane with catalysis by boron trifluoride •4 etherate. A problem with this polymerization was that yields were generally in the 50

Effect of end segment on physicochemical properties and platelet compatibility of poly(propylene glycol)-initiated poly(methyl methacrylate).

PubMed

Fukuda, Chihiro; Yahata, Chie; Kinoshita, Takuya; Watanabe, Takafumi; Tsukamoto, Hideo; Mochizuki, Akira

2017-10-01

It is well known that polyether-based copolymers have good blood compatibility, although many mechanisms have been proposed to explain their favorable performance. Our objective in carrying out the present study was to obtain a better understanding of the effect of the (poly)ether segment on blood compatibility. Therefore, we synthesized poly(propylene glycol) (PPG)-based initiators for atom transfer polymerization, where the number of propylene glycol (PG) units in the PPG (Pn(PG) was varied from 1 to 94. Methyl methacrylate (MMA) was polymerized using the initiators, resulting in the formation of polyMMAs with a PG-based ether part at the polymer terminal. We mainly investigated the effects of Pn(PG) on the surface properties and platelet compatibility of the PPG-polyMMA. X-ray photoelectron spectroscopy and surface contact angle (CA) analysis revealed the exposure of the PG units at the surface of the polymer. The platelet compatibility of the polymers was improved compared with a commercial polyMMA, even when Pn(PG) = 1. These results suggest that PG units have an important influence on favorable blood compatibility, regardless of the Pn(PG) value. We also investigated protein adsorption behavior in terms of the amount and deformation of fibrinogen adsorbed on the polymer surface.

Fire and heat resistant laminating resins based on maleimido substituted aromatic cyclotriphosphazene polymer

NASA Technical Reports Server (NTRS)

Kumar, Devendra (Inventor); Fohlen, George M. (Inventor); Parker, John A. (Inventor)

1987-01-01

4-Aminophenoxy cyclotriphosphazenes are reacted with maleic anhydride to produce maleamic acids which are converted to the maleimides. The maleimides are polymerized. By selection of starting materials (e.g., hexakis amino or trisaminophenoxy trisphenoxy cyclotriphosphazenes), selection of molar proportions of reactants, use of mixtures of anhydrides and use of dianhydrides as bridging groups a variety of maleimides and polymers are produced. The polymers have high limiting oxygen indices, high char yields and other useful heat and fire resistant properties making them useful as, for example, impregnants of fabrics.

Conductor-polymer composite electrode materials

DOEpatents

Ginley, D.S.; Kurtz, S.R.; Smyrl, W.H.; Zeigler, J.M.

1984-06-13

A conductive composite material useful as an electrode, comprises a conductor and an organic polymer which is reversibly electrochemically dopable to change its electrical conductivity. Said polymer continuously surrounds the conductor in intimate electrical contact therewith and is prepared by electrochemical growth on said conductor or by reaction of its corresponding monomer(s) on said conductor which has been pre-impregnated or pre-coated with an activator for said polymerization. Amount of the conductor is sufficient to render the resultant composite electrically conductive even when the polymer is in an undoped insulating state.

Proprietes ionochromes et photochromes de derives du polythiophene

NASA Astrophysics Data System (ADS)

Levesque, Isabelle

La synthese et la caracterisation de derives regioreguliers du polythiophene ont ete effectuees en solution et sur des films minces. La spectroscopie UV-visible de ces derives a permis de constater qu'ils peuvent posseder des proprietes chromiques particulieres selon le stimulus auquel ils sont soumis. Par exemple, une augmentation de la temperature permet en effet aux polymeres de passer d'une couleur violette a jaune, et ce, a l'etat solide aussi bien qu'en solution. Ces proprietes chromiques semblent regies par une transition conformationnelle (plane a non-plane) de la chaine principale. Ce travail avait pour but de mieux comprendre l'influence de l'organisation des chaines laterales sur les transitions chromiques. Deux derives synthetises possedant des chaines laterales sensibles aux cations alcalins se sont averes etre ionochromes en plus d'etre thermochromes. Il s'agit d'un polymere comportant des chaines laterales de type oligo(oxyethylene) et d'un autre comportant un groupement ether couronne specifique aux ions lithium. Les effets chromiques observes sont expliques par des interactions non-covalentes des cations avec les atomes d'oxygene des chaines laterales dans le cas du premier polymere, et par l'insertion de l'ion Li + dans la cavite de l'ether couronne dans le cas du second polymere. Ces interactions semblent provoquer une diminution de l'organisation induisant ainsi une torsion de la chaine principale. Les deux polymeres semblent specifiques a certains cations et pourraient donc servir comme detecteurs optiques. La specificite aux ions Li+ du second polymere pourrait aussi permettre la conduction ionique, en plus de la conductivite electronique caracteristique des polythiophenes, ce qui pourrait s'averer utile dans le cas de batteries legeres entierement faites de polymeres et de sels de lithium. D'autres derives comportant des chaines laterales de type azobenzene se sont averes etre photochromes en plus d'etre thermochromes. Le groupement lateral a la possibilite de changer de configuration de la forme trans a la forme cis lorsqu'il est soumis a une irradiation dans le domaine de l'ultraviolet ce qui provoque, selon toute evidence, un effet marque sur l'organisation des chaines laterales. Cela induit alors une torsion de la chaine principale thiophene entrainant une diminution de conjugaison marquee. Ces effets peuvent etre exploites entre autres dans l'ecriture optique. Il s'est avere que le polymere irradie peu conjugue peut etre force a retourner a son etat initial conjugue tres rapidement par un traitement electrochimique simple. En conclusion, on a pu prouver qu'une modification dans l'organisation des chaines laterales par un stimulus exterieur affecte considerablement la conformation de la chaine principale. Cela porte a croire que les chaines laterales stabilisent une conformation particuliere des polythiophenes.

Determination of erythromycin in human plasma, using column liquid chromatography with a polymeric packing material, alkaline mobile phase and amperometric detection.

PubMed

Nilsson, L G; Walldorf, B; Paulsen, O

1987-12-25

A method based on column liquid chromatography was developed for determination of plasma concentrations of erythromycin. PRP-1, a polymeric type of packing material suitable for chromatography and amperometric detection at high pH, was used. The effect of pH on the column performance and on the electrochemical response was studied. A pH of ca. 10 was found to be optimal. After extraction with tert.-butyl methyl ether, plasma concentrations down to 0.2 mumol/l could be measured, using automated sample injection. Oleandomycin was used as internal standard. The method was used for determination of plasma concentrations in a pharmacokinetic study under steady-state conditions.

On the mechanism of charge transport in low density polyethylene

NASA Astrophysics Data System (ADS)

Upadhyay, Avnish K.; Reddy, C. C.

2017-08-01

Polyethylene based polymeric insulators, are being increasingly used in the power industry for their inherent advantages over conventional insulation materials. Specifically, modern power cables are almost made with these materials, replacing the mass-impregnated oil-paper cable technology. However, for ultra-high dc voltage applications, the use of these polymeric cables is hindered by ununderstood charge transport and accumulation. The conventional conduction mechanisms (Pool-Frenkel, Schottky, etc.) fail to track high-field charge transport in low density polyethylene, which is semi-crystalline in nature. Until now, attention was devoted mainly to the amorphous region of the material. In this paper, authors propose a novel mechanism for conduction in low density polyethylene, which could successfully track experimental results. As an implication, a novel, substantial relationship is established for electrical conductivity that could be effectively used for understanding conduction and breakdown in polyethylene, which is vital for successful development of ultra-high voltage dc cables.

A preliminary report on the effects of paclitaxel-impregnated stents on sheep nasal mucosa.

PubMed

Herrmann, Brian W; Citardi, Martin J; Vogler, George; Gardner, Laura; Smith, Greg; Javer, Amin R; Burt, Helen M; Jackson, John; Kuhn, Frederick A

2004-01-01

Traditional frontal sinus stents serve only as mechanical devices. It has been proposed that stents also may serve as drug-delivery systems for the topical application of drugs that minimize postoperative scarring. Paclitaxel (Taxol), which has recognized antiscarring effects, may be incorporated via a polymeric formulation into standard rubber stents. The impact of topically applied paclitaxel on the morphology of the nasal mucosa is unknown. An adult sheep model was used for this study. A modified rubber T-tube stent (incorporating paclitaxel at varying dosages) was secured to each side of the septum in four animals (eight sides). An unmodified T-tube was placed on each side of one animal, a T-tube with the drug carrier (but no paclitaxel) was placed on each side of the second animal, and T-tubes with varying paclitaxel were placed on each side of the final two animals. After 4 weeks, animals were killed and the nasal mucosa was harvested. The nasal mucosa was sectioned and stained with hematoxylin and eosin. A pathologist then assessed the nasal mucosa for vascular congestion, glandular atrophy, chronic inflammation, mucosal metaplasia, and mucosal ulceration. No consistent histopathological differences were noted in the specimens. All specimens showed varying degrees of vascular congestion, glandular atrophy, chronic inflammation, and mucosal metaplasia; the paclitaxel-impregnated stents were not consistently associated with more severe mucosal injury. Finally, mucosal ulceration was noted to be very rare in all specimens. This preliminary report describes the impact of paclitaxel-impregnated stents on sheep nasal mucosa, which tolerated these stents very well. Because paclitaxel minimizes scarring reactions at very low concentrations, paclitaxel-impregnated stents may prove useful in clinical situations in which frontal sinus stenting is deemed necessary. Additional investigations with animal models, as well as clinical trials, may be warranted.

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

PubMed

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

2017-08-01

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

Amphiphilic Ferrocene-Containing PEG Block Copolymers as Micellar Nanocarriers and Smart Surfactants.

PubMed

Alkan, Arda; Wald, Sarah; Louage, Benoit; De Geest, Bruno G; Landfester, Katharina; Wurm, Frederik R

2017-01-10

An important and usually the only function of most surfactants in heterophase systems is stabilizing one phase in another, for example, droplets or particles in water. Surfactants with additional chemical or physical handles are promising in controlling the colloidal properties by external stimuli. The redox stimulus is an attractive feature; however, to date only a few ionic redox-responsive surfactants have been reported. Herein, the first nonionic and noncytotoxic ferrocene-containing block copolymers are prepared, carrying a hydrophilic poly(ethylene glycol) (PEG) chain and multiple ferrocenes in the hydrophobic segment. These amphiphiles were studied as redox-sensitive surfactants that destabilize particles as obtained in miniemulsion polymerization. Because of the nonionic nature of such PEG-based copolymers, they can stabilize nanoparticles even after the addition of ions, whereas particles stabilized with ionic surfactants would be destabilized by the addition of salt. The redox-active surfactants were prepared by the anionic ring-opening polymerization of ferrocenyl glycidyl ether, with PEG monomethyl ether as the macroinitiator. The resultant block copolymers with molecular weights (M n ) between 3600 and 8600 g mol -1 and narrow molecular weight distributions (M w /M n = 1.04-1.10) were investigated via 1 H nuclear magnetic resonance and diffusion ordered spectroscopy, size exclusion chromatography, and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. Furthermore, the block copolymers were used as building blocks for redox-responsive micelles and as redox-responsive surfactants in radical polymerization in miniemulsion to stabilize model polystyrene nanoparticles. Oxidation of iron to the ferrocenium species converted the amphiphilic block copolymers into double hydrophilic macromolecules, which led to the destabilization of the nanoparticles. This destabilization of nanoparticle dispersions may be useful for the formation of coatings and the recovery of surfactants.

Creation of biological module for self-regulating ecological system by the way of polymerization of composite materials in free space.

PubMed

Kondyurin, A; Lauke, B; Kondyurina, I; Orba, E

2004-01-01

The large-size frame of space ship and space station can be created with the use of the technology of the polymerization of fiber-filled composites and a liquid reactionable matrix applied in free space or on the other space body when the space ship or space station will be used during a long period of time. For the polymerization of the station frame the fabric impregnated with a long-life polymer matrix (prepreg) is prepared in terrestrial conditions and, after folding, can be shipped in a compact container to orbit and kept folded on board the station. In due time the prepreg is carried out into free space and unfolded. Then a reaction of matrix polymerization starts. After reaction of polymerization the durable frame is ready for exploitation. After that, the frame can be filled out with air, the apparatus and life support systems. The technology can be used for creation of biological frame as element of self regulating ecological system, and for creation of technological frame which can be used for a production of new materials on Earth orbit in microgravity conditions and on other space bodies (Mars, Moon, asteroids) for unique high price mineral extraction. Based on such technology a future space base on Earth orbit with volume of 10(6) m3 and a crew of 100 astronauts is considered. c2004 COSPAR. Published by Elsevier Ltd. All rights reserved.

Fire Safety Aspects of Polymeric Materials. Volume 7. Buildings

DTIC Science & Technology

1979-01-01

are used to collect and disperse condensation. These may be constructed of wood, metal (e.g., anodized aluminum ) or rigid plastic (e.g., PVC). The...Vice President-Science and Technology Aluminum Company of America 1501 Alcoa Building Pittsburgh, PA 15219 Dr. Jason M. Salsbury Director Chemical...decabromod- iphenyl ether) with or without antimony oxide . Part or all of the halogen com- ponent may be incorporated in the form of halogenated polymers

The Synthesis of Tetraamino Aryl Ethers.

DTIC Science & Technology

1975-01-01

FJSRL-TR-75-0001 with melting points over 500 C and solubilities restricted to strong acids such as sulfuric (H2S04) or methane sulfonic (CH3SO3H...Buchi Rotavapor. Melting points were determined on a Kofler melting point apparatus and are uncorrected. Elemefital microanalyses were per- formed by...Polymerizations in organic solvents, in melts and in polyphosphoric acid (PPA) or similar materials have been used suc- cessfully in their synthesis. The

Synthesis and Characterization of New Phosphazene Polymers.

DTIC Science & Technology

1988-01-21

reaction of a poly( alkyl /arylphosphazene). In this study, one-half of the methyl groups in [Ph(Me)PN]n (chosen for its solubility in THF as opposed to...polymerization reaction ; and (5) the derivative chemistry of the preformed poly( alkyl /arylphosphazenes)., Synthesis of Poly( alkyl /arylphosphazenes) SC A... vessels , these phosphoranimines quantitatively eliminate the silyl ether byproduct, Me3SiOCH2CF 3 , to form the poly( alkyl /arylphosphazenes). The synthesis

Polyethylene Oxide Films Polymerized by Radio Frequency Plasma-Enhanced Chemical Vapour Phase Deposition and Its Adsorption Behaviour of Platelet-Rich Plasma

NASA Astrophysics Data System (ADS)

Hu, Wen-Juan; Xie, Fen-Yan; Chen, Qiang; Weng, Jing

2008-10-01

We present polyethylene oxide (PEO) functional films polymerized by rf plasma-enhanced vapour chemical deposition (rf-PECVD) on p-Si (100) surface with precursor ethylene glycol dimethyl ether (EGDME) and diluted Ar in pulsed plasma mode. The influences of discharge parameters on the film properties and compounds are investigated. The film structure is analysed by Fourier transform infrared (FTIR) spectroscopy. The water contact angle measurement and atomic force microscope (AFM) are employed to examine the surface polarity and to detect surface morphology, respectively. It is concluded that the smaller duty cycle in pulsed plasma mode contributes to the rich C-O-C (EO) group on the surfaces. As an application, the adsorption behaviour of platelet-rich plasma on plasma polymerization films performed in-vitro is explored. The shapes of attached cells are studied in detail by an optic invert microscope, which clarifies that high-density C-O-C groups on surfaces are responsible for non-fouling adsorption behaviour of the PEO films.

Development of sample clean up methods for the analysis of Mycobacterium tuberculosis methyl mycocerosate biomarkers in sputum extracts by gas chromatography–mass spectrometry

PubMed Central

Nicoara, Simona C.; Turner, Nicholas W.; Minnikin, David E.; Lee, Oona Y.-C.; O'Sullivan, Denise M.; McNerney, Ruth; Mutetwa, Reggie; Corbett, Liz E.; Morgan, Geraint H.

2015-01-01

A proof of principle gas chromatography–mass spectrometry method is presented, in combination with clean up assays, aiming to improve the analysis of methyl mycocerosate tuberculosis biomarkers from sputum. Methyl mycocerosates are generated from the transesterification of phthiocerol dimycocerosates (PDIMs), extracted in petroleum ether from sputum of tuberculosis suspect patients. When a high matrix background is present in the sputum extracts, the identification of the chromatographic peaks corresponding to the methyl derivatives of PDIMs analytes may be hindered by the closely eluting methyl ether of cholesterol, usually an abundant matrix constituent frequently present in sputum samples. The purification procedures involving solid phase extraction (SPE) based methods with both commercial Isolute-Florisil cartridges, and purpose designed molecularly imprinted polymeric materials (MIPs), resulted in cleaner chromatograms, while the mycocerosates are still present. The clean-up performed on solutions of PDIMs and cholesterol standards in petroleum ether show that, depending on the solvent mix and on the type of SPE used, the recovery of PDIMs is between 64 and 70%, whilst most of the cholesterol is removed from the system. When applied to petroleum ether extracts from representative sputum samples, the clean-up procedures resulted in recoveries of 36–68% for PDIMs, allowing some superior detection of the target analytes. PMID:25728371

Simultaneous AuIII Extraction and In Situ Formation of Polymeric Membrane-Supported Au Nanoparticles: A Sustainable Process with Application in Catalysis.

PubMed

Mora-Tamez, Lucía; Esquivel-Peña, Vicente; Ocampo, Ana L; Rodríguez de San Miguel, Eduardo; Grande, Daniel; de Gyves, Josefina

2017-04-10

A polymeric membrane-supported catalyst with immobilized gold nanoparticles (AuNPs) was prepared through the extraction and in situ reduction of Au III salts in a one-step strategy. Polymeric inclusion membranes (PIMs) and polymeric nanoporous membranes (PNMs) were tested as different membrane-support systems. Transport experiments indicated that PIMs composed of cellulose triacetate, 2-nitrophenyloctyl ether, and an aliphatic tertiary amine (Adogen 364 or Alamine 336) were the most efficient supports for Au III extraction. The simultaneous extraction and reduction processes were proven to be the result of a synergic phenomenon in which all the membrane components were involved. Scanning electron microscopy characterization of cross-sectional samples suggested a distribution of AuNPs throughout the membrane. Transmission electron microscopy characterization of the AuNPs indicated average particle sizes of 36.7 and 2.9 nm for the PIMs and PNMs, respectively. AuNPs supported on PIMs allowed for >95.4 % reduction of a 0.05 mmol L -1 4-nitrophenol aqueous solution with 10 mmol L -1 NaBH 4 solution within 25 min. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Studies of new perfluoroether elastomeric sealants. [for aircraft fuel tanks

NASA Technical Reports Server (NTRS)

Basiulis, D. I.; Salisbury, D. P.

1981-01-01

Channel and filleting sealants were developed successfully from cyano and diamidoxime terminated perfluoro alkylene ether prepolymers. The prepolymers were polymerized, formulated and tested. The polymers and/or formulations therefrom were evaluated as to their physical, mechanical and chemical properties (i.e., specific gravity, hardness, nonvolatile content, corrosion resistance, stress corrosion, pressure rupture resistance, low temperature flexibility, gap sealing efficiency, tensile strength and elongation, dynamic mechanical behavior, compression set, fuel resistance, thermal properties and processability). Other applications of the formulated polymrs and incorporation of the basic prepolymers into other polymeric systems were investigated. A cyano terminated perfluoro alkylene oxide triazine was formulated and partially evaluated. The channel sealant in its present formulation has excellent pressure rupture resistance and surpasses present MIL specifications before and after fuel and heat aging.

Degradable polymeric nanoparticles by aggregation of thermoresponsive polymers and ``click'' chemistry

NASA Astrophysics Data System (ADS)

Dworak, Andrzej; Lipowska, Daria; Szweda, Dawid; Suwinski, Jerzy; Trzebicka, Barbara; Szweda, Roza

2015-10-01

This study describes a novel approach to the preparation of crosslinked polymeric nanoparticles of controlled sizes that can be degraded under basic conditions. For this purpose thermoresponsive copolymers containing azide and alkyne functions were obtained by ATRP of di(ethylene glycol) monomethyl ether methacrylate (D) and 2-aminoethyl methacrylate (A) followed by post polymerization modification. The amino groups of A were reacted with propargyl chloroformate or 2-azido-1,3-dimethylimidazolinium hexafluorophosphate, which led to two types of copolymers. Increasing the temperature of aqueous solutions of the mixed copolymers caused their aggregation into spherical nanoparticles composed of both types of chains. Their dimensions could be controlled by changing the concentration and heating rate of the solutions. Covalent stabilization of aggregated chains was performed by a ``click'' reaction between the azide and alkyne groups. Due to the presence of a carbamate bond the nanoparticles undergo pH dependent degradation under mild basic conditions. The proposed procedure opens a route to new carriers for the controlled release of active species.This study describes a novel approach to the preparation of crosslinked polymeric nanoparticles of controlled sizes that can be degraded under basic conditions. For this purpose thermoresponsive copolymers containing azide and alkyne functions were obtained by ATRP of di(ethylene glycol) monomethyl ether methacrylate (D) and 2-aminoethyl methacrylate (A) followed by post polymerization modification. The amino groups of A were reacted with propargyl chloroformate or 2-azido-1,3-dimethylimidazolinium hexafluorophosphate, which led to two types of copolymers. Increasing the temperature of aqueous solutions of the mixed copolymers caused their aggregation into spherical nanoparticles composed of both types of chains. Their dimensions could be controlled by changing the concentration and heating rate of the solutions. Covalent stabilization of aggregated chains was performed by a ``click'' reaction between the azide and alkyne groups. Due to the presence of a carbamate bond the nanoparticles undergo pH dependent degradation under mild basic conditions. The proposed procedure opens a route to new carriers for the controlled release of active species. Electronic supplementary information (ESI) available: GPC-MALLS chromatograms for P(D-co-A)_1 and P(D-co-A)_2 copolymers, absorbance spectra of P(D-co-A)_1, P(D-co-A)_2, P(D-co-A_Pr) and P(D-co-A_Az) after reaction with ninhydrine. See DOI: 10.1039/c5nr04448k

Constrained Geometry Organotitanium Catalysts Supported on Nanosized Silica for Ethylene (co)Polymerization.

PubMed

Li, Kuo-Tseng; Wu, Ling-Huey

2017-05-05

Supported olefin polymerization catalysts can prevent reactor-fouling problems and produce uniform polymer particles. Constrained geometry complexes (CGCs) have less sterically hindered active sites than bis-cyclopentadienyl metallocene catalysts. In the literature, micrometer-sized silica particles were used for supporting CGC catalysts, which might have strong mass transfer limitations. This study aims to improve the activity of supported CGC catalysts by using nanometer-sized silica. Ti[(C₅Me₄)SiMe₂(N t Bu)]Cl₂, a "constrained-geometry" titanium catalyst, was supported on MAO-treated silicas (nano-sized and micro-sized) by an impregnation method. Ethylene homo-polymerization and co-polymerization with 1-octene were carried out in a temperature range of 80-120 °C using toluene as the solvent. Catalysts prepared and polymers produced were characterized. For both catalysts and for both reactions, the maximum activities occurred at 100 °C, which is significantly higher than that (60 °C) reported before for supported bis-cyclopentadienyl metallocene catalysts containing zirconium, and is lower than that (≥140 °C) used for unsupported Ti[(C₅Me₄)SiMe₂(N t Bu)]Me₂ catalyst. Activities of nano-sized catalyst were 2.6 and 1.6 times those of micro-sized catalyst for homopolymerization and copolymerization, respectively. The former produced polymers with higher crystallinity and melting point than the latter. In addition, copolymer produced with nanosized catalyst contained more 1-octene than that produced with microsized catalyst.

Chiral micellar electrokinetic chromatography (CMEKC)-atmospheric pressure photoionization of benzoin derivatives using mixed molecular micelles

PubMed Central

He, Jun; Shamsi, Shahab A.

2012-01-01

In the present work we report, for the first time, the successful on-line coupling of chiral micellar electrokinetic chromatography (CMEKC) to atmospheric pressure photo-ionization mass spectrometry (APPI-MS). Four structurally similar neutral test solutes (e.g., benzoin derivatives) were successfully ionized by APPI-MS. The mass spectra in the positive ion mode showed that the protonated molecular ions of benzoins are not the most abundant fragment ions. Simultaneous enantioseparation by CMEKC and on-line APPI-MS detection of four photoinitiators: hydrobenzoin (HBNZ), benzoin (BNZ), benzoin methyl ether (BME), benzoin ethyl ether (BEE), were achieved using an optimized molar ratio of mixed molecular micelle of two polymeric chiral surfactants (polysodium N-undecenoxy carbonyl-L-leucinate and polysodium N-undecenoyl-L,L-leucylvalinate). The CMEKC conditions, such as voltage, chiral polymeric surfactant concentration, buffer pH, and BGE concentration, were optimized using a multivariate central composite design (CCD). The sheath liquid composition (involving % v/v methanol, dopant concentration, electrolyte additive concentration, and flow rate) and spray chamber parameters (drying gas flow rate, drying gas temperature, and vaporizer temperature) were also optimized with CCD. Models built based on the CCD results and response surface method was used to analyze the interactions between factors and their effects on the responses. The final overall optimum conditions for CMEKC-APPI-MS were also predicted and found in agreement with the experimentally optimized parameters. PMID:21500208

Development of SiC/SiC composites by PIP in combination with RS

NASA Astrophysics Data System (ADS)

Kotani, Masaki; Kohyama, Akira; Katoh, Yutai

2001-02-01

In order to improve the mechanical performances of SiC/SiC composite, process improvement and modification of polymer impregnation and pyrolysis (PIP) and reaction sintering (RS) process were investigated. The fibrous prepregs were prepared by a polymeric intra-bundle densification technique using Tyranno-SA™ fiber. For inter-bundle matrix, four kinds of process options utilizing polymer pyrolysis and reaction sintering were studied. The process conditions were systematically optimized through fabricating monoliths. Then, SiC/SiC composites were fabricated using optimized inter-bundle matrix slurries in each process for the first inspection of process requirements.

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

PubMed Central

Yeow, Jonathan; Xu, Jiangtao; Boyer, Cyrille

2016-01-01

Presented herein is a protocol for the facile synthesis of worm-like micelles by visible light mediated dispersion polymerization. This approach begins with the synthesis of a hydrophilic poly(oligo(ethylene glycol) methyl ether methacrylate) (POEGMA) homopolymer using reversible addition-fragmentation chain-transfer (RAFT) polymerization. Under mild visible light irradiation (λ = 460 nm, 0.7 mW/cm2), this macro-chain transfer agent (macro-CTA) in the presence of a ruthenium based photoredox catalyst, Ru(bpy)3Cl2 can be chain extended with a second monomer to form a well-defined block copolymer in a process known as Photoinduced Electron Transfer RAFT (PET-RAFT). When PET-RAFT is used to chain extend POEGMA with benzyl methacrylate (BzMA) in ethanol (EtOH), polymeric nanoparticles with different morphologies are formed in situ according to a polymerization-induced self-assembly (PISA) mechanism. Self-assembly into nanoparticles presenting POEGMA chains at the corona and poly(benzyl methacrylate) (PBzMA) chains in the core occurs in situ due to the growing insolubility of the PBzMA block in ethanol. Interestingly, the formation of highly pure worm-like micelles can be readily monitored by observing the onset of a highly viscous gel in situ due to nanoparticle entanglements occurring during the polymerization. This process thereby allows for a more reproducible synthesis of worm-like micelles simply by monitoring the solution viscosity during the course of the polymerization. In addition, the light stimulus can be intermittently applied in an ON/OFF manner demonstrating temporal control over the nanoparticle morphology. PMID:27340940

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

PubMed

Yeow, Jonathan; Xu, Jiangtao; Boyer, Cyrille

2016-06-08

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

The Construction of Metal-Organic Framework with Active Backbones by the Utilization of Reticular Chemistry

NASA Astrophysics Data System (ADS)

Choi, Eunwoo

With the principles of reticular chemistry, metal-organic frameworks with ultra-high porosity, chiral-recognition unit as a chiral stationary phase, metalloporhyrins for enhanced hydrogen adsorption and an intrinsic conductivity to form porous conductors, have been prepared. This dissertation presents how the principles of reticular chemistry were utilized to achieve in the preparations of metal-organic frameworks with a large surface area and active backbones. Through the simple isoreticular (having the same framework topology) expansion from MOF-177 composed with 1,3,5-tris(4'-carboxyphenyl-)benzene (BTB3-) as the strut; MOF-200 was prepared with 4,4',4"-(benzene-1,3,5-triyl-tris(benzene-4,1-diy1))tribenzoic acid an extension from BTB3- by a phenylene unit to yield one of the most porous MOFs with a Langmuir surface area of 10,400 m2. and the lowest density of 0.22 cm3.g-1. A successful thermal polymerization reaction at 325 °C inside of the pores of highly porous MOF, MOF-177, was performed and verified the integrity of the MOF structure even after the thermal reaction. 1,4-Diphenylbutadiyne that is known to polymerize upon heating to form a conjugated backbone was impregnated via solution-diffusion into MOF-177 and then subsequently polymerized by heat to form polymer impregnated MOF-177. Characterization was carried out using powder X-ray diffraction and volumetric sorption analyzer. MOF-1020 with a linear quaterphenyl dicarboxylate-based strut was designed to contain a chiral bisbinaphthyl crown-ether moiety for alkyl ammonium resolution was precisely placed into a Zn4O(CO2)6-based cubic MOF structure. Unfortunately, the chiral resolution was not achieved due to the sensitivity and the pore environment of MOF-1020. However, an interesting phenomenon was observed, where the loss of crystallinity occurs upon solvent removal while the crystallites remain shiny and crystalline, but it readily is restored upon re-solvation of the crystallites. This rare phenomenon was studied by powder X-ray diffraction and supported by gas adsorption and thermogravimetric analysis. Layered MOFs with metalloporphyrins with Zn, Cu, Co and Fe at their +2 oxidation states as struts were prepared to facilitate non-structural metal sites and tested for hydrogen adsorption and the binding enthalpies. Steep uptakes are indeed observed, but rather due to the optimal interlayer distance of 9 A for dihydrogen, and the binding enthalpies are 6.7 -- 7.6 kJ . mo1-1 which are not ·extraordinary. Although the metals did not seem to play a large role, a trend was observed where the binding enthalpies increase as the metals in the metalloporphyrins go from late to early transition metals. With the concept of conductive metal oxides, a journey of constructing conductive MOFs was taken by attempting the formation of metal-carbon bonds by linking transition metal ions with conjugated organic struts which are 1,4-benzenediisonitrile, 1,4-benzenediethynylide and p-cyanophenylethynylide. Among the attempted systems, a reaction of Cr(III) and 1,4-benzenediethynylide yielded an amorphous material with a BET (Brunauer-Emmett-Teller) surface area of 80 m2.g-1, hydrogen uptake of 47 cm 3. g-1 and a resistance of 20 MO. Also a crystalline compound was prepared by mimicking Prussian blue by using p-cyanophenylethynylide where one end can bind metal with ethynylic carbon and the other end with the cyano nitrogen by following the similar synthesis of Prussian blue analogues. The principles of reticular chemistry are demonstrated through each chapter and show how powerful and beneficial reticular chemistry is by allowing the predetermination of the structure and function. The details of the ways to approach an ideal compound and the synthetic aspects are also described in this dissertation.

Effect of temperature and cultivar on polyphenol retention and mass transfer during osmotic dehydration of apples.

PubMed

Devic, Emilie; Guyot, Sylvain; Daudin, Jean-Dominique; Bonazzi, Catherine

2010-01-13

Several cultivars of apples (Malus domestica) were chosen for their variable concentrations and compositions in phenolic compounds. Cubed samples (1 cm3) were subjected to osmotic dehydration, and the effect of temperature was studied at 45 and 60 degrees C. Water loss, sucrose impregnation, and the evolution of some natural components of the product were followed to quantify mass transfer. Ascorbic acid and polyphenols were quantified by HPLC for several osmotic dehydration times and regardless of the quantity of impregnated sugar. Changes in antioxidant components differed as a function of the nature of molecules. Their concentrations decreased in line with temperature, and few differences were observed between cultivars. Processing at a lower temperature (45 degrees C) caused a total loss in ascorbic acid but allowed the retention of between 74 and 85% of initial polyphenols, depending on the cultivar. Cultivars containing highly polymerized procyanidins (such as Guillevic) experienced less loss. Hydroxycinnamic acids and monomeric catechins displayed the most marked changes. Leaching with water into the soaking solution was the principal mechanism retained to explain these losses.

E12 sheet plastination: Techniques and applications.

PubMed

Ottone, Nicolas Ernesto; Baptista, Carlos A C; Latorre, Rafael; Bianchi, Homero Felipe; Del Sol, Mariano; Fuentes, Ramon

2017-10-30

Plastination is an anatomical technique that consists of replacing the liquids and fat of specimens by reactive polymers through forced impregnation in a vacuum. These are then polymerized to achieve the final result. E12 sheet plastination involves epoxy resin impregnation of thin (2-4 mm) and ultra-thin (<2 mm) tissue sheets, producing dry, transparent, odorless, non-toxic and long-lasting sheets. E12 sheet plastination techniques were reviewed using MEDLINE, EMBASE and SciELO databases, and manual searches. After searching, 616 records were found using the online and manual searches (MEDLINE, n: 207; EMBASE, n: 346; SciELO, n: 44; Manual search: 23). Finally, 96 records were included in this review (after duplicates and articles unrelated to the subject were excluded). The aim of this work was to review the E12 sheet plastination technique, searching for articles concerning views of it, identifying the different variants implemented by researchers since its creation by Gunther von Hagens, and to identify its applications from teaching and research in anatomy to morphological sciences. Clin. Anat., 2017. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

Adhesion of resin materials to S2-glass unidirectional and E-glass multidirectional fiber reinforced composites: effect of polymerization sequence protocols.

PubMed

Polacek, Petr; Pavelka, Vladimir; Ozcan, Mutlu

2013-12-01

To evaluate the effect of different polymerization sequences employed during application of bis-GMAbased particulate filler composites (PFC) or a flowable resin (FR) on fiber-reinforced composite (FRC). Unidirectional, pre-impregnated S2-glass fibers (Dentapreg) and multidirectional preimpregnated E-glass fibers (Dentapreg) (length: 40 mm; thickness: 0.5 mm) were obtained (N = 144, n = 12 per group) and embedded in translucent silicone material with the adhesion surface exposed. The resulting specimens were randomly divided into 12 groups for the following application sequences: a) FRC+PFC (photopolymerized in one step), b) FRC+FR (photopolymerized in one step), c) FRC+PFC (photopolymerized individually), d) FRC+FR (photopolymerized individually), e) FRC (photopolymerized)+intermediate adhesive resin and PFC (photopolymerized in one step), f) FRC (photopolymerized)+intermediate adhesive resin and FR (photopolymerized in one step). The sequences of unidirectional (groups a to f) were repeated for multidirectional (groups g to l) FRCs. PFCs were debonded from the FRC surfaces using the shear bond test in a universal testing machine (1 mm/min). On additional specimens from each FRC type, thermogravimetric analysis (TGA) was performed to characterize the fiber weight content (Wf) (N = 6, n = 3 per group). After debonding, all specimens were analyzed using SEM to categorize the failure modes. The data were statistically analyzed using 3-way ANOVA and Tukey's tests (α = 0.05). Significant effects of the FRC type (S2 or E-glass) (p < 0.01), resin type (PFC or FR) (p < 0.01) and polymerization protocol (p < 0.05) were observed on the bond strength (MPa). Interaction terms were also significant (p < 0.05). The multidirectional FRC groups (g to l) showed significantly lower bond strengths (2.3 ± 0.2 to 7.3 ± 0.3 MPa) than did the unidirectional FRC groups (a to f) (10.7 ± 0.6 to 24.4 ± 0.8 MPa). Among the unidirectional FRC groups, the highest values were obtained with protocol f (24.4 ± 0.8), followed by protocol e (18.6 ± 0.4). PFC adhesion to unidirectional FRC was lower when FRC and PFC were polymerized in one step (protocol a: 11.3 ± 0.5) than individual polymerization (protocol c: 14.1 ± 0.5). The opposite situation was true for FR (protocol b: 17.5 ± 0.4; protocol d: 10.7 ± 0.6). Groups a to f presented exclusively mixed failures (a combination of partial cohesive failure in the PFC and adhesive failure between the FRC and PFC) and groups g to l demonstrated only adhesive failure (intact FRC no cohesive failure of PFC). TGA revealed 55 ± 3 wt% fiber content for multidirectional and 60 ± 3 wt% for unidirectional FRCs tested. Multidirectional pre-impregnated E-glass fibers cannot be recommended in combination with the PFC and FR materials tested in this study. Application of an intermediate adhesive resin layer increases the adhesion of both PFC and FR to unidirectional FRC. FRC and FR can be polymerized in one step, but FRC and PFC combinations should be polymerized individually.

Synthesis and characterization of poly(L-alanine)-block-poly(ethylene glycol) monomethyl ether as amphiphilic biodegradable co-polymers.

PubMed

Zhang, Guolin; Ma, Jianbiao; Li, Yanhong; Wang, Yinong

2003-01-01

Di-block co-polymers of poly(L-alanine) with poly(ethylene glycol) monomethyl ether (MPEG) were synthesized as amphiphilic biodegradable co-polymers. The ring-opening polymerization of N-carboxy-L-alanine anhydride (NCA) in dichloromethane was initiated by amino-terminated poly(ethylene glycol) monomethyl ether (MPEG-NH2, M(n) = 2000) to afford poly(L-alanine)-block-MPEG. The weight ratio of two blocks in the co-polymers could be altered by adjusting the feeding ratio of NCA to MPEG-NH2. Their chemical structures were characterized on the basis of infrared spectrometry and nuclear magnetic resonance. According to circular dichroism measurement, the poly(L-alanine) chain on the co-polymers in an aqueous medium had a alpha-helix conformation. Two melting points from MPEG block and poly(L-alanine), respectively, could be observed in differential scanning calorimetry curves of the co-polymers, suggesting that a micro-domain phase separation appeared in their bulky states. The co-polymers could take up some water and the capacity was dependent on the ratio of poly(L-alanine) block to MPEG. Such co-polymers might be useful in drug-delivery systems and other biomedical applications.

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.

Discovery of Antibiotics-derived Polymers for Gene Delivery using Combinatorial Synthesis and Cheminformatics Modeling

PubMed Central

Potta, Thrimoorthy; Zhen, Zhuo; Grandhi, Taraka Sai Pavan; Christensen, Matthew D.; Ramos, James; Breneman, Curt M.; Rege, Kaushal

2014-01-01

We describe the combinatorial synthesis and cheminformatics modeling of aminoglycoside antibiotics-derived polymers for transgene delivery and expression. Fifty-six polymers were synthesized by polymerizing aminoglycosides with diglycidyl ether cross-linkers. Parallel screening resulted in identification of several lead polymers that resulted in high transgene expression levels in cells. The role of polymer physicochemical properties in determining efficacy of transgene expression was investigated using Quantitative Structure-Activity Relationship (QSAR) cheminformatics models based on Support Vector Regression (SVR) and ‘building block’ polymer structures. The QSAR model exhibited high predictive ability, and investigation of descriptors in the model, using molecular visualization and correlation plots, indicated that physicochemical attributes related to both, aminoglycosides and diglycidyl ethers facilitated transgene expression. This work synergistically combines combinatorial synthesis and parallel screening with cheminformatics-based QSAR models for discovery and physicochemical elucidation of effective antibiotics-derived polymers for transgene delivery in medicine and biotechnology. PMID:24331709

High Performance Solid Polymer Electrolytes for Rechargeable Batteries: A Self-Catalyzed Strategy toward Facile Synthesis.

PubMed

Cui, Yanyan; Liang, Xinmiao; Chai, Jingchao; Cui, Zili; Wang, Qinglei; He, Weisheng; Liu, Xiaochen; Liu, Zhihong; Cui, Guanglei; Feng, Jiwen

2017-11-01

It is urgent to seek high performance solid polymer electrolytes (SPEs) via a facile chemistry and simple process. The lithium salts are composed of complex anions that are stabilized by a Lewis acid agent. This Lewis acid can initiate the ring opening polymerization. Herein, a self-catalyzed strategy toward facile synthesis of crosslinked poly(ethylene glycol) diglycidyl ether-based solid polymer electrolyte (C-PEGDE) is presented. It is manifested that the poly(ethylene glycol) diglycidyl ether-based solid polymer electrolyte possesses a superior electrochemical stability window up to 4.5 V versus Li/Li + and considerable ionic conductivity of 8.9 × 10 -5 S cm -1 at ambient temperature. Moreover, the LiFePO 4 /C-PEGDE/Li batteries deliver stable charge/discharge profiles and considerable rate capability. It is demonstrated that this self-catalyzed strategy can be a very effective approach for high performance solid polymer electrolytes.

Interaction of platelets, fibrinogen and endothelial cells with plasma deposited PEO-like films

NASA Astrophysics Data System (ADS)

Yang, Zhilu; Wang, Jin; Li, Xin; Tu, Qiufen; Sun, Hong; Huang, Nan

2012-02-01

For blood-contacting biomedical implants like retrievable vena cava filters, surface-based diagnostic devices or in vivo sensors, limiting thrombosis and cell adhesion is paramount, due to a decrease even failure in performance. Plasma deposited PEO-like films were investigated as surface modifications. In this work, mixed gas composed of tetraethylene glycol dimethyl ether (tetraglyme) vapor and oxygen was used as precursor. It was revealed that plasma polymerization under high ratio of oxygen/tetraglyme led to deposition of the films that had high content of ether groups. This kind of PEO-like films had good stability in phosphate buffer solution. In vitro hemocompatibility and endothelial cell (EC) adhesion revealed low platelet adhesion, platelet activation, fibrinogen adhesion, EC adhesion and proliferation on such plasma deposited PEO-like films. This made it a potential candidate for the applications in anti-fouling surfaces of blood-contacting biomedical devices.

A plasticized polymer-electrolyte-based photoelectrochemical solar cell

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

Mao, D.; Ibrahim, M.A.; Frank, A.J.

1998-01-01

A photoelectrochemical solar cell based on an n-GaAs/polymer-redox-electrolyte junction is reported. Di(ethylene glycol) ethyl ether acrylate containing ferrocene as a redox species and benzoin methyl ether as a photoinitiator is polymerized in situ. Propylene carbonate is used as a plasticizer to improve the conductivity of the polymer redox electrolyte. For thin (1 {micro}m) polymer electrolytes, the series resistance of the cell is negligible. However, the short-circuit photocurrent density of the cell at light intensities above 10 mW/cm{sup 2} is limited by mass transport of redox species within the polymer matrix. At a light intensity of 70 mW/cm{sup 2}, a moderatemore » light-to-electrical energy conversion efficiency (3.1%) is obtained. The interfacial charge-transfer properties of the cell in the dark and under illumination are studied.« less

The analysis of thermoplastic characteristics of special polymer sulfur composite

NASA Astrophysics Data System (ADS)

Książek, Mariusz

2017-01-01

Specific chemical environments step out in the industry objects. Portland cement composites (concrete and mortar) were impregnated by using the special polymerized sulfur and technical soot as a filler (polymer sulfur composite). Sulfur and technical soot was applied as the industrial waste. Portland cement composites were made of the same aggregate, cement and water. The process of special polymer sulfur composite applied as the industrial waste is a thermal treatment process in the temperature of about 150-155°C. The result of such treatment is special polymer sulfur composite in a liquid state. This paper presents the plastic constants and coefficients of thermal expansion of special polymer sulfur composites, with isotropic porous matrix, reinforced by disoriented ellipsoidal inclusions with orthotropic symmetry of the thermoplastic properties. The investigations are based on the stochastic differential equations of solid mechanics. A model and algorithm for calculating the effective characteristics of special polymer sulfur composites are suggested. The effective thermoplastic characteristics of special polymer sulfur composites, with disoriented ellipsoidal inclusions, are calculated in two stages: First, the properties of materials with oriented inclusions are determined, and then effective constants of a composite with disoriented inclusions are determined on the basis of the Voigt or Rice scheme. A brief summary of new products related to special polymer sulfur composites is given as follows: Impregnation, repair, overlays and precast polymer concrete will be presented. Special polymer sulfur as polymer coating impregnation, which has received little attention in recent years, currently has some very interesting applications.

Simultaneous acoustic and dielectric real time curing monitoring of epoxy systems

NASA Astrophysics Data System (ADS)

Gkikas, G.; Saganas, Ch.; Grammatikos, S. A.; Aggelis, D. G.; Paipetis, A. S.

2012-04-01

The attainment of structural integrity of the reinforcing matrix in composite materials is of primary importance for the final properties of the composite structure. The detailed monitoring of the curing process on the other hand is paramount (i) in defining the optimal conditions for the impregnation of the reinforcement by the matrix (ii) in limiting the effects of the exotherm produced by the polymerization reaction which create unwanted thermal stresses and (iii) in securing optimal behavior in matrix controlled properties, such as off axis or shear properties and in general the durability of the composite. Dielectric curing monitoring is a well known technique for distinguishing between the different stages of the polymerization of a typical epoxy system. The technique successfully predicts the gelation and the vitrification of the epoxy and has been extended for the monitoring of prepregs. Recent work has shown that distinct changes in the properties of the propagated sound in the epoxy which undergoes polymerization is as well directly related to the gelation and vitrification of the resin, as well as to the attainment of the final properties of the resin system. In this work, a typical epoxy is simultaneously monitored using acoustic and dielectric methods. The system is isothermally cured in an oven to avoid effects from the polymerization exotherm. Typical broadband sensors are employed for the acoustic monitoring, while flat interdigital sensors are employed for the dielectric scans. All stages of the polymerization process were successfully monitored and the validity of both methods was cross checked and verified.

Long conducting polymer nanonecklaces with a `beads-on-a-string' morphology: DNA nanotube-template synthesis and electrical properties

NASA Astrophysics Data System (ADS)

Chen, Guofang; Mao, Chengde

2016-05-01

Complex and functional nanostructures are always desired. Herein, we present the synthesis of novel long conducting polymer nanonecklaces with a `beads-on-a-string' morphology by the DNA nanotube-template approach and in situ oxidative polymerization of the 3-methylthiophene monomer with FeCl3 as the oxidant/catalyst. The length of the nanonecklaces is up to 60 μm, and the polymer beads of around 20-25 nm in diameter are closely packed along the axis of the DNA nanotube template with a density of ca. 45 particles per μm. The formation of porous DNA nanotubes impregnated with FeCl3 was also demonstrated as intermediate nanostructures. The mechanisms for the formation of both the porous DNA nanotubes and the conducting polymer nanonecklaces are discussed in detail. The as-synthesized polymer/DNA nanonecklaces exhibit good electrical properties.Complex and functional nanostructures are always desired. Herein, we present the synthesis of novel long conducting polymer nanonecklaces with a `beads-on-a-string' morphology by the DNA nanotube-template approach and in situ oxidative polymerization of the 3-methylthiophene monomer with FeCl3 as the oxidant/catalyst. The length of the nanonecklaces is up to 60 μm, and the polymer beads of around 20-25 nm in diameter are closely packed along the axis of the DNA nanotube template with a density of ca. 45 particles per μm. The formation of porous DNA nanotubes impregnated with FeCl3 was also demonstrated as intermediate nanostructures. The mechanisms for the formation of both the porous DNA nanotubes and the conducting polymer nanonecklaces are discussed in detail. The as-synthesized polymer/DNA nanonecklaces exhibit good electrical properties. Electronic supplementary information (ESI) available. See DOI: 10.1039/c6nr01603k

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

High Energy Halogen Chemistry.

DTIC Science & Technology

1978-01-01

underwent addition of triflic acid and of hydrochloric acid . The oxetane was polymerized ~zith phosphorous pentaflucride to ~lve a polymer stable to 2900...in aqueous dioxane . The oxetane was not affected by boron trifluoride etherate In chloroform, or by methanolic solutions of sulfuric or triflic acids ...concentrated hydrochloric acid to give 3-chloro-2-fluoro-2-nitro-l-propanol. NO • i 2 NO2OH CF I + CF SOH— 3 CF SO OCH CCH OH O OH ~ 3 3 2 2~ 2 F NO NO

Injectible bodily prosthetics employing methacrylic copolymer gels

DOEpatents

Mallapragada, Surya K.; Anderson, Brian C.

2007-02-27

The present invention provides novel block copolymers as structural supplements for injectible bodily prosthetics employed in medical or cosmetic procedures. The invention also includes the use of such block copolymers as nucleus pulposus replacement materials for the treatment of degenerative disc disorders and spinal injuries. The copolymers are constructed by polymerization of a tertiary amine methacrylate with either a (poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) polymer, such as the commercially available Pluronic.RTM. polymers, or a poly(ethylene glycol) methyl ether polymer.

pH-sensitive methacrylic copolymer gels and the production thereof

DOEpatents

Mallapragada, Surya K [Ames, IA; Anderson, Brian C [Lake Bluff, IA

2007-05-15

The present invention provides novel gel forming methacrylic blocking copolymers that exhibit cationic pH-sensitive behavior as well as good water solubility. The copolymers are constructed by polymerization of a tertiary amine methacrylate with either a (poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) polymer, such as the commercially available Pluronic.RTM. polymers, or a poly(ethylene glycol)methyl ether polymer. The polymers may be used for drug and gene delivery, protein separation, as structural supplements, and more.

Chlorine resistant desalination membranes based on directly sulfonated poly(arylene ether sulfone) copolymers

DOEpatents

McGrath, James E [Blacksburg, VA; Park, Ho Bum [Austin, TX; Freeman, Benny D [Austin, TX

2011-10-04

The present invention provides a membrane, kit, and method of making a hydrophilic-hydrophobic random copolymer membrane. The hydrophilic-hydrophobic random copolymer membrane includes a hydrophilic-hydrophobic random copolymer. The hydrophilic-hydrophobic random copolymer includes one or more hydrophilic monomers having a sulfonated polyarylsulfone monomer and a second monomer and one or more hydrophobic monomers having a non-sulfonated third monomer and a fourth monomer. The sulfonated polyarylsulfone monomer introduces a sulfonate into the hydrophilic-hydrophobic random copolymer prior to polymerization.

Polysulfone - CNT composite membrane with enhanced water permeability

NASA Astrophysics Data System (ADS)

Hirani, Bhakti; Kar, Soumitra; Aswal, V. K.; Bindal, R. C.; Goyal, P. S.

2018-04-01

Polymeric membranes are routinely used for water purification. The performance of these conventional membranes can be improved by incorporating nanomaterials, such as metal oxide nanoparticle and carbon nanotubes (CNTs). This manuscript reports the synthesis and characterization of polysulfone (Psf) based nanocomposite membranes where multi wall carbon nanotubes (MWCNTs) and oleic acid coated Fe3O4 nanoparticles have been impregnated onto the polymeric host matrix. The performance of the membranes was evaluated by water permeability and solute rejection measurements. It was observed that the permeability of Psf membrane increases three times at 0.1% loading of MWCNT without compromise in selectivity. It was further observed that the increase in permeability is not affected upon addition of Fe3O4 nanoparticles into the membrane. In order to get a better insight into the membrane microstructure, small angle neutron scattering (SANS) studies were carried out. There is a good correlation between the water permeability and the pore sizes of the membranes as measured using SANS.

Mobile phase additives for enhancing the chromatographic performance of astaxanthin on nonendcapped polymeric C30-bonded stationary phases.

PubMed

Kaiser, Philipp; Surmann, Peter; Fuhrmann, Herbert

2009-01-01

Astaxanthin shows peak deformation and reduced peak area response when eluted with methanol and methyl tert-butyl ether on nonendcapped polymeric C30-bonded HPLC phases. The present study tested different column manufacturers, column batches, and ten mobile phase additives including acids, bases, buffers, complexing and antioxidant agents for improvement of peak shape and peak area response. Concerning chromatographic benefits and feasibility, ammonium acetate was found to be the best additive followed by triethylamine for all columns tested. Variation of the mobile phase pH equivalent and the column temperature showed no synergistic effects on peak shape and peak area response. Results indicate that peak tailing and variation of peak area response are due to different on-column effects. Possible mechanisms of the observed phenomenon will be discussed.

Analysis of the morphology, stability, and folding pathways of ring polymers with supramolecular topological constraints using molecular simulation and nonlinear manifold learning

NASA Astrophysics Data System (ADS)

Wang, Jiang; Ferguson, Andrew

Ring polymers offer a wide range of natural and engineered functions and applications, including as circular bacterial DNA, crown ethers for cation chelation, and ``molecular machines'' such as mechanical nanoswitches. The morphology and dynamics of ring polymers are governed by the chemistry and degree of polymerization of the ring, and intramolecular and supramolecular topological constraints such as knots or mechanically-interlocked rings. We perform molecular dynamics simulations of polyethylene ring polymers as a function of degree of polymerization and in different topological states, including a knotted state, catenane state (two interlocked rings), and borromean state (three interlocked rings). Applying nonlinear manifold learning to our all-atom simulation trajectories, we extract low-dimensional free energy surfaces governing the accessible conformational states and their relative thermodynamic stability. The free energy surfaces reveal how degree of polymerization and topological constraints affect the thermally accessible conformations, chiral symmetry breaking, and folding and collapse pathways of the rings, and present a means to rationally engineer ring size and topology to preferentially stabilize particular conformational states.

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.

Metallization of Various Polymers by Cold Spray

NASA Astrophysics Data System (ADS)

Che, Hanqing; Chu, Xin; Vo, Phuong; Yue, Stephen

2018-01-01

Previous results have shown that metallic coatings can be successfully cold sprayed onto polymeric substrates. This paper studies the cold sprayability of various metal powders on different polymeric substrates. Five different substrates were used, including carbon fiber reinforced polymer (CFRP), acrylonitrile butadiene styrene (ABS), polyether ether ketone (PEEK), polyethylenimine (PEI); mild steel was also used as a benchmark substrate. The CFRP used in this work has a thermosetting matrix, and the ABS, PEEK and PEI are all thermoplastic polymers, with different glass transition temperatures as well as a number of distinct mechanical properties. Three metal powders, tin, copper and iron, were cold sprayed with both a low-pressure system and a high-pressure system at various conditions. In general, cold spray on the thermoplastic polymers rendered more positive results than the thermosetting polymers, due to the local thermal softening mechanism in the thermoplastics. Thick copper coatings were successfully deposited on PEEK and PEI. Based on the results, a method is proposed to determine the feasibility and deposition window of cold spraying specific metal powder/polymeric substrate combinations.

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.

Single chain technology: Toward the controlled synthesis of polymer nanostructures

NASA Astrophysics Data System (ADS)

Lyon, Christopher

A technique for fabricating advanced polymer nanostructures enjoying recent popularity is the collapse or folding of single polymer chains in highly dilute solution mediated by intramolecular cross-linking. We term the resultant structures single-chain nanoparticles (SCNP). This technique has proven particularly valuable in the synthesis of nanomaterials on the order of 5 -- 20 nm. Many different types of covalent and non-covalent chemistries have been used to this end. This dissertation investigates the use of so-called single-chain technology to synthesize nanoparticles using modular techniques that allow for easy incorporation of functionality or special structural or characteristic features. Specifically, the synthesis of linear polymers functionalized with pendant monomer units and the subsequent intramolecular polymerization of these monomer units is discussed. In chapter 2, the synthesis of SCNP using alternating radical polymerization is described. Polymers functionalized with pendant styrene and stilbene groups are synthesized via a modular post-polymerization Wittig reaction. These polymers were exposed to radical initiators in the presence (and absence) of maleic anhydride and other electron deficient monomers in order to form intramolecular cross-links. Chapter 3 discusses templated acyclic diene metathesis (ADMET) polymerization using single-chain technology, starting with the controlled ring-opening polymerization of a glycidyl ether functionalized with an ADMET monomer. This polymer was then exposed to Grubbs' catalyst to polymerize the ADMET monomer units. The ADMET polymer was hydrolytically cleaved from the template and separated. Upon characterization, it was found that the daughter ADMET polymer had a similar degree of polymerization, but did not retain the low dispersity of the template. Chapter 4 details the synthesis of aldehyde- and diol-functionalized polymers toward the synthesis of SCNP containing dynamic, acid-degradable acetal cross-links. SCNP fabrication with these materials is beyond the scope of this dissertation.

Characterization of E 471 food emulsifiers by high-performance thin-layer chromatography-fluorescence detection.

PubMed

Oellig, Claudia; Brändle, Klara; Schwack, Wolfgang

2018-07-13

Mono- and diacylglycerol (MAG and DAG) emulsifiers, also known as food additive E 471, are widely used to adjust techno-functional properties in various foods. Besides MAGs and DAGs, E 471 emulsifiers additionally comprise different amounts of triacylglycerols (TAGs) and free fatty acids (FFAs). MAGs, DAGs, TAGs and FFAs are generally determined by high-performance liquid chromatography (HPLC) or gas chromatography (GC) coupled to mass selective detection, analyzing the individual representatives of the lipid classes. In this work we present a rapid and sensitive method for the determination of MAGs, DAGs, TAGs and FFAs in E 471 emulsifiers by high-performance thin-layer chromatography with fluorescence detection (HPTLC-FLD), including a response factor system for quantitation. Samples were simply dissolved and diluted with t-butyl methyl ether before a two-fold development was performed on primuline pre-impregnated LiChrospher silica gel plates with diethyl ether and n-pentane/n-hexane/diethyl ether (52:20:28, v/v/v) as the mobile phases to 18 and 75 mm, respectively. For quantitation, the plate was scanned in the fluorescence mode at UV 366/>400 nm, when the cumulative signal for each lipid class was used. Calibration was done with 1,2-distearin and amounts of lipid classes were calculated with response factors and expressed as monostearin, distearin, tristearin and stearic acid. Limits of detection and quantitation were 1 and 4 ng/zone, respectively, for 1,2-distearin. Thus, the HPTLC-FLD approach represents a simple, rapid and convenient screening alternative to HPLC and GC analysis of the individual compounds. Visual detection additionally enables an easy characterization and the direct comparison of emulsifiers through the lipid class pattern, when utilized as a fingerprint. Copyright © 2018 Elsevier B.V. All rights reserved.

Chiral micellar electrokinetic chromatography-atmospheric pressure photoionization of benzoin derivatives using mixed molecular micelles.

PubMed

He, Jun; Shamsi, Shahab A

2011-05-01

In the present work we report, for the first time, the successful on-line coupling of chiral MEKC (CMEKC) to atmospheric pressure photoionization MS (APPI-MS). Four structurally similar neutral test solutes (e.g. benzoin (BNZ) derivatives) were successfully ionized by APPI-MS. The mass spectra in the positive ion mode showed that the protonated molecular ions of BNZs are not the most abundant fragment ions. Simultaneous enantioseparation by CMEKC and on-line APPI-MS detection of four photoinitiators, hydrobenzoin, BNZ, benzoin methyl ether, benzoin ethyl ether, were achieved using an optimized molar ratio of mixed molecular micelle of two polymeric chiral surfactants (polysodium N-undecenoxy carbonyl-L-leucinate and polysodium N-undecenoyl-L,L-leucylvalinate). The CMEKC conditions, such as voltage, chiral polymeric surfactant concentration, buffer pH, and BGE concentration, were optimized using a multivariate central composite design (CCD). The sheath liquid composition (involving %v/v methanol, dopant concentration, electrolyte additive concentration, and flow rate) and spray chamber parameters (drying gas flow rate, drying gas temperature, and vaporizer temperature) were also optimized with CCD. Models built based on the CCD results and response surface method were used to analyze the interactions between factors and their effects on the responses. The final overall optimum conditions for CMEKC-APPI-MS were also predicted and found in agreement with the experimentally optimized parameters. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

RAFT polymerization of temperature- and salt-responsive block copolymers as reversible hydrogels.

PubMed

Hemp, Sean T; Smith, Adam E; Bunyard, W Clayton; Rubinstein, Michael H; Long, Timothy E

2014-05-13

Reversible-addition fragmentation chain transfer (RAFT) polymerization enabled the synthesis of novel, stimuli-responsive, AB and ABA block copolymers. The B block contained oligo(ethylene glycol) methyl ether methacrylate (OEG) and was permanently hydrophilic in the conditions examined. The A block consisted of diethylene glycol methyl ether methacrylate (DEG) and [2-(methacryloyloxy)ethyl]trimethylammonium chloride (TMA). The A block displayed both salt- and temperature-response with lower critical solution temperatures (LCSTs) dependent on the molar content of TMA and the presence of salt. Higher TMA content in the AB diblock copolymers increased the critical micelle temperatures (CMT) in HPLC-grade water due to an increased hydrophilicity of the A block. Upon addition of 0.9 wt% NaCl, the CMTs of poly(OEG- b -DEG 95 TMA 5 ) decreased from 50 °C to 36 °C due to screening of electrostatic repulsion between the TMA units. ABA triblock copolymers displayed excellent hydrogel properties with salt- and temperature-dependent gel points. TMA incorporation in the A block increased the gel points for all triblock copolymers, and salt-response increased with higher TMA composition in the A block. For example, poly(DEG 98 TMA 2 - b -OEG- b -DEG 98 TMA 2 ) formed a hydrogel at 40 °C in HPLC-grade water and 26 °C in 0.9 wt% NaCl aqueous solution. These salt- and temperature-responsive AB diblock and ABA triblock copolymers find applications as drug delivery vehicles, adhesives, and hydrogels.

Reduction in Wound Bioburden using a Silver-Loaded Dissolvable Microfilm Construct

PubMed Central

Herron, Maggie; Agarwal, Ankit; Kierski, Patricia R.; Calderon, Diego F.; Teixeira, Leandro B. C.; Schurr, Michael J.; Murphy, Christopher J.

2014-01-01

Silver is a widely used antimicrobial agent, yet when impregnated in macroscopic dressings, it stains wounds, can lead to tissue toxicity and can inhibit healing. Recently, we reported that polymeric nanofilms containing silver nanoparticles exhibit antimicrobial activity at loadings and release rates of silver that are 100x lower than conventional dressings. Here we report fabrication of composite microfilm constructs that provide a facile way to transfer the silver-loaded polymeric nanofilms onto wounds in vivo. The construct is fabricated from a silver nanoparticle-loaded polymeric nanofilm that is laminated with a micrometer-thick soluble film of polyvinylalcohol (PVA). When placed on a moist wound, the PVA dissolves, leaving the silver-loaded nanofilm immobilized on the wound-bed. In vitro, the immobilized nanofilms release <1 μg cm−2/day of silver over 30 days from skin-dermis and they kill 5 log10 CFUs of Staphylococcus aureus in 24 h. In mice, wounds inoculated with 105 CFU S. aureus presented up to 3 log10 less bacterial burden when treated with silver/nanofilms for 3 days, as compared to unmodified wounds. In uncontaminated wounds, silver/nanofilms allow normal and complete wound closure by re-epithelialization. We conclude that dissolvable microfilm constructs may overcome key limitations associated with current uses of silver in wound healing. PMID:24523027

Macrocyclic receptors immobilized to monodisperse porous polymer particles by chemical grafting and physical impregnation for strontium capture: a comparative study.

PubMed

Song, Yang; Du, Yi; Lv, Dachao; Ye, Gang; Wang, Jianchen

2014-06-15

Separation of strontium is of great significance for radioactive waste treatment and environmental remediation after nuclear accidents. In this work, a novel class of adsorbent (Crown-g-MPPPs) was synthesized by chemical grafting a macrocyclic ether receptor to monodisperse porous polymer particles (MPPPs) for strontium adsorption. Meanwhile, a counterpart material (Crown@MPPPs) with the receptor molecules immobilized to the MPPPs substrate by physical impregnation was prepared. To investigate how the immobilization manner and distribution of the receptors influence the adsorption ability, a comparative study on the adsorption behaviour of the two materials towards Sr(II) in HNO3 media was accomplished. Due to the shorter diffusion path and covalently-bonded structure, Crown-g-MPPPs showed faster adsorption kinetics and better stability for cycle use. While Crown@MPPPs had the advantages of facile synthesis and higher adsorption capacity, owing to the absence of conformational constraint to form complexation with Sr(II). Kinetic functions (Lagergren pseudo-first-order/pseudo-second-order functions) and adsorption isotherm models (Langmuir/Freundlich models) were used to fit the experimental data and examine the adsorption mechanism. On this basis, a chromatographic process was proposed by using Crown@MPPPs for an effective separation of Sr(II) (91%) in simulated high level liquid waste (HLLW). Copyright © 2014 Elsevier B.V. All rights reserved.

An investigation into the effects of different existing states of aluminum isopropoxide on copper-based catalysts for direct synthesis of dimethyl ether from syngas

NASA Astrophysics Data System (ADS)

Sun, Kai; Wang, Peng; Bian, Zhongkai; Huang, Wei

2018-01-01

Aluminum isopropoxide (AIP) is a vital raw material to produce high surface area alumina catalyst, which is used for catalytic applications, such as hydrocracking, Fischer-Tropsch and STD (syngas to dimethyl ether) reactions. However, the different existing states have an effect on hydrolysis and condensation in the process of precursor preparation. The Cu/Zn/Al slurry catalysts were prepared by aluminum isopropoxide, which were liquid state, crystalline state and solid state, utilizing a complete liquid phase preparation technology. In the dimethyl ether (DME) synthesis reaction, the aluminum resource of crystalline state was prepared for slurry catalyst, which presented high CO conversion and DME selectivity of 54.32% and 69.74%, respectively. Characterization results indicated that different forms of AIP have the variant coordination numbers of Al-O and polymerization degrees, and the catalyst prepared by crystalline state consists amount of tetra-coordinated Al and few hexa-coordinated Al, which can exert different hydrolysis and condensation process compared with other aluminum sources, and finally it contributes to the strong interaction between active site copper species and Zn/Al species, confirming more Cu+ is responsible for the synthesis of DME in the slurry reactor.

Organic monolith frits encased in polyether ether ketone tubing with improved durability for liquid chromatography.

PubMed

Park, Sin Young; Cheong, Won Jo

2015-09-01

This study introduces a preparation method for polymer-encased monolith frits with improved durability for liquid chromatography columns. The inner surface of the polyether ether ketone tubing is pretreated with sulfuric acid in the presence of catalysts (vanadium oxide and sodium sulfate). The tubing was rinsed with water and acetone, flushed with nitrogen, and treated with glycidyl methacrylate. After washing, the monolith reaction mixture composed of lauryl methacrylate, ethylene glycol dimethacrylate, initiator, and porogenic solvent was filled in the tubing and subjected to in situ polymerization. The tubing was cut into thin slices and used as frits for microcolumns. To check their durability, the frit slices were placed in a vial and a heavy impact was applied on the vial by a vortex mixer for various periods. The frits made in the presence of catalysts were found to be more durable than those made without catalysts. Furthermore, when the monolith-incorporated tubing was used as a chromatography column, the column prepared in the presence of catalysts resulted in a better separation efficiency. The separation performance of the columns installed with the polyether ether ketone encased monolith frits was comparable to that of the columns installed with the commercial stainless-steel screen frits. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Biofouling on polymeric heat exchanger surfaces with E. coli and native biofilms.

PubMed

Pohl, S; Madzgalla, M; Manz, W; Bart, H J

2015-01-01

The biofouling affinity of different polymeric surfaces (polypropylene, polysulfone, polyethylene terephthalate, and polyether ether ketone) in comparison to stainless steel (SS) was studied for the model bacterium Escherichia coli K12 DSM 498 and native biofilms originating from Rhine water. The biofilm mass deposited on the polymer surfaces was minimized by several magnitudes compared to SS. The cell count and the accumulated biomass of E. coli on the polymer surfaces showed an opposing linear trend. The promising low biofilm formation on the polymers is attributed to the combination of inherent surface properties (roughness, surface energy and hydrophobicity) when compared to SS. The fouling characteristics of E. coli biofilms show good conformity with the more complex native biofilms investigated. The results can be utilized for the development of new polymer heat exchangers when using untreated river water as coolant or for other processes needing antifouling materials.

Solid/liquid extraction equilibria of phenolic compounds with trioctylphosphine oxide impregnated in polymeric membranes.

PubMed

Praveen, Prashant; Loh, Kai-Chee

2016-06-01

Trioctylphosphine oxide based extractant impregnated membranes (EIM) were used for extraction of phenol and its methyl, hydroxyl and chloride substituted derivatives. The distribution coefficients of the phenols varied from 2 to 234, in the order of 1-napthol > p-chlorophenol > m-cresol > p-cresol > o-cresol > phenol > catechol > pyrogallol > hydroquinone, when initial phenols loadings was varied in 100-2000 mg/L. An extraction model, based on the law of mass action, was formulated to predict the equilibrium distribution of the phenols. The model was in excellent agreement (R(2) > 0.97) with the experimental results at low phenols concentrations (<800 mg/L). At higher phenols loadings though, Langmuir isotherm was better suited for equilibrium prediction (R(2) > 0.95), which signified high mass transfer resistance in the EIMs. Examination of the effects of ring substitution on equilibrium, and bivariate statistical analysis between the amounts of phenols extracted into the EIMs and factors affecting phenols interaction with TOPO, indicated the dominant role of hydrophobicity in equilibrium determination. These results improve understanding of the solid/liquid equilibrium process between phenols and the EIMs, and these will be useful in designing phenol recovery process from wastewater. Copyright © 2016 Elsevier Ltd. All rights reserved.

A ring to rule them all: a cyclic ketene acetal comonomer controls the nitroxide-mediated polymerization of methacrylates and confers tunable degradability.

PubMed

Delplace, Vianney; Guégain, Elise; Harrisson, Simon; Gigmes, Didier; Guillaneuf, Yohann; Nicolas, Julien

2015-08-18

2-Methylene-4-phenyl-1,3-dioxolane (MPDL) was successfully used as a controlling comonomer in NMP with oligo(ethylene glycol) methyl ether methacrylate (MeOEGMA) to prepare well-defined and degradable PEG-based P(MeOEGMA-co-MPDL) copolymers. The level of ester group incorporation is controlled, leading to reductions in molecular weight of up to 95% on hydrolysis. Neither the polymer nor its degradation products displayed cytoxicity. The method was also successfully applied to methyl methacrylate.

Biodegradation of coal-related model compounds. [C. versicolor

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

Campbell, J.A.; Stewart, D.L.; McCulloch, M.

1988-01-01

The details of the specific reactions of lignin biodegradation, and the biochemistry involved, have been primarily based on the use of low molecular weight compounds representing specific substructures rather than the complex, polymeric lignin material. The authors have studied the reactions of model compounds having coal-related functionalities (ester linkages, ether linkages, PAH) with the intact organisms, cell-free filtrate, and cell-free enzyme of C. versicolor to better understand the process of biosolubilization. Many of the degradation products have been identified by gas chromatography/mass spectrometry (GC/MS). Results are discussed.

Synthesis of the diazonium (perfluoroalkyl) benzenesulfonimide monomer from Nafion monomer for proton exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Mei, Hua; D'Andrea, Dan; Nguyen, Tuyet-Trinh; Nworie, Chima

2014-02-01

One diazonium (perfluoroalkyl) benzenesulfonimide monomer, perfluoro-3, 6-dioxa-4-methyl-7-octene benzenesulfonyl imide, has been synthesized from Nafion monomer for the first time. With trifluorovinyl ether and diazonium precursors, the partially-fluorinated diazonium PFSI monomer can be polymerized and will provide chemically bonding with carbon electrode in proton exchange membrane fuel cells. A systematic study of the synthesis and characterization of this diazonium PFSI monomer has been conducted by varying reaction conditions. The optimized synthesis method has been established in the lab.

30 s Response Time of K+ Ion-Selective Hydrogels Functionalized with 18-Crown-6 Ether Based on QCM Sensor.

PubMed

Zhang, Zhenxiao; Dou, Qian; Gao, Hongkai; Bai, Bing; Zhang, Yongmei; Hu, Debo; Yetisen, Ali K; Butt, Haider; Yang, Xiaoxia; Li, Congju; Dai, Qing

2018-03-01

Potassium detection is critical in monitoring imbalances in electrolytes and physiological status. The development of rapid and robust potassium sensors is desirable in clinical chemistry and point-of-care applications. In this study, composite supramolecular hydrogels are investigated: polyethylene glycol methacrylate and acrylamide copolymer (P(PEGMA-co-AM)) are functionalized with 18-crown-6 ether by employing surface initiated polymerization. Real-time potassium ion monitoring is realized by combining these compounds with quartz crystal microbalance. The device demonstrates a rapid response time of ≈30 s and a concentration detection range from 0.5 to 7.0 × 10 -3 m. These hydrogels also exhibit high reusability and K + ion selectivity relative to other cations in biofluids such as Na + , NH 4 + , Mg 2+ , and Ca 2+ . These results provide a new approach for sensing alkali metal ions using P(PEGMA-co-AM) hydrogels. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Dual-Responsive pH and Temperature Sensitive Nanoparticles Based on Methacrylic Acid and Di(ethylene glycol) Methyl Ether Methacrylate for the Triggered Release of Drugs.

PubMed

Khine, Yee Yee; Jiang, Yanyan; Dag, Aydan; Lu, Hongxu; Stenzel, Martina H

2015-08-01

A series of thermo-and pH-responsive poly(methyl methacrylate)-block-poly[methacrylic acid-co-di(ethylene glycol) methyl ether methacrylate] PMMA-b-P[MAA-co-DEGMA] block copolymers were synthesized by RAFT polymerization and self-assembled into micelles. The molar ratio of MAA was altered from 0-12% in order to modulate the lower critical solution temperature (LCST) of PDEGMA. The release of the drug albendazole from the micelle was strongly dependent on the temperature and the LCST value of the polymer. Systems below the LCST released the drug slowly while increasing the temperature above the LCST or decreasing the pH value to 5 resulted in the burst-like release of the drug. ABZ delivered in this pH-responsive drug carrier had a higher toxicity than the free drug or the drug delivered in a non-responsive drug carrier. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

PubMed

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

2017-11-01

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

Mechanism of in situ surface polymerization of gallic acid in an environmental-inspired preparation of carboxylated core-shell magnetite nanoparticles.

PubMed

Tóth, Ildikó Y; Szekeres, Márta; Turcu, Rodica; Sáringer, Szilárd; Illés, Erzsébet; Nesztor, Dániel; Tombácz, Etelka

2014-12-30

Magnetite nanoparticles (MNPs) with biocompatible coatings are good candidates for MRI (magnetic resonance imaging) contrasting, magnetic hyperthermia treatments, and drug delivery systems. The spontaneous surface induced polymerization of dissolved organic matter on environmental mineral particles inspired us to prepare carboxylated core-shell MNPs by using a ubiquitous polyphenolic precursor. Through the adsorption and in situ surface polymerization of gallic acid (GA), a polygallate (PGA) coating is formed on the nanoparticles (PGA@MNP) with possible antioxidant capacity. The present work explores the mechanism of polymerization with the help of potentiometric acid-base titration, dynamic light scattering (for particle size and zeta potential determination), UV-vis (UV-visible light spectroscopy), FTIR-ATR (Fourier-transformed infrared spectroscopy by attenuated total reflection), and XPS (X-ray photoelectron spectroscopy) techniques. We observed the formation of ester and ether linkages between gallate monomers both in solution and in the adsorbed state. Higher polymers were formed in the course of several weeks both on the surface of nanoparticles and in the dispersion medium. The ratio of the absorbances of PGA supernatants at 400 and 600 nm (i.e., the E4/E6 ratio commonly used to characterize the degree of polymerization of humic materials) was determined to be 4.3, similar to that of humic acids. Combined XPS, dynamic light scattering, and FTIR-ATR results revealed that, prior to polymerization, the GA monomers became oxidized to poly(carboxylic acid)s due to ring opening while Fe(3+) ions reduced to Fe(2+). Our published results on the colloidal and chemical stability of PGA@MNPs are referenced thoroughly in the present work. Detailed studies on biocompatibility, antioxidant property, and biomedical applicability of the particles will be published.

Synthesis and self-assembly of four-armed star copolymer based on poly(ethylene brassylate) hydrophobic block as potential drug carries

NASA Astrophysics Data System (ADS)

Chen, Jiucun; Li, Junzhi; Liu, Jianhua; Weng, Bo; Xu, Liqun

2016-05-01

A novel well-defined four-armed star poly(ethylene brassylate)- b-poly(poly(ethylene glycol)methyl ether methacrylate) (s-PEB- b-P(PEGMA)) was synthesized and self-assembled via the combination of ring-opening polymerization and reversible addition-fragmentation chain transfer polymerization (RAFT) in this work. It proceeded firstly with the synthesis of hydrophobic four-armed star homopolymer of ethylene brassylate (EB) via ROP with organic catalyst, followed by the esterification reaction of s-PEB with chain transfer agent. Afterward, RAFT polymerization of PEGMA monomer was initialed using PEB-based macro-RAFT agent, resulting in the target amphiphilic four-armed star copolymer. The obtained s-PEB- b-P(PEGMA) can assemble into micelles with PEB segments as core and P(PEGMA) segments as shell in aqueous solution. The self-assembly behavior was studied by dynamic light scattering and transmission electron microscope. The micelles of s-PEB- b-P(PEGMA) exhibited higher loading capacity of the anticancer drug doxorubicin (DOX). The investigation of DOX release from the micelles demonstrated that the release rate of the hydrophobic drug could be effectively controlled.

Blood clearance and biodistribution of polymer brush-afforded silica particles prepared by surface-initiated living radical polymerization.

PubMed

Ohno, Kohji; Akashi, Tatsuki; Tsujii, Yoshinobu; Yamamoto, Masaya; Tabata, Yasuhiko

2012-03-12

The physiological properties of polymer brush-afforded silica particles prepared by surface-initiated living radical polymerization were investigated in terms of the circulation lifetime in the blood and distribution in tissues. Hydrophilic polymers consisting mainly of poly(poly(ethylene glycol) methyl ether methacrylate) were grafted onto silica particles by surface-initiated atom transfer radical polymerization that was mediated by a copper complex to produce hairy hybrid particles. A series of hybrid particles was synthesized by varying the diameter of the silica core and the chain length of the polymer brush to examine the relationship between their physicochemical and physiological properties. The hybrid particles were injected intravenously into mice to investigate systematically their blood clearance and body distribution. It was revealed that the structural features of the hybrid particles significantly affected their in vivo pharmacokinetics. Some hybrid particles exhibited an excellently prolonged circulation lifetime in the blood with a half life of ∼20 h. When such hybrid particles were injected intravenously into a tumor-bearing mouse, they preferentially accumulated in tumor tissue. The tumor-targeted delivery was optically visualized using hybrid particles grafted with fluorescence-labeled polymer brushes.

Patent application for a process for production of effective catalysts for polymerization of unsaturated compounds (in German)

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

Ibing, G.

Organic compounds which contain one or more double carbon bonds per molecule frequently display the ability of polymerizing with each other and with other compounds. It is mainly compounds containing peroxide that serve as catalysts for such operations. Examples of recommended substances are hydrogen peroxide, ozone, perbenzoic acid, benzoin peroxide, peroxide-containing ethers, persulfates, etc. It was found that a catalyst of much greater effectiveness in the polymerization of unsaturated compounds can be obtained from one of the previously-known catalysts if the hydrocarbons are processed with lateral-chain substances (e.g., toluene, xylene, ethyl benzene, propyl benzene, diethyl benzene, etc.) in boiling heatmore » with damp air. In this process there develops a small measure of peroxide of previously unknown make-up, which possess outstanding catalytic effectiveness. For production of the catalyst, the aromatics are heated by return-flow cooler and conducted for several hours through an air stream which has been saturated with steam. Oxidation can be undertaken with other substances also; for example, oxygen, ozone, or compounds which give off oxygen. Activation with air, however, is the simplest way and yields the most effective catalyst. Examples of the process are provided.« less

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.

Implementing and Quantifying the Shape-Memory Effect of Single Polymeric Micro/Nanowires with an Atomic Force Microscope.

PubMed

Fang, Liang; Gould, Oliver E C; Lysyakova, Liudmila; Jiang, Yi; Sauter, Tilman; Frank, Oliver; Becker, Tino; Schossig, Michael; Kratz, Karl; Lendlein, Andreas

2018-04-23

The implementation of shape-memory effects (SME) in polymeric micro- or nano-objects currently relies on the application of indirect macroscopic manipulation techniques, for example, stretchable molds or phantoms, to ensembles of small objects. Here, we introduce a method capable of the controlled manipulation and SME quantification of individual micro- and nano-objects in analogy to macroscopic thermomechanical test procedures. An atomic force microscope was utilized to address individual electro-spun poly(ether urethane) (PEU) micro- or nanowires freely suspended between two micropillars on a micro-structured silicon substrate. In this way, programming strains of 10±1% or 21±1% were realized, which could be successfully fixed. An almost complete restoration of the original free-suspended shape during heating confirmed the excellent shape-memory performance of the PEU wires. Apparent recovery stresses of σ max,app =1.2±0.1 and 33.3±0.1 MPa were obtained for a single microwire and nanowire, respectively. The universal AFM test platform described here enables the implementation and quantification of a thermomechanically induced function for individual polymeric micro- and nanosystems. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

City sewer collectors biocorrosion

NASA Astrophysics Data System (ADS)

Ksiażek, Mariusz

2014-12-01

This paper presents the biocorrosion of city sewer collectors impregnated with special polymer sulphur binders, polymerized sulphur, which is applied as the industrial waste material. The city sewer collectors are settled with a colony of soil bacteria which have corrosive effects on its structure. Chemoautotrophic nitrifying bacteria utilize the residues of halites (carbamide) which migrate in the city sewer collectors, due to the damaged dampproofing of the roadway and produce nitrogen salts. Chemoorganotrophic bacteria utilize the traces of organic substrates and produce a number of organic acids (formic, acetic, propionic, citric, oxalic and other). The activity of microorganisms so enables the origination of primary and secondary salts which affect physical properties of concretes in city sewer collectors unfavourably.

A Green Method for Processing Polymers using Dense Gas Technology

PubMed Central

Yoganathan, Roshan B.; Mammucari, Raffaella; Foster, Neil R.

2010-01-01

Dense CO2 can be used as an environmentally-benign polymer processing medium because of its liquid-like densities and gas-like mass transfer properties.In this work, polymer bio-blends of polycarbonate (PC), a biocompatible polymer, and polycaprolactone (PCL), a biodegradable polymer were prepared. Dense CO2 was used as a reaction medium for the melt-phase PC polymerization in the presence of dense CO2-swollen PCL particles and this method was used to prepare porous PC/PCL blends. To extend the applicability of dense CO2 to the biomedical industry and polymer blend processing, the impregnation of ibuprofen into the blend was conducted and subsequent dissolution characteristics were observed.

Catalytic valorization of starch-rich food waste into hydroxymethylfurfural (HMF): Controlling relative kinetics for high productivity.

PubMed

Yu, Iris K M; Tsang, Daniel C W; Yip, Alex C K; Chen, Season S; Wang, Lei; Ok, Yong Sik; Poon, Chi Sun

2017-08-01

This study aimed to maximize the valorization of bread waste, a typical food waste stream, into hydroxymethylfurfural (HMF) by improving our kinetic understanding. The highest HMF yield (30mol%) was achieved using SnCl 4 as catalyst, which offered strong derived Brønsted acidity and moderate Lewis acidity. We evaluated the kinetic balance between these acidities to facilitate faster desirable reactions (i.e., hydrolysis, isomerization, and dehydration) relative to undesirable reactions (i.e., rehydration and polymerization). Such catalyst selectivity of SnCl 4 , AlCl 3 , and FeCl 3 was critical in maximizing HMF yield. Higher temperature made marginal advancement by accelerating the undesirable reactions to a similar extent as the desirable pathways. The polymerization-induced metal-impregnated high-porosity carbon was a possible precursor of biochar-based catalyst, further driving up the economic potential. Preliminary economic analysis indicated a net gain of USD 43-236 per kilogram bread waste considering the thermochemical-conversion cost and chemical-trading revenue. Copyright © 2017 Elsevier Ltd. All rights reserved.

Supramolecular self-assemblies of beta-cyclodextrins with aromatic tethers: factors governing the helical columnar versus linear channel superstructures.

PubMed

Liu, Yu; Fan, Zhi; Zhang, Heng-Yi; Yang, Ying-Wei; Ding, Fei; Liu, Shuang-Xi; Wu, Xue; Wada, Takehiko; Inoue, Yoshihisa

2003-10-31

A series of 6-O-(p-substituted phenyl)-modified beta-cyclodextrin derivatives, i.e., 6-O-(4-bromophenyl)-beta-CD (1), 6-O-(4-nitrophenyl)-beta-CD (2), 6-O-(4-formylphenyl)-beta-CD (3), 6-phenylselenyl-6-deoxy-beta-CD (4), and 6-O-(4-hydroxybenzoyl)-beta-CD (5), were synthesized, and their inclusion complexation behavior in aqueous solution and self-assembling behavior in the solid state were comparatively studied by NMR spectroscopy, microcalorimetry, crystallography, and scanning tunneling microscopy. Interestingly, (seleno)ethers 1-4 and ester 5 displayed distinctly different self-assembling behavior in the solid state, affording a successively threading head-to-tail polymeric helical structure for the (seleno)ethers or a mutually penetrating tail-to-tail dimeric columnar channel structure for the ester. Combining the present and previous structures reported for the relevant beta-CD derivatives, we further deduce that the pivot heteroatom, through which the aromatic substituent is tethered to beta-CD, plays a critical role in determining the helix structure, endowing the 2-fold and 4-fold axes to the N/O- and S/Se-pivoted beta-CD aggregates, respectively. This means that one can control the self-assembling orientation, alignment, and helicity in the solid state by finely tuning the pivot atom and the tether length. Further NMR and calorimetric studies on the self-assembling behavior in aqueous solution revealed that the dimerization step is the key to the formation of linear polymeric supramolecular architecture, which is driven by favorable entropic contributions.

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.

Strain and temperature measurement in pultrusion processes by fiber Bragg grating sensors

NASA Astrophysics Data System (ADS)

Tucci, Fausto; Rubino, Felice; Carlone, Pierpaolo

2018-05-01

Injection Pultrusion (IP) is one of the most effective processes, in terms of productivity and costs, to manufacture fiber reinforced polymers. In IP roving of fiber are driven through an injection chamber in which they are impregnated by the resin and then formed in a shaped die. The die is heated in order to cure the resin. Pultruded products are in most cases characterized by constant cross-section profile, whereas unidirectional long fibers are mainly used as reinforcing material. Two relevant phenomena occur within the injection chamber and the heated die, namely the impregnation of the fibers and the polymerization of the resin. Furthermore, thermal expansion, resin chemical shrinkage and the interaction between the die and the impregnated fibers strongly influence the process [1]. Clearly, thermal and mechanical fields significantly impact on these strictly chained behaviours. The use of thermocouples to evaluate temperature within pultrusion die is already widespread, but they are not capable to acquire any information concerning stress-strain levels. In the present work Fibers Bragg Gratings (FBG) sensors were used to measure thermal and strain profiles in selected material location within the injection chamber and the curing die. Being the differences among the spectres transmitted and received are related to the variations in both temperature and strain, commercial FBG sensors were opportunely modified and calibrated. The optical fibers were hooked to the fibers entering into the injection pultrusion die. Taking the pulling speed into account, each waveform acquired was correlated to a position within the die. Obtained data highlight the effect of the heat generation due to resin reaction as well as longitudinal strains related to the pulling force, the thermal expansion and the chemical shrinkage of the resin system.

Reduced sensitizing capacity of epoxy resin systems: a structure-activity relationship study.

PubMed

Niklasson, Ida B; Broo, Kerstin; Jonsson, Charlotte; Luthman, Kristina; Karlberg, Ann-Therese

2009-11-01

Epoxy resins can be prepared from numerous chemical compositions. Until recently, alternatives to epoxy resins based on diglycidyl ethers of bisphenol A (DGEBA) or bisphenol F (DGEBF) monomers have not received commercial interest, but are presently doing so, as epoxy resins with various properties are desired. Epoxy resin systems are known to cause allergic contact dermatitis because of contents of uncured monomers, reactive diluents, and hardeners. Reactive diluents, for example, glycidyl ethers, which also contain epoxide moieties, are added to reduce viscosity and improve polymerization. We have investigated the contact allergenic properties of a series of six analogues to phenyl glycidyl ether (PGE), all with similar basic structures but with varying carbon chain lengths and degrees of saturation. The chemical reactivity of the compounds in the test series toward the hexapeptide H-Pro-His-Cys-Lys-Arg-Met-OH was investigated. All epoxides were shown to bind covalently to both cysteine and proline residues. The percent depletion of nonreacted peptide was also studied resulting in 88% depletion when using PGE and 46% when using butyl glycidyl ether (5) at the same time point, thus revealing a large difference between the fastest and the slowest reacting epoxide. The skin sensitization potencies of the epoxides using the murine local lymph node assay (LLNA) were evaluated in relation to the observed physicochemical and reactivity properties. To enable determination of statistical significance between structurally closely related compounds, a nonpooled LLNA was performed. It was found that the compounds investigated ranged from strong to weak sensitizers, congruent with the reactivity data, indicating that even small changes in chemical structure result in significant differences in sensitizing capacity.

Biodegradable containers from green waste materials

NASA Astrophysics Data System (ADS)

Sartore, Luciana; Schettini, Evelia; Pandini, Stefano; Bignotti, Fabio; Vox, Giuliano; D'Amore, Alberto

2016-05-01

Novel biodegradable polymeric materials based on protein hydrolysate (PH), derived from waste products of the leather industry, and poly(ethylene glycol) diglycidyl ether (PEG) or epoxidized soybean oil (ESO) were obtained and their physico-chemical properties and mechanical behaviour were evaluated. Different processing conditions and the introduction of fillers of natural origin, as saw dust and wood flour, were used to tailor the mechanical properties and the environmental durability of the product. The biodegradable products, which are almost completely manufactured from renewable-based raw materials, look promising for several applications, particularly in agriculture for the additional fertilizing action of PH or in packaging.

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

Putting copper into action: copper-impregnated products with potent biocidal activities.

PubMed

Borkow, Gadi; Gabbay, Jeffrey

2004-11-01

Copper ions, either alone or in copper complexes, have been used for centuries to disinfect liquids, solids, and human tissue. Today copper is used as a water purifier, algaecide, fungicide, nematocide, molluscicide, and antibacterial and antifouling agent. Copper also displays potent antiviral activity. We hypothesized that introducing copper into clothing, bedding, and other articles would provide them with biocidal properties. A durable platform technology has been developed that introduces copper into cotton fibers, latex, and other polymeric materials. This study demonstrates the broad-spectrum antimicrobial (antibacterial, antiviral, antifungal) and antimite activities of copper-impregnated fibers and polyester products. This technology enabled the production of antiviral gloves and filters (which deactivate HIV-1 and other viruses), antibacterial self-sterilizing fabrics (which kill antibiotic-resistant bacteria, including methicillin-resistant Staphylococcus aureus and vancomycin-resistant Enterococci), antifungal socks (which alleviate symptoms of athlete's foot), and anti-dust mite mattress covers (which reduce mite-related allergies). These products did not have skin-sensitizing properties, as determined by guine pig maximization and rabbit skin irritation tests. Our study demonstrates the potential use of copper in new applications. These applications address medical issues of the greatest importance, such as viral transmissions; nosocomial, or healthcare-associated, infections; and the spread of antibiotic-resistant bacteria.

Synthesis and structural studies of lithium and sodium complexes with OOO-tridentate bis(phenolate) ligands: effective catalysts for the ring-opening polymerization of L-lactide.

PubMed

Huang, Yong; Tsai, Yueh-Hsuan; Hung, Wen-Chou; Lin, Chieh-Shen; Wang, Wei; Huang, Jui-Hsien; Dutta, Saikat; Lin, Chu-Chieh

2010-10-18

A series of lithium and sodium complexes with OOO-tridentate bis(phenolate) ligands have been synthesized and fully characterized. The reaction of 2,2'-dihydroxy-3,3',5,5'-tetrakis[(1-methyl-1-phenyl)ethyl]dibenzyl ether (L(1)-H(2)) with different ratios of (n)BuLi in toluene or tetrahydrofuran (THF) gave [Li(2)(L(1)-H)(2)] (1), [Li(4)L(1)(2)] (2), and [Li(2)L(1)(THF)(3)] (3), respectively. Similarly, [Na(L(1)-H)(THF)] (4), [Na(2)(L(1)-H)](2) (5), and [Na(4)L(1)(2)] (6) were prepared by the reaction of L(1)-H(2) and NaN[Si(CH(3))(3)](2) or sodium metal. In addition, the reaction of 2,2'-dihydroxy-3,3',5,5'-tetra-tert-butyldibenzyl ether (L(2)-H(2)) with (n)BuLi in toluene or THF yields Li(2)(L(2)-H)(2)] (7) and [Li(2)(L(2)-H)(2)(THF)(2)] (8), respectively. Further treatment of 7 with 2 mol equiv of benzyl alcohol provides [Li(2)(L(2)-H)(2)(BnOH)(2)] (9). Complexes 1-4 and 6-9 have been structurally characterized by single-crystal X-ray analysis. The dinuclear nature of complexes 1 and 3 was confirmed from their molecular structure. Complexes 2 and 6 illustrate tetranuclear species; however, complex 4 shows a mononuclear feature. A p-π interaction exists from the phenyl ring of the 2-(methyl-1-phenylethyl) groups to the central metal in complexes 2, 4, and 6, which could effectively stabilize the metal center. Among them, complexes 1, 2, and 5-9 displayed efficient catalytic behavior for the ring-opening polymerization of L-lactide in the presence of benzyl alcohol. Experimental results indicate that among these alkali-metal complexes, the sodium compound 6 displays a rapid catalytic polymerization of L-lactide in "living" fashion, yielding poly(L-lactide) with a controlled molecular weight and narrow polydispersity indices for a wide range of monomer-to-initiator ratios.

Polyfunctional epoxies. I - Rubber-toughened brominated and nonbrominated formulations for graphite composites. II - Nonrubber versus rubber-toughened brominated formulations for graphite composites

NASA Technical Reports Server (NTRS)

Nir, Z.; Gilwee, W. J.; Kourtides, D. A.; Parker, J. A.

1985-01-01

A new trifunctional epoxy resin, Tris-(hydroxyphenyl) methane triglycidyl ether, is compared to a state-of-the-art tetraglycidyl 4,4'-diaminodiphenyl methane (TGDDM), in graphite composites. Rubber-toughened brominated formulations of the epoxy resin are compared to nonbrominated ones in terms of their mechanical performance, environmental stability, thermochemical behavior, and flame retardancy. It is shown that the new resin performs almost the same way as the TGDDM does, but has improved glass transition temperature and environmental properties. Brominated polymeric additives (BPA) of different molecular weights are tested as a Br source to flame retardant graphite epoxy composites. The optimal molecular weight of the BPA and its polymeric backbone length are derived and compared with a 10 percent rubber-toughened formulation of the epoxy resin. Results indicate that when the Br content in the graphite composite is increased without the use of rubber, the mechanical properties improved. The use of BPAs as tougheners for graphite composites is also considered.

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

Thermomechanical Formation–Structure–Property Relationships in Photopolymerized Copper-Catalyzed Azide–Alkyne (CuAAC) Networks

PubMed Central

Baranek, Austin; Song, Han Byul; McBride, Mathew; Finnegan, Patricia; Bowman, Christopher N.

2016-01-01

Bulk photopolymerization of a library of synthesized multifunctional azides and alkynes was carried out toward developing structure–property relationships for CuAAC-based polymer networks. Multifunctional azides and alkynes were formulated with a copper catalyst and a photoinitiator, cured, and analyzed for their mechanical properties. Material properties such as the glass transition temperatures (Tg) show a strong dependence on monomer structure with Tg values ranging from 41 to 90 °C for the series of CuAAC monomers synthesized in this study. Compared to the triazoles, analogous thioether-based polymer networks exhibit a 45–49 °C lower Tg whereas analogous monomers composed of ethers in place of carbamates exhibit a 40 °C lower Tg. Here, the formation of the triazole moiety during the polymerization represents a critical component in dictating the material properties of the ultimate polymer network where material properties such as the rubbery modulus, cross-link density, and Tg all exhibit strong dependence on polymerization conversion, monomer composition, and structure postgelation. PMID:27867223

Microwave-assisted cationic polymerization of palm olein and their urea inclusion products

NASA Astrophysics Data System (ADS)

Soegijono, Bambang; Farid, Muhamad; Alim Mas'ud, Zainal

2018-01-01

Cationic polymerization is affected by the relative amount of unsaturated bond (C=C) in the compound. The enrichment of an unsaturated triglyceride fraction from oils may be performed using urea inclusion techniques. In this study, palm olein was enriched-unsaturated fraction using urea-methanol system. The palm olein and its urea-inclusion products were cationic polymerized with ethereal boron trifluoride catalyst and followed by irradiation using a commercial microwave (microwave-assisted). The microwave irradiated products were cured at 110 °C for 24 hours. Fatty acid composition of the palm olein and its urea-inclusion products were analyzed by gas chromatography. Iodine numbers, functional groups, and ultraviolet absorption spectra of all palm olein origin, urea inclusion products and polymerization products were analyzed using titrimetric, ultraviolet spectrophotometric, and Fourier Transform infrared spectrophotometric methods. Differential scanning calorimetric (DSC) was used to observe the thermal characteristics of the polymer. Urea-inclusion process increased the unsaturated fatty acid components as indicated by the increased iodine number, intensity of alkene band absorptions in the infrared spectra, and the absorbance of the ultraviolet spectra. The polymer formation is converting the C=C group to C-C, which is indicated by the opposite of the urea inclusion process. The curing process results in reformation of new C=C bonds that were similar to that of the urea inclusion process. The DSC thermogram curve shows that the enrichment process improves the thermal stability of the polymer formed.

Molecular architecture requirements for polymer-grafted lignin superplasticizers.

PubMed

Gupta, Chetali; Sverdlove, Madeline J; Washburn, Newell R

2015-04-07

Superplasticizers are a class of anionic polymer dispersants used to inhibit aggregation in hydraulic cement, lowering the yield stress of cement pastes to improve workability and reduce water requirements. The plant-derived biopolymer lignin is commonly used as a low-cost/low-performance plasticizer, but attempts to improve its effects on cement rheology through copolymerization with synthetic monomers have not led to significant improvements. Here we demonstrate that kraft lignin can form the basis for high-performance superplasticizers in hydraulic cement, but the molecular architecture must be based on a lignin core with a synthetic-polymer corona that can be produced via controlled radical polymerization. Using slump tests of ordinary Portland cement pastes, we show that polyacrylamide-grafted lignin prepared via reversible addition-fragmentation chain transfer polymerization can reduce the yield stress of cement paste to similar levels as a leading commercial polycarboxylate ether superplasticizer at concentrations ten-fold lower, although the lignin material produced via controlled radical polymerization does not appear to reduce the dynamic viscosity of cement paste as effectively as the polycarboxylate superplasticizer, despite having a similar affinity for the individual mineral components of ordinary Portland cement. In contrast, polyacrylamide copolymerized with a methacrylated kraft lignin via conventional free radical polymerization having a similar overall composition did not reduce the yield stress or the viscosity of cement pastes. While further work is required to elucidate the mechanism of this effect, these results indicate that controlling the architecture of polymer-grafted lignin can significantly enhance its performance as a superplasticizer for cement.

Effect of EtOH/MgCl(2) molar ratios on the catalytic properties of MgCl(2)-SiO(2)/TiCl(4) Ziegler-Natta catalyst for ethylene polymerization.

PubMed

Patthamasang, Supanan; Jongsomjit, Bunjerd; Praserthdam, Piyasan

2011-09-29

MgCl(2)-SiO(2)/TiCl(4) Ziegler-Natta catalysts for ethylene polymerization were prepared by impregnation of MgCl(2) on SiO(2) in heptane and further treatment with TiCl(4). MgCl(2)·nEtOH adduct solutions were prepared with various EtOH/MgCl(2) molar ratios for preparation of the MgCl(2)-supported and MgCl(2)-SiO(2)-supported catalysts in order to investigate the effect on polymerization performance of both catalyst systems. The catalytic activities for ethylene polymerization decreased markedly with increased molar ratios of [EtOH]/[MgCl(2)] for the MgCl(2)-supported catalysts, while for the bi-supported catalysts, the activities only decreased slightly. The MgCl(2)-SiO(2)-supported catalyst had relatively constant activity, independent of the [EtOH]/[MgCl(2)] ratio. The lower [EtOH]/[MgCl(2)] in MgCl(2)-supported catalyst exhibited better catalytic activity. However, for the MgCl(2)-SiO(2)-supported catalyst, MgCl(2) can agglomerate on the SiO(2) surface at low [EtOH]/[MgCl(2)] thus not being not suitable for TiCl(4) loading. It was found that the optimized [EtOH]/[MgCl(2)] value for preparation of bi-supported catalysts having high activity and good spherical morphology with little agglomerated MgCl(2) was 7. Morphological studies indicated that MgCl(2)-SiO(2)-supported catalysts have good morphology with spherical shapes that retain the morphology of SiO(2). The BET measurement revealed that pore size is the key parameter dictating polymerization activity. The TGA profiles of the bi-supported catalyst also confirmed that it was more stable than the mono-supported catalyst, especially in the ethanol removal region.

Optical properties of doped sol-gel silica glasses

NASA Astrophysics Data System (ADS)

King, Terence A.

1994-01-01

Sol-gel optical composites were developed and characterized for potential applications in optics, lasers, nonlinear optics, and optoelectronics. Post-doped xerogels were index matched by in-situ polymerization of monomers to form inorganic-organic composites of low scatter and high optical quality. Characterization of the microstructure was made by visible and IR absorption and Raman Spectroscopy and optical quality by attenuation and scatter measurement. Doping techniques were optimized using hypercritical drying and vacuum impregnation and doping distribution monitored by laser-induced fluorescence. One-tenth wavelength surfaces were formed by novel optical polishing. Organic molecular dopants were tested in laser and nonlinear systems. Initial third harmonic generation and Z-scan measurements have shown the potential for saturable absorption and optical limiting.

Heparin-mimicking multilayer coating on polymeric membrane via LbL assembly of cyclodextrin-based supramolecules.

PubMed

Deng, Jie; Liu, Xinyue; Ma, Lang; Cheng, Chong; Shi, Wenbin; Nie, Chuanxiong; Zhao, Changsheng

2014-12-10

In this study, multifunctional and heparin-mimicking star-shaped supramolecules-deposited 3D porous multilayer films with improved biocompatibility were fabricated via a layer-by-layer (LbL) self-assembly method on polymeric membrane substrates. Star-shaped heparin-mimicking polyanions (including poly(styrenesulfonate-co-sodium acrylate; Star-PSS-AANa) and poly(styrenesulfonate-co-poly(ethylene glycol)methyl ether methacrylate; Star-PSS-EGMA)) and polycations (poly(methyl chloride-quaternized 2-(dimethylamino)ethyl methacrylate; Star-PMeDMA) were first synthesized by atom transfer radical polymerization (ATRP) from β-cyclodextrin (β-CD) based cores. Then assembly of 3D porous multilayers onto polymeric membrane surfaces was carried out by alternating deposition of the polyanions and polycations via electrostatic interaction. The surface morphology and composition, water contact angle, blood activation, and thrombotic potential as well as cell viability for the coated heparin-mimicking films were systematically investigated. The results of surface ATR-FTIR spectra and XPS spectra verified successful deposition of the star-shaped supramolecules onto the biomedical membrane surfaces; scanning electron microscopy (SEM) and atomic force microscopy (AFM) observations revealed that the modified substrate had 3D porous surface morphology, which might have a great biological influence on the biointerface. Furthermore, systematic in vitro investigation of protein adsorption, platelet adhesion, human platelet factor 4 (PF4, indicates platelet activation), activate partial thromboplastin time (APTT), thrombin time (TT), coagulation activation (thrombin-antithrombin III complex (TAT, indicates blood coagulant)), and blood-related complement activation (C3a and C5a, indicates inflammation potential) confirmed that the heparin-mimicking multilayer coated membranes exhibited ultralow blood component activations and excellent hemocompatibility. Meanwhile, after surface coating, endothelial cell viability was also promoted, which indicated that the heparin-mimicking multilayer coating might extend the application fields of polymeric membranes in biomedical fields.

Application of a constant hole volume Sanchez-Lacombe equation of state to mixtures relevant to polymeric foaming.

PubMed

von Konigslow, Kier; Park, Chul B; Thompson, Russell B

2018-06-06

A variant of the Sanchez-Lacombe equation of state is applied to several polymers, blowing agents, and saturated mixtures of interest to the polymer foaming industry. These are low-density polyethylene-carbon dioxide and polylactide-carbon dioxide saturated mixtures as well as polystyrene-carbon dioxide-dimethyl ether and polystyrene-carbon dioxide-nitrogen ternary saturated mixtures. Good agreement is achieved between theoretically predicted and experimentally determined solubilities, both for binary and ternary mixtures. Acceptable agreement with swelling ratios is found with no free parameters. Up-to-date pure component Sanchez-Lacombe characteristic parameters are provided for carbon dioxide, dimethyl ether, low-density polyethylene, nitrogen, polylactide, linear and branched polypropylene, and polystyrene. Pure fluid low-density polyethylene and nitrogen parameters exhibit more moderate success while still providing acceptable quantitative estimations. Mixture estimations are found to have more moderate success where pure components are not as well represented. The Sanchez-Lacombe equation of state is found to correctly predict the anomalous reversal of solubility temperature dependence for low critical point fluids through the observation of this behaviour in polystyrene nitrogen mixtures.

Triblock copolymers encapsulated poly (aryl benzyl ether) dendrimer zinc(II) phthalocyanine nanoparticles for enhancement in vitro photodynamic efficacy.

PubMed

Huang, Yide; Yu, Huizhen; Lv, Huafei; Zhang, Hong; Ma, Dongdong; Yang, Hongqin; Xie, Shusen; Peng, Yiru

2016-12-01

A novel series of nanoparticles formed via an electrostatic interaction between the periphery of negatively charged 1-2 generation aryl benzyl ether dendrimer zinc (II) phthalocyanines and positively charged poly(L-lysin) segment of triblock copolymer, poly(L-lysin)-block-poly(ethylene glycol)-block-poly(L-lysin), was developed for the use as an effective photosensitizers in photodynamic therapy. The dynamic light scattering, atomic force microscopy showed that two nanoparticles has a relevant size of 80-150nm. The photophysical properties and singlet oxygen quantum yields of free dendrimer phthalocyanines and nanoparticles exhibited generation dependence. The intracellular uptake of dendrimer phthalocyanines in Hela cells was significantly elevated as they were incorporated into the micelles, but was inversely correlated with the generation of dendrimer phthalocyanines. The photocytotoxicity of dendrimer phthalocyanines incorporated into polymeric micelles was also increased. The presence of nanoparticles induced efficient cell death. Using a mitochondrial-sepcific dye rhodamine 123 (Rh123), our fluorescence microscopic result indicated that nanoparticles localized to the mitochondria. Copyright © 2016 Elsevier B.V. All rights reserved.

Field determination of microgram quantities of niobium in rocks

USGS Publications Warehouse

Ward, F.N.; Marranzino, A.P.

1955-01-01

A rapid, simple, and moderately accurate method was needed for the determination of traces of niobium in rocks. The method developed is based on the reaction of niobium(V) with thiocyanate ion in a 4M hydrochloric acid and 0.5M tartaric acid medium, after which the complex is extracted with ethyl ether. The proposed procedure is applicable to rocks containing from 50 to 2000 p.p.m. of niobium, and, with modifications, can be used on rocks containing larger amounts. Five determinations on two rocks containing 100 p.p.m. or less of niobium agree within 5 p.p.m. of the mean, and the confidence limits at the 95% level are, respectively, ??6 and ??4 p.p.m. The addition of acetone to the ether extract of the niobium thiocyanate inhibits the polymerization of the thiocyanate ion and stabilizes the solution for at least 20 hours. The proposed procedure permits the determination of 20 ?? of niobium in the presence of 1000 ?? of iron, titanium, or uranium; 500 ?? of vanadium; or 100 ?? of tungsten or molybdenum or both.

Evaluation of some properties of two fiber-reinforced composite materials.

PubMed

Lassila, Lippo V J; Tezvergil, Arzu; Lahdenperä, Milla; Alander, Pasi; Shinya, Akiyoshi; Shinya, Akikazu; Vallittu, Pekka K

2005-08-01

Water sorption, flexural properties, bonding properties, and elemental composition of photopolymerizable resin-impregnated fiber-reinforced composite (FRC) materials (everStick C&B and BR-100) (FPD) were evaluated in this study. Bar-shaped specimens (2 x 2 x 25 mm) were prepared for water sorption and flexural strength testing. The specimens (n = 6) were polymerized either with a hand light-curing unit for 40 s or, additionally, in a light-curing oven for 20 min and stored in water for 30 days. Water sorption was measured during this time, followed by measurements of flexural strength and modulus. A shear bond strength test was performed to determine the bonding characteristics of polymerized FRC to composite resin luting cement (Panavia-F), (n = 15). The cement was bonded to the FRC substrate and the specimens were thermocycled 5000 times (5-55 degrees C) in water. SEM/EDS were analyzed to evaluate the elemental composition of the glass fibers and the fiber distribution in cross section. ANOVA showed significant differences in water sorption according to brand (p < 0.05). Water sorption of everStick C&B was 1.86 wt% (hand-unit polymerized) and 1.94 wt% (oven polymerized), whereas BR-100 was 1.07 wt% and 1.17 wt%, respectively. The flexural strength of everStick C&B after 30 days' water storage was 559 MPa (hand-unit polymerized) and 796 MPa (oven-polymerized); for BR-100, the values were 547 MPa and 689 MPa, respectively. Mean shear bond strength of composite resin cement to the FRC varied between 20.1 and 23.7 MPa, showing no statistical difference between the materials. SEM/EDS analysis revealed that fibers of both FRC materials consist of the same oxides (SiO2, CaO, and Al2O3) in ratios. The distribution of fibers in the cross section of specimens was more evenly distributed in everStick C&B than in BR-100. The results of this study suggest that there are some differences in the tested properties of the FRC materials.

Alkaline Hydrolysis/Polymerization of 2,4,6-Trinitrotoluene: Characterization of Products by 13C and 15N NMR

USGS Publications Warehouse

Thorn, K.A.; Thorne, P.G.; Cox, L.G.

2004-01-01

Alkaline hydrolysis has been investigated as a nonbiological procedure for the destruction of 2,4,6-trinitrotoluene (TNT) in explosives contaminated soils and munitions scrap. Nucleophilic substitutions of the nitro and methyl groups of TNT by hydroxide ion are the initial steps in the alkaline degradation of TNT. Potential applications of the technique include both in situ surface liming and ex situ alkaline treatment of contaminated soils. A number of laboratory studies have reported the formation of an uncharacterized polymeric material upon prolonged treatment of TNT in base. As part of an overall assessment of alkaline hydrolysis as a remediation technique, and to gain a better understanding of the chemical reactions underlying the hydrolysis/polymerization process, the soluble and precipitate fractions of polymeric material produced from the calcium hydroxide hydrolysis of unlabeled and 15N-labeled TNT were analyzed by elemental analysis and 13C and 15N nuclear magnetic resonance spectroscopy. Spectra indicated that reactions leading to polymerization included nucleophilic displacement of nitro groups by hydroxide ion, formation of ketone, carboxyl, alcohol, ether, and other aliphatic carbons, conversion of methyl groups to diphenyl methylene carbons, and recondensation of aromatic amines and reduced forms of nitrite, including ammonia and possibly hydroxylamine, into the polymer. Compared to the distribution of carbons in TNT as 14% sp 3- and 86% sp2-hybridized, the precipitate fraction from hydrolysis of unlabeled TNT contained 33% sp3- and 67% sp 2-hybridized carbons. The concentration of nitrogen in the precipitate was 64% of that in TNT. The 15N NMR spectra showed that, in addition to residual nitro groups, forms of nitrogen present in the filtrate and precipitate fractions include aminohydroquinone, primary amide, indole, imine, and azoxy, among others. Unreacted nitrite was recovered in the filtrate fraction. The toxicities and susceptibilities to microbial or chemical degradation of the polymeric materials remain unknown.

Alkaline hydrolysis/polymerization of 2,4,6-Trinitrotoluene:  Characterization of products by 13C and 15N NMR

USGS Publications Warehouse

Thorn, Kevin A.; Thorne, Philip G.; Cox, Larry G.

2004-01-01

Alkaline hydrolysis has been investigated as a nonbiological procedure for the destruction of 2,4,6-trinitrotoluene (TNT) in explosives contaminated soils and munitions scrap. Nucleophilic substitutions of the nitro and methyl groups of TNT by hydroxide ion are the initial steps in the alkaline degradation of TNT. Potential applications of the technique include both in situ surface liming and ex situ alkaline treatment of contaminated soils. A number of laboratory studies have reported the formation of an uncharacterized polymeric material upon prolonged treatment of TNT in base. As part of an overall assessment of alkaline hydrolysis as a remediation technique, and to gain a better understanding of the chemical reactions underlying the hydrolysis/polymerization process, the soluble and precipitate fractions of polymeric material produced from the calcium hydroxide hydrolysis of unlabeled and 15N-labeled TNT were analyzed by elemental analysis and 13C and 15N nuclear magnetic resonance spectroscopy. Spectra indicated that reactions leading to polymerization included nucleophilic displacement of nitro groups by hydroxide ion, formation of ketone, carboxyl, alcohol, ether, and other aliphatic carbons, conversion of methyl groups to diphenyl methylene carbons, and recondensation of aromatic amines and reduced forms of nitrite, including ammonia and possibly hydroxylamine, into the polymer. Compared to the distribution of carbons in TNT as 14% sp3- and 86% sp2-hybridized, the precipitate fraction from hydrolysis of unlabeled TNT contained 33% sp3- and 67% sp2-hybridized carbons. The concentration of nitrogen in the precipitate was 64% of that in TNT. The 15N NMR spectra showed that, in addition to residual nitro groups, forms of nitrogen present in the filtrate and precipitate fractions include aminohydroquinone, primary amide, indole, imine, and azoxy, among others. Unreacted nitrite was recovered in the filtrate fraction. The toxicities and susceptibilities to microbial or chemical degradation of the polymeric materials remain unknown.

Advantages and drawbacks of Thiol-ene based resins for 3D-printing

NASA Astrophysics Data System (ADS)

Leonards, Holger; Engelhardt, Sascha; Hoffmann, Andreas; Pongratz, Ludwig; Schriever, Sascha; Bläsius, Jana; Wehner, Martin; Gillner, Arnold

2015-03-01

The technology of 3D printing is conquering the world and awakens the interest of many users in the most varying of applications. New formulation approaches for photo-sensitive thiol-ene resins in combination with various printing technologies, like stereolithography (SLA), projection based printing/digital light processing (DLP) or two-photon polymerization (TPP) are presented. Thiol-ene polymerizations are known for its fast and quantitative reaction and to form highly homogeneous polymer networks. As the resins are locally and temporally photo-curable the polymerization type is very promising for 3D-printing. By using suitable wavelengths, photoinitiator-free fabrication is feasible for single- and two photon induced polymerization. In this paper divinyl ethers of polyethylene glycols in combination with star-shaped tetrathiols were used to design a simple test-system for photo-curable thiol-ene resins. In order to control and improve curing depth and lateral resolution in 3D-polymerization processes, either additives in chemical formulation or process parameters can be changed. The achieved curing depth and resolution limits depend on the applied fabrication method. While two-/multiphoton induced lithography offers the possibility of micron- to sub-micron resolution it lacks in built-up speed. Hence single-photon polymerization is a fast alternative with optimization potential in sub-10-micron resolution. Absorber- and initiator free compositions were developed in order to avoid aging, yellowing and toxicity of resulting products. They can be cured with UV-laser radiation below 300 nm. The development at Fraunhofer ILT is focusing on new applications in the field of medical products and implants, technical products with respect to mechanical properties or optical properties of 3D-printed objects. Recent process results with model system (polyethylene glycol divinylether/ Pentaerithrytol tetrakis (3-mercaptopropionat), Raman measurements of polymer conversion and surface modifications using bifunctional crosslinkers are presented with advantages, drawbacks and a general outlook.

Enhancing the mechanical and in vitro performance of robocast bioglass scaffolds by polymeric coatings: Effect of polymer composition.

PubMed

Motealleh, Azadeh; Eqtesadi, Siamak; Pajares, Antonia; Miranda, Pedro

2018-08-01

The effect of different polymeric coatings, including natural and synthetic compositions, on the mechanical performance of 45S5 bioglass robocast scaffolds is systematically analyzed in this work. Fully amorphous 45S5 bioglass robocast scaffolds sintered at 550 °C were impregnated with natural (gelatin, alginate, and chitosan) and synthetic (polycaprolactone, PCL and poly-lactic acid, PLA) polymers through a dip-coating process. Mechanical enhancement provided by these coatings in terms of both compressive strength and strain energy density was evaluated. Natural polymers, in general, and chitosan, in particular, were found to produce the greater reinforcement. The effect of these coatings on the in vitro bioactivity and degradation behavior of 45S5 bioglass robocast scaffolds was also investigated through immersion tests in simulated body fluid (SBF). Coatings from natural polymers, especially chitosan, are shown to have a positive effect on the bioactivity of 45S5 bioglass, accelerating the formation of an apatite-like layer. Besides, most coating compositions reduced the degradation (weight loss) rate of the scaffold, which has a positive impact on the evolution of their mechanical properties. Copyright © 2018 Elsevier Ltd. All rights reserved.

Photoimageable composition

DOEpatents

Dentinger, Paul; Krafick, Karen L.; Simison, Kelby Liv

2005-02-22

The use of photoacid generators including an alkoxyphenylphenyliodonium salt and/or bis(t-butylphenyl)iodonium salt in a photoimageable composition helps improve resolution. Suitable photoimageable compositions includes: (a) a multifuctional polymeric epoxy resin that is dissolved in an organic solvent wherein the epoxy resin comprises oligomers of bisphenol A that is quantitatively protected by glycidyl ether and wherein the oligomers have an average functionality that ranges from about 3 to 12; and a photoacid generator comprising an alkoxyphenylphenyliodonium salt and/or bis(t-butylphenyl)iodonium salt. Preferred alkoxyphenylphenyliodonium salts include 4-octyloxyphenyl phenyliodonium hexafluoroantimonate and 4-methoxyphenyl phenyliodonium hexafluoroantimonate. The photoimageable composition is particularly suited for producing high aspect ratio microstructures.

The stability of new transparent polymeric materials: The epoxy trimethoxyboroxine system. Part 1: The preparation, characterization and curing of epoxy resins and their copolymers

NASA Technical Reports Server (NTRS)

Pearce, E.; Lin, S. C.

1981-01-01

The effects of resin composition, curing conditions fillers, and flame retardant additives on the flammability of diglycidyl ether of bisphenol-A (DGEBA) as measured by the oxygen index is examined. The oxygen index of DGEBA cured with various curing agents was between 0.198 to 0.238. Fillers and flame retardant additives can increase the oxygen index dependent on the material and the amount used. Changes in the basic cured resin properties can be anticipated with the addition of noncompatible additives. High flame resistant epoxy resins with good stability and mechanical properties are investigated.

Selective and Orthogonal Post-Polymerization Modification using Sulfur(VI) Fluoride Exchange (SuFEx) and Copper-Catalyzed Azide–Alkyne Cycloaddition (CuAAC) Reactions

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

Oakdale, James S.; Kwisnek, Luke; Fokin, Valery V.

2016-06-10

Functional polystyrenes and polyacrylamides, containing combinations of fluorosulfate, aromatic silyl ether, and azide side chains, were used as scaffolds to demonstrate the postpolymerization modification capabilities of sulfur(VI) fluoride exchange (SuFEx) and CuAAC chemistries. Fluorescent dyes bearing appropriate functional groups were sequentially attached to the backbone of the copolymers, quantitatively and selectively addressing their reactive partners. Furthermore, this combined SuFEx and CuAAC approach proved to be robust and versatile, allowing for a rare accomplishment: triple orthogonal functionalization of a copolymer under essentially ambient conditions without protecting groups.

Responsive polymer-based colloids for drug delivery and bioconversion

NASA Astrophysics Data System (ADS)

Kudina, Olena

Responsive polymer-based colloids (RPBC) are the colloidal structures containing responsive polymeric component which is able to adapt its physico-chemical properties to the environment by undergoing chemical and/or conformational changes. The goal of the dissertation is to develop and characterize several groups of RPBC with different morphological complexity and explore their potential in drug delivery and bioconversion. The role of RPBC morphology for these specific applications is discussed in details. Three groups of RPBC were fabricated: i. polymeric micelles; ii. mixed polymeric micelles; iii. hybrid polymer-inorganic particles. All fabricated RPBCs contain polymeric component in their structure. The dissertation investigates how the changes of the responsive polymeric component properties are reflected in morphologies of RPBC. The first group of RPBC, polymeric micelles, was formed by the self-assembly of amphiphilic invertible polymers (AIPs) synthesized in our group. AIPs self-assemble into invertible micellar assemblies (IMAs) in solvents of different polarity. In this work, IMAs ability to invert the structure as a response to the change in solvent polarity was demonstrated using 1H NMR spectroscopy and SANS. It was shown that the IMAs incorporate hydrophobic cargo either in the core or in the shell, depending on the chemical structure of cargo molecules. Following in vitro study demonstrates that loaded with drug (curcumin) IMAs are cytotoxic to osteosarcoma cells. Mixed polymeric micelles represent another, more complex, RPBC morphologies studied in the dissertation. Mixed micelles were fabricated from AIPs and amphiphilic oligomers synthesized from pyromellitic dianhydride, polyethylene glycol methyl ethers, and alkanols/cholesterol. The combination of selected AIP and oligomers based on cholesterol results in mixed micelles with an increased drug-loading capacity (from 10% w/w loaded curcumin in single component IMAs to 26%w/w in mixed micelles). Even more complex colloids are hybrid polymer-inorganic particles, the third RPBC group studied in dissertation. Material was designed as core--shell particles with superparamagnetic core engulfed by grafted polymer brushes. These particles were loaded with enzymes (cellulases), thus, are turned into enzymogels for cellulose bioconversion. The study demonstrates that such RPBCs can be used multiple times during hydrolysis and provide an about four-fold increase in glucose production in comparison to free enzymes.

Nitrogen-Containing Carbon Nanotube Synthesized from Polymelem and Activated Carbon Derived from Polymer Blend

NASA Astrophysics Data System (ADS)

Qin, Nan

Polymelem possesses a polymeric structure of heptazine (C6N 7) rings connected by amine bridges and our study has demonstrated that it is a promising precursor for the synthesis of nitrogen-containing carbon materials. Nitrogen-containing carbon nanotube (NCNT) was produced by pyrolyzing polymelem as a dual source of carbon and nitrogen with Raney nickel in a high pressure stainless steel cell. Activated carbon was produced from poly(ether ether ketone)/poly(ether imide) (PEEK/PEI blend) and incorporated with polymelem to enhance the hydrogen adsorption. Polymelem was successfully synthesized by pyrolyzing melamine at 450--650 °C and its structure was elucidated by 13C solid state NMR, FTIR, and XRD. The molecular weight determined by a novel LDI MS equipped with a LIFT mode illuminated that polymelem has both linear and cyclic connectivity with a degree of polymerization of 2--5 depending on the synthesis temperature. The decomposition products of polymelem were determined to be cyanoamide, dicyanoamide, and tricyanoamine. Tricyanoamine is the smallest carbon nitride molecule and has been experimentally confirmed for the first time in this study. When polymelem was decomposed in the presence of Raney nickel, homogenous NCNT with nitrogen content of ˜ 4--19 atom% was produced. A mechanism based on a detail analysis of the TEM images at different growth stages proposed that the NCNT propagated via a tip-growth mechanism originating at the nano-domains within the Raney nickel, and was accompanied with the aggregation of the nickel catalysts. Such NCNT exhibited a cup-stack wall structure paired with a compartmental feature. The nitrogen content, tube diameter and wall thickness greatly depended on synthesis conditions. The activated carbon derived from PEEK/PEI blend demonstrated a surface area up to ˜3000 m2/g, and average pore size of < 20 A. Such activated carbon exhibited a hydrogen storage capacity of up to 6.47 wt% at 40 bar, 77 K. The activated carbon has was incorporated with polymelem via a liquid penetration and a CVD method to modify its surface chemistry. The hydrogen adsorption energy of the polymelem doped activated carbon demonstrated a dramatic increase from ˜5 kJ/mol to ˜14 kJ/mol due to the higher polarizability of the polymelem.

Nanostructured hybrid hydrogels prepared by a combination of atom transfer radical polymerization and free radical polymerization

PubMed Central

Bencherif, Sidi A.; Siegwart, Daniel J.; Srinivasan, Abiraman; Horkay, Ferenc; Hollinger, Jeffrey O.; Washburn, Newell R.; Matyjaszewski, Krzysztof

2012-01-01

A new method to prepare nanostructured hybrid hydrogels by incorporating well-defined poly(oligo (ethylene oxide) monomethyl ether methacrylate) (POEO300MA) nanogels of sizes 110–120 nm into a larger three-dimensional (3D) matrix was developed for drug delivery scaffolds for tissue engineering applications. Rhodamine B isothiocyanate-labeled dextran (RITC-Dx) or fluorescein isothiocyanate-labeled dextran (FITC-Dx)-loaded POEO300MA nanogels with pendant hydroxyl groups were prepared by activators generated electron transfer atom transfer radical polymerization (AGET ATRP) in cyclohexane inverse miniemulsion. Hydroxyl-containing nanogels were functionalized with methacrylated groups to generate photoreactive nanospheres. 1H NMR spectroscopy confirmed that polymerizable nanogels were successfully incorporated covalently into 3D hyaluronic acid-glycidyl methacrylate (HAGM) hydrogels after free radical photo-polymerization (FRP). The introduction of disulfide moieties into the polymerizable groups resulted in a controlled release of nanogels from cross-linked HAGM hydrogels under a reducing environment. The effect of gel hybridization on the macroscopic properties (swelling and mechanics) was studied. It is shown that swelling and nanogel content are independent of scaffold mechanics. In-vitro assays showed the nanostructured hybrid hydrogels were cytocompatible and the GRGDS (Gly–Arg–Gly–Asp–Ser) contained in the nanogel structure promoted cell–substrate interactions within 4 days of incubation. These nanostructured hydrogels have potential as an artificial extracellular matrix (ECM) impermeable to low molecular weight biomolecules and with controlled pharmaceutical release capability. Moreover, the nanogels can control drug or biomolecule delivery, while hyaluronic acid based-hydrogels can act as a macroscopic scaffold for tissue regeneration and regulator for nanogel release. PMID:19592087

PZT/PLZT - elastomer composites with improved piezoelectric voltage coefficient

NASA Astrophysics Data System (ADS)

Harikrishnan, K.; Bavbande, D. V.; Mohan, Dhirendra; Manoharan, B.; Prasad, M. R. S.; Kalyanakrishnan, G.

2018-02-01

Lead Zirconate Titanate (PZT) and Lanthanum-modified Lead Zirconate Titanate (PLZT) ceramic sensor materials are widely used because of their excellent piezoelectric coefficients. These materials are brittle, high density and have low achievable piezoelectric voltage coefficients. The density of the sintered ceramics shall be reduced by burnable polymeric sponge method. The achievable porosity level in this case is nearly 60 - 90%. However, the porous ceramic structure with 3-3 connectivity produced by this method is very fragile in nature. The strength of the porous structure is improved with Sylgard®-184 (silicone elastomer) by vacuum impregnation method maintaining the dynamic vacuum level in the range of -650 mm Hg. The elastomer Sylgard®-184 is having low density, low dielectric constant and high compliance (as a resultant stiffness of the composites is increased). To obtain a net dipole moment, the impregnated ceramic composites were subjected to poling treatment with varying conditions of D.C. field and temperature. The properties of the poled PZT/PLZT - elastomer composites were characterized with LCR meter for measuring the dielectric constant values (k), d33 meter used for measuring piezo-electric charge coefficient values (d33) and piezo-electric voltage coefficient (g33) values which were derived from d33 values. The voltage coefficient (g33) values of these composites are increased by 10 fold as compared to the conventional solid ceramics demonstrates that it is possible to fabricate a conformable detector.

In situ formation of antimicrobial silver nanoparticles and the impregnation of hydrophobic polycaprolactone matrix for antimicrobial medical device applications.

PubMed

Tran, Phong A; Hocking, Dianna M; O'Connor, Andrea J

2015-02-01

Bacterial infection associated with medical devices remains a challenge to modern medicine as more patients are being implanted with medical devices that provide surfaces and environment for bacteria colonization. In particular, bacteria are commonly found to adhere more preferably to hydrophobic materials and many of which are used to make medical devices. Bacteria are also becoming increasingly resistant to common antibiotic treatments as a result of misuse and abuse of antibiotics. There is an urgent need to find alternatives to antibiotics in the prevention and treatment of device-associated infections world-wide. Silver nanoparticles have emerged as a promising non-drug antimicrobial agent which has shown effectiveness against a wide range of both Gram-negative and Gram-positive pathogen. However, for silver nanoparticles to be clinically useful, they must be properly incorporated into medical device materials whose wetting properties could be detrimental to not only the incorporation of the hydrophilic Ag nanoparticles but also the release of active Ag ions. This study aimed at impregnating the hydrophobic polycaprolactone (PCL) polymer, which is a FDA-approved polymeric medical device material, with hydrophilic silver nanoparticles. Furthermore, a novel approach was employed to uniformly, incorporate silver nanoparticles into the PCL matrix in situ and to improve the release of Ag ions from the matrix so as to enhance antimicrobial efficacy. Copyright © 2014. Published by Elsevier B.V.

Volatile organic compound concentrations in the South Coast Air Basin (CA) during the summers of 1995 and 1996

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

Zielinska, B.; Harshfield, G.; Fujita, E.

1997-12-31

Volatile organic compounds (VOC) were measured in California`s South Coast Air Basin (SoCAB) during the summers of 1995 and 1996 in order to determine the air quality impacts of the introduction in 1996 of California`s Phase 2 reformulated gasoline (RFG). Over 250 canister and 2,4-dinitrophenylhydrazine (DNPH)-impregnated cartridge samples were collected during each sampling campaign at four sampling sites--two source-dominated sites, a downwind receptor site, and a background site. Canister samples were analyzed for methane, speciated volatile hydrocarbons (C{sub 2}-C{sub 12}), carbon monoxide (CO), carbon dioxide (CO{sub 2}), and methyl tert-butyl ether (MTBE). DNPH were analyzed for C{sub 1}-C{sub 7} carbonylmore » compounds. This paper examines the changes in concentrations of C{sub 2}-C{sub 12} hydrocarbons in the SoCAB resulting from the introduction of Phase 2 RFG with particular emphasis on hydrocarbon species that are most affected by the reformulation.« less

Liquid-phase membrane extraction of targeted pesticides from manufacturing wastewaters in a hollow fibre contactor with feed-stream recycle.

PubMed

Đorđević, Jelena; Vladisavljević, Goran T; Trtić-Petrović, Tatjana

2017-01-01

A two-phase membrane extraction in a hollow fibre contactor with feed-stream recycle was applied to remove selected pesticides (tebufenozide, linuron, imidacloprid, acetamiprid and dimethoate) from their mixed aqueous solutions. The contactor consisted of 50 polypropylene hollow fibres impregnated with 5% tri-n-octylphosphine oxide in di-n-hexyl ether. For low-polar pesticides with log P ≥ 2 (tebufenozide and linuron), the maximum removal efficiency increased linearly from 85% to 96% with increasing the feed flow rate. The maximum removal efficiencies of more polar pesticides were significantly higher under feed recirculation (86%) than in a continuous single-pass operation (30%). It was found from the Wilson's plot that the mass transfer resistance of the liquid membrane can be neglected for low-polar pesticides. The pesticide removals from commercial formulations were similar to those from pure pesticide solutions, indicating that built-in adjuvants did not affect the extraction process.

Design, synthesis, and characterization of new phosphazene related materials, and study the structure property correlations

NASA Astrophysics Data System (ADS)

Tian, Zhicheng

The work described in this thesis is divided into three major parts, and all of which involve the exploration of the chemistry of polyphosphazenes. The first part (chapters 2 and 3) of my research is synthesis and study polyphoshazenes for biomedical applications, including polymer drug conjugates and injectable hydrogels for drug or biomolecule delivery. The second part (chapters 4 and 5) focuses on the synthesis of several organic/inorganic hybrid polymeric structures, such as diblock, star, brush and palm tree copolymers using living cationic polymerization and atom transfer radical polymerization techniques. The last part (chapters 6 and 7) is about exploratory synthesis of new polymeric structures with fluorinated side groups or cycloaliphatic side groups, and the study of new structure property relationships. Chapter 1 is an outline of the fundamental concepts for polymeric materials, as such the history, important definitions, and some introductory material for to polymer chemistry and physics. The chemistry and applications of phopshazenes is also briefly described. Chapter 2 is a description of the design, synthesis, and characterization of development of a new class of polymer drug conjugate materials based on biodegradable polyphosphazenes and antibiotics. Poly(dichlorophosphazene), synthesized by a thermal ring opening polymerization, was reacted with up to 25 mol% of ciprofloxacin or norfloxacin and three different amino acid esters (glycine, alanine, or phenylalanine) as cosubstituents via macromolecular substitutions. Nano/microfibers of several selected polymers were prepared by an electrospinning technique. Chapter 3 is concerned with the development of a class of injectable and biodegradable hydrogels based on water-soluble poly(organophosphazenes) containing oligo(ethylene glycol) methyl ethers and glycine ethyl esters. The hydrogels can be obtained by mixing alpha-cyclodextrin aqueous solution and poly(organophosphazenes) aqueous solution in various gelation rates depending on the polymer structures and the concentrations. The rheological measurements of the supramolecular hydrogels indicate a fast gelation process and flowable character under a large stain. Chapter 4 outlines the preparation of a number of amphiphilic diblock copolymers based on poly[bis(trifluoroethoxy)phosphazene] (TFE) as the hydrophobic block and poly(dimethylaminoethylmethacrylate) (PDMAEMA) as the hydrophilic block. The TFE block was synthesized first by the controlled living cationic polymerization of a phosphoranimine, followed by replacement of all the chlorine atoms using sodium trifluoroethoxide. To allow for the growth of the PDMAEMA block, 3-azidopropyl-2-bromo-2-methylpropanoate, an atom transfer radical polymerization (ATRP) initiator, was grafted onto the endcap of the TFE block via the 'click' reaction followed by the ATRP of 2-(dimethylamino)ethyl methacrylate (DMAEMA). Chapter 5 is a report on the design and assembly of polyphosphazene materials based on the non-covalent "host--guest" interactions either at the terminus of the polymeric main-chains or the pendant side-chains. The supramolecular interaction at the main chain terminus was used to produce amphiphilic palm-tree like pseudo-block copolymers via host-guest interactions between an adamantane end-functionalized polyphosphazene and a 4-armed beta-cyclodextrin (beta-CD) initiated poly[poly(ethylene glycol) methyl ether methacylate] branched-star type polymer. The formation of micelles of the obtained amphiphiles was analyzed by fluorescence technique, dynamic light scattering, transmission electron microscopy, and atomic force microscopy. Chapter 6 is an investigation of the influence of bulky fluoroalkoxy side groups on the properties of polyphosphazenes. A new series of mixed-substituent high polymeric poly(fluoroalkoxyphosphazenes) containing trifluoroethoxy and branched fluoroalkoxy side groups was synthesized and characterized by NMR and GPC methods. These polymers contained 19--29 mol% of di-branched hexafluoropropoxy groups or 4mol% of tri-branched tert-perfluorobutoxy groups, which serve as regio-irregularities to reduce the macromolecular microcrystallinity. The structure--property correlations of the polymers were then analyzed and interpreted by several techniques: specifically by the thermal behavior by DSC and TGA methods, the crystallinity by wide-angle X-ray diffraction, and the surface hydrophobicity/oleophobicity by contact angle measurements. (Abstract shortened by UMI.). Chapter 7 is an outline of the exploratory synthesis of a new series of phosphazene model cyclic trimers and single- and mixed- substituent high polymers containing cyclic aliphatic rings, --CnH2n-1 (where n = 4--8). The cylco-aliphatic side group containing phosphazenes expand the structural and property boundaries of phosphazene chemistry, and suggest additional approaches for studying slow macromolecular substitution reactions and substituent exchange reactions.

A novel anti-influenza copper oxide containing respiratory face mask.

PubMed

Borkow, Gadi; Zhou, Steve S; Page, Tom; Gabbay, Jeffrey

2010-06-25

Protective respiratory face masks protect the nose and mouth of the wearer from vapor drops carrying viruses or other infectious pathogens. However, incorrect use and disposal may actually increase the risk of pathogen transmission, rather than reduce it, especially when masks are used by non-professionals such as the lay public. Copper oxide displays potent antiviral properties. A platform technology has been developed that permanently introduces copper oxide into polymeric materials, conferring them with potent biocidal properties. We demonstrate that impregnation of copper oxide into respiratory protective face masks endows them with potent biocidal properties in addition to their inherent filtration properties. Both control and copper oxide impregnated masks filtered above 99.85% of aerosolized viruses when challenged with 5.66+/-0.51 and 6.17+/-0.37 log(10)TCID(50) of human influenza A virus (H1N1) and avian influenza virus (H9N2), respectively, under simulated breathing conditions (28.3 L/min). Importantly, no infectious human influenza A viral titers were recovered from the copper oxide containing masks within 30 minutes (< or = 0.88 log(10)TCID(50)), while 4.67+/-1.35 log(10)TCID(50) were recovered from the control masks. Similarly, the infectious avian influenza titers recovered from the copper oxide containing masks were < or = 0.97+/-0.01 log(10)TCID(50) and from the control masks 5.03+/-0.54 log(10)TCID(50). The copper oxide containing masks successfully passed Bacterial Filtration Efficacy, Differential Pressure, Latex Particle Challenge, and Resistance to Penetration by Synthetic Blood tests designed to test the filtration properties of face masks in accordance with the European EN 14683:2005 and NIOSH N95 standards. Impregnation of copper oxide into respiratory protective face masks endows them with potent anti-influenza biocidal properties without altering their physical barrier properties. The use of biocidal masks may significantly reduce the risk of hand or environmental contamination, and thereby subsequent infection, due to improper handling and disposal of the masks.

The effect of two fibre impregnation methods on the cytotoxicity of a glass and carbon fibre-reinforced acrylic resin denture base material on oral epithelial cells and fibroblasts.

PubMed

Sipahi, Cumhur; Ozen, Julide; Ural, A Ugur; Dalkiz, Mehmet; Beydemir, Bedri

2006-09-01

Acrylic resin dentures may have cytotoxic effects on oral soft tissues. However, there is sparse data about the cytotoxic effect of fibre-reinforced acrylic resin denture base materials. The purpose of this in vitro study was to determine the effect of two fibre impregnation methods on the cytotoxicity of a glass and carbon fibre-reinforced heat-polymerized acrylic resin denture base material on oral epithelial cells and fibroblasts. One hundred acrylic resin discs were assigned to five experimental groups (n = 20). One of the groups did not include any fibre. Two groups consisted of silane and monomer treated glass fibres (Vetrolex) impregnated into acrylic resin (QC-20) discs. The other two groups consisted of silane and monomer treated carbon fibres (Type Tenox J, HTA). Untreated cell culture was used as positive control. The human oral epithelial cell line and buccal fibroblast cultures were exposed to test specimens. The cytotoxicity of the test materials was determined by succinic dehydrogenase activity (MTT method) after 24 and 72 h exposures. Data were analysed with a statistical software program (SPSSFW, 9.0). A one-way analysis of variance (anova) test and Bonferroni test were used for the comparisons between the groups. All statistical tests were performed at the 0.95 confidence level (P < 0.05). After 24 and 72 h incubation, cell viability percentages of all experimental groups showed significant decrease according to the positive control cell culture. Fibroblastic cell viability percentages of silane and monomer treated fibre-reinforced groups were lower than the unreinforced group. Cell viability of monomer-treated groups displayed the lowest percentages. Elapsed incubation time decreased epithelial cell viability in silane-treated groups. Fibroblastic cell viability was not influenced by elapsed time except the unreinforced group.

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.

Quaternized polymeric microgels as metal free catalyst for H2 production from the methanolysis of sodium borohydride

NASA Astrophysics Data System (ADS)

Sahiner, Nurettin; Sengel, Sultan Butun

2016-12-01

Polymeric microgels derived from tris(2-amino ethyl)amine (TAEA) and glycerol diglycidyl ether as p(TAEA-co-GDE) via microemulsion polymerization techniques are protonated by 0.5 M HCl treatment as p(TAEA-co-GDE)-HCl). These microgels are then exposed to anion exchange reactions with differ ionic liquid forming salts, such as potassium thiocyanate (PTC), sodium dicyanamide (SDCA), ammonium hexafluorophosphate (AHFP), and sodium tetrafluoroborate (STFB) in aqueous medium for the preparation of p(TAEA-co-GDE) based ionic liquid colloidal microgels. These anions exchanged p(TAEA-co-GDE) ionic liquid colloids (ILCs) are directly used as catalyst for hydrogen (H2) generation from the methanol solution of sodium borohydride (NaBH4). Various parameters affecting the H2 production rate such as the catalyst types, NaBH4 amount, and the temperature are investigated. It is found that the methanolysis of NaBH4 catalyzed by p(TAEA-co-GDE)-HCl obeys the first order reaction kinetic. The activation energy, enthalpy and entropy of the protonated p(TAEA-co-GDE) microgels are calculated and found as the 30.37 kJ mol-1, 27.96 kJ mol-1, and -148.08 J mol-1 K-1, respectively. Furthermore, the hydrogen generation rate of 3018 mL min-1 g-1 catalyzed by p(TAEA-co-GDE)-HCl catalyst is attained.

Covalent Incorporation of Ionic Liquid into Ion-Conductive Networks via Thiol-Ene Photopolymerization.

PubMed

Tibbits, Andrew C; Yan, Yushan S; Kloxin, Christopher J

2017-07-01

Ene-functionalized ionic liquids with a range of different cationic groups and counteranions react stoichiometrically within a tetrathiol-divinyl ether formulation within 20 minutes to form thiol-ene polymers with measurable ionic conductivities via a photoinitiated polymerization and crosslinking reaction. Dynamic mechanical analysis indicates that these networks are more spatially heterogeneous and possess higher glass transition temperatures (T g ) compared with thiol-ene formulations without charge. While tuning the molar content of ionic liquid monomer is one method for adjusting the crosslink and charge densities of the thiol-ene polymeric ionic liquid networks, the presence of cation-anion interactions also plays a critical role in dictating the thermomechanical and conductive properties. Particularly, while cationic structure effects are not significant on the polymer properties, the use of a weakly coordinating hydrophobic anion (bistriflimide) instead of bromide-based networks results in an apparent decrease in hydrated ion conductivity (7.4 to 1.5 mS cm -1 ) and T g (-9.6 to -17.8 °C). © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Waterborne Polyurethane Coatings with Covalently Linked Black Dye Sudan Black B

PubMed Central

Sun, Wei; Xu, Haiyan; Xu, Fei

2017-01-01

Colored waterborne polyurethanes have been widely used in paintings, leathers, textiles, and coatings. Here, a series of black waterborne polyurethanes (WPUs) with different ratios of black dye, Sudan Black B (SDB), were prepared by step-growth polymerization. WPU emulsions as obtained exhibit low particle sizes and remarkable storage stability at the same time. At different dye loadings, essential structural, statistical and thermal properties are characterized. FTIR (fourier transform infrared) spectra indicate that SDB is covalently linked into waterborne polyurethane chains. All of the WPUs with covalently linked SDB show better color fastness and resistance of thermal migration than those with SDB mixed physically. Besides, WPUs incorporated SDB covalently with different polymeric diols, polytetramethylene ether glycol (PTMG), polypropylene glycol (PPG), poly-1, 4-butylene adipate glycol (PBA) and polycaprolactone glycol (PCL), were prepared to obtain different properties to cater to a variety of practical demands. By a spraying method, the black WPUs can be directly used as metal coatings without complex dyeing process by simply mixing coating additive and other waterborne resins, which exhibit excellent coating performance. PMID:29143785

Synthesis and characterization of polyphosphazene electrolytes including cyclic ether side groups

NASA Astrophysics Data System (ADS)

Fiedler, Carsten; Luerssen, Bjoern; Lucht, Brett; Janek, Juergen

2018-04-01

This paper presents the synthesis and detailed characterization of two polyphosphazene based polymers, including different cyclic ether side groups. The final polymers were obtained by a well-known method employing a living cationic polymerization and subsequent nucleophilic substitution. The synthesized polymers Poly [(1,3-dioxane-5-oxy) (1,3-dioxolane-4-methoxy)phosphazene] (DOPP) and Poly[bis(2-Tetrahydro-3-furanoxy)phosphazene] (THFPP) were mixed with varied amounts of lithium bis(trifluoromethane)sulfonamide (LiTFSI) and the interactions between the salt and the polymer chains were studied by Fourier transform infrared (FT-IR) and differential scanning calorimetry (DSC) measurements. Electrochemical characterization was performed by electrochemical impedance spectroscopy (EIS) and direct current polarization in the temperature range of 20-60 °C. These measurements were utilized to calculate the lithium transference number (t+), the lithium conductivity (σ) and its activation energy in order to elucidate the lithium transport behavior. Relatively high lithium transference numbers of 0.6 (DOPP) and 0.7 (THFPP) at 60 °C are found and reveal maximum lithium conductivities of 2.8·10-6 Sṡcm-1 and 9.0·10-7 Sṡcm-1 for DOPP and THFPP at 60 °C, respectively.

Fluorinated poly(ether sulfone) ionomers with disulfonated naphthyl pendants for proton exchange membrane applications

NASA Astrophysics Data System (ADS)

Hu, Zhaoxia; Lu, Yao; Zhang, Xulve; Yan, Xiaobo; Li, Na; Chen, Shouwen

2018-06-01

Proton exchange membranes based on fluorinated poly(ether sulfone)s with disulfonated naphthyl pendants (sSPFES) have been successfully prepared by post functionalization through polymeric SNAr reaction. Copolymer structure was confirmed by H-nuclear magnetic resonance spectroscopy and Fourier transform infrared spectroscopy, the physico-chemical properties of the sSPFES membranes were evaluated by thermogravimetric analysis, gel permeation chromatography, electro-chemical impedance spectroscopy, atomic force microscopy, Fenton, water-swelling and fuel cell test. The pendant grafting degree was controlled by varying the feeding amount of the disulfonaphthols, resulting in the ion exchange capacity about 1.28-1.73 mmol/g. The obtained sSPFES membranes were thermal stable, mechanical ductile, and exhibited dimensional change less than 17%, water uptake below 70%, and proton conductivity as high as 0.17-0.28 S/cm at 90°C in water. In a single H2/O2 fuel cell test at 80°C, the sSPFES-B-3.2 membrane (1.61 mmol/g) showed the maximum power output of 593-658 mW/cm2 at 60%-80% relative humidity, indicating their rather promising potential for fuel cell applications.

Understanding Side Reactions in K–O 2 Batteries for Improved Cycle Life

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

Ren, Xiaodi; Lau, Kah Chun; Yu, Mingzhe

2014-10-20

Superoxide based metal-air (or metal-oxygen) batteries, including potassium and sodium-oxygen batteries, have emerged as promising alternative chemistries in the metal-air battery family because of much improved round-trip efficiencies (>90%). In order to improve the cycle life of these batteries, it is crucial to understand and control the side reactions between the electrodes and the electrolyte. For potassium-oxygen batteries using ether-based electrolytes, the side reactions on the potassium anode have been identified as the main cause of battery failure. The composition of the side products formed on the anode, including some reaction intermediates, have been identified and quantified. Combined experimental studiesmore » and density functional theory (DFT) calculations show the side reactions are likely driven by the interaction of potassium with ether molecules and the crossover of oxygen from the cathode. To inhibit these side reactions, the incorporation of a polymeric potassium ion selective membrane (Nafion-K+) as a battery separator is demonstrated that significantly improves the battery cycle life. The K-O-2 battery with the Nafion-K+ separator can be discharged and charged for more than 40 cycles without increases in charging overpotential.« less

Fluorinated poly(ether sulfone) ionomers with disulfonated naphthyl pendants for proton exchange membrane applications

NASA Astrophysics Data System (ADS)

Hu, Zhaoxia; Lu, Yao; Zhang, Xulve; Yan, Xiaobo; Li, Na; Chen, Shouwen

2018-05-01

Proton exchange membranes based on fluorinated poly(ether sulfone)s with disulfonated naphthyl pendants (sSPFES) have been successfully prepared by post functionalization through polymeric SNAr reaction. Copolymer structure was confirmed by H-nuclear magnetic resonance spectroscopy and Fourier transform infrared spectroscopy, the physico-chemical properties of the sSPFES membranes were evaluated by thermogravimetric analysis, gel permeation chromatography, electro-chemical impedance spectroscopy, atomic force microscopy, Fenton, water-swelling and fuel cell test. The pendant grafting degree was controlled by varying the feeding amount of the disulfonaphthols, resulting in the ion exchange capacity about 1.28-1.73 mmol/g. The obtained sSPFES membranes were thermal stable, mechanical ductile, and exhibited dimensional change less than 17%, water uptake below 70%, and proton conductivity as high as 0.17-0.28 S/cm at 90°C in water. In a single H2/O2 fuel cell test at 80°C, the sSPFES-B-3.2 membrane (1.61 mmol/g) showed the maximum power output of 593-658 mW/cm2 at 60%-80% relative humidity, indicating their rather promising potential for fuel cell applications.

Room-Temperature Performance of Poly(Ethylene Ether Carbonate)-Based Solid Polymer Electrolytes for All-Solid-State Lithium Batteries.

PubMed

Jung, Yun-Chae; Park, Myung-Soo; Kim, Duck-Hyun; Ue, Makoto; Eftekhari, Ali; Kim, Dong-Won

2017-12-13

Amorphous poly(ethylene ether carbonate) (PEEC), which is a copolymer of ethylene oxide and ethylene carbonate, was synthesized by ring-opening polymerization of ethylene carbonate. This route overcame the common issue of low conductivity of poly(ethylene oxide)(PEO)-based solid polymer electrolytes at low temperatures, and thus the solid polymer electrolyte could be successfully employed at the room temperature. Introducing the ethylene carbonate units into PEEC improved the ionic conductivity, electrochemical stability and lithium transference number compared with PEO. A cross-linked solid polymer electrolyte was synthesized by photo cross-linking reaction using PEEC and tetraethyleneglycol diacrylate as a cross-linking agent, in the form of a flexible thin film. The solid-state Li/LiNi 0.6 Co 0.2 Mn 0.2 O 2 cell assembled with solid polymer electrolyte based on cross-linked PEEC delivered a high initial discharge capacity of 141.4 mAh g -1 and exhibited good capacity retention at room temperature. These results demonstrate the feasibility of using this solid polymer electrolyte in all-solid-state lithium batteries that can operate at ambient temperatures.

New monomers for high performance polymers

NASA Technical Reports Server (NTRS)

Gratz, Roy F.

1993-01-01

This laboratory has been concerned with the development of new polymeric materials with high thermo-oxidative stability for use in the aerospace and electronics industries. Currently, there is special emphasis on developing matrix resins and composites for the high speed civil transport (HSCT) program. This application requires polymers that have service lifetimes of 60,000 hr at 350 F (177 C) and that are readily processible into void-free composites, preferably by melt-flow or powder techniques that avoid the use of high boiling solvents. Recent work has focused on copolymers which have thermally stable imide groups separated by flexible arylene ether linkages, some with trifluoromethyl groups attached to the aromatic rings. The presence of trifluoromethyl groups in monomers and polymers often improves their solubility and processibility. The goal of this research was to synthesize several new monomers containing pendant trifluoromethyl groups and to incorporate these monomers into new imide/arylene ether copolymers. Initially, work was begun on the synthesis of three target compounds. The first two, 3,5-dihydroxybenzo trifluoride and 3-amino 5-hydroxybenzo trifluoride, are intermediates in the synthesis of more complex monomers. The third, 3,5-bis (3-amino-phenoxy) benzotrifluoride, is an interesting diamine that could be incorporated into a polyimide directly.

Influence of Solvent on the Drug-Loading Process of Amphiphilic Nanogel Star Polymers.

PubMed

Carr, Amber C; Piunova, Victoria A; Maarof, Hasmerya; Rice, Julia E; Swope, William C

2018-05-31

We present an all-atom molecular dynamics study of the effect of a range of organic solvents (dichloromethane, diethyl ether, toluene, methanol, dimethyl sulfoxide, and tetrahydrofuran) on the conformations of a nanogel star polymeric nanoparticle with solvophobic and solvophilic structural elements. These nanoparticles are of particular interest for drug delivery applications. As drug loading generally takes place in an organic solvent, this work serves to provide insight into the factors controlling the early steps of that process. Our work suggests that nanoparticle conformational structure is highly sensitive to the choice of solvent, providing avenues for further study as well as predictions for both computational and experimental explorations of the drug-loading process. Our findings suggest that when used in the drug-loading process, dichloromethane, tetrahydrofuran, and toluene allow for a more extensive and increased drug-loading into the interior of nanogel star polymers of the composition studied here. In contrast, methanol is more likely to support shallow or surface loading and, consequently, faster drug release rates. Finally, diethyl ether should not work in a formulation process since none of the regions of the nanogel star polymer appear to be sufficiently solvated by it.

Adverse eff ects of polymeric nanoparticle poly(ethylene glycol)- block-polylactide methyl ether (PEG-b-PLA) on steroid hormone secretion by porcine granulosa cells.

PubMed

Scsukova, Sona; Bujnakova, Mlynarcikova A; Kiss, A; Rollerova, E

2017-04-25

Development of nanoparticles (NPs) for biomedical applications, including medical imaging and drug delivery, is currently undergoing a dramatic expansion. Diverse effects of different type NPs relating to mammalian reproductive tissues have been demonstrated. Th e objective of this study was to explore the in vitro effects of polymeric nanoparticle poly(ethylene glycol)-blockpolylactide methyl ether (PEG-b-PLA NPs) on functional state and viability of ovarian granulosa cells (GCs), which play an important role in maintaining ovarian function and female fertility. The GCs isolated from porcine ovarian follicles were incubated with the different concentrations of PEG-b-PLA NPs (PEG average Mn=350 g/mol and PLA average Mn=1000 g/mol; 0.2-100 μg/ml) or poly(ethylene glycol) with an average molecular weight of 300 (PEG-300; 0.2- 40 mg/ml) in the presence or absence of stimulators, follicle-stimulating hormone (FSH; 1 μg/ml), androstenedione (100 nM), forskolin (10 μM) or 8Br-cAMP (100 μM), for different time periods (24, 48, 72 h). At the end of the incubation, progesterone and estradiol levels produced by GCs were measured in the culture media by radioimmunoassay. Th e viability of GCs was determined by the method using a colorimetric assay with MTT. Treatment of GCs with PEG-b-PLA NPs induced a significant decrease in basal as well as FSH-stimulated progesterone secretion above the concentration of 20 and 4 μg/ml, respectively. Moreover, PEG-b-PLA NPs reduced forskolin-stimulated, but not cAMP-stimulated progesterone production by GCs. A dose-dependent inhibition of androstenedione-stimulated estradiol release by GCs was found by the action of PEG-b-PLA NPs. Incubation of GCs with PEG-300 significantly inhibited basal as well as FSH-stimulated progesterone secretion above the concentration of 40 mg/ml. PEG-b-PLA NPs and PEG-300 significantly reduced the viability of GCs at the highest tested concentrations (100 μg/ml and 40 mg/ml, respectively). The obtained results indicate that polymeric NPs PEG-b-PLA might induce alterations in steroid hormone production by ovarian GCs and thereby could modify reproductive functions.

High-Performance Polymers Having Low Melt Viscosities

NASA Technical Reports Server (NTRS)

Jensen, Brian J.

2005-01-01

High-performance polymers that have improved processing characteristics, and a method of making them, have been invented. One of the improved characteristics is low (relative to corresponding prior polymers) melt viscosities at given temperatures. This characteristic makes it possible to utilize such processes as resin-transfer molding and resin-film infusion and to perform autoclave processing at lower temperatures and/or pressures. Another improved characteristic is larger processing windows that is, longer times at low viscosities. Other improved characteristics include increased solubility of uncured polymer precursors that contain reactive groups, greater densities of cross-links in cured polymers, improved mechanical properties of the cured polymers, and greater resistance of the cured polymers to chemical attack. The invention is particularly applicable to poly(arylene ether)s [PAEs] and polyimides [PIs] that are useful as adhesives, matrices of composite materials, moldings, films, and coatings. PAEs and PIs synthesized according to the invention comprise mixtures of branched, linear, and star-shaped molecules. The monomers of these polymers can be capped with either reactive end groups to obtain thermosets or nonreactive end groups to obtain thermoplastics. The synthesis of a polymeric mixture according to the invention involves the use of a small amount of a trifunctional monomer. In the case of a PAE, the trifunctional monomer is a trihydroxy- containing compound for example, 1,3,5-trihydroxybenzene (THB). In the case of a PI, the trifunctional monomer is a triamine for example, triamino pyrimidine or melamine. In addition to the aforementioned trifunctional monomer, one uses the difunctional monomers of the conventional formulation of the polymer in question (see figure). In cases of nonreactive end caps, the polymeric mixtures of the invention have melt viscosities and melting temperatures lower than those of the corresponding linear polymers of equal molecular weights. The lower melting temperatures and melt viscosities provide larger processing windows. In cases of reactive end caps, the polymeric mixtures of the invention have lower melt viscosities before curing and the higher cross-link densities after curing (where branching in the uncured systems would become cross-links in the cured systems), relative to the corresponding linear polymers of equal molecular weights. The greater cross-link densities afford increased resistance to chemical attack and improved mechanical properties.

In-depth analysis of switchable glycerol based polymeric coatings for cell sheet engineering.

PubMed

Becherer, Tobias; Heinen, Silke; Wei, Qiang; Haag, Rainer; Weinhart, Marie

2015-10-01

Scaffold-free cell sheet engineering using thermoresponsive substrates provides a promising alternative to conventional tissue engineering which in general employs biodegradable scaffold materials. We have previously developed a thermoresponsive coating with glycerol based linear copolymers that enables gentle harvesting of entire cell sheets. In this article we present an in-depth analysis of these thermoresponsive linear polyglycidyl ethers and their performance as coating for substrates in cell culture in comparison with commercially available poly(N-isopropylacrylamide) (PNIPAM) coated culture dishes. A series of copolymers of glycidyl methyl ether (GME) and glycidyl ethyl ether (EGE) was prepared in order to study their thermoresponsive properties in solution and on the surface with respect to the comonomer ratio. In both cases, when grafted to planar surfaces or spherical nanoparticles, the applied thermoresponsive polyglycerol coatings render the respective surfaces switchable. Protein adsorption experiments on copolymer coated planar surfaces with surface plasmon resonance (SPR) spectroscopy reveal the ability of the tested thermoresponsive coatings to be switched between highly protein resistant and adsorptive states. Cell culture experiments demonstrate that these thermoresponsive coatings allow for adhesion and proliferation of NIH 3T3 fibroblasts comparable to TCPS and faster than on PNIPAM substrates. Temperature triggered detachment of complete cell sheets from copolymer coated substrates was accomplished within minutes while maintaining high viability of the harvested cells. Thus such glycerol based copolymers present a promising alternative to PNIPAM as a thermoresponsive coating of cell culture substrates. Copyright © 2015 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Nanocomposites Derived from Carbon Nanofibers and a Hyperbranched Poly(Ether-Ketone): In Situ Polymerization, Chain-End Modification, and Properties (Preprint)

DTIC Science & Technology

2007-05-01

and Soxhlet - extracted with water for three days and methanol for three more days. It was then dried over P2O5 under reduced pressure at 120 °C...for 72 h to give the product in quantitative yield . Anal. Calcd. for C16.39H8O4: C, 73.22%; 6 H, 2.98%; O, 23.81%. Found: C, 72.94%; H, 3.12%; O...HBP-PEK)-g-VGCNF, 3e, to afford 0.47 (94% yield based on initial amount) of a black solid. Found: C, 98.66%; H, 0.93%; N, ɘ.20%; O, ɘ.10

Thermoswitchable Janus Gold Nanoparticles with Stimuli-Responsive Hydrophilic Polymer Brushes.

PubMed

Niu, Xiaoqin; Ran, Fen; Chen, Limei; Lu, Gabriella Jia-En; Hu, Peiguang; Deming, Christopher P; Peng, Yi; Rojas-Andrade, Mauricio D; Chen, Shaowei

2016-05-03

Well-defined thermoswitchable Janus gold nanoparticles with stimuli-responsive hydrophilic polymer brushes were fabricated by combining ligand exchange reactions and the Langmuir technique. Stimuli-responsive polydi(ethylene glycol) methyl ether methacrylate was prepared by addition-fragmentation chain-transfer polymerization. The polymer brushes were then anchored onto the nanoparticle surface by interfacial ligand exchange reactions with hexanethiolate-protected gold nanoparticles, leading to the formation of a hydrophilic (polymer) hemisphere and a hydrophobic (hexanethiolate) one. The resulting Janus nanoparticles showed temperature-switchable wettability, hydrophobicity at high temperatures, and hydrophilicity at low temperatures, due to thermally induced conformational transition of the polymer ligands. The results further highlight the importance of interfacial engineering in the deliberate functionalization of nanoparticle materials.

Defining an optimal surface chemistry for pluripotent stem cell culture in 2D and 3D

NASA Astrophysics Data System (ADS)

Zonca, Michael R., Jr.

Surface chemistry is critical for growing pluripotent stem cells in an undifferentiated state. There is great potential to engineer the surface chemistry at the nanoscale level to regulate stem cell adhesion. However, the challenge is to identify the optimal surface chemistry of the substrata for ES cell attachment and maintenance. Using a high-throughput polymerization and screening platform, a chemically defined, synthetic polymer grafted coating that supports strong attachment and high expansion capacity of pluripotent stem cells has been discovered using mouse embryonic stem (ES) cells as a model system. This optimal substrate, N-[3-(Dimethylamino)propyl] methacrylamide (DMAPMA) that is grafted on 2D synthetic poly(ether sulfone) (PES) membrane, sustains the self-renewal of ES cells (up to 7 passages). DMAPMA supports cell attachment of ES cells through integrin beta1 in a RGD-independent manner and is similar to another recently reported polymer surface. Next, DMAPMA has been able to be transferred to 3D by grafting to synthetic, polymeric, PES fibrous matrices through both photo-induced and plasma-induced polymerization. These 3D modified fibers exhibited higher cell proliferation and greater expression of pluripotency markers of mouse ES cells than 2D PES membranes. Our results indicated that desirable surfaces in 2D can be scaled to 3D and that both surface chemistry and structural dimension strongly influence the growth and differentiation of pluripotent stem cells. Lastly, the feasibility of incorporating DMAPMA into a widely used natural polymer, alginate, has been tested. Novel adhesive alginate hydrogels have been successfully synthesized by either direct polymerization of DMAPMA and methacrylic acid blended with alginate, or photo-induced DMAPMA polymerization on alginate nanofibrous hydrogels. In particular, DMAPMA-coated alginate hydrogels support strong ES cell attachment, exhibiting a concentration dependency of DMAPMA. This research provides a new avenue for stem cell culture and maintenance using an optimal organic-based chemistry.

Versatile and Rapid Postfunctionalization from Cyclodextrin Modified Host Polymeric Membrane Substrate.

PubMed

Deng, Jie; Liu, Xinyue; Zhang, Shuqing; Cheng, Chong; Nie, Chuanxiong; Zhao, Changsheng

2015-09-08

Surface modification has long been of great interest to impart desired functionalities to the bioimplants. However, due to the limitations of recent technologies in surface modification, it is highly desirable to explore novel protocols, which can advantageously and efficiently endow the inert material surfaces with versatile biofunctionalities. Herein, to achieve versatile and rapid postfunctionalization of polymeric membrane, we demonstrate a new strategy for the fabrication of β-cyclodextrin (β-CD) modified host membrane substrate that can recognize a series of well-designed guest macromolecules. The surface assembly procedure was driven by the host-guest interaction between adamantane (Ad) and β-CD. β-CD immobilized host membrane was fabricated via two steps: (1) epoxy groups enriched poly(ether sulfone) (PES) membrane was first prepared via in situ cross-linking polymerization and subsequently phase separation; (2) mono-6-deoxy-6-ethylenediamine-β-CD (EDA-β-CD) was then anchored onto the surface of the epoxy functionalized PES membrane to obtain PES-CD. Subsequently, three types of Ad-terminated polymers, including Ad-poly(styrenesulfonate-co-sodium acrylate) (Ad-PSA), Ad-methoxypoly(ethylene glycol) (Ad-PEG), and Ad-poly(methyl chloride-quaternized 2-(dimethylamino)ethyl methacrylate (Ad-PMT), were separately assembled onto the β-CD immobilized surfaces to endow the membranes with anticoagulant, antifouling, and antibacterial capability, respectively. Activated partial thromboplastin time (APTT), thrombin time (TT), and prothrombin time (PT) measurements were carried out to explore the anticoagulant activity. The antifouling capability was evaluated via protein adsorption and platelet adhesion measurements. Moreover, Staphyllococcous aureus (S. aureus) was selected as model bacteria to evaluate the antibacterial ability of the functionalized membranes. The results indicated that well-regulated blood compatibility, antifouling capability, and bactericidal activity could be achieved by the proposed rapid postfunctionalization on polymeric membranes. This approach of versatile and rapid postfunctionalization is promising for the preparation of multifunctional polymeric membrane materials to meet with various demands for the further applications.

Exposure to methylhexahydrophthalic anhydride (MHHPA) in two workplaces of the electric industry.

PubMed

Pfäffli, Pirkko; Hämeilä, Mervi; Riala, Riitta; Tornaeus, Jarkko; Wirmoila, Ritva

2004-04-01

Methylhexahydrophthalic anhydride (MHHPA) is a hardener for hot-cured epoxy resins employed as insulators in the electric industry. MHHPA has only been measured as an ingredient with other alicyclic anhydrides, albeit there are also large processes which use only MHHPA. We collected MHHPA vapour in a set of devices: Teflon filter, glass spiral, TenaxTA tube connected consecutively together. Elution was performed with a solvent mixture of methyl-tert-butyl ether (70%), acetonitrile (30%), and acetic anhydride (0.5%). By capillary GC-ECD, the regression was linear (0.9994) in the practical low concentration range of 0.04-1 microg ml(-1) being equal to 0.001-0.035 mg m(-3) in 30 l of air. The exposure was measured in two factories manufacturing electric appliances. The assembled objects were first impregnated with a liquid epoxy/hardener mixture, and then the resin hardened at elevated temperature. In condenser manufacturing, the operators' 8 h exposure ranged from 0.068 to 0.118 mg m(-3), and the short-term exposure was during operation at ovens mean 1.90 mg m(-3). The impregnation of coiled resistors and transfer of them to ovens caused the worst exposures, short-term mean 3.846 mg m(-3) and long-term mean 2.191 mg m(-3). During the 'baking', the ovens were closed and evacuated, but when the hot objects were moved out of the ovens, they continued during chilling to emit MHHPA, mean 0.366 mg m(-3). In the adjacent areas, assembling, control rooms, offices, the exposure was still significant, 0.017-0.043 mg m(3), due to leaks from the high exposure areas. Mechanical general ventilation and local exhausts were functioning. Respirators were available for short supervising of the hot equipment.

Polypyrrole electrodes doped with sulfanilic acid azochromotrop for electrochemical supercapacitors

NASA Astrophysics Data System (ADS)

Chen, S.; Zhitomirsky, I.

2013-12-01

In this work we demonstrate the feasibility of deposition of polypyrrole (PPy) films by electropolymerization on stainless steel substrates and fabrication of PPy powders by chemical polymerization using sulfanilic acid azochromotrop (SPADNS) as a new anionic dopant. The problem of low adhesion of PPy films to stainless steel substrates is addressed by the use of SPADNS, which exhibits chelating properties, promoting film formation. The use of fine particles, prepared by the chemical polymerization method, allows impregnation of Ni foams and fabrication of porous electrodes with high materials loading for electrochemical supercapacitors (ES). PPy films and Ni foam based PPy electrodes show capacitive behaviour in Na2SO4 electrolyte. The electron microscopy studies, impedance spectroscopy data and analysis of the SPADNS structure provide an insight into the factors, controlling capacitive behaviour. The Ni foam based electrodes offer advantages of improved capacitive behaviour at high materials loadings and good cycling stability. The area normalized and volume normalized specific capacitances are as high as 5.43 F cm-2 and 93.6 F cm-3, respectively, for materials loading of 35.4 mg cm-2. The capacitance retention of Ni foam based electrodes is 91.5% after 1000 cycles. The Ni foam based PPy electrodes are promising for application in ES.

Towards the preparation of realistic model Ziegler-Natta catalysts: XPS study of the MgCl 2/TiCl 4 interaction with flat SiO 2/Si(1 0 0)

NASA Astrophysics Data System (ADS)

Siokou, Angeliki; Ntais, Spyridon

2003-08-01

Despite of the wide use of supported Ti based Ziegler-Natta catalysts in the olefin polymerization industry, questions concerning the role of each one of the catalyst components in the polymerization process, have not found a satisfactory answer yet. This is mainly because of the high sensitivity of these systems to oxygen and atmospheric moisture that makes their study in an atomic level rather complicated. Realistic surface science models of the pre-activated SiO 2 supported MgCl 2/TiCl 4 and TiCl 4 Ziegler-Natta catalysts were prepared by spin coating on flat conductive SiO 2/Si(1 0 0) supports under inert atmosphere. This preparation technique resembles the wet chemical impregnation which is the industrial method of the catalyst preparation. XPS analysis showed that the catalyst precursor anchors on the silica surface through bonding of the Ti atoms with surface silanes or siloxanes, while Mg is attached to the Ti through chlorine bridges. Thermal treatment of the catalysts at 723 K leads to total Cl desorption when MgCl 2 is not present while a significant amount of the Ti atoms is reduced to the Ti 3+ state.

Flexural Strength of Polymethyl Methacrylate Repaired with Fiberglass.

PubMed

Golbidi, Fariba; Pozveh, Maryam Amini

2017-07-01

The purpose of this experimental study was to discover a method to increase the strength of repaired polymethyl methacrylate (PMMA) samples. In this experimental study, 40 specimens with the dimensions of 65×10×2.5mm 3 were fabricated using heat-curing acrylic resin. Sixteen specimens were repaired with fiberglass and self-curing PMMA, while 16 samples were repaired with self-curing PMMA. Eight specimens were left intact as the control group. Afterwards, the flexural strengths of the repaired and intact specimens were measured by three-point bending test in a universal testing machine. Data were analyzed with one-way analysis of variance (ANOVA) and Tukey's HSD and LSD tests. The level of significance was set at P<0.05. The mean flexural strength of the samples repaired with fiberglass was higher than that of the other repaired samples. However, the difference was statistically significant only with respect to the Meliodent group (P=0.008). Impregnated fiberglass could be used in the repair of denture bases to improve the flexural strength. In terms of the fracture site, it can be concluded that the lower flexural strength of the auto-polymerizing acryl compared to that of the heat-curing type was the main reason for the occurrence of fractures, rather than the weak bond between heat-curing and auto-polymerizing acrylic resins.

The role of microbial biofilms in deterioration of space station candidate materials.

PubMed

Gu, J D; Roman, M; Esselman, T; Mitchell, R

1998-01-01

Formation of microbial biofilms on surfaces of a wide range of materials being considered as candidates for use on the International Space Station was investigated. The materials included a fibre-reinforced polymeric composite, an adhesive sealant, a polyimide insulation foam, teflon cable insulation, titanium, and an aliphatic polyurethane coating. They were exposed to a natural mixed population of bacteria under controlled conditions of temperature and relative humidity (RH). Biofilms formed on the surfaces of the materials at a wide range of temperatures and RHs. The biofilm population was dominated by Pseudomonas aeruginosa, Ochrobactrum anthropi, Alcaligenes denitrificans, Xanthomonas maltophila, and Vibrio harveyi. The biocide, diiodomethyl-p-tolyl sulfone, impregnated in the polyurethane coating, was ineffective against microbial colonization and growth. Degradation of the polyurethane coatings was monitored with electrochemical impedance spectroscopy (EIS). The impedance spectra indicated that microbial degradation of the coating occurred in several stages. The initial decreases in impedance were due to the transport of water and solutes into the polymeric matrices. Further decreases were a result of polymer degradation by microorganisms. Our data showed that these candidate materials for space application are susceptible to biofilm formation and subsequent degradation. Our study suggests that candidate materials for use in space missions need to be carefully evaluated for their susceptibility to microbial biofilm formation and biodegradation.

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

PubMed

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

2017-12-01

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

Fast preparation of hybrid monolithic columns via photo-initiated thiol-yne polymerization for capillary liquid chromatography.

PubMed

Ma, Shujuan; Zhang, Haiyang; Li, Ya; Li, Yanan; Zhang, Na; Ou, Junjie; Ye, Mingliang; Wei, Yinmao

2018-02-23

Although several approaches have been developed to fabricate hybrid monoliths, it would still take a few hours to finish the formation of monoliths. Herein, photo-initiated thiol-yne polymerization was first adopted to in situ fabricate hybrid monoliths within the confines of UV-transparent fused-silica capillary. A silicon-containing diyne (1,3-diethynyltetramethyl-disiloxane, DYDS) was copolymerized with three multithiols, 1,6-hexanedithiol, trimethylolpropane tris(3-mercaptopropionate) and pentaerythriol tetrakis(3-mercaptopropionate), by using a binary porogenic system of diethylene glycol diethyl ether (DEGDE)/poly(ethylene glycol) (PEG200) within 10 min. Several characterizations of three hybrid monoliths (assigned as I, II and III, respectively) were performed. The results showed that these hybrid monoliths possessed bicontinuous porous structure, which was remarkably different from that via typical free-radical polymerization. The highest column efficiency of 76,000 plates per meter for butylbenzene was obtained on the column I in reversed-phase liquid chromatography (RPLC). It was observed that the efficiencies for strong-retained butylbenzene were almost close to those of weak-retained benzene, indicating a retention-independent efficient performance of small molecules on hybrid column I. The surface area of this hybrid monolith was very small in the dry state (less than 10.0 m 2 /g), and the chromatographic behavior of hybrid monolithic columns would be possibly explained by radical-mediated step-growth process of thiol-yne polymerization. Finally, the column I was applied for separation of BSA tryptic digest by cLC-MS/MS, indicating satisfactory separation ability for complicated samples. Copyright © 2018 Elsevier B.V. All rights reserved.

Development of high-productivity, strong cation-exchange adsorbers for protein capture by graft polymerization from membranes with different pore sizes

PubMed Central

Chenette, Heather C.S.; Robinson, Julie R.; Hobley, Eboni; Husson, Scott M.

2012-01-01

This paper describes the surface modification of macroporous membranes using ATRP (atom transfer radical polymerization) to create cation-exchange adsorbers with high protein binding capacity at high product throughput. The work is motivated by the need for a more economical and rapid capture step in downstream processing of protein therapeutics. Membranes with three reported nominal pore sizes (0.2, 0.45, 1.0 μm) were modified with poly(3-sulfopropyl methacrylate, potassium salt) tentacles, to create a high density of protein binding sites. A special formulation was used in which the monomer was protected by a crown ether to enable surface-initiated ATRP of this cationic polyelectrolyte. Success with modification was supported by chemical analysis using Fourier-transform infrared spectroscopy and indirectly by measurement of pure water flux as a function of polymerization time. Uniformity of modification within the membranes was visualized with confocal laser scanning microscopy. Static and dynamic binding capacities were measured using lysozyme protein to allow comparisons with reported performance data for commercial cation-exchange materials. Dynamic binding capacities were measured for flow rates ranging from 13 to 109 column volumes (CV)/min. Results show that this unique ATRP formulation can be used to fabricate cation-exchange membrane adsorbers with dynamic binding capacities as high as 70 mg/mL at a throughput of 100 CV/min and unprecedented productivity of 300 mg/mL/min. PMID:23175597

Comparison of collagen matrix treatment impregnated with platelet rich plasma vs bone marrow.

PubMed

Minamimura, Ai; Ichioka, Shigeru; Sano, Hitomi; Sekiya, Naomi

2014-02-01

This study has reported the efficacy of an autologous bone marrow-impregnated collagen matrix experimentally and clinically. Then, it reflected that platelet rich plasma (PRP) was as good a source of growth factors as bone marrow and available in a less invasive procedure. This study aimed to compare the efficacy of a PRP-impregnated collagen matrix with that of a bone marrow-impregnated collagen matrix by quantifying wound size and capillary density using genetically diabetic db/db mice. Bone marrow cells were obtained from femurs of ddy mice. Then, a small amount of collagen matrix was immersed in bone marrow suspension. This is called a bone marrow-impregnated collagen matrix. PRP was obtained from healthy human blood and a small amount of collagen matrix was immersed in PRP. This is called a PRP-impregnated collagen matrix. A bone marrow-impregnated collagen matrix and PRP-impregnated collagen matrix were applied to excisional skin wounds on a genetically healing-impaired mouse (n = 6) and wounds were evaluated 6 days after the procedure. Wounds were divided into two groups: PRP (n = 6), in which a PRP-impregnated collagen matrix was applied; and bone marrow (n = 6), in which collagen immersed in a bone marrow suspension was applied. There was no significant difference between the PRP and bone-marrow groups in the rate of vascular density increase or wound size decrease. The present study suggested that the PRP-impregnated collagen matrix promotes repair processes at least as strongly as the bone marrow-impregnated collagen matrix. Given lower invasiveness, the PRP-impregnated collagen matrix would have advantages in clinical use.

Comparison of EDTA and SDS as potential surface impregnation agents for lead adsorption by activated carbon

NASA Astrophysics Data System (ADS)

Chen, Wei-fang; Pan, Ling; Chen, Li-fang; Yu, Zhe; Wang, Qiong; Yan, Chang-cheng

2014-08-01

Ethylene diamine tetraacetic acid (EDTA) and sodium dodecyl sulfate (SDS) were employed to impregnate activated carbons for the purpose of lead removal. The mechanisms of surface impregnation and lead adsorption method of chemical regeneration were investigated. Results showed that the highest impregnation of EDTA and SDS on activated carbon was 0.33 and 0.96 mmol/g, respectively. Adsorption capacities for lead of EDTA and SDS impregnated activated carbons reached 0.29 and 0.24 mmol/g. Rapid small scale column tests of adsorption and regeneration were conducted. Lead adsorption was greatly enhanced by EDTA impregnation. In addition, EDTA impregnated adsorbent was able to be successful regenerated by HNO3 and thus reused.

Apple snack enriched with L-arginine using vacuum impregnation/ohmic heating technology.

PubMed

Moreno, Jorge; Echeverria, Julian; Silva, Andrea; Escudero, Andrea; Petzold, Guillermo; Mella, Karla; Escudero, Carlos

2017-07-01

Modern life has created a high demand for functional food, and in this context, emerging technologies such as vacuum impregnation and ohmic heating have been applied to generate functional foods. The aim of this research was to enrich the content of the semi-essential amino acid L-arginine in apple cubes using vacuum impregnation, conventional heating, and ohmic heating. Additionally, combined vacuum impregnation/conventional heating and vacuum impregnation/ohmic heating treatments were evaluated. The above treatments were applied at 30, 40 and 50  ℃ and combined with air-drying at 40 ℃ in order to obtain an apple snack rich in L-arginine. Both the impregnation kinetics of L-arginine and sample color were evaluated. The impregnated samples created using vacuum impregnation/ohmic heating at 50 ℃ presented a high content of L-arginine, an effect attributed primarily to electropermeabilization. Overall, vacuum impregnation/ohmic heating treatment at 50 ℃, followed by drying at 40 ℃, was the best process for obtaining an apple snack rich in L-arginine.

Oxidation resistant organic hydrogen getters

DOEpatents

Shepodd, Timothy J [Livermore, CA; Buffleben, George M [Tracy, CA

2008-09-09

A composition for removing hydrogen from an atmosphere, comprising a mixture of a polyphenyl ether and a hydrogenation catalyst, preferably a precious metal catalyst, and most preferably Pt. This composition is stable in the presence of oxygen, will not polymerize or degrade upon exposure to temperatures in excess of 200.degree. C., or prolonged exposure to temperatures in the range of 100-300.degree. C. Moreover, these novel hydrogen getter materials can be used to efficiently removing hydrogen from mixtures of hydrogen/inert gas (e.g., He, Ar, N.sub.2), hydrogen/ammonia atmospheres, such as may be encountered in heat exchangers, and hydrogen/carbon dioxide atmospheres. Water vapor and common atmospheric gases have no adverse effect on the ability of these getter materials to absorb hydrogen.

Carboranylcyclotriphosphazenes and their polymers. [thermal insulation

NASA Technical Reports Server (NTRS)

Allcock, H. R.; Obrien, J. P.; Scopelianos, A. G.; Fewell, L. L. (Inventor)

1981-01-01

Carboranyl-substituted polyphosphazenes are prepared by heat polymerizing a carboranyl halocyclophosphazene at 250 C for about 120 hours in the absence of oxygen and moisture. The cyclophosphazene is obtained by allowing a lithium carborane, e.g., the reaction product of methyl-o-carborane with n-butyllithium in ethyl ether, to react with e.g., hexachlorocyclotriphosphazene at ambient temperatures and in anhydrous conditions. For greater stability in the presence of moisture, the chlorine substituents of the polymer are then replaced by aryloxy or alkoxy groups, such as CF3CH2O. The new substantially inorganic polymers are thermally stable materials which produce a high char yield when exposed to extreme temperatures, and can thus serve to insulate less heat and fire resistant substances.

Nitroxide-mediated radical ring-opening copolymerization: chain-end investigation and block copolymer synthesis.

PubMed

Delplace, Vianney; Harrisson, Simon; Tardy, Antoine; Gigmes, Didier; Guillaneuf, Yohann; Nicolas, Julien

2014-02-01

Well-defined, degradable copolymers are successfully prepared by nitroxide-mediated radical ring opening polymerization (NMrROP) of oligo(ethylene glycol) methyl ether methacrylate (OEGMA) or methyl methacrylate (MMA), a small amount of acrylonitrile (AN) and cyclic ketene acetals (CKAs) of different structures. Phosphorous nuclear magnetic resonance allows in-depth chain-end characterization and gives crucial insights into the nature of the copoly-mer terminal sequences and the living chain fractions. By using a small library of P(OEGMA-co-AN-co-CKA) and P(MMA-co-AN-co-CKA) as macroinitiators, chain extensions with styrene are performed to furnish (amphiphilic) block copolymers comprising a degradable segment. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Facially Amphipathic Glycopolymers Inhibit Ice Recrystallization.

PubMed

Graham, Ben; Fayter, Alice E R; Houston, Judith E; Evans, Rachel C; Gibson, Matthew I

2018-05-02

Antifreeze glycoproteins (AFGPs) from polar fish are the most potent ice recrystallization (growth) inhibitors known, and synthetic mimics are required for low-temperature applications such as cell cryopreservation. Here we introduce facially amphipathic glycopolymers that mimic the three-dimensional structure of AFGPs. Glycopolymers featuring segregated hydrophilic and hydrophobic faces were prepared by ring-opening metathesis polymerization, and their rigid conformation was confirmed by small-angle neutron scattering. Ice recrystallization inhibition (IRI) activity was reduced when a hydrophilic oxo-ether was installed on the glycan-opposing face, but significant activity was restored by incorporating a hydrophobic dimethylfulvene residue. This biomimetic strategy demonstrates that segregated domains of distinct hydrophilicity/hydrophobicity are a crucial motif to introduce IRI activity, which increases our understanding of the complex ice crystal inhibition processes.

miktoarm polymer: controlled synthesis, characterization, and application as anticancer drug carrier

NASA Astrophysics Data System (ADS)

Lin, Wenjing; Nie, Shuyu; Xiong, Di; Guo, Xindong; Wang, Jufang; Zhang, Lijuan

2014-05-01

Amphiphilic A2(BC)2 miktoarm star polymers [poly(ɛ-caprolactone)]2-[poly(2-(diethylamino)ethyl methacrylate)- b- poly(poly(ethylene glycol) methyl ether methacrylate)]2 [(PCL)2(PDEA- b-PPEGMA)2] were developed by a combination of ring opening polymerization (ROP) and continuous activators regenerated by electron transfer atom transfer radical polymerization (ARGET ATRP). The critical micelle concentration (CMC) values were extremely low (0.0024 to 0.0043 mg/mL), depending on the architecture of the polymers. The self-assembled empty and doxorubicin (DOX)-loaded micelles were spherical in morphologies, and the average sizes were about 63 and 110 nm. The release of DOX at pH 5.0 was much faster than that at pH 6.5 and pH 7.4. Moreover, DOX-loaded micelles could effectively inhibit the growth of cancer cells HepG2 with IC50 of 2.0 μg/mL. Intracellular uptake demonstrated that DOX was delivered into the cells effectively after the cells were incubated with DOX-loaded micelles. Therefore, the pH-sensitive (PCL)2(PDEA- b-PPEGMA)2 micelles could be a prospective candidate as anticancer drug carrier for hydrophobic drugs with sustained release behavior.

Self-assembly of BODIPY based pH-sensitive near-infrared polymeric micelles for drug controlled delivery and fluorescence imaging applications.

PubMed

Liu, Xiaodong; Chen, Bizheng; Li, Xiaojun; Zhang, Lifen; Xu, Yujie; Liu, Zhuang; Cheng, Zhenping; Zhu, Xiulin

2015-10-21

Responsive block copolymer micelles emerging as promising imaging and drug delivery systems show high stability and on-demand drug release activities. Herein, we developed self-assembled pH-responsive NIR emission micelles entrapped with doxorubicin (DOX) within the cores by the electrostatic interactions for fluorescence imaging and chemotherapy applications. The block copolymer, poly(methacrylic acid)-block-poly[(poly(ethylene glycol) methyl ether methacrylate)-co-boron dipyrromethene derivatives] (PMAA-b-P(PEGMA-co-BODIPY), was synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization, and the molecular weight distribution of this copolymer was narrow (Mw/Mn = 1.31). The NIR fluorescence enhancement induced by the phenol/phenolate interconversion equilibrium works as a switch in response to the intracellular pH fluctuations. DOX-loaded PMAA-b-P(PEGMA-co-BODIPY) micelles can detect the physiological pH fluctuations with a pKa near physiological conditions (∼7.52), and showed pH-responsive collapse and an obvious acid promoted anticancer drug release behavior (over 58.8-62.8% in 10 h). Real-time imaging of intracellular pH variations was performed and a significant chemotherapy effect was demonstrated against HeLa cells.

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

NASA Astrophysics Data System (ADS)

Wang, Jingjing; Wei, Jun

2016-09-01

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

Improved surface hydrophilicity and antifouling property of polysulfone ultrafiltration membrane with poly(ethylene glycol) methyl ether methacrylate grafted graphene oxide nanofillers

NASA Astrophysics Data System (ADS)

Wang, Haidong; Lu, Xiaofei; Lu, Xinglin; Wang, Zhenghui; Ma, Jun; Wang, Panpan

2017-12-01

In this study, the GO-g-P(PEGMA) nanoplates were first synthesized by grafting hydrophilic poly (poly (ethylene glycol) methyl ether methacrylate) via surface-initiated atom transfer radical polymerization (SI-ATRP) method. A novel polysulfone (PSF) nanocomposite membrane using GO-g-P(PEGMA) nanoplates as nanofillers was fabricated. FTIR, TGA, 1H NMR, GPC and TEM were applied to verify the successful synthesis of the prepared nanoplates, while SEM, AFM, XPS, contact angle goniometry and filtration experiments were used to characterize the fabricated nanocomposite membranes. It was found that the new prepared nanofillers were well dispersed in organic PSF matrix, and the PSF/GO-g-P(PEGMA) nanocomposite membrane showed significant improvements in water flux and flux recovery rate. Based on the results of resistance-in-series model, the nanocomposite membrane exhibited superior resistance to the irreversible fouling. The excellent filtration and antifouling performance are attributed to the segregation of GO-g-P(PEMGA) nanofillers toward the membrane surface and the pore walls. Notably, the blended nanofillers appeared a stable retention in/on nanocomposite membrane after 30 days of washing time. The demonstrated method of synthesis GO-g-P(PEGMA) in this study can also be extended to preparation of other nanocomposite membrane in future.

Monounsaturated fatty acid ether oligomers formed during heating of virgin olive oil show agglutination activity against human red blood cells.

PubMed

Patrikios, Ioannis S; Mavromoustakos, Thomas M

2014-01-29

The present work focuses on the characterization of molecules formed when virgin olive oil is heated at 130 °C for 24 h open in air, which are found to be strong agglutinins. The hemagglutinating activity of the newly formed molecule isolated from the heated virgin olive oil sample was estimated against human red blood cells (RBCs). Dimers and polymers (high molecular weight molecules) were identified through thin layer chromatography (TLC) of the oil mixture. (1)H and (13)C nuclear magnetic resonance (NMR) and gas chromatography-mass spectroscopy (GC-MS) were the methods used for structural characterization. Among others, oligomerization of at least two monounsaturated fatty acids (FA) by an ether linkage between the hydrocarbon chains is involved. Light microscopy was used to characterize and visualize the agglutination process. Agglutination without fusion or lysis was observed. It was concluded that the heating of virgin olive oil open in air, among other effects, produces oligomerization as well as polymerization of unsaturated FA, possibly of monohydroxy, monounsaturated FA that is associated with strong hemagglutinating activity against human RBCs. The nutritional value and the effects on human health of such oligomers are not discussed in the literature and remain to be investigated.

Alternating Magnetic Field Controlled, Multifunctional Nano-Reservoirs: Intracellular Uptake and Improved Biocompatibility

NASA Astrophysics Data System (ADS)

Ghosh, Santaneel; Ghoshmitra, Somesree; Cai, Tong; Diercks, David R.; Mills, Nathaniel C.; Hynds, Dianna L.

2010-01-01

Biocompatible magnetic nanoparticles hold great therapeutic potential, but conventional particles can be toxic. Here, we report the synthesis and alternating magnetic field dependent actuation of a remotely controllable, multifunctional nano-scale system and its marked biocompatibility with mammalian cells. Monodisperse, magnetic nanospheres based on thermo-sensitive polymer network poly(ethylene glycol) ethyl ether methacrylate- co-poly(ethylene glycol) methyl ether methacrylate were synthesized using free radical polymerization. Synthesized nanospheres have oscillating magnetic field induced thermo-reversible behavior; exhibiting desirable characteristics comparable to the widely used poly- N-isopropylacrylamide-based systems in shrinkage plus a broader volumetric transition range. Remote heating and model drug release were characterized for different field strengths. Nanospheres containing nanoparticles up to an iron concentration of 6 mM were readily taken up by neuron-like PC12 pheochromocytoma cells and had reduced toxicity compared to other surface modified magnetic nanocarriers. Furthermore, nanosphere exposure did not inhibit the extension of cellular processes (neurite outgrowth) even at high iron concentrations (6 mM), indicating minimal negative effects in cellular systems. Excellent intracellular uptake and enhanced biocompatibility coupled with the lack of deleterious effects on neurite outgrowth and prior Food and Drug Administration (FDA) approval of PEG-based carriers suggest increased therapeutic potential of this system for manipulating axon regeneration following nervous system injury.

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.

Scalable creation of gold nanostructures on high performance engineering polymeric substrate

NASA Astrophysics Data System (ADS)

Jia, Kun; Wang, Pan; Wei, Shiliang; Huang, Yumin; Liu, Xiaobo

2017-12-01

The article reveals a facile protocol for scalable production of gold nanostructures on a high performance engineering thermoplastic substrate made of polyarylene ether nitrile (PEN) for the first time. Firstly, gold thin films with different thicknesses of 2 nm, 4 nm and 6 nm were evaporated on a spin-coated PEN substrate on glass slide in vacuum. Next, the as-evaporated samples were thermally annealed around the glass transition temperature of the PEN substrate, on which gold nanostructures with island-like morphology were created. Moreover, it was found that the initial gold evaporation thickness and annealing atmosphere played an important role in determining the morphology and plasmonic properties of the formulated Au NPs. Interestingly, we discovered that isotropic Au NPs can be easily fabricated on the freestanding PEN substrate, which was fabricated by a cost-effective polymer solution casting method. More specifically, monodispersed Au nanospheres with an average size of ∼60 nm were obtained after annealing a 4 nm gold film covered PEN casting substrate at 220 °C for 2 h in oxygen. Therefore, the scalable production of Au NPs with controlled morphology on PEN substrate would open the way for development of robust flexible nanosensors and optical devices using high performance engineering polyarylene ethers.

Alkali or alkaline earth metal promoted catalyst and a process for methanol synthesis using alkali or alkaline earth metals as promoters

DOEpatents

Tierney, J.W.; Wender, I.; Palekar, V.M.

1995-01-31

The present invention relates to a novel route for the synthesis of methanol, and more specifically to the production of methanol by contacting synthesis gas under relatively mild conditions in a slurry phase with a heterogeneous catalyst comprising reduced copper chromite impregnated with an alkali or alkaline earth metal. There is thus no need to add a separate alkali or alkaline earth compound. The present invention allows the synthesis of methanol to occur in the temperature range of approximately 100--160 C and the pressure range of 40--65 atm. The process produces methanol with up to 90% syngas conversion per pass and up to 95% methanol selectivity. The only major by-product is a small amount of easily separated methyl formate. Very small amounts of water, carbon dioxide and dimethyl ether are also produced. The present catalyst combination also is capable of tolerating fluctuations in the H[sub 2]/CO ratio without major deleterious effect on the reaction rate. Furthermore, carbon dioxide and water are also tolerated without substantial catalyst deactivation.

Development of Hollow-Fiber Liquid-Phase Microextraction Method for Determination of Urinary trans,trans-Muconic Acid as a Biomarker of Benzene Exposure

PubMed Central

Ghamari, Farhad; Bahrami, Abdulrahman; Yamini, Yadollah; Shahna, Farshid Ghorbani; Moghimbeigi, Abbas

2016-01-01

For the first time, hollow-fiber liquid-phase microextraction combined with high-performance liquid chromatography–ultraviolet was used to extract trans,trans-muconic acid, in urine samples of workers who had been exposed to benzene. The parameters affecting the metabolite extraction were optimized as follows: the volume of sample solution was 11 mL with pH 2, liquid membrane containing dihexyl ether as the supporter, 15% (w/v) of trioctylphosphine oxide as the carrier, the time of extraction was 120 minutes, and stirring rate was 500 rpm. Organic phase impregnated in the pores of a hollow fiber was extracted into 24 µL solution of 0.05 mol L−1 Na2CO3 located inside the lumen of the fiber. Under optimized conditions, a high enrichment factor of 153–182 folds, relative recovery of 83%–92%, and detection limit of 0.001 µg mL−1 were obtained. The method was successfully applied to the analysis of ttMA in real urine samples. PMID:27660405

Alkali or alkaline earth metal promoted catalyst and a process for methanol synthesis using alkali or alkaline earth metals as promoters

DOEpatents

Tierney, John W.; Wender, Irving; Palekar, Vishwesh M.

1995-01-01

The present invention relates to a novel route for the synthesis of methanol, and more specifically to the production of methanol by contacting synthesis gas under relatively mild conditions in a slurry phase with a heterogeneous catalyst comprising reduced copper chromite impregnated with an alkali or alkaline earth metal. There is thus no need to add a separate alkali or alkaline earth compound. The present invention allows the synthesis of methanol to occur in the temperature range of approximately 100.degree.-160.degree. C. and the pressure range of 40-65 atm. The process produces methanol with up to 90% syngas conversion per pass and up to 95% methanol selectivity. The only major by-product is a small amount of easily separated methyl formate. Very small amounts of water, carbon dioxide and dimethyl ether are also produced. The present catalyst combination also is capable of tolerating fluctuations in the H.sub.2 /CO ratio without major deleterious effect on the reaction rate. Furthermore, carbon dioxide and water are also tolerated without substantial catalyst deactivation.

Facile synthesis of fluorescent polymer nanoparticles by covalent modification-nanoprecipitation of amine-reactive ester polymers.

PubMed

Lee, Yeonju; Hanif, Sadaf; Theato, Patrick; Zentel, Rudolf; Lim, Jeewoo; Char, Kookheon

2015-06-01

Emission wavelength control in fluorescent nanoparticles (NPs) is crucial for their applications. In the case of inorganic quantum dots or dye-impregnated silica NPs, such a control is readily achieved by changing the size of the particles or choosing appropriate fluorescent dyes, respectively. A similar modular approach for controlling the emission wavelength of fluo-rescent polymer NPs, however, is difficult. This article reports on fluorescent polymer NPs, the synthesis of which provides a platform for a modular approach towards the preparation of fluorescent NPs of desired emission wavelength. Atom-transfer radical polymerization (ATRP) is employed to synthesize reactive ester polymers, which are then easily modified with a commercially available dye and subsequently subjected to nanoprecipitation. The resulting NPs, with low size polydispersity, show an enhanced emission quantum yield when compared with the same dye molecules in solution. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Solar-Driven Hydrogen Peroxide Production Using Polymer-Supported Carbon Dots as Heterogeneous Catalyst

NASA Astrophysics Data System (ADS)

Gogoi, Satyabrat; Karak, Niranjan

2017-10-01

Safe, sustainable, and green production of hydrogen peroxide is an exciting proposition due to the role of hydrogen peroxide as a green oxidant and energy carrier for fuel cells. The current work reports the development of carbon dot-impregnated waterborne hyperbranched polyurethane as a heterogeneous photo-catalyst for solar-driven production of hydrogen peroxide. The results reveal that the carbon dots possess a suitable band-gap of 2.98 eV, which facilitates effective splitting of both water and ethanol under solar irradiation. Inclusion of the carbon dots within the eco-friendly polymeric material ensures their catalytic activity and also provides a facile route for easy catalyst separation, especially from a solubilizing medium. The overall process was performed in accordance with the principles of green chemistry using bio-based precursors and aqueous medium. This work highlights the potential of carbon dots as an effective photo-catalyst.

Monolithic porous graphitic carbons obtained through catalytic graphitization of carbon xerogels

NASA Astrophysics Data System (ADS)

Kiciński, Wojciech; Norek, Małgorzata; Bystrzejewski, Michał

2013-01-01

Pyrolysis of organic xerogels accompanied by catalytic graphitization and followed by selective-combustion purification was used to produce porous graphitic carbons. Organic gels impregnated with iron(III) chloride or nickel(II) acetate were obtained through polymerization of resorcinol and furfural. During the pyrolysis stage graphitization of the gel matrix occurs, which in turn develops mesoporosity of the obtained carbons. The evolution of the carbon into graphitic structures is strongly dependent on the concentrations of the transition metal. Pyrolysis leads to monoliths of carbon xerogel characterized by substantially enhanced mesoporosity resulting in specific surface areas up to 400 m2/g. Removal of the amorphous carbon by selective-combustion purification reduces the xerogels' mesoporosity, occasionally causing loss of their mechanical strength. The graphitized carbon xerogels were investigated by means of SEM, XRD, Raman scattering, TG-DTA and N2 physisorption. Through this procedure well graphitized carbonaceous materials can be obtained as bulk pieces.

Poly(glycidyl ether)-Based Monolayers on Gold Surfaces: Control of Grafting Density and Chain Conformation by Grafting Procedure, Surface Anchor, and Molecular Weight.

PubMed

Heinen, Silke; Weinhart, Marie

2017-03-07

For a meaningful correlation of surface coatings with their respective biological response reproducible coating procedures, well-defined surface coatings, and thorough surface characterization with respect to layer thickness and grafting density are indispensable. The same applies to polymeric monolayer coatings which are intended to be used for, e.g., fundamental studies on the volume phase transition of surface end-tethered thermoresponsive polymer chains. Planar gold surfaces are frequently used as model substrates, since they allow a variety of straightforward surface characterization methods. Herein we present reproducible grafting-to procedures performed with thermoresponsive poly(glycidyl ether) copolymers composed of glycidyl methyl ether (GME) and ethyl glycidyl ether (EGE). The copolymers feature different molecular weights (2 kDa, 9 kDa, 24 kDa) and are equipped with varying sulfur-containing anchor groups in order to achieve adjustable grafting densities on gold surfaces and hence control the tethered polymers' chain conformation. We determined "wet" and "dry" thicknesses of these coatings by QCM-D and ellipsometry measurements and deduced anchor distances and degrees of chain overlap of the polymer chains assembled on gold. Grafting under cloud point conditions allowed for higher degrees of chain overlap compared to grafting from a good solvent like ethanol, independent of the used sulfur-containing anchor group for polymers with low (2 kDa) and medium (9 kDa) molecular weights. By contrast, the achieved grafting densities and thus chain overlaps of surface-tethered polymers with high (24 kDa) molecular weights were identical for both grafting methods. Monolayers prepared from an ethanolic solution of poly(glycidyl ether)s equipped with sterically demanding disulfide-containing anchors revealed the lowest degrees of chain overlap. The ratio of the radius of gyration to the anchor distance (2 R g /l) of the latter coating was found to be lower than 1.4, indicating that the assembly was rather in the mushroom-like than in the brush regime. Polymer chains with thiol-containing anchors of different alkyl chain lengths (C 11 SH vs C 4 SH) formed assemblies with comparable degrees of chain overlap with 2 R g /l values above 1.4 and are thus in the brush regime. Molecular weights influenced the achievable degree of chain overlap on the surface. Coatings prepared with the medium molecular weight polymer (9 kDa) resulted in the highest chain packing density. Control of grafting density and thus chain overlap in different regimes (brush vs mushroom) on planar gold substrates are attainable for monolayer coatings with poly(GME-ran-EGE) by adjusting the polymer's molecular weight and anchor group as well as the conditions for the grafting-to procedure.

Experimental Analysis of Critical Current and Alternating Current Losses of High-Temperature Superconductor Tape with Resin and Gallium-Indium-Tin

PubMed Central

Sun, Yajie; Zhang, Huiming; Meng, Yuanzhu

2018-01-01

This paper experimentally analyzes the critical current degradation and AC (alternating current) losses of second-generation (2G) high-temperature superconductor (HTS) tape during the impregnation process. Two impregnation materials were utilized: Gallium-Indium-Tin (GaInSn), and an epoxy resin, Araldite. The critical current of the impregnation materials was measured after different thermal cycles and compared with the tape with no impregnation process. The experimental results show that the critical current of Yttrium Barium Copper Oxide (YBCO) short samples varies between differently impregnated materials. The resin, Araldite, degraded the critical current; however, the GaInSn showed no degradation. Two degradation patterns with Araldite were identified due to the impregnation process, and the corresponding causes were analyzed. We further measured the AC losses of tapes impregnated with liquid metal at different frequencies, up to 600 Hz. Based on the experimental results, GaInSn liquid metal should be the most suitable impregnation material in terms of critical current degradation. PMID:29642490

Experimental Analysis of Critical Current and Alternating Current Losses of High-Temperature Superconductor Tape with Resin and Gallium-Indium-Tin.

PubMed

Yu, Dongmin; Sun, Yajie; Zhang, Huiming; Meng, Yuanzhu; Liu, Huanan

2018-04-08

This paper experimentally analyzes the critical current degradation and AC (alternating current) losses of second-generation (2G) high-temperature superconductor (HTS) tape during the impregnation process. Two impregnation materials were utilized: Gallium-Indium-Tin (GaInSn), and an epoxy resin, Araldite. The critical current of the impregnation materials was measured after different thermal cycles and compared with the tape with no impregnation process. The experimental results show that the critical current of Yttrium Barium Copper Oxide (YBCO) short samples varies between differently impregnated materials. The resin, Araldite, degraded the critical current; however, the GaInSn showed no degradation. Two degradation patterns with Araldite were identified due to the impregnation process, and the corresponding causes were analyzed. We further measured the AC losses of tapes impregnated with liquid metal at different frequencies, up to 600 Hz. Based on the experimental results, GaInSn liquid metal should be the most suitable impregnation material in terms of critical current degradation.

Mercury adsorption of modified mulberry twig chars in a simulated flue gas.

PubMed

Shu, Tong; Lu, Ping; He, Nan

2013-05-01

Mulberry twig chars were prepared by pyrolysis, steam activation and impregnation with H2O2, ZnCl2 and NaCl. Textural characteristics and surface functional groups were performed using nitrogen adsorption and FTIR, respectively. Mercury adsorption of different modified MT chars was investigated in a quartz fixed-bed absorber. The results indicated that steam activation and H2O2-impregnation can improve pore structure significantly and H2O2-impregnation and chloride-impregnation promote surface functional groups. However, chloride-impregnation has adverse effect on pore structure. Mercury adsorption capacities of impregnated MT chars with 10% or 30% H2O2 are 2.02 and 1.77 times of steam activated MT char, respectively. Mercury adsorption capacity of ZnCl2-impregnated MT char increase with increasing ZnCl2 content and is better than that of NaCl-impregnated MT char at the same chloride content. The modified MT char (MT873-A-Z5) prepared by steam activation following impregnation with 5% ZnCl2 exhibits a higher mercury adsorption capacity (29.55 μg g(-1)) than any other MT chars. Copyright © 2013 Elsevier Ltd. All rights reserved.

Effect of autohydrolysis on the wettability, absorbility and further alkali impregnation of poplar wood chips.

PubMed

Xu, Ningpan; Liu, Wei; Hou, Qingxi; Wang, Peiyun; Yao, Zhirong

2016-09-01

Autohydrolysis with different severity factors was performed on poplar wood chips prior to pulping, and the wettability, absorbility and the following impregnation of NaOH solution for the poplar wood chips were then investigated. The results showed that after autohydrolysis pretreatment the porosity, shrinkage and fiber saturation point (FSP) of the poplar wood chips were increased, while the surface contact angle decreased as the severity factor was increased. The autohydrolyzed chips absorbed more NaOH in impregnation that resulted in a low NaOH concentration in the bulk impregnation liquor (i.e., the impregnation liquor outside wood chips), while the concentration in the entrapped liquor (i.e., the impregnation liquor inside wood chips) was increased. Autohydrolysis substantially improved the effectiveness of alkali impregnation. Copyright © 2016 Elsevier Ltd. All rights reserved.

Potentiometric measurement of polymer-membrane electrodes based on lanthanum

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

Saefurohman, Asep, E-mail: saefurohman.asep78@Gmail.com; Buchari,, E-mail: saefurohman.asep78@Gmail.com; Noviandri, Indra, E-mail: saefurohman.asep78@Gmail.com

2014-03-24

Quantitative analysis of rare earth elements which are considered as the standard method that has a high accuracy, and detection limits achieved by the order of ppm is inductively coupled plasma atomic emission spectroscopy (ICPAES). But these tools are expensive and valuable analysis of the high cost of implementation. In this study be made and characterized selective electrode for the determination of rare earth ions is potentiometric. Membrane manufacturing techniques studied is based on immersion (liquid impregnated membrane) in PTFE 0.5 pore size. As ionophores to be used tri butyl phosphate (TBP) and bis(2-etylhexyl) hydrogen phosphate. There is no reportmore » previously that TBP used as ionophore in polymeric membrane based lanthanum. Some parameters that affect the performance of membrane electrode such as membrane composition, membrane thickness, and types of membrane materials studied in this research. Manufacturing of Ion Selective Electrodes (ISE) Lanthanum (La) by means of impregnation La membrane in TBP in kerosene solution has been done and showed performance for ISE-La. FTIR spectrum results for PTFE 0.5 pore size which impregnated in TBP and PTFE blank showed difference of spectra in the top 1257 cm{sup −1}, 1031 cm{sup −1} and 794.7 cm{sup −1} for P=O stretching and stretching POC from group −OP =O. The result showed shift wave number for P =O stretching of the cluster (−OP=O) in PTFE-TBP mixture that is at the peak of 1230 cm{sup −1} indicated that no interaction bond between hydroxyl group of molecules with molecular clusters fosforil of TBP or R{sub 3}P = O. The membrane had stable responses in pH range between 1 and 9. Good responses were obtained using 10{sup −3} M La(III) internal solution, which produced relatively high potential. ISE-La showed relatively good performances. The electrode had a response time of 29±4.5 second and could be use for 50 days. The linear range was between 10{sup −5} and 10{sup −1} M.« less

A Novel Anti-Influenza Copper Oxide Containing Respiratory Face Mask

PubMed Central

Borkow, Gadi; Zhou, Steve S.; Page, Tom; Gabbay, Jeffrey

2010-01-01

Background Protective respiratory face masks protect the nose and mouth of the wearer from vapor drops carrying viruses or other infectious pathogens. However, incorrect use and disposal may actually increase the risk of pathogen transmission, rather than reduce it, especially when masks are used by non-professionals such as the lay public. Copper oxide displays potent antiviral properties. A platform technology has been developed that permanently introduces copper oxide into polymeric materials, conferring them with potent biocidal properties. Methodology/Principal Findings We demonstrate that impregnation of copper oxide into respiratory protective face masks endows them with potent biocidal properties in addition to their inherent filtration properties. Both control and copper oxide impregnated masks filtered above 99.85% of aerosolized viruses when challenged with 5.66±0.51 and 6.17±0.37 log10TCID50 of human influenza A virus (H1N1) and avian influenza virus (H9N2), respectively, under simulated breathing conditions (28.3 L/min). Importantly, no infectious human influenza A viral titers were recovered from the copper oxide containing masks within 30 minutes (≤0.88 log10TCID50), while 4.67±1.35 log10TCID50 were recovered from the control masks. Similarly, the infectious avian influenza titers recovered from the copper oxide containing masks were ≤0.97±0.01 log10TCID50 and from the control masks 5.03±0.54 log10TCID50. The copper oxide containing masks successfully passed Bacterial Filtration Efficacy, Differential Pressure, Latex Particle Challenge, and Resistance to Penetration by Synthetic Blood tests designed to test the filtration properties of face masks in accordance with the European EN 14683:2005 and NIOSH N95 standards. Conclusions/Significance Impregnation of copper oxide into respiratory protective face masks endows them with potent anti-influenza biocidal properties without altering their physical barrier properties. The use of biocidal masks may significantly reduce the risk of hand or environmental contamination, and thereby subsequent infection, due to improper handling and disposal of the masks. PMID:20592763

Designing supported palladium-on-gold bimetallic nano-catalysts for controlled hydrogenation of acetylene in large excess of ethylene

NASA Astrophysics Data System (ADS)

Malla, Pavani

Ethylene is used as a starting point for many chemical intermediates in the petrochemical industry. It is predominantly produced through steam cracking of higher hydrocarbons (ethane, propane, butane, naphtha, and gas oil). During the cracking process, a small amount of acetylene is produced as a side product. However, acetylene must be removed since it acts as a poison for ethylene polymerization catalysts at even ppm concentrations (>5 ppm). Thus, the selective hydrogenation of acetylene to ethylene is an important process for the purification of ethylene. Conventional, low weight loading Pd catalysts are used for this selective reaction in high concentration ethylene streams. Gold was initially considered to be catalytically inactive for a long time. This changed when gold was seen in the context of the nanometric scale, which has indeed shown it to have excellent catalytic activity as a homogeneous or a heterogeneous catalyst. Gold is proved to have high selectivity to ethylene but poor at conversion. Bimetallic Au and Pd catalysts have exhibited superior activity as compared to Pd particles in semi-hydrogenation. Hydrogenation of acetylene was tested using this bimetallic combination. The Pd-on-Au bimetallic catalyst structure provides a new synthesis approach in improving the catalytic properties of monometallic Pd materials. TiO 2 as a support material and 0.05%Pd loading on 1%Au on titania support and used different treatment methods like washing plasma and reduction between the two metal loadings and was observed under 2:1 ratio. In my study there were two set of catalysts which were prepared by a modified incipient wetness impregnation technique. Out of all the reaction condition the catalyst which was reduced after impregnating gold and then impregnating palladium which was further treated in non-thermal hydrogen plasma and then pretreated in hydrogen till 250°C for 1 hour produced the best activity of 76% yield at 225°C. Stability tests were conducted on the catalysts which were followed by TGA analysis to analyze the coke formation on the catalyst in a period of time at a particular temperature. The catalysts were characterized by the hydrogen chemisorption and atomic absorption spectroscopy.

Self-assembly of BODIPY based pH-sensitive near-infrared polymeric micelles for drug controlled delivery and fluorescence imaging applications

NASA Astrophysics Data System (ADS)

Liu, Xiaodong; Chen, Bizheng; Li, Xiaojun; Zhang, Lifen; Xu, Yujie; Liu, Zhuang; Cheng, Zhenping; Zhu, Xiulin

2015-10-01

Responsive block copolymer micelles emerging as promising imaging and drug delivery systems show high stability and on-demand drug release activities. Herein, we developed self-assembled pH-responsive NIR emission micelles entrapped with doxorubicin (DOX) within the cores by the electrostatic interactions for fluorescence imaging and chemotherapy applications. The block copolymer, poly(methacrylic acid)-block-poly[(poly(ethylene glycol) methyl ether methacrylate)-co-boron dipyrromethene derivatives] (PMAA-b-P(PEGMA-co-BODIPY)), was synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization, and the molecular weight distribution of this copolymer was narrow (Mw/Mn = 1.31). The NIR fluorescence enhancement induced by the phenol/phenolate interconversion equilibrium works as a switch in response to the intracellular pH fluctuations. DOX-loaded PMAA-b-P(PEGMA-co-BODIPY) micelles can detect the physiological pH fluctuations with a pKa near physiological conditions (~7.52), and showed pH-responsive collapse and an obvious acid promoted anticancer drug release behavior (over 58.8-62.8% in 10 h). Real-time imaging of intracellular pH variations was performed and a significant chemotherapy effect was demonstrated against HeLa cells.Responsive block copolymer micelles emerging as promising imaging and drug delivery systems show high stability and on-demand drug release activities. Herein, we developed self-assembled pH-responsive NIR emission micelles entrapped with doxorubicin (DOX) within the cores by the electrostatic interactions for fluorescence imaging and chemotherapy applications. The block copolymer, poly(methacrylic acid)-block-poly[(poly(ethylene glycol) methyl ether methacrylate)-co-boron dipyrromethene derivatives] (PMAA-b-P(PEGMA-co-BODIPY)), was synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization, and the molecular weight distribution of this copolymer was narrow (Mw/Mn = 1.31). The NIR fluorescence enhancement induced by the phenol/phenolate interconversion equilibrium works as a switch in response to the intracellular pH fluctuations. DOX-loaded PMAA-b-P(PEGMA-co-BODIPY) micelles can detect the physiological pH fluctuations with a pKa near physiological conditions (~7.52), and showed pH-responsive collapse and an obvious acid promoted anticancer drug release behavior (over 58.8-62.8% in 10 h). Real-time imaging of intracellular pH variations was performed and a significant chemotherapy effect was demonstrated against HeLa cells. Electronic supplementary information (ESI) available: GPC, UV/vis, fluorescence, and MTT data of the as-prepared polymers; 1H NMR, 13C NMR, HRMS and FT-IR of organic molecules and polymers. See DOI: 10.1039/c5nr04655f

The effect of liquid hot water pretreatment on the chemical-structural alteration and the reduced recalcitrance in poplar.

PubMed

Li, Mi; Cao, Shilin; Meng, Xianzhi; Studer, Michael; Wyman, Charles E; Ragauskas, Arthur J; Pu, Yunqiao

2017-01-01

Hydrothermal pretreatment using liquid hot water (LHW) is capable of substantially reducing the cell wall recalcitrance of lignocellulosic biomass. It enhances the saccharification of polysaccharides, particularly cellulose, into glucose with relatively low capital required. Due to the close association with biomass recalcitrance, the structural change of the components of lignocellulosic materials during the pretreatment is crucial to understand pretreatment chemistry and advance the bio-economy. Although the LHW pretreatment has been extensively applied and studied, the molecular structural alteration during pretreatment and its significance to reduced recalcitrance have not been well understood. We investigated the effects of LHW pretreatment with different severity factors (log R 0 ) on the structural changes of fast-grown poplar ( Populus trichocarpa ). With the severity factor ranging from 3.6 to 4.2, LHW pretreatment resulted in a substantial xylan solubilization by 50-77% ( w/w , dry matter). The molecular weights of the remained hemicellulose in pretreated solids also have been significantly reduced by 63-75% corresponding to LHW severity factor from 3.6 to 4.2. In addition, LHW had a considerable impact on the cellulose structure. The cellulose crystallinity increased 6-9%, whereas its degree of polymerization decreased 35-65% after pretreatment. We found that the pretreatment severity had an empirical linear correlation with the xylan solubilization ( R 2  = 0.98, r  = + 0.99), hemicellulose molecular weight reduction ( R 2  = 0.97, r  = - 0.96 and R 2  = 0.93, r  = - 0.98 for number-average and weight-average degree of polymerization, respectively), and cellulose crystallinity index increase ( R 2  = 0.98, r  = + 0.99). The LHW pretreatment also resulted in small changes in lignin structure such as decrease of β- O -4' ether linkages and removal of cinnamyl alcohol end group and acetyl group, while the S/G ratio of lignin in LHW pretreated poplar residue remained no significant change compared with the untreated poplar. This study revealed that the solubilization of xylan, the reduction of hemicellulose molecular weights and cellulose degree of polymerization, and the cleavage of alkyl-aryl ether bonds in lignin resulted from LHW pretreatment are critical factors associated with reduced cell wall recalcitrance. The chemical-structural changes of the three major components, cellulose, lignin, and hemicellulose, during LHW pretreatment provide useful and fundamental information of factors governing feedstock recalcitrance during hydrothermal pretreatment.

Synthesis and characterization of polyaniline/MnWO4 nanocomposites as electrodes for pseudocapacitors

NASA Astrophysics Data System (ADS)

Saranya, S.; Selvan, R. Kalai; Priyadharsini, N.

2012-03-01

Polyaniline (PAni)/MnWO4 nanocomposite was successfully synthesized by in situ polymerization method under ultrasonication and the MnWO4 was prepared by surfactant assisted ultrasonication method. The thermal stability of PAni was determined by TG/DTA (Thermo Gravimetric/ Differential thermal analysis). The structural and morphological features of PAni, MnWO4 and PAni/MnWO4 composite was analyzed using Fourier transform infrared spectrometry, X-ray diffraction (XRD), scanning electron microscope (SEM) and Transmission electron microscope (TEM) images. The electro-chemical properties of PAni, MnWO4 and its composites with different weight percentage of MnWO4 loading were studied through cyclic voltammetry (CV) for the application of supercapacitors as active electrode materials. From the cyclic voltammogram, 50% of MnWO4 impregnated PAni showed a high specific capacitance (SC) of 481 F/g than their individual counterparts of PAni (396 F/g) and MnWO4 (18 F/g). The galvanostatic charge-discharge studies indicate the in situ polymerized composite shows greater specific capacitance (475 F/g) than the physical mixture (346 F/g) at a constant discharge current of 1 mA/cm2 with reasonable cycling stability. The charge transfer resistance (Rct) of PAni/MnWO4 composite (22 ohm) was calculated using electrochemical impedance spectroscopy (EIS) and compared with its physical mixture (58 ohm).

In situ polymerization of polyaniline in wood veneers.

PubMed

Trey, Stacy; Jafarzadeh, Shadi; Johansson, Mats

2012-03-01

The present study describes the possibility to polymerize aniline within wood veneers to obtain a semi-conducting material with solid wood acting as the base template. It was determined that it is possible to synthesize the intrinsically conductive polymer (ICP) polyaniline in situ within the wood structure of Southern yellow pine veneers, combining the strength of the natural wood structure with the conductivity of the impregnated polymer. It was found that polyaniline is uniformly dispersed within the wood structure by light microscopy and FT-IR imaging. A weight percent gain in the range of 3-12 wt % was obtained with a preferential formation in the wood structure and cell wall, rather than in the lumen. The modified wood was found to be less hydrophilic with the addition of phosphate doped polyaniline as observed by equilibrium water swelling studies. While wood itself is insulating, the modified veneers had conductivities of 1 × 10(-4) to 1 × 10(-9) S cm(-1), demonstrating the ability to tune the conductivity and allowing for materials with a wide range of applications, from anti-static to charge-dispersing materials. Furthermore, the modified veneers had lower total and peak heat releases, as determined by cone calorimetry, because of the char properties of the ICP. This is of interest if these materials are to be used in building and furniture applications where flame retardance is of importance. © 2012 American Chemical Society

Flexural Strength of Polymethyl Methacrylate Repaired with Fiberglass

PubMed Central

Golbidi, Fariba

2017-01-01

Objectives: The purpose of this experimental study was to discover a method to increase the strength of repaired polymethyl methacrylate (PMMA) samples. Materials and Methods: In this experimental study, 40 specimens with the dimensions of 65×10×2.5mm3 were fabricated using heat-curing acrylic resin. Sixteen specimens were repaired with fiberglass and self-curing PMMA, while 16 samples were repaired with self-curing PMMA. Eight specimens were left intact as the control group. Afterwards, the flexural strengths of the repaired and intact specimens were measured by three-point bending test in a universal testing machine. Data were analyzed with one-way analysis of variance (ANOVA) and Tukey’s HSD and LSD tests. The level of significance was set at P<0.05. Results: The mean flexural strength of the samples repaired with fiberglass was higher than that of the other repaired samples. However, the difference was statistically significant only with respect to the Meliodent group (P=0.008). Conclusions: Impregnated fiberglass could be used in the repair of denture bases to improve the flexural strength. In terms of the fracture site, it can be concluded that the lower flexural strength of the auto-polymerizing acryl compared to that of the heat-curing type was the main reason for the occurrence of fractures, rather than the weak bond between heat-curing and auto-polymerizing acrylic resins. PMID:29285033

Adhesive, elastomeric gel impregnating composition

DOEpatents

Shaw, David Glenn; Pollard, John Randolph; Brooks, Robert Aubrey

2002-01-01

An improved capacitor roll with alternating film and foil layers is impregnated with an adhesive, elastomeric gel composition. The gel composition is a blend of a plasticizer, a polyol, a maleic anhydride that reacts with the polyol to form a polyester, and a catalyst for the reaction. The impregnant composition is introduced to the film and foil layers while still in a liquid form and then pressure is applied to aid with impregnation. The impregnant composition is cured to form the adhesive, elastomeric gel. Pressure is maintained during curing.

Analyses and comparison of a novel, hybrid, multifunctional orthopedic composite and implant

NASA Astrophysics Data System (ADS)

Dicicco, Michael

In the orthopedic/medical device industry, 2, 2' -bis-(4-(2-hydroxy-3-methacryloxypropoxy)phenyl]propane (Bis-GMA)- and diurethanedimethacrylate (DUDMA)-based polymeric biomaterials have become well-known substitutes for polymethylmethacrylate (PMMA)- and ultra-high molecular weight polyethylene (UHMWPE)-based biomaterials, respectively. The development of these polymeric biomaterials cannot continue without direct comparison studies against currently marketed materials. The initiative for this research stems wholly from developing analytical methodologies that assist in qualifying novel biomaterials under development, by evaluating their chemical properties, performance, and safety. The goals of this research were: (i) Characterize the assay/quality of every resin component and quantify elution of extractable monomers from novel, DUDMA-based RHAKOSS(TM) implant, (ii) Determine degree of conversion (alpha) and rate of polymerization (Rp) for novel, Bis-GMA-based CORTOSS(TM) composite, (iii) Assess risk for radical-induced post-surgical cytotoxicity for CORTOSS, (iv) Determine if surface radical chemistries occur for sterilized RHAKOSS and assess its oxidative stability, and (v) Quantify antibiotic elution from antibiotic-impregnated CORTOSS and identify factors that control elution. The phenomena studied necessitated the utilization of several analytical spectroscopic techniques; fluorometry, differential scanning calorimetry (DSC), electron paramagnetic resonance (EPR), ultraviolet-visible (UV-VIS), attenuated total reflectance---Fourier-transform infrared (ATR-FTIR), and high performance liquid chromatography (HPLC). A battery of lateral chemical techniques were employed as well; including molecular derivatization/tagging, phase partitioning, spin-trapping, and thermal annealing. Results demonstrated that RHAKOSS monomer percent compositions were prepared according to formulations and monomer elution was virtually undetectable, serving as an empirical gauge to portend degree of polymerization (DOP). A high alpha was reported for CORTOSS and essentially all bifunctional monomers had at least one functional group polymerized, stressing low monomer elution potential. Regarding cytotoxicity, CORTOSS impeded further production of hydroxyl radicals (•OH), whereas RHAKOSS did not facilitate the Fenton reaction but displayed some chelating abilities. Residual radicals in RHAKOSS were easily terminated, thus not projected to form oxidative degradants. Additionally, significant antibiotic concentrations, over extended durations, eluted from CORTOSS in linear-type fashion, advocating a sustained therapeutic effect, and phase partitioning correlated antibiotic release to hydrophilicity. The incurred data comprehensively argues in favor of the excellent biocompatibility that CORTOSS and RHAKOSS inherently possess, and was definitive in rendering them as advanced biomaterials, possessing favorable chemical properties.

Studies on silicon NMR characterization and kinetic modeling of the structural evolution of siloxane-based materials and their applications in drug delivery and adsorption

NASA Astrophysics Data System (ADS)

Ambati, Jyothirmai

This dissertation presents studies of the synthetic processes and applications of siloxane-based materials. Kinetic investigations of bridged organoalkoxysilanes that are precursors to organic-inorganic hybrid polysilsesquioxanes are a primary focus. Quick gelation despite extensive cyclization is found during the polymerization of bridged silane precursors except for silanes with certain short bridges. This work is an attempt to characterize and understand some of the distinct features of bridged silanes using experimental characterization, kinetic modeling and simulation. In addition to this, the dissertation shows how the properties of siloxane-materials can be engineered for drug delivery and adsorption. The phase behavior of polymerizing mixtures is first investigated to identify the solutions that favor kinetic characterization. Microphase separation is found to cause gradual loss of NMR signal for certain initial compositions. Distortionless Enhancement by Polarization Transfer 29Si NMR is employed to identify the products of polymerization of some short-bridged silanes under no signal loss conditions. This technique requires knowing indirect 29Si-1H scalar coupling constants which sometimes cannot be measured due to second-order effects. However, the B3LYP density functional method with 6-31G basis set is found to predict accurate 29Si- 1H coupling constants of organoalkoxysilanes and siloxanes. The scalar coupling constants thus estimated are employed to resolve non-trivial coupled NMR spectra and quantitative kinetic modeling is performed using the DEPT Si NMR transients. In order to investigate the role of the organic bridging group, the structural evolution of bridged and non-bridged silanes are compared using Monte Carlo simulations. Kinetic and simulation models suggest that cyclization plays a key role right from the onset of polymerization for bridged silanes even more than in non-bridged silanes. The simulations indicate that the carbosiloxane rings formed from short-bridged precursors slow down but do not prevent gelation. The tuning of siloxane-based materials for adsorption technologies are also discussed here. In the first example, antioxidant enzyme loading is investigated as a means to reduce oxidative stress generated by silica nanoparticle drug carriers. Materials are engineered for promising enzyme loading and protection from proteolysis. Second, the potential of copper sulfate impregnation to enhance adsorption of ammonia by silica is explored by molecular simulation. KEYWORDS: Sol-gel Polymerization, Kinetic Investigation, Si NMR, Bridged Silanes, DFT Calculations.

Impregnation of Fenofibrate on mesoporous silica using supercritical carbon dioxide.

PubMed

Bouledjouidja, Abir; Masmoudi, Yasmine; Van Speybroeck, Michiel; Schueller, Laurent; Badens, Elisabeth

2016-02-29

Low oral bioavailability can be circumvented by the formulation of the poorly water soluble drug in ordered mesoporous silica (OMS-L-7). Fenofibrate is an orally administered, poorly water-soluble active pharmaceutical ingredient (API), used clinically to lower lipid levels. Fenofibrate was loaded into silica using two methods: incipient wetness and supercritical impregnation. This study investigates the impact of loading and the impact of varying supercritical carbon dioxide (scCO2) processing conditions. The objective is to enhance Fenofibrate loading into silica while reducing degree of the drug crystallinity, so as to increase the drug's dissolution rate and its bioavailability. The comparison of both impregnation processes was made in terms of impregnation yields and duration as well as physical characterization of the drug. While incipient wetness method led to a Fenofibrate loading up to 300 mgdrug/gsilica in 48 h of impregnation, the supercritical impregnation method yielded loading up to 485 mgdrug/gsilica in 120 min of impregnation duration, at 16 MPa and 308 K, with a low degree of crystallinity (about 1%) comparable to the crystallinity observed via the solvent method. In addition to the enhancement of impregnation efficiency, the supercritical route provides a solvent-free alternative for impregnation. Copyright © 2015 Elsevier B.V. All rights reserved.

Replacement of hazardous chromium impregnating agent from silver/copper/chromium-impregnated active carbon using triethylenediamine to remove hydrogen sulfide, trichloromethane, ammonia, and sulfur dioxide.

PubMed

Wu, Li-Chun; Chung, Ying-Chien

2009-03-01

Activated carbon (AC) is widely used as an effective adsorbent in many applications, including industrial-scale air purification systems and air filter systems in gas masks. In general, ACs without chemical impregnation are good adsorbents of organic vapors but poor adsorbents of low-molecular-weight or polar gases such as chlorine, sulfur dioxide (SO2), formaldehyde, and ammonia (NH3). Impregnated ACs modified with metallic impregnating agents (ASC-carbons; e.g., copper, chromium, and silver) enhance the adsorbing properties of the ACs for simultaneously removing specific poisonous gases, but disposal of the chromium metal salt used to impregnate the ACs has the potential to result in situations that are toxic to both humans and the environment, thereby necessitating the search for replaceable organic impregnating agents that represent a much lower risk. The aim of this study was to assess the gas removal efficiency of an AC in which the organic impregnating agent triethylenediamine (TEDA) largely replaced the metallic impregnating agent chromium. We assessed batch and continuous adsorption capacities in situ for removing simulated hydrogen sulfide (H2S), trichloromethane (CHCl3), NH3, and SO2 gases. Brunauer-Emmet-Teller measurements and scanning electron microscopy analyses identified the removal mechanism by which TEDA-impregnated AS-carbon (dechromium ASC-carbon) adsorbs gases and determined the removal capacity for H2S, CHCl3, NH3, and SO2 to be 311, 258, 272, and 223 mg/g-C, respectively. These results demonstrate that TEDA-impregnated AS-carbon is significantly more efficient than ASC-carbon in adsorbing these four gases. Organic TEDA-impregnating agents have also been proven to be a reliable and environmental friendly agent and therefore a safe replacement of the hazardous chromium found in conventional ASC-carbon used in removing toxic gases from the airstream.

Stabilized sulfur binding using activated fillers

DOEpatents

Kalb, Paul D.; Vagin, Vyacheslav P.; Vagin, Sergey P.

2015-07-21

A method of making a stable, sulfur binding composite comprising impregnating a solid aggregate with an organic modifier comprising unsaturated hydrocarbons with at least one double or triple covalent bond between adjacent carbon atoms to create a modifier-impregnated aggregate; heating and drying the modifier-impregnated aggregate to activate the surface of the modifier-impregnated aggregate for reaction with sulfur.

Secondary polymer layered impregnated tile

NASA Technical Reports Server (NTRS)

Tran, Huy K. (Inventor); Rasky, Daniel J. (Inventor); Szalai, Christine E. (Inventor); Carroll, Joseph A. (Inventor); Hsu, Ming-ta S. (Inventor)

2005-01-01

A low density organic polymer impregnated preformed fibrous ceramic article includes a plurality of layers. A front layer includes ceramic fibers or carbon fibers or combinations of ceramic fibers and carbon fibers, and is impregnated with an effective amount of at least one organic polymer. A middle layer includes polymer impregnated ceramic fibers. A back layer includes ceramic fibers or carbon fibers or combinations of ceramic fibers and carbon fibers, and is impregnated with an effective amount of at least one low temperature pyrolyzing organic polymer capable of decomposing without depositing residues.

Effect of hydrogen peroxide on the three-dimensional polymer network in composites.

PubMed

Durner, Jürgen; Stojanovic, Marija; Urcan, Ebru; Spahl, Werner; Haertel, Ursula; Hickel, Reinhard; Reichl, Franx-Xaver

2011-06-01

Less data are available about the effects of hydrogen peroxide on the three-dimensional polymer network of polymerized composites. Therefore the study was performed to test the effects of hydrogen peroxide on the three-dimensional polymer network in composites. Polymerized specimens from Tetric Flow®, Tetric Ceram® and Filtek™ Supreme XT were bleached with Opalescence® PF 15% for 5h or PF 35% for 0.5h, respectively, and then stored in methanol for 1d and 7d. Controls were unbleached specimens. The eluates were analyzed by gas chromatography/mass spectrometry. More methacrylic acid (MAA), bisphenol-A (BPA), ethoxylated bisphenol-A-dimethacrylate (BisEMA), hydroquinone monomethyl ether (HQME), 1,10-decanediol dimethacrylate (DDDMA) and/or triethylene glycol dimethacrylate (TEGDMA) were eluted from bleached specimens compared with non bleached controls (1d). The highest DDDMA amount of 419.8 μmol/l was found in the eluates after 7d in Tetric Flow® specimens treated with PF 15. The highest HQME amount of 159.6 μmol/l was found in eluates from Tetric Ceram® specimens treated with PF after 7d. The highest TEGDMA amount of 178.7 μmol/l was found in eluates from Filtek™ Supreme XT specimens treated with PF 35 after 7d. Bleaching with hydrogen peroxide has an effect on the three-dimensional polymer network in polymerized composites leading to an increase in the release of unpolymerized monomers, additives and unspecific oxidative products. Copyright © 2011 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Polymeric film application for phase change heat transfer

NASA Astrophysics Data System (ADS)

Bart, Hans-Jörg; Dreiser, Christian

2018-06-01

The paper gives a concise review on polymer film heat exchangers (PFHX) with a focus on polyether ether ketone (PEEK) foil as heat transfer element, mechanically supported by a grid structure. In order to promote PFHX applications, heat transfer performance and wetting behavior are studied in detail. Surface modifications to improve wetting are discussed and correlations are presented for critical Reynolds numbers to sustain a stable liquid film. Scaling phenomena related to surface properties and easily adaptable cleaning-in-place (CIP) procedures are further content. The contribution of the foil thickness and material selection on thermal performance is quantified and a correlation for enhanced aqueous film heat transfer for the grid supported PFHX is given. The basic research results and the design criteria enable early stage material selection and conceptual apparatus design.

Characterization of poly(L-lactide/Propylene glycol) based polyurethane films using ATR-FTIR spectroscopy

NASA Astrophysics Data System (ADS)

Manap, Siti Munirah; Ahmad, Azizan; Anuar, Farah Hannan

2016-11-01

A polyurethane films consisting of PLLA, PPG and PLLA-PPG were prepared using solution casting method. Three types of polyurethane were prepared: PPLA:PMDI, PPG:PMDI and PLLA-PPG:PMDI in the presence of polymeric diphenylmethane diisocyanate (PMDI) as the coupling agent and catalyst, Sn(Oct)2. The aim of this research was to improve the physicals properties of PLLA and PPG homopolymers through copolymerization between the two polymers. The homopolymers and polyurethane films were characterized using ATR-FTIR spectroscopy. Chemical reaction between PLLA, PPG and PMDI before and after the reaction were confirmed by observing the shifting of wavenumber for the carbonyl and ether group. Other than that, the additional band for N-H after the reaction indicated that the reaction was successful.

Method for absorbing hydrogen using an oxidation resisant organic hydrogen getter

DOEpatents

Shepodd, Timothy J [Livermore, CA; Buffleben, George M [Tracy, CA

2009-02-03

A composition for removing hydrogen from an atmosphere, comprising a mixture of a polyphenyl ether and a hydrogenation catalyst, preferably a precious metal catalyst, and most preferably platinum, is disclosed. This composition is stable in the presence of oxygen, will not polymerize or degrade upon exposure to temperatures in excess of 200.degree. C., or prolonged exposure to temperatures in the range of 100-300.degree. C. Moreover, these novel hydrogen getter materials can be used to efficiently remove hydrogen from mixtures of hydrogen/inert gas (e.g., He, Ar, N.sub.2), hydrogen/ammonia atmospheres, such as may be encountered in heat exchangers, and hydrogen/carbon dioxide atmospheres. Water vapor and common atmospheric gases have no adverse effect on the ability of these getter materials to absorb hydrogen.

Low loading of carbon nanotubes to enhance acoustical properties of poly(ether)urethane foams

NASA Astrophysics Data System (ADS)

Basirjafari, Sedigheh; Malekfar, Rasoul; Esmaielzadeh Khadem, Siamak

2012-11-01

The aim of this paper is to fabricate a sound absorber flexible semi-open cell polymeric foam based on polyether urethane (PEU) with carboxylic functionalized multi-walled carbon nanotubes (COOH-MWCNTs) as an energy decaying filler at low loadings up to 0.20 wt. %. This paper provides the relationship between the mentioned foam microstructure via field emission scanning electron microscopy and different acoustical and non-acoustical properties of PEU/COOH-MWCNT composites. Addition of just 0.05 wt. % COOH-MWCNTs enhanced the sound absorption coefficient of the mentioned nanocomposite foam over the entire frequency range. Raman spectra revealed the better dispersion of COOH-MWCNTs in the PEU matrix leading to more stress transfer between them to cause a significant dissipation of energy.

A high-spin and durable polyradical: poly(4-diphenylaminium-1,2-phenylenevinylene).

PubMed

Murata, Hidenori; Takahashi, Masahiro; Namba, Kazuaki; Takahashi, Naoki; Nishide, Hiroyuki

2004-02-06

A purely organic, high-spin, and durable polyradical molecule was synthesized: It is based on the non-Kekulé- and non-disjoint design of a pi-conjugated poly(1,2-phenylenevinylene) backbone pendantly 4-substituted with multiple robust arylaminium radicals. 4-N,N-Bis(4-methoxy- and -tert-butylphenyl)amino-2-bromostyrene 5 were synthesized and polymerized with a palladium-phosphine catalyst to afford the head-to-tail-linked polyradical precursors (1). Oxidation of 1 with the nitrosonium ion solubilized with a crown ether gave the aminium polyradicals (1(+)()) which were durable (half-life > 1 month) at room temperature in air. A high-spin ground state with an average S = (4.5)/2 for 1a(+) was proved even at room temperature by magnetic susceptibility, magnetization, ESR, and NMR measurements.

Kinetics of the reactions of the acid anhydrides with aromatic amines in aprotic solvents. M.S. Thesis. Final Report

NASA Technical Reports Server (NTRS)

Sugg, E.; Mason, J. G.

1983-01-01

Work has revealed that diamine derivatives of diphenylmethane (IV), diphenyl ether (V), benzophenone (IV), fluorene (VII), and fluorenone (VIII) polymerizations with pyromellitic dianhydride in DMA were dependent on the basicity of the amine compound. The correlation between the basicity of the amine and its reactivity with phthalic anhydride was determined. Basicity measurements were made by potentiometric titration of each amine in an acetonitrile-water solvent system, from which the pKa of the amine could be determined. Reactivity was defined in terms of the second order rate constant derived form spectrophotometric examination of the reaction between each amine and phthalic anhydride in DMA. This reaction was expected to proceed in either one (for a monoamine) or two (for a diamine) stages.

Polymeric film application for phase change heat transfer

NASA Astrophysics Data System (ADS)

Bart, Hans-Jörg; Dreiser, Christian

2018-01-01

The paper gives a concise review on polymer film heat exchangers (PFHX) with a focus on polyether ether ketone (PEEK) foil as heat transfer element, mechanically supported by a grid structure. In order to promote PFHX applications, heat transfer performance and wetting behavior are studied in detail. Surface modifications to improve wetting are discussed and correlations are presented for critical Reynolds numbers to sustain a stable liquid film. Scaling phenomena related to surface properties and easily adaptable cleaning-in-place (CIP) procedures are further content. The contribution of the foil thickness and material selection on thermal performance is quantified and a correlation for enhanced aqueous film heat transfer for the grid supported PFHX is given. The basic research results and the design criteria enable early stage material selection and conceptual apparatus design.

Modification of fast-growing Chinese Fir wood with unsaturated polyester resin: Impregnation technology and efficiency

NASA Astrophysics Data System (ADS)

Ma, Qing; Zhao, Zijian; Yi, Songlin; Wang, Tianlong

In this study, Chinese Fir was impregnated with unsaturated polyester resin to enhance its properties. Samples 20 mm × 20 mm × 20 mm in size were split into different sections with epoxy resin and tinfoil and subjected to an impregnation experiment under various parameters. Vacuum degree was -0.04 MPa, -0.06 MPa or -0.08 MPa and vacuum duration was 15 min, 30 min, or 45 min. The results indicated that impregnation weight percent gain is linearly dependent on curing weight percent gain. Vacuum duration appears to have less influence on the curing weight percent gain than vacuum degree, and impregnation was most successful at the transverse section compared to other sections. The optimal impregnation parameters were 30 min modification under -0.08 MPa vacuum followed by 120 min at atmospheric pressure for samples 200 mm × 100 mm × 20 mm in size. Uneven distribution of weight percent gain and cracking during the curing process suggested that 30 min post-processing at -0.09 MPa vacuum was the most effective way to complete the impregnation process. The sample's bending strength and modulus of elasticity increased after impregnation treatment. Bending strength after impregnation without post-processing reached 112.85%, but reached 71.65% with vacuum-processing; modulus of elasticity improved 67.13% and 58.28% without and with post-processing, respectively.

Removal of hydrogen sulfide and sulfur dioxide by carbons impregnated with triethylenediamine.

PubMed

Wu, Li-Chun; Chang, Tsu-Hua; Chung, Ying-Chien

2007-12-01

Activated carbon (AC) adsorption has long been considered to be a readily available technology for providing protection against exposure to acutely toxic gases. However, ACs without chemical impregnation have proven to be much less efficient than impregnated ACs in terms of gas removal. The impregnated ACs in current use are usually modified with metalloid impregnation agents (ASC-carbons; copper, chromium, or silver) to simultaneously enhance the chemical and physical properties of the ACs in removing specific poisonous gases. These metalloid agents, however, can cause acute poisoning to both humans and the environment, thereby necessitating the search for organic impregnation agents that present a much lower risk. The aim of the study reported here was to assess AC or ASC-carbon impregnated with triethylenediamine (TEDA) in terms of its adsorption capability for simulated hydrogen sulfide (H2S) and sulfur dioxide (SO2) gases. The investigation was undergone in a properly designed laboratory-scale and industrial fume hood evaluation. Using the system reported here, we obtained a significant adsorption: the removal capability for H2S and SO2 was 375 and 229 mg/g-C, respectively. BET measurements, element analysis, scanning electron microscopy, and energy dispersive spectrometry identified the removal mechanism for TEDA-impregnated AC to be both chemical and physical adsorption. Chemical adsorption and oxidation were the primary means by which TEDA-impregnated ASC-carbons removed the simulated gases.

Impregnated active carbons to control atmospheric emissions: influence of impregnation methodology and raw material on the catalytic activity.

PubMed

Alvim-Ferraz, Maria C M; Gaspar, Carla M T B

2005-08-15

Previous studies have reported the influence of raw material on the catalytic activity of metal oxides impregnated in activated carbons. However, knowledge was as yet quite scarce for impregnation performed before activation. The main objective of the study here reported was the development of such knowledge. Olive stones, pinewood sawdust, nutshells, and almond shells were recycled to prepare the activated carbons. Transition metal oxides (CoO, Co3O4, and CrO3) were impregnated aiming to prepare activated carbons to be used for the complete catalytic oxidation of benzene. When impregnation was performed after activation the impregnated species were deposited on the internal surface, blocking part of the initial porous texture. When impregnation was performed before activation, the metal species acted as catalysts during the activation step, allowing better catalyst distribution on a more well-developed mesoporous texture. Co3O4 was the best catalyst and almond shells were the best support. With this catalyst/support pair a conversion of 90% was possible at 404 K, the lowest temperature of all the carbons studied. Good conversions were obtained at temperatures that guarantee carbon stability (lower than 575 K). It was concluded that activated carbon was a suitable support for metal oxide catalysts aiming for the complete oxidation of benzene, especially when a suitable porous texture is induced, by performing the impregnation step before activation.

Advanced clay nanocomposites based on in situ photopolymerization utilizing novel polymerizable organoclays

NASA Astrophysics Data System (ADS)

Kim, Soon Ki

Polymer nanocomposite technology has had significant impact on material design. With the environmental advantages of photopolymerization, a research has recently focused on producing nanocomposites utilizing inexpensive clay particles based on in situ photopolymerization. In this research, novel polymerizable organoclays and thiol-ene photopolymerization have been utilized to develop advanced photopolymer clay nanocomposites and to overcome several limitations in conventional free radical photopolymers. To this end, factors important in nanocomposite processes such as monomer composition, clay dispersion, and photopolymerization behavior in combination with the evolution of ultimate nanocomposite properties have been investigated. For monomer-organoclay compositions, higher chemical compatibility of components induces enhanced clay exfoliation, resulting in photopolymerization rate increases due to an amplified clay template effect. Additionally, by affecting the stoichiometric ratio between thiol and acrylate double bond in the clay gallery, thiolated organoclays enhance thiol-ene copolymerization with increased final thiol conversion while acrylated organoclays encourage acrylate homopolymerization. In accordance with the reaction behavior, incorporation of thiolated organoclays makes polymer chains more flexible with decreased glass transition temperature due to higher formation of thio-ether linkages while adding acrylated organoclays significantly increases the modulus. Photopolymer nanocomposites also help overcome two major drawbacks in conventional free radical photopolymerization, namely severe polymerization shrinkage and oxygen inhibition during polymerization. With addition of a low level of thiol monomers, the oxygen inhibition in various acrylate systems can be overcome by addition of only 5wt% thiolated organoclay. The same amount of polymerizable organoclay also induces up to 90% decreases in the shrinkage stress for acrylate or thiol-acrylate systems. However, nonreactive clays do not reduce the stress substantially and even decreases the polymerization rate in air. Additionally, the clay morphology and polymerization behavior are closely related with evolution of ultimate nanocomposite performance. Use of polymerizable organoclay significantly improves overall toughness of nanocomposites by increasing either modulus or elongation at break based on the type of polymerizable organoclay, which demonstrates the promise of this technology as a modulation and/or optimization tool for nanocomposite properties.

Separation and purification of polyphenols from red wine extracts using high speed counter current chromatography.

PubMed

Li, Yuanyuan; Li, Lingxi; Cui, Yan; Zhang, Shuting; Sun, Baoshan

2017-06-01

Polyphenols are important compounds of red wine owing to their contribution to sensory properties and antioxidant activities. In this study, high-speed counter-current chromatography (HSCCC) coupled with semi-preparative HPLC was used for large-scale separation and purification of polyphenols from red wine extracts. With the solvent system of hexane-ethyl acetate-water (1-50-50), various oligomeric procyanidins including monomer catechin, epicatechin, dimers B1, B2; phenolic acids including coutaric acid, caftaric acid and other type of polyphenols were largely separated within 370min and most of these compounds presented high yields (0.97mg to 13.79mg) with high purity (90.34% to 98.91%) after the semi-preparative HPLC isolation. Using the solvent system of Methyl tert-Butyl Ether (MTBE) - n-butyl alcohol- acetonitrile-water (1-40-1-50, acidified with 0.01% trifluoroacetic acid (TFA)) by one-step HSCCC of 100mg of the red wine extracts, the major anthocyanins, i.e., malvidin-3-O-glucoside, delphinidin-3-O-glucoside and peonidin-3-O-glucoside, as well as two polymeric proanthocyanidin fractions were successfully separated one another within 320min. The yields of malvidin-3-O-glucoside, delphinidin-3-O-glucoside and peonidin-3-O-glucoside were 12.12mg, 1.78mg and 11.57mg with the purity of 92.74%, 91.03% and 91.21%, respectively. Thiolysis-UPLC analysis indicated that the two polymeric proanthocyanidin fractions presented high purity, with mean degree of polymerization of 7.66±0.12 and 6.20±0.09, respectively. The further experiments on the antioxidant activities by DPPH radical test, FRAP assay and ABTS method showed that all of the isolated procyandins and anthocyanins and the two polymeric proanthocyanidin fractions, with exception of phenolic acids possessed much greater antioxidant activities compared to standard Trolox andl-ascorbic acid (2-14 times). Copyright © 2017 Elsevier B.V. All rights reserved.

Study of porous silicon optical waveguides impregnated with organic dyes

NASA Astrophysics Data System (ADS)

Pirasteh, P.; Charrier, J.; Dumeige, Y.; Chaillou, A.; Guendouz, M.; Haji, L.

2007-01-01

Planar waveguides were made using oxidised porous silicon layers. Then, they were impregnated with Congo Red or Disperse Red 1 dyes. Optical losses were investigated before and after impregnation. In our case, the losses of impregnated waveguides were always higher than those of non-impregnated ones. In order to achieve a better understanding of the origin of these losses, we not only studied the absorbance of solutions which would impregnate the porous layers but also the reflectance spectra of the obtained composite materials. According to the measurements, the increase in losses in the visible spectrum depends on the intrinsic absorption of the dye while in NIR, the increase would be due to an accumulation of dried dye on the surface of the waveguide which would give rise to the surface scattering losses.

A Mathematical Model for Continuous Fiber Reinforced Thermoplastic Composite in Melt Impregnation

NASA Astrophysics Data System (ADS)

Ren, Feng; Yu, Yang; Yang, Jianjun; Xin, Chunling; He, Yadong

2017-06-01

Through the combination of Reynolds equation and Darcy's law, a mathematical model was established to calculate the pressure distribution in wedge area, which contributed to the forecast effect of processing parameters on impregnation degree of the fiber bundle. The experiments were conducted to verify the capacity of the proposed model with satisfactory results, which means that the model is effective in predicting the influence of processing parameters on impregnation. From the mathematical model, it was known that the impregnation degree of the fiber bundle would be improved by increasing the processing temperature, number and radius of pins, or decreasing the pulling speed and the center distance of pins, which provided a possible solution to the difficulty of melt with high viscosity in melt impregnation and optimization of impregnation processing.

Iron-impregnated granular activated carbon for arsenic removal from drinking water

NASA Astrophysics Data System (ADS)

Chang, Qigang

A new multi-step iron impregnation method was developed in this study to impregnate GAC with a high amount of iron that possesses desired characteristics: stable, even distribution, and high arsenic adsorption capacity. Research was carried out to investigate the impact of the amount of impregnated iron on arsenic adsorption properties: capacity, affinity, and kinetics. Fe-GACs were characterized in terms of the amount, stability, distribution, morphology, and species of impregnated iron. It was found that a high amount of iron was stably impregnated in GAC. Scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS) analysis demonstrated that the impregnated iron was evenly distributed on the internal surface of GAC. Impregnated iron formed nano-size particles and existed in both crystalline (akaganeite) and amorphous iron. Arsenic adsorption tests were conducted using Fe-GACs with iron content of 1.64--28.90% in a low arsenic concentration that is typical for drinking water treatment. The amount of impregnated iron affects arsenic maximum adsorption capacity (qm) but has little impact on the Langmuir constant h (the affinity of adsorbent for adsorbate). The qm for both As(V) and As(III) adsorptions increased significantly with increase of the amount of impregnated iron up to 13.59%. Further increase of iron amounts caused a gradual decrease of qm for As(V). BET analysis indicated impregnated iron possesses the highest surface area at iron content of 13.59%. A new second-order kinetic model was developed to investigate the impact of the amounts of impregnated iron on arsenic adsorption kinetics. With iron content increased from 1.64% to 28.90%, the intrinsic adsorption rate constants reduced from 4.6x10-2 1/hr to 1.18x10 -3 1/hr, which indicates that impregnated iron slows arsenic intraparticle diffusion rate in Fe-GAC. The decreased arsenic intraparticle diffusion rate was most likely caused by reduced pore size of Fe-GACs. Column tests were conducted to investigate the performance of Fe-GACs in real implementations using groundwater taken from a former superfund site in North Dakota. Fe-GACs can remove arsenic below 10 microg/L and the performance of Fe-GACs was significantly enhanced with increasing empty bed contact time.

Clinical review: Efficacy of antimicrobial-impregnated catheters in external ventricular drainage - a systematic review and meta-analysis.

PubMed

Wang, Xiang; Dong, Yan; Qi, Xiang-Qian; Li, Yi-Ming; Huang, Cheng-Guang; Hou, Li-Jun

2013-07-25

To assess the efficacy of antimicrobial-impregnated catheters in preventing catheter-related infections during external ventricular drainage (EVD), we performed a meta-analysis and systematic review. We systematically searched Medline, Embase, and the Cochrane Library. All randomized controlled trials (RCTs) and nonrandomized prospective studies (NPSs) related to antimicrobial-impregnated EVD catheters were included. The primary outcome was the rate of cerebrospinal fluid infection (CFI). The secondary outcomes included the rate of time-dependent CFI and catheter bacterial colonization. We further performed subgroup analysis, meta-regression analysis, and microbial spectrum analysis. Four RCTs and four NPSs were included. The overall rate of CFIs was 3.6% in the antimicrobial-impregnated catheter group and 13.7% in the standard catheter group. The pooled data demonstrated that antimicrobial-impregnated catheters were superior to standard catheters in lowering the rate of CFIs (odds ratio (OR) = 0.25, 95% confidence interval (CI) = 0.12 to 0.52, P <0.05). In survival analysis, the 20-day infection rate was significantly reduced with the use of antimicrobial-impregnated catheters (hazard ratio = 0.52, 95% CI = 0.29 to 0.95, P <0.05). Furthermore, a significantly decreased rate of catheter bacterial colonization was noticed for antimicrobial-impregnated catheters (OR = 0.37, 95% CI = 0.21 to 0.64, P <0.05). In subgroup analyses, although significant results remained for RCTs and NPSs, a subgroup difference was revealed (P <0.05). Compared with standard catheters, a significantly lower rate of CFIs was noticed for clindamycin/rifampin-impregnated catheters (OR = 0.27, 95% CI = 0.10 to 0.73, P <0.05) and for minocycline/rifampin-impregnated catheters (OR = 0.11, 95% CI = 0.06 to 0.21, P <0.05). However, no statistical significance was found when compared with silver-impregnated catheters (OR = 0.33, 95% CI = 0.07 to 1.69, P = 0.18). In microbial spectrum analysis, antimicrobial-impregnated catheters were shown to have a lower rate of Gram-positive bacterial infection, particularly the coagulase-negative Staphylococcus. In conclusion, the use of antimicrobial-impregnated EVD catheters could be beneficial for the prevention of CFI and catheter bacterial colonization. Although antibiotic-coated catheters seem to be effective, no sufficient evidence supports the efficacy of silver-impregnated catheters.

Clinical review: Efficacy of antimicrobial-impregnated catheters in external ventricular drainage - a systematic review and meta-analysis

PubMed Central

2013-01-01

To assess the efficacy of antimicrobial-impregnated catheters in preventing catheter-related infections during external ventricular drainage (EVD), we performed a meta-analysis and systematic review. We systematically searched Medline, Embase, and the Cochrane Library. All randomized controlled trials (RCTs) and nonrandomized prospective studies (NPSs) related to antimicrobial-impregnated EVD catheters were included. The primary outcome was the rate of cerebrospinal fluid infection (CFI). The secondary outcomes included the rate of time-dependent CFI and catheter bacterial colonization. We further performed subgroup analysis, meta-regression analysis, and microbial spectrum analysis. Four RCTs and four NPSs were included. The overall rate of CFIs was 3.6% in the antimicrobial-impregnated catheter group and 13.7% in the standard catheter group. The pooled data demonstrated that antimicrobial-impregnated catheters were superior to standard catheters in lowering the rate of CFIs (odds ratio (OR) = 0.25, 95% confidence interval (CI) = 0.12 to 0.52, P <0.05). In survival analysis, the 20-day infection rate was significantly reduced with the use of antimicrobial-impregnated catheters (hazard ratio = 0.52, 95% CI = 0.29 to 0.95, P <0.05). Furthermore, a significantly decreased rate of catheter bacterial colonization was noticed for antimicrobial-impregnated catheters (OR = 0.37, 95% CI = 0.21 to 0.64, P <0.05). In subgroup analyses, although significant results remained for RCTs and NPSs, a subgroup difference was revealed (P <0.05). Compared with standard catheters, a significantly lower rate of CFIs was noticed for clindamycin/rifampin-impregnated catheters (OR = 0.27, 95% CI = 0.10 to 0.73, P <0.05) and for minocycline/rifampin-impregnated catheters (OR = 0.11, 95% CI = 0.06 to 0.21, P <0.05). However, no statistical significance was found when compared with silver-impregnated catheters (OR = 0.33, 95% CI = 0.07 to 1.69, P = 0.18). In microbial spectrum analysis, antimicrobial-impregnated catheters were shown to have a lower rate of Gram-positive bacterial infection, particularly the coagulase-negative Staphylococcus. In conclusion, the use of antimicrobial-impregnated EVD catheters could be beneficial for the prevention of CFI and catheter bacterial colonization. Although antibiotic-coated catheters seem to be effective, no sufficient evidence supports the efficacy of silver-impregnated catheters. PMID:23890254

Apparatus for coating and impregnating filament with resin

DOEpatents

Robinson, S.C.; Pollard, R.E.

1986-12-17

The present invention is directed to an apparatus for evenly coating and impregnating a filament with binder material. Dimension control and repeatability of the coating and impregnating characteristics are obtained with the apparatus.

Dielectric characterization of high-performance spaceflight materials

NASA Astrophysics Data System (ADS)

Kleppe, Nathan; Nurge, Mark A.; Bowler, Nicola

2015-03-01

As commercial space travel increases, the need for reliable structural health monitoring to predict possible weaknesses or failures of structural materials also increases. Monitoring of these materials can be done through the use of dielectric spectroscopy by comparing permittivity or conductivity measurements performed on a sample in use to that of a pristine sample from 100 μHz to 3 GHz. Fluctuations in these measured values or of the relaxation frequencies, if present, can indicate chemical or physical changes occurring within the material and the possible need for maintenance/replacement. In this work, we establish indicative trends that occur due to changes in dielectric spectra during accelerated aging of various high-performance polymeric materials: ethylene vinyl alcohol (EVOH), Poly (ether ether ketone) (PEEK), polyphenylene sulfide (PPS), and ultra-high molecular weight polyethylene (UHMWPE). Uses for these materials range from electrical insulation and protective coatings to windows and air- or space-craft parts that may be subject to environmental damage over long-term operation. Samples were prepared by thermal exposure and, separately, by ultraviolet/water-spray cyclic aging. The aged samples showed statistically-significant trends of either increasing or decreasing real or imaginary permittivity values, relaxation frequencies, conduction or the appearance of new relaxation modes. These results suggest that dielectric testing offers the possibility of nondestructive evaluation of the extent of age-related degradation in these materials.

Interfacial Chemistry Regulation via a Skin-Grafting Strategy Enables High-Performance Lithium-Metal Batteries

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

Gao, Yue; Zhao, Yuming; Li, Yuguang C.

The lithium (Li) metal anode suffers severe interfacial instability from its high reactivity toward liquid electrolytes, especially carbonate-based electrolytes, resulting in poor electrochemical performance of batteries that use 4 V high-capacity cathodes. In this paper, we report a new skin-grafting strategy that stabilizes the Li metal–liquid electrolyte interface by coating the Li metal surface with poly((N-2,2-dimethyl-1,3-dioxolane-4-methyl)-5-norbornene-exo-2,3-dicarboximide), a chemically and electrochemically active polymer layer. This layer, composed of cyclic ether groups with a stiff polycyclic main chain, serves as a grafted polymer skin on the Li metal anode not only to incorporate ether-based polymeric components into the solid-electrolyte interphase (SEI) butmore » also to accommodate Li deposition/dissolution under the skin in a dendrite/moss-free manner. Consequently, a Li-metal battery employing a Li metal anode with the grafted skin paired with LiNi 0.5Co 0.2Mn 0.3O 2 cathode has a 90.0% capacity retention after 400 charge/discharge cycles and a capacity of 1.2 mAh/cm 2 in a carbonate-based electrolyte. Finally, this proof-of-concept study provides a new direction for regulating the interfacial chemistry of Li metal anodes and for enabling high-performance Li-metal batteries.« less

Interfacial Chemistry Regulation via a Skin-Grafting Strategy Enables High-Performance Lithium-Metal Batteries

DOE PAGES

Gao, Yue; Zhao, Yuming; Li, Yuguang C.; ...

2017-10-06

The lithium (Li) metal anode suffers severe interfacial instability from its high reactivity toward liquid electrolytes, especially carbonate-based electrolytes, resulting in poor electrochemical performance of batteries that use 4 V high-capacity cathodes. In this paper, we report a new skin-grafting strategy that stabilizes the Li metal–liquid electrolyte interface by coating the Li metal surface with poly((N-2,2-dimethyl-1,3-dioxolane-4-methyl)-5-norbornene-exo-2,3-dicarboximide), a chemically and electrochemically active polymer layer. This layer, composed of cyclic ether groups with a stiff polycyclic main chain, serves as a grafted polymer skin on the Li metal anode not only to incorporate ether-based polymeric components into the solid-electrolyte interphase (SEI) butmore » also to accommodate Li deposition/dissolution under the skin in a dendrite/moss-free manner. Consequently, a Li-metal battery employing a Li metal anode with the grafted skin paired with LiNi 0.5Co 0.2Mn 0.3O 2 cathode has a 90.0% capacity retention after 400 charge/discharge cycles and a capacity of 1.2 mAh/cm 2 in a carbonate-based electrolyte. Finally, this proof-of-concept study provides a new direction for regulating the interfacial chemistry of Li metal anodes and for enabling high-performance Li-metal batteries.« less

Curing kinetics and thermomechanical properties of latent epoxy/carbon fiber composites

NASA Astrophysics Data System (ADS)

Dalle Vacche, S.; Michaud, V.; Demierre, M.; Bourban, P.-E.; Månson, J.-A. E.

2016-07-01

In this work, resins based on diglycidyl ether of bisphenol A (DGEBA) epoxy and a latent hardener, dicyandiamide (DICY), as well as carbon fiber (CF) composites based on them, were prepared with three commercial accelerators: a methylene bis (phenyl dimethyl urea), a cycloaliphatic substituted urea, and a modified polyamine. The curing kinetics of the three DGEBA/DICY/accelerator systems were investigated by chemorheology and differential scanning calorimetry (DSC), in isothermal and over temperature change conditions. Differences in the reaction onset temperature, and in the glass transition temperature (Tg) were highlighted. For curing of thick resin samples, a slow curing cycle at the lowest possible temperature was used, followed by high temperature (160 - 180 °C) post-curing. Indeed, fast curing at higher temperatures caused the formation of hot spots and led to local burning of the samples. The obtained thermomechanical properties, assessed by ultimate tensile testing and dynamic mechanical analysis (DMA) in single cantilever configuration, were all in the expected range for epoxy resins, with tensile moduli close to 3 GPa and Tg > 140 °C. The longterm stability of these resins at room temperature was verified by DSC. Composite samples were prepared by hand lay-up by manually impregnating four layers of 5-harness satin CF textile, and curing in vacuum bag. Impregnation quality and void content were assessed by optical microscopy. The flexural properties of the post-cured composites were assessed by three-point bending test at room temperature and showed no relevant differences, all composites having bending moduli of 45 - 50 GPa. Finally, composites cured with a faster high temperature curing cycle (20 min at 140 °C) were prepared with the DGEBA/DICY/ methylene bis (phenyl dimethyl urea) system, obtaining similar properties as with the slower curing cycle, showing that the prepreg system allowed more flexibility in terms of curing cycle than the bulk resin samples.

The identity of Romanian amber (rumanite) with Baltic amber (succinite).

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

Stout, E. C.; Beck, C. W.; Anderson, K. B.

Romanian amber (rumanite) has been considered to be a separate species of fossil resin for more than a century. While earlier investigators held it to be very similar to succinite (Baltic amber), modern scholars have assigned it a distinctly different botanical origin. We have found that almost all of the constituents of the ether-soluble fractions of 13 specimens of authentic rumanite identified by gas chromatography-mass spectrometry have previously been reported in the soluble fraction of succinite, including succinic acid and its monoterpene esters. Additionally and significantly, the soluble fraction of rumanite contains a number defunctionalized compounds that do not preexistmore » in succinite, but that are produced by pyrolysis of whole succinite or of its insoluble polymeric fraction. Simultaneous methylation pyrolysis-gas chromatography-mass spectrometry of the polymeric fraction of seven of the rumanite specimens yielded further copious amounts of dimethyl succinate, a number of diterpene resin acid methyl esters, and additional defunctionalized compounds known to be pyrolysis products of succinite. The evidence shows conclusively that the botanical origin of rumanite is not distinct from that of succinite. Rather, rumanite is a succinite that has suffered partial thermal degradation in the course of the folding of the Oligocene Kliwa sandstone formation in which it is most commonly found.« less

Effect of diblock copolymer properties on the photophysical properties of dendrimer silicon phthalocyanine nanoconjugates

NASA Astrophysics Data System (ADS)

Chen, Kuizhi; Pan, Sujuan; Zhuang, Xuemei; Lv, Hafei; Que, Shoulin; Xie, Shusen; Yang, Hongqin; Peng, Yiru

2016-07-01

1-2 generation poly(benzyl aryl ether) dendrimer silicon phthalocyanines with axially disubstituted cyano terminal functionalities (G n -DSiPc(CN)4 n , (G n = n-generation dendrimer, n = 1-2)) were synthesized. Their structures were characterized by elemental analysis, IR, 1H NMR, and ESI-MS. Polymeric nanoparticles (G n -DSiPc(CN)4 n /m) were formed through encapsulating G n -DSiPc(CN)4 n into three monomethoxyl poly(ethylene glycol)-poly(ɛ-caprolactone) diblock copolymers (MPEG-PCL) with different hydrophilic/hydrophobic proportion, respectively. The effect of dendritic generation and the hydrophilic/hydrophobic proportion of diblock copolymers on the UV/Vis and fluorescence spectra of G n -DSiPc(CN)4 n and G n -DSiPc(CN)4 n /m were studied. The photophysical properties of polymeric nanoparticles exhibited dendritic generation and hydrophilic/hydrophobic proportion dependence. The fluorescence intensities and lifetimes of G n -DSiPc(CN)4 n /m were lower than the corresponding free dendrimer phthalocyanines. G n -DSiPc(CN)4 n encapsulated into MPEG-PCL with hydrophilic/hydrophobic molecular weight ratio 2000:4000 exhibited excellent photophysical property. The mean diameter of MPEG2000-PCL2000 micelles was about 70 nm, which decreased when loaded with G n -DSiPc(CN)4 n .

pH-responsive micelles based on (PCL)2(PDEA-b-PPEGMA)2 miktoarm polymer: controlled synthesis, characterization, and application as anticancer drug carrier.

PubMed

Lin, Wenjing; Nie, Shuyu; Xiong, Di; Guo, Xindong; Wang, Jufang; Zhang, Lijuan

2014-01-01

Amphiphilic A2(BC)2 miktoarm star polymers [poly(ϵ-caprolactone)]2-[poly(2-(diethylamino)ethyl methacrylate)-b- poly(poly(ethylene glycol) methyl ether methacrylate)]2 [(PCL)2(PDEA-b-PPEGMA)2] were developed by a combination of ring opening polymerization (ROP) and continuous activators regenerated by electron transfer atom transfer radical polymerization (ARGET ATRP). The critical micelle concentration (CMC) values were extremely low (0.0024 to 0.0043 mg/mL), depending on the architecture of the polymers. The self-assembled empty and doxorubicin (DOX)-loaded micelles were spherical in morphologies, and the average sizes were about 63 and 110 nm. The release of DOX at pH 5.0 was much faster than that at pH 6.5 and pH 7.4. Moreover, DOX-loaded micelles could effectively inhibit the growth of cancer cells HepG2 with IC50 of 2.0 μg/mL. Intracellular uptake demonstrated that DOX was delivered into the cells effectively after the cells were incubated with DOX-loaded micelles. Therefore, the pH-sensitive (PCL)2(PDEA-b-PPEGMA)2 micelles could be a prospective candidate as anticancer drug carrier for hydrophobic drugs with sustained release behavior.

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.

Macroporous polyacrylamide monolithic gels with immobilized metal affinity ligands: the effect of porous structure and ligand coupling chemistry on protein binding.

PubMed

Plieva, Fatima; Bober, Beata; Dainiak, Maria; Galaev, Igor Yu; Mattiasson, Bo

2006-01-01

Macroporous polyacrylamide gels (MPAAG) with iminodiacetic acid (IDA) functionality were prepared by (i) chemical modification of polyacrylamide gel, (ii) co-polymerization of acrylamide with allyl glycidyl ether (AGE) and N,N'metylene-bis(acrylamide) (MBAAm) followed by coupling IDA ligand or (iii) by copolymerization of acrylamide and MBAAm with functional monomer carrying IDA-functionality (1-(N,N-bis(carboxymethyl)amino-3-allylglycerol). Screening for optimized conditions for the production of the MPAAG with required porous properties was performed in a 96-well chromatographic format that allowed parallel production and analysis of the MPAAG prepared from reaction mixtures with different compositions. Scanning electron microscopy of the fabricated MPAAG revealed two different types of the porous structures: monomodal macroporous structure with large interconnected pores separated by dense non-porous pore walls in case of plain gels or gels produced via copolymerization with AGE. The other type of the MPAAG (gel produced via co-polymerization with functional monomer carrying IDA-functionality) had bimodal pore structure with large interconnected pores separated by the pore walls pierced through with micropores. The effect of different modifications of MPAAG monoliths and of porous structure of the MPAAG (monomodal and bimodal porous structure) on protein binding has been evaluated. Copyright 2006 John Wiley & Sons, Ltd.

Impregnation of Ibuprofen into Polycaprolactone using supercritical carbon dioxide

NASA Astrophysics Data System (ADS)

Yoganathan, Roshan; Mammucari, Raffaella; Foster, Neil R.

2010-03-01

Polycaprolactone (PCL) is a Food and Drug Administration (FDA) approved biodegradable polyester used in tissue engineering applications. Ibuprofen is an anti-inflammatory drug which has good solubility in supercritical CO2 (SCCO2). The solubility of CO2 in PCL allows for the impregnation of CO2-soluble therapeutic agents into the polymer via a supercritical fluid (SCF) process. Polymers impregnated with bio-active compounds are highly desired for medical implants and controlled drug delivery. In this study, the use of CO2 to impregnate PCL with ibuprofen was investigated. The effect of operating conditions on the impregnation of ibuprofen into PCL was investigated over two pressure and two temperature levels, 150bar and 200bar, 35°C and 40 °C, respectively. Polycaprolactone with drug-loadings as high as 27% w/w were obtained. Impregnated samples exhibited controlled drug release profiles over several days.

40 CFR Table 6 to Subpart Jj of... - VHAP of Potential Concern

Code of Federal Regulations, 2011 CFR

2011-07-01

... glycol butyl ether, ethylene glycol ethyl ether (2-ethoxy ethanol), ethylene glycol hexyl ether, ethylene..., ethylene glycol mono-2-ethylhexyl ether, diethylene glycol butyl ether, diethylene glycol ethyl ether... glycol propyl ether, triethylene glycol butyl ether, triethylene glycol ethyl ether, triethylene glycol...

Bio-inspired surfactant assisted nano-catalyst impregnation of Solid-Oxide Fuel Cell (SOFC) electrodes

DOE PAGES

Ozmen, Ozcan; Zondlo, John W.; Lee, Shiwoo; ...

2015-11-02

A bio-inspired surfactant was utilized to assist in the efficient impregnation of a nano-CeO₂ catalyst throughout both porous Solid Oxide Fuel Cells (SOFC’s) electrodes simultaneously. The process included the initial modification of electrode pore walls with a polydopamine film. The cell was then submersed into a cerium salt solution. The amount of nano-CeO₂ deposited per impregnation step increased by 3.5 times by utilizing this two-step protocol in comparison to a conventional drip impregnation method. The impregnated cells exhibited a 20% higher power density than a baseline cell without the nano-catalyst at 750°C (using humid H₂ fuel).

The Future of Carbon Dioxide for Polymer Processing in Tissue Engineering

PubMed Central

Bhamidipati, Manjari; Scurto, Aaron M.

2013-01-01

The use of CO2 for scaffold fabrication in tissue engineering was popularized in the mid-1990s as a tool for producing polymeric foam scaffolds, but had fallen out of favor to some extent, in part due to challenges with pore interconnectivity. Pore interconnectivity issues have since been resolved by numerous dedicated studies that have collectively outlined how to control the appropriate parameters to achieve a pore structure desirable for tissue regeneration. In addition to CO2 foaming, several groups have leveraged CO2 as a swelling agent to impregnate scaffolds with drugs and other bioactive additives, and for encapsulation of plasmids within scaffolds for gene delivery. Moreover, in contrast to CO2 foaming, which typically relies on supercritical CO2 at very high pressures, CO2 at much lower pressures has also been used to sinter polymeric microspheres together in the presence of cells to create cell-seeded scaffolds in a single step. CO2 has a number of advantages for polymer processing in tissue engineering, including its ease of use, low cost, and the opportunity to circumvent the use of organic solvents. Building on these advantages, and especially now with the tremendous precedent that has paved the way in defining operating parameters, and making the technology accessible for new groups to adapt, we invite and encourage our colleagues in the field to leverage CO2 as a new tool to enhance their own respective unique capabilities. PMID:23289736

Reverse Micelle Synthesis and Characterization of Supported Pt/Ni Bimetallic Catalysts on gamma-Al2O3

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

B Cheney; J Lauterbach; J Chen

2011-12-31

Reverse micelle synthesis was used to improve the nanoparticle size uniformity of bimetallic Pt/Ni nanoparticles supported on {gamma}-Al{sub 2}O{sub 3}. Two impregnation methods were investigated to optimize the use of the micelle method: (1) step-impregnation, where Ni nanoparticles were chemically reduced in microemulsion and then supported, followed by Pt deposition using incipient wetness impregnation, and (2) co-impregnation, where Ni and Pt were chemically reduced simultaneously in microemulsion and then supported. Transmission electron microscopy (TEM) was used to characterize the particle size distribution. Atomic absorption spectroscopy (AAS) was used to perform elemental analysis of bimetallic catalysts. Extended X-ray absorption fine structuremore » (EXAFS) measurements were utilized to confirm the formation of the Pt-Ni bimetallic bond in the step-impregnated catalyst. CO pulse chemisorption and Fourier transform infrared spectroscopy (FTIR) studies of 1,3-butadiene hydrogenation in a batch reactor were performed to determine the catalytic activity. Step-impregnated Pt/Ni catalyst demonstrated enhanced hydrogenation activity over the parent monometallic Pt and Ni catalysts due to bimetallic bond formation. The catalyst synthesized using co-impregnation showed no enhanced activity, behaving similarly to monometallic Ni. Overall, our results indicate that reverse micelle synthesis combined with incipient wetness impregnation produced small, uniform nanoparticles with bimetallic bonds that enhanced hydrogenation activity.« less

Electromembrane extraction combined with gas chromatography for quantification of tricyclic antidepressants in human body fluids.

PubMed

Davarani, Saied Saeed Hosseiny; Najarian, Amin Morteza; Nojavan, Saeed; Tabatabaei, Mohammad-Ali

2012-05-06

Recent advances in electromembrane extraction (EME) methodology calls for effective and accessible detection methods. Using imipramine and clomipramine as model therapeutics, this proof-of-principle work combines EME with gas chromatography analysis employing a flame ionization detector (FID). The drugs were extracted from acidic aqueous sample solutions, through a supported liquid membrane (SLM) consisting of 2-nitrophenyl octyl ether (NPOE) impregnated on the walls of the hollow fiber. EME parameters, such as SLM composition, type of ion carrier, pH and the composition of donor and acceptor solutions, agitation speed, extraction voltage, and extraction time were studied in detail. Under optimized conditions, the therapeutics were effectively extracted from different matrices with recoveries ranging from 90 to 95%. The samples were preconcentrated 270-280 times prior to GC analysis. Reliable linearity was also achieved for calibration curves with a regression coefficient of at least 0.995. Detection limits and intra-day precision (n=3) were less than 0.7 ng mL(-1) and 8.5%, respectively. Finally, method was applied to determination and quantification of drugs in human plasma and urine samples and satisfactory results were achieved. Copyright © 2012 Elsevier B.V. All rights reserved.

Self-disinfecting plastics for intravenous catheters and prosthetic inserts.

PubMed Central

Kingston, D.; Seal, D. V.; Hill, I. D.

1986-01-01

A disinfectant (2,4,4'-trichloro-2'-hydroxydiphenyl ether: Irgasan, Ciba-Geigy) was incorporated into plastic washers fabricated from ethylvinyl acetate (EVA), polyethylene, polypropylene or TPX. Plastics containing 0.2 and 2% Irgasan gave zones of inhibition on nutrient and blood agar plates seeded with micro-organisms (Staphylococcus aureus, Staph. epidermidis, Escherichia coli, Proteus mirabilis or Candida albicans) even after thorough washing. Exceptionally, C. albicans was inhibited only by 2% Irgasan, and EVA gave good inhibition only against the staphylococci. Similar washers of each plastic were implanted subcutaneously into the flanks of rabbits; before insertion each was washed, had thread woven into it and was surrounded by a plasma clot containing 2 X 10(8) Staph. aureus. All the plastics without Irgasan gave rise to abscesses, none of the plastics impregnated with 2% Irgasan did, though from 2 out of 12 sites small numbers of Staph. aureus were isolated at post mortem. Using either clinical or bacteriological criteria, the results were highly significant (P less than 0.00001 and P less than 0.001 respectively), demonstrating the effectiveness of this technique in preventing plastic-associated infection. Images Fig. 2 Fig. 2(Contd.) PMID:3517154

Studies of the kinetics and mechanisms of perfluoroether reactions on iron and oxidized iron surfaces

NASA Technical Reports Server (NTRS)

Napier, Mary E.; Stair, Peter C.

1992-01-01

Polymeric perfluoroalkylethers are being considered for use as lubricants in high temperature applications, but have been observed to catalytically decompose in the presence of metals. X-ray photoelectron spectroscopy (XPS) and temperature programmed desorption (TPD) were used to explore the decomposition of three model fluorinated ethers on clean polycrystalline iron surfaces and iron surfaces chemically modified with oxygen. Low temperature adsorption of the model fluorinated ethers on the clean, oxygen modified and oxidized iron surfaces was molecular. Thermally activated defluorination of the three model compounds was observed on the clean iron surface at remarkably low temperatures, 155 K and below, with formation of iron fluoride. Preferential C-F bond scission occurred at the terminal fluoromethoxy, CF3O, of perfluoro-1-methoxy-2-ethoxy ethane and perfluoro-1-methoxy-2-ethoxy propane and at CF3/CF2O of perfluoro-1,3-diethoxy propane. The reactivity of the clean iron toward perfluoroalkylether decomposition when compared to other metals is due to the strength of the iron fluoride bond and the strong electron donating ability of the metallic iron. Chemisorption of an oxygen overlayer lowered the reactivity of the iron surface to the adsorption and decomposition of the three model fluorinated ethers by blocking active sites on the metal surface. Incomplete coverage of the iron surface with chemisorbed oxygen results in a reaction which resembles the defluorination reaction observed on the clean iron surface. Perfluoro-1-methoxy-2-ethoxy ethane reacts on the oxidized iron surface at 138 K, through a Lewis acid assisted cleavage of the carbon oxygen bond, with preferential attack at the terminal fluoromethoxy, CF3O. The oxidized iron surface did not passivate, but became more reactive with time. Perfluoro-1-methoxy-2-ethoxy propane and perfluoro-1,3-diethoxy propane desorbed prior to the observation of decomposition on the oxidized iron surface.

Preparation and characterization of a siloxane containing bismaleimide

NASA Technical Reports Server (NTRS)

Maudgal, S.; St. Clair, T. L.

1984-01-01

A novel siloxane containing bismaleimide has been prepared by reacting maleic anhydride, benzophenonetetracarboxylic dianhydride and bis(gamma-aminopropyl)tetramethyldisiloxane. Characterization of this monomer was done by comparing its nuclear magnetic resonance spectrum (NMR) to those of model compounds. Solubility of the prepolymer was tested in amide, chlorinated and ether solvents. Films were cast from solution as well as by melt processing and a cure cycle was determined. Infrared spectrum (IR) of the resulting film was obtained. Thermal polymerization was investigated by differential scanning calorimetry (DSC). Thermal properties of the cured resin were followed by means of thermogravimetric analysis (TGA), torsional braid analysis (TBA) and dynamic mechanical analysis (DMA). Thermomechanical analysis (TMA) was used to study the effect of postcure on the glass transition temperature (Tg) of the resin. Adhesive strength of the resin was obtained at ambient temperature.

Construction of protein-resistant pOEGMA films by helicon plasma-enhanced chemical vapor deposition.

PubMed

Lee, Bong Soo; Yoon, Ok Ja; Cho, Woo Kyung; Lee, Nae-Eung; Yoon, Kuk Ro; Choi, Insung S

2009-01-01

This paper describes the formation of protein-resistant, poly(ethylene glycol) methyl ether methacrylate (pOEGMA) thin films by helicon plasma-enhanced chemical vapor deposition (helicon-PECVD). pOEGMA was successfully grafted onto a silicon substrate, as a model substrate, without any additional surface initiators, by plasma polymerization of OEGMA. The resulting pOEGMA films were characterized by ellipsometry, FT-IR spectroscopy, X-ray photoelectron spectroscopy and contact angle goniometry. To investigate the protein-resistant property of the pOEGMA films, four different proteins, bovine serum albumin, fibrinogen, lysozyme and ribonuclease A, were tested as model proteins for ellipsometric measurements. The ellipsometric thickness change for all the model proteins was less than 3 A, indicating that the formed pOEGMA films are protein-resistant. (c) Koninklijke Brill NV, Leiden, 2009

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

Wang, Hua; Zhou, Feng; Ren, Gerui

In this article, the SuFEx-based polycondensation between bisalkylsulfonyl fluorides (AA monomers) and bisphenol bis(t-butyldimethylsilyl) ethers (BB monomers) using [Ph 3P=N-PPh 3] +[HF 2] - as the catalyst is described. The AA monomers were prepared via the highly reliable Michael addition of ethenesulfonyl fluoride and amines/anilines while the BB monomers were obtained from silylation of bisphenols by t-butyldimethylsilyl chloride. With these reactions, a remarkable diversity of monomeric building blocks was achieved by exploiting readily available amines, anilines, and bisphenols as starting materials. The SuFEx-based polysulfonate formation reaction exhibited excellent efficiency and functional group tolerance, producing polysulfonates with a variety of sidemore » chain functionalities in >99 % conversion within 10 min to 1 h. When bearing an orthogonal group on the side chain, the polysulfonates can be further functionalized via click-chemistry-based post-polymerization modification.« less

Supercritical impregnation and optical characterization of loaded foldable intraocular lenses using supercritical fluids.

PubMed

Bouledjouidja, Abir; Masmoudi, Yasmine; Li, Yanfeng; He, Wei; Badens, Elisabeth

2017-10-01

To prepare drug-loaded intraocular lenses (IOLs) used to combine cataract surgery with postoperative complication treatment through supercritical impregnation while preserving their optical properties. Aix-Marseille Université, CNRS, Centrale Marseille, Laboratoire de Mécanique, Modélisation & Procédés Propres, Marseille, France, and He University Eye Hospital, Liaoning Province, China. Experimental study. Supercritical impregnations of commercial foldable IOLs used in cataract surgery with ciprofloxacin (an antibiotic) and dexamethasone 21-phosphate disodium salt (an antiinflammatory drug) were performed in a noncontinuous mode. Impregnation amounts were determined through drug-release kinetic studies. The optical characterizations of IOLs were determined by evaluating the dioptric power and the imaging quality by determining the modulating transfer function (MTF) at a specified spatial frequency according to the International Organization for Standardization (ISO 11979-2:2014). Transparent IOLs presenting an effective impregnation were obtained with a prolonged drug delivery during approximately 10 days. Optical characterizations (dioptric powers and MTF values) show preserved optical properties after supercritical treatment/impregnation. Supercritical treatments/impregnations do not damage the optical properties of IOLs and are therefore adequate for the preparation of delivery devices used for cataract surgery. Copyright © 2017. Published by Elsevier Inc.

Organogelator-Cellulose Composite for Practical and Eco-Friendly Marine Oil-Spill Recovery.

PubMed

Prathap, Annamalai; Sureshan, Kana M

2017-08-01

Marine oil spills pose serious threats to the ecosystem and economy. There is much interest in developing sorbents that can tackle such spills. We have developed a novel sorbent by impregnating cellulose pulp with a sugar-derived oleogelator, 1,2:5,6-di-O-cyclohexylidene-mannitol. The gelator molecules mask the surface-exposed hydroxyl groups of cellulose fibrils by engaging them in H-bonding and expose their hydrophobic parts making the fibers temporarily hydrophobic (water contact angle 110°). This sorbent absorbs oil effectively, selectively and instantly from oil-water mixtures due to its hydrophobicity. Then the gelator molecules get released uniformly in the oil and later self-assemble to fibers, as evident from SEM analysis, congealing the oil within the matrix. This hierarchical entrapment of the oil by non-covalent polymeric fibers within a covalent polymer matrix makes the gel very strong (230-fold increase in the yield stress) and rigid, making it suitable for practical use. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Superparamagnetic IPN gels of carrageenan/PHEMA excelling in shape retention.

PubMed

Tsuru, Takahiro; Sugimura, Kazuki; Nishio, Yoshiyuki

2017-12-15

Iron oxide nanoparticles-incorporated carrageenan (CAR)/PHEMA composites of interpenetrating network (IPN) type were successfully prepared by in situ ferrite synthesis in the polymer network. The IPN structure was constructed at CAR/PHEMA compositions of 15/85 and 40/60 (wt/wt) by polymerization and cross-linking of 2-hydroxyethylmethacrylate as an impregnating solvent of CAR gels. As a result of this IPN construction, the composites were firm and showed a good shape-retentivity in their gelatinous state. SQUID magnetometry and X-ray diffractometry were conducted for evaluation of the magnetic property of the inorganic-hybridized IPN composites. Magnetite particles with 10-30nm sizes were distributed inside the IPNs treated with the repeatable ferrite synthesis; thereby, the hybrids displayed a superparamagnetic character at ambient temperature. Specifically, the 40/60 CAR/PHEMA IPN imparted a practically passable value (10-15emu (g sample) -1 ) of saturation magnetization. The present IPN system offers a potential for application as a biocompatible magnetic material used in hydro-surroundings. Copyright © 2017 Elsevier Ltd. All rights reserved.

Development of PMMA membranes functionalized with hydroxypropyl-beta-cyclodextrins for controlled drug delivery using a supercritical CO(2)-assisted technology.

PubMed

Temtem, M; Pompeu, D; Jaraquemada, G; Cabrita, E J; Casimiro, T; Aguiar-Ricardo, A

2009-07-06

Cyclodextrin-containing polymers have proved themselves to be useful for controlled release. Herein we describe the preparation of membranes of poly(methylmethacrylate) (PMMA) containing hydroxypropyl-beta-cyclodextrins (HP-beta-CDs) using a supercritical CO(2)-assisted phase inversion method, for potential application as drug delivery devices. Results are reported on the membrane preparation, physical properties, and drug elution profile of a model drug. The polymeric membranes were obtained with HP-beta-CD contents ranging from 0 to 33.4 wt%, by changing the composition of the casting solution, and were further impregnated with ibuprofen using supercritical carbon dioxide (scCO(2)) in batch mode. The influence of the membrane functionalization in the controlled release of ibuprofen was studied by performing in vitro experiments in buffer solution pH at 7.4. The release of the anti-inflammatory drug could be tuned by varying the cyclodextrin content on the membranes.

Guar gum based biodegradable, antibacterial and electrically conductive hydrogels.

PubMed

Kaith, Balbir S; Sharma, Reena; Kalia, Susheel

2015-04-01

Guar gum-polyacrylic acid-polyaniline based biodegradable electrically conductive interpenetrating network (IPN) structures were prepared through a two-step aqueous polymerization. Hexamine and ammonium persulfate (APS) were used as a cross linker-initiator system to crosslink the poly(AA) chains on Guar gum (Ggum) backbone. Optimum reaction conditions for maximum percentage swelling (7470.23%) were time (min) = 60; vacuum (mmHg) = 450; pH = 7.0; solvent (mL) = 27.5; [APS] (mol L(-1)) = 0.306 × 10(-1); [AA] (mol L(-1)) = 0.291 × 10(-3) and [hexamine] (mol L(-1))=0.356 × 10(-1). The semi-interpenetrating networks (semi-IPNs) were converted into IPNs through impregnation of polyaniline chains under acidic and neutral conditions. Fourier transform infra-red spectroscopy (FTIR), thermogravimetric analysis (TGA) and scanning electron microscopy (SEM) techniques were used to characterize the semi-IPNs and IPNs. Synthesized semi-IPNs and IPNs were further evaluated for moisture retention in different soils, antibacterial and biodegradation behavior. Copyright © 2015 Elsevier B.V. All rights reserved.

Tunable Electromagnetic Coupling in Plasmonic Nanostructures Mediated by Thermoresponsive Polymer Brushes.

PubMed

Nguyen, Mai; Kanaev, Andrei; Sun, Xiaonan; Lacaze, Emmanuelle; Lau-Truong, Stéphanie; Lamouri, Aazdine; Aubard, Jean; Felidj, Nordin; Mangeney, Claire

2015-11-24

A smart and highly SERS-active plasmonic platform was designed by coupling regular arrays of nanotriangles to colloidal gold nanorods via a thermoresponsive polymer spacer (poly(N-isopropylacrylamide), PNIPAM). The substrates were prepared by combining a top-down and a bottom-up approach based on nanosphere lithography, surface-initiated controlled radical polymerization, and colloidal assembly. This multistep strategy provided regular hexagonal arrays of nanotriangles functionalized by polymer brushes and colloidal gold nanorods, confined exclusively on the nanotriangle surface. Interestingly, one could finely tune the gold nanorod impregnation on the polymer-coated nanostructures by adjusting the polymer layer thickness, leading to highly coupled plasmonic systems for intense SERS signal. Moreover, the thermoresponsive properties of the PNIPAM brushes could be wisely handled in order to monitor the SERS activity of the nanostructures coupled via this polymer spacer. The coupled hybrid plasmonic nanostructures designed in this work are therefore very promising smart platforms for the sensitive detection of analytes by SERS.

Evaluation of biodegradable polymers as encapsulating agents for the development of a urea controlled-release fertilizer using biochar as support material.

PubMed

González, M E; Cea, M; Medina, J; González, A; Diez, M C; Cartes, P; Monreal, C; Navia, R

2015-02-01

Biochar constitutes a promising support material for the formulation of controlled-release fertilizers (CRFs). In this study we evaluated the effect of different polymeric materials as encapsulating agents to control nitrogen (N) leaching from biochar based CRFs. Nitrogen impregnation onto biochar was performed in a batch reactor using urea as N source. The resulting product was encapsulated by using sodium alginate (SA), cellulose acetate (CA) and ethyl cellulose (EC). Leaching potential was studied in planted and unplanted soil columns, monitoring nitrate, nitrite, ammonium and urea concentrations. After 90 days, plants were removed from the soil columns and plant yield was evaluated. It was observed that the ammonium concentration in leachates presented a maximum concentration for all treatments at day 22. The highest concentration of N in the leachates was the nitrate form. The crop yield was negatively affected by all developed CRFs using biochar compared with the traditional fertilization. Copyright © 2014 Elsevier B.V. All rights reserved.

Sulfonimide-containing poly(arylene ether)s and poly(arylene ether sulfone)s, methods for producing the same, and uses thereof

DOEpatents

Hofmann, Michael A.

2006-11-14

The present invention is directed to sulfonimide-containing polymers, specifically sulfonimide-containing poly(arylene ether)s and sulfonimide-containing poly(arylene ether sulfone)s, and processes for making the sulfonimide-containing poly(arylene ether)s and sulfonimide-containing poly(arylene ether sulfone)s, for use conductive membranes and fuel cells.

FIELD STUDIES OF IMPREGNATED CONCRETE PIPE

EPA Science Inventory

The follow-on study (initiated in June 1980) continued to monitor performance of 1,400 ft of impregnated concrete pipe installed in several Texas cities. The performance of concrete pipe has been compared with that of sulfur-impregnated concrete pipe; hydrofluoric acid (HF)-treat...

Improving Cull Cow Meat Quality Using Vacuum Impregnation.

PubMed

Leal-Ramos, Martha Y; Alarcón-Rojo, Alma D; Gutiérrez-Méndez, Néstor; Mújica-Paz, Hugo; Rodríguez-Almeida, Felipe; Quintero-Ramos, Armando

2018-05-07

Boneless strip loins from mature cows (50 to 70 months of age) were vacuum impregnated (VI) with an isotonic solution (IS) of sodium chloride. This study sought to determine the vacuum impregnation and microstructural properties of meat from cull cows. The experiments were conducted by varying the pressure, p 1 (20.3, 71.1 kPa), and time, t 1 (0.5, 2.0, 4.0 h), of impregnation. After the VI step, the meat was kept for a time, t 2 (0.0, 0.5, 2.0, 4.0 h), in the IS under atmospheric pressure. The microstructural changes, impregnation, deformation, and porosity of the meat were measured in all the treatments. Impregnation and deformation levels in terms of volume fractions of the initial sample at the end of the vacuum step and the VI processes were calculated according to the mathematical model for deformation-relaxation and hydrodynamic mechanisms. Scanning electron microscopy (SEM) was used to study the microstructure of the vacuum-impregnated meat samples. Results showed that both the vacuum and atmospheric pressures generated a positive impregnation and deformation. The highest values of impregnation X (10.5%) and deformation γ (9.3%) were obtained at p 1 of 71.1 kPa and t 1 of 4.0 h. The sample effective porosity ( ε e ) exhibited a significant interaction ( p < 0.01) between p 1 × t 1 . The highest ε e (14.0%) was achieved at p 1 of 20.3 kPa and t 1 of 4.0 h, whereas the most extended distension of meat fibers (98 μm) was observed at the highest levels of p ₁, t ₁, and t ₂. These results indicate that meat from mature cows can undergo a vacuum-wetting process successfully, with an IS of sodium chloride to improve its quality.

Process of Making Boron-Fiber Reinforced Composite Tape

NASA Technical Reports Server (NTRS)

Belvin, Harry L. (Inventor); Cano, Roberto J. (Inventor); Johnston, Norman J. (Inventor); Marchello, Joseph M. (Inventor)

2002-01-01

The invention is an apparatus and method for producing a hybrid boron reinforced polymer matrix composition from powder pre-impregnated fiber tow bundles and a linear array of boron fibers. The boron fibers are applied onto the powder pre-impregnated fiber tow bundles and then are processed within a processing component having an impregnation bar assembly. After passing through variable-dimension forming nip-rollers, the powder pre-impregnated fiber tow bundles with the boron fibers become a hybrid boron reinforced polymer matrix composite tape. A driving mechanism pulls the powder pre-impregnated fiber tow bundles with boron fibers through the processing line of the apparatus and a take-up spool collects the formed hybrid boron-fiber reinforced polymer matrix composite tape.

Vacuum powder injector and method of impregnating fiber with powder

NASA Astrophysics Data System (ADS)

Working, Dennis C.

1993-05-01

A method and apparatus uniformly impregnate stranded material with dry powder such as low solubility, high melt flow polymer powder to produce, for example, composite prepregs. The stranded material is expanded in an impregnation chamber by an influx of air so that the powder, which may enter through the same inlet as the air, penetrates to the center of the stranded material. The stranded material then is contracted for holding the powder therein. The stranded material and powder may be pulled through the impregnation chamber in the same direction by vacuum. Larger particles of powder which do not fully penetrate the stranded material may be combed into the stranded material and powder which does not impregnate the stranded material may be collected and reused.

Vacuum powder injector and method of impregnating fiber with powder

NASA Technical Reports Server (NTRS)

Working, Dennis C. (Inventor)

1993-01-01

A method and apparatus uniformly impregnate stranded material with dry powder such as low solubility, high melt flow polymer powder to produce, for example, composite prepregs. The stranded material is expanded in an impregnation chamber by an influx of air so that the powder, which may enter through the same inlet as the air, penetrates to the center of the stranded material. The stranded material then is contracted for holding the powder therein. The stranded material and powder may be pulled through the impregnation chamber in the same direction by vacuum. Larger particles of powder which do not fully penetrate the stranded material may be combed into the stranded material and powder which does not impregnate the stranded material may be collected and reused.

21 CFR 529.1003 - Flurogestone acetate-impregnated vaginal sponge.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Flurogestone acetate-impregnated vaginal sponge... § 529.1003 Flurogestone acetate-impregnated vaginal sponge. (a) Specifications. Each vaginal sponge... ewes during their normal breeding season. (2) Limitations. Using applicator provided, insert sponge...

A study of ignition of metal impregnated carbons: the influence of oxygen content in the activated carbon matrix.

PubMed

van der Merwe, M M; Bandosz, T J

2005-02-01

A study of the reason for the early ignition of coconut-based impregnated carbon in comparison with the peat-based impregnated carbon was conducted. The surface features of carbons were evaluated using various physicochemical methods. The metal analysis of the initial carbon indicated that the content of potassium was higher in the coconut-based carbon. The surface functional group analysis revealed the presence of similar surface species; however, the peat-based carbon was more acidic in its chemical nature. Since the oxygen content was higher in the peat-based carbon, the early ignition of the coconut-based material was attributed to its higher affinity to chemisorb oxygen, which leads to exothermic effects. This conclusion was confirmed by performing oxidation of coconut-based carbon prior to impregnation. This process increased the ignition temperature for Cu/Cr impregnated coconut-based material from 186 to 289 degrees C and for the Cu/Zn/Mo impregnated carbon from 235 to 324 degrees C.

Continuous fiber thermoplastic prepreg

NASA Technical Reports Server (NTRS)

Wilson, Maywood L. (Inventor); Johnson, Gary S. (Inventor)

1993-01-01

A pultrusion machine employing a corrugated impregnator vessel to immerse multiple, continuous strand, fiber tow in an impregnating material, and an adjustable metered exit orifice for the impregnator vessel to control the quantity of impregnating material retained by the impregnated fibers, is provided. An adjustable height insert retains transverse rod elements within each depression of the corrugated vessel to maintain the individual fiber tows spread and in contact with the vessel bottom. A series of elongated heating dies, transversely disposed on the pultrusion machine and having flat heating surfaces with radiused edges, ensure adequate temperature exposed dwell time and exert adequate pressure on the impregnated fiber tows, to provide the desired thickness and fiber/resin ratio in the prepreg formed. The prepreg passing through the pulling mechanism is wound on a suitable take-up spool for subsequent use. A formula is derived for determining the cross sectional area opening of the metering device. A modification in the heating die system employs a heated nip roller in lieu of one of the pressure applying flat dies.

Impregnation of cinnamaldehyde into cassava starch biocomposite films using supercritical fluid technology for the development of food active packaging.

PubMed

de Souza, Ana Cristina; Dias, Ana M A; Sousa, Hermínio C; Tadini, Carmen C

2014-02-15

In this work, supercritical solvent impregnation (SSI) has been tested for the incorporation of natural compounds into biocomposite materials for food packaging. Cinnamaldehyde, with proved antimicrobial activity against fungi commonly found in bread products, was successfully impregnated on biocomposite cassava starch based materials using supercritical carbon dioxide as solvent. Different process experimental conditions were tested (pressure, impregnation time and depressurization rate) at a fixed temperature (35 °C) in order to study their influence on the amount of impregnated cinnamaldehyde as well as on the morphology of the films. Results showed that all conditions permitted to impregnate antimicrobial active amounts superior to those previously obtained using conventional incorporation methods. Moreover, a significant decrease of the equilibrium water vapor sorption capacity and water vapor permeability of the films was observed after SSI processing which is a clear advantage of the process, considering the envisaged applications. Copyright © 2013 Elsevier Ltd. All rights reserved.

Ca and Fe modified biochars as adsorbents of arsenic and chromium in aqueous solutions.

PubMed

Agrafioti, Evita; Kalderis, Dimitrios; Diamadopoulos, Evan

2014-12-15

This work investigated the production of Ca and Fe modified biochars in order to use them for the removal of arsenic As(V) and chromium Cr(VI) from aqueous solutions. Rice husk was impregnated with CaO at an impregnation ratio 0.114, while both rice husk and the organic fraction of municipal solid wastes were impregnated with Fe(0) and Fe(3+) at impregnation ratios 0.114 and 0.23. The modified biochars exhibited high As(V) removal capacity (>95%), except for the case of rice husk impregnated with Fe(0), whose removal capacity reached only 58%. All modified biochars exhibited much better As(V) removal capacity compared to the non-impregnated biochars. However, the Cr(VI) removal rates were not as high as the As(V) ones. The maximum Cr(VI) removal was observed in the case of rice husk biochar impregnated with 2.3% w/w Fe(3+), whereas the majority of impregnation agents examined did not manage to enhance the biochars' Cr(VI) removal ability. The equilibrium study showed that the Freundlich model can adequately describe the sorption process for the majority of samples examined. Analysis of the amount of Fe present in the equilibrium solutions suggested that the main mechanisms of As(V) and Cr(VI) removal were possibly metal precipitation and electrostatic interactions between the modified biochars and the adsorbate. Copyright © 2014 Elsevier Ltd. All rights reserved.

Laser-acoustic transcutaneous drug delivery: A new trend in administration of drugs

NASA Astrophysics Data System (ADS)

Zharov, Vladimir P.; Latyshev, Alexei S.

1999-03-01

This work deals with the principles of transcutaneous drug delivery technique which uses optoacoustic (OA) effect. Laser OA impregnation, enhanced laser OA impregnation, simple laser and laser OA injections are presented. Drug impregnation mathematical model and preliminary experiments on laser injection are described.

IMPREGNATION OF CONCRETE PIPE FOR CORROSION RESISTANCE AND STRENGTH IMPROVEMENT

EPA Science Inventory

The program was undertaken to field test concrete sewer pipe that had been impregnated with sulfur or hydrofluoric acid. This program was a follow-on to a previous laboratory study sponsored by EPA entitled, Impregnation of Concrete Pipe, 11024EQE 06/71. In a subsequent grant ext...

IN-FLIGHT CAPTURE OF ELEMENTAL MERCURY BY A CHLORINE-IMPREGNATED ACTIVATED CARBON

EPA Science Inventory

The paper discusses the in-flight capture of elemental mercury (Hgo) by a chlorine (C1)-impregnated activated carbon. Efforts to develop sorbents for the control of Hg emissions have demonstrated that C1-impregnation of virgin activated carbons using dilute solutions of hydrogen ...

Kl-impregnated Oyster Shells as a Solid Catalyst for Soybean Oil Transesterificaton

USDA-ARS?s Scientific Manuscript database

Research on inexpensive and green catalysts is needed for economical production of biodiesel. The goal of the research was to test KI-impregnated oyster shell as a solid catalyst for transesterification of soybean oil. Specific objectives were to characterize KI-impregnated oyster shell, determine t...

A Comparative Study of Raw and Metal Oxide Impregnated Carbon Nanotubes for the Adsorption of Hexavalent Chromium from Aqueous Solution

PubMed Central

Qureshi, Muhammad I.; Al-Baghli, Nadhir

2017-01-01

The present study reports the use of raw, iron oxide, and aluminum oxide impregnated carbon nanotubes (CNTs) for the adsorption of hexavalent chromium (Cr(VI)) ions from aqueous solution. The raw CNTs were impregnated with 1% and 10% loadings (weight %) of iron oxide and aluminum oxide nanoparticles using wet impregnation technique. The synthesized materials were characterized using scanning electron microscopy (SEM) and thermogravimetric analysis (TGA). Batch adsorption experiments were performed to assess the removal efficiency of Cr(VI) ions from water and the effects of pH, contact time, adsorbent dosage, and initial concentration of the Cr(VI) ions were investigated. Results of the study revealed that impregnated CNTs achieved significant increase in the removal efficiency of Cr(VI) ions compared to raw CNTs. In fact, both CNTs impregnated with 10% loading of iron and aluminum oxides were able to remove up to 100% of Cr(VI) ions from aqueous solution. Isotherm studies were carried out using Langmuir and Freundlich isotherm models. Adsorption kinetics of Cr(VI) ions from water was found to be well described by the pseudo-second-order model. The results suggest that metallic oxide impregnated CNTs have very good potential application in the removal of Cr(VI) ions from water resulting in better environmental protection. PMID:28487625

Carbonization of heavy metal impregnated sewage sludge oriented towards potential co-disposal.

PubMed

Dou, Xiaomin; Chen, Dezhen; Hu, Yuyan; Feng, Yuheng; Dai, Xiaohu

2017-01-05

Sewage sludge (SS) is adopted as a stabilizer to immobilize externally impregnated heavy metals through carbonization oriented towards the co-disposal of SS and some hazardous wastes. Firstly Cu and Pb were impregnated into SS to ascertain the impregnating capacity and leaching behaviours of heavy metals in the resulting sewage sludge char (SSC). Meanwhile, scanning electron microscopy (SEM) and X-ray diffraction (XRD) were employed to detect the heavy metal phase in the SSC. The results showed that within 400-800°C and an impregnating concentration ≨0.5wt%, more than 90% of the externally impregnated Cu and Pb were remained in the SSC and immobilized. And higher temperatures helped produce non-hazardous SSC. In addition, SEM and XRD analyses revealed that externally impregnated heavy metals could be converted into stable forms and evenly distributed throughout the SSC. In the second step municipal solid waste incineration fly ash (FA) was kneaded into SS and subjected to carbonization; it has been proved that the heavy metals in FA can be well immobilized in the resulting char when FA: SS mass ratio is 1:5. Those results show that sewage sludge can be co-carbonized with wastes contaminated with heavy metals to achieve co-disposal. Copyright © 2016 Elsevier B.V. All rights reserved.

Development of the chromatographic partitioning of cesium and strontium utilizing two macroporous silica-based calix[4]arene-crown and amide impregnated polymeric composites: PREC partitioning process.

PubMed

Zhang, Anyun; Kuraoka, Etsushu; Kumagai, Mikio

2007-07-20

To partition effectively Cs(I) and Sr(II), two harmful heat emitting nuclides, from a highly active liquid waste by extraction chromatography, two kinds of macroporous silica-based polymeric materials, Calix[4]arene-R14/SiO(2)-P and TODGA/SiO(2)-P, were synthesized. Two chelating agents, 1,3-[(2,4-diethyl-heptylethoxy)oxy]-2,4-crown-6-calix[4]arene (Calix[4]arene-R14), an excellent supramolecular compound having molecular recognition ability for Cs(I), and N,N,N',N'-tetraoctyl-3-oxapentane-1,5-diamide (TODGA) were impregnated and immobilized into the pores of SiO(2)-P particles support by a vacuum sucking technique. The loading and elution of 11 typical simulated fission and non-fission products from 4.0M or 2.0M HNO(3) were performed at 298K. It was found that in the first column packed with the Calix[4]arene-R14/SiO(2)-P, all of the simulated elements were separated effectively into two groups: (1) Na(I), K(I), Sr(II), Fe(III), Ba(II), Ru(III), Pd(II), Zr(IV), and Mo(VI) (noted as Sr-group); (2) Cs(I)-Rb(I) (Cs-group) by eluting with 4.0M HNO(3) and distilled water, respectively. The harmful element Cs(I) flowed into the second group along with Rb(I) because of their close sorption and elution properties towards Calix[4]arene-R14/SiO(2)-P, while Sr(II) showed no sorption and flowed into Sr-containing group. In the second column packed with TODGA/SiO(2)-P, the Sr-group was separated into (1) Ba(II), Ru(III), Na(I), K(I), Fe(III), and Mo(VI) (non-sorption group); (2) Sr(II); (3) Pd(II); and (4) Zr(IV) by eluting with 2.0M HNO(3), 0.01M HNO(3), 0.05M DTPA-pH 2.5, and 0.5M H(2)C(2)O(4), respectively. Sr(II) adsorbed towards TODGA/SiO(2)-P flowed into the second group and showed the excellent separation efficiency from others. Based on the elution behavior of the tested elements, an advanced PREC (Partitioning and Recovery of two heat generators from an acidic HLW (high activity liquid waste) by Extraction Chromatography) process was proposed.

Effects of sulfur impregnation temperature on the properties and mercury adsorption capacities of activated carbon fibers (ACFs)

USGS Publications Warehouse

Hsi, H.-C.; Rood, M.J.; Rostam-Abadi, M.; Chen, S.; Chang, R.

2001-01-01

Laboratory studies were conducted to determine the role of sulfur functional groups and micropore surface area of carbon-based adsorbents on the adsorption of Hg0 from simulated coal combustion flue gases. In this study, raw activated carbon fibers that are microporous (ACF-20) were impregnated with elemental sulfur between 250 and 650 ??C. The resulting samples were saturated with respect to sulfur content. Total sulfur content of the sulfur impregnated ACF samples decreased with increasing impregnation temperatures from 250 and 500 ??C and then remained constant to 650 ??C. Results from sulfur K-edge X-ray absorption near-edge structure (S-XANES) spectroscopy showed that sulfur impregnated on the ACF samples was in both elemental and organic forms. As sulfur impregnation temperature increased, however, the relative amounts of elemental sulfur decreased with a concomitant increase in the amount of organic sulfur. Thermal analyses and mass spectrometry revealed that sulfur functional groups formed at higher impregnation temperatures were more thermally stable. In general, sulfur impregnation decreased surface area and increased equilibrium Hg0 adsorption capacity when compared to the raw ACF sample. The ACF sample treated with sulfur at 400 ??C had a surface area of only 94 m2/g compared to the raw ACF sample's surface area of 1971 m2/g, but at least 86% of this sample's surface area existed as micropores and it had the largest equilibrium Hg0adsorption capacities (2211-11343 ??g/g). Such a result indicates that 400 ??C is potentially an optimal sulfur impregnation temperature for this ACF. Sulfur impregnated on the ACF that was treated at 400 ??C was in both elemental and organic forms. Thermal analyses and CS2extraction tests suggested that elemental sulfur was the main form of sulfur affecting the Hg0 adsorption capacity. These findings indicate that both the presence of elemental sulfur on the adsorbent and a microporous structure are important properties for improving the performance of carbon-based adsorbents for the removal of Hg0 from coal combustion flue gases.

Effects of properties of manganese oxide-impregnated catalysts and flue gas condition on multipollutant control of Hg0 and NO.

PubMed

Chiu, Chun-Hsiang; Hsi, Hsing-Cheng; Lin, Hong-Ping; Chang, Tien-Chin

2015-06-30

This research investigated the effects of manganese oxide (MnOx) impregnation on the physical/chemical properties and multi pollutant control effectiveness of Hg(0) and NO using a V2O5-WO3/TiO2-SiO2 selective catalytic reduction (SCR) catalyst. Raw and MnOx-treated SCR samples were bean-shaped nanoparticles with sizes within 10-30 nm. Impregnating MnOx of ≤ 5 wt% caused limited changes in physical properties of the catalyst. The decrease in surface area when the impregnated MnOx amount was 10 wt% may stem from the pore blockage and particle growth or aggregation of the catalyst. Mn(4+) was the main valence state of impregnated MnOx. Apparent crystallinity of MnOx was not observed based on X-ray diffraction. MnOx impregnation enhanced the Hg(0) oxidation and NO/SO2 removal of SCR catalyst. The 5 and 10% MnOx-impregnated samples had the greatest multi pollutant control potentials for Hg(0) oxidation and NO removal; however, the increasing SO2 removal that may be mainly due to SO2-SO3 conversion should be cautioned. HCl and O2 greatly promoted Hg(0) oxidation. SO2 enhanced Hg(0) oxidation at ≤ 200 ppm while NO and NH3 consistently inhibited Hg(0) oxidation. Elevating flue gas temperature enhanced Hg(0) oxidation. Overall, MnOx-impregnated catalysts show stable and consistent multi pollutant removal effectiveness under the test conditions. Copyright © 2015 Elsevier B.V. All rights reserved.

Dual-Functional Polyethylene Glycol-b-polyhexanide Surface Coating with in Vitro and in Vivo Antimicrobial and Antifouling Activities.

PubMed

Zhi, Zelun; Su, Yajuan; Xi, Yuewei; Tian, Liang; Xu, Miao; Wang, Qianqian; Padidan, Sara; Li, Peng; Huang, Wei

2017-03-29

In recent years, microbial colonization on the surface of biomedical implants/devices has become a severe threat to human health. Herein, surface-immobilized guanidine derivative block copolymers create an antimicrobial and antifouling dual-functional coating. We report the preparation of an antimicrobial and antifouling block copolymer by the conjugation of polyhexanide (PHMB) with either allyl glycidyl ether or allyloxy polyethylene glycol (APEG; MW 1200 and 2400). The allyl glycidyl ether modified PHMB (A-PHMB) and allyloxy polyethylene glycol 1200/2400 modified PHMB (APEG 1200/2400 -PHMB) copolymers were grafted onto a silicone rubber surface as a bottlebrush-like coating, respectively, using a plasma-UV-assisted surface-initiated polymerization. Both A-PHMB and APEG 1200/2400 -PHMB coatings exhibited excellent broad-spectrum antimicrobial properties against Gram-negative/positive bacteria and fungi. The APEG 2400 -PHMB coating displayed an improved antibiofilm as well as antifouling properties and a long reusable cycle, compared with two other coatings, due to its abundant PEG blocks among those copolymers. Also, the APEG 2400 -PHMB-coated silicone coupons were biocompatible toward mammalian cells, as revealed by in vitro hemocompatibile and cytotoxic assays. An in vivo study showed a significant decline of Escherichia coli colonies with a 5-log reduction, indicating the APEG 2400 -PHMB coating surface worked effectively in the rodent subcutaneous infection model. This PHMB-based block copolymer coating is believed to be an effective strategy to prevent biomaterial-associated infections.

76 FR 14910 - Small Diameter Graphite Electrodes From the People's Republic of China: Initiation of Anti...

Federal Register 2010, 2011, 2012, 2013, 2014

2011-03-18

... correct grade of petroleum coke mix, and have been baked, formed, carbonized, impregnated, and graphitized... required for the production of SDGE (e.g., raw material handling, mixing, forming, baking, impregnating... production process, demonstrating how raw materials are formed, baked, impregnated (if needed), re-baked...

Impacts of amount of impregnated iron in granular activated carbon on arsenate adsorption capacities and kinetics.

PubMed

Chang, Qigang; Lin, Wei; Ying, Wei-Chi

2012-06-01

Iron-impregnated granular activated carbons (Fe-GAC) can remove arsenic effectively from water. In this study, Fe-GACs with iron content of 1.64 to 28.90% were synthesized using a new multi-step procedure for the investigation of effects of iron amount on arsenic adsorption capacities and kinetics. Langmuir model satisfactorily fit arsenic adsorption on Fe-GACs. The maximum arsenic adsorption capacity (q(m)) increased significantly with iron impregnation and reached 1,867 to 1,912 microg/g with iron content of 9.96 to 13.59%. Further increase of iron content (> 13.59%) caused gradual decrease of q(m). It was found that the amount of impregnated iron showed little impact on the affinity for arsenate. Kinetic study showed that the amount of impregnated iron affected the arsenic intraparticle diffusion rate greatly. The pseudo-second-order kinetic model fit arsenic adsorption kinetics on Fe-GACs better than the pseudo-first-order model. The arsenic adsorption rate increased with increasing of iron content from 1.64% to 13.59%, and then decreased with more impregnated iron (13.59 to 28.90%).

Selection of best impregnated palm shell activated carbon (PSAC) for simultaneous removal of SO2 and NOx.

PubMed

Sumathi, S; Bhatia, S; Lee, K T; Mohamed, A R

2010-04-15

This work examines the impregnated carbon-based sorbents for simultaneous removal of SO(2) and NOx from simulated flue gas. The carbon-based sorbents were prepared using palm shell activated carbon (PSAC) impregnated with several metal oxides (Ni, V, Fe and Ce). The removal of SO(2) and NOx from the simulated flue gas was investigated in a fixed-bed reactor. The results showed that PSAC impregnated with CeO(2) (PSAC-Ce) reported the highest sorption capacity among other impregnated metal oxides for the simultaneous removal of SO(2) and NOx. PSAC-Ce showed the longest breakthrough time of 165 and 115 min for SO(2) and NOx, respectively. The properties of the pure and impregnated PSAC were analyzed by BET, FTIR and XRF. The physical-chemical features of the PSAC-Ce sorbent indicated a catalytic activity in both the sorption of SO(2) and NOx. The formation of both sulfate (SO(4)(2-)) and nitrate (NO(3-)) species on spent PSAC-Ce further prove the catalytic role played by CeO(2). 2009 Elsevier B.V. All rights reserved.

A Modeling Approach to Fiber Fracture in Melt Impregnation

NASA Astrophysics Data System (ADS)

Ren, Feng; Zhang, Cong; Yu, Yang; Xin, Chunling; Tang, Ke; He, Yadong

2017-02-01

The effect of process variables such as roving pulling speed, melt temperature and number of pins on the fiber fracture during the processing of thermoplastic based composites was investigated in this study. The melt impregnation was used in this process of continuous glass fiber reinforced thermoplastic composites. Previous investigators have suggested a variety of models for melt impregnation, while comparatively little effort has been spent on modeling the fiber fracture caused by the viscous resin. Herein, a mathematical model was developed for impregnation process to predict the fiber fracture rate and describe the experimental results with the Weibull intensity distribution function. The optimal parameters of this process were obtained by orthogonal experiment. The results suggest that the fiber fracture is caused by viscous shear stress on fiber bundle in melt impregnation mold when pulling the fiber bundle.

Photogeneration of H2O2 in SPEEK/PVA aqueous polymer solutions.

PubMed

Little, Brian K; Lockhart, PaviElle; Slaten, B L; Mills, G

2013-05-23

Photolysis of air-saturated aqueous solutions containing sulphonated poly(ether etherketone) and poly(vinyl alcohol) results in the generation of hydrogen peroxide. Consumption of oxygen and H2O2 formation are initially concurrent processes with a quantum yield of peroxide generation of 0.02 in stirred or unstirred solutions within the range of 7 ≤ pH ≤ 9. The results are rationalized in terms of O2 reduction by photogenerated α-hydroxy radicals of the polymeric ketone in competition with radical-radical processes that consume the macromolecular reducing agents. Generation of H2O2 is controlled by the photochemical transformation that produces the polymer radicals, which is most efficient in neutral and slightly alkaline solutions. Quenching of the excited state of the polyketone by both H3O(+) and OH(-) affect the yields of the reducing macromolecular radicals and of H2O2. Deprotonation of the α-hydroxy polymeric radicals at pH > 9 accelerate their decay and contribute to suppressing the peroxide yields in basic solutions. Maxima in [H2O2] are observed when illuminations are performed with static systems, where O2 reduction is faster than diffusion of oxygen into the solutions. Under such conditions H2O2 can compete with O2 for the reducing radicals resulting in a consumption of the peroxide.

Polymer Brush-Functionalized Chitosan Hydrogels as Antifouling Implant Coatings.

PubMed

Buzzacchera, Irene; Vorobii, Mariia; Kostina, Nina Yu; de Los Santos Pereira, Andres; Riedel, Tomáš; Bruns, Michael; Ogieglo, Wojciech; Möller, Martin; Wilson, Christopher J; Rodriguez-Emmenegger, Cesar

2017-06-12

Implantable sensor devices require coatings that efficiently interface with the tissue environment to mediate biochemical analysis. In this regard, bioinspired polymer hydrogels offer an attractive and abundant source of coating materials. However, upon implantation these materials generally elicit inflammation and the foreign body reaction as a consequence of protein fouling on their surface and concomitant poor hemocompatibility. In this report we investigate a strategy to endow chitosan hydrogel coatings with antifouling properties by the grafting of polymer brushes in a "grafting-from" approach. Chitosan coatings were functionalized with polymer brushes of oligo(ethylene glycol) methyl ether methacrylate and 2-hydroxyethyl methacrylate using photoinduced single electron transfer living radical polymerization and the surfaces were thoroughly characterized by XPS, AFM, water contact angle goniometry, and in situ ellipsometry. The antifouling properties of these new bioinspired hydrogel-brush coatings were investigated by surface plasmon resonance. The influence of the modifications to the chitosan on hemocompatibility was assessed by contacting the surfaces with platelets and leukocytes. The coatings were hydrophilic and reached a thickness of up to 180 nm within 30 min of polymerization. The functionalization of the surface with polymer brushes significantly reduced the protein fouling and eliminated platelet activation and leukocyte adhesion. This methodology offers a facile route to functionalizing implantable sensor systems with antifouling coatings that improve hemocompatibility and pave the way for enhanced device integration in tissue.

Surface chemical immobilization of bioactive peptides on synthetic polymers for cardiac tissue engineering.

PubMed

Rosellini, Elisabetta; Cristallini, Caterina; Guerra, Giulio D; Barbani, Niccoletta

2015-01-01

The aim of this work was the development of new synthetic polymeric systems, functionalized by surface chemical modification with bioactive peptides, for myocardial tissue engineering. Polycaprolactone and a poly(ester-ether-ester) block copolymer synthesized in our lab, polycaprolactone-poly(ethylene oxide)-polycaprolactone (PCL-PEO-PCL), were used as the substrates to be modified. Two pentapeptides, H-Gly-Arg-Gly-Asp-Ser-OH (GRGDS) from fibronectin and H-Tyr-Ile-Gly-Ser-Arg-OH (YIGSR) from laminin, were used for the functionalization. Polymeric membranes were obtained by casting from solutions and then functionalized by means of alkaline hydrolysis and subsequent coupling of the bioactive molecules through 1-(3-dimethylaminopropyl)-3-ethylcarbodimide hydrochloride/N-hydroxysuccinimide chemistry. The hydrolysis conditions, in terms of hydrolysis time, temperature, and sodium hydroxide concentration, were optimized for the two materials. The occurrence of the coupling reaction was demonstrated by infrared spectroscopy, as the presence on the functionalized materials of the absorption peaks typical of the two peptides. The peptide surface density was determined by chromatographic analysis and the distribution was studied by infrared chemical imaging. The results showed a nearly homogeneous peptide distribution, with a density above the minimum value necessary to promote cell adhesion. Preliminary in vitro cell culture studies demonstrated that the introduction of the bioactive molecules had a positive effect on improving C2C12 myoblasts growth on the synthetic materials.

Multifunctional reduction-responsive SPIO&DOX-loaded PEGylated polymeric lipid vesicles for magnetic resonance imaging-guided drug delivery

NASA Astrophysics Data System (ADS)

Wang, Sheng; Yang, Weitao; Du, Hongli; Guo, Fangfang; Wang, Hanjie; Chang, Jin; Gong, Xiaoqun; Zhang, Bingbo

2016-04-01

Multifunctional superparamagnetic iron-oxide (SPIO)-based nanoparticles have been emerging as candidate nanosystems for cancer diagnosis and therapy. Here, we report the use of reduction- responsive SPIO/doxorubicin (DOX)-loaded poly(ethylene glycol) monomethyl ether (PEG)ylated polymeric lipid vesicles (SPIO&DOX-PPLVs) as a novel theranostic system for tumor magnetic resonance imaging (MRI) diagnosis and controlled drug delivery. These SPIO&DOX-PPLVs are composed of SPIOs that function as MR contrast agents for tumor enhancement and PPLVs as polymer matrices for encapsulating SPIO and antitumor drugs. The in vitro characterizations show that the SPIO&DOX-PPLVs have nanosized structures (˜80 nm), excellent colloidal stability, good biocompatibility, as well as T 2-weighted MRI capability with a relatively high T 2 relaxivity (r 2 = 213.82 mM-1 s-1). In vitro drug release studies reveal that the release rate of DOX from the SPIO&DOX-PPLVs is accelerated in the reduction environment. An in vitro cellular uptake study and an antitumor study show that the SPIO&DOX-PPLVs have magnetic targeting properties and effective antitumor activity. In vivo studies show the SPIO&DOX-PPLVs have excellent T 2-weighted tumor targeted MRI capability, image-guided drug delivery capability, and high antitumor effects. These results suggest that the SPIO&DOX-PPLVs are promising nanocarriers for MRI diagnosis and cancer therapy applications.

A Facile Strategy for Catalyst Separation and Recycling Suitable for ATRP of Hydrophilic Monomers Using a Macroligand.

PubMed

Jiang, Xiaowu; Wu, Jian; Zhang, Lifen; Cheng, Zhenping; Zhu, Xiulin

2016-01-01

How to simply and efficiently separate and recycle catalyst has still been a constraint for the wide application of atom transfer radical polymerization (ATRP), especially for the polymerization systems with hydrophilic monomers because the polar functional groups may coordinate with transition metal salts, resulting in abundant catalyst residual in the resultant water-soluble polymers. In order to overcome this problem, a latent-biphasic system is developed, which can be successfully used for ATRP catalyst separation and recycling in situ for various kinds of hydrophilic monomers for the first time, such as poly(ethylene glycol) monomethyl ether methacrylate (PEGMA), 2-hydroxyethyl methacrylate (HEMA), 2-(dimethylamino)ethyl methacrylate (DMAEMA), N,N-dimethyl acrylamide (DMA), and N-isopropylacrylamide (NIPAM). Herein, random copolymer of octadecyl acrylate (OA), MA-Ln (2-(bis(pyridin-2-ylmethyl)amino)ethyl acrylate), and POA-ran-P(MA-Ln) is designed as the macroligand, and heptane/ethanol is selected as the biphasic solvent. Copper(II) bromide (CuBr2 ) is employed as the catalyst, PEG-bound 2-bromo-2-methylpropanoate (PEG350 -Br) as the water-soluble ATRP initiator and 2,2'-azobis(isobutyronitrile) (AIBN) as the azo-initiator to establish an ICAR (initiators for continuous activator regeneration) ATRP system. Importantly, well-defined water-soluble polymers are obtained even though the recyclable catalyst is used for sixth times. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The effect of coumaryl alcohol incorporation on the structure and composition of lignin dehydrogenation polymers.

PubMed

Harman-Ware, Anne E; Happs, Renee M; Davison, Brian H; Davis, Mark F

2017-01-01

Lignin dehydrogenation polymers (DHPs) are polymers generated from phenolic precursors for the purpose of studying lignin structure and polymerization processes. Here, DHPs were synthesized using a Zutropfverfahren method with horseradish peroxidase and three lignin monomers, sinapyl (S), coumaryl (H), and coniferyl (G) alcohols, in the presence of hydrogen peroxide. The H monomer was reacted with G and a 1:1 molar mixture of S:G monomers at H molar compositions of 0, 5, 10, and 20 mol% to study how the presence of the H monomer affected the structure and composition of the recovered polymers. At low H concentrations, solid-state NMR spectra suggest that the H and G monomers interact to form G:H polymers that have a lower average molecular weight than the solely G-based polymer or the G:H polymer produced at higher H concentrations. Solid-state NMR and pyrolysis-MBMS analyses suggest that at higher H concentrations, the H monomer primarily self-polymerizes to produce clusters of H-based polymer that are segregated from clusters of G- or S:G-based polymers. Thioacidolysis generally showed higher recoveries of thioethylated products from S:G or S:G:H polymers made with higher H content, indicating an increase in the linear ether linkages. Overall, the experimental results support theoretical predictions for the reactivity and structural influences of the H monomer on the formation of lignin-like polymers.

Poly(arylene ether)s containing pendent ethynyl groups

NASA Technical Reports Server (NTRS)

Hergenrother, Paul M. (Inventor); Jensen, Brian J. (Inventor)

1996-01-01

Poly(arylene ether)s containing pendent ethynyl and substituted ethynyl groups and poly(arylene ether) copolymers containing pendent ethynyl and substituted ethynyl groups are readily prepared from bisphenols containing ethynyl and substituted ethynyl groups. The resulting polymers are cured up to 350.degree. C. to provide crosslinked poly(arylene ether)s with good solvent resistance, high strength and modulus.

Poly(arylene ether)s containing pendent ethynyl groups

NASA Technical Reports Server (NTRS)

Hergenrother, Paul M. (Inventor); Jensen, Brian J. (Inventor)

1994-01-01

Poly(arylene ether)s containing pendent ethynyl and substituted ethynyl groups and poly(arylene ether) copolymers containing pendent ethynyl and substituted ethynyl groups are readily prepared from bisphenols containing ethynyl and substituted ethynyl groups. The resulting polymers are cured up to 350 C to provide crosslinked poly(arylene ether)s with good solvent resistance, high strength and modulus.

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

Ozmen, Ozcan; Zondlo, John W.; Lee, Shiwoo

A bio-inspired surfactant was utilized to assist in the efficient impregnation of a nano-CeO₂ catalyst throughout both porous Solid Oxide Fuel Cells (SOFC’s) electrodes simultaneously. The process included the initial modification of electrode pore walls with a polydopamine film. The cell was then submersed into a cerium salt solution. The amount of nano-CeO₂ deposited per impregnation step increased by 3.5 times by utilizing this two-step protocol in comparison to a conventional drip impregnation method. The impregnated cells exhibited a 20% higher power density than a baseline cell without the nano-catalyst at 750°C (using humid H₂ fuel).

Photoimageable composition

DOEpatents

Simison, Kelby Liv; Dentinger, Paul

2003-11-11

The use of selected buffering amines in a photoimageable composition prevents process bias which with conventional photoresists causes designed features to be distorted, especially in corners and high resolution features. It is believed that the amines react with the catalysts, e.g., photoacids, generated to create an inert salt. The presence of the amines also increases resolution. Suitable photoimageable compositions includes: (a) a multifunctional polymeric epoxy resin that is dissolved in an organic solvent wherein the epoxy resin comprises oligomers of bisphenol A that is quantitatively protected by glycidyl ether and wherein the oligomers have an average functionality that ranges from about 3 to 12; (b) a photoactive compound; and (c) an amine that is selected from the group consisting of triisobutylamine, 1,8-bis(dimethylamino)naphthalene (also known as PROTON SPONGET.TM.), 2,2'-diazabicyclo[2.2.2] octane and mixtures thereof. The photoimageable composition is particularly suited for producing high aspect ratio metal microstructures.

Removal of heavy metals from waste streams

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

Spence, M.D.; Kozaruk, J.M.; Melvin, M.

1988-07-19

A method for removing heavy metals from effluent water is described comprising performing sequentially the following steps: (a) adding from 7-333 ppm of an anionic surfactant to the effluent water to provide coagulatable heavy metal ion; (b) adjusting the effluent water pH to within the range of 8 to 10, (c) providing from 10-200 ppm of a cationic coagulant to coagulate the heavy metal ion, (d) providing from 0.3 to 5.0 ppm of a polymeric flocculant whereby a heavy metal containing floc is formed for removal from the effluent water, and, (e) then removing the floc from the effluent water,more » wherein the anionic surfactant is sodium lauryl ether sulfate. The cationic coagulant is selected from the group consisting of diallyl dimethylammonium chloride polymer, epichlorohydrin dimethylamine polymer, ethylene amine polymer, polyaluminum chloride, and alum; and the flocculant is an acrylamide/sodium acrylate copolymer having an RSV greater than 23.« less

SuFEx-Based Polysulfonate Formation from Ethenesulfonyl Fluoride-Amine Adducts

DOE PAGES

Wang, Hua; Zhou, Feng; Ren, Gerui; ...

2017-05-18

In this article, the SuFEx-based polycondensation between bisalkylsulfonyl fluorides (AA monomers) and bisphenol bis(t-butyldimethylsilyl) ethers (BB monomers) using [Ph 3P=N-PPh 3] +[HF 2] - as the catalyst is described. The AA monomers were prepared via the highly reliable Michael addition of ethenesulfonyl fluoride and amines/anilines while the BB monomers were obtained from silylation of bisphenols by t-butyldimethylsilyl chloride. With these reactions, a remarkable diversity of monomeric building blocks was achieved by exploiting readily available amines, anilines, and bisphenols as starting materials. The SuFEx-based polysulfonate formation reaction exhibited excellent efficiency and functional group tolerance, producing polysulfonates with a variety of sidemore » chain functionalities in >99 % conversion within 10 min to 1 h. When bearing an orthogonal group on the side chain, the polysulfonates can be further functionalized via click-chemistry-based post-polymerization modification.« less

Robust synthesis of epoxy resin-filled microcapsules for application to self-healing materials.

PubMed

Bolimowski, Patryk A; Bond, Ian P; Wass, Duncan F

2016-02-28

Mechanically and thermally robust microcapsules containing diglycidyl ether bisphenol A-based epoxy resin and a high-boiling-point organic solvent were synthesized in high yield using in situ polymerization of urea and formaldehyde in an oil-in-water emulsion. Microcapsules were characterized in terms of their size and size distribution, shell surface morphology and thermal resistance to the curing cycles of commercially used epoxy polymers. The size distribution of the capsules and characteristics such as shell thickness can be controlled by the specific parameters of microencapsulation, including concentrations of reagents, stirrer speed and sonication. Selected microcapsules, and separated core and shell materials, were analysed using thermogravimetric analysis and differential scanning calorimetry. It is demonstrated that capsules lose minimal 2.5 wt% at temperatures no higher than 120°C. These microcapsules can be applied to self-healing carbon fibre composite structural materials, with preliminary results showing promising performance. © 2016 The Author(s).

Role of gelsolin interaction with actin in regulation and creation of actin nuclei in chemotactic peptide activated polymorphonuclear neutrophils.

PubMed Central

Deaton, J D; Guerrero, T; Howard, T H

1992-01-01

In vitro Ca++ activates gelsolin to sever F-actin and form a gelsolin-actin (GA) complex at the+end of F-actin that is not dissociated by ethylene glycol-bis(beta-aminoethyl ether)-N,N,N',N'-tetraacetic acid (EGTA) but is separated by EGTA+PIP/PIP2. The gelsolin blocks the+end on the actin filament, but the-end of the filament can still initiate actin polymerization. In thrombin activated platelets, evidence suggests that severing of F-actin by gelsolin increases GA complex, creates one-end actin nucleus and one cryptic+end actin nucleus per cut, and then dissociates to yield free+ends to nucleate rapid actin assembly. We examined the role of F-actin severing in creation and regulation of nuclei and polymerization in polymorphonuclear neutrophils (PMNs). At 2-s intervals after formyl peptide (FMLP) activation of endotoxin free (ETF) PMNs, change in GA complex was correlated with change in+end actin nuclei,-end actin nuclei, and F-actin content. GA complex was quantitated by electrophoretograms of proteins absorbed by antigelsolin from cells lysed in 10 mM EGTA,+end actin nuclei as cytochalasin (CD) sensitive and-end actin nuclei as CD insensitive increases in G-pyrenyl actin polymerization rates induced by the same PMNs, and F-actin content by NBDphallacidin binding to fixed cells. Thirty three percent of gelsolin was in GA complex in basal ETF PMNs; from 2-6 s, GA complexes dissociate (low = 15% at 10 s) and sequentially+end nuclei and F-actin content and then-end nuclei increase to a maximum at 10 s. At > s GA complex increase toward basal and + end nuclei and F-actin content returned toward basal. These kinetic data show gelsolin regulates availability of + end nuclei and actin polymerization in FMLP. However, absence of an initial increase in GA complex or - end nucleating activity shows FMLP activation does not cause gelsolin to sever F- or to bind G-actin to create cryptic + end nuclei in PMNs; the results suggest the + nucleus formation is gelsolin independent. PMID:1337290

Role of gelsolin interaction with actin in regulation and creation of actin nuclei in chemotactic peptide activated polymorphonuclear neutrophils.

PubMed

Deaton, J D; Guerrero, T; Howard, T H

1992-12-01

In vitro Ca++ activates gelsolin to sever F-actin and form a gelsolin-actin (GA) complex at the+end of F-actin that is not dissociated by ethylene glycol-bis(beta-aminoethyl ether)-N,N,N',N'-tetraacetic acid (EGTA) but is separated by EGTA+PIP/PIP2. The gelsolin blocks the+end on the actin filament, but the-end of the filament can still initiate actin polymerization. In thrombin activated platelets, evidence suggests that severing of F-actin by gelsolin increases GA complex, creates one-end actin nucleus and one cryptic+end actin nucleus per cut, and then dissociates to yield free+ends to nucleate rapid actin assembly. We examined the role of F-actin severing in creation and regulation of nuclei and polymerization in polymorphonuclear neutrophils (PMNs). At 2-s intervals after formyl peptide (FMLP) activation of endotoxin free (ETF) PMNs, change in GA complex was correlated with change in+end actin nuclei,-end actin nuclei, and F-actin content. GA complex was quantitated by electrophoretograms of proteins absorbed by antigelsolin from cells lysed in 10 mM EGTA,+end actin nuclei as cytochalasin (CD) sensitive and-end actin nuclei as CD insensitive increases in G-pyrenyl actin polymerization rates induced by the same PMNs, and F-actin content by NBDphallacidin binding to fixed cells. Thirty three percent of gelsolin was in GA complex in basal ETF PMNs; from 2-6 s, GA complexes dissociate (low = 15% at 10 s) and sequentially+end nuclei and F-actin content and then-end nuclei increase to a maximum at 10 s. At > s GA complex increase toward basal and + end nuclei and F-actin content returned toward basal. These kinetic data show gelsolin regulates availability of + end nuclei and actin polymerization in FMLP. However, absence of an initial increase in GA complex or - end nucleating activity shows FMLP activation does not cause gelsolin to sever F- or to bind G-actin to create cryptic + end nuclei in PMNs; the results suggest the + nucleus formation is gelsolin independent.

High temperature in-situ synchrotron-based XRD study on the crystal structure evolution of C/C composite impregnated by FLiNaK molten salt.

PubMed

Feng, Shanglei; Yang, Yingguo; Li, Li; Zhang, Dongsheng; Yang, Xinmei; Xia, Huihao; Yan, Long; Tsang, Derek K L; Huai, Ping; Zhou, Xingtai

2017-09-06

An in-situ real-time synchrotron-based grazing incidence X-ray diffraction was systematically used to investigate the crystal structural evolution of carbon fiber reinforced carbon matrix (C/C) composite impregnated with FLiNaK molten salt during the heat-treatment process. It was found that the crystallographic thermal expansion and contraction rate of interlayer spacing d 002 in C/C composite with FLiNaK salt impregnation is smaller than that in the virgin sample, indicating the suppression on interlayer spacing from FLiNaK salt impregnated. Meanwhile the crystallite size L C002 of C/C composite with FLiNaK salt impregnation is larger than the virgin one after whole heat treatment process, indicating that FLiNaK salt impregnation could facilitate the crystallization of C/C composite after heat treatment process. This improved crystallization in C/C composite with FLiNaK salt impregnation suggests the synthetic action of the salt squeeze effect on crooked carbon layer and the release of internal residual stress after heating-cooling process. Thus, the present study not only contribute to reveal the interaction mechanism between C/C composite and FLiNaK salt in high temperature environment, but also promote the design of safer and more reliable C/C composite materials for the next generation molten salt reactor.

Radiolabeled cholesteryl ethers: A need to analyze for biological stability before use.

PubMed

Manual Kollareth, Denny Joseph; Chang, Chuchun L; Hansen, Inge H; Deckelbaum, Richard J

2018-03-01

Radiolabeled cholesteryl ethers are widely used as non-metabolizable tracers for lipoproteins and lipid emulsions in a variety of in vitro and in vivo experiments. Since cholesteryl ethers do not leave cells after uptake and are not hydrolyzed by mammalian cellular enzymes, these compounds can act as markers for cumulative cell uptakes of labeled particles. We have employed [ 3 H]cholesteryl oleoyl ether to study the uptake and distribution of triglyceride-rich emulsion particles on animal models. However, questionable unexpected results compelled us to analyze the stability of these ethers. We tested the stability of two commercially available radiolabeled cholesteryl ethers - [ 3 H]cholesteryl oleoyl ether and [ 3 H]cholesteryl hexadecyl ether from different suppliers, employing in vitro , in vivo and chemical model systems. Our results show that, among the two cholesteryl ethers tested, one ether was hydrolyzed to free cholesterol in vitro , in vivo and chemically under alkaline hydrolyzing agent. Free cholesterol, unlike cholesteryl ether, can then re-enter the circulation leading to confounding results. The other ether was not hydrolyzed to free cholesterol and remained as a stable ether. Hence, radiolabeled cholesteryl ethers should be analyzed for biological stability before utilizing them for in vitro or in vivo experiments.

Impregnating Coal With Calcium Carbonate

NASA Technical Reports Server (NTRS)

Sharma, Pramod K.; Voecks, Gerald E.; Gavalas, George R.

1991-01-01

Relatively inexpensive process proposed for impregnating coal with calcium carbonate to increase rates of gasification and combustion of coal and to reduce emission of sulfur by trapping sulfur in calcium sulfide. Process involves aqueous-phase reactions between carbon dioxide (contained within pore network of coal) and calcium acetate. Coal impregnated with CO2 by exposing it to CO2 at high pressure.

Resin impregnation of cellulose nanofibril films facilitated by water swelling

Treesearch

Yan Qing; Ronald Sabo; Zhiyong Cai; Yiqiang Wu

2013-01-01

Flexible composite films were produced by impregnating aqueous phenol formaldehyde (PF) resin into water-swollen cellulose nanofibril (CNF) films. CNF films were prepared using a pressurized filtration method in combination with freeze drying. The freeze-dried films were swollen with water then impregnated with PF resin by soaking in aqueous resin solutions of varying...

Impregnation of bio-oil from small diameter pine into wood for moisture resistance

Treesearch

Thomas J. Robinson; Brian K. Via; Oladiran Fasina; Sushil Adhikari; Emily Carter

2011-01-01

Wood pyrolysis oil consists of hundreds of complex compounds, many of which are phenolic-based and exhibit hydrophobic properties. Southern yellow pine was impregnated with a pyrolysis oil-based penetrant using both a high pressure and vacuum impregnation systems, with no significant differences in retention levels. Penetrant concentrations ranging from 5-50% pyrolysis...

Electrochemically triggered release of acetylcholine from scCO2 impregnated conductive polymer films evokes intracellular Ca2+ signaling in neurotypic SH-SY5Y cells.

PubMed

Löffler, Susanne; Seyock, Silke; Nybom, Rolf; Jacobson, Gunilla B; Richter-Dahlfors, Agneta

2016-12-10

Implantable devices for electronically triggered drug release are attractive to achieve spatial and temporal control over drug concentrations in patients. Realization of such devices is, however, associated with technical and biological challenges. Among these are containment of drug reservoirs, lack of precise control cues, as well as the charge and size of the drug. Here, we present a method for electronically triggered release of the quaternary ammonium cation acetylcholine (ACh) from an impregnated conductive polymer film. Using supercritical carbon dioxide (scCO 2 ), a film of PEDOT/PSS (poly(3,4)-ethylenedioxythiophene doped with poly(styrenesulfonate)) is impregnated with the neurotransmitter acetylcholine. The gentle scCO 2 process generated a dry, drug-impregnated surface, well suited for interaction with biological material, while maintaining normal electrochemical properties of the polymer. Electrochemical switching of impregnated PEDOT/PSS films stimulated release of ACh from the polymer matrix, likely due to swelling mediated by the influx and efflux of charged and solvated ions. Triggered release of ACh did not affect the biological activity of the drug. This was shown by real-time monitoring of intracellular Ca 2+ signaling in neurotypic cells growing on the impregnated polymer surface. Collectively, scCO 2 impregnation of conducting polymers offers the first one-step, dopant-independent drug impregnation process, potentially facilitating loading of both anionic and cationic drugs that can be dissolved in scCO2 on its own or by using a co-solvent. We foresee that scCO 2 -loaded devices for electronically triggered drug release will create novel opportunities when generating active bio-coatings, tunable for specific needs, in a variety of medical settings. Copyright © 2016 Elsevier B.V. All rights reserved.

Bacterial adhesion forces to Ag-impregnated contact lens cases and transmission to contact lenses.

PubMed

Qu, Wenwen; Busscher, Henk J; van der Mei, Henny C; Hooymans, Johanna M M

2013-03-01

To measure adhesion forces of Pseudomonas aeruginosa, Staphylococcus aureus, and Serratia marcescens to a rigid contact lens (CL), standard polypropylene, and Ag-impregnated lens cases using atomic force microscopy and determine bacterial transmission from lens case to CL. Adhesion forces of bacterial strains to Ag-impregnated and polypropylene lens cases and a rigid CL were measured using atomic force microscopy. Adhesion forces were used to calculate Weibull distributions, from which transmission probabilities from lens case to CL were derived. Transmission probabilities were compared with actual transmission of viable bacteria from a lens case to the CL in 0.9% NaCl and in an antimicrobial lens care solution. Bacterial transmission probabilities from polypropylene lens cases based on force analysis coincided well for all strains with actual transmission in 0.9% NaCl. Bacterial adhesion forces on Ag-impregnated lens cases were much smaller than that on polypropylene and CLs, yielding a high probability of transmission. Comparison with actual bacterial transmission indicated bacterial killing due to Ag ions during colony-forming unit transmission from an Ag-impregnated lens case, especially for P. aeruginosa. Transmission of viable bacteria from Ag-impregnated lens cases could be further decreased by use of an antimicrobial lens care solution instead of 0.9% NaCl. Bacterial transmission probabilities are higher from Ag-impregnated lens cases than from polypropylene lens cases because of small adhesion forces, but this is compensated for by enhanced bacterial killing due to Ag impregnation, especially when in combination with an antimicrobial lens care solution. This calls for a balanced combination of antimicrobial lens care solutions and surface properties of a lens case and CL.

Etude de l'isolation hybride en vue de son application dans les transformateurs de puissance

NASA Astrophysics Data System (ADS)

Kassi, Koutoua Simon

For nearly a century the conventional insulation (oil / cellulose complex) was the type of insulation used in the power transformers and most electrical power equipments. But the cellulose paper, the solid part of this insulation has many weaknesses. Indeed, the aging of cellulose paper in power transformers is accelerated by moisture, oxygen, metal catalysts, temperature, etc.). The risk of failures is thereby increased. Another major weakness of cellulose paper is its inability to protect the electrical transformer windings against the harmful effects of corrosive sulfur. Given all the weaknesses of cellulose paper, several studies have been conducted to evaluate the performance of aramid paper, which has better thermal properties. The aramid paper is currently used as high temperature insulation, combined with high fire point oils (synthetic and vegetable oils), mainly in electric traction transformers. The hybrid solid insulation is associated with mineral oil or with high fire point oils; it finds application in transformers of fixed and mobile substations. Manufacturing technology is controlled by manufacturers but operators of electrical networks do not have baseline data (standards) as diagnostic tools, allowing them to monitor the health/condition of the isolation in this new type of transformer. The overall objective of this research was to study the hybrid insulation and to demonstrate its potential use in power transformers. This overall objective has been subdivided into three specific objectives, namely: (i) improving the diagnostic of the condition of solid hybrid insulation and conventional solid insulation; (ii) diagnosing the condition of oils sampled from hybrid, high temperature and conventional insulation and finally (iii) investigating the ability of aramid paper and cellulose paper to protect the copper (electrical windings) against harmful effects of corrosive sulfur. In order to achieve these objectives, thermal accelerated aging were conducted in laboratory : • according to ASTM D1934 (American Society for Testing and Materials), four different type of insulation samples were considered, namely the oil impregnated hybrid insulation, oil impregnated cellulose insulation, oil impregnated high temperature insulation and paperless oil samples. Following the aging procedure, a local overheating (thermal fault) was applied on the paper sample using an experimental setup designed in our laboratory (first and second specific objectives). • according to the IEC (International Electrotechnical Commission)-62535, for mineral, synthetic, vegetable and silicones oils (third specific objective). The degree of polymerization by viscosimetry and the determination of the carbon oxides by dissolved gas analysis (DGA) were determined to assess the condition of the paper in conventional insulation compared to that of the hybrid insulation. Our results indicate that cellulose paper in the hybrid insulation is less degraded when compared to the conventional insulation. Since the life of a transformer is directly related to the solid insulation, these results suggest that hybrid transformer insulation has a higher life than conventional ones. Subsequently, a very good correlation between amounts of oxides of carbon and degree of polymerization was established. This relationship might help improving the accuracy when interpreting the results of the DGA for transformers (first specific objective). Regarding the second specific objective, we used four physicochemical diagnosis techniques (dissolved decay products 'DDP', Turbidity, interfacial tension (IFT) and water content) to assess comparatively the quality of oils sampled from the four types of insulation. According to our results, the oil of the hybrid insulation indicated better quality at a certain stage of aging and especially after the application of thermal stress on the solid insulation. For the third specific objective, a qualitative study followed by a quantitative ones provided the following results: aramid paper better protects copper against corrosive sulfur in mineral oil; synthetic ester oils are not corrosive; the vegetable oil is not corrosive but in the presence of cellulose paper, a degree of corrosiveness is observed and the aramid paper promotes formation of corrosive sulfur in silicone oils. Based on the obtained results, the feasibility of using hybrid insulation in power transformers is possible. Keywords : power transformer; hybrid insulation; high temperature insulation; conventional insulation; sub-stations; aramid paper; cellulose paper; degree of polymerization; dissolved gases analysis (DGA); mineral oils; vegetable oils; synthetic oils; corrosive sulfur.

Electrochemical properties of a lithium-impregnated metal foam anode for thermal batteries

NASA Astrophysics Data System (ADS)

Choi, Yu-Song; Yu, Hye-Ryeon; Cheong, Hae-Won

2015-02-01

Lithium-impregnated metal foam anodes (LIMFAs) are fabricated and investigated. The LIMFAs are prepared by the impregnation of lithium into molten-salt-coated nickel metal foam. A single cell with the LIMFA exhibits a specific capacity of 3009 As g-1. For comparison, a single cell with a LiSi alloy anode is also discharged, demonstrating a specific capacity of 1050 As g-1. These significant improvements can be attributed to the large amount of lithium impregnated into the metal foam as well as the molten lithium holding capability of the foam. Due to their excellent electrochemical properties, LIMFAs are suitable for use in thermal batteries.

IMPREGNATION OF GRAPHITE SPECIMENS USING THE FURFURYL ALCOHOL IMPREGNATION PROCESS. Project DRAGON

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

Martina, R.A.; Vohler, O.J.

1964-11-15

This report gives the results of the furfuryl alcohol impregnation treatment of graphite fuel rods and end plugs done by Sigri Kohlefabrikate GmbH, Meitingen, from May 1962 till April 1964. By impregnating the components two and three times, resp. the permeability was decreased, starting from a coefficient of about 5 x 10{sup -2}cm{sup 2}sec{sup -1}, to a value of 10{sup -6} - 10{sup -7}cm{sup 2}sec{sup -1}. The rejects as occured with the first batches were finally diminished to a negligible amount by studying the single steps of treatment. (auth)

Degradation free epoxy impregnation of REBCO coils and cables

NASA Astrophysics Data System (ADS)

Barth, C.; Bagrets, N.; Weiss, K.-P.; Bayer, C. M.; Bast, T.

2013-05-01

In applications utilizing high-temperature superconductors (HTS) under high mechanical loads as high-field magnets or rotors of generators and motors, the rare-earth-barium-copper-oxide (REBCO) tapes have to be stabilized mechanically. This is achieved using support structures of structural materials and filling the voids in the support through the impregnation of the tapes. The impregnation prevents movement of the tapes and distributes mechanical loads evenly. With high mechanical strengths and low sensitivities to rapid temperature changes, epoxy resins are desired materials for the impregnation of superconductor tapes. However, a strong decrease of the current-carrying capabilities was observed in previous epoxy-impregnated REBCO coils. In this work the thermal expansion mismatches between epoxy resins and REBCO tapes are identified as the cause of these degradations. Fillers are used to reduce the thermal expansions of glues and resins. Mixtures with varying filler contents are analyzed systematically. Their thermal expansions and the corresponding degradations of short REBCO tape samples are measured. A mixture of epoxy resin and filler is found which allows degradation-free impregnation of REBCO tapes. This mixture is validated on a 1.2 m long 15 × 5 Roebel-assembled-coated-conductor (RACC) cable from Industrial Research Limited (IRL).

Impregnation of Scots pine and beech with tannin solutions: effect of viscosity and wood anatomy in wood infiltration.

PubMed

Tondi, G; Thevenon, M F; Mies, B; Standfest, G; Petutschnigg, A; Wieland, S

The impregnation process of Scots pine and beech samples with tannin solutions was investigated. The two materials involved in the process (impregnation solution and wood samples) are studied in depth. Viscosity of mimosa tannin solutions and the anatomical aspect of beech and Scots pine were analysed and correlated. The viscosity of tannin solutions presents a non-newtonian behaviour when its pH level increases, and in the case of addition of hexamine as a hardener, the crosslinking of the flavonoids turns out to be of great importance. During the impregnation of Scots pine ( Pinus sylvestris L.) and beech ( Fagus sylvatica L.), the liquid and solid uptakes were monitored while taking into consideration the different conditions of the impregnation process. This method allowed to identify the best conditions needed in order to get a successful preservative uptake for each wooden substrate. The penetration mechanism within the wood of both species was revealed with the aid of a microscopic analysis. Scots pine is impregnated through the tracheids in the longitudinal direction and through parenchyma rays in the radial direction, whereas in beech, the penetration occurs almost completely through longitudinal vessels.

A systematic review on the efficiency of cerium-impregnated activated carbons for the removal of gas-phase, elemental mercury from flue gas.

PubMed

Sowlat, Mohammad Hossein; Kakavandi, Babak; Lotfi, Saeedeh; Yunesian, Masud; Abdollahi, Mohammad; Rezaei Kalantary, Roshanak

2017-05-01

In the present systematic review, we aimed to collect and analyze all the relevant evidence on the efficiency of cerium-impregnated versus virgin-activated carbons (ACs) for the removal of gas-phase elemental mercury (Hg 0 ) from the flue gas of coal-fired power plants and to assess the effect of different calcination and operational parameters on their efficiency. A total of eight relevant papers (out of 1193 hits produced by the search) met the eligibility criteria and were included in the study. Results indicated that the Hg 0 adsorption capacity of cerium-impregnated ACs is significantly higher than that of virgin ACs, depending highly on the impregnation and operational parameters. It was noticed that although cerium-impregnated ACs possessed smaller surface areas and pore volumes, their Hg 0 removal efficiencies were still higher than their virgin counterparts. An increased Hg 0 removal efficiency was in general found by increasing the operational adsorption temperature as high as 150-170 °C. Studies also indicated that NO, SO 2 , and HCl have promoting impacts on the Hg 0 removal efficiency of Ce-impregnated ACs, while H 2 O has an inhibitory effect.

Molecular dimensions and surface diffusion assisted mechanically robust slippery perfluoropolyether impregnated mesoporous alumina interfaces

NASA Astrophysics Data System (ADS)

Rowthu, Sriharitha; Balic, Edin E.; Hoffmann, Patrik

2017-12-01

Accomplishing mechanically robust omniphobic surfaces is a long-existing challenge, and can potentially find applications in bioengineering, tribology and paint industries. Slippery liquid impregnated mesoporous α-Al2O3 interfaces are achieved with water, alkanes, water based and oil based high viscosity acrylic paints. Incredibly high abrasion-resistance (wear coefficients ≤10-8 mm3 N-1 m-1) and ultra-low friction coefficients (≥0.025) are attained, attributing to the hard alumina matrix and continuous replenishment of perfluoropolyether aided by capillarity and surface diffusion processes. A variety of impregnating liquids employed suggest that large molecules, faster surface diffusion and lowest evaporation rate generate the rare combination of high wear-resistance and omniphobicity. It is noteworthy that these novel liquid impregnated Al2O3 composites exhibit outstanding load bearing capacity up to 350 MPa; three orders of magnitude higher than achievable by the state of the art omniphobic surfaces. Further, our developed thermodynamic calculations suggest that the relative thermodynamic stability of liquid impregnated composites is linearly proportional to the spreading coefficient (S) of the impregnating liquid with the matrix material and is an important tool for the selection of an appropriate matrix material for a given liquid.

Supercritical impregnation of cinnamaldehyde into polylactic acid as a route to develop antibacterial food packaging materials.

PubMed

Villegas, Carolina; Torres, Alejandra; Rios, Mauricio; Rojas, Adrián; Romero, Julio; de Dicastillo, Carol López; Valenzuela, Ximena; Galotto, María José; Guarda, Abel

2017-09-01

Supercritical impregnation was used to incorporate a natural compound with antibacterial activity into biopolymer-based films to develop active food packaging materials. Impregnation tests were carried out under two pressure conditions (9 and 12MPa), and three depressurization rates (0.1, 1 and 10MPamin -1 ) in a high-pressure cell at a constant temperature equal to 40°C. Cinnamaldehyde (Ci), a natural compound with proven antimicrobial activity, was successfully incorporated into poly(lactic acid) films (PLA) using supercritical carbon dioxide (scCO 2 ), with impregnation yields ranging from 8 to 13% w/w. Higher pressure and slower depressurization rate seem to favor the Ci impregnation. The incorporation of Ci improved thermal, structural and mechanical properties of the PLA films. Impregnated films were more flexible, less brittle and more resistant materials than neat PLA films. The tested samples showed strong antibacterial activity against the selected microorganisms. In summary, this study provides an innovative route to the development of antibacterial biodegradable materials, which could be used in a wide range of applications of active food packaging. Copyright © 2017 Elsevier Ltd. All rights reserved.

Degradation of the performance of an epoxy-impregnated REBCO solenoid due to electromagnetic forces

NASA Astrophysics Data System (ADS)

Matsuda, T.; Okamura, T.; Hamada, M.; Matsumoto, S.; Ueno, T.; Piao, R.; Yanagisawa, Y.; Maeda, H.

2018-03-01

Recently, degradation of a high-field REBCO coil due to strong electromagnetic forces, has been identified. This issue is related to a conductor movement, forming a kink in the conductor body, and hence epoxy impregnation should be effective to prevent it. The purpose of this paper is to examine the effect of epoxy impregnation on the electromagnetic force-induced degradation of a REBCO coil. We made an epoxy impregnated solenoid coil and charged it at 4.2 K in an external field of 11 T. A notable characteristic behavior, which is different from that of a dry or paraffin impregnated coil, was observed in the coil's performance. The coil did not show any normal voltage below 408 A, at 65% on the coil load line, but it showed a sudden voltage jump at 408 A, resulted from a sudden fracture of the REBCO conductor. The outward bending, combined with a strong circumferential stress, caused the REBCO layer to fracture. Although epoxy impregnation is effective to suppress a conductor movement inside the winding, avoiding self-supported sites at a coil edge is required to eliminate degradation of the thin and flexible REBCO conductor.

40 CFR 414.70 - Applicability; description of the bulk organic chemicals subcategory.

Code of Federal Regulations, 2010 CFR

2010-07-01

... Monomethyl Ether *Dimer Acids Dioxane Ethane Ethylene Glycol Monophenyl Ether *Ethoxylates, Misc. Ethylene Glycol Dimethyl Ether Ethylene Glycol Monobutyl Ether Ethylene Glycol Monoethyl Ether Ethylene Glycol...

Unit costs for house spraying and bednet impregnation with residual insecticides in Colombia: a management tool for the control of vector-borne disease.

PubMed

Kroeger, A; Ayala, C; Medina Lara, A

2002-06-01

A study of unit costs and cost components of two malaria-control strategies (house spraying and bednet impregnation with residual insecticides) was undertaken in 11 malaria-endemic states (departamentos) of Colombia, using data provided by control staff on self-administered questionnaires. The accuracy of the data was verified by personal visits, telephone conversations and complementary information from 10 other states. Allthe financial-cost components of the malaria-control operations carried out in the previous 6 months and the results of the control operations themselves (including the numbers of houses sprayed and numbers of bednets impregnated/day) were recorded. The information was stratified according to whether the target communities were 'near' or 'far away' from an operational base, the far-away communities being those that needed overnight stays by the control staff. The main variables analysed were unit costs/house treated, and annual cost/person protected. The results show that house spraying was generally more expensive for the health services than bednet impregnation. This is particularly the case in 'nearby' communities, where most of those at-risk live. In such communities, spraying one house was 7.2 times more expensive than impregnating one bednet. Even if only those sleeping under an impregnated net were assumed to be protected, the unit costs/person protected in a 'nearby' community were twice as high for house spraying than for bednet impregnation. In 'nearby' communities, where technicians could return to the operational base each evening, insecticides made up 80% of the total spraying costs and 42% of the costs of bednet impregnation. In 'far-away' communities, however, salaries and 'per diems' were the most important cost components, representing, respectively, 23% and 22% of the costs of spraying, and 34% plus 27% of the costs of impregnation. Insecticide wastage and non-use of discounts on insecticide prices (available through the national Ministry of Health) increased the overall costs considerably. The multiple uses of these cost calculations for district health managers are presented.

Electrically assisted liquid-phase microextraction combined with capillary electrophoresis for quantification of propranolol enantiomers in human body fluids.

PubMed

Tabani, Hadi; Fakhari, Ali Reza; Shahsavani, Abolfath; Gharari Alibabaou, Hossein

2014-05-01

In this study, electromembrane extraction (EME) combined with cyclodextrin (CD)-modified capillary electrophoresis (CE) was applied for the extraction, separation, and quantification of propranolol (PRO) enantiomers from biological samples. The PRO enantiomers were extracted from aqueous donor solutions, through a supported liquid membrane (SLM) consisting of 2-nitrophenyl octyl ether (NPOE) impregnated on the wall of the hollow fiber, and into a 20-μL acidic aqueous acceptor solution into the lumen of hollow fiber. Important parameters affecting EME efficiency such as extraction voltage, extraction time, pH of the donor and acceptor solutions were optimized using a Box-Behnken design (BBD). Then, under these optimized conditions, the acceptor solution was analyzed using an optimized CD-modified CE. Several types of CD were evaluated and best results were obtained using a fused-silica capillary with ammonium acetate (80 mM, pH 2.5) containing 8 mM hydroxypropyl-β-CD as a chiral selector, applied voltage of 18 kV, and temperature of 20°C. The relative recoveries were obtained in the range of 78-95%. Finally, the performance of the present method was evaluated for the extraction and determination of PRO enantiomers in real biological samples. © 2014 Wiley Periodicals, Inc.

Bioinspired Transparent Laminated Composite Film for Flexible Green Optoelectronics.

PubMed

Lee, Daewon; Lim, Young-Woo; Im, Hyeon-Gyun; Jeong, Seonju; Ji, Sangyoon; Kim, Yong Ho; Choi, Gwang-Mun; Park, Jang-Ung; Lee, Jung-Yong; Jin, Jungho; Bae, Byeong-Soo

2017-07-19

Herein, we report a new version of a bioinspired chitin nanofiber (ChNF) transparent laminated composite film (HCLaminate) made of siloxane hybrid materials (hybrimers) reinforced with ChNFs, which mimics the nanofiber-matrix structure of hierarchical biocomposites. Our HCLaminate is produced via vacuum bag compressing and subsequent UV-curing of the matrix resin-impregnated ChNF transparent paper (ChNF paper). It is worthwhile to note that this new type of ChNF-based transparent substrate film retains the strengths of the original ChNF paper and compensates for ChNF paper's drawbacks as a flexible transparent substrate. As a result, compared with high-performance synthetic plastic films, such as poly(ethylene terephthalate), poly(ether sulfone), poly(ethylene naphthalate), and polyimide, our HCLaminate is characterized to exhibit extremely smooth surface topography, outstanding optical clarity, high elastic modulus, high dimensional stability, etc. To prove our HCLaminate as a substrate film, we use it to fabricate flexible perovskite solar cells and a touch-screen panel. As far as we know, this work is the first to demonstrate flexible optoelectronics, such as flexible perovskite solar cells and a touch-screen panel, actually fabricated on a composite film made of ChNF. Given its desirable macroscopic properties, we envision our HCLaminate being utilized as a transparent substrate film for flexible green optoelectronics.

Rapid, Efficient and Versatile Strategies for Functionally Sophisticated Polymers and Nanoparticles: Degradable Polyphosphoesters and Anisotropic Distribution of Chemical Functionalities

NASA Astrophysics Data System (ADS)

Zhang, Shiyi

The overall emphasis of this dissertation research included two kinds of asymmetrically-functionalized nanoparticles with anisotropic distributions of chemical functionalities, three degradable polymers synthesized by organocatalyzed ring-opening polymerizations, and two polyphosphoester-based nanoparticle systems for various biomedical applications. Inspired by the many hierarchical assembly processes that afford complex materials in Nature, the construction of asymmetrically-functionalized nanoparticles with efficient surface chemistries and the directional organization of those building blocks into complex structures have attracted much attention. The first method generated a Janus-faced polymer nanoparticle that presented two orthogonally click-reactive surface chemistries, thiol and azido. This robust method involved reactive functional group transfer by templating against gold nanoparticle substrates. The second method produced nanoparticles with sandwich-like distribution of crown ether functionalities through a stepwise self-assembly process that utilized crown ether-ammonium supramolecular interactions to mediate inter-particle association and the local intra-particle phase separation of unlike hydrophobic polymers. With the goal to improve the efficiency of the production of degradable polymers with tunable chemical and physical properties, a new type of reactive polyphosphoester was synthesized bearing alkynyl groups by an organocatalyzed ring-opening polymerization, the chemical availability of the alkyne groups was investigated by employing "click" type azide-alkyne Huisgen cycloaddition and thiol-yne radical-mediated reactions. Based on this alkyne-functionalized polyphosphoester polymer and its two available "click" type reactions, two degradable nanoparticle systems were developed. To develop the first system, the well defined poly(ethylene oxide)-block-polyphosphester diblock copolymer was transformed into a multifunctional Paclitaxel drug conjugate by densely attaching the polyphosphoester block with azide-functionalized Paclitaxel by azide-alkyne Huisgen cycloaddition. This Paclitaxel drug conjugate provides a powerful platform for combinational cancer therapy and bioimaging due to its ultra-high Paclitaxel loading (> 65 wt%), high water solubility (>6.2 mg/mL for PTX) and easy functionalization. Another polyphosphoester-based nanoparticle system has been developed by a programmable process for the rapid and facile preparation of a family of nanoparticles with different surface charges and functionalities. The non-ionic, anionic, cationic and zwitterionic nanoparticles with hydrodynamic diameters between 13 nm to 21 nm and great size uniformity could be rapidly prepared from small molecules in 6 h or 2 days. The anionic and zwitterionic nanoparticles were designed to load silver ions to treat pulmonary infections, while the cationic nanoparticles are being applied to regulate lung injuries by serving as a degradable iNOS inhibitor conjugates. In addition, a direct synthesis of acid-labile polyphosphoramidate by organobase-catalyzed ring-opening polymerization and an improved two-step preparation of polyphosphoester ionomer by acid-assisted cleavage of phosphoramidate bonds on polyphosphoramidate were developed. Polyphosphoramidate and polyphosphoester ionomers may be applied to many applications, due to their unique chemical and physical properties.

Molecular structure impacts on secondary organic aerosol formation from glycol ethers

NASA Astrophysics Data System (ADS)

Li, Lijie; Cocker, David R.

2018-05-01

Glycol ethers, a class of widely used solvents in consumer products, are often considered exempt as volatile organic compounds based on their vapor pressure or boiling points by regulatory agencies. However, recent studies found that glycol ethers volatilize at ambient conditions nearly as rapidly as the traditional high-volatility solvents indicating the potential of glycol ethers to form secondary organic aerosol (SOA). This is the first work on SOA formation from glycol ethers. The impact of molecular structure, specifically -OH, on SOA formation from glycol ethers and related ethers are investigated in the work. Ethers with and without -OH, with methyl group hindrance on -OH and with -OH at different location are studied in the presence of NOX and under "NOX free" conditions. Photooxidation experiments under different oxidation conditions confirm that the processing of ethers is a combination of carbonyl formation, cyclization and fragmentation. Bulk SOA chemical composition analysis and oxidation products identified in both gas and particle phase suggests that the presence and location of -OH in the carbon bond of ethers determine the occurrence of cyclization mechanism during ether oxidation. The cyclization is proposed as a critical SOA formation mechanism to prevent the formation of volatile compounds from fragmentation during the oxidation of ethers. Glycol ethers with -CH2-O-CH2CH2OH structure is found to readily form cyclization products, especially with the presence of NOx, which is more relevant to urban atmospheric conditions than without NOx. Glycol ethers are evaluated as dominating SOA precursors among all ethers studied. It is estimated that the contribution of glycol ethers to anthropogenic SOA is roughly 1% of the current organic aerosol from mobile sources. The contribution of glycol ethers to anthropogenic SOA is roughly 1% of the current organic aerosol from mobile sources and will play a more important role in future anthropogenic SOA formation.

Adsorption of Toluene and Paraxylene from Aqueous Solution Using Pure and Iron Oxide Impregnated Carbon Nanotubes: Kinetics and Isotherms Study

PubMed Central

Abbas, Aamir; Ihsanullah; Al-Baghli, Nadhir A. H.

2017-01-01

Multiwall carbon nanotubes (CNTs) and iron oxide impregnated carbon nanotubes (CNTs-iron oxide) were investigated for the adsorption of hazardous toluene and paraxylene (p-xylene) from aqueous solution. Pure CNTs were impregnated with iron oxides nanoparticles using wet impregnation technique. Various characterization techniques including thermogravimetric analysis, scanning electron microscopy, elemental dispersion spectroscopy, X-ray diffraction, and nitrogen adsorption analysis were used to study the thermal degradation, surface morphology, purity, and surface area of the materials. Batch adsorption experiments show that iron oxide impregnated CNTs have higher degree of removal of p-xylene (i.e., 90%) compared with toluene (i.e., 70%), for soaking time 2 h, with pollutant initial concentration 100 ppm, at pH 6 and shaking speed of 200 rpm at 25°C. Pseudo-second-order model provides better fitting for the toluene and p-xylene adsorption. Langmuir and Freundlich isotherm models demonstrate good fitting for the adsorption data of toluene and p-xylene. PMID:28386208

Fully synthetic taped insulation cables

DOEpatents

Forsyth, Eric B.; Muller, Albert C.

1984-01-01

A high voltage oil-impregnated electrical cable with fully polymer taped insulation operable to 765 kV. Biaxially oriented, specially processed, polyethylene, polybutene or polypropylene tape with an embossed pattern is wound in multiple layers over a conductive core with a permeable screen around the insulation. Conventional oil which closely matches the dielectric constant of the tape is used, and the cable can be impregnated after field installation because of its excellent impregnation characteristics.

The influence of FLiNaK salt impregnation on the mechanical properties of a 2D woven C/C composite

NASA Astrophysics Data System (ADS)

Zhang, Dongsheng; Xia, Huihao; Yang, Xinmei; Feng, Shanglei; Song, Jinliang; Zhou, Xingtai

2017-03-01

Impregnating of molten LiF-NaF-KF salt (LiF-NaF-KF: 46.5-11.5-42 mol%, FLiNaK) into a 2D woven C/C composite was performed at 650 °C under different pressure. The weight gain and mechanical properties change of the 2D woven C/C composite after FLiNaK salt impregnation were measured. The FLiNaK salt distribution into the 2D woven C/C composite was observed by X-ray computed tomography (X-ray CT) and scanning electron microscopy. The results showed that the weight gain of the 2D woven C/C composite increased with increasing impregnating pressure. In X-ray CT images, FLiNaK salt was distributed into the open pores and fissures among fiber bundles and neighboring plies. The interlaminar shear strength, compressive strength, and flexural strength of the 2D woven C/C composite increased with the increase of weight gain. The influence of FLiNaK salt impregnation on the mechanical properties was attributed to the coupling effect of re-densification of FLiNaK salt impregnation and residual stress formed in 2D woven C/C composite.

An artificial test substrate for evaluating electron microscopic immunocytochemical labeling reactions.

PubMed

Gagne, G D; Miller, M F

1987-08-01

We describe an artificial substrate system for optimization of labeling parameters in electron microscope immunocytochemical studies. The system involves use of blocks of glutaraldehyde-polymerized BSA into which a desired antigen is incorporated by a simple soaking procedure. The resulting antigen-impregnated artificial substrate can then be fixed and embedded identically to a piece of tissue. The BSA substrate can also be dried and then sectioned for immunolabeling with or without chemical fixation and without exposing the antigen to dehydrating agents and embedding resins. The effects of various fixation and embedding procedures can thus be evaluated separately. Other parameters affecting immunocytochemical labeling, such as antibody and conjugate concentration, can also be evaluated. We used this system, along with immunogold labeling, to determine quantitatively the optimal fixation and embedding conditions for labeling of hepatitis B surface antigen (HbsAg), human IgG, and horseradish peroxidase. Using unfixed and unembedded HBsAg, we were able to detect antigen concentrations below 20 micrograms/ml. We have shown that it is not possible to label HBsAg within resin-embedded cells using conventional aldehyde fixation protocols and polyclonal antibodies.

Properties of indirect composites reinforced with monomer-impregnated glass fiber.

PubMed

Tanoue, Naomi; Sawase, Takashi; Matsumura, Hideo; McCabe, John F

2012-07-01

Sufficient flexural strength is required for long-term clinical use of fixed partial dentures made with fiber-reinforced composite. The flexural strengths of indirect composite materials reinforced with a monomer-preimpregnated glass fiber material were determined to evaluate the compatibility of the composites to glass fiber material. Four types (microhybrid, nanohybrid, microfilled, and minifilled) of indirect composites and a unidirectional long glass fiber material were selected for investigation. The composites were placed on a fiber plate and polymerized in accordance with the respective manufacturer's instructions. Rectangular bar fiber-composite specimens were machined and the flexural strength was calculated. The flexural strength of each indirect composite was also measured. The microfilled composite with the lowest filler content (70 wt%) exhibited the highest increase ratio using the fiber, although its strength without fiber reinforcement was the lowest (62.1 MPa). The fiber-microhybrid specimen demonstrated the highest mean strength (355.9 MPa), although the filler content of the microhybrid composite was comparatively low (73 wt%). The type of composite material should be considered for the selection of an optimal fiber-composite combination.

Conversion of "Waste Plastic" into Photocatalytic Nanofoams for Environmental Remediation.

PubMed

de Assis, Geovania C; Skovroinski, Euzébio; Leite, Valderi D; Rodrigues, Marcelo O; Galembeck, André; Alves, Mary C F; Eastoe, Julian; de Oliveira, Rodrigo J

2018-03-07

Plastic debris is a major environmental concern, and to find effective ways to reuse polystyrene (PS) presents major challenges. Here, it is demonstrated that polystyrene foams impregnated with SnO 2 are easily generated from plastic debris and can be applied to photocatalytic degradation of dyes. SnO 2 nanoparticles were synthesized by a polymeric precursor method, yielding specific surface areas of 15 m 2 /g after heat treatment to 700 °C. Crystallinity, size, and shape of the SnO 2 particles were assessed by X-ray diffraction (XRD) and transmission electron microscopy (TEM), demonstrating the preparation of crystalline spherical nanoparticles with sizes around 20 nm. When incorporated into PS foams, which were generated using a thermally induced phase separation (TIPS) process, the specific surface area increased to 48 m 2 /g. These PS/SnO 2 nanofoams showed very good efficiency for photodegradation of rhodamine B, under UV irradiation, achieving up to 98.2% removal. In addition the PS/SnO 2 nanofoams are shown to retain photocatalytic activity for up to five reuse cycles.

Charge Stabilized Crystalline Colloidal Arrays As Templates For Fabrication of Non-Close-Packed Inverted Photonic Crystals

PubMed Central

Bohn, Justin J.; Ben-Moshe, Matti; Tikhonov, Alexander; Qu, Dan; Lamont, Daniel N.

2010-01-01

We developed a straightforward method to form non close-packed highly ordered fcc direct and inverse opal silica photonic crystals. We utilize an electrostatically self assembled crystalline colloidal array (CCA) template formed by monodisperse, highly charged polystyrene particles. We then polymerize a hydrogel around the CCA (PCCA) and condense the silica to form a highly ordered silica impregnated (siPCCA) photonic crystal. Heating at 450 °C removes the organic polymer leaving a silica inverse opal structure. By altering the colloidal particle concentration we independently control the particle spacing and the wall thickness of the inverse opal photonic crystals. This allows us to control the optical dielectric constant modulation in order to optimize the diffraction; the dielectric constant modulation is controlled independently of the photonic crystal periodicity. These fcc photonic crystals are better ordered than typical close-packed photonic crystals because their self assembly utilizes soft electrostatic repulsive potentials. We show that colloidal particle size and charge polydispersity has modest impact on ordering, in contrast to that for close-packed crystals. PMID:20163800

Silica Modified with Polyaniline as a Potential Sorbent for Matrix Solid Phase Dispersion (MSPD) and Dispersive Solid Phase Extraction (d-SPE) of Plant Samples

PubMed Central

Sowa, Ireneusz; Wójciak-Kosior, Magdalena; Strzemski, Maciej; Sawicki, Jan; Staniak, Michał; Dresler, Sławomir; Szwerc, Wojciech; Mołdoch, Jarosław; Latalski, Michał

2018-01-01

Polyaniline (PANI) is one of the best known conductive polymers with multiple applications. Recently, it was also used in separation techniques, mostly as a component of composites for solid-phase microextraction (SPME). In the present paper, sorbent obtained by in situ polymerization of aniline directly on silica gel particles (Si-PANI) was used for dispersive solid phase extraction (d-SPE) and matrix solid–phase extraction (MSPD). The efficiency of both techniques was evaluated with the use of high performance liquid chromatography with diode array detection (HPLC-DAD) quantitative analysis. The quality of the sorbent was verified by Raman spectroscopy and microscopy combined with automated procedure using computer image analysis. For extraction experiments, triterpenes were chosen as model compounds. The optimal conditions were as follows: protonated Si-PANI impregnated with water, 160/1 sorbent/analyte ratio, 3 min of extraction time, 4 min of desorption time and methanolic solution of ammonia for elution of analytes. The proposed procedure was successfully used for pretreatment of plant samples. PMID:29565297

A high power lithium thionyl chloride battery for space applications

NASA Technical Reports Server (NTRS)

Shah, Pinakin M.

1993-01-01

A high power, 28 V, 330 A h, active lithium thionyl chloride battery has been developed for use as main and payload power sources on an expendable launch vehicle. Nine prismatic cells, along with the required electrical components and a built-in heater system, are efficiently packaged resulting in significant weight savings over presently used silver-zinc batteries. The high rate capability is achieved by designing the cells with a large electrochemical surface area and impregnating an electrocatalyst, polymeric phthalocyanine, into the carbon cathodes. Passivation effects are reduced with the addition of sulfur dioxide into the thionyl chloride electrolyte solution. The results of conducting a detailed thermal analysis are utilized to establish the heater design parameters and the thermal insulation requirements of the battery. An analysis of cell internal pressure and vent characteristics clearly illustrates the margins of safety under different operating conditions. Performance of fresh cells is discussed using polarization scan and discharge data at different rates and temperatures. Self-discharge rate is estimated based upon test results on cells after storage. Results of testing a complete prototype battery are described.

In vitro study of transverse strength of fiber reinforced composites.

PubMed

Mosharraf, R; Hashemi, Z; Torkan, S

2011-01-01

Reinforcement with fiber is an effective method for considerable improvement in flexural properties of indirect composite resin restorations. The aim of this in-vitro study was to compare the transverse strength of composite resin bars reinforced with pre-impregnated and non-impregnated fibers. Thirty six bar type composite resin specimens (3×2×25 mm) were constructed in three groups. The first group was the control group (C) without any fiber reinforcement. The specimens in the second group (P) were reinforced with pre-impregnated fibers and the third group (N) with non-impregnated fibers. These specimens were tested by the three-point bending method to measure primary transverse strength. Data were statistically analyzed with one way ANOVA and Tukey's tests. There was a significant difference among the mean primary transverse strength in the three groups (P<0.001). The post-hoc (Tukey) test showed that there was a significant difference between the pre-impregnated and control groups in their primary transverse strength (P<0.001). Regarding deflection, there was also a significant difference among the three groups (P=0.001). There were significant differences among the mean deflection of the control group and two other groups (P(C&N)<.001 and P(C&P)=.004), but there was no significant difference between the non-and pre-impregnated groups (P(N&P)=.813). Within the limitations of this study, it was concluded that reinforcement with fiber considerably increased the transverse strength of composite resin specimens, but impregnation of the fiber used implemented no significant difference in the transverse strength of composite resin samples.

Isolation and characterization of an ether-type polyurethane-degrading micro-organism and analysis of degradation mechanism by Alternaria sp.

PubMed

Matsumiya, Y; Murata, N; Tanabe, E; Kubota, K; Kubo, M

2010-06-01

To degrade ether-type polyurethane (ether-PUR), ether-PUR-degrading micro-organism was isolated. Moreover, ether-PUR-degrading mechanisms were analysed using model compounds of ether-PUR. A fungus designated as strain PURDK2, capable of changing the configuration of ether-PUR, has been isolated. This isolated fungus was identified as Alternaria sp. Using a scanning electron microscope, the grid structure of ether-PUR was shown to be melted and disrupted by the fungus. The degradation of ether-PUR by the fungus was analysed, and the ether-PUR was degraded by the fungus by about 27.5%. To analyse the urethane-bond degradation by the fungus, a degraded product of ethylphenylcarbamate was analysed using GC/MS. Aniline and ethanol were detected by degradation with the supernatant, indicating that the fungus secreted urethane-bond-degrading enzyme(s). PURDK2 also degraded urea bonds when diphenylmethane-4,4'-dibutylurea was used as a substrate. The enzyme(s) from PURDK2 degraded urethane and urea bonds to convert the high molecular weight structure of ether-PUR to small molecules; and then the fungus seems to use the small molecules as an energy source. Ether-PUR-degrading fungus, strain PURDK2, was isolated, and the urethane- and urea-bonds-degrading enzymes from strain PURDK2 could contribute to the material recycling of ether-PUR.

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

Not Available

Phillips Petroleum Co. is poised to license its high conversion process to produce fuel ethers for blending in reformulated gasolines. The technology has been proven in a Phillips semiworks at Bartlesville, Okla. The process can produce methyl tertiary butyl ether, ethyl tertiary butyl ether, tertiary amyl methyl ether, or tertiary amyl ethyl ether with typical refinery process equipment and techniques. Phillips said it can achieve conversion levels of 92-99%, depending on the ether. The ether produced is determined by which hydrocarbon fraction is used for feedstock and which alcohol is chosen for reaction. The process is described.

Chlorhexidine-impregnated cloths to prevent skin and soft-tissue infection in Marine recruits: a cluster-randomized, double-blind, controlled effectiveness trial.

PubMed

Whitman, Timothy J; Herlihy, Rachel K; Schlett, Carey D; Murray, Patrick R; Grandits, Greg A; Ganesan, Anuradha; Brown, Maya; Mancuso, James D; Adams, William B; Tribble, David R

2010-12-01

Community-associated methicillin-resistant Staphylococcus aureus (CA-MRSA) causes skin and soft-tissue infection (SSTI) in military recruits. To evaluate the effectiveness of 2% chlorhexidine gluconate (CHG)-impregnated cloths in reducing rates of SSTI and S. aureus colonization among military recruits. A cluster-randomized (by platoon), double-blind, controlled effectiveness trial. Marine Officer Candidate School, Quantico, Virginia, 2007. Military recruits. Application of CHG-impregnated or control (Comfort Bath; Sage) cloths applied over entire body thrice weekly. Recruits were monitored daily for SSTI. Baseline and serial nasal and/or axillary swabs were collected to assess S. aureus colonization. Of 1,562 subjects enrolled, 781 (from 23 platoons) underwent CHG-impregnated cloth application and 781 (from 21 platoons) underwent control cloth application. The rate of compliance (defined as application of 50% or more of wipes) at 2 weeks was similar (CHG group, 63%; control group, 67%) and decreased over the 6-week period. The mean 6-week SSTI rate in the CHG-impregnated cloth group was 0.094, compared with 0.071 in the control group (analysis of variance model rate difference, 0.025  ± 0.016; P = .14). At baseline, 43% of subjects were colonized with methicillin-susceptible S. aureus (MSSA), and 2.1% were colonized with MRSA. The mean incidence of colonization with MSSA was 50% and 61% (P = .026) and with MRSA was 2.6% and 6.0% (P = .034) for the CHG-impregnated and control cloth groups, respectively. CHG-impregnated cloths applied thrice weekly did not reduce rates of SSTI among recruits. S. aureus colonization rates increased in both groups but to a lesser extent in those assigned to the CHG-impregnated cloth intervention. Antecedent S. aureus colonization was not a risk factor for SSTI. Additional studies are needed to identify effective measures for preventing SSTI among military recruits. ClinicalTrials.gov identifier: NCT00475930.

Synthesis of arborescent model polymer structures by living carbocationic polymerization for structure-property studies

NASA Astrophysics Data System (ADS)

Dos Santos Freire, Lucas

Polyisobutylene is fully saturated, therefore exhibits outstanding chemical, oxidative and thermal stability,1 which makes it ideally suitable as a model to study mechanical and viscoelastic properties of elastomers, and to correlate properties with structure. The main objective of this dissertation was to develop a fundamental understanding of the mechanism of the synthesis of arborescent (hyperbranched) polyisobutylene (arbPIB) by inimer-type (initiator-monomer) living carbocationic polymerization. The strategy for the effective synthesis of arbPIBs consists of copolymerizing the 4-(2-methoxyisopropyl)styrene (IUPAC name: p-vinylcumyl methyl ether) (IB) via controlled/living carbocationic polymerization using TiCl4 coinitiator. In situ FTIR monitoring showed that the self-condensing vinyl polymerization (SCVP) of MeOIM is possible, and that when copolymerizing MeOIM and IB, a nearly alternating structure and multiple end groups are obtained. arbPIB was synthesized and the repeatability of the polymerization was demonstrated. It was found that higher branching was obtained with increasing [MeOIM] and that branching did not further increase if additional IB was added after the MeOIM had reacted completely. No evident changes were observed when switching solvents from Hx/MeCl to a MeCHx/MeCl mixture. Branching parameters showed that arbPIBs have a behavior between polydisperse stars and polycondensates with the number of branches increasing linearly with molecular weight. Novel arbPIB-based block copolymers (TPEs) were synthesized and it was found that copolymers with low Tg short end blocks and less than 5 mol% of a second monomer exhibit thermoplastic elastomeric properties. The materials were strongly reinforced when compounded with carbon black. arbPIB-b-PS are prospective biomaterials and the establishment of reliable methods for evaluating their short and long term properties is a subject of great importance. A dynamic fatigue testing methodology was developed for small, soft rubbery specimens that can be implanted into small animals and re-tested after explantation. Higher ultimate tensile strength and lower elongation at break were measured on microdumbbells than on standard dumbbells. Fatigue testing microdumbbells induced higher stresses at the same strain rate, thus presenting the worst case scenario and being appropriate for fatigue tests. The fatigue limit of linear polystyrene-b-polyisobutylene- b-polystyrene (SIBS) and analogous arbPIB- b-PS samples were determined by using stepwise increasing strain tests developed for fatigue analysis. The presence of branching and a broader molecular weight distribution arbPIB-b-PS led to better mechanical stability and higher fatigue limit than in analogous linear SIBS samples.

A new route to synthesize aryl acetates from carbonylation of aryl methyl ethers

PubMed Central

Yang, Youdi; Li, Shaopeng; Han, Buxing

2018-01-01

Ether bond activation is very interesting because the synthesis of many valuable compounds involves conversion of ethers. Moreover, C–O bond cleavage is also very important for the transformation of biomass, especially lignin, which abundantly contains ether bonds. Developing efficient methods to activate aromatic ether bonds has attracted much attention. However, this is a challenge because of the inertness of aryl ether bonds. We proposed a new route to activate aryl methyl ether bonds and synthesize aryl acetates by carbonylation of aryl methyl ethers. The reaction could proceed over RhCl3 in the presence of LiI and LiBF4, and moderate to high yields of aryl acetates could be obtained from transformation of various aryl methyl ethers with different substituents. It was found that LiBF4 could assist LiI to cleave aryl methyl ether bonds effectively. The reaction mechanism was proposed by a combination of experimental and theoretical studies. PMID:29795781

Unimolecular Micelles of Amphiphilic Cyclodextrin-Core Star-Like Copolymers with Covalent pH-Responsive Linkage of Anticancer Prodrugs.

PubMed

Jia, Tao; Huang, Shuo; Yang, Cangjie; Wang, Mingfeng

2017-08-07

Multifunctional stable and stimuli-responsive drug delivery systems are important for efficient cancer treatment due to their advantages such as enhanced cancer-targeting efficiency, improved pharmacokinetics, minimized drug leaching, and reduced undesirable side effects. Here we report a robust and pH-responsive anticancer drug delivery system based on unimolecular micelles of star-like amphiphilic copolymers. The polymers (denoted as CPOFs) were facilely synthesized via one-step atom transfer radical polymerization of functionalizable benzoaldehyde and hydrophilic poly[(oligo ethylene glycol) methyl ether methacrylate] as comonomers from the core of heptakis [2,3,6-tri-o-(2-bromo-2-methyl propionyl]-β-cyclodextrin as the initiator. Doxorubicin (DOX) as an anticancer drug was covalently linked to the benzoaldehyde groups of CPOFs through pH-sensitive Schiff-base bonds. The DOX-conjugated polymers, denoted as CPOF-DOX, formed robust unimolecular micelles with an average diameter of 18 nm in aqueous media. More importantly, these unimolecular micelles showed higher drug loading capacity and more controllable drug release characteristics, compared to our previous unimolecular micelles of β-cyclodextrin-poly(lactic acid)-b-poly[(oligo ethylene glycol) methyl ether methacrylates] that physically encapsulated DOX via hydrophobic interaction. Moreover, the CPOF-DOX unimolecular micelles could be internalized by human cervical cancer HeLa cells in a stepwise way and showed less cytotoxicity compared to carrier-free DOX. We foresee that CPOF-DOX would provide a promising robust and controllable anticancer drug delivery system for future animal study and clinical trials for cancer treatment.

Adsorption induced enzyme denaturation: the role of polymer hydrophobicity in adsorption and denaturation of alpha-chymotrypsin on allyl glycidyl ether (AGE)-ethylene glycol dimethacrylate (EGDM) copolymers.

PubMed

Lahari, Challa; Jasti, Lakshmi S; Fadnavis, Nitin W; Sontakke, Kalpana; Ingavle, Ganesh; Deokar, Sarika; Ponrathnam, Surendra

2010-01-19

Effects of changes in hydrophobicity of polymeric support on structure and activity of alpha-chymotrypsin (E.C. 3.4.21.1) have been studied with copolymers of allyl glycidyl ether (AGE) and ethylene glycol dimethacrylate (EGDM) with increasing molar ratio of EGDM to AGE (cross-link density 0.05 to 1.5). The enzyme is readily adsorbed from aqueous buffer at room temperature following Langmuir adsorption isotherms in unexpectedly large amounts (25% w/w). Relative hydrophobicity of the copolymers has been assessed by studying adsorption of naphthalene and Fmoc-methionine by the series of copolymers from aqueous solutions. Polymer hydrophobicity appears to increase linearly on increasing cross-link density from 0.05 to 0.25. Further increase in cross-link density causes a decrease in naphthalene binding but has little effect on binding of Fmoc-Met. Binding of alpha-chymotrypsin to these copolymers follow the trend for Fmoc-methionine binding, rather than naphthalene binding, indicating involvement of polar interactions along with hydrophobic interactions during binding of protein to the polymer. The adsorbed enzyme undergoes extensive denaturation (ca. 80%) with loss of both tertiary and secondary structure on contact with the copolymers as revealed by fluorescence, CD and Raman spectra of the adsorbed protein. Comparison of enzyme adsorption behavior with Eupergit C, macroporous Amberlite XAD-2, and XAD-7 suggests that polar interactions of the EGDM ester functional groups with the protein play a significant role in enzyme denaturation.

Catalytic oxidation of dimethyl ether

DOEpatents

Zelenay, Piotr; Wu, Gang; Johnston, Christina M.; Li, Qing

2016-05-10

A composition for oxidizing dimethyl ether includes an alloy supported on carbon, the alloy being of platinum, ruthenium, and palladium. A process for oxidizing dimethyl ether involves exposing dimethyl ether to a carbon-supported alloy of platinum, ruthenium, and palladium under conditions sufficient to electrochemically oxidize the dimethyl ether.

Resin impregnation process for producing a resin-fiber composite

NASA Technical Reports Server (NTRS)

Palmer, Raymond J. (Inventor); Moore, William E. (Inventor)

1994-01-01

Process for vacuum impregnation of a dry fiber reinforcement with a curable resin to produce a resin-fiber composite, by drawing a vacuum to permit flow of curable liquid resin into and through a fiber reinforcement to impregnate same and curing the resin-impregnated fiber reinforcement at a sufficient temperature and pressure to effect final curing. Both vacuum and positive pressure, e.g. autoclave pressure, are applied to the dry fiber reinforcement prior to application of heat and prior to any resin flow to compact the dry fiber reinforcement, and produce a resin-fiber composite of reduced weight, thickness and resin content, and improved mechanical properties. Preferably both a vacuum and positive pressure, e.g. autoclave pressure, are also applied during final curing.

Applicability of vacuum impregnation to modify physico-chemical, sensory and nutritive characteristics of plant origin products--a review.

PubMed

Radziejewska-Kubzdela, Elżbieta; Biegańska-Marecik, Róża; Kidoń, Marcin

2014-09-19

Vacuum impregnation is a non-destructive method of introducing a solution with a specific composition to the porous matrices of fruit and vegetables. Mass transfer in this process is a result of mechanically induced differences in pressure. Vacuum impregnation makes it possible to fill large volumes of intercellular spaces in tissues of fruit and vegetables, thus modifying physico-chemical properties and sensory attributes of products. This method may be used, e.g., to reduce pH and water activity of the product, change its thermal properties, improve texture, color, taste and aroma. Additionally, bioactive compounds may be introduced together with impregnating solutions, thus improving health-promoting properties of the product or facilitating production of functional food.

Polyethylene barrier impregnated with lambda-cyhalothrin for exclusion of subterranean termites (Isoptera: Rhinotermitidae) from structures.

PubMed

Su, Nan-Yao; Ban, Paul; Scheffrahn, Rudolf H

2004-04-01

Polyethylene film impregnated with lambda-cyhalothrin was placed over a sand plot and covered with a concrete slab to allow insecticide movement into the sand for a period of 5.5 yr. Discs of polyethylene film and sand beneath them were sampled annually for 5 yr and at 5.5 yr for bioassay with the Formosan and eastern subterranean termite. Results demonstrated that sufficient quantities of lambda-cyhalothrin were released from the impregnated polyethylene film into adjacent sand to prevent termite penetration. The impregnated film has less environmental impact than conventional liquid termiticides because the insecticide is held in the polymer. Other advantages include its dual function as a construction moisture barrier and ease in verifying its proper installation.

Porous and non-porous water soluble polymer nanospheres

NASA Astrophysics Data System (ADS)

Henselwood, Fred William

Water soluble polymer nanospheres have been prepared from the photo-cross-linking of diblock copolymer micelles formed either in water or in N,N-dimethylformamide/water mixtures. The diblock copolymers utilized in this study were poly(2-cinnamoyl-ethyl methacrylate)-block-poly(acrylic acid), poly ((2-cinnamoylethyl methacrylate)-random-(2-octanoylethyl methacrylate)) -block-poly(acrylic acid), and poly ((2-cinnamoyl-ethyl methacrylate)-random-(2-oleoylethyl methacrylate)) -block-poly(acrylic acid). These polymers were synthesized by the functionalization of diblock copolymers prepared by anionic polymerization. The photo-cross-linking was achieved through the dimerization of cinnamoyl groups by ultraviolet irradiation. Transmission electron microscopy confirmed that the polymer nanospheres had an inner core region formed by the cinnamoyl containing polymer blocks, and an outer shell layer formed by the acrylic acid polymer blocks. The hydrodynamic radius of the polymer nanospheres in water was approximately 50 to 75 nm as determined by dynamic light scattering. It has been found that the polymer nanospheres, when in water, could be readily impregnated with organic molecules. Fluorescence measurements showed that the polymer nanospheres could uptake polyaromatic hydrocarbons by the direct mixing of polyaromatic hydrocarbons with the polymer nanospheres in water. Perylene was found to be between 2.0 × 10sp5 and 4.0 × 10sp5 times more soluble in the core region of the polymer nanospheres than in water. The addition of divalent cations was shown to induce aggregation of the polymer nanospheres and resulted in the precipitation of the polymer nanospheres along with any captured perylene. This suggests that the polymer nanospheres may be useful in water remediation. Porous polymer nanospheres were prepared by the incorporation of low molecular weight polymeric porogens within the core region of the polymer nanospheres. Following photo-cross-linking the polymeric porogens were extracted out of the polymer nanospheres resulting in pore formation. Perylene loading experiments revealed that the loading of the porous polymer nanospheres was 41% higher than that achieved for non-porous polymer nanospheres prepared from the same initial diblock copolymer. This indicates that the porous polymer nanospheres may be preferred over the non-porous polymer nanospheres in applications such as drug delivery.

Tumor-targeting peptide conjugated pH-responsive micelles as a potential drug carrier for cancer therapy.

PubMed

Wu, Xiang Lan; Kim, Jong Ho; Koo, Heebeom; Bae, Sang Mun; Shin, Hyeri; Kim, Min Sang; Lee, Byung-Heon; Park, Rang-Woon; Kim, In-San; Choi, Kuiwon; Kwon, Ick Chan; Kim, Kwangmeyung; Lee, Doo Sung

2010-02-17

Herein, we prepared tumor-targeting peptide (AP peptide; CRKRLDRN) conjugated pH-responsive polymeric micelles (pH-PMs) in cancer therapy by active and pH-responsive tumor targeting delivery systems, simultaneously. The active tumor targeting and tumoral pH-responsive polymeric micelles were prepared by mixing AP peptide conjugated PEG-poly(d,l-lactic acid) block copolymer (AP-PEG-PLA) into the pH-responsive micelles of methyl ether poly(ethylene glycol) (MPEG)-poly(beta-amino ester) (PAE) block copolymer (MPEG-PAE). These mixed amphiphilic block copolymers were self-assembled to form stable AP peptide-conjugated and pH-responsive AP-PEG-PLA/MPEG-PAE micelles (AP-pH-PMs) with an average size of 150 nm. The AP-pH-PMs containing 10 wt % of AP-PEG-PLA showed a sharp pH-dependent micellization/demicellization transition at the tumoral acid pH. Also, they presented the pH-dependent drug release profile at the acidic pH of 6.4. The fluorescence dye, TRITC, encapsulated AP-pH-PMs (TRITC-AP-pH-PMs) presented the higher tumor-specific targeting ability in vitro cancer cell culture system and in vivo tumor-bearing mice, compared to control pH-responsive micelles of MPEG-PAE. For the cancer therapy, the anticancer drug, doxorubicin (DOX), was efficiently encapsulated into the AP-pH-PMs (DOX-AP-pH-PMs) with a higher loading efficiency. DOX-AP-pH-PMs efficiently deliver anticancer drugs in MDA-MB231 human breast tumor-bearing mice, resulted in excellent anticancer therapeutic efficacy, compared to free DOX and DOX encapsulated MEG-PAE micelles, indicating the excellent tumor targeting ability of AP-pH-PMs. Therefore, these tumor-targeting peptide-conjugated and pH-responsive polymeric micelles have great potential application in cancer therapy.

Palladium-Catalyzed Reductive Insertion of Alcohols into Aryl Ether Bonds

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

Wang, Meng; Gutiérrez, Oliver Y.; Camaioni, Donald M.

Pd/C catalyzes C-O bond cleavage of aryl ethers (diphenyl ether and cyclohexyl phenyl ether) by methanol in H2. The aromatic C-O bond is cleaved by reductive methanolysis, which is initiated by Pd-catalyzed partial hydrogenation of one phenyl ring to form an enol ether. The enol ether reacts rapidly with methanol to form a ketal, which generates methoxycyclohexene by eliminating phenol or an alkanol. Subsequent hydrogenation leads to methoxycyclohexane.

The effect of coumaryl alcohol incorporation on the structure and composition of lignin dehydrogenation polymers

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

Harman-Ware, Anne E.; Happs, Renee M.; Davison, Brian H.

Lignin dehydrogenation polymers (DHPs) are polymers generated from phenolic precursors for the purpose of studying lignin structure and polymerization processes. Here, DHPs were synthesized using a Zutropfverfahren method with horseradish peroxidase and three lignin monomers, sinapyl (S), coumaryl (H) and coniferyl (G) alcohols, in the presence of hydrogen peroxide. The H monomer was reacted with G and a 1:1 molar mixture of S:G monomers at H molar compositions of 0, 5, 10 and 20 mol% to study how the presence of the H monomer affected the structure and composition of the recovered polymers. At low H concentrations, solid state NMRmore » spectra suggest that the H and G monomers interact to form G:H polymers that have a lower average molecular weight than the solely G-based polymer or the G:H polymer produced at higher H concentrations. Solid-state NMR and pyrolysis-MBMS analyses suggest that at higher H concentrations, the H monomer primarily self-polymerizes to produce clusters of H-based polymer that are segregated from clusters of G- or S:G-based polymers. Thioacidolysis generally showed higher recoveries of thioethylated products from S:G or S:G:H polymers made with higher H content, indicating an increase in the linear ether linkages. Overall, the experimental results support theoretical predictions for the reactivity and structural influences of the H monomer on the formation of lignin-like polymers.« less

Semi-interpenetrating solid polymer electrolyte based on thiol-ene cross-linker for all-solid-state lithium batteries

NASA Astrophysics Data System (ADS)

Suk, Jungdon; Lee, Yu Hwa; Kim, Do Youb; Kim, Dong Wook; Cho, Song Yun; Kim, Ji Man; Kang, Yongku

2016-12-01

We developed highly promising solid polymer electrolytes (SPEs) based on a novel cross-linker containing star-shaped phosphazene with poly(ethylene oxide) (PEO) branches with very high ionic conductivity (7.6 × 10-4 S cm-1), improved mechanical stability, and good electrochemical stability for all-solid-state lithium batteries. In particular, allyl groups were introduced at the ends of the cross-linker in order to overcome the easy self-polymerization of existing cross-linking acrylate end groups. A novel semi-interpenetrating network (semi-IPN) SPE was prepared by in-situ radical polymerization of a precursor solution containing lithium salt, poly(ethylene glycol) dimethyl ether as a plasticizer, and a mixture of pentaerythritol tetrakis(3-mercaptopropionate) and a synthesized hexakis(allyloxy)cyclotriphosphazene (thiol-ene PAL) as the cross-linker. Batteries employing LiFePO4 as the cathode, lithium foil as the anode, and the SPE thin film as the electrolyte were assembled and tested. At ambient temperature, the initial discharge capacity was 147 mAh/g at 0.1 °C and 132 mAh/g at 0.5 °C, and 97% of the capacity was retained at the 100th cycle. All-solid-state pouch-package lithium cells assembled with the SPEs exhibited stable electrochemical performance, even under a severely wrinkled state. These outstanding properties of SPEs based on thiol-ene PAL demonstrate feasibility for practical battery applications with improved reliability and safety.

The effect of coumaryl alcohol incorporation on the structure and composition of lignin dehydrogenation polymers

DOE PAGES

Harman-Ware, Anne E.; Happs, Renee M.; Davison, Brian H.; ...

2017-11-30

Lignin dehydrogenation polymers (DHPs) are polymers generated from phenolic precursors for the purpose of studying lignin structure and polymerization processes. Here, DHPs were synthesized using a Zutropfverfahren method with horseradish peroxidase and three lignin monomers, sinapyl (S), coumaryl (H) and coniferyl (G) alcohols, in the presence of hydrogen peroxide. The H monomer was reacted with G and a 1:1 molar mixture of S:G monomers at H molar compositions of 0, 5, 10 and 20 mol% to study how the presence of the H monomer affected the structure and composition of the recovered polymers. At low H concentrations, solid state NMRmore » spectra suggest that the H and G monomers interact to form G:H polymers that have a lower average molecular weight than the solely G-based polymer or the G:H polymer produced at higher H concentrations. Solid-state NMR and pyrolysis-MBMS analyses suggest that at higher H concentrations, the H monomer primarily self-polymerizes to produce clusters of H-based polymer that are segregated from clusters of G- or S:G-based polymers. Thioacidolysis generally showed higher recoveries of thioethylated products from S:G or S:G:H polymers made with higher H content, indicating an increase in the linear ether linkages. Overall, the experimental results support theoretical predictions for the reactivity and structural influences of the H monomer on the formation of lignin-like polymers.« less

RATE CONSTANTS FOR THE REACTIONS OF OH RADICALS AND CL ATOMS WITH DI-N-PROPYL ETHER AND DI-N-BUTYL ETHER AND THEIR DEUTERATED ANALOGS. (R825252)

EPA Science Inventory

Using relative rate methods, rate constants for the gas-phase reactions of OH radicals and Cl atoms with di-n-propyl ether, di-n-propyl ether-d₁₄, di-n-butyl ether and di-n-butyl ether-d₁₈ have been measured at 296 ? 2 K and atmos...

Shaped platinum nanoparticles directly synthesized inside mesoporous silica supports

NASA Astrophysics Data System (ADS)

Kim, Jiwhan; Bae, Youn-Sang; Lee, Hyunjoo

2014-10-01

It is difficult to deposit shape-controlled nanoparticles into a mesoporous framework while preserving the shape. For shaped platinum nanoparticles, which are typically 5-10 nm in size, capillary inclusion by sonication or the formation of a mesoporous framework around the shaped platinum nanoparticles has been attempted, but the nanoparticles aggregated or their shapes were degraded easily. In this work, we directly nucleated platinum on the surface inside a mesoporous silica support and controlled the overgrowth step, producing cubic shaped nanoparticles. Mercaptopropyltrimethoxysilane was used as an anchoring agent causing nucleation at the silica surface, and it also helped to shape the nanoparticles. Platinum nanocubes, which were synthesized with polymeric capping agents separately, were deposited inside the mesoporous silica by sonication, but most of the nanoparticles were clogged at the entrance to the pores, and the surface of the platinum had very few sites that were catalytically active, as evidenced by the small H2 uptake. Unshaped platinum nanoparticles, which were prepared by conventional wet impregnation, showed a similar amount of H2 uptake as the in situ shaped platinum cubes, but the selectivity for pyrrole hydrogenation was poorer towards the production of pyrrolidine. The mesoporosity and the residual thiol groups on the surface of the in situ shaped Pt nanocubes might cause a high selectivity for pyrrolidine.It is difficult to deposit shape-controlled nanoparticles into a mesoporous framework while preserving the shape. For shaped platinum nanoparticles, which are typically 5-10 nm in size, capillary inclusion by sonication or the formation of a mesoporous framework around the shaped platinum nanoparticles has been attempted, but the nanoparticles aggregated or their shapes were degraded easily. In this work, we directly nucleated platinum on the surface inside a mesoporous silica support and controlled the overgrowth step, producing cubic shaped nanoparticles. Mercaptopropyltrimethoxysilane was used as an anchoring agent causing nucleation at the silica surface, and it also helped to shape the nanoparticles. Platinum nanocubes, which were synthesized with polymeric capping agents separately, were deposited inside the mesoporous silica by sonication, but most of the nanoparticles were clogged at the entrance to the pores, and the surface of the platinum had very few sites that were catalytically active, as evidenced by the small H2 uptake. Unshaped platinum nanoparticles, which were prepared by conventional wet impregnation, showed a similar amount of H2 uptake as the in situ shaped platinum cubes, but the selectivity for pyrrole hydrogenation was poorer towards the production of pyrrolidine. The mesoporosity and the residual thiol groups on the surface of the in situ shaped Pt nanocubes might cause a high selectivity for pyrrolidine. Electronic supplementary information (ESI) available: Fig. S1-S9. See DOI: 10.1039/c4nr03951c

Community cooperatives and insecticide-treated materials for malaria control: a new experience in Latin America.

PubMed

Kroeger, Axel; Aviñna, Ana; Ordoñnez-Gonzalez, José; Escandon, Celia

2002-11-15

Insecticide-treated materials (ITMs) are effective in substantially reducing the burden of malaria and other vector-borne diseases; but how can high coverage rates of ITMs be achieved and maintained? In south Mexico and on the Pacific and Atlantic coasts of Colombia 14 community-based cooperatives offering three different kinds of ITM services (sale of impregnation services; sale of impregnated nets; production of nets and sale of impregnated nets) were formed and supervised by a national health service (IMSS-SOLIDARIDAD, Mexico) and by an academic institution (the Colombian Institute of Tropical Medicine) along with local district health services. The objectives of this research were to analyse the processes and results of this approach and to identify the favourable and limiting factors. The methods used for data collection and analysis were group discussions, individual and semi-structured interviews with users and non-users of ITMs, individual in-depth interviews with cooperative members and supervisors, checks of sales book and observation of impregnation services. Coverage with unimpregnated nets was above 50% in all study areas. The fastest increase of ITM coverage was achieved through the exclusive sale of impregnation services. Low-cost social marketing techniques were used to increase demand. The large-scale production of nets in two cooperatives was only possible with the aid of an international NGO which ordered impregnated bednets for their target group. A number of favourable and limiting factors relating to the success of ITM cooperatives were identified. Of particular importance for the more successful Mexican cooperatives were: a) support by health services, b) smaller size, c) lesser desire for quick returns and d) lower ITM unit costs. ITM community cooperatives supported and supervised by the health services have good potential in the Latin American context for achieving and maintaining high impregnation rates.

W-incorporated CoMo/{lambda}-Al{sub 2}O{sub 3} hydrodesulfurization catalyst. I. Catalytic activities

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

Lee, D.K.; Lee, I.C.; Park, S.K.

1996-03-01

The promotional effect of tungsten in the CoMo/{gamma}-Al{sub 2}O{sub 3} catalyst was studied for series of W-incorporated CoMo/{gamma}-Al{sub 2}O{sub 3} catalysts with different content of tungsten. Two series of the catalysts were prepared by changing the impregnation order of cobalt and tungsten onto a base Mo/{gamma}-Al{sub 2}O{sub 3} catalyst. Impregnation of tungsten was achieved under the condition that the pH of an aqueous impregnating solution of W anion was controlled to 9.5. The hydrodesulfurization (HDS) and hydrogenation (HYD) activities of the sulfided catalysts were evaluated by thiophene HDS and ethylene HYD reactions at atmospheric pressure, respectively. Low-temperature O{sub 2} chemisorptionmore » at 195 K was conducted for the sulfided catalysts in order to determine the W-incorporation effects on the surface concentration of coordinatively unsaturated sites related to the catalytic activities. The dependence of catalytic activities on tungsten content showed initially an increase and subsequent decrease with increasing tungsten content. The maximum promotion of HDS and HYD activities occurred at a low content of tungsten corresponding to 0.025 in W/(W + Mo) atomic ratio regardless of the impregnation order of tungsten and cobalt. Oxygen uptake correlated well with catalytic activities. In general, the catalysts prepared by impregnating tungsten onto the CoMo/{gamma}-Al{sub 2}O{sub 3} showed higher activities than the catalysts prepared by impregnating tungsten onto Mo/{gamma}-Al{sub 2}O{sub 3} prior to impregnation of cobalt. 37 refs., 7 figs., 2 tabs.« less

Effect of chlorhexidine/silver sulfadiazine-impregnated central venous catheters in an intensive care unit with a low blood stream infection rate after implementation of an educational program: a before-after trial.

PubMed

Schuerer, Douglas J E; Zack, Jeanne E; Thomas, James; Borecki, Ingrid B; Sona, Carrie S; Schallom, Marilyn E; Venker, Melissa; Nemeth, Jennifer L; Ward, Myrna R; Verjan, Linda; Warren, David K; Fraser, Victoria J; Mazuski, John E; Boyle, Walter A; Buchman, Timothy G; Coopersmith, Craig M

2007-08-01

Current guidelines recommend using antiseptic- or antibiotic-impregnated central venous catheters (CVCs) if, following a comprehensive strategy to prevent catheter-related blood stream infection (CR-BSI), infection rates remain above institutional goals based on benchmark values. The purpose of this study was to determine if chlorhexidine/silver sulfadiazine-impregnated CVCs could decrease the CR-BSI rate in an intensive care unit (ICU) with a low baseline infection rate. Pre-intervention and post-intervention observational study in a 24-bed surgical/trauma/burn ICU from October, 2002 to August, 2005. All patients requiring CVC placement after March, 2004 had a chlorhexidine/silver sulfadiazine-impregnated catheter inserted (post-intervention period). Twenty-three CR-BSIs occurred in 6,960 catheter days (3.3 per 1,000 catheter days)during the 17-month control period. After introduction of chlorhexidine/silver sulfadiazine-impregnated catheters, 16 CR-BSIs occurred in 7,732 catheter days (2.1 per 1,000 catheter days; p = 0.16). The average length of time required for an infection to become established after catheterization was similar in the two groups (8.4 vs. 8.6 days; p = 0.85). Chlorhexidine/silver sulfadiazine-impregnated catheters did not result in a statistically significant change in the microbiological profile of CR-BSIs, nor did they increase the incidence of resistant organisms. Although chlorhexidine/silver sulfadiazine-impregnated catheters are useful in specific patient populations, they did not result in a statistically significant decrease in the CR-BSI rate in this study, beyond what was achieved with education alone.

Elution of platinum from carboplatin-impregnated calcium sulfate hemihydrate beads in vitro.

PubMed

Tulipan, Rachel J; Phillips, Heidi; Garrett, Laura D; Dirikolu, Levent; Mitchell, Mark A

2016-11-01

OBJECTIVE To characterize the elution of platinum from carboplatin-impregnated calcium sulfate hemihydrate (CSH) beads in vitro. SAMPLE 60 carboplatin-impregnated CSH beads and 9 CSH beads without added carboplatin (controls). PROCEDURES Carboplatin-impregnated CSH beads (each containing 4.6 mg of carboplatin [2.4 mg of platinum]) were placed into separate 10-mL plastic tubes containing 5 mL of PBSS in groups of 1, 3, 6, or 10; 3 control beads were placed into a single tube of PBSS at the same volume. Experiments were conducted in triplicate at 37°C and a pH of 7.4 with constant agitation. Eluent samples were collected at 1, 2, 3, 6, 12, 24, and 72 hours. Samples were analyzed for platinum content by inductively coupled plasma-mass spectrometry. RESULTS The mean concentration of platinum released per carboplatin-impregnated bead over 72 hours was 445.3 mg/L. Cumulative concentrations of platinum eluted increased as the number of beads per tube increased. There was a significant difference in platinum concentrations over time, with values increasing over the first 12 hours and then declining for all tubes. There was also a significant difference in percentage of total incorporated platinum released into tubes with different numbers of beads: the percentage of eluted platinum was higher in tubes containing 1 or 3 beads than in those containing 6 or 10 beads. CONCLUSIONS AND CLINICAL RELEVANCE Carboplatin-impregnated CSH beads eluted platinum over 72 hours. Further studies are needed to determine whether implantation of carboplatin-impregnated CSH beads results in detectable levels of platinum systemically and whether the platinum concentrations eluted locally are toxic to tumor cells.

Infection rates of rifampin/gentamicin-coated Titan Coloplast penile implants. Comparison with Inhibizone-impregnated AMS penile implants.

PubMed

Dhabuwala, Chirpriya; Sheth, Sheila; Zamzow, Brent

2011-01-01

It is a common practice to soak Titan(®) Coloplast penile implants in antibiotic solution prior to implantation. Experience with Inhibizone impregnation suggests that rifampin coating significantly reduces infection rates of penile implant surgery. In this article we describe the results of coating Titan Coloplast penile implants with rifampin/gentamicin solution. To compare infection rates of Titan(®) Coloplast penile implants coated with vancomycin/gentamycin, rifampin/gentamicin, and Inhibizone-impregnated American Medical Systems (AMS) penile implants. Chart review was done for all Mentor/Coloplast and AMS implant surgeries performed at our center between the dates January 1, 2002 and February 8, 2010. Infection rates for Titan(®) Coloplast penile implants coated with vancomycin/gentamycin, rifampin/gentamicin, and Inhibizone-impregnated (AMS) penile implants were compared. Infection rates for penile implants coated with different antibiotics. Infection rates for Titan(®) Coloplast penile implants coated with vancomycin/gentamycin and Inhibizone-impregnated (AMS) penile implants was 4.4% and 1.3%, respectively (P = 0.05). None of the rifampin/gentamicin-coated Titan(®) Coloplast penile implants have developed infection. Rifampin is the common antibiotic both in rifampin/gentamicin-coated Coloplast implants and Inhibizone(®) . The infection rate in this combined rifampin/gentamicin-coated Titan Coloplast implants and Inhibizone-coated AMS implants group was 0.63% (P = 0.03). Both rifampin/gentamicin-coated Titan(®) Coloplast penile implants and Inhibizone-impregnated (AMS) penile implants appear to have lower infection rates compared with vancomycin/gentamycin-coated Titan(®) Coloplast penile implants The present study does not suggest superiority of rifampin/gentamicin-coated Titan(®) Coloplast penile implants or Inhibizone-impregnated (AMS) penile implants but we strongly suggest that all Titan(®) Coloplast penile implants should be coated with rifampin/gentamicin solution. © 2010 International Society for Sexual Medicine.

Vapour breakthrough behaviour of carbon tetrachloride - A simulant for chemical warfare agent on ASZMT carbon: A comparative study with whetlerite carbon

NASA Astrophysics Data System (ADS)

Srivastava, Avanish Kumar; Shah, Dilip K.; Mahato, T. H.; Roy, A.; Yadav, S. S.; Srivas, S. K.; Singh, Beer

2013-06-01

ASZMT and whetlerite carbon was prepared by impregnation of active carbon with ammonical salts of Cu (II), Ag (I), Zn (II), Mo (VI), TEDA and Cu (II), Ag (I), Cr (VI), NaOH, C5H5N respectively using incipient wetness technique. Thereafter, impregnated carbon systems were characterized using scanning electron microscopy, energy dispersive X-ray, atomic absorption spectroscopy, thermogravimetry and surface characterization techniques. Impregnated carbon systems were evaluated under dynamic conditions against carbon tetrachloride (CCl4) vapour that was used as a simulant for the persistent chemical warfare agents for testing breakthrough times of filter cartridges and canisters of gas masks in the national approval test of respirators. The protective potential of ASZMT carbon was compared with the whetlerite carbon which is presently used in NBC filtration system. The effect of CCl4 concentration, test flow rate, temperature and relative humidity on the breakthrough behaviour of the impregnated carbon systems has also been studied. The study clearly indicated that the whetlerite carbon possessed breakthrough time greater than ASZMT carbon. However, ASZMT carbon provided adequate protection against CCl4 vapours and can be used as an alternative to whetlerite carbon that contain Cr(VI), which is reported to be carcinogenic and having lesser shelf life. The study indicated the breakthrough time of impregnated carbon systems were found to decrease with the increase of the CCl4 concentration and flow rate. The variation in temperature and relative humidity did not significantly affect the breakthrough behaviour of impregnated carbon systems at high vapour concentration of CCl4 whereasbreak through time of impregnated carbon systems reduced by an increase of relative humidity at low CCl4 vapour concentration.

Impregnation of Composite Materials: a Numerical Study

NASA Astrophysics Data System (ADS)

Baché, Elliott; Dupleix-Couderc, Chloé; Arquis, Eric; Berdoyes, Isabelle

2017-12-01

Oxide ceramic matrix composites are currently being developed for aerospace applications such as the exhaust, where the parts are subject to moderately high temperatures (≈ 700 ∘C) and oxidation. These composite materials are normally formed by, among other steps, impregnating a ceramic fabric with a slurry of ceramic particles. This impregnation process can be complex, with voids possibly forming in the fabric depending on the process parameters and material properties. Unwanted voids or macroporosity within the fabric can decrease the mechanical properties of the parts. In order to design an efficient manufacturing process able to impregnate the fabric well, numerical simulations may be used to design the process as well as the slurry. In this context, a tool is created for modeling different processes. Thétis, which solves the Navier-Stokes-Darcy-Brinkman equation using finite volumes, is expanded to take into account capillary pressures on the mesoscale. This formulation allows for more representativity than for Darcy's law (homogeneous preform) simulations while avoiding the prohibitive simulation times of a full discretization for the composing fibers at the representative elementary volume scale. The resulting tool is first used to investigate the effect of varying the slurry parameters on impregnation evolution. Two different processes, open bath impregnation and wet lay-up, are then studied with emphasis on varying their input parameters (e.g. inlet velocity).

Enhanced Adsorption of Selenium Ions from Aqueous Solution Using Iron Oxide Impregnated Carbon Nanotubes

PubMed Central

Bakather, Omer Y.; Khraisheh, Majeda; Nasser, Mustafa S.

2017-01-01

The aim of this research was to investigate the potential of raw and iron oxide impregnated carbon nanotubes (CNTs) as adsorbents for the removal of selenium (Se) ions from wastewater. The original and modified CNTs with different loadings of Fe2O3 nanoparticles were characterized using high resolution transmission electron microscopy (HRTEM), scanning electron microscopy (SEM), X-ray diffractometer (XRD), Brunauer, Emmett, and Teller (BET) surface area analyzer, thermogravimetric analysis (TGA), zeta potential, and energy dispersive X-ray spectroscopy (EDS). The adsorption parameters of the selenium ions from water using raw CNTs and iron oxide impregnated carbon nanotubes (CNT-Fe2O3) were optimized. Total removal of 1 ppm Se ions from water was achieved when 25 mg of CNTs impregnated with 20 wt.% of iron oxide nanoparticles is used. Freundlich and Langmuir isotherm models were used to study the nature of the adsorption process. Pseudo-first and pseudo-second-order models were employed to study the kinetics of selenium ions adsorption onto the surface of iron oxide impregnated CNTs. Maximum adsorption capacity of the Fe2O3 impregnated CNTs, predicted by Langmuir isotherm model, was found to be 111 mg/g. This new finding might revolutionize the adsorption treatment process and application by introducing a new type of nanoadsorbent that has super adsorption capacity towards Se ions. PMID:28555093

Processing effects in production of composite prepreg by hot melt impregnation

NASA Astrophysics Data System (ADS)

Chmielewski, C.; Jayaraman, K.; Petty, C. A.

1993-06-01

The hot melt impregnation process for producing composite prepreg has been studied. The role of the exit die is highlighted by operating without impregnation bars. Experimental results show that when a fiber tow is pulled through a resin bath and then through a wedge shaped die, the total resin mass fraction and the extent of resin impregnation in the tow increase with the processing viscosity. The penetration of resin into a fiber bundle is greater when the resin viscosity is higher. This trend is unchanged over a range of tow speeds up to the breaking point. A theoretical model is developed to describe the effect of processing conditions and die geometry on the degree of impregnation. Calculations with this model indicate that for a given die geometry, the degree of impregnation increases from 58 percent to 90 percent as the ratio of the clearance between the tow and the die wall, to the total die gap is decreased from 0.15 to 0.05. Physical arguments related to the effective viscosity of the prepreg show that the clearance ratio is independent of the tow speed, but decreases as the ratio of the effective shear viscosity of the prepreg to the resin viscosity increases. This provides a connection between the experimental results obtained with varying resin viscosity and the computational results obtained with varying clearance values at the die inlet.

NIOSH Manual of Analytical Methods (third edition). Fourth supplement

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

Not Available

1990-08-15

The NIOSH Manual of Analytical Methods, 3rd edition, was updated for the following chemicals: allyl-glycidyl-ether, 2-aminopyridine, aspartame, bromine, chlorine, n-butylamine, n-butyl-glycidyl-ether, carbon-dioxide, carbon-monoxide, chlorinated-camphene, chloroacetaldehyde, p-chlorophenol, crotonaldehyde, 1,1-dimethylhydrazine, dinitro-o-cresol, ethyl-acetate, ethyl-formate, ethylenimine, sodium-fluoride, hydrogen-fluoride, cryolite, sodium-hexafluoroaluminate, formic-acid, hexachlorobutadiene, hydrogen-cyanide, hydrogen-sulfide, isopropyl-acetate, isopropyl-ether, isopropyl-glycidyl-ether, lead, lead-oxide, maleic-anhydride, methyl-acetate, methyl-acrylate, methyl-tert-butyl ether, methyl-cellosolve-acetate, methylcyclohexanol, 4,4'-methylenedianiline, monomethylaniline, monomethylhydrazine, nitric-oxide, p-nitroaniline, phenyl-ether, phenyl-ether-biphenyl mixture, phenyl-glycidyl-ether, phenylhydrazine, phosphine, ronnel, sulfuryl-fluoride, talc, tributyl-phosphate, 1,1,2-trichloro-1,2,2-trifluoroethane, trimellitic-anhydride, triorthocresyl-phosphate, triphenyl-phosphate, and vinyl-acetate.

HPLC-Based Mass Spectrometry Characterizes the Phospholipid Alterations in Ether-Linked Lipid Deficiency Models Following Oxidative Stress

PubMed Central

Drechsler, Robin; Chen, Shaw-Wen; Dancy, Blair C. R.; Mehrabkhani, Lena

2016-01-01

Despite the fact that the discovery of ether-linked phospholipids occurred nearly a century ago, many unanswered questions remain concerning these unique lipids. Here, we characterize the ether-linked lipids of the nematode with HPLC-MS/MS and find that more than half of the phosphoethanolamine-containing lipids are ether-linked, a distribution similar to that found in mammalian membranes. To explore the biological role of ether lipids in vivo, we target fatty acyl-CoA reductase (fard-1), an essential enzyme in ether lipid synthesis, with two distinct RNAi strategies. First, when fard-1 RNAi is initiated at the start of development, the treated animals have severely reduced ether lipid abundance, resulting in a shift in the phosphatidylethanolamine lipid population to include more saturated fatty acid chains. Thus, the absence of ether lipids during development drives a significant remodeling of the membrane landscape. A later initiation of fard-1 RNAi in adulthood results in a dramatic reduction of new ether lipid synthesis as quantified with 15N-tracers; however, there is only a slight decrease in total ether lipid abundance with this adult-only fard-1 RNAi. The two RNAi strategies permit the examination of synthesis and ether lipid abundance to reveal a relationship between the amount of ether lipids and stress survival. We tested whether these species function as sacrificial antioxidants by directly examining the phospholipid population with HPLC-MS/MS after oxidative stress treatment. While there are significant changes in other phospholipids, including polyunsaturated fatty acid-containing species, we did not find any change in ether-linked lipids, suggesting that the role of ether lipids in stress resistance is not through their general consumption as free radical sinks. Our work shows that the nematode will be a useful model for future interrogation of ether lipid biosynthesis and the characterization of phospholipid changes in various stress conditions. PMID:27893806

Curing of Furfuryl Alcohol-Impregnated Parts

NASA Technical Reports Server (NTRS)

Lawton, J. W.; Brayden, T. H.

1983-01-01

Delamination problem in reinforced carbon/carbon parts impregnated with oxalic acid-catalyzed furfuryl alcohol overcome by instituting two additional quality-control tests on alcohol and by changing curing conditions.

CO2-assisted high pressure homogenization: a solvent-free process for polymeric microspheres and drug-polymer composites.

PubMed

Kluge, Johannes; Mazzotti, Marco

2012-10-15

The study explores the enabling role of near-critical CO(2) as a reversible plasticizer in the high pressure homogenization of polymer particles, aiming at their comminution as well as at the formation of drug-polymer composites. First, the effect of near-critical CO(2) on the homogenization of aqueous suspensions of poly lactic-co-glycolic acid (PLGA) was investigated. Applying a pressure drop of 900 bar and up to 150 passes across the homogenizer, it was found that particles processed in the presence of CO(2) were generally of microspherical morphology and at all times significantly smaller than those obtained in the absence of a plasticizer. The smallest particles, exhibiting a median x(50) of 1.3 μm, were obtained by adding a small quantity of ethyl acetate, which exerts on PLGA an additional plasticizing effect during the homogenization step. Further, the study concerns the possibility of forming drug-polymer composites through simultaneous high pressure homogenization of the two relevant solids, and particularly the effect of near-critical CO(2) on this process. Therefore, PLGA was homogenized together with crystalline S-ketoprofen (S-KET), a non-steroidal anti-inflammatory drug, at a drug to polymer ratio of 1:10, a pressure drop of 900 bar and up to 150 passes across the homogenizer. When the process was carried out in the presence of CO(2), an impregnation efficiency of 91% has been reached, corresponding to 8.3 wt.% of S-KET in PLGA; moreover, composite particles were of microspherical morphology and significantly smaller than those obtained in the absence of CO(2). The formation of drug-polymer composites through simultaneous homogenization of the two materials is thus greatly enhanced by the presence of CO(2), which increases the efficiency for both homogenization and impregnation. Copyright © 2012 Elsevier B.V. All rights reserved.

Fungicidal values of bio-oils and their lignin-rich fractions obtained from wood/bark fast pyrolysis.

PubMed

Mohan, Dinesh; Shi, Jenny; Nicholas, Darrel D; Pittman, Charles U; Steele, Philip H; Cooper, Jerome E

2008-03-01

Pine wood, pine bark, oak wood and oak bark were pyrolyzed in an auger reactor. A total of 16 bio-oils or pyrolytic oils were generated at different temperatures and residence times. Two additional pine bio-oils were produced at the National Renewable Energy Laboratory in a fluidized-bed reactor at different temperatures. All these bio-oils were fractionated to obtain lignin-rich fractions which consist mainly of phenols and neutrals. The pyrolytic lignin-rich fractions were obtained by liquid-liquid extraction. Whole bio-oils and their lignin-rich fractions were studied as potential environmentally benign wood preservatives to replace metal-based CCA and copper systems that have raised environmental concerns. Each bio-oil and several lignin-rich fractions were tested for antifungal properties. Soil block tests were conducted using one brown-rot fungus (Gloeophyllum trabeum) and one white-rot fungus (Trametes versicolor). The lignin-rich fractions showed greater fungal inhibition than whole bio-oils for a impregnation solution 10% concentration level. Water repellence tests were also performed to study wood wafer swelling behavior before and after bio-oil and lignin-rich fraction treatments. In this case, bio-oil fractions did not exhibit higher water repellency than whole bio-oils. Comparison of raw bio-oils in soil block tests, with unleached wafers, at 10% and 25% bio-oil impregnation solution concentration levels showed excellent wood preservation properties at the 25% level. The good performance of raw bio-oils at higher loading levels suggests that fractionation to generate lignin-rich fractions is unnecessary. At this more effective 25% loading level in general, the raw bio-oils performed similarly. Prevention of leaching is critically important for both raw bio-oils and their fractions to provide decay resistance. Initial tests of a polymerization chemical to prevent leaching showed some success.

Probing the Role of Zr Addition versus Textural Properties in Enhancement of CO 2 Adsorption Performance in Silica/PEI Composite Sorbents

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

Sakwa-Novak, Miles A.; Holewinski, Adam; Hoyt, Caroline B.

2015-08-08

Polymeric amines such as poly(ethylenimine) (PEI) supported on mesoporous oxides are promising candidate adsorbents for CO 2 capture processes. One important aspect to the design and optimization of these materials is a fundamental understanding of how the properties of the oxide support such as pore structure, particle morphology, and surface properties affect the efficiency of the guest polymer in its interactions with CO 2. Previously, the efficiency of impregnated PEI to adsorb CO 2 was shown to increase upon the addition of Zr as a surface modifier in SBA-15. But, the efficacy of this method to tune the adsorption performancemore » has not been explored in materials of differing textural and morphological nature. These issues are directly addressed via the preparation of an array of SBA-15 support materials with varying textural and morphological properties, as well as varying content of zirconium doped into the material. Zirconium is incorporated into the SBA-15 either during the synthesis of the SBA-15, or postsynthetically via deposition of Zr species onto pure-silica SBA-15. The method of Zr incorporation alters the textural and morphological properties of the parent SBA-15 in different ways. Importantly, the CO 2 capacity of SBA-15 impregnated with PEI increases by a maximum of ~60% with the quantity of doped Zr for a “standard” SBA-15 containing significant microporosity, while no increase in the CO 2 capacity is observed upon Zr incorporation for an SBA-15 with reduced microporosity and a larger pore size, pore volume, and particle size. Finally, adsorbents supported on SBA-15 with controlled particle morphology show only modest increases in CO 2 capacity upon inclusion of Zr to the silica framework. The data demonstrate that the textural and morphological properties of the support have a more significant impact on the ability of PEI to capture CO 2 than the support surface composition.« less

Probing the Role of Zr Addition versus Textural Properties in Enhancement of CO₂ Adsorption Performance in Silica/PEI Composite Sorbents.

PubMed

Sakwa-Novak, Miles A; Holewinski, Adam; Hoyt, Caroline B; Yoo, Chun-Jae; Chai, Song-Hai; Dai, Sheng; Jones, Christopher W

2015-09-01

Polymeric amines such as poly(ethylenimine) (PEI) supported on mesoporous oxides are promising candidate adsorbents for CO2 capture processes. An important aspect to the design and optimization of these materials is a fundamental understanding of how the properties of the oxide support such as pore structure, particle morphology, and surface properties affect the efficiency of the guest polymer in its interactions with CO2. Previously, the efficiency of impregnated PEI to adsorb CO2 was shown to increase upon the addition of Zr as a surface modifier in SBA-15. However, the efficacy of this method to tune the adsorption performance has not been explored in materials of differing textural and morphological nature. Here, these issues are directly addressed via the preparation of an array of SBA-15 support materials with varying textural and morphological properties, as well as varying content of zirconium doped into the material. Zirconium is incorporated into the SBA-15 either during the synthesis of the SBA-15, or postsynthetically via deposition of Zr species onto pure-silica SBA-15. The method of Zr incorporation alters the textural and morphological properties of the parent SBA-15 in different ways. Importantly, the CO2 capacity of SBA-15 impregnated with PEI increases by a maximum of ∼60% with the quantity of doped Zr for a "standard" SBA-15 containing significant microporosity, while no increase in the CO2 capacity is observed upon Zr incorporation for an SBA-15 with reduced microporosity and a larger pore size, pore volume, and particle size. Finally, adsorbents supported on SBA-15 with controlled particle morphology show only modest increases in CO2 capacity upon inclusion of Zr to the silica framework. The data demonstrate that the textural and morphological properties of the support have a more significant impact on the ability of PEI to capture CO2 than the support surface composition.

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

Sakwa-Novak, Miles A.; Holewinski, Adam; Hoyt, Caroline B.

Polymeric amines such as poly(ethylenimine) (PEI) supported on mesoporous oxides are promising candidate adsorbents for CO2 capture processes. An important aspect to the design and optimization of these materials is a fundamental understanding of how the properties of the oxide support such as pore structure, particle morphology, and surface properties affect the efficiency of the guest polymer in its interactions with CO2. Previously, the efficiency of impregnated PEI to adsorb CO2 was shown to increase upon the addition of Zr as a surface modifier in SBA-15. However, the efficacy of this method to tune the adsorption performance has not beenmore » explored in materials of differing textural and morphological nature. Here, these issues are directly addressed via the preparation of an array of SBA-15 support materials with varying textural and morphological properties, as well as varying content of zirconium doped into the material. Zirconium is incorporated into the SBA-15 either during the synthesis of the SBA-15, or postsynthetically via deposition of Zr species onto pure-silica SBA-15. The method of Zr incorporation alters the textural and morphological properties of the parent SBA-15 in different ways. Importantly, the CO2 capacity of SBA-15 impregnated with PEI increases by a maximum of ~60% with the quantity of doped Zr for a “standard” SBA-15 containing significant microporosity, while no increase in the CO2 capacity is observed upon Zr incorporation for an SBA-15 with reduced microporosity and a larger pore size, pore volume, and particle size. Finally, adsorbents supported on SBA-15 with controlled particle morphology show only modest increases in CO2 capacity upon inclusion of Zr to the silica framework. The data demonstrate that the textural and morphological properties of the support have a more significant impact on the ability of PEI to capture CO2 than the support surface composition.« less

Graphite having improved thermal stress resistance and method of preparation

DOEpatents

Kennedy, Charles R.

1980-01-01

An improved method for fabricating a graphite article comprises the steps of impregnating a coke article by first heating the coke article in contact with a thermoplastic pitch at a temperature within the range of 250.degree.-300.degree. C. at a pressure within the range of 200-2000 psig for at least 4-10 hours and then heating said article at a temperature within the range of 450.degree.-485.degree. C. at a pressure of 200-2000 psig for about 16-24 hours to provide an impregnated article; heating the impregnated article for sufficient time to carbonize the impregnant to provide a second coke article, and graphitizing the second coke article. A graphite having improved thermal stress resistance results when the coke to be impregnated contains 1-3 wt.% sulfur and no added puffing inhibitors. An additional improvement in thermal stress resistance is achieved when the second coke article is heated above about 1400.degree. C. at a rate of at least 10.degree. C./minute to a temperature above the puffing temperature.

Comparative studies on Aedes aegypti and Aedes albopictus adult females trespassing commercial nets.

PubMed

Andrade, Carlos F S; Cabrini, Isaías

2010-03-01

ABSTRACT. The abilities of Aedes aegypti and Ae. albopictus females in trespassing 5 different commercial nets, 2 nets impregnated with deltamethrin or permethrin and 3 non-impregnated nets (Guarany, Perame, and Ricca), were compared. The evaluating parameters were their percent trespassing success, the median trespassing time (TT50), and the relation between mosquito wing sizes and their trespassing success. Some mosquito behavioral traits were also observed. The trespassing success, directly related to opening areas, was found to be lower with impregnated nets for both species. The differences between the mosquito species were significant among all the nets except Ricca. Aedes albopictus showed a very high success rate in trespassing the non-impregnated Perame net and a lower success rate in trespassing Guarany. Aedes albopictus also showed a very high success rate in trespassing pyrethroid-impregnated nets. The TT50 values for the Ricca and Guarany nets were not significantly different between the species, but a significantly lower TT50 value was found for the net with the largest opening (Ricca). The smaller wingspan of Ae. albopictus seems to explain the higher trespassing success of this species.

Effects of different freezing methods on calcium enriched papaya (Carica papaya L.).

PubMed

Lovera, Nancy N; Ramallo, Laura; Salvadori, Viviana O

2018-06-01

The effect of calcium impregnation on drip loss, colour, mechanical properties, sensory perception and freezing time on frozen-thawed papaya was studied, evaluating different freezing methods: cryogenic, tunnel and household freezer freezing. Osmotic dehydration as pre-treatment was also evaluated. Freezing in liquid nitrogen was considered an inappropriate method for papaya preservation due to cracking. Calcium impregnation and osmotic dehydration increased tissue firmness and decreased freezing time (freezing time for fresh, calcium impregnated and osmo-dehydrated fruit was 23, 17 and 5 min in a tunnel and 118, 83 and 60 min in a household freezer, respectively). Calcium lactate was the most effective way to protect tissue's firmness before and after a freeze-thaw cycle (maximum stress values approx. 300-400% of the raw tissue for tunnel freezing and 260% for household freezer). Microstructure analysis showed better tissue integrity retention in papaya samples impregnated with calcium lactate than in those with calcium gluconate, after a freezing-thawing cycle, in agreement with the drip loss results. In spite of these results, consumers preferred frozen papaya without pre-treatment or impregnated with calcium gluconate.

Radionuclide-binding compound, a radionuclide delivery system, a method of making a radium complexing compound, a method of extracting a radionuclide, and a method of delivering a radionuclide

DOEpatents

Fisher, Darrell R.; Wai, Chien M.; Chen, Xiaoyuan

2000-01-01

The invention pertains to compounds which specifically bind radionuclides, and to methods of making radionuclide complexing compounds. In one aspect, the invention includes a radionuclide delivery system comprising: a) a calix[n]arene-crown-[m]-ether compound, wherein n is an integer greater than 3, and wherein m is an integer greater than 3, the calix[n]arene-crown-[m]-ether compound comprising at least two ionizable groups; and b) an antibody attached to the calix[n]arene-crown-[m]-ether compound. In another aspect, the invention includes a method of making a radium complexing compound, comprising: a) providing a calix[n]arene compound, wherein n is an integer greater than 3, the calix[n]arene compound comprising n phenolic hydroxyl groups; b) providing a crown ether precursor, the crown ether precursor comprising a pair of tosylated ends; c) reacting the pair of tosylated ends with a pair of the phenolic hydroxyl groups to convert said pair of phenolic hydroxyl groups to ether linkages, the ether linkages connecting the crown ether precursor to the calix[n]arene to form a calix[n]arene-crown-[m]-ether compound, wherein m is an integer greater than 3; d) converting remaining phenolic hydroxyl groups to esters; e) converting the esters to acids, the acids being proximate a crown-[m]-ether portion of the calix[n]arene-crown-[m]-ether compound; and f) providing a Ra.sup.2+ ion within the crown-[m]-ether portion of the calix[n]arene-crown-[m]-ether compound.

In Situ Synthesis of Antimicrobial Silver Nanoparticles within Antifouling Zwitterionic Hydrogels by Catecholic Redox Chemistry for Wound Healing Application.

PubMed

GhavamiNejad, Amin; Park, Chan Hee; Kim, Cheol Sang

2016-03-14

A multifunctional hydrogel that combines the dual functionality of both antifouling and antimicrobial capacities holds great potential for many bioapplications. Many approaches and different materials have been employed to synthesize such a material. However, a systematic study, including in vitro and in vivo evaluation, on such a material as wound dressings is highly scarce at present. Herein, we report on a new strategy that uses catecholic chemistry to synthesize antimicrobial silver nanoparticles impregnated into antifouling zwitterionic hydrogels. For this purpose, hydrophobic dopamine methacrylamide monomer (DMA) was mixed in an aqueous solution of sodium tetraborate decahydrate and DMA monomer became soluble after increasing pH to 9 due to the complexation between catechol groups and boron. Then, cross-linking polymerization of zwitterionic monomer was carried out with the solution of the protected dopamine monomer to produce a new hydrogel. When this new hydrogel comes in contact with a silver nitrate solution, silver nanoparticles (AgNPs) are formed in its structure as a result of the redox property of the catechol groups and in the absence of any other external reducing agent. The results obtained from TEM and XRD measurements indicate that AgNPs with diameters of around 20 nm had formed within the networks. FESEM images confirmed that the silver nanoparticles were homogeneously incorporated throughout the hydrogel network, and FTIR spectroscopy demonstrated that the catechol moiety in the polymeric backbone of the hydrogel is responsible for the reduction of silver ions into the AgNPs. Finally, the in vitro and in vivo experiments suggest that these mussel-inspired, antifouling, antibacterial hydrogels have great potential for use in wound healing applications.

Rapid vacuum sintering: A novel technique for fabricating fluorapatite ceramic scaffolds for bone tissue engineering.

PubMed

Denry, Isabelle; Goudouri, Ourania-Menti; Harless, Jeffrey; Holloway, Julie A

2018-01-01

Macroporous bioceramic scaffolds are often fabricated via the foam replica technique, based on polymeric foam impregnation with a glass slurry, followed by slow heat treatment to allow for drying, polymeric burnout, and sintering of the glass particles. As a consequence, the process is time consuming and complicated by concurrent crystallization of the glass, often leading to incomplete sintering. Our goal was to investigate the effect of heating rate on sintering behavior, architecture, and mechanical properties of fluorapatite-based glass and glass-ceramic scaffolds. Glass scaffolds were prepared and sintered by rapid vacuum sintering (RVS) at 785°C under vacuum at a fast heating rate (55°C/min.) or without vacuum at a slow heating rate (2°C/min.). Two additional groups were further crystallized at 775°C/1 h. XRD confirmed the presence of fluorapatite for crystallized scaffolds. All groups presented interconnected porosity with a pore size in the 500 μm range. Scaffolds produced by RVS exhibited an excellent degree of sintering while scaffolds produced by slow sintering were incompletely sintered. The mean compressive strength was significantly higher for the RVS groups (1.52 ± 0.55 and 1.72 ± 0.61 MPa) compared to the slow-sintered groups (0.54 ± 0.30 and 0.45 ± 0.26 MPa). Meanwhile, the total production time was reduced by more than 12 h by using the RVS technique. © 2017 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 106B: 291-299, 2018. © 2017 Wiley Periodicals, Inc.

Vapor intrusion risk of fuel ether oxygenates methyl tert-butyl ether (MTBE), tert-amyl methyl ether (TAME) and ethyl tert-butyl ether (ETBE): A modeling study.

PubMed

Ma, Jie; Xiong, Desen; Li, Haiyan; Ding, Yi; Xia, Xiangcheng; Yang, Yongqi

2017-06-15

Vapor intrusion of synthetic fuel additives represents a critical yet still neglected problem at sites contaminated by petroleum fuel releases. This study used an advanced numerical model to investigate the vapor intrusion potential of fuel ether oxygenates methyl tert-butyl ether (MTBE), tert-amyl methyl ether (TAME), and ethyl tert-butyl ether (ETBE). Simulated indoor air concentration of these compounds can exceed USEPA indoor air screening level for MTBE (110μg/m 3 ). Our results also reveal that MTBE has much higher chance to cause vapor intrusion problems than TAME and ETBE. This study supports the statements made by USEPA in the Petroleum Vapor Intrusion (PVI) Guidance that the vertical screening criteria for petroleum hydrocarbons may not provide sufficient protectiveness for fuel additives, and ether oxygenates in particular. In addition to adverse impacts on human health, ether oxygenate vapor intrusion may also cause aesthetic problems (i.e., odour and flavour). Overall, this study points out that ether oxygenates can cause vapor intrusion problems. We recommend that USEPA consider including the field measurement data of synthetic fuel additives in the existing PVI database and possibly revising the PVI Guidance as necessary. Copyright © 2017 Elsevier B.V. All rights reserved.

[Potentially toxic antibiotics concentrations after administration using impregnated dressing in a severe burned patient: A case report].

PubMed

Dupouey, Julien; Wiramus, Sandrine; Albanese, Jacques; Guilhaumou, Romain; Blin, Olivier

2016-10-01

Severe burned patients present high risk of skins infections, frequently due to Pseudomonas aeruginosa. Impregnated dressings with amikacin or colistin could be a good alternative to obtain effective concentration directly at the infected site. Therapeutic drug monitoring for these antibiotics is currently recommended after an intravenous administration to obtain effective and non-toxic plasmatic concentrations. However, data are lacking about systemic exposition and risk of toxicity after an administration with impregnated dressings. We report the case of a severe burned patient with cutaneous infection treated with amikacin and colistin impregnated dressings, for which plasmatic pharmacokinetic profiles were performed. Copyright © 2016 Société française de pharmacologie et de thérapeutique. Published by Elsevier Masson SAS. All rights reserved.

Modeling and Experiment of Melt Impregnation of Continuous Fiber-reinforced Thermoplastic with Pins

NASA Astrophysics Data System (ADS)

Yang, Jian-Jun; Xin, Chun-Ling; Tang, Ke; Zhang, Zhi-Cheng; Yan, Bao-Rui; Ren, Feng; He, Ya-Dong

2016-05-01

Melt impregnation is a crucial method for continuous fiber-reinforced thermoplastic. It was developed several years ago for thermosetting plastic, but it is very popular now in the thermoplastic matrices, with a much higher viscosity. In this paper, we propose a mathematic model based on Darcy's law, which combined with processing parameters and material physical parameters. Then we use this model to predict the influence of processing parameters on the degree of impregnation of the prepreg, and the trend of prediction is consistent with the experimental results. Therefore, the exhaustive numerical study enables to define the optimal processing conditions for a perfect impregnation. The results are shown to be effective tools for finding optimal pulling speed, pin number and pressure for a given fluid/fibers pair.

Applicability of Vacuum Impregnation to Modify Physico-Chemical, Sensory and Nutritive Characteristics of Plant Origin Products—A Review

PubMed Central

Radziejewska-Kubzdela, Elżbieta; Biegańska-Marecik, Róża; Kidoń, Marcin

2014-01-01

Vacuum impregnation is a non-destructive method of introducing a solution with a specific composition to the porous matrices of fruit and vegetables. Mass transfer in this process is a result of mechanically induced differences in pressure. Vacuum impregnation makes it possible to fill large volumes of intercellular spaces in tissues of fruit and vegetables, thus modifying physico-chemical properties and sensory attributes of products. This method may be used, e.g., to reduce pH and water activity of the product, change its thermal properties, improve texture, color, taste and aroma. Additionally, bioactive compounds may be introduced together with impregnating solutions, thus improving health-promoting properties of the product or facilitating production of functional food. PMID:25244012

Study on pyrolysis characteristics of lignocellulosic biomass impregnated with ammonia source.

PubMed

Li, Kai; Zhu, Changpeng; Zhang, Liqiang; Zhu, Xifeng

2016-06-01

The current study presents the pyrolysis characteristics of rice husk impregnated with different kinds of ammonia source (ammonium acetate, urea, ammonium sulfate and ammonium dihydrogen phosphate) in a fixed bed reactor. The introduction of ammonia source in pyrolysis process achieved the conversation from carbonyl compounds to nitrogenous heterocyclic compounds. The liquid product of urea-impregnated biomass has higher content of nitrogenous heterocyclic compounds (8.35%) and phenols (30.4%). For ammonium sulfate and ammonium dihydrogen phosphate-impregnated biomass, the quantity of compounds in liquid products reduces remarkably, and the gas products are rich in CO and H2. All the solid products of pyrolysis have great potential application in biochar-based fertilizer and activated carbon for their high N content. Copyright © 2016 Elsevier Ltd. All rights reserved.

Activated carbon fibers and engineered forms from renewable resources

DOEpatents

Baker, Frederick S

2013-02-19

A method of producing activated carbon fibers (ACFs) includes the steps of providing a natural carbonaceous precursor fiber material, blending the carbonaceous precursor material with a chemical activation agent to form chemical agent-impregnated precursor fibers, spinning the chemical agent-impregnated precursor material into fibers, and thermally treating the chemical agent-impregnated precursor fibers. The carbonaceous precursor material is both carbonized and activated to form ACFs in a single step. The method produces ACFs exclusive of a step to isolate an intermediate carbon fiber.

Activated carbon fibers and engineered forms from renewable resources

DOEpatents

Baker, Frederick S.

2010-06-01

A method of producing activated carbon fibers (ACFs) includes the steps of providing a natural carbonaceous precursor fiber material, blending the carbonaceous precursor material with a chemical activation agent to form chemical agent-impregnated precursor fibers, spinning the chemical agent-impregnated precursor material into fibers, and thermally treating the chemical agent-impregnated precursor fibers. The carbonaceous precursor material is both carbonized and activated to form ACFs in a single step. The method produces ACFs exclusive of a step to isolate an intermediate carbon fiber.

Activation of water soluble amines by halogens for trapping methyl radioactive iodine from air streams

DOEpatents

Deitz, Victor R.; Blachly, Charles H.

1977-01-01

Gas adsorbent charcoals impregnated with an aqueous solution of the reaction product of a tertiary amine and elemental iodine or bromine are better than 99 per cent efficient in trapping methyl iodine.sup.131. The chemical addition of iodine or bromine to the tertiary amine molecule increases the efficiency of the impregnated charcoal as a trapping agent, and in conjunction with the high flash point of the tertiary amine raises the ignition temperature of the impregnated charcoal.

Boundary lubrication, thermal and oxidative stability of a fluorinated polyether and a perfluoropolyether triazine

NASA Technical Reports Server (NTRS)

Jones, W. R., Jr.; Snyder, C. E., Jr.

1979-01-01

Boundary lubricating characteristics, thermal stability, and oxidation-corrosion stability were determined for a fluorinated polyether and a perfluoropolyether triazine. A ball-on-disk apparatus, a tensimeter, and oxidation-corrosion apparatus were used. Results were compared to data for a polyphenyl ether and a C-ether. The polyether and triazine yielded better boundary lubricating characteristics than either the polyphenyl ether or C-ether. The polyphenyl ether had the greatest thermal stability (443 C) while the other fluids had stabilities in the range 389 to 397 C. Oxidation-corrosion results indicated the following order of stabilities: perfluoropolyether trizine greater than polyphenyl ether greater than C-ether greater than fluorinated polyether.

Sinterable Ceramic Powders from Laser-Heated Gases.

DTIC Science & Technology

1988-02-01

ether . carboxylic acid. and aldehyde clases: water is also included.Acrigto William and Goodman.’ a single crystalline sili- The single-crstalline...represent commonly available organic families, Including aliphatic and aromatic hydrocarbons, chlorides, ethers , ketones , esters, alcohols, aldehydes...Hydrocarbons Ketone Amine Chlorides Low-alcohols 8f . Ether Ester - _Aldehyde Ether Ketones High-alcohols 04 Carboxylic Ester I acid Ether o . Nitrile

New polymeric precursors to SiNCB, BN, and La(3)Ni(2)B(2)N(3) materials

NASA Astrophysics Data System (ADS)

Wideman, Thomas W.

Boron-containing non-oxide ceramics demonstrate a number of important structural, electronic and physical properties. However, the lack of general synthetic routes to generate these materials with controlled composition, under moderate conditions, and in processed forms, has hampered both scientific studies and practical applications. The goal of the work described in this dissertation was to develop efficient new polymeric precursor routes to boron-containing materials including SiNCB ceramics composites, boron nitride fibers, and quaternary metal boro-nitride superconductors. Two types of polyborosilazane precursors to SiNCB ceramics were developed. Borazine-co-silazane copolymers were prepared through the thermal copolymerization of borazine with two silazanes, tris(trimethylsilylamino)silane, and 1,1,3,3,5,5 -hexamethylcyclotrisilazane. Polyborosilazanes with pendent boron-containing species were obtained by the modification of preformed hydridopolysilazane polymers with three monofunctional boranes: pinacolborane, 2,4-diethylborazine and 1,3-dimethyl-1,3-diaza-2-boracyclopentane. Pyrolyses of both types of polyborosilazanes produced SiNCB ceramics with controllable boron contents, enhanced thermal stabilities, and reduced crystallinity. Processible polymeric precursors to BN were also achieved by the chemical modification of polyborazylene, (Bsb3Nsb3Hsb{˜ 4}rbrack sb{x}, with diethylamine, dipentylamine, and hexamethyldisilazane. The modified polymers, unlike the parent polyborazylene, do not crosslink at low temperatures, and therefore proved to be ideal melt-spinnable precursors to BN ceramic fibers. A new polymeric precursor route to the recently discovered Lasb3Nisb2Bsb2Nsb3 superconductor (Tc = 12K) was developed by reacting lanthanum and nickel powders dispersed in the polyborazylene, to produce the intermetallic in excellent yields. The use of the polymer as a "reagent" provided a controllable, solid state source of nitrogen, and allows for the large scale syntheses of Lasb3Nisb2Bsb2Nsb3 and other quaternary metal boro-nitrides. Two new preparations of borazine, Bsb3Nsb3Hsb6, a key molecular unit in many of the polymers described above, have also been developed. Chemical investigations and practical applications of borazine-based preceramic polymers have been limited by the inefficient syntheses and high cost of borazine, which may now be prepared in 55-65% yields by the convenient, inexpensive the reaction of ammonium and borohydride salts, and the decomposition of ammonia borane, in high-boiling ether solutions.

A new high-speed hollow fiber based liquid phase microextraction method using volatile organic solvent for determination of aromatic amines in environmental water samples prior to high-performance liquid chromatography.

PubMed

Sarafraz-Yazdi, A; Mofazzeli, F; Es'haghi, Z

2009-07-15

A new and fast hollow fiber based liquid phase microextraction (HF-LPME) method using volatile organic solvents coupled with high-performance liquid chromatography (HPLC) was developed for determination of aromatic amines in the environmental water samples. Analytes including 3-nitroaniline, 3-chloroaniline and 4-bromoaniline were extracted from 6 mL basic aqueous sample solution (donor phase, NaOH 1 mol L(-1)) into the thin film of organic solvent that surrounded and impregnated the pores of the polypropylene hollow fiber wall (toluene, 20 microL), then back-extracted into the 6 mL acidified aqueous solution (acceptor phase, HCl 0.5 mol L(-1)) in the lumen of the two-end sealed hollow fiber. After the extraction, 5 microL of the acceptor phase was withdrawn into the syringe and injected directly into the HPLC system for the analysis. The parameters influencing the extraction efficiency including the kind of organic solvent and its volume, composition of donor and acceptor phases and the volume ratio between them, extraction time, stirring rate, salt addition and the effect of the analyte complexation with 18-crown-6 ether were investigated and optimized. Under the optimal conditions (donor phase: 6 mL of 1 mol L(-1) NaOH with 10% NaCl; organic phase: 20 microL of toluene; acceptor phase: 6 microL of 0.5 mol L(-1) HCl and 600 mmol L(-1) 18-crown-6 ether; pre-extraction and back-extraction times: 75 s and 10 min, respectively; stirring rate: 800 rpm), the obtained EFs were between 259 and 674, dynamic linear ranges were 0.1-1000 microg L(-1) (R>0.9991), and also the limits of detection were in the range of 0.01-0.1 micro gL(-1). The proposed procedure worked very well for real environmental water samples with microgram per liter level of the analytes, and good relative recoveries (91-102%) were obtained for the spiked sample solutions.

Hyperbranched PEGmethacrylate linear pDMAEMA block copolymer as an efficient non-viral gene delivery vector.

PubMed

Mathew, Asha; Cao, Hongliang; Collin, Estelle; Wang, Wenxin; Pandit, Abhay

2012-09-15

A unique hyperbranched polymeric system with a linear poly-2-dimethylaminoethyl methacrylate (pDMAEMA) block and a hyperbranched polyethylene glycol methyl ether methacrylate (PEGMEMA) and ethylene dimethacrylate (EGDMA) block was designed and synthesized via deactivation enhanced atom transfer radical polymerisation (DE-ATRP) for efficient gene delivery. Using this unique structure, with a linear pDMAEMA block, which efficiently binds to plasmid DNA (pDNA) and hyperbranched polyethylene glycol (PEG) based block as a protective shell, we were able to maintain high transfection levels without sacrificing cellular viability even at high doses. The transfection capability and cytotoxicity of the polymers over a range of pDNA concentration were analysed and the results were compared to commercially available transfection vectors such as polyethylene imine (branched PEI, 25 kDa), partially degraded poly(amido amine)dendrimer (dPAMAM; commercial name: SuperFect(®)) in fibroblasts and adipose tissue derived stem cells (ADSCs). Copyright © 2012 Elsevier B.V. All rights reserved.

Curcumin-Loading-Dependent Stability of PEGMEMA-Based Micelles Affects Endocytosis and Exocytosis in Colon Carcinoma Cells.

PubMed

Chang, Teddy; Trench, David; Putnam, Joshua; Stenzel, Martina H; Lord, Megan S

2016-03-07

Polymeric micelles were formed from poly(poly(ethylene glycol) methyl ether methacrylate)-block-poly(styrene) (P(PEGMEMA)-b-PS) block copolymer of two different chain lengths. The micelles formed were approximately 16 and 46 nm in diameter and used to encapsulate curcumin. Upon loading of the curcumin into the micelles, their size increased to approximately 34 and 80 nm in diameter, respectively, with a loading efficiency of 58%. The unloaded micelles were not cytotoxic to human colon carcinoma cells, whereas only the smaller loaded micelles were cytotoxic after 72 h of exposure. The micelles were rapidly internalized by the cells within minutes of exposure, with the loaded micelles internalized to a greater extent owing to their enhanced stability compared to that of the unloaded micelles. The larger micelles were more rapidly internalized and exocytosed than the smaller micelles, demonstrating the effect of micelle size and drug loading on drug delivery and cytotoxicity.

The study on the application of low polymerization degree PODE2

NASA Astrophysics Data System (ADS)

Xue, Zhenzhen; Shang, Hongyan; Zhang, Zailong; Cui, Chuntao; Zhao, Shidong

2017-05-01

Polyoxymethylene dimethyl ethers (PODEn) are a kind of excellent diesel blending components. Due to the low flash point of PODE2, it is not appropriate to be used as diesel blending component, so in this paper, the application of PODE2 have been studied. It seems that PODE2 is a kind of excellent green rubber solvent oil without sulfur and aromatic. Moreover, the application of PODE2 as gasoline blending component is investigated and it is found that the Research Octane Number(RON) of gasoline product and the RON of four different gasoline components(including hydrofining gasoline, hydrocracking light naphtha, catalytic reforming gasoline and mixed gasoline with 80vol% hydrofining gasoline and 20vol% catalytic reforming gasoline) is all slightly decreased to some extent respectively, which indicates that there is no apparently synergistic effect between PODE2 and the gasoline components, but PODE2 can effectively reduce the sulfur content, olefin content, aromatic content and can suppress the vapor pressure of gasoline.

A novel method for the fabrication of microfluidic devices by photopolymerization of polymethylmethacrylate

NASA Astrophysics Data System (ADS)

Forstater, Jacob; Augustine, Brian; Hughes, Chris

2006-11-01

We have developed a new technique for the rapid fabrication of structures useful for microfluidic devices called micromolding by photopolymerization in capillaries (μ-PIC). The technique involves the replication of features from a silicon master in which features on the order of tens to hundreds of microns have been formed by crystallographic etching. The negative of the features is then transferred to a sheet of polymethylmethacrylate (PMMA) by placing the PMMA sheet over the silicon master and injecting a solution of methylmethacrylate monomer with a benzoin methyl ether photoinitiator. This solution is drawn between the PMMA and the silicon by capillary action forming a liquid layer that is no more than a few hundred microns thick. This liquid is then polymerized by exposure to ultraviolet light for less than a half hour. The features transferred in this manner have nearly identical surface structure and roughness. Analysis of these surfaces and structures by atomic force microscopy and scanning electron microscopy will be presented.

A convergent approach to biocompatible polyglycerol "click" dendrons for the synthesis of modular core-shell architectures and their transport behavior.

PubMed

Wyszogrodzka, Monika; Haag, Rainer

2008-01-01

Dendrimers are an important class of polymeric materials for a broad range of applications in which monodispersity and multivalency are of interest. Here we report on a highly efficient synthetic route towards bifunctional polyglycerol dendrons on a multigram scale. Commercially available triglycerol (1), which is highly biocompatible, was used as starting material. By applying Williamson ether synthesis followed by an ozonolysis/reduction procedure, glycerol-based dendrons up to the fourth generation were prepared. The obtained products have a reactive core, which was further functionalized to the corresponding monoazido derivatives. By applying copper(I)-catalyzed 1,3-dipolar cycloaddition, so-called "click" coupling, a library of core-shell architectures was prepared. After removal of the 1,2-diol protecting groups, water-soluble core-shell architectures 24-27 of different generations were obtained in high yields. In the structure-transport relationship with Nile red we observe a clear dependence on core size and generation of the polyglycerol dendrons.

Dielectric properties of transformer paper impregnated by mineral oil based magnetic fluid

NASA Astrophysics Data System (ADS)

Timko, M.; Kopčanský, P.; Marton, K.; Tomčo, L.; Koneracká, M.

2010-01-01

The influence of combined magnetic and electric field on permittivity of transformer paper used in power transformers was observed. Transformer paper was impregnated by pure transformer oil ITO 100 and magnetic fluids based on transformer oil ITO 100 with different concentrations of magnetite nanoparticles. The measurements were carried out with help of high precision capacitance bridge. The electric intensity between circular planar electrodes was in the region of weak electric field (E > 106 V/m). The increase of electric permittivity of transformer paper impregnated by magnetic fluid opposite pure transformer paper was observed. The experiments showed that permittivity of insulator system consisting of pure transformer paper and impregnated transformer paper naturally depends on number of paper layers. The magnetodielectric effect was found to be dependent on magnetite nanoparticles concentration in magnetic fluids.

Synthesis of K2O/Zeolite catalysts by KOH impregnation for biodiesel production from waste frying oil

NASA Astrophysics Data System (ADS)

Fitriana, N.; Husin, H.; Yanti, D.; Pontas, K.; Alam, P. N.; Ridho, M.; Iskandar

2018-03-01

K2O/Zeolite compounds were successfully synthesized using KOH as starting material and natural zeolite as support. The catalysts were calcined at 500°C for 3 h and then characterized by X-Ray Diffractometer (XRD) and Scanning Electron Microscopy (SEM). The SEM images reveal that the zeolite and K2O/zeolite particles are irregular in shape (100 to 400 nm). The independent variables were impregnated amounts of KOH (15 - 25%), catalyst to oil ratios of 1.0 - 6.0 wt.%, and reaction time of 2 h. The highest biodiesel yield of 95% was produced from the reaction with 2.1 wt.% catalyst of 25% KOH impregnated. The properties of produced biodiesel complied with SNI. The catalytic stability test showed that the 25% KOH impregnated catalyst was stable.

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

Nacapricha, D.; Taylor, C.

Studies have been performed on potassium-iodide-impregnated charcoals of the type used in the nuclear industry for trapping radioiodine released during nuclear fission. The effects of various parameters on the trapping efficiency of methyl iodide have been investigated. A variation in particle size within a bulk charcoal caused poor precision in K value measurements because of differences in surface area, pore volume, and bed density, leading to differences in the deposition of the impregnant. Precision is improved by sieving the charcoal to a narrower size because smaller particles have a higher porosity. This finding is supported by surface area and poremore » measurements. Two methods of impregnation are compared by measuring K values and the deposition of potassium iodide. Charcoal impregnated by rotary evaporation exhibits both higher K values and higher potassium iodide contents than sprayed charcoal. Two designs of spraying drum are compared: a drum with helical vanes allows more efficient deposition and more uniform distribution of impregnant than a drum with axial vanes. A decrease in the K value with increasing humidity correlates with the available surface area. A similar correlation exists between water content and available pore volume. Aging of potassium-iodide-impregnated charcoal, caused by the formation of oxygen complexes on the surface, is associated with significant falls in K value. K values of charcoals also can be restored to at least their original values by heat treatment in the absence of air. 12 refs., 6 figs., 1 tab.« less

Comparison of Fluoridated Miswak and Toothbrushing with Fluoridated Toothpaste on Plaque Removal and Fluoride Release.

PubMed

Baeshen, Hosam; Salahuddin, Sabin; Dam, Robel; Zawawi, Khalid H; Birkhed, Dowen

2017-04-01

Dental caries and periodontal diseases are all induced by oral biofilm (dental plaque). This study was conducted to evaluate if fluoride-impregnated miswak is as effective in plaque removal and fluoride release as toothbrushing with fluoride toothpaste. This single-blind, randomized, crossover study was conducted at the Department of Cariology, University of Gothenburg, Gothenburg, Sweden, from February 2010 to January 2011. Fifteen healthy subjects participated in this study. The participants were instructed to use the following: (1) 0.5% NaF-impregnated miswak, (2) nonfluoridated miswak, (3) toothbrush with nonfluoride toothpaste, and (4) toothbrush with 1450 ppm fluoride toothpaste. Each method was used twice a day for 1 week after which plaque amount and fluoride concentration in resting saliva were measured. There was a 1-week washout period between each method. No significant difference between miswak and tooth-brushing was found regarding plaque removal on buccal and lingual surfaces. A somewhat higher fluoride concentration in resting saliva was found after using impregnated miswak when compared with toothbrushing with fluoride toothpaste (p < 0.05). Miswak and toothbrushing showed the same plaque removing effect on buccal and lingual surfaces. Miswak impregnated with 0.5% NaF resulted in a higher concentration of fluoride in saliva than brushing with 1450 ppm fluoride toothpaste. Miswak impregnated with 0.5% NaF and toothbrushing results in comparable plaque removal and about the same fluoride concentration in saliva even it was somewhat higher for impregnated miswak.

Supercritical CO2 impregnation of PLA/PCL films with natural substances for bacterial growth control in food packaging.

PubMed

Milovanovic, Stoja; Hollermann, Gesa; Errenst, Cornelia; Pajnik, Jelena; Frerich, Sulamith; Kroll, Stephen; Rezwan, Kurosch; Ivanovic, Jasna

2018-05-01

Biodegradable polymers with antibacterial properties are highly desirable materials for active food packaging applications. Thymol, a dietary monoterpene phenol with a strong antibacterial activity is abundant in plants belonging to the genus Thymus. This study presents two approaches for supercritical CO 2 impregnation of poly(lactic acid)(PLA)/poly(ε-caprolactone)(PCL) blended films to induce antibacterial properties of the material: (i) a batch impregnation process for loading pure thymol, and (ii) an integrated supercritical extraction-impregnation process for isolation of thyme extract and its incorporation into the films, operated in both batch or semi-continuous modes with supercritical solution circulation. The PCL content in films, impregnation time and CO 2 flow regime were varied to maximize loading of the films with thymol or thyme extract with preserving films' structure and thermal stability. Representative film samples impregnated with thymol and thyme extract were tested against Gram (-) (Escherichia coli) and Gram(+) (Bacillus subtilis) model strains, by measuring their metabolic activity and re-cultivation after exposure to the films. The film containing thymol (35.8 wt%) showed a strong antibacterial activity leading to a total reduction of bacterial cell viability. Proposed processes enable fast, controlled and organic solvent-free fabrication of the PLA/PCL films containing natural antibacterial substances at moderately low temperature, with a compact structure and a good thermal stability, for potential use as active food packaging materials. Copyright © 2018 Elsevier Ltd. All rights reserved.

Biodegradation of bis(1-chloro-2-propyl) ether via initial ether scission and subsequent dehalogenation by Rhodococcus sp. strain DTB.

PubMed

Moreno Horn, Marcus; Garbe, Leif-Alexander; Tressl, Roland; Adrian, Lorenz; Görisch, Helmut

2003-04-01

Rhodococcus sp. strain DTB (DSM 44534) grows on bis(1-chloro-2-propyl) ether (DDE) as sole source of carbon and energy. The non-chlorinated diisopropyl ether and bis(1-hydroxy-2-propyl) ether, however, did not serve as substrates. In ether degradation experiments with dense cell suspensions, 1-chloro-2-propanol and chloroacetone were formed, which indicated that scission of the ether bond is the first step while dehalogenation of the chlorinated C(3)-compounds occurs at a later stage of the degradation pathway. Inhibition of ether scission by methimazole suggested that the first step in degradation is catalyzed by a flavin-dependent enzyme activity. The non-chlorinated compounds 1,2-propanediol, hydroxyacetone, lactate, pyruvate, 1-propanol, propanal, and propionate also supported growth, which suggested that the intermediates 1,2-propanediol and hydroxyacetone are converted to pyruvate or to propionate, which can be channeled into the citric acid cycle by a number of routes. Total release of chloride and growth-yield experiments with DDE and non-chlorinated C(3)-compounds suggested complete biodegradation of the chlorinated ether.

Some actions of substituted choline phenyl ethers, particularly of choline 2:6-xylyl ether

PubMed Central

Edge, N. D.; Mason, D. F. J.; Wyllie, J. H.

1957-01-01

Marked nicotine-like stimulant properties are possessed by choline phenyl ether and choline o-tolyl ether, and to a decreasing extent by choline 2:6-xylyl ether and choline 2:4:6-mesityl ether. The compounds all show neuromuscular blocking properties, which are of short duration and pass from mainly decamethonium-like to mainly curare-like as more methyl groups are added to the phenyl nucleus. This series of compounds also possesses muscarinic, weak anti-adrenaline and vasodilator properties, as well as long-lasting local anaesthetic effects in the two compounds tested by intradermal injection. PMID:13460236

Catalyst Of A Metal Heteropoly Acid Salt That Is Insoluble In A Polar Solvent On A Non-Metallic Porous Support And Method Of Making

DOEpatents

Wang. Yong; Peden. Charles H. F.; Choi. Saemin

2004-11-09

The present invention includes a catalyst having (a) a non-metallic support having a plurality of pores; (b) a metal heteropoly acid salt that is insoluble in a polar solvent on the non-metallic support; wherein at least a portion of the metal heteropoly acid salt is dispersed within said plurality of pores. The present invention also includes a method of depositing a metal heteropoly acid salt that is insoluble in a polar solvent onto a non-metallic support having a plurality of pores. The method has the steps of: (a) obtaining a first solution containing a first precursor of a metal salt cation; (b) obtaining a second solution containing a second precursor of a heteropoly acid anion in a solvent having a limited dissolution potential for said first precursor; (c) impregnating the non-metallic support with the first precursor forming a first precursor deposit within the plurality of pores, forming a first precursor impregnated support; (d) heating said first precursor impregnated support forming a bonded first precursor impregnated support; (e) impregnating the second precursor that reacts with the precursor deposit and forms the metal heteropoly acid salt.

Catalyst of a metal heteropoly acid salt that is insoluble in a polar solvent on a non-metallic porous support and method of making

DOEpatents

Wang, Yong [Richland, WA; Peden, Charles H. F. [West Richland, WA; Choi, Saemin [Richland, WA

2002-10-29

The present invention includes a catalyst having (a) a non-metallic support having a plurality of pores; (b) a metal heteropoly acid salt that is insoluble in a polar solvent on the non-metallic support; wherein at least a portion of the metal heteropoly acid salt is dispersed within said plurality of pores. The present invention also includes a method of depositing a metal heteropoly acid salt that is insoluble in a polar solvent onto a non-metallic support having a plurality of pores. The method has the steps of: (a) obtaining a first solution containing a first precursor of a metal salt cation; (b) obtaining a second solution containing a second precursor of a heteropoly acid anion in a solvent having a limited dissolution potential for said first precursor; (c) impregnating the non-metallic support with the first precursor forming a first precursor deposit within the plurality of pores, forming a first precursor impregnated support; (d) heating said first precursor impregnated support forming a bonded first precursor impregnated support; (e) impregnating the second precursor that reacts with the precursor deposit and forms the metal heteropoly acid salt.

Development of hydroxyapatite/polyvinyl alcohol bionanocomposite for prosthesis implants

NASA Astrophysics Data System (ADS)

Karthik, V.; Pabi, S. K.; Chowdhury, S. K. Roy

2018-02-01

Hydroxyapatite (Ca10(PO4)6(OH)2) has similar structural and chemical properties of natural bone mineral and hence widely used as a bone replacement substitute. Natural bone consists of hydroxyapatite and collagen. For mimicking the natural, in the present work, a sintered porous hydroxyapatite component has been vacuum impregnated with Polyvinyl alcohol (PVA), which has better properties like biocompatibility, biodegradability and water- solubility. Hydroxyapatite powders have been made into nanosize to reduce the melting point and hence the sintering temperature. In the present investigation high energy ball mill is used to produce nano-hydroxyapatite powders in bulk quantity by optimizing the milling parameters using stainless steel grinding media. Pellets of 10 mm diameter have been produced from nano- hydroxyapatite powders under different uniaxial compaction pressures. The pellets have been sintered to form porous compacts. The vacuum impregnation of sintered pallets with PVA solution of different strength has been done to find the optimum impregnation condition. Microhardness, compressive strength, wear loss and haemocompatibility of hydroxyapatite ceramics have been studied before and after impregnation of PVA. The nano- hydroxyapatite/PVA composites have superior mechanical properties and reduced wear loss than the non-impregnated porous nano-hydroxyapatite ceramics.